Stevens rearrangement of anilinium salts by the action sodium carbonate hexahydrate

Article abstract of DOI:10.1023/B:RUGC.0000016031.82173.59

Anilinium salts containing an allyl-like group together with various functionally substituted receiving groups undergo Stevens rearrangement by the action of sodium carbonate hexahydrate in the absence of a solvent. As a result, both N-methylaniline deriv

Full text of DOI:10.1023/B:RUGC.0000016031.82173.59

Russian Journal of General Chemistry, Vol. 73, No. 10, 2003, pp. 1608 1610. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 10, 2003,
pp. 1701 1703.
Original Russian Text Copyright
2003 by Shakhbazyan, Babakhanyan, Grigoryan, Kocharyan.
Stevens Rearrangement of Anilinium Salts By the Action
Sodium Carbonate Hexahydrate
L. G. Shakhbazyan, A. V. Babakhanyan, Dzh. V. Grigoryan, and S. T. Kocharyan
Institute of Organic Chemistry, National Academy of Sciences of Armenia, Erevan, Armenia
Abovyan Armenian State Pedagogical University, Erevan, Armenia
Received January 17, 2002
Abstract Anilinium salts containing an allyl-like group together with various functionally substituted
receiving groups undergo Stevens rearrangement by the action of sodium carbonate hexahydrate in the
absence of a solvent. As a result, both N-methylaniline derivatives and nucleophilic substitution products
are formed.
It is known that the presence of a phenyl group in
an ammonium complex prevents Stevens and Som-
melet rearrangements by the action of classical basic
reagents [1]. However, N-benzyl-N,N-dimethylanili-
nium salt in liquid ammonia in the presence of sodium
amide undergoes mainly Sommelet rearrangement [2],
while butyllithium promotes Stevens rearrangement
[3]. Also, the Stevens rearrangement of the benzylide
formed by reaction of dehydrobenzene with benzyl-
dimethylamine have been reported [4, 5]. An ana-
logous reaction occurred with N-benzyl-N-methyl-
anilinium iodide by the action of phenyllithium [4].
As follows from published data, Stevens and Som-
melet rearrangements of anilinium salts are promoted
only by strong bases at relatively low temperatures.
Taking into account the above stated, it was
interesting to effect Stevens rearrangement of anili-
nium salts in the presence of weak bases, specifically
in the presence of sodium carbonate hexahydrate. For
this purpose, we have synthesized anilinium salts
Ia Ie and treated them with Na2CO3 10H2O without
solvent. We have found that under these conditions
salts Ia Ie undergo mainly Stevens rearrangement to
afford functionally substituted aniline derivatives in
good yields (Table 1).
R
CH3
CH3
Na2CO3 10H2O
N CHCHCH=CH2 +
X
N CH2CH=CHR
CH3
CH2CH=CHR
Br
CH2X
C6H5
+
C6H5
N
C6H5
IIa IIe
IIIa, IIIb
Ia Ie
I, II, R = H, X = COOCH3 (a), COCH3 (b), COC6H5 (c), C6H4Cl-p (e); R = CH3, X = COC6H5 (d). III, R = H (a),
CH3 (b).
The data in Table 1 show that the yield of the rear-
rangement product from salt Ia is low. This may be
due to the easy elimination of the methoxycarbonyl-
methyl group from anilinium salts by the action of
bases to give a nucleophilic substitution product,
methyl methoxyacetate [1]. The Stevens rearrange-
ments of salts Ia Ie in the presence of sodium
carbonate hexahydrate are accompanied by formation
of nucleophilic substitution products, N-2-propenyl-
and N-(2-butenyl)-N-methylanilines IIIa and IIIb
(yield 16 40%). Compounds IIIa and IIIb were
identified by comparing with authentic samples
(GLC). According to the GLC data, the reaction
mixtures also contained other nucleophilic substitution
products, in particular methyl(methoxycarbonylme-
thyl)- [1] and methyl(phenacyl)anilines [6]. These
products were also obtained by independent synthesis,
by reaction of N-methylaniline with methyl bromo-
acetate or phenacyl bromide. The fraction of the
nucleophilic substitution products in the product
mixtures is 5 7% (GLC).
1070-3632/03/7310-1608$25.00 2003 MAIK Nauka/Interperiodica

STEVENS REARRANGEMENT OF ANILINIUM SALTS BY THE ACTION
1609
Table 1. Reaction of anilinium salts Ia Ie with sodium carbonate hexahydrate
Rear-
Found,
%
Calculated,
%
Nucleophilic
substitution
product
bp,
(p, mm)
or mp,
C
Initial range- Yield,
n2D0
Formula
salt
ment
product
%
C
C
H
N
C
H
N
(yield, %)
I
IIa
IIb
IIc
IId
18
56
110 112 (2)
114 116 (4)
1.5430 71.63 7.80 5.01 C13H17NO2
1.5521 76.43 8.83 5.67 C13H17NO
81.11 7.27 5.53 C18H21NO
71.23 7.51 6.39
76.85 8.37
81.51 7.17 5.28
81.72 7.52 5.01
IIIa (40)
6.90 IIIa (48)
Ib
Ic
Id
62.5 113 115
IIIa (23)
IIIb (21)
65
68
169 170 (1.5)
105 106
106 107
81.41 7.59 5.41 C19H21NO
Ie
IIe
71.87 6.48 4.83 C18H18ClNOa 72.12 6.01 4.67
IIIa (16)
a
Found Cl, %: 11.61. Calculated Cl, %: 11.85.
Table 2. IR and 1H NMR spectra of compounds IIa IIe
Comp.
no.
1
IR spectrum, , cm
1H NMR spectrum, , ppm (J, Hz)
IIa
IIb
IIc
IId
IIe
920, 990, 1640, 3015, 3085 (CH=CH2); 1040, 1120, 2.64 s (3H, NCH3), 2.40 2.80 m (2H, CH2), 3.18 3.37 m
1245, 1740 (COO); 690, 755, 1600, 3025, 3065 (C6H5) (1H, NCH), 3.40 s (3H, OCH3), 4.70 5.32 m (2H, CH2=);
5.33 6.20 m (1H, CH=), 6.22 7.30 m (5H, C6H5)
920, 990, 1640, 3015, 3085 (CH=CH2), 1715 (CO), 1.82 s (3H, CH3CO), 2.30 2.60 m (2H, CH2), 2.70 s (3H,
695, 755, 1600, 3030, 3070 (C6H5)
NCH3), 3.20 3.36 m (1H, NCH), 4.60 5.20 m (2H, CH2=),
5.30 6.00 m (1H, CH=), 6.4 7.25 m (5H, C6H5)
915, 990, 1645, 3015, 3085 (CH=CH2), 1685 (CO), 2.40 2.82 m (2H, CH2), 3.0 s (3H, NCH3), 4.15 4.40 m
695, 750, 1600, 3035, 3065 (C6H5)
(1H, NCH), 4.80 5.50 m (2H, CH2=), 5.50 6.20 m (1H,
CH=), 6.40 8.00 m (10H, C6H5)
920, 985, 1645, 3015, 3085 (CH=CH2), 1685 (CO), 1.10 d and 1.25 d (3H, CH3CH, J 7), 3.06 s (3H, NCH3),
695, 1600, 3030, 3065 (C6H5)
2.86 3.50 m (2H, NCHCH), 4.85 5.18 m (2H, CH2=),
5.75 6.04 m (1H, CH=), 6.55 8.20 (10H, C6H5)
915, 990, 1640, 3015, 3085 (CH=CH2), 1680 (CO), 2.45 2.85 m (2H, CH2), 3.0 s (3H, NCH3), 4.20 4.40 m
695, 750, 845, 1600, 3030, 3065 (C6H5, C6H4Cl-p) (1H, NCH), 4.65 5.30 m (2H, CH2=), 5.30 6.0 m (1H,
CH=), 6.40 8.0 m (9H, C6H5, C6H4Cl)
The structure of the products was confirmed by the
IR and H NMR spectra, and the purity of compounds
IIa and IIb was checked by GLC (Tables 1, 2).
Initial anilinium salts were synthesized by reactions
of N-2-propenyl- or N-2-butenyl-N-methylaniline
with methyl bromoacetate, bromoacetone, phenacyl
bromide, or p-chlorophenacyl bromide according to
the procedure reported in [6]. All salts Ia Ie are
hygroscopic. N-2-Propenyl- and N-2-butenyl-N-
methylanilines were prepared as described in [7].
1
EXPERIMENTAL
The IR spectra were recorded on UR-20 and
Specord IR-75 spectrometers from samples dispersed
1
in mineral oil or pelleted with KBr. The H NMR
Stevens rearrangement of salts Ia Ie (general
procedure). Powdered sodium carbonate hexahydrate,
0.045 mol, was added to 0.015 mol of salt Ia Ie.
The mixture was thoroughly stirred and ground over
a period of 30 min and was heated for 3 5 h at 50
60 C. The mixture was then treated with diethyl ether
and water, the ether layer was separated, and the
aqueous layer was extracted with two portions of
ether. The ether extracts were combined, dried over
spectra were obtained on a Perkin Elmer R-12B
instrument (60 MHz) from solutions in carbon tetra-
chloride containing HMDS as internal reference. GLC
analysis was performed on an LKhM-80 chromato-
graph equipped with a thermal conductivity detector;
a 2000 3-mm column was packed with 10% of
Apiezon L on Inerton-AW (0.20 0.25 mm); carrier
gas helium, flow rate 60 80 ml/min.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 10 2003

1610
SHAKHBAZYAN et al.
magnesium sulfate, and evaporated. The residue was
subjected to vacuum distillation to isolate nucleo-
philic substitution and rearrangement products (from
salts Ia, Ib, and Id); in the reactions with salts Ic and
Ie, only nucleophilic substitution product IIIa was
isolated by vacuum distillation of the residue, whereas
the rearrangement product was identified without
distillation by IR and 1H NMR spectra (Tables 1, 2).
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