The method of obtaining 1 alkenyl-1-(iso-butyl)-aluminofluoride

 

(57) Abstract:

Usage: in chemistry alyuminiiorganicheskikh of soedinenii, in particular in the production method of 1-alkenyl-1-ethyl-1-(ISO-butyl)aluminofluoride f-crystals: Chr CR A1(C1) i BU, where R is phenyl, propyl, butyl. The essence of the invention: synthesis of these substances lead by the reaction of di-R-substituted acetylene with diisobutylaluminium when their molar ratio equal to (35 25) 10 room temperature in the presence of 3 to 7 mol. dicyclopentadienyltitanium. The reaction time is 24 to 48 h, the yield of the target products 87 99% 1 table.

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 proposed compounds may find application as components of catalytic systems in the processes of polymerization and oligomerization of olefin and diene hydrocarbons, as well as in ORGANOMETALLIC and fine organic synthesis, in particular in the synthesis of Z-olefins with high stereoselectivity.

A method of obtaining a dialkyl(alkenyl)Alans [1] reaction hydroalumination reactions of disubstituted acetylenes with dialkylated get alkanolamides, namely 1 alkenyl-1-(ISO-butyl)aluminofluoride.

A method of obtaining bis-(diisopropylamino)alkenylamine [2] reaction hydroalumination reactions of disubstituted acetylenes using bis-(diisopropylamino)aluminiumhydride in benzene at room temperature under the action of 5 mol. catalyst Cu2TiCl2. The reaction proceeds according to the scheme:

RC CR + HAl(NPri2)2C C

However, the known method does not allow to get alkanolamides, namely 1 alkenyl-1-(ISO-butyl)aluminofluoride.

Thus, in the literature there is no information on the synthesis of 1-alkenyl-1-(ISO-butyl)aluminofluoride.

The aim of the invention is the development of new types of higher alkenylsilanes, namely 1 alkenyl-1- (ISO-butyl)Alamogordo.

This goal is achieved by the interaction of disubstituted acetylenes (R--R) with diisobutylaluminium (i-Bu2AlCl), taken in a molar ratio of (35-25):10, preferably 30:10 at room temperature (22-23aboutC) for 48-24 hours, preferably 36 hours, in the presence of a catalyst dicyclopentadienyl - titjikala (Cf2TiC2) in an amount of 3-7 mol. preferably 5 mol. In these conditions, the yield of 1-Alka is isobutylene.

R - R + i-Bu2AlCl-Bui< / BR>
The catalyst Cf2TiCl2in the amount of more than 7 mol. in relation to the disubstituted acetylene does not lead to a significant increase in the yield of the target product. The use amount is less than 3 mol. in relation to the disubstituted acetylene reduces output 1 alkenyl-1-(ISO-butyl)aluminofluoride, due to reduced catalytically active sites in the reaction mixture. At a higher temperature (for example, 50about(C) has not been a significant increase in the yield of the target products, which is connected, possibly with the formation of the products of seals. At lower temperatures (for example,aboutC) decreases the reaction rate. The reaction proceeds in aliphatic (hexane, octane, cyclohexane), aromatic (benzene, toluene) solvents or without solvent.

Fundamental differences of the proposed method lies in the fact that in the proposed method for hydroalumination reactions of disubstituted acetylenes used i-Bu2AlCl, and during the reaction are formed alkenylsilanes.

The proposed method, in contrast to the known, allows you to receive an individual 1 alkenyl-1-(ISO-butyl)aluminum chlorides, synthesis of which in the literature is not Here argon placed 30 mmol i-Bu2AlCl in 5 ml of benzene, 10 mmol of diphenylacetylene (Ph--Ph) and 0.5 mmol Cp2TiCl2, stirred for 36 h at room temperature (22-23aboutC). Get 1-(1',2'-diphenylvinyl)-1-(ISO-butyl)aluminised exit 94% yield of the target product is determined by the product of the hydrolysis. After treatment of the reaction mixture with 5% HCl solution allocates 1,69 g of CIS-stilbene (2). Lateralis leads respectively to CIS-deuterostomia (3).

Ph Ph

Physico-chemical characterization of the CIS deuterostomia (3): nD281,5140.

IR spectrum (cm-1): 3030, 2940, 2245, 1600, 1400, 995, 940, 760, 720. An NMR spectrum13With (, m D.):

< / BR>
The PMR spectra ( , memorial plaques): 6,56 s (1H, CH), 7,20 (10H, Ph). M+181.

Other examples of this method, shown in the table.

In all examples of the solvent used benzene. The nature of the solvent has little effect on the yield of the target product. The reaction was carried out at room temperature.

The METHOD of OBTAINING 1 ALKENYL-1-(ISO-BUTYL)-ALUMINOFLUORIDE General formula

< / BR>
where R is C3H7C4H9C6H5,

characterized in that the corresponding disubstituted acetylene is subjected to interaction with diisobutyldimethoxysilane in relation to the disubstituted acetylene within 24-48 hours

 

Same patents:

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!