一种苯并噻唑类稳定烯醇的合成及晶体结构

doi:10.7503/cjcu20130621

摘要/Abstract

摘要：

以2-甲基苯并噻唑和1,3-丙磺酸内酯为起始原料, 合成了一种菁染料中间体2-(2-乙氧基-1-丁烯基)-1-(3-磺酸丙基)苯并噻唑(3). 该染料中间体极易水解, 对其水解产物(4e)采用红外光谱、核磁共振、质谱、元素分析和X射线单晶衍射分析等方法进行了表征. MS结果显示水解产物4e的分子量为327; 在¹³C NMR谱图中, 烯醇结构中与羟基相连的碳的化学位移为194.05, 与之相连的另一个双键碳的化学位移为δ 92.52; 在IR谱图中, 1618 cm^-1处存在烯醇的特征吸收峰; 通过X射线单晶衍射分析测定了水解产物的结构, 进一步证实该水解产物是一种存在共轭芳基结构的稳定烯醇.

关键词: 苯并噻唑, 烯醇, 晶体结构

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

中图分类号:

O626

TrendMD:

霍宝龙, 薛灵伟, 杨运旭, 杨超, 李大芝, 王爱志, 禹菲菲, 胡碧玮. 一种苯并噻唑类稳定烯醇的合成及晶体结构. 高等学校化学学报, 2014, 35(2): 270.

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

图/表 7

参考文献 18

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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