The way the joint production of 1-[3 - ateltico -(5.2.1.05, 9) -oct-7 - en-2-yl] -1-ethyl - 1-haralan and 1-[3 - ateltico (5.2.1.05,9) -oct-6 - en-2-yl] -1-ethyl-1 - haralan

 

(57) Abstract:

Usage: in chemistry alyuminiiorganicheskikh compounds, in particular in the production method of 1-(3-ateltico[5.2.1.05,9] Dec-7-EN - 2-yl) -1 - ethyl-1-chlorine and 1-(3-ateltico [5.2.1.05,9] Oct-6 - EN-2 - yl) -1 - ethyl - 1-chlorine (they differ in the position Putilkovo Deputy in relation to the aluminum atom) and can be used as acetalization oligo - and polymerization of olefins and dienes. The essence of the invention: synthesis of these substances lead by the reaction of Dicyclopentadiene with diethylaluminium when their molar ratio equal to 10:(10-12), mostly 10:11, room temperature (23-25C) and normal pressure in the presence of a bimetallic catalyst is titanium tetrachloride with contour dibutylaminoethanol (1:1), taken in an amount of 2-5 (better 3) mol. in relation to Dicyclopentadiene in an argon atmosphere and in the medium aliphatic solvent (hexane, heptane or cyclohexane). The reaction time is 8-12 hours the yield of target products 70-82% 1 table.

The invention relates to new alyuminiiorganicheskikh connections, specifically to 1-(3-ateltico[5,2,1,05,9]-Oct-7-EN-2-yl)-1 - ethyl-1-haralan [1] and 1-(3-ateltico[5,2,1,05,9] -Oct-6-EN-2-yl)-1-et + -Cl

(1) (2)

The proposed compounds may find application in thin organic and ORGANOMETALLIC synthesis, and can also be used as socialization processes oligo - and polymerization of olefins and dienes.

A method of obtaining highest dialkylaminoalkyl [1] the interaction of diethylacetanilide (Et2AlCl) with a-olefins, taken in a molar ratio of 1:4 at room temperature in the presence of catalytic amounts of Zr(OBu)4(2 mol.) in absolute toluene or heptane. Along with dialkylamino-chlorides are formed in equimolar quantities methylaniline. The reaction proceeds according to the scheme:

Et2AlCl + 4R 2R + 2(R )2AlCl

The disadvantages of this method:

1. Low selectivity of the reaction. Along with the target products are formed methylaniline.

2. By a known method cannot be obtained 1-(3-ethyl-tricyclo[5,2,1,05,9] -Oct-7-EN-2-yl)-1-ethyl-1-chlorine - ralan and 1-(3-ateltico[5,2,1,05,9]-Oct-6-EN-2-yl)-1-ethyl-1-Harlan.

A method of obtaining highest dialkylaminoalkyl 2 interaction of diisobutylaluminium (i-Bu2AlCl) with a-olefins, taken in a molar ratio of 1:2 at room temperature for 6 h Ave the s proceeds according to the scheme:

R+ i-Bu2AlCl (R )2AlCl

The known method does not allow to obtain the compounds (1) and (2).

Thus, in the literature there is no information on the synthesis of 1-(3-ethyl-Trillo[5,2,1,05,9] -Oct-7-EN-2-yl)-1-ethyl-1-chloral - on and 1-(3-ateltico[5,2,1,05,7]-Oct-6-EN-2-yl)-1-ethyl-1-haralan.

The aim of the invention is to develop a synthesis of new types of higher alyuminiiorganicheskikh compounds, namely 1-(3-ateltico[5,2,1,05,9]-Oct-7-EN-2-yl)-1-ethyl-1-chloro - Alan and 1-(3-ateltico[5,2,1,05,9]-Oct-6-EN-2-yl)-1-ethyl-1-haralan with high yields.

This is achieved by the interaction tricyclo-[5,2,1,02,6] -3,8-decadiene (Dicyclopentadiene) with Et2AlCl, taken in a molar ratio of 10: (10-12), mostly 10:11, in the presence of a bimetallic catalyst TiCl4i-Bu2AlH (1:1) in an amount of 2-5 mol. towards Dicyclopentadiene, preferably 3 mol. in an argon atmosphere at room temperature (23-25aboutand normal pressure in aliphatic solvents (hexane, heptane, cyclohexane). The reaction time is 8-12 hours, the yield of the target products 70-82%

+ Et2AlCl

Products (1) and (2) are formed in the ratio of 1:1 and only with the participation of Et2All and b is B>3, AlEtCl2i-Bu2AlCl, (i-Bu3Al) or other catalyst (for example, Cf2ZrCl2, Zr(OB)4, Ti(OBu)4Cp2TiCl2, ZrCl4target products (1) and (2) are not formed.

The conduct of a specified reaction in the presence of catalyst is more than 5 mol. does not lead to a significant increase in the yield of the target products. Use calization less than 2 mol. reduces the output alyuminiiorganicheskikh compounds (1) and (2) that is associated with a decrease in active sites in the reaction mass. Experiments were performed at room temperature (23-25aboutC). At a higher temperature (for example, 50about) increases the amount of seal products, at a lower temperature (for example, 0o)decreases the reaction rate. Changing the ratio of initial reagents or catalyst components in the direction of increasing the content of Et2AlCl towards Dicyclopentadiene or i-Bu2AlH towards TiCl4does not lead to a significant increase in the yield of target products. The reduction in the number of Et2AlCl in relation to the original Dicyclopentadiene or i-Bu2AlH towards TiCl4reduces the yield of the target product.

Significant differences of the proposed method:

Are-olefins and diisobutylaluminium (i-Bu2AlCl), a reaction catalyzes Cp2ZrCl2in the proposed method to obtain the target product (1) and (2) apply Et2AlCl and Dicyclopentadiene, and the reaction catalyzes the bimetallic catalyst TiCl4i-Bu2AlH.

The proposed method has the following advantages.

The method allows to obtain, using available reagents and catalyst 1-(3-ateltico[5,2,1,05,9] -Oct-7-EN-2-yl)-1 - ethyl-1-Chlorella (1) and 1-(3-ateltico[5,2,1,05,9]-Oct-6-EN-2-yl)-1-chlorin (2), the synthesis of which are not described in literature.

P R I m e R 1. In a glass reactor with a volume of 50 ml, mounted on a magnetic stirrer in an argon atmosphere at a temperature (-5aboutC) put 0.3 mmol TiCl4, 0.3 mmol i-Bu2AlH in 1 ml of hexane, 10 mmol of Dicyclopentadiene and 11 mmol Et2AlCl 3 ml of hexane, warmed to room temperature (23-25aboutC), stirred for 10 hours Get 1-(3-italtecnica-[5,2,1,05,9] Dec-7-EN-2-yl)-1-ethyl-1-Harlan (1) and 1-(3-ateltico- [2,2,1,05,9]-Oct-6-EN-2-yl)-1-ethyl-1-Chlorella (2). The yield of the target products (1) and (2) were determined from the products of hydrolysis. When the hydrolysis is allocated ethane to form 2-ethyl-tricyclo- [5,2,1,05,9]-Oct-6-ene (3) and 2-ateltico-[5,2,1,05,9]P>5,9]-Oct-6-ene (5) and 2-ethyl-3-datarecall-[5,2,1,05,9]-Oct-7-ene (6) according to the scheme:

< / BR>
An NMR spectrum13( M. D.) connection (3): 44,13 d (1), 41,13 d (2), 33,30 t (3), 38,71 d (4), 53,75 d (5), 130,81 d (6), 132,57 d (7), 32,40 t (8), 41,89 d (C9), 387,40 t (C10), 29,30 t (11), 12,29 to (13), M+(t/f) 162.

An NMR spectrum13( M. D.) connection (4): 45,69 d (1), 40,07 d (2), 31,99 t (3), 35,63 d (4), 42,56 d (5), 33,64 t (6), 132,57 d (7), 130,38 d (8), 52,42 d (9), 38,40 (10), 29,78 t (11), 12,46 to (12), M+(t/f) 162.

An NMR spectrum13With ( , m D. ) connection (5): 45,66 d (1), 35,48 d (C2), 33,30 d (3), 39,95 d (4), 52,40 d (5), 132,61 d (C6), 130,12 d (7), 31,98 t (8), 42,54 d (9), 38,56 d (10), 29,10 t (11), to 12.44 (WITH12), M+(t/f) 163.

An NMR spectrum13( M. D.) connect (6): 44,08 d (1), 41,11 d (2), 29,89 d (3), 41,84 d (4), 41,54 d (5), 32,38 t (6), 130,87 d (7), 132,61 d (8), 53,73 d (9), 38,38 t (10), 29,18 t (11), 12,25 to (12), M+(t/p) 163.

Other examples of the method shown in the table.

The reaction was carried out at to the, clohexane) has virtually no effect on the total yield of (1) and (2). In all experiments, the ratio(1): (2) 1:1. The best is the ratio of TiCl4i-Bu2AlH 1:1. Higher temperature increases the yield of the target product. At a lower temperature decreases the reaction rate.

THE WAY THE JOINT PRODUCTION OF 1-[3-ATELTICO-(5 2 1 05,9)-OCT-7-EN-2-YL]-1-ETHYL-1-HARALAN AND 1-[3-ATELTICO(5 2 1 05,9)-OCT-6-EN-2-YL]-1-ETHYL-1-HARALAN formula

< / BR>
< / BR>
characterized in that tricyclo-(5,2,1,02,6)- 3,8-decadien subjected to interaction with diethylaluminium in a molar ratio of 10 10 12 in the presence of 2 to 5 mol. in relation to the original diene with a catalyst containing titanium tetrachloride and isobutylamine hydride at a molar ratio of 1 to 1, and the process is conducted in an argon atmosphere at room temperature, normal pressure in aliphatic solvent for 8 to 12 hours

 

Same patents:

The invention relates to new alyuminiiorganicheskikh connections, specifically to 1-(endo-tricyclo-[52105,9]-Oct-7-EN-2-yl) -1-(i-butyl)-1-haralan (1) and 1-(endo-tricyclo-[5.2.1.05,9]-Oct-6-EN-2-yl)-1-(i-BU - Tyl)-1-haralan (2), which differ in the position of the double bond relative to the aluminum atom, of formula:

< / BR>
The proposed connection (1) (2) can be applied in thin organic or ORGANOMETALLIC synthesis

The invention relates to new alyuminiiorganicheskikh connections, specifically to 1,4-bis-[(N, N-dialkylamino)-Aluma] TRANS-2,3-dealkylation, General formula I

(R2N)AlAl(NR2)

where R2N Et2NN

R1C3H7C4H9C5H11

The invention relates to new alyuminiiorganicheskikh connections, specifically to 1-alkenyl-1-(ISO-butyl)aluminofluoride General formula (I)

-Bui< / BR>
(1) where R is C3H7WITH4H9

The invention relates to new alyuminiiorganicheskikh connections, specifically to 1-alkenyl-1-(ISO-butyl)-1-chloralum General formula (I)

iH9-where R is phenyl,3H7WITH4H9

The invention relates to the production of complex compounds and accordingly chelate complexes of antibiotics with bivalent and/or trivalent metals, use them to get antiulcer drugs, new complex compounds and accordingly chelate complexes of antibiotics with bivalent and/or trivalent metals

The invention relates to methods for the joint production of new alyuminiiorganicheskikh compounds, specifically to 1 - (5 - butalbital - [2.2.1] - hept - 2 - yl) - 1 - (i - butyl) - 1 - chlorine (1) and 1 - (6 - butalbital - [2.2.1] -hept-2 - yl) -1- (i-butyl) - 1 - chlorine (2), which differ in the position Putilkovo Deputy in relation to the atom of aluminum f-crystals 1 and 2 and can find application in thin organic or ORGANOMETALLIC synthesis

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!