PHOSPHONIUM-IODONIM YLIDES IN NUCLEOPHILIC SUBSTITUTION REACTIONS
205
trum (CD CN), δ, ppm: 3.55 br.s (3H, OCH ), 7.4–7.8 m
–0.72 m (CI), 13.13 s (CH ), 59.73 s (OCH ), 63.07 s
3
3
3
3
31
m
o
(
15H ). P NMR spectrum (CD CN), δ, ppm: 29.08 s.
(OCH ), 130.41 d (C , J 13.2 Hz), 133.98 d (C , J
2 CP CP
arom
3
13
p
C NMR spectrum (CD CN), δ, ppm: 53.17 s (OCH ),
10.1 Hz), 135.55 d (C , J 3.0 Hz), 164.81 m (CO).
3
3
CP
i
i
m
1
18.86 s (C ), 124.40 d (C , J 94.7 Hz), 130.53 (C ,
CP
(1-Bromo-2,2-diethoxyvinyl)triphenylphos-
m
p
JCP 12.8 Hz), 132.73 s (C ), 132.98 s (C ), 134.17 s (C°),
1
1
phonium borofluoride (V). Reaction time 24 h. Yield
p
34.77 d (C°, JCP 10.4 Hz), 134.83 d (C , J 2.8 Hz),
1
CP
0.085 g (50%). H NMR spectrum (DMSO-d ), δ, ppm:
6
68.53 d (C=O, JCP 14.3 Hz). Found, %: C 52.35; H 3.92.
0.94 t (3H, CH ), 1.22 t (3H, CH ), 4.02 m (4H, 2CH ),
3
3
2
C H BF IO P. Calculated, %: C 52.66; H 3.90.
31
27
23
4
2
7.75–7.89 m (15Harom). P NMR spectrum (DMSO-d ),
6
Phenyliodoniumcyanomethylenetriphenyl-
δ, ppm: 25.79 s.
phosphorane borofluoride (IIIc). To 5 ml of anhydrous
methanol was gradually added 0.01 gram-atom of sodium
metal, and after its complete dissolution a solution of
{
1-Chloro-2-ethoxy-2-[(trimethylsilyl)oxy]vinyl}-
triphenylphosphonium borofluoride (VI). To a solu-
tion of 0.2 g (0.314 mmol) of ylide IIIa in 5 ml of anhy-
drous dichloromethane 0.034 g (0.314 mmol) of
trimethylsilyl chloride was added. The reaction mixture
was stirred for 4 h under argon flow. The end of reaction
was established by disappearance of ylide IIIa (TLC
monitoring). Yield 0.17 g (100%). H NMR spectrum
CDCl ), δ, ppm: 0.07 d (3H, SiMe ), 0.23 d.d (6H, SiMe ),
.06 t (3H, CH ), 4.12 q (2H, CH ), 7.70–7.92 m
3 2
15Harom). P NMR spectrum (CDCl ), δ, ppm: 29.37 s.
0.01 mol of phosphonium salt Ia in 5 ml of anhydrous
methanol was dropwise added. The reaction mixture was
cooled with ice water for 1 h to achieve complete pre-
cipitation of sodium chloride. The solution of ylide IIc
was filtered off from the sodium chloride precipitate,
cooled to 0°C, and a solution of 0.01 mol of phenyliodoso
acetate in 8 ml of anhydrous methanol was added main-
taining the temperature of the reaction mixture below 0°C.
1
(
1
(
13
3
3
3
31
3
Then 0.01 mol of 40% HBF solution was added main-
4
C NMR spectrum (CDCl ), δ, ppm: 0.05 s, 0.20 s
SiMe ), 13.47 s (CH ), 49.15 d (C , J 54.9 Hz),
3
taining the temperature of the reaction mixture at 0°C.
The solution was stirred at this temperature for 1 h, then
1
(
6
(
(
3
3
CP
i
4.84 s (OCH ), 115.54 d (C , J 87.0 Hz), 130.38 d
2 CP
5
ml of ethyl ether was added, and the stirring was con-
m
o
C , J 13.2 Hz), 134.51 d (C , J 11.0 Hz), 135.80 d
CP CP
tinued for 1 h more. The separated precipitate was fil-
tered off, washed with ether, and dried in air. Yield 70%,
p
C , J 2.9 Hz), 157.17 s (CO).
CP
(
2-Ethoxy-1-{phenyl[(trifluoroacetyl)oxy]-λ3-
–
1
–)
mp 190–191°C. IR spectrum, ν, cm : 1150 (BF , 2160
4
iodanil}-2-[(trifluoroacetyl)oxy]-vinyl)(triphenyl)-
phosphonium borofluoride (VII). To a solution of
.2 g (0.314 mmol) of ylide IIIa in 5 ml of anhydrous
dichloromethane 0.132 g (0.628 mmol) of trifluoroacetic
anhydride was added. The reaction mixture was stirred
for 4 h under argon flow. The end of reaction was estab-
lished by disappearance of ylide IIIa (TLC monitoring).
The solvent was removed on a rotary evaporator. The
residue was washed with anhydrous ethyl ether. Yield
1
(
7
2
(
CN). H NMR spectrum (DMSO-d ), δ, ppm: 7.2–
.8 m (15H ). P NMR spectrum (CH CN), δ, ppm:
arom 3
6
31
0
13
5.7 s. C NMR spectrum (DMSO-d ), δ, ppm: 0.01 d
6
1
i
C , J 123.9 Hz), 118.76 s (C ), 119.45 d (CN,
CP
i
m
JCP 2.8 Hz), 119.85 d (C , J 93.0 Hz), 129.92 d (C ,
JCP 12.7 Hz), 131.25 s (C ), 131.62 s (C ), 133.05 s (C°),
33.58 d (C°, JCP 10.4 Hz), 134.59 d (C , J 2.8 Hz).
CP
m
p
p
1
CP
Alkylation of ylide IIIa. General procedure. To
a solution of 0.2 g (0.314 mmol) of ylide IIIa in 5 ml of
anhydrous dichloromethane 0.628 mmol of alkyl halide
was added. The reaction mixture was stirred under ar-
gon flow. The end of reaction was established by disap-
pearance of ylide IIIa (TLC monitoring). The solvent
was removed on a rotary evaporator. The residue was
washed with anhydrous ethyl ether.
–1
–
0
(
(
.2 g (80%). IR spectrum, ν, cm : 1080 (BF ), 1445
4
1
PC H ), 1590 (C=C), 1750 (C=O). H NMR spectrum
6 5
CDCl ), δ, ppm: 0.96 t (3H, CH ), 4.06 q, 4.10 q (2H,
3
3
31
CH ), 7.70–7.92 m (15Harom). P NMR spectrum
2
13
(
(
(
CDCl ), δ, ppm: 27.37 s, 27.60 s. C NMR spectrum
3
CDCl ), δ, ppm: 13.26 s (CH ), 64.97 s (OCH ), 69.51 d
3
3
2
1
i
C , J 65.2 Hz), 113.66 d (C , J 87.8 Hz), 130.28 s
CP
CP
p
m
m
(
2-Ethoxy-1-iodo-2-methoxyvinyl)triphenyl-
(C ), 130.70 d (C , JCP 13.2 Hz), 134.32 s (C ), 134.42 d
o
p
phosphonium borofluoride (IV). Reaction time 6 h.
(C , JCP 11.0 Hz), 136.46 d (C , JCP 3.6 Hz), 137.46 s
o
–
1
–
(C ), 161.47 s (C=O), 187 s (CO).
Yield 0.18 g (100%). IR spectrum, ν, cm : 1080 (BF ),
4
1
1
1
7
590 (C=C). H NMR spectrum (DMSO-d ), δ, ppm:
.00 t (3H, CH ), 3.38 s (3H, OCH ), 4.05 q (2H, CH ),
.48–7.82 m (15H ). P NMR spectrum (DMSO-d ),
δ, ppm: 23.59 s. C NMR spectrum (DMSO-d ), δ, ppm:
The study was carried out under a financial support of
the Russian Foundation for Basic Research (grant no.
05-03-33054) and of the President of the Russian Fed-
eration (grant for supporting the leading scientific schools
6
3
3
2
31
arom
6
13
6
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 2 2007