Notes
J . Org. Chem., Vol. 64, No. 23, 1999 8697
orange band eluted with CCl4:CH2Cl2 (40:60) and gave a green
lustrous solid identified as 5,10,15,20-tetraphenyl-25,29-disel-
enasapphyrin. Yield 70 mg, 20%; mp decomposes above 350 °C.
1H NMR (300 MHz, CDCl3): δ 11.99 (br s, 1H), 10.57 (d, J ) 6
Hz, 2H), 10.30 (d, J ) 6 Hz, 2H), 8.99 (d, J ) 4 Hz, 2H), 8.88 (d,
J ) 4 Hz, 2H), 8.41-8.45 (m, 4H), 7.91-7.77 (m, 16H), -0.55
(s, 2H). MS (electro spray): m/z 810 (100%) [(M + 2)+]. Anal.
Calcd for C48H31N3Se2: C, 71.38; H, 3.87; N, 5.20. Found: C,
71.42; H, 3.64; N, 5.39%. UV-vis (CH2Cl2) λmax [nm] (ꢀ): 530
(48000), 659 (5100), 714 (8900), 787 (2600), 889 (3200); UV-vis
(CH2Cl2/1 equiv of TFA) λmax[nm] (ꢀ): 538 (33000), 755 (6400),
mg, 0.424 mmol), 5,10-diphenyl-16-thiatripyrrane (167 mg, 0.424
mmol), TFA (0.033 mL, 0.424 mmol), and chloranil (313 mg,
1.272 mmol) under similar reaction conditions as mentioned
above gave a purple solid identified as 5,10,15,20-tetraphenyl-
27-thia-25,29-diselenasapphyrin. Yield 112 mg, 32%; mp decom-
poses above 350 °C. 1H NMR (300 MHz, CDCl3): δ 10.57 (d, J
) 6 Hz, 2H), 10.27 (d, J ) 6 Hz, 2H), 8.79 (d, J ) 3 Hz, 2H),
8.75 (d, J ) 3 Hz, 2H), 8.40-8.37 (m, 4H), 7.94-7.72 (m, 16H),
1
-0.68 (s, 2H). H NMR (300 MHz, CDCl3/TFA): δ 10.16 (d, J )
4 Hz, 2H), 10.01 (d, J ) 4 Hz, 2H), 9.26 (d, J ) 4 Hz, 2H), 9.16
(d, J ) 4 Hz, 2H), 8.63 (m, 8H), 7.84-8.09 (m, 12H), -0.65 (s,
2H). MS (electro spray): m/z 827 (50%) [(M+2)+]. Anal. Calcd
for C48H30N2SSe2: C, 69.90; H, 3.67; N, 3.40. Found: C, 69.63;
H, 3.82; N, 3.33%. UV-vis (CH2Cl2) λmax[nm] (ꢀ): 523 (84200),
644 (12400), 695 (17400), 795 (4000), 903 (4300); UV-vis (CH2-
Cl2/1 equiv of TFA) λmax[nm] (ꢀ): 535 (62000), 699 (9700), 767
800 (9000), 840 (8000). UV-vis (CH2Cl2/2.5 equiv of TFA) λmax
-
[nm] (ꢀ): 545 (48000), 815 (15800).
5,10,15,20-Tetr a p h en yl-27-N-m eth yl-25,29-d iselen a sa p -
p h yr in (6b). 5,5′-Bis(phenylhydroxymethyl)-2,2′-biselenophene-
(200 mg, 0.424 mmol), 5,10-diphenyl-16-N-methyltripyrrane (166
mg, 0.424 mmol), TFA (0.033 mL, 0.424 mmol), and chloranil
(313 mg, 1.272 mmol) under similar reaction conditions as
mentioned above gave a green lustrous solid identified as
5,10,15,20-tetraphenyl-27-N-methyl-25,29-diselenasapphyrin.
(14000), 856 (11100). UV-vis (CH2Cl2/2.5 equiv of TFA) λmax
-
[nm] (ꢀ): 546 (103000), 731 (17000), 805 (34300), 856 (26600).
5,10,15,20-Tetr a p h en yl-25,27,29-tr iselen a sa p p h yr in (6e).
5,5′-Bis(phenylhydroxymethyl)-2,2′-biselenophene (200 mg, 0.424
mmol), 5,10-diphenyl-16-selenatripyrrane (188 mg, 0.424 mmol),
TFA (0.033 mL, 0.424 mmol), and chloranil (313 mg, 1.272 mmol)
under similar reaction conditions as mentioned above gave a
purple solid identified as 5,10,15,20-tetraphenyl-25,27,29-trise-
lenasapphyrin. Yield 105 mg, 28%; mp decomposes above 350
°C. 1H NMR (300 MHz, CDCl3): δ 10.54 (d, J ) 6 Hz, 2H), 10.24
(d, J ) 3 Hz, 2H), 8.76 (d, J ) 3 Hz, 2H), 8.61 (d, J ) 3 Hz, 2H),
8.39-8.36 (m, 6H), 7.93-7.69 (m, 14H), -0.82 (s, 2H). 1H NMR
(300 MHz, CDCl3/TFA): δ 10.36 (d, J ) 4 Hz, 2H), 10.14 (d, J )
6 Hz, 2H), 8.99 (d, J ) 6 Hz, 2H), 8.89 (d, J ) 4 Hz, 2H), 8.45-
8.38 (m, 8H), 8.00-7.75 (m, 12H), -0.98 (s, 2H). MS (electro
spray): m/z 873 (50%) [(M + 1)+]. Anal. Calcd for C48H30N2Se3:
C, 66.14; H, 3.47; N, 3.21. Found: C, 66.32; H, 3.21; N, 3.42%.
UV-Vis (CH2Cl2) λmax[nm] (ꢀ): 527 (88000), 643 (18900), 690
(18300), 803 (sh, 8100), 899 (7500); UV-Vis (CH2Cl2/1 equiv of
TFA) λmax[nm] (ꢀ): 536 (63300), 646 (13500), 698 (15600), 756
1
Yield 90 mg, 26%; mp decomposes above 350 °C. H NMR (300
MHz, CDCl3): δ 10.48 (d, J ) 4 Hz, 2H), 10.22 (d, J ) 6 Hz,
2H), 8.98 (d, J ) 4 Hz, 2H), 8.83 (d, J ) 4 Hz, 2H), 8.37-8.40
(m, 4H), 7.94-7.84 (m, 16H), 2.36 (s, 3H), -0.36 (s, 2H). MS
(electro spray): m/z 824 (30%) [(M + 2)+]. Anal. Calcd for
C
49H33N3Se2: C, 71.62; H, 4.05; N, 5.11. Found: C, 71.89; H, 4.42;
N, 5.32%. UV-vis (CH2Cl2) λmax[nm] (ꢀ): 531 (19600), 662 (1600),
715 (3300), 784 (1100), 883 (1100); UV-vis (CH2Cl2/1 equiv of
TFA) λmax[nm] (ꢀ): 538 (13500), 807 (3300), 847 (3200). UV-vis
(CH2Cl2/2.5 equiv of TFA) λmax[nm] (ꢀ): 548 (15800), 757 (sh,
1700), 822 (4600).
5,10,15,20-Te t r a p h e n yl-27-oxa -25,29-d ise le n a sa p p h y-
r in (6c). 5,5′-Bis(phenylhydroxymethyl)-2,2′-biselenophene (200
mg, 0.424 mmol), 5,10-diphenyl-16-oxatripyrrane (160 mg, 0.424
mmol), TFA (0.033 mL, 0.424 mmol), and chloranil (313 mg,
1.272 mmol) under similar reaction conditions as mentioned
above gave a green lustrous solid identified as 5,10,15,20-
tetraphenyl-27-oxa-25,29-diselenasapphyrin. Yield 72 mg, 21%;
mp decomposes above 350 °C. 1H NMR (300 MHz, CDCl3): δ
10.19 (d, J ) 3 Hz, 2H), 10.01 (d, J ) 6 Hz, 2H), 8.82 (d, J ) 6
Hz, 2H), 8.70 (d, J ) 3 Hz, 2H), 8.35-8.28 (m, 8H), 7.91-7.73
(m, 12H), 0.31 (s, 2H). 1H NMR (300 MHz, CDCl3/TFA): δ 10.18
(d, J ) 4 Hz, 2H), 10.00 (d, J ) 4 Hz, 2H), 8.80 (d, J ) 4 Hz,
2H), 8.70 (d, J ) 4 Hz, 2H), 8.36-8.26 (m, 8H), 7.88-7.71 (m,
12H), -0.31 (s, 2H). MS (electro spray): m/z 811 (55%) [(M +
2)+]. Anal. Calcd for C48H30N2OSe2: C, 71.29; H, 3.74; N, 3.46.
Found: C, 71.42; H, 3.96; N, 3.27%. UV-vis (CH2Cl2) λmax[nm]
(ꢀ): 532 (96000), 652 (9800), 709 (14300), 818 (1100), 928 (4200);
UV-vis (CH2Cl2/1 equiv of TFA) λmax[nm] (ꢀ): 541 (71200), 662
(3700), 714 (5600), 796 (11300), 862 (11200). UV-Vis (CH2Cl2/
2.5 equiv of TFA) λmax[nm] (ꢀ): 550 (91400), 785 (15700), 856
(13000).
(19500), 862 (13300). UV-vis (CH2Cl2/2.5 equiv of TFA) λmax
[nm] (ꢀ): 543 (65000), 686 (15000), 759 (21300), 862 (16000).
-
Ack n ow led gm en t. This work was supported by a
grant from the Department of Science and Technology
and Council of Scientific and Industrial Research, New
Delhi, India, to T.K.C.
Su p p or tin g In for m a tion Ava ila ble: X-ray structural
data for 5e and 6b, including X-ray experimental, summaries
of crystallographic parameters, atomic coordinates, anisotropic
displacement parameters, bond lengths and bond angles. This
material is available free of charge via the Internet at
http://pubs.acs.org.
5,10,15,20-Tet r a p h en yl-27-t h ia -25,29-d iselen a sa p p h y-
r in (6d ). 5,5′-Bis(phenylhydroxymethyl)-2,2′-biselenophene (200
J O990729U