CA1204452A - Process for the preparation of aromatic amines - Google Patents
Process for the preparation of aromatic aminesInfo
- Publication number
- CA1204452A CA1204452A CA000389541A CA389541A CA1204452A CA 1204452 A CA1204452 A CA 1204452A CA 000389541 A CA000389541 A CA 000389541A CA 389541 A CA389541 A CA 389541A CA 1204452 A CA1204452 A CA 1204452A
- Authority
- CA
- Canada
- Prior art keywords
- carrier
- noble metal
- preparation
- catalyst
- amine
- 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
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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Abstract of the disclosure:
The invention provides a process for the preparation of aromatic amines by passing cyclohexanone azines or cyclohexenone azines in the gaseous phase over a catalyst containing at least one noble metal of the 8th subgroup of the Periodic Table.
The invention provides a process for the preparation of aromatic amines by passing cyclohexanone azines or cyclohexenone azines in the gaseous phase over a catalyst containing at least one noble metal of the 8th subgroup of the Periodic Table.
Description
~2~4~
- 2 - HOE 80/F 256 Subject of the present invention is a process for the preparation of aromatic amine by reaction of cyclohexanone azines or cyclohexenone azines in the gaseous phase in the presence of catalysts containing noble metals of the Thea subgroups of the Periodic Table.
Aromatic amine are intermediates for various apply-cations, for example for distaffs, medicaments or plant protecting agents.
Hitherto, aromatic amine have been prepared mainly by reduction of the corresponding aromatic vitro compounds, ox by reaction of the corresponding phenols with ammonia at elevated temperature and pressure.
Thus, these processes depend on the availability of the corresponding vitro compounds and phenols, respectively.
Since in the nitration of aromatic compounds different isomers are formed in any case, the problem of separation arises often, which has to be solved either before the reduction, that is, in the stage of the vitro compounds, or after the reduction, that is, in the amine stage. React lion of phenols with ammonia requires much technological and apparatus expenditure. Moreover, these phenols are often obtained from bituminous coal tar, so for example sum. m-xylenol.
It was therefore the object of the present invention to provide a method for preparing aromatic amine which is independent of aromatic preliminary stages and starts from simple aliphatic basis substances such as cycloali-phatic kittens.
Cyclic kittens, for example cyclohexanone, are pro-pared on a large scale by oxidation of cycloaliphatic compounds. Unsaturated cyclic kittens, for example 3,5-dialkylcyclohexenones, are easily obtainable from aide-hypes and kowtow esters (see German Offenlegungsschrift No. 2,654,850).
According to I Horning (~T.Am.Chem.Soc. 69, 1907 (19~7)), cyclohexenone is converted to aniline by reacting the cyclohexenone with hydrazine and catalytically de-hydrogel~atincr the cyclohexenone amine so formed in the liquid phase at temperatures of from 136 to Sweeney tile ~2044~
Aromatic amine are intermediates for various apply-cations, for example for distaffs, medicaments or plant protecting agents.
Hitherto, aromatic amine have been prepared mainly by reduction of the corresponding aromatic vitro compounds, ox by reaction of the corresponding phenols with ammonia at elevated temperature and pressure.
Thus, these processes depend on the availability of the corresponding vitro compounds and phenols, respectively.
Since in the nitration of aromatic compounds different isomers are formed in any case, the problem of separation arises often, which has to be solved either before the reduction, that is, in the stage of the vitro compounds, or after the reduction, that is, in the amine stage. React lion of phenols with ammonia requires much technological and apparatus expenditure. Moreover, these phenols are often obtained from bituminous coal tar, so for example sum. m-xylenol.
It was therefore the object of the present invention to provide a method for preparing aromatic amine which is independent of aromatic preliminary stages and starts from simple aliphatic basis substances such as cycloali-phatic kittens.
Cyclic kittens, for example cyclohexanone, are pro-pared on a large scale by oxidation of cycloaliphatic compounds. Unsaturated cyclic kittens, for example 3,5-dialkylcyclohexenones, are easily obtainable from aide-hypes and kowtow esters (see German Offenlegungsschrift No. 2,654,850).
According to I Horning (~T.Am.Chem.Soc. 69, 1907 (19~7)), cyclohexenone is converted to aniline by reacting the cyclohexenone with hydrazine and catalytically de-hydrogel~atincr the cyclohexenone amine so formed in the liquid phase at temperatures of from 136 to Sweeney tile ~2044~
- 3 - -JOE 80/F 256 presence of Pd/C catalysts:
ON _ N _ Pd/C
.
However, an economic manufacture of aromatic amine according to this process is impossible because of the yields attaining merely about 50 I.
There has now been found a process for the pro-parathion of aromatic amine of the formulae It or It ` NH2 It in which R1 through R5 each are hydrogen or C1-C6-alkyl, or one of these radicals is phenol, which comprises passing a cyclohexenone amine or cyclohexanone amine of the formulae Ida or Jib Ida : Irk in which R1 through R5 are as defined above, in the gaseous phase, at a temperature of from 200 to 500~C, over a catalyst containing at least one noble metal of the Thea subgroup of the Periodic Table.
The compounds of the formula Ida can be prepared according to the following scheme (German Offenlegungs-shrift No. 2,654,850; Ann. 281 104 (1894~):
us
ON _ N _ Pd/C
.
However, an economic manufacture of aromatic amine according to this process is impossible because of the yields attaining merely about 50 I.
There has now been found a process for the pro-parathion of aromatic amine of the formulae It or It ` NH2 It in which R1 through R5 each are hydrogen or C1-C6-alkyl, or one of these radicals is phenol, which comprises passing a cyclohexenone amine or cyclohexanone amine of the formulae Ida or Jib Ida : Irk in which R1 through R5 are as defined above, in the gaseous phase, at a temperature of from 200 to 500~C, over a catalyst containing at least one noble metal of the Thea subgroup of the Periodic Table.
The compounds of the formula Ida can be prepared according to the following scheme (German Offenlegungs-shrift No. 2,654,850; Ann. 281 104 (1894~):
us
- 4 - HOE 80/F 256 O ' O
I 2 + CRY ODOR -~2 COO
ODOR ~,~H21 ~12 COOP
. COREY
COY
Clue ~;~ R1~
2 ..
The cyclohexanone azines of the formula Jib are pro-pared from cycloaliphatic kittens such as-cyclohexanoner methylcyclohexanone, cyclohexenyl-cyclohexanone, and hydrazine.
Generally the radicals R1 through R5 together have no more than 12 carbon atoms. The C1-C6-alkyl radicals for which R1 through R5 may stand can be linear, branched or cyclic. One of the radicals R1 through R5 may alter-natively be a phenol radical, optionally substituted for example by halogen, C1-C6-alkyl.or C1-C6-alkoxy. Prefer-ably, however, it is unsubstituted or monosubstituted.
For the conversion of the azines to amine according to the invention, Thor are generally used catalysts con-twining ruthenium, rhodium, palladium, iridium or plating us or mixtures thereof; palladium, platinum or palladium/
platinum being preferred.
Normally, carrier catalysts, for example on carton, Sue, Allah, alumosilicates, spineless, chromium oxide/
Sue
I 2 + CRY ODOR -~2 COO
ODOR ~,~H21 ~12 COOP
. COREY
COY
Clue ~;~ R1~
2 ..
The cyclohexanone azines of the formula Jib are pro-pared from cycloaliphatic kittens such as-cyclohexanoner methylcyclohexanone, cyclohexenyl-cyclohexanone, and hydrazine.
Generally the radicals R1 through R5 together have no more than 12 carbon atoms. The C1-C6-alkyl radicals for which R1 through R5 may stand can be linear, branched or cyclic. One of the radicals R1 through R5 may alter-natively be a phenol radical, optionally substituted for example by halogen, C1-C6-alkyl.or C1-C6-alkoxy. Prefer-ably, however, it is unsubstituted or monosubstituted.
For the conversion of the azines to amine according to the invention, Thor are generally used catalysts con-twining ruthenium, rhodium, palladium, iridium or plating us or mixtures thereof; palladium, platinum or palladium/
platinum being preferred.
Normally, carrier catalysts, for example on carton, Sue, Allah, alumosilicates, spineless, chromium oxide/
Sue
- 5 - HOE 80/F 256 aluminum oxide, or zealots as carriers, are employed.
The concentration of the noble metal on the carrier is generally from 0.05 to 10, preferably 0.2 to 5, and especially 0.3 to 2.5, weight %, each relative to the weight of the carrier. The noble metals are applied to the carrier as compounds, and preferably reduced before starting the reaction, for example by passing hydrogen over them.
The catalyst may be arranged in the form of a solid bed, moving bed or fluidized bed.
The reaction temperature is generally from 200 to 500C, preferably 250 to 400C, and especially 270 to 380C.
The reaction is usually carried out under reduced pressure of down to about 10 mar, or under normal pressure; elevated pressure of up to about 20 bars, how-ever, being possible, Preferably, a carrier gas is used for the transport of the amine over the catalyst. Suitable carrier gases are particularly hydrogen, nitrogen, NH3, argon, COY, methane, steam, ethylene or propylene.
Before the reaction, the amine may be diluted with readily volatile solvents such as hydrocarbons, ethers, especially glycol and polyglycol dialkyl ethers, or water.
The following Examples illustrate the invention.
The liter amounts of No and Ho are relative to the standard (0C, 1.013 bar).
E X A M P L E 1:
In a glass reactor having a diameter of 18 mm and a length of I cm, there were arranged from top to bottom first a glass ball layer having a thickness of 5cm, immediately thereafter a catalyst layer having a thickness of 16 cm and consisting of 1 weight of Pod on Sue balls. In a No current, the reactor was heated to 300C, subsequently activated for 2 hours at 280C
with I l/h of nitrogen and 6 lull of hydrogen. There after, 100 g of a mixture of 80 g of dimethyl-diglycol and 20 g of 3,5-dimethyl-cyclohexell-2-one~azine-1 boo 105C) and simultaneously I l of nitrogen and Lowe ~5Z
The concentration of the noble metal on the carrier is generally from 0.05 to 10, preferably 0.2 to 5, and especially 0.3 to 2.5, weight %, each relative to the weight of the carrier. The noble metals are applied to the carrier as compounds, and preferably reduced before starting the reaction, for example by passing hydrogen over them.
The catalyst may be arranged in the form of a solid bed, moving bed or fluidized bed.
The reaction temperature is generally from 200 to 500C, preferably 250 to 400C, and especially 270 to 380C.
The reaction is usually carried out under reduced pressure of down to about 10 mar, or under normal pressure; elevated pressure of up to about 20 bars, how-ever, being possible, Preferably, a carrier gas is used for the transport of the amine over the catalyst. Suitable carrier gases are particularly hydrogen, nitrogen, NH3, argon, COY, methane, steam, ethylene or propylene.
Before the reaction, the amine may be diluted with readily volatile solvents such as hydrocarbons, ethers, especially glycol and polyglycol dialkyl ethers, or water.
The following Examples illustrate the invention.
The liter amounts of No and Ho are relative to the standard (0C, 1.013 bar).
E X A M P L E 1:
In a glass reactor having a diameter of 18 mm and a length of I cm, there were arranged from top to bottom first a glass ball layer having a thickness of 5cm, immediately thereafter a catalyst layer having a thickness of 16 cm and consisting of 1 weight of Pod on Sue balls. In a No current, the reactor was heated to 300C, subsequently activated for 2 hours at 280C
with I l/h of nitrogen and 6 lull of hydrogen. There after, 100 g of a mixture of 80 g of dimethyl-diglycol and 20 g of 3,5-dimethyl-cyclohexell-2-one~azine-1 boo 105C) and simultaneously I l of nitrogen and Lowe ~5Z
- 6 - HOE 80/F 256 28 l of hydrogen were passed from above over the catalyst heated at 260C by means of an electric heater.
During the second hour, 48 g of product were ox-twined at the reactor outlet. The result of a gas chrome autograph analysis (GO) was 7.7 g of 3,5-dimethylaniline, that is, 78 % of theory, and 1.2 g of dixylylamine - 13 of theory.
Jo OH
>=/
H3C' SHEA
dixylylamine Using the reactor and catalyst as described in En-ample 1, a mixture of 20 g of 3-methyl-5-propyl-cyclo-hexen-2-one-azine-1 boo 5 198 - 200C) and 80 g of Tulane was reacted for 3 hours at 300C. Simultaneously, 60 l or No and 30 l of Ho were passed over the catalyst within this period of time. The product condensed at the reactor outlet contained according to GO annuluses 14 g of 3-methyl-5-propylaniline - 70 % of theory (b.p.1 106C).
Using the reactor and catalyst as described in En-ample 1, a mixture of 20 g of cyclohexanone amine and of di-n-butyl ether was reacted for 2 hours at 270 - 280C. Simultaneously, 40 1 of No and 28 l of Ho were passed within this time over the catalyst The pro duct collected at the reactor outlet contained according to GO analysis 15.1 g of aniline, 2.7 g of diphènylamine and 1.0 g of unrequited cyclohexanone amine.
During the second hour, 48 g of product were ox-twined at the reactor outlet. The result of a gas chrome autograph analysis (GO) was 7.7 g of 3,5-dimethylaniline, that is, 78 % of theory, and 1.2 g of dixylylamine - 13 of theory.
Jo OH
>=/
H3C' SHEA
dixylylamine Using the reactor and catalyst as described in En-ample 1, a mixture of 20 g of 3-methyl-5-propyl-cyclo-hexen-2-one-azine-1 boo 5 198 - 200C) and 80 g of Tulane was reacted for 3 hours at 300C. Simultaneously, 60 l or No and 30 l of Ho were passed over the catalyst within this period of time. The product condensed at the reactor outlet contained according to GO annuluses 14 g of 3-methyl-5-propylaniline - 70 % of theory (b.p.1 106C).
Using the reactor and catalyst as described in En-ample 1, a mixture of 20 g of cyclohexanone amine and of di-n-butyl ether was reacted for 2 hours at 270 - 280C. Simultaneously, 40 1 of No and 28 l of Ho were passed within this time over the catalyst The pro duct collected at the reactor outlet contained according to GO analysis 15.1 g of aniline, 2.7 g of diphènylamine and 1.0 g of unrequited cyclohexanone amine.
Claims (3)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of an aromatic amine of the formulae Ia or Ib Ia Ib wherein R1 through R5 each are hydrogen or C1-C6-alkyl, or one of these radicals is phenyl, in which a cyclohexenone azine or cyclohexanone azine of the formula IIa or IIb IIa IIb wherein R1 through R5 are as defined above, is passed in the gaseous phase, at a temperature of from 200 to 500°C, over a catalyst containing at least one noble metal of the 8th subgroup of the Periodic Table.
2. A process as claimed in claim 1 wherein the noble metal is selected from the group of palladium, platinum and mixtures thereof.
3. A process as claimed in claim 1 or claim 2 in which the catalyst is supported on a carrier and the concentration of the noble metal on the carrier is from 0.05 to 10 weight %, relative to the weight of the carrier.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3041892.9 | 1980-11-06 | ||
| DE19803041892 DE3041892A1 (en) | 1980-11-06 | 1980-11-06 | METHOD FOR PRODUCING AROMATIC AMINES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1204452A true CA1204452A (en) | 1986-05-13 |
Family
ID=6116124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000389541A Expired CA1204452A (en) | 1980-11-06 | 1981-11-05 | Process for the preparation of aromatic amines |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0051802B1 (en) |
| JP (1) | JPS57108043A (en) |
| CA (1) | CA1204452A (en) |
| DE (2) | DE3041892A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4100514A1 (en) * | 1991-01-10 | 1992-07-16 | Bayer Ag | Di:phenylamine and derivs. prodn. from corresp. N=cyclohexylidene aniline |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT961240B (en) * | 1972-06-24 | 1973-12-10 | Snam Progetti | PROCEDURE FOR THE PRODUCTION OF DIPHENYLAMINE AND ITS DERIVATIVES |
-
1980
- 1980-11-06 DE DE19803041892 patent/DE3041892A1/en not_active Withdrawn
-
1981
- 1981-10-28 EP EP81109097A patent/EP0051802B1/en not_active Expired
- 1981-10-28 DE DE8181109097T patent/DE3168530D1/en not_active Expired
- 1981-11-05 JP JP56176589A patent/JPS57108043A/en active Pending
- 1981-11-05 CA CA000389541A patent/CA1204452A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE3041892A1 (en) | 1982-06-09 |
| DE3168530D1 (en) | 1985-03-07 |
| JPS57108043A (en) | 1982-07-05 |
| EP0051802A1 (en) | 1982-05-19 |
| EP0051802B1 (en) | 1985-01-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |