CN115093341B - 一种2-环戊烯-1-醇衍生物及其合成方法和应用 - Google Patents
一种2-环戊烯-1-醇衍生物及其合成方法和应用 Download PDFInfo
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- CN115093341B CN115093341B CN202210924582.7A CN202210924582A CN115093341B CN 115093341 B CN115093341 B CN 115093341B CN 202210924582 A CN202210924582 A CN 202210924582A CN 115093341 B CN115093341 B CN 115093341B
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
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- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000006196 deacetylation Effects 0.000 claims abstract description 4
- 238000003381 deacetylation reaction Methods 0.000 claims abstract description 4
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- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
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- FDJOLVPMNUYSCM-WZHZPDAFSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+3].N#[C-].N([C@@H]([C@]1(C)[N-]\C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C(\C)/C1=N/C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C\C1=N\C([C@H](C1(C)C)CCC(N)=O)=C/1C)[C@@H]2CC(N)=O)=C\1[C@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]1[C@@H](O)[C@@H](N2C3=CC(C)=C(C)C=C3N=C2)O[C@@H]1CO FDJOLVPMNUYSCM-WZHZPDAFSA-L 0.000 description 1
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- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 description 1
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/82—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a ring other than a six-membered aromatic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing within the same carbon skeleton a carboxylic group or a thio analogue, or a derivative thereof, and a carbon atom having only two bonds to hetero atoms with at the most one bond to halogen, e.g. keto-carboxylic acids
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P7/00—Arthropodicides
- A01P7/04—Insecticides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/40—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/45—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C255/46—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of non-condensed rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental Sciences (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Health & Medical Sciences (AREA)
- Insects & Arthropods (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于有机合成技术领域,公开一种2‑环戊烯‑1‑醇衍生物及其合成方法,其以α‑羰基环丙酰胺化合物和1,3‑二羰基化合物为原料,以有机碱为催化剂,溶于有机溶剂中,在80~100℃条件下进行[3+2]环合/脱乙酰基/氧气氧化反应,快速构建系列多官能化的2‑环戊烯‑1‑醇类化合物;反应条件温和,结构多样化,易操作,具有步骤经济性,收率高的优势。本发明2‑环戊烯‑1‑醇衍生物具有优良的杀虫活性,在农药领域具有良好的应用前景。
Description
技术领域
本发明属于有机合成技术领域,尤其是涉及一种2-环戊烯-1-醇衍生物及其合成方法和应用。
背景技术
环戊烯-2-醇及其衍生物是多种天然产物和医药中间体的重要组成部分,多年来研究人员通过从天然产物中分离、结构修饰及化学合成手段得到了功能各异的含环戊烯-2-醇核心骨架的化合物,其在抗菌、抗肿瘤、抗病毒、抗HIV、杀虫除螨、除草等药理活性方面的表现出了优良的生物活性,例如卡巴韦(抗HIV)/环虫菊酯(除草)等;而且它还可以用于调配日化用品及食用香精,如槭内酯。除此之外,它们也被认为是天然产物neplanocineAfredericamycinA analogue,jasmonoids以及(-)-swainsonine的关键合成中间体。近年来环戊烯-2-醇骨架的构建引起药物学家和合成化学研究者的广泛关注,并已取得了显著成效。目前,环戊烯-2-醇及其类似物常用的合成方法主要包括:一、环戊呋喃-2-酮或1,2-环氧戊烷的开环重排反应,复分解反应等,例如,通过环戊二烯和醛酸分子间成环或环戊烯羧酸分子内环合反应形成的环戊烯并环戊内酯中间体,进一步开环合成环戊烯-2-醇类化合物(Tetrahedron:Asymmetry1997,22,3785;J.Org.Chem.1993,58,5298);二、利用维生素B12催化的1,2-环氧环戊烷的开环反应(Helv.Chim.Acta.,1991,74,1425)以及环戊烯的氧化反应(Angew.Chem.,Int.Ed.,2007,46,5951)。然而,上述常规的合成方法往往存在起始原料复杂、普适性较低、反应条件苛刻、繁琐的合成步骤、最终产率低下等缺点。
发明内容
为解决上述问题,本发明的目的是提供一种2-环戊烯-1-醇衍生物及其合成方法和应用。
为实现上述发明目的,本发明采用如下技术方案:
一种2-环戊烯-1-醇衍生物,其结构式为:
其中,R2选自Me、Et、Ph、4-MePh、4-MeOPh、4-ClPh、2-MePh、2,4-Me2C6H3、2-ClPh、Bn、naphth中的一种;
R3选自Me、Et、Ph、4-MePh、2-BrPh、2-MePh、4-NO2Ph、2-furyl中的一种;
R4选自Me、Et、Cyclohexyl、CF3、CONHPh、CONH(4-MePh)、CONH(4-MeOPh)、CONH(4-ClPh)、CONH(2-MePh)、CONHCH2Ph、CN、Ph、4-MePh、2-BrPh、2-MePh、4-NO2Ph、4-MeOPh、4-COOMePh、naphth中的一种。
一种2-环戊烯-1-醇衍生物的合成方法,其以α-羰基环丙酰胺化合物A和1,3-二羰基化合物B为原料,以有机碱为催化剂,溶于有机溶剂中,在80~100℃条件下进行[3+2]环合/脱乙酰基/氧气氧化反应,制备得到2-环戊烯-1-醇类化合物C;
反应路线如下:
其中,R1选自Me、Et、Ph中的一种;
R2选自Me、Et、Ph、4-MePh、4-MeOPh、4-ClPh、2-MePh、2,4-Me2C6H3、2-ClPh、Bn、naphth中的一种;
R3选自Me、Et、Ph、4-MePh、2-BrPh、2-MePh、4-NO2Ph、2-furyl中的一种;
R4选自Me、Et、Cyclohexyl、CF3、CONHPh、CONH(4-MePh)、CONH(4-MeOPh)、CONH(4-ClPh)、CONH(2-MePh)、CONHCH2Ph、CN、Ph、4-MePh、2-BrPh、2-MePh、4-NO2Ph、4-MeOPh、4-COOMePh、naphth中的一种。
进一步地,上述的α-羰基环丙酰胺化合物A和1,3-二羰基化合物B的摩尔比为1:1~1.2mmol,α-羰基环丙酰胺化合物A、有机溶剂和有机碱的用量之比为1mmol:8~10mL:1~1.5mmol。
进一步地,上述的有机碱为1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)、N,N-二甲基乙醇胺(DABCO)、4-二甲氨基吡啶(DMAP)、1,5-二氮杂双环[4.3.0]-5-壬烯(DBN)、吡啶中的一种。
进一步地,上述的有机溶剂为N,N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、N-甲基吡咯烷酮(NMP)、乙腈、乙醇中的一种。
进一步地,上述的反应时间为8~10h。
进一步地,上述的2-环戊烯-1-醇衍生物的合成方法,其用薄层色谱TLC监测反应进程,待反应物A完全消失后,向反应体系中加水停止反应,再用萃取剂萃取,合并有机相;有机相用干燥剂干燥,过滤、浓缩、柱层层析,获得2-环戊烯-1-醇类化合物C。
更进一步地,上述的萃取剂为二氯甲烷、乙酸乙酯、***或氯仿。
更进一步地,上述的有机相干燥剂为无水硫酸钠、无水氯化钙或无水硫酸镁。
本发明的另一目的是提供一种2-环戊烯-1-醇衍生物在制备杀虫药物中的应用。
进一步地,上述的杀虫药物是防治蚜虫、小菜蛾、棉铃虫、斜纹夜蛾之类害虫的药物。
杀虫活性测试:以农业害虫进行室内普筛活性实验,采用浸渍法测试本发明2-环戊烯-1-醇类化合物C的杀虫活性,在普筛浓度下(500μg/mL),2-环戊烯-1-醇类化合物C具有良好的杀虫活性,不同害虫(蚜虫、小菜蛾、棉铃虫、斜纹夜蛾)的死亡率均在55%~80%之间。
由于采用如上所述的技术方案,本发明具有如下优越性:
本发明2-环戊烯-1-醇衍生物的合成方法,其合成路线简洁高效,利用ɑ-羰基环丙酰胺化合物和1,3-二羰基化合物作为起始原料,在温和的反应条件下通过分子间的[3+2]环合反应/脱乙酰基/氧气氧化反应的串联反应过程,快速构建系列多官能化的2-环戊烯-1-醇类化合物;所用原料成本低廉易得,具有较高的氧化还原经济性和路线经济性,反应条件温和,结构多样化,易操作,具有步骤经济性,收率高的优势。
本发明2-环戊烯-1-醇衍生物,其具有优良的杀虫活性,对多种农业害虫,如蚜虫、小菜蛾等,具有良好的防治作用,在农药领域具有良好的应用前景。
附图说明
图1是实施例1中的目标产物C1的氢谱图;
图2是实施例3中的目标产物C3的氢谱图。
具体实施方式
参照以下实施例可以对本发明作进一步详细说明;但是,以下实施例仅仅是例证,本发明并不局限于这些实施例。
实施例1
向50mL耐压瓶中加入α-羰基环丙酰胺A1(0.203g,1mmol)、乙酰丙酮B1(0.1mL,1mmol)、DMF(6mL),然后,缓慢加入DBU(0.15mL,1mmol),80℃搅拌10h;TLC监测反应,A1完全消失后,将反应液倾入冰水中,剧烈搅拌后,用二氯甲烷萃取三次(3×10mL),合并有机相,然后用无水硫酸钠干燥,旋蒸除去溶剂,柱层析分离纯化,得白色产物C10.23g,产率为88%。
具体反应式为:
化合物C1的1HNMR(CDCl3,400MHz):δ:1.99-2.04(m,4H),2.34(s,3H),2.62-2.68(m,1H),2.82-2.85(m,2H),3.20(s,1H),7.15(t,J=8.0Hz,1H),7.33-7.37(q,J=4.0Hz,2H),7.57(d,J=8.0Hz,2H),8.29(s,1H)。
化合物C1的杀虫活性测试:以棉蚜虫为测试对象,采用浸渍法;称取10mg化合物C1样品,再用5mL移液枪取2mL丙酮/甲醇混合溶剂溶解,加入18mL含有0.1%吐温-80的水溶液,充分混匀,得500μg/mL的测定液。结果表明棉蚜虫24h后的死亡率达到70%。
实施例2
向50mL耐压瓶中加入α-羰基环丙酰胺A2(0.217g,1mmol)、苯甲酰丙酮B2(0.16mL,1mmol)、DMSO(6mL),然后,缓慢加入DBU(0.15mL,1mmol),90℃搅拌10h;TLC监测反应,A2完全消失后,将反应液倾入冰水中,剧烈搅拌后,用二氯甲烷萃取三次(3×10mL),合并有机相,然后用无水硫酸钠干燥,旋蒸除去溶剂,柱层析分离纯化,得白色产物C20.28g,产率为85%。
具体反应式为:
化合物C2的1HNMR(CDCl3,400MHz):δ:1.96-2.01(m,4H),2.37(s,3H),2.65-2.68(m,1H),2.81-2.86(m,2H),3.24(s,1H),7.05(d,J=8.0Hz,2H),7.49(d,J=8.0Hz,2H),7.52(t,J=4.0Hz,1H)7.55-7.58(m,2H),7.71-7.73(m,2H),8.74(s,1H)。
化合物C2的杀虫活性测试:以小菜蛾为测试对象,采用浸渍法;称取10mg化合物C2样品,再用5mL移液枪取2mL丙酮/甲醇混合溶剂溶解,加入18mL含有0.1%吐温-80的水溶液,充分混匀,得500μg/mL的测定液。结果表明小菜蛾48h后的死亡率达到55%。
实施例3
向50mL耐压瓶中加入α-羰基环丙酰胺A1(0.203g,1mmol)、乙酰乙酸乙酯B3(0.14mL,1.1mmol)、NMP(8mL),然后,缓慢加入DMAP(0.15g,1.2mmol),100℃搅拌8h;TLC监测反应,A1完全消失后,将反应液倾入冰水中,剧烈搅拌后,用乙酸乙酯萃取三次(3×10mL),合并有机相,然后用无水硫酸钠干燥,旋蒸除去溶剂,柱层析分离纯化,得白色产物C30.23g,产率为81%。
具体反应式为:
化合物C3的1HNMR(CDCl3,400MHz):δ:1.30-1.33(t,J=6.0Hz,3H),2.17(s,3H),2.27(m,1H),2.83-2.85(m,2H),3.50-3.54(t,J=8.0Hz,1H),4.20-4.25(q,J=8.0Hz,2H),7.11-7.18(m,2H),7.32-7.36(m,2H),7.52-7.54(d,J=8.0Hz,2H)。
化合物C3的杀虫活性测试:以棉蚜虫为测试对象,采用浸渍法;称取10mg化合物C3样品,再用5mL移液枪取2mL丙酮/甲醇混合溶剂溶解,加入18mL含有0.1%吐温-80的水溶液,充分混匀,得500μg/mL的测定液。结果表明棉蚜虫24h后的死亡率达到73%。
实施例4
向50mL耐压瓶中加入α-羰基环丙酰胺A4(0.217g,1mmol)、1,3-二苯基-1,3-丙二酮B5(0.224g,1.0mmol)、乙醇(10mL),然后,加入DABCO(0.1g,1.2mmol),95℃搅拌10h;TLC监测反应,A4完全消失后,将反应液倾入冰水中,剧烈搅拌后,用***萃取三次(3×10mL),合并有机相,然后用无水氯化钙干燥,旋蒸除去溶剂,柱层析分离纯化,得白色产物C50.27g,产率为71%。
具体反应式为:
化合物C5的1HNMR(CDCl3,400MHz):δ:2.11-2.15(m,1H),2.27-2.29(m,1H),2.36-2.38(m,2H),4.33(s,1H),7.05-7.12(m,2H),7.27-7.35(m,4H),7.78-7.86(m,5H),8.01-8.04(m,4H),8.95(s,1H)。
化合物C5的杀虫活性测试:以棉铃虫为测试对象,采用浸渍法。称取10mg化合物C5样品,再用5mL移液枪取2mL丙酮/甲醇混合溶剂溶解,加入18mL含有0.1%吐温-80的水溶液,充分混匀,得500μg/mL的测定液。结果表明棉铃虫24h后的死亡率达到66%。
实施例5
向50mL耐压瓶中加入α-羰基环丙酰胺A5(0.217g,1mmol)、乙酰乙酰苯胺B6(0.177g,1.0mmol)、DMF(10mL),然后,加入DBU(0.2mL,1.3mmol),100℃搅拌8h;TLC监测反应,A5完全消失后,将反应液倾入冰水中,剧烈搅拌后,用***萃取三次(3×10mL),合并有机相,然后用无水硫酸钠干燥,旋蒸除去溶剂,柱层析分离纯化,得白色产物C60.26g,产率为74%。
具体反应式为:
化合物C6的1HNMR(CDCl3,400MHz):δ:1.73(s,3H),2.21-2.24(m,1H),2.29-2.32(m,1H),2.41-2.44(m,2H),4.47(s,2H),6.93-6.96(m,1H),7.18-7.27(m,3H),7.32-7.44(m,2H),7.55-7.61(m,2H),7.73-7.78(s,2H),8.92(s,1H),8.99(s,1H)。
化合物C6的杀虫活性测试:以小菜蛾为测试对象,采用浸渍法;称取10mg化合物C6样品,再用5mL移液枪取2mL丙酮/甲醇混合溶剂溶解,加入18mL含有0.1%吐温-80的水溶液,充分混匀,得500μg/mL的测定液。结果表明小菜蛾48h后的死亡率达到57%。
实施例6
向50mL耐压瓶中加入α-羰基环丙酰胺A6(0.257g,1mmol)、乙酰乙酰萘胺B7(0.227g,1.0mmol)、DMSO(9mL),然后,加入吡啶(0.1mL,1.2mmol),80℃搅拌9.5h;TLC监测反应,A6完全消失后,将反应液倾入冰水中,剧烈搅拌后,用氯仿萃取三次(3×10mL),合并有机相,然后用无水氯化钙干燥,旋蒸除去溶剂,柱层析分离纯化,得白色产物C70.26g,产率为68%。
具体反应式为:
化合物C7的1HNMR(CDCl3,400MHz):δ:1.71(s,3H),2.21-2.25(m,1H),2.30-2.32(m,1H),2.42-2.46(m,2H),7.11-7.16(m,1H),7.22-7.27(m,4H),7.35-7.41(m,2H),7.66-7.73(m,3H),7.84-7.91(m,2H),8.88(s,1H),8.94(s,1H)。
化合物C7的杀虫活性测试:以蚜虫为测试对象,采用浸渍法;称取10mg化合物C7样品,再用5mL移液枪取2mL丙酮/甲醇混合溶剂溶解,加入18mL含有0.1%吐温-80的水溶液,充分混匀,得500μg/mL的测定液。结果表明蚜虫24h后的死亡率达到61%。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种2-环戊烯-1-醇衍生物,其特征是:其为以下结构式中的任一种:
2.一种权利要求1所述的2-环戊烯-1-醇衍生物的合成方法,其特征是:其以α-羰基环丙酰胺化合物A和1,3-二羰基化合物B为原料,以有机碱为催化剂,溶于有机溶剂中,在80~100℃条件下进行[3+2]环合/脱乙酰基/氧气氧化反应,制备得到2-环戊烯-1-醇类化合物C;所述α-羰基环丙酰胺化合物A和1,3-二羰基化合物B的摩尔比为1:1~1.2mmol,α-羰基环丙酰胺化合物A、有机溶剂和有机碱的用量之比为1mmol:8~10mL:1~1.5mmol;
反应路线如下:
2-环戊烯-1-醇类化合物C为以下结构式中的任一种:
3.根据权利要求2所述的2-环戊烯-1-醇衍生物的合成方法,其特征是:其有机碱为1,8-二氮杂双环[5.4.0]十一碳-7-烯、N,N-二甲基乙醇胺、4-二甲氨基吡啶、1,5-二氮杂双环[4.3.0]-5-壬烯、吡啶中的一种。
4.根据权利要求2所述的2-环戊烯-1-醇衍生物的合成方法,其特征是:其有机溶剂为N,N-二甲基甲酰胺、二甲基亚砜、N-甲基吡咯烷酮、乙腈、乙醇中的一种。
5.根据权利要求2所述的2-环戊烯-1-醇衍生物的合成方法,其特征是:其反应时间为8~10h。
6.根据权利要求2所述的2-环戊烯-1-醇衍生物的合成方法,其特征是:其用薄层色谱TLC监测反应进程,待反应物A完全消失后,向反应体系中加水停止反应,再用萃取剂萃取,合并有机相;有机相用干燥剂干燥,过滤、浓缩、柱层层析,获得2-环戊烯-1-醇类化合物C。
7.根据权利要求2所述的2-环戊烯-1-醇衍生物的合成方法,其特征是:其萃取剂为二氯甲烷、乙酸乙酯、***或氯仿;有机相干燥剂为无水硫酸钠、无水氯化钙或无水硫酸镁。
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