Process for the preparation of symmetrical and unsymmetrical azines and mixtures thereof

Claim 2

The process for the preparation of symmetrical azines of the formulas ##EQU17## and unsymmetrical azines of the formulas ##EQU18##and mixtures of azines (I), (II) and (IV), and (I), (III) and (V), wherein R 1 , R 2 , R 3 and R 4 each is hydrogen, a straight-chain alkyl radical of from 1 to 12 carbon atoms, a branched-chain alkyl radical or a cycloalkyl radical of from 3 to 12 carbon atoms or a phenyl radical, the aforesaid radicals being unsubstituted or substituted with one or more halogen atoms or carbamyl, carboxylic, nitro, amino, nitroso, hydroxy, methoxy or sulphonic acid groups; and in which case R 1 and R 2 can be the same or different radicals, R 3 is a radical different from R 1 and R 2 , R 3 and R 4 are radicals different from each other, and each are different radicals from R 1 and R 2 ; or R 1 and R 2 , or R 1 and R 3 , or R 3 and R 4 of either or both the >C=N-- moieties together form an alkylene radical of from 3 to 11 carbon atoms, said alkylene radical being unsubstituted or substituted by one or more of the above atoms or groups, which comprises reacting a carbonyl compound of the formula ##EQU19##alone or together with a different carbonyl compound ##EQU20##or ##EQU21##wherein R 1 , R 2 , R 3 and R 4 each has the same meaning as defined above, with ammonia and hydrogen peroxide in the presence of cyanogen or a nitrile of the formula R.sup.5 (CN).sub.n (IX) wherein n is a integer of from 1 to 6 and R 5 is a saturated aliphatic or alicyclic radical of from 1 to 12 carbon atoms or a benzene or pyridine radical, the aforesaid radical being unsubstituted or substituted with one or more of the above atoms or groups.

Claim 3

A process for the preparation of azines which comprises reacting ammonia, hydrogen peroxide and a carbonyl compound selected from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeric aldehyde, pivalaldehyde, oenanthal, hexahydrobenzaldehyde, p-nitrobenzaldehyde, β-methoxypropionaldehyde, acetone, 2-butanone, 2-pentanone, 3-pentanone, methylisopropylketone, methylisobutylketone, methylcyclohexylketone, acetophenone, benzophenone, cyclobutanone, cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 4-methylcyclohexanone, 2,4-dimethylcyclohexanone, 3,3,5-trimethylcyclohexanone, cycloheptanone, cyclooctanone, cyclodecanone and cyclododecanone, and mixtures thereof, in the presence of cyanogen or a nitrile selected from acetonitrile, propionitrile, butyronitrile, isobutyronitrile, cyclohexylcarboxylic nitrile, benzonitrile, a toluenenitrile, paramethoxybenzonitrile, metachlorobenzonitrile, paranitrobenzonitrile, mono, di and tri chloroacetonitrile, glycolonitrile, ε-hydroxycapronitrile, cyanoacetic acid and its alkyl esters, β-cyanopropionic acid and its alkyl esters, β-cyanopyridine, nicotinic nitrile, isonicotonic nitrile, acrylonitrile, methacrylonitrile, crotonitrile, Δ-3-tetrahydrobenzonitrile, 3,4-epoxyhexahydrobenzonitrile, β,β'-dicyanoethylsulphide, -sulphoxide and -sulphone, malononitrile, succiononitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, α-methyleneglutaronitrile, a dihydromuconic nitrile, a phthalonitrile, iminodiacetonitrile, nitrilotriacetonitrile, ethylenediametetracetonitrile, β-hydroxypropionitrile, β,β'-oxydipropionitrile, β-aminopropionitrile, β,β'-iminodipropionitrile, nitrilotripropionitrile, β-alkoxypropionitriles and nitriles obtained by cyanoethylation with acrylonitrile or methylacrylonitrile of ethylene glycol, propylene glycol, glycerol, sorbitol, acetic acid, alkyl ε-hydroxycaproates, mono- and dimethylamine, and mono- and diethylamine.

Claim 4

A process for the preparation of azines which comprises reacting ammonia, hydrogen peroxide and a carbonyl compound selected from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeric aldehyde, pivalaldehyde, oenanthal, hexahydrobenzaldehyde, p-nitrobenzaldehyde, β-methoxypropionaldehyde, acetone, 2-butanone, 2-pentanone, 3-pentanone, methylisopropylketone, methylisobutylketone, methylcyclohexylketone, acetophenone, benzophenone, cyclobutanone, cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 4-methylcyclohexanone, 2,4-dimethylcyclohexanone, 3,3,5-trimethylcyclohexanone, cycloheptanone, cyclooctanone, cyclodecanone and cyclododecanone, and mixtures thereof, in the presence of cyanogen or a nitrile selected from acetonitrile, propionitrile, butyronitrile, isobutyronitrile, cyclohexylcarboxylic nitrile, benzonitrile, a toluenenitrile, paramethoxybenzonitrile, metachlorobenzonitrile, paranitrobenzonitrile, mono, di and tri chloroacetonitrile, glycolonitrile, ε-hydroxycapronitrile, cyanoacetic acid and its alkyl esters, β-cyanopropionic acid and its alkyl esters, β-cyanopyridine, nicotinic nitrile, isonicotonic nitrile, acrylonitrile, methacrylonitrile, crotonitrile, Δ-3-tetrahydrobenzonitrile, 3,4-epoxyhexahydrobenzonitrile, β,β'-dicyanoethylsulphide, -sulphoxide and -sulphone, malononitrile, succiononitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, α-methyleneglutaronitrile, a dihydromuconic nitrile, a phthalonitrile, iminodiacetonitrile, nitrilotriacetonitrile, ethylenediametetracetonitrile, β-hydroxypropionitrile, β,β'-oxydipropionitrile, β-aminopropionitrile, β,β'-iminodipropionitrile, nitrilotripropionitrile, β-alkoxypropionitriles and nitriles obtained by cyanoethylation with acrylonitrile or methylacrylonitrile of ethylene glycol, propylene glycol, glycerol, sorbitol, acetic acid, alkyl ε-hydroxycaproates, mono- and dimethylamine, and mono- and diethylamine.

Claim 5

The process of claim 1 wherein one aldehyde conforming to the formula of carbonyl compound (VI) is reacted.

Claim 6

The process of claim 2 wherein the aldehyde is formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valerylaldehyde, pivaldehyde, oenanthal, hexahydrobenzaldehyde, p-nitrobenzaldehyde, or β-methoxypropionaldehyde.

Claim 7

The process of claim 1 wherein one ketone conforming to the formula of carbonyl compound (VI) is reacted.

Claim 8

The process of claim 4 wherein the ketone is acetone, 2-butanone, 2-pentanone, 3-pentanone, methylisopropylketone, methylisobutylketone, methycyclohexylketone, acetophenone, benzophenone, cyclobutanone, cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 4-methylcyclohexanone, 2,4-dimethylcyclohexanone, 3,3,5-trimethylcyclohexanone, cycloheptanone, cyclooctanone, cyclodecanone or cyclododecanone.

Claim 9

The process of claim 1 wherein the carbonyl compound (VI) is reacted together with the different carbonyl compound (VII) or (VIII).

Claim 10

The process of claim 7 wherein both carbonyl compounds (VI) and (VII) or (VI) and (VIII) are aldehydes.

Claim 11

The process of claim 7 wherein both carbonyl compounds (VI) and (VII) or (VI) and (VIII) are ketones.

Claim 12

The process of claim 7 wherein the carbonyl compound (VI) is an aldehyde and the carbonyl compound (VII) or (VIII) is a ketone.

Claim 13

The process of claim 1 wherein the nitrile is obtained by cyanoethylation of active-hydrogen compounds with acrylonitrile or methacrylonitrile.

Claim 14

The process of claim 11 wherein the active-hydrogen compound is water, ammonia, an alkanol, polyol, carboxylic acid, hydroxyacid, hydroxyester, or primary or secondary alkylaminated compound.

Claim 15

The process of claim 1 wherein the nitrile is acetonitrile, propionitrile, butyronitrile, isobutyronitrile, cyclohexylcarboxylic nitrile, benzonitrile, ortho, meta or paratoluenenitrile, paramethoxybenzonitrile, metachlorobenzonitrile, paranitrobenzonitrile, mono, di and tri chloroacetonitrile, glycolonitrile, ε-hydroxycapronitrile, cyanoacetic acid and its alkyl esters, β-cyanopropionic acid and its alkyl esters, β-cyanopyridine, nicotinic nitrile, isonicotinic nitrile, acrylonitrile, methacrylonitrile, crotonitrile, Δ-3 tetrahydrobenzonitrile, 3,4-epoxyhexahydrobenzonitrile, β,β'-dicyanoethylsulphide, -sulphoxide or -sulphone, malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, a-methyleneglutaronitrile, dihydromuconic nitriles, phthalonitriles, iminodiacetonitrile, nitrilotriacetonitrile or ethylenediaminetetracetonitrile.

Claim 16

The process of claim 1 wherein the nitrile is added to the reaction medium.

Claim 17

The process of claim 1 wherein the nitrile is formed in situ within the reaction medium.

Claim 18

The process of claim 1 wherein from about 0.2 to about 5 moles of carbonyl compound and ammonia per mole of hydrogen peroxide are reacted.

Claim 19

The process of claim 16 wherein from about 1 to about 10 molar equivalents of nitrile per mole of hydrogen peroxide are present in the reaction mixture.

Claim 20

The process of claim 1 wherein a catalyst is added which catalyst is an ammonium salt or an alkaline metal salt of an aliphatic or aromatic carboxylic acid or arylsulphonic acid having less than 20 carbon atoms, the anion of which is a halogen atom or a sulphate, nitrate, phosphate, pyrophosphate, borate, carbonate, formate, acetate, propionate, butyrate, isobutyrate, hexanoate, octanoate, dodecanoate, stearate, oxalate, succinate, glutarate, adipate, benzoate, phthalate, methanesulphonate, ethanesulphonate, benzenesulphonate, or p-toluenesulphonate group.