A method of obtaining optically active dimeric complexes (1s, 2s)-1,7,7-trimethyl-2-[(dialkylamino)oxy]-bicyclo[2.2.1] heptanol

 

(57) Abstract:

Describes a method of obtaining optically active dimeric complexes (1S,2S)-1,7,7-trimethyl-2 [(dialkylamino)oxy]bicyclo[2.2.1] heptanol General formula I, where R = C2H5the h3H7i-C4H9according to which (1S,2S)-1,7,7-trimethylbicyclo[2.2.1] heptane-2-he (camphor) is subjected to interaction with diacylhydrazine aluminum HAlR2where R is defined above, in a molar ratio of 10 : (10-12) in an argon atmosphere at room temperature (~20oC) and normal pressure in the environment of benzene within 0.5 to 1.5 hours New compounds may find application in thin organic and ORGANOMETALLIC synthesis, in particular, to obtain enantiomerically pure products with high optical yields. table 1.

The invention relates to methods of producing new derivatives of aluminum, particularly to a method of obtaining optically active dimeric complexes (1S, 2S)-1,7,7-trimethyl-2-[(dialkylamino)oxy] bicyclo[2.2.1] heptanol General formula (I):

< / BR>
where R = C2H5the h3H7i-C4H9.

The proposed method can find application in thin organic and ORGANOMETALLIC synthesis, in particular when lli, L. Bertero, L. Lardicci. Nickel Catalyzed Stereodifferentiating Displacement Reaction Between Prochiral 1 - Alkenes and Optically Active Organoaluminium Solvates// Tetrahedron Lett., v. 22, 1981, p. 883-886) obtain optically active alyuminiiorganicheskikh compounds (2) interaction disubstituted terminal alkenes with triisobutylaluminum in the presence of Ni-containing catalysts and chiral ligands at room temperature for 40 h in scheme 1 (see the end of the description).

The known method cannot be obtained optically active dimeric complexes (1S,2S)-1,7,7-trimethyl-2-[(dialkylamino)oxy]bicyclo[2.2.1]heptanol (1).

The known method ([2] M. L. Sierra, R. Kumar, V. Srini, J. Mel, J. P. Oliver. Synthesis and Spectroscopic Investigations of Alkylaluminium Alkoxides Derived from Optically Active Alcohols// Organometallics, v. l1, 1992, p. 206-214) obtain optically active aluminum alkoxides (3) interaction trialkylamines with optically active alcohol at room temperature according to scheme 2 (see the end of the description).

The known method does not allow to obtain optically active dimeric complexes (1S,2S)-1,7,7-trimethyl-2-[(dialkylamino)oxy]bicyclo[2.2.1]heptanol (1).

Thus, in the literature no information on regioselective synthesis of optically active dimeric complexes (1S,2S)-1,7,7-trimethyl-2-[(dialkylamino)biorganics compounds, namely, dimeric complexes (1S,2S)-1,7,7-trimethyl-2-[(dialkylamino)oxy]bicyclo[2.2.1]heptanol (1).

The proposed method is carried out by the interaction of (1S,2S)-1,7,7-trimethyl-bicyclo[2.2.1]heptane-2-it (camphor) with diacylhydrazine aluminum lR2(R = C2H5the h3H7i-C4H9), taken in a molar ratio of 10:(10-12), preferably 10:11, in an argon atmosphere at room temperature (~20oC) and normal pressure in benzene. The reaction time is 0.5-1.5 h, preferably 1 h Output dimeric complexes (1S,2S)-1,7,7-trimethyl-2-[(dialkylamino)oxy] bicyclo[2.2.1] heptanol 82-98%. The reaction proceeds according to the scheme 3 (see end of description).

Optically active dimeric complexes (1S, 2S)-1,7,7-trimethyl-2-[(dialkylamino)oxy] bicyclo[2.2.1] heptanol (1) are formed only with the participation of (1S,2S)-1,7,7-trimethyl-bicyclo[2.2.1]heptane-2-she and dialkylamides aluminum HAlR2. In the presence of other chiral ketones or other aluminum compounds (e.g., lt3, lui3Et2AlCl, EtAlCl2target products (1) are not formed.

Changing the ratio of initial reagents in the direction of increasing the content HAlR2in relation to camphor does not lead to further increase of the temperature (for example, 40o(C) did not increase the yield of the target product, and at a lower temperature (for example, 0oC) decreases the reaction rate.

Significant differences of the proposed method:

1. In the proposed method are used as initial reagents dialkylaminomethyl (HAlR2and optically active ketone (camphor). In the known method are used as initial reagents trialkylamine (AlR3and optically active alcohol.

The proposed method has the following advantages:

1. The method allows to obtain high regiospecificity optically active dimeric complexes (1S,2S)-1,7,7-trimethyl-2-[(dialkylamino)oxy]bicyclo[2.2.1]heptanol (1), the synthesis of which are not described in literature.

The method is illustrated by the following examples:

Example 1. In a glass reactor with a volume of 50 ml, mounted on a magnetic stirrer, an argon atmosphere was placed 11 mmol HAl(i-Bu)2in 9 ml6H6. To this mixture in small portions, add 10 mmol (1S,2S)-1,7,7-trimethyl-bicyclo[2.2.1] heptane-2-it(camphor), stirred for 1 h at room temperature (~20oC). Receive dimer (1S,2S)-1,7,7-trimethyl-2-[(diisobutylaluminum)oxy] bicyclo[2.2.1] heptane with access)oxy] bicyclo[2.2.1]heptane (, M. D., of 22.5 MHz, WITH6D6):

< / BR>
Other examples of the method are given in table. 1.

A method of obtaining optically active dimeric complexes (1S, 2S)-1,7,7-trimethyl-2-[(dialkylamino)oxy] -bicyclo[2.2.1] heptanol General formula I (see graphic part),

where R= C2H5the h3H7i-C4H9,

wherein the (1S, 2S)-1,7,7-trimethylbicyclo[2.2.1] heptane-2-he (camphor) interacts with diacylhydrazine aluminum HAlR2R is defined above, at a molar ratio of 10: (10-12) in an argon atmosphere at room temperature (~ 20oC) and normal pressure in the environment of benzene within 0.5 to 1.5 hours

 

Same patents:

The invention relates to methods for new alyuminiiorganicheskikh compounds (AOC), specifically to a joint process for the preparation of 1-ethyl-2-alkyladamantanes (1) and 1-ethyl-2-methylene-3-alkyladamantanes (2) General formula:

< / BR>
< / BR>
where R=n-C6H13the h8H17< / BR>
The proposed method AOC can be used in industrial organic synthesis, in particular polymerization processes, which play a role of socialization

The invention relates to the synthesis of aluminum and gallium complexes phthalocyaninato acids, which can be used as dyes, catalysts of oxidation reactions of various substrates, and products for optical and electronic products and medicine

The invention relates to methods for new alyuminiiorganicheskikh compounds (AOC), specifically to a method for producing 1-ethyl-2-methylene-3-alkylamidoamines (1) and 1-ethyl-1,1-di(ALK-1'-EN-3'-yl)Alans (2) the General formula

< / BR>
< / BR>
R=H-C6H13n-C8H17< / BR>
The proposed method for AOC can be used in industrial organic synthesis, in particular polymerization processes, which play a role of socialization

The invention relates to new compounds having an element of group III, associated with mono - or dianions tridentate ligand, the method of their production and their use in particular as a catalyst for (co)polymerization

The invention relates to catalysts, in particular to a catalyst for producing 1,2-bis(dialkylamino)-1-arylamino

The invention relates to catalysts, in particular to a catalyst for producing 1,2-bis(dialkylamino)-1,2-diphenylethylene

The invention relates to the field of catalysts, in particular a catalyst to obtain 1-alkoxy-2,3-diphenylethylamine

FIELD: chemistry of metalloorganic compounds, chemical technology.

SUBSTANCE: invention relates to a method for preparing aluminum-organic compounds of the general formula (I) wherein R means ethyl (Et), n-propyl (n-Pr), n-butyl (n-Bu). Method involves interaction of di-substituted acetylenes with ethylaluminum dichloride (EtAlCl2) in the presence of metallic Mg and a catalyst in argon atmosphere under atmosphere pressure and room temperature for 8 h followed by addition of maleic anhydride at temperature -5°C and stirring the reaction mass at room temperature for 8 h. The yield of the end product is 56-78%. Proposed compounds can be used in fine organic and metalloorganic synthesis and as co-catalysts in processes of oligo- and polymerization of olefins and coupled dienes.

EFFECT: improved preparing method.

2 cl, 1 tbl, 1 ex

FIELD: chemistry of metalloorganic compounds, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing polyalkoxyalumoxanes of the general formula: RO{[-Al(OR)-O-]x[-Al(OR*)-O-]y}zH wherein z = 3-100; x + y = 1; R*/Al = 0.05-0.95; R means CnH2n+1; n = 1-4; R* means -C(CH3)=CHC(O)CnH2n+1; -C(CH3)=CHC(O)OCnH2n+1, and preparing a silica-free binding agent based on thereof for producing refractory corundum ceramics for precise casting by melting out models. Method is carried out by interaction of organoaluminum compound with alcohol and chelating agent in an organic solvent medium wherein compound of the general formula: AlL3 is used as organoaluminum compound wherein L means CnH2n+1, CnH2n+1O, (CnH2n+1)2AlO[(CnH2n+1)AlO]t wherein n = 1-4 and t = 2-10 that is subjected for interaction with water, alcohol and chelating agent at temperature 0-250°C wherein compound of the formula R*OH is used as a chelating agent wherein R* means -C(CH3)=CHC(O)CnH2n+1; -C(CH3)=CHC(O)CnH2n+1 in the mole ratio H2O : ROH : R*OH = p : x : y wherein p = 0.001-1; x = 0.05-0.95; y = 0.05-0.95, and x + y = 1. Also, invention describes a silica-free binding agent based on chelated polyalkoxyalumoxanes in the following ratio of components, wt.-%: chelated polyalkoxyalumoxane, 5-90, and aliphatic alcohol, the balance, up to 100. Invention provides preparing air-stable polyalkoxyalumoxanes and a silica-free binding agent based on thereof, simplifying technology in preparing the corundum composition suspension and fitness period of suspension is prolonged.

EFFECT: improved preparing method, improved and valuable properties of compounds.

3 cl, 3 tbl, 2 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for treatment of aluminum alcoholates. Method involves passing aluminum alcoholates through a column filled with extrudates of aluminum oxide in γ-form with pore volume from 0.4 to 0.8 cm3/g prepared by preliminary hydrolysis of aluminum alcoholates, molding the prepared aluminum oxide to extrudates with diameter from 1.6 to 3 mm and length 3-4 mm and their following purification by calcinations at temperature 400-500°C. As a rule, the treatment of alcoholates is carried out at temperature 20-150°C in column for 1-5 h. Method provides the development of simple and available technology for treatment of aluminum alcoholates with hydrocarbon chain length from C3 to C6 and above from impurities up to the level 10-3-10-4 wt.-%.

EFFECT: improved treatment method.

2 cl, 5 ex

FIELD: chemistry of metalloorganic compounds, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing higher organoaluminum compounds, namely, to trialkyl aluminum. Method is carried out by interaction of aluminum preliminary subjected for activation with triethyl aluminum, hydrogen and olefin or olefin hydrocarbons at increased temperature and pressure. Activation of aluminum is carried out by interaction of aluminum, triethyl aluminum and part of olefin or olefin hydrocarbon and kept at temperature 40-50°C followed by feeding hydrogen and by increasing temperature to 125-135°C, kept at this temperature for 0.5-2 h, the remained amount of olefin or olefin hydrocarbon is fed and kept the formed reaction mass at temperature 135-155°C for 5-10 h. method provides enhancing conversion of olefins in the process for synthesis of trialkyls aluminum that are used broadly in different branches of industry, in particular, in production of polyolefins, higher saturated alcohols and others.

EFFECT: improved preparing method.

2 cl, 5 ex

FIELD: chemistry of organometallic compounds, chemical technology, organic synthesis.

SUBSTANCE: invention relates to a method for synthesis of new organoaluminum compounds. Method involves interaction of phenylallyl acetylene with ethylaluminum dichloride in the presence of metallic magnesium and zirconacene dichloride as a catalyst in argon atmosphere at room temperature in tetrahydrofuran medium for 8-12 h. Synthesized organoaluminum compound can be used as a component of catalytic systems in processes of oligomerization and polymerization of olefins and diene hydrocarbons, and in fine and industrial organic and organometallic synthesis also.

EFFECT: improved method of synthesis.

2 cl, 1 tbl, 9 ex

FIELD: chemistry, chemical technology.

SUBSTANCE: invention relates to quaternized phthalocyanines and their using for treatment of water against bacterial pollution. Invention describes novel quaternized phthalocyanines representing poly-(trialkylammoniomethyl)-substituted zinc and aluminum phthalocyanines that are sensitizing agents in formation of singlet oxygen by effect of visible light. Also, invention relates to a method for photodisinfection of water by using these quaternized phthalocyanines or their mixtures with dyes of acridine, rhodamine or phenothiazine series and radiation in visible range in the presence of oxygen that provides the effective treatment of water against bacterial pollution.

EFFECT: valuable properties of compounds, improved method of water treatment.

3 cl, 5 tbl, 16 ex

FIELD: medicine, in particular photosensitizing agents for photodynamic therapy.

SUBSTANCE: invention relates to quaternary phthalocyanines of general formula MPc(CH2X)nCln, wherein Pc is phthalocyanine rest C32H16N8; M is Zn, AlY; n = 6-8; X is Y is Cl, OH, OSO3H, useful as photosensitizing agents in photodynamic therapy having high photoinduced activity in vivo and in vitro.

EFFECT: new class of effective photosensitizing agents useful in treatment of various tumors by photodynamic therapy.

1 dwg, 8 ex

FIELD: medicine, in particular photosensitizing agents for antimicrobial photodynamic therapy.

SUBSTANCE: invention relates to new photosensitizing agents for antimicrobial photodynamic therapy namely cationic phthalocyanines of general formula MPc(CH2X)nCln, wherein Pc is phthalocyanine rest C32H16N8; M is Zn, AlY; n = 6-8; X is Y is Cl, OH, OSO3H. Claimed agents is characterized by wide range of antimicrobial activity. Single complex action of nontoxic in darkness micromolar (up to 2.0 muM) concentration thereof and low dose of red irradiation make it possible to produce high inactivation levels (up to 97-99 %) both gram-negative bacteria and yeast fungi of genus Candida.

EFFECT: improved agents for treatment of various severe complications of inflammation diseases.

3 dwg, 13 ex, 2 tbl

FIELD: chemistry of metalloorganic compounds, chemical technology, metalloorganic synthesis.

SUBSTANCE: invention relates to a method to synthesis of 1-chloro-2,3,4,5-tetraalkylaluminacyclopenta-2,4-dienes. Method is carried out by interaction of disubstituted acetylenes with aluminum trichloride in the presence of metallic magnesium and zirconacen dichloride as a catalyst in argon atmosphere at room temperature for 8-12 h. Invention provides using available reagents and simplifying method.

EFFECT: improved method of synthesis.

1 tbl, 12 ex

FIELD: chemistry of metalloorganic compounds, chemical technology.

SUBSTANCE: invention relates to organic synthesis, namely, to a method for synthesis of novel organoaluminum compounds. Method involves interaction of phenylallylacetylene with dialkylaminoaluminum dichloride in the presence of metallic magnesium and zircocene dichloride as a catalyst, in argon atmosphere at room temperature, in tetrahydrofuran medium for 8-12 h. Invention provides simplifying method and using available reagents.

EFFECT: improved method of synthesis.

1 tbl, 11 ex

Up!