Stevens rearrangement of ammonium salts containing 2-propynyloxy or tert-butoxycarbonylmethyl groups

Article abstract of DOI:10.1007/s11176-005-0143-z

The Stevens rearrangement of ammonium salts containing 2-alkenyl, 2-alkynyl, or benzyl groups along with 2-propynyloxy or tert- butoxycarbonylmethyl was studied. Under the action of a suspension of sodium phenolate in benzene the salts containing a 2-prop

Full text of DOI:10.1007/s11176-005-0143-z

Russian Journal of General Chemistry, Vol. 74, No. 8, 2004, pp. 1221 1226. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004,
pp. 1321 1326.
Original Russian Text Copyright
2004 by Babakhanyan, Ovakimyan, Grigoryan, Kocharyan.
Stevens Rearrangement of Ammonium Salts Containing
2-Propynyloxy or tert-Butoxycarbonylmethyl Groups
A. B. Babakhanyan, S. A. Ovakimyan, V. V. Grigoryan, and S. T. Kocharyan
Abovyan Armenian State Pedagogical University, Erevan, Armenia
Institute of Organic Chemistry, National Academy of Sciences of Armenia, Erevan, Armenia
Received October 1, 2002
Abstract The Stevens rearrangement of ammonium salts containing 2-alkenyl, 2-alkynyl, or benzyl groups
along with 2-propynyloxy or tert-butoxycarbonylmethyl was studied. Under the action of a suspension of
sodium phenolate in benzene the salts containing a 2-propynyloxycarbonylmethyl group form 2-propynyl
esters of 2-dialkylamino-4-pentenoic acids, whereas with sodium methylate as the basic reagent, rearrange-
ment is preceded by an almost complete transesterification. The salts containing a tert-butoxycarbonylmethyl
group undergo almost no transesterification under the action of sodium methylate. The tert-butyl fragment in
the ester group of the salt with a benzyl group exerts a fairly strong effect on the regiochemistry of the rear-
rangement and on the prototropic isomerization of the 3,2-Stevens rearrangement of the salts with 2-butynyl
or 3-phenyl-2-propynyl groups.
Ammonium salts containing an alkoxycarbonyl-
methyl group undergo complete hydrolysis by the
ester group under the action of alkali metal hydroxides
[1], whereas sodium alcoholates produce their trans-
esterification [2, 3]. Appropriate choice of the basic
component may allow rearrangement without trans-
esterification. Kocharyan et al. could effect rearran-
gement of allyldimethyl(methoxycarbonyl)ammonium
bromide without transesterification under the action of
sodium phenolate [3].
The present work was devoted to the Stevens re-
arrangement of ammonium salts Ia Ip containing
2-propynyloxy- or tert-butoxycarbonylmethyl groups.
The salts were prepared in high yields by reactions of
unsaturated tertiary amines with propynyl [4] (Ia Ig)
or tert-butyl [5] (Ih Il) esters of monochloroacetic
acid (Table 1).
CHR2CR3=CR4R5
CH2COOR6
Ia Il
R4R5CCR3=CHR2
R12NCHCOOR6
IIa IIl
R7ONa
+
R12NCHR2CR3=CR4R5 + ClCH2COOR6
R12N
Cl
Ia Ig, IIa IIg, R6 = CH2C CH, R7 = C6H5; R1 = CH3, R2 = R3 = R4 = R5 = H (a); R1 = R3 = CH3, R2 = R4 = R5 = H (b);
R1 = R5 = CH3, R2 = R3 = R4 = H (c); R1 = CH3, R2 = R3 = R4 = H, R5 = C6H5 (d); R21 = (CH2)5, R2 = R3 = R4 = H, R5 =
CH3 (e); R12 = (CH2)5, R2 = R3 = H, R4 = R5 = CH3 (f); R1 = CH3, R2 = CH2CH=CH2, R3 = R4 = R5 = H (g). Ih Il, IIh
IIl, R6 = R7 = C(CH3)3, R2 = H; R1 = CH3, R3 = R4 = R5 = H (h); R1 = R3 = CH3, R4 = R5 = H (i); R1 = R5 = CH3, R3 =
R4 = H (j); R12 = (CH2)5, R3 = R4 = H, R5 = CH3 (k); R1 = CH3, R3 = R4 = H, R5 = C6H5 (l).
CH2CH=CH2
CHCH=CH2
It was shown that the reaction of salts Ia If with a
+
benzene suspension of sodium phenolate takes exclu-
sively the way of the 3,2-Stevens rearrangement to
form propynyl 2-dialkylamino-4-pentenoates IIa IIf
(Table 2). The rearrangement of salt Ig under the
same conditions yields 2-propynyl 2-dimethylamino-
4,7-octadienoate (IIg) (Table 2).
(CH3)2N
CH2COOCH2C CH
Cl
Ig
C6H5ONa
benzene
(CH3)2NCH CH2CH=CHCH2CH=CH2
COOCH2C CH
IIg
1070-3632/04/7408-1221 2004 MAIK Nauka/Interperiodica

1222
BABAKHANYAN et al.
Table 1. Yields, constants, and elemental analyses of salts Ia Ip
Found, %
Calculated
Comp. no. Yield, %
mp,
C
Formula
Cl
N
Cl
N
a
Ia
Ib
Ic
Id
Ie
If
Ig
Ih
Ii
Ij
Ik
Il
Im
In
Io
Ip
75
80
82
85
86
87
78
90
89
86
70
94
68
93
60
92
16.08
15.20
15.18
12.02
12.98
12.29
13.65
15.01
14.15
14.19
12.21
11.45
14.28
11.41
24.94
12.40
6.37
6.01
5.99
4.65
5.11
4.69
5.37
5.89
5.58
5.57
4.80
4.38
5.59
4.48
4.88
4.86
C10H16ClNO2
C11H18ClNO2
C11H18ClNO2
C16H20ClNO2
C14H22ClNO2
C15H24ClNO2
C13H20ClNO2
C11H22ClNO2
C12H24ClNO2
C12H24ClNO2
C15H28ClNO2
C17H26ClNO2
C12H22ClNO2
C17H24ClNO2
C12H23Cl2NO2
C15H24ClNO2
16.29
15.30
15.30
12.07
13.04
12.40
13.75
15.07
14.23
14.23
12.26
11.39
14.34
11.47
25.00
12.43
6.43
6.05
6.05
4.77
5.15
4.90
5.43
5.94
5.61
5.61
4.84
4.49
5.66
4.52
4.93
4.90
a
a
125 128
118 120
a
123 125
96 98
105 107
132 133
151 153
163 164
135 137
145 146
125 126
65 66
a
Hygroscopic substances.
Table 2. Yields, constants, and elemental analyses of products of rearrangement of salts Ia Ip
Found, %
Calculated
Starting Rearrangement Yield,
mp,
(p, mm Hg)
C
n2D0
Formula
salt no. product no.
%
C
H
N
C
H
N
Ia
Ib
Ic
Id
Ie
If
Ig
Ih
Ii
Ij
Ik
Il
Im
In
Io
Ip
IIa
IIb
IIc
IId
IIe
IIf
IIg
IIh
IIi
IIj
IIk
IIl
IIm
IIn
IIo
IIp
32
30
85 87 (6)
94 96 (8)
1.4752 65.90
1.4792 67.15
8.42
8.45
8.53
6.88
8.62
8.87
8.35
7.33 C10H15NO2 66.30
7.44 C11H17NO2 67.70
6.88 C11H17NO2 67.70
5.15 C16H19NO2 74.71
6.09 C14H21NO2 71.49
5.25 C15H23NO2 72.29
5.97 C13H19NO2 70.59
7.29 C11H21NO2 66.33 10.55
6.90 C12H23NO2 67.60 10.79
6.39 C12H23NO2 67.60 10.79
5.41 C15H27NO2 71.15 10.67
4.77 C17H25NO2 74.18
6.41 C12H21NO2 68.25
5.40 C17H23NO2 74.72
6.43 C12H21NO2 68.25
5.18 C15H23NO2 72.30
8.29
8.72
8.72
7.39
8.94
9.24
8.60
7.73
7.18
7.18
5.45
5.96
5.62
6.33
7.04
6.57
6.57
5.53
5.09
6.63
5.13
6.63
5.62
29 102 104 (12) 1.4747 67.80
40 148 151 (6)
34 105 108 (3)
35 130 132 (5)
1.4948 75.02
1.4898 71.03
1.4835 72.66
47 119 120 (1.5) 1.4886 70.98
51
66
46
53 54 (1)
54 56 (1)
54 55 (1)
1.4330 65.99 10.41
1.4356 65.83 10.37
1.4360 67.21 10.53
52 111 112 (3)
70 104 105 (1)
48
54 143 142 (2)
58 64 65 (1)
49 110 111 (1)
1.4554 70.98 10.52
a
75.01
1.4578 68.02
1.4626 74.38
1.4840 68.67
1.4844 71.93
8.42
9.82
8.53
9.55
9.11
9.09
9.95
8.42
9.95
9.24
67 68 (3)
a
Compound IIl is a crystalline substance, mp 44 45 C.
The example of salt Ia was used to show that under
rearrangement-without-transesterification product in
the mixture is 5.5%.
the action of sodium methylate rearrangement is ac-
companied by an almost complete transesterification.
1
According GLC and H NMR data, the content of the
The example of salts of Ih Ip containing a tert-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 8 2004

STEVENS REARRANGEMENT OF AMMONIUM SALTS
CH2CH=CH2
1223
CH2CH=CH2
+
CH3ONa
+ IIa
(CH3)2N
(CH3)2N CHCOOCH3
benzene
CH2COOCH2C CH
Cl
II a
butoxycarbonylmethyl substituent was used to elu-
cidate the effect of steric and electronic factors on the
Stevens rearrangement and rearrangement transesteri-
fication product ratio. As known, tert-butyl esters of
carboxylic acids are hardly transesterified [6]. We
found that salts Ih Il under the action of sodium
methylate undergo 3,2-Stevens rearrangement to form
than 5 8%. To obtain pure target products, salts Ih
Ip were subjected to rearrangement under the action
of sodium tert-butylate in tert-butanol.
We earlier showed that the methoxycarbonylmethyl
analog of aminoester IIl undergoes thermal isomeriza-
tion to form a 1,2-Stevens rearrangement product [7].
It was found that aminoester IIl is more susceptible to
thermal isomerization than its methoxycarbonylmethyl
analog, which appears to be explained by the steric
effect of the ester tert-butyl group (Tables 2 and 3).
tert-butyl
2-dialkylamino-4-pentenoates
IIh IIl
(Table 2). Therewith, the content of transesterification
rearrangement products in the mixture is no higher
C6H5
t
(CH3)2N CHCHCH=CH2
(CH3)2N CHCH2CH=CHC6H5
COOC(CH3)3
COOC(CH3)3
IIl
II l
The rearrangement of 2-butynyl- and 3-phenyl-2-
propynyl-containing salts Im and In under the action
of a basic agent gives rise to allenic aminoesters IIm
and IIn. It should be noted that with sodium me-
thylate or tert-butylate as basic agents, the regio-
chemistry of the rearrangement of these salts is the
same (3,2 rearrangement). However, rearrangement
products IIm and IIn with a tert-butoxycarbonyl
group undergo no allene diene prototropic isomeriza-
tion, as observed earlier [8], whereas the transesteri-
fication rearrangement product isomerizes into con-
jugated diene II m. The content of compound II m in
the mixture is 7% (GLC).
With salt In, we failed to isolate the dienic amino-
ester because of its tarring [8]. The different behaviors
of the allenic methyl and tert-butyl esters can be
explained in terms of the steric effect of the tert-butyl
group that prevents access of the basic reagent to the
-proton of the 3,2-rearrangement product and renders
isomerization impossible.
With salt Ip containing a 3-chloro-2-butenyl group,
two rearrangement pathways (a and b) are theoretical-
ly possible. The formation of 1,3-dienic aminoester
IIp from salt Ip rules out pathway b that leads to
allenic aminoester IIm, as with salt Im.
Table 3. IR and 1H NMR spectra of compounds IIa IIp and II l
Comp.
no.
1
IR spectrum, , cm
1H NMR spectrum (CCl4), , ppm (J, Hz)
IIa
IIb
IIc
915, 985, 1640, 3030, 3085 (CH=CH2); 1075, 2.23 s (6H, NCH3), 1.9 2.55 m (2H, CH2), 2.65 3.60 m (2H,
1130, 1730 (COO); 2130, 3300 (C CH)
NCH, CH), 4.20 m (2H, OCH2), 4.40 5.40 m (2H, CH2=),
5.40 6.20 m (1H, CH=)
890, 1640, 3085 (C=CH2); 1040, 1070, 1150, 1.77 s (3H, CH3), 2.22 2.53 m (2H, CH2), 2.34 s (6H,
1730 (COO); 2125, 3300 (C CH)
NCH3), 2.72 m (1H, CH), 3.43 t (1H, NCH, J 7.2 ), 4.12 m
(2H, OCH2), 4.77 m (2H, CH2=)
920, 990, 1640, 3030, 3085 (CH=CH2); 1070, 0.71 and 0.83 d (3H, CH3CH, J 7.0), 2.26 s (6H, NCH3),
1130, 1730 (COO); 2120, 3300 (C CH)
2.71 m (1H, CH), 2.8 m (NCHCH), 4.50 4.72 m (2H,
OCH2), 4.80 5.20 m (2H, CH2=), 5.20 6.03 m (1H, CH=)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 8 2004

1224
BABAKHANYAN et al.
Table 3. (Contd.)
Comp.
no.
1
IR spectrum, , cm
1H NMR spectrum (CCl4), , ppm (J, Hz)
IId
700, 770, 1600, 3030, 3090 (C6H5); 915, 985, 2.32 s (6H, CH3), 3.05 4.20 m (5H, CH2, CHCH, NCH),
1640 (CH=CH2); 1130, 1730 (COO); 2120, 3300 4.79 m (2H, CH2=), 5.42 6.03 m (1H, CH=), 7.20 s (5H,
(C CH)
C6H5)
IIe
920, 980, 1640, 3030, 3085 (CH=CH2); 1025, 0.72 and 0.85 d (3H, CH3CH, J 7.0), 1.03 1.97 m (6H,
1140, 1730 (COO); 2120, 3305 (C CH)
, -CH2), 2.05 2.65 m (4H, -CH2), 2.75 m (3H, NCHCH,
CH), 4.45 4.70 m (2H, OCH2), 5.20 m (2H, CH2=), 5.65
6.20 m (1H, CH=)
IIf
915, 985, 1640, 3025, 3085 (CH=CH2); 1070, 0.93 and 0.98 s (6H, CH3C), 1.2 1.7 m (6H, , -CH2), 2.05
1130, 1730 (COO); 2125, 3305 (C CH)
2.65 m (4H, -CH2), 2.71 m (1H, CH), 2.85 s (1H, NCH),
4.42 4.68 m (2H, OCH2), 5.15 m (2H, CH2=), 5.72 6.30 m
(1H, CH=)
IIg
IIh
IIi
920, 990, 1640, 1645, 3035, 3085 (CH=CH2, 2.28 s (6H, NCH3), 2.20 2.50 m (4H, CH2), 3.18 t (1H,
CH=CH); 1070, 1135, 1730 (COO); 2130, 3300 NCH, J 7.3 ), 4.15 s (2H, OCH2), 4.4 6.2 m (5H, CH2=,
(C CH)
CH=)
925, 990, 1630, 1830, 3015, 3085 (CH=CH2); 1.29 s [9H, C(CH3)3], 2.17 s (6H, NCH3), 1.85 2.25 m (2H,
1035, 1060, 1250, 1710 (COO)
CH2), 2.95 t (1H, NCH, J 8.0), 4.55 5.10 m (2H, CH2=),
5.20 5.65 m (1H, CH=)
890, 1630, 1800, 3080 (C=CH2); 1035, 1065, 1.19 s [9H, C(CH3)3], 1.43 d.d (3H, CH3C=, J1 0.8, J2 1.2),
1245, 1705 (COO)
1.80 2.09 m (2H, CH2), 2.1 s (6H, NCH3), 2.89 t (1H, NCH,
J 7.8), 4.20 m (2H, CH2=)
IIj
920, 990, 1625, 1830, 3015, 3085 (CH=CH2); 0.72 d and 0.83 d (3H, CH3CH, J 7.0), 1.25 s and 1.29 s [9H,
1035, 1065, 1250, 1705 (COO)
C(CH3)3], 2.24 s and 2.29 s (6H, NCH3), 2.60 m (1H,
CH3CH), 3.40 d.d (1H, NCH, J 10.2), 4.60 5.10 m (2H,
CH2=), 5.20 6.1 m (1H, CH=)
IIk
925, 985, 1625, 1825, 3015, 3085 (CH=CH2); 0.71 d and 0.82 d (3H, CH3CH, J 7.0), 1.1 1.6 m [15H,
1035, 1065, 1250, 1710 (COO)
C(CH3)3, , -CH2], 2.0 2.7 m (5H, CH3CH, -CH2),
3.38 d.d (1H, NCH, J 10.3), 4.50 5.10 m (2H, CH2=), 5.20
6.05 m (1H, CH=)
IIl
690, 765, 1600, 1668, 3035, 3070 (C6H5); 925, 1.19 s and 1.25 s [9H, C(CH3)3], 2.20 s (6H, NCH3), 3.81
990, 1625, 1830, 3015, 3085 (CH=CH2); 1035, 4.02 m (2H, CHCH), 4.80 5.20 m (2H, CH2=), 5.81 6.35 m
1070, 1250, 1705 (COO)
IIm 870, 1945 (C=C=CH2); 1035, 1070, 1250, 1705 1.30 s [9H, C(CH3)3], 1.67 t (3H, CH3C=, J 3.21), 2.32 s
(COO) (6H, NCH3), 3.58 d (1H, NCH, J 3.2), 4.52 m (2H, CH2=)
(1H, CH=), 7.15 m (5H, C6H5)
IIn
690, 770, 1600, 1668, 3035, 3070 (C6H5); 870, 1.41 s [9H, C(CH3)3], 2.41 s (6H, NCH3), 4.12 d (1H, NCH,
1940 (C=C=CH2); 1035, 1070, 1250, 1705 J 3.2), 5.18 s (2H, CH2=), 7.21 7.50 m (5H, C6H5)
(COO)
IIo
IIp
II l
920, 970, 990, 1620, 1630, 1825, 3015, 3085 1.20 s [9H, C(CH3)3], 1.60 s (3H, CH3C=), 2.20 s (6H,
(C=C CH=CH2); 1035, 1070, 1250, 1705 (COO) NCH3), 4.1 5.1 m (2H, CH2=), 5.8 6.7 m (1H, CH=)
690, 770, 1600, 1667, 3035, 3070 (C6H5); 1035, 1.18 s [9H, C(CH3)3], 2.19 s (6H, NCH3), 2.8 3.2 m (2H,
1070, 1250, 1710 (COO)
CH2), 3.67 d.d (1H, NCH, J1 4.5, J2 9.0), 7.23 m (5H, C6H5)
690, 770, 1600, 1668, 3035, 3070 (C6H5); 975, 1.19 s [9H, C(CH3)3], 2.08 s (6H, NCH3), 2.0 2.4 m (2H,
1630 (CH=CH); 1035, 1070, 1250, 1710 (COO) CH2), 3.02 t (1H, NCH, J 7.0), 5.7 6.6 m (2H, CH=CH),
7.0 m (5H, C6H5)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 8 2004

STEVENS REARRANGEMENT OF AMMONIUM SALTS
1225
The resulting data suggest that the 3-chloro-2-
butenyl group is directly involved into the rearrange-
ment of salt Io to form a chlorine-containing amino-
ester that further eliminates hydrogen chloride, yield-
ing dienic aminoester IIo.
II a
R C=C=CH2
(CH3)2N CH COOC(CH3)3
IIm, IIn
(CH3)3CONa
(CH3)3COH
CH2C CR
+
(CH3)2N
CH2COOC(CH3)3
R C=C=CH2
Cl
CH3ONa
benzene
Im, In
IIm, IIn + (CH3)2N CHCOOCH3
R
(CH3)2NC=CCH=CH2
COOCH3
II m
a
Cl CH3
CH2CH=CClCH3
CH2COOC(CH3)3
+
(CH3)3CONa
(CH3)3COH
(CH3)2NCHC CH=CH2
COO(CH3)3
(CH3)2N
Cl
(CH3)3CO
(CH3)3CO
CH3
b
Im
(CH3)2NC=C CH=CH2
COO(CH3)3
IIo
IIm
1
According to H NMR data, salt Ip that contains
tert-butoxycarbonylmethyl and benzyl groups under
the action of sodium tert-butylate of the possible
Stevens and Sommelet rearrangements is involved
exclusively into the former one.
At the same time, it should be noted that the
methoxycarbonylmethyl analog of salt Ip under the
action of sodium methylate forms a mixture of
Stevens and Sommelet rearrangement products in a
52:48 ratio [9].
CH2C6H5
+
The rearrangement of allyl(methoxycarbonylme-
thyl)dimethylammonium bromide under the action of
sodium tert-butylate in tert-butanol gave 55% of
transesterification rearrangement product IIh and
6.3% of the rearrangement-without-transesterification
product (GLC).
(CH3)2N
CH2COOC(CH3)3
Cl
Ip
CH2C6H5
(CH3)3CONa
(CH3)3COH
(CH3)2NCHCOOC(CH3)3
IIp
(CH3)3CONa
CH2CH=CH2
+
(CH3)2NCHCH2CH=CH2 + (CH3)2NCHCH2CH=CH2
(CH3)2N
(CH3)3COH
CH2COOCH3
Br
COOCH3
COOC(CH3)3
IIh
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 8 2004

1226
BABAKHANYAN et al.
To find out whether transesterification precedes
tinued, the mixture was heated for 15 min at 50 55 C
and diluted with ether and water. Further workup was
performed as described above. According to GLC data,
the transesterification rearrangement and rearrange-
ment-without-transesterification product ratio is
(93 95):(5 6)%. Distillation gave 2.1 g (53%) of
tert-butyl 2-dimethylamino-4-pentenoate (IIh), bp
55 57 C (3 mm Hg), n2D0 1.4332 (Table 2).
rearrangement, aminoester IIa was treated with
sodium methylate under the rearrangement conditions
of salt Ia. The lack of transesterification products (1H
NMR and GLC data) points to the fact rearrangement
is preceded by transesterification. The structure of the
rearrangement products and their purity were proved
1
by H NMR and IR (Table 3) and GLC data.
Thermal isomerization of aminoester IIl. Amin-
oester IIl, 0.015 mol, was heated at 175 180 C for
12 h in an ampule and then treated with diethyl ether.
The solvent was removed to obtain 3.5 g (85%) of tert-
butyl 2-dimethylamino-5-phenyl-4-pentenoate (II l),
bp 120 122 C (1 mm Hg), n2D0 1.5008 (Table 2).
Found, %: C 74.58; H 9.38; N 5.42. C17H25NO2.
Calculated, %: C 74.18; H 9.09; N 5.09.
EXPERIMENTAL
The IR spectra were obtained on UR-20 and
Specord IR-75 spectrophotometers. The 1H NMR
spectra were measured on Perkin Elmer R-12B
(60 MHz) and Varian Mercury-300 (300 MHz) spec-
trometers in CCl4 solutions, internal reference TMS.
Gas chromatography was performed on an LKhM-80
instrument, thermal conductivity detector, column
temperature 100 220 C (16 deg/min), packing 10%
Apiezon L on Inerton AW (0.20 0.25 mm), carrier
gas helium, rate 60 ml/min.
REFERENCES
1. Stevens, T.S., Snedden, W.W., Stiller, E.T., and
Thomson, T., J. Chem. Soc., 1930, no. 2, p. 2119.
Rearrangement of salts Ia Ip. A mixture of
0.01 mol of salt Ia Ip and 0.02 mol of sodium phe-
nolate or methylate in 15 20 ml of absolute benzene
or sodium tert-butylate in 15 ml of absolute tert-
butanol was intermittently stirred and ground. After
heat release had discontinued, the mixture was heated
for 15 20 min at 50 55 C, cooled to room tempera-
ture, and diluted with water and diethyl ether. The
ether layer was separated, and the aqueous layer was
extracted with two portions of ether. The combined
ethereal extracts were dried over magnesium sulfate,
the solvents were removed, and the residue was
distilled in a vacuum (Table 2).
2. Paton, J.M., Pauson, P.L., and Stevens, T.S., J. Chem.
Soc. C, 1969, no. 16, p. 2130.
3. Kocharyan, S.T., Ogandzhanyan, S.M., Razina, T.L.,
and Babayan, A.T., Arm. Khim. Zh., 1977, vol. 3,
no. 12, p. 977.
4. Eryshev, B.Ya., Yatsenko, B.P., Smirnova, T.A., Ku-
tepov, D.F., and Brysin, Yu., Zh. Prikl. Khim., 1978,
vol. 51, no. 14, p. 953.
5. Organic Syntheses, Ann. vols. 20 25, 1940 1945.
Translated under the title Sintezy organicheskih pre-
paratov, Kazanskii, B.A., Ed., Moscow: Inostrannaya
literatura, 1952, vol. 3, p. 124.
6. Bader, A.R., Cummings, L.O., and Vogel, H.A., J. Am.
Chem. Soc., 1951, vol. 73, no. 9, p. 4195.
With salts Ih Im and Io, the residue was subjected
to GLC analysis to measure the contents of transeste-
rification rearrangement and rearrangement-without-
transesterification products. The ratio of these two
products in the mixture is (5.5 7):(93 94.5)%.
7. Kocharyan, S.T., Voskanyan, V.S., Grigoryan, V.V.,
Panosyan, G.A., and Babayan, A.T., Arm. Khim. Zh.,
1985, vol. 38, no. 1, p. 37.
8. Kocharyan, S.T., Ogandzhanyan, S.M., and Ba-
bayan, A.T., Arm. Khim. Zh., 1976, vol. 29, no. 5,
p. 409.
Rearrangement of allyl(methoxycarbonylme-
thyl)dimethylammonium chloride under the action
of sodium tert-butylate. Sodium tert-butylate ob-
tained by heating of 0.04 mol of sodium in 30 ml of
absolute tert-butanol was added to 0.02 mol in 15 ml
of absolute benzene. After heat release had discon-
9. Babayan, A.T., Kocharyan, S.T., and Ogandzha-
nyan, S.M., Arm. Khim. Zh., 1976, vol. 3, no. 12,
p. 401.
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