CN102191560B - 一种3-氧代齐墩果酸单晶及其培养方法 - Google Patents
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Abstract
本发明涉及一种3-氧代齐墩果酸单晶及其培养方法。所述的3-氧代齐墩果酸单晶,它的粉末X衍射在下述衍射角2θ有特征峰:5.120,10.200,15.320,20.500,28.640;属单斜晶系,空间群为C2,晶包内分子数Z=4,常温下呈白色针状结晶。所述的3-氧代齐墩果酸单晶是将3-氧代齐墩果酸粗品经过重结晶处理,再经溶剂缓慢挥发培养而得到。按照本发明培养得到的3-氧代齐墩果酸晶体,纯度高,培养操作方法简单易行,用时短,对粗产品纯度要求不高,工艺简单。
Description
技术领域
本发明涉及一种3-氧代齐墩果酸单晶及其培养方法。
背景技术
3-氧代齐墩果酸为五环三萜类化合物齐墩果酸的衍生物,体外实验表明,3-氧代齐墩果酸对人口腔表皮癌,人结肠癌细胞,人肺癌细胞,人纤维肉瘤细胞 ,人前列腺癌细胞,人肾癌细胞和人胃癌细胞有抑制活性。3-氧代齐墩果酸,分子式为C30H46O3,化学名为3-氧代-12-烯-28-齐墩果酸,该化合物结构如下:
合成3-氧代齐墩果酸的化学反应路线为已知应用(3-氧代齐墩果酸的制备方法见中国专利200410064929.7、中国专利201010551826.9),常规途径为齐墩果酸3-位羰基经氧化反应,得到产物3-氧代齐墩果酸,反应得率较高,但是由于反应原料齐墩果酸的强溶解性,反应产物中原料难以完全除尽,产物纯度难以保证,常规处理方法是利用色谱学方法进行分离,但分离耗时且折损率高。另外,对CCDC(Cambridge Structural
Database)、Acta E(晶体学报E)进行晶体数据检索,未发现3-氧代齐墩果酸的单晶结构描述信息。
单晶结构分析可以提供一个化合物在固态中所有原子的精确空间位置, 包括原子的连接形式、分子构象、准确的键长和键角等数据,从而为化学、材料科学和生命科学等研究提供广泛而重要的信息。单晶培养的方法多种多样, 如溶剂缓慢挥发法、溶剂热法、扩散法、共结晶法等。
本发明提供的方法在于利用重结晶手段,选择合适的重结晶体系,利用溶剂缓慢挥发法,培养得到3-氧代齐墩果酸单晶,使得氧化产物3-氧代齐墩果酸与原料齐墩果酸实现良好的分离,经晶体学实验研究验证为单晶,测定其晶体结构属单斜晶系,为白色针状结晶,形态良好,纯度高达99%,培养方法重现性好,所得产品可作为上游产品进行加工生产山楂酸以及其他齐墩果酸衍生物。也可成为医药、材料和化工领域的原料。
发明内容
本发明的目的在于提供一种3-氧代齐墩果酸晶体,以及该3-氧代齐墩果酸单晶的制备方法。
本发明提供了一种3-氧代齐墩果酸晶体,该3-氧代齐墩果酸晶体的化合物名称为:3-氧代-12烯-28-齐墩果酸,化学结构式为:
所述的晶体,它的粉末X衍射在下述衍射角2θ有特征峰:5.120,
10.200,15.320,20.500,28.640;该晶体是单晶结构,属单斜晶系,空间群为C2,晶包内分子数Z=4,常温下呈白色针状结晶。
本发明还提供了一种制备上述3-氧代齐墩果酸单晶的方法,将 3-氧代齐墩果酸粗品(3-氧代齐墩果酸的制备方法见中国专利200410064929.7、中国专利201010551826.9),经过重结晶处理得到上述结晶,经溶剂缓慢挥发培养得到所述的3-氧代齐墩果酸单晶。
上述的3-氧代齐墩果酸晶体是通过以下方法重结晶生成的:
称取3-氧代齐墩果酸粗品,按每克粗品中加入10~20ml的比例加入重结晶溶剂,重结晶溶剂最优选择为甲醇:石油醚:丙酮为8~12:1~4:1~2(体积比),其中丙酮可由异丙醇、氯仿或乙酸乙酯代替,温度控制在40~60℃进行回流处理,待溶解达饱和状态后,利用溶剂缓慢挥发法,在恒温培养箱中放置,培养时间为2~10天,放置温度为8~25℃即可析出白色针状结晶。将此结晶碾成粉末,X-射线测试结果数据见表1。将得到晶体经过单晶衍射测试,证实结构为3-氧代齐墩果酸,且属单斜晶系,单晶分析数据见表2,表3。
按照本发明培养得到的3-氧代齐墩果酸晶体,纯度高,培养操作方法简单易行,用时短,对粗产品纯度要求不高,工艺简单。解决了现有技术中存在的合成产物3-氧代齐墩果酸与原料齐墩果酸分离难度大,目标产物纯度低,影响下游生产等缺点,提供的方法能够制备3-氧代齐墩果酸结晶,培养结晶得到所述的3-氧代齐墩果酸单晶。
附图说明
图1是3-氧代齐墩果酸的粉末X-射线衍射图谱。
图2是3-氧代齐墩果酸立体结构投影图。
具体实施方式
3-氧代齐墩果酸粗品的制备过程:(制备参照CN101974064 A)
原料齐墩果酸与琼斯试剂发生反应,3-位羟基被氧化成为3-位羰基,形成3-氧代齐墩果酸,具体实施例如下:
在N2保护下,将齐墩果酸溶解于丙酮与DMF的混合溶剂中,丙酮-DMF比例为3ml:0.2-1.5ml;混合溶剂与齐墩果酸用量比为20-30ml:1g;在0℃下,按照齐墩果酸和琼斯试剂1g:3-5ml的比例,缓慢滴加琼斯试剂;滴加完毕后,升至室温反应1-3小时;监测反应完毕,降温至0℃,缓慢滴加异丙醇,齐墩果酸与异丙醇用量比为1g:20-35ml;反应体系倒入冰水中析出固体,抽滤干燥得白色固体3-羰基齐墩果酸。
实施例1:
称取3-氧代齐墩果酸粗品4.0g,加入60ml重结晶溶剂,其中甲醇:石油醚:丙酮的用量为45ml:10ml:5ml。50℃回流处理,待溶解达饱和状态,且观察有少量固体析出时,停止回流,利用溶剂缓慢挥发法,在恒温培养箱中放置,温度设置为12℃,培养时间为5天,白色针状结晶析出。将该结晶碾成粉末,进行该3-氧代齐墩果酸粉末的X-射线衍射测试,测定条件为管压:40kV,管流:100mA,Cu Kα辐射,石墨弯晶单色器DS=SS=1°,RS=0.3 mm。扫描速度:10(°).min-1, 步进间隔:0.02°。经由计算机分析软件将实验得到的X射线衍射数据进行平滑处理、Kα 2峰剥离、自动寻峰定位,得到了3-氧代齐墩果酸的衍射角度(2θ)、晶面间距 d (nm)、相对丰度(I/I0 )等晶体参数,图1为其x-粉末衍射图谱。数据见表 1。
表1:3-氧代齐墩果酸粉末X-射线衍射测试结果
2theta | d-value | I/Io |
5.120 | 17.2455 | 70 |
5.760 | 15.3307 | 8 |
7.620 | 11.5922 | 13 |
8.060 | 10.9604 | 6 |
10.200 | 8.6651 | 40 |
11.560 | 7.6486 | 6 |
12.180 | 7.2606 | 6 |
12.780 | 6.9210 | 8 |
14.100 | 6.2759 | 21 |
14.840 | 5.9646 | 27 |
15.320 | 5.7788 | 69 |
16.180 | 5.4735 | 32 |
18.500 | 4.7920 | 7 |
19.060 | 4.6525 | 9 |
20.500 | 4.3288 | 100 |
23.060 | 3.8537 | 7 |
23.600 | 3.7667 | 17 |
24.980 | 3.5617 | 19 |
25.700 | 3.4635 | 33 |
27.560 | 3.2338 | 7 |
28.640 | 3.1143 | 58 |
30.040 | 2.9723 | 9 |
30.960 | 2.8860 | 47 |
33.900 | 2.6421 | 11 |
38.020 | 2.3648 | 9 |
38.980 | 2.3087 | 9 |
另外选取尺寸为0.20 mm×0.10 mm×0.10 mm 的单晶, 用荷兰Enraf Noius公司的CAD4/PC 型单晶衍射仪进行检测。测量方法为ψ 扫描,用石墨单色化的MoKa 射线辐射, 在293K 温度下, 在θ=9~13°, 0﹤h﹤9, 0﹤k﹤29, 0﹤L﹤12范围内以25 个衍射点精确测定取向矩阵和晶胞参数。在θ=9~13°扫描范围内共收集到3086 个衍射点,其中独立衍射点3032 个, 选择I>I(2σ)的2025个衍射点用于结构测定和修正。分析结果表明: 晶体属单斜晶系, 空间群:C2, 晶胞参数: a=35.504(7)Å, b=7.4420(15)Å,c=11.894(2)Å,β=104.15(3)°; 晶包体积V=3047.3(11)Å;晶包内分子数Z=4。利用几何计算法和差值Fourier法解析晶体结构,最终收敛偏差因子R1=0.068, wR2=0.189, 拟合优度s=1.01, w = 1/[σ2(Fo 2)+(0.1P)2+1.8P], 其中P=(Fo2+2Fc2)/3。 最终确定化学计量式为【C30H46O3,2(CH4O)】计算分子量为518.75,其中包含两分子溶剂甲醇。计算晶体密度为值1.131g/cm3。化合物的分子结构图如说明书中所示,图2为所述分子立体结构投影图。原子坐标参数及等价温度因子见表2,成键原子的键长和键角见附表3。
表2:原子坐标参数及等价温度因子
x | y | z | U iso*/U eq | |
O1 | 0.56984 (14) | 0.3704 (7) | 0.6694 (4) | 0.0714 (14) |
O2 | 0.57503 (16) | 0.6440 (6) | 0.6000 (4) | 0.0797 (16) |
O3 | 0.86698 (13) | −0.0423 (7) | 0.8367 (4) | 0.0691 (13) |
O4 | 0.5869 (2) | 0.1135 (8) | 0.8329 (5) | 0.135 (3) |
O5 | 0.57412 (18) | 0.7628 (8) | −0.1944 (5) | 0.0917 (17) |
C1 | 0.53446 (19) | 0.3137 (11) | 0.2787 (5) | 0.0637 (19) |
C2 | 0.53864 (18) | 0.4128 (10) | 0.3927 (5) | 0.0582 (17) |
C3 | 0.57973 (17) | 0.3964 (8) | 0.4751 (5) | 0.0438 (14) |
C4 | 0.59256 (15) | 0.1979 (8) | 0.4882 (4) | 0.0406 (13) |
C5 | 0.58628 (16) | 0.1039 (9) | 0.3705 (5) | 0.0527 (15) |
C6 | 0.54517 (18) | 0.1152 (10) | 0.2945 (5) | 0.0588 (18) |
C7 | 0.63377 (15) | 0.1766 (7) | 0.5616 (5) | 0.0398 (13) |
C8 | 0.66595 (16) | 0.3075 (8) | 0.5502 (4) | 0.0391 (13) |
C9 | 0.64967 (16) | 0.4996 (8) | 0.5162 (5) | 0.0496 (15) |
C10 | 0.60989 (16) | 0.5039 (9) | 0.4317 (5) | 0.0506 (15) |
C11 | 0.64226 (16) | 0.0357 (8) | 0.6321 (5) | 0.0445 (14) |
C12 | 0.68120 (16) | −0.0070 (8) | 0.7099 (5) | 0.0478 (15) |
C13 | 0.71376 (14) | 0.1212 (7) | 0.6983 (4) | 0.0354 (12) |
C14 | 0.69776 (16) | 0.3164 (7) | 0.6688 (5) | 0.0367 (12) |
C15 | 0.75128 (15) | 0.1013 (7) | 0.7992 (4) | 0.0364 (12) |
C16 | 0.78228 (15) | 0.2279 (7) | 0.7689 (4) | 0.0365 (12) |
C17 | 0.76750 (16) | 0.4231 (7) | 0.7566 (5) | 0.0431 (14) |
C18 | 0.73138 (15) | 0.4399 (7) | 0.6579 (5) | 0.0429 (13) |
C19 | 0.76629 (16) | −0.0925 (7) | 0.7970 (5) | 0.0423 (14) |
C20 | 0.80683 (16) | −0.1211 (8) | 0.8725 (5) | 0.0483 (15) |
C21 | 0.83587 (17) | 0.0082 (8) | 0.8480 (5) | 0.0441 (14) |
C22 | 0.82511 (16) | 0.2096 (8) | 0.8412 (5) | 0.0416 (13) |
C23 | 0.51674 (19) | 0.0142 (12) | 0.3494 (7) | 0.077 (2) |
C24 | 0.5442 (2) | 0.0311 (14) | 0.1773 (6) | 0.089 (3) |
C25 | 0.57537 (16) | 0.4726 (9) | 0.5867 (5) | 0.0508 (15) |
C26 | 0.68253 (17) | 0.2374 (10) | 0.4484 (4) | 0.0520 (16) |
C27 | 0.67962 (17) | 0.3878 (8) | 0.7654 (5) | 0.0474 (15) |
C28 | 0.74436 (16) | 0.1350 (8) | 0.9202 (4) | 0.0459 (14) |
C29 | 0.83238 (19) | 0.2783 (9) | 0.9667 (5) | 0.0585 (17) |
C30 | 0.85227 (18) | 0.3094 (10) | 0.7822 (6) | 0.0605 (18) |
C31 | 0.5973 (3) | 0.2021 (14) | 0.9310 (7) | 0.106 (3) |
C32 | 0.5522 (3) | 0.6967 (14) | −0.1224 (8) | 0.100 (3) |
H1A | 0.5510 | 0.3707 | 0.2351 | 0.076* |
H1B | 0.5078 | 0.3240 | 0.2336 | 0.076* |
H1C | 0.5692 | 0.4363 | 0.7273 | 0.107* |
H2A | 0.5197 | 0.3658 | 0.4317 | 0.070* |
H2B | 0.5328 | 0.5389 | 0.3765 | 0.070* |
H4A | 0.5756 | 0.1377 | 0.5301 | 0.049* |
H4B | 0.5846 | 0.0066 | 0.8464 | 0.202* |
H5A | 0.6039 | 0.1562 | 0.3286 | 0.063* |
H5B | 0.5932 | −0.0218 | 0.3837 | 0.063* |
H5C | 0.5932 | 0.7018 | −0.2049 | 0.138* |
H9A | 0.6482 | 0.5631 | 0.5862 | 0.060* |
H9B | 0.6679 | 0.5639 | 0.4820 | 0.060* |
H10A | 0.6120 | 0.4556 | 0.3577 | 0.061* |
H10B | 0.6013 | 0.6276 | 0.4195 | 0.061* |
H11A | 0.6221 | −0.0437 | 0.6332 | 0.053* |
H12A | 0.6884 | −0.1282 | 0.6932 | 0.057* |
H12B | 0.6791 | −0.0049 | 0.7896 | 0.057* |
H13A | 0.7215 | 0.0806 | 0.6287 | 0.042* |
H16A | 0.7831 | 0.1929 | 0.6902 | 0.044* |
H17A | 0.7616 | 0.4611 | 0.8284 | 0.052* |
H17B | 0.7877 | 0.5012 | 0.7420 | 0.052* |
H18A | 0.7383 | 0.4130 | 0.5856 | 0.051* |
H18B | 0.7225 | 0.5635 | 0.6539 | 0.051* |
H19A | 0.7486 | −0.1733 | 0.8226 | 0.051* |
H19B | 0.7661 | −0.1240 | 0.7178 | 0.051* |
H20A | 0.8061 | −0.1098 | 0.9532 | 0.058* |
H20B | 0.8151 | −0.2424 | 0.8608 | 0.058* |
H23A | 0.5168 | 0.0670 | 0.4231 | 0.116* |
H23B | 0.5244 | −0.1095 | 0.3602 | 0.116* |
H23C | 0.4911 | 0.0215 | 0.2995 | 0.116* |
H24A | 0.5616 | 0.0949 | 0.1412 | 0.133* |
H24B | 0.5183 | 0.0377 | 0.1288 | 0.133* |
H24C | 0.5521 | −0.0924 | 0.1879 | 0.133* |
H24A | 0.5616 | 0.0949 | 0.1412 | 0.133* |
H26A | 0.6622 | 0.2345 | 0.3785 | 0.078* |
H26B | 0.6928 | 0.1185 | 0.4661 | 0.078* |
H26C | 0.7029 | 0.3159 | 0.4381 | 0.078* |
H27A | 0.6991 | 0.3927 | 0.8371 | 0.071* |
H27B | 0.6591 | 0.3090 | 0.7737 | 0.071* |
H27C | 0.6694 | 0.5061 | 0.7454 | 0.071* |
H28A | 0.7191 | 0.0914 | 0.9223 | 0.069* |
H28B | 0.7459 | 0.2615 | 0.9364 | 0.069* |
H28C | 0.7638 | 0.0731 | 0.9774 | 0.069* |
H29A | 0.8592 | 0.2614 | 1.0054 | 0.088* |
H29B | 0.8164 | 0.2126 | 1.0068 | 0.088* |
H29C | 0.8261 | 0.4038 | 0.9662 | 0.088* |
H30A | 0.8483 | 0.2681 | 0.7037 | 0.091* |
H30B | 0.8787 | 0.2872 | 0.8232 | 0.091* |
H30C | 0.8470 | 0.4359 | 0.7824 | 0.091* |
H31A | 0.5764 | 0.2008 | 0.9690 | 0.158* |
H31B | 0.6033 | 0.3240 | 0.9157 | 0.158* |
H31C | 0.6198 | 0.1463 | 0.9800 | 0.158* |
H32A | 0.5312 | 0.7780 | −0.1221 | 0.150* |
H32B | 0.5683 | 0.6851 | −0.0451 | 0.150* |
H32C | 0.5419 | 0.5812 | −0.1500 | 0.150* |
表3:成键原子的键长和键角
O1—C25 | 1.296 (6) | C16—H16A | 0.9800 |
O1—H1C | 0.8500 | C17—C18 | 1.517 (7) |
O2—C25 | 1.286 (8) | C17—H17A | 0.9700 |
O3—C21 | 1.205 (7) | C17—H17B | 0.9700 |
C1—C2 | 1.518 (9) | C18—H18A | 0.9700 |
C1—C6 | 1.525 (10) | C18—H18B | 0.9700 |
C1—H1A | 0.9700 | C19—C20 | 1.514 (8) |
C1—H1B | 0.9700 | C19—H19A | 0.9700 |
C2—C3 | 1.551 (8) | C19—H19B | 0.9700 |
C2—H2A | 0.9700 | C20—C21 | 1.490 (8) |
C2—H2B | 0.9700 | C20—H20A | 0.9700 |
C3—C25 | 1.486 (8) | C20—H20B | 0.9700 |
C3—C10 | 1.524 (8) | C21—C22 | 1.545 (9) |
C3—C4 | 1.542 (8) | C22—C30 | 1.518 (8) |
C4—C7 | 1.518 (7) | C22—C29 | 1.539 (8) |
C4—C5 | 1.532 (8) | C23—H23A | 0.9600 |
C4—H4A | 0.9800 | C23—H23B | 0.9600 |
C5—C6 | 1.520 (8) | C23—H23C | 0.9600 |
C5—H5A | 0.9700 | C24—H24A | 0.9600 |
C5—H5B | 0.9700 | C24—H24B | 0.9600 |
C6—C24 | 1.521 (9) | C24—H24C | 0.9600 |
C6—C23 | 1.527 (10) | C26—H26A | 0.9600 |
C7—C11 | 1.330 (8) | C26—H26B | 0.9600 |
C7—C8 | 1.533 (7) | C26—H26C | 0.9600 |
C8—C9 | 1.558 (8) | C27—H27A | 0.9600 |
C8—C26 | 1.560 (7) | C27—H27B | 0.9600 |
C8—C14 | 1.578 (7) | C27—H27C | 0.9600 |
C9—C10 | 1.520 (8) | C28—H28A | 0.9600 |
C9—H9A | 0.9700 | C28—H28B | 0.9600 |
C9—H9B | 0.9700 | C28—H28C | 0.9600 |
C10—H10A | 0.9700 | C29—H29A | 0.9600 |
C10—H10B | 0.9700 | C29—H29B | 0.9600 |
C11—C12 | 1.498 (8) | C29—H29C | 0.9600 |
C11—H11A | 0.9300 | C30—H30A | 0.9600 |
C12—C13 | 1.531 (7) | C30—H30B | 0.9600 |
C12—H12A | 0.9700 | C30—H30C | 0.9600 |
C12—H12B | 0.9700 | O4—C31 | 1.312 (10) |
C13—C15 | 1.567 (7) | O4—H4B | 0.8200 |
C13—C14 | 1.568 (7) | O5—C32 | 1.380 (10) |
C13—H13A | 0.9800 | O5—H5C | 0.8500 |
C14—C18 | 1.537 (7) | C31—H31A | 0.9600 |
C14—C27 | 1.542 (7) | C31—H31B | 0.9600 |
C15—C28 | 1.539 (7) | C31—H31C | 0.9600 |
C15—C19 | 1.540 (7) | C32—H32A | 0.9600 |
C15—C16 | 1.556 (7) | C32—H32B | 0.9600 |
C16—C17 | 1.539 (8) | C32—H32C | 0.9600 |
C16—C22 | 1.559 (7) |
C25—O1—H1C | 108.3 | C18—C17—H17A | 109.5 |
C2—C1—C6 | 113.2 (6) | C16—C17—H17A | 109.5 |
C2—C1—H1A | 108.9 | C18—C17—H17B | 109.5 |
C6—C1—H1A | 108.9 | C16—C17—H17B | 109.5 |
C2—C1—H1B | 108.9 | H17A—C17—H17B | 108.1 |
C6—C1—H1B | 108.9 | C17—C18—C14 | 114.4 (4) |
H1A—C1—H1B | 107.8 | C17—C18—H18A | 108.7 |
C1—C2—C3 | 113.4 (5) | C14—C18—H18A | 108.7 |
C1—C2—H2A | 108.9 | C17—C18—H18B | 108.7 |
C3—C2—H2A | 108.9 | C14—C18—H18B | 108.7 |
C1—C2—H2B | 108.9 | H18A—C18—H18B | 107.6 |
C3—C2—H2B | 108.9 | C20—C19—C15 | 113.9 (5) |
H2A—C2—H2B | 107.7 | C20—C19—H19A | 108.8 |
C25—C3—C10 | 109.7 (5) | C15—C19—H19A | 108.8 |
C25—C3—C4 | 111.6 (5) | C20—C19—H19B | 108.8 |
C10—C3—C4 | 108.8 (5) | C15—C19—H19B | 108.8 |
C25—C3—C2 | 104.3 (5) | H19A—C19—H19B | 107.7 |
C10—C3—C2 | 112.0 (5) | C21—C20—C19 | 113.3 (5) |
C4—C3—C2 | 110.4 (5) | C21—C20—H20A | 108.9 |
C7—C4—C5 | 112.5 (4) | C19—C20—H20A | 108.9 |
C7—C4—C3 | 112.2 (5) | C21—C20—H20B | 108.9 |
C5—C4—C3 | 111.8 (5) | C19—C20—H20B | 108.9 |
C7—C4—H4A | 106.6 | H20A—C20—H20B | 107.7 |
C5—C4—H4A | 106.6 | O3—C21—C20 | 121.2 (6) |
C3—C4—H4A | 106.6 | O3—C21—C22 | 121.2 (6) |
C6—C5—C4 | 115.0 (5) | C20—C21—C22 | 117.6 (5) |
C6—C5—H5A | 108.5 | C30—C22—C29 | 108.1 (5) |
C4—C5—H5A | 108.5 | C30—C22—C21 | 108.8 (5) |
C6—C5—H5B | 108.5 | C29—C22—C21 | 106.9 (5) |
C4—C5—H5B | 108.5 | C30—C22—C16 | 110.3 (5) |
H5A—C5—H5B | 107.5 | C29—C22—C16 | 114.6 (5) |
C5—C6—C24 | 109.0 (5) | C21—C22—C16 | 108.0 (4) |
C5—C6—C1 | 107.5 (6) | C6—C23—H23A | 109.5 |
C24—C6—C1 | 109.7 (7) | C6—C23—H23B | 109.5 |
C5—C6—C23 | 110.9 (6) | H23A—C23—H23B | 109.5 |
C24—C6—C23 | 108.7 (6) | C6—C23—H23C | 109.5 |
C1—C6—C23 | 111.0 (6) | H23A—C23—H23C | 109.5 |
C11—C7—C4 | 118.9 (5) | H23B—C23—H23C | 109.5 |
C11—C7—C8 | 119.8 (5) | C6—C24—H24A | 109.5 |
C4—C7—C8 | 121.2 (5) | C6—C24—H24B | 109.5 |
C7—C8—C9 | 111.6 (4) | H24A—C24—H24B | 109.5 |
C7—C8—C26 | 106.7 (5) | C6—C24—H24C | 109.5 |
C9—C8—C26 | 107.0 (5) | H24A—C24—H24C | 109.5 |
C7—C8—C14 | 109.5 (4) | H24B—C24—H24C | 109.5 |
C9—C8—C14 | 109.4 (4) | O2—C25—O1 | 118.7 (6) |
C26—C8—C14 | 112.6 (4) | O2—C25—C3 | 119.7 (6) |
C10—C9—C8 | 114.6 (5) | O1—C25—C3 | 121.5 (6) |
C10—C9—H9A | 108.6 | C8—C26—H26A | 109.5 |
C8—C9—H9A | 108.6 | C8—C26—H26B | 109.5 |
C10—C9—H9B | 108.6 | H26A—C26—H26B | 109.5 |
C8—C9—H9B | 108.6 | C8—C26—H26C | 109.5 |
H9A—C9—H9B | 107.6 | H26A—C26—H26C | 109.5 |
C9—C10—C3 | 112.4 (5) | H26B—C26—H26C | 109.5 |
C9—C10—H10A | 109.1 | C14—C27—H27A | 109.5 |
C3—C10—H10A | 109.1 | C14—C27—H27B | 109.5 |
C9—C10—H10B | 109.1 | H27A—C27—H27B | 109.5 |
C3—C10—H10B | 109.1 | C14—C27—H27C | 109.5 |
H10A—C10—H10B | 107.9 | H27A—C27—H27C | 109.5 |
C7—C11—C12 | 126.1 (5) | H27B—C27—H27C | 109.5 |
C7—C11—H11A | 116.9 | C15—C28—H28A | 109.5 |
C12—C11—H11A | 116.9 | C15—C28—H28B | 109.5 |
C11—C12—C13 | 114.5 (5) | H28A—C28—H28B | 109.5 |
C11—C12—H12A | 108.6 | C15—C28—H28C | 109.5 |
C13—C12—H12A | 108.6 | H28A—C28—H28C | 109.5 |
C11—C12—H12B | 108.6 | H28B—C28—H28C | 109.5 |
C13—C12—H12B | 108.6 | C22—C29—H29A | 109.5 |
H12A—C12—H12B | 107.6 | C22—C29—H29B | 109.5 |
C12—C13—C15 | 113.0 (4) | H29A—C29—H29B | 109.5 |
C12—C13—C14 | 110.9 (4) | C22—C29—H29C | 109.5 |
C15—C13—C14 | 116.9 (4) | H29A—C29—H29C | 109.5 |
C12—C13—H13A | 104.9 | H29B—C29—H29C | 109.5 |
C15—C13—H13A | 104.9 | C22—C30—H30A | 109.5 |
C14—C13—H13A | 104.9 | C22—C30—H30B | 109.5 |
C18—C14—C27 | 109.3 (5) | H30A—C30—H30B | 109.5 |
C18—C14—C13 | 109.1 (4) | C22—C30—H30C | 109.5 |
C27—C14—C13 | 110.3 (4) | H30A—C30—H30C | 109.5 |
C18—C14—C8 | 110.5 (4) | H30B—C30—H30C | 109.5 |
C27—C14—C8 | 110.0 (4) | C31—O4—H4B | 109.5 |
C13—C14—C8 | 107.6 (4) | C32—O5—H5C | 119.5 |
C28—C15—C19 | 107.6 (4) | O4—C31—H31A | 109.5 |
C28—C15—C16 | 113.7 (4) | O4—C31—H31B | 109.5 |
C19—C15—C16 | 107.2 (4) | H31A—C31—H31B | 109.5 |
C28—C15—C13 | 113.6 (4) | O4—C31—H31C | 109.5 |
C19—C15—C13 | 108.0 (4) | H31A—C31—H31C | 109.5 |
C16—C15—C13 | 106.4 (4) | H31B—C31—H31C | 109.5 |
C17—C16—C15 | 110.5 (4) | O5—C32—H32A | 109.5 |
C17—C16—C22 | 113.5 (4) | O5—C32—H32B | 109.5 |
C15—C16—C22 | 118.0 (4) | H32A—C32—H32B | 109.5 |
C17—C16—H16A | 104.4 | O5—C32—H32C | 109.5 |
C15—C16—H16A | 104.4 | H32A—C32—H32C | 109.5 |
C22—C16—H16A | 104.4 | H32B—C32—H32C | 109.5 |
C18—C17—C16 | 110.8 (4) |
C6—C1—C2—C3 | 55.5 (8) | C7—C8—C14—C27 | −61.9 (5) |
C1—C2—C3—C25 | −170.1 (6) | C9—C8—C14—C27 | 60.8 (5) |
C1—C2—C3—C10 | 71.3 (7) | C26—C8—C14—C27 | 179.6 (5) |
C1—C2—C3—C4 | −50.1 (7) | C7—C8—C14—C13 | 58.3 (5) |
C25—C3—C4—C7 | −68.4 (6) | C9—C8—C14—C13 | −179.0 (4) |
C10—C3—C4—C7 | 52.7 (6) | C26—C8—C14—C13 | −60.2 (6) |
C2—C3—C4—C7 | 176.1 (5) | C12—C13—C15—C28 | −58.8 (6) |
C25—C3—C4—C5 | 164.1 (5) | C14—C13—C15—C28 | 71.8 (6) |
C10—C3—C4—C5 | −74.7 (6) | C12—C13—C15—C19 | 60.5 (6) |
C2—C3—C4—C5 | 48.6 (6) | C14—C13—C15—C19 | −168.9 (4) |
C7—C4—C5—C6 | 178.1 (5) | C12—C13—C15—C16 | 175.3 (4) |
C3—C4—C5—C6 | −54.6 (7) | C14—C13—C15—C16 | −54.0 (6) |
C4—C5—C6—C24 | 175.0 (6) | C28—C15—C16—C17 | −67.2 (6) |
C4—C5—C6—C1 | 56.2 (7) | C19—C15—C16—C17 | 174.0 (4) |
C4—C5—C6—C23 | −65.3 (8) | C13—C15—C16—C17 | 58.7 (5) |
C2—C1—C6—C5 | −55.8 (8) | C28—C15—C16—C22 | 65.7 (6) |
C2—C1—C6—C24 | −174.2 (5) | C19—C15—C16—C22 | −53.1 (6) |
C2—C1—C6—C23 | 65.7 (7) | C13—C15—C16—C22 | −168.4 (4) |
C5—C4—C7—C11 | −89.4 (6) | C15—C16—C17—C18 | −62.3 (6) |
C3—C4—C7—C11 | 143.5 (5) | C22—C16—C17—C18 | 162.6 (4) |
C5—C4—C7—C8 | 86.9 (6) | C16—C17—C18—C14 | 56.8 (6) |
C3—C4—C7—C8 | −40.2 (7) | C27—C14—C18—C17 | 72.7 (6) |
C11—C7—C8—C9 | −152.6 (5) | C13—C14—C18—C17 | −48.0 (6) |
C4—C7—C8—C9 | 31.2 (7) | C8—C14—C18—C17 | −166.1 (5) |
C11—C7—C8—C26 | 90.8 (6) | C28—C15—C19—C20 | −69.3 (6) |
C4—C7—C8—C26 | −85.4 (6) | C16—C15—C19—C20 | 53.4 (6) |
C11—C7—C8—C14 | −31.3 (7) | C13—C15—C19—C20 | 167.7 (4) |
C4—C7—C8—C14 | 152.5 (5) | C15—C19—C20—C21 | −53.2 (6) |
C7—C8—C9—C10 | −37.1 (7) | C19—C20—C21—O3 | −133.2 (6) |
C26—C8—C9—C10 | 79.3 (6) | C19—C20—C21—C22 | 48.6 (7) |
C14—C8—C9—C10 | −158.5 (5) | O3—C21—C22—C30 | 18.1 (8) |
C8—C9—C10—C3 | 55.0 (7) | C20—C21—C22—C30 | −163.6 (5) |
C25—C3—C10—C9 | 60.5 (6) | O3—C21—C22—C29 | −98.4 (6) |
C4—C3—C10—C9 | −61.8 (7) | C20—C21—C22—C29 | 79.8 (6) |
C2—C3—C10—C9 | 175.9 (5) | O3—C21—C22—C16 | 137.8 (5) |
C4—C7—C11—C12 | 179.7 (5) | C20—C21—C22—C16 | −43.9 (6) |
C8—C7—C11—C12 | 3.4 (9) | C17—C16—C22—C30 | −62.0 (6) |
C7—C11—C12—C13 | −4.0 (9) | C15—C16—C22—C30 | 166.5 (5) |
C11—C12—C13—C15 | 166.6 (5) | C17—C16—C22—C29 | 60.2 (6) |
C11—C12—C13—C14 | 33.0 (7) | C15—C16—C22—C29 | −71.3 (6) |
C12—C13—C14—C18 | −180.0 (4) | C17—C16—C22—C21 | 179.2 (5) |
C15—C13—C14—C18 | 48.4 (6) | C15—C16—C22—C21 | 47.7 (6) |
C12—C13—C14—C27 | 60.0 (6) | C10—C3—C25—O2 | 41.0 (8) |
C15—C13—C14—C27 | −71.7 (6) | C4—C3—C25—O2 | 161.7 (6) |
C12—C13—C14—C8 | −60.0 (6) | C2—C3—C25—O2 | −79.2 (7) |
C15—C13—C14—C8 | 168.3 (4) | C10—C3—C25—O1 | −142.7 (5) |
C7—C8—C14—C18 | 177.3 (5) | C4—C3—C25—O1 | −22.0 (7) |
C9—C8—C14—C18 | −60.0 (5) | C2—C3—C25—O1 | 97.2 (6) |
C26—C8—C14—C18 | 58.8 (6) |
实施例2:
称取3-氧代齐墩果酸粗品5.0g,加入50ml重结晶溶剂,其中甲醇:石油醚:丙酮的用量比为40ml:5ml:5ml。60℃回流处理,待产物完全溶解,且观察有少量固体析出时,停止回流,利用溶剂缓慢挥发法,在恒温培养箱中放置,温度设置为25℃,培养时间为2天,白色针状结晶析出,经显微镜观测,有3-氧代齐墩果酸单晶形成。
实施例3:
称取3-氧代齐墩果酸粗品4.5g,加入90ml重结晶溶剂,其中甲醇:石油醚:丙酮的用量比为60ml:20ml:10ml。40℃回流处理,待产物完全溶解,且观察有少量固体析出时,停止回流,利用溶剂缓慢挥发法,在恒温培养箱中放置,温度设置为8℃,培养时间为10天,白色针状结晶析出,经显微镜观测,有3-氧代齐墩果酸单晶。
实施例4:
称取3-氧代齐墩果酸粗品4.0g,加入60ml重结晶溶剂,其中甲醇:石油醚:异丙醇的用量比为46ml:5ml:9ml。50℃回流处理,待产物完全溶解,且观察有少量固体析出时,停止回流,利用溶剂缓慢挥发法,在恒温培养箱中放置,温度设置为18℃,培养时间为4天,白色针状结晶析出,经显微镜观测,有3-氧代齐墩果酸单晶。
实施例5:
称取3-氧代齐墩果酸粗品4.0g,加入65ml重结晶溶剂,其中甲醇:石油醚:氯仿的用量比为50ml:5ml:10ml。55℃回流处理,待产物完全溶解,且观察有少量固体析出时,停止回流,利用溶剂缓慢挥发法,在恒温培养箱中放置,温度设置为15℃,培养时间为6天,白色针状结晶析出,经显微镜观测,有3-氧代齐墩果酸单晶。
实施例6:
称取3-氧代齐墩果酸粗品4.0g,加入40ml重结晶溶剂,其中甲醇:石油醚:乙酸乙酯的用量比为25ml:8ml:7ml。60℃回流处理,待产物完全溶解,且观察有少量固体析出时,停止回流,利用溶剂缓慢挥发法,在恒温培养箱中放置,温度设置为20℃,培养时间为3天,白色针状结晶析出,经显微镜观测,有3-氧代齐墩果酸单晶。
Claims (3)
2.一种培养权利要求1所述的3-氧代齐墩果酸单晶的方法,其特征在于称取3-氧代齐墩果酸粗品,按每克粗品10~20ml的比例加入重结晶溶剂,温度控制在40~60℃进行回流处理,待溶解达饱和状态后,利用溶剂缓慢挥发法,在恒温培养箱中放置,培养时间为2~10天,放置温度为8~25℃即可析出白色针状结晶;所述的重结晶溶剂是甲醇、石油醚和丙酮的混合液,其中甲醇:石油醚:丙酮的体积比为8~12:1~4:1~2。
3. 根据权利要求2所述的培养3-氧代齐墩果酸单晶的方法,其特征在于所述的丙酮由异丙醇、氯仿或乙酸乙酯替代。
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