An unusual reaction of isatoic anhydride with acetyl-and benzoyl-methylenetriphenylphosphoranes [6]

Full text of DOI:10.1007/s10593-006-0213-0

Chemistry of Heterocyclic Compounds, Vol. 42, No. 8, 2006
AN UNUSUAL REACTION OF ISATOIC
ANHYDRIDE WITH ACETYL- AND BENZOYL-
METHYLENETRIPHENYLPHOSPHORANES
E. N. Kozminykh1, V. I. Goncharov2, R. A. Aitken3, V. O. Kozminykh4, and K. Sh. Lomidze4
Keywords: 2-substituted 2-(triphenylphosphoranylidene)methyl-1,2-dihydro-4H-3,1-benzoxazin-4-
ones, isatoic anhydride, reactions with acetyl- and benzoylmethylenetriphenylphosphoranes.
There are published data on the C-acylation of ethyl triphenylphosphoranylideneacetate with isatoic
anhydride [3,1-benzoxazine-2,4(H)-dione] (1) leading to the formation of 3-(triphenylphosphoranylidene)-
quinoline-2,4(1H,3H)-dione [1,2]. As a result of the reaction of compound 1 with 1-triphenyl-
phosphoranylidene-2-propanone (acetylmethylenetriphenylphosphorane) (2a) or 2-triphenylphosphoranylidene-
1-phenylethanone (benzoylmethylenephosphorane) (2b) we unexpectedly isolated the products from O-acylation
of the latter followed by decarboxylation of the intermediate ylide and heterocyclization, i.e., the 2-substituted 2-
(triphenylphosphoranylidenemethyl)-1,2-dihydro-4H-3,1-benzoxazin-4-ones 3a,b.
+
PPh3
R
PPh3
O
2a,b
O
O
–
O
R
N
H
O
O
1
+
PPh3
+
PPh3
O
O
–
O
R
R
–
– CO2
NH
N
H
CO2
O
O
4
2
O
H
3
5
6
15
O
17
16
1
P
18
19
PPh3
8
N
N
H
14
7
R
9
H
10
13
3
3a,b
11
12
3 b
2, 3 a R = Me, b R = Ph
__________________________________________________________________________________________
1
Moscow State University of Technologies and Management, Perm Branch, Perm 614065, Russia;
2
3
e-mail: kvonstu@yahoo.com. Stavropol State Medical Academy, Stavropol 355023, Russia. St. Andrews
University, Fife KY1695T, Great Britain; e-mail: raa@st-and.ac.uk. Perm State Pedagogical University, Perm
4
614990, Russia; e-mail: kvo@perm.ru. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8,
pp. 1272-1274, August, 2006. Original article submitted February 19, 2006.
0009-3122/06/4208-1107©2006 Springer Science+Business Media, Inc.
1107

The structure of compounds 3a,b is confirmed by the NMR spectra and agrees well with previously
obtained data on the structural features of ylides [3].
Compounds 3a,b have bactericidal activity against standard strains of Staphylococcus aureus P-209 and
Escherichia coli M17, acting on bacterial cultures at a minimum suppressing concentration of up to 62.5 µg/ml.
Reaction of Isatoic Anhydride (1) with Acetyl- or Benzoylmethylenetriphenylphosphoranes. A
mixture of isatoic anhydride 1 (0.82 g, 5.0 mmol) and acetylmethylenetriphenylphosphorane 2a (1.59 g,
5.0 mmol) [4] or benzoylmethylenetriphenylphosphorane 2b (1.90 g, 5.0 mmol) [4] in dioxane (80-100 ml) was
boiled for 3-5 h (TLC). The solvent was evaporated, and the residue was rubbed with ether and
tetrachloromethane and recrystallized from ethyl acetate. Compounds 3a and 3b were obtained.
2-Methyl-2-triphenylphosphoranylidenemethyl-1,2-dihydro-4H-3,1-benzoxazin-4-one
(3a).
Yield 1.40 g (64%); mp 139-140°C (ethyl acetate). IR spectrum (Specord M-80, thin layer in vaseline oil),
1
ν, cm-1: 3273 (NH), 1788, 1728 (C=O), 1592, 1570 (C=Carom, Ph3P=CH). H NMR spectrum (RYa-2310, 60
MHz, DMSO-d6, HMDS), δ, ppm: 1.88 (3H, s, CH3); 3.78 (1H, br. s, NH); 4.15 (1H, br. s, CH in Ph3P=CH–);
7.10-7.82 (19H, m, 3C6H5, C6H4). Found, %: C 76.69; H 5.72; N 3.06; P 6.88. C28H24NO2P. Calculated, %:
C 76.87; H 5.53; N 3.20; P 7.08.
2-Phenyl-2-triphenylphosphoranylidenemethyl-4H-3,1-benzoxazin-4-one (3b). Yield 1.89 g (72%);
mp 198-199°C (ethyl acetate). IR spectrum (Specord M-80, thin layer in Vaseline oil), ν, cm-1: 3292 (NH), 1780,
1732 (C=O), 1620, 1584, 1502 (C=Carom, Ph3P=CH). 1H NMR spectrum (Gemini-300, 300 MHz, in
deuterochloroform, TMS), δ, ppm (J, Hz) (the numbering of the carbon atoms is arbitrary, see the scheme): 2.90
(1H, br. s, NH); 4.45 (1H, br. s, C(15)H); 6.79 (1H, d, J = 8.4, C(7)H); 6.91 (1H, t, J = 7.8, C(12)H); 7.10-7.12 (3H,
group of signals, C(4)H, C(5)H, C(6)H); 7.20-7.26 (7H, group of signals, C(10)H, C(14)H, and 5CH in Ph3P=);
7.31-7.35 (3H, group of signals, C(11); C(13); and 1CH in Ph3P=); 7.43-7.50 (6H, group of signals, 6CH in Ph3P=);
7.69-7.72 (3H, group of signals, 3CH in Ph3P=). 13C NMR spectrum (Gemini-300 BB, 75 MHz, TMS,
deuterochloroform), δ, ppm (J, Hz) (the numbering of the carbon atoms is arbitrary, see the scheme): 51.4 (C(15)
,
J = 111.0), 109.3 (C(1)), 115.3 (C(7)), 123.0, 128.8, 128.9, 136.2 (C(4)-C(6), C(12)), 126.0 (C(16), J = 91), 126.3,
127.3 (C(10), C(11)), 128.4 (C(18), J = 13), 131.7 (C(19), J = 2), 132.5 (C(17), J = 11), 141.0, 146.9 (C(3), C(9)), 159.4
(C(8)), 184.2 (C(2)). 31P NMR spectrum (Gemini-300 BB, 121 MHz, H3PO4, deuterochloroform), δ, ppm: +16.6.
Found, %: C 79.11; H 5.37; M 2.65; P 6.03. C33N26NO2P. Calculated, %: C 79.34; H 5.25; N 2.80; P 6.20.
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