CN104326889B - 乙二醇二-8-(4-羟基-1-四氢萘酮)醚及合成方法 - Google Patents
乙二醇二-8-(4-羟基-1-四氢萘酮)醚及合成方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/753—Unsaturated compounds containing a keto groups being part of a ring containing ether groups, groups, groups, or groups
- C07C49/755—Unsaturated compounds containing a keto groups being part of a ring containing ether groups, groups, groups, or groups a keto group being part of a condensed ring system with two or three rings, at least one ring being a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
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Abstract
本发明公开了乙二醇二‑8‑（4‑羟基‑1‑四氢萘酮）醚及合成方法，乙二醇二‑8‑（4‑羟基‑1‑四氢萘酮）醚是4,8‑二羟基‑1‑四氢萘酮的衍生物，熔点310‑312K，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99.12%，反应总收率为17‑23%。
Description
技术领域
本发明涉及4,8-二羟基-1-四氢萘酮的衍生物，具体涉及乙二醇二-8-(4-羟基-1-四氢萘酮)醚及合成方法。
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Sclerotinia sclerotium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乙二醇二-8-(4-羟基-1-四氢萘酮)醚及合成方法，乙二醇二-8-(4-羟基-1-四氢萘酮)醚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：乙二醇二-8-(4-羟基-1-四氢萘酮)醚，其分子式为C22H22O6，结构式为：熔点310-312K，溶于水、乙醇、丙酮及氯仿，为外消旋体，[α]20 D＝±0°(c1.3,CH2Cl2)。
乙二醇二-8-(4-羟基-1-四氢萘酮)醚的合成方法，步骤如下：
(1)将0.27g 4,8-二苯甲酰酯基-1-四氢萘酮溶于12-15ml甲醇，加0.12-0.17g碳酸铯搅拌均匀，室温反应2h，除去甲醇，每次15ml乙酸乙酯萃取，共萃取三次，合并萃取液，用35-45ml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，1:5-7的乙酸乙酯：石油醚洗脱，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12-15ml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5-7ml二溴乙烷，升温至50℃反应90-120min，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25-40ml萃取，有机相用30-50ml饱和食盐水除盐，35-40g无水硫酸钠除水后，减压浓缩至干，得淡黄色粒状晶体：乙二醇二-8-(4-苯甲酰基-1-四氢萘酮)醚，其分子式为C36H30O6；
(3)将上述C36H30O6溶于10-12ml甲醇，加入1当量的盐酸，室温下反应4h，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30-50ml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，乙酸乙酯洗脱，得到乙二醇二-8-(4-羟基-1-四氢萘酮)醚无色粒状晶体。采用高效液相色谱法测定该无色粒状晶体，其纯度达到99.12％。反应总收率为17-23％。
与现有技术相比，本发明的优点在于乙二醇二-8-(4-羟基-1-四氢萘酮)醚及合成方法，乙二醇二-8-(4-羟基-1-四氢萘酮)醚是4,8-二羟基-1-四氢萘酮的衍生物，熔点310-312K，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99.12％，反应总收率为17-23％。
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乙二醇二-8-(4-羟基-1-四氢萘酮)醚的方法：将0.27g 4,8-二苯甲酰酯基-1-四氢萘酮溶于12-15ml甲醇，加0.12-0.17g碳酸铯搅拌均匀，室温反应2h，除去甲醇，每次15ml乙酸乙酯萃取，共萃取三次，合并萃取液，用35-45ml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，1:5-7的乙酸乙酯：石油醚洗脱，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12-15ml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5-7ml二溴乙烷，升温至50℃反应90-120min，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25-40ml萃取，有机相用30-50ml饱和食盐水除盐，35-40g无水硫酸钠除水后，减压浓缩至干，得淡黄色粒状晶体：乙二醇二-8-(4-苯甲酰基-1-四氢萘酮)醚，其分子式为C36H30O6；将上述C36H30O6溶于10-12ml甲醇，加入1当量的盐酸，室温下反应4h，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30-50ml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，乙酸乙酯洗脱，得到乙二醇二-8-(4-羟基-1-四氢萘酮)醚无色粒状晶体，反应总收率为17-23％。采用高效液相色谱法测定，得到纯度达到99.12％。其熔点310-312K，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
将获得的乙二醇二-8-(4-羟基-1-四氢萘酮)醚配置成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。0.01m处理液可以使莴苣种子发芽势降低23％，发芽率降低17％；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。0.01m处理液可以使莴苣实生苗胚根长度降低12％、胚芽长度降低9％、鲜重降低10％，0.5mM处理液实生苗无生长迹象。
实施例3
将获得的乙二醇二-8-(4-羟基-1-四氢萘酮)醚配置成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。0.01m处理液可以使萝卜种子发芽势降低12％，发芽率降低19％；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。0.01m处理液可以使萝卜实生苗胚根长度降低10％、胚芽长度降低7％、鲜重降低9％；0.5mM处理液实生苗无生长迹象。
实施例4
将获得的乙二醇二-8-(4-羟基-1-四氢萘酮)醚配置成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。0.01m处理液可以加速黄瓜种子萌发过程，种子发芽势增加40％，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43％，种子发芽率降低38％。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。0.01m处理液可以加速黄瓜实生苗生长，胚根长度增加47％、胚芽长度增加56％、鲜重增加60％；0.5mM处理液显著降低黄瓜实生苗生长，胚根长度降低75％、胚芽长度降低61％、鲜重降低55％。
Claims (2)
1.乙二醇二-8-(4-羟基-1-四氢萘酮)醚，其特征在于分子式为C22H22O6，结构式为：熔点310-312K，溶于水、乙醇、丙酮及氯仿，为外消旋体。
2.权利要求1所述的乙二醇二-8-(4-羟基-1-四氢萘酮)醚的合成方法，其特征在于步骤如下：
(1)将0.27g 4,8-二苯甲酰酯基-1-四氢萘酮溶于12-15ml甲醇，加0.12-0.17g碳酸铯搅拌均匀，室温反应2h，除去甲醇，每次15ml乙酸乙酯萃取，共萃取三次，合并萃取液，用35-45ml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，1:5-7的乙酸乙酯：石油醚洗脱，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12-15ml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5-7ml二溴乙烷，升温至50℃反应90-120min，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25-40ml萃取，有机相用30-50ml饱和食盐水除盐，35-40g无水硫酸钠除水后，减压浓缩至干，得淡黄色粒状晶体：乙二醇二-8-(4-苯甲酰基-1-四氢萘酮)醚，其分子式为C36H30O6；
(3)将上述C36H30O6溶于10-12ml甲醇，加入1当量的盐酸，室温下反应4h，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30-50ml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，乙酸乙酯洗脱，得到乙二醇二-8-(4-羟基-1-四氢萘酮)醚无色粒状晶体。
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