The process of co-produce 1-ethyl-3,6 - dialkylhydroxylamines and 1-ethyl-3,5 - dialkylhydroxylamines

 

(57) Abstract:

Describes how the joint production of 1-ethyl-3,6-dialkylhydroxylamines formula 1 and 1-ethyl-3,5 - dialkylhydroxylamines formula (2), where R= n-C4H9,n-C6H13; R'=n-C3H17i-C3H7n-C5H11, characterized in that the olefins of the formula where R is as defined above, is subjected to the interaction with triethylaluminium (AlEt3in the presence of catalyst zirconatetitanate (Cp2ZrCl2) in a molar ratio in an argon atmosphere for 8 hours followed by the addition of hexane, cooled the reaction mixture to -10oWith and addition of the catalyst odnoklasniki copper (CuCl) and the aldehyde of the formula R'-CHO, where R' is as defined above, in a molar ratio of CuCl:R CHO= (0,8-1,2): (10-14) and stirring the reaction mass for 6-10 h at room temperature and normal pressure. The resulting compounds may find application in thin organic and ORGANOMETALLIC synthesis, as well as socialization in the processes of oligo - and polymerization of olefins and dienes. 1 PL.

< / BR>

The present invention relates to methods for new alyuminiiorganicheskikh connections s the General formula (1) and (2):

< / BR>
< / BR>
where R=n-C4H9the h6H13; R'=h3H7i-C3H7the h5H11< / BR>
The proposed compounds may find application in thin organic and ORGANOMETALLIC synthesis, as well as socialization in the processes of oligo - and polymerization of olefins and dienes.

The known method ([1] , L. I. the Zakharkin, L. A. Savin. WPI. An SSSR, Ser. chem. , 1960, 6, 1039-1043) obtain chelate alyuminiiorganicheskikh compounds (3) the interaction of i-Bu2AlH-functionalproperty-olefins according to scheme 1 (see the end of the description).

The known method does not allow to obtain 1-ethyldichlorosilane (1) and (2).

The known method ([2] , L. I. the Zakharkin, L. A. Savin, Phys. An SSSR, OHP, 1962, 5, 824-827) obtain 1-isobutyltrimethoxysilane (4) the interaction of allyl alcohol with triisobutylaluminum at -5 - -10oC, followed by addition of i-Bu2A1H and heated for 6 hours to 125-130oWith scheme 2.

The known method does not allow to obtain 1-ethylcyclohexane (1) and (2).

Thus, in the literature there are no data on the joint to obtain 1-ethyl-3,6-dialkylhydroxylamines (1) and 1-ethyl-3,5-dialkyl 1-ethyl-3,5-dialkylhydroxylamines (2).

The essence of the method lies in the interaction in the atmosphere of inert gas-olefins of General formula , where R=n-C4H9the h6H13with triethylaluminium (AlEt3in the presence of catalyst zirconatetitanate (Cp2ZrC12), taken in a molar ratio

< / BR>
preferably 10:12:0,5, at room temperature (20-22oC) for 8 hours followed by cooling the reaction mixture to -10oWith and addition of the catalyst odnoklasniki copper (SIS) and the aldehyde of General formula

< / BR>
where R'= n-C3H7i-C3H7the h5H11taken in a molar ratio of CuCl: R CHO= (0,8-1,2): (10-14) preferably 1:12, followed by stirring at room temperature for 6-10 hours, preferably 8 hours.

The total yield of 1-ethyl-3,6-dialkylhydroxylamines (1) and 1-ethyl-3,5-dialkylhydroxylamines (2) is 62-78%, the ratio(1):(2)~1,5:1.

The reaction proceeds according to the scheme 3.

The conduct of a specified reaction in the presence of copper catalyst is greater than 12 mol.% in relation to the original-olefin does not lead to a significant increase in the yield of the target products. The use of the catalyst is less than 0.8 mol.% reduces the release of AOC (1) and (2) that Sacchi at a higher temperature (for example, 40o(C) does not increase the yield of the target products. At a lower temperature (for example, 0oC) decreases the reaction rate.

Significant differences of the proposed method.

In the proposed method are used as starting compounds, olefins, Et3A1, aldehydes, catalysts Cp2ZrC12and CuCl, which causes the formation of 1-ethyl-3,6-dialkylhydroxylamines (1) and 1-ethyl-3,5-dialkylhydroxylamines (2). In the known method are used as starting compounds, allyl alcohol, i-VI3Al and i-Bu2AlH.

The proposed method has the following advantages.

1. The method allows to obtain 1-ethyl-3,6-dialkilsuljfoksidih (1) and 1-ethyl-3,5-dialkilsuljfoksidih (2), 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 in an argon atmosphere, placed 10 mmol octene-1, 12 mmol Et3A1, 0.5 mmol Cp2ZrCl2and stirred for 8 hours, then add 6 ml of hexane, cooled to -10oWith add 1 mmol CuC1 and 12 mmol butyric aldehyde. The temperature was adjusted to room and perimenapausal (2) with a total yield of 72% and a ratio of(1): (2)~1,5:1.

The total yield and the ratio of target products was determined by the products of hydrolysis. When the hydrolysis is obtained 1-ethyl-3-propyl-6-hexyltrichlorosilane (1) and 1-ethyl-3-propyl-5-hexyltrichlorosilane (2) form 7-methylcatechol-4 (5) and 6-ethyldecyl-4 (6), identified by spectral methods. (For further info, see scheme 4).

An NMR spectrum13With (, m D.) 7-methyltricyclo-4 (5): 14,09 to (1), 18,80 t (2), 34,95 t (3), 72,04 d (4), 39,63 t (5), 27,09 t (6), 32,90 d (7), 27,02 t (8), 32,81 t (9), 26,65 t (10), 31,92 t (11), cushion 22.66 t (12), 14,06 to (13), 19,68 to (14).

An NMR spectrum13With (, m DV): 6-ethyldecyl-4 (6): 14,10 C (1), 18,83 t (2), 32,95 t (3), 69,70 d (4), 41,81 t (5), 35,53 d (6), 40,39 t (7), 26,64 t (8), 29,89 t (9), 31,91 t (10), cushion 22.66 t (11), 14,06 to (12), 25,54 t (13), 10,84 (WITH14).

Other examples of the method are given in table 1.

The reaction was carried out at room temperature (20-22o(C) in hexane. The ratio of products (1) and (2) was in all experiments ~1.5:1.

The process of co-produce 1-ethyl-3,6-dialkylhydroxylamines formula 1 and 1-ethyl-3,5 - di-Christ. H7i-C3H7n-C5H11,

characterized in that the olefins of the formula

< / BR>
where R is as defined above

subjected to interaction with triethylaluminium (AlEt3in the presence of catalyst zirconatetitanate (Cp2ZrCl2) in a molar ratio in the atmosphere of argon for 8 h followed by the addition of hexane, cooled the reaction mixture to -10oWith and addition of the catalyst odnoklasniki copper (CuCl) and the aldehyde of the formula

R'-CHO,

where R' is as defined above,

in a molar ratio of CuCl : R CHO= (0,8-1,2): (10-14) and stirring the reaction mass for 6-10 h at room temperature and normal pressure.

 

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

The invention relates to a catalyst, particularly a catalyst to obtain 1-alkoxy-2-arialunicodems

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!