DE1667081A1 - Catalyst for reductive alkylation - Google Patents

Description

THü GüODYüAii I ¹ IKJa AND RUBBiIH 00ΜΪΑΝΥ, Aicron, Ohio, 44316, USA

Catalyst for reductive alkylation

The invention relates to novel and very effective catalytic ^ Systems and processes to which the same may be applied. The invention particularly relates to improved catalytic converters Systems that are very useful in reductive alkylation reactions are appropriate.

.Reductive alkylation reactions such as those between an amine, a nitro or a nitroso compound occur if a Reaction with an aldehyde or ketone takes place in the presence of hydrogen, are üoxicherweise for the production of N-alkylsubsti applied amines, such reductive alkylation reactions are known to be caused by certain metal cataiysaGoren catalyzed. Many of the previously known metal catalysts, however, are reasonably effective for promoting the Alkylation reactions also tend to promote one or more inconvenient new reactions. So lead reductive alkylation reactions using an amine, one Water, an aldehyde or a ketone often leads to the reduction of a substantial portion of an aldehyde or ketone in the corresponding alcohol, another inconvenient competing Heaction when applying the nitro, nitroso or amine resolution in an aryl bond is the reduction of the aromatic ring.

109822/1845

In JS Patent (U.S. Patent Application SN 426,408; a improved and very effective catalytic system for the reductive alkylation reactions described. The catalytic ^ System «e is a nickel catalyst in combination with free Sulfur or sulfur-containing compounds. jYes Apply composed of sulfur or sulfur-containing compounds with the nickel alkylation catalyst leads to an increase in the yields, as in the reductive alkylation reactions can be obtained without promoting inconvenient Ndoene reactions will.

It is an object of the invention,

Systems

further and improved very effective catalytic / for the reductive Create alkylation reactions. Generally speaking, it is a task here to catalyze reductive alkylation Ka propose that lead to high yields of the desired N-alkyl-substituted amine. A special of the The object of the invention is to create a reductive alkylation catalyst which leads to a high yield leads to the desired N-alkyl-substituted area, without that inexpedient side reactions are promoted and in particular the reduction of the aldehyde or ketones in the form of the .alkylating agent in the appropriate alcohol is avoided. Another problem underlying the invention is to provide a to provide an improved process for the formation of N-alkyl substituted amines in high yield.

Proceed according to the instructions to achieve some of the specified Task; positions such that a two-component catalytic system is used, while a three-component system is used to achieve other tasks catalytic system is applied so in an effective manner

109822/1845 -3-

reductively to nitro, nitroso or amine compounds. alkylate. The two component system has concentrated metallic nickel or nickel dispersed on an inert one Carrier material and a non-sulfuric acid, i.e. sulfur-free acid, and sulfur-containing acids where the sulfur is in the form of an -S- kestes. The three

ö
components-containing system consists of the two-component system and a modifier, consisting of free sulfur or sulfur-containing compounds which have at least part of this sulfur in the form of a -S- and / or an -S- radical,

According to the invention, nickel catalysts can generally be used, to make the improved catalytic masses. The term "N ^ ckelkkelkatalysator" used here includes the the following products:

(l) relatively pure metallic nickel that is finely divided into May be in the form

(2J metallic nickel, which continues with small amounts of further Metals such as cobalt, chromium and zirconium is modified and (3; metallic nickel in pure form or modified with minor Amounts of other metals on an inert carrier, such as gravel clock, charcoal, clays, alumina, etc. Examples of suitable sulfur-free acids and sulfur enthalpy

, tending acids, in which the sulfur in the form of a -S- best

present are sulfonic acids and organic acids and inorganic acids Acids Not Containing Sulfur * In the two-component system, the preferred acids become Be oleic acid, i'oluene, sulfonic acid and oxalic acid. The particular preferred acid in the two-component system is Sulfuric acid, the preferred acids in the three-component

109822/1845 - 4 -

System are aromatic sulfonic acids and the particularly preferred Acid is toluenesulfonic acid.

Examples of suitable sulfur-containing compounds which can be used as Modifying agent for the catalyst in the three-component system can be used are sulfur and:

1. Mercaptans, 2. Sulfenylthiocyanates, 3. Sulfenamiöe, 4. sulfenic esters, 5. sulfenic anhydrides, 6. thiophosphites, 7. thiophosphates, 8. thioorthoesters, 9. alkyl thiosulfates, 10. thiosulfonic esters, 11. thiosulfine esters, 12. thiosulfite esters, 13. hydroxy mercaptans, 14. alkoxy mercaptans, 15. cyanomercaptans, 16. aldehyde mercaptans, 17. ketomercaptans, 18. sulfide mercaptans, P 19. aminomercaptans, 20. mercapto acids, 21. organic sulfides, 22. inorganic sulfides, 23. hydroxydisulfides, 24. aminodisulfides, 25. aldehyde sulfides, 26. ketosulfides, 27. thioamines, 28. Gyanosulfide, 29. Heterocyclic compounds, the ring sulfur contain, 30.thiones, 31.sulphidic acids, 32.

acids, 33rd mercaptals, 34th mercaptols, 35. disulfides, 36. poly sulfides, 37th thioacids, 38th thiolester, 39th thionester, 40th thioanhydride, 4L dithioic acids, 42nd thioamides, 43rd thiol carbon ester, 44th thionocarbon ester, 45th dithiocarbon ester, 46th dithiol carbon

ester, 47th dithiol carbon salts, 48th trithiocarbon ester, 49th trithiocarboxylic salts, 50th fhiolcarbamine ester, 51th thiioncarbamine ester, 52. Dithiocarbamic acid ester, 53. 'Jhiolcarbazate, 54 · Thiuram- " raonosulfide, 55th thiuram disulfide, 56th thiuram polysulfide, 57. thioureas, 58. isothiuronium salts, 59. thiols, 60. Thiosemicarbazide, 61. Thiocarbazo4, 62. Sulfur halides, 63. sulfoxides, 64 · sulfidic acid esters.

In addition to the above-mentioned compound classes that are used in effective as a sulfur-containing modifier can be used according to the invention, all compounds which are a multiple of any one of the characteristics specified above Have groups, are also used.

Among the preferred sulfur-containing modifiers elevated sulfur and the following classes of soulfurcontained-

the compounds selected from the classes listed above

Α -5-

- 5 selects are:

Thioliarnäöffe, sulfidic acids, mercapto acids, thioamides, disulfid acids, thiuram disulfides, mercaptans of the ring sulfur containing Heterocycles, disulfides of the ring sulfur-containing heterocycles, Hing-sulfur-containing heterocycles, disulfides, cyanosulfides, sulfoxides, thioacids, organic sulfides, mercaptans, Dithio acids, sulfides of heterocyclic compounds containing ring sulfur, sulfidic acid esters.

The modifying agents which can be used according to the invention and are particularly preferred are those compounds which, when used with a nickel catalyst and an acid according to the invention, lead to a catalytic system which, with respect to the Catalyzing a reduktivη alkylation reduction effective so as to form the desired N-alkyl-substituted amine compounds in at least 95% yield. These particularly preferred modifying agents include sulfur and the following classes of sulfur-containing compounds:

Sulphic acids, thiuram disulphides, cyanosulphides, sulphoxides, organic sulphides, mercaptans of heterocyclic compounds containing hing sulfur, sulphides of heterocyclic compounds containing hing sulfur, heterocyclic compounds containing hing sulfur.

The particularly preferred three component catalytic system consists of a nickel catalyst. Thiodipropionic acid and toluenesulfonic acid. This three component system is generally versus the two component System preferred.

Any of the aldehydes and ketones normally employed in a conventional reductive alkylation reaction can be used in the practice of the invention. Typical examples of suitable aldehydes and ketones are methyl ethyl ketone, itothyl mobutyl ketone, methyl ethyl ketone, methyl hexyl ketone, butyl aldehyde and benaldehyde. 109822/1845 _-6 .

166/081

The amine or amine precursors required to carry out the Reactions contemplated according to the invention are useful are all of the primary amines or amine precursors which form primary amines of the type normally used in a conventional red active alkylation reaction. Typical examples of suitable amines or amine precursors are aniline, p-nitrodiphenylamine, p-aminodiphenylamine and o-phenylenediamines and p-nitrosodiphenylamine.

The amount of in the two-component and three-component systems to be used acid will vary somewhat depending on the specific reductive = alkylation reaction in which the Catalyst to be applied is the sulfur-containing Modifying agent that serves to modify the catalyst (if it is a three-component system) and the acids, however, it is generally found that 0.005 to 0.100 gram molecular weight of the acid per 100 grams of the nickel in the metal catalyst should be employed. The amount of sulfur-containing product required to be codified The nickel catalyst used will also vary somewhat depending on the particular reductive Alkylation reaction in which the catalyst is to be applied, the sulfur-containing modifying agent which is suitable for the Modifying the Catalyst Applied and the Acid · In general, it has been found to be from 0.05 to about 8.0 grams present Sulfur should be applied per 100 g of nickel in the metal catalyst

The nickel catalyst and the sulfur-containing modifier (if a three-component system is used) and the acid can be added separately to the reaction mixture or »it can be added or added in

109822/1845 - 7 -

Combination or in any order. One possibility, but not the only way in which such physical mixing can be carried out in an expedient manner, is that the nickel catalyst is slurried in a solvent and the acid (modifier containing the acid and sulfur) is added dissolved in the same solvent and then mixing and removing the solvent occurs. The reductive Alkylierungsreefction is normally carried out at temperatures from 50 to 240 ⁰ C. Since a reductive alkylation reaction is carried out with hydrogen, it is necessary to carry out the reaction under considerable pressure. The pressures normally used are around 17.5-140 kg / cm, in some cases they can be much higher at 280-350 kg / cm.

To make the reductive alkylation reaction in particularly effective Ways to catalyze are catalytic devices according to the invention System in an amount of 0.10 to 8 grams based on the weight of nickel present per mole of primary amine in the reaction mixed applied.

When carrying out a reductive alkylation reaction in which catalytic systems according to the invention are expediently carried out are used, the amine-nitro, or nitroso compound in a suitable reaction vessel together with an aldehyde or , Introduced ketone, which is employed as the alkylating agent and further becomes a catalytic one in the manner described above System applied. The aldehyde or kecon alkylating agent is normally used in excess and acts as a a solvent for the reactants and thus there is no need for further thinning agents in the form of solvents to apply in the reaction. However, others can also be used

109822/1845

dissolving diluents such as ethyl alcohol, ieobutyl alcohol, Benzene or toluene can be used if the aldehyde or ketone alkylating agent is not in such excess An amount sufficient to act as a solvent for the reactants is used. The mixture w ill on a Reaction temperature of 50 to 24O ° G heated and hydrogen under introduced into the reaction vessel at a pressure of 17.5 to 140 kg / cm. Let the reaction take a sufficient amount of time Play to see the reaction participants converted to the To achieve N-alkyl substituted amine. Then the one on the The pressure on the reaction vessel is relieved and the product is obtained by distilling off the volatile constituents. That Applying catalytic systems according to the invention leads to high yields of the reductively alkylated product. Applying the In accordance with the invention, catalytic components consisting of three components Systems makes it possible to carry out the reaction at relatively high temperatures, where the same can be carried out easily without noticeable Conversion of the aldehyde or ketone as an alkylating agent into the corresponding alcohols takes place. Reductive alkylation reactions of the type described can either rudimentarily or run continuously.

The manufacture of the catalytic systems and inventions Gegemäßη their application in reductive alkylation reactions is based on explained a number of implementation examples.

Example 1 represents a control reaction using only one kick catalyst. Examples 2 to 13 illustrate Reactions using the two-component system.

- 9 -109822/1845

example 1

138 g of the distilled p-arenodiphenylamine, 300 g of methyl isobutyl ketone and 2 g of a 63% nickel-on-kieselguhr catalyst are introduced into a 1 liter autoclave equipped with a stirrer. (This catalyst is a commercially available product from Ohemetron Corporation under the name G-49-A). The mixture is heated for 4 hours at 165 ⁰ O under a hydrogen pressure of 52.5-70 kg / cm. The product obtained is then removed from the autoclave and filtered. It is then distilled at 200 ° 0 of the distillation flask under a pressure of 15 to 25 mm Hg.

he follows

The analysis of the volatile components and the product / agent Gas chromatography. The volatile components show 10.0- / 0 the original ketones than reduced in the corresponding alcohol. Analysis of the product shows a 75% yield to N-4-methyl-2-pentyl-n ° -phenyl-p-phenylenediamine.

Examples 2 to 13 are carried out in the same manner as the example 1 with the exception that different 3ures are used in combination with the nickel catalyst.

Examples 2 to

at
game
No. acid g acid
per g
Kataly
sator solution io off
prey ° jb ketone redu
adorns in
alcohol 2 iDseig- 0.0088 Ethanol ⁺⁺ 77.3 10.9 3 iäseig- 0.0175 fl 78.5 11.1 4th Vinegar- 0.0350 H 81.1 11.5. 5 Oxal » 0.0065 Wasasr 7.7 6th öxai ™ 0.0130 «9 88.9 3.2 ff ösal * 0 * 0260 ' '89.7 4.5 8th ΐοΐαοΐβαΐίοη- 0.0115 iistiiaaol "*"" ¹ " 9ös2 4.7 9 Tolueneuifoo- 0.0229 H 85 fl 6.3 10 'foluenesulfone- 0.0458 IP 89.0 5.6 109822 / ι s 4 ε - 10 -

acid - 10 - solution "Jo off
prey 1667081 redu-
Al- Sclxwef el- g acid
per g Ka
catalyst water 90.3 at
game
No. ii 0.0070 Il 91.8 ψ ketone
adorns in
alcohol LI ir 0.0140 ti 87.5 3.1 12th 0.0280 2.8 13th 1.8

⁺⁺ gives absolute A exhy! alcohol in the above table and in all following tables.

The above numerical values show that the presence of an acid tends to improve the percentage yield in each case. Oxalic acid, toluenesulfonic acid and sulfuric acid continue to lead a decrease in the amount of ketone that is reduced in alcohol. This is especially true where sulfuric acid is used became.

Example 14 provides a control reaction using only a nickel catalyst. Examples 15 to 66 are carried out in the same way as Example 14 with the exception that the odd numbered examples employing various sulfur-containing compounds with combination with the nickel catalyst while the even-numbered examples apply both Scheefel-containing compounds as well as acids in combination with the nickel catalyst will «The untold examples 15 to 65 explain Reactiööer * aater applying two components Syet-ieftj according to dsr irs-patent script (US-Pa centanmelia im g SK 42UiGsK Explain the gijsMdzeiilÄgeB 16 bxs 66

üo

- Il 109822/1845

166/081

- li -

Example 14

In a 1 1 autoclave, which is equipped with ^ tBirer, are 138 grams of distilled p-aminodiphenylamine, 300 grams of methyl isobutyl ketone and 2 g of a 6370 Nicke 1-auf-K.ie se lguhr catalyst introduced. The iieaktion is 4 hours at a temperature of

165 ⁰ C carried out under a hydrogen pressure of 52.5-70 kg / cm. The product obtained is then removed from the autoclave and filtered, and ^{the distillation flask is then distilled at 205 °} C. under a pressure of 20 mm Hg. The analysis of the volatile constituents and the product is carried out by gas chromatography. The volatiles showed that 26 _f ^ 6> of the ketones originally used have been reduced in the entsprechenaen alcohols, Analysis of the product leads to a 57.8 # lgen yield of NA »-1l! Ethylä2» pentyl-N ^l -phenylp -phenylenediamine.

Examples 15 to 66

UEs combination en from 63 $ nickel-on-kieselguhr catalyst and various schwefeleathaltende "modifying agents in the manufacture of N-4-Metiiyl-2-pefityl-S ^ä -pl3, enyl-p-phenylenediamine evaluated, in two Pällen at Is it present and in the presence of an acid, Aqx ToluolaulfoHaäurs _? using the same concentration of reactants and nickel catalyst and the same reaction conditions as described in the example. The organic must be added to the reaction mixture either as a solution or as a solid, as shown in column 2 of the following table, the effectiveness of the catalyst used!, Vw '-'as zuÄ-Sauaeagefasst, Ms loluolsalf on acid is added in absolute ethanol *

- 12 109822/1845

at sulfur-containing modes solid g modes g Schwe Acid g Enamel f, ' ■ ■ game fixing agent or Lö fication fel pro Toluene- Point yield No. sung medium per g Kataly sulfone ⁰ C g Kataly sator acid sator per g Kataly sator 15th Thiodipropionic acid Ethanol 0.0258 0.0047 _ 35-44 81.7 16 Thiodipropionic acid Ethane oil 0.0258 θ, 0047 0.0229 48-51 100 17th j £ ylol monosulfide Methanol 0.0331 0.0044 - 43-47 93.8 18th Xylene monosulfide Methanol 0.0331 0.0044 0.0229 45-48 100 19th 'fhioanisol Methanol 0.0180 0.0047 - 43-48 93.8 20th Thioanisole Methanol 0.0180 0.0047 0.0229 41-45 100 21st Thiodipropionitrile Methanol 0.0206 0.0047 - 44-48 97.4 22nd Thiodipropionitrile Methanol 0.0206 0.0047 0.0229 47-r50 98.8 23 Benzothiazole Methanol 0.0200 0.0047 - 43-48 92.5 24 Benzothiazole Methanol 0.0200 0.0047 0.0229 45-50 98.3 25th Mercaptobenzothiazole fixed 0.0240 0.0 ^ 46 - 77.5 26th Kercap romp zo tjaiazol fixed Ο, Θ24Ο 0.0046 0.0229 45-49 97.9 27 Di-tert-butyl sulfide Methanol 0.0211 0.0046 - 42 _T 48 97.3 ι 28 Di-tert-butyl sulfide Methanol 0.0211 0.0046 0.0229 46-50 97.8 _H. 295 Benzothiazole monosulfide fixed 0.0290 0.0047 - 40-48 83.0 µ 30th Benzotniazoimonosulfide fixed 0.0290 0.0047 0.0229 44-48 97.0 ι 31 S-alkyl (C-6) mereapto- propionic acid Methanol 0.0284 0.0048 - 44-48 94.5 32 S-alkyl (C-6) mercaptopropion- acid Methanol 0.0284 0.0048 0.0229 44-49 96.7 33 Dimethyl sulfoxide benzene 0.0113 0.0046 - 46-50 94.1 34 Dimethyl sulfoxide Henzol 0.0113 0.0046 0.0229 47-50 96.6 35 fetraraethylthiuram monosulfide fixed 0.0150 0.0034 - - 79.0 36 Tetramethylthiuram monosulfide fixed 0.0150 0.0034 0.0229 41-47 95.4 37 sulfur fixed 0.0138 0.0138 - 42-48 92.4 38 sulfur fixed 0.0138 0.0138 0.0229 45-49 95.3 ^ i. 39 Diisooctyltjaiodiprionic acid Ethanol 0.0582 0.0046 - 38-47 86.0 σ-. 40 Diisooctylthiodipropionic acid Ethanol 0.0582 0.0046 0.0229 42-48 94.9 he. 41 ß-mercaptopropionic acid Methanol 0.0154 0.0047 - 40-47 93.5 ^ At ß-mercaptopropio acid Methanol 0.0154 0.0047 0.0229 44-48 94.8 c

N-4-methyl-2-pentyl-N'-phenyl-p-phenylenediamine.

OO

at sulfur-containing modes fixed g mode g sulfur Acid g Enamel * Off ^T - 166/08 game fixing agent or fizie- per g To Iu oil s ul- Point prey Mr. solution communication Kat & ysator fonic acid ° 0 tel pro per g Ka g Kataly catalyst Ditniodibenzoic acid sator 43 Bithiodibenzoic acid fixed 0.0410 0.0043 91.1 44 TetrametJaylthiuram disuifid fixed 0.0410 0.0043 0.0229 47-50 94.5 45 letramethylthiuraiadisulfide fixed 0.0179 0.0046 - 38-46 89.2 46 n-butyl sulfoxide fixed 0.0179 0.0046 0.0229 43-48 94.5 47 n-butyl sulfoxide Methanol 0.0234 0.0046m - 35-45 80.7 48 Xhiobenzoic acid Methanol 0.0234 0.0046 0.0229 40-47 94.3 49 Thiobenzoic acid Methanol 0.0200 0.0046 - 37-46 81.5 50 Thiourea Me uhan oil 0.0200 0.0046 0.0229 93.9 - » 51 Thiourea Ethane oil 0.0110 0.0047 - 38-47 84.3 O 52 Di thiobenzoic acid Ethane oil 0.0110 0.0047 0.0229 44-49 92.0 co 53 Ifttniobenzoic acid fixed 0.0410 0.0043 - 91.1 OO 54 Thiomalinaic acid fixed 0.0410 0.0043 0.0229 45-49 91.5 fO 55 Thiomalic acid Ethanol 0.0109 0.0024 - 74.5 " ■> » 56 Benzothiazole disulfide Ethane oil 0.0109 0.0024 0.0229 40-47 91.0 η _ » 57 Benzothiazole disulfide fixed 0.0240 0.0047 - 82.4 ^ co 58 4-methylthiophenol fixed 0.0240 0.0047 0.0229 39-46 90.6 ι J> 59 4-Me thy lthi opium oil Methanol 0.0178 0.0046 - 40-44 83.8 cn 60 Benzyl disulfide Methanol 0.0178 0.0046 0.0229 40-46 90.5 61 Benzyl disulfide fixed 0.0180 0.0047 - 39-45 84.0 62 Morpholine disulfide fixed 0.0180 0.0047 0.0229 41-46 88.5 63 Morpholiodisulfide fixed 0 0168 0.0046 - 37-45 83.7 64 Sodium sulfide fixed 0.0168 0.0046 0.0229 40-46 87.5 65 Sodium sulfide fixed 0.0110 0.0045 - 4 «- 61.6 66 fixed 0.0110 0.0045 0.0229 74.4 I.
H +++ H-4-methyl-2-p & entyl-H'-phenyl-p-phenylenediamine.

ibb / 081

The Yields of the table above show that the addition of a Acid to catalytic] systems based on nickel catalyst / sulfur containing modifier to increase the percentage yield in reductive alkylation reactions leads. Me numerical values further show that the melting point ranges become narrower by applying an acid, indicating that the alkylation products were of a high degree of purity.

Examples 67 to 78

It becomes the three component catalytic of the present invention System with the catalytic system made of nickel catalyst Sulfur-containing modifying agents in various reductive alkylation systems that do not use the p-arenodiphenylamine / methyl isobutyl ketone system The same experimental conditions are used as in Example 14 described, applied. The effectiveness of the various catalytic Catalyst Systems is summarized in the following column. The ihiodipropionic acid is dissolved in absolute Ethanol as the sulfur-containing modifier in in each case at a concentration of 0.0258 g of sulfur-containing Modifiers applied per gram of the catalyst. This leads to a sulfur concentration of 0.0047 g sulfur per g of the catalyst. The! Toluenesulfonic acid is in absolute ethanol in a concentration of 0.0229 g per g of the catalyst added.

109822/1845

bB / 081

example
No.

Alkylation system

catalytic system melting

point ⁰ O prey

67 184 g p-aminodipjienylamine nickel / modifier and 288 g of 2-octanone

68 184 g p-aminodiphenylamine nickel / modifier / and 288 g of 2-octanone acid

69 184 g p-aminodiphenylamine nickel / modifying m. 48-51 and 288 g of ethyl methyl ketone

70 184 g p-aminodiphenylamine nickel / modifying agent / 50-52 and 288 g of methylethyl acid

ketone

71 184 g p-atninidiphenylamine nickel / modifying m. 48-51 and 288 g of Meohyläthy1-

ketone +

72 184 g p-aminodiphenylarain nickel / modifying m. 49.5-51.5 and 288 g of ethylethyl acid

ketone +

93 g aniline and 400 g methyl isobutyl ketone

93 g aniline and 400 g methyl isobutyl ketone

54 grams of p-phenylenediamine and 400 g of 2-octanone

54 g of p-i'henylenediamine and 400 g of 2-octanone

175 g of p-nitrodiphenylarain and 295 g of methylethylkexone

175 g of p-nitrodiphenylamine and 295 g of methyl ethyl ketone

Nickel / Moidifzierungsra.

Nickel / modifier /
acid

Nickel / modifier

Nickel / modifier /
acid

Nickel / modifier

Nickel / modifier /
acid

44-48

45-58

98.4 100

46.3 65.0 88.6 92.3 94.0

+ Versuc.il at 140 ⁰ G.

The percentage yields in the objjpn table show that the inventive cataiyxic system contributes to an increase in the losses "Leads to different types of alkylation systems. Jis understands that in, those cases where the percentage yield is close to the theoretical value lies; it is impossible to determine the percentage by the addition of the acid To significantly increase yield, j & iner of the benefits of using a Acid in such systems is that it makes the application of lower alkylation temperatures is allowed to come in handy theoretical yields, another advantage is that that higher reaction rates for a given reaction temperature

109822/1845 - 16 -

1b67081

.- 16 -

The percentage yield values in Examples 69, 70, 71 and 72 are given as an indication of such an effect. In the latter two examples, the Alkylierungeraaktion #ird at reduced! Temperature of 140 ⁰ C instead of 165 ⁰ C., while still practically theoretical yields.

Examples 79 to 84

Various acids are evaluated for the production of N-4-methyl-2-pentyl-N ¹ -phenyl-p-phenylenediamine using a three component catalytic system using the same experimental reactants and conditions as are used is described in Example 14. Thiodipropionic acid dissolved in absolute ethanol is used as the modifier in each pail at a concentration of 0.0258 grams of the modifier per gram of the catalyst. the

zuSäuren are added in solution / and the solvents sinα in the Column 3 of the following table. The effectiveness of the various Acids is summarized in the following table:

at acid solvent g of acid per Enamel yield game
No. g catalyst point ⁰ C 79 - - - 38-44 89.3 80 Sulfur- water 0.0140 48-50.5 99.9 81 Vinegar- Ethanol 0.0175 48-50.5 98.6 82 Oxalic water 0.0260 48-50.5 97.7 83 Hydrochloric acid water 0.0049 46-48 95.6 84 Oleic acid Methanol 0.0820 47-50 95.1

The above numerical values show that other than organic Sulphonic acids can find use in the practice of the invention.

- 17 109822/1845

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Examples 85 to 88

.Ss are pre-modified catalytic systems produced by the nickel catalyst in absolute terms. Ae than oil slurried and that Sulfur-containing modifiers and the acid are also added dissolved in absolute ethanol. The slurry is mixed well and dried in a vacuum oven. The free-flowing, solid, pre-modified systems are then replaced of the normal catalytic systems using the same feed and conditions as described in Example 14 to produce N-4-methyl-2-pentyl-N'-phenyl-p-phenylenediamine. isines the pre-modified nickel catalyst / sulfur containing Modifying agent and nickel catalyst / sulfur-containing modifying agent / acid-catalytic systems are used. Me effectiveness of these pre-modified systems is compared in the following table:

For example, sulfur-containing modifi- g sulfuric acid game modifier free of charge per g of Soluol-No, medium g of catalysis sulfone

per g of catalytic acid Sohmelztalysator per g point 5έ

Cataly- ⁰ O Aussator prey

85 Thiodipropionic acid 0.0258 0.0047 0.0229 46-50 93.9 86 Thiodipropionic acid 0.0258 0.0047 - 48-51 97.7 87 Xylene monosulfide 0.0331 0.0044 0.0229 46-49 95.8 88 Xylene monosulfide 0.0331 0.0044 48-50 96.7

The numerical values in the table above show that the invention

you as

according to catalytic systems are also effective if / pre-modified catalytic systems are produced and that the addition of an acid increases the percentage yield. In summary, the JS patent application (US patent application SN 426,4oüj showed that applying eohulphur-containing Products together with a nickel catalysis boron

109822/1845 -18-

reductive alkylation reactions increased without inconvenient Side reactions are encouraged. Due to the present refinancing it is now shown that the use of different acids in combination with nickel catalysts leads to improved performance in reductive alkylation reactions and in some cases to one Reduction of inappropriate side reactions leads to. Furthermore, it is shown according to the invention that the use of different Schwefelenthal Gender products in combination with the nickel catalyst acid system leads to even greater yields than either using them the nickel catalyst / sulfur-containing product or nickel catalyst / acid systems can be achieved without undesirable neoene reactions be promoted.

109822/1845

Claims (10)

Patent Attorneys Ibb / Ubi Dipi.-ing. Walter Meissner jQ Dipi.-ing. Herbert Tischer 1 BERLIN 33, HERBERT8TRA8SE 22 MÜNCHEN Telephone: 8 87 72 37 - Wire word: Invention BerKn Postal check account: W. Meissner, Berlin West 12282 ^ ",,, Bank account: W. Meissner, Berilner Bank A, -GL, Depka 36 * "_" .... q "/ rpiiMpwAl m rlen" · ♦ "** Beriln-Halensee, Kurfarstendamm ISO ^ BERLIN 33 (GRUNEWALD), the" Herbertstrasse 22 The Goodyear Tire and Rubber Oompany 6153 patent applications 1. Catalytic system, characterized in that the same Ca; a nickel catalyst and b) at least one acid selected from the group consisting of sulfur-free acids and sulfur-containing acids in which the sulfur is in the form of a -S- best, It Has 0. 2. Catalytic system according to claim 1, characterized in that the acid is a sulfur-free acid. 3. Catalytic system according to. Claim 1, characterized in that as a third component there is at least one sulfur-containing product selected from the group consisting of Schwefex and sulfur-containing compounds is selected, at least part of the sulfur being present in 3? orm at least one Hestes, who is selected from the group consisting of -S- and -S- « If 4. Catalytic system according to claim 1, characterized in that that the third component used is a sulfur-emthaluendes product which is selected from the group consisting of sulfur, thioureas, Sulfidic acids, mercapto acids, thioamides, disulfidic acid, thiuram disulfides, Mercaptans of sulfur-containing heterocyclic compounds, disulfides of ring-sulfur-containing heterocyclic compounds Compounds, heterocyclic compounds containing ring sulfur, disulfides, oyanosulfides, sulfoxides, thioacids, organic sulfides, mercaptans, dithio acids, sulfides ring sulfur containing heterocyclic compounds and sulfidic acid esters, where da ^ ac ^ efelegilwltende product in the cataly- mo table system is present in an amount such that 0.10 to 4.0 grams of the sulfur present in the compound is present per 100 grams of nickel are, as well as the acid in the catalytic system in one Amount of from 0.005 to 0.100 grams molecular weight of the acid per 100 grams of nickel is present in the metal catalyst. 5. Catalytic system according to claim 1, characterized in that that the acid is toluenesulfonic acid and the catalytic system contains thiodipropionic acid as a third component. 6. Process for making an N-alkyl substituted amine by means of implementing a product that consists of the group selected from amine compounds, nitro compounds and nitroso compounds is, with a product selected from the group consisting of aldehydes and ketones in the presence of hydrogen, a characterized in that the .Reaktion in the presence of a catalytic Amount of a catalytic system according to claim 1 is carried out 7. The method according to claim 6, characterized in that a catalytic System according to claim 2 is applied 8. The method according to claim 6, characterized in that a catalytic System according to claim 3 is applied. 9 · The method according to claim 6, characterized in that a catalytic System according to claim 4 is applied. 10. The method according to claims 6, characterized in that a catalytic Syetem according to claim 5 is applied. The patent attorney Dipl.-Ing. W. Meissner Dipl.-Ing. H. Tischer 109822/1845