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US3984451A
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Method for preparing hydrazo-bis-acetonitriles
Assignee: Produits Chimiques Ugine Kuhlmann
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Filing: 1975-05-21
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Granted: 1976-10-05
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Expires: 1995-05-21
Abstract
Abstract This invention relates to a method for preparing hydrazo-bis-acetonitriles of the general formula: ##EQU1## wherein R 1 and R 2 have the same meaning hereinafter given, which comprises: A. i. reacting a carbonyl compound of the general formula: ##EQU2## wherein R 1 and R 2 have the same meaning hereinafter given, with ammonia and hydrogen peroxide in the presence of cyanogen or a nitrile of the formula R.sub.3 (CN).sub.n (III) wherein n is an integer from 1 to 6 and R 3 is an unsubstituted or substituted saturated aliphatic, acyclic or cyclic radical of from 1 to 12 carbon atoms or a benzenyl or pyridinyl radical, to form a symmetrical azine of the formula ##EQU3## ii. oxidizing a secondary alcohol of ##EQU4## wherein R 1 and R 2 have the same meaning hereinafter given, at a temperature and pressure which is sufficient to maintain the alcohol in the liquid phase and result in a liquid phase mixture containing the peroxidic products of the auto-oxidation of the alcohol [v] and reacting auto-oxidation products with ammonia and cyanogen or the nitrile R 3 (CN) n of formula (III) to form the symmetrical azine of formula (IV) b. eliminating unreacted ammonia from the medium resulting from (a); C. reacting the azine of formula (IV) contained in the ammonia-free medium resulting from (b) with at least two moles of hydrocyanic acid per mole of azine; and D. recovering the hydrazo-bis-acetonitrile of formula (I).
Inventors
- 👤 Francis Weiss
- 👤 Jean-Pierre Schirmann
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-06 11:51
CPC Classifications
C; C07; C07C; C07C251/00; C07C251/72; C07C251/88; C07C255/00
Claims Analysis
Total Claims: 27
Claim 1
Independent Claim
390 words
A method for preparing hydrazo-bis-acetonitriles of the general formula ##EQU5## wherein R 1 is hydrogen and R 2 or R 1 and R 2 each is a straight chain alkyl radical of from 1 to 12 carbon atoms, a branched chain alkyl radical of from 3 to 12 carbon atoms, a cycloalkyl radical of from 3 to 12 carbon atoms or a phenyl radical or R 1 and R 2 together form a straight or branched chain alkylene radical of from 4 to 12 carbon atoms being unsubstituted or substituted with one or more chloro, bromo or fluoro atoms or nitro or methoxy groups, which consists essentially of: a. reacting in a single reaction medium (i) a carbonyl compound of the general formula ##EQU6## wherein R 1 is hydrogen and R 2 or R 1 and R 2 each is a straight chain alkyl radical of from 1 to 12 carbon atoms, a branched chain alkyl radical of from 3 to 12 carbon atoms, a cycloalkyl radical of from 3 to 12 carbon atoms or a phenyl radical or R 1 and R 2 together form a straight or branched chain alkylene radical of from 4 to 12 carbon atoms being unsubstituted or substituted with one or more chloro, bromo or fluoro atoms or nitro or methoxy groups, (ii) ammonia, (iii) hydrogen peroxide, and (iv) cyanogen or a nitrile of the formula R.sub.3 (CN).sub.n (III) wherein n is an integer from 1 to 6 and R 3 is a straight chain alkyl radical of from 1 to 12 carbon atoms, a branched chain alkyl radical of from 3 to 12 carbon atoms, a cycloalkyl radical of from 3 to 12 carbon atoms or a benzene or pyridine radical, said radical being unsubstituted or substituted with one or more halogen atoms or carbamyl, carboxylic, nitro, hydroxy, epoxy, or sulfonic acid groups, to form a symmetrical azine of the formula ##EQU7## b. eliminating unreacted ammonia from the medium resulting from (a) by evaporating unreacted ammonia at atmospheric or reduced pressure, or by neutralizing the unreacted ammonia with at least a stoichiometric amount of hydrochloric acid, phosphoric acid, sulfuric acid, formic acid or acetic acid; c. reacting the ammonia-free medium resulting from (b) with at least two moles of hydrocyanic acid per mole of azine; and d. recovering the hydrazo-bis-acetonitrile of Formula (I).
Claim 2
Independent Claim
390 words
A method for preparing hydrazo-bis-acetonitriles of the general formula ##EQU5## wherein R 1 is hydrogen and R 2 or R 1 and R 2 each is a straight chain alkyl radical of from 1 to 12 carbon atoms, a branched chain alkyl radical of from 3 to 12 carbon atoms, a cycloalkyl radical of from 3 to 12 carbon atoms or a phenyl radical or R 1 and R 2 together form a straight or branched chain alkylene radical of from 4 to 12 carbon atoms being unsubstituted or substituted with one or more chloro, bromo or fluoro atoms or nitro or methoxy groups, which consists essentially of: a. reacting in a single reaction medium (i) a carbonyl compound of the general formula ##EQU6## wherein R 1 is hydrogen and R 2 or R 1 and R 2 each is a straight chain alkyl radical of from 1 to 12 carbon atoms, a branched chain alkyl radical of from 3 to 12 carbon atoms, a cycloalkyl radical of from 3 to 12 carbon atoms or a phenyl radical or R 1 and R 2 together form a straight or branched chain alkylene radical of from 4 to 12 carbon atoms being unsubstituted or substituted with one or more chloro, bromo or fluoro atoms or nitro or methoxy groups, (ii) ammonia, (iii) hydrogen peroxide, and (iv) cyanogen or a nitrile of the formula R.sub.3 (CN).sub.n (III) wherein n is an integer from 1 to 6 and R 3 is a straight chain alkyl radical of from 1 to 12 carbon atoms, a branched chain alkyl radical of from 3 to 12 carbon atoms, a cycloalkyl radical of from 3 to 12 carbon atoms or a benzene or pyridine radical, said radical being unsubstituted or substituted with one or more halogen atoms or carbamyl, carboxylic, nitro, hydroxy, epoxy, or sulfonic acid groups, to form a symmetrical azine of the formula ##EQU7## b. eliminating unreacted ammonia from the medium resulting from (a) by evaporating unreacted ammonia at atmospheric or reduced pressure, or by neutralizing the unreacted ammonia with at least a stoichiometric amount of hydrochloric acid, phosphoric acid, sulfuric acid, formic acid or acetic acid; c. reacting the ammonia-free medium resulting from (b) with at least two moles of hydrocyanic acid per mole of azine; and d. recovering the hydrazo-bis-acetonitrile of Formula (I).
Claim 3
Dependent Claim
22 words
The method of claim 1 wherein the carbonyl compound (II) is acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valerylaldehyde, pivalaldehyde, oenanthal, hexahydrobenzaldehyde, p-nitrobenzaldehyde or β-methoxy-propionaldehyde.
Claim 4
Dependent Claim
32 words
The method of claim 1 wherein the carbonyl compound (II) is 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 or cyclododecanone.
Claim 5
Dependent Claim
17 words
The method of claim 1 wherein the nitrile is added to the reaction medium of step (a).
Claim 6
Dependent Claim
25 words
The method 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 7
Dependent Claim
27 words
The method of claim 1 wherein from about 1 to about 10 molar equivalents of nitrile per mole of hydrogen peroxide are present in the reaction medium.
Claim 8
Dependent Claim
72 words
The method of claim 1 wherein from about 0.01 to 2% by weight of an ammonium or alkaline metal salt of a hydracid, mineral oxyacid, aromatic or aliphatic carboxylic acid or alkyl or arylsulfonic acid, all of the above having less than about 20 carbon atoms, and wherein the anions are stable under the oxidizing conditions of the reaction medium is added as a catalyst to the reaction medium of step (a).
Claim 9
Dependent Claim
28 words
The method of claim 1 wherein at least part of the unreacted carbonyl compound (II) present in the reaction medium is removed therefrom before carrying out step (c).
Claim 10
Dependent Claim
21 words
The method of claim 1 wherein hydrocyanic acid is used in excess up to about 100% of the theoretically required amount.
Claim 11
Dependent Claim
22 words
The method of claim 1 wherein the temperature of the reaction of step (c) is maintained between about 0° and 100° C.
Claim 12
Dependent Claim
34 words
The method of claim 1 wherein step (b) is carried out by neutralizing the unreacted ammonia with at least a stoichiometric amount of hydrochloric acid, phosphoric acid, sulfuric acid, formic acid or acetic acid.
Claim 13
Dependent Claim
79 words
The method of claim 1 wherein the nitrile (III) is acetonitrile, propionitrile, butyronitrile, isobutyronitrile, cyclohexylcarboxylic nitrile, benzonitrile, a tolunitrile, a cyanopyridine, mono-, di- or trichloroacetonitrile, m-chlorobenzonitrile, p-methoxybenzonitrile, p-nitrobenzonitrile, m-trifluoromethylbenzonitrile, glycolonitrile, epsilon-hydroxycapronitrile, cyanoacetic acid, an amide or alkyl ester of cyanoacetic acid, an amide or alkyl ester of beta-cyanopropionic acid, malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, a phthalonitrile, beta-hydroxypropionitrile, β,β'-oxydipropionitrile, a β-alkoxypropionitrile or a nitrile prepared from the cyanoethylation with acrylonitrile or methacrylonitrile of ethyleneglycol, propyleneglycol, glycerol, sorbitol or water.
Claim 14
Dependent Claim
22 words
The method of claim 12 wherein the nitrile prepared by cyanoethylation is formed in situ within the reaction medium of step (a).
Claim 15
Independent Claim
428 words
A method for preparing hydrazo-bis-acetonitriles of the general formula ##STR11## wherein R 1 is hydrogen and R 2 or R 1 and R 2 each is a straight chain alkyl radical of from 1 to 12 carbon atoms, a branched chain alkyl radical of from 3 to 12 carbon atoms, a cycloalkyl radical of from 3 to 12 carbon atoms or a phenyl radical or R 1 and R 2 together form a straight or branched chain alkylene radical of from 4 to 12 carbon atoms being unsubstituted or substituted with one or more chloro, bromo or fluoro atoms or nitro or methoxy groups, which consists essentially of: a. oxidizing a secondary alcohol of the general formula ##STR12## wherein R 1 and R 2 each is a straight chain alkyl radical of from 1 to 12 carbon atoms, a branched chain alkyl radical of from 3 to 12 carbon atoms, a cycloalkyl radical of from 3 to 12 carbon atoms or a phenyl radical or R 1 and R 2 together form a straight or branched chain alkylene radical of from 4 to 12 carbon atoms being unsubstituted or substituted with one or more chloro, bromo or fluoro atoms or nitro or methoxy groups, with molecular oxygen or a gaseous mixture consisting essentially of molecular oxygen, at a temperature and pressure which is sufficient to maintain the alcohol in the liquid phase to produce a mixture containing the peroxidic products of the auto-oxidation of the alcohol (V), said mixture being free of heavy metal ions, and reacting the auto-oxidation products with ammonia and cyanogen or a nitrile of the formula R.sub.3 (CN).sub.n (III) wherein n is an integer from 1 to 6 and R 3 is a straight chain alkyl radical of from 1 to 12 carbon atoms, a branched chain alkyl radical of from 3 to 12 carbon atoms, a cycloalkyl radical of from 3 to 12 carbon atoms or a benzene or pyridine radical, said radical being unsubstituted or substituted with one or more halogen atoms or carbamyl, carboxylic, nitro, hydroxy, epoxy, or sulfonic acid groups, to form a symmetrical azine of the formula ##STR13## b. eliminating unreacted ammonia from the medium resulting from (a) by evaporating unreacted ammonia at atmospheric or reduced pressure, or by neutralizing the unreacted ammonia with at least a stoichiometric amount of hydrochloric acid, phosphoric acid, sulfuric acid, formic acid or acetic acid; c. reacting the ammonia-free medium resulting from (b) with at least two moles of hydrocyanic acid per mole of azine; and d. recovering the hydrazo-bis-acetonitrile of formula (I).
Claim 16
Independent Claim
428 words
A method for preparing hydrazo-bis-acetonitriles of the general formula ##STR11## wherein R 1 is hydrogen and R 2 or R 1 and R 2 each is a straight chain alkyl radical of from 1 to 12 carbon atoms, a branched chain alkyl radical of from 3 to 12 carbon atoms, a cycloalkyl radical of from 3 to 12 carbon atoms or a phenyl radical or R 1 and R 2 together form a straight or branched chain alkylene radical of from 4 to 12 carbon atoms being unsubstituted or substituted with one or more chloro, bromo or fluoro atoms or nitro or methoxy groups, which consists essentially of: a. oxidizing a secondary alcohol of the general formula ##STR12## wherein R 1 and R 2 each is a straight chain alkyl radical of from 1 to 12 carbon atoms, a branched chain alkyl radical of from 3 to 12 carbon atoms, a cycloalkyl radical of from 3 to 12 carbon atoms or a phenyl radical or R 1 and R 2 together form a straight or branched chain alkylene radical of from 4 to 12 carbon atoms being unsubstituted or substituted with one or more chloro, bromo or fluoro atoms or nitro or methoxy groups, with molecular oxygen or a gaseous mixture consisting essentially of molecular oxygen, at a temperature and pressure which is sufficient to maintain the alcohol in the liquid phase to produce a mixture containing the peroxidic products of the auto-oxidation of the alcohol (V), said mixture being free of heavy metal ions, and reacting the auto-oxidation products with ammonia and cyanogen or a nitrile of the formula R.sub.3 (CN).sub.n (III) wherein n is an integer from 1 to 6 and R 3 is a straight chain alkyl radical of from 1 to 12 carbon atoms, a branched chain alkyl radical of from 3 to 12 carbon atoms, a cycloalkyl radical of from 3 to 12 carbon atoms or a benzene or pyridine radical, said radical being unsubstituted or substituted with one or more halogen atoms or carbamyl, carboxylic, nitro, hydroxy, epoxy, or sulfonic acid groups, to form a symmetrical azine of the formula ##STR13## b. eliminating unreacted ammonia from the medium resulting from (a) by evaporating unreacted ammonia at atmospheric or reduced pressure, or by neutralizing the unreacted ammonia with at least a stoichiometric amount of hydrochloric acid, phosphoric acid, sulfuric acid, formic acid or acetic acid; c. reacting the ammonia-free medium resulting from (b) with at least two moles of hydrocyanic acid per mole of azine; and d. recovering the hydrazo-bis-acetonitrile of formula (I).
Claim 17
Dependent Claim
32 words
The method of claim 14 wherein the alcohol (V) is selected to be isopropanol, 2-butanol, 2-pentanol, 3-methyl-2-butanol, 4-methyl-2-pentanol, 2-octanol, 1-cyclohexylethanol, 1-phenylethanol, diphenylcarbinol, cyclobutanol, cyclopentanol, cyclohexanol, 2-methylcylohexanol, 3-methylcyclohexanol, 3,3,5-trimethylcyclohexanol, cycloheptanol, cyclooctanol or cyclododecanol.
Claim 18
Dependent Claim
40 words
The method of claim 14 wherein from about 0.01 to 2% by weight of a ketone peroxide, hydrogen peroxide, tertiobutyl peroxide of azobisisobutyronitrile is added to the reaction medium of step (a) to facilitate the oxidation of the alcohol (V).
Claim 19
Dependent Claim
27 words
The method of claim 14 wherein unreacted alcohol (V) is removed from the mixture of peroxidic products before reacting the latter with ammonia, cyanogen or nitrile (III).
Claim 20
Dependent Claim
27 words
The method of claim 14 wherein ammonia is utilized in step (a) at a level of from about 0.2 to 5 moles per equivalent of peroxidic oxygen.
Claim 21
Dependent Claim
28 words
The method of claim 14 wherein nitrile (III) is utilized in step (a) at a level of from about 1 to 10 moles per equivalent of peroxidic oxygen.
Claim 22
Dependent Claim
33 words
The method of claim 14 wherein the reaction of the auto-oxidation products of step (a) with ammonia, and cyanogen or nitrile (III) is maintained at a temperature between about 0° and 100° C.
Claim 23
Dependent Claim
79 words
The method of claim 14 wherein the nitrile (III) is acetonitrile, propionitrile, butyronitrile, isobutyronitrile, cyclohexylcarboxylic nitrile, benzonitrile, a tolunitrile, a cyanopyridine, mono-, di- or trichloroacetonitrile, m-chlorobenzonitrile, p-methoxybenzonitrile, p-nitrobenzonitrile, m-trifluoromethylbenzonitrile, glycolonitrile, epsilon-hydroxycapronitrile, cyanoacetic acid, an amide or alkyl ester of cyanoacetic acid, an amide or alkyl ester of beta-cyanopropionic acid, malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, a phthalonitrile, beta-hydroxypropionitrile, β,β'-oxydipropionitrile, a β-alkoxypropionitrile or a nitrile prepared from the cyanoethylation with acrylonitrile or methacrylonitrile of ethyleneglycol, propyleneglycol, glycerol, sorbitol or water.
Claim 24
Dependent Claim
68 words
The method of claim 14 wherein from about 0.01 to 2% by weight of an ammonium or alkaline metal salt of a hydracid, mineral oxyacid, aromatic or aliphatic carboxylic acid or alkyl or arylsulfonic acid containing less than about 20 carbon atoms and wherein the anions are stable under the oxidizing conditions of the reaction medium is added as a catalyst to the reaction medium of step (a).
Claim 25
Dependent Claim
34 words
The method of claim 14 wherein step (b) is carried out by neutralizing the unreacted ammonia with at least a stoichiometric amount of hydrochloric acid, phosphoric acid, sulfuric acid, formic acid or acetic acid.
Claim 26
Dependent Claim
21 words
The method of claim 14 wherein hydrocyanic acid is used in excess up to about 100% of the theoretically required amount.
Claim 27
Dependent Claim
22 words
The method of claim 14 wherein the temperature of the reaction of step (c) is maintained between about 0° and 100° C.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1979-10-05 | 1980-04-05 | 1980-10-05 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1983-10-05 | 1984-04-05 | 1984-10-05 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1987-10-05 | 1988-04-05 | 1988-10-05 | $7700.00 | Window Closed / Lapsed |