8/13/2019 Synthesis and Properties of Azoles and Their Derivatives XVII. 1 (2 Cyanoethyl) 2 Substituted 2 Imidazolines 1975 Chemistry of Heterocyclic Compou

1/2

S Y N T H E S I S A N D P R O P E R T I E S O A Z O L E SA N D T H E I R D E R I V A T I V E SXVI .* 1-(2-CYANOETHYL)-2-S UBSTITUTED 2-IMIDAZOLINES

G. A. Shv ekh gei mer and V. I . Kel are v UDC 547.781.5.07:543.422.4

A method is proposed for the synthesis of 1- (2-cyanoethyl) -2-subst i tu ted 2- imidazo l ines;the method is based on react ion of N-(2-cyanoethyl)ethyle nediamine wi th the hydroc hlor idesof methyl imino esters of carboxyl ic acids.

2-Substi t uted {midazolines containing a 2-cya noethyl group in the 1 posit io n may be of int eres t asintermediates for the synthesis of o ther funct ional der ivat ives of 2-subst i tu ted imidazol ines and var iousheteroc ycl ic compounds containing an imidazolyl grouping in the molecule . There recent ly was a communi-cation [2] regar ding the addition of some 2-a lky lim ida zol ine s to the activated double bond of acr ylo nit r i l ein the prese nce of ion-exchange resi ns. In the presen t res ear ch we decided to use condensat ion of the hy-drochlo r ides of methyl imino est ers of carboxyl i c acids wi th N-(2-cyanoethyl)ethylenedia mine ([) for theprepa rat io n of 1- (2-cyanoe thyl) -2- subst i tu ted imidazol i nes. In s tudying this react ion we found that 1 ,2-disubst i tu ted imidaz ol ines ( [ IIa-e) are formed in high yields under mi ld condi t ions.

CH2CH2CN- C H ~ O H ~ /NH2CH2CH2NHCH2CH2N + R_C~NH.HCI ROCH~ -NH4CI

l I I a - e I l l a - el , l l l a R=CH 3; R=CaHsCH2;C R=C6Hs; d R=NO2C CHs)2CH2CH2; R=CH3C(NO2)2CH2CH

Compounds l l la-e are hygroscopic, quite soluble in alcohols and methylene chloride, and insoluble in hydro-carb ons and ethe r. They cannot be purif i ed by vacuum disti l lat io n. Thus decomposi tion with the forma tionof 2-m eth yl- 2-i mid az oli ne was obse rved during an attempt to vacuum disti l l imidazol ine l lIa at 100 ~ (1 ram).Compounds I l l a-e were there fore purif i ed with a column fil led with AI203.

The IR spec tra of l l l a-e contain an absorp tion band at 2240 cm -i , which is re late d to the C-=N stret ch-ing vibration s, and an intense abso rptio n band at 1605-1615 c m -1, which is rela ted to the C = N stre tchi ngvibrations [3].

E X P E R I M E N T A LN-(2-C yanoe thyl)e thyle nedia mine (I) . This compound was obtained in 70% yield by cyanoethy lation

of ethy lened iamin e ( the mol ar ratio of ethyl enedi amine to acry lon itr i le was 2 : 1) and had bp 97-98 ~ (1 mm)and n~ 1.4720 [4].

1- (2-C yanoe thyl) -2-me thyl -2- imi dazol ine ( [Ha) . A 5.42-g (0.05 mole) sa mple of methyl iminoacetatehyd roc hlo rid e ([Ia) [5] was added with st ir ri ng at 0 ~ to a solut ion of 5.65 g (0.05 mole) of I in 25 ml of ab-solut e m etha nol, and the mi xtu re was st ir re d at 0 ~ for 1 h and at 60 ~ for 2 h. It was then coole d to 0 ~ anda solution of sodium methoxide (1.15 g of sodium in 20 ml of methanol) was added dropwise . The prec ip i-* See [1] for com mun ica tio n XVI.

I . M. Gubkin Moscow Insti tute of the Petr och emi cal and Gas Industr y. Tran sla ted from KhimiyaGet erot sik lic hes kikh Soedinenii , No. 12, pp. 1674-1675, De cembe r, 1973. Original art i cle submi tted Decem-ber 12, 1972.

9 19 75 P lenum Publ i sh ing Corpora t ion , 22 7 Wes t 17 th S t r ee t , Ne w York , N . Y . 10011 . N o pa r t o f t h i s pub l i ca tion m ay be r eproduced ,s tored in a retrieval sys tem , or transm it ted, in any form or by any means , electronic, mechanical , pho tocop ying, microf i lming,recording or otherwise, with ou t wri t te n permission o f the publisher . A cop y of this ar t icle is avai lable fro m the publisher fo r $15.00.

8/13/2019 Synthesis and Properties of Azoles and Their Derivatives XVII. 1 (2 Cyanoethyl) 2 Substituted 2 Imidazolines 1975 Chemistry of Heterocyclic Compou

2/2

TABLE I. I- (2-Cyanoethyl)-2- Substituted 2-ImidazolinesCompound

aIIlbcIIId

rap, ~

137--13998--100I04,5--I05125--125,5

crystalliza-tionolventMethanolMethanolCyclohexaneEthanol

Picratesempirical formula

CTHnNa. C6HaN307C~aH sN3.C6HzNaOzCI~HI~Ns.C6HaNaO7CuHIsN402.C6H3NsO7

f o u n d ~ o _ calc.,

. 9 4 i 1 8 i 7 i5 1 0 4 1 1 1 9 2 1 5 1 3 4,1119,017 2 3 6 ~ I2 0 9 7 2 3 6 5 2 1 14 3 3 4 8 2 1 0 4 3 7 4 8 2 0 988909294

tare was rem oved by filtrati on, and the filtrat e was passe d through a column filled with activity-I I AI203.The solvent was remo ved by distillation, and the resid ual oil was vacuu m-dri ed over KOH.

Compounds IIIb-d were sim ila rly obtained from IIb [5], IIc [6], and IId [7], respec tiv ely. The yieldsof the products and the properties of their pic rates are pre sented in Table 1.

1-(2 -Cya noet hyl) -2- (3,3 -di nitr obut yl) -2-i mida zoli ne (IIIe). A 4.56-g (0.019 mole) sample of methyl4,4- dini tro imi nova ler ate hydroc hlori de (IIe) [8] was added with st irr ing at 0 ~ to a solution of 2.15 g (0.019mole) of I in 20 ml of absolute methanol, afte r which the mix ture was st ir red at 0 ~ for 1 h and at 40 ~ for2 h. It was then coole d to 0 ~ and a so lutio n of 0.73 g (0.02 mole) of dry HC1 in 10 m of absolute methan olwas added dr0pwise. The preci pitat e was remov ed by filtration, the filtrat e was evaporated, and the res i-due was vac uum- dri ed. Stor age in the cold for 48 h gave 4.77 g (93%) of the hydro chl ori de of IIIe with mp142-14 3 ~ (absolut e met hano l). Foun d: N 22.7; C1 11.5%. C10H15N504"HC1. Ca lc ul at ed : N 22.9; C1 11.6%.

1~2.34.5.6.7 .

8 .

L I T E R A T U R E C I T E D

G. A. Shve khg ei mer , E . V. Ar sl an ov, and A. Bar ans ki, Roc zn. C hem. , 4_~6, 2381 (1972).V. I. Isagulyants, V. I. Frolov, V. A. Tromfimov, R. I. Fedorova, and A. Yu. Adzhiev, Zh. Prikl.Kh im., 4_~8, 2120 (1970).A. Bellamy, Infr ared Spectra of Complex Molecules, Wiley (1958).A. P. Ter en t ' ev and A. N. Kos t, Zh. Ob shc h. Khim., 2._~0, 2069 (1950).A. Pinner, Die Imid oath er und ihre Derivate, Berl in (1892).G. I. Bra z, G. V. Myasnikova , A. Ya. Yakubovich, V. P. Bazov, I. E. Karda sh, and A. N. Prav edni kov,Khim. Geterotsikl. Soedin., 215 (1967).V. P. Dukhovskoi, V. D. Tyurin, and G. A. Shvekhgeimer, Trudy Moskovsk Inst. Neftekhim. i GazovoiProm., Neftekhim i Neftepererabotka, 3, 12 (1969).G. A. Shvekhgeimer and G. A. Mikheichev, Khim. Geterotsikl. Soedin., 678 (1971).

1516