化合物6:C17H28O3,无色油状物,1H NMR (CDCl3, 400MHz): δH5.75 (1H, dd, J = 17.4,10.9 Hz, H-1), 5.05 (1H, ddd, J = 11.0, 10.9, 4.2 Hz, H-8), 4.91 (1H, d, J = 10.8 Hz, H-2a), 4.88 (1H, dd, J = 17.5 Hz, H-2b), 4.84(1H, m, H-3a), 4.59 (1H, brs, H-3b), 2.04 (3H, s, H-Ac), 1.79 (1H, dd, J = 11.7, 3.0 Hz, H-11), 1.69 (3H, s, H-13), 1.18 (3H, s, H-14), 1.17 (3H, s,H-15), 1.05 (3H, s, H-12);13CNMR (CDCl3, 100MHz) 数据见表2。其NMR数据与文献[9]报道的7-acetoxy-elema-1,3-dien-8-ol一致。
化合物7:C15H24O2,无色油状物,ESIMS (positive) m/z 259 [M + Na]+,1H NMR (CDCl3, 500MHz): δH 5.34 (1H, m, H-3),3.71 (1H, dd, J = 6.1, 10.2 Hz, H-1), 1.74 (3H, m, H-14), 0.92 (3H, d, J= 6.8 Hz, H-12), 0.89 (3H, d, J = 6.8 Hz, H-13), 0.70 (3H, s, H-15);13CNMR (CDCl3, 125MHz) 数据见表2。其MS及NMR数据与文献[10]报道的1-naphthalenone一致中国论文网。
化合物8:C15H24O2,无色油状物,1H NMR (CDCl3, 400MHz): δH3.59 (1H, dd, J = 4.7, 11.2 Hz, H-1), 2.30 (1H, m, H-11), 1.94 (1H, m, H-7), 1.66 (3H, brs, H-14), 0.91 (3H, d, J = 6.9 Hz, H-12), 0.90 (3H, s, H-15), 0.86 (3H, d, J = 6.9 Hz, H-13);13CNMR (CDCl3, 100MHz) 数据见表1。其NMR数据与文献[11]报道的acarusnol一致。
表2化合物6-9、15、16的13CNMR数据
No.
|
6
|
7
|
8
|
9
|
14
|
15
|
No.
|
6
|
14
|
15
|
1
|
148.2
|
74.9
|
76.7
|
45.3
|
41.2
|
44.6
|
16
|
|
222.1
|
218.4
|
2
|
110.8
|
31.7
|
26.6
|
80.5
|
67.0
|
72.8
|
17
|
|
66.3
|
65.2
|
3
|
112.7
|
121.5
|
32.1
|
48.5
|
74.4
|
72.9
|
18
|
|
13.7
|
13.6
|
4
|
146.2
|
131.4
|
139.1
|
37.4
|
77.8
|
77.3
|
19
|
|
15.9
|
17.5
|
5
|
52.0
|
61.1
|
136.4
|
51.2
|
44.6
|
50.6
|
20
|
|
18.6
|
18.1
|
6
|
44.7
|
210.8
|
206.8
|
21.4
|
25.8
|
26.6
|
21
|
|
13.8
|
13.7
|
7
|
72.8
|
57.0
|
57.4
|
33.8
|
33.7
|
32.8
|
Ac
|
169.7
|
|
|
8
|
72.7
|
27.3
|
21.5
|
35.4
|
35.3
|
34.1
|
Ac
|
21.7
|
|
|
9
|
29.0
|
34.5
|
36.8
|
74.7
|
56.7
|
56.8
|
|
|
|
|
10
|
41.0
|
45.3
|
42.9
|
27.3
|
38.2
|
35.7
|
|
|
|
|
11
|
52.0
|
26.3
|
25.7
|
27.9
|
21.1
|
20.5
|
|
|
|
|
12
|
17.4
|
18.7
|
18.1
|
36.6
|
39.1
|
38.6
|
|
|
|
|
13
|
24.6
|
21.7
|
21.0
|
25.8
|
43.3
|
42.2
|
|
|
|
|
14
|
26.1
|
9.9
|
20.6
|
31.8
|
51.6
|
50.3
|
|
|
|
|
15
|
28.5
|
18.7
|
18.3
|
29.5
|
39.4
|
38.2
|
|
|
|
|
化合物9:C15H24O2,白色粉末,1H NMR (C5D5N, 500MHz): δH4.13 (1H, t, J = 7.9Hz, H-2), 3.56 (1H, brs, H-9),1.19 (3H, s, H-14), 1.10 (3H, s, H-15), 0.89 (3H, s, H-13);13CNMR (C5D5N, 125MHz) 数据见表2。其NMR数据与文献[12]报道的colvane-2β,9α-diol一致。
化合物10:C30H48O3,白色粉末;1H NMR (C5D5N, 400MHz): δH5.54 (1H, m, H-12), 3.51 (1H, dd, J = 9.5, 6.30 Hz, H-3), 2.68 (1H, d, J= 11.3 Hz, H-18), 1.67 (1H, t, J = 8.8 Hz, H-9), 1.29 (3H, s, H-23),1.26 (3H, s, H-27), 1.10 (3H, s, H-26), 1.07 (3H, s, H-25), 1.04 (3H, d, J= 6.4 Hz, H-29), 0.99 (3H, d, J = 6.4 Hz, H-30), 0.92 (3H, s, H-24);13CNMR (C5D5N, 100MHz) 数据见表3。其NMR数据与文献[13]报道的乌苏酸(ursolic acid)一致。
化合物11:C30H48O4,白色粉末,1H NMR (C5D5N, 400MHz): δH 5.46 (1H,brs, H-12), 3.62 (1H, ddd, J = 11.0, 8.2, 4.3Hz, H-2), 2.96 (1H, d, J= 8.2 Hz, H-3), 1.36 (3H, s, H-23), 1.20 ( 3H, H-27), 1.19 (3H, s, H-26), 1.14(3H, s, H-25), 1.10 (3H, s, H-24), 1.06 (3H, s, H-29), 1.03 (3H, s, H-30);13CNMR (CDCl3, 100MHz) 数据见表3。其NMR数据与文献[14]报道的马斯里酸(maslinicacid)一致。
表3 化合物10-13的13CNMR数据
No.
|
10
|
11
|
12
|
13
|
No.
|
10
|
11
|
12
|
13
|
1
|
39.1
|
47.8
|
48.0
|
48.1
|
16
|
24.9
|
24.0
|
24.9
|
24.9
|
2
|
28.2
|
68.6
|
68.6
|
68.9
|
17
|
48.1
|
46.5
|
48.1
|
48.0
|
3
|
78.1
|
83.9
|
83.9
|
78.3
|
18
|
53.6
|
42.0
|
53.6
|
53.6
|
4
|
39.4
|
39.9
|
40.1
|
43.7
|
19
|
39.5
|
46.7
|
39.5
|
39.5
|
5
|
55.8
|
55.9
|
56.0
|
48.1
|
20
|
39.4
|
31.0
|
39.4
|
39.4
|
6
|
18.8
|
18.9
|
18.9
|
18.6
|
21
|
31.1
|
34.3
|
31.1
|
30.0
|
7
|
33.6
|
33.2
|
33.6
|
33.2
|
22
|
37.5
|
33.3
|
37.5
|
37.5
|
8
|
40.0
|
39.9
|
39.9
|
40.1
|
23
|
28.9
|
29.4
|
29.4
|
66.6
|
9
|
48.1
|
48.2
|
48.1
|
48.0
|
24
|
15.7
|
16.9
|
17.7
|
14.4
|
10
|
37.3
|
38.6
|
38.5
|
38.4
|
25
|
16.6
|
17.5
|
17.5
|
17.5
|
11
|
23.7
|
23.7
|
23.8
|
23.9
|
26
|
17.6
|
17.7
|
17.0
|
17.6
|
12
|
125.7
|
122.5
|
125.6
|
125.6
|
27
|
24.0
|
26.2
|
23.9
|
23.8
|
13
|
139.3
|
144.9
|
139.3
|
139.3
|
28
|
180.0
|
180.2
|
179.9
|
179.9
|
14
|
42.5
|
42.2
|
42.6
|
42.6
|
29
|
17.5
|
33.2
|
17.5
|
17.5
|
15
|
28.7
|
28.3
|
28.7
|
28.7
|
30
|
21.5
|
23.8
|
21.4
|
21.4
|
化合物12:C30H48O4,白色粉末,1H NMR (C5D5N, 400MHz): δH5.45 (1H, m, H-12), 4.10 (1H, dt, J = 10.2, 4.3, 4.3 Hz, H-2), 3.33 (1H,d, J = 10.2 Hz, H-3), 2.61 (1H, d, J = 11.2 Hz, H-18), 1.27 (3H,s, H-23), 1.19 (3H, s, H-27), 1.07 (3H, s, H-26), 1.04 (3H, s, H-25), 0.97 (3H, d, J = 5.0 Hz, H-29), 0.96 (3H, s, H-24), 0.94 (3H, d, J = 5.9 Hz, H-30);13CNMR (C5D5N, 100MHz) 数据见表3。其NMR数据与文献[15]报道的2α-羟基乌苏酸(2α-hydroxyoxyursolicacid)一致。
化合物13:C30H48O5,白色粉末甾体,1H NMR (C5D5N, 400MHz): δH 5.44(1H, brs, H-12), 4.22-4.26 (1H, m, H-2), 4.21 (1H, d, H-3), 2.60 (1H, d, J = 11.4 Hz, H-18), 1.12 (3H, s, H-27), 1.06 (3H, s, H-26),1.05 (3H×2, s, H-24, 25), 0.94(3H, d, J = 6.4 Hz, H-29), 0.90 (3H, d, J = 6.5 Hz, H-30);13CNMR (C5D5N, 100MHz) 数据见表3中国论文网。其NMR数据与文献[16]报道的猕猴桃酸 B(eriantic acid B)一致。
化合物14:C21H34O4,无色针晶(甲醇),1H NMR (CD3OD, 400MHz): δH 4.04 (1H, m, H-2), 3.83(1H, t, J = 2.9 Hz, H-3), 3.71 (1H, t, J = 3.0 Hz, H-4), 1.05(3H, t, J = 7.5 Hz, H-21), 0.72 (3H, s, H-18);13CNMR (CD3OD, 100MHz) 数据见表2。其NMR数据与文献[17]报道的2α,3α,4β-trihydroxypregnan-16-one一致。
化合物15:C21H34O4,无色针晶(甲醇),1H NMR (CD3OD, 400MHz): δH 4.55 (1H, m, H-2), 4.18(1H, brs, H-4), 3.85 (1H, t, J = 3.4 Hz, H-3), 1.62 (3H, s, H-19), 1.04(3H, t, J = 7.5 Hz, H-21), 0.57 (3H, s, H-18);13CNMR (CD3OD, 100MHz) 数据见表2。其NMR数据与文献[17]报道的2β,3β,4β-trihydroxypregnan-16-one一致。
3 讨论
本研究还将印楝粗提物及化合物1-4进行了杀虫活性的实验,结果表明印楝粗提物及化合物1-4对所选昆虫无明显抑制活性。并且本次化学成分研究中未分离得到印楝素A这一主要昆虫拒食及杀虫活性物质,这两种之间是否关联还有待进一步的研究。本研究还从印楝的枝叶中首次分离得到了化合物6-15。
参考文献
[1]Pandhawa N S, Parmar B S. Neem [M]. New DelHi: India and New ageInternational (P) Limited, 1996. 6.
[2]Biswas K, Chattopadhyay I, BanerjeeR K, Bandyopadhyay U. Biological activities and medicinal properties ofneem (Azadirachta indica) [J]. CurrSci, 2002, 82(11): 1336-1345.
[3]Kumar M, Kobori M, Takenaka M, Nakahara K, Shinmoto H,Tsushida T. Inhibition of colon cancer (HT-29) cell proliferation by atriterpenoid isolated from Azadirachta indica is accompanied by cellcycle arrest and up-regulation of p21 [J]. Planta Med, 2006, 72(10): 917-923.
[4]Thakurta P, Bhowmik P, Mukherjee S, Hajra T K, Patra A,Bag P K. Antibacterial, antisecretory and antihemorrhagic activity of Azadirachtaindica used to treat cholera and diarrhea in India [J]. J Ethnopharmacol, 2007, 111(3): 607-612.
[5]Parida M M, Upadhyay C, PandyaG, Jana A M. Inhibitory potential of neem (Azadirachtaindica Juss) leaves on Dengue virus type-2 replication [J]. J Ethnopharmacol, 2002, 79(2): 273-278.
[6]Bokel M,Cramer R,Gutzeit H,Reeb S, Kraus W. Tetranortriterpenoids related to nimbin and nimbolidefrom Azadirachta indica A. Juss (Meliaceae) [J]. Tetrahedron, 1990, 46(3): 775-782
[7]Kraus W, Cramer R, Pentanortriterpenoideaus Azadirachta indica A. Juss (Meliaceae) [J]. Chem Ber, 1981, 114: 2375-2381.
[8]Siddiqui S, Siddiqui B S, Ghiasuddin,Faizi S. Tetracyclic triterpenoids of the fruitcoats of Azadirachta indica [J]. J Nat Prod, 1991, 54(2): 408-415.
[9]Paul C, Konig W A, Wu C L. Sesquiterpenoidconstituents of the liverworts Lepidozia fauriana and Lepidoziavitrea [J]. Phytochemistry, 2001, 58(5):789-798.
[10]Niwa M, Iguchi M, YamamuraS. Biogenetic Model Reactions of Epoxygermacrones [J]. Bull Chem Soc Jpn, 1976, 49(11):3137-3144.
[11]Nawamaki K, Kuroyanagi M. Sesquiterpenoidsfrom Acorus calamus as germination inhibitors [J]. Phytochemistry, 1996, 43(6):1175-1182.
[12]Heymann H, Tezuka Y, KikcuhiT, Supritna S. Constituents of Sindora sumatranaMIQ.I. Isolation and NMR Spectral Analysis of Sesquiterpenes from the DriedPods [J]. Chem Pharm Bull, 1994, 42(1): 138-146.
[13]潘萍,孙启时.大叶紫珠的化学成分[J]. 沈阳药科大学学报, 2006, 23(9):565-567.
[14]许琼,陈国庆,范金胤,张萌佳,李厦,杨世林,李笑然.苎麻根化学成分研究[J]. 中国中药杂志, 2009, 34(20):2610-2612.
[15]姚志容,李军,周思祥,张芸,屠鹏飞.枸骨叶中的三萜类成分[J]. 中国中药杂志, 2009, 34(8):999-1001.
[16]梁洁,甄汉深,李生茂,张薇薇,王新盛,梁臣艳.广西产美味猕猴桃根正丁醇部位化学成分研究[J]. 中国中药杂志, 2008, 33(11): 1275-1277.
[17]Ketwaru, P.; Klass, J.;Tinto, W. F.; McLean, S.; Reynolds, W. F., Pregnane Steroids from Trichiliaschomburgkii [J]. J NatProd, 1993, 56(3): 430-431.
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