The way to obtain 1-ethyl-2-aryl-3-methylenecyclopropane

 

(57) Abstract:

Describes how to obtain 1-ethyl-2-aryl-3-methylenecyclopropane General formula (1)

,

where Ar= Ph, n-CH3RH, characterized in that orielley General formula Ar -== where Ar is defined above, is subjected to the interaction with ethylaminoethanol EtAlCl2and metallic magnesium, taken in a molar ratio Ar==:EtAlCl2:Mg= 10:(10-14):(10-14) accordingly, in the presence of a catalyst of titaniumdioxide (Cp2TiCl2) in an amount of 2 to 6 mol.% in relation to Arellano in the environment of tetrahydrofuran, the reaction is carried out in an argon atmosphere at room temperature (~20oC) and normal pressure within 6-10 hours Proposed method of obtaining may find application in industrial organic synthesis, in particular in polymerization processes where the resulting compounds play a role socialization. table 1.

The present invention relates to methods for new alyuminiiorganicheskikh compounds (AOC), specifically to a method for producing 1-ethyl-2-aryl-3-methylenecyclopropane General formula (1)

< / BR>
where Ah=Ph, n-CH3PH.

The proposed method for AOC may find application in industrial the e compounds of metals of variable valence and AOC is a unique catalysts for stereoregular poly - and oligomerization of olefins and dienes. In thin organic and ORGANOMETALLIC syntheses high reactivity AOC allows to solve the basic problem - the creation of new relationships With-and With the conversion of functional groups. Therefore, EPA is widely used as intermediates in the synthesis of a large range of functional derivatives of organic compounds ([1] , Kuchin, A. C., Tolstikov, A. Preparative alyuminiiorganicheskikh synthesis. Syktyvkar, 1997, 208).

The known method ([2] , Dzhemilev, U. M., A. Ibragimov,, Zolotarev A. P., Muslumov P. P., Tolstikov, L. Izv. THE USSR ACADEMY OF SCIENCES. Ser. chem., 1989, S. 207) obtaining substituted five-membered cyclic AOC General formula (2) reaction of triethylaluminum with a-olefins in the presence of a catalyst Cp2ZrCl2at room temperature (~20oC) outputs 80-95% scheme

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where R is alkyl.

The known method cannot be obtained substituted three-membered cyclic AOC, namely, 1-ethyl-2-aryl-3-methylenecyclobutane (1).

The known method ([3], Ibragimov, A. G., Khafizova L. O., Satenaw, K., Khalilov L. M., Yakovlev, L. G., S. Rusakov Century, Dzhemilev, U. M. Izvestiya an. Ser. chem., 1999, S. 1594) obtaining substituted three-membered cyclic AOC, namely, 1-ethyl-2-arylaliphatic3with arylolefins

< / BR>
in the presence of a catalyst Cp2ZrCl2with a total yield of cyclic AOC >90% and the content of 1-ethyl-2-arialunicodems (3) ~7%. The reaction proceeds according to the scheme

< / BR>
where Ah=Ph, n-CH3PH, o-CH3PH.

The known method does not allow to obtain 1-ethyl-2-aryl-3-methylenecyclopropane (1).

Thus, in the literature there are no data on the regioselective synthesis of 1-ethyl-2-aryl-3-methylenecyclopropane (1).

We propose a method to obtain new types of three-membered cyclic AOC, namely, 1-ethyl-2-aryl-3-methylenecyclopropane (1).

The proposed method is carried out by interaction Arellano General formula Ar -== where Ar=Ph, n-CH3RH, with ethylaminoethanol (EtAlCl2) and metallic magnesium (powder), taken in a molar ratio Ar==:EtAlCl2:Mg= 10:(10-14):(10-14), mostly 10: 12: 12, in the presence of a catalyst of titanzincoated (Cp2TiCl2) in an amount of 2-6 mol. % towards Arellano, preferably 4 mol.%, in an argon atmosphere at room temperature (~ 20oC) and normal pressure in THF. The reaction time is 6-10 hours, preferably 8 hours Output 1-ethyl-2-aryl-3-methylenecyclopropane 60-82%. the HN (1) are formed only with the participation of EtAlCl2and titanium catalyst Cp2TiCl2. In the presence of other aluminum compounds (e.g., i-Bu2AlCl, (i-Bu3Al, i-Bu2AlH, lt3Et2AlCl) or other catalysts (e.g., Zr(acac)4, Zr(OBu)4Pd(acac)2, Ni(ASAS)2, FeCl3target products (1) are not formed.

The conduct of a specified reaction in the presence of a titanium catalyst Cp2TiCl2more than 6 mol.% does not lead to a significant increase in the yield of the target products. The use of the catalyst is less than 2 mol. % reduces output 1-ethyl-2-aryl-3-methylenecyclopropane (1), which is connected, possibly, with a reduction of catalytically active sites in the reaction mass. The syntheses were carried out at room temperature (~20oC). At a higher temperature (for example, 40oC) there is an observed increase in the yield of the target product, and at a lower temperature (for example, 0oC) decreases the reaction rate.

Changing the ratio of initial reagents in the direction of increasing the content of EtAlCl2or Mg in relation to the original Arellano does not lead to a significant increase in the yield of target products (1).

Significant differences of the proposed method:

1. In the proposed CSP is holding the catalyst Cp2TiCl2that lead to the formation of 1-ethyl-2-aryl-3-methylenecyclopropane (1). In the known method are used as initial reagents triethylamine deposits (lt3), ailelerini (AG) and zirconium bearing catalyst Cp2ZrCl2that lead to the formation of predominantly five-membered cyclic AOC and in the amount of ~7% 1-ethyl-2-arialunicodems (3).

The proposed method has the following advantages:

1. The method allows to obtain high regiospecificity 1-ethyl-2-aryl-3-methylenecyclopropane (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 10 ml of THF, 10 mmol of phenylaline, 12 mmol Mg (powder) at a temperature of ~0oWith 0.4 mmol Cf2Til2and 12 mmol EtAlCl2, stirred for 8 h at ~20oC.

Get 1-ethyl-2-phenyl-3-methylenecyclopropane (1) yield was 73%. The yield of target products was determined by the products of hydrolysis. When the hydrolysis of 1-ethyl-2-phenyl-3-methylenecyclopropane (1) is formed Olivenza (4), identified by comparison with Svea of laterality (2). When lateralize (1) is obtained 2,3-dideuterio-3-phenyl-1-propene (5), identified by NMR13C. Identification using NMR13With directly AOC (1) is difficult due to the broadening of the signals of the carbon atoms due to the quadrupolar relaxation by nuclei Al27< / BR>
(ial=5/2).

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An NMR spectrum13With (, m D.) 2,3-dideuterio-3-phenyl-1-propene (5): 115.63 t (1), 39.80 t (3), 143.91 (WITH4), 128,34 d (5), 128,37 d (6), 126.03 (WITH7).

Other examples of the method shown in the table.

The way to obtain 1-ethyl-2-aryl-3-methylenecyclopropane General formula (1)

< / BR>
where Ar= Ph, n-CH3RH,

characterized in that orielley General formula

Ar-== ,

where AG is defined above,

subjected to interaction with ethylaminoethanol EtAlCl2and metallic magnesium, taken in a molar ratio Ar==:EtAlCl2:Mg= 10:(10-14):(10-14) accordingly, in the presence of a catalyst of titaniumdioxide (Cf2TiCl2) in an amount of 2-6 mol. % towards Arellano in the environment of tetrahydrofuran, the reaction is carried out in an argon atmosphere at room temperature (~ 20oC) and normal pressure within 6-10 hours

 

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