棘孢曲霉中分离的2个新化合物

doi:10.7503/cjcu20141146

摘要/Abstract

摘要：

从土壤真菌棘孢曲霉(Aspergillus aculeatus)中分离得到2个新化合物和2个已知化合物, 采用质谱(MS)、一维核磁共振波谱(1D NMR)、异核多键相关谱(HMBC)、异核单量子相关谱(HSQC)和旋转坐标NOE谱(ROESY)等方法对化合物的结构进行了鉴定, 化合物2的顺反构型通过ROESY数据进一步确定. 鉴定结果表明, 2个新化合物分别为2-(2'-4'-6'-三羟基)-7-羟基-5-甲基色原酮{2-(2',4',6'-trihydroxyphenyl)-(7-hydroxy-5-methyl)chromone}(1)和(E)-4-羟基-3-[(3-甲基-4-羟基-2-丁烯)氧代]苯甲酸{(E)-4-hydroxy-3-[(4-hydroxy-3-methylbut-2-en-1-yl)oxy]benzoic acid}(2); 2个已知化合物分别为(S)-2-[(2'-羟基)丙基]-5-甲基-7-羟基色原酮{2-(2'-hydroxypropyl)-5-methyl-7-hydroxychromone}(3)和(3R,4S)-8-羟基-3,4,5-三甲基-6酮-4,6-二氢-3H-异色烯-7-羧酸{(3R,4S)-8-hydroxy-3,4,5-trimethyl-6-oxo-4,6-dihydro-3H-isochromene-7-carboxylic acid}(4). 活性测试结果表明, 这4个化合物均表现出一定的抗氧化活性.

关键词: 真菌, 棘孢曲霉, 核磁共振, 黄酮, 抗氧化活性

Abstract:

In order to investigate new bioactive compounds, a piece of fungi Aspergillus aculeatus was obtained from the Jinyun mountain soil in Chongqing, China. By fermentation using Potato Dextrose(PD) within 14 d at 28 ℃, the extraction of ethyl acetate(103 g) was obtained. The extraction was then used for isolation of compounds through a series of study by classical separation methods, for example Octadecyl Silane(ODS) and Sephadex LH-20. Two new compounds 2-(2',4',6'-trihydroxy phenyl)benzene-(7-hydroxy-5-methyl) chromone(1) and (E)-4-hydroxy-3-[(4-hydroxy-3-methylbut-2-en-1-yl)oxy] benzoic acid(2) were obtained. The structures were elucidated using mass spectrometry(MS), one demensional nuclear magnetic resonance spectroscopy(1D NMR), heteronuclear multiple bond correlation(HMQC), heteronuclear single quanturn correlation(HMBC) and rotating-frame overhauser effect spectroscopy(ROESY). Other two known compounds 2-(2'-hydroxypropyl)-5-methyl-7-hydroxychromone(3) and (3R, 4S)-8-hydroxy-3,4,5- trime-thyl-6-oxo-4,6-dihydro-3H-isochromene-7-carboxylic acid(4) were obtained. Compounds 2 to 4 exhibited some 2,2-diphenyl-1-picrylhydrazyl(DPPH) antioxidant activity.

Key words: Fungi, Aspergillus aculeatus, Nuclear magnetic resonance spectroscopy(NMR), Flavanoid, Antioxidant activity

中图分类号:

O629.9

TrendMD:

徐燕, 田沙沙, 俞和, 杨文智, 朱华结. 棘孢曲霉中分离的2个新化合物. 高等学校化学学报, 2015, 36(6): 1107.

XU Yan, TIAN Shasha, YU He, YANG Wenzhi, ZHU Huajie. Isolation and Identification of Two New Compounds from Aspergillus Aculeatus^†. Chem. J. Chinese Universities, 2015, 36(6): 1107.

图/表 5

参考文献 21

[1]	Shi X. L., Wang J. F., Yao H., Chem. J. Chinese Universities, 2013, 34(2), 381—385
	(时晓磊, 王加付, 姚华.高等学校化学学报, 2013,34(2), 381—385)
[2]	Zhang M. X., Liu Y. Y., Sun W., Yang X. H., Wang G. S., Chem. J. Chinese Universities, 2011, 32(11), 2554—2557
	(张沐新, 刘银燕, 孙薇, 杨晓红, 王广树.高等学校化学学报, 2011,32(11), 2554—2557)
[3]	Kentaro S., Jun S., Young W. N., Toru N., Shu T., Takayoshi W., Biochem. J., 2013, 452, 211—221
[4]	Li H. J., Cai Y. T., Chen Y. Y., Lan W. J., Chem. Res. Chinese Universities, 2010, 26(3), 415—419
[5]	Wen Z. B., Pei Y. H., Tian L., Adv. Mar. Sci., 2004, 22, 371—376
	(温占波, 裴月湖, 田黎. 海洋科学进展, 2004, 22, 371—376)
[6]	Wan Y. M., Gu J. F., Anti. Infect. Pharm., 2013, 10, 241—247
	(万钰萌, 顾觉奋. 抗感染药学, 2013, 10, 241—247)
[7]	Nattha I., Chulabhorn M., Somsak R., Prasat K., J. Nat. Prod., 2011, 74, 1650—1652
[8]	Gajendra S., Naika P. K., J. Agric. Food Chem., 2011, 59, 7341—7345
[9]	Liu Y., Li Q. S., Zhu H. L., Meng Z. L., Xiang H. Y., Xie Q. H., Chem. Res. Chinese Universities, 2013, 29(5), 917—923
[10]	Tani S., Kanamasa S., Sumitani J., Arai M., Kawaguchi T., Curr. Genet., 2012, 58, 93—104
[11]	Wang Y., Li Z.L., Liu T., Tian L., Pei Y. H., Hua H. M., Acta Pharmaceutica Sinica, 2014, 49, 68—71
[12]	Ma Y. Y., Chen Y. R., Zhang W. N., Sun H., Xia W. J., Acta Microbiologica Sinica, 2014, 54, 62—68
[13]	Sorensen A., Ahring B. K., Lubeck M., Ubhayasekera W., Bruno K. S., Culley D. E., Lubeck P. S., Can. J. Microbio., 2012, 58, 1035—1046
[14]	Petersen L. M., Holm D. K., Gotfredsen C. H., Larsen T. O., Planta Med., 2012, 78, 1159—1164
[15]	Lene M. P., Casper H., Jens C. F., Charlotte H. G., Thomas O. L., Molecules, 2014, 19, 10898—10921
[16]	Khamthong N., Rukachaisirikul V., Tadpetch K., Kaewpet M., Phongpaichit S., Preedanon S., Sakayaroj J., Arch. Pharm. Res., 2012, 35, 461—468
[17]	Yoshiki K., Gen-ichiro N., Ltsuo N., Chem. Pharm. Bull., 1984, 32, 3493—3500
[18]	Ushio S., Yutaka E., Hiroshi N., Yoshiaki I., Shoken K., Yoichi I., Tetrahedron, 1983, 39, 3583—3591
[19]	Chai Y. J., Cui C. B., Li C. W., Wu C. J., Tian C. K., Hua W., Marine Drugs, 2012, 10, 559—582
[20]	Andrey M., Edson R.F., Helvetica Chimica Acta, 2011, 94, 835—841
[21]	Li Y. P., Xu Y., Xu E. N., Sun H. B., J. Hygiene Res., 1998, 27, 75—78(李燕萍, 许杨, 徐尔尼, 孙红斌. 卫生研究, 1998,27, 75—78)

C atom	¹³C NMR(150 MHz, DMSO-d₆), δ	¹H NMR(600 MHz, DMSO-d₆), δ	HMBC
C2	164.5(C)
C3	112.1(CH)	6.21(Overlap, 1H)	C2, C4, C4a, C1'
C4	182.2(C)
C4a	111.7(C)
C5	139.4(C)
C6	109.2(CH)	6.21(Overlap, 1H)	C4, C4a , C9
C7	157.5(C)
C8	100.8(CH)	6.28(d, J=1.9 Hz, 1H)	C4a , C6, C7, C8a
C8a	160.3(C)
C9	20.3(CH₃)	2.14(s, 3H)	C4a , C5, C6
C1'	104.2(C)
C2'	162.0(C)
C3'	99.3(CH)	6.21(Overlap, 1H)	C2, C4, C1'
C4'	164.8(C)
C5'	94.3(CH)	6.35(d, J=1.9 Hz, 1H)	C1', C4', C6'
C6'	158.7(C)

C atom	¹³C NMR(150 MHz, DMSO-d₆), δ	¹H NMR(600 MHz, DMSO-d₆), δ	HMBC
C2	164.5(C)
C3	112.1(CH)	6.21(Overlap, 1H)	C2, C4, C4a, C1'
C4	182.2(C)
C4a	111.7(C)
C5	139.4(C)
C6	109.2(CH)	6.21(Overlap, 1H)	C4, C4a , C9
C7	157.5(C)
C8	100.8(CH)	6.28(d, J=1.9 Hz, 1H)	C4a , C6, C7, C8a
C8a	160.3(C)
C9	20.3(CH₃)	2.14(s, 3H)	C4a , C5, C6
C1'	104.2(C)
C2'	162.0(C)
C3'	99.3(CH)	6.21(Overlap, 1H)	C2, C4, C1'
C4'	164.8(C)
C5'	94.3(CH)	6.35(d, J=1.9 Hz, 1H)	C1', C4', C6'
C6'	158.7(C)

C atom	¹³C NMR(150 MHz, CD₃OD), δ	¹H NMR(600 MHz, CD₃OD), δ	HMBC
C1	121.8(C)
C2	114.5(CH)	7.58(d, J=1.8 Hz, 1H)	C1, C3, C4, C6, C13
C3	146.1(C)
C4	151.6(C)
C5	114.6(CH)	6.86(d, J=7.8 Hz, 1H)	C1, C2, C3, C4, C13
C6	124.0(CH)	7.56(dd, J=7.8, 1.8 Hz, 1H)	C2, C4, C13
C8	65.3(CH₂)	4.75(d, J=6.3 Hz, 2H)	C3, C9, C10, C11, C12
C9	119.3(CH)	5.78(t, J=6.3 Hz, 1H)	C10, C11, C12
C10	140.1(C)
C11	66.4(CH₂)	4.01(s, 2H)	C9, C10,C12
C12	12.6(CH₃)	1.78(s, 3H)	C9, C10, C11
C13	168.7(C)

C atom	¹³C NMR(150 MHz, CD₃OD), δ	¹H NMR(600 MHz, CD₃OD), δ	HMBC
C1	121.8(C)
C2	114.5(CH)	7.58(d, J=1.8 Hz, 1H)	C1, C3, C4, C6, C13
C3	146.1(C)
C4	151.6(C)
C5	114.6(CH)	6.86(d, J=7.8 Hz, 1H)	C1, C2, C3, C4, C13
C6	124.0(CH)	7.56(dd, J=7.8, 1.8 Hz, 1H)	C2, C4, C13
C8	65.3(CH₂)	4.75(d, J=6.3 Hz, 2H)	C3, C9, C10, C11, C12
C9	119.3(CH)	5.78(t, J=6.3 Hz, 1H)	C10, C11, C12
C10	140.1(C)
C11	66.4(CH₂)	4.01(s, 2H)	C9, C10,C12
C12	12.6(CH₃)	1.78(s, 3H)	C9, C10, C11
C13	168.7(C)