Sot., 79, 5710 (1957). THERMAL REACTION OF ALLYLAMINES WITH ETHYL DIAZOACETATE. R. M. Marvanov~ R. N. Fakhretdinov, and U. M. Dzhemilev.
4,5-Tetramethylene-2-imidazolinone (XIV). A mixture of 1.8 g 2-bromocyclohexanone (XII!) [6], 0.8 g K2C03 and 4 g urea was heated for i h at !40-150~ and then for 15 min at 150-160QC, cooled~ diluted with water and ether, andleft overnight. The precipitate was filtered off and washed with water and ether to yield 0.4 g (32%) (XIV), dec. 338-340~ (from ethanol) [7], Rf 0.72 (i:I ethyl acetate-ethanol). PMR spectrum (CF3COaH, ~, ppm): 130 hr. s (CH2CH2), 2.50 hr. s (CH2CH2). CONCLUSIONS 2-1midazolinones weresynthesized by heating ~-bromoketones with urea in ethyleneglycol in the presence of potassium carbonate. LITERATURE CITED i.
2. 3. 4. .
6. 7.
R. Duschinsky and L. A. Dolan, J. Am. Chem. Soc., 68, 2350 (1946). S. I. Zav'yalov and O. V. Dorofeeva, Izv. Akad. Nauk SSSR, Ser. Khim., 692 (1983). S. I. Zav'yalov and N. E. Knyaz'kova, Izv. Akad. Nauk SSSR, Ser. Khim., 217 (1983). S. I. Zav'yalov, A. G. Zavozin, and G. I. Ezhova, Izv. Akad. Nauk SSSR, Ser. Khim., 2626 (1981). A. Kirrmann, R. Freymann, and P. Duhamel, Bull. Soc. Chim. Fr., 1240 (1961). H. Schmid and P. Karrer, Helv. Chim. Acta, 29, 575, 579 (1946)~ G. De Stevens and A. Halamandaris, J. Am. Chem. Sot., 79, 5710 (1957).
THERMAL REACTION OF ALLYLAMINES WITH ETHYL DIAZOACETATE R. M. Marvanov~ R. N. Fakhretdinov, and U. M. Dzhemilev
UDC 541.ii:542.91:547.333:547.235.4
In our previous work [I], we showed that the react,on,of allylamines with ethyl diazoacetate (EDA) in the presence of catalytic amounts of copper complexes under mild conditions gives esters of nontrivial amino acids by the insertion of carboethoxycarbene (CEC) into the allylic C-H bond and concurrent isomerization of the starting amines. In order to expand the range of application of this method and select the optimal parameters for this reaction, we studied the effect of the reaction conditions and structure of the starting al!ylamines on the direction and yield of the products of the reaction of EDA with various allylamines. EDA was found to react with allylamines also in the absence of catalyst at II0-175~ to give the corresponding unsaturated branched amino acid in rather high yields. Hence, all the subsequent experiments on the reaction of allylamines with EDA were carried out under thermal conditions. Thus, for example, heating N-2,7-octadienylpiperidine (I) with an equivalent amount of EDA at 140~ in o-xylene gives the ethyl ester of 3-piperidyl-3-vinyl-7-octenecarboxylic acid (II) in 64% yield. The yield of (II) relative to temperature goes through a maximum (80%) at 175~ (Fig. i). The N-2,7-octadienyl derivatives of morpholine, hexamethyleneimine, dimethylamine, and diethylamine react similarly with EDA and are converted to the corresponding branched amino acid esters in 61, 65, 72, and 75% yield, respectively. RmN_/~_R
~ x, c H c o , ~ RR~N /-~.R~ CU--Ln
CH2C02Et (II)--(VI)
R2 = (CH2)aCH --CH2.
In the case of the N-2,7-octadienyl derivatives of aromatic secondary amines (methylaniline and ethylaniline), the reaction with EDA proceeds more vigorously and the yields of the Institute of Chemistry, Bashkir Branch, Academy of Sciences of the USSR, Ufa. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1680-1682, July, 1985. Original article submitted December 6, 1984.
0568-5230/85/3407-1537509.50
9 1986 Plenum Publishing Corporation
1537
Yield, % log
L
._
2g tOO
l#O
160
T,~
Fig. i. Effect of reaction temperature on the yield of ester (II) in the reaction of 14 m moles (I) and 14 mmoles EDA in 50 ml o-xylene over 3 h. TABLE i. Reaction of Allylamines with Ethyl Diazoacetate under Thermal Conditions (14 mmoles allylamine, 14 mmoles EDA in 50 ml EDA at 140=C for 3-4 h) Starting allylamine Reactio~ product R R'
(CIlz)~
(II)
64
(III)
61
o/CII,CHe (tit2).
Yield, ~tarting allylamine [eaction Yield, % ~roduct % R 1t'
65
(IV)
Me
Me
(v)
72
Et
Et
(vi)
75
Me
Ph
(vID
87
Et
Ph
(viii)
87
products of skeletal isomerization and CEC insertion are somewhat higher than in the experiments with aliphatic amines (Table 1). RPhN_/~_(CH2)aCH=CH~ N~CHCO~Et> CU--Ln
| 4 BPhN~v~/~
(VII), (VIII)
CH2CO2Et 9
We should note that skeletal isomerization of the allylamines studied is not observed in the absence of EDA. Thus, the reaction of EDA with allylamines at elevated temperatures features not only the insertion of CEC at the active allylic C--H bond but also a concurrent skeletal isomerization of the starting allylamlnes. These results and literature data [2, 3] for the formation of branched amino acids from EDA and allylamines indicate the following scheme. In the first step~ CEC generated thermally from EDA is stabilized by coordination with the nitrogen atom due to its unshared electron pair. The polarization of the starting allylamine molecule as a result of complexation with CEC leads to breakage of the allylic N-C bond in (IX). Subsequent stabilization of the molecule occurs with the formation of unsaturated amine (II). /
N~C~Co2zt i
175 ~
-'~HCO~
.4----
' "~%/k (u)
1538
gx)
EXPERIMENTAL Samples of the allylamines were obtained according to our previous procedure [4]. The PMR spectra were taken on a Tesla BS-480B spectrometer in CCI~ with HMDS as the internal standard. The IR spectra were taken neat on a UR-20 spectrophotometer. The gas--liquid chromatographic analyses of the amine mixtures were carried out on a Khrom-41 chromatograph with a flame ionization detector and a 2.4 m • 3 mm column packed with 5% SE-30 silicone on Chromatone with helium gas carrier. The mass spectra were taken on an MKh-13-06 mass spectrometer with 70 eV ionizing voltage and 200~ ionization chamber temperature. General Method for the Reaction of EDA with Allylamines. A sample of 14 mmoles EDA in i0 mi o-xylene was added with stirring to a solution of 14 mmoles allylamine in 40 ml abs. o-xylene at 140~ and maintained for 3-4 h at constant 140~ Then, the solvent was distilled off and the residue was fractionated in vacuum on a Widmer column. The results obtained are given in Table i. The pure compounds have the following indices.
Ethyl ester of 3-piPeridyl-3-vinyl-7-octenoic acid (II), bp I19~ (! mm), nD =~ 1.4781 [i]. Ethyl ester of 3-morpholyl-3-vinyl-7-octenoic acid (III), bp 173~ (i mm), n D 2 0 1.4793 [i]. Ethyl ester of 3-hexamethyleneamino-3-vinyl-7-octenoi c acid (IV), bp 95~ (2 mm), n D 2 O 1.4781. IR spectrum (~, cm-~): 920, I000, 3090 (CH=CH2), 1730 (C02Et). PMR spectrum (~, ppm): 1.27 t (3H, CH3, J = 7 Hz), 1.52 m (12H, CH=), 2.0 m (2H, CH2-C=C), 2.64 m (4H, N-CH2), 3.1 m (2H, CH2), 4.14 q (2H, CO2CH2, J = 7 Hz), 4.96 m (4H, C=CH2), 5.6 m (2H, CH=C). M + 293 Ethyl ester 3-dimethylamine-3-vinyl-7-octenoic acid (V), bp I12~ (i ram), nD =: 1.4560. IR spectrum ( ~ cm-~): 920, i000, 3082 (CH=CH2), 1728 (C02Et). PMR spectrum (6, ppm): 1.26 t (3Hi CH3, J = 6 Hz), 1.5 m (4H, CH2), 2.0 m (2H, CH2C=C)~ 2.22 s (6H, CH3NCH3), 2.9 m (2H, CH2CO2), 4.10 q (2H, CO2CH2, J = 7 Hz), 4.94 m (4H, C=CH2), 5.5 m (2H, CH=C). M+ 239.
Ethyl ester of 3-diethylamino-3-vinyl-7-octenoic acid (Vl), bp I15~ (i mm), nD 23 1.4551. !R spectrum (9, cm-~): 920, i000, 3090 (CH=CH2), 1725 (CO2Et), 1380, 1460 (CHs). PMR spectrum (~, ppm): 1.08 t (6H, CH~, J = 7 Hz), 1.29 t (3H, CH~, J = 7 Hz), 1.5 m (4H, CH~), 2.0 m (2H, CHiC=C), 2.4 q (4H, NCH~, J = 7 Hz), 3.0 m (2H, CH~CO~), 4.14 q (2H, CO~CH~, J = 7 Hz), 4.98 m (4H, C=CH=), 5.6 m (2H, CH=C). M + 267. N-Methyl-N-(l-vinyl-4-carboethoxymethyl)-5-hexenylaniline (VII), bp 163~ (2 mm), nD ~~ 1.5195. IR spectrum (~, cm-:): 920, i000 (C=CH=), 1735 (CO=Et), PMR spectrum (~, ppm): 1.12 t (3H, CHs), 1.40 m (4H, CH~), 2.0 m (3H, CHC=C, CH~--CO=), 2.8 s (3H, NCH~), 4.08 q (2H, CO=CH~, J = 7 Hz), 4.2 m (IH, NCHC=C), 4.96 m (4H, C=CH=), 5.4 m (2H, CH=C), 6.68 m, 7.08 m (5H, C~Hs). M+ 301. ~ C NMR spectrum (~, ppm, calculated/experimental): 113.3/ 114.63 t (C ~) 144.5/138.52 d (C =) 39.38/44.58 d (C ~) 30.68/26.11 t (C ~) 30.05/31.14 t (C'), 71.46/65.21 d (C~), 137.3/138.39 d (C~), 115.10/116.97 t (C~), 39.12/33.62 t (C~). N-Ethy!-N-
