CN104355979B - 4-羟基-8-(2,3-二羟基丙氧基)-1-四氢萘酮及合成方法 - Google Patents
4-羟基-8-(2,3-二羟基丙氧基)-1-四氢萘酮及合成方法 Download PDFInfo
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Abstract
本发明公开了4-羟基-8-(2,3-二羟基丙氧基)-1-四氢萘酮及合成方法,4-羟基-8-(2,3-二羟基丙氧基)-1-四氢萘酮是4,8-二羟基-1-四氢萘酮的衍生物,熔点420-422K,溶于水、乙醇、丙酮及氯仿,为外消旋体,具有显著抑制植物种子萌发和幼苗生长的作用。其合成方法工艺简单,产物纯度高,达到99.08%,反应总收率为32-43%。
Description
技术领域
本发明涉及4,8-二羟基-1-四氢萘酮的衍生物,具体涉及4-羟基-8-(2,3-二羟基丙氧基)-1-四氢萘酮及合成方法。
背景技术
4,8-二羟基-1-四氢萘酮(4,8-DHT),化学名4,8-dihydroxy-1-tetralone,无色细簇针状结晶,其中4位与羟基相连的碳为一个手性碳,具有抗肿瘤、抗真菌、降血糖及免疫调节等作用。4,8-DHT的左旋对映体(–)被称为regiolone,右旋对映体(+)被称为isosclerone,4,8-DHT还有外消旋体。Regiolone最早是从青核桃中鉴定出的,可用于治疗皮肤瘙痒及痛等病症。Isosclerone最早是从Sclerotiniasclerotium中分离鉴定出,后来从一些真菌中也分离出了该化合物,它能引起葡萄灰色斑点病。山核桃中就发现外消旋体的4,8-DHT。
发明内容
本发明所要解决的技术问题是提供一种4-羟基-8-(2,3-二羟基丙氧基)-1-四氢萘酮及合成方法,其具有显著抑制植物种子萌发和幼苗生长的作用。
本发明解决上述技术问题所采用的技术方案为:4-羟基-8-(2,3-二羟基丙氧基)-1-四氢萘酮,其分子式为C13H16O5,结构式为:熔点420-422K,溶于水、乙醇、丙酮及氯仿,为外消旋体,[α]20 D=±0°(c1.3,CH2Cl2)。
4-羟基-8-(2,3-二羟基丙氧基)-1-四氢萘酮的合成方法,步骤如下:
将0.37g4,8-二苯甲酰酯基-1-四氢萘酮溶于12-15ml甲醇,加0.4-0.6g碳酸铯搅拌均匀,室温反应2h,除去甲醇,每次20ml乙酸乙酯萃取,共萃取三次,合并萃取液,用45-60ml饱和食盐水除盐,减压浓缩至干燥,以重量比1:1与300-400目硅胶混匀,过200-300目硅胶柱,用体积比1:8的乙酸乙酯:石油醚混合液洗脱,洗脱液减压浓缩至干燥,得到淡黄色粒状晶体:4-苯甲酰基-8-羟基-1-四氢萘酮,其分子式为C17H14O4;将上述C17H14O4溶于10ml无水四氢呋喃,加入1.2当量的氢化钠,室温下反应30min,再加入3.5-5ml环氧溴丙烷,升温至50℃反应30-45min,氯化铵淬灭反应,减压浓缩至干,用体积比1:1的乙酸乙酯和水混合液25ml萃取,有机相用45-60ml饱和食盐水除盐,再加50g无水硫酸钠除水后,减压浓缩至干,得淡黄色粒状晶体:4-苯甲酰基-8-(2-环氧基丙氧基)-1-四氢萘酮,其分子式为C20H18O5;将上述C20H18O5溶于7.5-10ml甲醇,加入1当量的碳酸铯,室温下反应30min,除去甲醇,每次15-20ml乙酸乙酯萃取,共萃取三次,合并萃取液,用25-30ml饱和食盐水除盐,减压浓缩至干燥,以重量比1:1与300-400目硅胶混匀,过200-300目硅胶柱,用体积比1:5的乙酸乙酯:石油醚混合液洗脱,洗脱液减压浓缩至干,得到:4-羟基-8-(2-环氧丙氧基)-1-四氢萘酮,其分子式为C13H14O4;将上述C13H14O4溶于5-7ml水,在70℃反应24h,减压浓缩至干燥,以重量比1:1与300-400目硅胶混匀,过200-300目硅胶柱,用乙酸乙酯洗脱,洗脱液减压浓缩至干,得到4-羟基-8-(2,3-二羟基丙氧基)-1-四氢萘酮的淡黄色针状晶体。采用高效液相色谱法测定,纯度达到99.08%。
与现有技术相比,本发明的优点在于4-羟基-8-(2,3-二羟基丙氧基)-1-四氢萘酮及合成方法,4-羟基-8-(2,3-二羟基丙氧基)-1-四氢萘酮是4,8-二羟基-1-四氢萘酮的衍生物,熔点420-422K,溶于水、乙醇、丙酮及氯仿,为外消旋体,具有显著抑制植物种子萌发和幼苗生长的作用。其合成方法工艺简单,产物纯度高,达到99.08%,反应总收率为32-43%。
附图说明
图1为本发明的合成示意图。
具体实施方式
以下结合附图实施例对本发明作进一步详细描述。
实施例1
一种以4,8-二苯甲酰酯基-1-四氢萘酮为原料合成外消旋4-羟基-8-(2,3-二羟基丙氧基)-1-四氢萘酮的方法:将0.37g4,8-二苯甲酰酯基-1-四氢萘酮溶于12-15ml甲醇,加0.4-0.6g碳酸铯搅拌均匀,室温反应2h,除去甲醇,每次20ml乙酸乙酯萃取,共萃取三次,合并萃取液,用45-60ml饱和食盐水除盐,减压浓缩至干燥,以重量比1:1与300-400目硅胶混匀,过200-300目硅胶柱,用体积比1:8的乙酸乙酯:石油醚混合液洗脱,洗脱液减压浓缩至干燥,得到淡黄色粒状晶体:4-苯甲酰基-8-羟基-1-四氢萘酮,其分子式为C17H14O4;将上述C17H14O4溶于10ml无水四氢呋喃,加入1.2当量的氢化钠,室温下反应30min,再加入3.5-5ml环氧溴丙烷,升温至50℃反应30-45min,氯化铵淬灭反应,减压浓缩至干,用体积比1:1的乙酸乙酯和水混合液25ml萃取,有机相用45-60ml饱和食盐水除盐,再加50g无水硫酸钠除水后,减压浓缩至干,得淡黄色粒状晶体:4-苯甲酰基-8-(2-环氧基丙氧基)-1-四氢萘酮,其分子式为C20H18O5;将上述C20H18O5溶于7.5-10ml甲醇,加入1当量的碳酸铯,室温下反应30min,除去甲醇,每次15-20ml乙酸乙酯萃取,共萃取三次,合并萃取液,用25-30ml饱和食盐水除盐,减压浓缩至干燥,以重量比1:1与300-400目硅胶混匀,过200-300目硅胶柱,用体积比1:5的乙酸乙酯:石油醚混合液洗脱,洗脱液减压浓缩至干,得到:4-羟基-8-(2-环氧丙氧基)-1-四氢萘酮,其分子式为C13H14O4;将上述C13H14O4溶于5-7ml水,在70℃反应24h,减压浓缩至干燥,以重量比1:1与300-400目硅胶混匀,过200-300目硅胶柱,用乙酸乙酯洗脱,洗脱液减压浓缩至干,得到4-羟基-8-(2,3-二羟基丙氧基)-1-四氢萘酮的淡黄色针状晶体。反应总收率为32-43%,采用高效液相色谱法测定,得到纯度达到99.81%。熔点420-422K,溶于水、乙醇、丙酮及氯仿,为外消旋体,[α]20 D=±0°(c1.3,CH2Cl2)。
实施例2
将获得的4-羟基-8-(2,3-二羟基丙氧基)-1-四氢萘酮配置成0.01mM、0.05mM、0.1mM和0.5mM的处理液作对莴苣种子萌发抑制实验,取100粒测试物种种子均匀摆放在铺有两层滤纸、大小15×20cm发芽盒,加10ml不同浓度处理液(对照组为去离子水),每个处理设置3个重复。培养条件为光周期25℃,12h;暗周期15℃,12h。种子萌发以胚根突破种皮为标准,第四天和第七天记录莴苣种子发芽数。0.01mM处理液可以使莴苣种子发芽势降低51%,发芽率降低59%;0.1mM和0.5mM处理液种子不发芽。用0.01mM、0.05mM、0.1mM和0.5mM的处理液作对莴苣实生苗生长抑制实验,取胚根突破种皮种子100粒均匀摆放在铺有两层滤纸、大小15×20cm发芽盒,加入10ml不同浓度处理液(对照组为去离子水),每个处理设置3个重复。培养条件为光周期25℃,12h;暗周期15℃,12h。每隔一天从发芽盒中随机取5粒种子测其胚根、胚芽长度及鲜重,共测6次。0.01mM处理液可以使莴苣实生苗胚根长度降低39%、胚芽长度降低21%、鲜重降低35%,0.1mM和0.5mM处理液实生苗无生长迹象。
实施例3
将获得的4-羟基-8-(2,3-二羟基丙氧基)-1-四氢萘酮配置成0.01mM、0.05mM、0.1mM和0.5mM的处理液作对萝卜种子萌发抑制实验,取100粒测试物种种子均匀摆放在铺有两层滤纸、大小15×20cm发芽盒,加10ml不同浓度处理液(对照组为去离子水),每个处理设置3个重复。培养条件为光周期25℃,12h;暗周期15℃,12h。种子萌发以胚根突破种皮为标准,第四天和第十天记录萝卜种子发芽数。0.01mM处理液可以使萝卜种子发芽势降低35%,发芽率降低44%;0.5mM处理液种子不发芽。用0.01mM、0.05mM、0.1mM和0.5mM的处理液作对萝卜实生苗生长抑制实验,取胚根突破种皮种子100粒均匀摆放在铺有两层滤纸、大小15×20cm发芽盒,加入10ml不同浓度处理液(对照组为去离子水),每个处理设置3个重复。培养条件为光周期25℃,12h;暗周期15℃,12h。每隔一天从发芽盒中随机取5粒种子测其胚根、胚芽长度及鲜重,共测6次。0.01mM处理液可以使萝卜实生苗胚根长度降低32%、胚芽长度降低19%、鲜重降低24%;0.5mM处理液实生苗无生长迹象。
实施例4
将获得的4-羟基-8-(2,3-二羟基丙氧基)-1-四氢萘酮配置成0.01mM、0.05mM、0.1mM和0.5mM的处理液作对黄瓜种子萌发抑制实验,取100粒测试物种种子均匀摆放在铺有两层滤纸、大小15×20cm发芽盒,加10ml不同浓度处理液(对照组为去离子水),每个处理设置3个重复。培养条件为光周期25℃,12h;暗周期15℃,12h。种子萌发以胚根突破种皮为标准,第四天和第八天记录黄瓜种子发芽数。0.01mM处理液可以加速黄瓜种子萌发过程,种子发芽势增加12%,种子发芽率数据无变化;0.5mM处理液显著抑制黄瓜种子萌发过程,种子发芽势降低82%,种子发芽率降低90%。用0.01mM、0.05mM、0.1mM和0.5mM的处理液作对黄瓜实生苗生长抑制实验,取胚根突破种皮种子100粒均匀摆放在铺有两层滤纸、大小15×20cm发芽盒,加入10ml不同浓度处理液(对照组为去离子水),每个处理设置3个重复。培养条件为光周期25℃,12h;暗周期15℃,12h。每隔一天从发芽盒中随机取5粒种子测其胚根、胚芽长度及鲜重,共测6次。0.01mM处理液可以加速黄瓜实生苗生长,胚根长度增加20%、胚芽长度增加16%、鲜重增加23%;0.5mM处理液显著降低黄瓜实生苗生长,胚根长度降低94%、胚芽长度降低75%、鲜重降低75%。
Claims (2)
1.4-羟基-8-(2,3-二羟基丙氧基)-1-四氢萘酮,其特征在于分子式为C13H16O5,结构式为:熔点420-422K,溶于水、乙醇、丙酮及氯仿,为外消旋体。
2.权利要求1所述的4-羟基-8-(2,3-二羟基丙氧基)-1-四氢萘酮的合成方法,其特征在于步骤如下:
(1)将0.37g4,8-二苯甲酰酯基-1-四氢萘酮溶于12-15ml甲醇,加0.4-0.6g碳酸铯搅拌均匀,室温反应2h,除去甲醇,每次20ml乙酸乙酯萃取,共萃取三次,合并萃取液,用45-60ml饱和食盐水除盐,减压浓缩至干燥,以重量比1:1与300-400目硅胶混匀,过200-300目硅胶柱,用体积比1:8的乙酸乙酯:石油醚混合液洗脱,洗脱液减压浓缩至干燥,得到淡黄色粒状晶体:4-苯甲酰基-8-羟基-1-四氢萘酮,其分子式为C17H14O4;
(2)将上述C17H14O4溶于10ml无水四氢呋喃,加入1.2当量的氢化钠,室温下反应30min,再加入3.5-5ml环氧溴丙烷,升温至50℃反应30-45min,氯化铵淬灭反应,减压浓缩至干,用体积比1:1的乙酸乙酯和水混合液25ml萃取,有机相用45-60ml饱和食盐水除盐,再加50g无水硫酸钠除水后,减压浓缩至干,得淡黄色粒状晶体:4-苯甲酰基-8-(2-环氧基丙氧基)-1-四氢萘酮,其分子式为C20H18O5;
(3)将上述C20H18O5溶于7.5-10ml甲醇,加入1当量的碳酸铯,室温下反应30min,除去甲醇,每次15-20ml乙酸乙酯萃取,共萃取三次,合并萃取液,用25-30ml饱和食盐水除盐,减压浓缩至干燥,以重量比1:1与300-400目硅胶混匀,过200-300目硅胶柱,用体积比1:5的乙酸乙酯:石油醚混合液洗脱,洗脱液减压浓缩至干,得到:4-羟基-8-(2-环氧丙氧基)-1-四氢萘酮,其分子式为C13H14O4;
(4)将上述C13H14O4溶于5-7ml水,在70℃反应24h,减压浓缩至干燥,以重量比1:1与300-400目硅胶混匀,过200-300目硅胶柱,用乙酸乙酯洗脱,洗脱液减压浓缩至干,得到4-羟基-8-(2,3-二羟基丙氧基)-1-四氢萘酮的淡黄色针状晶体。
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