SYNTHESIS AND XVI!.

* THEIR

AND

PROPERTIES

OF

AZOLES

DERIVATIVES

1 - ( 2 - C Y A N O E T H Y L ) - 2 - S U B S T I T U T E D 2-IMIDAZOLINES G. A . Shvekhgeimer and V. I. Kelarev UDC 547.781.5.07:543.422.4

A method is p r o p o s e d f o r the s y n t h e s i s of 1 - ( 2 - c y a n o e t h y l ) - 2 - s u b s t i t u t e d 2 - i m i d a z o l i n e s ; the m e t h o d is b a s e d on r e a c t i o n of N - ( 2 - c y a n o e t h y l ) e t h y l e n e d i a m i n e with the h y d r o c h l o r i d e s of m e t h y l i m i n o e s t e r s of c a r b o x y l i c a c i d s .

2 - S u b s t i t u t e d { m i d a z o l i n e s containing a 2 - c y a n o e t h y l group in the 1 p o s i t i o n m a y be of i n t e r e s t as i n t e r m e d i a t e s f o r the s y n t h e s i s of o t h e r functional d e r i v a t i v e s of 2 - s u b s t i t u t e d i m i d a z o l i n e s and v a r i o u s h e t e r o c y c l i c compounds containing an i m i d a z o l y l grouping in the m o l e c u l e . T h e r e r e c e n t l y was a c o m m u n i c a t i o n [2] r e g a r d i n g the addition of s o m e 2 - a l k y l i m i d a z o l i n e s to the a c t i v a t e d double bond of a c r y l o n i t r i l e in the p r e s e n c e of i o n - e x c h a n g e r e s i n s . In the p r e s e n t r e s e a r c h we decided to use c o n d e n s a t i o n of the hyd r o c h l o r i d e s of m e t h y l imino e s t e r s of c a r b o x y l i c a c i d s with N - ( 2 - c y a n o e t h y l ) e t h y l e n e d i a m i n e ([) f o r the p r e p a r a t i o n of 1 - ( 2 - c y a n o e t h y l ) - 2 - s u b s t i t u t e d i m i d a z o l i n e s . In studying t h i s r e a c t i o n we found that 1,2d i s u b s t i t u t e d i m i d a z o l i n e s ([IIa-e) a r e f o r m e d in high y i e l d s u n d e r m i l d conditions.

CH2CH2CN -CH~OH ~ / NH2CH2CH2NHCH2CH2 CN+ R_C~NH.HCI "OCH~ -NH4CI
l !l,lll a II a - e Ill

R a-e

R=CH3;

b

R=CaHsCH2;C R=C6Hs; d R=NO2C(CHs)2CH2CH2; e R=CH3C(NO2)2CH2CH 2

Compounds l l l a - e a r e h y g r o s c o p i c , quite soluble in a l c o h o l s and m e t h y l e n e c h l o r i d e , and insoluble in h y d r o c a r b o n s and e t h e r . They cannot be p u r i f i e d by vacuum d i s t i l l a t i o n . Thus d e c o m p o s i t i o n with the f o r m a t i o n of 2 - m e t h y l - 2 - i m i d a z o l i n e was o b s e r v e d during an a t t e m p t to vacuum d i s t i l l i m i d a z o l i n e l l I a at 100 ~ (1 ram). Compounds I l l a - e w e r e t h e r e f o r e p u r i f i e d with a c o l u m n f i l l e d with AI203. The IR s p e c t r a of l l l a - e contain an a b s o r p t i o n band at 2240 c m - i , which is r e l a t e d to the C-=N s t r e t c h ing v i b r a t i o n s , and an intense a b s o r p t i o n band at 1605-1615 c m -1, which is r e l a t e d to the C = N s t r e t c h i n g v i b r a t i o n s [3]. EXPERIMENTAL N - ( 2 - C y a n o e t h y l ) e t h y l e n e d i a m i n e (I). This compound was obtained in 70% y i e l d by c y a n o e t h y l a t i o n of e t h y l e n e d i a m i n e (the m o l a r r a t i o of e t h y l e n e d i a m i n e to a c r y l o n i t r i l e was 2 : 1) and had bp 97-98 ~ (1 mm) and n~ 1.4720 [4]. 1 - ( 2 - C y a n o e t h y l ) - 2 - m e t h y l - 2 - i m i d a z o l i n e ([Ha). A 5.42-g (0.05 mole) s a m p l e of m e t h y l i m i n o a c e t a t e h y d r o c h l o r i d e ([Ia) [5] was added with s t i r r i n g at 0 ~ to a solution of 5.65 g (0.05 mole) of I in 25 ml of a b solute m e t h a n o l , and the m i x t u r e was s t i r r e d at 0 ~ for 1 h and at 60 ~ f o r 2 h. It was then cooled to 0 ~ and a solution of s o d i u m m e t h o x i d e (1.15 g of s o d i u m in 20 ml of methanol) was added d r o p w i s e . The p r e c i p i * See [1] f o r c o m m u n i c a t i o n XVI. I. M. Gubkin Moscow I n s t i t u t e of the P e t r o c h e m i c a l and Gas I n d u s t r y . T r a n s l a t e d f r o m K h i m i y a G e t e r o t s i k l i c h e s k i k h Soedinenii, No. 12, pp. 1674-1675, D e c e m b e r , 1973. O r i g i n a l a r t i c l e s u b m i t t e d D e c e m b e r 12, 1972.

9 19 75 Plenum Publishing Corporation, 22 7 West 17th Street, New York, N. Y. 10011. No part o f this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, microfilming, recording or otherwise, without written permission o f the publisher. A copy o f this article is available from the publisher for $15.00.

Zh. Pravednikov. A 4..7. D. Pinner.5%. A. V.9 4 i1 . and the filtrate was passed through a column filled with activity-II AI203.C y a n o e t h y l ) .9 72. 12 (1969). A. Geterotsikl. C1 11.. Wiley (1958).5 21. A.02 mole) of dry HC1 in 10 m! of absolute methanol was added dr0pwise. of the products and the p r o p e r t i e s of their p i c r a t e s are presented in Table 1. T e r e n t ' e v and A.d i n i t r o i m i n o v a l e r a t e hydrochloride (IIe) [8] was added with s t i r r i n g at 0 ~ to a solution of 2. Neftekhim. and A. Khim. I. G. Compound I . C10H15N504"HC1. and the residual oil was vacuum-dried o v e r KOH.2069 (1950). 7. The solvent was r e m o v e d by distillation. . 2.3 4. V. Ya.15 g (0. Die Imidoather und ihre Derivate.3 4. 3 . V.2120 (1970). Compounds IIIb-d were s i m i l a r l y obtained f r o m IIb [5]. Chem. G.3 6.9. and A.9 94 tare was r e m o v e d by filtration.0 43. 6.2 . 3. Shvekhgeimer and G. I. G. 4_~8. % rap. Roczn. Soedin. Obshch.Substituted 2-Imidazolines Picrates crystallization solvent found. respectively.(2-Cyanoethyl)-2.8i .77 g (93%) of the hydrochloride of IIIe with mp 142-143 ~ (absolute methanol). A.1119. Soedin. 1516 . G. V. Bellamy. Khim.. 215 (1967).. Kardash. A. Storage in the cold for 48 h gave 4.C6HaNaO7 72. I n f r a r e d Spectra of Complex Molecules. Kost.5 IIlb Methanol CTHnNa. Khim.7 4. A. 3. after which the mixture was s t i r r e d at 0 ~ for 1 h and at 40 ~ for 2 h. Braz.C6HaN307 . Adzhiev..1119. Shvekhgeimer. A. 8. P. V. 2381 (1972). I. Geterotsikl. IIc [6]. Zh.8 20. The yields 1 . N. P. Berlin (1892). E.i m i d a z o l i n e (IIIe). P.~I20. R.56-g (0. Arslanov.019 mole) sample of methyl 4 . It was then cooled to 0 ~ and a solution of 0. and IId [7]. ~o _ calc.C6HzNaOz 510 4. ~ empirical formula I IIIa 137--139 98--100 IIIc I04.73 g (0. A.7i 88 Methanol C~aHsN3.6%. I.C6H3NsO7 43. C1 11. the filtrate was evaporated._~0. 5.3 6. I. Bazov. i Gazovoi P r o m . Prikl. LITERATURE 1~ CITED 2. A.2 . The precipitate was r e m o v e d by filtration. and A.d i n i t r o b u t y l ) .( 3 . Khim. Myasnikova. Mikheichev. Yakubovich. V. Isagulyants..1 92 Ethanol CuHIsN402.( 2 .2151. 678 (1971).019 mole) of I in 20 ml of absolute methanol. Found: N 22.TABLE I. N.. V. Neftekhim i Neftepererabotka. Baranski. Dukhovskoi. V.5--I05 IIId 125--125. Tromfimov. Frolov. E. and G. Fedorova.0190 Cyclohexane CI~HI~Ns. 4. Yu. Shvekhgeimer. Trudy Moskovsk Inst. 4_~6. 4 . Calculated: N 22.8 21. Tyurin. and the r e s i due was vacuum-dried.