REACTION OF 2-SUBSTITUTED 1-PHENYL-1,2-DIHYDRO-4H-3,1,2-BENZOXAZA...
1869
2
2
3
3
23
27
formation of dipolar intermediate A which is stabilized
via intramolecular nucleophilic replacement at the car-
bonyl carbon atom with formation of a new C–C bond
closing azaphosphepine ring.
C , J = 14.1, J = 3.0), 61.03 t.t (t) (C or C ,
CP
CH
1
1
1
2
27
23
JCH = 152.4, J = 29.7), 61.75 t.t (t) (C or C ,
JCH = 152.6, J = 30.8), 113.54 t.t.m (t.t) (C or C ,
CF
2
24
28
CF
2
2
JCF = 251.2, JCF = 28.1, JCH = 4.0, 3.4), 113.86 t.t.m
2
8
24
1
2
2
(
t.t) (C or C , J = 251.2, J = 28.1, J = 4.0,
.4–3.5), 108.81 t.d.t.m (t.t) (C or C , J = 250.5,
CF
Reaction of bis(2,2,3,3-tetrafluoropropyl)
CF CF CH
2
5
29 1
3
2
-(4-chlorobenzylidene)malonate (I) with 2-substi-
1
2
29
J
= 192.7, J = 33.6), 108.91 t.d.t.m (t.t) (C or
tuted 1-phenyl-1,2-dihydro-4H-3,1,2-benzoxaza-
phosphinin-4-ones IIa and IIb (general procedure).
A mixture of 0.03 mol of diester I and 0.03 mol of
benzoxazaphosphinine IIa or IIb in 15 ml of methyl-
ene chloride was kept for 2 months at room tempera-
ture. The solvent was distilled off to leave compound
IIIa or IIIb as a light red thick oily liquid.
CH
CF
1
2
5
1
2
C , J = 250.5, J = 193.4, J = 35.7), 130.85 d.t
FC
CH
CF
3
0
1
3
(
(
d) (C , J = 122.4, J = 7.5), 131.04 d.d.d.d (d)
C , C , J = 162.6, J = 9.0, J = 8.0–8.1),
128.68 d.d.d (d) (C , C , JCH = 162.6, JCP = 12.8,
PC CH
3
1
35
1
2
3
CH
CP
1
CH
3
2
34
2
3
33
1
3
JCH = 8.0), 132.73 d.t.d (d) (C , JCH = 160.7, JCH =
4
8.1, JCP = 2.8); the signals were assigned with account
taken of the results of APT experiment. F NMR spec-
trum, δ , ppm: major diastereoisomer: –124.22 m and
124.44 m (2F, CF ), –137.99 br.m and –138.66 br.m
2F, CHF , J = 53.4 Hz); minor diastereoisomer:
125.19 m and –125.75 m (2F, CF ); –140.05 br.d and
138.70 br.d (2F, CHF , J = 51.9 Hz). Mass spec-
trum: m/z 773 [M] .
19
Bis(2,2,3,3-tetrafluoropropyl) 3-(4-chlorophenyl)-5-
5
F
oxo-1,2-diphenyl-1,2,3,4-tetrahydro-1,2λ -benzaza-
–
(
2
phosphepine-4,4-dicarboxylate 2-oxide (IIIa) (dia-
stereoisomer ratio 10:1) was precipitated with diethyl
ether–pentane (1:1); the major isomer was isolated as
a light pink powder. Yield 78%, mp 59°C. IR spec-
2
2 FH
–
–
2
2
2
FH
+
–
1
trum, ν, cm : 2920, 2854, 1758, 1686, 1594, 1460,
1
7
377, 1283, 1250, 1197, 1163, 1111, 1015, 976, 837,
Bis(2,2,3,3-tetrafluoropropyl) 3-(4-chlorophen-
yl)-2-ethoxy-5-oxo-1-phenyl-1,2,3,4-tetrahydro-
1
53, 721, 698, 554. H NMR spectrum, δ, ppm (J, Hz):
2
5
major diastereoisomer: 4.01 br.d.t (1H, OCH , J
=
1,2λ -benzazaphosphepine-4,4-dicarboxylate 2-ox-
2
HH
3
2
1
1
2.5, J = 12.5), 4.29 br.d.t (1H, OCH , J = 12.5,
ide (IIIb) (diastereoisomer ratio 5:3). H NMR spec-
HF
2
HH
3
2
3
2
JHF = 13.2), 4.41 br.d.t (1H, OCH , J = 13.2, J
=
trum, δ, ppm: major isomer: 4.53 d (1H, 3-H, J
=
2
HH
HF
HP
2
3
2
1
4
2.5), 4.63 br.d.t (1H, OCH , J = 12.5, J = 12.5),
.53 d (1H, 3-H, J = 12.5), 5.70 t.t (1H, CHF ,
12.5 Hz), 5.58 t (1H, CHF , J = 57.0 Hz), 5.88 t
2
HH
HF
2 HF
2
2
3
(1H, CHF , J = 57.2 Hz), 1.07 t (3H, CH , J
=
HH
HP
2
2
HF
3
2
3
2
13
JHF = 52.8, J = 3.7), 5.99 t.t (1H, CHF , J
=
7.3 Hz). C NMR spectrum, δ , ppm (J, Hz): major
C
HF
2
HF
3
3
3
1
5
2.8, J = 5.1), 6.85 d (1H, 9-H, J = 7.3), 7.02 d
diastereoisomer: 48.12 d.d.t (d) (C , J = 125.5,
JCH = 127.7, J = 3.0), 72.21 d (s) (C , J = 5.4),
CH CH
190.83 br.d.d (s) (C , J = 5.7, 4.6), 135.03 d.d (s)
(C , JCH = 160.1, JCH = 7.0), 123.96 d.m (d) (C ,
HF HH
CP
3
1
3
4 2
(
2H, 11-H, 15-H, J = 8.1), 7.10 m (3H, 12-H, 13-H,
HH
3
4
5 3
1
4-H), 7.95 d.d (1H, 6-H, JHH = 7.3, J = 1.5).
HH
CH
1
3
8
1
3
9
C NMR spectrum, δ ppm (J, Hz) (hereinafter, multi-
C
1
3
9a 2
plicity of the corresponding signal in the proton-de-
coupled spectrum is given in parentheses): major dia-
JCH = 159.5, J = 2.2), 142.03 m (d) (C , J
=
CP
CP
1
0
2
5.5), 140.90 m (d) (C , J = 6.1), 122.48 d.d.d (s)
CP
3
1
11
15
1
3
stereoisomer: 48.13 br.d.d.t (d) (C , J = 81.87,
(C , C , J = 159.5, J = 5.7, 7.0), 123.57 d.t (s)
PC
CH CH
1
2
3
3
4
13
1
3
16
JCH = 127.2, J = 3.5–3.7), 71.74 br.d.d (d) (C ,
JCH = 6.0, J = 1.6–1.7), 193.24 br.d.d (d) (C ,
JCH = 4.7–5.0), 128.22 m (d) (C , J = 3.0),
(C , J = 159.1, J = 7.5), 134.56 m (d) (C ,
CH CH
CH
2
5
2
19
22
J
= 2.8), 136.80 m (s) (C ), 164.60 br.d (d) (C or
CP
CP
26
5a
3
3
26
22
3
C , JCP = 12.2), 163.43 br.d (d) (C or C , JCP
=
=
=
CP
6
1
3
23
27
2
1
1
1
1
1
3
8
1
32.49 d.d (s) (C , J
27.62 d.d (s) (C , J
35.32 d.d (s) (C , J
30.50 br.d.m (d) (C , J = 163.1, J = 6.2, J
.0), 143.21 d.d.m (d) (C ), 142.64 m (d) (C , J
.7–9.0, J = 4.6), 125.84 d.m (d) (C , C , J
64.9, J = 3.1), 129.26 d.d (s) (C , C , J
61.1, J = 8.4), 125.69 d.t (s) (C , J = 162.9,
= 165.0, J
= 164.8, J
= 163.4, J
= 8.3),
= 8.0),
= 8.6),
12.2), 61.31 t.t.m (t) (C or C , J = 29.3, J
CH
CH
CH
CH
CH
CH
CF CH
7
1
3
27
23
1
2
149.9), 61.41 t.t.m (t) (C or C , J = 149.9, J
CH
28
CF
8
1
3
24
29.3), 113.5–113.7 four t.t (C , C ), 109.12 d.t.t.m
9
1
3
3
25
29
1
1
=
=
=
=
(t.t) (C or C , J = 242.2–245.0, J = 197.0,
CH
a
CH
CP
CH
CH
CH
CF CH
9
10
3
2
29
25
1
JCF = 34.8), 108.99 d.t.t.m (t.t) (C or C , J
=
CF
2
11
15
1
1
2
242.2–245.0, J = 197.0, J = 34.8), 64.56 t.d.q (d)
CP
CH CF
3
12
14
1
30
1
2
3
(C , J = 148.4, J = 6.6, J = 4.5), 15.27 q.d.t
CP CH
CP
CH
31
3
13
1
1
3
3
1
(d) (C , J = 127.6, J = 6.6, J = 3.0–3.5);
CH
CH
CH CP CH
3
16
3
1
J
= 7.4), 132.71 m (br.s) (C ), 133.26 br.d (br.s)
minor diastereoisomer: 47.14 d.d.t (d) (C , J
=
CP
CH
1
7
21
1
18
20
1
3
(
C , C , J = 166.6), 128.53 br.d (br.s) (C , C ,
132.1, J = 128.0–130.0, J = 2.7–3.0), 73.71 d (s)
CH
CH CH
1
19
3
2
4
2
5 3
JCH = 167.6), 134.89 t.t.d (d) (C , J = 10.5, J
=
=
(C , JCH = 5.8), 191.29 br.d.d (s) (C , JCH = 5.1, 3.8–
CH
22
CH
5
26
3
8
1
3
3
8
.0, J = 2.7), 163.04 d.d.t (d) (C or C , J
.7–9.0, J = 6.3, J = 3.2), 164.04 d.t (d) (C or
4.0), 136.04 d.d (s) (C , J = 164.0, J = 6.5),
CP
CH
26
CH CH
3
2
9
1
3
128.10 d.m (d) (C , J = 163.0, J = 1.8), 143.86 m
CH CP
CP
CH
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 12 2009