Intramolecular 1,5-hydride shift in products of stevens 3,2-rearrangement of ammonium salts containing 3-phenyl-2-propynyl group

Article abstract of DOI:10.1023/B:RUJO.0000003157.80528.0a

In products of Stevens 3,2-rearrangement of ammonium salts containing alongside alkoxycarbonylmethyl also 3-phenyl-2-propynyl group an intramolecular 1,5-hydride shift is observed resulting in immonium salts which transform into aminoesters of enamine str

Full text of DOI:10.1023/B:RUJO.0000003157.80528.0a

Russian Journal of Organic Chemistry, Vol. 39, No. 6, 2003, pp. 814 819. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 6, 2003,
pp. 864 868.
Original Russian Text Copyright
2003 by Babakhanyan, Ovsepyan, Kocharyan, Panosyan.
Intramolecular 1,5-Hydride Shift in Products of Stevens
3,2-Rearrangement of Ammonium Salts Containing
3-Phenyl-2-propynyl Group
A. V. Babakhanyan1, V. S. Ovsepyan2, S. T. Kocharyan2, and G. A. Panosyan3
1Abovyan Armenien State Pedagogical University
2Institute of Organic Chemistry, National Academy of Sciences of Armenia, Yerevan, 375091 Armenia
3Center for Investigation of Molecular Structure, Yerevan, Armenia
Received January 18, 2002
Abstract In products of Stevens 3,2-rearrangement of ammonium salts containing alongside alkoxycarbon-
ylmethyl also 3-phenyl-2-propynyl group an intramolecular 1,5-hydride shift is observed resulting in
immonium salts which transform into aminoesters of enamine structure. The hydrolysis of the latter provides
the lower aliphatic aldehydes and the corresponding aminoesters. An acid treatment of the reaction mixture
affords a mixture of hydrogenated and nonhydrogenated esters of -ketoacids originating from the mixture of
1,3-diene aminoesters. At treating with concn. HCl of the obtained mixture the nonhydrogeneted ketoester
undergoes cyclization into 4-methyl-3-phenyl-2-buten-1,4-olide.
We showed formerly that ammonium salts contain-
ing both alkoxycarbonylmethyl and 4-penten-2-yl
groups treated with sodium alkoholate underwent
Sievens 3,2-rearrangement providing products that
suffered an intramolecular 1,5-hydride shift [1, 2].
Further treatment of the products with hydrochloric
acid resulted in formation of hydrogenated and non-
hydrogenated products.
migrations the most interesting are transannular
1,3- and 1,5-hydride shifts [5, 6].
This report concerns the study of hydride shift in
the products of Stevens 3,2-rearrangement of
ammonium salts containing both alkoxycarbonyl-
methyl and 4-penten-2-yl. To this end ammonium
salts Ia f were synthesized and subjected to treat-
ment with sodium alcoholates in ether (benzene)
(Table 1).
It is known from published sources that tertiary
amines containing -hydrogen atoms are potential
donors of hydride ions [3, 4] that are used for inter-
molecular hydrogenation of multiple bonds, also
nitrogen-containing. Among intramolecular hydride
The formation of compounds obtained may be
rationalized by the following scheme including A and
B pathways. According to path A in the products of
Stevens 3,2-rearrangement occurs a hydride shift
Table 1. Hydrogenated and nonhydrogenated products of Stevens rearrangement of salts Ia f
Initial Amino- Yield, bp,
C
Ratio of
hydrogenated
and initial
amines in
Found,%
H
Calculated,
%
salt, ester
compd.
%
(mmHg)
Formula
C
N
C
H
N
no.
the mixture
Ia
Ib
Ic
Id
Ie
If
VIa
VIb
18 116 119 (3)
16 161 164 (3)
95: 5
94: 6
96: 4
93: 7
94: 6
92: 8
71.54 5.73
73.74 8.27
72.89 8.21
74.48 8.37
73.74 8.57
74.39 8.88
5.77 C14H19NO2 + 13H17N 72.56 8.20
5.48 C15H21NO2 + 13H17N 73.37 8.53
5.36 C15H21NO2 + 15H21N 73.25 8.55
5.85 C16H23NO2 + 15H21N 74.16 8.87
5.01 C16H23NO2 + 17H25N 74.15 8.90
4.78 C17H25NO2 + 17H25N 74.88 9.18
6.07
5.75
5.70
5.43
5.39
5.14
VIc 14.5 148 152 (1)
VId 11.3 155 160 (1)
VIe 13.2 173 180 (1)
VIf 18.7 200 206 (3)
1070-4280/03/3906-0814$25.00 2003 MAIK Nauka/Interperiodica

816
BABAKHANYAN et al.
followed by prototropic isomerization leading to
hydrogenated aminoesters VIa f, VIIa f and keto-
esters VIIIa, b, and along path B only prototropic
isomerization takes place affording aminoesters
IIa f, IXa f and ketoesters Xa, b (Table 1).
In both cases arise the corresponding aminoesters of
enamine structure IVa f, Va f, VIIa f, IXa f
which on hydrolysis with diluted hydrochloric acid
furnish esters of hydrogenated and nonhydrogenated
ketoacids VIIIa, b, Xa, b (Table 1).
I, II, VI, VII, IX, R = R = H (a, R = H, R = Me (b), R = Me, R = H (c), R = R = Me (d),
R = Et, R = H (e), Me (f), (VIII, X, R = H (a), Me (b).
1
In the H NMR spectrum of the primary product
of Stevens 3,2-rearrangement obtained from salt Ia
before the acid treatment the integral intensity of
protons attached to multiple bonds is significantly
higher than expected. Besides in case of formation of
immonium salt IIIa as a single intermediate pro-
duct the amount of amine compounds in the ether
solution should be a lot smaller than that actually
observed. This data show that immonium salt IIIa if
not completely, at least mainly transforms into
compounds IVa, Va under the action of methyl-
ate anion [2].
saturated ketoesters would be converted into lactone
XI, and the hydrogenated ketoesters VIIIa, b
would remain intact. We really obtained by this
procedure ketoesters VIIIa, b and lactone XI
in pure state. The lactone was also prepared by an
independent synthesis through hydrolysis of Stevens
rearrangement product obtained from dimethylmeth-
oxy(ethoxy)carbonylmethyl(3-phenyl-2-propynyl)am-
monium bromides.
Ketoester Xa we synthesized earlier [7].
Thus the spectral and experimental data permit a
statement that at 1,5-hydride shift in the products of
3,2-rearrangement of the salts under study the inter-
mediately forming immonium salts IIIa f under
the reaction conditions mainly transform into amino-
In order to isolate individual products VIIIa, b
the mixture of ketoesters VIIIa, b, Xa, b was
treated with concn. HCl. We presumed that the un-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 6 2003

INTRAMOLECULAR 1,5-HYDRIDE SHIFT
817
esters IVa f, Va f which in their turn are
converted into the final products. Formation of
reaction products along path a is also probable. For
instance, the treatment with water of the dry residue
of salt Ia after reaction revealed the presence of
compounds VIa, VIIIa and of acetaldehyde; the
latter was identified as 2,4-dinitrophenylhydrazone
(4%).
by means of GLC were identified and quantitatively
determined the initial dialkyl(3-phenyl-2-propynyl)-
amines (8 14%). When needed after adding NaOH to
the reaction residue and extraction with ether of alkyl-
and dialkylamines their amounts and nature were
determined by GLC (Table 1).
(b) To a dispersion of 0.03 mol of salts Ia f in
20 ml of anhydrous ether (benzene) was added
sodium alcoholate prepared from 0.06 mol of sodium.
On completion of heat evolution the mixture was kept
for 20 30 min at 30 33 C in ether of for 10 15 min
at 75 78 C in benzene. In the organic layer the
content of amine products was determined by titration
(81 89%).
The structure of compounds obtained was
1
established with the use of IR and H NMR spectro-
scopy (Table 2), and their purity was checked by
GLC.
EXPERIMENTAL
IR spectra were recorded on spectrophotometers
UR-20 and Specord 75IR, 1H NMR spectra were
registered on spectrometers Perkin-Elmer R-12B and
Varian Mercury-300 at operating frequencies 60 and
300 MHz from solutions in CCl4 and DMSO-d6 with
TMS as internal reference. GLC analysis was carried
out on chromatograph LKhM-8MD equipped with
catharometer, a column 2000 3mm, stationary phase
5% OV-17 on Chromaton N-Super, oven temperature
The solid precipitate was washed with anhydrous
ether (3 10 ml). The solvent was removed in a
vacuum. The residue was investigated with the use of
1
GLC, H NMR, and IR spectroscopy, then it was
acidified with 1.5 N HCl. Further workup was as
described under procedure a. To the solid reaction
residue was added water, extracted with ether (3
10 ml), the extract was dried with magnesium sulfate,
the solvent was distilled off, and in this distillate
acetaldehyde was determined as dinitrophenylhydr-
azone. The composition of the residue was identified
by GLC by comparison with the known samples
obtained by procedure (a).
1
175 200 C, gas carrier helium, flow rate 60 ml min .
General procedure of rearrangement. (a) To a
dispersion of 0.03 mol of salts Ia f in 20 ml of
anhydrous ether (benzene) was added sodium
alcoholate prepared from 0.06 mol of sodium. The
reaction mixture was thoroughly stirred. On comple-
tion of heat evolution the mixture was boiled for
20 min more, and then ether and water were added.
The organic layer was separated, the water layer was
twice extracted with ether. The combined extracts
were treated with 1.5 N HCl till acid pH. The
products other than amines were extracted into ether
(3 10 ml), dried with magnesium sulfate, and
evaporated. In the ether extract an aldehyde was
determined as 2,4-diphenylhydrazone. Ketoesters
VIIIa, b; Xa, b were isolated by distillation
(Tables 1, 2). From the water layer after treating with
potassium carbonate (0 5 C) the amine derivatives
were extracted into ether (3 10 ml), dried with
magnesium sulfate, and the solvent was removed.
Aminoethers VIa f were isolated by distillation. The
results are compiled in tABLE 1. In the ether extracts
Reaction of methyl 3-phenyl-2-oxopenten-3-ate
with concn. HCl. To 3.06 g (0.015 mol) of ketoester
VIIIa at stirring was added dropwise 2 ml of
concn. HCl. The mixture was stirred for 2.5 h at
55 56 C. The separated precipitate was filtered off
and washed with hexane. We obtained 2.5 g (87%)
3-hydroxy-5-methyl-4-phenyltetrahydrofuran-2-one
(XI), mp 140 141 C (from alcohol). Found, %:
C 69.02; H 5.53. C11H10O3. Calculated, %: C 69.47;
H 5.26.
Similarly from ethyl 3-phenyl-2-oxopenten-3-ate
was obtained lactone XI in 81% yield.
Reaction of ketoesters VIIIa, Xa mixture with
concn. HCl. To 3 g (0.015 mol) of ketoesters VIIIa,
Xa mixture (52: 48) was added at stirring dropwise
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 6 2003

818
BABAKHANYAN et al.
Table 2. IR and 1H NMR spectra of compounds VIa f, VIIIa b, Xa b, XI
1
Compd.
IR spectrum, cm
1H NMR spectrum, (DMSO-d6), , ppm (J, Hz)
VIa
690, 725, 770, 1485, 1530, 1610, 1830, 1890, 0.90 t (3H, CH2CH3, J 7), 1.55 br.s (1H, NH), 1.72 d
3035, 3065, 3085 (C6H5), 790, 830, 1640, (CH=C), (3H, CH3CH=, J 8), 2.32 q (2H, CH2 CH3), 3.52 s
1070, 1145, 1240, 1735 (COO), 3375 (NH) (3H, OCH3), 4.18 s (1H, NCH), 5.69 q(1H, CH3CH=),
7.15 s (5H, C6H5)
VIb
VIb
VId
VIe
VIf
700, 730, 775, 1480, 1590, 1610, 1810, 1890, 1065, 1150, 1240, 1735 (COO), 3400 (NH)
3030, 3065, 3080 (C6H5), 790, 835, 1640 (CH=C), 0.91 t (3H, CH2CH3, J 7.1), 1.23 t (3H, OCH2CH3, J ),
7
1065, 1150, 1240, 1735 (COO), 3400 (NH)
1.57 br.s (1H, NH), 1.72 d (3H, CH3 CH=, J 8), VIc
2.18 q (2H, CH2 CH3), 3.53 q (2H, OCH2), 4.17 s
(1H, NCH), 5.68 q (1H, CH=), 7.15 m (5H, C6H5)
710, 725, 770, 1485, 1590, 1610, 1810, 1830, 0.80 t (3H, CH3(CH2)2, J 7.1), 1.25 m (2H,
1890, 3035, 3070, 3085(C6H5), 790, 830, 1640 CH2CH2CH3), 1.49 br.s (1H, NH), 1.73 d(3H,
(CH=C), 1070, 1145, 1235, 1735(COO), 3380(NH) CH3CH=), 2.30 t (2H, CH2CH2CH3, J 7.3), 3.47 s
(3H, OCH3), 4.17 s (1H, NCH), 5.67 q (1H, CH=,
J 8), 7.16 m (5H, C6H5)
700, 725, 765, 1485, 1590, 1610, 1810, 1890, 0.81 t [3H, CH3(CH2)2, J 7.1], 1.22 t (3H, OCH2CH3,
3035, 3070, 3085 (C6H5), 790, 835, 1640 (CH=C), J 7), 1.24 m (2H, CH2 CH2CH3), 1.51 br.s (1H, NH),
1070, 1145, 1240, 1740 (COO), 3390 (NH) 1.73 d(3H, CH3CH=), 2.29 t (2H, CH2CH2CH3, J 7.3),
3.48 q (2H, OCH2), 4.16 s (1H, NCH), 5.67 q (1H,
CH=, J 8), 7.16 m (5H, C6H5)
700, 730, 770, 1485, 1590, 1605, 1830, 1890, 0.70 t [3H, CH3(CH2)3, J 7.1], 1.22 m (4H,
3035, 3070, 3085 (C6H5), 790, 825, 1695 (CH=C), CH2CH2CH2CH3), 1.52 br.s (1H, NH), 1.73 d (3H,
1065, 1140, 1240, 1735 (COO), 3090 (NH)
CH3CH=), 2.28 t (2H, CH2CH2CH2CH3, J 7.3), 3.47 s
(3H, OCH3), 4.14 s (1H, NCH), 5.65 q (1H, CH=,
J 7.3), 7.15 m (5H, C6H5)
710, 725, 765, 1485, 1590, 1610, 1810, 1830, 0.76 t [3H, CH3(CH2)3, J 7.1], 1.21 m (4H,
1890, 3035, 3070, 3085 (C6H5), 790, 825, 1640 CH2CH2CH2CH3), 1.23 t (3H, CH3CH2O), 1.51 m (1H,
(CH=C), 1070, 1145, 1240, 1735(COO), 3380(NH) NH), 1.72 d (3H, CH3CH=), 2.28 t (2H,
CH2CH2CH2CH3, J 7.3), 3.51 q (2H, OCH2), 4.14 s
(1H, NCH), 5.65 q(1H, CH=, J 7.3), 7.13 m (5H, C6H5)
VIIIa
Xa
700, 725, 770, 1480, 1590, 1610, 1810, 1830, 1890, 0.85 t (3H, CH3CH2, J 7), 1.77 and 2.07 m (2H,
3030, 3065, 3080 (C6H5), 1675 (C=O), 1070, 1080, CH3CH2), 3.75 s (3H, OCH3), 4.29 m (1H, CH),
1140, 1240, 1735 (COO)
7.10 7.45 m (5H, C6H5)
705, 730, 770, 1485, 1585, 1610, 1830, 1890, 3035, 1.94 d (3H, CH3CH=, J 8), 3.87 s (3H, OCH3), 7.0 q
3065, 3080 (C6H5), 790, 835, 1640 (CH=C), 1677 (1H, CH=), 7.10-7.45 m (5H, C6H5)
(C=O), 1075, 1145, 1240, 1740 (COO)
VIIIb
Xb
690, 730, 770, 1485, 1585, 1610, 1810, 1830, 1890, 0.90 t (3H, CH3CH2, J 7), 1.23 t (3H, CH3CH2O, J 7),
3030, 3065, 3085 (C6H5), 1675 (C=O), 1070, 1140, 1.75 and 2.06 m (2H, CH3CH2), 4.16 q (2H,
1240, 1735 (COO)
CH3CH2O), 4.25 m (1H, CH), 7.09-7.44 m (5H, C6H5)
700, 720, 765, 1485, 1590, 1605, 1830, 1890, 3035, 1.32 t (3H, CH3CH2O, J 7), 1.92 d (CH3CH=, J 8),
3070, 3085 (C6H5), 790, 835, 1640 (CH=C), 1675 4.32 q (2H, CH3CH2O), 7.04 q (1H, CH3CH=), 7.09
3070, 3085 (C6H5), 790, 835, 1640 (CH=C), 1675 7.44 m (5H, C6H5)
(C=O), 1070, 1145, 1240, 1735 (COO)
XI
710, 775, 1590, 1705, 1960, 3035, 3065, 3085 (C6H5), 1.44 d (3H, CH3CH, J 6.6), 5.10 q (1H, CH3CH),
1125, 1080, 1245, 1745(COO), 3100 3500(OH)
7.52 br.s (1H, OH), 7.4 m (5H, C6H5)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 6 2003

INTRAMOLECULAR 1,5-HYDRIDE SHIFT
3 ml of concn. HCl. The stirring at 55 60 C was
819
REFERENCES
continued for 10 h, the reaction mixture was then
cooled, the separated precipitate was filtered off and
washed with hexane. We obtained 1.2 g of lactone XI
(76% with respect to ketoester Xa), mp 140 141 C
(from alcohol). No depression of melting point was
observed in a sample mixed with compound obtained
in the previous experiment. The solvent was removed
from the filtrate, and the residue was distilled in a
vacuum. We obtained 0.7 g of compound VIIIa (44%
with respect to ketoester VIIIa in the initial mixture),
bp 96 98 C (1 mm Hg), n2D0 1.5078.
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Similarly from 3.3 g (0.015 mol) of ketoesters
VIIIb, Xb in 40: 60 ratio and 3 ml of 36% HCl we
obtained 1.2 g (73%) of lactone XI (with respect to
ketoester Xb), mp 140 141 C (from alcohol), and
0.53 g (41%) of compound VIIIb (with respect to
ketoester VIIIb in the initial mixture ), bp 96 98 C
(2 mm Hg), n2D0 1.5107.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 6 2003