DE959094C - Process for the production of isonitrons - Google Patents

Description

ISSUED FEBRUARY 28, 1957

F 10269 IVb 112 p

Addition to patent 952

The subject of patent 952 895 is em procedure for the production of isonitrons, which is ordered therein, Schiff bases, as they are e.g. B. in known Way by condensation of oxo compounds with primary amines are available with Per compounds to handle, advantageously at temperatures below 50 °, in particular at temperatures between -10 and + 20 °, as well as in the presence of inert solvents.

The present invention is a further development of the method of the main patent. It has been found that this simplifies the process for producing isonitrons lets that one oxo compound with a primary amine, optionally with concomitant use an inert solvent, mixes and adds a per compound to this mixture.

An isolation of the Schiff's base, which is also presumably an intermediate product in the present process forms is omitted here. The present procedure is therefore particularly special in those cases advantageous, in which it is difficult to prepare the Schiff base pure or in good yield.

example 1

To 198 g (2 mol) of cyclohexylamine, the 220 g of anhydrous Soda are added, 196 g (2 mol) of cyclohexanone are run in with stirring. If that The mixture that has become warm has cooled to room temperature again, it is diluted with 1.5 liters of ether and leaves with stirring 200 g of 76% peracetic acid (2 mol) drop in, keeping an internal temperature of -10 to 0 ° by cooling with a cold mixture will. After stirring for 2 hours at room temperature

the peracetic acid is used up. Sufficient water is added to dissolve the suspended salt, mainly sodium acetate, and the ethereal layer is dried over anhydrous potash. After the ether has evaporated, the residue is distilled in an oil pump vacuum. After a short lead, the isonitron goes over at 90 to 95 ⁰ / 0.3 mm. Yield: 320 g = 82% of theory.

Example 2

To a solution of 60 g (1 mol) of ethylenediamine in 600 ecm of ether, to which 140 g of anhydrous potash have been added, 196 g (2 mol) of cyclohexanone are added dropwise while stirring and cooling with a cold mixture. After standing for 2 hours at room temperature, 200 g of 76% peracetic acid are added dropwise with stirring, the temperature being kept at -10 to 0 ° by cooling with a cold mixture. After stirring for a further 3 hours at room temperature, the resulting crystal slurry is suctioned off and washed thoroughly with water. After drying, 60 g of diisonitrone with a melting point of 105 ° to 106 ° are obtained. From the ethereal layer by cooling to - 20 ⁰ nor 36 g of Diisonitrons of melting point 103 to 105 ⁰ obtained which after recrystallization from ether or petroleum ether is 106 to 107 ^0th Yield: 96 g = 39% of theory.

C ₁₄ H ₂₄ O ₂ N ₂ (252.3)

Calculated: C 66.63%, Ή 9.59%, N ii, io%, active oxygen 12.68%;

found: C 66.39%, H 9> ⁶ 5% " ^N ", 10%, 66.20% 9> ⁶ 9%>".""/ ο,

active oxygen 12.30%.

Example 3

A solution of 106 g (1 mol) of benzaldehyde in 100 ecm of ether is allowed to drip into a solution of 59 g of isopropylamine in 200 ecm of ether with stirring and cooling in a cold mixture. After ^χ / ₂ hours 140 g of 74% strength perbutyric (1 mol) in the same manner dropwise. After stirring for a further 20 hours at room temperature, the ethereal solution is washed neutral with 30% potash solution and dried over potash. The isonitron distills after evaporation of the ether at 64 to 68 ° / 0.9 mm. Yield: 115 g = 71% of theory.

C ₁₀ H ₁₃ ON (163.2)

Calculated: C 73.59%, H 8.03%, N 8.58%, active oxygen 9.80%;

found: C 73.91%. H 7.95%, N 8.44%, 73.95%, 8.10%, 8.62%, active oxygen 9.40%.

Example 4

288 g (4 mol) of butyraldehyde in 300 ecm of ether are allowed with stirring and cooling in a cold mixture a solution of 236 g (4 mol) of isopropylamine in

Drip in 800 ecm of ether at an internal temperature of -20 to -10 °. After 1 hour, 400 g of 76% strength peracetic acid (4 mol) are added dropwise in the same way. After standing for 3 hours at room temperature, the ether solution is neutralized with 30% potash solution and dried over potash. The ether is distilled off at normal pressure and the isonitron in a water jet vacuum. 366 g of a pleasantly smelling liquid with a boiling point of 43 to 46 ^° / 13 mm = 71% of theory are obtained.

C ₇ H ₁₅ ON (129.2)

Calculated: C 65.07%, H 11.70%, N 10.84%, active oxygen 12.38%;

found: C 65.30%, H 11.89%, N 10.34%, 65.55%, 11.91%, 10.35%, active oxygen 12.00%.

Example 5

To a solution of 148 g (2.5 mol) of isopropylamine in 1 liter of anhydrous acetone, to which 250 g of anhydrous soda has been added, 225 g of 84% peracetic acid (2.5 mol) are added with stirring and cooling with a cold mixture at -20 to Drip in 0 ° internal temperature. After stirring for a further 2 hours at room temperature, the sodium acetate formed is filtered off with suction and washed out with acetone. The solution is allowed to dry over potash, the excess acetone is distilled off and the isonitron is then driven over in a weak vacuum. One Avail- as 170 g of a pleasant-smelling liquid of boiling point 50 to 52 ^0/63 mm = 59% of theory.

C ₆ H ₁₈ ON (115.2)

Calculated: C 62.57%, H 11.38%, N 12.16%, active oxygen 13.89%;

found: C 62.27%, H 11.11%, N 12.07%, 62.31%, 11.41%, I2, oq%, active oxygen 13.50%.

Example 6

■ To a mixture of 19.6 g {0.2 mol) of cyclohexanone, 19.8 g (0.2 mol) of cyclohexylamine and 12 g of anhydrous sodium carbonate is allowed under stirring and cooling with ice-water at 10 to 20 ⁰ internal temperature 480 g of a Add dropwise 4.8% solution of peroxymonosulphuric acid (Caro's acid) (0.2 mol). After stirring for a further hour at room temperature, the non-aqueous layer is taken up with ether, the ethereal solution is dried over potash, the solvent is removed and the residue is distilled in vacuo. At 98 to 100 ° / 1 mm, Ii g of the corresponding isonitron pass over. Yield: 28% of theory.

Example 7

A mixture of 149 g (1.5 moles) of cyclohexylamine, 174 g (3 mol) acetone, 250 ecm ether and 135 g anhydrous Soda is mixed with stirring and cooling in a cold mixture at -10 to 0 ° internal temperature with 207 g (1.5 mol) benzoperic acid added to 21 ether. To

After stirring for a further 24 hours at room temperature, enough water is added to the mixture so that all the salts are dissolved. The layers are then separated and the aqueous layer is shaken out again with ether. The combined ether solutions are worked up by distillation after drying over potash. Obtained at 70 to 74 ^0/8 mm 198 g of the corresponding Isonitrons. Yield: 82% of theory.

Example 8

57 g of 30% strength hydrogen peroxide ( ¹ Z ₂ mol) are added dropwise to a mixture of 49 g ( ¹ Z ₂ mol) of cyclohexanone and 49.5 g ( ¹ I ₂ mol) of cyclohexylamine, with stirring, whereupon the temperature rises to about 60 ° increases. After stirring for a further 24 hours, during which the mixture cools to room temperature, the reaction product is shaken out with ether, the ether solution is dried over potash and worked up by distillation. At 93 to 97 ° / 0.6 mm, the same isonitrone distilled over as in Example 1. Yield: 31 g = 32 ° / ₀ of theory.

Claims (1)

PATENT CLAIM: Further development of the process for the production of isonitrons according to patent 952 895, characterized in that an oxo compound with a primary amine, optionally using an inert solvent, .mixes and this mixture a per compound admits. © 609550/461 7.56 (609 809 2.57)