CN104370713B - 4-(2,3-二羟基丙氧基)-8-羟基-1-四氢萘酮及合成方法 - Google Patents
4-(2,3-二羟基丙氧基)-8-羟基-1-四氢萘酮及合成方法 Download PDFInfo
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Abstract
本发明公开了4-(2,3-二羟基丙氧基)-8-羟基-1-四氢萘酮及合成方法,4-(2,3-二羟基丙氧基)-8-羟基-1-四氢萘酮是4,8-二羟基-1-四氢萘酮的衍生物,熔点467-469K,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99.23%,反应总收率为17-22%。
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-(2,3-二羟基丙氧基)-8-羟基-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-(2,3-二羟基丙氧基)-8-羟基-1-四氢萘酮及合成方法,4-(2,3-二羟基丙氧基)-8-羟基-1-四氢萘酮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-(2,3-二羟基丙氧基)-8-羟基-1-四氢萘酮,其分子式为C13H16O5,结构式为:熔点467-469K,溶于水、乙醇、丙酮及氯仿,为外消旋体,[α]20 D=±0°(c1.3,CH2Cl2)。
4-(2,3-二羟基丙氧基)-8-羟基-1-四氢萘酮的合成方法,步骤如下:
(1)将0.36g4,8-二苯甲酰酯基-1-四氢萘酮溶于12-15ml无水四氢呋喃,加1.2当量的氢化钠搅拌均匀,反应30min,再加入2.5当量的苄溴,升温至50℃反应5h,氯化铵淬灭反应,减压浓缩至干,体积比1:1的乙酸乙酯和水混合液25-30ml萃取,有机相用35-50ml饱和食盐水除盐,35-50g无水硫酸钠除水,减压浓缩至干,与300-400目硅胶(重量比)1:1混匀,过200-300目硅胶柱,1:6-8的乙酸乙酯:石油醚洗脱,得到:4-苯甲酰基-8-苯甲氧基-1-四氢萘酮,其分子式为C24H20O4;
(2)将上述C24H20O4溶于10-12ml甲醇,加入1.0当量的碳酸铯,室温下反应2h,除去甲醇,每次20-25ml乙酸乙酯萃取,共萃取三次,合并萃取液,用50-75ml饱和食盐水除盐,减压浓缩至干,与300-400目硅胶(重量比)1:1混匀,过200-300目硅胶柱,1:5的乙酸乙酯:石油醚洗脱,得到:4-羟基-8-苯甲氧基-1-四氢萘酮,其分子式为C17H16O3;
(3)将上述C17H16O3溶于5-10ml无水四氢呋喃,加入1.2当量的氢化钠,反应30min,再加入环氧溴丙烷,升温至50℃反应5h,氯化铵淬灭反应,减压浓缩至干,体积比1:1的乙酸乙酯和水混合液35ml萃取,有机相用50-75ml饱和食盐水除盐,35g无水硫酸钠除水后,减压浓缩至干,得到:4-(2-环氧丙氧基)-8-苯甲氧基-1-四氢萘酮,其分子式为C20H20O4;
(4)将上述C20H20O4溶于7-9ml甲醇,再加入0.1当量的钯碳,反应4h,除去甲醇,每次12-15ml乙酸乙酯萃取,共萃取三次,合并萃取液,用25ml饱和食盐水除盐,减压浓缩至干燥,得到:4-(2-环氧丙氧基)-8-羟基-1-四氢萘酮,其分子式为C13H14O4;
(5)将上述C13H14O4溶于20ml水,在70℃下反应24h,减压浓缩至干燥,与300-400目硅胶(重量比)1:1混匀,过200-300目硅胶柱,乙酸乙酯洗脱,得到4-(2,3-二羟基丙氧基)-8-羟基-1-四氢萘酮无色针状晶体。采用高效液相色谱法测定,纯度达到99.23%。
与现有技术相比,本发明的优点在于4-(2,3-二羟基丙氧基)-8-羟基-1-四氢萘酮及合成方法,4-(2,3-二羟基丙氧基)-8-羟基-1-四氢萘酮是4,8-二羟基-1-四氢萘酮的衍生物,熔点467-469K,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99.23%,反应总收率为17-22%。
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-(2,3-二羟基丙氧基)-8-羟基-1-四氢萘酮的方法:(1)将0.36g4,8-二苯甲酰酯基-1-四氢萘酮溶于12-15ml无水四氢呋喃,加1.2当量的氢化钠搅拌均匀,反应30min,再加入2.5当量的苄溴,升温至50℃反应5h,氯化铵淬灭反应,减压浓缩至干,体积比1:1的乙酸乙酯和水混合液25-30ml萃取,有机相用35-50ml饱和食盐水除盐,35-50g无水硫酸钠除水,减压浓缩至干,与300-400目硅胶(重量比)1:1混匀,过200-300目硅胶柱,1:6-8的乙酸乙酯:石油醚洗脱,得到:4-苯甲酰基-8-苯甲氧基-1-四氢萘酮,其分子式为C24H20O4;
(2)将上述C24H20O4溶于10-12ml甲醇,加入1.0当量的碳酸铯,室温下反应2h,除去甲醇,每次20-25ml乙酸乙酯萃取,共萃取三次,合并萃取液,用50-75ml饱和食盐水除盐,减压浓缩至干,与300-400目硅胶(重量比)1:1混匀,过200-300目硅胶柱,1:5的乙酸乙酯:石油醚洗脱,得到:4-羟基-8-苯甲氧基-1-四氢萘酮,其分子式为C17H16O3;
(3)将上述C17H16O3溶于5-10ml无水四氢呋喃,加入1.2当量的氢化钠,反应30min,再加入环氧溴丙烷,升温至50℃反应5h,氯化铵淬灭反应,减压浓缩至干,体积比1:1的乙酸乙酯和水混合液35ml萃取,有机相用50-75ml饱和食盐水除盐,35g无水硫酸钠除水后,减压浓缩至干,得到:4-(2-环氧丙氧基)-8-苯甲氧基-1-四氢萘酮,其分子式为C20H20O4;
(4)将上述C20H20O4溶于7-9ml甲醇,再加入0.1当量的钯碳,反应4h,除去甲醇,每次12-15ml乙酸乙酯萃取,共萃取三次,合并萃取液,用25ml饱和食盐水除盐,减压浓缩至干燥,得到:4-(2-环氧丙氧基)-8-羟基-1-四氢萘酮,其分子式为C13H14O4;
(5)将上述C13H14O4溶于20ml水,在70℃下反应24h,减压浓缩至干燥,与300-400目硅胶(重量比)1:1混匀,过200-300目硅胶柱,乙酸乙酯洗脱,得到4-(2,3-二羟基丙氧基)-8-羟基-1-四氢萘酮无色针状晶体。采用高效液相色谱法测定,纯度达到99.23%。其熔点467-469K,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-(2,3-二羟基丙氧基)-8-羟基-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90%,发芽率降低87%;0.05mM、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85%、胚芽长度降低72%、鲜重降低81%,0.05mM、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-(2,3-二羟基丙氧基)-8-羟基-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80%,发芽率降低78%;0.1mM、0.5mM处理种子不发芽。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79%、胚芽长度降低70%、鲜重降低77%;0.1mM、0.5mM处理实生苗无生长迹象。
实施例4
将获得的4-(2,3-二羟基丙氧基)-8-羟基-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处理液种子发芽势降低72%,种子发芽率降低60%;0.5mM处理种子不发芽。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处理液胚根长度降低59%、胚芽长度降低46%、鲜重降低55%,0.5mM处理实生苗无生长迹象。
Claims (2)
1.4-(2,3-二羟基丙氧基)-8-羟基-1-四氢萘酮,其特征在于分子式为C13H16O5,结构式为:熔点467-469K,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-(2,3-二羟基丙氧基)-8-羟基-1-四氢萘酮的合成方法,其特征在于步骤如下:
(1)将0.36g4-苯甲酰酯基-1-四氢萘酮溶于12-15ml无水四氢呋喃,加1.2当量的氢化钠搅拌均匀,反应30min,再加入2.5当量的苄溴,升温至50℃反应5h,氯化铵淬灭反应,减压浓缩至干,体积比1:1的乙酸乙酯和水混合液25-30ml萃取,有机相用35-50ml饱和食盐水除盐,35-50g无水硫酸钠除水,减压浓缩至干,与300-400目硅胶(重量比)1:1混匀,过200-300目硅胶柱,1:6-8的乙酸乙酯:石油醚洗脱,得到:4-苯甲酰基-8-苯甲氧基-1-四氢萘酮,其分子式为C24H20O4;
(2)将上述C24H20O4溶于10-12ml甲醇,加入1.0当量的碳酸铯,室温下反应2h,除去甲醇,每次20-25ml乙酸乙酯萃取,共萃取三次,合并萃取液,用50-75ml饱和食盐水除盐,减压浓缩至干,与300-400目硅胶(重量比)1:1混匀,过200-300目硅胶柱,1:5的乙酸乙酯:石油醚洗脱,得到:4-羟基-8-苯甲氧基-1-四氢萘酮,其分子式为C17H16O3;
(3)将上述C17H16O3溶于5-10ml无水四氢呋喃,加入1.2当量的氢化钠,反应30min,再加入环氧溴丙烷,升温至50℃反应5h,氯化铵淬灭反应,减压浓缩至干,体积比1:1的乙酸乙酯和水混合液35ml萃取,有机相用50-75ml饱和食盐水除盐,35g无水硫酸钠除水后,减压浓缩至干,得到:4-(2-环氧丙氧基)-8-苯甲氧基-1-四氢萘酮,其分子式为C20H20O4;
(4)将上述C20H20O4溶于7-9ml甲醇,再加入0.1当量的钯碳,反应4h,除去甲醇,每次12-15ml乙酸乙酯萃取,共萃取三次,合并萃取液,用25ml饱和食盐水除盐,减压浓缩至干燥,得到:4-(2-环氧丙氧基)-8-羟基-1-四氢萘酮,其分子式为C13H14O4;
(5)将上述C13H14O4溶于20ml水,在70℃下反应24h,减压浓缩至干燥,与300-400目硅胶(重量比)1:1混匀,过200-300目硅胶柱,乙酸乙酯洗脱,得到4-(2,3-二羟基丙氧基)-8-羟基-1-四氢萘酮无色针状晶体。
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