GB1589334A - Process for the preparation of aromatic amines from a, -unsaturated cycloaliphatic ketoximes - Google Patents
Process for the preparation of aromatic amines from a, -unsaturated cycloaliphatic ketoximes Download PDFInfo
- Publication number
- GB1589334A GB1589334A GB5034177A GB5034177A GB1589334A GB 1589334 A GB1589334 A GB 1589334A GB 5034177 A GB5034177 A GB 5034177A GB 5034177 A GB5034177 A GB 5034177A GB 1589334 A GB1589334 A GB 1589334A
- Authority
- GB
- United Kingdom
- Prior art keywords
- oxime
- mixture
- ketoxime
- acetic anhydride
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 36
- 238000002360 preparation method Methods 0.000 title claims description 6
- 150000004982 aromatic amines Chemical class 0.000 title abstract description 8
- -1 oxime hydrochlorides Chemical class 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 150000002923 oximes Chemical class 0.000 claims abstract description 11
- 125000001424 substituent group Chemical group 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- WNPVAXLJVUXYFU-UHFFFAOYSA-N n-cyclohex-2-en-1-ylidenehydroxylamine Chemical class ON=C1CCCC=C1 WNPVAXLJVUXYFU-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 8
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical compound O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical group CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 6
- CZZZABOKJQXEBO-UHFFFAOYSA-N 2,4-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1 CZZZABOKJQXEBO-UHFFFAOYSA-N 0.000 claims description 5
- 239000012346 acetyl chloride Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims description 5
- ZFODTVHJGBCNSI-UHFFFAOYSA-N n-(3-methylcyclohex-2-en-1-ylidene)hydroxylamine Chemical compound CC1=CC(=NO)CCC1 ZFODTVHJGBCNSI-UHFFFAOYSA-N 0.000 claims description 5
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 125000005036 alkoxyphenyl group Chemical group 0.000 claims description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 3
- 150000001555 benzenes Chemical class 0.000 claims description 3
- 125000005059 halophenyl group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- VGAMRAGPPDEQHF-UHFFFAOYSA-N n-(3,5-dimethylcyclohex-2-en-1-ylidene)hydroxylamine;hydrochloride Chemical compound Cl.CC1CC(C)=CC(=NO)C1 VGAMRAGPPDEQHF-UHFFFAOYSA-N 0.000 claims description 3
- 125000006501 nitrophenyl group Chemical group 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- QOSLKKIVSIPIFE-UHFFFAOYSA-N 1,5-dimethylcyclohexene Chemical group CC1CCC=C(C)C1 QOSLKKIVSIPIFE-UHFFFAOYSA-N 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- JENJCURQWOPYRR-UHFFFAOYSA-N n-(3-methylcyclohex-2-en-1-ylidene)hydroxylamine;hydrochloride Chemical compound Cl.CC1=CC(=NO)CCC1 JENJCURQWOPYRR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- KRRRZSQJUONQBV-UHFFFAOYSA-N C1C=CC=C2C(=NO)C([N+]([O-])=O)CCC21 Chemical compound C1C=CC=C2C(=NO)C([N+]([O-])=O)CCC21 KRRRZSQJUONQBV-UHFFFAOYSA-N 0.000 description 1
- CPZAWKPBXNSNAK-UHFFFAOYSA-N N-(3,4,4a,5-tetrahydro-2H-naphthalen-1-ylidene)hydroxylamine Chemical compound C1(CCCC2CC=CC=C12)=NO CPZAWKPBXNSNAK-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005115 alkyl carbamoyl group Chemical group 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- XSCFKJGIAYKLRV-UHFFFAOYSA-N n-naphthalen-1-ylnitramide Chemical compound C1=CC=C2C(N[N+](=O)[O-])=CC=CC2=C1 XSCFKJGIAYKLRV-UHFFFAOYSA-N 0.000 description 1
- 238000011328 necessary treatment Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The aromatic amines are prepared from the corresponding cyclohex-2-en-1-one oximes by heating with agents which eliminate water. The cyclohex-2-en-1-one oximes may carry inert substituents or may be condensed with cycloaliphatic or aromatic rings. By using the oxime hydrochlorides instead of the free oximes, the yields of amines are considerably increased.
Description
(54) PROCESS FOR THE PREPARATION OF AROMATIC AMINES FROM
a, ss -UNSATURATED CYCLOALIPHATIC KETOXIMES (71) We, HOECHST AKTIENGESELLSCHAFT, a body corporate organised according to the laws of the Federal Republic of Germany, of 6230 Frankfurt/Main 80, Postfach 80 03 20, Federal Republic of Germany, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
The present invention relates to processes for the preparation of aromatic amines from a, p-unsaturated cycloaliphatic ketoximes.
In the aromatisation named after Semmler and Wolff, aromatic amines are obtained from a, ss-unsaturated aliphatic ketoximes, formally by elimination of water (Houben-Weyl:
Methoden der org. Chemie (Methods of Organic Chemistry), volume 10/4 (1968) 265, Krauch-Kunz, Reakionen der Organischen Chemie (Reactions in Organic Chemistry), 5th edition, 585 and Org. React. 11. 1).
The earlier literature references do not quote any yields, but it is reported that by-products appear, sometimes to a considerable extent.
Satisfactory yields are obtained, according to Schroeter (Ber. 63, (1930) 1316), when tetrahydronaphthalone oxime is converted to a-naphthylamine. The oxime is reacted with acetic anhydride, while passing HCI gas through the reaction mixture, and 56% of the theoretical yield of a-naphthylamine hydrochloride is obtained. Hardy and Ward (J. Chem.
Soc. 1956, 1979-81) obtained similar yields in the conversion of nitrotetrahydronaphthalone oxime to nitronaphthylamine (38-45 % of theory).
Concentrated sulphuric acid, 20 % strength hydrochloric acid, polyphosphoric acid, acetic anhydride and acetyl chloride are described in the literature as suitable "watereliminating agents". The processes outlined above cannot be used for an economical, large-scale manufacture of aromatic amines because, inter alia, the necessary treatment of effluent entails high costs.
It has now been found that the yields of aromatic amines may be considerably increased if an oxime hydrochloride is used in place of a free oxime. Thus, symmetrical m-xylidine is obtained from 3,5-dimethylcyclohexenone oxime hydrochloride and acetic anhydride in a yield of 86 % of theory, whilst the yield is only about 25 % when the pure oxime is used.
it is very surprising that this modification of the reaction generally results in such an increase in yield.
The present invention provides a process for the preparation of a compound whose carbon skeleton is or includes the unit
which compriscs reacting the hydrochloride of a ketoxime whose carbon skeleton is or includes the unit
with a water eliminating agent.
Preferably the reaction mixture is heated to initiate the reaction.
The starting material may in principle be the hydrochloride of any cyclohex-2-en-1-one oxime, provided that any substituent present does not react with the water-eliminating agent to produce by-products, and the substituents. if any. must be such as to permit an aromatisation of the cyclohexene ring.
Preferred cyclohex-2-cn-l-one oximes are those which are substituted by one or more of the same or different groups selected from lower alkyl and unsubstituted or substituted phenyl groups, or those which are fused to one or more cycloaliphatic and/or aromatic rings: if the cyclohexene ring is fused to an aromatic ring, the cyclohexene double bond may form part of the aromatic system. Preferably a fused ring is a benzene nucleus fused in the 2.3-, 4,5- or 5,6- positions of the cyclohexene ring.
Substituents which may be present in a benzene ring if it is itself present in the ketoxime, i.e. which may be present in a phenyl substituent of a cyclohex-2-en-1-one oxime or in an aromatic ring fused thereto. and which are stable and inert under the reaction conditions include, especially. lower alkyl. lower alkoxy, nitro, trifluoromethyl, carbamoyl, sulphamoyl. N-lower alkyl-sulphamoyl, N-lower alkyl-carbamoyl, N,N-di (lower alkyl)sulphamoyl and N,N-di(lower alkyl)- carbamoyl groups and halogen atoms, especially chlorine atoms. Preferably the ketoxime is a cvclohex-2-en-1-one oxime substituted by one or more of the same or different substituents selected from lower alkyl. phenyl, lower alkylphenyl. lower alkoxyphenyl. nitrophenyl, trifluoromethylphenyl, carbamoylphenyl, N-lower alkyl-carbamoylphenyl, sulphamoylphenyl. N-lower alkyl-sulphamoylphenyl and halophenyl groups. Preferably the cyclohex-2-en-1-one oxime is substituted by a lower alkyl group, a phenyl group or a phenyl group substituted by one or more of the substituents listed above; for example, the ketoxime may be 3.5-dimethylcyclohex-2-en-l-one oxime or 3-methylcyclohex-2-en- 1-one oxime.
The increase in yield when using the process of the invention makes it possible to manufacture, in an economical manner, aromatic amines which are accessible only with difficulty by other routes. Due to the high yields. there are also. in general no significant problems in working-up.
In the process of the invention. the water-eliminating agent is, especially, acetic anhydride or acetic chloride or, preferably, a mixture of the two. Sulphuric acid, hydrochloric acid or a polyphosphoric acid may also be used but the yields obtained with these are generally less good.
Advintageously. the oxime hydrochloride is introduced continuously or batchwise into the water-eliminating agent. The reaction is strongly exothermic. If the water-eliminating agent is preheated. the reaction can readily be controlled by the rate of introduction of the oxime hydiochloiitle. The oxime hydrochloride can be introduced either in the solid form or dissolved in a solvent. Glacial acetic acid is a particularly suitable solvent. It is also possible to prepare the oxime hydrochloride in situ. for example by reacting the a, li-unsaturated cycloaliphatic ketoxime in the solvent with a calculated amount of hydrogen chloride gas before adding the water-eliminating agent.
The reaction may suitably be carried out at a temperature in the range of from 0 C to 2()() C; a temperature in the range of from 2()0C to 140 C, especially tA() C to 140 C, is especially suitable. The reaction may be carried out under reflux. or the heat of reaction may be utilised for distilling off the solvent or the hydrated water-eliminating agent, for example acetic acid. formed. If the liquid reaction product and excess water-eliminating agent are distillcd off after the reaction has ended and an acylating water-eliminating agent has been used, then an intermediate acetamino compound, may also be isolated. In general. however, this intermediate compound is immediately processed further to give the frce aminc.
In some cascs it may be ndvantageous to carry out the reaction in the presence of hydrogen chloride. In this case. however. it must be noted that the metcring in of the hydrogen chloride must be matched to the particular oxime hvdrochloride. In general, the yield falls is the amount of hydrogen chloride increases and the yield is usually at a maximum when pure oxime hx drochloride is employed.
The amines manufactured by the process according to the invention are valuable intermediate products, for example for the manufacture of colourants.
The following Examples illustrate the inventions; percentages are by weight.
Example I
175 g of 3,5-dimethylcyclohex-2-en-1-one oxime hydrochloride were slowly introduced into 375 g of warm acetic anhydride at 800C. During this procedure, the temperature rose to the boiling point of the mixture. When all the oxime hydrochloride had been introduced, the acetic acid and the excess acetic anhydride were distilled off completely under a waterpump vacuum, 350 ml of water and 340 g of 31% strength hydrochloric acid were added to the residue and the mixture was boiled under reflux for 2 hours. After the dark-coloured solution had been clarified, the pH was adjusted to at least 10 with about 564 g of 33 % strength sodium hydroxide solution and the aqueous phase was separated at room temperature from the symmetrical m-xylidine which had separated out. The aqueous phase was extracted.
This gave 104 g (86 % of theory) of crude m-xylidine of boiling point 70-72"C/0.5 mm Hg.
Example 2
125 g of 3-methylcyclohex-2-en- l-one oxime (1 mole) were dissolved in 250 g of acetic acid and 38 g of hydrogen chloride gas were passed into the solution. A thick, white, readily stirrable suspension was formed, and this was warmed to 800C in order to dissolve the 3-methylcyclohexenone oxime hydrochloride which had formed. This solution was added to 350 g of acetic anhydride at room temperature and the mixture was then gradually warmed to the boiling point of the mixture. The further procedure was as indicated in Example 1.
This gave 87 g of m-toluidine, corresponding to 81 % of the theoretical yield; boiling point 203"C.
WHAT WE CLAIM IS: 1. A process for the preparation of a compound whose carbon skeleton is or includes the ' unit.
which comprises reacting the hydrochloride of a ketoxime whose carbon skeleton is or includes the unit
with a water-eliminating agent.
2. A process as claimed in claim 1, wherein the ketoxime is a cyclohex-2-en-l-one oxime substituted by one or more of the same or different substituents selected from lower alkyl, phenyl, lower alkylphenyl, lower alkoxyphenyl, nitrophenyl, trifluoromethylphenyl, carbamoylphenyl. N-lower alkyl-carbamoylphenyl, sulphamoylphenyl, N-lower alkylsulphamoylphenyl and halophenyl groups.
3. A process as claimed in claim 1, wherein the ketoxime is a cyclohex-2-en-1-one which is fused with one or more cycloaliphatic and/or aromatic rings.
4. A process as claimed in claim 3, wherein the ketoxime is a cyclohex-2-en-1-one which is fused with a benzene nucleus in the 2,3-,4,5- or 5,6- positions of the cyclohexene ring.
5. A process as claimed in claim 1, wherein the ketoxime is 3,5-dimethylcyclohex-2-en l-one oxime or 3-methylcyclohex-2-en-1-one oxime.
6. A process as claimed in any one of claims 1 to 5, wherein the water-eliminating agent is acetyl chloride or acetic anhydride or a mixture thereof.
7. A process as claimed in claim 6, wherein the water-eliminating agent is a mixture of acetyl chloride and acetic anhydride.
8. A process as claimed in any one of claims 1 to 7, wherein the reaction is carried out at a temperature in the range of from 0 to 2000C.
9. A process as claimed in claim 8, wherein the reaction is carried out at a temperature in the range of from 20 to 14() C.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (12)
- **WARNING** start of CLMS field may overlap end of DESC **.The amines manufactured by the process according to the invention are valuable intermediate products, for example for the manufacture of colourants.The following Examples illustrate the inventions; percentages are by weight.Example I175 g of 3,5-dimethylcyclohex-2-en-1-one oxime hydrochloride were slowly introduced into 375 g of warm acetic anhydride at 800C. During this procedure, the temperature rose to the boiling point of the mixture. When all the oxime hydrochloride had been introduced, the acetic acid and the excess acetic anhydride were distilled off completely under a waterpump vacuum, 350 ml of water and 340 g of 31% strength hydrochloric acid were added to the residue and the mixture was boiled under reflux for 2 hours. After the dark-coloured solution had been clarified, the pH was adjusted to at least 10 with about 564 g of 33 % strength sodium hydroxide solution and the aqueous phase was separated at room temperature from the symmetrical m-xylidine which had separated out. The aqueous phase was extracted.This gave 104 g (86 % of theory) of crude m-xylidine of boiling point 70-72"C/0.5 mm Hg.Example 2125 g of 3-methylcyclohex-2-en- l-one oxime (1 mole) were dissolved in 250 g of acetic acid and 38 g of hydrogen chloride gas were passed into the solution. A thick, white, readily stirrable suspension was formed, and this was warmed to 800C in order to dissolve the 3-methylcyclohexenone oxime hydrochloride which had formed. This solution was added to 350 g of acetic anhydride at room temperature and the mixture was then gradually warmed to the boiling point of the mixture. The further procedure was as indicated in Example 1.This gave 87 g of m-toluidine, corresponding to 81 % of the theoretical yield; boiling point 203"C.WHAT WE CLAIM IS: 1. A process for the preparation of a compound whose carbon skeleton is or includes the ' unit.which comprises reacting the hydrochloride of a ketoxime whose carbon skeleton is or includes the unitwith a water-eliminating agent.
- 2. A process as claimed in claim 1, wherein the ketoxime is a cyclohex-2-en-l-one oxime substituted by one or more of the same or different substituents selected from lower alkyl, phenyl, lower alkylphenyl, lower alkoxyphenyl, nitrophenyl, trifluoromethylphenyl, carbamoylphenyl. N-lower alkyl-carbamoylphenyl, sulphamoylphenyl, N-lower alkylsulphamoylphenyl and halophenyl groups.
- 3. A process as claimed in claim 1, wherein the ketoxime is a cyclohex-2-en-1-one which is fused with one or more cycloaliphatic and/or aromatic rings.
- 4. A process as claimed in claim 3, wherein the ketoxime is a cyclohex-2-en-1-one which is fused with a benzene nucleus in the 2,3-,4,5- or 5,6- positions of the cyclohexene ring.
- 5. A process as claimed in claim 1, wherein the ketoxime is 3,5-dimethylcyclohex-2-en l-one oxime or 3-methylcyclohex-2-en-1-one oxime.
- 6. A process as claimed in any one of claims 1 to 5, wherein the water-eliminating agent is acetyl chloride or acetic anhydride or a mixture thereof.
- 7. A process as claimed in claim 6, wherein the water-eliminating agent is a mixture of acetyl chloride and acetic anhydride.
- 8. A process as claimed in any one of claims 1 to 7, wherein the reaction is carried out at a temperature in the range of from 0 to 2000C.
- 9. A process as claimed in claim 8, wherein the reaction is carried out at a temperature in the range of from 20 to 14() C.
- 10. A process as claimed in claim 9. wherein the reaction is carried out at a temperaturein the range of from 80 to 14() C.
- 11. A process as claimed in claim 1, carried out substantially as described in either of the Examples herein.
- 12. A compound whose carbon skeleton is or includes the unitwhenever prepared by a process as claimed in any one of claims 1 to 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/045,833 US4247479A (en) | 1976-12-03 | 1979-06-05 | Process for the manufacture of aromatic amines from α, β-unsaturated cycloaliphatic ketoximes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762654852 DE2654852C3 (en) | 1976-12-03 | 1976-12-03 | Process for the preparation of aromatic amines from α, ß-unsaturated cycloaliphatic ketoximes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1589334A true GB1589334A (en) | 1981-05-13 |
Family
ID=5994613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB5034177A Expired GB1589334A (en) | 1976-12-03 | 1977-12-02 | Process for the preparation of aromatic amines from a, -unsaturated cycloaliphatic ketoximes |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS6054948B2 (en) |
| CH (1) | CH630336A5 (en) |
| DE (1) | DE2654852C3 (en) |
| FR (1) | FR2372793A1 (en) |
| GB (1) | GB1589334A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0103990A1 (en) * | 1982-09-16 | 1984-03-28 | Uniroyal, Inc. | Process for making diarylamines |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3041848A1 (en) * | 1980-11-06 | 1982-06-09 | Hoechst Ag, 6000 Frankfurt | METHODS OF PRODUCING 3,5-DIMETHYLANILINE (SYM. M-XYLIDINE) |
| DE3041836A1 (en) * | 1980-11-06 | 1982-06-09 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING AROMATIC AMINES |
| WO2007053755A1 (en) * | 2005-11-03 | 2007-05-10 | Boehringer Ingelheim International Gmbh | Process for preparing substituted anisidines |
-
1976
- 1976-12-03 DE DE19762654852 patent/DE2654852C3/en not_active Expired
-
1977
- 1977-11-30 CH CH1466477A patent/CH630336A5/en not_active IP Right Cessation
- 1977-12-02 GB GB5034177A patent/GB1589334A/en not_active Expired
- 1977-12-02 JP JP14409677A patent/JPS6054948B2/en not_active Expired
- 1977-12-05 FR FR7736520A patent/FR2372793A1/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0103990A1 (en) * | 1982-09-16 | 1984-03-28 | Uniroyal, Inc. | Process for making diarylamines |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2372793B1 (en) | 1983-10-07 |
| DE2654852C3 (en) | 1979-05-31 |
| JPS6054948B2 (en) | 1985-12-03 |
| JPS5371023A (en) | 1978-06-24 |
| FR2372793A1 (en) | 1978-06-30 |
| DE2654852A1 (en) | 1978-06-15 |
| CH630336A5 (en) | 1982-06-15 |
| DE2654852B2 (en) | 1978-10-05 |
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