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reduced pressure distillation at 100 °C/0.06 mmHg to give a colorless
liquid (yield = 0.71 g, 73%).
140.29 (i-Ph−CH3), 141.78 (i-Ph−S). GPC data for 5d: Mw = 8.5 ×
104; PDI = 1.4. DSC data for 5d: Tg = 54.7 °C.
N-Silyltolylsulfonamide, 8d. 1H NMR (CDCl3) δ(ppm): 0.14 (s,
9H, Me3Si), 2.42 (s, 3H, CH3−Ph), 2.54 (s, NH), 7.44 (d, 2H; CH
C−CH3, Jom = 8 Hz), 7.98 (d, 2H; CHC−S, Jom = 8 Hz). 13C NMR
(CDCl3) δ(ppm): 2.49 (CH3−Si), 21.80 (CH3−Ph), 127.05 (o-Ph),
130.22 (m-Ph), 141.73 (i-Ph-S), 146.58 (i-Ph−CH3).
ASSOCIATED CONTENT
* Supporting Information
■
S
Details of calculated structures and MOs for N-(trimethylsilyl)-
methanesulfonamide model compounds; calculated .mol files
for the model compounds are available from the authors upon
request. This material is available free of charge via the Internet
Attempted Synthesis of N-Silylmethylsulfonimidoyl Chlor-
ide, 6a. A solution of 8a (0.194 g, 1.04 mmol) in toluene (ca. 25 mL)
was prepared in a round-bottom flask equipped with a magnetic
stirring bar, gas inlet, and rubber septum in an inert atmosphere. Et3N
(0.436 mL, 3.13 mmol) was added dropwise to the reaction mixture,
resulting in the formation of a yellow suspension. The reaction mixture
was cooled in a dry ice/acetone bath to −78 °C, and SOCl2 (0.152
mL, 2.09 mmol) was added dropwise to the solution; the resulting
mixture was stirred at this temperature for 2 h.
AUTHOR INFORMATION
Corresponding Author
+14169795044.
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6a: 1H NMR (reaction mixture at 2 h): 1H NMR (CDCl3) δ
(ppm): 0.53 (s, Me3Si, 9H), 3.31 (s, Me−S, 3H).
Notes
The cooling bath was subsequently removed, and the reaction
mixture was warmed to room temperature which resulted in the
formation of a dark brown color. Analysis of the reaction mixture by
1H NMR of the nonvolatile components of the reaction mixture
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
A.R.M. acknowledges the Ryerson University FEAS Dean’s
Research Fund and the Ryerson Experiential Learning
Academic Research Assistant Program for support. D.A.F.
acknowledges the Natural Sciences and Engineering Research
Council of Canada for support. R.A.G. acknowledges the
Natural Sciences and Engineering Research Council of Canada
and the Ryerson University FEAS Dean’s Research Fund for
support. B.P. acknowledges the Ryerson University Research
Opportunity program for support.
indicated that decomposition of 6a occurs in solution when the sample
is held at ambient temperature of −35 °C for periods of longer than
2−3 h. After removal of the solvent and volatile by products in vacuo, a
tacky dark brown solid remained. The sample was purified by
precipitation from CH2Cl2 to Et2O three times yielding a tacky off-
white powder, 5a. GPC analysis of this powder showed that
poly(methyloxothiazene) was one of the products of the decom-
position.
5a: 1H NMR (CDCl3) δ (ppm): 3.18 ppm (s, 3H, Me−S);
(CD3)2SO) δ (ppm) 3.54 (s, 3H, Me−S).
General Procedure for the in Situ Synthesis of Polyox-
othiazenes. A solution of 8a (0.748 g, 4.03 mmol) in toluene (ca. 40
mL) prepared in a round-bottom flask equipped with a magnetic
stirring bar, gas inlet and rubber septum in an inert atmosphere. Et3N
(1.68 mL, 12.1 mmol) was added dropwise to the reaction mixture,
resulting in the formation of a yellow suspension. The reaction mixture
was cooled in a dry ice/acetone bath to −78 °C, and SOCl2 (0.585
mL, 8.05 mmol) was added dropwise to the solution; the resulting
mixture was stirred at this temperature for 60 min. The cooling bath
was subsequently removed, and the reaction mixture warmed to room
temperature, which resulted in the immediate formation of a dark
brown color. A solution of PCl5 (8.2 mg, 0.039 mmol) in toluene was
added to the reaction mixture and the subsequently allowed to stir for
2 h. Solvent and impurities were removed in vacuo, yielding a gummy,
brown product. The material was purified by precipitation from
CH2Cl2 solution into Et2O three times, resulting in a light brown
powder (polymer yield: 0.29 g, 94%).
REFERENCES
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Poly(methyloxothiazene), 5a. 1H NMR ((CD3)2SO) δ (ppm):
1
3.54 (s, 3H, Me−S). H NMR (CDCl3) δ (ppm): 3.18 ppm (s, 3H,
Me−S). 13C NMR (CDCl3) δ (ppm): 43.20 (Me3S). GPC data for 5a:
Mw = 3.3 × 105; PDI = 1.2. DSC data for 5a: Tg = 40.9 °C.
The same procedure was followed for the preparation of polymers
5b−d, substituting 5b−d, respectively. Additional precipitations were
required to remove final traces of HNEt3Cl, which has similar
solubility properties to 5b−d.
Poly(ethyloxothiazene), 5b. Yield: 0.20 g (79%) based on 5b (0.51
g, 2.8 mmol). 1H NMR ((CD3)2SO) δ (ppm): 3.45 (Br, CH3−CH2−
S). GPC data for 5b: Mw = 6.7 × 104, PDI = 1.6. DSC data for 5b: Tg
= 32.8 °C.
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Poly(phenyloxothiazene), 5c. Yield: 0.35 g, 81% based on 5c (0.72
g, 3.1 mmol). 1H NMR ((CD3)2SO) δ (ppm): 7.33−7.62 (m, Ar, 5H).
13C NMR (CDCl3) δ (ppm): 126.28 (o-Ph), 128.14 (p-Ph), 128.85
(m-Ph), 132.16 (i-Ph-S). GPC data for 5c: Mw = 1 × 105, PDI = 1.3.
DSC data for 5c: Tg = 32.2 °C.
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=
9.7 Hz), 7.14 (d, Ar, 2H, Jom = 9.7 Hz), 2.28 (s, CH3−Ar). 13C NMR
(CDCl3) δ (ppm): 21.31 (CH3−Ph), 125.90 (o-Ph), 128.81 (m-Ph),
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dx.doi.org/10.1021/ma302424u | Macromolecules XXXX, XXX, XXX−XXX