70 Pashinnik, Borovikov, and Shermolovich
MS: m/z (%) = 311 (M+, 100). Anal. Calcd for
C14H14FNO2S2 (311.4): C, 54.00; H, 4.53; N, 4.50; S,
20.59. Found: C, 54.28; H, 4.64; N, 4.32; S, 20.37.
The Reaction of Triphenylphosphine with Phenyl-
N-(p-toluenesulfonyl)-sulfinimidoyl Fluoride (2a).
(a) The ratio of 6:7:5a in the reaction mixture was
1:0.24:0.87 (based on 31P NMR). Yield of 5a: 88%
(based on 31P NMR); 31P NMR (CHCl3): δ = 46.64 (s).
Yield of 8a: 78%; mp 60–62◦C (from ethanol) (Lit.
[19], 62–63◦C). Yield of triphenylphosphine oxide:
55%; mp 157–158◦C (from benzene) (Lit. [6], 156◦C).
Yield of 10a: 53%; mp 152–153◦C (from ethanol) (Lit.
p-Nitrophenyl-N-(p-toluenesulfonyl)-sulfinimidoyl
Fluoride (2c). Yield, 61%; mp 118–120◦C (de-
comp.); 19F NMR (CH3CN): δ = −3.19 (s, 1F); 1H
NMR (CDCl3): δ = 2.44 (s, 3H, CH3), 7.35 (d, 2H,
JHH = 8.10 Hz, Ar-H), 7.88 (d, 2H, JHH = 8.10 Hz,
Ar-H), 8.16 (d, 2H, JHH = 8.60 Hz, Ar-H), 8.45 (d,
2H, JHH = 8.60 Hz, Ar-H); IR (KBr): ν = 1060 (S N).
MS: m/z (%) = 342 (M+, 100). Anal. Calcd for
C13H11FN2O4S2 (342.4): C, 45.79; H, 3.24; N, 8.18; S,
18.73. Found: C, 45.61; H, 3.18; N, 8.45; S, 18.53.
1
[13], 152–153◦C). H NMR (CDCl3): δ = 2.35 (s, 6H,
CH3), 7.11 (d, 4H, JHH = 8.00 Hz, Ar-H), 7.30–7.42
(m, 3H, Ar-H), 7.56–7.59 (m, 2H, Ar-H), 7.67 (d, 4H,
JHH = 8.00 Hz, Ar-H). Yield of 7, 6%; mp 184–187◦C
(Lit. [14], 186–188◦C); 31P NMR (CHCl3): δ = 11.93
1
(s); H NMR (CDCl3): δ = 2.30 (s, 3H, CH3), 7.01 (d,
2H, JHH = 8.10 Hz, Ar-H), 7.42–7.51 (m, 8H, Ar-H),
7.55–7.60 (m, 3H, Ar-H), 7.70–7.77 (m, 6H, Ar-H).
(b) Yield of 8a: 54%. Yield of triphenylphosphine
oxide: 91%. Yield of 7: 72%.
General Procedure for the Reaction of
Triphenylphosphine with Fluorides 2a–c
(a) A solution of triphenylphosphine (0.60 g, 2.29
mmol) in benzene (10 mL) was added for 0.5 h to
2a–c (2.05 mmol) in benzene (20 mL). The reac-
tion mixture was stirred for 4 h at room temper-
ature, evaporated in vacuum, and analyzed. In ac-
cordance with 31P and 19F NMR (CHCl3) data, the
reaction mixture contained triphenyldifluorophos-
The Reaction of Triphenylphosphine with p-Tolyl-
N-(p-toluenesulfonyl)-sulfinimidoyl Fluoride (2b).
(a) The ratio of 6:7:5b in the reaction mixture was
1:0.28:0.86 (based on 31P NMR). Yield of 5b: 86%
(based on 31P NMR); 31P NMR (CHCl3): δ = 45.77
(s). Yield of 8b: 64%; mp 44–45◦C (from ethanol)
(Lit. [20], 45–46◦C). Yield of triphenylphosphine ox-
ide: 58%. Yield of 10b: 55%; mp 148–149◦C (from
ethanol) (Lit. [13], 149◦C); 1H NMR (CDCl3): δ = 2.39
(s, 9H, CH3), 7.18 (d, 4H, JHH = 8.20 Hz, Ar-H), 7.22
19
phorane 6 { F NMR: δ = –41.3 ppm (d, 2F, JPF = 664
Hz) [15]; 31P NMR: δ = –58.4 ppm (t, JPF = 663.5 Hz)
[16]}, phosphine imide 7 (31P NMR: δ = 11.9 ppm (s)
[17]), traces of triphenylphosphine oxide (31P NMR:
δ = 25.9 ppm (s) [18]), and salts 5a–c. The reaction
mixture was hydrolyzed by stirring the solution for
30 h on air with 1 mL of water. The solvent was
evaporated in vacuum. Compounds 8a,b were ex-
tracted from residue with ether (5 mL × 4), and com-
pounds 8c precipitated after dissolution of evapo-
rated reaction mixture in chloroform (10 mL). Triph-
enylphosphine oxide was extracted from the residue
with ether (20 mL × 3). Insoluble in ether, residue
was crystallized from ethanol to obtain compounds
10a–c. The filtrate was evaporated and washed with
benzene (2 mL) to get the residue of 7.
(d, 2H, JHH = 8.50 Hz, Ar-H), 7.54 (d, 2H, JHH
=
8.50 Hz, Ar-H), 7.65 (d, 4H, JHH = 8.20 Hz, Ar-H).
Yield of 7: 5%.
(b) Yield of 8b: 48%. Yield of triphenylphosphine
oxide: 96%. Yield of 7: 61%.
The Reaction of Triphenylphosphine with p-
Nitrophenyl-N-(p-toluenesulfonyl)-sulfinimidoyl Flu-
oride (2c). The ratio of 6:7:5c in the reaction mix-
ture was 1:0.17:0.92 (based on 31P NMR). Yield of
5c: 91.5% (based on 31P NMR); 31P NMR (CHCl3):
δ = 44.55 (s). Yield of 8c: 79%; mp 180–181◦C
(from benzene) (Lit. [4], 182–183◦C). Yield of triph-
enylphosphine oxide: 66%. Yield of 10c: 62%; mp
(b) The suspension of 2a,b (3.36 mmol) in benzene
(20 mL) was added for 0.5 h to triphenylphosphine
(1.35 g, 5.15 mmol) in benzene (20 mL). The reac-
tion mixture was stirred at room temperature for 3
h and analyzed. On the basis of 19F and 31P NMR
(C6H6) data, the reaction mixture contained 6 and 7.
Then, water (1 mL) was added to the mixture, which
was stirred for 12 h (hydrolysis of 6), and evapo-
rated in vacuum. Compounds 8a,b were extracted
from the evaporated residue with ether (10 mL × 4).
Then, triphenylphosphine oxide was extracted from
the residue with ether (30 mL × 3), and the solvent
was evaporated in vacuum. Insoluble in ether, com-
pound 7 was crystallized from benzene.
1
163–165◦C (from ethanol) (Lit. [13], 165–166◦C); H
NMR (CDCl3): δ = 2.39 (s, 6H, CH3), 7.18 (d, 4H,
JHH = 8.20 Hz, Ar-H), 7.68 (d, 4H, JHH = 8.20 Hz,
Ar-H), 7.76 (d, 2H, JHH = 8.90 Hz, Ar-H), 8.12 (d, 2H,
JHH = 8.90 Hz, Ar-H). Yield of 7: 4%.
The Reaction of Triphenylphosphine with p-
Nitrophenyl-N-(p-toluenesulfonyl)-sulfinimidoyl Ch-
loride (3). Either the solution of triphenylphos-
phine (1.26 g, 4.81 mmol) in benzene(15 mL) was
Heteroatom Chemistry DOI 10.1002/hc