PL106373B1 - METHOD OF MAKING ALPHA-NITRONITRILES - Google Patents

Description

Patent description was published: August 15, 1980 106373 Int. Cl.1- C07C 121/00 Creators of the invention: Hanna Piotrowska, Zygmunt Matacz Authorized by the patent: Warsaw University of Technology, Warsaw (Poland) The method of producing "-nitronitriles The subject of invention is the method of manufacture The compounds of cc-nitronitriles of the general formula are shown in in the drawing in which R1 and R2 are each separated no, they represent alkyl groups with 1-6 carbon atoms, the same or different, or R1 and R2 together with the atom the carbon meme to which the creations are attached a five-, six- or seven-membered ali-ring fatal, 1,3-dioxane ring or ring N-allkylpiperidine while A is gnupe. cyan (CN).

Until now, α-fndtiromditriles have usually been produced by reactions of azo compounds of formula R1R2 (CN) C - N = N - CfGNDRiR2 with dioxide nitrogen or by exchange of bromine with the ni-group it is dissolved in the appropriate α-hromonitrile. These ways are bothersome due to the fact that they are output azo compounds and oHbromonitriles require many staged synthesis.

There are no disadvantages to the above-mentioned method the formation of a-vitronium and acrylic according to the invention.

The method according to the invention consists in using salt a nitro compound of the general formula shown in the drawing in which R1 and R2 are given above and A is hydrogen, submit the reaction with alkali metal cyanide and that an oxidizing agent such as iron cyanide potassium or sodium persulfate, potassium or amomium, in the aquatic environment.

The method according to the invention is characterized by simplicity of implementation, and the substrates used are years old wo available.

The subject matter of the invention is closer to the period lions in the embodiments.

Example I. In a solution of 4.4 g (0.11 mol) sodium hydroxide in 50 ml of water dissolve 8.9 (0.1 mol) 2-nitropropane and 10 g (0.2 mol) cyanide sodium. 50 ml of eiteru is added and at temperature At 0-5 ° C, a solution of 66 g (0.2 mol) of iron is added dropwise potassium jug in 200 ml of water. Everything is mixed up within 0.5 hours, separates the organic layer, and the aqueous layer was extracted with 2 X 50 mL of ether. Mon. the combined ether extracts are washed with water and dried more magnesium persulfate. The ether distils , come under reduced pressure, and the remainder subjected to vacuum distillation, obtaining 2.4 g (21%) 2C cyano-2-iniitropane at bp 72-74 ° C / 12 mm Hg, melting point temperature of 35-35.5 ° C.

Elemental analysis: for the pattern C ^ H. fP2N2 calcd: 42.1% C; 5.3% H; 24.6% N; found: 42.4% C; 5.4% H; 24.4% N.

Example II. In a solution of 4.4 g (0.11 mol) sodium hydroxide dissolves 8.9 (0.1 mol) 2Tniitropane and 10 g (0.2 mol) of sodium cyanide. Do¬ 50 ml of ether are added and the temperature is 0-5 ° C a solution of 0.1 mol of sodium persulfate is added dropwise. Ca¬ it is processed, as in example I, obtained Jac 2.6 g (23%) of 2-cyano-2H-nitroproipane at a temperature 106 373 106 373 boiling point 72-74 ° C / 12 mm Hg and temperature mp 35-36 ° C.

Example III. By following example I, with 16.1 g (0.1 m) of 2,2-diMy 1 Lo - 5-tarodiofcsa and the same amount of other substrates there was obtained 7 ', 5 g of 2,2-diethyl-5,5-dinitrodiioxa- nu ^ 1.3, which is 45% of the theoretical amount.

Example IV. By following example I, with 6.5 g (0.05 m) of nitrocylklohexane, 4.9 g (0.1 m) NaCN, 2.2 g (0.55 m) NaOH and 33.1 g (0.1 m) KiFe (CN) 6 obtained 5.2 g of 1-cyanonitrocyclohek- sainu, which is 60% of theoretical yield.

Example V. By following the example day IV, with 9.3 g of N4N4-utyl-4-nitropiperidine and other substra mano 4.75 g N-in4) iUityl-4,4-dwU) niitrolpipeyrifidine, which is 45% of theoretical value. and

Claims (1)

1. Claim: A process for the preparation of α-nitro-they, triM, having the general formula as shown in the figure, wherein R1 and R2, each separately, are alkyl groups with 1 to 6 carbon atoms, the same or different, or R1 and R2 together with the carbon atom to which they are attached, they form a five-six- or seven-membered aliphatic ring, a 1,3-diaxane ring or an N-alkylpiperidine ring, while A is a cyano (CN) group, characterized in that the salt of the nitro compound The general formula is shown in the figure, in which R1 and R2 have the meaning given above, and the hydrogen atom is released, reacted with alkali metal cyanide - and with an oxidizing agent such as potassium iron cyanide or sodium persulfate, potassium ltUb ammonium in an aqueous environment. R1 NO2 C / \ R2 A READING ROOM of the PZGraf Patent Office. Koszalin D-1702 95 copies A-4 Price PLN 45