DE2736228A1 - REDUCTION AND ALKYLATION OF P-NITROSOARYLAMINES WITH PLATINUM METAL SULFIDE CATALYSTS - Google Patents

Description

TlEDTKE - Bühling - KlNNE - GrU * E

Uipl.-Chem. G. Buehling

-M- I Dipl.-Ing. R. Kinne

^ Dipl.-Ing. P. Grupe

27 36 228 Bavarlarlng 4, P.O. Box 20 24

8000 Munich 2

Tel .: (0 89) 53 96 53 Telex: 5-24845 tipat cable: Germaniapatent Munich

August 11, 1977 B 8355 / case F-5369

Uniroyal Inc. New York / USA

Reduction and reductive alkylation of p-nitrosoarylamines with platinum metal sulfide catalysts

description

The invention relates to the use of Sulphides of the platinum metals ruthen, rhodium, palladium, osmium, Iridium or platinum as heterogeneous hydrogenation catalysts for the hydrogenation of p-nitrosoarylamines with the formation of p-aminoarylamines and for the reductive alkylation of p-nitrosoarylamines with ketones to form p-alkylaminoarylamines. The invention is worth the combination of two factors fully, one is that the p-nitrosoarylamine are commercially available and the other is the effectiveness and selectivity of the sulphides of the platinum metals in the desired conversion of the p-nitrosoarylamines into the p-aminoarylamines and into the p-alkylaminoarylamines.

The p-nitrosoarylamines are well known in the art.

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Dresdner Bank (Munich) Account 3839 BM Postscheck (Munich) KIo. β70-43-β04

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The platinum metal sulfide catalysts are important for the process according to the invention because they enable the desired hydrogenations in a manner in which little or no side reactions, such as nuclear hydrogenation,

Cleavage of the C-N bonds and reduction of ketones too

Alcohols that are generally obtained when using non-sulfidic catalysts such as platinum, palladium, nickel or Copper chromite finds, play. In addition, they are relatively insensitive to poisons that these other catalysts hinder in a severe way. Furthermore, they are much more active than the base metal sulphides such as the sulphides of nickel, Cobalt, iron and molybdenum and can therefore be used under milder temperature and pressure conditions that are economically desirable and to avoid undesirable side reactions lead, be used.

The catalyst can be prepared in situ or after previous preparation and isolation to give the reaction mixture can be added. Commercially available catalysts can be used use. The catalyst can be in the form of a bulk powder or in the form of a catalyst supported on a suitable support such as carbon or alumina and used. The catalyst can be in the form of a powder for liquid phase slurry and for gas phase fluidized bed process or in pellet or granule form for liquid phase or gas phase fixed bed processes can be produced and used.

The reactions can be done in a batch or a

continuous system, with tank or pipeline reactors, in the liquid phase with slurry or fixed bed catalysts, or in the gas phase with fluid bed or fixed bed catalysts be carried out in a manner known in the art.

The p-nitrosoarylamines can through the N atom Alkyl or aryl groups may be substituted. The alkyl groups

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can be straight-chain, branched or cyclic groups. The aryl groups may be of any type such as phenyl and naphthyl, and can on the ring by one or more groups, ^e wi alkyl, alkoxy, aryloxy, halogen, carboxyl groups and carboxyl derivative groups by thioether groups, etc., are not attacked undesirably during the hydrogenation, be substituted.

Examples of p-nitrosoarylamines which can be used according to the invention are:

4-nitrosoaniline 4-nitroso-N-methylaniline

4-nitroso-N-ethylaniline

4- ^N itroso-N-propylaniline

4-M.troso-N-isopropylaniline 4-nitroso-N-butylaniline 4-Nltroso-N-s • -butylaniline

4-nitroso-N-isoamylaniline

4-nitroso-N-dodecylaniline ^ -Nitroso-N-octadecylaniline 4-N.itroso-N-benzylaniline

4-nitroso-H- (. Ti, -methylbenzyl) -aniline

4- ^N itroso-N-phenethylaniline

4- ^N itroso-N- (3-phenylpropyl) -aniU _J n

4-nitroso-N- (1-ethyl-4-methylpentyl) aniline

^ -Nltroso-N-cyclohexylaniline 4-nitroso-N-3> 3ί5-tΓilnethylcyclohexylanilin

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il-nitroso-N-cyclooctyleniline

4-nitroso-N-ethyl-2-toluidine ^ -Nitroso-N-methyl-S-toluidine 4-nitroso-N-benzyl-2-toluidine

h- Nltroso-N-benzyl-3-toluidine

4-nitroso-N- (3-phenylpropyl) -3-toluidine

il-nitroso-N-methyl-2-anisidine 10

4-nitroso-N-ethyl-3-anisidine 4-nitroso-N-butylanthranilic acid ^ -Nitroso-N-isopropyl-S-chloroaniline 4-nitroso-N-s -butyl-3-chloroaniline

4-nitroso-N-ethyl-2,6-diethylaniline 4-nitroso-N-methyl-3,5-dimethylaniline

4-nitroso-N-isopropyl-2,5-dimethoxyaniline

4-nitrosodiphenylarain

4-nitroso-4 ^f -t-butyldiphenylarain

il-nitroso-S-chlorodiphenylamine

k- nitroso-3-methyldiphenylamine

The ketones used in the reductive alkylation

can be of any type such as dialkyl, alkylaryl, and diaryl ketones, and the alkyl groups can be cyclic be like in cyclohexanone and substituted cyclohexanones. The molar ratio of ketone to nitroso compound is in the reductive alkylation suitably at least 1/1 and can generally have a value from 1/1 to 20/1.

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_λ Usually a molar ratio of 1/1 to 3/1 is sufficient, although a molar ratio of 1/1 to 1.1 / 1 is also suitable. The excess ketone is primarily used as a solvent. In processes on an industrial scale, the ketone is Nitroso ratio generally kept relatively low, whereas higher molar ratios of ketone to nitroso group may be appropriate when carrying out the process according to the invention on a laboratory scale.

Examples of suitable ketones are acetone, 2-butanone, di-n-hexyl ketone, 2,6-dimethyl-3-heptanone, 2,6-dimethyl-4-heptanone, 3,5-dimethyl-4-heptanone, 2,4 -Dimethyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, mesityl oxide, 4-methyl-3-heptanone, S-methyl-2-hexanone, 3-methyl-2-pentanone, 10-nonadecanone, 2-nonanone, 5-nonanone, 2-octanone, 3-octanone, 4-octanone, 2-pentanone, 3-pentanone, 2-undecanone, 6-undecanone, 2-dodecanone, Isophorone, methylcyclopentyl ketone, ethyl cyclohexyl ketone, Benzophenone, 4-methoxybenzophenone, 2-methylbenzophenone, 4-methylbenzophenone, 2,4,5-trimethoxybenzophenone, 2,4,6-trimethoxybenzophenone, acetophenone, 2-chloroacetophenone, 4-chloroacetophenone, 2-methoxyacetophenone, 3-methoxyacetophenone, 4-Methoxyacetophenone, 2-Methy! Acetophenon, 3-Methy! Acetophenon, 4-methyl acetophenone. Cyclohexanone, cyclopentanone, 3-methyl cyclohexanone, methyl naphthyl ketone and others.

The hydrogenation process is generally carried out in the presence of an inert organic solvent, the solvent being present in an amount which keeping the nitroso compound at least partially in solution when the nitroso compound is a solid at the desired process temperature.

It is generally sufficient if a volume of solvent is used which is the volume of the nitroso compound by 0.2 to 10 times. When performing a

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reductive alkylation can, in addition to an excess of the ketone, a solvent may be present. Such solvents are, for example, aliphatic or cycloaliphatic alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, isobutyl and n-butyl alcohol, s-butyl alcohol, t-butyl alcohol, η-amyl alcohol ,. Isoamyl alcohol, t-amyl alcohol, n-hexyl alcohol, cyclohexanol, n-octyl alcohol, 2-ethylhexanol, n-decyl alcohol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, ethylene glycol, propylene glycol, Glycerine and others; Ethers such as diethyl ether, di-n-propyl ether, Diisopropyl ether, methyl n-butyl ether, ethyl n-butyl ether, Di-n-butyl ether, di-n-amyl ether, diisoamyl ether, di-n-hexyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Ethylene glycol dibutyl ether, 1,3-dioxolane, 1,4-dioxane, tetra hydrofuran; Alcohol ethers such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, 2-butoxyethanol, Tetrahydrofurfuryl alcohol, among others; Esters such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, Isobutyl acetate, methylamyl acetate, 2-ethylhexyl acetate, diethyl succinate, et al .; Nitriles such as acetonitrile, propionitrile, butyro- nitrile et al .; Amides such as formamide, acetamide, propionamide, N, N-diethylformamide, N, N-dimethy1formamide, N, N-dimethylacetamide, N, N-diethylacetamide and others ^ hydrocarbons such as n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethyl butane, cyclohexane, n-heptane, 3-methylhexane, n-octane, 2,2,4- Trimethylpentane, 2,3,4-trimethylpentane, n-decane, decalin, Benzene, toluene, xylenes, etc.

According to the invention there is accordingly a compound with the structural formula

NHR

where R is hydrogen, alkyl with 1 to 30 carbon atoms, generally with 1 to 18 carbon atoms, namely primary, secondary

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or tertiary, straight or branched alkyl (preferably with 1 to 12 carbon atoms), cycloalkyl with 5 to 8 carbon atoms (preferably with 5 to 6 carbon atoms), alkaryl (often alkylphenyl) with 7 to 10 carbon atoms (preferably with 7 to 8 carbon atoms), aralkyl with 7 to 9 carbon atoms (preferably benzyl) or Is phenyl and where

1 2 3

R is hydrogen or a group with the formula -CHR R

is wherein R and R are the same or different and alkyl (straight-chain or branched) with 1 to 10 carbon atoms (preferably with 1 to 5 carbon atoms}, cycloalkyl with 5 to 8 carbon atoms (preferably with 5 to 6 carbon atoms), aryl with 6 to 10 carbon atoms

2 3

(preferably phenyl) or R and R in combination with one another are a polymethylene with 4 to 5 carbon atanes, which is connected on both sides to the same carbon atom and a group such as Forms cyclopentyl or cyclohexyl,

produced by having a compound having the structural formula

O = N (S) -NHR

where R is defined as described above, with hydrogen in the presence or absence of a ketone with

2 3 2 3
of the formula O = CR R, where R and R are defined as described above, in contact. The process is carried out at a pressure between 7 kPa and 70,000 kPa or higher, generally between 70 kPa and 35,000 kPa (preferably between 700 kPa and 20,000 kPa, in particular between 700 kPa and 10,000 kPa), and at a temperature between 5 ° C and 250 ° C (preferably between 5 ° C and 220 ° C) carried out in the presence of a catalytically effective amount of a platinum metal sulfide.

From the above description it can be seen that the method according to the invention has two embodiments:

I) hydrogenation of the nitroso compounds having the formula described above with formation

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the corresponding amines,

II) Reductive alkylation of the nitroso compounds with the formation of N-substituted anilines.

In particular, the process of the first embodiment proceeds according to the following scheme:

(I)

while the second embodiment is written as follows can be:

(II) O = N- ^ VIIHR + O = CR R + 3H ₂ >

H
CH (R ² ) (R ³ ) -N-Zq) -NHR +

The process temperatures vary somewhat depending on whether a hydrogenation (I) or a reductive alkylation (II) is desired, i.e.

o "I II

Temperature,

general 5-120 50-250

preferably 5-100 100-220

particularly preferably 30-100 125-200

However, for all practical purposes, steps I and II can be combined with one another, i.e. that one at a relatively low temperature (about 20 cjmit the reductive alkylation begins and eventually increases the temperature to a level more suitable for maintaining reductive alkylation (about 150 ° C).

Conditions can be modified to provide an economically optimal combination of temperature, To ensure pressure, catalyst level and cycle time for the given starting material and catalyst.

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From a preferred aspect, the invention is directed to a hydrogenation process as described above (in which no ketone is present) carried out in the presence of a solvent.

In another preferred aspect , the invention is directed to a method of reductive alkylation as described above (in which a ketone is present), in the formulas given above

R is hydrogen, alkyl with 1 to 12 carbon atoms, cycloalkyl with 5 or 6 carbon atoms, alkaryl with 7 or 8 carbon atoms, Benzyl or phenyl and

1 2 3 2 3

R is a group with the formula -CHR R, in which R and R are identical or different and are alkyl with 1 to 5 carbon atoms, Cycloalkyl with 5 or 6 carbon atoms or phenyl, or

2 3
R and R combined with each other are pentamethylene,

and wherein the pressure is between 700 kPa and 10,000 kPa, the temperature between 5 ° C and 220 ° C and the molar ratio of the ketone to the p-nitrosoarylamine compound is between 1/1 and 20/1.

The following examples serve to explain the invention in more detail. The pressure values given below indicate the pressure by which the atmospheric pressure is exceeded, which is designated by the abbreviation UA (above atmospheric pressure).

example 1

Hydrogenation of 4-nitrosodiphenylamine with formation of N-phenyl-p-phenylenediamine

A. 19.8 g (0.10 mol) of 4-nitrosodiphenylamine, 145 ml of 2-propanol and 1.65 g of 5% platinum sulfide on carbon were placed in a 265 ml autoclave (trademark Magne D * sh) given. The autoclave was closed, first with nitrogen and then

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purged with hydrogen. Then hydrogen was added, up to a pressure of 2.76 MPa. was achieved. The reaction mixture was under a pressure of 2.07 MPa U.A. for 0.7 hours. up to 3.45 MPa U.A. heated to 25 ° C to 35 ° C with stirring, at this point the gas absorption suddenly stopped at about 102% of theory. The autoclave was cooled and from Pressure relieved. The reaction product was discharged and filtered through Celite (trademark) filter aid to remove the Remove catalyst. Gas-liquid chromatography

IQ and infrared analysis showed that the filtrate was N-phenyl-pphenylenediamine contained.

B. Example 1A was repeated using benzene instead of 2-propanol as the solvent. The gas ^ 5 Absorption ceased after 1.3 h at 25 ° C to 4O ⁰ C and a pressure of 3.45 MPa oa up to 5.52 MPa above sea level at about the theoretical value. N-phenyl-p-phenylenediamine was identified by gas-liquid chromatography and infrared analysis.

C. 59.5 g (0.30 moles) of 4-nitrosodiphenylamine, 110 ml of benzene and 1.65 g of 5% platinum sulfide on carbon were placed in a 265 ml autoclave (Magne Dash, Trade Mark). The autoclave was closed and flushed first with nitrogen and then with hydrogen. Then hydrogen was added until a pressure of 4.14 MPa o.A. was achieved. The reaction mixture was heated ^{to about 90 ° C. without stirring.} Stirring was then started and the pressure was increased to 3.45 MPa above sea level. up to 5.52 MPa above sea level held. The temperature rose exothermically to about 150 ° C. in less than 0.2 h than the gas absorption

2Q suddenly stopped at around the theoretical value. After treating the reaction product, N-phenyl-p-phenylenediamine was identified as described in Example 1A.

Example 2

Reductive alkylation of 4-nitrosodiphenylamine with acetone

A. 19.8 g (0.10 mol) 4-nitrosodiphenylamine,

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145 ml (2.0 mol) of acetone and 1.65 g of 5% platinum sulfide Carbon were placed in a 265 ml autoclave (Magne Dash, Trademarks). The autoclave was closed and flushed first with nitrogen and then with hydrogen. Then became

Hydrogen added until a pressure of 2.76 MPa U.A.

was achieved. The reaction mixture was stirred for 10.5 hours under a pressure of 2.07 MPa above sea level up to 3.45 MPa above sea level heated to 20 ° C to 30 ° C. A relatively rapid gas absorption of about 0.2 mol was completed in about 1 hour, followed by exhibits a slow absorption of about 0.1 mol. The autoclave was freed from pressure. The reaction product was discharged and filtered through Celite filter aid to remove the catalyst remove. After removing the unreacted ketone on a rotary evaporator, the residue became a product hold, which had a melting point of 73 ° C to '77 ⁰ C. Infrared analysis indicated that the product contained 19.7 g (87% yield) of W-isopropyl-N'-phenyl-p-phenylenediamine.

B. 59.4 g (0.30 mol) 4-nitrosodiphenylamine, 175 ml

Acetone (2.4 moles) and 2.5 g of platinum oxide were placed in a 600 ml autoclave (Magne Dash, trademark). The autoclave was sealed, flushed first with nitrogen and then with hydrogen. Hydrogen sulfide was added until a Pressure of 34 5 kPa U.A. was reached, then became hydrogen added until a pressure of 8.96 MPa Ü.A. was achieved. The reaction mixture was heated to 90.degree. C. under a for 0.5 h Pressure of 8.27 MPa above sea level up to 9.65 MPa U.A. heated with stirring, which was then heated to 110 ° C for 1 hour. In the last Little or no gas was absorbed for 0.3 hours. The autoclave was chilled and relieved of pressure. The reaction product was discharged and filtered through Celite filter aid to remove the catalyst. The excess acetone was through Removed distillation under reduced pressure. The residue contained what was detected by colorimetric analysis

3 $ 1.5 g (yield 3%) N-phenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine was identified by means of infrared analysis.

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C. Example 2Λ was made using 1.65 g

Repeated 5% rhodium sulfide on carbon as a catalyst. The reaction mixture was kept under pressure for 12 hours of 2.07 MPa U.A. up to 3.45 MPa U.A. with stirring to 75 ° C heated. After removal of the catalyst and solvent, infrared analysis of the residue showed Product indicated that 18.5 g (yield 82%) of N-isopropyl-N'-phenylp-phenylenediamine were present.

D. Example 2A was prepared using 1.65 g of 5% « Repeated ruthenium sulfide on carbon as a catalyst. The reaction mixture was stirred under a pressure of 2.76 UPa U.A. for 5.5 hours. up to 4.14 MPa U.A. heated to 175 ° C. with stirring. By means of infrared analysis, N-Iso propyl-N'-phenyl-p-phenylenediamine identified.

Example 3

Reductive alkylation of 4-nitrosodiphenylamine with cyclohexanone.

19.8 g (0.10 mol) 4-nitrosodiphenylamine, 145 ml (1.4

mol) Cyclohexanone and 1.65 g of 5% platinum sulfide on carbon were placed in a 265 ml autoclave (Magne Dash »trademark). The autoclave was closed, only with

__ nitrogen and then purged with hydrogen. Then became Hydrogen added until a pressure is 2.76 MPa U.A. achieved. The reaction mixture was stirred under a pressure of 2.07 MPa U.A. for 1.3 hours. up to 3.45 MPa U.A. with stirring to 25 ° C Heated to 30 ° C, then heated to 75 ° C for 5.8 hours. Of the

, _ Autoclave was cooled and depressurized. The reaction product was discharged and filtered through Celite filter aid » to remove the catalyst. Removal of the solvent in a rotary evaporator gave the residue a product containing 22 g (yield 83%) of N-cyclohexyl-N'-phenylp-phenylenediamine as shown by infrared analysis.

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Example 4

Reductive alkylation of 4-nitrosodiphenylamine with methyl isobutyl ketone

19.8 g (0.10 mol) 4-nitrosodiphenylamine, 145 ml (1.2 mol) methyl isobutyl ketone and 1.65 g of 5% platinum sulfide Carbon were placed in a 265 ml autoclave (Magne Dash, Trademarks). The autoclave was closed and flushed first with nitrogen and then with hydrogen. Then became Hydrogen added until a pressure of 2.76 MPa U.A. was achieved. The reaction mixture was under for 1.8 h a pressure of 2.07 MPa U.A. up to 3.45 MPa U.A. warmed to 20 ° C to 30 ° C with stirring, then 0.7 h heated to 30 ° C to 90 ° C and 1 hour to 90 ° C to 95 ° C, with no gas being absorbed in the last 0.5 hour. Of the Autoclave was cooled and depressurized. The reaction product was discharged and filtered through Celite filter aid filtered to remove the catalyst. The solvent was removed on a rotary evaporator.

The comparison of the relative areas in the analysis by means of gas-liquid chromatography showed that the residue ^{product contained about 21.5 g of N- (1,3-dimethylbutyU-N 1} -phenyl-p-phenylenediamine.

Example 5

Reductive alkylation of 2-isopropyl-4'-nitrosodiphenylamine with acetone

370 g (1.52 mol) 2-isopropyl-4'-nitrosodiphenylamine, 475 ml (6.5 mol) of acetone and 4.0 g of 5% platinum sulfide on carbon were placed in a 2-1 autoclave (Magne Drive, Trademarks). The autoclave was closed and flushed first with nitrogen and then with hydrogen. Hydrogen was then added until a pressure of 4.83 MPa U.A. was achieved. The reaction mixture was allowed to run for 2.5 hours

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under a pressure of 3.4 5 MPa U.A. up to 5.52 MPa U.A. under Stirring heated to 35 ° C to 85 ° C and then heated to 85 ° C to 90 ° C for 3 h, with little in the last 0.8 h or no gas has been absorbed. The autoclave was cooled and relieved of pressure. The reaction product was discharged and filtered through Celite filter aid to remove the catalyst. The filtrate was distilled. A fraction boiling between 156 ° C at 0.3 mmHg ^and 160 ° C at 0.15 mmHg was recrystallized from hexane to give 305 g (Yield 75%) N-isopropyl-N ¹ - (2-isopropylphenyU-p-phenylenediamine with a melting point of 56 ° C. to 57 ° C. A further 27.5 g (yield 7%) were recovered from the hexane mother liquors The material purified by a second distillation followed by recrystallization from hexane melted at 57 ° C to 58 ° C.

Example 6

Reductive alkylation of 2-s-butyl-4'-nitrosodiphenylamine with acetone

76 g (0.30 mol) 2-s-butyl-4'-nitrosodiphenylamine,

330 ml (4.5 mod) of acetone and 4.0 g of 5% platinum sulfide on carbon were placed in a 1-1 autoclave (Magne Drive, Trademarks). The autoclave was closed, flushed first with nitrogen and then with hydrogen and then under a hydrogen pressure of 5.52 MPa U.A. set. Dab The reaction mixture was stirred under a pressure of 2.76 MPa U.A. for 0.8 hours. up to 5.52 MPa above sea level with stirring to 25 ° C to 70 ° C heated, then heated to 70 ° C to 75 ° C for 3 h,

with little or no gas being absorbed in the last full hour 30th

became. The autoclave was cooled and depressurized.

The reaction product was discharged and filtered through Celite filter aid to remove the catalyst. the Distillation of the filtrate gave 77 g (91% yield) of one

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boiling between 180 ° C at 1.5 mmHg and 174 ° C at 0.9 iranHg

Product. After recrystallizing twice from hexane

melted this N-isopropyl-N '- (2-s-butylphenyl) phenylenediamine

at 32.5 ° C to 33 ° C.

Example 7

Reductive alkylation of 2,2'-diisopropyl-4-nitrosodiphenylamine with acetone

10 ° g (0.354 mol) of 2,2'-diisopropyl-4-nitrosodiphenylamine, 300 ml (4.1 mol) of acetone and 4.0 g of 5% platinum sulfide on carbon were placed in a 1-1 autoclave (Magne Drive, Trade Mark). The autoclave was closed, first purged with nitrogen and then with hydrogen and then under a hydrogen pressure of 5.52 MPa U.A. set The reaction mixture was stirred under a pressure of 2.76 MPa o.A. for 0.5 h. up to 5.52 MPa U.A. with stirring to 25 ° C to 85 ° C heated, then heated to 85 ° C to 90 ° C for 2.5 h, with little or no gas being absorbed in the last 1.5 hours became. The autoclave was cooled and depressurized. That Reaction product was discharged and passed through CeIite filter aid filtered to remove the catalyst. Distillation of the filtrate gave 101 g (92% yield) of one between 169 ° C and 171 ° C at 0.6 mmHg to 0.8 mmHg boiling product. To This fraction was recrystallized twice from hexane 2,2'-Diisopropyl-4-isopropylaminodiphenylamine with a Melting point of 86 ° C to 87 ° C obtained.

Example 8

Conversion of aniline into N- (1,3-dimethylbutyl) -N '- (1-ethyl-4-methylpentyl) -p-phenylenediamine

A. 279> 4 g (3.0 mol) of aniline, 424 g (3.30 mol) of ethyl isoamyl ketone and 8.0 g of 5% platinum sulfide on carbon placed in a 2-1 autoclave (Magne Drive, trademark). The autoclave was closed, flushed first with nitrogen and then with hydrogen and placed under a hydrogen pressure of

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4.83 MPa o.r. The reaction mixture was heated for 6.3 hours under a pressure of 3.45 MPa (generally up to 5.52 MPa above sea level with stirring to 100 ° C. to 10 ° C., then at 125 ° C. for 5.8 hours The autoclave was cooled and depressurized. The reaction product was discharged and filtered through Celite filter aid to remove the catalyst. The filtrate was distilled. A fraction boiling from 74 ° C to 88 ° C weighed ° C at 0.5 romHg 114 g. It consisted of N- (l-ethyl-4-lnethylpentyl) ^{<^} Q aniline and a small amount of ketone and was discarded. a second fraction having a boiling point of 89 ° C to 1O3 ° C. at 0.5 mmHg weighed 455 g. Gas-liquid chromatography showed that the second fraction consisted of N- (1-ethyl-4-methylpentyl) aniline with a purity of about 99%.

B. A mixture of 205 g (1.0 mol) of N- (1-ethyl-4-methylpentyl) -aniline 300 ml of toluene and a solution of 76 g (1.1 mol) of sodium nitrite in 150 ml of water was in a 2-1 three-necked flask fitted with a stirrer, a thermometer and a dropping funnel was cooled to 15 ° C. To the stirred mixture were over a period of 0.8 h 184 ml of 6N sulfuric acid were added dropwise at about 15 ° C. Stirring was continued for an additional 2 hours. The mixture was transferred to a separatory funnel, the toluene solution was separated from the aqueous phase and several times with Washed water until it was neutral.

C. To the 3Q solution of N-nitroso-N- (1-ethyl-4-methylpentyl) -aniline in Toluene placed in a 2-1 three-necked flask with a stirrer, thermometer and dropping funnel was used a solution of 73 g (2.0 mol) of dry hydrogen chloride in 124 ml of methanol over a period of 1 hour at 25 ° C to 30 ° C added. The reaction mixture was allowed to continue for 3.5 hours

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touched. Then, with stirring and cooling, 330 ml 6N sodium hydroxide added slowly. The reaction mixture was poured into a separatory funnel, the aqueous Layer separated and the toluene layer good washed with water.

D. The solution of 4-nitroso-N- (1-ethyl-4-methylpentyl) aniline in toluene obtained as described above (500 ml), 150 ml (1.2 mol) methyl isobutyl ketone and 7.0 g

^ ₀ 5% platinum sulfide on carbon was poured into a 2-1- Autoclaves (Magne Drive, Trademark) given. The autoclave was closed, flushed first with nitrogen and then with hydrogen and placed under a hydrogen pressure of 2.76 MPa above sea level. set. The autoclave was about 0.1 hours under a _w Pressure of 1.79 MPa above sea level up to 2.76 MPa above sea level under PUhren Heated 30 ° C to 50 ° C, then about 0.1 h with stirring and under a pressure of 2.07 MPa U.A. up to 4.14 MPa o.a. heated to 50 ° C to 95 ° C. The reaction mixture was then stirred under a pressure of 3.4 5 MPa over a period of 5.5 hours. up to 4.14 MPa o.A. heated to 120 ° C to 125 ° C with stirring, little or no gas being absorbed in the last 4 h. The autoclave was cooled and depressurized. The reaction product was discharged and filtered through Celite filter aid, to remove the catalyst. The filtrate was distilled and 274 g of a fraction boiling at 0.55 mmHg between 155 ° C and 164 ° C were collected. The comparison of the relative Areas on analysis by gas-liquid chromatography indicated that about 95% of this fraction consisted of N- (1,3-dimethylbutyl) -N '- (1-ethyl-4-methylpentyl) -p-phenylenediamine.

Example 9

Reductive alkylation of 4-nitroso-N-cyclohexylaniline with ethyl isoamyl ketone

102 g (0.50 mol) 4-nitroso-N-cyclohexylaniline, 116 al (° ^'75 mol) and 6.5 g ÄthyIisoamylketon Stiges platinum sulfide on carbon was (in a 2-1 autoclave Magne

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Drive, trademark). The autoclave was closed, flushed first with nitrogen and then with hydrogen and placed under a hydrogen pressure of 2.76 MPa above sea level. set. The autoclave was operated for about 0.1 hour under a pressure of 1.38 MPa UA to 3.45 MPa o.A. stirred at 30 ° C to 55 ° C and then with stirring and under a pressure of 4.14 MPa Ü.A. up to 4.83 MPa above sea level Heated to about 200 ^° C. for 3.5 hours. The autoclave was cooled and depressurized. The reaction product was discharged and filtered through Celite filter aid to remove the catalyst. The filtrate was distilled to give a fraction boiling at 0.8 mmHg between 184 ° C and 185 ° C. The comparison of the relative areas in the analysis by means of gas-liquid chromatography showed that this Frakttlph contained about 95 g of N-cyclohexyl-N '- (1-ethyl ^ -methylpentyD-Ig p-phenylenediamine.

Example 10

Reductive alkylation of 4-nitroso-N- (1,4-dimethylpentyl) aniline with methyl isoamyl ketone.

A. 500 ml of a toluene solution containing 220 g (1.0 mol)

4-nitroso-N- (1,4-dimethylpentyl) -aniline and 136 g (1.19 mol) Methyl isoamyl ketone and 7.0 g of 5% platinum sulfide on carbon were placed in a 2-1 autoclave (Magne Drive, Trademarks). The autoclave was closed, flushed first with nitrogen and then with hydrogen and opened Hydrogen pressure of 2.76 MPa above sea level brought. The reaction mixture was stirred under a pressure of 1.38 MPa over a period of 0.8 hours. up to 3.45 MPa o.a. heated with stirring to 30 ° C to 140 ° C and then for 5 h under a pressure of 3.45 MPa U.A. to 4.14 MPa o.a. heated to 140 ° C with little or no gas being absorbed in the last 4.3 h. The autoclave was cooled and relieved of pressure. The reaction product was discharged and filtered through Celite filter aid to remove the catalyst

remove. The filtrate was distilled, leaving 277 g of 35

N, N ¹ - bis (1,4-dimethylpentyl) -p-phenylenediamine obtained, its

for the most part had a boiling point between 164 ° C and 169 ° C at 0.9 mmHg. The comparison of the relative areas in the analysis

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by gas-liquid chromatography showed the product to be about 98% pure.

B. 66 5 ml of a toluene solution consisting of 0.40 mol of N- (1.4-

4-nitroso-N- (1,4-dimethylpentyl) aniline and 68.5 g (0.60 mol) of methyl isoamyl ketone obtained from dimethylpentyl) aniline and 5.0 g of 5% platinum sulfide on carbon was placed in a 2-1 autoclave (.Magne Drive, trademark). The autoclave was closed, first with nitrogen and

^ O then flushed with hydrogen and brought to a hydrogen pressure of 4.83 MPa UA. The reaction mixture was stirred under a pressure of 4.14 MPa o.A. for 0.6 hours. up to 5.17 MPa above sea level heated with stirring at 27 ° C to 170 ° C and then heated 4.0 hours at 170 ⁰ C, whereby in the last full hour little or no gas was absorbed. The reaction product was discharged and filtered through Celite filter aid, to remove the catalyst. The filtrate was separated into an aqueous and an organic phase. The solvent was removed from the organic phase in a rotary evaporator removed under reduced pressure. The liquid residue consisted of 113.5 g, which contained about 92% N, N'-bis- (1,4-dimethylpentyl) -p-phenylenediamine, which was determined by the Comparison of the relative areas when analyzed by gas-liquid chromatography was shown.

Example 11

Reductive alkylation of 4-nitroso-N-isopropylaniline with acetone

123 g (0.75 mol) 4-nitroso-N-isopropylaniline, 48.0 g (0.825 mol) acetone, 290 ml 2-propanol and 2.5 g 5% platinum sulfide on carbon were placed in a 1-1 autoclave (Magne Drive, trademark). The autoclave was closed, flushed first with nitrogen and then with hydrogen and under set a hydrogen pressure of 4.14 MPa UA. The reaction mixture was stirred for 1.2 hours at a pressure of 3.45 MPa o.A. up to 5.52 MPa above sea level heated with stirring to 23 ° C to 15O ⁰ C, then was heated 6.1 h at 150 ° C to 155 ° C, wherein in the

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Little or no gas was absorbed in the last full hour.

The autoclave was cooled and depressurized. The reaction product was discharged and filtered through a Celite filter sleeve, to remove the catalyst. After removing the solution means in a rotary evaporator under reduced The pressure obtained was 139 g of a solid residue with a melting point of 43 ° C. to 46 ° C., which contained about 95% Ν, Ν'-diisopropyl-p-phenylenediamine, which was shown by comparing the relative areas in the analysis by means of gas-liquid chromatography ge was showing.

Example 12

Reductive alkylation of 4-nitroso-N-s-butylaniline with methyl ethyl ketone

655 ml of a toluene solution consisting of 0.39 mol of N-s-butyl

4-nitroso-N-s-butylaniline obtained aniline contained 34 g (0.47 mol) of methyl ethyl ketone and 5.0 g of 5% platinum sulfide on carbon were placed in a 2-1 autoclave (Magne Drive, Trademarks). The autoclave was closed, flushed first with nitrogen and then with hydrogen and opened 4.83 MPa hydrogen pressure U.A. The reaction mixture was left under a pressure of 3.45 MPa U.A. for 0.5 hours. up to 4.83 MPa etc. heated to 34 ° C to 150 ° C with stirring and then heated to 150 ° C for 1.3 hours, with 0.8 in the last h little or no gas was absorbed. The autoclave was cooled and depressurized. The reaction product was discharged and filtered through Celite filter aid to remove the catalyst to remove. After removing the solvent in one A rotary evaporator under reduced pressure gave 82 g of a residue product containing about 99% Ν, Ν'-di-s-butyl-pphenylenediamine, which can be demonstrated by comparing the relative Areas shown when analyzed by gas-liquid chromatography.

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The following example serves to further explain the benefit of using a platinum sulfide instead of a platinum catalyst in the reductive alkylation of a p-nitrosoarylamine, namely of 4-nitrosodiphenylamine, to form the corresponding p-alkylaminoarylamine, viz of N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, as a catalyst used.

Example 13

A. 19.8 g (0.10 mol) 4-nitrosodiphenylamine, 20 ml (ca 0.16 mol) methyl isobutyl ketone, 220 ml toluene and 0.50 g 5% platinum sulfide on carbon was added to a 1-1 autoclave (Magne Drive, Trademark). The autoclave was closed and flushed first with nitrogen and then with hydrogen and to a hydrogen pressure of 3.45 MPa above sea level brought. After the initial reaction at low temperature the reaction mixture was under a pressure of 4.28 MPa o.A. for 3.9 hours. up to 4.72 MPa above sea level with stirring to 180 ° C 185 C with little or no gas being absorbed in the last 0.7 h. The autoclave was cooled and depressurized freed. The reaction product was discharged and filtered through Celite filter aid to remove the catalyst. The filtrate was concentrated on a hot plate and then on a rotary evaporator under reduced pressure to Evaporated to dryness. The residue consisted of 2 5.3 g (yield of the crude product 94%) of N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine with a purity of about 96% and also contained about 3% N-phenyl-p-phenylenediamine, as shown by the comparison the relative areas when analyzed by gas-liquid chromatography was shown.

B. 19.8 g (0.10 mol) 4-nitrosodiphenylamine, 20 ml (approx 0.16 mol) methyl isobutyl ketone, 220 ml toluene and 0.50 g 5% platinum on carbon was placed in a 600 ml autoclave (Magne Drive, trademark). The autoclave was closed first flushed with nitrogen and then with hydrogen and then to a hydrogen pressure of 4.83 MPa above sea level brought. After an initial, quick reaction at

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At a low temperature, the reaction mixture was left under a pressure of 4.41 MPa ti.A. for 4.0 hours. up to 4.72 MPa U.A. under Stirring heated to about 180 ° C with little or no gas being absorbed in the last full hour. The treatment of the reaction product as described in Part A gave 21.0 g of a residue containing about 45% N- (1,3-dimethylbutyD.-N'-phenylp-phenylenediamine and contained about 50% N-phenyl-p-phenylenediamine, as shown by comparing the relative areas when analyzed by gas-liquid chromatography became.

Similar results were obtained using palladium-osmium and iridium sulfides as catalysts.

The method according to the invention can also be applied to nitroso compounds with the general formula

-.NHR
- "vx
20th

where R is defined as described above and X is Substituents such as fluorine, chlorine, bromine, lower alkyl, lower alkoxy, etc., and where η can be 1 to 4, indicate be turned.

Claims (5)

TlEDTKE - BüHLING - KlNNE - GfHIPE Dipl.-Chem. G. Bühling Dipl.-Ing. R. Kinne Ο 7 O C O O Q Dipl.-Ing. P. Grupe ^ * Bavariaring 4, P.O. Box 20 24 8000 Munich 2 Tel .: (0 89) 53 96 53 Telex: 5-24845 tipat cable: Germaniapatent Munich August 11, 1977 B 8355 / case F-5369 Claims ( 1./Procedure for the production of a connection with the structural formula R ¹ HN WHR where R is hydrogen, alkyl with 1 to 18 carbon atoms, cycloalkyl with 5 to 8 carbon atoms, aralkyl with 7 to 9 carbon atoms, alkaryl with 7 to 10 carbon atoms or phenyl, 25 R is hydrogen or a group that has the formula 2 3 2 3 -CHR R where R and R are the same or different and Alkyl with 1 to 10 carbon atoms, cycloalkyl with 5 to 8 carbon atoms, 2 3 are aryl with 6 to 10 carbon atoms or R and R are one with one another Form a polymethylene group with 4 to 5 carbon atoms that are the same on both sides C atom is bonded, characterized in that a p-nitrosoarylamine with the structural formula O = N (()) NHR where R is defined as described above, with hydrogen in the absence or presence of a ketone 809807/0817 / ^ö Dresdner Bank (Munich) Mon. 3939 «« Positcheck (Munich) KIu 6/0 43 a04 - / - 21 ^ 228 2 3 2 3 Formula 0 = CR R, where R and R are defined as described above, under a pressure of 70 kPa to 35,000 kPa at a temperature of 5 ° C to 250 ° C in the presence of a catalytically effective amount of a platinum metal sulfide in Brings contact. 2. The method according to claim 1, characterized in that no ketone is used and the reaction in the presence of one Solvent performs. 3. The method according to claim 1, characterized in that that one uses a ketone, whereby R is hydrogen, alkyl having 1 to 12 carbon atoms, cycloalkyl with 5 or 6 carbon atoms, alkaryl with 7 or 8 carbon atoms, benzyl or phenyl, R is a group having the formula -CHR R wherein 2 3
R and R are identical or different and are alkyl with 1 to 5 carbon atoms, cycloalkyl with 5 or 6 carbon atoms or phenyl or in which r _{un <} jr form pentamethylene with one another, that the ketone is used in a molar ratio of 1/1 to 20/1, based on the p-nitrosoarylamine compound and that the reaction at a pressure of 700 kPa to Ul performs. 20,000 kPa and at a temperature between 5 ° C and 220 ° C 4. The method according to any one of the preceding claims, characterized in that the p-nitrosoarylamine in the form of 4-nitrosodiphenylamine, 2-isopropyl-4'-nitrosodiphenylamine, 2-s-butyl-4'-nitrosodiphenylamine, 4-nitroso- N- (1-ethyl-4-methylpentyl) -aniline, 4-nitroso-N-cyclohexylaniline, 4-nitroso-N- (1,4-dimethylpentyl) -aniline, 4-nitroso-N-isopropylaniline or 4-nitroso Ns-butylaniline is used. 809807/0817 ORIGINAL INSPECTBD -3- B 8355 5. The method according to any one of the preceding claims with the exception of claim 2, characterized in that one a ketone in the form of acetone, cyclohexanone, methyl isobutyl ketone, ethyl isoamyl ketone, methyl isoamyl ketone or Methyl ethyl ketone is used. 809807/0817