2012
J.S. Dhau et al. / Journal of Organometallic Chemistry 696 (2011) 2008e2013
slowly brought to room temperature and hydrolyzed. Yield: 1.26 g,
(70%), viscous oil. 1H NMR: CDCl3, 400 MHz
(ppm): 8. 05 (2H, s),
7.05 (2H, s), 2.36 (3H, s), 2.11 (6H, s). 13C NMR: CDCl3, 400 MHz
(ppm): 152.01, 147.36, 137.07, 132.57, 129.06, 19.39, 17.60, 5.21. MS
(EI, 70 eV) m/z (relative intensity): 201 (100), 186 (64), 121 (99), 106
(75), 92 (25), 77 (61). Anal. (%) Calcd for C8H11NSe: C, 48.02, H, 5.54,
N, 7.00. Found: C, 48.33, H, 5.75, N, 7.13.
4.5. 3-(Carbylselenomethyl)-2,6-bis(selenomethyl)-5-picoline (10)
d
LDA (27.9 mmol) was added slowly to the BF3-complexed 3,5-
lutidine (2, 9 mmol) in a drop-wise manner via cannula. Elemental
selenium (2.20 g, 27.9 mmol) was added to the orange brown
solution at ꢁ78 ꢀC. After the complete dissolution of selenium, the
blackish brown solution was cooled to ꢁ78 ꢀC and iodomethane
(3.96 g, 1.73 ml, 27.9 mmol) was added to it. The reaction mixture
was slowly brought to the room temperature and hydrolyzed. Yield
d
4.2.4. 2-Thiomethyl-3,5-lutidine (6a)
Elemental selenium in the above procedure was replaced with
0.18 g, (5%). 1H NMR: CDCl3, 400 MHz
(2H, s), 2.43 (3H, s), 2.42 (3H, s), 2.09 (3H, s), 1.88 (3H, s). 13C NMR:
CDCl3, 400 MHz (ppm): 152.10, 150.27, 136.13, 131.55, 128.04,
d (ppm): 6.92 (1H, s), 3.58
elemental sulfur. Yield: 0.72 g, (52%), viscous oil. 1H NMR: CDCl3,
400 MHz
d
(ppm): 8.06 (2H, s), 7.05 (2H, s), 2.48 (3H, s), 2.15 (3H, s),
(ppm): 155.08, 146.47,
d
2.13 (3H, s). 13C NMR: CDCl3, 400 MHz
d
24.39, 18.24, 4.94, 4.49, 4.08. MS (EI, 70 eV) m/z (relative intensity):
389 (16), 294 (100), 279 (32), 198 (33), 118 (33), 103 (55), 93 (37), 88
(16), 77 (70). Anal. (%) Calcd for C10H15NSe3: C, 31.12, H, 3.91, N, 3.62.
Found: C, 30.92, H, 3.15, N, 3.52.
137.54, 130.38, 128.29, 18.35, 17.61, 13.05. MS (EI, 70 eV) m/z (rela-
tive intensity): 153 (82), 138 (16), 120 (100), 106 (40), 92 (26), 77
(38).
4.2.5. 2-Telluromethyl-3,5-lutidine (6c)
4.6. Crystal structure determination and refinement
Elemental selenium in the procedure 4.2.3 was replaced with
elemental tellurium. Yield: 1.36 g, (61%), viscous oil. 1H NMR:
Single-crystal X-ray data were collected using graphite-mono-
ꢀ
CDCl3, 400 MHz
d
(ppm): 8.18 (2H, s), 7.08 (2H, s), 2.30 (3H, s), 2.22
(ppm): 148.45,
chromated Mo K
a
radiation (
l
¼ 0.71073 A) on “Bruker SMART
(3H, s), 2.19 (3H, s). 13C NMR: CDCl3, 400 MHz
d
APEX CCD diffractometer” at 100 K. The linear absorption coeffi-
cients, scattering factors for the atoms and the anomalous disper-
sion corrections were taken from the International Tables for X-ray
Crystallography [18]. The program SMART [19] was used for col-
lecting frames of data, indexing reflections, and determining lattice
parameters. The data integration and reduction were processed
with SAINT [19] software. An empirical absorption correction was
applied to the collected reflections with SADABS [20] using XPREP
[21]. All the structures were solved by the direct method using the
program SHELXS-97 [22] and were refined on F2 by the full-matrix
least-squares technique using the SHELXL-97 program package. All
non-hydrogen atoms were refined with anisotropic displacement
parameters in all the structure. All other relevant information about
the data collection and refinement are presented in Table 4.
139.58, 136.91, 136.11, 129.87, 21.82, 17.58, ꢁ15.34. MS (EI, 70 eV) m/
z (relative intensity): 251 (25, 130Te), 236 (22), 121 (70), 106 (100),
77 (56).
4.3. General procedure 2: dilithiation of 3,5-lutidine
LDA (26.4 mmol) was added slowly to the BF3-complexed 3,5-
lutidine (2, 12 mmol) via cannula. The color of suspension changed
from white to orange brown in about 10 min. The orange brown
solution was stirred for 15 min at ꢁ78 ꢀC.
4.3.1. 2,6-Bis(selenomethyl)-3,5-lutidine (7)
Elemental selenium (2.08 g, 26.4 mmol) was added to the above
solution at ꢁ78 ꢀC. The temperature was raised slowly until
complete dissolution of selenium took place. The blackish brown
solution was again cooled to ꢁ78 ꢀC and iodomethane (3.74 g,
1.64 ml, 26.4 mmol) was added to it. The reaction mixture was
slowly brought to the room temperature, hydrolyzed and purified.
Acknowledgements
We are thankful to the CSIR, New Delhi, India, for financial
support. Additional support from SAP by UGC, New Delhi, is also
acknowledged. We are also thankful to Mr. Avtar Singh, CIL, Punjab
University, Chandigarh, for NMR spectra. Thanks are also acknowl-
edged to Prof. P. Bhardwaj and Dr. Kamlesh Thapliyal, and Dr. Sar-
vendra Kumar IIT, Kanpur, for single-crystal X-ray studies on 5 and 7.
Yield: 2.6 g, (64%), mp 79e80 ꢀC. 1H NMR: CDCl3, 400 MHz
6.94 (1H, s), 2.50 (6H, s), 2.16 (6H, s). 13C NMR: CDCl3, 400 MHz
(ppm): 151.34, 136.90, 128.65, 18.48, 5.40. MS (EI, 70 eV) m/z
d (ppm):
d
(relative intensity): 295 (35), 280 (7), 214 (100), 200 (23), 185 (8),
120 (36), 105 (30), 90 (8), 77 (81). Anal. (%) Calcd for C9H13NSe2: C,
36.89, H, 4.47, N, 4.78. Found: C, 36.98, H, 4.25, N, 4.54.
Appendix A. Supplementary material
CCDC 786929 and 786928 contain the supplementary crystal-
lographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via www.
4.4. 6-Selenomethyl-2-thiomethyl-3,5-lutidine (9)
To a reaction mixture containing 4a (12 mmol), LDA (13.2 mmol)
was added in a drop-wise manner via cannula at ꢁ78 ꢀC. The
solution turned from viscous yellow to yellowish brown. Elemental
selenium (1.04 g, 13.2 mmol) was added to the reaction mixture
and after all the selenium had dissolved, iodomethane (3.74 g,
1.64 ml, 26.4 mmol) was added at ꢁ78 ꢀC. The reaction mixture was
slowly brought to the room temperature, hydrolyzed and purified.
Yield: 0.75 g, (25%), mp 70e71 ꢀC. 1H NMR: CDCl3, 400 MHz
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d
(ppm): 6.96 (1H, s), 2.61 (3H, s), 2.49 (3H, s), 2.16 (3H, s), 2.15 (3H,
s). 13C NMR: CDCl3, 400 MHz
d
(ppm): 154.59, 150.80, 137.22, 127.77,
126.27, 18.50, 17.45, 13.24, 5.35. MS (EI, 70 eV) m/z (relative inten-
sity): 247 (58), 215 (5), 166 (100), 152 (26), 137 (7), 105 (10), 92 (18),
77 (47). Anal. (%) Calcd for C9H13NSSe: C, 43.72, H, 5.26, N, 5.66.
Found: C, 44.28, H, 4.98, N, 5.33.