SU472127A1 - The method of obtaining iminoketon - Google Patents

Description

It refers to the region of the receptacle of jfl-imino-hetomes.

The compounds obtained are not described in the international survey and find the quality of the yugut; nalimerization atalpzator, plasticizers and antioxidants for rubber, as well as for pharmaceutical purposes.

There are known methods for preparing compound with unsubstituted nmino-group C NH, interfering with organometallic compounds with n trilo.m.

A proposed p-imino preparation method; ciOHOD consists in: m, that halidketones are reacted with zinc and nitrile; .i; i aliphatic or a1) somatic lipi acids are heated in an ethnocyte medium, followed by hydrolysis of the resulting zinc salt and extraction of the desired product by known methods.

The proposed method is simple to use, uses available raw materials and provides an opportunity to obtain the desired products with a good yield.

The obtained compounds are white crystalline substances that are readily soluble in benzene, sr1Irta, chloroform, (lueTOHe. The structure of p-iminoketones is proven by electrical nitrogen analysis, IR spectroscopy and hydrolysis of 5-7% with; acid by acid in p PC spectra

synthesized r-nkinoketoiov have nnte 1sivnaya nablozhen | 1e carbonyl group

area x 1680-1690 cm

.705-

and

valsit oscillations

1725 cm-1 C

Nro are in the 1520-x-communication areas 1530 cm- and 1620-1650 cm-. In the area of 3280-3340 cm, there are observed kohbani

 . „, LN-svzp in vnde ishrokoi strip that

roBOpirr about the participation of hydrogen in the formation of hydrogen 1st bond.

General reaction conditions.

In a flask equipped with a thermometer, a stirrer and a channel funnel, as well as a reverse hopper, zinc is placed in a wide variety of chips and coated with water-free ethyl acetate. In the process of expanding iPSI and ointment, a mixture of a-bromotopa and nitrile in a ratio of 1.5: 1 is added. The reaction proceeds epergiche. After stirring up the dropping of the mixture, the contents of the flask are heated for another 6-8 hours, then cooled and decomposed with 10% acetic acid. The ethyl acetate layer is separated and washed with a saturated solution of HNSO3, then with water and dried with anhydrous XajSOj. After distilling off the solvent, the products are dispersed from the ether.

Synthesis of 2-amio-3,3-di1 1-methyl-4-phenyl-1-buchaion.

0.15 g of zinc atom is introduced into a three-necked flask and the ethyl acetate m is closed. While stirring, the mixture consisting of a-bromisobutyropheonia (0.15 g mol and acetonitrile (0.1 g-mol)) is added dropwise. After the completion of the dropping, the mixture is heated for 6 hours, then cooled and decomposed by 10% acetic acid. acid.The organic layer is washed with water, a solution of Xa2PSO3, again with water and dried with calcined Na2SO4. After the solvent is distilled off, the reaction product is recrystallized from petroleum ether (yield 66%, t. Silt. 78-79 ° C.

Hydrolysis with 5% hydrochloric acid.

In a flask equipped with a reflux condenser, 4 g of 2-imino-3,3-dimethyl-4phenyl-4-butanone, 40 ml of 5% hydrochloric acid, 20 ml of ethanol are placed. The contents of the flask are heated in a water bath for 48 hours. The organic layer is extracted with ether, washed with water and dried with NaaSO 4. The ether is distilled off, and the p-diketone CeHsCOC (CH3) 2C0CH3 is distilled in vacuo.

t kip. 98-100 ° C / 3 mm. Hg Art.

Found,%: C 72.13; H 11.85.

C 2li24O2

Calculated,%: C 72.02; H 12.0.

Synthesis of 1-imino-2,2-dimethyl-1,3-diphenyl-3-propanoia.

A zinc (0.15 g-ato.m) in the form of fine chips and ethyl acetate are placed in a stellodon flask equipped with a stirrer, a reflux condenser and a dropping funnel. A mixture of cc-bromoisobutyrophenone (0.15 g-mol) and benzopitrile (0.1 g-mol) is added via canals.

The mixture is heated for 6 hours, then cooled and decomposed with 10% acetic acid.

ACID. At the same time, a precipitate falls out, which is filtered off and recrystallized from toluene.

Yield 79%; m.p. 164-165 ° C.

Synthesis of 1-imino-2,2-dimethyl-1-phenyl-3-butapon.

In the flask, supplied with a stirrer, a reflux condenser, and a dropping voropkon, the zinc in the form of fine chips and ethyl acetate. A mixture of a-bromoisoyl methyl methyl ketone (0.15 g-mol) and benzonitrile (0.1 g-mol) is added over the canal. Then, the reaction mixture of Mass 1 is aggravated for 7 h, cooled and decomposed with 10% acetic acid. The organic layer is separated from the aqueous, washed with NaHCOs, water and dried with Na2SO4. Ethyl acetate is heated, the product is recrystallized.

Yield 54%; m.p. 77-78 ° C.

Hydrolysis of 57 ° -sun with hydrochloric acid gives β-diketone.

SPZSOS (SPZ) 2SOSbP5

T. Kip. 84-85 ° C / 3 mm Hg. Art.

Found,%: C 72.25; H 11.96.

C | 2H24O2

Calculated,%; C, 72.0; P 12.0. Synthesized in a similar manner: (3 aminoketones are presented in the table.

Subject invention

A method for producing p-iminoketones, characterized in that cz-haloketones are reacted with cyac and aliphatic or aromatic acid nitriles when heated in ethyl acetate with subsequent. hydrolysis of the zinc salt formed at the n and m and the release of the target product by known methods.