Synthesis and Crystal Structure of Stable Benzothiazole Enol†

doi:10.7503/cjcu20130621

Abstract

Abstract:

As an important organic functional compound, 2-methylbenzothiazole derivatives has been widely used in sensitizing dyes. In the process of sythesis of dyes, the dye intermediates could be hydrolyzed to form another substance easily. In order to determine the structure of the new substance, a dye intermediate, named 2-(2-ethoxy-1-butenyl)-1-(3-sulfopropyl)benzothiazole(3), was synthesized using 2-methyl benzothiazole and 1,3-propane sultone as the starting material, then hydrolyzed in water to form the new substance(4e), which was characterized by IR, ¹H NMR, ¹³C NMR, MS, elemental analysis and X-ray diffraction methods. The MS spectrum showed the molecular weight of the product was 327, which was corresponding to the target compound 4e. The ¹³C NMR spectrum showed the chemical shift of the carbon that connected to the enol hydroxyl group was δ 194.05, and the chemical shift of the carbon that connected to the double bond was 92.52, which implied the existence of enol structure. The IR spectrum also showed the enol hydroxyl characteristic absorption peak at 1618 cm^-1. X-Ray diffraction displayed the structure of the target compound intuitively. Through the characterizations of the compound, the new substance was comfirmed to be a stable enol that contained the conjugated aromatic structure.

Key words: Benzothiazole, Enol, Crystal structure

CLC Number:

O626

TrendMD:

HUO Baolong, XUE Lingwei, YANG Yunxu, YANG Chao, LI Dazhi, WANG Aizhi, YU Feifei, HU Biwei. Synthesis and Crystal Structure of Stable Benzothiazole Enol^†[J]. Chem. J. Chinese Universities, 2014, 35(2): 270.

Figures/Tables 7

References 18

[1]	Hart H., Chem. Rev., 1979, 79, 515—528
[2]	Nakabayashi T. J., J. Am. Chem. Soc., 1960, 82(2), 390—391
[3]	Rappoport Z., Biali S. E., Acc. Chem. Res., 1988, 21(12), 442—449
[4]	Mukhopadhyaya J. K., Sklenak S., Rappoport Z., J. Am. Chem. Soc., 2000, 122(7), 1325—1328
[5]	Campbell R. D., Gilow H. M., J. Am. Chem. Soc., 1962, 84(8), 1440—1443
[6]	Gero A., J. Org. Chem., 1954, 19(12), 1960—1963
[7]	Capon B., Guo B. Z., Kwok F. C., Siddhanta A. K., Zucco C., Acc. Chem. Res., 1988, 21(4), 135—140
[8]	Xu Z. L., Huang N. Z., Chin. J. Org. Chem., 1996, 16, 440—444
	(许遵乐, 黄乃正.有机化学, 1996, 16, 440—444)
[9]	Hu Q. S., Xi Z. F., Chin. J. Org. Chem., 2008, 28(11), 1864—1874
	(胡乔舒, 席振峰.有机化学,2008, 28(11), 1864—1874)
[10]	Sun Y. D., Jiang H. F., Wu W. Q., Zeng W., Wu X., Org. Lett., 2013, 15(7), 1598—1601
[11]	Fabrizio P., Fredric M. M., J. Org. Chem., 2008, 73(7), 1960—1963
[12]	James A. S., Sylvain L., Stephen J. M., Matthew A. C., J. Am. Chem. Soc., 2003, 125(19), 5594—5595
[13]	Simonsson T., Biol. Chem., 2001, 36(8), 621—628
[14]	Demchuck M. I., Ishcenko A. A., Mikhailov V. P., Avdeeva V. I., Chem. Phys. Lett., 1988, 14(4), 99—103
[15]	Gaggini F., Porcheddu A., Reginato G., Rodriquez M., Taddei M., J. Comb. Chem., 2004, 6, 805—810
[16]	Mishra A., Behera R.K., Behera P. K., Chem. Rev., 2000, 100, 1973—2011
[17]	Wu T., Peng X. J., Hu M. M., Liu F., Fan J. L., Chem. J. Chinese Universities, 2012, 33(7), 1407—1412
	(吴彤, 彭孝军, 胡明明, 刘飞, 樊江丽.高等学校化学学报,2012, 33(7), 1407—1412)
[18]	Yan W. P., Peng B. X., Chin. J. Org. Chem., 1994, 14, 59—64
	(闫文鹏, 彭必先.有机化学, 1994, 14, 59—64)

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Empirical formula	C₁₄H₁₇NO₄S₂	Calculated density/(Mg·m^-3)	1.471
Formula weight	327.42	Absorption coefficient/mm^-1	0.36
T/K	293(2)	F(000)	728
λ/nm	0.071073	Crystal size	0.25 mm×0.17 mm×0.10 mm
Crystal system	Monoclinic	θ range for data collection/(°)	3.0—25.0
Space group	P2₁/c	Index range	-10≤h≤9, -12≤k≤11, -20≤l≤20
a/nm	0.84908(3)	Reflections collected/unique	5971/2735(R_int=0.020)
b/nm	1.06870(5)	Refinement method	Full-matrix least-square on F²
c/nm	1.73192(7)	Goodness-of-fit on F²	1.054
V/nm³	1.56021(11)	Data/restraints/parameters	2735/3/204
β/(°)	96.893(4)	Final R indices[I>2σ(I)]	R₁=0.034, wR₂=0.081
Z	20

Empirical formula	C₁₄H₁₇NO₄S₂	Calculated density/(Mg·m^-3)	1.471
Formula weight	327.42	Absorption coefficient/mm^-1	0.36
T/K	293(2)	F(000)	728
λ/nm	0.071073	Crystal size	0.25 mm×0.17 mm×0.10 mm
Crystal system	Monoclinic	θ range for data collection/(°)	3.0—25.0
Space group	P2₁/c	Index range	-10≤h≤9, -12≤k≤11, -20≤l≤20
a/nm	0.84908(3)	Reflections collected/unique	5971/2735(R_int=0.020)
b/nm	1.06870(5)	Refinement method	Full-matrix least-square on F²
c/nm	1.73192(7)	Goodness-of-fit on F²	1.054
V/nm³	1.56021(11)	Data/restraints/parameters	2735/3/204
β/(°)	96.893(4)	Final R indices[I>2σ(I)]	R₁=0.034, wR₂=0.081
Z	20

C1—C2	0.1386(3)	C7—C8	0.1359(3)	C11—C12	0.1525(3)
C1—C6	0.1394(3)	C7—C13	0.1412(3)	C12—S1	0.1787(2)
C1—N1	0.1402(2)	C8—O1	0.1322(2)	C13—N1	0.1346(2)
C2—C3	0.1381(3)	C8—C9	0.1492(3)	C13—S2	0.1727(19)
C3—C4	0.1386(3)	C9—C14	0.1521(3)	O2—S1	0.14559(15)
C4—C5	0.1369(3)	C10—N1	0.1479(2)	O3—S1	0.14493(15)
C5—C6	0.1395(3)	C10—C11	0.1514(3)	O4—S1	0.14451(14)
C6—S2	0.1738(2)
C2—C1—N1	127.67(17)	C7—C8—C9	122.76(18)	C13—N1—C10	122.79(16)
C6—C1—N1	111.38(17)	C8—C9—C14	113.64(17)	C1—N1—C10	122.52(15)
C2—C3—C4	121.60(2)	N1—C10—C11	110.72(14)	O4—S1—O3	112.62(9)
C4—C5—C6	118.04(19)	C10—C11—C12	114.15(16)	O4—S1—O2	113.42(9)
C1—C6—C5	120.64(18)	C11—C12—S1	114.00(13)	O3—S1—O2	112.01(10)
C1—C6—S2	111.20(15)	N1—C13—C7	124.03(17)	O4—S1—C12	106.46(9)
C5—C6—S2	128.16(15)	N1—C13—S2	111.73(14)	O3—S1—C12	105.74(10)
C8—C7—C13	123.92(18)	C7—C13—S2	124.24(14)	O2—S1—C12	105.86(9)
O1—C8—C7	118.92(18)	C13—N1—C1	114.64(15)	C13—S2—C6	91.05(9)
O1—C8—C9	118.32(17)

C1—C2	0.1386(3)	C7—C8	0.1359(3)	C11—C12	0.1525(3)
C1—C6	0.1394(3)	C7—C13	0.1412(3)	C12—S1	0.1787(2)
C1—N1	0.1402(2)	C8—O1	0.1322(2)	C13—N1	0.1346(2)
C2—C3	0.1381(3)	C8—C9	0.1492(3)	C13—S2	0.1727(19)
C3—C4	0.1386(3)	C9—C14	0.1521(3)	O2—S1	0.14559(15)
C4—C5	0.1369(3)	C10—N1	0.1479(2)	O3—S1	0.14493(15)
C5—C6	0.1395(3)	C10—C11	0.1514(3)	O4—S1	0.14451(14)
C6—S2	0.1738(2)
C2—C1—N1	127.67(17)	C7—C8—C9	122.76(18)	C13—N1—C10	122.79(16)
C6—C1—N1	111.38(17)	C8—C9—C14	113.64(17)	C1—N1—C10	122.52(15)
C2—C3—C4	121.60(2)	N1—C10—C11	110.72(14)	O4—S1—O3	112.62(9)
C4—C5—C6	118.04(19)	C10—C11—C12	114.15(16)	O4—S1—O2	113.42(9)
C1—C6—C5	120.64(18)	C11—C12—S1	114.00(13)	O3—S1—O2	112.01(10)
C1—C6—S2	111.20(15)	N1—C13—C7	124.03(17)	O4—S1—C12	106.46(9)
C5—C6—S2	128.16(15)	N1—C13—S2	111.73(14)	O3—S1—C12	105.74(10)
C8—C7—C13	123.92(18)	C7—C13—S2	124.24(14)	O2—S1—C12	105.86(9)
O1—C8—C7	118.92(18)	C13—N1—C1	114.64(15)	C13—S2—C6	91.05(9)
O1—C8—C9	118.32(17)

Selected bond	Torsion angle(°)	Selected bond	Torsion angle(°)
C1—C6—N1—C2	0.48	C7—C13—S2—N1	0.37
C1—C13—N1—C10	1.46	C7—C8—O1—C9	0.15
C12—O2—S1—03	42.85	C12—O2—S1—04	42.13
C12—O4—S1—03	34.57	O2—O3—S1—04	29.91