SU732267A1 - Carborane-containing aliphatic nitriles as intermediate products in synthesis of carboranylpropionic acid - Google Patents

Description

The invention relates to new carborane-containing aliphatic nitriles having an ethylene group between the carbon atom of the carbor new core and the reactive nitrile group, specifically the carb-containing aliphatic nitrile of the general formula (I): RC-CCH sy, r eRn-n, cn „-C-cn2 ,, - cn2CH2CN, as an intermediate product in the synthesis of carboranyl propionic acid. Two types of aliphatic carborane-containing nitriles are known, in which the cyanogen group is associated with or directly with carboranic lromoyl through a methylene group. The reaction of lithiumcarborane with cyanogen chloride 1 or with cyanic acid phenyl ester 2 yields cyanocoranees of the general formula RC-CCN Cyanmethyl carborane derivatives and a method for their preparation are also known, based on the dehydration of carboranylacetic acid amide 3 or sodium carotene nitride with chloroacetonitrile 4 J. The preparation of carborane-containing nitriles is based on the use of or hardly accessible derivatives of carboran and other components - (for example, chloroacetonitrile or phenyl esters of cyano acid) or on the use of organometallic derivatives, which requires special equipment and technology. A known method for producing carboranyl propionic acid is that the corresponding acetylene carboxylic ester is reacted with a decarborane in the presence of an acetonitrile type catalyst at 50-110 ° C in a solution of toluene or xylene, followed by hydrolysis of the carborancarboxylic acid ester. The yield is 40-50% 5. However, this method of obtaining carboranyl propionic acid requires the use of hard-to-reach acetyl carboxylic esters and is not of a general nature. The object of the invention is carboxylated aliphatic nitriles as an intermediate in the synthesis of carboranyl propionic acid. Carboranylpropionic acid IS-CCH SNDSOON is known. The two-stage process with a total yield of more than 40-50%. The use of the proposed compounds as an intermediate in the synthesis of carboranyl propionic acids greatly simplifies the method of their preparation and increases the yield to 9.0-95%. The indicated properties of the compounds according to the invention are determined by the structure of general formula (I). Carjors n-containing aliphatic nitriles are white crystalline substances with a melting point of 135 ° C to 225 ° C. The structure of the obtained cyanoethylcarboranes was proved by IR spectroscopy, mass spectrometry and elemental analysis. In the IR spectra of cyanethyl carborons, there are characteristic stretching vibration bands for B – H and C – H bonds of the Carboric nucleus in the region of 2600–3050–3060 cm – J, respectively, and for the group in the region of 2260 cm. Carborane or its derivative of the general formula VyuNyu ch, e - n, -c ,, - s-si, - sn, sn2cm, si .... when the ratio of o-carboran: acryloniryl is 1 t 10 in a polar organic solvent (for example, tetrahydrofuran, dioxane, pyridine, acetonitrile, dimethylformamide) at 20-60 ° C in the presence of a basic type catalyst selected from a number such as sodium hydroxide and potassium pyridine, dimethyl aniline, Rodionov catalyst - (alcohol solution of ethoxy dimethyl phenyl ammonium), - triton B (40% solution of trimethyl benzyl ammonium hydroxide). . The yield of the target product 60-95%. The proposed carborane-containing aliphatic nitriles are prepared in a manner that consists in the ability of o-carboran and its monosubstituted to react in cyanethylation by adhering via C-H bond to the acrylonitrile in the presence of a catalyst, in an amount of from 1 to 5% by weight of the amount of acrylonitrile. introduced into the reaction. The best results were obtained when using Triton B as a catalyst (40% aqueous solution of trimethylbenzylammonium hydroxide). 0.5% hydroquinone can be added to prevent the polymerization of acrylonitrile. The following examples illustrate the process for the preparation of carborane-containing aliphatic nitriles., Example 1. Method for preparing 1, 2-di (cyanthyl) -o-carboran and 1-cyanoethyl-o-carboran. To 10 g (0.07 mol) of o-carboran in 30 ml of dioxane was added 0.5 ml of catalyst: Triton B (40% aqueous solution of trimethylbenzylammonium hydroxide) at 20 ° C, then 8.7 ml (0.14 mole) acrylonitrile. Stand the solution for 10 hours and pour it into 200 ml of water. The precipitated precipitate is filtered off, washed with water and exhausted in a desiccator over a vacuum or under vacuum. After separation on a column filled with silica gel (eluent: petroleum ether and then a mixture of petroleum flute ether and benzene), 4.1 g of 1-cyanoethyl-o-carboran (mp 138-139 ° C) and 6.9 g (40 %) 1,2-di (cyan ethyl) -o-carboran (mp 224-225 ° C). 1-cyanoethyl-o-carborane Molecular mass 197 (mass spectrometrically). Found,%: C 31.80; H 7.46; B 54.55; N 7.12. C Well Calculated,%: C 30.47; H 7.61; : B 54.82; N 7.11. Molecular weight-197. IR Spectrum: (C-H) 3060 cm,) (B-H) 2600 cm () 2260 CM-I 1,2-di (cyanoethyl) -o-carborane. MS mass 250 (mass spectrometrically). Found,%: .N 10.80. C6, Calculated,%: N, 11.20. Molecular weight 250. IR spectrum: (B – H) 2600 cm—, () 2260 Example 2. 1.-Cyanethyl-o-carbonoan and 1,2-di (cyanethyl) -o-carborane. Analogously to Example 1, from 10 g (0.07 mol) of o-carboran in 20 ml of tetrahydrofuran and 40.4 ml (5 times excess) of acrylonitrile, 3.4 g of 1-cyanoethyl-o-carboran and 10.35 g (60 %) 1,2-di (cyanoethyl) -o-carborane, identical to the products of example 1. Example 3. 1-Cyanethyl-o-carboran and 1,2-di (cyanoethyl) -o-carborane. Analogously to Example 1, from 5 g (0.035 mol) of o-carboran in 40 ml of pyridine and 8.7 ml of acrylonitrile, 0.7 g of 1-cyanoethyl-o-carboran and 3.6 g (45%) of 1,2-di ( cyanethyl) -o-carboran, identical to the products of example 1.

Example 4. 1-Tsiachetil-o-carboran and 1,2-di (cyanoethyl) -o-carborane,

A solution of 5 g (0.015 mol) of o-carboran in 20 ml of acetonitrile, 17.4 ml of acrylonitrile and 1 ml of 10% KOH solution in water is kept for 4 hours, poured into 100 ml of water and extracted with ether. Dried over MdZod. After distillation of the solvents and separation on the column, 0.7 g of 1-cyanoethyl-o-carboran and 6.4 g (75%) of 1,2-di (cyanoethyl) -o-carboran, identical to the products of example 1, are obtained

Example 5. 1-ID (anethyl-o-carboran and 1,2-di (cyanoethyl) -o-carborane.

Analogously to example 1 of 5 g (0.035 mol) of o-carboran 26.1 ml of acrylonitrile in 25 ml of dimethylformamide in the presence of a Rodionova catalyst (ethoxytrimethylphenylammonium alcohol solution) receive 1 g of 1-cyanoethyl-o-carboran and 4.8 g (60%) 1,2-di (cyanethyl) -o-carboran, identical to the products of example 1.

Example 6. 1-Methyl-2-cyanoethyl-o-carboran.

To 10 g (0.06 mol) of 1-methyl-o-carboran in 30 ml of acetonitrile is added with Triton B and 32.8 m of acrylonitrile are added. After 3 h, it is poured into 100 ml of water, the precipitated precipitate is filtered and dried in a desiccator over recrystallization is carried out from heptane-chloroform mixtures. 10.6 g (80%) of 1-methyl-2-cyanoethyl-o-carboran, m.p. 163-164 ° C

Molecular weight 211 (mass spectrometrically),

Found,%: C 33.91; H 8.07; B 50.88; N 6.71.

Sat N, Bfo N.

Calculated,%: C 34.12; H 8.06;

B5.18; N6.64.

Molecular weight 211. IR spectrum (B – H) 2000 cm, l) () 2260 cm

Example 7. 1-Methyl-2-cyanoethyl-o-carboran.

Analogously to Example 6, from 5 g (0.03 mol) of 1-methyl-o-carbor ana in 30 ml of tetrahydrofuran with a catalyst with 1 ml of IN solution of NaOH and 16.4 ml of acrylonitrile, 3.5 g (60%) of 1-methyl- 2-cyanethyl-o-carboran, identical to the product from example 6.

Example 8. 1-Methyl-2-cyanoethyl-o-carboran.

Analogously to example 6, out of 10 g (0.06 mol) of 1-methyl-o-carbrrane in 50 ml of dioxane with Rodinov catalyst (ethoxytrimethylphenylammonium solution) and 8.2 ml of acrylonitrile, 6.6 g (50%) of 1-methyl-2 are obtained - cyanoethyl-o-carboran, identical to the product of example b,

Example 9. 1-Isopropenyl-2-cyanoethyl-o-carboran.

Out of 10 g (0.05 mol) of isopropenyl-o-carboran in 25 ml of acetonitrile, add triton B at 2 ° C and add 10.7 ml of acrylonitrile. Poured into 100 ml of water, the precipitated precipitate is filtered and dried in a desiccator over PriOg. Recrystallization is carried out from a mixture of heptane-chloroform.

- Obtain 10.8 g (85%) of 1-isopropenyl 2-cyanoethyl-o-carboran with so pl. 114115C.

Molecular weight 237 (mass spectrometrically).

Found,%: C 40.57; H 7.76 B 45.44; N 5.92.

C t H.,.

Calculated,%: C 40.51; H 8.02

845.57; N 5.91.

5 molecular weight 237. IR spectrum:

- (B – H) 2600 cm) 1) () 2260 cm. Example 10. Similarly to the example.

9 and 5 g (0.03 mol) of isopropenyl-o-carboran in 30 ml of dioxane with dimethylalanine catalyst and 10.7 ml of acrylonitrile, 2.7 g (43%) of 1-isopropenyl-2-diethynyl-o-carboran, identical to the product, are obtained. in Example 9. Example. Similarly, for example, RU 9 out of 5 g (0.03 mol) of isopropenyl-o-carboran with a Rodiono catalyst. Ba and 8.7 ml of acrylonitrile, obtain 3.3 g (52%) of isopropenyl-2-cyanoethyl -o-carborane, identical to the product from example 9.

Example 2. -Phenyl-2-cyanoethyl-o-carboran.

From 0 g (0.045 mol) of 1-phenyl-o-carboran in 50 ml of acetonitrile, triton B is added at 20 ° C and 5 3.3 ml of acrylonitrile are introduced. Poured into water, the precipitated precipitate is filtered off and dried in a desiccator over fyOf. The recrystallization is carried out from a mixture of hexane-chloroform. Obtain 0 7.5 g (61%) -phenyl-2-cyanoethyl-o-carboran with so pl. 82-183 p.

Molecular weight 273 (mass spectrometrically).

Found,%: C 48.47; H 7.11;

B 39.42; N 5.08.

5 and f9 10

Calculated,%: C 48.35; H 6.96; B 39.56; N 5.13.

Molecular mass 273. IR spectrum: - (B – H) 2600 cm, - () 2270 cm ––. 0 EXAMPLE 13 1-Phenyl-2-cyanoethyl-o-carboran,

Analogously to example 12 of 5 g (0.023 mol) of 1-phenyl-o-carboran; in 40 ml of dimethylformamide with the Rodionov catalyst and 26.6 ml of acrylonitrile, 2.7 g (44%) -phenyl-2-cyanoethyl-o-carboran, identical to the product from example 12, is obtained.

Example 14. 1-Phenyl-2-cyan Q ethyl-o-carboran.

As in Example 12, out of 5 g (0.023 mol) -phenyl-o-carboran in 30 ml of tetrahydrofuran and 5 g of pyridine were added 5.3 ml of acrylonitrile. 65 Get 2.1 g (35%) -phenyl-2-cyanoethyl-o-carborane, identical to the product from example 12.

Example 15, Preparation of dicyanethyl bis-carboranyl benzene.

As in Example 1, 0.5 ml of Triton B catalyst and 9 ml of acrylonitrile are added to 5 g (0.014 mol) of bis-carboranyl benzene in 30 ml of tetrahydrofuran. After dividing on a column filled with silica gel (eluent: chloroform), 3.3 g (50%) of Dicyanethyl-bis-carboranoylbenzene (T..PL. 201-202 0) are obtained.

Molecular weight 468 (mass spectrometrically).

Found,%: C 40.74; H 6.84; In 46.26; N 6.00.

C-16

Calcd.,%: C 41.03; H 6.84; At 46.15; N 5, .98.

Molecular mass 468.IR spectrum x (B – H) 2600 cm-, (CsN) 2260 cm

Claims (1)

Claims of CarbourN containing aliphatic nitriles of general formula (D): UC-CCW, J  . where R-U.-CH c tu rC H rCHjCM CNC .and as an intermediate product in the synthesis of carboranylpropionic acid; Sources of information taken into account in the examination 1, Zakharkin L, I., Lvov L.I., Synthesis of 1-phenyl-2-cyanophenone and phenylbaren aldehyde. JOH, 1966, No. 36, p. 761, 2, USSR Copyright Certificate No. 476271, cl. C 07 F 5/02, C 07 D 107/02, 1975. 3, Zakharkin L.I., Grebennikov A, B, Lvov I.A. Synthesis of some nitrogen-containing derivatives of the baren. USSR Academy of Sciences, a series of Chemistry, 1970, p.106, 4, USSR Author's Certificate No. 465089, cl. C 07 F 5/02, C 07 D 107/02, 1974. 55. L.I. Zakharkin, Chapovsky Yu, A., Bratsev V, A, Stanko VI Synthesis of carboxylic acids of the barn series. JOH, 1966, 36, s, 878,