Method for preparing 1-chloro-2,3,4,5-tetraalkylaluminacyclopenta-2,4-dienes

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

 

The present invention relates to the field of ORGANOMETALLIC synthesis, specifically to a method for producing 1-chloro-2,3,4,5-tetraalkylammonium-2,4-dienes of General formula (1):

These compounds may find application as components of catalytic systems in the processes of oligomerization and polymerization of olefins and diene hydrocarbons, as well as in thin, industrial organic and ORGANOMETALLIC synthesis.

The known method [J.J.Eisch, W.C.Kaska. J. Am. Chem. Soc., 88, 2976 (1966)] obtain 1,2,3,4,5-substituted aluminosilicate (2) reaction carboalumination tolana (Ph≡-Ph) using triphenylamine (AlPh3) at temperatures above 100°With subsequent cyclization of the resulting alkenylamine at 200°schema:

The known method does not allow to obtain 1-chloro-2,3,4,5-tetraalkylammonium-2,4-diene (1).

The known method [Hongyun Fang, Changjia Zhao, Li Guotao and Zhenfeng Xi. Reaction of aluminacyclopentadienes with aldehydes affording cyclopentadiene derivatives. Tetrahedron, 59, (2003), 3779-3786] obtain 1-chloro-2,3,4,5-tetraalkylammonium-2,4-dienes (1) the interaction of 1,4-delicio-1,3-dienes derived from 1,4-diid-1,3-butadiene and t-BuLi, with aluminum trichloride according to the scheme:

The disadvantages of this method:

1. The method is two-stage and n is the first stage applies pyrophoric t-BuLi.

2. The reaction with t-BuLi is at low temperature (-78° (C) and requires additional energy consumption.

Proposed a new method for producing 1-chloro-2,3,4,5-tetraalkylammonium-2,4-dienes (1).

The method consists in the interaction of disubstituted acetylenes of the formula R-≡-R, where R=C2H5the h3H7the h4H9with aluminum trichloride (AlCl3) and metallic magnesium (Mg, powder) in the presence of a catalyst of zirconatetitanate Cp2ZrCl2taken in a molar ratio of R-≡-R:(AlCl3):Mg:Cp2ZrCl2=10:(10-14):(10-14):(0.8-1.2), preferably 10:12:12:1. The reaction is carried out in an argon atmosphere at room temperature (˜20°C) and atmospheric pressure. The reaction time is 8-12 hours, the yield of the target products 68-90%. As a solvent it is necessary to use tetrahydrofuran (THF), in other ethereal solvents (ether, dioxane) and the reaction selectivity and the yield of the target product (1) is reduced.

The reaction takes place according to the scheme:

Target products (1) are formed only with the participation of the disubstituted acetylene trichloride, aluminium, metal Mg as an acceptor halide ions and catalyst Cp2ZrCl2. In the presence of other aluminum compounds (e.g., EtAlCl2Et2AlCl, Et3Al, ISO-Bu3Al from is-Bu 2AlCl, ISO-Bu2AlH) or other transition metal complexes (for example, Zr(acac)4Cp2TiCl2Pd(acac)2, Ni(acac)2, Fe(ASAS)3target products (1) are not formed.

Conducting the reaction in the presence of a catalyst Cp2ZrCl2more than 12 mol.% with respect to the acetylene does not lead to a significant increase in the yield of the target products (1). Use in the reaction of the catalyst Cp2ZrCl2less than 8 mol.% reduces the release of AOC (1), which is associated with a reduction of catalytically active sites in the reaction mass. Experiments were performed at room temperature (˜20°). At a higher temperature (for example, 50° (C) increases the amount of seal products, at a lower temperature (e.g., 0° (C) decreases the reaction rate.

Changing the ratio of initial reagents in the direction of increasing the content of AlCl3or Mg in relation to the acetylene does not lead to a significant increase in the yield of target products (1). The reduction in the number of AlCl3or Mg relative to acetylene reduces the output of the AOC (1).

Significant differences of the proposed method:

If in the known method, the synthesis is carried out in two stages at low temperature (-78° (C) using hard-1,4-Diod-1,3-butadiene and pyrophoric t-BuLi, in the proposed method, the reaction is carried out in one with adieu at room temperature using available acetylenes and catalytic amounts Cp 2ZrCl2.

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 10 ml of tetrahydrofuran, 1 mmol Cp2ZrCl210 mmol of Gex-3-ina, 12 g-at. Mg (powder) and at a temperature of ˜0°12 mmol of aluminum trichloride (AlCl3). Stirred at room temperature (˜20° (C) 10 hours. Get 1-chloro-2,3,4,5-Tetraethylenepentamine-2,4-diene (1). The yield of the target product was determined by the hydrolysis product. When the hydrolysis AOC (1) is formed 4,5-detract-3,5-diene (5) with the release of ˜78%, and at lateralize 3.6-dideuterio-4,5-detract-3,5-diene (6).

The spectral characteristics of the products of hydrolysis (5) and laterality (6).

An NMR spectrum1H (CDCl3that δ, ppm) 4,5-detract-3,5-diene (5): 0.88-1.00 m (N, CH3), 1.97-2.16 m (8H, =C-CH2), 5.45-5.80 m (2H, -C=CH-).

An NMR spectrum13With (δ, ppm) 4,5-detract-3,5-diene (5): 14.15 (1,8), 14.21 (10,12), 22.19 (2,7), 22.35 (9,11), 123.18 (3,6), 139.61 (4,5).

An NMR spectrum1H (CDCl3that δ, ppm) 3,6-dideuterio-4,5-detract-3,5-diene (6): 0.88-1.00 m (N, CH3), 1.97-2.16 m (8H, -S-CH2).

An NMR spectrum13With (δ, ppm) 3,6-dideuterio-4,5-detract-3,5-diene (6): 14.13 (1,8), 14.24 (10,12), 22.17 (C2,7), 22.37 (9,1 ), 123.15 t (3,6I , JCD24,0 Hz), 139.59 (4,5).

Other examples of the method are given in table 1.

Table 1
№ p/pR-≡-RThe molar ratio of R-≡-R:AlCl3:Mg:Cp2ZrCl2mmolReaction time, hoursOutput (1), %
1Gex-3-in10:12:12:11078
210:14:12:11083
310:10:12:11074
410:12:14:11080
510:12:10:11073
610:12:12:1.21090
710:12:12:0.81068
810:12:12:11281
910:12:12:1872
11Oct-4-in10:12:12:11075
12 Dec-5-in10:12:12:11070

All experiments were performed at room temperature (˜20° (C) in tetrahydrofuran.

The way to obtain 1-chloro-2,3,4,5-tetraalkylammonium-2,4-dienes of General formula (I)

characterized in that the disubstituted acetylene General formula R-≡-R, where R=C2H5the h3H7The h4H9interacts with aluminum trichloride and metallic magnesium in the presence of a catalyst of zirconatetitanate (Cp2ZrCl2) in a molar ratio of R-≡-R:AlCl3:Mg:Cp2ZrCl2=10:(10-14):(10-14):(0.8-1.2) in an argon atmosphere at normal pressure in tetrahydrofuran for 8-12 hours



 

Same patents:

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: 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: 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: 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 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: 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 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: 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

The invention relates to a method of obtaining new alyuminiiorganicheskikh compounds which may find application as components of catalytic systems in the processes of oligomerization and polymerization of olefin and diene hydrocarbons, and fine organic and ORGANOMETALLIC syntheses

The invention relates to a method of obtaining a new alyuminiiorganicheskikh connection, which can be applied in thin organic synthesis, and as acetalization in oligo - and polymerization of Alifanov and conjugated dienes

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!