DE1445792A1 - Process for the preparation of iminopyrrolidones - Google Patents

Description

Process for the preparation of iminopyrrolidones

The invention is a process for the production of new iminopyrrolidones. It has been found that enamines whose ß-carbon atom is substituted by alkyl radicals is to react with isocyanates and isonitriles to iminopyrrolidones. The surprising course of the reaction is the implementation as an example of isobutenyl pyrrolidine, cyclohexyl isonitrile and phenyl isocyanate explained:

c-

CH = C

CH,

H> -H = CI

Q-H = C = O

During the implementation, it does not matter in which order the components are put together. In general, the

A 9163

14457S2

Reaction in an organic solvent at temperatures between +40 and +150 ⁰ C, preferably between 60 and 100 ⁰ C by. As the organic solvent, hydrocarbons such as benzene, toluene, xylene and cyclohexane can be used. Acetonitrile and dimethylformamide have proven to be particularly suitable solvents. The new iminopyrrolidones correspond to the general formula:

wherein RJ is an alkyl, aryl, substituted aryl, cycloalkyl, aroyl or arylsulfonyl group. R «can be alkyl, cycloalkyl or a substituted aryl group. R, and R. are alkyl groups, where R, and R. as ring members with the nitrogen atom can form a ring which can also keep heteroatoms ent. R, - and Rg denote an alkyl group, where R, - and Rg together as ring members can also form a hydrocarbon ring.

If diisocyanates or diisonitriles or bis-enamines are used in the reaction , the corresponding bicyclic iminopyrrolidones are formed. For example, the following 2minopyrrolidone corresponding to the formula given above image, igänglicht by the process "

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1-phenyl-2-cyclohexylimino-3-pyrrolidino-4,4-dimethyl-pyrroli (lon _f 1-phenyl - ^ - cyclohexylimino ^ -piperidino ^, 4-diaethyl-pyrrolidone, 1-phenyl - ^ - cyclohexylimino - ^ - morpholino ^, 4-dimethyl-pyrrolidone, 1- (4-chlorophenyl) -2-cyclohexylimino-3-pyrrolidino-4,4-dimethylpyrrolidone, 1- (4-chlorophenyl) ^ -cyclohexylimino ^ -piperidino ^, 4-dimethylpyrrolidone , 1- (4-chlorophenyl-2-cyclohexylimino-3-morpholino-4,4-dimethylpyrrolidone, 1- (3-chlorophenyl) -2-cyclohexylimino-3-pyrrolidino-4,4-dimethylpyrrolidone, 1- (3-chlorophenyl ) -2-cyclohexylimino-3-piperidino-4,4-dimethylpyrrolidone, 1- (3-chlorophenyl) -2-cyclohexylimino-3-morpholino ~ 4 _} 4-diniethylpyrrolidone, 1- (3,4-dichlorophenyl) -2- cyclohexylimino-3-pyΓrolidino-4,4-dimethylpyrrolidone, 1- (3,4-dichlorophenyl) -2-cyclohexylimino-3-morpholino-4,4-dimethylpyrrolidone, 1- (4-nitrophenyl) -2-cyclohexylimino-3- pyrrolidino-4,4-dimethylpyrrolidone, 1- (4-nitrophenyl) -2-cyclohexylimino-3-piperidino-4,4-dimethylpyrrolidone, 1-phenyl-2-tert-butyl-imino-3-pyrrolidino-4,4 -dimethyl- pyrrolidone _t 1_ (4 ._. chlorophenyl) -2-tert-butyl-imino-3-niorpholino-4,4-diinethylpyrrolidone,

Le A 9163

1-haphthyl - ^ - cyclohexylimino ^ -pyrrolidino ^ 1 4-dimethyl-pyrrolidone, 1-haphthyl-2-tert. -butyl-imino-3-morpholino-4,4-dimethyl-pyrrolidone ^ i-phenyl ^ -benzylimino ^ -pyrrolidino ^, 4-dimethyl-pyrrolidone, 1. (4-chlorophenyl) -2-benzylimino-3-piperidino -4,4-dimethyl-pyrrolldon,

1- (3 _f 4-dichlorophenyl) -2-benzylimino-3-niorpholino-4t4-dimethylpyrrolidone, 1-methyl-cyclohexyl-imino-3-pyrrolidino, 4-dimethyl-pyrrolidone, 1-ethyl-2-cyclohexyl -imino-3-moΓpholino-4,4-dimethyl-pyΓrolidon _f 1-Oyclohexyl-2-cyclohexyl-imino-3-pyΓΓoli.dino-4,4-dimethylpyrrolidone, 1-cyclohexyl-2-teΓt.-butyl-imino- 3-piperidirLO-4,4-dimethylpyrrolidone, 1-tosyl ^ -cyclohexyl-imino ^ -pyrrolidino- ^ »4-dimethyl-pyrrolidone, 1-ToByl-2-tert-butyl-imino-3-piperidino-4,4 -dimethyl-pyrrolidone, 1-benaoyl ^ -cyclohexylimino ^ -pyrrolidino ^, 4-dimethyl-pyrrolidone, 1-Bβnzoyl-2-benzylimino-3-lnorpholino-4,4-dimethyl-pyrrolidone, 1-phenyl-2- (4 -imino-azobenzene) -3-pyrrolidino-4,4-dimethylpyrrolidone, 1- (4-chlorophenyI) -2- (4-iminoazobenzene) -3-piperidino-4,4-dimethylpyrrolidone, 1-phenyl-2- (3-nitro -2-methyl-phenylimino) -3-pyrrolidino-4,4-dlmethyl-pyrrolidone, 1- (4-chlorophenyl) -2- (3-nitro-2-methyl-phenylimino) -3-piperidino-4,4- dimethyl-pyrrolidone, 1- (3-chlorophenyl) -2- (2-chloro-6-methyl-phenylimino) -3-pyrrolidino-4,4-dimet hyl-pyrrolidone, 1-methoxymethyl-2- (3-nitro-2-methyl-phenylimino) -3-pyrrolidono- 4,4-dinethyl-pyrrolidone, 8CÄ9C1 / 072§

Le A 9163 - 5 -

1 - (3-chlorophenyl J ^ -cyclohexylimino ^ -N-methyl-piperaiino- 4,4-dimethyl-pyrrolidone,

1- (314-dichlorophenyl) -2-tert-butylimino-3-N-meth # l-piperaBino * - 4,4-dimethyl-pyrrolidone,

i-Toeyl ^ -benzylimino ^ -N-methyl-piperaelno- ^ A-dimethylpyrrolidone,

1-phenyl-2-cyclohexylimino ~ 3-pyrrolidino-4,4-epirt >> oyclohexan pyrrolidon-5,

1,4-bis- ^ ~ 1- (2-cyelohexylimino-3-pyΓΓolidino-4t4-dimethylpyrrolidone-527-phenylenediamine,

1,4-Bia- / ~ 1 * imino-2-pyrrolidino-3,3-dimethyl-5-phenyl-pyrrolidone-4 ^ diphenyl ether,

N, N'-Di- ^ ~ 1- (2,2-dimethyl ^ -phenyl-i-cyclohexylimino ^ pyrrolidone-

For the method according to the invention, those preferably come into consideration Enamines are:

Isobutenylmorpholine, isobutenylpiperidine, isobutenyl-N-piperazine, Isobutenyl-di-n-butylamine, isobutenyl-dimethylamine and isobutenyldi-n-isopropylamine. The enamines of hexahydrobenzaldehyde, tetrahydrobenzaldehyde and tetrahydrotolylaldehyde can also be used secondary amines, preferably dimethylamine, diethylamine, di-npropylamine, Diisopropylamine, di-n-butylamine, diisobutylamine, piperidine, «/", Ss- or ^ -pipecoline, hexamethyleneimine, morpholine, H-methylpiperazine can be used as starting products. Also with Bie enamines the reaction can be carried out, for example with de »diisobutenylpiperazine. The following isocyanates can be used:

Ie A 9163 8OiSiO 1 / O72i -6-

Aryliaoeyanate and arylene diisocyanates, which by alkyl, alkoxy, Carboxyalkyl, halogen or nitro groups can be substituted. Alkyl isocyanates, alkylene diisocyanates, cycloalkyl isocyanates, Aryl sulfonyl isocyanates and benzoyl isocyanates. The following compounds are preferably used: alkyl isocyanates, their Alkyl group has 1-6 carbon atoms, phenyl isocyanates such as Phenyl isocyanate, chlorophenyl isocyanate and toluene isocyanate, as well the tosyl isooyanate. Examples of isonitriles that may be mentioned are: aryl isonitriles and arylenediisonitriles, which are optionally by Alkyl, alkoxy, carboxyalkyl, halogen, nitro groups or the phenylazo group can be substituted, such as. B. Phenylisonitrile «, 4-chlorophenylisonitrile, 4-bromophenylisonitrile, 4,4'-dimethoxy-benzhydryl-isonitrile, 4,4'-diethoxy ^ -nitro-e-inethylphenyl-isonitrile, 4-isocyan-3,3'-diraethyl-azobenzene, 4-carboxy-

phenylethyl-phenyl-isonitrll, 4-carboxy-methyl-yisonitrile, 4-carboxy-

phenylbutylTdsonitrile, naphthylene-2,6-diisonitrile, alkyl and alkylene diisonitriles such as B. tert-butyl isonitrile, 1,6-hexamethylene diisonitrile, and cycloalkylisonitriles such as cyclohexylisonitrile, methylcyclohexylisonitrile, and heterocyclic isonitriles such as 2-isocyanate diphenylene oxide, 3-isocyanate diphenylene oxide.

The new compounds resulting from the process can be used for the production of pharmaceuticals and crop protection agents be used.

Le A 9163 - 6a -

808901/072

Example 1 ;

-CH -

C.
N-

CO

¹ 3.9 g of isobutenylpiperidine are dissolved together with 10.8 g of cyclohexyl isonitrile in 25 ml of dimethylformamide. Dasu lets you add drops of 11.9 g Phenylisoeyanat. The temperature rises to 33 ° C. The mixture is heated for half an hour at 50 ⁰ C. Upon cooling, 33 g crystallize a compound, which after redissolution of acetonitrile from 95 - 97 ⁰ C melts.

Le A 9163 - - \ -

Analysis: C23H ₅₅ H ₅ O ₁ (367)

Calc .: C: 75.45 H: 9.03 N: 11.45 Found: C: 75.5 H: 9.2 N: 11.7

Example 2 :

yN-CH -

/ h \ _n = c ^ .co

25.0 g of isobutenylpyrrolidine are dissolved together with 21.6 g of cyclohexyliaonitrile in 80 ecm of acetonitrile. 23.8 g of phenyl isocyanate are added dropwise and the mixture is then heated to 60 ° ^{above sea level} for 1/2 hour. After cooling kristallisferen 67 g of a compound from that of 102 - 104 ⁰ C melts.
Analysis: C ₂₂ H ₅₁ N ₅ O ₁ (353) Calculated: C 74.8 H 8.8 N 11.8 Found: C 74.2 H 9.0 N 12.0

Example 3 t {- \ ^ - CH,

¹ N-CH - C ^ °

3 h) - * - c. / C «o;

25 g of isobutenylpyrrolidine are added together with 21.6 g of cyclohexylieonitrile Dissolved in 80 ecm of acetonitrile. 30.8 g are added dropwise to this

^leA9163 ac8 »oi / QT2O

p-chlorophenyllooeyanate. The temperature rises to 70 ^° C. during this process. Is maintained for one hour at 70 ⁰ C. After cooling, 68 g crystallize from a compound of tril · 118 after TJmI en whether from acetone - melts 120 °!.

Analysis! C ₂₂ H ₅₀ H ₅ O ₁ Cl _t (387.5) Calcd .: C 67.9 H 7.7 »10.7 Found: C 67.9-H 7.7 I 10.9

(li-CH - C

Example 4 : / V

- CH - C ^

-CH

3 -N = C

27.8 g of isofcutenylpiperidine and 21.6 g of cyclohexylisonitrile are used together with 3OfB g of 4-chlorophenyl isocyanate in 80 ecm of acetonitrile given. The course of the reaction is the same as in Example 3, 63 g are obtained, which after dissolving from ethanol of 12B ^ - T25 ° ö joke.

Analysis: C ₂₅ H ₅₂ H ₅ O ₁ Cl ₁ (401.5) Calcd .: C 68.7 H 7.9 'K 10.45 Found: C 68 _r 7 H 8.2 H 10.5

Im A 9163 - 9 -

BaiBpiel 5:

Ή T

1445732

28.2 g isobutenylmorpholine, 21.6 g cyclohexyl! Son! tril and 50.8 g of 4-chlorophenyl isoeyanate are heated to 80 ^° C. in 80 ml of acetonitrile in 1 hour. After cooling, 50 g of a compound according to the redissolution of benzene of 168 - 171 ⁰ C melts.

Analysis:

(4-03.5)

E.g .: C 65.6 H 7.45 N 10.4
Found i C 65.9 H 7.8 N 10.6

Example 6;

N-CH -

H N-N = C

25 S Ieobutenylpyrrolidin are dissolved together with 21.6 g of cyclohexylisonitrile in 100 ecm acetonitrile. 30.8 g of 3-chlorophenyl isocyanate are added dropwise to this. The temperature rises to 70 ^° C. during this process. The mixture is heated to the boil for 1/4 hour. Upon cooling, 68 g crystallize a: from compound .the after reprecipitation from ethanol at 103 - 106 ⁰ C melts.

Le A 9163

aoago1 / OT20

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Analysis: C ₂₂ H ₃₀ H ₃ O ₁ Cl ₁ (387.5) At: C 67.9 H 7.7 N 10.7 Found: C 67.8 H 7.9 N 10.2

Example 7 :

/ N-CH - C

CH, CH,

-N =

Cl

27.8 g of isobutenylpiperidine are dissolved together with 21.6 g of cyolohexyl isonitrile in 80 ecm of dimethylformamide. 30.8 g of 3-chlorophenyl isocyanate are added dropwise to this. The reaction sequence is the same as in Example 4. This gives 64 g of melting point 120-123 ⁰ C. Analysis: C ₂₃ H ₃₂ N ₃ O ₁ Cl ₁ (401.5) Calc .: C 68.7 H 7.97 N 10.45 Found: C 69.3 H 8.3 N 10.4

Example 8 :

0 N-CH -

H> -N = C

.CH ₃ CH,

28.2 g of isobutenylmorph.oline, 21.6 g of cyclohexylisonitrile and 30.8 g of 3-chlorophepyl isocyanate are dissolved in 80 ecm of acetonitrile and heated to the boil for 1 hour. Upon cooling, 25, .§ a compound of 146 - 148 ⁰ C melts.

Ie A 9163

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Analysis: C ₂ 2 ^H 30 ^N 3 ⁰ 2 ^Gl 1 ^ί4 ° ³ » ⁵⁾ Calc .: C 65.6 H 7.45 N 10.4 Found: C 65.5 H 7.5 N 10.6

Example 9:

C-

CH - C

CH

• GH,

H> -N =

25 g of isobutenylpyrrolidine, 21.6 g of cyclohexylisonitrile and 38 g of 3,4-dichlorophenyl isoyanate are dissolved in 100 ecm of acetonitrile. The temperature rises to 70 ^° C. during this process. It is stirred for 1/2 hour after at 70 ⁰ C, while cooling, 69 g of a compound according to the redissolution of dimethylformamide of 127 - 13O ⁰ C melts.

Analysis: O ₂₂ H ₂ ^ O ₁ H ₅ Cl ₂ (422) .. Calculated: C 62.6 H 6.87 N 9.95 Found: C 62.6 H 6.9 N 9.9

Example 10:

N-CH - C

.CH, CH,

-N = C.

JSO

Cl

Cl

27.8 g of isobutenylpiperidine, 21.6 g of cyclohexylieonitrile and B8 g 3,4-dichlorophenyl isocyanate are dissolved in 150 ecm acetonitrile.

Le A 9163

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The temperature rises to 6O ⁰ C. The mixture is heated for 1/2 hour at 70 ⁰ C. Upon cooling, 61 g crystallize from a substance after the ümlösen of dimethylformamide of 141 - melts H3 ° C.

me: C ₂₅ H ₅₁ O ₁ N ₅ Cl ₂ (436) Bur: C 63.3 H 7.1 N 9.63 Found: C 63.7 H 7.3 N 9.6

Example 11 : | N-CH - C

"'CH,

-CH ₂ -N = CC = ON

25 g of isobutenylpyrrolidine are dissolved together with 23.4 g of benzyl isonitrile in 100 ecm of acetonitrile. 23.8 g of phenyl isoeyanate are added dropwise to this. The temperature rises to 80 ^° C. during this process. Upon cooling, 41 g crystallize from a compound, which after redissolution of benzene of 92 - 94 ⁰ C melt. Analysis: C ₂₅ H ₂ ^ N ₅ O ₁ (361) Calculated: C 76.6 H 7.7 N 11.62 Found: C 76.7 H 7.8 N 11.6

Example 12 :! VcH - C

r \ r * TT * r r% / ^ t_ f \

V / "QH ₂ -N = C

Cl

23.4 g Isobutenylpyrrolidin, 25 g phenylisocyanate and Benzylιsonitril 30.8 g 4-0hlor xtril gege in 100 cc Aceto 1. The temperature rises to 80 ⁰ C. Heat sum for a quarter of an hour

8OS801 / O72O

Boil and then cool down. This gives 64 g of a compound according to the redissolution of benzene of 83 - 84 ⁰ C melts.

Analysis: C ₂₅ H ₂₆ K ₅ O ₁ Cl ₁ (395.5) Calcd. 4 C 70.0 H 6.7 N 10.62 oef .: C 70.0 H 6.7 N 10.6

Example 13 : N-CH - .ι

(CH _x ), CN = C C = O

CH,

12.5 g of isobutenylpyrrolidine, 8.3 g of tert-butyl isonitrile and 11.9 g of phenyl isocyanate are added together to 50 ecm of acetonitrile. The temperature slowly rises to 60 ⁰ C. Upon cooling, one obtains 27 g of a compound according to the redissolution of acetonitrile from 89 - 91 ⁰ C melts.

Analysis: O ₂ O ^H 3O ^N 3 ° 1 ⁽⁵²⁸⁾ Calcd .: C 73.2 H 9.15 N 12.78 Cef .: C 72.8 H 9.4 N 12.8

Example 14 : Γ ~ \ _CH

, ^ CH ₃ C = O

12.5 g of isobutenylpyrrolidine, 8.3 g of tert-butyl isonitrile and 15.4 g of 4-chlorophenyl isocyanate are added to 40 ecm of dimethylformamide.

L A 9t63 - 14 -

doaaot / 072Q

1445782

The temperature rises to 62 C. During cooling, 30 g crystallize out after the reprecipitation from acetonitrile 84-85 ⁰ C

melt.

Analysis: C ₂₀ H ₂₉ N ₅ O ₁ Cl ₁ (362.5)

Calc .: C 66.5 H 7.76 N 11.32 Found: C 66.51 H 7.9 N 11.7

Example 15 ;

CH - H N-CH
³

H> -N = C

ΘΗ, CH,

30.8 g of N-methyl-N ^f -isobutenyl-piperazine, 21.6 g of cyclohexyl! Sonitril and 30.8 g of 3-chlorophenyl isocyanate were combined in 100 cc of acetonitrile, and then heated for 2 hours at 8O ⁰ C. Upon cooling, one obtains 32 g of a compound according to the redissolution of acetonitrile from 103 - 104 ⁰ C melts.
Analysis: C ₂₅ H ₅₅ N ₄ O ₁ Cl ₁ (416.5)
Calc .: C 66.3 H 7.93 N 13.42
Found: C 66.4 H 8.2 N 13.3

Example 16:

CH ₅ -N

N-CH -

CH

3 CH,

H> -N = C

Le A 9163

8CS & 01/0720

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30.8 g of N-Jfethyl-N'-isobutenyi-piperazine, 21.6 g of cyclohexyl! Βonitril and 37.8 g of 3,4-dichlorophenyl isocyanate were combined in 100 cc of acetonitrile and heated for 1 hour at 80 ⁰ C. Upon cooling, one obtains 20 g of a compound according to the redissolution of acetonitrile from 115 - 119 ⁰ C melts. Analysis: ^C 23 ^H 32 ^N 4. ° 1 ^C1 2 (* ⁵¹ °) Calc .: C 61.3 H 7.1 N 12.4 Found: C 61.2 H 7.3 N 12.5

Example 17: N-CH - C

0 *

12.5 g of isobutenylpyrrolidine and 10.6 g of cyclohexylisonitrile are dissolved in 60 ecm of acetonitrile. 19.7 g of p-tosyl isocyanate are added dropwise to this. The temperature rises to 65 ^° C. during this process. Upon cooling, 40 g crystallize from a compound, which after redissolution of acetonitrile from 110 - 113 ⁰ C melts.

Analysis: ^C 23 ^H 33 ^Ii 3 ^O 3 ^S i (431) Calculated: C 64.0 H 7.67 N 9.75 Found: C 63.6 H 7.7 U 9.8

Le A 9163 - 16 -

808 ^ 01/0720

1445752

Case 18 :

(H-CH -

H NN = CC = ON '

SO ₂ -

13.9 g of isobutenylpiperidine and 10.8 g of cyclohexylisonitrile are dissolved in 60 ccs of acetonitrile. 19.7 g of p-tosyl isooyanate are added dropwise to this. The reaction mixture heats up to 76 ⁰ C. Upon cooling, 36 g crystallize from a compound which, after recrystallising from Aoetonitril of 131 - 132 ° C melts.

Analysis: C ₂₄ H ₃₅ N ₃ O ₃ S ₁ (445) Calculated: C 64.7 H 7.85 N 9.4 Found: C 64.7 H 8.0 N 9.4

Example 19 :

0 N-CH - C

1 t

-N = CC = O SO ₂ -

14.1 g of isobutenylmorpholine are dissolved together with 10.8 g of cyclohexylisonitrile in 50 ecm of acetonitrile. 19.7 g of p-tosyl isocyanate are added dropwise to this. The temperature rises to 70 ° C. The mixture is subsequently stirred at 70 ^° C. for 1 hour, cooled and the precipitate which has separated out is filtered off with suction. This gives 30 g, of 129 - 131 ⁰ C melt.

C ₂₃ H ₃₃ N ₃ O ₄ S ₁ (447) Calc .: C 61.7 H 7.37 N 9.2 oef .: C 61.7 H 7.5 N 9.4

- 17 -

Example 20 ;

Q N-CH- I ^ -CH,

(CH,), C-N = CL, C = O

⁵ * ^ W

19 »3 g of tetrahydrotolylidenemorpholine are dissolved together with 8.3 g of tert-butyl onitrile in 50 ecm of acetonitrile. To this are added 15.4 g of p-Chlorphenylisoeyanat and heated for 2 hours at 80 ⁰ C. Upon cooling, 25 g crystallize from a compound, which after redissolution of acetonitrile from 122 - 125 ⁰ C melts.
Analysis: C ₂₄ H ₅₅ N ₅ O ₂ Cl ₁ (430.5)
Bar .: C 67.0 H 7.77 N 9.75
Found: C 67.2 H 7.7 N 9.9

Example 21t (ΓΛ-CH- / ~ V -CH

H> -N = C CO

19.3 g of tetrahydrotolylidene morpholine are dissolved together with 10.8 g of cyclohexylisonitrile in 50 ecm of acetonitrile. 19.7 g of p-tosyl isocyanate are added dropwise. The reaction mixture warms up to 64 ° C. The mixture is stirred at this temperature for 1 hour and then cooled with ice. 45 g of a compound crystallized out and melted at 158-159 ° C. after being redissolved from acetonitrile.

Ie A 9163 - 18 -

Analyee: C ₃₇ H ₅₇ I ₄ I ₅ S ₁ (499) Calc .: C 64.85 H 7.4 N 8.42 Found: C 64.7 H 7.4 N 8.4

Example ° 2

~~ N-CH - C

I, ^ CH ₃

H> -N = C ^ .C = O

CH

25 g of isobutenylpyrrolidine, 11.4 g of methyl isocyanate and 2T, 6 g of Cyolo hexylieonitril are heated to boiling in 80 ecm of acetonitrile for 3 hours. All important components are then distilled off in vacuo. 50 g of a reddish colored oil are obtained. Analysis: C ₁₇ H ₂₉ N ₅ O ₁ (291) Calcd .: C 69.7 H 9.95 N 14.4 ßef .: C 68.6 H 9.9 N 14.1

Example 23 : ι — ν _nw

- CC

CH ₃

C ¹ -

25.0 g Isobutenylpyrrolidin, 21 g of cyclohexyl isocyanate and 24.8 g cyclohexylisonitrile are heated to 9 hours on 12O ⁰ C in 100 cc of dimethylformamide. A slight cloudiness is then suctioned off. Upon cooling, 29 g of a substance are obtained which naoh

Le A 9163 - 19 -

808801/0720

% Q

the Ualöeen from acetonitrile from ^{79-81 0} C melts.

Analysis: C ₂₂ H ₅₇ N ₃ O ₁ (359) Calculated: C 73.5 H 10.3 N 11.7 Found: C 73.3 H 10.4 N 11.8.

Example 24 ;

27.8 g Isobutenylpiperidin, 21.6 g cyclohexylisonitrile and 24.8 g of cyclohexyl isocyanate are heated 7 hours to 12O ⁰ C in 100 cc of dimethylformamide. Upon cooling "Analyeei crystallize C 22 g of a compound, melting 102-104 ⁰ C ₂₃ H ₃₉ N ₃ O ₁ (373) Ber .: C 73,6 H 10.42 H 11.22. C 73, 6 H 10.5 N 11.5

Example 25 ? Γ "Λ ^ —_

N-CH - cr ^

s ι

* l - ^ * 0 0-0

13.9 g of isobutenylpyrrolidine are dissolved together with 20.7 g of p-isonitriloazobenzene in 100 ecm of acetonitrile. 11.9 g of phenyl isocyanate are added dropwise to this. The temperature rises to 4O ⁰ C. The mixture is heated for 1/2 hour at 8O ⁰ C and then cooled. 22 g of a compound aua crystallize which, after being redissolved from acetonitrile, melts 124-126 ° f.

Le A 9163 "80 8801/0? 2.0 - 20 -

Analysis: ^G 2B ^E

Calc .: C 74.4 H 6.42 N 15.5 βef: C 73.7 H 6.5 N 15.6

Example 26 :

25.0 g of isobutenylpyrrolidine, 32.4 g of 3-nitro-6-methyl-phenylisonitrile and 23.8 g of phenyl isoeyanate are combined with cooling in 100 ecm of acetonitrile. The temperature should not rise above 60 ⁰ C. Hach Cooling gives 65 g of a compound according to the redissolution of acetonitrile from 164 - 165 ⁰ C melts.

Analysis: C ₂ 2 ^H 24 ^N 4 ° 3 Calc .: C 67.25 H 6.13 N 14.3 Found: C 67.7 H 6.4 N 13.9

Example 27 : _ _un

-QE-G

CH

14.5 g Isobutenylpyrrolidin, 16.2 g of 3-HITRO-6-methyl-phenylisonitrile and 8.7 g of methoxymethyl isocyanate are heated in 50 cc acetonitrile rer agrees and 1 hour at 50 ⁰ C. After cooling, adds 1 mixture of 10 cc of methanol and 10 cc water. In this case, 17 g crystallize a substance from lie according ^fl n üalöaen au "acetonitrile from 84 - 85 ⁰ C melts.

80880 t / 0720 SAD

Analysis: C ₁₉ H ₂₆ N ₄ O ₄ (374)
B «r: C 61.0 H 6.96 Ii 14.9
Found: C 61.0 H 7 * 1 N 14.9

Example 28 :

c-

H> -

C = O

28 g of isobutenylpiperidine and 22 g of cyclohexyliaonitrile are dissolved in 100 ecm of acetonitrile. To this end, 34 g of G-naphthyl isocyanate in 50 ecm of acetonitrile are added dropwise. The temperature rises in the process

80 ⁰ C on. The mixture is stirred for 4 hours at this temperature and, after cooling, the precipitated precipitate is filtered off with suction. 70 g of a compound are obtained which, after dissolving from methanol, of

130 - 131 ⁰ C melts. Analysis: C ₂ ^ H ₃₅ N ₃ O ₁ (417.6) Calculated: C 77.8 H 8.5 N 10.1 gel. : C 77.0 H 8.4 N 10.1

Example 29 :

CH

CH, ι Q-CH

- C = O

£ "• 28.0 g Ieobutenylpiperidin and 22 g cyclohexylisonitrile in 150 cc of dimethylformamide are added at 90 ⁰ C with stirring, 16 g Phenylendiisocyanat- (1,4). The temperature rises to 110 ^° C. during this process. The mixture is stirred for 1 hour at 11O ⁰ C. and then allowed to cool. Thereby crystallize 45 g of a compound represented by the ümlösen of toluene of 211 - 212 ⁰ C melts. Analysis: C ₄₀ H ₆₀ H ₅ O ₂ (657) Calculated: C 73.2 H 9.2 H 12.8 Found: C 74.6 H 9.2 N 12.3

Example 30 ; /

^K * - CH-N N-CH-C

⁵ ^

I I

H> -N = C C = O

^ N

50 ecm of acetonitrile are added to 15.4 g of N-methyl-N'-isobutenylpiperazine and 10.8 g of cyclohexylonitrile. 19.7 g of p-toeyl isocyanate are added dropwise to this. The reaction mixture heats up to 70 ⁰ C. After cooling, 31 g d a compound of 148 - 151 ⁰ C melts.

Analysis: C ₂₄ H ₅₆ N ₄ O ₅ S ₁ (460) Calculated: C 62.6 H 7.82 N 12.15 Qef .: C 62.3 H 7.8 N 12.1

Le A 9163 - 23 -

8C98C1 / 0720

Example 31 : CH- „. / - \ ^ CH,

⁵ ^ C -CH-N N- CH -CtT CH- · ^s ''

O = CL C = N N = C C = O

N ' ¹ K

^S0 2

94 g of N-N'-diisobutenylpiperazine are dissolved together with 16.6 g of tert-butylisonitrile in 50 ecm of acetonitrile. 39.4 g of i-toeyl isocyanate are added to this. The temperature of the reaction mixture B rises to $ ⁴⁰ C. The mixture is stirred for 1/2 hour, cooled and the precipitate which has separated out is filtered off with suction. This gives 54 g of a compound which, after IEM redissolution of acetonitrile from 166 - 167 ⁰ C melts.

analysis: C ₃₈ H ₅₄ N ₅ O ₆ S ₂ (757)
3er .; C 60.4 H 7.17 N 11.28
lef .: C 60.5 H 7.4 N 11 _r 2

L ® A 9163 - 24 -

809801/0720

Claims (3)

Claims; 1. A process for preparing dialkylamino-imino-pyrrolidones, characterized in that enamines whose ß-ständigea -ragt carbon atom alkyl radicals unsctet with isocyanates and isonitriles, in an organic solvent at temperatures between 4-0 and 15O ⁰ C 2. The method according to claim 1, characterized in that ■ * & & lt organic solvent acetonitrile is used. 3.) Dialkylamino-imino-pyrrolidones of the formula ^s - * N
N SS Ro-N, ^{2 R} ^ wherein Rj is an alkyl, aryl, substituted aryl, cycloalkyl, aroyl or arylsulfonyl group. Rp can be alkyl, cycloalkyl or a substituted aryl group, R, and R are alkyl groups, where R, and R ^, as ring members with the nitrogen atom can form a ring which can also contain heteroatoms. R ₅ and Rr denote an alkyl group, where R ^ and R ^ together as ring members can also form a hydrocarbon ring. . copy Le A 9163