DE1902560A1 - Process for the carbonylation of amines - Google Patents

Description

The present invention relates to a new process for the carbonylation of amines, in which the amines to be carbonylated be brought into contact with carbon monoxide in the presence of a catalyst containing rhodium or iridium.

In contrast to the methods of the prior art, in which it is necessary at high carbon monoxide pressures and elevated To work temperatures, the present invention is based on the surprising finding that salts or complexes of rhodium or iridiums enable these carbonylation reactions at low temperatures and pressures.

According to a preferred embodiment of the present invention, rhodium and iridium are used in the form of their halides and preferably as chlorides or in the form of such complexes

909835/1 553

-2-

which correspond to the following general formulas: MZLn (GO) and RnXT ( ^G0 ) _m

in which M rhodium or iridium, Z a hydrogen atom or a Halogen atom, preferably a chlorine atom, X a halogen atom, preferably a chlorine atom, X a monovalent organic radical having preferably 2 "to 10 carbon atoms and at least one Carbon -carbon double) indung "mean.

The symbols n, m, ρ and L are defined below. ■

. According to a preferred embodiment, MZLn (GO) consists of MHGO (TPP) ₃ or MGl (CO) (TPP) ₂ , where (TPP) denotes triphenylphosphine.

Other examples of usable complexes are: dichlorodirhodium tetraethylene, dichlorodirhodium tetracarbonyl, Dichlordirhodiumdicarbonyldiethylen, Dichlordirhodium-1,6-cyclodecadiene, Dichlorodirhodium tetrallyl.

The complex of the formula HhXI (GO) ^ explained above lies

r ") pm

mostly in the form RhXI (C0) _{m 2} .

The carbonylation reaction proceeds according to the following equation • Sche-ia from:

RR ₁ R ₁ ^ ^ R ₁

+ CO- »· ¹ ^ N - CHO and / or % Έ - CO - N ^x + H _{? 2} R ₂ "R ₂ '^ ₂

where R ₁ and R ₂ denote a hydrogen atom and / or a monovalent hydrocarbon radical which preferably contains 1 to 20 carbon atoms and optionally one or more organic χ -iktionelle sites, such as alcohol, acidv. ir ester functions; the radicals R ₁ and R ₂ together can also denote a ring-shaped radical

% -3-909835 / 1553

ORIGINAL INSPECTED

While the simplest case of carbonylation is one of a single type of amine, this reaction can also be carried out with a mixture of at least two different amines, in which case, in addition to other different amides, disubstituted asymmetrical IT, K " ¹ ureas, for example according to the following equation scheme:

^E l \ ^R l \ op ^ % ^ s ^ l

JX s * \ ^ tS "* · £ ί ο Χίο

d. d d d

obtained, where R ₁ 'and Rp ^{1 have} the same meaning as the symbols R- and Rp defined above.

R ,, Rp, R, 'and R2 ¹ can mean, for example, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals or any other radical in which the aryl group is replaced by a monovalent heterocyclic group.

Non-limiting examples of the amines mentioned above include: ethylamine, n-propylamine, n-butylamine, isopropylamine, Oyclohexylamine, aniline, toluidine, dipropylamine, dibutylamine, piperidine, ethanolamine, glycocoll, and their derivatives, for example their halogen derivatives, provided they are compatible with the catalyst system used.

It should be emphasized that the best results so far have been achieved with the primary aliphatic amines, which applies to both the production of formamides and ureas.

L, have formamides and ureas prepared according to the invention numerous applications as solvents, pharmaceuticals, Hardeners for epoxy resins, antioxidants and stabilizers for rubbers and other polymers; they also serve as Intermediate products in various syntheses, such as

-4-909835 / 1553

- Sheet 4- for those of resins or plastics.

The amounts obtained at the same time in the carbonylation reaction of amides and ureas vary with the catalyst and the used amines. A mixture is often obtained that consists of 50 to 90 mol% urea and 10 to 50 mol% amide, the Degree of conversion, based on the amines used, up to 95% amounts to.

It was also surprisingly found in accordance with the present invention that it is possible both to increase the degree of conversion of the amines up to a value of almost 100 % and to control the reaction in the sense of amide formation that the selectivity of the reaction in relation to the amides is almost 100 % .

Such results were obtained using a catalyst system which consists of a rhodium complex of the formula RhXX (CO) explained above and at least one compound which has the general formula AR-R ¹¹ R ¹ ″, which has also been explained above.

In the above formulas, η denotes the numbers 2 · or 3 u * xd ρ and m 0, 1, 2, 3 or 4-, with at least one of the two symbols ρ and m having a value other than zero. L denotes a coordination molecule of the formula AR ¹ R ¹¹ R ¹ ", in which A is an element of group V ^ of the Periodic Table of the Elements and R ¹ , R" and E ¹ "are considered individually monovalent hydrocarbon radicals and 2 and 2 are divalent hydrocarbon radicals which form a ring with the atom A; these radicals can also contain hydrogen and carbon, as well as at least one element from group V ^ of the Periodic Table of the Elements.

It has been found that the «reactivity and the selectivity of the reaction depend both on the nature of the radicals R ¹ , R" and R ¹ ", the

9 0 9 8 3 5/1553 -5-

- sheet 5 -

"bond AR ¹ R" R ' ^f ', as well as on the molar ratio AR ¹ R "R ^f · '/ RhXT (CO) _m the use of triphenylphosphine, which favors the formation of urea more; it is therefore possible ^{to influence or control the carbonylation reaction as desired by selecting the radicals R 1} R "R '"'. In general, one can say that the alkylphosphines influence the reaction more in terms of the formation of amides than arylphosphines.

Another way of influencing or controlling the degree of conversion and the selectivity of the reaction is to ^{vary the molar ratio AR 1} R "R ¹¹ VRhXT (CO) _m , the degree of conversion and the selectivity with respect to amide formation increasing with the size of this ratio If it is desired to control the reaction with a view to amide formation, it is preferable that this ratio is greater than 1, and preferably between 2 and 10.

According to a preferred embodiment of the carbonylation process according to the invention, this is carried out in a reaction vessel that has been freed from all impurities, the amine or amines to be carbonylated optionally in a customary solvent, such as an aromatic hydrocarbon, a saturated hydrocarbon, a. . _: Alcohol or an ether, together with the catalyst or the catalyst solution, are present in dissolved form.

The catalyst or the catalytic system is preferably introduced in such an amount that its weight is 0.05 to 56 and preferably 0.1 to 0.5% of the weight of that to be carbonylated Amine is.

The reaction vessel is then filled with a carbon monoxide atmosphere at a pressure which can be between 1 and 100 atmospheres. ,

9098 35/1553 ORIG.NAUNSPECTED

- sheet 6 -

It should be emphasized that the order of addition of the reactants is not of critical importance.

The reaction temperature is generally between O and 3OO ° C and preferably between 100 and 200 ⁰ C.

The following examples, which are in no way intended to be "limiting, serve to further explain the subject matter of the invention.

Example 1: · '-

k 0.6 g Sh H (CO) ^ (Olpp). (TPP = Tr iphenylphosphin), and then 56 w n-butylamine in 20 cmr dissolved benzene are fed into a ¹ autoclave. Then there is carbon monoxide at a pressure of 70 bar and increasing the temperature to 150 ⁰ C. After 8 hours Heaktionsdauer obtained after evaporation of the solvent and recrystallization 15 g of di-n-butyl urea and 17 g of n-butylformamide.

- Example 2:

0.4 g Rh H (CO) (EPP), and then 56 cm ^ n-butylamine in benzene dissolved are placed in an autoclave. Then carbon monoxide is added to the autoclave at a pressure of 10 bar and heats it to 150 ° C. After a reaction time of 15 hours, the solvent is removed; 15 g of di-n-butylurea are obtained and 17 g of n-butylformamide.

Example 3: "-

0.12 g of rhodium trichloride trihydrate are placed in an autoclave and then 41 cm- ^ n-butylamine. Then the autoclave Filled with carbon monoxide under a pressure of 67 bar and then heated to 150 ° C., after a reaction time of 10 hours is obtained 25 g of di-n-butylurea and 10 g of n-butylformamide.

Example 4;

First 0.4 g of Ir Gl (CO) (ίΠΡΡ) ρ and. then entered 56 cur n-butylamine. Then you fill the

909835/1553 ~ ⁷ ~

ORIGINAL INSPECTED

- sheet 7 -

Autoclave "at a pressure of 60 bar with carbon monoxide and heated to 120 ⁰ C. After 9 hours, Se acti ons life is obtained 20 g of di-n-butyl urea and 12 g of n-butylformamide.

Examples 5 to

In these examples, the process conditions are always the same.

In each example 0.197 S of a rhodium complex of the formula Eh XX (CO) is dissolved in 10 cnr benzene under an inert atmosphere. If the compound, AR ¹ R ¹¹ R ^{1! L} is added, it is added in benzene in varying amounts before or after the complex Rh XY (CO) _m . Then you are 6 cm - * - ctd i of be carbonylated Anri- pr added and the solchermasseÄ prepared solution in 50? of the amine to be carbonylated, which is located in an autoclave. Carbon monoxide is then added until an OO pressure of 50 atmospheres has been reached and the temperature is then raised to 160 O. A decrease in pressure is then usually observed. When the pressure has stabilized, the mixture is allowed to cool and the resulting solution is subjected distillation, for the purpose of isolation and analysis of the ingredients. Insofar as the process conditions are described differently than "above", they are given in the following table.

-8th-

909835/1553

Example catalytic system game

"or Catalyst Molars Used Conversion Selectivity ** V ^ age- ^ _n degree of elution * in _{addition to} " with regard to urine AE ¹ E ¹¹ E ¹ "/" ^ ¹¹ " ¹ ^ amides in % substances in%

10

11th

12 13

CD
O
CD
OO 7th Rh ₂ Cl cn
- ^ __λ
cn
cn
OJ 8th η

+ Triethylphosphine

+ Phenyldi-, ethylphosphine

+ Tricyclohexylphosphine

+ Tripheny lpho sphin

+ Ethylene- "bis -dime thylpho sphin

+ Tr ime thylpho sphin

It Il

iso

C ₄ H ₉ KH ₂

iso

7th

C ₄ H ₉ KH ₂

C ₄ H ₉ KH ₂
η C,

C ₄ H ₉ KH ₂

C ₄ H ₉ KH ₂

C ₄ H ₉ KH ₂
C ₄ H ₉ KH ₂

82

83
92

93

94
95

84.5
86

97
95

4-6.5

100
100

98.5

40 42 35 33

90 92

79.5 80

78 79

70

100 100

98

60 58 65 67

10 8

20.5 20

22 21

30th

0 0

ro cn σ) ο

- sheet 9 -

* The degree of conversion relates to the amines (= molar ratio: converted amines / introduced amines)

** The selectivity with respect to the amides (or ureas) corresponds the ratio: number of moles of amides or ureas obtained / number of reacted amine moles (ratio multiplied by. 2 in the case of ureas).

-10- / Patent claims:

909835/1553

Copy

Claims (18)

Claims 1.) Process for carbonization, i.e. for the introduction of GO "or in amines by bringing these amines into contact Carbon monoxide, characterized in that one is in the presence a catalyst works that contains Hhodium or Iridium in the form of a salt or a complex. 2.) The method according to claim 1, characterized in that the rhodium salt or the iridium salt is a halide. 5 ») Method according to claim 1, characterized in that the Rhodium salt or the iridium salt is a chloride. 4.) The method according to claim 1, characterized in that the rhodium complexes and the iridium complexes the following general formulas correspond to: MZ Ln (GO) and RhXI (CO) _m in which M is rhodium or iridium, Z is a hydrogen atom or a halogen atom, X is a halogen atom, X is a monovalent organic radical with at least one carbon-carbon double bond, η 2 or 3, ρ and m 0, 1, 2, 3 and 4 - Wherein at least one of these two symbols ρ and m mean a value other than zero, and L means a coordination molecule of the formula AR ¹ R ¹¹ R ¹¹¹ , in which A stands for an element of group V of the Periodic Table of the Elements and R ', R "and R ¹¹¹ each individually represent a monovalent hydrocarbon radical and two' and two, considered to be divalent hydrocarbon radicals which form a ring with the atom A, these radicals or radicals also being hydrogen and carbon, as well as at least one element of group V ^ of the periodic 909835/1 5 53 - ¹¹ - - Sheet 11 System of Elements May contain. 5.) The method according to claim 4-, characterized in that Z and X each represent a chlorine atom. 6.) Process according to claim 4, characterized in that the complexes used correspond to the formulas MH (CO) (TPP), and MOl (CO) (TPP) ₂ , where (TPP) stands for triphenylphosphine. 7.) Process for the carbonylation of amines according to claim 4-, characterized in that a catalytic system is used which consists of at least one compound of the formula RhXY (CO) and at least one compound of the general formula AR ¹ R "R ¹ " , where A is an element of group V ^ of the Periodic Table and the symbols R ¹ , R "and H" ^1, considered individually, each represent monovalent hydrocarbon radicals and two and two taken together represent divalent hydrocarbon radicals which form a ring with atom A, these Free radicals or radicals can also contain hydrogen and carbon, as well as at least one element from group V, of the Periodic Table of the Elements. 8.) Process according to Claims 1 to 7, characterized in that the weight of the catalytic system is 0.05 to 5 % of the weight of the amine to be carbonylated. 9.) Process according to claims 1 to 7 »characterized in that the weight of the catalytic system is 0.1 to 0.5 % of the weight of the amine to be carbonylated. 10.) The method according to claim 7i, characterized in that the molar ratio AR ¹ R ¹¹ R ¹ ″ / RhXX (C0) _{m is} above 1. 11.) The method according to claim 7, characterized in that 909835/1553 - sheet 12 - the molar ratio AR ¹ R "R ¹ · '/ RhXT (CO) between 2 and ρ m lies. 12.) The method according to claim 1, characterized in that the carbon monoxide pressure is between 1 and 100 atmospheres. 13.) The method according to claim 1, characterized in that the reaction temperature is ^{between 0 and 300 0C.} 14.) Process according to claim 1, characterized in that the reaction temperature is between 100 and 200 ° C. 15 ·) Process according to claims 4 to 7> characterized in that the expression AR ¹ R "R ¹ '· stands for a phosphine. 16.) Carbonylation catalyst for amines, characterized in that that it corresponds to the definition given in claim 4. 17.) Catalytic system, characterized in that it is the corresponds to the definition given in claim 7. 18.) Amides and ureas, characterized in that they according to the procedure described in claims 1 to 15 were produced or can be produced. 909835/1 553