CN114409624B - 一种从哈茨木霉菌中分离得到的色酮类化合物及其制备方法和用途 - Google Patents
一种从哈茨木霉菌中分离得到的色酮类化合物及其制备方法和用途 Download PDFInfo
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Abstract
本发明公开一种从哈茨木霉菌中分离得到的色酮类化合物及其制备方法和应用。所述化合物结构式下所示,式中,R1选自H或CH2OH,R2选自CH2OH或CH2OCOCH3。本发明实验证实所述化合物具有杀虫活性,其中新化合物5‑羟基‑3‑乙酸甲酯基‑2‑甲基‑7‑甲氧基色酮(H‑4)杀虫活性较好。本发明为色酮类化合物在杀虫方面的应用提供了新的选择。
Description
技术领域
本发明属于药物化学技术领域,具体涉及一种从哈茨木霉菌中分离得到的色酮类化合物及其制备方法和用途。
背景技术
海洋真菌在特殊的生存环境下,生命力强,具有奇特的代谢途径和防御体制,能够产生大量结构新颖、功能丰富的生物活性代谢产物,引起了国内外科学家的密切关注,成为当前最具有开发前景的海洋天然产物新药源,同时也是世界药物研发新型先导化合物的热点之一(付逸群等,2019)。到目前为止,研究者们从海洋真菌的次级代谢产物中分离鉴定出大量的结构新颖的化合物,这些化合物表现出良好的抗肿瘤、抗菌或抗病毒等药理学活性(冯婷玉,2011;李学恭,2008),已从海洋真菌的发酵产物中发现了1500余种新的次级代谢产物,这些化合物的性质非常典型地代表了海洋真菌的化学防御机制(吴泽宏等,2017)。研究者们估计在海洋中,海洋真菌存在量可能达到10000种以上,而已经被分离鉴定的海洋真菌只有其十分之一,因此,研究者们认为对海洋真菌次级代谢产物的研究工作还有很大的前景(Jones et al.,2015)。
目前,关于海洋真菌次级代谢产物的生物活性研究主要集中在抗菌活性、抗肿瘤活性、抗病毒活性和抗炎活性等。海洋真菌次生代谢产物的抗虫活性研究报道相对较少。海洋真菌源化合物的杀虫活性相关研究较少。
由于昆虫的抗药性发展迅速(束放,2010;徐燕,2010),急需新型生物杀虫剂来防治害虫,研究发现从海洋微生物中可筛选出对农业害虫具有杀虫活性的新型微生物资源(刘济宁,2004),由于危害农业生产的害虫生长在陆地环境下,对海洋药物可能不易产生抗药性,即来源于海洋生物的具有杀虫活性的次生代谢产物也许更适合研发杀虫剂。到目前为止,关于筛选海洋生物杀虫活性化合物的研究报道并不多见。
发明内容
鉴于现有技术的不足,本发明首先从哈茨木霉菌中分离得到几个结构新颖的色酮类化合物。另一方面,本发明还提供了这些化合物的制备方法和用途。
本发明技术方案主要包括以下内容:
从哈茨木霉菌中分离得到的色酮类化合物,其结构式如式I所示:
式中,R1选自H或CH2OH,R2选自CH2OH或CH2OCOCH3。
优选的,R1选自H,R2选自CH2OCOCH3。具体结构如下:
另一方面,本发明还提供了所述色酮类化合物的制备方法。在一个实施例中,本发明以采用常规方法筛选得到的哈茨木霉菌为例,对该菌的发酵物进行分离纯化后得到目标化合物。本发明所能使用的哈茨木霉菌并不限于实施例中所述的菌株,技术人员还可以采用市售或其他常规方式所得到的哈茨木霉菌,并结合本发明所提供的制备方法进行目标化合物的分离。本发明不对菌株的来源进行特别限定。
所述色酮类化合物的制备方法,包括以下步骤:
(1)将哈茨木霉菌接种于海水PDB培养基中摇床培养,得发酵种子液;
(2)将发酵种子液接种于海水大米固体培养基,静置发酵培养,得发酵物;
(3)发酵结束后,用乙酸乙酯浸泡发酵物,过滤,浓缩,得发酵物浸膏;
(4)将发酵物浸膏进行硅胶柱洗脱,先以石油醚-乙酸乙酯为洗脱剂进行梯度洗脱,再以乙酸乙酯-甲醇为洗脱剂进行梯度洗脱;得到的馏分用TCL进行分析后,合并相似馏分,得到馏分Fr.1~Fr.18,经过分离纯化得到权利要求1所述化合物。
优选的,石油醚-乙酸乙酯的洗脱梯度V/V为100:0,96:4,89:11,87:13,85:15,83:17,80:20,77:23,73:27,70:30,65:35,60:40,55:45,45:55,35:65,25:75,15:85,0:100;乙酸乙酯-甲醇的洗脱梯度V/V为85:15,70:30,40:60,0:100。
优选的,静置发酵培养的时间为45d。
优选的,用乙酸乙酯浸泡发酵物的时间为3d。
优选的,所述分离纯化为:Fr.3经正向硅胶柱,以体积比93:7的石油醚:乙酸乙酯为洗脱剂,分离得到馏分Fr.3-1,馏分Fr.3-1再经凝胶柱,以甲醇为洗脱剂,洗脱得到化合物H-4;Fr.10经过凝胶柱,以体积比1:1的甲醇:氯仿为洗脱剂,分离得到馏分Fr.10-1,馏分Fr.10-1再经凝胶柱,以甲醇为洗脱剂,洗脱得到化合物H-9;
化合物H-4结构式为:
化合物H-9结构式为:
另外,基于本发明所公开的化合物结构,技术人员也可以依据常规的化学合成原理对本发明所述的化合物进行人工合成,从而得到所述化合物。
本发明还进一步发现了所述化合物具有良好的杀虫活性。所述的色酮类化合物的结构式如式I所示:
式中,R1选自H或CH2OH,R2选自H、CH2OH或CH2OCOCH3。
具体的,所述虫为伊蚊属昆虫。更具体的,所述虫为埃及伊蚊。
本发明所取得的效果:
本发明从哈茨木霉菌中分离到5个色酮类化合物,其中包含两个具有杀虫活性的新化合物,而新化合物5-羟基-3-乙酸甲酯基-2-甲基-7-甲氧基色酮(H-4)表现出良好的杀虫活性,推测其结构上(-CH2OCOCH3)基团的存在是杀虫活性的关键。该类化合物的活性报道较少,因此本发明为色酮类化合物在杀虫活性方面上的测定填补了空白。
附图说明
图1:化合物H-1的结构
图2:化合物H-4的结构和主要HMBC相关
图3:化合物H-6的结构
图4:化合物H-7的结构
图5:化合物H-9的结构和主要HMBC相关
图6:化合物H-4的1H-NMR图谱
图7:化合物H-4的13C-NMR图谱
图8:化合物H-4的HSQC图谱
图9:化合物H-4的HMBC图谱
具体实施方式
为了更好理解本发明技术内容,下面提供具体实施例,对本发明做进一步的说明。
实验例1-海洋真菌的分离与纯化
1.海水培养基的制备
将200g去皮马铃薯加热煮熟并用玻璃棒戳烂,用八层纱布过滤得到滤液,滤液中加入20g葡萄糖和20g琼脂,然后加海水定容至1000mL,取150mL于250mL的三角瓶中,得海水PDA培养基。将海水PDA培养基、海水、移液枪头、培养皿(90mm)和试管(20mL),于121℃高压灭菌锅灭菌20min,备用。
2.海洋真菌培养
超净工作台无菌操作,将冷却至50℃左右的培养基中各加入50μg/mL青霉素和链霉素,摇匀后,趁热倒入培养皿中,封口。观察3-5d无污染后,备用。
无菌操作下,取适量从海南省东寨港红树林采集的海泥样品置于100mL的三角瓶中(含50mL的无菌海水),玻璃棒搅拌均匀,静置。从三角瓶中吸取1mL上清液于20mL的试管中(内含9mL无菌海水),配制成10-1的浓度梯度,依次稀释,得到10-2、10-3、10-4和10-5的浓度梯度。取150μL各浓度溶液加入含有青霉素和链霉素的PDA培养基上(3个重复),用涂布器涂布均匀,后将培养皿封口,倒置培养。
3.海洋真菌分离纯化
每日观察倒置培养的培养基中微生物的生长情况,用接种针挑取出新长出来的真菌菌丝接种到空白培养基上,待新培养基上的真菌长出菌丝,再用平板划线法或点接法不断的分离纯化,直至得到纯的真菌菌种,经鉴定,该菌为哈茨木霉菌(Trichodermaharzianum)。
4.菌种保藏
将80%甘油通过高压蒸汽灭菌后待用,将菌种用无菌水配制成高浓度菌悬液,把80%灭菌甘油加入菌悬液中,配制成含10%~30%甘油的菌悬液,保藏于-80℃超低温冰箱中。
实验例2真菌发酵培养与发酵物的提取
(1)发酵种子液制备
在无菌操作下,将纯化的海洋真菌哈茨木霉菌接种在已灭菌的500mL三角瓶中(装有200mL海水PDB培养基),放入摇床(180rpm,26℃)培养1d后,得发酵种子液。
海水PDB培养基:马铃薯200g,葡萄糖20g,海水定容至1000mL。
(2)菌株发酵培养
在无菌操作下,取发酵种子液3mL接种于已灭菌的1000mL三角瓶中(装有80g大米和100mL海水),静置培养45d。
(3)发酵物的提取
发酵结束后,采用乙酸乙酯对发酵物浸泡3d,过滤,经抽滤减压浓缩得到发酵物浸膏,重复3次。合并3次所得发酵物浸膏于封口瓶中用于杀虫活性检测。
实验例3哈茨木霉菌次级代谢产物的提取与分离
通过海水大米固体培养基(大米80g,海水100mL)扩大发酵培养哈茨木霉菌(Trichoderma harzianum),从160个发酵瓶中经减压浓缩得到乙酸乙酯浸膏共389.45g,以60-100目硅胶拌样(硅胶与样品的比例在1:1左右),用200-300目的硅胶装柱分离样品。粗提取物(即乙酸乙酯浸膏)用薄层层析法(TCL)进行分析后,先用石油醚-乙酸乙酯系统按体积比(100:0,96:4,89:11,87:13,85:15,83:17,80:20,77:23,73:27,70:30,65:35,60:40,55:45,45:55,35:65,25:75,15:85,0:100)进行正向硅胶柱色谱洗脱,再用乙酸乙酯-甲醇系统按体积比(85:15,70:30,40:60,0:100)进行正向硅胶柱色谱洗脱。得到的馏分再用TCL进行分析后,合并相似馏分共得到18个馏分(Fr.1~Fr.18),经过分离纯化得到目标化合物。所述分离纯化为:Fr.1经(MeOH:CHCl3=1:1)凝胶柱洗脱得到化合物H-1;Fr.3经(PE:EtOAc=93:7)正向硅胶柱分离得到Fr.3-1,再经甲醇凝胶柱洗脱得到化合物H-4;Fr.5经过甲醇凝胶柱洗脱得到化合物H-6和H-7;Fr.10经过(MeOH:CHCl3=1:1)凝胶柱分离得到Fr.10-1,再经甲醇凝胶柱洗脱得到化合物H-9。得到5-羟基-2,3-二甲基-7-甲氧基色酮(H-1)、5-羟基-3-羟甲基-2-甲基-7-甲氧基色酮(H-6)和5-羟基-2-羟甲基-3-甲基-7-甲氧基色酮(H-7),并且分离到2个新化合物5-羟基-3-乙酸甲酯基-2-甲基-7-甲氧基色酮(H-4)和5-羟基-2,3-二羟甲基-7-甲氧基色酮(H-9)。
化合物的结构鉴定:
化合物H-1:透明针状晶体(甲醇);ESI-MS(m/z):221.0812[M+H]+给出分子离子峰,结合1H-NMR和13C-NMR谱推导其分子式为C12H12O4;1H-NMR(400MHz,CDCl3)给出2个甲基氢信号δH 2.00(s,H-C(10),3H),2.38(s,H-C(9),3H);1个芳香甲氧基氢信号δH 3.84(s,H-C(7-OMe),3H);1对偶联芳香族质子氢信号δH 6.31(d,J=2.4Hz,H-C(8),1H),6.32(d,J=2.4Hz,H-C(6),1H)和1个螯合苯酚羟基氢信号δH 12.94(s,H-C(5-OH),1H)。13C-NMR(101MHz,CDCl3)共给出12个碳信号,包括1个碳基碳信号δC 181.9(C=O,C-4);1个甲氧基碳信号δC 55.7(CH3,C-7-OMe);2个甲基碳信号δC 18.4(CH3,C-9),9.1(CH3,C-10);2个芳香碳信号δC 97.6(CH,C-6),91.8(CH,C-8);6个季碳(4个经氧化脱粘)信号δC 165.1(C=C,C-7),162.5(C=C,C-2),162.0(C=C,C-5),157.6(C=C,C-8a),115.1(C=C,C-3),104.7(C=C,C-4a)。其NMR数据与文献(Takenka et al.,2000)报道一致,故鉴定为5-羟基-2,3-二甲基-7-甲氧基色酮,结构式见图1。
化合物H-4:褐色针状晶体(甲醇);HR-ESI-MS(m/z):301.0683[M+Na]+(计算值为C14H14O6Na,301.0688),给出分子离子峰,结合1H-NMR和13C-NMR谱推导其分子式为C14H14O6;1H-NMR(600MHz,CDCl3)给出2个甲基氢信号δH 2.11(s,H-C(12),3H),2.52(s,H-C(9),3H);1个芳香甲氧基氢信号δH 3.88(s,H-C(7-OMe),3H);1个亚甲基氢信号δH 5.11(s,H-C(10),2H);1对偶联芳香族质子氢信号δH 6.38(s,H-C(6,8),2H)和1个螯合苯酚羟基氢信号δH12.65(s,H-C(5-OH),1H)。13C-NMR(151MHz,CDCl3)共给出14个碳信号,包括2个碳基碳信号δC 180.9(C=O,C-4),171.0(C=O,C-4);1个亚甲基碳信号δC 56.5(CH2,C-10);1个甲氧基碳信号δC 55.8(CH3,C-7-OMe);2个甲基碳信号δC 20.9(CH3,C-12),18.4(CH3,C-9);2个芳香碳信号δC 98.1(CH,C-6),92.5(CH,C-8);6个季碳(4个经氧化脱粘)信号δC 167.4(C=C,C-2),165.6(C=C,C-7),162.3(C=C,C-5),157.5(C=C,C-8a),114.6(C=C,C-3),104.8(C=C,C-4a)。为了进一步确定该化合物的化学结构,对其2D-NMR波谱数据进行了深入分析。首先结合化合物的1D-NMR数据以及HSQC谱图中相关耦合信号,对化合物的碳氢信号进行了归属(表1)。在此基础上,利用HMBC谱中的耦合信号,对化合物的平面结构进行了深入解析。通过HMBC谱中的关键相关点:H-6→C-4a,5,7,8;H-8→C-4a,6,7,8a;7-OMe→C-7;5-OH→C-4a,5,6;H3-9→C-2,3等与文献(Takenka et al.,2000)数据比对推测其为色酮类化合物。另外,由HSQC谱中可以清楚地看到δH 5.11(H-10)对应δC 56.5(C-10);δH 2.11(H-12)对应δC 20.9(C-12);说明C-10和C-12上的氢是化学等价的。以及HMBC谱中甲基氢δH 2.11(H-12)与δC 171.0(C-11);亚甲基氢δH 5.11(H-10)与δC 171.0(C-11),δC 180.9(C-4),δC 114.6(C-3)和δC 167.4(C-2);推测出基团(-CH2OCOR)连接于C-3。最终推导出新化合物的平面结构,结构式见图2。将化合物命名为5-羟基-3-乙酸甲酯基-2-甲基-7-甲氧基色酮。
表1化合物H-4的核磁共振数据
化合物H-6:透明针状晶体(甲醇);ESI-MS(m/z):259.0503[M+Na]+给出分子离子峰,结合1H-NMR和13C-NMR谱推导其分子式为C12H12O5;1H-NMR(600MHz,CDCl3)给出1个甲基氢信号δH 2.47(s,H-C(9),3H);1个芳香甲氧基氢信号δH 3.87(s,H-C(7-OMe),3H);1个羟甲基氢信号δH 4.62(s,H-C(10),2H);1对偶联芳香族质子氢信号δH 6.35(d,J=2.3Hz,H-C(8),1H),6.36(d,J=2.3Hz,H-C(6),1H)和1个螯合苯酚羟基氢信号δH 12.53(s,H-C(5-OH),1H)。13C-NMR(151MHz,CDCl3)共给出12个碳信号,包括1个碳基碳信号δC 182.3(C=O,C-4);1个羟甲基碳信号δC 56.8(CH2OH,C-10);1个甲氧基碳信号δC 55.8(CH3,C-7-OMe);1个甲基碳信号δC 17.9(CH3,C-9);2个芳香碳信号δC 98.1(CH,C-6),92.3(CH,C-8);6个季碳(4个经氧化脱粘)信号δC 165.7(C=C,C-7),164.5(C=C,C-2),162.1(C=C,C-5),157.7(C=C,C-8a),118.3(C=C,C-3),104.9(C=C,C-4a)。其NMR数据与文献(Takenka et al.,2000)报道一致,故鉴定为5-羟基-3-羟甲基-2-甲基-7-甲氧基色酮,结构式见图3。
化合物H-7:无色针状晶体(甲醇);ESI-MS(m/z):259.0503[M+Na]+给出分子离子峰,结合1H-NMR和13C-NMR谱推导其分子式为C12H12O5;1H-NMR(600MHz,CD3OD)给出1个甲基氢信号δH 2.49(s,H-C(10),3H);1个芳香甲氧基氢信号δH 3.85(s,H-C(7-OMe),3H);1个羟甲基氢信号δH 4.54(s,H-C(9),2H)和1对偶联芳香族质子氢信号δH 6.31(d,J=2.3Hz,H-C(6),1H),6.47(d,J=2.3Hz,H-C(8),1H)。13C-NMR(151MHz,CD3OD)共给出12个碳信号,包括1个碳基碳信号δC 182.7(C=O,C-4);1个羟甲基碳信号δC 56.4(CH2OH,C-9);1个甲氧基碳信号δC 54.5(CH3,C-7-OMe);1个甲基碳信号δC 18.1(CH3,C-10);2个芳香碳信号δC 99.0(CH,C-6),93.2(CH,C-8);6个季碳(4个经氧化脱粘)信号δC167.2(C=C,C-7),168.5(C=C,C-2),163.2(C=C,C-5),159.2(C=C,C-8a),119.7(C=C,C-3),105.9(C=C,C-4a)。其NMR数据与文献(Takenka et al.,2000)报道一致,故鉴定为5-羟基-2-羟甲基-3-甲基-7-甲氧基色酮,结构式见图4。
化合物H-9:白色针状晶体(甲醇);HR-ESI-MS(m/z):253.0704[M+H]+(计算值为C12H13O6,253.0712),给出分子离子峰,结合1H-NMR和13C-NMR谱推导其分子式为C12H12O6;1H-NMR(600MHz,DMSO-D6)给出1个芳香甲氧基氢信号δH 3.86(s,H-C(7-OMe),3H);2个羟甲基氢信号δH 4.42(s,H-C(10),2H),4.57(s,H-C(9),2H);2个羟基氢信号δH 4.92(t,H-C(9-OH),1H),5.67(s,H-C(10-OH),1H);1对偶联芳香族质子氢信号δH 6.39(d,J=2.1Hz,H-C(6),1H),6.60(d,J=2.1Hz,H-C(8),1H)和1个螯合苯酚羟基氢信号δH 12.89(s,H-C(5-OH),1H)。13C-NMR(151MHz,DMSO-D6)共给出12个碳信号,包括1个碳基碳信号δC 181.7(C=O,C-4);2个羟甲基碳信号δC 51.9(CH2OH,C-10),56.6(CH2OH,C-19);1个甲氧基碳信号δC 58.9(CH3,C-7-OMe);2个芳香碳信号δC 98.5(CH,C-6),92.8(CH,C-8);6个季碳(4个经氧化脱粘)信号δC 167.7(C,C-2),165.8(C,C-7),161.8(C,C-5),157.7(C,C-8a),119.3(C,C-3),104.9(C,C-4a)。为了进一步确定该化合物的化学结构,对其2D-NMR波谱数据进行了深入分析。首先结合化合物的1D-NMR数据以及HSQC谱图中相关耦合信号,对化合物的碳氢信号进行了归属(表2)。在此基础上,利用HMBC谱中的耦合信号,对化合物的平面结构进行了深入解析。通过HMBC谱中的关键相关点:H-6→C-4a,5,7,8;H-8→C-4a,6,7,8a;7-OMe→C-7;5-OH→C-4a,5,6等与文献(Takenka et al.,2000)数据比对推测其为色酮类化合物。另外,由HSQC谱中可以清楚地看到δH 4.57(H-9)对应δC 56.6(C-9);δH 4.42(H-10)对应δC 51.9(C-10);说明C-9和C-10上的氢是化学等价的。以及HMBC谱中亚甲基氢δH 4.57(H-12)与δC167.7(C-2)和δC 119.3(C-3);亚甲基氢δH 4.42(H-10)与δC 181.7(C-4),δC 119.3(C-3)和δC 167.7(C-2);羟基δH 4.92(9-OH)与δC 56.6(C-9);羟基δH 5.67(10-OH)与δC 51.9(C-10);推测出两个羟基基团分别连接于C-9和C-10,形成的羟甲基分别连接于C-2和C-3,最终推导出新化合物的平面结构。命名为5-羟基-2,3-二羟甲基-7-甲氧基色酮,结构式见图5。
表2新化合物H-9的核磁共振数据
实验例3化合物的杀虫活性测试
化合物溶液的配制:称取25mg供试化合物,加入1mL二甲基亚砜溶解,用去离子水定容至50mL,得到化合物质量浓度为500μg/mL的药液,备用。以相同质量浓度的鱼藤酮作为药剂对照,以含等量溶剂的去离子水溶液作为空白对照。
杀虫活性的测定:采用浸渍法测定各化合物对埃及伊蚊3龄幼虫的杀虫活性。每处理重复3次,每重复用滴管吸取20只大小均一、发育一致的埃及伊蚊3龄幼虫。死亡标准:虫体僵直、尾部明显变黑,浮于药液上或沉于底部。
以500μg/mL的浓度对5个单体化合物的杀埃及伊蚊3龄幼虫活性进行评价,分别计算处理12h、24h、36h埃及伊蚊幼虫的死亡率,筛选出杀虫活性好的化合物测定对埃及伊蚊幼虫的半数致死中浓度(LC50)。结果见表3、表4。
采用DPS v9.50软件统计分析不同处理间的差异显著性(Duncan’s新复极差测定法),毒力测定分析采用毒力回归方法(董存柱等,2011)。
表3化合物对埃及伊蚊3龄幼虫的致死率和差异性比较
1)同列数据后不同小写字母表示差异显著(P<0.05,DMRT法)
2)-:无毒杀作用。
由结果(表3)可知,化合物H-1、H-6、H-7和化合物H-9杀虫活性较弱,因此仅测定化合物H-4对埃及伊蚊3龄幼虫的杀虫活性。
表4化合物H-4对埃及伊蚊3龄幼虫的LC50值
以上所述仅为本发明的较佳实施例而已,并不用限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (5)
1.从哈茨木霉菌中分离得到的色酮类化合物的制备方法,其特征在于,包括以下步骤:
(1)将哈茨木霉菌接种于海水PDB培养基中摇床培养,得发酵种子液;
(2)将发酵种子液接种于海水大米固体培养基,静置发酵培养,得发酵物;
(3)发酵结束后,用乙酸乙酯浸泡发酵物,过滤,浓缩,得发酵物浸膏;
(4)将发酵物浸膏进行硅胶柱洗脱,先以石油醚-乙酸乙酯为洗脱剂进行梯度洗脱,再以乙酸乙酯-甲醇为洗脱剂进行梯度洗脱;得到的馏分用TCL进行分析后,合并相似馏分,得到馏分Fr.1~Fr.18,经过分离纯化得到色酮类化合物;
所述色酮类化合物,其结构式如下所示:
2.根据权利要求1所述的制备方法,其特征在于,石油醚-乙酸乙酯的洗脱梯度V/V为100:0,96:4,89:11,87:13,85:15,83:17,80:20,77:23,73:27,70:30,65:35,60:40,55:45,45:55,35:65,25:75,15:85,0:100;乙酸乙酯-甲醇的洗脱梯度V/V为85:15,70:30,40:60,0:100。
3.根据权利要求1所述的制备方法,其特征在于,静置发酵培养的时间为45d。
4.根据权利要求1所述的制备方法,其特征在于,用乙酸乙酯浸泡发酵物的时间为3d。
5.根据权利要求1所述的制备方法,其特征在于,所述分离纯化为:Fr.10经过凝胶柱,以体积比1:1的甲醇:氯仿为洗脱剂,分离得到馏分Fr.10-1,馏分Fr.10-1再经凝胶柱,以甲醇为洗脱剂,洗脱得到化合物H-9;化合物H-9结构式为:
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