1,5-Hydride shift in products of Stevens 3,2-rearrangement of methyl(alkyl)(alkoxycarbonylmethyl)-(3-phenyl-2- propynyl)ammonium bromides

Article abstract of DOI:10.1007/s11176-005-0014-7

The products of the Stevens 3,2-rearrangement of ammonium salts containing methyl and other (ethyl, propyl, butyl) alkyl groups along with 3-phenylprop-2-ynyl, under the reaction conditions undergo, roughly by half, intramolecular hydride shift with inter

Full text of DOI:10.1007/s11176-005-0014-7

Russian Journal of General Chemistry, Vol. 74, No. 9, 2004, pp. 1376 1382. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 9, 2004,
pp. 1484 1490.
Original Russian Text Copyright
2004 by Ovsepyan, Babakhanyan, Manukyan, Kocharyan.
1,5-Hydride Shift in Products of Stevens 3,2-Rearrangement
of Methyl(alkyl)(alkoxycarbonylmethyl)-
(3-phenyl-2-propynyl)ammonium Bromides
V. S. Ovsepyan, A. V. Babakhanyan, M. O. Manukyan, and S. T. Kocharyan
Institute of Organic Chemistry, National Academy of Sciences of Armenia, Erevan, Armenia
Abovyan Armenian State Pedagogical University, Erevan, Armenia
Received November 5, 2002
Abstract The products of the Stevens 3,2-rearrangement of ammonium salts containing methyl and other
(ethyl, propyl, butyl) alkyl groups along with 3-phenylprop-2-ynyl, under the reaction conditions undergo,
roughly by half, intramolecular hydride shift with intermediate formation of immonium salts. The latter
convert into enamino esters whose hydrolysis involving alkyl groups at the nitrogen atom gives rise to lower
aliphatic aldehydes and the corresponding amino esters. Treatment with dilute hydrochloric acid of the reac-
tion mixture containing enamino esters results in formation of hydrogenated and nonhydrogenated alkyl esters
of -keto acids. This mixture was reacted with concentrated hydrochloric acid to obtain 3-hydroxy-5-methyl-
4-phenylfuran-2(5H)-one from the nonhydrogenated keto ester and to isolate pure the hydrogenated keto ester.
Earlier we showed that the products of the Stevens
3,2-rearrangement of ammonium salts containing
methoxy(ethoxy)carbonylmethyl, pent-4-en-2-ynyl,
and alkyl (alkyl C2H5) groups undergo 1,5-hydride
shift to form hydrogenated and nonhydrogenated keto
esters [1, 2].
studied ammonium bromides containing, along with
methyl, alkoxycarbonylmethyl, and 3-phenylprop-2-
ynyl groups, ethyl, propyl, or butyl groups.
The synthesis of starting amines IIIa IIIc
(Tables 1 and 2) and target ammonium salts IVa IVf
(Tables 3 and 4) was performed by Scheme 1.
Proceeding with this research we synthesized and
Scheme 1.
CH3
FeCl3
CH3NHCH2CH2CN + CH2O + HC CC6H5
N CH2C CC6H5
dioxane
NCCH2CH2
I
BrCH2COOR CH3
CH2C CC6H5
CH2COOR
CH3
R
RX
R
+
CH3
NaOH
H2O
+
N
N CH2C CC6H5
N
R
CH2C CC6H5
NCCH2CH2
Br
X
IIa IIc
IIIa IIIc
IVa IVc
I IV, R = C2H5 (a), C3H7 (b), C4H9 (c); IV, R = CH3 (a, c, e), C2H5 (b, d, f); II, X = Br (a, b), I (c).
In the synthesis of amines IIIa IIIc we made use
of the fact that ammonium salts exceptionally easily
lose the 2-cyanoethyl group on thermal and alkaline
cleavage. According to published data, the thermal
cleavage of acrylonitrile begins at 75 80 C and vi-
gorously proceeds at 100 110 C [3]. We found that
the retro Michael reaction of (2-cyanoethyl)am-
monium salts IIa IIc occurs already at 45 50 C. It
should be noted that the synthesis of salts IIa IIc in-
volves formation of salts Va Vc with two identical
alkyl groups. The formation of the latter salts can be
explained by the fact that salts IIa IIc readily split off
acrylonitrile to give amines IIIa IIIc which further
react in situ with one more alkyl halide molecule,
yielding ammonium salts Va Vc (Scheme 2).
1070-3632/04/7409-1376 2004 MAIK Nauka/Interperiodica

1,5-HYDRIDE SHIFT IN PRODUCTS OF STEVENS 3,2-REARRANGEMENT
1377
Table 1. Yields, constants, and elemental analyses of amines I and IIIa IIIc
Found, %
H
Calculated, %
Starting
salt
Yield,
%
bp,
(1 mm Hg)
C
Amine
n2D0
Formula
M
C
N
C
H
N
I
58
52.6
72
153 156
96 99
97 100
102 105
1.5375 78.39 7.10 13.72
1.4971 82.67 8.19 7.71
1.5292 82.93 9.53 7.02
1.5302 84.07 9.04 6.54
C13H14N2
C12H15N
C13H17N
C14H19N
78.79 7.07 14.14 198
83.24 8.67 8.09 173
83.42 9.09 7.49 187
83.58 9.45 6.97 201
IIa
IIb
IIc
IIIa
IIIb
IIIc
52.7
Scheme 2.
Table 2. Yields, constants, and elemental analyses of salts
Va Vc
R
+
RX
IIIa IIIc
CH3 N CH2C CC6H5
Found, %
Br (I)
Calculated, %
Br (I)
Yield,
%
R
Salta
Formula
X
Va Vc
N
N
V, R = C2H5 (a), C3H7 (b), C4H9 (c); X = Br (a, b), I (c).
Va 23
Vb 26
28.97 5.41 C14H20BrN
26.52 4.32 C16H24BrN
28.37 4.96
27.03 4.73
(26.62) 2.94
To bring ammonium salts IVa IVf into Stevens
rearrangement, a suspension of sodium alcoholate in
ether or benzene was used. The rearrangement results
are shown in Table 4 and its proposed directions,
in Scheme 3.
Vc 21.5 (26.03) 3.57 C18H28IN
a
The salts are hygroscopic.
specifically, by the Stevens rearrangement of dimethyl-
alkoxycarbonylmethyl(3-phenyl-2-propynyl)ammo-
nium bromides followed by hydrolysis of the rear-
rangement products, dienic amino esters (Scheme 4).
Route A involves hydride shift in the 3,2-rearran-
gement products, resulting in formation of immonium
salts VIIa VIIf. The latter react with base for a mix-
ture of amino esters VIIIa VIIIf and their prototropic
rearrangement products IXa IXf (route b) [2]. Route
B involves exclusively the prototropic rearrangement
of the rest part of 3,2-rearrangement products VIa
VIf, affording amino esters XIIIa XIIIf. In both
cases, acid treatment of the reaction mixtures gave
hydrogenated amino esters Xa, Xb and keto esters
XIIa, XIIb, as well as nonhydrogented keto esters
XIVa, XIVb, lower aliphatic aldehydes, and primary
and secondary amines (Table 4). Keto esters XIVa,
XIVb were also obtained by independent synthesis,
Keto ester XIVa we prepared earlier [4].
1
As seen from the H NMR spectrum of the Stevens
rearrangement products of salt IVa, the integral in-
tensity of vinyl proton signals is larger that expected.
Furthermore, on the assumption that the hydride shift
involves no other intermediates than VIIa, the per-
centage of amine reaction products (83%) should be
much lower than is actually observed.
Thus, the obtained evidence suggests that under
the action of the basic agent immonium salt VIIa
Table 3. Yields, constants, and elemental analyses of salts IVa IVf
Found, %
Calculated, %
1
Salt
mp, C Yield, % IR spectrum, , cm
Formula
Br
N
Br
N
IVaa
76
72
75
60
85
93
1745 (COO), 2230 (C C)
1740 (COO), 2235 (C C)
1750 (COO), 2240 (C C)
1745 (COO), 2230 (C C)
1750 (COO), 2230 (C C)
1750 (COO), 2235 (C C)
24.93
23.90
23.13
22.12
22.20
22.29
4.90
3.75
4.52
4.43
4.35
3.25
C15H20BrNO2
C16H22BrNO2
C16H22BrNO2
C17H24BrNO2
C17H24BrNO2
C18H26BrNO2
25.54
23.53
23.53
22.60
22.60
21.74
4.29
4.12
4.12
3.95
3.95
3.80
IVba
IVc 112 114
IVd 107 109
IVe 110 111
IVf
115 116
a
The salts are hygroscopic.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 9 2004

1378
OVSEPYAN et al.
Scheme 3.
IVa IVf
RCH2ONa
A
ether (benzene)
B
VIa VIf
CHCH2R
H
CH3
N
CHC(C6H5)=C=CH2
H
O
C6H5
RCH2CH2
CH3
COOCH2R
VIa VIf
NC=C CH=CH2
COOCH2R
CH2R
XIIIa XIIIf
RCH2CH2
CH CH2R
H+,
+
N
NH
CH3
H2O
CH3
CHC(C6H5)=CHCH3
COOCH2R
VIIa VIIf
C6H5
CH3CH=C CCOOCH2R
a
b
O
OCH2R
CH3NCH=CHR
CH3NCH=CHR
XIVa, XIVb
R CH2COOCCHC=CHCH3
+ R CH2COOCC=CCH2CH3
36% HCl
C6H5
VIIIa VIIIf
C6H5
IXa IXf
OH
O
C6H5
CH3
H+,
H2O
H+,
H+,
H2O
RCH2CHO
RCH2CHO
O
XV
RCH2CHO
H2O
CH3NHC=C(C6H5)CH2CH3
CH3NHCHC(C6H5)=CHCH3
COOCH2R
XIa, XIb
COOCH2R
Xa, Xb
H+,
CH3NH2
H2O
CH3CH2CH(C6H5)CCOOCH2R
O
XIIa, XIIb
IV, VI IX, XIII, R = R = H (a), R = H, R = CH3 (b), R = CH3, R = H (c), R = R = CH3 (d), R = C2H5, R = H (e), R =
C2H5, R = CH3 (f); X XII, XIV, R = H (a), CH3 (b).
Scheme 4.
C6H5
(CH3)2NC=CCH=CH2
COOR
C6H5
CH2C CC6H5
CH2COOR
+
H+, H2O
36% HCl
RONa
ether
XV
(CH3)2N
CH3CH=C CCOOR
Br
O
XIVa, XIVb
XIV, R = CH3 (a), C2H5 (b).
mostly converts into amino esters VIIIa, IXa by
route b.
tion residue of salt IVa with dilute hydrochloric acid
we obtained trace amounts of compounds Xa, XIIa,
as well as acetaldehyde as 2,4-dinitrophenylhydrazone.
Hydrogenated reaction products are partially
formed by route a. Thus by treatment of the dry reac-
The structure of the synthesized compounds was
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 9 2004

1,5-HYDRIDE SHIFT IN PRODUCTS OF STEVENS 3,2-REARRANGEMENT
1379
Table 4. Hydrogenated and nonhydrogenated Stevens rearrangement products of salts IVa IVf
Found, %
Ratio of
Calculated, %
Amino Yield, hydrogenated
bp,
C
Salt
Formula
ester
%
and starting (p, mm Hg)
amines in the
C
H
N
C
H
N
mixture
IVa
IVb
IVc
IVd
IVe
IVf
IXa
IXb
IXc
IXd
IXe
IXf
15.5
14.4
12.7
13
15
14.8
93: 7
95: 5
93: 7
94: 6
96: 4
93: 7
97 105 (2) 71.37 7.31 6.13 C13H17NO2 + C12H15N 71.91 7.81 6.49
100 108 (1) 73.07 7.71 5.59 C14H19NO2 + C12H15N 72.52 8.17 6.09
98 106 (1) 71.31 7.49 6.04 C13H17NO2 + C13H17N 71.97 7.84 6.46
103 109 (1.5) 73.05 7.68 5.74 C14H19NO2 + C13H17N 72.65 8.20 6.08
99 105 (1) 71.06 7.33 7.02 C13H17NO2 + C14H19N 71.69 7.82 6.41
102 108 (1) 72.27 7.79 5.68 C14H19NO2 + C14H19N 72.80 8.23 6.07
Table 4. (Contd.)
Salt
Keto esters
XI: XII ratio, %
Total yield, %
bp, C (p, mm Hg)
IVa
IVb
IVc
IVd
IVe
IVf
XIa XIIIa
XIb XIIIb
XIa XIIIa
XIb XIIIb
XIa XIIIa
XIb XIIIb
45: 55
42: 58
26: 74
21: 79
39: 61
43: 57
33.5
36.2
40.4
41.8
43.4
50.3
112 118 (3)
119 125 (2)
106 112 (1)
112 116 (1)
110 116 (2)
112 117 (1)
Found, %
Calculated, %
Amines
Salt
Formula
Aldehyde, % mp, Ca
CH3NHR
CH3NH2,
C
H
C
H
%
%
R
IVa 58.31
IVb 60.71
IVc 58.02
IVd 60.55
IVe 57.97
IVf 61.38
7.43
8.09
7.92
8.44
7.52
7.91
C7H10O3 +C7H12O3
C8H12O3 +C8H14O3
C7H10O3 +C7H12O3
C8H12O3 +C8H14O3
C7H10O3 +C7H12O3
C8H12O3 +C8H14O3
58.76
61.07
58.47
60.84
58.60
61.13
7.66
8.40
8.11
8.74
7.92
8.31
CH3CHO
CH3CHO
C2H5CHO
C2H5CHO
C3H7CHO
C3H7CHO
163 164
163
19
18
17
19.5
22
21
23 C2H5
21 C2H5
20 C3H7
22 C3H7
25 C4H9
24.5 C4H9
154
154 155
121 122
121 122
a
Melting point of 2,4-dinitrophenylhydrazone.
1
established by H and IR spectroscopy (Table 5), and
their purity was controlled by GLC.
80 chromatograph, thermal conductivity detector,
1
oven temperature 30 220 C (16 deg min ), 2000
3 mm, 10% of Apieson L on Inerton-AW (0.20
0.25 mm), carrier gas (helium) 60 ml min .
1
EXPERIMENTAL
The IR spectra were recorded on UR-20 and
Specord IR-75 instruments. The 1H NMR spectra were
obtained Perkin Elmer R-12B and Varian Mercury-
300 spectrometers at 60 and 300 MHz, internal
reference TMS in CCl4 and D3CSOCD3.
N-(2-Cyanoethyl)-N-methyl-N-(3-phenylprop-2-
ynyl)amine (I) was prepared by the Mannich reaction
[5] from 54.3 g of N-(2-cyanoethyl)-N-methylamine,
65.9 g of phenylacetylene, 29.1 g of Paraform, 2 g of
FeCl3 7H2O, and 180 ml of dioxane. Yield 31.7 g
(58%), bp 154 157 C (1 mm Hg), n2D0 1.5395. Found,
%: C 78.36; H 6.68; N 13.69. C13H14N2. Calculated,
Gas chromatography was performed on an LKhM-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 9 2004

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OVSEPYAN et al.
1
Table 5. IR and H NMR spectra of compounds I, IIIa IIIc, Va Vc, Xa, Xb, XIIa, XIIb, XIVa, and XIV, XIVb
Comp.
no.
1
IR spectrum, , cm
1H NMR spectrum, , ppm (J, Hz)
I
690, 730, 770, 1610, 3030, 3065, 3085 2.11 s (3H, NCH3), 1.9 3.0 m (4H, NCH2CH2), 3.51 s (2H,
(C6H5), 2240 (C C), 2230 (C N) NCH2C C), 7.18 m (5H, C6H5)
695, 730, 770, 1605, 3035, 3070, 3085 1.00 t (3H, CH3CH2, J 7.1), 2.30 s (3H, NCH3), 2.50 q (2H,
(C6H5), 2240 (C C) CH3CH2), 3.50 s (2H, NCH2), 7.25 7.41 m (5H, C6H5)
690, 725, 770, 1610, 3035, 3075, 3080 0.81 t (3H, CH3CH2CH2, J 7.0), 1.25 m (2H, CH2CH2CH3), 2.30 t
IIIa
IIIb
(C6H5), 2240 (C C)
(2H, CH2CH2CH3, J 7.3), 2.33 s (3H, NCH3), 3.50 s (2H,
CH2C C), 7.24 7.40 m (5H, C6H5)
IIIc
700, 730, 770, 1610, 3030,3070, 3085 (C6H5), 0.71 t (3H, CH3CH2CH2CH2, J 7.1), 1.21 m (4H, CH2CH2CH2
2240 (C C)
H3), 2.28 t (3H, NCH2, J 7.3), 2.31 s (3H, NCH3), 3.51 s (2H,
NCH2C C), 7.23 7.40 m (5H, C6H5)
Va
Vb
690, 760,1595, 3030, 3075 (C6H5), 2220 1.24 t (6H, NCH2CH3, J 7.0), 3.0 s (3H, NCH3), 3.42 q (4H,
(C C) NCH2CH3), 4.20 s (2H, NCH2C C), 7.35 m (5H, C6H5)
695, 760, 1598, 3030, 3075 (C6H5), 2225 0.95 t (6H, NCH2CH2CH3, J 7.1), 1.20 m (4H, NCH2CH2CH3),
(C C)
2.8 3.4 m (7H, NCH2CH2CH3, NCH3), 4.20 s (2H, NCH2C C),
7.37 m (5H, C6H5)
Vc
Xa
Xb
695, 760, 1598, 3030, 3075 (C6H5), 2225 0.93 t (6H, NCH2CH2CH2CH3, J 7.1), 1.22 m (8H, NCH2CH2
(C C)
CH2CH3), 2.8 3.5 m (7H, NCH2CH2CH2CH3, NCH3), 4.17 s (2H,
NCH2C C), 7.34 m (5H, C6H5)
690, 730, 770, 1610, 3030, 3065, 3085 2.36 s (3H, NCH3), 1.54 br.s (1H, NH), 1.73 d (3H, CH3CH=, J 8),
(C6H5), 790, 830, 1640 (CH=C), 1070, 1145, 3.53 s (3H, OCH3), 4.17 s (1H, NCH), 5.68 q (1H, CH=), 7.16 m
1240, 1735 (COO), 3330 (NH)
(5H, C6H5)
695, 730, 1610, 3035, 3065, 3080 (C6H5), 1.22 t (3H, CH3CH2O, J 7), 2.31 s (3H, NCH3), 1.54 br.s (1H, NH),
790, 835, 1640, (CH=C), 1070, 1140, 1245, 1.73 d (3H, CH3CH=, J 8), 3.53 q (2H, CH3CH2O), 4.17 s (1H,
1735 (COO), 3330 (NH)
NCH), 5.68 q (1H, CH3CH=), 7.15 m (5H, C6H5)
XIIa
XIIb
695, 730, 1610, 3030, 3065, 3085 (C6H5), 0.85 t (3H, CH3CH2, J 7), 1.77 and 2.07 m (2H, CH3CH2), 3.75 s
1675, (C=O), 1075, 1140, 1245, 1735 (COO) (3H, OCH3), 4.29 m (1H, CH), 7.10 7.45 m (5H, C6H5)
690, 730, 770, 1605, 3035, 3070, 3080 (C6H5), 0.90 t (3H, CH3CH2, J 7), 1.23 t (3H, CH3CH2O, J 7), 1.75 and
1675 (C=O), 1070, 1140, 1240, 1735 (COO) 2.06 (2H, CH3CH2), 4.16 q (2H, CH3CH2O), 4.25 m (1H, CH),
7.09 7.44 m (5H, C6H5)
XIVa 700, 730, 770, 1610, 3035, 3065, 3080 (C6H5) 1.93 d (3H, CH3CH=, J 8), 3.85 s (3H, OCH3), 7.0 q (1H, CH=),
790, 835, 1640 (CH=C), 1675 (C=O), 1070, 7.10 7.45 m (5H, C6H5)
1140, 1240, 1735 (COO)
XIVb 700, 720, 770, 1605, 3035, 3070, 3080 (C6H5), 1.32 t (3H, CH3CH2O, J 7), 1.92 d (3H, CH3CH=, J 8), 4.32 q (2H,
790, 835, 1640 (CH=C), 1675 (C=O), 1070, CH3CH2O), 7.04 q (1H, CH3CH=), 7.09 7.44 m (5H, C6H5)
1145, 1240, 1735 (COO)
1
%: C 78.78; H 7.07; N 14.14. The H NMR and IR
spectral data are given in Table 5.
and then cooled to room temperature and treated with
ether (3 15 ml). The combined extracts were dried
with magnesium sulfate, and amines IIIa IIIc were
distilled. The resulting data are given in Table 1. The
N-Alkyl-N-methyl-N-(3-phenylprop-2-ynyl)-
amines IIIa IIIc (general procedure). Alkyl bromide, aqueous layer was acidified with HBr or HI, and the
0.17 mol, was added to 0.15 mol of amine I, and the
mixture was heated at 45 50 C for 15 16 h to obtain
a mixture of N-alkyl-N-(2-cyanoethyl)-N-methyl-N-
(3-phenylprop-2-ynyl)- and N,N-dialkyl-N-methyl-N-
(3-phenylprop-2-ynyl)ammonium halides, that were
thoroughly washed with absolute ether, dried, and
treated with 0.3 mol of 20% sodium hydroxide. The
reaction mixture was heated at 60 65 C for 30 min
water was removed in a water-jet-pump vacuum. The
residue was diluted with absolute alcohol, and the
inorganic salt was filtered off. The alcohol was re-
moved by distillation to obtain compounds Va Vc
(Table 2).
N-Alkyl-N-(alkoxycarbonyl)-N-methyl-N-(3-
phenylprop-2-ynyl)ammonium bromides IVa IVf.
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1,5-HYDRIDE SHIFT IN PRODUCTS OF STEVENS 3,2-REARRANGEMENT
1381
1
Alkyl bromoacetate, 0.025 mol, was added dropwise
to 0.025 mol of amine IIIa IIIc in 5 ml of absolute
ether. The mixture was left to stand for 48 h at room
temperature. The salt that formed was washed with
several portions of absolute ether, filtered, and dried
(Table 3).
and H NMR to identify keto ester XIIa using as
reference the sample prepared by procedure a. The
aqueous layer was treated with potash (0 5 C) and
ether. The ether extract was dried with magnesium
sulfate, and the solvent was distilled off. The residue
contained amino ester Xa (GLC data).
Rearrangement of salts IVa IVf. a. Sodium
alkoxide obtained from 0.06 mol of sodium was
added to a suspension of 0.03 mol of salt IVa IVf in
20 ml of absolute ether (benzene). The reaction mix-
ture was shaken and ground. When heat release was
no longer observed, the mixture was refluxed for
20 min, after which ether and water were added. The
combined ether extracts were acidified with 1.5 N
HCl. Nonamine reaction products were extracted with
ether (3 10 ml), the extracts were dried with magne-
sium sulfate, and the solvent and low-boiling products
were distilled off. In the distillate, aldehydes were
determined as 2,4-dinitrophenylhydrazones. The re-
sidue was distilled in a vacuum to isolate keto esters
XIIa, XIIb, XIVa, and XIVb (Tables 2 and 4). The
aqueous layer was treated with potash (0 5 C), and
amine products were extracted with ether (3 10 ml),
the extracts were dried with magnesium sulfate, and
the solvent was removed. Vacuum distillation gave
aminoesters Xa, Xb and the starting amines. The
latter were identified and quantified (7 12% in the
mixture) by GLC (Table 4). Alkyl- and dialkylamines
were salted out (if required) from the reaction residue
and extracted with ether, after which they were iden-
tified and quantified by GLC (Table 4).
3-Hydroxy-5-methyl-4-phenyl-furan-2(5H)-one
(XV) was prepared from 5.1 g of methyl 2-oxo-3-
phenylpent-3-enoate (XIVa) and conc. HCl by the
procedure in [2]. Yield 4 g (84%), mp 140 141 C
1
(from alcohol). IR spectrum, , cm : 710, 775, 1590,
1705, 1960, 3035, 3085 (C6H5), 1130, 1080, 1250,
1
1745, (COO), 3100 3500 (OH). H NMR spectrum,
, ppm: 1.43 d (3H, CH3CH, J 6.6 Hz), 5.10 q (1H,
CH3CH), 7.52 br.s (1H, OH), 7.4 m (5H, C6H5).
Found, %: C 69.02; H 5.53. C11H10O3. Calculated %:
C 69.47; H 5.26.
Lactone XV was also prepared from 4.47 g of ethyl
2-oxo-3-phenylpent-3-enoate (XIVb). Yield 3.9 g
(82%), mp 140 141 C (from alcohol). The sample
gave no melting point depression in mixture with that
prepared from keto ester XIVa.
Reaction of mixture of keto esters XIIa and
XIVa with concentrated hydrochloric acid. Concen-
trated HCl, 3 ml, was added dropwise with stirring to
a 45:55 mixture of keto esters XIIa and XIVa. The
resulting mixture was stirred at 55 60 C for 10 h and
cooled. The precipitate that formed was filtered off
and washed with hexane to obtain 1.1 g (70%) of
lactone XV (per keto ester XIVa), mp 140 141 C
(from alcohol). The sample gave no melting point
depression in mixture with that prepared from keto
b. Sodium alkoxide obtained from 0.06 mol of
sodium was added to a suspension of 0.03 mol of salt
IVa in 20 ml of absolute ether (benzene). When heat
release was no longer observed, the mixture was re-
fluxed for 20 30 min in ether or 10 15 min in ben-
zene. The organic layer was separated, and the solid
material was washed with absolute ether (3 10 ml).
Amine products were determined by titration in the
organic layer (83%), and evaporated in a vacuum. The
1
ester XIVb. The H and IR spectral data are given
above.
The solvent was removed from the filtrate, and the
residue was distilled in a vacuum to obtain 0.64 g
(46%) of hydrogenated keto ester XIIa (per keto ester
1
residue was analyzed by GLC, H NMR, and IR spec-
troscopy, after which it was acidified with 1.5 N HCl.
Further workup was performed as described in proce-
dure a.
1
XIIa), bp 96 98 C (1 mm Hg), n2D0 1.5075. The H
and IR spectral data are given in Table 5.
Dilute HCl was added to the solid reaction residue,
and the resulting mixture was treated with ether (3
5 ml), the extract was dried with magnesium sulfate,
and the solvent was distilled off. Acetaldehyde was
determined in the distillate as 2,4-dinitrophenylhydra-
zone (yield 3.6%, mp 163 164 C). The sample gives
no melting point depression in mixture with an
authentic sample. The residue was analyzed by GLC
In a similar way, by the reaction of a 42:58 mix-
ture of keto esters XIIb and 3 ml of conc. HCl we ob-
tained 1.16 g (70%) of lactone XV (per keto ester
XIVb), mp 140 141 C (from alcohol) and 0.58 g
(41%) of hydrogenated keto ester XIIb (per keto ester
XIIb), bp 107 108 C (1 mm Hg), n2D0 1.5173. The 1H
and IR spectral data are given in Table 5.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 9 2004

1382
OVSEPYAN et al.
3. Babayan, A.T., Martirosyan, G.T., Grigoryan, D.V.,
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