The process of co-producing 1,2-bis(ditylum)-1-methylene - 2-alkylamino and 1,4-bis(ditylum)-1,4-dialkylanilines

 

(57) Abstract:

Describes how the joint production of 1,2-bis(ditylum)-1-methylene-2-alkylamino formula (1) and 1,4-bis(ditylum)-1,4-dialkyldimethyl formula (2), where R=n-C6H13the h8H17the h9H19, characterized in that alkylarene General formula R-==, where R is as defined above, is subjected to the interaction with diethylaluminium Et2AlCl and metallic magnesium in a molar ratio R-==:Et2AlCl:Mg=10:(2025):(1014) in the presence of a catalyst of titanzincoated in the amount of 2-6 mol. % towards alkylamino in the environment of THF at room temperature and normal pressure for 8-12 hours the New compounds 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 synthesis. 1 PL.

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The invention relates to methods for new alyuminiiorganicheskikh compounds (AOC), particularly to a method for producing 1,2-bis(ditylum)-1-methylene-2-alkylamino (1) and 1,4-bis(ditylum)-1,4-dialkylanilines (2) of the General formula (1) and (2):

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R=n-C6H13n the coefficients of catalytic systems in the processes of oligomerization and polymerization of olefin and diene hydrocarbons, as well as in thin organic and ORGANOMETALLIC synthesis.

The known method ([1] , L. I. the Zakharkin, L. L. Savin. WPI. An SSSR, Ser. chem. , 1967, S. 78-84) obtain dialuminium compounds, in particular 1,4-bis(Diisobutylene)butane and 1,4-bis(Diisobutylene)-2-methylbutane hydroalumination of butadiene or isoprene with diisobutylaluminium (i-Bu2AlH) in an autoclave at a temperature of 80-85oWith over 13 hours scheme

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The disadvantages of this method.

1. Hydroalumination conjugated 1,3-dienes accompanied by the formation of seal products, in addition, the conversion of 1,3-dienes does not exceed 50%.

2. The known method does not allow to obtain 1,2-bis(ditylum)-1-methylene-2-alkylidene (1) and 1,4-bis(ditylum)-1,4-dialkylaminoalkyl (2).

The known method (G. Dozzi, S. Cucinella, A. Mazzei. J. Were Obtained. Chem., 164(1979) p. 1-10) obtain dialuminium compounds, in particular 1,4-bis(dialume)-2-methylbutane hydroalumination of isoprene using an amine complex of aluminum hydride (l3N(CH3)3in the presence of catalyst titanzincoated (Cp2TiCl2) at a temperature of 80ofor 1 hour. Hydrolysis obtained Deluminator connection leads to isopentane with vyhne AOC (1) and (2).

Thus, in the literature there are no data on the joint to obtain 1,2-bis(ditylum)-1-methylene-2-alkylamino (1) and 1,4-bis(ditylum)-1,4-dialkylanilines (2).

We propose a new method for simultaneous obtaining 1,2-bis(ditylum)-1-methylene-2-alkylamino (1) and 1,4-bis(ditylum)-1,4-dialkylanilines (2).

The essence of the method lies in the interaction alkylamino General formula R-==, where R=n-C6H13n-C8H17n-C9H19with diethylaluminium (Et2AlCl) and metallic magnesium (powder), taken in a molar ratio R-==: Et2AlCl: Mg= 10:(2025):(1014), mostly 10:22:12, in the presence of a catalyst of titanzincoated (Cp2TiC12) in an amount of 2 to 6 mol.% in relation to alkylamino, preferably 4 mol.% in an argon atmosphere at room temperature (~ 22oC) and normal pressure in tetrahydrofuran (THF). The reaction time is 8-12 hours, preferably 10 hours. The total yield of 1,2-bis(ditylum)-1-methylene-2-alkylamino (1) and 1,4-bis(ditylum)-1,4-dialkylanilines (2) is 93%, the ratio(1):(2)~1:1.

The reaction proceeds according to the scheme

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R=n-C6H13n-C8H17the h9H19< / BR>
1,2-bis(ditylum)-1-IU the l and titanium catalyst Cf2iCl2. In the presence of other aluminum compounds, such as Bu2iAlCl, VI3iA1, Bu2iAlH, 1t3, EtAlC12or other catalyst (for example, Zr(OBu)n, Zr(acac)4Pd(acac)2, Ni(ASAS)2, NiCl2, FeC13target products (1) and (2) 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 the release of AOC (1) and (2) that is connected, probably, with a reduction of catalytically active sites in the reaction mass. The synthesis was carried out at a temperature of ~20oC. At higher temperatures, for example 50oSince, there is no significant increase in the yield of the target products. At a lower temperature, for example 0oWith reduced reaction rate.

Changing the ratio of initial reagents in the direction of increasing the content of Et2AlCl or Mg in relation to the original alkylamino does not lead to a significant increase in the yield of target products (1) and (2).

Significant differences of the proposed method.

In the known method are used amine kakaet in the presence of metallic Mg, alkylarene, and as alyuminiiorganicheskikh connection is Et2A1Cl.

The proposed method, in contrast to the known, allows to obtain 1,2-bis(ditylum)-1-methylene-2-alkylidene (1) and 1,4-bis(ditylum)-1,4-dialkylaminoalkyl (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 was placed 10 ml of THF, 10 mmol of n-octylamine, 12 mmol Mg (powder) at a temperature of ~0oWith 0.4 mmole Cf2TiCl2and 22 mmole Et2AlCl, stirred for 10 hours at ~20oC.

Get 1,2-bis(ditylum)-1-methylene-2-(n-octyl)ethane (1) and 1,4-bis(ditylum)-1,4-dioctyladipate (2) with a total yield of 84% and a ratio of(1): (2)~ 1: 1. Communities the yield of target products was determined by the products of hydrolysis. During the hydrolysis of unsaturated AOC 1,2-bis(ditylum)-1-methylene-2-(n-octyl)ethane (1) and 1,4-bis(ditylum)-1,4-dioctyladipate (2) of form n-undec-1-ene (3) and n-docosa-9,13-diene (4), identified by comparison with known samples. When lateralize AOC (1) and (2) obtained respectively 2,3-digitronic-1-ene (5) and 10,13-digitaladams-9,13-diene (6), identified with the help of I IS I , JC-D=19.0 Hz), 29.62 t (4), 29.42 t (5), 29.54 t (6), 29.20 t (7), 29.20 t (8), 32.09 t (9), 22.87 t (10), 14.16 (WITH11). M+156.

An NMR spectrum13With (, m D.): 10,13-digitaladams-9,13-diene (6): 14.05 (WITH1), 22.62 t (2), 31.96 t (3), 29.20 t (4), 29.20 t (5), 29.54 t (6), 29.78 t (7), 27.44 t (8), 130.25 (WITH9), 128.83 (WITH10I , JC-D=23.0 Hz), 27.44 t (11). M+308.

Other examples of the method shown in the table.

The reaction was carried out at room temperature (~20oC) in THF. The ratio of products (1) and (2) was in all experiments ~1:1.

The process of co-producing 1,2-bis(ditylum)-1-methylene-2-alkylamino formula (1) and 1,4-bis(ditylum)-1,4-dialkylanilines formula (2)

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where R= n-C6H13the h8H17the h9H19,

characterized in that alkylarene formula R-= = , where R is as defined above, is subjected to the interaction with diethylaluminium Et2AlCl and metallic magnesium in a molar ratio R-= = : Et2AlCl: Mg= 10 : (2025) : (1014) in the presence of a catalyst of titanzincoated in the amount of 2-6 mol. % towards alkylamino environment THF is

 

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