(2H, d), 3.36 (2H, d). 13CNMR (CDCl3 , 62.9 MHz)
d ¼ 134.2, 118.0, 117.0, 80.2, 72.9, 69.2, 32.5.
Table 5 The formation constants K for complexation of SCNꢀ with
some Co(II)-tetraarylporphyrins at 25 ꢂC
Catalyst
K/molꢀ1 dm3
3-Chloro-2-hydroxypropyl thiocyanate (2f). IR (neat): n SCN
(2168 cmꢀ1); 1HNMR (CDCl3 , 250 MHz) d ¼ 4.1 (1H, m), 3.7
(4H, m), 2.64 (1H, br s). 13CNMR (CDCl3 , 62.9 MHz)
d ¼ 117.8, 71.2, 46.1, 43.4.
5.1(ꢃ0.1) ꢁ 102
3.1(ꢃ0.05) ꢁ 103
1. 9(ꢃ0.1) ꢁ 101
8.5(ꢃ0.15) ꢁ 102
4(ꢃ0.2) ꢁ 102
II
Co TPP
II
Co T(p-OHP)P
II
Co T(3-Py)P
II
Co T(p-ClP)P
2-Hydroxyoctyl thiocyanate (2g). IR (neat): n SCN (2162
cmꢀ1); 1HNMR (CDCl3 , 250 MHz) d ¼ 3.91 (1H, m), 3.15
(1H, dd, J ¼ 13, J ¼ 3.5 Hz), 2.95 (1H, dd, J ¼ 13, J ¼ 7.5
Hz), 2.69 (1H, br s), 1.2–1.6 (10H, m), 0.88 (3H, m). 13CNMR
(CDCl3 , 62.9 MHz) d ¼ 113.2, 70.6, 41.5, 36.3, 32.0, 29.4,
25.8, 22.9, 14.4.
II
Co T(p-NO2P)P
(0.1 mmol) in CH2Cl2 (5 mL) was added and the mixture was
stirred under reflux for 20–170 min (in the case of Fe, Co, Mn,
Ni, Cu, and Zn metals, under nitrogen atmosphere). The reac-
tion was monitored by TLC or GC. After completion of the
reaction, the mixture was filtered and the solvent was evapo-
rated. Chromatography of the crude product was performed
on a column of silica gel eluted first with hexane for separation
of thiirane, followed by using C6H14–CH2Cl2 (1:1) for the
separation of 2-hydroxyethyl thiocyanate as a pale-yellow
liquid. Then, the metalloporphyrin complex was recovered
by elution with chloroform–ethyl acetate.
Acknowledgements
We gratefully acknowledge the support of this work by the
Shiraz University Research Council.
References
2-Hydroxy-2-phenylethyl thiocyanate (2a)7,12. IR (neat): n
1
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1
SCN (2160 cmꢀ1); HNMR (CDCl3 , 250 MHz) d ¼ 7.3 (5H,
m), 5.0 (1H, dd), 3.1–3.3 (2H, m), 2.4–2.9 (1H, br s). 13CNMR
(CDCl3 , 62.9 MHz) d ¼ 135.8, 129.5, 128.3, 126.2, 113.0, 72.9,
42.4.
2
3
4
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SCN (2163 cmꢀ1); 1HNMR (CDCl3 , 250 MHz) d ¼ 7.27
(2H, m), 6.92 (3H, m), 5.0 (1H, m), 4.2 (2H, d), 3.64 (2H, d).
13CNMR (CDCl3 , 62.9 MHz) d ¼ 158.0, 130.0, 122.0, 115.1,
114.9, 78.2, 67.2, 33.6.
2-Hydroxycyclohexyl thiocyanate (2c)7,9. IR (neat): n SCN
1
(2165 cmꢀ1); HNMR (CDCl3 , 250 MHz) d ¼ 2.95 (1H, m),
2.35 (1H, m), 2.15 (1H, s), 1.80 (2H, m), 1.65 (2H, m), 1.20–
1.50 (4H, m). 13CNMR (CDCl3 , 62.9 MHz) d ¼ 110.0, 72.0,
55.0, 34.5, 32.5, 30.5, 27.0.
2-Hydroxy-3-isopropoxypropyl thiocyanate (2d)33b. IR (neat):
n SCN (2170 cmꢀ1); 1HNMR (CDCl3 , 250 MHz) d ¼
3.74 (1H, m), 3.57 (3H, m), 3.33 (2H, d), 3.17 (1H, br s), 1.1
(6H, d, J ¼ 6 Hz). 13CNMR (CDCl3 , 62.9 MHz) d ¼
114.5, 79.4, 73.2, 67.6, 38.2, 23.0, 22.0.
5
3-Allyloxy-2-hydroxypropyl thiocyanate (2e)7. IR (neat): n
SCN (2158 cmꢀ1); 1HNMR (CDCl3 , 250 MHz) d ¼ 5.81
(1H, m), 5.1–5.25 (2H, m), 4.7 (1H, brs), 3.98 (3H, m), 3.6
6
7
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Fig. 3 Absorption spectra of Co TPP as catalyst (2 ꢁ 10ꢀ5 M) in the
II
presence of different concentrations of styrene oxide at 25 ꢂC in
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T h i s j o u r n a l i s Q T h e R o y a l S o c i e t y o f C h e m i s t r y a n d t h e
C e n t r e N a t i o n a l d e l a R e c h e r c h e S c i e n t i f i q u e 2 0 0 4
950
N e w . J . C h e m . , 2 0 0 4 , 2 8 , 9 4 6 – 9 5 1