DE1048277B - Process for the preparation of ring-alkylated aromatic amines - Google Patents

Description

The subject of patent 951 501 is a process for the preparation of ring-alkylated aromatic amines, which consists in allowing olefins to act on aromatic amines in the presence of aluminum or its alloys and the reaction at elevated temperatures, preferably around 200 to 350 ⁰ C, and elevated pressures, preferably around 100 to 200 atm.

In further processing of the inventive concept on which the main patent is based, * ° found that ring-alkylated aromatic amines in a particularly uniform form and with even better Yields can be obtained when using olefins in the presence of Friedel-Crafts catalysts or Full earths with the simultaneous presence of metallic aluminum or aluminum compounds aromatic amines can act on aromatic amines.

In practice, additions of metallic aluminum to aluminum chloride and boron fluoride have proven particularly useful or bleaching earth.

As Friedel-Crafts catalysts (see e.g. Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Vol. IV, Part 2, p. 67) can contain a large number of Metal and non-metal halides are used, as well as certain substances that split off hydrogen ions, which are collectively referred to as Lewis acids, antibases or Ansolvo acids.

The same olefins and aromatic amines can be subjected to the new process as The starting material for the process of the main patent is used, ie ethylene and its homologues, such as in particular Propylene, butylene and isobutylene, but also cycloolefins and aromatic substituted olefins.

The aluminum used is expediently made by adding a small amount of mercury (II) chloride activated.

The amount of aluminum used or of the aluminum compounds of the aromatic amine can be varied within wide limits. Generally enough. 10 to 100%, calculated on the amount of the basic catalyst which suitably is used in the amine to be alkylated, in amounts of 1 to 10 ° / _0, bereclmet. For example, the propylation of aniline achieves excellent results

for the production of nucleus alkylated
aromatic amines

Addition to patent 951 501

Applicant:

Paint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk

Dr. Rudolf Stroh, Leverkusen-Bayerwerk,

Dr. Josef Ebersberger, Leverkusen,
Dr. Hans Haberland, Leverkusen-Bayerwerk,

and Dr. Wilhelm Hahn, Cologne,
have been named as inventors

Results when using 6% aluminum chloride and 2% aluminum, calculated on that used Amine. In some cases, however, it can also be advantageous to add larger or smaller amounts of catalyst use.

The reaction conditions are the same as in the main patent. A particular advantage of the process according to the invention is that the reaction products are more uniform, ie that the N-alkylation of the amines and the polymerization of the olefin are suppressed in favor of the core alkylation. With bleaching earth alone is obtained, for example, at 300 ⁰ C in addition to the nucleus-alkylated anilines with propylene and N-isopropylaniline and N, N-diisopropylaniline; if the aluminum anilide is also present, only core alkylation takes place.

Propylation of the aniline in the presence of

a) 2% fuller's earth and

b) 2% fuller's earth and 2% aluminum.

Catalyst type

N-isopropylaniline

Mole percent

2-isopropyl

aniline mole percent

Ν, Ν-diisopropylaniline
Mole percent

2,6-diisopropylaniline
Mole percent

2,4,6-TrUsO-propylaniline
Mole percent

aniline
sales

Reaction temperature 30 ° C

a) 5.5 49.3 12.9 21.9 0 91.4 b) 0 59.7 0 23.3 0 85.7 80Ϊ 728/280

With more catalyst (10%) or at higher reaction ^{temperatures (340 °} C.), more highly alkylated anilines are also formed in the presence of fuller's earth alone, ζ. B. with propylene 2,4,6-triisopropylaniline. This is also suppressed by the presence of the aluminum anilide, so that only 2-isopropylaniline and 2,6-diisopropylaniline are formed; unless one

too much propylene presses (up to about 1.5 to 2 moles of propylene per mole of aniline). If you carry a larger amount If propylene is added, 2,4,6-triisopropylaniline is also formed (see Example 2).

Propylation of the aniline in the presence of

a) 10 ° / ₀ bleaching earth and

b) 10 ° / ₀ bleaching earth and 2% aluminum.

Catalyst type

N-isopropyl

aniline
Mole percent

2-isopropyl

aniline
Mole percent

Ν, Ν-diisopropylaniline mole percent 2,6-diisopropylaniline
Mole percent

2,4,6-triisopropylaniline

Mole percent

aniline
sales

Reaction temperature ^{300 0 C}

a) 0 46.6 0 34.9 C. 42.4 3.0 85.9 b) 0 56.8 0 32.1 34.9 0 93.9 a) 0 38.6 13.2 98.7 b) 0 49.8 Reaction temperature 340 ° 0 92.1 0 0

The situation is similar with aluminum chloride or aluminum chloride and aluminum anilide as catalysts. At lower temperatures N-alkylation in addition to core alkylation, at higher temperatures with aluminum chloride alone 2-, 2,6- and 2,4,6-substitution, in the presence of the mixed catalyst, in both cases only formation of 2-isopropylaniN and 2,6- Diisopropylaniline.
Propylation of the aniline in the presence of

a) 2% aluminum chloride

b) 2% aluminum chloride and 2% aluminum as anilide.

Catalyst type

N-isopropyl

aniline
Mole percent

2-isopropyl

aniline
Mole percent

N, N-diisopropylaniline mole percent 2,6-diisopropylaniline
Mole percent

2,4,6-triisopropylaniline
Mole percent

aniline
sales

Reaction temperature ^{250 ° C}

a)
b) 20.8
0 28.0
33.6 18.0
0 31.7
59.0 0
0 40.3
46.0 0
0 15.8
3.1 300 ⁰ C 14.5
27.3 340 ° C 18.0
14.8 0
0 85.0
38.5 Reaction temperature Reaction temperature a)
b) 20.3
0 0
0 71.8
88.6 a)
b) 0
0 4.5
0 67.2
69.1

By varying the test conditions accordingly, it is even possible to use 2,6-DiisopropylaniHn Main product can be made with a yield of up to 80% (see examples).

Aluminum chloride alone, like most Friedel-Crafts catalysts also promotes the polymerization of the olefin to resins and liquid, higher ones Hydrocarbons. This polymerization can be caused by the presence of aluminum or its anilides can be completely prevented. There is only nuclear substitution of the amine in the two ortho positions.

Compared to the process catalyzed solely with aluminum anilides, the present process has the advantage of greater reaction rate and more complete conversion. Aniline can be z. B. in the presence of aluminum anilide completely in a few hours in the two ortho positions, but not propylate. The propylation is very slow from the start and finally comes to a complete standstill. You can z. , At 250 ° C anneal example of aniline in the presence of Aluniiniumanilid, corresponding to 2% aluminum, very little, at 300 ⁰ C in 4 hours and 0.24 mole at 340 ⁰ C in 4 hours 0.95 moles of propylene per mole of aniline . With a mixed catalyst consisting of 2% fuller's earth 11 ::: 1 2 ° / ₀ aluminum as anilide, the uptake of propylene in 4 hours at 250 ° C is already 1.09 mol; at 300 ⁰ C and 1.59 moles at 340 ° C 1.60 moles per mole of aniline. Aluminum chloride accelerates the reaction in a similar way. With a catalyst consisting of 6% aluminum chloride and 2 ⁰ I ₀ aluminum as anilide, you can, for. B. add 2.19 moles of propylene per mole of aniline in 4 hours at 300 ⁰ _{C, while with 5 ° / 0} aluminum in the same time only 0.50 moles are consumed. In the presence of the aluminum, a considerable amount of unconverted aniline is always recovered, while the mixed catalysts described in the present process permit quantitative or almost quantitative conversions.

However, there are also considerable differences in the ethylation of aniline between the simple aluminum anilide as a catalyst and the mixed catalyst with aluminum chloride. In the presence of 2.5% aluminum powder, aniline e.g. B. at 300 ⁰ C in 6 hours on 1.9 moles of ethylene per mole of aniline. Working up gives 78 to 79% 2,6-diethylaniline, calculated on the aniline used. In the presence of 2% aluminum and 6% aluminum chloride, on the other hand, exactly 2 moles of aniline are taken up ^{in 1 1} ₂ hours, likewise at 300 ^{° C.} Rectification gives 91 ⁰ Z ₀ 2,6-diethylaniline. Another advantage is the low reaction temperature

5 6

rature; because already at 250 ⁰ C 2 mol tion results in 33.6% 2-isopropylaniline and 3.1% 2,6-diiso-ethylene consumed in 3 hours and 2,6-diethylaniline in an auspropylaniline. None of the experiments resulted in a yield of more than 90% of the theoretical value. liquid and not resinous polymerization products of the

Working up is expediently carried out in such a way that the olefin is removed. N-propylation does not occur either. The off-reaction mixture Stirred with dilute sodium hydroxide solution, 5 bags are all in mol percent of aniline used to decompose the anilide formed. The further charged.

processing takes place as in the main patent. Example 6 obtained

new products can be used for the same purposes as stated in the main patent. In 300 parts by weight of aniline there are 18 parts by weight From studies by Woroshzow and Joffe io aluminum chloride dissolved and mixed with 6 parts by weight of AIu- (cf. Chemisches Zentralblatt, 1955, p. 4809, 4810) is a miniumgrieß or powder added. The mixture is in Process for the core alkylation of aniline with olefins heated to 300 ° C in an autoclave. This is where education takes place known as the vapor phase in the presence of kaolin. At the aluminum anilide held by the presence this process, in which no Friedel-Crafts-Kataly- the aluminum chloride is promoted, so that an actuator or bleaching earths are used, a sublimate is not absolutely necessary. but only low yields. Ethylene is then pressed up to a pressure of 200 atm

on. The response goes through a very quick one

Example 1 Noticeable decrease in pressure. The pressure will be so long

added until the reaction has ended. In I ¹ Z ₂ hours

300 parts by weight of aniline, 6 parts by weight of fuller's earth, 20 2 moles of ethylene are consumed per mole of aniline. The 6 parts by weight of aluminum powder and 0.2 parts by weight of reaction product is stirred with water, and the mixture is heated ^{to 340 ° C. in an autoclave using sodium sublimate.} alkali made alkaline and fractionally distilled. Propylene is then obtained up to a pressure of 250 atm in addition to a small forerun and one is also pressed and the pressure is renewed to the extent that the small residue is only 2,6-diethylaniline. The yield increases. In 4 hours, 1.1 moles of propylene per mole of 25 is 91% of theory. Aniline consumed. It is worked up with water

stirred, made alkaline and the amine mixture removed

separates. With fractional distillation, 62%

Isopropylaniline and 28% 2,6-diisopropylaniline obtained. The same approach as described in Example 6 is used

with an aniline consumption of 93%. 30 at 25O ⁰ C with ethylene under a pressure of 150 to

200 atm treated. In 3 hours, 2 moles of ethylene Example 2 are consumed per mole of aniline. 2,6-diethylaniline is obtained

in a yield of more than 90%. 150 parts by weight of aniline, 15 parts by weight of fuller's earth,

3 parts by weight of aluminum powder and 0.1 part by weight of 35 Example 8

Sublimate are made in the same way as in Example 1

described, treated with propylene. In 4 hours 18 g of aluminum chloride are dissolved in 300 g of aniline,

2.78 moles of propylene are consumed. Work-up This forms a considerable amount of heat happens as in example 1. The aniline consumption is aniline-aluminum chloride complex. You then put 6 g quantitatively. During the distillation, 4% 2-isopropyl aluminum grit or powder is added and the mixture is heated aniline, 46% 2,6-DüsopiOpylaniline and 43% 2,4,6-triiso in an autoclave at 300 ° C. The aluminum goes, get propylaniline. promoted by the aluminum chloride complex, under

r> ":" ";" i ο hydrogen development and formation of an aluminum

amlids in solution. If you now press ethylene on, so

300 parts by weight of aniline, 6 parts by weight of aluminum 45 are dissolved in 1 ¹ J ₂ hours, about 2 moles of ethylene per mole of aluminum chloride and 6 Gewichtsteüe be received in a Anüin and there is obtained 2,6-diethylaniline in autoclave at 300 ° C heated and propylene pressed on. a yield of 90.8% of theory. The reaction is soon noticeable through the decrease in pressure. The pressure is added to Example 9 from time to time. Aniline conversion of 50 is obtained in 10 hours

of 88.6%. Rectification yields 59.0% 2-isopropyl- 6 g of aluminum grit or powder with 300 g

aniline and 27.3% 2,6-diisopropylanine. Aniline and 0.1 to 2 g of sublimate in an autoldav

200 ⁰ C heated. The aluminum goes under bonding

Example 4 i ⁿ solution. The reaction mixture is cooled, the

55 formed hydrogen relaxed, 18 g aluminum

200 Gewichtsteüe aniline are added in the presence of chloride and then heated to 300 ⁰ C. The 12 parts by weight of aluminum chloride and 4 parts by weight of ethylene are consumed very quickly. Aluminum in the same way and at the same temperature In 50 minutes, 2 moles of ethylene are propylated to the aniline in Example 3. One receives with a Prolagert. The yield of 2,6-diethylaniline is 92.0% pylene consumption of 2.09 moles per mole of aniline quantita- 60 of theory.

tive aniline conversion. The rectification gives 10.2% Example 10

2-isopropylaniline, 79.2% 2,6-diisopropylaniline and 5.8%

2,4,6-triisopropylaniline. 300 g of aniline are mixed with 6 g of aluminum chloride and 6 g

_R. · 1 ς aluminum heated ^{to 300 ° C. in an autoclave.} then

.Example ö _5g ^^ ^^ γΐβη up to a pressure of 200 atm.

300 parts by weight of aniline are pressed in the presence of. The consumption of ethylene has ended after 100 to 110 minutes with 12 parts by weight of aluminum chloride and 6 parts by weight and is 2.08 moles per mole of amine. The dispensing aluminum at 250 ⁰ C propylated. The yield of 2,6-diethylamine is 90.3%. 4 hours a propylene consumption of 0.45 mol per mol in a comparative experiment without aluminum chloride

Anüin. The aniline conversion is 38.5%. The distillation 70 is the Äthylenaufnahme in 4 hours at 300 ⁰ C.

1.84 moles per mole of aniline and the yield 86.7% of 2,6-diethylaniline. In addition, 5.3% is 2-ethylaniua educated.

Example il

300 g of aniline are heated to 300 ° C with 6 g of aluminum and 6 g of tin tetrachloride and with ethylene under treated at a pressure of 200 atm. In 100 minutes 2 moles of ethylene per mole of aniline are taken up and 96.0% 2,6-diethylaniline obtained.

Example 12

Instead of the tin tetrachloride used in Example 11, 2 percent by weight of zinc chloride is added. The yield of 2,6-diethylaniline is 83.3% of theory and 6.9% 2-ethylaniline.

Example 13

20th

Instead of the catalyst used in Example 11 2 percent by weight boron fluoride and 2 percent by weight aluminum are used. 2,6-diethylaniline is obtained in good yield in addition to a little 2-ethylaniline.

Example 14

When carrying out the procedure described in Example 11 using 2 percent by weight Titanium tetrachloride and 2 percent by weight of aluminum, calculated on the amine, are 1.96 moles of ethylene per mole Attached to aniline and 3% 2-ethylaniline and 87.5% 2,6-diethylaniline.

104 ° C) obtained in a yield of 47.4% of theory in addition to unchanged aniline.

Example 19

200 g of aniline are heated ^{to 250 °} C. in an autoclave with 20 g of fuller's earth and 4 g of aluminum. A little sublimate is added to activate the aluminum. 2.11 moles per mole of aniline of the isobutylene pressed in are consumed in 4 hours. The yield is 62.3% mono-tert-butylanuene and 12.3% ditert. -butylaniline.

Example 20

200 g of aniline are heated to 200 ° C. in the presence of 8 g of boron fluoride and 4 g of aluminum and under pressure treated with isobutylene. In 4 hours, 1.48 mol of isobutylene and 30.9% of mono-tert-butylane are consumed and 29.8% di-tert-butylanuene.

Example 21

300 g of o-toluidine are mixed with 6 g of aluminum chloride and 6 g of aluminum and heated to 300 ° C. in an autoclave heated. The injected propylene is consumed quickly.

1.06 mol per mole of amine are added on in 2 hours. This gives 2-methyl-6-äthylanüin (Kp. _I0 102 ° C) in a yield of 87.4% of theory.

Example 22 Example 15

Are in place of the titanium tetrachloride used in Example 14 If 2 percent by weight of silicon tetrachloride is used, 2.05 moles of ethylene are consumed per mole of aniline and obtained with complete aniline conversion 95.5% 2,6-diethylaniline.

300 g of o-toluidine are heated ^{to 300 °} C. with 12 g of aluminum chloride and 6 g of aluminum. The propylene that is pressed in is quickly absorbed with the formation of 2-Me ^ yI-O-ISOPrOPyIaHiIm. The yield is 73.0%, the boiling point 108 to HO ⁰ C at 10 torr.

Example 23

300 g of m-toluidine are in the same way as in Example 20 indicated, ethylated. Example 16 is obtained in 1 hour with an ethylene consumption of 1.91 moles per mole of amine

3-methyl-2,6-diethylaniline (b.p. _lo 125 ° C) in an off-300 g of aniline, 18 g of vanadium trichloride and 6 g of aluminum 45 booty of 92.8%.

nium grits are heated to 300 ° C in an autoclave. Then the ethylene pressed in up to a pressure of 200 atm is quickly absorbed. The reaction is complete in I ¹ J ₂ hours. 1.85 moles per mole of aniline

Example 24

Following the procedure of Example 23, p-toluidine is ethylated. With an ethylene consumption of

consumed per mole of amine. The yield of 2,6-diethyl 50 2 moles per mole of amine is obtained 94.4% of 4-methyl-2,6-di-

aniline is 85% of theory.

Example 17

200 g of aniline are mixed with 12 g of aluminum chloride and 4 g of aluminum and heated to 300 ° C. in an autoclave heated. Butylene is then injected using a high pressure pump up to a pressure of 250 atm. The reaction is soon noticeable through the decrease in pressure that occurs. Receives in the work-up a butylaniline boiling point 108 to 110 ° C (10 Torr) and a dibutylaniline boiling point 140 ° C (10 torr).

Example 18

200 g of aniline are heated to 200 ° C. with 12 g of aluminum chloride and 4 g of aluminum in an autoclave. Then isobutylene is injected. In 6 hours the olefin consumption is 0.53 mol per mol of aniline. The only reaction product is mono-tert.-butylaniline (b.p. _la ethylaniline (b.p. _lo 122 ° C).

Example 25

200 g of p-toluidine are heated with 12 g of aluminum chloride and 4 g of aluminum at 28O ⁰ C. The propylene that is injected is absorbed quickly. The rectification gives 4-methyl-2,6-diisopropylaniline with a boiling point of 132 to 133 ^° C. (10 Torr) in a yield of 66.1%.

Example 26

60 200 parts by weight of 2,4-Toluylenediamine with 8 parts by weight of anhydrous aluminum chloride and

6g 150 parts by weight of a solution of aluminum anilide in Aniline (containing 2% aluminum) heated to 280 ° C in an autoldav and 200 atm of ethylene pressed on. The olefin is consumed very quickly. After the pressure has dropped to 100 to 150 atmospheres, it is again

Additional ethylene injected. After taking 100 weight

share ethylene, the reaction rate falls sharply Example 30

away. If you interrupt the ethylation now, you get

When working up the batch, 70% of the amount used is obtained by following the procedure of Example 29

Aniline returned unchanged. The remainder is present as 2-ethyl from 20% aniline and 80% 2,6-to] uylenediamine with the aniline. The 2,4-toluenediamine is in 95% off as described there 5 the same quantities of catalyst, yield reacted at 28O ⁰ C with ethylene in the l-methyl-3,5-diäthylphenylendiamin- (2,4). You almost get passed over. This is a pale yellow, viscous liquid quantitatively the l-methyl-SS-diäthylphenylendiaminkeit from Kp. _5150-151 ⁰ C. The diacetyl compound (2.6) and according to the reaction time varying amounts forms colorless needles, mp. 310 to 311 ⁰ C. of 2-ethylaniline and 2,6-diethylaniline.

If the ethylation is not interrupted and the io.

If the reaction comes to an end, around 50 more times are required. Example al

parts by weight of ethylene and added to the formation of 300 parts by weight of 2,6-toluene diamine with

2-ethylaniline consumed. Working up the batch 6 parts by weight of aluminum powder, 8 parts by weight takes place by stirring with aqueous sodium hydroxide solution to anhydrous aluminum chloride and 0.2 "parts by weight Removal of the catalyst and subsequent fractional mercury chloride heated to 280 ° C. in an autoclave. As soon ned distillation of the amines. the resulting hydrogen pressure the formation of the

The aluminum anilide solution used can easily be indicated by aluminum amide when ethylene is consumed Heating of aniline with aluminum to the boiling point (100 to 200 atü). The reaction is extreme point of the amine with evolution of hydrogen and quantitatively leads to the formation of 1-methyl sites. 20 3,5-diethylphenylenediamine (2.6), which after extracting Example 27 reaction product with dilute sodium hydroxide solution

60 to 8O ⁰ C has a freezing point of 52 ° C, the

Following the procedure of Example 26, 200 Ge are increased to 58 ° C. after the distillation, parts by weight of 2,6-tolylenediamine with 150 parts by weight. -, O ₉

of the anilide solution described and 8 parts by weight of Example 32

Aluminum chloride reacted with ethylene at 280 ° C. The 200 parts by weight of diphenylamine are mixed with 150 parts

Ethylene uptake takes place very quickly and is substantially parts by weight of an aluminum anilide solution (with a slower rate, after 2 moles of olefin per mole of diamine is equivalent to 2% Al) and 8 parts by weight of anhydrous. If the reaction is interrupted on this aluminum chloride at 280.degree. C. with ethylene at a temperature of 200 atmospheres and the batch is treated as in Example 1. When the pressure is written down to 100 to 150 atmospheres, most of the aniline is unchanged and has fallen, and more ethylene is injected each time. In the diamine quantitatively in the l-methyl-3,5-diethyl period of 1 ¹ ₂ hours I 160 parts by weight are converted phenylenediamine (2.6). This boils under ethylene. The liquid reaction product was added 5 Torr 152-155 ° C as a colorless oil, which is at 58 ⁰ C with dilute sodium hydroxide solution and the Aminerstarrt. The diacetyl compound crystallizes in a colored mixture separated by fractional distillation, loose needles with a melting point of 324 to 326 ° C. At first, 2,6-diethylaniline is produced in a yield of

further exposure to ethylene, the aniline is obtained in 95% of theory. Diphenylamine is no more 2-ethylaniline and finally in the 2,6-diethylaniline, but is present as diethyldiphenylamine, converted. a pale yellow one boiling below 5 torr at 159 ° C

Example 28 ⁴ ° ^Ö1 ( ^K ? · ^{10 173 to 174} ° ^c ) · ^The yield is 93% of the

Theory.

200 parts by weight of technical tolamine (about 70% r H N C ?? =! 3? \

2,4-toluylenediamine and 30% 2,6-dolylenediamine) become ^ 'VT r ^ 98 0 / _H ο _ςη ο / ν fi 99 ο / ·

according to the method of Example 26 in the presence of Calculated .... C 85.28%, H 8.50%, N 6.22%,

8 parts by weight aluminum chloride and 150 parts by weight 45 found C 84.87%, H 8.30%, N 6.16%.

share the aluminum anilide solution at 280 to 300 ⁰ C with that obtainable in the usual way from this amine

Ethylene implemented. The course of the reaction is the same. Nitrosamine forms light brown flakes from the melt in Examples 1 and 2. The diamines are at point 63 to 65 ° C.

the corresponding diethyl derivatives implemented (from C H ON (254 32)

loot 95% of theory). The mixture of these dietary 50 " ^{1S 2} / '/" _CCi - _n , TT ₇₁ O ₀ / xrnnoo;

th Diamine boils below 5 torr from 150 to 154 ° C as Calculated .... C 75.56%, H 7.13%, N 11.02%;

hay-yellow oil. The monoamine content of the reaction found C 75.55%, H 6.85%, N 10.93%.

The mixture consists of aniline, depending on the duration of the etherification. The nitrosamine can be mixed with hydrogen chloride

Rearrange 2-ethylaniline and 2,6-diethylaniline in various alcohol ethers to form the 4-nitroso compound (melting point ratios. 55 100 to 102 ⁰ C). This nitroso compound provides the

Example 29 alkaline hydrolysis of o-ethylaniline. This is

showed that the one ethyl group in the 2-position of the

1000 parts by weight of a mixture of 80% 2,4-tolu-diphenylamine entered and the second ethyl group ylenediamine and 20% aniline are seated in the presence of in the other core, either in the 2- or 3-position. 15 parts by weight of aluminum, 20 parts by weight of aluminum - 60 Since, according to all previous experience with core alkynium chloride and 0.8 parts by weight of mercury chloride in the presence of aluminum catalysts, none is heated in the autoclave to 280 to 300 ° C, with aluminum substitution the amine of bp. ₅ nium goes into solution with evolution of hydrogen. 159 ⁰ C before the 2,2'-diethyldiphenylamine. This consti-If one now presses on ethylene at 200 atmospheres, this tution is also confirmed by the ultrared spectrum, and is absorbed very quickly. The reaction is after 65 _.

would take a lot of long out of 400 parts by weight of ethylene - example όό

samer. The 2,4-toluenediamine is now in 95% 800 parts by weight of diphenylamine, 200 parts by weight

Yield as l-methyl-3,5-diethylphenylenediamine- (2,4) aniline, 15 parts by weight of aluminum powder, 18 parts by weight. The aniline is 60% unchanged. The remainder is in parts of aluminum chloride and 0.5 part by weight of mercury 2-ethylaniline passed over. 70 chloride are at 280 to 300 ° C with ethylene in an autoclave

11 12

implemented. The ethylene pressure is repeatedly increased to 200 atm. Total will be

Repressing held at 150 to 200 atmospheres. Added within 160 to 180 parts by weight of ethylene, after which

390 to 400 parts by weight of ethylene are consumed for 90 minutes - the reaction comes to a standstill. The reaction

taken. The reaction product is mixed for removal by steam distillation in the mono-

of the catalyst is stirred with sodium hydroxide solution, the organic 5 amine and benzidine components are separated. The distillate

niche layer separated and fractionally distilled. consists mainly of 2,6-diethylaniline besides little

Practically only 2,6-diethylaniline (yield: 95% 2-ethylaniline. The ethylated benzidine is highly viscous)

of theory) and 2 ₎ 2'-diethyldiphenylamine of bp ₅ oil, which consists mainly of tetraethylbenzidine.

159 ° C obtained (yield 92% of theory). This can be done according to that described in Example 35

ίο method to be separated.
Example 34

Example 37

600 parts by weight of m-phenylenediamine, 450 parts by weight of aluminum anilide solution containing 2% aluminum, 300 g of 2-ethylaniline are added in an autoclave and 15 parts by weight of anhydrous aluminum chloride 15 together with 6 g of aluminum powder and 18 g of aluminum verdene in an autoclave at 290 ° C heated with ethylene chloride to 300 ° C. Set over the course of 2 hours. To the extent that the ethylene is consumed, 1.12 mol are consumed by the pressure of a liquid pump to about 200 atm. By repressing propylene. The amine is getting olefin pressurized. Completely implemented in 4 to 5 hours. 2-Ethyl-6-isopropyl becomes a total of 450 to 500 parts by weight of ethylene on aniline in a yield of 85.2% of theory. Kp. ₁₀ taken. The reaction product is diluted with 118 to 120 ° C. The benzoyl compound sodium hydroxide solution obtained therefrom, stirred to remove the catalyst, melts at 246 to 247 ° C.
and rectified in a vacuum. One receives 70 to 80% of the

used aniline back. The remainder is 2-ethyl example 38

aniline originated. The diamine gives a uniform 25

boiling product, bp. 170 ° C _lo, in which the analysis of 200 g of o-Chloraniün, 12 g of aluminum chloride and 4 g

after a triethylphenylenediamine is present. The yield aluminum grits are in an autoclave at 250 ° C

is 90% of theory. heated and with ethylene at a pressure of 200 at

Analysis: C ₁₂ H ₂₀ N ₂ (molecular weight 192.30)! ^ FI " ^ ^ Y ^ T ^ ^SClmeU ÄT! ^And ^

j ii 20 ² ^ ^ö "'.,", 30 added to the measure of consumption. After 4 hours smd

Calculated .... C74.95%, H 0.48%, N 4.57%; _{Implemented 95%} ^ ^g _{amine Service. The yield at}

found ZZt'irjr g! ° S ° ' ^{N 14> 55 / o} · 2-ethyl ^ ddaKuu] m; dffi as the only reaction product

C 75, UU / ₀ , H ΐυ, όΌ I ₀ , is 83.1% of theory. Kp. _Lo 108 to

The diacetyl compound of this 2,4,6-triethyl-phenylene-110 ° C, b.p. ₅ 96 ° C.

diamins- (l) melts at 318 to 320 ° C. 35 _Analysis C ₈ H ₁₀ NCl (molecular weight 155.5)

_Ώ . . , oc Calculated C 61.74%, H 6.43%, N 9.00%, Cl 22.83%;

Example from found C 61.64%, H 6.45%, N 9.13%, Cl 22.8%.

250 parts by weight of benzidine, 150 parts by weight of a The acyl compounds obtained therefrom have the following

aniline aluminum anilide solution with 2% aluminum- 40 low melting point:

content and 9 parts by weight of anhydrous aluminum chloride _Λ ,,. , ,,,.,. .,., ^ "

are at 280 ° C with ethylene at 200 atm for the reaction acetyl combustion 115 to 116 ° C

brought. The uptake of ethylene starts immediately. The benzoyl compound 140 to 142 ° C

The pressure is renewed through occasional repressing. .

Olefin repeatedly added to 200 atmospheres. After about 45 Example 39

The reaction comes to a standstill for 3 hours. 180 to 200 g of m-Chloräthylanüia are in the presence of 12 g

200 parts by weight of ethylene reacted during this time. AlCl ₃ and 4 g of aluminum powder at 240 ° C and one

The monoamine content is ethylated to an ethylene pressure of 200 atm by steam distillation. In the course of

of the reaction product is distilled off. It consists of 90% 3 hours, 2.05 moles of ethylene are consumed. Man

from 2,6-diethylaniline in addition to a little 2-ethylaniline. The 5 ° receives as the only reaction product 3-chloro-2,6-diethyl

Ethylated benzidine is a viscous oil, the aniline in a yield of 94.3% of theory. Kp. _Lo

boiling below 7 torr at about 250 to 260 ° C. It contains 138 ⁰ C, bp ₅ 124 ° C.

about 80% tetraethylbenzidine, which can be found in _Aml C ₁₀ H ₁₄ NQ (molecular weight 183.5)

Water poorly soluble dihydroxy chloride from the lower _ J ~ Z.- " _n " ^ ", -"",m"

Can separate ethylated fractions. The dihydro- 55 ^ I ^ r S'S Ι ^ ΑΙΙ ^ ΛΙ ° 'Γ ίϊ Jf

chloride melts at 229 to 231 ° C. The diacetyl compounds found C 65.40%, H 7.52%, N 7.66%, Cl 19.50%.

Dung forms colorless crystals with a melting point of 346 ° to 348 ° C. The benzoyl compound obtained therefrom melts

Analysis for C ₂₁ H ₃₂ O ₂ N ₂ (molecular weight 380.51) If the acylation is interrupted prematurely, the result is

Calculated C 75.75%, H 8.48%, N 7.36%; 6 ₀ in addition to unchanged starting material, the following

found C 75.70%, H 8.50%, N 7.49%. Links:

Kp. _Ισ connection F
Example 36 5-ClLlor-2-ethylaniline 116 165 to 166

™ _n r · ,,, ·, τ, · ■, ·., Nn r- ■ -u ± ± -ι α -i- “3-chloro-2-ethylanuine 124 141 to 142

200 parts by weight of benzidine, IUU parts by weight of aniline, 65 _iri i _{O (} - j: - + t, "i -r -too λ ca -urr

, "...... .. ..". . _Ha "· τ j. i · ι o-Lhlor-2,6-diethylanihn 138 154 to 155

6 parts by weight of aluminum powder and 18 parts by weight

anhydrous aluminum chloride are in an autoclave -d · · 1 4η

heated to 300 ° C and then injected 200 atmospheres of ethylene. -iceispiei ^ u

The reaction takes place with ethylene consumption. The 300 g of diphenylamine, 18 g of aluminum chloride and 6 g

Pressure is applied by occasionally pushing in Olefin 70. Aluminum is heated to 200 ° C in an autoclave.

The ethylene pressed in at a pressure of 165 atm is absorbed very quickly. Will be in 40 minutes Consumed 2 moles of ethylene per mole of amine. The work-up gives when the diphenylamine conversion is complete the only reaction product in almost quantitative yield diethyldiphenylamine.

Example 41

200 g N-ethylaniline, 12 g of aluminum chloride, 4 g of aluminum powder and 46 g of aniline are äthyliert in an autoclave at 250 ⁰ C and an ethylene pressure of 200 atm. A little more than 1 mol of ethylene, based on both amines, is absorbed in 1 to 2 hours. In the work-up, in addition to a few percent unchanged N-ethylaniline, a mixture of 2, N-diethylaniline and 2,6-diethylaniline is obtained. The yield of 2, N-diethylaniline is 85% of theory, calculated on the N-ethylaniline used. Kp. ₁₀ 102 to 103 ⁰ C.

Analysis C ₁₀ H ₁₅ N (molecular weight 149.23)
Calculated .... C 80.48%, H 10.13%, N 9.39%;
found C 80.44%, H 10.15%, N 9.32%.

Claims (1)

Claim: Further development of the process for the preparation of ring-alkylated aromatic amines by action of olefins in the liquid phase to aromatic amines in the presence of aluminum or the Aluminum compounds of aromatic amines at elevated temperature and pressure according to Patent 951 501, characterized in that the reaction with the simultaneous presence of Friedel-Crafts catalysts or bleaching earth is carried out. Considered publications:
Chemisches Zentralblatt, 1955, p. 4809, 4810. © 809 728/280 12.58