螺[二苯并[a,j]氧杂蒽-14,9'-芴]的合成及性质

doi:10.7503/cjcu20130375

摘要/Abstract

摘要：

芴酮与2-萘酚在硫酸和3-巯基丙酸的作用下反应得到化合物螺[二苯并[a,j]氧杂蒽-14,9'-芴]. 采用核磁共振、质谱、红外光谱和元素分析等对该化合物进行了表征, 并通过X射线衍射法测得了其晶体结构, 确定该化合物是通过二苯并[a,j]氧杂蒽中的含氧六元杂环和芴中的五元环共用一个碳原子形成一个螺环. 利用荧光光谱和热分析等手段对该化合物的性质进行了研究, 结果表明其最大荧光发射峰为366 nm, 熔点为297 ℃, 热分解温度为329 ℃, 具有较高的热稳定性.

关键词: 螺环, 氧杂蒽, 芴, 晶体结构

Abstract:

Spiro[fluorene-9,9'-xanthene](SFX) and its derivatives as the unit of organic optoelectronic materials have attracted much attention due to their promising thermal and photophysical properties. By tuning the conjugated degree and the steric of SFX, we designed a novel compound spiro[dibenzo[a,j]xanthene-14,9'-fluorene] and anticipated that it would have better performance than SFX. The reaction of 9H-fluoren-9-one and naphthalen-2-ol under the conditions of sulfuric acid and 3-mercaptopropanoic acid gave the target compound spiro[dibenzo[a,j]xanthene-14,9'-fluorene]. The compound was characterized by NMR, MS, IR spectra, elemental analysis and X-ray structural determination. The crystal data of the compound showed that a spiro ring was formed through the six-membered heterocyclic ring in dibenzo[a,j]xanthene sharing one carbon atom with the five-membered ring in fluorene. The photophysical and thermal properties were investigated by UV-Vis absorption, photoluminescence spectra, thermogravimetric analysis(TGA) and differential scanning calorimetry(DSC). The maximum emission wavelength of the compound was found at 366 nm, and it showed a high thermal stability with a melting point of 297 ℃ and a decomposition temperature of 329 ℃. The results indicated that spiro[dibenzo[a,j]xanthene-14,9'-fluorene] could be used in the organic optoelectronic polymers to enhance their performance.

Key words: Spiro ring, Xanthene, Fluorene, Crystal structure

中图分类号:

O621.3

TrendMD:

陈木子, 尤永芝, 张勇, 李海燕, 方魏. 螺[二苯并[a,j]氧杂蒽-14,9'-芴]的合成及性质. 高等学校化学学报, 2014, 35(1): 63.

CHEN Muzi, YOU Yongzhi, ZHANG Yong, LI Haiyan, FANG Wei. Synthesis and Properties of Spiro[dibenzo[a, j]xanthene-14,9'-fluorene]. Chem. J. Chinese Universities, 2014, 35(1): 63.

图/表 7

Fig.1 Molecular structure of spiro[dibenzo[a,j] xanthene-14,9'-fluorene]

Table 1 Crystallographic data and refinements for spiro[dibenzo[a,j]xanthene-14,9'-fluorene]

Empirical formula	C₃₃H₂₀O	V/nm³	4.4191(11)
Formula weight	432.49	Z	8
Temperature/K	293(2)	D_c/(g·c $m - 3$ )	1.300
λ(Mo Kα)/nm	0.071070	Absorption coefficient/mm^-1	0.077
Crystal system, space group	Orthorhombic, Pbcn	F(000)	1808
a/nm	1.6599(2)	Crystal size	0.80 mm×0.60 mm×0.10 mm
b/nm	0.78609(11)	2θ_max/(°)	3.11—25.34
c/nm	3.3867(5)	Number of reflns. collected	16281
α/(°)	90.00	Number of indep. reflns	3823
β/(°)	90.00	Goodness-of-fit on F²	1.100
γ/(°)	90.00	Final R[I>2σ(I)]	0.0987, 0.1672

Table 1 Crystallographic data and refinements for spiro[dibenzo[a,j]xanthene-14,9'-fluorene]

Empirical formula	C₃₃H₂₀O	V/nm³	4.4191(11)
Formula weight	432.49	Z	8
Temperature/K	293(2)	D_c/(g·c $m - 3$ )	1.300
λ(Mo Kα)/nm	0.071070	Absorption coefficient/mm^-1	0.077
Crystal system, space group	Orthorhombic, Pbcn	F(000)	1808
a/nm	1.6599(2)	Crystal size	0.80 mm×0.60 mm×0.10 mm
b/nm	0.78609(11)	2θ_max/(°)	3.11—25.34
c/nm	3.3867(5)	Number of reflns. collected	16281
α/(°)	90.00	Number of indep. reflns	3823
β/(°)	90.00	Goodness-of-fit on F²	1.100
γ/(°)	90.00	Final R[I>2σ(I)]	0.0987, 0.1672

Fig.2 ORTEP diagram of spiro[dibenzo[a,j] xanthene-14,9'-fluorene]

Table 2 Selected bond lengths(nm) and bond angles(°) for spiro[dibenzo[a,j]-xanthene-14,9'-fluorene]

O1—C10	1.366(6)	C20—C21	1.549(6)
O1—C11	1.390(5)	C21—C22	1.525(6)
C1—C21	1.563(5)	C21—C33	1.547(6)
C10—O1—C11	119.8(3)	C20—C21—C22	113.2(3)
C1—C21—C20	109.8(3)	C20—C21—C33	111.3(3)
C1—C21—C22	112.2(3)	C22—C21—C33	101.3(3)
C1—C21—C33	108.7(3)

Table 3 Selected dihedral angles(°) for spiro[dibenzo[a,j]xanthene-14,9'-fluorene]

C28—C29—C30—C31—C32—C33 and C22—C23—C24—C25—C26—C27	3.301(141)
C1—C2—C3—C4—C5—C6—C7—C8—C9—C10 and C22—C23—C24—C25—C26—C27	88.261(114)
C1—C2—C3—C4—C5—C6—C7—C8—C9—C10 and C28—C29—C30—C31—C32—C33	85.375(113)
C11—C12—C13—C14—C15—C16—C17—C18—C19—C20 and C22—C23—C24—C25—C26—C27	89.272(119)
C11—C12—C13—C14—C15—C16—C17—C18—C19—C20 and C28—C29—C30—C31—C32—C33	87.687(119)

Fig.3 UV-Vis absorption(a) and emission(b) spectra of spiro[dibenzo[a,j]xanthene-14,9'-fluorene] in C2H5OH(1×10-6 mol/L)

Fig.4 TGA(A) and DSC(B) curves of spiro[dibenzo[a,j]xanthene-14,9'-fluorene]

参考文献 21

[1]	Wei R. B., Liu Y., Guo J. J., Liu B., Zhang D. W., Chinese J. Org. Chem., 2008, 28(3), 390—397
	(魏荣宝, 刘洋, 郭金晶, 刘博, 张大为.有机化学, 2008,28(3), 390—397)
[2]	Wei R. B., Zhang D. W., Liang Y., Liu B., Chinese J. Org. Chem., 2008, 28(8), 1366—1378
	(魏荣宝, 张大为, 梁娅, 刘博.有机化学, 2008,28(8), 1366—1378)
[3]	Greenblatt M. S., Benntt W. P., Hollstein M., Harris C. C., Cancer Res., 1994, 54, 4855—4878
[4]	Minoo D., Mostafa B., Elham A., Catal. Commun., 2008, 9, 939—942
[5]	Liu D., Yu Y., Zhang S. H., Liu C. S., Luo G. X., Chin. J. Synth. Chem., 2007, 15(4), 516—518
	(刘迪, 于杨, 张少华, 刘春生, 罗根祥.合成化学, 2007,15(4), 516—518)
[6]	Wang G. L., Yin X. N., Zhang C., Pan H. Y., Mao R. Z., Fan X. S., J. Henan Normal Univ. (Natural Science Edition), 2011, 39(2), 80—82
	(王国利, 尹雪娜, 张春, 潘卉妍, 毛润泽, 范学森.河南师范大学学报(自然科学版), 2011, 39(2), 80—82)
[7]	Neslihan S., Engin A. U., J. Mol. Catal. A: Chem., 2004, 219, 227—232
[8]	Zhao T. F., Zhao D. F., Sun X. S., Cheng L. B., Journal of Chemical Industry and Engineering, 1998, 49(4), 515—520
	(赵同丰, 赵德丰, 孙孝森, 程侣柏.化工学报, 1998,49(4), 515—520)
[9]	Zhang H., Zhao T. F., Wang B. R., Zhao D. F., Spectroscopy and Spectral Analysis, 1998, 18(4), 425—428
	(张华, 赵同丰, 王璧人, 赵德丰.光谱学与光谱分析, 1998,18(4), 425—428)
[10]	Qian X. H., Ren S. W., Journal of East China Institute of Chemical Technology, 1987, 13(1), 11—15
	(钱旭红, 任绳武.华东化工学院学报, 1987,13(1), 11—15)
[11]	Tang C., Liu F., Xu H., Huang W., Progress in Chemistry, 2007, 19(10), 1553—1561
	(唐超, 刘烽, 徐慧, 黄维.化学进展, 2007,19(10), 1553—1561)
[12]	Zhou E. J., Cong J. Z., Zhao M. X., Zhang L. Z., Hashimoto K., Keisuke T. K., Chem. Commun., 2012, 48, 5283—5285
[13]	Huo Y. P., Fang X. M., Huang B. H., Zhang K., Nie X. L., Zeng H. P., Chinese J. Org. Chem., 2012, 32, 1169—1185
	(霍延平, 方小明, 黄宝华, 张焜, 聂晓李, 曾和平. 有机化学, 2012, 32, 1169—1185)
[14]	Chu Z. Z., Wang D., Zhang C., Zou D. C., Acta Phys. Chim. Sin., 2012, 28(8), 2000—2007
	(初增泽, 王丹, 张超, 邹德春.物理化学学报, 2012,28(8), 2000—2007)
[15]	Tseng Y. H., Shih P. I., Chien C. H., Dixit A. K., Shu C. F., Liu Y. H., Lee G. H., Macromolecules, 2005, 38, 10055—10060
[16]	Xie L. H., Liu F., Tang C., Hou X. Y., Hua Y. R., Fan Q. L., Huang W., Org. Lett., 2006, 8, 2787—2790
[17]	Chu Z. Z., Wang D., Zhang C., Fan X., Tang Y. W., Chen L., Zou D. C., Macromolecular Rapid Commun., 2009, 30(20), 1745—1750
[18]	Chu Z. Z., Wang D., Zhang C., Wang F. Z., Wu H. W., Lv Z. B., Hou S. C., Fan X., Synth. Met., 2012, 162(7), 614—620
[19]	Poriel C., Cocherel N., Rault-berthelot J., Vignau L., Jeannin O., Chem. Eur. J., 2011, 17, 12631—12635
[20]	Wang Z. S., Liu C. J., Chem. J. Chinese Universities, 2012, 33(3), 507—510
	(王昭申, 刘晨江.高等学校化学学报, 2012,33(3), 507—510)
[21]	Sheldrick G.M., SHELXS-97, Program for the Solution of Crystal Structure, University of Göttingen,Göttingen, 1997