Reactions of N- and C-alkenylanilines: IV. Synthesis of heterocycles by oxidation of N-acyl-o-(1-alkenyl)anilines with hydrogen peroxide

Article abstract of DOI:10.1023/A:1022572909355

Heterocyclic compounds of the 4H-3,1-benzoxazine and cyclopenta[b]indole series were synthesized by oxydation of N-acyl derivatives of 2-(1-alkenyl)anilines with hydrogen peroxide. The structure of the oxidation products is determined by the reaction cond

Full text of DOI:10.1023/A:1022572909355

Russian Journal of Organic Chemistry, Vol. 38, No. 10, 2002, pp. 1525 1533. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 10, 2002,
pp. 1577 1584.
Original Russian Text Copyright
2002 by Gataullin, Nasyrov, Abdrakhmanov, Tolstikov.
Reactions of N- and C-Alkenylanilines: IV.* Synthesis
of Heterocycles by Oxidation of N-Acyl-o-(1-alkenyl)anilines
with Hydrogen Peroxide
R. R. Gataullin, M. F. Nasyrov, I. B. Abdrakhmanov, and G. A. Tolstikov
Institute of Organic Chemistry, Ufa Research Center, Russian Academy of Sciences,
pr. Oktyabrya 71, Ufa, 450054 Bashkortostan, Russia
e-mail: chemorg@anrb.ru
Received February 22, 2002
Abstract Heterocyclic compounds of the 4H-3,1-benzoxazine and cyclopenta[b]indole series were syn-
thesized by oxydation of N-acyl derivatives of 2-(1-alkenyl)anilines with hydrogen peroxide. The structure
of the oxidation products is determined by the reaction conditions, substituent in the ortho-position of the
aromatic ring, protecting group, and alkenyl radical structure.
Some 4H-3,1-benzoxazines are known to exhibit
a strong biological activity [2]. These compounds are
usually synthesized from o-aminobenzyl alcohol
derivatives [3]. We recently proposed a procedure for
preparation of 4H-3,1-benzoxazines from o-(1-al-
kenyl)anilides by reaction with bromine, N-bromo-
succinimide, or hydrogen chloride [4]. In continuation
of our studies aimed at developing new methods for
selective heterocyclization of alkenyl-substituted aryl-
amines with a view to obtain 3,1-benzoxazine deriva-
tives, in the present work we examined oxidation of
acylated o-(1-alkenyl)anilines with hydrogen peroxide
under various conditions. We found that the result of
the reaction of o-(1-alkenyl)aniline derivatives with
hydrogen peroxide is strongly affected by the sub-
stituent in the aromatic ring, protecting group on the
nitrogen atom, and structure of the alkenyl fragment.
The reaction of anilides I [5], II [6], III [7], and
IV with H2O2 in acetonitrile in the presence of NaOH
afforded, respectively, 3,1-benzoxazines V, VI [5],
VII [6], and VIII in good yields. Benzoxazines V,
VII, and VIII were also obtained by treatment of
anilides I, II, and IV with 50% H2O2 in methanol in
the presence of Na2WO4 and H3PO4 (Scheme 1). It
should be noted that anilides III and IX did not
undergo oxidation under these conditions, and they
were recovered from the reaction mixtures. Analysis
of the NMR spectra of anilides III and IX showed
that these compounds, unlike their analogs I, II,
and IV having no methyl substituent in the ortho-
position, exist in the enol form (structures X and XI
in Scheme 1).
By reaction of N-ethoxycarbonyl derivatives XII,
XIII [5], and XIV XVI with H2O2 in MeOH in the
Scheme 1.
I, V, R = R = H; II, VII, R = H, R = Me; III, VI, X, R = Me, R = H; IV, VIII, R = H, R = OMe; IX, XI, R = R = Me.
____________
*
For communication III, see [1].
1070-4280/02/3810-1525$27.00 2002 MAIK Nauka/Interperiodica

1526
GATAULLIN et al.
Scheme 2.
XII, XVII, n = 1, R = R = H; XIII, XVIII, n = 1, R = Me, R = H; XIV, XIX, n = 1, R = H, R = OMe; XV, XX, n = 1,
R = OMe, R = H; XVI, XXI, n = 2, R = R = H.
Scheme 3.
XIII, XXII, R = Me; XV, XXIII, R = OMe.
Scheme 4.
XII, XXV, R = H; XXIV, XXVI, R = Me.
presence of Na2WO4 and H3PO4 we obtained 3,1-ben-
zoxazin-2-ones XVII [5] and XVIII XXI (Scheme 2)
as the only products.
nitrile in the presence of sodium hydroxide. As
a result, a mixture of four compounds XXXIII
XXXVI was formed, from which methyl ether
XXXIII and cyclopentaindole XXXVI were isolated.
In the above reactions, all products are likely to be
formed via transformations of intermediate epoxy
derivative B. Intramolecular cyclization of ketone C
yields indoles XXVIII and XXXVI. Ethers XXIX,
XXX, XXXIII, and XXXIV and alcohols XXXI and
XXXV are products of further transformations of
intermediate carbocation D (Scheme 5).
With the goal of obtaining hydroxyalkyl-substituted
3,1-benzoxazines and 3,1-benzoxazin-2-ones, alkenyl-
anilines XXXVII XXXIX [9] were subjected to
isomerization into the corresponding 2-(1-methyl-1-
butenyl)anilines XL XLII by the action of potassium
hydroxide at 300 C. Compounds XL XLII were
treated with acetic anhydride and ethyl chloroformate
to obtain N-acyl derivatives XLIII XLV, and the
latter were oxidized with hydrogen peroxide in MeOH
Both methyl and methoxy group in anilides XIII
[5] and XV exert similar ortho effects, and the oxida-
tion of these compounds with H2O2 in MeCN in the
presence of NaOH gives 3,1-benzoxazines XXII [5]
and XXIII (Scheme 3). By contrast, anilides XII and
XXIV having no ortho-substituent give rise to forma-
tion of 1,2,3,3a,4,8b-hexahydrocyclopenta[b]indoles
XXV [5] and XXVI (Scheme 4) under analogous
conditions. Presumably, the oxidation (as with cyclo-
pentenylbenzenes [8]) initially gives ketone A which
readily undergoes cyclization to indole. In the oxida-
tion of amide XXVII, the yield of indole derivatives
XXVIII is smaller. The reaction leads to formation of
a mixture of isomeric methyl ethers XXIX and XXX
and allyl-type alcohol XXXI (Scheme 5). Analogous
pattern was observed in the oxidation of N-tosyl
derivative XXXII with hydrogen peroxide in aceto-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 10 2002

REACTIONS OF N- AND C-ALKENYLANILINES: IV.
1527
Scheme 5.
XXVII XXXI, R = MeSO2; XXXII XXXVI, R = p-TolSO2.
Scheme 6.
XXXVII, XL, XLIII, R = R = H; XXXVIII, XLI, XLIV, XLVII, R = Me, R = H;
XXXIX, XLII, XLVI, R = R = Me.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 10 2002

1528
GATAULLIN et al.
Table 1. Yields, melting points, Rf values, and elemental analyses of compounds IV, VIII, XIV XVI, XVIII XXI,
XXIII, XXIV, XXVI XXVIII, XXXII, XXXIII, XXXVI, and XL XLIX
Found, %
H
Calculated, %
H
Comp.
no.
Yield,
%
mp, C, or Rf
Formula
(eluent)
C
N
C
N
IV
VIII
XIV
92
73
92
97
166
72.55
67.70
68.75
7.50
6.61
7.40
5.97
5.28
5.27
C14H17NO2
C14H17NO3
C15H19NO3
72.70
68.00
68.94
7.41
6.93
7.33
6.06
5.66
5.36
0.73 (hexane
EtOAc, 3: 1)
0.65 (hexane
EtOAc, 3: 1)
0.7 (hexane
EtOAc, 3: 1)
142
XV
89
92
68.90
73.55
7.25
7.80
5.35
5.77
C15H19NO3
C15H19NO2
68.94
73.44
7.33
7.81
5.36
5.71
XVI
XVIII
XIX
XX
XXI
XXIII
XXIV
89
81
87
83
80
90
66.75
62.41
62.35
66.67
66.61
72.98
6.21
5.79
5.73
6.20
6.57
7.61
5.78
5.31
5.40
5.67
4.87
5.60
C13H15NO3
C13H15NO4
C13H15NO4
C13H15NO3
C15H19NO4
C15H19NO2
66.94
62.64
62.64
66.94
66.97
73.44
6.48
6.07
6.07
6.48
6.91
7.81
6.00
5.62
5.62
6.00
5.05
5.71
213
150 152
233
90
0.6 (hexane
EtOAc, 3: 1)
0.6
XXVI
74
84
35
90
27
66.62
60.55
56.67
69.09
63.08
7.10
6.45
5.73
6.16
6.38
5.07
5.98
5.24
4.32
3.93
C15H19NO3
C12H15NO2S
C12H15NO3S
C18H19NO2S
C19H23NO4S
68.94
60.73
56.90
68.98
63.13
7.33
6.37
5.97
6.11
6.41
5.36
5.90
5.53
4.47
3.88
XXVII
XXVIII
XXXII
XXXIII
78 82
114
94 98
0.3 (hexane
EtOAc, 3: 1)
0.4 (hexane
EtOAc, 3: 1)
0.7 (CHCl3)
0.7 (CHCl3)
0.7 (CHCl3)
0.6 (hexane
EtOAc, 4: 1)
0.6 (hexane
EtOAc, 3: 1)
110
XXXVI
32
65.48
5.78
4.43
C18H19NO3S
65.63
5.81
4.25
XL
XLI
XLII
XLIII
74
36
48
93
82.08
82.17
82.60
72.18
9.15
9.69
10.55
8.05
8.57
7.97
7.35
5.89
C11H15N
C12H17N
C13H19N
C14H19NO2
81.94
82.23
82.48
72.07
9.38
9.78
10.12
8.21
8.69
7.99
7.40
6.00
XLIV
95
72.80
8.66
5.55
C15H21NO2
72.84
8.56
5.66
XLV
88
74
76
77
76
77.92
67.08
66.11
72.52
67.12
9.05
7.26
6.97
8.27
7.32
6.08
5.38
5.67
5.34
5.37
C15H21NO
C14H19NO3
C13H17NO3
C15H21NO2
C14H19NO3
77.88
67.45
66.36
72.84
67.45
9.15
7.68
7.28
8.56
7.68
6.05
5.62
5.95
5.66
5.62
XLVI
XLVII
XLVIII
XLIX
185 187
123 125
144 147
0.5 (hexane
EtOAc, 3: 1)
containing Na2WO4 and H3PO4. As a result, benzoxa-
zinones XLVI and XLVII and benzoxazine XLVIII
were isolated (Scheme 6). The oxidation of N-ethoxy-
carbonylaniline XLIII with H2O2 in acetonitrile in
the presence of NaOH gave epoxy derivative XLIX.
The structure of the oxidation products was proved
by elemental analyses and spectral data (Tables 1 3).
The double bond configuration in alkenylanilines XL
XLII was determined on the basis of our previous
data for structurally related compounds [4]. The spec-
tral parameters of previously known benzoxazine and
cyclopentaindole derivatives were consistent with
1
those reported in [5]. In the H NMR spectrum of
XLIX, the CH proton of the oxirane ring appears as
a triplet at 3.02 ppm (J = 5.43 Hz). Signals from
the C1 and C2 atoms of the oxirane fragment in
XLIX are located at
60.69 (s) and 66.05 ppm (d),
C
respectively.
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REACTIONS OF N- AND C-ALKENYLANILINES: IV.
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Table 2. 1H NMR spectra of compounds IV, VIII, IX, XI, XIV XVI, XVIII XXI, XXIII, XXIV, XXVI XXXVI,
and XL XLIX in CDCl3
Comp.
no.
Chemical shifts , ppm (J, Hz)
IV
1.92 q (2H, CH2, J = 7.46), 2.02 s (3H, CH3), 2.43 2.62 m (4H, 2CH2), 3.69 s (3H, OCH3), 5.85 s
(1H, CH), 6.63 6.71 m (3H, Harom), 7.71 s (1H, NH)
VIII
IX, XIa
1.72 2.53 m (6H, 3CH2), 2.63 s (3H, CH3), 3.13 br.s (1H, OH), 3.80 s (3H, OCH3), 4.45 br.s
(1H, CHO), 6.70 s (1H, 5-H), 6.77 d (1H, 7-H, J = 8.44), 7.49 d (1H, 8-H, J = 8.51)
1.96 q (2H, CH2, J = 7.40), 2.13 s (1H, CH3), 2.20 s and 2.24 s (3H, CH3), 2.28 s and 2.32 s (3H,
CH3), 2.49 d.t (2H, CH2, J1 = 1.98, J2 = 7.35), 2.61 d.t (2H, CH2, J1 = 1.84, J2 = 7.34), 5.82 t (J = 2.00),
5.96 t (J = 2.04), 6.94 d (1H, 5-H, J = 4.20), 7.00 d (1H, 3-H, J = 5.83)
1.90 q (2H, CH2, J = 7.34), 1.23 s (3H, CH3), 2.41 2.60 m (4H, 2CH2), 3.72 s (3H, OCH3), 4.12 q (2H,
OCH2, J = 7.19), 5.78 s (1H, CH), 6.61 6.72 m (3H, Harom), 7.85 s (1H, NH)
1.20 t (3H, CH3, J = 7.02), 1.92 q (2H, CH2, J = 7.38), 2.44 t.d (2H, CH2, J1 = 7.33, J2 = 2.35), 2.64 t.d
(2H, CH2, J1 = 7.33, J2 = 2.60), 3.74 s (3H, CH3), 4.11 q (2H, OCH2, J = 7.15), 5.94 t (1H, CH, J =
1.95), 6.33 s (1H, NH), 6.74 d (2H, Harom, J = 7.27), 6.88 d (1H, Harom, J = 7.88), 7.12 t (1H, Harom, J =
8.04)
XIV
XV
XVI
1.32 t (3H, CH3, J = 7.19), 1.67 1.84 m (4H, 2CH2), 2.21 s (4H, 2CH2), 4.23 q (2H, OCH2, J = 7.18),
5.74 s (1H, CH), 6.95 7.08 m (3H, Harom), 7.23 t (1H, Harom, J = 6.86), 8.07 s (1H, NH)
1.71 2.19 m (4H, 2CH2), 2.28 s (3H, CH3), 2.4 2.6 m (2H, CH2), 3.31 br.s (1H, OH), 4.19 d (1H, CHO,
J = 7.17), 6.96 t (1H, Harom, J = 7.54), 7.09 d (2H, Harom, J = 9.01), 8.70 s (1H, NH)
1.44 2.12 m (4H, 2CH2), 2.20 2.42 m (2H, CH2), 3.56 br.s (1H, OH), 3.55 s (3H, OCH3),
3.88 br.s (1H, CHO), 6.62 6.77 m (3H, Harom), 9.69 s (1H, NH)
1.72 2.32 m (4H, 2CH2), 2.28 2.51 m (2H, CH2), 3.03 br.s (1H, OH), 3.78 s (3H, OCH3),
4.12 d (1H, CHO, J = 4.76), 6.78 d (1H, Harom, J = 7.99), 6.80 d (1H, Harom, J = 7.83), 6.93 t (1H, 6-H,
J = 7.95), 7.57 s (1H, NH)
XVIII
XIXb
XX
XXIb
1.01 2.22 m (8H, 4CH2), 3.56 s (1H, CHO), 4.66 br.s (1H, OH), 6.64 d (2H, Harom, J = 7.51),
6.8 7.0 m (2H, Harom), 9.72 s (1H, NH)
XXIII
1.36 t (3H, CH3, J = 7.12), 1.7 2.3 m (4H, 2CH2), 2.4 2.6 m (2H, CH2), 2.73 br.s (1H, OH),
3.86 s (3H, OCH3), 4.14 d (1H, CHOH, J = 4.62), 4.40 q (2H, OCH2, J = 6.95), 6.82 d (1H, Harom, J =
6.57), 6.84 d (1H, Harom, J = 7.33), 7.02 t (1H, 6-H, J = 8.06)
XXIV
XXVI
1.20 t (3H, CH3, J = 6.11), 1.93 q (2H, CH2, J = 7.28), 2.12 s (3H, CH3), 2.42 2.57 m (4H, 2CH2),
4.08 q (2H, CH2O, J = 7.01), 5.67 s (1H, CH), 6.72 7.03 m (3H, Harom), 7.69 br.s (1H, NH)
1.38 t (3H, CH3, J = 7.12), 1.54 1.71 m (2H, CH2), 1.74 1.90 m (2H, CH2), 2.18 2.39 m (2H, CH2),
2.32 s (3H, CH3), 3.52 3.62 m (1H, CH), 4.38 q (2H, CH2, J = 6.7), 6.87 7.20 m (3H, Harom), 7.50 br.s
(1H, OH)
XXVII
2.02 q (2H, CH2, J = 7.43), 2.58 br.s (2H, CH2), 2.66 br.s (2H, CH2), 2.33 s (3H, CH3), 5.89 s (1H,
CH), 7.00 s (1H, NH), 7.11 t (1H, 5-H, J = 7.64), 7.22 7.28 m (2H, 6-H, 4-H), 7.56 d (1H, 3-H, J =
8.02)
XXVIII 1.55 1.86 m (2H, CH2), 2.12 2.57 m (4H, 2CH2), 3.06 s (3H, CH3), 3.59 d.d (1H, CH, J1 = 4.24, J2 = 8.85),
4.34 s (1H, OH), 7.02 t (1H, Harom, J = 7.38), 7.14 7.27 m (3H, Harom
)
XXIX,
XXX,
1.55 2.76 m (CH2), 2.89 s (CH3), 3.04 s (CH3), 3.06 s (CH3), 3.12 s (CH3), 3.15 s (CH3), 3.58 s (OCH),
4.42 d (OCH, J = 6.09), 3.93 s (OCH), 6.06 d ( CH, J = 2.45), 7.05 7.66 m (Harom), 8.83 s (NH), 9.12 s
(NH), 9.38 s (NH)
XXXIa
XXXII
1.92 q (2H, CH2, J = 7.32), 2.29 t.d (2H, CH2, J1 = 7.53, J2 = 2.12), 2.36 s (3H, CH3), 2.50 t.d (2H, CH2,
CH2, J1 = 7.56, J2 = 2.30), 5.57 t (1H, CH, J = 1.98), 7.04 7.22 m (7H, Harom, NH), 7.62 d (2H, Harom
J = 8.27)
,
XXXIII 1.50 1.72 m (2H, CH2), 1.97 2.31 m (4H, 2CH2), 2.38 s (3H, CH3), 2.97 s (1H, OH), 3.09 s (3H, OCH3),
3.81 s (1H, CHO), 7.00 7.14 m (2H, Harom), 7.26 d (2H, Harom, Ts, J = 8.01), 7.56 7.68 m (2H, Harom),
7.83 d (2H, Harom, Ts, J = 8.05), 9.20 br.s (1H, NH)
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GATAULLIN et al.
Table 2. (Contd.)
Comp.
no.
Chemical shifts , ppm (J, Hz)
XXXIV, 1.53 2.52 m (CH2), 2.36 s (CH3), 2.41 s (CH3), 3.01 s (OCH3), 4.27 d (OCH, J = 6.26), 4.80 d (OCH, J =
XXXVa
XXXVI
6.37), 5.38 t ( CH, J = 2.50), 7.00 7.82 m (Harom), 8.98 s (NH), 9.44 s (NH)
1.51 2.47 m (6H, 3CH2), 2.40 s (3H, CH3), 3.61 d.d (1H, CH, J1 = 5.10, J2 = 9.16), 4.32 s (1H, OH), 7.08
7.40 m (4H, Harom), 7.38 d (2H, Harom, Ts, J = 8.41), 7.92 d (2H, Harom, Ts, J = 8.37)
1.01 t (3H, CH3, J = 7.5), 1.91 q (2H, CH2, J = 7.40), 1.95 s (3H, CH3), 3.80 br.s (2H, NH2), 5.56 t (1H,
CH, J = 7.12), 6.73 d (1H, 6-H, J = 8.04), 6.82 t (1H, 4-H, J = 7.67), 7.01 d (1H, 3-H, J = 7.38), 7.11 t
(1H, 5-H, J = 7.74)
XL
XLI
1.01 d.t (3H, CH3, J1 = 1.44, J2 = 7.39), 1.92 t (2H, CH2, J = 7.02), 2.06 s (3H, CH3), 2.28 s (3H, CH3),
3.71 br.s (2H, NH2), 5.68 t (1H, CH, J = 7.06), 6.79 t (1H, 5-H, J = 7.34), 6.92 d (1H, 4-H, J = 7.39),
7.07 d (1H, 3-H, J = 7.38)
XLII
1.07 t (3H, CH3, J = 7.40), 1.07 q (2H, CH2, J = 7.29), 2.11 s (3H, CH3), 2.30 s (3H, CH3), 2.38 s (3H,
CH3), 3.64 br.s (2H, NH2), 5.72 t.d (1H, CH, J1 = 7.23, J2 = 1.51), 6.80 s (1H, 3-H), 6.95 s (1H, 5-H)
0.92 t (3H, CH3, J = 6.30), 1.32 t (3H, CH3, J = 6.09), 1.80 q (2H, CH2, J = 7.18), 2.02 s (3H, CH3), 4.17 q
(2H, CH2O, J = 7.14), 5.70 t (1H, CH, J = 7.42), 6.84 br.s (1H, NH), 7.03 7.32 m (3H, Harom), 8.10 d
(1H, Harom, J = 8.13)
XLIII
XLIV
XLV
0.94 t (3H, CH3, J = 7.37), 1.07 t (3H, CH3, J = 7.23), 1.80 q (2H, CH2, J = 7.30), 1.92 s (3H, CH3), 2.29 s
(3H, CH3), 4.19 q (2H, CH2, J = 7.13), 5.47 t (1H, CH, J = 7.05), 6.09 br.s (1H, NH), 6.82 t (1H, 5-H,
J = 7.22), 6.92 d (1H, 4-H, J = 7.25), 7.09 d (1H, 3-H, J = 7.30)
1.08 t (3H, CH3, J = 7.38), 1.10 q (2H, CH2, J = 7.25), 2.10 s (3H, CH3), 2.15 s (3H, CH3), 2.32 s (3H,
CH3), 2.36 s (3H, CH3), 5.68 t.d (1H, CH, J1 = 7.19, J2 = 1.47), 6.83 s (1H, 3-H), 6.94 s (1H, 5-H),
8.10 s (1H, NH)
XLVI
XLVII
XLVIII
XLIX
0.97 t (3H, CH3, J = 7.42), 1.4 1.7 m (2H, CH2), 1.71 s (3H, CH3), 2.26 s (3H, CH3), 2.30 s (3H, CH3),
2.52 br.s (1H, OH), 3.77 d.d (1H, CHO, J1 = 2.60, J2 = 10.05), 6.84 s (1H, 5-H), 6.93 s (1H, 7-H), 8.39 s
(1H, NH)
0.94 t (3H, CH3, J = 7.29), 1.4 1.6 m (2H, CH2), 1.71 s (3H, CH3), 2.26 s (3H, CH3), 3.11 br.s (1H, OH),
3.78 d.d (1H, CHO, J1 = 2.58, J2 = 9.40), 6.95 t (1H, 6-H, J = 7.51), 7.03 d (1H, 5-H, J = 7.38), 7.07 d
(1H, 7-H, J = 7.24), 7.39 s (1H, NH)
0.62 t (3H, CH3, J = 7.40), 1.57 s (3H, CH3), 2.08 s (3H, CH3), 1.9 2.1 m (2H, CH2), 2.33 s (3H, CH3),
2.68 s (3H, CH3), 3.50 d (1H, CHO, J = 6.02), 5.0 br.s (1H, OH), 6.64 s (1H, 5-H), 7.03 s (1H, 7-H),
7.62 s (1H, NH)
0.97 t (3H, CH3, J = 7.04), 1.0 1.2 m (2H, CH2O), 1.29 t (3H, CH3, J = 6.98), 1.56 s (3H, CH3), 3.02 t (1H,
CHO, J = 5.43), 4.19 q (2H, CH2, J = 6.88), 6.96 t (1H, 5-H, J = 7.01), 7.04 d (1H, 3-H, J = 6.34), 7.23 t
(1H, 4-H, J = 7.00), 8.10 d (1H, 6-H, J = 7.84), 8.38 s (1H, NH)
a
Mixture of isomers.
In DMF-d7.
b
EXPERIMENTAL
The H and 13C NMR spectra were recorded on
Oxidation of anilides with the system H2O2
MeOH Na2WO4 H3PO4 (typical procedure). To
a mixture of 0.5 g (2.48 mmol) of appropriate anilide,
50 mg (0.17 mmol) of Na2WO4 in 0.2 ml of water,
and 1 drop of concentrated phosphoric acid in 5 ml
of methanol we added 0.34 g (4.98 mmol) of 50%
hydrogen peroxide. The mixture was kept for 24 h
at 30 C, 50 ml of methylene chloride was added,
and the organic phase was washed with saturated
solutions of Na2CO3 and Na2S2O3 and with water
and dried over MgSO4.
1
a Bruker AM-300 spectrometer at 300.13 MHz for
1H and 75.47 MHz for 13C using TMS as internal
reference. The purity of the products was checked by
GLC on a Chrom-5 chromatograph equipped with
a flame-ionization detector (1200 3.5-mm column,
stationary phase SE-30 on Chromaton, carrier gas
helium, oven temperature programming at 12 C/min)
and by TLC on Silufol UV-254 plates.
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REACTIONS OF N- AND C-ALKENYLANILINES: IV.
1531
Table 3. 13C NMR spectra of compounds IV, VIII, IX, XI, XIV XVI, XVIII XXI, XXIII, XXIV, XXVI XXXVI,
and XL XLIX in CDCl3
Comp.
no.
Chemical shifts C, ppm
IV
23.14, 33.46, 35.97 (3CH2), 23.75 (CH3), 55.06 (OCH3), 111.99 (C3), 113.44 (C5), 124.93 (C6), 127.39 (C2),
130.16 (C2 ), 131.81 (C1 ), 140.41 (C1), 156.24 (C4), 168.48 (C O)
VIII
IX, XIa
19.86 (CH3), 19.33, 31.17, 36.87 (3CH2), 55.79 (OCH3), 79.64 (CHOH), 97.85 (C4), 112.40 (C7), 113.87
(C5), 119.68 (C8), 121.84 (C4a), 123.69 (C8a), 159.97 (C6), 168.62 (C N)
18.24 (CH3), 20.79, 20.85 (CH3), 22.87 (CH3), 23.64, 23.70 (C4 ), 33.36 (C3 ), 35.66, 35.91 (C5 ); singlets:
129.93, 130.87, 135.69, 136.06, 136.19, 136.29, 136.83, 137.50; doublets: 127.47, 130.01 (Ar), 126.71
(C3), 129.85 (C5), 129.18, 130.91 (C2 ), 141.13, 141.56 (C1), 169.12, 173.44 (C O)
XIV
23.19, 34.05, 36.17 (3CH2), 14.35 (CH3), 55.54 (OCH3), 60.23 (OCH2), 111.90 (C3), 114.32 (C5), 124.62
(C6), 126.99 (C2), 129.86 (C2 ), 131.65 (C1 ), 140.56 (C1), 155.44 (C4), 154.38 (C O)
XV
14.31 (CH3), 23.40, 33.11, 35.05 (3CH2), 55.36 (OCH3), 60.78 (OCH2), 109.02 (C5), 120.02 (C3), 122.73
(C2), 126.66 (C4), 129.18 (C2 ), 136.48 (C1), 140.96 (C1 ), 141.03 (C6), 154.51 (C O)
XVI
14.35 (CH3), 21.68, 22.72, 25.10, 29.68 (4CH2), 60.86 (OCH2), 118.79 (C6), 122.58 (C2 ), 127.20 (C4),
128.01 (C3), 128.16 (C5), 133.49 (C1 ), 134.17 (C2), 135.43 (C1), 153.40 (C O)
XVIII
XIXb
XX
16.82 (CH3), 20.19, 31.50, 33.43 (3CH2), 75.94 (CHOH), 93.85 (C4), 119.47 (C4a), 122.56 (C5), 122.82
(C8), 123.72 (C6), 131.11 (C7), 133.77 (C8a), 152.51 (C O)
20.52, 32.88, 34.04 (3CH2), 55.79 (OCH3), 75.81 (CHOH), 93.77 (C4), 113.30 (C7), 114.25 (C5), 115.03
(C8), 123.04 (C4a), 130.83 (C8a), 151.60 (C6), 155.51 (C O)
20.20, 31.56, 33.53 (3CH2), 55.89 (OCH3), 76.09 (CHOH), 94.12 (C4), 110.71 (C7), 117.90 (C5), 120.09
(C4a), 122.66 (C6), 124.71 (C8a), 145.14 (C8), 151.20 (C O)
XXIb
XXIII
XXIV
XXVI
XXVII
19.29, 21.16, 29.28, 30.12 (4CH2), 67.57 (CHOH), 84.12 (C4), 114.71 (C8), 122.86 (C6), 125.45 (C4a),
127.53 (C5), 129.30 (C7), 136.64 (C8a), 151.74 (C O)
14.28 (CH3), 20.59, 31.36, 34.00 (3CH2), 56.13 (OCH3), 64.56 (OCH2), 75.23 (CHOH), 93.42 (C4), 111.97
(C7), 117.31 (C5), 123.81 (C4a), 124.10 (C6), 130.94 (C8a), 151.77 (C8), 155.43 (C N)
14.4, 20.4 (2CH3), 23.1, 33.6, 36.4 (3CH2), 60.8 (CH2O), 122.4 (C1 ), 128.0 (C6), 128.1 (C2 ), 129.1 (C3),
129.8 (C5), 132.1 (C2), 132.3 (C4), 140.5 (C1), 153.7 (C O)
14.6, 20.9 (CH3), 25.5 (C2), 34.0 (C1), 42.2 (C3), 53.2 C(8b), 61.8 (OCH2), 103.7 (C3a), 114.2 (C5), 125.0
(C8), 128.2 (C6), 129.5 (C7), 132.7 (C8a), 141.8 (C4a), 153.1 (C O)
23.05, 33.65, 36.85 (3CH2), 39.30 (CH3), 119.28 (C6), 124.25 (C4), 127.87 (C3), 128.39 (C5), 129.27 (C2),
131.10 (C2 ), 133.50 (C1), 139.70 (C1 )
XXVIII 25.07 (C2), 33.67 (C1), 39.71 (CH3), 43.29 (C3), 54.12 (C8b), 106.96 (C3a), 111.75 (C7), 123.27 (C5), 124.93
(C8), 127.87 (C6), 132.08 (C8a), 140.71 (C4a)
XXIX,
XXX,
19.37, 20.24, 28.10, 30.56, 31.42, 31.80, 32.38, 34.45 (8CH2), 39.25, 39.45, 40.57 (3CH3SO2), 50.10, 51.58
(2CH3O), 76.23, 78.20, 79.23 (3HCO), 88.87, 92.34 (2CO), 118.1 143.12 (Ar)
XXXIa
XXXII
21.30 (CH3), 23.02, 33.59, 36.76 (3CH2); doublets: 121.04, 124.42, 126.91, 127.52, 127.92, 129.34, 130.58;
singlets: 130.17, 133.18, 136.15, 139.76, 143.63
XXXIII 20.50 (CH3), 21.45, 31.13, 31.54 (3CH2), 52.01 (OCH3), 77.32 (CHOH), 89.48 (C1 ), 118.62, 122.96,
124.83, 127.23, 128.21, 129.19, 129.59, 136.84, 137.08, 143.75 (Ar)
XXXIV, 19.49, 27.93, 30.47, 32.00, 34.38 (5CH2), 21.43, 21.51 (2CH3), 50.07 (CH3O), 76.33, 79.42 (2HCO),
XXXVa
XXXVI
92.45 (CO), 120.07 144.10 (Ar)
21.10 (CH3), 25.30 (C2), 33.56 (C1), 43.65 (C3), 53.80 (C8b), 107.05 (C3a), 112.20, 122.43, 124.58, 126.73,
127.68, 129.73, 131.69, 136.95, 140.44, 143.97 (arom.)
XL
14.3 (CH3), 22.5, (CH2), 24.5 (CH3), 114.9 (C6), 118.5 (C4), 127.6 (C3), 127.8 (C2), 128.9 (C5), 131.2 (C2 ),
133.0 (C1 ), 142.7 (C1)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 10 2002

1532
GATAULLIN et al.
Table 3. (Contd.)
Comp.
no.
Chemical shifts C, ppm
XLI
14.17, 17.73, 24.48 (CH3), 22.44 (CH2), 117.70 (C4), 121.85 (C6), 126.33 (C3), 127.43 (C2), 128.64 (C2 ),
131.13 (C5), 133.23 (C1 ), 140.72 (C1)
XLII
14.23, 17.72, 20.42, 24.63 (4CH3), 22.51 (CH2), 120.04 (C6), 126.74 (C2 ), 127.65 (C4), 129.47 (C3), 130.96
(C5), 133.45 (C2), 138.25 (C1 ), 142.20 (C1)
XLIII
XLIV
XLV
14.1, 14.5 (2CH3), 22.4, (CH2), 24.8 (CH3), 61.0 (CH2O), 118.2 (C4), 122.7 (C2), 127.5 (C5), 128.0 (C2 ),
130.6 (C6), 131.6 (C1 ), 132.7 (C3), 134.3 (C1), 153.5 (C O)
13.98, 15.00, 18.55, 20.50, 23.89 (4CH3), 22.72 (CH2), 60.43 (OCH2), 118.02 (C4), 121.79 (C6),
126.22 (C3), 128.11 (C2), 128.74 (C2 ), 131.50 (C5), 133.34 (C1 ), 140.62 (C1), 152.00 (C=O)
14.57, 18.02, 20.22, 23.17, 24.93 (5CH3), 24.41 (CH2), 119.14 (C6), 126.33 (C2 ), 127.25 (C4), 129.23 (C3),
131.04 (C5), 133.05 (C2), 138.85 (C1 ), 141.04 (C1), 165.03 (C O)
XLVI
XLVII
XLVIII
XLIX
10.87, 16.81, 20.92, 21.61 (4CH3), 23.59 (CH2), 77.39 (CHOH), 87.85 (C4), 122.50 (C8), 122.65 (C4a),
123.41 (C5), 130.68 (C6), 131.40 (C7), 132.30 (C8a), 152.20 (C N)
10.75, 16.85, 21.21 (3CH3), 23.51 (CH2), 77.17 (CHOH), 87.87 (C4), 122.61 (C8), 122.73 (C5), 122.87
(C4a), 122.98 (C6), 130.57 (C7), 133.00 (C8a), 152.45 (C N)
9.91, 18.37, 19.20, 20.56, 23.27 (5CH3), 22.49 (CH2), 77.64 (CHOH), 91.67 (C4), 122.43 (C5), 123.66 (C8),
124.94 (C4a), 126.99 (C6), 131.65 (C7), 138.63 (C8a), 171.59 (C N)
9.86, 14.35, 24.92 (3CH3), 23.37 (CH2), 60.69 (C1 ), 63.40 (OCH2), 66.05 (CHO), 119.99 (C6), 122.13 (C4),
125.69 (C2), 127.08 (C3), 127.92 (C5), 137.30 (C1), 153.62 (C O)
a
Mixture of isomers.
In DMF-d7.
b
Oxidation of anilides with the system H2O2
Compounds XLIII and XLIV were synthesized as
follows. Ethyl chloroformate, 1.3 g (12 mmol), was
added dropwise under vigorous stirring at 20 C to
a suspension of 10 mmol of amine XL or XLI and
2.76 g (20 mmol) of K2CO3 in 20 ml of methylene
chloride. After 1 h, 2 ml of water was added, the
mixture was stirred, the precipitate was filtered off,
and the filtrate was washed with water and dried over
MgSO4. The solvent was removed under reduced
pressure to obtain compounds XLIII and XLIV as
yellow oily substances.
NaOH MeOH MeCN. A solution of 0.2 g of NaOH
in a mixture of 5 g of methanol and 5 g of acetonitrile
was added to 8.66 mmol of appropriate anilide, and
1 g (29.4 mmol) of 50% hydrogen peroxide (excess)
was added dropwise. The reaction was accompanied
by evolution of oxygen and by a slight exothermic
effect. The mixture was kept for 2 h, 10 ml of a sa-
turated solution of Na2S2O3 was added, and the
mixture was extracted with methylene chloride. The
extract was dried over MgSO4 and evaporated under
reduced pressure. To remove tar-like impurities, the
yellow oily residue was passed through a column
charged with 5 g of silica gel using hexane ethyl
acetate (2:1) as eluent.
Compounds XL XLII were synthesized by heating
a mixture of amine XXXVII XXXIX and an equal
amount (by weight) of potassium hydroxide for 1 h
at 300 C. The products were isolated by fractional
distillation under reduced pressure.
Compound XLV was obtained by mixing 10 mmol
of amine XLII with 12 mmol of acetic anhydride on
cooling, followed by evaporation of acetic acid and
recrystallization of the product from benzene.
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