Method of telomerization of diene with conjugated double bonds, catalyst and bidentate ligand used in indicated method

FIELD: organic synthesis and catalysts.

SUBSTANCE: invention relates to improved method of telomerization of diene with conjugated double bonds, wherein said diene interacts with a compound having active hydrogen atom and selected from group, consisting of alkanols, hydroxyaromatic compounds, carboxylic acids, and water, in presence of telomerization catalyst based on VIII group metal source and bidentate ligand. The latter is depicted by general formula (I): R1R2M1-R-M2R3R4, wherein M1 and M2 independently represent P; R1, R2, R3, and R4 independently represent monovalent aliphatic group or R1, R2, and M1 jointly and/or R3, R4, and M2 jointly independently represent cycloaliphatic group with 5-12 carbon atoms in cycle, wherefrom one atom is M1 or M2; and R represents (i) bivalent organic bridge group, which is unsubstituted alkylene group or alkylene group substituted by lower alkyl groups optionally incorporating oxygen as heteroatom, or (ii) group containing two benzene rings bound to each other or to alkylene groups, which in turn are linked to M1 and M2. Invention also relates to novel bidentate ligands, which can be utilized in the method of invention and having following general formulas: R1R2M1-V-M2R3R4 (II) and Q1Q2M1-Q5-Ar1-Q6-M2Q3Q4 (III). Invention further relates to improved method for production of 1-octene involving 1,3-butadiene telomerization step to form 1-substituted 2,7-octadiene.

EFFECT: expanded synthetic possibilities in conjugated dienes area.

10 cl, 1 dwg, 1 tbl, 10 ex

 

The present invention relates to a method of telomerization diene with conjugated double bonds and a catalyst and a bidentate ligand, which can be used in this way. In particular the present invention relates to a method of telomerization butadiene and catalyst and bidentate ligand, which can be used in this way.

Telomerization butadiene known in this field, for example, from WO-A-9210450. WO-A-9210450 describes the reaction of telomerization, where 1,3-butadiene interacts with a compound containing an active hydrogen atom and having the formula R-H in the presence of catalyst telomerization, forming a 1-substituted-2,7-octadien formula CH2=CH-CH2-CH2-CH2-CH=CH-CH2-R, where R is the residue of a compound containing an active hydrogen atom. WO-A-9210450 describes a wide range of catalysts telomerization. Described in example a catalyst telomerization is a catalyst based on palladium-acetylacetonate/triphenylphosphine. With this catalyst telomerization selectivity for product telomerization, linear 1-methoxy-2,7-octadiene is 89.4 per cent.

Although in the description casually mentioned the possibility of using diphosphine ligands, namely bis(diphenylphosphino)ethane, diphosphinic ligand is not disclosed in the examples.

The present invention is the development of ways of telomerization diene with conjugated double bonds, where the reaction telomerization can be carried out with high selectivity for linear product telomerization.

To date, installed that telomerization diene with conjugated double bonds can be carried out with high selectivity for linear product telomerization in the presence of catalytic systems.

Thus, the present invention relates to a method of telomerization diene with conjugated double bonds, where the diene with conjugated double bonds interacts with a compound containing an active hydrogen atom and having the formula R-H in the presence of catalyst telomerization based on:

(a) a source of metal of group VIII,

(b) a bidentate ligand,

where the bidentate ligand has the General formula I

R1R2M1-R-M2R3R4(I)

in which M1and M2independently mean P, As or Sb;

R1, R2, R3and R4independently denote a monovalent aliphatic group;

or R1, R2and M1together and/or R3, R4and M2together independently denote optionally substituted aliphatic cyclic group, at least 5 atoms in the cycle, one of which means the atom M1or M2respectively;

and R means vocalistul organic bridging group.

The use of such a specific catalyst system results in improved selectivity with respect to the linear product when reaching speeds of reaction, much larger 500 mol of diene with conjugated double bonds/mole metal of group VIII/hour.

The diene with conjugated double bonds preferably contains from 4 to 20, more preferably from 4 to 8 carbon atoms per molecule. The diene with conjugated double bonds may be substituted or unsubstituted and may contain a number of heteroatoms. Examples of dienes with conjugated double bonds, which can be used include 1,3-butadiene, isoprene 1,3-pentadiene, 1,3-hexadiene. Preferably the diene with conjugated double bonds is unsubstituted, and is preferably a diene with conjugated double bonds contains only carbon atoms. Most preferably the diene with conjugated double bonds mean 1,3-butadiene.

By way of telomerization 1,3-butadiene can be obtained 1-substituted-2,7-octadiene. 1-Substituted-2,7-octadiene can be used in a method of producing 1-octene containing essentially unbranched olefins C8-isomers. This method is presented as an example in WO-A-9210450. This invention also relates to a method for producing 1-octene, including:

(a) telomerization 1,3-butadiene, as described ZV is camping, with the formation of 1-substituted-2,7-octadiene;

(b) hydrogenation of 1-substituted-2,7-octadiene from stage a), which gives 1-substituted octane;

(C) splitting of the 1-substituted octane from step b) formation of 1-octene.

Stage a) of this method may be performed as described here. Stages b) and c) is usually performed as described in WO-A-9210450.

The diene with conjugated double bonds, is used as starting compound, may contain small amounts of other saturated or unsaturated hydrocarbons. For example, raw C4-hydrocarbon mixture can be used as raw material for 1,3-butadiene. This raw C4the mixture may contain in addition to 1,3-butadiene other C4-hydrocarbons such as butenes and butanes.

Containing the active hydrogen compound R-H can mean any compound with reactive hydrogen atom. Examples of such containing active hydrogen compounds include alkanols, hydroxy-aromatic compounds, carboxylic acids, ammonia, primary and secondary amines and water.

Preferred containing active hydrogen compounds include water, alkanols and hydroxy-aromatic compounds.

The alkanols which may be used in the method according to the invention include monatomic and polyatomic alcohols which may be linear or branched,saturated or unsaturated. The preferred alkanols for the method according to the invention are alkanols containing from 1 to 20, more preferably from 1 to 6 carbon atoms in the molecule, and arcangioli containing from 2 to 20, more preferably from 2 to 6 carbon atoms in the molecule. Suitable alkanols for the method according to the invention include methanol, ethanol, ethanediol, propanol, 1,2-propandiol, 1,3-propandiol, isopropanol, butanol, 1,2-butanediol, 1,4-butanediol, Isobutanol, trebujena, pentanol, hexanol, hexanediol, cyclohexanol and cyclohexanediol. Of them, preferred are methanol, ethanol and phenol. Methanol and phenol is particularly preferred.

Examples of hydroxy-aromatic compounds are aromatic compounds containing one or more cycles, such as phenol, benzyl alcohol, Cresols, Xylenol, carbonaceous, naphthol, and polyhydric compounds such as resorcinol, hydroquinone and pyrocatechin. Can also be used alkyl-, alkoxy - and/or halogen-substituted aromatic hydroxy-compounds.

Examples of carboxylic acids that can be used in the method according to the invention include aliphatic carboxylic acids containing up to 20 carbon atoms. Preferred carboxylic acids are acids containing from 1 to 6 carbon atoms, such as, for example, acetic acid, propionic acid, m is Slana acid. Examples of suitable aromatic carboxylic acids include benzoic acid and tawalkana acid. Can also be used dicarboxylic acids, such as adipic acid and phthalic acid.

Examples of amine compounds which can be used in the method according to the invention are ammonia and primary and secondary amines. Suitable amine compounds include, for example, primary aliphatic amines, such as methylamine, ethylamine, butylamine, dodecylamine, and the like; primary aromatic amines such as aniline, toluidine, benzylamine and the like; secondary amines such as dimethylamine, diethylamine, N-methylaniline, dicyclohexylamine, methylhexanamine and the like; as well as polyamine, such as phenylenediamine, Ethylenediamine; and heterocyclic amines such as piperidine.

The reaction telomerization carried out in the presence of the specific catalyst.

The metal of group VIII, preferably selected from metals, including rhodium, Nickel, palladium and platinum. Of these preferred metals palladium and platinum. Palladium is preferable.

Examples of suitable sources of metals are metallic platinum or palladium, and platinum or palladium on a carrier. Other suitable sources include platinum or palladium of katianna the complexes, which can be converted into a Pd(0) or Pt(0) in the course of interaction. Examples of such platinum or palladium cationic complexes include carboxylates of platinum or palladium. The preferred source of palladium is tetrakis(dibenzalacetone)palladium. Bidentate ligand has the General formula I

R1R2M1-R-M2R3R4(I)

in which M1and M2independently mean P, As or Sb;

R1, R2, R3and R4independently denote a monovalent aliphatic group;

or R1, R2and M1together and/or R3, R4and M2together independently denote optionally substituted aliphatic cyclic group, at least 5 atoms in the cycle, one of which means the atom M1or M2respectively;

and R is the divalent organic bridging group.

In the bidentate ligand of the formula I M1and M2preferably are identical, and more preferably both mean phosphorus atoms.

Divalent organic bridging group R preferably contains from 1 to 6 and more preferably from 2 to 6 atoms in the bridge. Assume that the expression "bridge", as used here, means the shortest connection between atoms M1and M2.

Suitable bridging groups include substituted and unsubstituted alkylene group. Allenova group may contain one or more heteroatoms such as Si, N, O, S, at the bridge, but preferably contains in the bridge only carbon atoms. Allenova group may be substituted by one or more groups, preferably substituted by two groups. The substituents can contain one or more heteroatoms. Examples of unsubstituted alkilinity bridging groups include methylene, ethylene and trimethylene group. Examples of substituted alkilinity bridging groups include, for example, 2,2-dimethyltrimethylene (i.e. neopentylene), 2,2-diethyl-trimethylene, 2,2-dimethyltrimethylene, 2-methyl,2-hydroxymethyl-trimethylene (i.e. neopentyl), 2.2 dihydroxypyrrolidine (i.e. neopentylglycol). Preferred alkionovymi bridge groups are ethylene, trimethylene and neopentylene group, preferably connecting respectively the atom M1and M2on the first, second or third carbon atom, such as 1,2-ethylene, 1,3-trimethylene or 1,3-neopentylene group. Of these groups, particularly preferred neopentylene group. Preferably neopentylene bridge group substituted by one or more hydroxy groups.

Bridging group may also contain one or the more aliphatic or aromatic cyclic structures. Preferably such bridging group still contains a total of from 2 to 6 carbon atoms in the bridge. Particularly preferred bridging group contains two aromatic cyclic structure, preferably two benzene cycle. Such aromatic cyclic structure is preferably connected with each other and with two alkionovymi groups, which, in turn, are connected respectively with M1and M2.

Alkylene group is preferably attached to an aromatic cyclic structures located opposite in the ortho-positions of the carbon atoms through which linked aromatic cyclic structure.

In a preferred embodiment, the R1, R2R3and R4independently means a primary, secondary or tertiary alkyl group. Preferably the alkyl group contains from 1 to 10 carbon atoms, more preferably from 1 to 6 carbon atoms. Examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, sec-pentyl, cyclopentyl, hexyl, cyclohexyl. Preferably R1, R2, R3and R4independently mean a primary alkyl group. Examples of suitable primary alkyl groups include methyl, ethyl and propyl. Preferably the group R1-R4mean the same primary alkyl groups. Most preferably, R1-R4means a methyl or ethyl group.

In another preferred variant the execution of R1, R2and M1together and/or R3, R4and M2together independently denote optionally substituted aliphatic cyclic group with at least 5 atoms in the cycle, one of which means the atom M1or M2respectively.

Under the "cyclic group" refers to monocyclic or polycyclic group, such as a bicyclic or tricyclic group. Preferred cyclic groups are bicyclic group. Cyclic group contains at least one heteroatom, i.e. the atom M1or M2respectively, but may contain more heteroatoms. Suitable heteroatoms, which may optionally be present in the cyclic group include P, As, Sb, O, N, S and Si. Optionally substituted aliphatic cyclic group contains at least 5 atoms in the cycle. Preferably a cyclic group contains from 6 to 20 atoms in the cycle, more preferably from 6 to 12 atoms in the loop.

Preferably both M1and M2mean phosphorus and as R1, R2and M1together, and R3, R4and M2together mean phosphabicyclo group. In most predpochtitelno embodiment, the aliphatic cyclic group contains 9 atoms in the cycle and forms a 9-phosphabicyclononanes group. 9-Phosphabicyclononanes group may correspond to several isomeric structures. For the purposes of the invention the preferred isomers [3,3,1] and [4,2,1]. R1, R2and M1together and/or R3, R4and M2together can have the same or each different isomeric structures. Preferably R1, R2and M1together and/or R3, R4and M2together have the structure [3,3,1].

One or both phosphabicyclononanes ring can be substituted by one or more suitable hydratability groups containing carbon atoms and/or heteroatoms. Suitable substituents include groups containing heteroatoms such as Halogens, sulfur, phosphorus, oxygen and nitrogen. Examples of such groups include chloride, bromide, iodide, thiol and a group of General formula-Y1-OH, -Y1-CO-OH, -Y1-SH, -S-Y1-On-Y1, -CO-Y1, -NH2, -NHY1, -NY1Y2, -CO-NY1Y2, -OH, -PO4, -NO2, -NOH, -CO, -SO2, -S,-OH, where Y1and Y2independently mean C1-C10is an alkyl group. If phosphabicyclononanes ring is substituted, the ring is preferably substituted carbon-containing group. Such carbon-containing group may, however, include additional heteroatoms such as Halogens, sulfur, oxygen and nitrogen, or above heterogroup. P is edocfile substituted phosphabicyclo-alkyl ring substituted alkyl groups, preferably with 1-10 carbon atoms, more preferably 1-4 carbon atoms. Can be used a linear, branched or cyclic group. Suitable alkyl groups include methyl, ethyl, propyl, isopropyl, butyl and isobutyl. It is more appropriate to use a methyl group. If phosphabicyclononanes ring is substituted, the ring may be mono - or poly-substituted, and preferably disubstituted. More preferably phosphabicyclononanes ring is substituted by two methyl groups. Phosphabicyclononanes ring can be substituted on all carbon atoms of the cycle. However, the use of cycles with substituents on some of the carbon atoms may be more advantageous. It is convenient to use phosphabicyclononanes ring with two substituents on the carbon atoms, is suitable carbon atom 1, 2, 8 and the carbon atom 4, 5 or 6.

Examples of suitable bidentate ligands include:

1,3-bis(diethylphosphino)propane;

1,3-bis(dimethylphosphino)propane;

1,3-bis-(1,4-cyclooctylamino)propane, ie,

1,3-PP'bis-(9-phosphabicyclo[4,2,1]nonyl)propane;

1,3-bis-(1,5-cyclooctylamino)propane, ie,

1,3-PP'bis-(9-phosphabicyclo[3,3,1]nonyl)propane;

1,2-bis-(1,4-cyclooctylamino)ethane, ie,

1,2-PP'bis(9-phosphabicyclo[4,2,1]nonyl)ethane;

1,2-bis-(1,5-cyclooctadiene the but)ethane, i.e.

1,2-PP'bis-(9-phosphabicyclo[3,3,1]nonyl)ethane;

2,2-dimethyl,1,3-PP'bis-(9-phosphabicyclo[3,3,1]nonyl)propane;

2-methyl,2-hydroxymethyl,1,3-PP'bis-(9-phosphabicyclo[3,3,1]-nonyl)propane;

2,2-dimethyl,1,3-PP'bis-(9-phosphabicyclo[4,2,1]nonyl)propane;

2-methyl,2-hydroxymethyl,1,3-PP'bis(9-phosphabicyclo[4,2,1]-nonyl)propane;

2,2'-bis-(1,4-cyclooctylmethyl)-1,1'-diphenyl;

2,2'-bis-(1,5-cyclooctylmethyl)-1,1'-diphenyl, and mixtures thereof.

Some of bidentate ligands, which can be used according to the present invention, are considered as new.

In addition, the present invention concerns also a bidentate ligand of the formula II,

R1R2M1-V-M2R3R4(II)

in which M1and M2independently mean P, As or Sb;

R1, R2, R3and R4independently denote a monovalent aliphatic group;

or R1, R2and M1together and/or R3, R4and M2together independently denote optionally substituted aliphatic cyclic group, at least 5 atoms in the cycle, one of which means the atom M1or M2respectively;

and V means bridging group consisting of trimethylene group associated with M1or M2the average carbon atom which has two dopolnitelnye with non-hydrogen atom.

R1, R2M1M2, R3and R4mean the same groups as described above.

V means bridging group consisting of trimethylene group associated with M1or M2the average carbon atom which has two additional relationships with non-hydrogen atom. The average atom may have two additional relationships with one non-hydrogen atom, i.e. a double bond, or an average atom may have two additional communication with a separate non-hydrogen atoms.

Examples of non-hydrogen atoms with which a secondary carbon group may form a double bond include heteroatoms, such as oxygen, nitrogen, sulfur or silicon. In addition, the average carbon atom may be linked to a double bond with another carbon atom.

However, preferably the average carbon has two additional relationships with two separate non-hydrogen atoms. In a preferred embodiment, the bridging group V means a group having the formula

-C(V1)-C(V3;V4)-C(V2)- (IV)

where V1 and V2 independently denote optionally substituted alkyl group with 1-4 carbon atoms, such as methyl, ethyl, propyl and isopropyl, or hydrogen, and V3 and V4 independently mean a non-hydrogen group.

Each of V3 and V4 may mean a separate group, or V3, V4 and the average carbon atom together may form tsiklicheskoe the group.

If V3, V4 and the average carbon atom together form a cyclic group, the cyclic group preferably contains from 3 to 10 atoms in the cycle, more preferably from 3 to 6 atoms in the cycle. Cyclic atoms can be heteroatoms, or the carbon atoms, but preferably carbon atoms.

However, preferably each of V3 and V4 independently means a hydrocarbon group containing carbon atoms and/or heteroatoms. Suitable for this purpose hydrocarbon groups include groups containing heteroatoms, such as sulfur, phosphorus, oxygen and nitrogen. Examples of such groups include groups of the General formula X1-OH, -X1-CO-OH,-X1-SH, -S,-X1, -O-X1, -CO-X1, -NH2, -NHX1, -NX1-X2, -CO-NX1-X2, -OH, -PO4, -NO2, -NOH, -CO, -SO2, -S,-OH, where X1and X2independently mean alkyl or alkilinity group with 1-10 carbon atoms. Preferably V3 and/or V4 mean carbon-containing group. Such carbon-containing group may, however, contain additional heteroatoms such as Halogens, sulfur, oxygen and nitrogen, or above heterogroup. Preferably V3 and/or V4 denote a group selected from the group comprising: methyl, ethyl, propyl, hydroxymethyl and hydroxyethyl.

Preferred bidentate diphosphine corresponding to the formula II include

2,2-dimethyl-1,3-bis-(1,4-cyclooctylamino)propane;

2-methyl-2-hydroxymethyl-1,3-bis-(1,4-cyclooctene-phosphino)propane;

2.2-dihydroxymethyl-1,3-bis-(1,4-cyclooctylamino)-propane;

2,2-dimethyl-1,3-bis-(1,5-cyclooctylamino)propane;

2-methyl-2-hydroxymethyl-1,3-bis-(1,5-cyclooctane-phosphino)propane;

2.2-dihydroxymethyl-1,3-bis-(1,5-cyclooctylamino)-propane.

Such ligands can be obtained by:

i) interaction P-cyclooctylamine (phosphabicyclononanes), utility education lifecycleexception (phosphabicyclononanes).

ii) introducing toilet-group 3-methyl-3-oxetanemethanol by interacting with p-toluensulfonate in dichloromethane as solvent at 0°C in the presence of pyridine.

iii) phosphide with stage i) with toilet-substituted oxetanes with stage ii), for example, at 0°C was for the first group and in the conditions of heating under reflux to the boiling point for the second group was, for example, in tetrahydrofuran as a solvent.

An illustrative example of such interaction is shown in the drawing.

The present invention also concerns a bidentate ligand of the formula (III),

Q1Q2M1-Q5-Ar1-Ar2-Q6-M2Q3Q (III)

where M1and M2independently mean P, As or Sb;

Q1, Q2and M1together and Q3, Q4and M2together independently denote optionally substituted aliphatic cyclic group, at least 5 atoms in the cycle, one of which means the atom M1or M2respectively;

each of Q5and Q6independent means optionally substituted alkylene group

and Ar1and Ar2independently denote optionally substituted aromatic group. Bidentate diphosphine ligands containing dimethylethanolamine bridge, known in this field.

WO-A-8707600 describes bidentate diphosphine containing dimethylethanolamine bridge and substituted for each of the phosphorus atoms of two additional groups.

However, WO-A-8707600 does not contain descriptions of bidentate diphosphine, in which the phosphorus atom is part of an aliphatic cyclic group.

M1and M2mean the same above-mentioned groups. The advantages of using the above-mentioned cases.

Q1, Q2and M1together and Q3, Q4and M2together independently denote optionally substituted cyclic group, at least 5 atoms in the cycle, one of which means the atom M1or M2respectively. The advantages which have the same cases, that indicated above for the cyclic groups represented by R1, R2and M1together and R3, R4and M2together, respectively.

Each of Q5and Q6independent means optionally substituted alkylenes group. Preferably such Allenova group contains from 1 to 6, more preferably from 1 to 4 carbon atoms. Allenova group may be substituted by one or more hydratability groups. If Allenova group is substituted, the group is preferably a substituted alkyl groups, preferably 1-6, more preferably 1-4 carbon atoms.

Preferably Allenova group is unsubstituted. Preferably both alkylene groups are the same and preferably both alkylene group mean unsubstituted methylene or ethylene group. Most preferably both, Q5and Q6denote unsubstituted methylene group.

Each Ar1and Ar2independently means an aromatic group. Preferably the aromatic group contains from 6 to 20 carbon atoms, more preferably from 6 to 14 carbon atoms. Examples of suitable aromatic groups include phenyl, naphthyl, tenantry and anthracene. Of these groups, phenyl groups are preferred. The aromatic group may be substituted by one the or more heteroatoms and/or hydratability groups. Used for this purpose gidrolabilna groups include alkyl, alkoxy and carbonyl groups. Preferably the aromatic group is unsubstituted. The aromatic group preferably connected to each other via the carbon atom next to the carbon atom connected with alkalinous group.

Preferred bidentate diphosphine corresponding to the formula III includes

2,2'-bis-(1,4-cyclooctylmethyl)-1,1'-diphenyl;

2,2'-bis-(1,5-cyclooctylmethyl)-1,1'-diphenyl, and mixtures thereof.

Such ligands can be obtained by the interaction between P-cyclooctylamine (phosphabicyclononanes), utility education lifecycleexception (phosphabicyclononanes). Last phosphide is subjected to interaction with 2,2'-dimethyl-1,1 diphenylene group, substituted suitable leaving group, preferably a tozilaty, mesylates and triflate, in appropriate circumstances. Preferred aliphatic groups are groups containing a cyclic sulfate structure as leaving groups, such as cyclic substituted or unsubstituted complex lenderswhen esters, also called cyclic alkyl sulphates.

For example, 2,2'-bis-(1,4-cyclooctylmethyl)-1,1'-diphenyl can be obtained by the interaction of phosphabicyclononanes, utility with about the education of the corresponding literotica and the subsequent interaction of literotica, for example, when 0°C in tetrahydrofuran, di-n-tosylate ether 2,2'-dimethyl-1,1 diphenyl where tosylate group substituted by a methyl group.

P-cyclooctylamine (phosphabicyclononanes) can usually be obtained, as described by Elsner et al. (Chem. Abstr. 1978, vol. 89, 180154x).

The present invention also relates to a catalytic system containing:

I) a source of metal of group VIII;

II) bidentate ligand meeting the above General formula II or III.

The catalytic system according to the present invention can be successfully applied to telomerization dienes with conjugated double bonds.

The amount of used catalyst telomerization is not critical, and can be used in any catalytically effective amount. In most cases you can use a number in the range from 0.000001 to 1 and preferably from 0.000005 to 0.01 gram-atom of metal of group VIII per mole of diene with conjugated double bonds. To achieve high catalytic efficiencies without returning the catalyst to re-cycle use less than 0,0001, preferably less 0,00005 and more preferably less than 0,00002 gram-atom of metal of group VIII per mole of diene with conjugated double bonds.

Bidentate ligand is usually used in a relative amount from 1 to 20 mol, prepact the tion from 2 to 15 moles of bidentate ligand per gram-atom of metal of group VIII. Bidentate ligand may be added in the form of individual compounds to the reaction mixture, or area, or to a catalytic feed solution, or may be included in the complex of a metal of group VIII.

The method according to the present invention, it is preferable to carry out essentially in the absence of oxygen, because the oxygen interacts with the bidentate ligand and, therefore, may result in reduced catalytic activity. In the method according to the present invention one or more reagents and/or received the product can play the role of a diluent. Therefore, there is no need to use a separate solvent. Typically, however, the carbonylation reaction can be carried out with the additional presence of a solvent. The following solvents are recommended saturated hydrocarbons such as paraffins and isoalkanes. Other suitable solvents include ethers, such as 2,5,8-dioxanone (diglyme), diethyl ether and anisole, ketones, such as methylethylketone. Solvents containing sulfones or essentially consisting of sulfones, are also preferred. Sulfones particularly preferred, for example, diallylsulfide, such as dimethyl sulfone and diethylsulfate, and cyclic sulfones such as sulfolane (tetrahydrothiophene-2,2-dioxide), sulfolane, 2-methylsulfone 2-methyl-4-ethylsulfonyl.

The temperature at which carry out the reaction telomerization, is not decisive. As a rule, can be used in temperatures ranging from room temperature to 150°C. Preferably the reaction temperature is from 40 to 100°C and more preferably from 50 to 100°C.

The pressure at which carry out the reaction telomerization is not decisive. Typically, the reaction pressure is in the range from 1 to 10 bar.

The reaction telomerization can be made continuous, properities and periodic methods.

The invention is illustrated by the following limitiruyuschie examples.

Examples 1-9 is an example of the comparison A

Experiments carried out in C Hastelloy autoclave of 250 ml. of the Catalyst telomerization receive separately in 5 ml of a solution of 0.25 mmol of Pd(dibenzalacetone)2and 0.3 mmol bidentate ligand in methanol, as indicated in the table. The solution of catalyst contribute to the autoclave in an atmosphere of nitrogen in the environment of alcohol and optional additional inert solvent, as indicated in the table. The autoclave is closed, vacuum pump and inside 15 ml of 1,3-butadiene.

Then the reactor was tightly closed and the contents heated to the temperature indicated in the table. The temperature of the support during such interaction, as indicated in the table. After that, the autoclave ohlajdauche room temperature and the contents analyzed standard GC. Installed the reaction rate and the selectivity for linear 1-substituted 2,7-octadiene shown in the table. Produced byproducts include vinylcyclohexane and ethers monobutyl.

Ethers monobutyl can be very useful for a wide range of other applications. The reaction rate is defined as the average speed 90% conversion of butadiene.

ExampleEnvironmentBidentate ligandTemperatureReaction time (hours)The reaction rate (mol/mol/h)The selectivity for the linear product telomerization
120 ml of methanol/

40 ml of diglyme
BDEPP700,5140091,5
220 ml of methanol/ 40 ml NMRBDEPP700,5100090
320 ml of methanol/

40 ml of diglyme
BDMPP700,25200094
420 ml of methanol/

40 ml of diglyme
BCOPP701,550093
5 50 ml of methanolMHBCOPP700,25300095
650 ml of methanolBCOPE700,25200094
750 g phenol/

40 ml of diglyme
BCOPE600,5150090
850 ml of methanol1,4-BCOPMBIncreases from 70 to 85n.d.n.d.961
950 ml of methanol1,5-BCOPMB70n.d.n.d.922
And50 ml of methanolDPPP705n.d.-3

n.d.= not determined

BDEPP = 1,3-bis(diethylphosphino)propane

BDMPP = 1,3-bis(dimethylphosphino)propane

BCOPP = a mixture of 1,3-bis-(1,4-cyclooctylamino)propane and 1,3-bis-(1,5-cyclooctylamino)propane

BCOPE = a mixture of 1,2-bis-(1,4-cyclooctylamino)ethane and 1,2-bis(1,5-cyclooctylamino)ethane

MHBCOPP = 2-methyl,2-hydroxymethyl, 1,3-bis-(1,4-

cyclooctylamino)propane

1,4-BCOPMB = 2,2'-bis-(1,4-cyclooctylmethyl)-1,1'-diphenyl

1,5-BCOPMB = 2,2'-bis-(1,5-cyclooctylmethyl)-1,1'-diphenyl

NMP = N-methyl-2-pyrrolidone

DPPP = 1,3-is IP(diphenylphosphino)propane

1= forms only 4% of the product of telomerization, while 59% received ethers monobutyl

2= produced only 31% of the product of telomerization, while 59% received ethers monobutyl

3= received only traces ethers

1. How telomerization diene with conjugated double bonds, where the diene with conjugated double bonds interacts with a compound containing an active hydrogen atom and selected from the group consisting of alkanols, hydroxyaromatic compounds, carboxylic acids and water, in the presence of catalyst telomerization based on:

(a) a source of metal of group VIII,

(b) a bidentate ligand,

where the bidentate ligand has the General formula I

,

in which M1and M2independently denote P;

R1, R2, R3and R4independently denote a monovalent aliphatic group;

or R1, R2and M1together and/or R3, R4and M2together independently denote an aliphatic cyclic group, with 5-12 atoms in the cycle, one of which means the atom M1or M2, respectively;

and R is the divalent organic bridging group, which is unsubstituted alkylenes group,

or alkilinity group substituted by the groups lower alkyl, where these groups are the lower alkyl may contain oxygen as a heteroatom; or a group containing two benzene rings connected with each other or with alkionovymi groups, which in turn are linked to M1and M2.

2. The method according to claim 1, where the diene with conjugated double bonds mean 1,3-butadiene.

3. The method according to claim 1 or 2, which contains an active hydrogen compound means water, alkanol or hydroxyaromatic connection.

4. Bidentate ligand of the formula II,

,

where M1and M2independently denote P;

R1, R2and M1together and/or R3, R4and M2together independently denote an aliphatic cyclic group with 5-12 atoms in the cycle, one of which means the atom M1or M2, respectively;

and V means bridging group consisting of trimethylene group having an average carbon atom associated with the two groups of lower alkyl, where the group of the lower alkyl may have oxygen as heteroatom.

5. Bidentate ligand according to claim 4, where the bidentate ligand selected from the group comprising: 2,2-dimethyl-1,3-bis-(1,4-cyclooctylamino)propane, 2-methyl-2-hydroxymethyl-1,3-bis-(1,4-cyclooctylamino)propane or 2,2-is hydroxymethyl-1,3-bis-(1,4-cyclooctylamino)propane; 2,2-dimethyl-1,3-bis-(1,5-cyclooctylamino)propane, 2-methyl-2-hydroxymethyl-1,3-bis-(1,5-cyclooctylamino)propane or 2,2-dihydroxymethyl-1,3-bis-(1,5-cyclooctylamino)propane.

6. Bidentate ligand of the formula (III),

,

where M1and M2independently denote P;

Q1, Q2and M1together and Q3, Q4and M2together independently denote an aliphatic cyclic group with 6 to 12 atoms in the cycle, one of which means the atom M1or M2, respectively;

each of Q5and Q6independent means alkylene group;

and Ar1and Ar2independently denote an aromatic group containing from 6 to 20 carbon atoms.

7. Bidentate ligand of claim 6, where the bidentate ligand means 2,2'-bis-(1,4-cyclooctylmethyl)-1,1'-diphenyl or 2,2'-bis-(1,5-cyclooctylmethyl)-1,1'-diphenyl.

8. Catalytic system for telomerization diene with conjugated double bonds, containing

I) a source of metal of group VIII,

II) bidentate ligand according to one of claims 4-7.

9. The method according to claim 1 performed in the presence of the catalyst according to item 8.

10. The way to obtain 1-octene, including

(a) telomerization 1,3-butadiene according to one of claims 1 to 3 or 9 with the formation of 1-substituted-2,7-octadiene;

(b) selective is the W 1-substituted-2,7-octadiene from stage a), give 1-substituted octane;

(c) splitting of the 1-substituted octane from step b) formation of 1-octene.



 

Same patents:

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of 1,3-bis-(diethylphosphinomethyl)-benzene of the formula: Invention proposes two methods of synthesis. By the first method diethylphosphine is subjected for interaction with 1,3-bis-(dibromomethyl)-benzene and formed phosphonium salt is treated with potassium carbonate. By the second method diethylphosphine borane complex is subjected for interaction with 1,3-bis-(dibromomethyl)-benzene in mixture of toluene and alkali aqueous solution followed by treatment of formed 1,3-bis-(diethylphosphinomethyl)-benzene borane complex with fluoboric acid dimethyletherate and sodium hydrocarbonate solution. Compound can be used as a ligand for homogenous catalysts in hydrogenation, cross-linking, polymerization and carbonylation reactions. Proposed methods for synthesis of the end substance are simple in realization and don't require using components combustible in contact with air and complex procedures.

EFFECT: improved method of synthesis.

2 cl, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to derivatives of urea. Method is carried out by oxidation of diphenylchlorophosphine with sulfuryl chloride at temperature 20-25°C in carbon tetrachloride medium. Formed diphenylphosphinic acid chloroanhydride is subjected for interaction with sodium cyanate in acetonitrile medium in the presence of anhydrous magnesium chloride as a catalyst at temperature 20-25°C followed by the addition reaction of formed diphenylphosphoryl isocyanate to n-alkylamines at temperature 20-25°C in acetonitrile medium used as a solvent. Invention provides simplifying method and synthesis of highly pure substance and decreasing energetic and economy consumptions. Synthesized compounds can be used in technology for treatment of radioactive waste in radiochemical manufacture.

EFFECT: improved method of synthesis.

5 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a catalytic system comprising metallocene compound of the formula: wherein CpI and CpII represent carboanions with the cyclopentanedienyl-containing structure wherein from to all hydrogen atoms can be substituted; D means a donor atom possessing at least one electron pair; A means an acceptor atom that in its state it has electronic hole and D and A are bound by the reversible coordination bond and wherein a donor group receives a positive (partial) charge and an acceptor group - a negative (partial) charge; M means a transient metal of III, IV, V or VI subgroup of Mendeleyev's periodic law; x means anionic equivalent or η-complex compound of transient metals of the formula: (IIIa) or, respectively, (IIIb) wherein η means the charged or electrically neutral system that can be condensed with unsaturated or saturated rings; D means a donor atom or A with a transient metal M chosen from this group is carried out either directly or through a spacer and D and A are bound by a coordination bond as given above; X means anionic equivalent; n value depends on charge of M metals, and η means a number 0, 1, 2, 3, 4. Donor-acceptor structure promotes to stability of catalyst being up to high temperatures, i. e. without significant decrease of the catalyst activity and provides preparing polyethylenes with enhanced molecular mass and increased boiling point value. Also, invention relates to a method for preparing alpha-olefins.

EFFECT: valuable properties of catalyst, improved polymerization method.

7 cl, 10 ex

The invention relates to a method for removal of water-soluble sulfated triarylphosphines sulfite compounds, which consists in at least partial removal of sulfite compounds by reducing the pH of the solution of the initial compounds to values below or equal to 4, and maintain the specified pH of the solution up until the weight concentration of sulfite in the solution will not reach values below 100 ppm

The invention relates to the chemistry of organophosphorus compounds with s-R connection, namely to obtain alkyl(phenyl)phosphine-Baranovka complex of the General formula R2PHBH3(1), where R is alkyl or phenyl, which are used as starting substances for the synthesis of water-soluble catalysts used in the production of polymers

The invention relates to the field of chemistry of organophosphorus compounds, namely the method of production of triphenylphosphine, which may find application as astrigent ions of heavy metals in the catalyst composition in the industrial hydrogenation reactions, gidrauxilirovania, hydroformylation, etc

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

< / BR>
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 an improved method of hydrocyanide aliphatic organic compounds with unsaturated ethylene communication, in particular aliphatic compounds containing one double ethylene bond, interaction with hydrogen cyanide in the presence of an aqueous solution of a catalyst containing a compound of transition metal, such as Nickel, and a water-soluble phosphine of General formula I or General formula II, where d is an integer from 1 to 2; D is alkyl or cycloalkyl, possibly containing one or more substituents; Ar1, AG2, AG3identical or different arily containing one or more substituents; a, b, e, f each denotes 0 or 1; C is an integer from 0 to 3; g is an integer from 1 to 2

FIELD: organic synthesis.

SUBSTANCE: invention relates to improved method of preparing title compounds depicted by general formula: , wherein R1 = R2 = H : R = N(CH3)2, OCH3, C(CH3)3; R1 = H, R2 = CH3 : R = N(CH3)2, C(CH3)3; R1 = R2 = CH3 : R = N(CH3)2, which are intermediates in synthesis of biologically active products, via reaction of 1,3-dehydroadamantane or homologues thereof with benzene derivatives selected from series: N,N-dimethylaniline, anisole, and tert-butylbenzene at molar ratio of reactants1:(5-6), respectively, in a benzene derivative at 120-130°C for 5-6 h.

EFFECT: expanded synthetic possibilities.

6 ex

FIELD: petrochemical industry; method of reprocessing of the hydrocarbon mixture containing isobutene.

SUBSTANCE: the invention is pertaining to the field of petrochemical industry, in particular, to the method of reprocessing of the hydrocarbon mixture containing isobutene. The invention provides, that conduct the chemical transformation of isobutene and non-tertiary alcohol (alcohols) in the reactionary zone (zones) at presence of the solid acid catalyst at the temperature of 30-100°C predominantly in the alkyl-tret.butyl ester (esters) and isobutene dimers. Then from the reaction mixture distill at least hydrocarbons C4 in the rectification zone and it is possible to use the subsequent hydrogenation of the formed isobutene dimers. At that in the reactionary zone (zones) as the source substances feed the non-tertiary alcohol (alcohols) and isobutene in the hydrocarbon mixture in the molar ratio from 0.1 up to 0.9 and hold the temperature and the time of the contact to the catalyst providing transformation of the major part of the alcohol (alcohol) into the alkyl-tret.butyl ester (esters) and not resulting in the domination of the reverse reaction of decomposition of the formed epy alkyl-tret.butyl ester (esters) in the end of the reaction zone and to the significant increase of the amount of the non-tertiary alcohol (alcohol) in the gating out of it stream. The technical result of the invention is the increased quality of the final product.

EFFECT: the invention ensures the increased quality of the final product.

15 cl, 3 dwg, 10 ex

FIELD: petrochemical industry, chemical technology.

SUBSTANCE: invention relates to a method for combined synthesis of methyl-tert.-butyl and methylisobutyl esters that are used as high-octane additive to motor fuels. Method involves treatment of isobutylene-containing fraction with methanol in liquid phase at heating, under pressure, in the presence of sulfocation-exchange resin in H+-form as a catalyst. Then reaction products are separated in fractionating column wherein dimethyl ether and isobutanol are added additional to the raw composition in the following mole ratio of components: methanol : isobutylene : dimethyl ether : isobutanol = (0.71-0.82):1:(0.21-0.33):(0.21-0.33), respectively, and treated in liquid phase. Temperature in the reaction zone is maintained in the range 50-70°C and pressure - 1.6 mPa. Invention provides the possibility for simultaneous synthesis of different esters and simplifying the process.

EFFECT: improved preparing method.

1 tbl, 2 dwg, 5 ex

FIELD: petroleum chemistry, chemical technology.

SUBSTANCE: method involves processing hydrocarbon raw comprising as minimum tert.-pentenes and other C5-hydrocarbons to yield one or some high-octane products comprising alkyl-tert.-pentyl ester wherein methyl or ethyl represents alkyl. Method involves liquid-phase chemical interaction of tert.-pentenes with methyl alcohol or ethyl alcohol in the presence of acid solid catalyst at 25-100°C for two steps and intermediate distillation of hydrocarbons. At the first step conversion of tert.-pentenes is 40-88% and at this step 80% of C5-hydrocarbons, not less, is distilled off from the reaction mixture, among them the greater part of unreacted 2-methyl-butene-2 and, preferably, the greater part of alcohol and with removal of high-octane residue wherein the concentration of alkyl-tert.-pentyl ester exceeds as minimum the total concentration of C5-hydrocarbons. At the second step in distillate obtained at the first step, possibly, with additional addition of alcohol and/or hydrocarbon raw comprising tert.-pentenes and/or hydrocarbon raw comprising isobutene method involves conversion of 40% tert.-pentenes feeding to the second step and high-octane flow is prepared wherein the total concentration of C5-hydrocarbons exceeds the concentration of alkyl-tert.-pentyl ester. Invention provides simplifying technology of the process.

EFFECT: improved method of processing.

11 cl, 3 dwg, 1 tbl, 11 ex

FIELD: organic chemistry, chemical industry in particular distillation of organic substance mixtures.

SUBSTANCE: dimethyl ether of high purity is obtained from reaction mixtures in process of synthesis of dimethyl ether from carbon oxide, carbon dioxide and hydrogen, or simultaneous synthesis of dimethyl ether with methanol, or methanol dehydration. Dimethyl ether in recovered from reaction mixture in distillation column under pressure with dimethyl ether discharge. Dissolved gases are removed in stripping column before feeding into distillation column. Pressure in stripping column is maintained in limits of 7-31 ata. As stripping column plate-type column or packed column is used. In packed column conditions sufficient for phase inversion are maintained. Dimethyl ether is discharged in form of distillate and/or in form of upper side cut with or without admixture discharge.

EFFECT: decreased carbon dioxide content in finished product, increased dimethyl ether yield.

5 cl, 7 tbl, 4 dwg, 6 ex

FIELD: industrial organic synthesis.

SUBSTANCE: methyl tert-butyl ether is obtained synthetically from methanol and isobutene on sulfonic cationite catalyst. Reaction mass is processed consecutively in three columns, the second downstream column having additional reaction zone. Isobutane-containing stream from the top of the first column is introduced into second column under catalyst bed, bottom product from second column into first column, isobutane-enriched stream from the top of the second column into third column to remove methanol. Commercial methyl tert-butyl ether is recovered as bottom product from the first downstream column. Exhausted isobutane fraction is withdrawn as top stream from the third downstream column. Gas portion of reaction mixture and part of phlegm from the first column is combined with starting material and third-column bottom product is fed as phlegm. Additional amount of methyl tert-butyl ether is obtained by decomposing 2,4,4-trimethylpentenes via reaction with methanol on sulfonic cationite catalyst, which is achieved by addition of 1 to 23% of 2,4,4-trimethylpentenes to methanol supplied into top part of second column.

EFFECT: reduced consumption of isobutene and increased production of target product.

1 dwg, 6 tbl, 6 ex

FIELD: petroleum chemistry, chemical technology.

SUBSTANCE: method involves at least two stages and each stage involves reaction zone(s) with strong acid solid catalyst and zone(s) of distillation off of unreacted C4-hydrocarbons and with feeding distilled off hydrocarbons after the first stage to the second stage. At the first stage chemical conversion is carried out in the presence of C1- or C2-alcohol and after distillation off of unreacted C4-hydrocarbons flow(s) containing mainly C1- or C2-alkyl-tert.-butyl ester and/or mixture of indicated ester with isobutene dimmers are removed. At the second stage hydrocarbon flow containing 3.5% of isobutene, not less, and impurities of C1- or C2-alcohol and other oxygen-containing compounds formed at the first stage is fed, and a polar component is fed also possibly wherein water is used in the molar ratio to isobutene = from 0.005:1 to 0.1:1, and/or (C1-C4)-alcohols(s). In reaction zone at the second stage is additional contact of C4-hydrocarbons with catalyst is carried out wherein conversion of isobutene is 50%, not less. After distillation off of unreacted C4-hydrocarbons vat flow is removed that comprises mainly dimmers of isobutene and/or co-dimers of isobutene with n.-butenes and/or C1- or C2-alkyl-tert.-butyl ester, and also possibly tert.-butanol and/or dimmers of n.-butenes.

EFFECT: improved processing method, enhanced effectiveness of process.

10 cl, 4 dwg, 10 ex

FIELD: organic chemistry, petroleum chemistry, chemical technology.

SUBSTANCE: method involves feeding isobutene-isobutylene-containing fraction to the combined synthesis of methyl-tert.-butyl ester and isobutylene dimmers by interaction with methanol at temperature 40-100 C in the presence of sulfocation-exchange resin as a catalyst. The combined esterification and oligomerization reaction is carried out in the mole ratio methanol : isobutylene = from 0.05-1.0 to 0.5-1.0 and volume rate of feeding reagents 2 h-1, not less. Also, method involves separation of the prepared reaction mixture for methyl-tert.-butyl ester, fraction of isobutylene dimmers and depleted isobutene fraction. Fraction of dimmers is separated at stage of distinct distillation off or rectification under reduced pressure 0.007-0.02 MPa. Invention provides increase yield of the end products, i. e. methyl-tert.-butyl ester and isobutylene dimmers.

EFFECT: improved preparing method.

FIELD: petroleum chemistry, chemical technology.

SUBSTANCE: method involves successive carrying out stages for producing gas-synthesis, synthesis of dimethyl ether and synthesis of gasoline from gas-phase flow containing dimethyl ether and fractionation of products in gasoline synthesis. Gas-synthesis is prepared by method of high-rapid nonequilibrium partial oxidation with formation in outlet of the corresponding stage of the complex process the mole value ratio H2/CO in fresh gas-synthesis in the range 1.35-1.65 that is not typical for equimethanol technology. Invention provides schemes and parameters in fractionation of vapor-gaseous mixture in outlet from reactor compartment in synthesis of dimethyl ether and combinations of schemes with recycle of unreacted and flowing gases are taken for the complex scheme.

EFFECT: improved producing method.

5 cl, 3 dwg, 1 ex

FIELD: petroleum chemistry, chemical technology.

SUBSTANCE: method for preparing high-octane product comprising ethyl-tert.-alkyl ester(s) from hydrocarbon raw containing tert.-C4- and/or -C5-alkenes and ethanol involves zone of heteroazeotropic rectifying drying ethanol, reaction zone(s) of chemical interaction of dried alcohol with tert.-alkene(s) in the presence of solid strong-acid catalyst and possible zone(s) of distillation off of unreacted hydrocarbons from the reaction mixture containing ethyl-tert.-alkyl ester(s). Alkane(s) and/or alkene(s) with boiling point from 27°C to 75°C are used as selective heteroazeotropic agent(s) or as components of these agents. Vapor flow containing mainly indicated hydrocarbon(s) and water are added above zone of heteroazeotropic drying and after its condensation and separating into layers hydrocarbon layer is recovered to the zone of heteroazeotropic drying, and aqueous layer practically no containing a heteroazeotropic agent is removed. From bottom zone of heteroazeotropic drying the flow containing dried ethanol as minimum is removed that is fed to zone(s) of indicated chemical interaction with tert.-alkenes.

EFFECT: improved preparing method.

8 cl, 3 tbl, 1 dwg, 5 ex

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