Novel phosphazene applied on carrier catalyst, novel compound and its application

FIELD: chemistry.

SUBSTANCE: in phosphazene, applied on carrier, catalyst for cyclic monomer polymerisation or for substituent substitution in compound or for carrying out reaction with formation of carbon-carbon bond, carrier is insoluble in used solvent and has group, which is able to form bond with group described with general formula (1) where n is integer in interval from 1 to 8 and represents number of phosphazene cations, Zn- is anion of compound, containing atoms of active hydrogen in form obtained as result of release of n protons from compound, which contains atoms of active hydrogen, in which there are , at most, 8 atoms of active hydrogen; each of a, b, c and d represents positive integer equal 3 or less; R represents similar or different hydrocarbon groups, containing from 1 to 10 carbon atoms, and two R, located on each common nitrogen atom, can be bound with each other with formation of ring structure; R1 represents hydrogen atom or hydrocarbon group, containing from 1 to 10 carbon atoms; D represents direct bond or divalent group able to bind N with carrier. Described are phosphazene compound and phosphazene salts and methods of cyclic monomer polymerisation, substitution of substituent in compound and carrying out of reaction with formation of carbon-carbon bond using applied on carrier catalyst. According to invention method polymerisation of cyclic monomers, substitution of substituents, reactions with formation of carbon-carbon bond, etc. can be carried out with extremely high efficiency.

EFFECT: increase of efficiency of carrying out different organic reactions and absence of activity decrease even after removal and re-use of catalyst, economic benefit.

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BACKGROUND of the INVENTION

1. The technical field

The present invention relates to a new supported on a carrier catalyst, to a new pospisilova connection and to the use of the catalyst. More specifically, the invention relates to pospisilova supported on a carrier catalyst in which the carrier forms a link with the group, opisyvayuschaya General formula (1); new pospisilova connection and the new phosphazene salts, which are suitable for use in obtaining deposited on the catalyst carrier; and a method of polymerization of the cyclic monomer, method of substitution of the substituent and the carrying out of the reaction with obtaining carbon-carbon using deposited on the catalyst carrier.

2. The level of technology

Phosphatemia salt, vpisivaushiesya next next General formula (9):

(where n is an integer in the range from 1 to 8 and represents the number phosphazenes cations and Znrepresents the anion of n-valent compounds containing active hydrogen atoms, in the form obtained by releasing n protons of compounds containing active hydrogen atoms, which has at most 8 active hydrogen atoms to the oxygen atom or the nitrogen atom, a, b, c and d represent is a positive integer, equal to 3 or less or 0, respectively, with the proviso that they are all not 0 at the same time, R represents the same or different hydrocarbon groups containing from 1 to 10 carbon atoms, and two R's located on each common nitrogen atom may be linked to each other to form a ring structure), known as the compound that promotes the flow of various catalytic reactions due to the formation of a stable cation and selection of counterions (see document JP-A No. 10-77289). This compound is effective at carrying out various catalytic reactions, but it is relatively difficult to obtain, it is expensive, and thus, it is desirable to reuse the catalyst. At the same time, it is known that phosphazene connection with the binding site (so-called phosphazene base), forms a bond with the functional group of the carrier and is obtained in the form supported on a carrier, and it is also known that such deposited on the carrier of the catalyst used for polymerization of accelerated (see publication of international patent application No. WO01/90220).

The above supported on a carrier, the catalyst is suitable for use, but it custom made organic polymer carrier forms a bond directly or op is sledovane with the nitrogen atom, related to the phosphorus atom in the center. This leads to the problem lies in the fact that the stability of the cation of the low from the point of view of its chemical structure, and therefore, probably, it will decompose. Cation phosphazene salt having the skeleton, vpisivaushiesya General formula (9), characterized by high stability, manifested in its chemical structure. However, the commonly used method was impossible phosphazene salt having the skeleton, vpisivaushiesya General formula (9), apply to the carrier, to thereby obtain such deposited on the catalyst carrier. In addition, it was unknown the introduction of a binding site in phosphazene salt, opissyvayusya General formula (9), and was unknown in the effective application of phosphazene salt, opisyvayuschaya General formula (9), to the media following the receipt and use of phosphazene salt containing the binding site, while maintaining its operational characteristics as such.

Therefore, there is a need to get supported on a carrier catalyst having the function phosphazene salt, opisyvayuschaya General formula (9)as such, and thus, it is desirable to develop such deposited on the catalyst carrier.

SUMMARY of INVENTION

The inventors of the present invention to perform the intensive research of the catalyst with the purpose of solving the above problem and as a result found that, what to get deposited on the catalyst carrier having the skeleton, vpisivaushiesya General formula (9), and, thus, to solve the above problem can be used a specific product partial transformation patterns obtained from phosphazene salt, opisyvayuschaya General formula (9), and, thus, created the invention in its entirety.

Specifically, the invention relates to pospisilova supported on a carrier catalyst in which the carrier forms a link with the group, opisyvayuschaya General formula (1):

(where n is an integer in the range from 1 to 8 and represents the number phosphazenes cations and Znrepresents an anion compounds containing active hydrogen atoms, in the form obtained by releasing n protons of compounds containing active hydrogen atoms, which has at most 8 active hydrogen atoms. Each of a, b, c and d represents a positive integer equal to 3 or less. R represent identical or different hydrocarbon groups containing from 1 to 10 carbon atoms, and two R's located on each common nitrogen atom may be linked to each other to form a ring structure. R1represents a hydrogen atom or glevodorodnogo group, containing from 1 to 10 carbon atoms. D represents a direct bond or a divalent group capable of binding with N carrier).

In addition, the invention relates to a new pospisilova connection, opisyvaemye General formula (2):

(where a, b, c and d represents a positive integer equal to 3 or less, respectively. R represent identical or different hydrocarbon groups containing from 1 to 10 carbon atoms, and two R's located on each common nitrogen atom may be linked to each other to form a ring structure);

new pospisilova connection, opisyvaemye General formula (3):

(where each of a, b, c and d represents a positive integer equal to 3 or less. G represents an oxygen atom or a sulfur atom. R represent identical or different hydrocarbon groups containing from 1 to 10 carbon atoms, and two R's located on each common nitrogen atom may be linked to each other to form a ring structure);

the new phosphazene salt, opisyvayuschaya General formula (4):

(where each of a, b, c and d represents a positive integer equal to 3 or less, respectively. R represent Soboh the same or different hydrocarbon groups, containing from 1 to 10 carbon atoms, and two R's located on each common nitrogen atom may be linked to each other to form a ring structure. X represents a halogen atom, and X-represents an anion of a halogen atom, which may be identical or different in comparison with X); and

the new phosphazene salt, opisyvayuschaya General formula (5):

(where n is an integer in the range from 1 to 8 and represents the number phosphazenes cations and Znrepresents an anion compounds containing active hydrogen atoms, in the form obtained by releasing n protons of compounds containing active hydrogen atoms, which has at most 8 active hydrogen atoms. Each of a, b, c and d represents a positive integer equal to 3 or less. R represent identical or different hydrocarbon groups containing from 1 to 10 carbon atoms, and two R's located on each common nitrogen atom may be linked to each other to form a ring structure. R1represents a hydrogen atom or a hydrocarbon group containing from 1 to 10 carbon atoms. D' represents a monovalent group which forms a link with N, with the proviso that it is different from the atom in Dorada and saturated hydrocarbon group), which are suitable for use in obtaining catalyst supported on a carrier.

The invention also relates to the new phosphazene salt, opisyvayuschaya General formula (6):

(where n is an integer in the range from 1 to 8 and represents the number phosphazenes cations and Znrepresents an anion compounds containing active hydrogen atoms, in the form obtained by releasing n protons of compounds containing active hydrogen atoms, which has at most 8 active hydrogen atoms. Each of a, b, c and d represents a positive integer equal to 3 or less. R represent identical or different hydrocarbon groups containing from 1 to 10 carbon atoms, and two R's located on each common nitrogen atom may be linked to each other to form a ring structure. Rather it represents a hydrocarbon group containing from 1 to 20 carbon atoms. In addition, R1represents a hydrogen atom or a hydrocarbon group containing from 1 to 10 carbon atoms. Each of R2, R3, R4and R5represents a hydrogen atom or a hydrocarbon group containing from 1 to 8 carbon atoms, e is in the range from 0 to 200), as one site is titeling embodiments phosphazene salt, opisyvayuschaya General formula (5);

the new phosphazene salt, opisyvayuschaya General formula (7):

(where n is an integer in the range from 1 to 8 and represents the number phosphazenes cations and Znrepresents an anion compounds containing active hydrogen atoms, in the form obtained by releasing n protons of compounds containing active hydrogen atoms, which has at most 8 active hydrogen atoms. Each of a, b, c and d represents a positive integer equal to 3 or less. R represent identical or different hydrocarbon groups containing from 1 to 10 carbon atoms, and two R's located on each common nitrogen atom may be linked to each other to form a ring structure. R1represents a hydrogen atom or a hydrocarbon group containing from 1 to 10 carbon atoms. M represents a group containing an unsaturated bond carbon-carbon), as another preferred embodiments phosphazene salt, opisyvayuschaya General formula (5); and

the new phosphazene salt, opisyvayuschaya General formula (8):

(where m is an integer in the range from 1 to 3 and represents the number phosphazenes ka the ions, associated with the silicon atom, n' is an integer in the range from 1 to 8 and represents the number of silicon compounds, which phosphazenes cations form a bond, n is a multiplier for m and n', and Znrepresents an anion compounds containing active hydrogen atoms, in the form obtained by releasing n protons of compounds containing active hydrogen atoms, which has at most 24 active hydrogen atom. Each of a, b, c and d represents a positive integer equal to 3 or less. R represent identical or different hydrocarbon groups containing from 1 to 10 carbon atoms, and two R's located on each common nitrogen atom may be linked to each other to form a ring structure. Represents a hydrocarbon group containing from 1 to 20 carbon atoms. In addition, R1represents a hydrogen atom or a hydrocarbon group containing from 1 to 10 carbon atoms. T represents a functional group in which the connection Si-T can be destroyed by hydrolysis), as the preferred embodiments phosphazene salt, opisyvayuschaya General formula (5).

The invention also relates to a method of polymerization of the cyclic monomer, in which the use you described the e deposited on the catalyst carrier, the way to replace the Deputy, which use the above-described deposited on the catalyst carrier, and the method of carrying out the reaction in which the above-described deposited on the carrier of the catalyst used in the reactions with formation of carbon-carbon.

Phosphazenes supported on a carrier, the catalyst corresponding to the present invention is highly effective at carrying out a variety of organic reactions and, in addition, shows no reduction activity even after removing and re-use of the catalyst, and thus, it can be effectively reused, and it is also economically advantageous. In addition, phosphazene connection and phosphatemia salt of the invention are intermediate compounds which can easily obtain the above-described deposited on the catalyst carrier of the invention, but are also catalysts which are suitable for use in carrying out various organic reactions. In addition, in accordance with the method of the invention the polymerization of cyclic monomers, the substitution of the substituents, the reaction with the formation of carbon-carbon and the like can be performed with extremely high efficiency.

DESCRIPTION of IMPLEMENTATION OPTIONS

the alley herein, the invention will be described in detail.

In the General formulas from (1) to (8) R are the same or different hydrocarbon groups containing from 1 to 10 carbon atoms. In the hydrocarbon group represented by the symbol R, especial limitation is imposed, and it may represent an aliphatic hydrocarbon group or aromatic hydrocarbon group. Aliphatic hydrocarbon group includes, for example, alkyl group containing from 1 to 10 carbon atoms, such as methyl, ethyl and sawn; alkenylphenol group containing from 2 to 10 carbon atoms, such as vinyl and allyl; alkylamino group containing from 2 to 10 carbon atoms, such as etinilnoy and proponila, and the aromatic hydrocarbon group includes, for example, aryl group containing from 6 to 10 carbon atoms, such as phenyl and naftalina; and aracelio group containing 7 to 10 carbon atoms, such as benzyl and penicilina. R preferably represents an aliphatic hydrocarbon group, and more preferably methyl group and ethyl group.

In the General formulas from (1) to (8) two R's located on each common nitrogen atom may be linked to each other to form a ring structure. The group obtained by combining with each other two R's located on each common atom AZ is the includes, for example, alkylenes group containing from 2 to 10 carbon atoms, such as ethylene, tetramethylene and pentamethylene; cycloalkenyl group containing from 3 to 10 carbon atoms, such as cyclohexylurea; alkynylamino group containing from 2 to 10 carbon atoms, such as venelinova; cycloalkenyl group containing from 3 to 10 carbon atoms, such as cyclohexadienone; Allenova group containing from 6 to 20 carbon atoms, such as fenelonov and naftalanovaja; and Aracinovo group containing from 8 to 20 carbon atoms, such as phenylethylene. Among them preferred are tetramethylurea and pentamethylene. Such ring structure may form part or all of the amount of each common nitrogen atom, to which two atoms R form a connection.

In the General formulas from (1) to (8) each of a, b, c and d represents a positive integer equal to 3 or less. Preferably they represent a positive integer equal to 2 or less, and the preferred combination of a, b, c and d includes (2, 1, 1, 1) and (1, 1, 1, 1) regardless of the order of a, b, c and d, and particularly preferred combination is a(1, 1, 1, 1).

In the General formulas(1), (5), (6), (7) and (8) R1represents a hydrogen atom or a hydrocarbon group containing from 1 to 10 atoms of plastics technology : turning & is Yes. In the hydrocarbon group represented by the symbol R1special limitation is imposed, and it may be an aliphatic hydrocarbon group or aromatic hydrocarbon group. Aliphatic hydrocarbon group and aromatic hydrocarbon group include the same specific examples as those listed above for R in General formulas from (1) to (8). R1preferably represents an aliphatic hydrocarbon group, and more preferably methyl group or ethyl group.

In the General formula (1) D is a direct bond or a divalent group capable of forming a bond between N and the media. The divalent group represented by the symbol D may form a bond between the nitrogen atom in phosphazenes the cation and the media, and special restrictions not imposed until then, until it begins to impede the achievement of the objectives of the invention.

As described above, D can be any D until then, until he begins to impede the achievement of the purpose of the invention, and it can form a bond with the nitrogen atom phosphazenes cations through a carbon atom or to form a bond with the nitrogen atom phosphazenes cations through a heteroatom. However, from the point of view of bond strength is preferred to form a relationship with atom azo is and phosphazenes cations through the carbon atom.

The distance between the nitrogen atom present in phosphazenes cations, and the media special limitation is imposed, it is clear that, in the spirit of the invention. However, the number of atoms constituting the main chain of D depends on the size of the media, but in General it is in the range from approximately 1 to 600, and from the viewpoint of increasing the concentration of catalyst deposited on the carrier of the catalyst, it is preferably in the range from 1 to 300, and more preferably from 1 to 100.

In addition, from the viewpoint of obtaining preferred to phosphazene compounds (2) and (3), phosphazene salt(4), (5), (6), (7) and (8), which are suitable for use in obtaining deposited on the catalyst carrier of the invention, or a compound which, in addition, has a reactive group that is connected with them, would react with the carrier, which previously would introduce a functional group that can react with the above-mentioned compounds in mild conditions obtaining D. In the case of obtaining using this method of getting their binding sites represent a communication containing heteroatom, typically an oxygen atom, a nitrogen atom, a sulfur atom and the like, such as in the case of a simple ester, complex ester, simple tiefer, complex t is aafire, amine, amide, and the like.

In addition, for example, as one example, it may be preferable to phosphatemia salt (7), suitable for use in obtaining deposited on the catalyst carrier of the invention, and the compound having a curable functional group, would be depolimerization, or to phosphatemia salt (8) and the silicon compound having a hydrolyzable group, such as alkoxysilane and the like, would be depolimerization that would provide a synthesis of the carrier and simultaneously receiving D.

The divalent group represented by D includes, for example, hydrocarbon group which may contain a heteroatom such as oxygen atom, sulfur atom, nitrogen atom and silicon atom, specifically, alkylenes group containing from 1 to 50 carbon atoms, such as methylene, ethylene, 1,2-dimethylethylene and pentamethylene; cycloalkenyl group containing from 3 to 50 carbon atoms, such as cyclohexylurea; alkynylamino group containing from 2 to 50 carbon atoms, such as venelinova and propylea; cycloalkenyl group containing from 3 to 50 atoms carbon, such as cyclohexadienone; Allenova group containing from 6 to 100 carbon atoms, such as fenelonov and naftalanovaja; Aracinovo group containing from 7 is about 100 carbon atoms, such as phenylmethylene; a hydrocarbon group comprising a combination of hydrocarbon groups, such as fenilmetilovy; those in which a part of hydrogen atoms in the above hydrocarbon group substituted by a heteroatom such as oxygen atom, nitrogen atom, sulfur atom and a silicon atom, or a hydrocarbon group containing the above-mentioned heteroatom; those in which a part of carbon atoms in the above hydrocarbon group substituted by a heteroatom such as oxygen atom, nitrogen atom, sulfur atom and a silicon atom, for example, a group of alkylenedioxy containing from 1 to 50 carbon atoms, such as tetramethoxy; group cycloalkylation containing from 3 to 50 carbon atoms, such as cyclohexylamine; group alkalinity containing from 1 to 50 carbon atoms, such as tetramethylbenzidine; group alkylenediamine containing from 1 to 50 carbon atoms, such as N,N-dimethylethylenediamine; group arrangiarsi containing from 6 to 100 carbon atoms, such as phenyleneoxy; and a divalent group, opissyvayusya next next General formula (10):

(where a represents a hydrocarbon group containing from 1 to 20 carbon atoms. R2, R3, R4and R5represent a hydrogen atom or a hydrocarbon group, sotiriadou is from 1 to 8 carbon atoms. J represents an oxygen atom, a sulfur atom or NR6which may be identical or different, and R6represents a hydrogen atom or a hydrocarbon group containing from 1 to 8 carbon atoms. A' represents a direct bond or a hydrocarbon group containing from 1 to 20 carbon atoms, e is in the range from 0 to 200). In addition, a specific description of A, R2, R3, R4, R5and e are the same as in General formula (6), as described next. R6is the same as in the case of the characters from R2to R5. In the hydrocarbon group represented by the symbol A'special limitation is imposed, and it may represent an aliphatic hydrocarbon group or aromatic hydrocarbon group. Specific examples of aliphatic hydrocarbon groups and aromatic hydrocarbon groups are the same as in the case, And in the General formula (6), as described next.

In addition, as the divalent group represented above by D, a hydrocarbon group which may contain a heteroatom such as oxygen atom, sulfur atom, nitrogen atom and silicon atom, may have a structure phosphazene salt, opisyvayuschaya next next General formula 11):

(where n, Zn, a, b, c, d, R, and R1have the same meanings as in General formula (1)).

D preferably represents a divalent group, opissyvayusya General formula (10), and more preferably a group in which J represents oxygen and e is in the range from 0 to 30.

In the General formulas(1), (5), (6), (7) and (8) Znrepresents an anion compounds containing active hydrogen atoms, in the form obtained by releasing n protons of compounds containing active hydrogen atoms, which has at most 8 active hydrogen atoms (General formula(1), (5), (6) and (7)) or, at most, 24 active hydrogen atom (General formula (8)). The anion compounds containing active hydrogen atoms represented by the symbol Znspecial limitation is imposed, and it can be any anion which can form ion pair with phosphazenes cation. The compound containing the active hydrogen atoms and forming Znincludes the compound having the active hydrogen atom on the oxygen atom, nitrogen atom or sulfur atom, inorganic acid, and the like.

Among the compounds, which are Znthe connection that has the active hydrogen atom on an oxygen atom includes, for example the EP, water; carboxylic acids such as monocarboxylic acid containing from 1 to 20 carbon atoms, and polyvalent carboxylic acid containing from 2 to 20 carbon atoms, which have from 2 to 6 carboxyl groups; carbamine acid containing from 1 to 20 carbon atoms; sulfonic acids containing from 1 to 20 carbon atoms; alcohols, such as monohydroxy alcohols containing from 1 to 20 carbon atoms, and polyhydric alcohols containing from 2 to 20 carbon atoms, which have from 2 to 8 hydroxyl groups; phenols, containing from 6 to 20 carbon atoms; which have from 1 to 3 hydroxyl groups, sugars or their derivatives; and polyalkylene having active hydrogen atoms in its limit positions.

Monocarboxylic acid containing from 1 to 20 carbon atoms include, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, triperoxonane acid, stearic acid and oleic acid; aliphatic monocarboxylic acid containing an aromatic ring, such as phenylacetic acid; alicyclic monocarboxylic acids such as cyclohexanecarbonyl acid; and aromatic monocarboxylic acids such as benzoic acid and 2-carboxynaphthalene.

Polyvalent carboxylic acid containing from 2 to 20 carbon atoms to which e have from 2 to 6 carboxyl groups, include, for example, aliphatic polyvalent carboxylic acids such as oxalic acid and malonic acid; and aromatic polyvalent carboxylic acids such as phthalic acid and trimellitate acid.

Carbamine acid containing from 1 to 20 carbon atoms include, for example, N,N-diethylcarbamoyl acid, N-carboxyaniline and N,N'-dicarboxy-2,4-toluylenediamine. Sulfonic acid containing from 1 to 20 carbon atoms includes, for example, aliphatic sulfonic acids, such as methanesulfonate acid and triftormetilfullerenov acid; aliphatic sulfonic acids containing heterocycles, such as 2-morpholinobutyrophenone acid and 3-(N-morpholino)propanesulfonic acid; aromatic sulfonic acids such as benzolsulfonat acid, p-toluensulfonate acid, 4-nitrobenzenesulfonic acid, 4,4'-biphenylmethanol acid, 2-naphthalenesulfonate acid and perilalbany acid; and heterocyclic sulfonic acids, such as 3-pyridinesulfonamide acid.

Monohydroxy alcohols containing from 1 to 20 carbon atoms include, for example, aliphatic monohydroxy alcohols, such as methanol, allyl alcohol and krotilova alcohol; alicyclic monohydroxy alcohols, such as Cyclopentanol; and aliphatic monohydroxy alcohols, soda is containing aromatic ring, such as benzyl alcohol. Polyhydric alcohols containing from 2 to 20 carbon atoms, which have from 2 to 8 hydroxyl groups include, for example, aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, butanediol, trimethylolpropane, glycerin, diglycerin alcohol and pentaerythritol; alicyclic polyhydric alcohols such as 1,4-cyclohexanediol.

Phenols containing from 6 to 20 carbon atoms which have 1 to 3 hydroxyl groups include, for example, monovalent phenols such as phenol, cresol, NITROPHENOL, chlorophenol, naphthol, atrorubens, 9-phenanthrol and 1-hydroxypyrene; and divalent phenols such as catechin, dihydroxynaphthalene and bisphenol A. Sugars or their derivatives include, for example, sugars, such as glucose, sorbitol, dextrose, fructose and sucrose or their derivatives; and the like. Polyalkylene having active hydrogen atoms in its limit positions include, for example, polyethylene oxide, polypropyleneoxide and polyalkyloxy, which are copolymers of such oxides, characterized srednekamennogo molecular weight in the range of 100 to 50,000 and having from 2 to 8 of the limit positions and 1 to 8 hydroxyl groups in terminal positions.

Among the compounds, which are Znthe compound containing at what we active hydrogen, which has an active hydrogen atom on the nitrogen atom, includes, for example, ammonia; amines such as primary amines containing from 1 to 20 carbon atoms, secondary amines containing from 2 to 20 carbon atoms, polyvalent amines containing from 2 to 20 carbon atoms, which have 2 or 3 primary or secondary amino groups, saturated cyclic secondary amines containing from 4 to 20 carbon atoms, unsaturated cyclic secondary amines containing from 4 to 20 carbon atoms, and cyclic polyvalent amines containing from 4 to 20 carbon atoms that have 2 or 3 secondary amino group; and amides, such as unsubstituted or N-monosubstituted acid amides containing from 2 to 20 carbon atoms, cyclic amides containing 5-7-membered ring, and imides of dicarboxylic acids containing from 4 to 10 carbon atoms.

Primary amines containing from 1 to 20 carbon atoms include, for example, aliphatic primary amines such as methylamine, ethylamine and Propylamine; alicyclic primary amines, such as cyclohexylamine; aliphatic primary amines containing an aromatic ring, such as benzylamine and β-phenylethylamine; and aromatic primary amines, such as aniline and toluidine.

Secondary amines containing from 2 to 20 carbon atoms include, for example, aliphatic secondary amines, the e as dimethylamine, methylethylamine and dipropylamine; alicyclic secondary amines, such as dicyclohexylamine; and aromatic secondary amines, such as N-methylaniline and diphenylamine. Multivalent amines containing from 2 to 20 carbon atoms, which have 2 or 3 primary or secondary amino group include, for example, Ethylenediamine, di(2-amino-ethyl)amine, hexamethylenediamine were three(2-amino-ethyl)amine and N,N'-dimethylethylenediamine. Saturated cyclic secondary amines containing from 4 to 20 carbon atoms include, for example, pyrrolidine, piperidine, morpholine and 1,2,3,4-tetrahydroquinolin. Unsaturated cyclic secondary amines containing from 4 to 20 carbon atoms include, for example, 3-pyrrolin, pyrrole, indole, carbazole, imidazole, pyrazole and purine.

Cyclic polyvalent amines containing from 4 to 20 carbon atoms, which have 2 or 3 secondary amino groups, include, for example, piperazine, pyrazin and 1,4,7-triazacyclononane. Unsubstituted or N-monosubstituted acid amides containing from 2 to 20 carbon atoms include, for example, ndimethylacetamide, N-methylpropionamide, amide N-methylbenzoic acid and amide N-utilitarios acid. Cyclic amides containing 5-7-membered ring include, for example, 2-pyrrolidone and ε-caprolactam. Imides of dicarboxylic acids containing from 4 to 10 carbon atoms include, for example, succinic acid imide, imide m is Lanovoy acid and phthalimide.

Among the compounds, which are Znthe compound containing active hydrogen atoms, which has an active hydrogen atom on the sulfur atom includes, for example, hydrogen sulfide; tosporte, such as monohydroxy tosporte containing from 1 to 20 carbon atoms, and polyhydric tosporte containing from 2 to 20 carbon atoms; and thiophenol containing from 6 to 20 carbon atoms. Monohydroxy tosporte containing from 1 to 20 carbon atoms include, for example, aliphatic monohydroxy tosporte, such as methanethiol, ethanthiol and allylmercaptan; aliphatic monohydroxy tosporte containing aromatic ring, such as benzylmercaptan; and alicyclic monohydroxy tosporte, such as cyclopentylamine and cyclohexylurea. Polyhydric tosporte containing from 2 to 20 carbon atoms include, for example, 1,2-acondition, 1,3-PROPANEDIOL, 1,2,3-propanetriol and 2,3-di(mercaptomethyl)-1,4-butanediol.

Thiophenol containing from 6 to 20 carbon atoms include, for example, monohydroxy thiophenol, such as thiophenol, thiocresol and tinefol; and the diatomic thiophenol, such as 1,2-benzodithiol.

Among the compounds, which are Zninorganic acids include hydrogen halides such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide; boric acid, Tetra is tarboro acid, phosphoric acid, phosphorous acid, hexaphosphoric acid, hydrogen cyanide, ticinobuy acid, nitric acid, sulfuric acid, carbonic acid and perchloro acid.

Among the compounds containing active hydrogen atoms, preferred are the above-described inorganic acid and the above-described compounds containing active hydrogen atoms, having an active hydrogen atom to the oxygen atom, and more preferred are the above-described hydrogen halides, aliphatic monohydroxy alcohols, alicyclic monohydroxy alcohols, aliphatic monohydroxy alcohols containing an aromatic ring, aliphatic polyhydric alcohols, alicyclic polyhydric alcohols, saccharides or derivatives thereof, polyethylene oxide, polypropyleneoxide or polyalkyloxy, which are copolymers of such oxides, characterized srednekamennogo molecular weight in the range of 100 to 50,000 and having from 2 to 8 the limit positions and 1 to 8 hydroxyl groups in terminal positions.

As for the Znin an appropriate case, the anions can be selected in accordance with reactions as a preference for anions varies depending on the types of reactions using the catalyst of the invention. For example, for the polymerization of cyclic monomers, t is such as accelerated and the like, preferred are anions, the resulting release of the active hydrogen atom from a compound having an active hydrogen atom to the oxygen atom, and for alkylation of phenolic hydroxyl groups are preferred anions of halogen atoms.

In the General formulas(1), (5), (6) and (7) n is the number phosphazenes cations, as well as the number of protons released from compounds containing active hydrogen atoms, which has at most 8 active hydrogen atoms, n is an integer in the range from 1 to 8, and preferably an integer in the range from 1 to 3. In addition, as specific examples pospisilova skeleton, opisyvayushchego General formula (1), various options are described in the documents JP-A No. 10-77289, JP-A No. 2000-355606, JP-A No. 2004-107266 and the like, in which the invention may be applied to such known pospisilova the skeleton.

In the General formula (8) m represents the number phosphazenes cations associated with the silicon atom, m represents an integer in the range from 1 to 3. In addition, n' represents the number of silicon compounds of the group, including the skeleton phosphazenes cation forms a bond, n' represents an integer in the range from 1 to 8, and preferably an integer in the range of the e from 1 to 3. In addition, n is a multiplier for m and n' represents the total number phosphazenes cations and the amount of protons released from compounds containing active hydrogen atoms, which has at most 24 active hydrogen atom, n is an integer in the range from 1 to 24, and preferably an integer in the range from 1 to 9.

In the General formula (4), X represents a halogen atom, and X-represents an anion of a halogen atom. The halogen atom represented by X includes, for example, fluorine atom, chlorine atom and bromine atom, but among them, preferred are a chlorine atom and a bromine atom. The anion of the halogen atom represented by the symbol X-includes, for example, anions of fluorine atom, chlorine atom and bromine atom, among them preferred are anions of chlorine atom and bromine atom. X-may be an anion of a halogen atom, which is the same as X, or may be an anion of a halogen atom, which is different from X.

In the General formula (5) D' represents a monovalent group capable of forming a bond with N (with the proviso that the atom of hydrogen and saturated hydrocarbon group are excluded). On the monovalent group represented by the symbol D', a special limitation is imposed as long as she will be a group other than a hydrogen atom and a saturated hydrocarbon group which can form a bond with the nitrogen atom present in phosphazenes cation. D' includes, for example, hydrocarbon group containing a heteroatom such as oxygen atom, sulfur atom, nitrogen atom and silicon atom, and a group including a reactive functional group containing unsaturated bond carbon-carbon and the like, and among those that are given as examples above D, D' may correspond to variants in which a hydrocarbon linking group containing a heteroatom is hydrogen, halogen atom, silicon and the like.

Preferred embodiments, vpisivaushiesya General formula (5), are given next.

(i) Phosphatemia salt, where D' represents a monovalent group, opissyvayusya next next General formula (12):

(where A, R2, R3, R4, R5J and e have the same meaning as in the above General formula (10)) in the hydrocarbon group containing a heteroatom such as oxygen atom, sulfur atom, nitrogen atom and silicon atom. In addition, a specific description of A, R2, R3, R4, R5and e are the same as in General formula (6, presented next. If J will represent NR6then R6will represent the same thing as a radical in the range of R2to R5.

(ii) Phosphatemia salt, vpisivaushiesya General formula (6).

In the General formula (6) And represents a hydrocarbon group containing from 1 to 20 carbon atoms. Hydrocarbon group containing from 1 to 20 carbon atoms represented by the symbol And may be aliphatic hydrocarbon group or aromatic hydrocarbon group of up until it would represent a divalent hydrocarbon group. Divalent hydrocarbon group includes, for example, alkylenes group containing from 1 to 20 carbon atoms, such as methylene, ethylene, trimethylene and metilidinovy; cycloalkenyl group containing from 3 to 20 carbon atoms, such as cyclohexylurea; alkynylamino group containing from 2 to 20 carbon atoms, such as venelinova and propylea; cycloalkenyl group containing from 3 to 20 carbon atoms, such as cyclohexadienone; Allenova group containing from 6 to 20 carbon atoms, such as fenelonov and naftalanovaja; Aracinovo group containing from 7 to 20 carbon atoms, such as phenylmethylene; and a group comprising a combination of these groups, such as Fe is esenmyradova and killenemy. Among them preferred are Allenova group, Allenova group, Arakelova group and a group comprising a combination of these groups, and more preferred are a methylene group, ethylene group, fenelonov group and killenemy group.

In the General formula (6) R2, R3, R4and R5represent a hydrogen atom or a hydrocarbon group containing from 1 to 8 carbon atoms. The hydrocarbon group represented by the symbols R2, R3, R4and R5may be an aliphatic hydrocarbon group or aromatic hydrocarbon group. Among specific examples of R and R1in the General formulas from (1) to (6) aliphatic hydrocarbon group and aromatic hydrocarbon group include, for example, those which contain from 1 to 8 carbon atoms. R2, R3, R4and R5preferably represent hydrogen or an aliphatic hydrocarbon group, and more preferably hydrogen or methyl group. In the General formula (6) is in the range from 0 to 200. Preferably e is in the range from 0 to 100, and more preferably from 0 to 30.

(iii) Phosphatemia salt, vpisivaushiesya General formula (7).

In the General formula (7) M is a group containing an unsaturated bond carbon-carbon. For such groups the special limitation is imposed as long while it will contain unsaturated bond carbon-carbon, and it includes, for example, aliphatic hydrocarbon group containing an unsaturated bond carbon-carbon bonds, including alkenylphenol group, such as vinyl, catilina and allyl, and alkylamino group, such as etinilnoy and proponila; an aromatic hydrocarbon group containing an unsaturated bond carbon-carbon bonds, including stielow, vinylbenzyl and stellately; a group containing an unsaturated bond of carbon-carbon and carbonyl group, such as acrylic group, metakrila group, cinnamonny group and acetylanthranilic group. In addition, the M group includes, in addition to the above groups forms a bond hydrocarbon group and the like. Among them, preferred is a group containing a double bond carbon-carbon bonds, such as vinyl, catilina, allyl, Strelna, vinylbenzene, stellately, acrylic, metakrila, or group, which in addition to the above groups forms a bond hydrocarbon group and the like, and more preferred is a group containing a double bond carbon-carbon bonds in its limit position, such as vinyl, allyl, Strelna, vinylbenzene, stellately, acrylic, metakrila, Il the group, in addition to the above groups forms a bond hydrocarbon group and the like.

(iv) Phosphatemia salt, vpisivaushiesya General formula (8).

In the General formula (8) represents a hydrocarbon group containing from 1 to 20 carbon atoms. Hydrocarbon group containing from 1 to 20 carbon atoms represented by the symbol V, is a divalent hydrocarbon group, and may be an aliphatic hydrocarbon group or aromatic hydrocarbon group. Divalent hydrocarbon group includes, for example, alkylenes group containing from 1 to 20 carbon atoms, such as methylene, ethylene, trimethylene and metilidinovy; cycloalkenyl group containing from 3 to 20 carbon atoms, such as cyclohexylurea; alkynylamino group containing from 2 to 20 carbon atoms, such as venelinova and propylea; cycloalkenyl group containing from 3 to 20 carbon atoms, such as cyclohexadienone; Allenova group containing from 6 to 20 carbon atoms, such as fenelonov and naftalanovaja; Aracinovo group containing from 7 to 20 carbon atoms, such as phenylmethylene; and a group comprising a combination of these groups, such as fenilmetilovy and killenemy. Among them preferred are Allenova g is the SCP, Allenova group, Arakelova group and a group comprising a combination of these groups, and more preferred are a methylene group, ethylene group, fenelonov group and killenemy group. In addition, T represents a functional group in which the connection Si-T can be destroyed by hydrolysis, and T includes, for example, halogen atom such as F, Cl, Br and I, or an alkoxy group such as methoxy group, a group of ethoxy, a propoxy group and a group of butoxy.

Later in this document phosphazenes supported on a carrier, the catalyst of the invention, which has a group, opissyvayusya General formula (1)associated with the carrier, described in more detail with bringing the explanations of how to obtain it.

As for pospisilova deposited on the catalyst carrier of the invention, the carrier of the group, vpisivaushiesya General formula (1), forms a bond, a special limitation is imposed as long as it is insoluble in the solvent used for the reaction, and can be used any of them, which has a group capable of forming a bond with the group, opisyvayuschaya General formula (1). As such carriers known different ways, for example, different types of such media are described on pages 133 to 163 in the "Catalyst Lecture Vol. 10 (Indusrial Catalyst Reaction 4) Detailed Exposition on Catalyst, Catalyst Institute Ed. First release, Kodansha, (1986). Specifically, the inorganic carrier, typical representatives of which are metal oxides, such as SiO2, Al2O3, MgO, TiO2, SnO2, ZnO, and ZrO2; complex metal oxides, such as SiO2-Al2O3, SiO2-MgO, SiO2-ZrO2and zeolite, a metal salt of a solid acid, such as a metal salt of heteroalicyclic and a metal salt of a solid phosphoric acid, a layered compound such as mica and montmorillonite; and clay mineral, such as diatomaceous earth, organic polymer carrier, typical representatives of which are organic polymer in which the main chain, such as polystyrene, pyridine, polybutadiene and polyvinyl chloride, is bond carbon-carbon; organic polymer containing in its main chain oxygen atom, such as polyacrylic acid and poly(meth)acrylate; an organic polymer containing in its main chain nitrogen atom, such as polyamide, polyurethane, and polyimide; an organic polymer containing in its main chain atom of silicon, such as polysiloxane and polysilane; and organic polymer containing in its main chain atom of sulfur, such as polysulfide and polysulfone; and crosslinked organic polymer carrier, typical representatives of the United vtorogo are polymers, in which the above-described organic polymer carrier has a suitable crosslinked structure. Among these carriers is preferred media, such as a metal oxide, an organic polymer, in which the main chain is a bond of carbon-carbon crosslinked organic polymer in which the main chain is a bond of carbon-carbon, and more preferred are SiO2stitched and unstitched polystyrene and stitched and unstitched polyethylene. Use the medium in which such a carrier is injected group capable of forming a bond with the group, opisyvayuschaya General formula (1) in the invention. As for how the introduction of these groups in the media, that pages from 136 to 137 and pages from 149 to 150 references shown various examples, the representatives of which are the way in which on the surface of SiO2a hydroxyl group is introduced into reaction with SOCl2and replaced by chlorine, and after that enter into interaction, the way in which the hydroxyl group on the surface of SiO2subjected to chlorination, is introduced into reaction with phenyllithium, and then substitute the phenyl group, which is subjected to chlorotoluron and enter into interaction, the way in which the polystyrene is subjected to chlorotoluron and enter into interaction, and the like. In addition, t is the train can be mentioned method, in which the alkoxysilane having chloromethylene group, is used for hydrolysis-polycondensation involving other alkoxysilane and the like, or injected into the silanol group of silica gel as a result of sililirovanie. As an alternative method of forming relationships with the media using the way in which when using alkoxysilane with chloromethylene group, alkoxysilyl group provide an opportunity to form a relationship in order to carry out the synthesis of phosphazene salt, and then the resulting product is subjected to hydrolysis-polycondensation involving other alkoxysilane and the like, or imposed on the media as a result of sililirovanie when using silanol groups in the silica gel.

In a specific method of obtaining deposited on the catalyst carrier first get phosphazene connection, vpisivaushiesya General formula (2) (hereinafter in this document called "phosphazenes compound (2)"), phosphazene connection, vpisivaushiesya General formula (3) (hereinafter referred to in this document called "phosphazenes compound (3)"), phosphazene salt, opissyvayusya General formula (4) (hereinafter referred to in this document called "phosphazene salt (4)"), phosphazene salt, opissyvayusya General formula (5) (hereinafter referred to in this document called emuu "phosphazene salt (5)"), phosphazene salt, opissyvayusya General formula (6) (hereinafter referred to in this document called "phosphazene salt (6)"), phosphazene salt, opissyvayusya General formula (7) (hereinafter referred to in this document called "phosphazene salt (7)") and phosphazene salt, opissyvayusya General formula (8) (hereinafter referred to in this document called "phosphazene salt (8)"), which are intermediate compounds suitable for use in obtaining pospisilova deposited on the catalyst carrier of the invention. In accordance with this first next will be described a method of obtaining phosphazene compounds (2) and (3) and salts phosphazenes(4), (5), (6), (7) and (8).

Phosphazene compound (2) can be obtained by the reaction between phosphazene salt, opisyvayuschaya next next General formula (13), for example, and the connection is obtained by substitution of hydrogen in the compound containing the active hydrogen atoms, alkali metal or alkaline earth metal, at a relatively high temperature.

(where n is an integer in the range from 1 to 8 and represents the number phosphazenes cations, Qnrepresents an anion capable of forming an ion pair with phosphazenes cation. Each of a, b, c and d represents n is a positive integer, equal to 3 or less. R represent identical or different hydrocarbon groups containing from 1 to 10 carbon atoms, and two R's located on each common nitrogen atom may be linked to each other to form a ring structure).

Such anion Qnspecial limitation is imposed, and may be any Qnwhich forms phosphazene connection, vpisivaushiesya General formula (2). As phosphazenes salts known phosphazenes salts described in JP-A No. 10-77289 and JP-A No. 2000-355606, those whose anions are anions of halogen atoms such as chlorine, are described in the document "Furka Comprehensive Catalog 1995/96" Furka Fine Chemical, and the like. Qncan be any Qnthat does not prevent the passage of the described reactions, and they can also be inorganic anions.

In connection obtained by substitution of hydrogen in the above-described compound containing active hydrogen atoms, alkali metal or alkaline earth metal, alkali metal or alkaline earth metal include metallic lithium, metallic sodium, metallic potassium, metallic cesium, metallic magnesium, metallic calcium, metallic strontium and metallic barium.

The compound containing active hydrogen atoms, includes compounds is s, containing active hydrogen atoms, from which the Znand particularly preferred are alcohols, phenols, teopista, thiophenol and amines.

The reaction between phosphazene salt, opisyvayuschaya General formula (13), and a compound obtained by substitution of hydrogen in the above-described compound containing active hydrogen atoms, alkali metal or alkaline earth metal, can be performed in the same way as the reaction of obtaining phosphazene salt, opisyvayuschaya above General formula (9)described in the document JP-A No. 10-77289, except that the reaction temperature is set to a relatively high temperature, as described above. Specifically, for example, it may be held in accordance with the following further conditions.

The amount used of the compounds obtained by substitution of hydrogen in the compound containing the active hydrogen atoms, alkali metal or alkaline earth metal is in the range of usually 1 to 10 equivalents, preferably 1 to 5 equivalents, and more preferably from 1 to 2 equivalents, per one equivalent of phosphazene salt, opisyvayuschaya General formula (13).

The reaction solvent particular limitation is imposed as long as he does not Bud is t to impede the reaction, and can be used any known solvent. Their specific examples include aliphatic or aromatic hydrocarbons, such as n-hexane, benzene, toluene, tetralin; aliphatic or aromatic halogenated hydrocarbons, such as methylene chloride, chloroform and o-dichlorobenzene; ethers, such as diethyl ether and tetrahydrofuran; NITRILES, such as acetonitrile and propionitrile; polar aprotic solvents such as N,N-dimethylformamide, dimethylsulfoxide, sulfolan, triamide hexamethylphosphoric acid and 1,3-dimethyl-2-imidazolidinone, and they can be used individually or in combination of two or more types.

The reaction temperature can be appropriately adjusted depending on the type, concentration and the like, which is associated with the reagent, but it is a relatively high temperature, in other words, is in the range in General from 80 to 300°C, preferably from 100 to 250°s, and more preferably from 120 to 200°C. the Pressure during the reaction may be any pressure selectable from the reduced pressure, normal pressure or increased pressure, but it is in the range preferably from 10 to 500 kPa (absolute pressure; this will be used later in this document), and more preferred is sustained fashion from 100 to 300 kPa. The reaction time may appropriately be adjusted depending on the reaction temperature, the type of the reaction system and the like, but it is in the range in General from 0.1 to 100 hours, preferably from 1 to 50 hours, and more preferably from 2 to 20 hours.

Selection pospisilova connection (2) from the reaction solution after completion of the reaction can be carried out in accordance with a commonly used method. For example, a solution containing phosphazene compound (2)may be obtained by separation of the solid content present in the reaction solution, as a result of filtration, centrifugation and the like. The solution is concentrated to dryness in order to obtain phosphazene connection (2) in a solid phase. In addition, if desired, it is possible to additionally clear as a result of recrystallization and the like.

Phosphazene compound (2)obtained as described above can additionally be introduced into the reaction with the compound, vpisivaushiesya the following formula: X-D' (where X represents a halogen atom, D' is the same as D' in the General formula (5)), with phosphazene salt (5).

For example, phosphazene compound (2) can additionally be introduced into the reaction with the compound, vpisivaushiesya presented the above formula: X-D', which is compound (a), vpisivaushiesya the following formula: X-E-Y (where X represents a halogen atom, E represents a hydrocarbon group which may contain oxygen atom, sulfur atom or nitrogen atom, Y represents a hydroxyl group, a mercapto group or an amino group which is protected by a protective group), such as a connection, where the protective group Y represents alkylsilane group to receive phosphazene salt (5), and then removing the protection and, thus obtaining a structure having a hydroxyl group, a mercapto group or an amino group then there is phosphazene salt (5) and phosphazene salt (6) as its preferred embodiments. Alternatively, in accordance with the known method Y after removing the protection gets a chance to react or to polymerization with the Deputy, such as accelerated or substituted alkylenes, the oxygen of which is substituted on sulfur, nitrogen and the like, is received by phosphazene salt (5) and phosphazene salt (6) as its preferred embodiments, which are in their limit positions have a hydroxyl group, a mercapto group or amino group.

The reaction between phosphazenes compound (2) and compound (a) can be conducted under the following conditions. The solvent of the reaction is predstavljaet a same as in the case of obtaining the above-described pospisilova connection (2). The reaction temperature can be appropriately adjusted depending on the type, concentration and the like, which is associated with the reagent, but it is in the range in General from 78 to 100°C, preferably from 50 to 80°s, and more preferably from 0 to 50°C. the Pressure during the reaction may be any pressure selectable from the reduced pressure, normal pressure or increased pressure, but it is in the range preferably from 10 to 500 kPa, and more preferably from 100 to 300 kPa. The reaction time may appropriately be adjusted depending on the reaction temperature, the type of the reaction system and the like, but it is in the range in General from 0.1 to 100 hours, preferably from 1 to 80 hours, and more preferably from 2 to 50 hours. Phosphazene salt (5) and (6) can be isolated from the reaction solution by a commonly used method. For example, phosphazene salt (5) and (6) can be obtained in solid form or in the form of a viscous liquid resulting from the separation of the solid content present in the reaction solution, as a result of filtration, centrifugation and the like, and then concentrating the filtrate to dryness. If necessary, they can dopolnitelnost when using recrystallization, column chromatography and the like.

In addition, phosphazene connection (2), for example, you can enter into reaction with the compound, vpisivaushiesya above formula: X-D', which is a compound (a'), vpisivaushiesya the following formula: X-L (where X represents a halogen atom, and L represents a group containing an unsaturated bond carbon-carbon), with phosphazene salt (7).

The reaction between phosphazenes compound (2) and compound (a') can be, for example, if the following conditions. The solvent of the reaction is the same as in the case described above obtain pospisilova connection (2). The temperature of the heating can properly be adjusted depending on the type, concentration and the like, which is associated with the reagent, but it is in the range in General from 78 to 100°C, preferably from 50 to 80°s, and more preferably from 0 to 50°C. the Pressure during the heating may be any pressure selectable from the reduced pressure, normal pressure or increased pressure, but it is in the range preferably from 10 to 500 kPa, and more preferably from 100 to 300 kPa. The reaction time may appropriately be adjusted depending on the reaction temperature, the type of reaction systems and the like, but it is in the range in General from 0.1 to 100 hours, preferably from 0.5 to 80 hours, and more preferably from 2 to 50 hours. Phosphazene salt (7) can be isolated from the reaction solution by a commonly used method. For example, phosphazene salt (7) can be obtained in solid form as a result of separation of the solid content present in the reaction solution, as a result of filtration, centrifugation and the like, and then concentrating the filtrate to dryness. If necessary, can be cleaned using recrystallization, column chromatography and the like.

In addition, phosphazene connection (2) you can enter into reaction with the compound, vpisivaushiesya above formula: X-D', which is an organosilicon compound (a), vpisivaushiesya the following formula: X-E'-Y' (where X represents a halogen atom, E' represents a hydrocarbon group, Y' represents a silyl group containing hydrolyzable group, such as at least one halogen atom or alkoxy group), with phosphazene salt (8)having a silyl group containing hydrolyzable group associated with it.

The reaction between phosphazenes compound (2) and compound (a) can be performed, for example, when the following on the more conditions. The solvent of the reaction is the same as in the case described above obtain pospisilova connection (2). The reaction temperature can be appropriately adjusted depending on the type, concentration and the like, which is associated with the reagent, but it is in the range in General from 78 to 100°C, preferably from 50 to 80°s, and more preferably from 0 to 50°C. the Pressure during the heating may be any pressure selectable from the reduced pressure, normal pressure or increased pressure, but it is in the range preferably from 10 to 500 kPa, and more preferably from 100 to 300 kPa. The reaction time may appropriately be adjusted depending on the reaction temperature, the type of the reaction system and the like, but it is in the range in General from 0.1 to 100 hours, preferably from 1 to 80 hours, and more preferably from 2 to 50 hours. In addition, to obtain a highly polar product of reaction (8) and after that immediate removal of the product from the system as the reaction solvent use non-polar solvent, thus, this option is preferred from the point of view of mode of carrying out the reaction, easier way to clean, improve the selectivity and the like, and preferably it is the fast mode of carrying out the reaction.

On the other hand, phosphazene compound (3) can be obtained by heating phosphazene salt, opisyvayuschaya General formula (13), where the anion is hydroxyl anion or mercapto-anion at a temperature exceeding room temperature, in the presence or in the absence of solvent. Heating, for example, can be carried out in accordance with the following further conditions. The reaction solvent used in the same way as in the case of obtaining pospisilova connection (2). The temperature of the heating can properly be adjusted depending on the type, concentration and the like, which is associated with the reagent, but we can mention a temperature above room temperature, i.e. in the range in General from 50 to 300°C, preferably from 80 to 250°s, and more preferably from 100 to 200°C. the Pressure during the heating can be any pressure that you select from low, normal or elevated pressure, but it is in the range preferably from 10 to 500 kPa, and more preferably from 100 to 300 kPa. The heating time can be appropriately adjusted depending on the heating temperature, the type of the reaction system and the like, but it is in the range in General from 1 to 240 hours, preferably from 2 to 200 hours, and more preferred the equipment from 5 to 150 hours.

Selection pospisilova connection (3) from the reaction solution after completion of the heating can be carried out in accordance with commonly used methods. For example containing solution can be obtained by adding to the reagent aliphatic or aromatic hydrocarbons, such as n-pentane, n-hexane, cyclohexane, benzene, toluene, xylene, tetralin, and excretion of insoluble fractions as a result of filtration, centrifugation and the like. The solution can be concentrated to dryness to obtain a solid pospisilova connection (3) in the form of a solid phase. In addition, if necessary, you can also make and cleanup as a result of recrystallization and the like.

Phosphazene salt (4) can be obtained by the reaction between the previously obtained phosphazenes compound (3) and, for example, halogenation agent such as phosgene, thionyl chloride, thienylboronic, pentachloride phosphorus, trichloride phosphorus, 2,2-dichloro-1,3-dimethylimidazolidin, 2,2-debtor-1,3-dimethylimidazolidin. The reaction is carried out in accordance with the following further conditions.

The amount of halogenation agent is in the range in General from 1 to 10 equivalents, preferably 1 to 5 equivalents, and more preferably from 1 to 2 equivalents, per 1 equivalent is UNT pospisilova connection (3). The solvent of the reaction is the same as in the case of obtaining the above-described pospisilova connection (2). The reaction temperature can be appropriately adjusted depending on the type, concentration and the like, which is associated with the reagent, but it is in the range in General from 78 to 200°C, preferably from 50 to 150°s, and more preferably from 0 to 100°C. the Pressure during the reaction can be any pressure that you select from low, normal or elevated pressure, but it is in the range preferably from 10 to 500 kPa, and more preferably from 100 up to 300 kPa.

The reaction time may appropriately be adjusted depending on the reaction temperature, the type of the reaction system and the like, but it is in the range in General from 0.1 to 300 hours, preferably from 0.5 to 200 hours, and more preferably from 2 to 150 hours. The allocation of phosphazene salt (4) from the reaction solution after completion of the reaction can be carried out in accordance with commonly used methods. For example, the reaction solution was concentrated to dryness to obtain phosphazene salt (4) in the form of a solid phase. In addition, if necessary, you can also make and cleanup as a result of recrystallization and the like.

Meanwhile, pofesen ewww salt (4) is injected into the reaction with compound (b), an example of which is a compound having a protective group, such as alkylsilane group, vpisivaushiesya the following formula: R1-NH-E-Y (where R1is the same as in the General formula(1), (5), (6), (7) and (8), E and Y are the same as in the compound (a)), with phosphazene salt (5); then Y remove protection and get the structure of the compounds having hydroxyl group, mercapto group or amino group, i.e. phosphoserine salt (5) and phosphazene salt (6) as its preferred embodiments. In addition, Y after removing the protection makes possible the reaction of accelerated or oxygen with the Deputy, such as sulfur, nitrogen and the like, using well-known means; or the establishment of conditions for polymerization can be obtained phosphazene salt (5) and phosphazene salt (6) as its preferred embodiments, end the provisions of which have views of the hydroxyl group, mercapto group, amino group and the like.

The reaction between pospisilova salt (4) and compound (b), for example, can be carried out in accordance with the following further conditions. The solvent of the reaction is the same as in the case of obtaining the above-described pospisilova connection (2). The reaction temperature can is about properly adjusted depending on the type, concentration and the like, which is associated with the reagent, but it is in the range in General from 78 to 200°C, preferably from 50 to 150°s, and more preferably from 0 to 100°C. the Pressure during the reaction can be any pressure that you select from low, normal or elevated pressure, but it is in the range preferably from 10 to 500 kPa, and more preferably from 100 to 300 kPa. The reaction time may appropriately be adjusted depending on the reaction temperature, the type of the reaction system and the like, but it is in the range in General from 0.1 to 200 hours, preferably from 0.5 to 150 hours, and more preferably from 2 to 100 hours. The allocation of phosphazene salt (5) or (6) of the reaction solution can be carried out in accordance with commonly used methods. For example, the solid content of the reaction solution is produce as a result of filtration, centrifugation and the like. The solution is concentrated to dryness to obtain phosphazene salt (5) or (6) in the form of a solid phase or a viscous liquid. In addition, if necessary, can be cleaned using recrystallization, column chromatography and the like.

In phosphazenes salts(5), (6), (7) and (8), obtained as described above, Znthe ri can be replaced by the desired anion in accordance with the well-known way. For example, the substitution can be carried out according to the method of introduction into contact with the compound having the desired anion, in particular by way of ion exchange using an ion-exchange resin containing the desired anion, and the like, by way of handling salt of an alkali metal or alkali earth metal salt containing the desired anion, and the like.

Phosphazenes supported on a carrier, the catalyst of the invention can be obtained by carrying out the reaction with the carrier that has been modified for the reaction with phosphazenes compound (2) or (3) or a salt phosphazenes(4), (5), (6), (7) or (8) with phosphazenes compound (2) or (3) or a salt phosphazenes(4), (5), (6), (7) or (8). In particular, for example, phosphazene connection (2) or phosphazene salt (5) or (6) is injected into the reaction with the halogenated hydrocarbon residue and the like in the carrier, thereby causing the media, which, thus, makes it possible for. In addition, in the case of use as a carrier aminomethylpropanol media supported on a carrier, the catalyst can be obtained by the reaction between pospisilova salt (4) and laminirovannyy hydrocarbon residue. In addition, in the case of use as a carrier of silica gel phosphazene salt (8) can podvergnutsya when using a silanol group, which is present on the surface of silica gel, in accordance with the known method of obtaining deposited on the catalyst carrier.

The reaction between phosphazenes compound (2) or forastieri salts (4), (5) or (6) and the carrier is carried out, for example, if the following conditions.

The solvent of the reaction is the same as in the case of obtaining the above-described pospisilova connection (2). The reaction temperature can be appropriately adjusted depending on the type, concentration and the like, which is associated with the reagent, but it is in the range in General from 78 to 200°C, preferably from -50 to 150°s, and more preferably from 0 to 100°C. the Pressure during the reaction can be any pressure that you select from low, normal or elevated pressure, but it is in the range preferably from 10 to 500 kPa, and more preferably from 100 to 300 kPa. The reaction time may appropriately be adjusted depending on the reaction temperature, the type of the reaction system and the like, but it is in the range in General from 0.1 to 500 hours, preferably from 0.5 to 300 hours, and more preferably from 2 to 200 hours. Selection pospisilova supported on a carrier of the catalyst from the reaction solution after completion of the reaction can be conducted is consistent with commonly used methods. For example, phosphazenes supported on a carrier, the catalyst (1), as a solid phase contained in the reaction solution, produce as a result of filtration, centrifugation and the like. In addition, if necessary, can be cleaned in the washing water, a suitable solvent, and the like.

In addition, the reaction between phosphazene salt (8) and the carrier can be, for example, if the following conditions.

Phosphazene salt (8) is applied to the media in bringing it into contact with the commercially available silica gel and heating. At the moment you can use the solvent of the reaction. The reaction solvent particular limitation is imposed as long as it is inert with respect to the silica gel and phosphazene salt (8), but it is preferable non-polar solvent, such as benzene, toluene, hexane and the like. The reaction temperature is in the range in General from 0 to 200°C, preferably from 20 to 150°s, and more preferably from 40 to 120°C. the Pressure during the reaction may be any pressure selectable from the reduced pressure, normal pressure or increased pressure, but it is in the range preferably from 10 to 500 kPa, and more prepact the tion from 100 to 300 kPa. The reaction time may appropriately be adjusted depending on the reaction temperature, the type of the reaction system and the like, but it is in the range in General from 0.1 to 100 hours, preferably from 1 to 50 hours, and more preferably from 2 to 20 hours. After the separation of the silica gel as a result of filtering the resulting product is washed with a solvent and the like, and thereafter dried to obtain pospisilova deposited on the catalyst carrier.

After the reaction between phosphazenes compound (2) or a salt phosphazenes(4), (5), (6) or (8), and the media that modify halogenated hydrocarbon residues aminirovanie hydrocarbon residues and the like, unreacted halogenated hydrocarbon residues or aminirovanie hydrocarbon residues can be deactivated using the normal way. For example, halogenated hydrocarbon residue can be deactivated as a result of processing an alcoholate of an alkali metal or alkali earth metal alcoholate, and the like with the substitution therefore of the halogen atom in the alkoxy group and a simple ether. In addition, aminirovanie hydrocarbon residue can be deactivated as a result of replacement with the use of salt is Christmas metal or alkaline earth metal and alkylation of the amino group by alkylhalogenide and the like with tertiary aministrator.

On the other hand, for example, for the synthesis of the carrier and at the same time obtain pospisilova deposited on the catalyst carrier phosphazene salt (7) and the compound containing the polymerized functional group, such as the so-called vinyl monomer, such as styrene, an ester of (meth)acrylic acid and the like, can be depolimerizuet in accordance with commonly used method (e.g., "4thEdition Experimental Chemistry Lecture, Vol. 28 (Polymer Synthesis)", The Chemical Society of Japan, Maruzen, 1992, pp. 31 to 38, pp. 120 to 152).

In addition, in accordance with the known method phosphazene salt (8) and the other alkoxysilane can be subjected to hydrolysis-polycondensation and synthesize the media and at the same time to get phosphazenes supported on a carrier catalyst. This method can be implemented, for example, in accordance with the following further conditions.

In the method of applying to the media when using hydrolysis-polycondensation of alkoxysilane, which can form the matrix of the silica gel, and phosphazene salt (8) obtain a homogeneous solution when using a polar solvent, such as methanol, ethanol and the like, which is inert with respect to the alkoxysilane and water, and is soluble in water. Here we add hydrochloric acid, and receive an acidic environment, then Xu is and add about 1 equivalent of water in calculating the hydrolyzable group, and the mixture is heated with stirring. The reaction temperature can be appropriately adjusted depending on the type, concentration and the like, which is associated with the reagent, but it is in the range in General from 0 to 200°C, preferably from 20 to 150°s, and more preferably from 40 to 100°C. the Pressure during the reaction may be any pressure selectable from the reduced pressure, normal pressure or increased pressure, but it is in the range preferably from 10 to 500 kPa, and more preferably from 100 up to 300 kPa. The reaction time may appropriately be adjusted depending on the reaction temperature, the type of the reaction system and the like, but it is in the range in General from 0.1 to 100 hours, preferably from 1 to 50 hours, and more preferably from 2 to 20 hours.

After that, the reaction mixture was added an excess of water, and the reaction mixture immediately turned into a gel as a result of its premises in an alkaline environment, such as in the case of ammonia. At the moment, from the viewpoint of improving durability of catalytic structures are effective continued heating in an alkaline medium and maintaining for a long period of time. Phosphazenes supported on a carrier, the catalyst after completion of the reaction can be distinguished when used in the research Institute of the conventional method. For example, phosphazenes supported on a carrier, the catalyst can be obtained by selection using filtration, centrifugation and the like in relation to the solid content present in the reaction solution, and in addition, washing with water and drying.

In pospisilova supported on a carrier of the catalyst obtained as described above, Znin accordance with the well-known method can be replaced by the desired anion, which would be suitable for that type of reaction in which used catalyst. For example, the substitution can be carried out according to the method of introduction into contact with the compound having the desired anion, in particular by way of ion exchange using an ion-exchange resin containing the desired anion, and the like, by way of handling salt of an alkali metal or alkali earth metal salt containing the desired anion, and the like.

Phosphazenes supported on a carrier, the catalyst obtained as described above is suitable for use as a catalyst for various organic reactions, and, in particular, it is suitable for use as a catalyst for polymerization of the cyclic monomer and the substitution of the substitute. In addition, phosphazene compounds (2) and (3 and phosphazene salt (4), (5), (6), (7) and (8) of the invention, which are suitable for use in obtaining pospisilova deposited on the catalyst carrier of the invention may themselves be suitable for use as catalyst in various reactions.

In addition, phosphazenes cations in pospisilova supported on a carrier catalyst, vpisivaushiesya General formula (1), and in phosphazenes salts, opissyvayusya General formula (4), General formula (5), General formula (6), General formula (7), General formula (8), General formula (9), General formula (11) and the General formula (13), described limiting structural formulas, in each of which the positive charge is localized on the Central phosphorus atom. In addition, you may be prompted several limiting structural formulas. The actual positive charge is delocalized, respectively, in all the structures of all the skeletons.

In the method of polymerization of the cyclic monomer of the invention, examples of the cyclic monomer include alkalinity, lactones, lactams, lactides, cyclic carbonates, anhydrides (α-amino)-N-carboxylic acids, cyclic phosphates, cyclic esters of phosphonic acids and cyclic siloxanes. As the method of polymerization of the cyclic monomer using pospisilova caused the CSOs on the catalyst carrier of the invention as an example hereinafter will be described the polymerization of accelerated.

On accelerated particular limitation is imposed, but examples may include epoxy compounds such as ethylene oxide, propylene oxide, 1,2-butylenes, 2,3-butylenes, styrene oxide, cyclohexanone, epichlorohydrin, epibromohydrin, metallically ether, allylglycidyl ether, phenylglycidyl ether, and can be used individually or in mixture of two or more components. On the level of content pospisilova deposited on the catalyst carrier, provided for carrying out polymerization accelerated, special restrictions are not imposed, but it ranges in General from 1 x 10-15up to 5 x 10-1mol, and preferably from 1 x 10-7up to 1 x 10-2the mole.

On the way of polymerization of accelerated particular limitation is imposed, but it is preferable to use conventional methods, demonstrated, for example, in the documents JP-A No. 10-77289 and 2000-327769. In General phosphazenes supported on a carrier, the catalyst added to the reactor, if necessary together with an active hydrides, solvent and the like, and by-products, if necessary, removed. Then use the method of supplying the required number of alkalinized at one time or way of periodic or continuous feed.

Substitution Deputy and with the use of phosphazenes deposited on the catalyst carrier of the invention may include, for example, alkylation or dialkylamino phenolic hydroxyl group substitution in the case of halogen-free aliphatic or aromatic halides and alkoxy group, thioalkyl group, amino group, fluoride, ceanography, carboxyl group and group aryloxy, substitution in the case of aliphatic or aromatic sulphonate compounds and alkoxy group, thioalkyl group, amino group, fluoride, ceanography, carboxyl group and group aryloxy and transesterification in the case of aliphatic or aromatic carboxylate compounds and alkoxy group. In the method of substitution Deputy using pospisilova deposited on the catalyst carrier of the invention as an example hereinafter will be described the alkylation of phenolic hydroxyl group.

As a result of the reaction between the aromatic compound having at least one hydroxyl group associated with its aromatic ring, and complex fluids carbonic acid in the presence of phosphazenes deposited on the catalyst carrier of the invention can be obtained aromatic ethers, in which the hydroxyl group in the aromatic compound is subjected to esterification with simple ether. For example, the reaction between the compound having one is a hydroxyl group in the aromatic ring, such as phenol, and complex dialkylamino ester of carbonic acid, such as dimethylcarbonate, you can get simple aromatic ether, in which the hydroxyl group of the aromatic compound is substituted by an alkoxy group. In that case, if the aromatic compound having at least one hydroxyl group associated with its aromatic ring, will represent a compound with multiple hydroxyl groups, then in accordance with the reaction conditions for the reaction with the aromatic ring may be obtained in connection with one or more hydroxyl groups, subjected to esterification with simple ether.

The above described aromatic compound and complex fluids carbonic acid, which can be used as materials of the raw materials, are described in the document JP-A No. 2004-107266. On the level of content pospisilova deposited on the catalyst carrier, provided for carrying out the alkylation of phenolic hydroxyl groups, special restrictions are not imposed, but it is generally in the range from 1 x 10-7up to 10 mol when based on 1 mol of phenolic hydroxyl groups, and special limitation is imposed on the method of carrying out the reaction. For example, it is preferable to use the normal way, trademonster the Bank incorporated in the document JP-A No. 2004-107266. In the General case, the method is realized in the result of the reaction between the aromatic compound having at least one hydroxyl group in its aromatic ring, and complex fluids carbonic acid in the solvent complex diapir carbonic acid. If necessary, can be used and other solvents.

At the level of the solvent content is no limit, but it can be determined depending on the reaction conditions such as the type and number of aromatic compounds having at least one hydroxyl group in its aromatic ring, the type and number of complex diapir carbonic acid, the reaction temperature and pressure. The conditions such as reaction temperature, pressure and the like, particular limitation is imposed up until when using these terms will get simple aromatic ether. The reaction temperature and pressure in the General case are in the range of from 0°, 250°C and 1 ATM. up to 100 ATM. The reaction time is not constant in accordance with the type and amount of compounds having at least one hydroxyl group directly related to its aromatic ring, the type and number of complex diapir carbonic acid, the type and amount of catalyst, temperature is Roy reaction, the pressure of the reaction and the type and amount of solvent used, but in General it is in the range from 15 minutes to 100 hours. The use pospisilova deposited on the catalyst carrier of the invention as a catalyst in the reaction described above can be very effective to obtain the target product.

The reaction of the formation of carbon-carbon using pospisilova deposited on the catalyst carrier of the invention includes, for example, aldorino reaction, Michael reaction, the reaction Knoevenagel, the reaction Peterson, Perkin reaction, the reaction Darzens, reduces tollens ' reaction and the reaction Thorpe, but in regard to the formation of carbon-carbon using pospisilova deposited on the catalyst carrier of the invention, as an example, the following are explanations for the aldol reaction.

In case of presence of a carbonyl compound such as aldehyde and ketone, in an alkaline environment is the so-called andolina reaction (condensation) education β-hydroxycarbonyl connection or α,β-unsaturated carbonyl compounds.

The number pospisilova supported on a carrier of the catalyst used in the reaction, special restrictions are not imposed, but it is in the range in General from 1 x 107 up to 10 mol, and preferably from 1 x 10-3to 1 mol, per one mol of carbonyl compounds. On the way the reaction of the special limitation is imposed, and can be used a known method. Usually carbonyl compound as a reagent in the presence of catalyst introduced into the reaction when using inert solvent or the carbonyl compounds as a solvent.

The amount used of the solvent is no limit, and can be appropriately determined depending on the reaction conditions, such as type and quantity of carbonyl compounds, the reaction temperature, pressure reactions, and so podrobnee. Temperature and pressure for the reaction are usually in the range of from -78°, 250°and from 1 ATM to 100 ATM, respectively. The reaction time varies according to the type and quantity of carbonyl compounds, the type and amount of catalyst, reaction temperature, pressure reactions, the type and amount of solvent and the like, but in General it is in the range from 15 minutes to 100 hours. The use pospisilova deposited on the catalyst carrier of the invention as a catalyst in the reaction described above can be effectively obtain the target product.

Examples

<> The invention will be described in detail in connection with the following examples, but the invention is not restricted by them.

Example 1

Synthesis of 1,1,1-Tris{[Tris(dimethylamino)phosphoramidite]amino}-3,3-bis(dimethylamino)-3-methylamino-1λ5,3λ5diphosphate (hereinafter referred to in this document abbreviated denoted as PZNB)

In a glass flask of 1 l equipped with a stirrer, which was kept in an atmosphere of nitrogen, was introduced 54 g of chloride tetrakis[Tris(dimethylamino)phosphorylcholine]phosphonium and 13 g of potassium-1-occultist. This was added 450 ml of tetralin and received a suspension. Under stirring, the suspension was heated to 185°C for 5 hours and then cooled to room temperature. The resulting suspension was filtered under nitrogen atmosphere and washed with 100 ml of tetralin with getting 531 g of a yellow solution. Part of the solution was added to the benzene-d6, and as an internal standard when measuring method31P NMR was used triamide hexamethylphosphoric acid. In this case, the observed quintuplet corresponding to 1 atom of phosphorus, in the area of 30.3 ppm, doublet, corresponding to 3 phosphorus atoms, in the field 6,79 ppm, doublet, corresponding to 1 atom of phosphorus, in the field 16,04 ppm, and the concentration PZNB in the solid phase was 0,163 mmol/G. furthermore, according to the results is the ATA analysis method FD-MS (mass spectroscopy with a field desorption) observed peak 725, appropriate medicationabana molecules PZNB. When conducting a yellow solution distillation under reduced pressure received 62,0 g light yellow solid phase. The results of the analysis of the solid phase methods31P NMR and FD-MS consisted of the same thing and results for yellow solution.

Example 2

Synthesis deposited on a polymeric carrier chloride phosphazene

In a glass flask of 1 l equipped with a stirrer, which was kept in a nitrogen atmosphere, was added and stirred at room temperature for 1 hour, 51 g of resin based on polystyrene subjected to klimatisierung, (54 mmol in the calculation of the chlorine atoms) (produced in the company Argonaut Technologies, Inc., ArgoPore-Cl, 1.05 mmol Cl/g) and 430 g of tetralin. After this addition was added 343 g of the solution PZNB obtained in example 1 (56 mmol analysis on PZNB), tetraline and the mixture was continuously stirred for 4 days. The thus obtained suspension was filtered under nitrogen atmosphere and washed using 500 ml of tetralin and 2 l of a mixed solvent, characterized by the ratio of 1:1 molecular masses in a mixture of 1,4-dioxane:methanol. The remaining solids were dried at 70°With under reduced pressure of 1 mm Hg, and received 72 g deposited on a polymeric carrier chloride phosphazene. For an hour and the solid phase measured by the method 31P NMR using tetrafluoroborate tetrakis(dimethylamino)phosphonium as an internal standard. In this case, the observed peak corresponding to 1 atom of phosphorus, in the area of 35.4 ppm, the peak corresponding to 4 atoms of phosphorus, in the area of 5.8 ppm, and the concentration phosphazenes cations in the solid phase according to the measurement method31P NMR was 0,427 mmol/g

Example 3

Synthesis deposited on a polymeric carrier hydroxide of phosphazene

In a glass flask of 1 l equipped with a stirrer and a fridge, which was kept in an atmosphere of nitrogen, was introduced and stirred at room temperature for 1 hour 49 g deposited on the polymeric carrier chloride phosphazene (21 mmol analysis on phosphazenes cations)obtained in example 2, and 400 ml of methanol. After this was added a solution obtained by dissolving 9.7 g of sodium methoxide in 100 ml of methanol, and within 8 hours were heated at boiling conditions flavobacteria, and then cooling to room temperature. The resulting suspension was filtered, washed with water, subjected to processing by injection into contact with 880 g of 4%aqueous sodium hydroxide solution and washed with water addition. The remaining solid phase was dried by heating at 70°With under reduced giving the situation, equal to 1 mm Hg, and received 49 g deposited on the polymeric carrier hydroxide of phosphazene. Concentration phosphazenes cations in the solid phase according to the measurement method31P NMR was 0,431 mmol/g In addition, according to the results of elemental analysis of chlorine atoms were not observed, and the anion was quantitatively hydroxide.

Example 4

Synthesis deposited on a polymeric carrier iodide of phosphazene

8 g deposited on a polymeric carrier hydroxide of phosphazene (3.4 mmol analysis on phosphazenes cations)obtained in example 3, as the gaskets were placed in a column. The column was subjected to processing by injection into contact with 210 g of 4%aqueous solution of sodium chloride, and optionally washed with water. After this column was subjected to processing by injection into contact with 61 g of 4%aqueous solution of sodium iodide and again washed with water. Upon completion of processing, the solid phase was dried by heating at 70°With under reduced pressure of 1 mm Hg, and got deposited on the polymeric carrier iodide of phosphazene. Concentration phosphazenes cations in the solid phase according to the measurement method31P NMR was 0,352 mmol/G. In addition, the concentration of iodine atoms in the solid phase according to the results of elementorganic was 0,358 mmol/g

Example 5

Synthesis of iodide of phosphazene having a hydroxyl group

In a glass flask of 300 ml equipped with a stirrer, which was kept in an atmosphere of nitrogen, was introduced 4,3 g (16 mmol) simple tert-butyldimethylsilyl(4-chloromethylbenzene)ether and 79 g of the solution PZNB obtained in example 1 (13 mmol analysis on PZNB), tetraline and the mixture was stirred over night at room temperature. Upon completion of the reaction, tetralin drove under reduced pressure and under stirring was added 100 ml of hexane. Hexane was removed as a result of decanting. Such washing with hexane collectively conducted five times, and the resulting mixture was dried by heating at 70°With under reduced pressure of 1 mm Hg. After that, when conducting cooling the flask in ice was added to the solution (1.0 M, 14 mmol) of tetrabutylammonium fluoride in tetrahydrofuran (hereafter in this document referred to as THF) and the mixture was stirred at 40°C for 3 hours, and then was added 14 ml (14 mmol) of 1 N. aqueous solution of hydrochloric acid and, in addition, continuously stirred. Thereafter, under reduced pressure, THF and water drove away. To the residue was added 250 ml of methylene chloride to obtain a solution and the solution was washed with water using a separating funnel. The methylene chloride layer which are condensed and received 10.8 g of a viscous fluid. Then, to the obtained viscous liquid was added 70%aqueous solution of ethylamine, seeking its dissolution. The resulting solution was placed in a glass flask of 300 ml equipped with a stirrer. Here under stirring was added 4.6 g of sodium iodide in 70%solution of ethylamine and 80 ml of water and the reaction mixture was allowed to proceed for 5 days. Precipitated crystals were filtered off, washed with water and dried under heating at 70°With under reduced pressure of 1 mm Hg, to obtain 7.0 g of the iodide of phosphazene having a hydroxyl group, in the form of white crystals. Part of the solution was added to the benzene-d6, and as an internal standard when measuring method31P NMR was used triamide hexamethylphosphoric acid. In this case, the observed quintuplet corresponding to 1 atom of phosphorus in the area account for 33.2 ppm, doublet, corresponding to 3 atoms of phosphorus in the field was 7.45 ppm, doublet, corresponding to 1 atom of phosphorus, in the field 8,68 ppm, and the degree of purity was 96,5%. In addition, according to the results of the analysis according to the method of FD-MS observed peak 846 corresponding medicationabana phosphazenes cations.

Example 6

Synthesis of iodide of phosphazene containing polypropyleneoxide as a side chain

In the autoclave with a volume of 70 ml, which was kept in the atmosphere is fere nitrogen, was introduced to 5.1 g (5.2 mmol) of iodide of phosphazene obtained in example 5, 0.01 g (0.26 mmol) of potassium hydride and 30 ml of THF and the mixture was heated up to 80°With stirring for 3 hours, and then cooled to room temperature. Then added 3.0 g (52 mmol) of propylene oxide and were heated to 80°under stirring for 20 hours. Upon completion of the reaction, the reaction solution was cooled to room temperature and was added 0.3 ml (0.3 mmol) of 1 N. aqueous solution of hydrochloric acid. After washing with water, the reaction solution was dried under heating at 70°With under reduced pressure of 1 mm Hg, and obtained 8.0 g of a viscous fluid. Part of the solution was added to the dimethyl sulfoxide-d6 (hereafter in this document referred to as DMSO-d6), and as an internal standard when measuring method31P NMR was used triamide hexamethylphosphoric acid. In this case, the observed quintuplet corresponding to 1 atom of phosphorus, in the field - 33,1 ppm, doublet, corresponding to 3 phosphorus atoms, in the field 7,56 ppm, doublet, corresponding to 1 atom of phosphorus, in the field 8,79 ppm, and the degree of purity amounted to 100.6%. In addition, according to the results of the analysis according to the method of FD-MS observed peak corresponding srednekamennogo molecular weight (Mn) 1412 and molecular mass distribution (M/Mn) of 1.02. Therefore, it was found that as a result of adding in the framework of the "living" polymerization was the introduction of the side chain with the receipt of iodide of phosphazene containing decamer of propylene oxide.

Examples 7 to 11

Synthesis of iodide of phosphazene containing polyalkylated as a side chain

The synthesis was carried out according to the same method as in example 6, except that changed the number and types of polyalkylated, so as a side chain was produced by the introduction of a wide range of polyalkyleneglycol, thus synthesizing iodide of phosphazene. The results shown in table 1.

Table 1
Type alkylene-oxideThe molar ratio accelerated/iodide phosphate deposits in keep-IOMSrednekislye the molecular-lar weight (Mn) according to the results of the analysis according to the method of FD-MSMolecular weight distribution (Mw/Mn) according to the results of the analysis according to the method of FD-MSThe average number of added links accelerated calculated by Mn (proportional to the number of iodide of phosphazene)
Example 7Propylene oxide20,018931,0118,0
Example 8Ethylene oxide7,310871,015,5
Example 912,611791,017,6
Example 1019,515341,01the 15.6
Example 1131,120511,0127,4

Example 12

Synthesis deposited on a polymeric carrier hydroxide of phosphazene

In a glass flask with a volume of 50 ml, which was kept in an atmosphere of nitrogen, was introduced 0.2 g (5.2 mmol) of potassium hydride and 9 ml of N,N-dimethylformamide (hereinafter referred to in this document referred to as DMF), in addition, of 7.3 g of the solution of iodide of phosphazene obtained in example 6, (5.2 mmol) in DMF, and the mixture was stirred at room temperature for 3 hours. In another glass flask of 100 ml capacity equipped with a stirrer, which was kept in an atmosphere of nitrogen, was introduced in 5.0 g of resin based on polystyrene subjected to chlorotoluron (5.2 mmol in the calculation of the chlorine atoms) (produced in the company Argonaut Technologies, Inc., ArgoPore-Cl, 1.05 mmol Cl/g), and 50 ml of DMF, and the mixture was stirred at room temperature for 1 hour. After this was added the whole amount of the solution previously obtained potassium salt of Jodi is and phosphazene in DMF and, in addition, conducted continuous stirring for 20 hours. Upon completion the reaction was conducted by filtration. The resin obtained in the form of the remaining solid phase, washed in to conventional Soxhlet extractions 1,4-dioxane is used as a solvent, and dried under heating at 70°With under reduced pressure of 1 mm Hg. After drying the resin and 35 ml of methanol were placed in a glass flask with a volume of 100 ml equipped with a stirrer and a fridge, which was kept in nitrogen atmosphere, and the mixture was stirred at room temperature for 1 hour, this solution was added (20 ml), 2.5 g of sodium methoxide in methanol and within 8 hours were heated at boiling conditions flavobacteria, and then cooling to room temperature. The resulting suspension was filtered, washed with water, subjected to processing by injection into contact with 34 g of 4%aqueous sodium hydroxide solution and washed with water addition. After that, the remaining solid phase was dried at 70°With under reduced pressure of 1 mm Hg, and received 5.3g deposited on a polymeric carrier hydroxide of phosphazene. For part of the solid phase measured by the method31P NMR using as an internal standard tetrafluoroborate those whom races(dimethylamino)phosphonium. In this case, the observed peak corresponding to 1 atom of phosphorus, in the field - to 35.7 ppm, the peak corresponding to 4 atoms of phosphorus, in the field of 5.7 ppm, and the concentration phosphazenes cations in the solid phase was 0,122 mmol/g as measured according to the method31P NMR.

Examples 13 to 17

Synthesis deposited on a polymeric carrier hydroxide of phosphazene

The reaction was carried out in the same way as in example 12, except that instead of the iodide of phosphazene obtained in example 6 and used in example 12 was used iodide of phosphazene obtained in examples 7 to 11, therefore synthesized a wide range printed on the polymeric carrier hydroxides of phosphazene. The results shown in table 2.

Table 2
Used iodide of phosphazeneThe shift in the spectrum of31P NMR (ppm, (the number of phosphorus atoms))Concentration phosphazenes cations (mmol/g)
Example 13Example 7- 35,6 (1), 5,5 (4)0,089
Example 14Example 8- 35,5 (1), 5,9 (4)0,202
Example 15Example 9- 35,4 (1), 6,0 (4)0,196
Note the R 16 Example 10- 35,2 (1), 5,8 (4)0,229
Example 17Example 11- 35,0 (1), 5,8 (4)has 0.168

Example 18

Synthesis of bis(dimethylamino){[Tris({[Tris(dimethylamino)phosphoramidite]amino})phosphoramidite]amino}phosphine oxide (hereinafter referred to in this document abbreviated denoted as PZND)

When using the method described in document JP-A No. 11-240893 in aqueous solution was obtained 7607 g hydroxide tetrakis[Tris(dimethylamino)phosphorylcholine]phosphonium. The distillation for aqueous solution was carried out at reduced pressure in the range from 50 to 100 mm of mercury at 60°obtaining as a solid phase 180 g of hydroxide tetrakis[Tris(dimethylamino)phosphorylcholine]phosphonium. The solid phase was transferred into a glass flask with a volume of 5 l and heated at 130°C for 5 days under the flow of nitrogen through the tube for input of nitrogen with a flow rate of 10 ml/min After cooling to approximately room temperature was added 3 l of hexane and using a mixing device, and the mixture was stirred for 30 minutes. Upon completion of mixing, the contents were left at rest for the deposition of insoluble fractions. Insoluble fractions were separated in the decanting and received clear and colourless solution in hexane. n-Hexane from a solution of Otho the Yali at normal pressure. At that moment, when collected, approximately 2.8 l n-Hexane, the distillation was stopped. n-Hexane was further removed under reduced pressure in the range from 1 to 20 mm Hg and received 110 g of white solids. Part of the solid phase was added DMSO-d6, internal standard measuring method31P NMR was used triamide hexamethylphosphoric acid. In this case, the observed quintuplet corresponding to 1 atom of phosphorus, in the field - 25,46 ppm, doublet, corresponding to 1 atom of phosphorus in the field was 7.08 ppm, doublet, corresponding to 3 phosphorus atoms, in the field 8,64 ppm, and the degree of purity was 97,5%. In addition, according to the results of the analysis according to the method of FD-MS observed peak 711 corresponding medicationabana molecules PZND.

Example 19

Synthesis of chloride 1,1,1-Tris{[Tris(dimethylamino)phosphoramidite]amino}-3,3-bis(dimethylamino)-3-chloro-3λ5-diphosphate-1 Deposit (hereinafter referred to in this document abbreviated denoted as PZND-Cl)

In a glass flask of 500 ml equipped with a stirrer, which was kept in nitrogen atmosphere, 50 ml of THF was dissolved 30 g (42 mmol) PZND obtained in example 18. At room temperature was added to 7.3 g (43 mmol) of 2,2-dichloro-1,3-dimethylimidazolidine in the form of a solid phase, and then for approximately 3 hours spent boiling conditions phlegm is education. After cooling to room temperature, THF drove away under reduced pressure, and then sequentially added 50 ml of THF and 200 ml of diethyl ether. After boiling under conditions of flavobacteria within 30 minutes the resulting mixture was thoroughly mixed and cooled to room temperature to precipitate a white solid phase. The solid phase was filtered in a nitrogen atmosphere and dried under reduced pressure of 1 mm Hg, to obtain 26 g of white solids. Part of the solid phase was added to the DMSO-d6, internal standard measuring method31P NMR was used triamide hexamethylphosphoric acid. In this case, the observed octets corresponding to 1 atom of phosphorus, in the field - 29,81 ppm, doublet, corresponding to 1 atom of phosphorus in the field to 6.22 ppm and a doublet corresponding to 3 phosphorus atoms, in the field 12,04 ppm, and the degree of purity was 99.5%. In addition, according to the results of the analysis according to the method of FD-MS observed peak 730 corresponding medicationabana molecules PZND-Cl.

Example 20

Synthesis of chloride phosphazene with a group of siloxy

In a glass flask of 300 ml equipped with a stirrer, which was kept in an atmosphere of nitrogen, was introduced 21 g (27 mmol) PZND-Cl obtained in example 19, 150 ml of o-dichlorobenzene, and 9.1 g (52 mm is l) simple tert-butyldimethylsilyl(2-amino-ethyl)ether and 4.7 g (27 mmol) of Tris(dimethylamino)phospholane and reaction in the mixture at 120° With was allowed to proceed for 24 hours, then were cooled to room temperature. The reaction mixture was washed with water, a layer of o-dichlorobenzene were distillation under reduced pressure and then washed using 200 ml of diethyl ether. The washed solid phase was dried at normal pressure and got 82 g of white solids. Part of the solid phase was added to THF-d8, and as an internal standard when measuring method31P NMR was used complex tri-n-butyl ether phosphoric acid. In this case, the observed octets corresponding to 1 atom of phosphorus, in the field - 27,52 ppm, doublet, corresponding to 1 atom of phosphorus, in the field 9,77 ppm and a doublet corresponding to 3 phosphorus atoms, in the field 10,45 ppm

Example 21

Synthesis of iodide of phosphazene having a hydroxyl group

In a glass flask of 500 ml equipped with a stirrer, which was kept in an atmosphere of nitrogen was introduced 200 ml of THF, of 10.9 g (455 mmol) of sodium hydride and 67 g (470 mmol) under the conditions, and the mixture was stirred at room temperature for 2 hours. After this was added 41 g of the solution of chloride of phosphazene obtained in example 20 (45 mmol)in THF and the mixture was additionally stirred at room temperature for 16 hours. Upon completion of the reaction, the suspension of hoteltravel and and washed using THF, and THF drove away from the filtrate under reduced pressure. The obtained solid phase is again dissolved in 300 ml of methylene chloride and the insoluble fraction was filtered, and the methylene chloride from the filtrate drove under reduced pressure to obtain 41 g of white solids. In a glass flask of 500 ml equipped with a stirrer, which was kept in an atmosphere of nitrogen, was introduced above a white solid phase and 200 ml of THF, and the mixture was cooled on ice under stirring. This was added 41 ml of a solution of tetrabutylammonium fluoride (1.0 M, 41 mmol) in THF and the mixture was stirred at room temperature for 30 minutes. For separation of liquid to the reaction solution was added 300 ml of water and 300 ml of methylene chloride and a layer of organic solvent, the solvent is kept at reduced pressure to obtain a solid phase, which was subjected to recrystallization from 70%aqueous solution of ethylamine, thereby obtaining 29 g of white solids. Part of the solid phase was added to the DMSO-d6, internal standard measuring method31P NMR was used triamide hexamethylphosphoric acid. In this case, the observed quintuplet corresponding to 1 atom of phosphorus, in the field - 33,34 ppm, doublet, corresponding to 3 phosphorus atoms, in the area of 7.60 ppm and a doublet corresponding to 1 atom of phosphorus, about the Asti 7,79 ppm, and the degree of purity was 100%.

Example 22

Synthesis deposited on a polymeric carrier hydroxide of phosphazene

In a glass flask with a volume of 100 ml, which was kept in an atmosphere of nitrogen, was introduced 0.7 g (29 mmol) of sodium hydride and 50 ml of DMF and to this was further added a solution of 25.2 g of the iodide of phosphazene obtained in example 21 (28 mmol), in DMF, and the mixture was stirred at room temperature for 3 hours. In another glass flask of 500 ml equipped with a stirrer, which was kept in an atmosphere of nitrogen, was introduced to 26.6 g of resin based on polystyrene subjected to chlorotoluron (28 mmol in the calculation of the chlorine atoms) (produced in the company Argonaut Technologies, Inc., ArgoPore Cl, 1.05 mmol Cl/g), and 300 ml of DMF, and the mixture was stirred at room temperature for 2 hours. Then this was added the whole amount of the solution previously obtained sodium salt of iodide of phosphazene in DMF and the mixture was additionally stirred for 20 hours. Upon completion of the reaction, the resulting mixture was filtered, and the resin obtained in the form of the remaining solid phase, washed five times using 50 ml of methanol, and dried under heating at 70°With under reduced pressure of 1 mm Hg. In a glass flask of 500 ml equipped with a stirrer was built in the ICOM, which was kept in an atmosphere of nitrogen, was introduced dried resin and 200 ml of methanol, and the mixture was stirred at room temperature for 1 hour. This solution was added (100 ml) 7.9 g of sodium methoxide in methanol and within 8 hours the mixture was heated at boiling conditions flavobacteria, and then cooled to room temperature. The resulting suspension was filtered and washed with water, subjected to processing by injection into contact with 527 g of 4%aqueous sodium hydroxide solution and washed with water addition. Thus, the remaining solid phase was dried at 70°With under reduced pressure of 1 mm Hg, to obtain 35 g deposited on a polymeric carrier hydroxide of phosphazene. For part of the solid phase measured by the method31P NMR using tetrafluoroborate tetrakis(dimethylamino)phosphonium as an internal standard. In this case, the observed peak corresponding to 1 atom of phosphorus, in the area of 35.5 ppm, and the peak corresponding to 4 moles of phosphorus, in the area of 5.9 ppm, and the concentration phosphazenes cations in the solid phase according to the measurement method31P NMR was 0,371 mmol/g

Example 23

Synthesis deposited on a polymeric carrier chloride phosphazene

17,4 g deposited on a polymeric carrier hydroxide of phosphazene (6.6 mmol in ruscetta phosphazenes cations), obtained in example 22, as the gaskets were placed in a column and subjected to processing by injection into contact with 398 g of 4%aqueous solution of sodium chloride, and optionally washed with water. Then after processing the solid phase was dried at 70°With under reduced pressure of 1 mm Hg, and got deposited on the polymeric carrier chloride phosphazene. Concentration phosphazenes cations in the solid phase according to the measurement method31P NMR was 0,368 mmol/g

Example 24

Synthesis of chloride phosphazene with a group of siloxy

The reaction was carried out in the same way as in example 20, except that instead of simply tert-butyldimethylsilyl(2-amino-ethyl)ether used in example 20, used a simple diethylene glycol(tert-butyldimethylsilyl)(2-amino-ethyl)ether. According to the results of the analysis according to the method of FD-MS observed peak 958 corresponding medicationabana molecules chloride phosphazene with a group of siloxy.

Example 25

Synthesis of hexaflurophosphate phosphazene having a hydroxyl group

The reaction was carried out in the same way as in example 21, except that instead of chloride phosphazene used in example 21 was used chloride phosphazene obtained in example 24, and received a white solid phase. In glass flasks is a volume of 50 ml was injected 3.0 g of the above solid phase, 20 ml of 70%solution of ethylamine and 0.5 g of hexaflurophosphate sodium and the mixture for some time was stirred. A suspension of the resulting mixture was filtered, and the filtrate was allowed to settle for passing recrystallization to obtain 1.3 g of white solid crystals. Part of the solid phase was added to the DMSO-d6, internal standard measuring method31P NMR was used triamide hexamethylphosphoric acid. In this case, the observed quintuplet corresponding to 1 atom of phosphorus, in the field - 33,31 ppm, doublet, corresponding to 3 phosphorus atoms, in the field 7,58 ppm, doublet, corresponding to 1 atom of phosphorus, in the field 7,72 ppm and septet corresponding to 1 atom of phosphorus in the field to 57.0 ppm, and the degree of purity was 91.4 per cent. In addition, according to the results of the analysis according to the method of FD-MS observed peak 858 corresponding medicationabana part phosphazenes cations.

Example 26

Synthesis deposited on a polymeric carrier hexaphosphate phosphazene

In a glass flask with a volume of 50 ml, which was kept in an atmosphere of nitrogen, was introduced 0.07 g (1.7 mmol) of potassium hydride and 10 ml of DMF, there was additionally added 1.3 g (1.3 mmol) of hexaflurophosphate phosphazene obtained in example 25, and the mixture was stirred at room temperature for 3 hours. In another glass to the BU volume of 100 ml, equipped with a stirrer, which was kept in an atmosphere of nitrogen, was introduced 1.1 g of the resin based on polystyrene subjected to chlorotoluron (1.3 mmol in the calculation of the chlorine atoms) (produced in the company Argonaut Technologies, Inc., ArgoPore Cl, 1.20 mmol Cl/g), and 15 ml of DMF, and the mixture was stirred at room temperature for 1 hour. Then this was added the whole amount of the solution previously obtained potassium salt of hexaflurophosphate phosphazene in DMF and the mixture was additionally stirred for 24 hours. Upon completion of the reaction, the resulting mixture was filtered, and the resin obtained in the form of the remaining solid phase, washed in to conventional Soxhlet extractions 1,4-dioxane is used as a solvent, and then dried by heating at 70°With under reduced pressure of 1 mm Hg, to obtain 1.1 g deposited on a polymeric carrier hexaphosphate phosphazene. For part of the solid phase measured by the method31P NMR using tetrafluoroborate tetrakis(dimethylamino)phosphonium as an internal standard. In this case, the observed peak corresponding to 1 atom of phosphorus, in the field - to 35.7 ppm, and the peak corresponding to 4 moles of phosphorus, in the area of 5.9 ppm, and the concentration phosphazenes cations in the solid phase according to the measurement method31P NMR is left 0,266 mmol/g

Example 27

Synthesis deposited on a polymeric carrier hydroxide of phosphazene

In a glass flask with a volume of 50 ml equipped with a stirrer and a fridge, which was kept in an atmosphere of nitrogen, was introduced all the number printed on the polymeric carrier hexaphosphate phosphazene obtained in example 26, and 10 ml of methanol, and the mixture was stirred at room temperature for 1 hour. This was added 10 ml of a solution of 1.0 g of sodium methoxide in methanol and within 8 hours the mixture was heated at boiling conditions flavobacteria, and then cooled to room temperature. The resulting suspension was filtered and washed with water, subjected to processing by injection into contact with 34 g of 4%aqueous sodium hydroxide solution and washed with water. After that, the remaining solid phase was dried at 70°With under reduced pressure of 1 mm Hg, and obtained 1.1 g deposited on a polymeric carrier hydroxide of phosphazene. For part of the solid phase measured by the method31P NMR using as an internal standard tetrafluoroborate tetrakis(dimethylamino)phosphonium. In this case, the observed peak corresponding to 1 atom of phosphorus, in the field - to 35.7 ppm, and the peak corresponding to 4 moles of phosphorus, in the area of 5.9 ppm, and the concentration phosphazenes of kaminow solid phase was 0,297 mmol/g as measured according to the method 31P NMR.

Example 28

Synthesis deposited on a polymeric carrier hydroxide of phosphazene

In a glass flask with a volume of 100 ml equipped with a stirrer, which was kept in an atmosphere of nitrogen, was introduced 4.7 grams of resin based on polystyrene subjected to chlorotoluron (2.0 mmol in the calculation of the chlorine atoms) (produced in the company Argonaut Technologies, Inc., Argo-Gel-Wang Cl, 0.43 mmol Cl/g), and 20 g of tetralin, and the mixture was stirred at room temperature for 1 hour. Then this was added 17.8 g of a solution PZNB obtained in example 1 (2.7 mmol analysis on PZNB), tetraline and the mixture, in addition, was continuously stirred for 4 days. The thus obtained suspension was filtered under nitrogen atmosphere and washed using 50 ml of tetralin and 200 ml of a mixed solvent, characterized by a mass ratio of 1:1 in a mixture of 1,4-dioxane: methanol. Received the remaining solid phase was dried at 70°With under reduced pressure of 1 mm Hg, and received 5.0 g deposited on a polymeric carrier chloride phosphazene. For part of the solid phase measured by the method31P NMR using tetrafluoroborate tetrakis(dimethylamino)phosphonium as an internal standard. In this case, the observed peak corresponding to 1 atom of phosphorus, in the area of 35.4 ppm and the peak correspond to the s 4 moles of phosphorus, in the area of 5.8 ppm, and the concentration phosphazenes cations in the solid phase according to the measurement method31P NMR was 0,316 mmol/year After that, in a glass flask with a volume of 50 ml equipped with a stirrer and a fridge, which was kept in an atmosphere of nitrogen, was introduced 2.3 g of the obtained pre-printed on the polymeric carrier chloride phosphazene (6.1 mmol analysis on phosphazenes cations) and 10 ml of methanol, and the mixture was stirred at room temperature for 1 hour. Then of 0.37 g of sodium methoxide was dissolved in 10 ml of methanol and the solution was added over 8 hours was heated at boiling conditions flavobacteria, and then cooled to room temperature. The resulting suspension was filtered and washed with water, subjected to processing by injection into contact with 80 g of 4%aqueous sodium hydroxide solution and washed with water. After that, the remaining solid phase was dried by heating at 70°With under reduced pressure of 1 mm Hg, and obtained 2.3 g deposited on a polymeric carrier hydroxide of phosphazene. Concentration phosphazenes cations in the solid phase according to the measurement method31P NMR was 0,312 mmol/g In addition, according to the results of elemental analysis of chlorine atoms were not observed, and the anion of the bundle the military was the hydroxide.

Examples from 29 to 30

Synthesis deposited on a polymeric carrier hydroxide of phosphazene

The reaction was carried out in the same way as in example 28, except that changed the types of resins based on polystyrene subjected to klimatisierung used in example 28, thus synthesizing various deposited on a polymeric carrier hydroxides of phosphazene. The results shown in table 3.

Table 3
Name resin based on polystyrene subjected to klimatisierungThe levels of chlorinated resin (mmol/g)The shift in the spectrum of31P NMR (ppm, the number of phosphorus atoms given in parentheses)Concentration phosphazenes cations (mmol/g)
Example 29Resin 2-pyridine-co-Merrifield, produced in the company

Advanced ChemTech
1,0- 34,8 (1), 6,2 (4)0,463
Example 30JandaJels Cl, manufactured by Aldrich company0,70- 35,5 (1), 5,8 (4)0,165

Example 31

Synthesis deposited on a polymeric carrier hydroxide of phosphazene

In a glass flask with a volume of 50 ml, which was kept in an atmosphere of nitrogen, was introduced is 0.18 g (4.6 mmol) of potassium hydride and 20 ml of DMF, this solution was added 5.0 g of iodide of phosphazene obtained in example 9, (3.7 mmol) in DMF, and the mixture was stirred at room temperature for 5 hours. In another glass flask with a volume of 200 ml equipped with a stirrer, which was kept in an atmosphere of nitrogen, was introduced 3.6 g of resin based on polystyrene subjected to chlorotoluron (3.6 mmol in the calculation of the chlorine atoms) (manufactured by Advanced ChemTech, resin 2-pyridine-co-Merrifield, 1.0 mmol Cl/g), and 50 ml of DMF, and the mixture was stirred at room temperature for 1 hour. Then this was added the whole amount of the solution previously obtained potassium salt of iodide of phosphazene in DMF and the mixture was additionally stirred for 62 hours. Upon completion of the reaction, the resulting mixture was filtered, and the resin obtained in the form of the remaining solid phase, washed in to conventional Soxhlet extractions 1,4-dioxane is used as a solvent, and then dried by heating at 70°With under reduced pressure of 1 mm Hg. The dried resin and 50 ml of methanol were introduced into a glass flask with a volume of 200 ml equipped with a stirrer and a fridge, which was kept in nitrogen atmosphere, and the mixture was stirred at room temperature for 1 hour. This solution was added (10 ml), 2.6 g of sodium methoxide in IU is anole and within 8 hours the mixture was heated at boiling conditions flavobacteria, and then cooled to room temperature. The resulting suspension was filtered and washed with water, subjected to processing by injection into contact with 161 g of 4%aqueous sodium hydroxide solution and washed with water. After that, the remaining solid phase was dried at 70°With under reduced pressure of 1 mm Hg, and obtained 3.6 g deposited on a polymeric carrier hydroxide of phosphazene. For part of the solid phase measured by the method31P NMR using as an internal standard tetrafluoroborate tetrakis(dimethylamino)phosphonium. In this case, the observed peak corresponding to 1 atom of phosphorus, in the field or 34.7 ppm, and the peak corresponding to 4 moles of phosphorus, in the area of 6.0 ppm, and the concentration phosphazenes cations in the solid phase was was 0.138 mmol/g as measured according to the method31P NMR.

Example 32

Synthesis deposited on a polymeric carrier hydroxide of phosphazene

In a glass flask with a volume of 50 ml, which was kept in an atmosphere of nitrogen, was introduced 0.1 g (2.4 mmol) of potassium hydride and 10 ml of DMF, and this solution was added 3.3 grams of iodide of phosphazene obtained in example 9 (2.6 mmol), in DMF, and the mixture was stirred at room temperature for 5 hours. In another glass flask of 100 ml capacity equipped with a stirrer, which was kept in the atmosphere is fere nitrogen, entered 3.1 g of the resin based on polystyrene subjected to chlorotoluron (2.2 mmol in the calculation of the chlorine atoms) (manufactured by Aldrich company, JandaJels C1, 0.70 mmol Cl/g), and 30 ml of DMF, and the mixture was stirred at room temperature for 1 hour. Then this was added the whole amount of the solution previously obtained potassium salt of iodide of phosphazene in DMF and the mixture was additionally stirred for 45 hours. Upon completion of the reaction, the resulting mixture was filtered, and the resin obtained in the form of the remaining solid phase, washed in to conventional Soxhlet extractions 1,4-dioxane is used as a solvent, and then dried by heating at 70°With under reduced pressure of 1 mm Hg. The dried resin and 40 ml of methanol were introduced into a glass flask of 100 ml capacity equipped with a stirrer and a fridge, which was kept in nitrogen atmosphere, and the mixture was stirred at room temperature for 1 hour. This solution was added (10 ml) 2.4 g of sodium methoxide in methanol and within 8 hours the mixture was heated at boiling conditions flavobacteria, and then cooled to room temperature. The resulting suspension was filtered and washed with water, subjected to processing by injection into contact with 89 g of 4%aqueous hydroxide solution intothree and washed with water. After that, the remaining solid phase was dried at 70°With under reduced pressure of 1 mm Hg, and obtained 2.2 g deposited on a polymeric carrier hydroxide of phosphazene. For part of the solid phase measured by the method31P NMR using as an internal standard tetrafluoroborate tetrakis(dimethylamino)phosphonium. In this case, the observed peak corresponding to 1 atom of phosphorus, in the area of 34.8 ppm, and the peak corresponding to 4 moles of phosphorus, in the area of 6.2 ppm, and the concentration in the solid phase was 0,078 mmol/g as measured according to the method31P NMR.

Example 33

Synthesis of iodide of phosphazene with stielow group

In a glass flask of 300 ml equipped with a stirrer, which was kept in an atmosphere of nitrogen, was administered to 96 g of the solution PZNB (15 mmol analysis on PZNB) tetraline and 73 ml of o-dichlorobenzene, and the mixture was cooled on ice under stirring. This was added dropwise 2.7 g (18 mmol) of 4-vinylbenzoate and the resulting mixture was stirred at room temperature overnight. Upon completion of the reaction, tetralin and o-dichlorobenzene drove under reduced pressure and obtained viscous liquid with an orange color. This was added 60 ml of hexane and after stirring hexane was removed as a result of decanting. Washing with hexane wire is whether 3 times, and the precipitated solids were dissolved by adding 230 ml of 70%aqueous solution of ethylamine. This was added 2.4 g (16 mmol) of sodium iodide and 15 ml of water, the mixture was stirred at room temperature for 1 hour, and then the resulting mixture was allowed to stand for 4 days. Precipitated crystals were filtered off and then washed with water and hexane to obtain pale yellow crystals. The thus obtained crystals were subjected to recrystallization using a mixed solvent obtained from ethyl acetate and hexane, and the precipitated crystals were filtered off, washed with hexane and then dried under heating at 70°With under reduced pressure of 1 mm Hg, to obtain as white crystals 8.7 g of iodide of phosphazene with stielow group. Part of the solid phase was added to the benzene-d6, and as an internal standard when measuring method31P NMR was used triamide hexamethylphosphoric acid. In this case, the observed quintuplet corresponding to 1 atom of phosphorus, in the field - 33,7 ppm, doublet, corresponding to 3 atoms of phosphorus in the field to 7.50 ppm and a doublet corresponding to 1 atom of phosphorus, in the field 8,77 ppm, and the degree of purity was 96.1 per cent. In addition, according to the results of the analysis method the FD-MS observed peak 841, appropriate medicationoveruse phosphatherium cation.

Example 34

Synthesis of iodide of phosphazene having allyl group

The reaction was carried out in the same way as in example 33, except that instead of 4-vinylbenzoate used in example 33 was used an equimolar amount of allylchloride. Part of the obtained compounds were added to the benzene-d6, and as an internal standard when measuring method31P NMR was used triamide hexamethylphosphoric acid. In this case, the observed quintuplet corresponding to 1 atom of phosphorus, in the area of 33.6 ppm, doublet, corresponding to 3 phosphorus atoms, in the field 7,58 ppm and a doublet corresponding to 1 atom of phosphorus, in the field 8,83 ppm, and the degree of purity was 97.1 per cent.

Example 35

Synthesis deposited on a polymeric carrier iodide and hydroxide of phosphazene

In a glass flask with a volume of 50 ml equipped with a stirrer, which was kept in an atmosphere of nitrogen, was introduced 0,082 g (0.50 mmol) of 2,2'-azobisisobutyronitrile, 0.97 g (0.96 mmol) of iodide of phosphazene obtained in example 33, was added 20 ml of toluene, and the mixture was stirred. This was placed 10,52 g (101,0 mmol) of Monomeric styrene and after stirring the resulting mixture at 100°C for 7 hours the mixture was cooled to -77°for damping rejection the mixture was poured into 1.5 l of methanol, and was obtained a white precipitate. The precipitate was filtered and dried under heating at 70°With under reduced pressure of 1 mm Hg, to obtain 4.4 g deposited on a polymeric carrier iodide of phosphazene in the form of a white solid phase.

Obtained 3.6 g deposited on a polymeric carrier iodide of phosphazene as gaskets were placed in a column and subjected to processing by injection into contact with a 4%aqueous solution mixture of sodium chloride/methanol and was further washed with methanol and water. After processing the solid phase was dried by heating at 70°With under reduced pressure of 1 mm Hg, with getting deposited on the polymeric carrier hydroxide of phosphazene. For part of the solid phase measured by the method31P NMR using tetrafluoroborate tetrakis(dimethylamino)phosphonium as an internal standard. In this case, the observed peak corresponding to 1 atom of phosphorus, in the area of 35.1 ppm, the peak corresponding to 4 atoms of phosphorus, in the area of 5.6 ppm, and the concentration phosphazenes cations in the solid phase according to the measurement method31P NMR was 0,1039 mmol/g Solid phase consisted of a copolymer which was obtained by carrying out the copolymerization at a molar ratio of 1:84 in the system phosphatemia salt having stielow group:Monomeric tis the ol. In addition, according to the analysis by GPC method (based on standard polystyrene) observed a polymer characterized by srednekamennogo molecular weight (Mn) 8536 and molecular weight distribution (Mw/Mn) of 1.76.

Example 36

Synthesis of chloride phosphazene with trimethoxysilyl group - 1

In a glass flask with a volume of 100 ml, which was kept in nitrogen atmosphere, in 100 ml of dry hexane was dissolved 3.0 ml (12.2 mmol) of 4-(chloromethyl)phenethyltrimethoxysilane. To the solution at room temperature was added dropwise 50 g of the solution PZNB (0,220 mmol/g to 11.0 mmol/g PZNB) tetraline. Simultaneously with parabalym addition produced compartment light brown oily substance. Upon completion pocataligo adding the resulting mixture was additionally stirred for 30 minutes. Light brown oily substance was separated from the colorless supernatant liquid, and then there was added 5 ml of dry methanol. The mixture four times washed with 15 ml of dry hexane. The solution is kept under reduced pressure and got a 10.5 g of an oily substance with an orange color. On the basis of the results obtained in accordance with the methods1H,13C and31P NMR, the main component of the obtained oily substance was desirable chloride phosphazene is, having trimethoxysilyl group. Identification results obtained in accordance with the methods1H,13C and31P NMR, shown next.

1H NMR (CDCl3, 270 MHz): to 7.15 (m, 4H), 4,13 (d, 2H), 3,57 (s, 9H), 2,8-2,5 (m, 71H), and 1.00 (m, 2H).

13C NMR (CDCl3, 270 MHz): 143,2, 135,8, 127,9, 127,8, 53,2, 50,5, 37,4-36,8, 34,0, 28,3, 11,3.

31P NMR (CDCl3, 109,3 MHz): to 7.25 (d, 1P), of 5.92 (d, 3P), -34,9 (kV, 1P).

Based on the results obtained in accordance with the method31P NMR, oily substance that contains as a main component the above-mentioned chloride phosphazene with trimethoxysilyl group, as a by-product contains a compound vpisivaushiesya General formula (5), where a = b = c = d = 1, R = R1= Me, D' = H, n = 1 and Z = Cl. In addition, the observed degree of purity chloride phosphazene with trimethoxysilyl group, an oily substance, as defined in method1H NMR on the basis of the integral ratio between the peaks of using NMe2was approximately 80%.

Example 37

Synthesis of chloride phosphazene with trimethoxysilyl group - 2

In a glass flask with a volume of 100 ml, which was kept under nitrogen atmosphere, 30 ml of dry hexane was dissolved of 0.87 ml (4.0 mmol) of 4-(chloromethyl)phenyltrimethoxysilane. To the solution at room temperature was added dropwise 15 g rest the RA PZNB (0,220 mmol/g to 3.3 mmol/g PZNB) tetraline. Simultaneously with parabalym addition produced compartment light brown oily substance. Upon completion pocataligo adding the resulting mixture was additionally stirred for 30 minutes. Light brown oily substance was separated from the colorless supernatant liquid, and then there was added 2 ml of dry methanol. The mixture four times washed using 5 ml of dry hexane. The solution is kept under reduced pressure and got 2,90 g of oily substance with an orange color. On the basis of the results obtained in accordance with the methods1H,13C and31P NMR, the main component of the obtained oily substance was desirable chloride phosphazene with trimethoxysilyl group. Identification results obtained in accordance with the methods1H,13C and31P NMR, shown next.

1H NMR (CDCl3, 270 MHz): to 7.61 (m, 2H), 7,26 (d, 2H), 4,21 (d, 2H), 3,64 (s, 9H), 2,8-2,5 (m, 69H).

13C NMR (CDCl3, 270 MHz): 141,4, 134,9, 134,7, 127,3, 53,6, 50,1, 37,5-36,8, 34,3.

31P NMR (CDCl3, 109,3 MHz): 7,33 (d, 1P), 5,94 (d, 3P), -34,9 (kV, 1P).

Based on the results obtained in accordance with the method31P NMR, oily substance that contains as a main component the above-mentioned chloride phosphazene with trimethoxysilyl GRU is PU, as a by-product contains a compound vpisivaushiesya General formula (5), where a = b = c = d = 1, R = R1= Me, D' = H, n = 1 and Z = Cl. In addition, the observed degree of purity chloride phosphazene with trimethoxysilyl group, an oily substance, as defined in method1H NMR on the basis of the integral ratio between the peaks of using NMe2was approximately 50%.

Example 38

Synthesis of bromide phosphazene with trimethoxysilyl group

In a glass flask with a volume of 100 ml, which was kept under nitrogen atmosphere, 30 ml of dry hexane was dissolved 0.75 ml (4.0 mmol) of 3-bromopropionitrile. To the solution at room temperature was added dropwise 15 g of the solution PZNB (0,220 mmol/g to 3.3 mmol/g PZNB) tetraline. Simultaneously with parabalym addition produced compartment light brown oily substance. Upon completion pocataligo adding the resulting mixture was additionally stirred for 30 minutes. Light brown oily substance was separated from the colorless supernatant liquid, and then there was added 2 ml of dry methanol. The mixture four times washed using 5 ml of dry hexane. The solution is kept under reduced pressure and got 3,10 g of oily substance with an orange color. Based on the results obtained in accordance with the methods 1H,13C and31P NMR, the main component of the obtained oily substance was desirable bromide phosphazene with trimethoxysilyl group. Identification results obtained in accordance with the methods1H,13C and31P NMR, shown next.

lH NMR (CDCl3, 270 MHz): to 3.58 (s, 9H), 2,9-2,5 (m, 71H), and 1.56 (m, 2H), 0,53 (m, 2H).

13C NMR (CDCl3, 270 MHz): 52,2, 50,6, 37,3-36,9, 34,0, 21,5, 6,5.

31P NMR (CDCl3, 109,3 MHz): of 6.20 (d, 1P), 6,00 (d, 3P), -35,1 (kV, 1P).

Based on the results obtained in accordance with the method31P NMR, oily substance that contains as a main component bromide phosphazene with trimethoxysilyl group, as a by-product contains a compound vpisivaushiesya General formula (5), where a = b = c = d = 1, R = R1= Me, D' = H, n = 1 and Z = Br. In addition, the observed degree of purity of bromide phosphazene with trimethoxysilyl group, an oily substance, as defined in method1H NMR on the basis of the integral ratio between the peaks of using NMe2was approximately 70%.

Example 39

Obtaining silica gel, which is a carrier for chloride phosphazene, by way of hydrolysis-polycondensation - 1

In a two-neck round-bottom glass flask with a volume of 100 ml, equipped with a mixing device is the your, thermometer, refrigerator and the like, introduced 7,40 g (6.2 mmol) crude crude chloride phosphazene with trimethoxysilyl group obtained in example 36, 50.0 g (0.24 mol) of tetraethoxysilane, 50 ml of ethanol and 0.80 ml (9.2 mmol) of 36%hydrochloric acid. Here for 10 minutes was added dropwise to 10.0 g of water, and then the mixture for 3 hours, stirred at 60°C. After the resulting mixture was allowed to cool, added to 50.0 g of water and was added dropwise to 2.0 ml of 28%aqueous ammonia solution, which ensured rapid solidification of the reaction mixture. The resulting mixture was allowed to stand at room temperature for 3 days and twice washed with 100 ml of water, subjected to ion exchange. The obtained solid phase for 4 hours, dried at 100°With under reduced pressure of 1 mm Hg, and got to 20.9 g of silica gel, which is a carrier for chloride phosphazene (number printed on the carrier chloride phosphazene: 0.30 mmol/g). The specific surface area, measured by the method of adsorption is carried gaseous nitrogen amounted to 432 m2/g and pore volume for pores having a diameter in the range of 9 to 500 Åamounted to 0.30 cm3/, According to the method31P NMR in the solid state exhibits the peaks and in the areas of 35.2 (1R) ppm, the 13.4-5,8 (3P) ppm and - 36,4 (1R) ppm

Example 40

Obtaining silica gel, which is a carrier for chloride phosphazene, by way of hydrolysis-polycondensation - 2

In a two-neck round-bottom glass flask of 100 ml capacity equipped with a stirrer, thermometer, refrigerator and the like, introduced 5,95 g (5.0 mmol) crude crude chloride phosphazene with trimethoxysilyl group obtained in example 36, to 20.8 g (0.10 mol) of tetraethoxysilane, 20 ml of ethanol and of 0.60 ml (6,9 mmol) of 36%hydrochloric acid. Here for 10 minutes was added dropwise 5.0 g of water, and then the mixture for 3 hours, stirred at 60°C. After the resulting mixture was allowed to cool, added to 20.0 g of water and was added dropwise 1.0 ml of 28%aqueous ammonia solution, which ensured rapid solidification of the reaction mixture. The resulting mixture was allowed to stand at room temperature for 3 days and twice washed using 50 ml of water, subjected to ion exchange. The obtained solid phase for 4 hours, dried at 80°With under reduced pressure of 1 mm Hg, and obtained 11.1 g of silica gel, which is a carrier for chloride phosphazene (number printed on the carrier chloride phosphazene: 0.45 mmol/g). The area at the part surface, measured by the method of adsorption is carried gaseous nitrogen was 277 m2/g and pore volume for pores having a diameter in the range of 9 to 500 Å, 0.59 cm3/year

Example 41

Obtaining silica gel, which is a carrier for chloride phosphazene, by way of sililirovanie

In a two-neck round-bottom glass flask of 50 ml equipped with a stirrer, thermometer, refrigerator and the like, in an atmosphere of nitrogen was introduced and 2.26 g (1.9 mmol) crude crude chloride phosphazene with trimethoxysilyl group obtained in example 36, of 5.00 g of silica gel (made in a company Called Kanto Chemical Co. Ltd., 60N) and 20 ml of dry toluene, and the mixture was heated and stirred at boiling conditions flavobacteria within 12 hours. The resulting mixture was filtered and after twice washing with 20 ml of methanol obtained solid phase for 4 hours, dried at 80°With under reduced pressure of 1 mm Hg, to obtain 6.50 g of silica gel, which is a carrier for chloride phosphazene (number printed on the carrier chloride phosphazene: 0.24 mmol/g). The specific surface area, measured by the method of adsorption is carried gaseous nitrogen amounted to 447 m2/g and pore volume for pores having a diameter in the range of 9 to 500 Å, SOS is avsl 0,47 cm 3/, According to the method31P NMR in the solid state was observed peaks in areas 5,71 (4P) ppm and -36,1 (1R) ppm

Example 42

Obtaining silica gel, which is a carrier for the hydroxide of phosphazene - 2

11.1 g of silica gel, which is a carrier for chloride phosphazene of 3.33 mmol analysis on phosphazenes cations)obtained in example 39, as the gaskets were placed in a column. After passing through the column 30,0 ml (30 mmol) of an aqueous solution of ammonia with a concentration of 1 mol/l (SV = 3) column was washed with water, subjected to ion exchange, and methanol. After processing the solid phase for 6 hours, dried at 80°With under reduced pressure of 1 mm Hg, and received of 11.0 g of silica gel, which is a carrier for the hydroxide of phosphazene, (quantity printed on the media hydroxide of phosphazene: 0.30 mmol/g). According to the results of elemental analysis of chlorine atoms were not observed. In addition, the specific surface area, measured by the method of adsorption is carried gaseous nitrogen, was $ 454 m2/g and pore volume for pores having a diameter in the range of 9 to 500 Å, was 0.36 cm3/, According to the method31P NMR in the solid state was observed peaks in the areas of 5.75 (4P) ppm and -36,1 (1R) ppm

Example 43

Obtaining silica gel, which is a carrier for the hydroxide of phosphazene - 3

3,24 g Seeley is agile, which is a carrier for chloride phosphazene (1,46 mmol analysis on phosphazenes cations)obtained in example 40, as gaskets were placed in a column. After passing through the column 29,2 ml (29.2 mmol) of an aqueous solution of ammonia with a concentration of 1 mol/l (SV = 4) column was washed with water, subjected to ion exchange, and methanol. After processing the solid phase for 6 hours, dried at 80°With under reduced pressure of 1 mm Hg, and got a 3.15 g of silica gel, which is a carrier for the hydroxide of phosphazene, (quantity printed on the media hydroxide of phosphazene: 0.45 mmol/g).

Example 44

Obtaining silica gel, which is a carrier for the hydroxide of phosphazene - 1

of 2.72 g of silica gel, which is a carrier for chloride phosphazene (of 0.65 mmol analysis on phosphazenes cations)obtained in example 41, as the gaskets were placed in a column. After passing through the column of 6.3 ml (6.3 mmol) of an aqueous solution of ammonia with a concentration of 1 mol/l (SV = 4) column was washed with water, subjected to ion exchange, and methanol. After processing the solid phase for 6 hours, dried at 80°With under reduced pressure of 1 mm Hg, and obtained 2.65 g of silica gel, which is a carrier for the hydroxide of phosphazene (number printed on the media hydroxide fosfate the I: 0.24 mmol/g). According to the results of elemental analysis of chlorine atoms were not observed. In addition, the specific surface area, measured by the method of adsorption is carried gaseous nitrogen amounted to 428 m2/g and pore volume for pores having a diameter in the range of 9 to 500 Åwas 0,50 cm3/, According to the method31P NMR in the solid state was observed peaks in areas 5,95 (4P) ppm and -36,1 (1R) ppm

Example 45

Alkylation of the phenolic hydroxyl group when using as a catalyst deposited on a polymeric carrier iodide of phosphazene

In a glass flask with a volume of 100 ml equipped with a stirrer and a fridge, which was kept in an atmosphere of nitrogen, was introduced 2.7 g deposited on a polymeric carrier iodide of phosphazene (1.0 mmol in calculating phosphazenes cations)obtained in example 4 0,49 g (5.2 mmol) of phenol and 30 ml of dimethylcarbonate, and the mixture for 18 hours, heated at boiling conditions flavoursome with stirring and then cooled to room temperature. Upon completion of the reaction liquid supernatant of the suspension was partially collected and subjected to analysis by the method of gas chromatography. Thus, it was found that the degree of conversion of phenol was 99.4%and the yield of the target anisole was equal 91,0%. In addition, upon completion of the reaction, suspense who was filtered, washed in to conventional Soxhlet extractions with dimethylcarbonate used as a solvent, and dried under heating at 70°With under reduced pressure of 1 mm Hg, with the extraction of 2.7 g deposited on a polymeric carrier iodide of phosphazene.

Comparative example 1

The reaction was carried out in the same way as in example 45, except that 2.7 g deposited on a polymeric carrier iodide of phosphazene (1.0 mmol in calculating phosphazenes cations)used in example 45, are not used. Conducted analysis by the method of gas chromatography, and, thus, it was found that the conversion of phenol was not fully and completely impossible to achieve the target of anisole.

Comparative example 2

The reaction was carried out in the same way as in example 45, except that instead of 2.7 g deposited on a polymeric carrier iodide of phosphazene (1.0 mmol in calculating phosphazenes cations)used in example 45, using 1.0 mmol of iodide tetrakis[Tris(dimethylamino)phosphorylcholine]phosphonium. Conducted analysis by the method of gas chromatography, and, thus, it was found that the conversion of phenol was completely, and the yield of the target anisole accounted for 93.4%. It was found that deposited on the polymeric carrier IO the ID phosphazene contain active catalyst, equivalent to what takes place in case of no applied on the polymeric carrier iodide of phosphazene.

Examples from 46 to 54

Sending the extracted catalyst for recycling

The reaction was carried out in the same way as in example 45, except that instead of printed on the polymeric carrier iodide of phosphazene used in example 45, used the extracted deposited on a polymeric carrier iodide of phosphazene obtained in example 45, and upon completion of the reaction, deposited on a polymeric carrier iodide of phosphazene removed. In addition, the extracted deposited on a polymeric carrier iodide of phosphazene in the reaction used repeatedly. The results shown in table 4.

Table 4
The used catalystThe degree of conversion of phenol (%)The output of anisole (%)
Example 45Deposited on a polymeric carrier iodide of phosphazene obtained in example 499,491,0
Example 46Deposited on a polymeric carrier iodide of phosphazene extracted in example 4599,5for 93.4
Example 47Deposited on a polymeric carrier iodide phosphazene is, extracted in example 46100a 94.2
Example 48Deposited on a polymeric carrier iodide of phosphazene extracted in example 4710091,9
Example 49Deposited on a polymeric carrier iodide of phosphazene extracted in example 4810094,5
Example 50Printed on10088,7
polymeric media iodide of phosphazene extracted in example 49
Example 51Deposited on a polymeric carrier iodide of phosphazene extracted in example 5010090,2
Example 52Deposited on a polymeric carrier iodide of phosphazene extracted in example 5110091,8
Example 53Deposited on a polymeric carrier iodide of phosphazene extracted in example 5210092,8
Example 54Deposited on a polymeric carrier iodide of phosphazene extracted in example 5310095,9

In addition, according to measurements carried out according to the method31P NMR, concentration phosphazenes cations deposited on the polymer is of the l-iodide of phosphazene, extracted in example 54, was 0,345 mmol/g, and no removal of iodide of phosphazene due to repeated use, was not observed.

Example 55

Polymerization of polyalkylated when using as a catalyst deposited on a polymeric carrier hydroxide of phosphazene

In the autoclave with a volume of 70 ml, equipped with a thermometer, a pressure gauge, a stirrer and an inlet pipe for accelerated, which was kept in an atmosphere of nitrogen, was introduced 1.0 g (11 mmol) of glycerol, 0.3 g deposited on a polymeric carrier hydroxide of phosphazene (0.13 mmol analysis on phosphazenes cations)obtained in example 3, and 34 g of propylene oxide, the autoclave was tightly closed and the mixture was heated up to 80°under stirring. At the moment the pressure in the autoclave was increased to 0.3 MPa (gauge pressure). After that, the pressure decrease due to the consumption of propylene oxide, but the reaction is continued until, while reducing the pressure did not stop. Upon completion of the reaction, the resulting mixture was cooled to room temperature, and the residual propylene oxide drove away under reduced pressure. The slurry from the autoclave was collected, diluted with the use of THF, and then was filtered. In addition, the remaining solid phase sufficiently washed with and the use of THF, and THF from the filtrate drove and got 32 g polypropyleneoxide colorless and odorless. Activity during polymerization (the number of received polypropyleneoxide on one mol of catalyst and per unit time) was $ 10.9 g/mmol·h.

Comparative example 3

The reaction was carried out in the same way as in example 55, except that instead of printed on the polymeric carrier hydroxide of phosphazene used in example 55, used 0.06 g (1.6 mmol) of potassium hydroxide. It was possible to obtain 30 g of polypropyleneoxide, but the activity during polymerization was only 0,29 g/mmol·h.

Examples 56 to 58

The reaction was carried out in the same way as in example 55, except that used the autoclave of 300 ml, and instead of glycerin used in example 55, used the types and amounts of alcohol and the number of propylene oxide shown in table 5. The results shown in table 5.

Table 5
The type of alcoholsThe number of used-used alcohol (g)The number of used-used of propylene oxide (g)The number of received-aqueous polypropyleneoxide (g)Catalytic Activ-ity (g/mmol·the AU)
Example 561-phenyl-2-propanol17,7831019,6
Example 571-Phenoxyethanol16,810512010,2
Example 583-phenyl-1-propanol16,21091238,9

Examples from 59 to 69

The reaction was carried out in the same way as in example 55, except that used autoclave with a volume of 70 ml or 300 ml, and instead deposited on the polymeric carrier hydroxide of phosphazene used in example 55, the used amount of glycerin and the number of propylene oxide shown in table 6. The results shown in table 6.

1,0
Table 6
Catalyst typeThe number of used-aqueous glycerol (g)The molar ratio of glycerol/catThe amount of propylene oxide (g)The number of received polypropyleneoxide (g)Catalytic activity (g/

mmol·

h)
Example 55Deposited on a polymeric carrier hydroxide of phosphazene obtained in example 385343210,9
Example 59Deposited on a polymeric carrier hydroxide of phosphazene obtained in example 31,58211010824,3
Example 60Deposited on a polymeric carrier hydroxide of phosphazene obtained in example 122,69384807,1
Example 61Deposited on a polymeric carrier hydroxide of phosphazene obtained in example 142,9839598of 5.4
Example 62Deposited on a polymeric carrier hydroxide of phosphazene obtained in example 222,98310210413,2
Example 63Deposited on a polymeric carrier hydroxide of phosphazene obtained in example 273,1861031012,8
Example 64Deposited on a polymeric carrier hydroxide of phosphazene obtained in example 281,0833232the 11.6
Example 65Deposited on a polymeric carrier, the hydroxide phosphate the Oia, obtained in example 291,279434412,2
Example 66Deposited on a polymeric carrier hydroxide of phosphazene obtained in example 301,282383916,0
Example 67Deposited on a polymeric carrier hydroxide of phosphazene obtained in example 311,58351499,9
Example 68Deposited on a polymeric carrier hydroxide of phosphazene obtained in example 321,186363614.4V
Example 69Deposited on a polymeric carrier hydroxide of phosphazene obtained in example 320,688343419,1
Comparative example 3The potassium hydroxide1,0734300,3

Examples 70 to 72

Removing and departure for recycling printed on the polymeric carrier hydroxide of phosphazene

In the autoclave of 300 ml equipped with a thermometer, a pressure gauge, a stirrer and an inlet pipe for accelerated, which was kept in almost the re nitrogen, introduced 3.2 g glycerol, 2.5 g deposited on a polymeric carrier hydroxide of phosphazene obtained in example 17, and 104 g of propylene oxide, the autoclave was tightly closed and the mixture was heated up to 80°under stirring. At the moment the pressure in the autoclave was increased to 0.32 MPa (gauge pressure). After that, the pressure decrease due to the consumption of propylene oxide, but the reaction is continued until, while reducing the pressure did not stop. Upon completion of the reaction, the resulting mixture was cooled to room temperature, and the residual propylene oxide drove away under reduced pressure. The slurry from the autoclave was collected, diluted with the use of THF, and then was filtered. In addition, the remaining solid phase sufficiently washed using THF and THF from the filtrate drove under reduced pressure and obtained 103 g polypropyleneoxide colorless and odorless. Activity during polymerization (the number of received polypropyleneoxide on one mol of catalyst and per unit time) was 2.0 g/mmol·the hour. In addition, upon completion of filtration, the remaining solid phase was dried by heating at 70°C under reduced pressure of 1 mm Hg, to extract the catalyst. After all the number of the extracted catalyst, 2.7 g of glycerol and 85 g are impregnated is anoxia was injected into the autoclave with a volume of 300 ml, and the mixture was subjected to polymerization at 80°and recycling at the end of the reaction to obtain 87 g of polypropyleneoxide and extracted catalyst. In addition, the extracted catalyst was applied to the polymerization together with 2.7 g of glycerin and 86 g of propylene oxide to obtain 85 g of polypropyleneoxide. It was found that the second and third catalytic activity was 1.9 g/mmol·HR and 2.0 g/mmol·h, respectively, and deposited on a polymeric carrier hydroxide of phosphazene in the invention, no decrease in activity was not observed even after removing and departure on recycling as a catalyst.

Examples from 73 to 81

Removing and departure for recycling for deposited on a polymeric carrier hydroxide of phosphazene

The reaction was carried out in the same way as in example 69, except that after removing used all the number printed on the carrier of the catalyst used in the polymerization of example 69. In addition, upon completion of the polymerization, the catalyst was recovered and repeatedly used in the subsequent reactions in the same way. The results shown in table 7.

Catalytic activity (g/mmol·h) Deposited on a polymeric carrier hydroxide of phosphazene extracted in example 80
Table 7
The used catalyst
Example 69Deposited on a polymeric carrier hydroxide of phosphazene obtained in example 3219,1
Example 73Deposited on a polymeric carrier hydroxide of phosphazene extracted in example 6918,9
Example 74Deposited on a polymeric carrier hydroxide of phosphazene extracted in example 7316,9
Example 75Deposited on a polymeric carrier hydroxide of phosphazene extracted in example 74the 17.3
Example 76Deposited on a polymeric carrier hydroxide of phosphazene extracted in example 7516,4
Example 77Deposited on a polymeric carrier hydroxide of phosphazene extracted in example 7619,2
Example 78Deposited on a polymeric carrier hydroxide of phosphazene extracted in example 7714.4V
Example 79Deposited on a polymeric carrier hydroxide of phosphazene extracted in example 7816,4
Example 80Deposited on a polymeric carrier hydroxide of phosphazene extracted in example 7912,1
Example 8114,0

Even after ten repeated cycles of polymerization processes, as it was found that the catalyst had sufficient catalytic activity.

Example 82

Polymerization of polyalkylated when using as a catalyst deposited on a polymeric carrier hydroxide of phosphazene

In the autoclave with a volume of 70 ml, equipped with a thermometer, a pressure gauge, a stirrer and an inlet pipe for accelerated, which was kept in an atmosphere of nitrogen, was introduced 0.6 g (7.0 mmol) of glycerol, 0.9 g deposited on a polymeric carrier hydroxide of phosphazene (0.09 mmol analysis on phosphazenes cations)obtained in example 35, and 33 g of propylene oxide, the autoclave was tightly closed and the mixture was heated up to 80°under stirring. At the moment the pressure in the autoclave was increased to 0.3 MPa (gauge pressure). After that, the pressure decrease due to the consumption of propylene oxide, but the reaction is continued until, while reducing the pressure did not stop. Upon completion of the reaction, the resulting mixture was cooled to room temperature, and the residual propylene oxide drove away under reduced pressure. The slurry from the autoclave was collected, diluted but the normal hexane, and then was filtered. In addition, the filtrate is sufficiently washed with normal hexane and normal hexane from the filtrate drove under reduced pressure and got 33 g polypropyleneoxide colorless and odorless. Activity during polymerization (the number of received polypropyleneoxide on one mol of catalyst and per unit time) was 12.4 g/mmol·h.

Examples from 83 to 84

Removing and departure for recycling printed on the polymeric carrier hydroxide of phosphazene

The remaining solid phase obtained in example 82, upon completion of the filtration was dried under heating at 70°C under reduced pressure of 1 mm Hg, to extract the catalyst. After all the number of the extracted catalyst, 0.6 g of glycerin and 30 g of propylene oxide was introduced into the autoclave with a volume of 70 ml and in the same way as in example 82, the mixture was subjected to polymerization at 80°and processing upon completion of the reaction with 30 g of polypropyleneoxide and extracted catalyst. In addition, the extracted catalyst was applied to the polymerization together with 0.5 g of glycerin and 29 g of propylene oxide to obtain 29 g of polypropyleneoxide. It was found that the second and third catalytic activity was 10.6 g/mmol·hour and 14.7 g/mmol·h, respectively, and applied Apolinary media hydroxide of phosphazene in the invention, no decrease in activity was not observed even after removing and departure on recycling as a catalyst.

Example 85

Andolina condensation of acetone when using as a catalyst of silica gel, which is a carrier for the hydroxide of phosphazene

In a round bottom glass flask with a volume of 50 ml was administered 1.0 g of silica gel, which is a carrier for the hydroxide of phosphazene, (0.45 mmol analysis on phosphazenes cations)obtained in example 43, and 26.5 g (0.45 mol) of acetone, and the mixture was stirred at room temperature under nitrogen atmosphere. After 8 hours portion of the liquid supernatant of the suspension was collected and subjected to analysis by the method of gas chromatography. Thus, it was found that the degree of conversion of acetone was 3.5%, and selectivity to obtain diacetone alcohol and metaloxide were equal 97,2% and 2.8%, respectively.

Example 86

Andolina condensation of acetone when using as a catalyst of silica gel, which is a carrier for the hydroxide of phosphazene

In a round bottom glass flask with a volume of 50 ml was administered 1.0 g of silica gel, which is a carrier for the hydroxide of phosphazene (0.24 mmol analysis on phosphazenes cations)obtained in example 44, and 14.0 g (0.24 mol) of acetone, and the mixture was stirred at room temperature under nitrogen atmosphere. After 8 hours portion of the liquid supernatant of the suspension was collected and subjected to analysis by the method of gas chromatography is. Thus, it was found that the degree of conversion of acetone was 1.3%and the selectivity to obtain diacetone alcohol was 100%.

Comparative example 4

The reaction was carried out in the same way as in example 85, except that instead of silica gel, which is a carrier for the hydroxide of phosphazene used in example 85, used 0.34 g (0.45 mmol) hydroxide tetrakis[Tris(dimethylamino)phosphorylcholine]phosphonium. After 8 hours portion of the liquid supernatant of the suspension was collected and subjected to analysis by the method of gas chromatography. Thus, it was found that the degree of conversion of acetone was 8.0%and the selectivity to obtain diacetone alcohol and metaloxide were equal to 78.2% and 21.3%, respectively.

The scheme of chemical reactions for each example

Example 1. PZNB

Example 2. Deposited on a polymeric carrier chloride phosphazene

Example 3. Deposited on a polymeric carrier hydroxide of phosphazene

Example 4. Deposited on a polymeric carrier iodide of phosphazene

Example 5. Iodide of phosphazene having a hydroxyl group

Examples 6 to 11. Iodide FOS is Azania, containing polyalkylated in its side chain

Examples 12 to 17. Deposited on a polymeric carrier hydroxide of phosphazene

Example 18. PZND

Example 19. PZND-Cl

Example 20. Chloride phosphazene with a group of siloxy

Example 21. Iodide of phosphazene having a hydroxyl group

Example 22. Deposited on a polymeric carrier hydroxide of phosphazene

Example 23. Deposited on a polymeric carrier chloride phosphazene

Example 24. Chloride phosphazene with a group of siloxy

Example 25. Hexaphosphate phosphazene having a hydroxyl group

Example 26. Deposited on a polymeric carrier hexaphosphate phosphazene

Example 27. Deposited on a polymeric carrier hydroxide of phosphazene

Examples 28 to 30. Deposited on a polymeric carrier hydroxide of phosphazene

Examples from 31 to 32. Deposited on a polymeric carrier hydroxide fo is phazania

Example 33. Iodide of phosphazene with stielow group

Example 34. Iodide of phosphazene having allyl group

Example 35. Deposited on a polymeric carrier iodide and hydroxide of phosphazene

Example 36. Chloride phosphazene with trimethoxysilyl group 1

Example 37. Chloride phosphazene with trimethoxysilyl group, 2

Example 38. Bromide phosphazene with trimethoxysilyl group

Examples from 39 to 40. Silica gel, which is a carrier for chloride phosphazene (method of hydrolysis-polycondensation)

Example 41. Silica gel, which is a carrier for chloride phosphazene (method of sililirovanie)

Examples 42 to 44. Silica gel, which is a carrier for the hydroxide of phosphazene

Phosphazenes supported on a carrier, the catalyst of the invention is suitable for use as a catalyst for various organic reactions and, in particular, the catalyst for polymerization of cyclic monomers and substitution of alternates. the moreover, each connection selected from pospisilova connection and phosphazene salt of the invention is an intermediate compound, which is suitable for use in obtaining pospisilova deposited on the catalyst carrier of the invention, and the catalyst, which in itself is suitable for use in carrying out various organic reactions.

1. Phosphazenes supported on a carrier of a catalyst for polymerization of the cyclic monomer or substitution of the substituent in the compound or the reaction with the formation of carbon-carbon, in which the carrier is insoluble in the solvent and has a group capable of forming a bond with the group, opisyvayuschaya General formula (1):

where n is an integer in the range from 1 to 8 and represents the number phosphazenes cations, a Znrepresents an anion compounds containing active hydrogen atoms, in the form obtained by releasing n protons of compounds containing active hydrogen atoms, which has at most 8 active hydrogen atoms; each of a, b, C and d represents a positive integer equal to 3 or less; R represents the same or different angle is ogorodnya group, containing from 1 to 10 carbon atoms, and two R's located on each common nitrogen atom may be linked to each other to form a ring structure; R1represents a hydrogen atom or a hydrocarbon group containing from 1 to 10 carbon atoms; D represents a direct bond or a divalent group capable of binding N with the media.

2. Phosphazene connection, vpisivaushiesya General formula (3):

where each of a, b, C and d represents a positive integer equal to 3 or less; G represents the group =NR, oxygen atom or sulfur atom; R represents the same or different hydrocarbon groups containing from 1 to 10 carbon atoms, and two R's located on each common nitrogen atom may be linked to each other to form a ring structure.

3. Phosphatemia salt, vpisivaushiesya General formula (4):

where each of a, b, C and d represents a positive integer equal to 3 or less, respectively; R represents the same or different hydrocarbon groups containing from 1 to 10 carbon atoms, and two R's located on each common nitrogen atom may be linked to each other to form a ring structure; X the submitted is a halogen atom, and X-represents an anion of a halogen atom, which may be identical or different in comparison with X.

4. Phosphatemia salt, vpisivaushiesya General formula (5):

where n is an integer in the range from 1 to 8 and represents the number phosphazenes cations, a Znrepresents an anion compounds containing active hydrogen atoms, in the form obtained by releasing n protons of compounds containing active hydrogen atoms, which has at most 8 active hydrogen atoms; each of a, b, C and d represents a positive integer equal to 3 or less; and R represent identical or different hydrocarbon groups containing from 1 to 10 carbon atoms, and two R's located on each common nitrogen atom may be linked to each other to form a ring structure; R1represents a hydrogen atom or a hydrocarbon group containing from 1 to 10 carbon atoms; D' represents a monovalent group which forms a link with N, with the proviso that it is different from a hydrogen atom and a saturated hydrocarbon group.

5. Phosphatemia salt, vpisivaushiesya General formula (6):

where n is an integer in the range : the zone from 1 to 8 and represents the number phosphazenes cations, a Znrepresents an anion compounds containing active hydrogen atoms, in the form obtained by releasing n protons of compounds containing active hydrogen atoms, which has at most 8 active hydrogen atoms; each of a, b, C and d represents a positive integer equal to 3 or less; and R represent identical or different hydrocarbon groups containing from 1 to 10 carbon atoms, and two R's located on each common nitrogen atom may be linked to each other to form a ring structure; And is a hydrocarbon group containing from 1 to 20 carbon atoms; alternatively, R1represents a hydrogen atom or a hydrocarbon group containing from 1 to 10 carbon atoms; each of R2, R3, R4and R5represents a hydrogen atom or a hydrocarbon group containing from 1 to 8 carbon atoms, e is in the range from 0 to 200.

6. Phosphatemia salt, vpisivaushiesya General formula (7):

where n is an integer in the range from 1 to 8 and represents the number phosphazenes cations, a Znrepresents an anion compounds containing active hydrogen atoms, in the form obtained by releasing n protons from the unity, containing active hydrogen atoms, which has at most 8 active hydrogen atoms; each of a, b, C and d represents a positive integer equal to 3 or less; and R represent identical or different hydrocarbon groups containing from 1 to 10 carbon atoms, and two R's located on each common nitrogen atom may be linked to each other to form a ring structure; R1represents a hydrogen atom or a hydrocarbon group containing from 1 to 10 carbon atoms; M represents a group containing an unsaturated bond carbon-carbon bonds.

7. Phosphatemia salt, vpisivaushiesya General formula (8):

where m is an integer in the range from 1 to 3 and represents the number phosphazenes cations associated with the silicon atom, n' is an integer in the range from 1 to 8 and represents the number of silicon compounds, which phosphazenes cations form a bond, n is a multiplier for m and n', a, Znrepresents an anion compounds containing active hydrogen atoms, in the form obtained by releasing n protons of compounds containing active hydrogen atoms, which has at most 24 active hydrogen atom; each of a, b, C and d represents the t a positive integer, equal to 3 or less, and R represent the same or different hydrocarbon groups containing from 1 to 10 carbon atoms, and two R's located on each common nitrogen atom may be linked to each other to form a ring structure; In represents a hydrocarbon group containing from 1 to 20 carbon atoms; alternatively, R1represents a hydrogen atom or a hydrocarbon group containing from 1 to 10 carbon atoms; T represents a functional group in which the connection Si-T can be destroyed by hydrolysis.

8. The method of polymerization of the cyclic monomer using deposited on the catalyst carrier according to claim 1.

9. The method of substitution of the substituent in connection with the use deposited on a catalyst carrier according to claim 1.

10. The method of carrying out the reaction with the formation of carbon-carbon using deposited on the catalyst carrier according to claim 1.



 

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The invention relates to a method for producing 1-phenyl-TRANS-3,4-dialkylphosphorous General formula

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where R = n-C4H9the h6H13n-C8H17that is in interaction-olefins with atelecommunications and metallic magnesium in the presence of a catalyst Cp2ZrCl2in an argon atmosphere in the environment of the solvent for 8 h followed by the addition at a temperature of -15oWith CuCl as catalyst and phenyldichlorophosphine, followed by stirring the reaction mass for 8-12 h at room temperature

The invention relates to a method for producing salts retinylidene, which are intermediates in the production of-carotene and other carotenoids, and may find application in pharmaceutical industry

The invention relates to the derivatives of aminothiophene F.-ly (R1O)(R2S)P(O)-N[(CH2)nCN] C(O)R3(II) where R1is methyl or ethyl; R2- n-propyl or sec-butyl; R3- (C1- C4-alkoxygroup; (C1- C4-allylthiourea, phenyl, phenoxy; n = 1 or 2, which are active in the fight against harmful insects, nematodes and mites at low acute toxicity towards mammals
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