P. Haiss, K.-P. Zeller
FULL PAPER
plet (δ = 2.86 ppm, CD2 H) and a triplet (δ = 2.89 ppm, CDH2) for
the residual protons remained (ca. 3% 1H by integration against
internal dioxane). Work-up as described[1] and recrystallization
from dry methanol furnished pure [D9]1 iodide. 1H NMR (D2O)
spectroscopy with dioxane as internal reference indicates a small
131.5 (C-3), 136.1 (C-1Ј), 142.9 (C-2), 150.1 (C-1) ppm. MS
(70 eV): m/z (%) = 243 (Ͻ 1), [M+·], 137 (14), 91 (100).
3-Methyl-2-nitrobiphenyl (12): Compound 12 was obtained as
colourless crystals (m. p. 85–85.5 °C, ref.[12a]: m. p. 85–85.5 °C);
yield 74 mg (50% calculated for consumed starting material). 1H
NMR (400 MHz, CDCl3): δ = 2.30 (s, 3 H, CH3), 7.19 (m, 2 H, 4-
H, 6-H), 7.25 (m, 1 H, 5-H), 7.28 (m, 1 H, 4Ј-H), 7.30–7.39 (m, 4
H, 3Ј/5Ј-H, 2Ј/6Ј-H) ppm. 13C NMR (100 MHz, CDCl3): δ = 17.4
(CH3), 128.0 (C-3Ј/5Ј), 128.4 (C-4Ј*), 128.6 (C-6*), 128.7 (C-2Ј/6Ј),
129.7 (C-1Ј), 130.0 (C-4**), 130.2 (C-5**), 134.3 (C-1), 136.7 (C-
3), 150.8 (C-2) ppm. MS (70 eV): m/z (%) = 213 (33) [M+·], 196
(99), 185 (77), 168 (76), 165 (89), 156 (100), 152 (78), 142 (26), 139
(25) (*,** exchangeable).
1
increase of the H content to 5% after work-up. The deuteriation
degree of 95% was confirmed by mass spectrometry. In the heated
inlet probe of the EI source, the deuteriated sulfonium iodide de-
composes into dimethyl sulfide and iodomethane, whose deuter-
iation degrees were determined from the corresponding M+· ions.
Methylation of Nitrobenzenes 7–9
General Procedure: Sodium hydride in paraffin (2.5 mmol NaH)
was suspended in dry DMF (6.5 mL) and cooled in an ice bath.
After addition of trimethylsulfonium iodide (2.5 mmol) and stirring
for several min, the nitrobenzenes (1.25 mmol) dissolved in DMF
(1 mL) were added, and the mixture was warmed up to room tem-
perature over 16 h. The reaction mixture was poured onto ice and
extracted with light petroleum (5ϫ20 mL). The extracts were
washed with brine (2ϫ25 mL), dried with Na2SO4, and the solvent
was removed. Flash chromatography with mixtures of PE 40/60
and CH2Cl2 furnished the methylation products and unreacted
starting compounds.
Acknowledgments
The authors thank Mrs. Claudia Krause for careful mass spectro-
metric measurements.
[1] W. v. E. Doering, A. K. Hoffman, J. Am. Chem. Soc. 1955, 77,
521–526.
[2] J. Shorter in The Chemistry of the Sulfonium Group (Ed.: J. M.
Stirling), John Wiley and Sons, Chichester, 1981, part 1, pp.
222–224.
[3] G. Boche, J. C. N. Lohrenz, J. Cieslowski, W. Koch in The
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Sulfur-Containing Functional Groups (Eds.: S. Patai, Z. Rappo-
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Padwa, D. Bellus), Thieme Verlag Stuttgart, New York, 2004,
vol. 27, pp. 21–104.
1-Methoxy-3-methyl-2-nitrobenzene (10): Compound 10 was ob-
tained as a yellow oil; yield: 58 mg of 10 (42% calculated for con-
sumed starting material); the spectroscopic data agree with those
given in the SDBS database and ref.[28] 1H NMR (400 MHz,
.
CDCl3): δ = 2.29 (s, 3 H, CH3), 3.86 (s, 3 H, OCH3), 6.84 (d, J =
7.8 Hz, 1 H, 4-H), 6.86 (d, J = 8.3 Hz, 1 H, 6-H), 7.29 (t, J =
8.1 Hz, 1 H, 5-H) ppm. 13C NMR (100 MHz, CDCl3): δ = 16.9
(CH3), 56.2 (OCH3), 109.9 (C-6), 122.5 (C-4), 130.6 (C-5), 130.9
(C-3), 142.0 (C-2), 150.7 (C-1) ppm. MS (70 eV): m/z (%) = 167
(98) [M+·], 150 (100) [[M – OH]+], 135 (9), 120 (8), 105 (26), 91
(67), 77 (37).
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Methylation of 3-Deuterio-2-nitroanisole ([D]7): This reaction was
performed as described for the unlabelled compound 7 and pro-
duced a methylation compound consisting of 96% unlabelled 10
and 4% monolabelled [D]10. This follows from the relative inten-
sities for the peaks at m/z 167 and 168 (100:13) in the molecular
ion region, after correction for the natural 13C 4% deuterium incor-
poration into the methyl group was calculated. MS analysis of the
recovered nitroanisole revealed complete retention of the deuterium
incorporation.
Methylation of 2-Nitroanisole (7): This reaction was carried out as
described before, except that perdeuteriated trimethylsulfonium
[14] H. M. Bell, W. Vanderslice, A. Spehar, J. Org. Chem. 1969, 34,
1
iodide was applied. H NMR (400 MHz, CDCl3): δ = 2.24–2.30
3923–3930.
(m, 0.03 H, composed of a triplet for CDH2 and a quintuplet for
CD2 H, JC,D = 2.3 Hz, the approximate intensity ratio is 1:8), 3.87
(s, 3 H, OCH3), 6.85 (m, 2 H, 4-H, 6-H), 7.29 (m, 1 H, 5-H) ppm.
The molecular ion peak region of the EI-MS showed the following
intensity distribution. m/z (%) = 171 (9), 170 (100), 169 (37), 168
(5), 167 (Ͻ 1). This corresponds to a composition of 70% [D3]10,
26.5% [D2]10 and 3.5% [D]10.
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Crystallogr., Sect. C 1994, 50, 1101–1104.
[17] For the role of the sulfurane intermediates in organic sulfur
chemistry see: J. Drabowicz, P. Lyzwa, M. Mikolajczyk in The
Chemistry of Functional Groups Suppl. S, The Chemistry of the
Sulfur-Containing Functional Groups (Eds.: S. Patai, Z. Rappo-
port), J. Wiley and Sons, Chichester, 1993, pp. 799–956.
[18] M. Makosza, Chem. Soc. Rev. 2010, 39, 2855–2868 and refer-
ences cited therein.
[19] J. K. Borchardt, R. Hargreaves, W. H. Saunders Jr., Tetrahe-
dron Lett. 1972, 13, 2307–2308.
[20] F. G. Bordwell, Acc. Chem. Res. 1988, 21, 456–463.
[21] M. Schwörer, J. Wirz, Helv. Chim. Acta 2001, 84, 1441–1458.
[22] J. Lelievre, P. G. Farrell, F. Terrier, J. Chem. Soc. Perk. Trans.
2 1986, 333–336.
1-Benzyloxy-3-methyl-2-nitrobenzene (11): Compound 11 was ob-
tained as a yellow oil; yield: 92 mg (44% calculated for consumed
starting material). 1H NMR spectroscopic data agree with those
1
reported in ref.[29]. H NMR (400 MHz, CDCl3): δ = 2.31 (s, 3 H,
CH3), 5.16 (s, 2 H, CH2), 6.85 (d, J = 7.8 Hz, 1 H, 4-H), 6.89 (d,
J = 8.3 Hz, 1 H, 6-H), 7.25 [t (broad), J = 8.1 Hz, 1 H, 5-H], 7.33
(m, 1 H, 4Ј-H), 7.65 (m, 4 H, 3Ј/5Ј-H, 2Ј/6Ј-H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 17.4 (CH3), 71.3 (CH2), 112.0 (C-6), 123.3
(C-4), 127.4 (C-2Ј/6Ј), 128.6 (C-4Ј), 129.1 (C-3Ј/5Ј), 130.9 (C-5), [23] L.-J. Chen, L. T. Burka, Tetrahedron Lett. 1998, 39, 5351–5354.
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