CN111440046B - 一种鳞翅目害虫桃潜叶蛾性信息素(s)-14-甲基-1-十八碳烯的合成方法 - Google Patents
一种鳞翅目害虫桃潜叶蛾性信息素(s)-14-甲基-1-十八碳烯的合成方法 Download PDFInfo
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- CN111440046B CN111440046B CN202010147436.9A CN202010147436A CN111440046B CN 111440046 B CN111440046 B CN 111440046B CN 202010147436 A CN202010147436 A CN 202010147436A CN 111440046 B CN111440046 B CN 111440046B
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- octadecene
- benzyloxy
- sex pheromone
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- NAEZQVWAWSVOSD-IBGZPJMESA-N 14S-Methyl-1-octadecene Chemical compound CCCC[C@H](C)CCCCCCCCCCCC=C NAEZQVWAWSVOSD-IBGZPJMESA-N 0.000 title claims abstract description 42
- NAEZQVWAWSVOSD-UHFFFAOYSA-N -14-Methyl-1-octadecene Natural products CCCCC(C)CCCCCCCCCCCC=C NAEZQVWAWSVOSD-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000000877 Sex Attractant Substances 0.000 title claims abstract description 37
- 241000607479 Yersinia pestis Species 0.000 title claims description 16
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- 238000010189 synthetic method Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 241001581015 Lyonetia clerkella Species 0.000 claims abstract description 24
- 150000007530 organic bases Chemical class 0.000 claims abstract description 22
- -1 lithium aluminum hydride Chemical compound 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
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- 230000001590 oxidative effect Effects 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000007239 Wittig reaction Methods 0.000 claims abstract description 15
- 230000009471 action Effects 0.000 claims abstract description 15
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 14
- CXEFZVVLTJQWBF-UHFFFAOYSA-N 4-phenylmethoxybutanoic acid Chemical compound OC(=O)CCCOCC1=CC=CC=C1 CXEFZVVLTJQWBF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012280 lithium aluminium hydride Substances 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000004714 phosphonium salts Chemical group 0.000 claims abstract description 6
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims abstract description 4
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- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 4
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims abstract description 4
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 claims abstract description 4
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 11
- 238000004440 column chromatography Methods 0.000 claims description 10
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- FZQJOJHCQVORFU-PXNSSMCTSA-N (4S)-4-benzyl-3-[(2S)-2-methyl-4-phenylmethoxybutanoyl]-1,3-oxazolidin-2-one Chemical compound C[C@@H](CCOCc1ccccc1)C(=O)N1[C@@H](Cc2ccccc2)COC1=O FZQJOJHCQVORFU-PXNSSMCTSA-N 0.000 claims description 8
- PPWAXELJUXMDJA-IBGZPJMESA-N (4s)-4-benzyl-3-(4-phenylmethoxybutanoyl)-1,3-oxazolidin-2-one Chemical compound C([C@@H]1CC=2C=CC=CC=2)OC(=O)N1C(=O)CCCOCC1=CC=CC=C1 PPWAXELJUXMDJA-IBGZPJMESA-N 0.000 claims description 8
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 8
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- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 claims description 8
- PDJUBGULOXIPGS-SFHVURJKSA-N (13S)-13-methylheptadecanal Chemical compound CCCC[C@H](C)CCCCCCCCCCCC=O PDJUBGULOXIPGS-SFHVURJKSA-N 0.000 claims description 7
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- OSQNEAVQIKPMKL-NSHDSACASA-N (2s)-2-methyl-4-phenylmethoxybutan-1-ol Chemical compound OC[C@@H](C)CCOCC1=CC=CC=C1 OSQNEAVQIKPMKL-NSHDSACASA-N 0.000 claims description 6
- MUPPEBVXFKNMCI-QMMMGPOBSA-N (3s)-3-methylheptan-1-ol Chemical compound CCCC[C@H](C)CCO MUPPEBVXFKNMCI-QMMMGPOBSA-N 0.000 claims description 6
- KKFRYFDYAVLCHJ-QMMMGPOBSA-N (3s)-3-methylheptanal Chemical compound CCCC[C@H](C)CC=O KKFRYFDYAVLCHJ-QMMMGPOBSA-N 0.000 claims description 6
- LGZMUUBPTDRQQM-UHFFFAOYSA-N 10-Bromo-1-decanol Chemical compound OCCCCCCCCCCBr LGZMUUBPTDRQQM-UHFFFAOYSA-N 0.000 claims description 6
- PBNODBPMDVIJCQ-QHCPKHFHSA-N C(C)(C)(C)[Si](OCCCCCCCCCCCC[C@H](CCCC)C)(C)C Chemical compound C(C)(C)(C)[Si](OCCCCCCCCCCCC[C@H](CCCC)C)(C)C PBNODBPMDVIJCQ-QHCPKHFHSA-N 0.000 claims description 6
- JKPUXYBWGSXNBD-YOIVXCQUSA-N C[C@@H](CCOCC1=CC=CC=C1)\C=C\CC Chemical compound C[C@@H](CCOCC1=CC=CC=C1)\C=C\CC JKPUXYBWGSXNBD-YOIVXCQUSA-N 0.000 claims description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 6
- OJOFMLDBXPDXLQ-VIFPVBQESA-N (4s)-4-benzyl-1,3-oxazolidin-2-one Chemical compound C1OC(=O)N[C@H]1CC1=CC=CC=C1 OJOFMLDBXPDXLQ-VIFPVBQESA-N 0.000 claims description 5
- SRYOTJAZYZLPMY-UHFFFAOYSA-N 10-bromodecoxy-tert-butyl-dimethylsilane Chemical compound CC(C)(C)[Si](C)(C)OCCCCCCCCCCBr SRYOTJAZYZLPMY-UHFFFAOYSA-N 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
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- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- RCBVKBFIWMOMHF-UHFFFAOYSA-L hydroxy-(hydroxy(dioxo)chromio)oxy-dioxochromium;pyridine Chemical compound C1=CC=NC=C1.C1=CC=NC=C1.O[Cr](=O)(=O)O[Cr](O)(=O)=O RCBVKBFIWMOMHF-UHFFFAOYSA-L 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006646 Dess-Martin oxidation reaction Methods 0.000 claims description 3
- NKLCNNUWBJBICK-UHFFFAOYSA-N dess–martin periodinane Chemical group C1=CC=C2I(OC(=O)C)(OC(C)=O)(OC(C)=O)OC(=O)C2=C1 NKLCNNUWBJBICK-UHFFFAOYSA-N 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- ATVZKYLKSPOLRS-UHFFFAOYSA-M CCCCCCCCCC(O[Si](C)(C)C(C)(C)C)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.[Br-] Chemical compound CCCCCCCCCC(O[Si](C)(C)C(C)(C)C)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.[Br-] ATVZKYLKSPOLRS-UHFFFAOYSA-M 0.000 claims description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 4
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/34—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen reacting phosphines with aldehydes or ketones, e.g. Wittig reaction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
本发明公开一种桃潜叶蛾性信息素(S)‑14‑甲基‑1‑十八碳烯的合成方法,该方法以γ‑丁内酯为原料,先将其进行开环并与氯化苄生成4‑苄氧基丁酸,再与(S)‑4‑苄基‑2‑噁唑烷酮反应。后在有机碱作用下与碘甲烷反应,诱导出手性甲基。在四氢铝锂作用下还原成醇,再氧化成醛并与三苯基丙基溴化膦发生wittig反应。Wittig反应后,Pt/C做催化剂,催化加氢消去双键,再以Pd/C做催化剂脱去苄基成醇,将醇氧化成醛。1,10‑癸二醇单溴代后,再用TBSCl单保护,后与三苯基膦反应成季鏻盐。醛与季鏻盐发生Wittig反应,以Pt/C做催化剂催化加氢消去双键。脱去TBS单保护成醇,后氧化成醛。醛与甲基三苯基溴化膦wittig反应得到信息素(S)‑14‑甲基‑1‑十八碳烯。本发明反应条件温和,在反应过程中保持了手性甲基、未发生消旋。
Description
技术领域
本发明涉及化学合成技术领域。具体地说是一种鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法。
背景技术
桃潜叶蛾Lyonetia clerkella L.是一种鳞翅目潜叶蛾科的常见害虫,是桃叶片上的重要害虫,世代重叠现象普遍,多种虫态并存。桃潜叶蛾每年发生约7代,幼虫孵化后,在叶组织内潜食为害,串成弯曲蛀道,叶的表皮不破裂,可由叶面透视,影响叶片的正常生理活动使其枯死脱落。
昆虫性信息素具有以下优点:其作用方式独特、生物活性高、专一性强;害虫不易产生耐药性,对天敌无害;明显减少农药使用量与环境污染,减少农产品中农药残留量;使用简便,防治成本低。是一种环境友好型的绿色农药。
桃潜叶蛾性信息素被证明只有(S)-14-甲基-1-十八碳烯有生物活性,R 构型的没有生物活性,外消旋体生物活性只有S构型的一半。
关于桃潜叶蛾性信息素的合成方法国内外有许多研究,主要是手性源合成法,以天然手性源为原料,再用格氏试剂偶联法延长碳链得到。
最早报道合成(S)-14-甲基-十八碳烯的是Katto等(Kato M,Mori K.1985.Synthesis of the enantiomers of 14-methyl-1-Octadeeene,the sex pheromoneof the peach leafminer moth.Agricultural and Biological Chemistry,1985,49(8):2479-2480),以(R)-β-羟基异丁酸甲酯和十二碳烯基溴化镁为起始原料,经过上保护基与脱保护基、格氏试剂偶联等反应合成了(S)-14-甲基-十八碳烯,总收率仅为6.5%。同年,Mori等(MoriK, Kato M.Pheromone Syntheses,LXXVII.New Synthesis of theEnantiomers of 14-Methyl-1-octadecene,the Pheromone of Lyonetia clerkella L.)通过使用(R)-香茅酸为原料,经过还原、酯化、臭氧化、格氏试剂偶联等反应,合成了(S)-14-甲基-十八碳烯。天然手性源原料价格昂贵且不易得到。格式试剂偶联法的缺点是偶联试剂比较昂贵,操作条件苛刻,产率相比 wittig反应比较低。
Sota(SATO,Rikio,et al."Biological activity of (R)-and (S)-14-methyl-1-octadecene,as the chiral component of the sex pheromone of the peachleafminer moth,Lyonetia clerkella Linne (Lepidoptera:Lyonetiidae)."AppliedEntomology and Zoology 20.4 (1985):411-415.)以正己酸为起始原料,通过三步反应同时结合结晶拆分法获得了手性试剂(S)-3-甲基-1-己醇,进一步制得(S)构型的wittig试剂(ylid),再以1,12-十二二醇为原料,经过六步反应合成了(S)-14-甲基-1- 十八碳烯。
1991年陈子康等(陈子康,祝钧.手性桃潜蛾性信息素的新合成路线 [J].有机化学,1991(5):530-533.)以2-甲基己酸为原料,利用生物碱进行拆分后得到纯的(S)-2-甲基己酸,然后通过还原、溴代、偶联等反应最终得到(S)-14-甲基-1-十八碳烯,总收率31.1%。
张涛等(Zhang T,Ma W L,Li T R,et al.A facile asymmetric synthesis of(S)-14-methyl-1-octadecene,the sex pheromone of the peach leafminer moth[J].Molecules,2013,18(5):5201-5208.)以(S)-4- 苄基-2-恶唑烷酮为原料,诱导得到手性片段,另一个片段以1,9-壬二醇为原料,经过一系列反应得到(S)-14-甲基-1-十八碳烯,总收率30.1%。
关于桃潜叶蛾性信息素的合成方法还有很多,都存在步骤过长或原料昂贵等缺点。
发明内容
为此,本发明所要解决的技术问题在于提供一种原料便宜易得、操作简便的鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法。
为解决上述技术问题,本发明提供如下技术方案:
一种鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,包括如下步骤:
(1)以γ-丁内酯为原料,先开环,后与氯化苄反应生成4-苄氧基丁酸;
(2)4-苄氧基丁酸与(S)-4-苄基-2-噁唑烷酮反应生成(S)-4-苄基 -3-(4-(苄氧基)丁酰基)-2-恶唑烷酮;
(3)在有机碱作用下(S)-4-苄基-3-(4-(苄氧基)丁酰基)-2-恶唑烷酮与碘甲烷反应生成(S)-4-苄基-3-((S)-4-(苄氧基)-2-甲基丁酰基) -2-恶唑烷酮;
(4)(S)-4-苄基-3-((S)-4-(苄氧基)-2-甲基丁酰基)-2-恶唑烷酮在四氢铝锂作用下被还原成(S)-4-(苄氧基)-2-甲基-1-丁醇;
(5)(S)-4-(苄氧基)-2-甲基-1-丁醇经过氧化剂氧化得到(S)-4- (苄氧基)-2-甲基-1-丁醛;
(6)(S)-4-(苄氧基)-2-甲基-1-丁醛与三苯基丙基溴化膦在有机碱的作用下发生wittig反应得到(S,E)-3-甲基-1-苄氧基-4-庚烯;
(7)(S,E)-3-甲基-1-苄氧基-4-庚烯先在Pt/C做催化剂条件下,催化加氢消去双键,后在Pd/C做催化剂条件下脱去苄氧基生成(S)-3-甲基 -1-庚醇;
(8)(S)-3-甲基-1-庚醇经过氧化剂氧化得到(S)-3-甲基-1-庚醛;
(9)1,10-癸二醇经过单溴代反应得到10-溴癸醇;
(10)10-溴癸醇在碱做催化剂条件下与TBSCl经过单保护反应得到10-溴-1-(叔丁基二甲基甲硅烷氧基)-癸烷;
(11)10-溴-1-(叔丁基二甲基甲硅烷氧基)-癸烷与三苯基膦反应,得到1-(叔丁基二甲基甲硅烷氧基)-癸基三苯基溴化膦;
(12)1-(叔丁基二甲基甲硅烷氧基)-癸基三苯基溴化膦与(S)-3- 甲基-1-庚醛在有机碱的作用下发生wittig反应得到(S,E)-13-甲基-10- 烯-1-叔丁基二甲基甲硅烷氧基十七烷;
(13)(S,E)-13-甲基-10-烯-1-叔丁基二甲基甲硅烷氧基十七烷在Pt/C做催化剂条件下,催化加氢消去双键得到(S)-13-甲基-1-叔丁基二甲基甲硅烷氧基十七烷;
(14)(S)-13-甲基-1-叔丁基二甲基甲硅烷氧基十七烷在有机碱催化剂四丁基氟化铵作用下,脱去TBS官能团保护,得到(S)-13-甲基-1-十七烷醇;
(15)(S)-13-甲基-1-十七烷醇经过氧化剂氧化得到(S)-13-甲基-1- 十七烷醛;
(16)(S)-13-甲基-1-十七烷醛与甲基三苯基季鏻盐在有机碱作用下发生wittig反应得到目标产物桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯。
上述鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,在步骤(1)中,溶剂为甲苯,并加入固体氢氧化钠;在步骤(2)中, (S)-4-苄基-2-噁唑烷酮为Evans模板,4-苄氧基丁酸与溶剂四氢呋喃THF 的质量体积比为1:20g/mL。
上述鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,在步骤(3)中,(S)-4-苄基-3-(4-(苄氧基)丁酰基)-2-恶唑烷酮与碘甲烷的当量比为1:(4-5)eq,所述有机碱为三乙胺。
上述鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,在步骤(4)中,(S)-4-苄基-3-((S)-4-(苄氧基)-2-甲基丁酰基) -2-恶唑烷酮与四氢铝锂的当量比为1:4eq。
上述鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,在步骤(5)、步骤(8)和步骤(15)中,所述氧化剂为戴斯-马丁氧化剂、氯铬酸吡啶嗡盐或重铬酸吡啶嗡盐。
上述鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,在步骤(6)中,wittig反应所用的有机碱为双(三甲基硅基)氨基钠 NaHMDS,双(三甲基硅基)氨基钠NaHMDS与三苯基丙基溴化膦的当量比为 1.25:1.5eq;在步骤(12)和步骤(16)中,wittig反应的有机碱为双(三甲基硅基)氨基钠NaHMDS或正丁基锂,滴加有机碱时的温度为-30~-20℃,在步骤(12)中:有机碱与1-(叔丁基二甲基甲硅烷氧基)-癸基三苯基溴化膦的的当量比为1.25:1.5eq;在步骤(16)中:有机碱与甲基三苯基溴化膦的当量比为1.25:1.5eq;步骤(6)、(12)和(16)中:滴加有机碱时的温度为-30~-20℃。
上述鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,在步骤(2)、(3)、(4)、(5)、(6)、(8)、(10)、(12)、(15)和(16) 的反应体系都为惰性气体保护体系,惰性气体为氮气或氩气。
上述鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,在步骤(7)和步骤(13)中,所用的溶剂为甲醇,反应体系温度为25-45 ℃,催化剂的加入量为反应底物的5-10wt%。
上述鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,所述步骤(1)、(9)和(11)所用的溶剂为甲苯;所述步骤(2)、(3)、 (4)、(6)、(12)、(14)和(16)所用的溶剂为四氢呋喃;步骤(5)、(8) 和(15)所用的溶剂为二氯甲烷。
上述鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,在步骤(1)-(16)中,当反应溶剂为二氯甲烷时,所用萃取溶剂是二氯甲烷;当反应溶剂为其它溶剂时,所用萃取溶剂是乙酸乙酯;在步骤(1) -(16)中的后处理中,加入水相;在步骤(16)中:所得目标产物桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯先用乙酸乙酯进行萃取,用无水硫酸镁干燥后用柱层析的方法进行纯化。
本发明的技术方案取得了如下有益的技术效果:
本发明以γ-丁内酯为原料,通过手性EVANS模板诱导手性甲基,对端基官能团进行单保护与去保护,经过还原反应,氧化反应,催化加氢,并以 wittig反应增长碳链,得到目标产物。本发明反应条件温和,在反应过程中手性甲基并未消旋。
在本申请中,作为优选的技术方案,有机碱以溶液形式加入。
目标产物桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯可用柱层析的方法进行纯化,最优选为硅胶柱。
在本发明中,氧化反应所用的氧化剂可为戴斯-马丁氧化剂、PCC氧化剂或PDC氧化剂,三者产率基本相同;PDC作为氧化剂,后处理方便,故最优选重铬酸吡啶嗡盐作为氧化剂。
本发明中的萃取有机溶剂为石油醚、二氯甲烷、四氢呋喃、乙酸乙酯、甲苯等,当溶剂为二氯甲烷时,所用萃取溶剂最优选是二氯甲烷。当溶剂为其它溶剂时,所用萃取溶剂最优选是乙酸乙酯。优选萃取次数为3次。
本发明中,后处理时会加入水相洗去有机碱等杂质,加入的水量优选为反应体系体积的0.25倍,优选洗涤次数为三次。
在本发明中,洗涤后的有机相要用常见的中性干燥剂除水,如无水硫酸镁或无水硫酸钠等,干燥后过滤,减压浓缩。
附图说明
图1本发明鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法的合成路线图。
具体实施方式
本实施例鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,具体包括如下步骤(合成路线如图1所示)。
步骤(1)γ-丁内酯制得4-苄氧基丁酸
取500mL三口瓶加入γ-丁内酯(50g,580.79mmol,1eq),甲苯250mL,加入NaOH(104.54g,2.61mol,5eq),滴加苄氯(294.08g,2.32mol,4eq)。加热回流48h。气相色谱GC检测无原料点,500mL水分液,保留水相。水相用二氯甲烷萃取(200mL×3,即每次用200mL二氯甲烷萃取,共萃取3 次),冰浴下将水相pH调至2-3,水相用乙酸乙酯萃取(200mL×3,即每次用200mL乙酸乙酯萃取,共萃取3次),合并有机相,饱和食盐水洗涤(200 mL×3,即每次用200mL饱和食盐水洗涤,共洗涤3次)。无水硫酸镁干燥,减压旋蒸得到4-苄氧基丁酸105g,收率93.68%。
步骤(2)(S)-4-苄基-3-(4-(苄氧基)丁酰基)-2-恶唑烷酮的合成
氩气保护下,500mL三口瓶,称取4-苄氧基丁酸(18g,92.68mmol,1eq),加入无水四氢呋喃360mL,-78℃下滴加三乙胺(25.83mL,185.35mmol,2eq),再滴加三甲基乙酰氯(13.61mL,111.21mmol,1.2eq),搅拌20min后室温反应1h。-78℃下加入氯化锂(11.79g,278.03mmol,3eq)和(S)-4-苄基-2- 噁唑烷酮(18.06g,101.94mmol,1.1eq)溶于无水四氢呋喃,然后再滴加至反应体系中。滴加完毕后反应1h,自然升温,反应过夜。150mL水淬灭。乙酸乙酯萃取(200mL×3,即每次用200mL乙酸乙酯萃取,共萃取3次),合并有机相,饱和食盐水洗涤(200mL×3,即每次用200mL饱和食盐水洗涤,共洗涤3次)。无水硫酸镁干燥,过滤,旋干,柱层析得到黄色油状液体35.45g,收率87.43%。
步骤(3)(S)-4-苄基-3-((S)-4-(苄氧基)-2-甲基丁酰基)-2-恶唑烷酮的合成
氩气保护下,向500mL三口瓶中加入(S)-4-苄基-3-(4-(苄氧基)丁酰基)-2-恶唑烷酮(23g,65.08mmol,1eq),无水四氢呋喃250mL,在-78 ℃下滴加NaHMNDS(65.08mL,130.16mmol,2eq,c=2M),反应30min后滴加碘甲烷(46.19g,325.4mmol,5eq),反应2h后,将温度调至-50℃,反应过夜。-50℃下,用饱和氯化铵溶液淬灭,水相用乙酸乙酯萃取(200mL×3,即每次用200mL乙酸乙酯萃取,共萃取3次),饱和食盐水洗涤(200mL ×3,即每次用200mL饱和食盐水洗涤,共洗涤3次)。无水硫酸镁干燥,过滤,浓缩。柱层析得到无色油状液体12.12g,收率50.18%。
步骤(4)(S)-4-(苄氧基)-2-甲基-1-丁醇的合成
氩气保护下,500mL三口瓶中加四氢铝锂(4.54g,29.94mmol,4eq),再加入无水四氢呋喃200mL。称取(S)-4-苄基-3-((S)-4-(苄氧基)-2- 甲基丁酰基)-2-恶唑烷酮(11g,29.94mmol,1eq),用无水四氢呋喃溶解,冰浴下,将其滴入体系中,自然升温,搅拌过夜。冰浴下,向体系中依次加入1:2:3=H2O:10wt%NaOH:H2O淬灭(先加入与四氢铝锂等质量的水,1克四氢铝锂一毫升水;再加入质量分数为10%的氢氧化钠溶液,氢氧化钠溶液的质量是四氢铝锂质量的2倍【1克四氢铝锂加2毫升氢氧化钠溶液】;最后再加水的质量是四氢铝锂质量的3倍,即1克四氢铝锂3毫升水;本步骤四氢铝锂是4.54克,依次加4.54mL H2O,9.08mL10wt%NaOH,13.62mL H2O)。乙酸乙酯萃取(200mL×3,即每次用200mL乙酸乙酯萃取,共萃取3次)。无水硫酸镁干燥,过滤,浓缩,柱层析得到无色油状液体5.01g,收率85.97%。
步骤(5)(S)-4-(苄氧基)-2-甲基-1-丁醛的合成
取250mL三口瓶,称取(S)-4-(苄氧基)-2-甲基-1-丁醇(4.5g,23.16 mmol,1eq),加入150mL二氯甲烷,并加入4.5g的硅胶,氩气保护。冰浴下,加入氯铬酸吡啶嗡盐(5.99g,20.8mmol,1.2eq)。恢复室温,反应5h。点板检测,无原料点,直接旋干,柱层析。得到无色油状液体3.9g,收率 87.58%。
步骤(6)(S,E)-3-甲基-1-苄氧基-4-庚烯的合成
250mL三口瓶,称取正丙基溴季鏻盐(3.31g,8.58mmol,1.1eq),氩气保护。加入无水四氢呋喃150mL,冰浴下,加入n-BuLi(3.28mL,8.19 mmol,1.0eq,c=2.5M),缓慢恢复室温,反应1~2h。冰浴下,缓慢滴加溶于无水四氢呋喃的(S)-4-(苄氧基)-2-甲基-1-丁醛5(1.5g,7.8mmol,1eq),缓慢恢复室温,反应过夜。点板检测,无醛。饱和氯化铵溶液淬灭,用乙酸乙酯萃取(50mL×3,即每次用50mL乙酸乙酯萃取,共萃取3次),饱和食盐水洗涤(50mL×3,即每次用50mL饱和食盐水洗涤,共洗涤3次),无水硫酸镁干燥,过滤,旋干,柱层析得到无色油状液体1.5g,收率88.05%。
步骤(7)(S)-3-甲基-1-庚醇的合成
称取(S,E)-3-甲基-1-苄氧基-4-庚烯(3g,13.74mmol)于125mL的单口瓶,加入100mL甲醇,然后加入Pt/C(底物质量的10%)做催化剂,将容器内充满氢气,在内部加压下搅拌,45℃下反应12h。点板检测,待体系中原料反应完全,向其中加入Pd/C(底物质量的10%)继续催化,换气将容器内充满氢气,在内部加压下继续搅拌,45℃下反应12h,点板检测,抽滤,减压浓缩。得到无色油状液体1.5g,收率83.83%。
步骤(8)(S)-3-甲基-1-庚醛的合成
取250mL三口瓶,称取(S)-3-甲基-1-庚醇(1.5g,11.52mmol,1eq),加入150mL二氯甲烷,加入1.5g硅胶,氩气保护。冰浴下,加入氯铬酸吡啶嗡盐(2.98g,13.82mmol,1.2eq),缓慢恢复室温,反应5h。点板检测,无原料点,直接旋干过柱。得到无色油状液体0.95g,收率64.33%。
步骤(9)10-溴癸醇的合成
取250mL单口瓶,称取(5g,28.69mmol,1eq)1,10-癸二醇,加入 125mL甲苯,加入HBr(3.73mL,32.99mmol,1.15eq,W=48%),上接分水器与冷凝管,加热回流过夜。点板检测,无原料点,用饱和亚硫酸氢钠溶液洗涤(50mL×3,即每次用50mL饱和亚硫酸氢钠溶液洗涤,共洗涤3次),乙酸乙酯萃取(50mL×3,即每次用50mL乙酸乙酯萃取,共萃取3次),合并有机相,无水硫酸镁干燥,抽滤,旋干过柱。得到淡黄色油状液体6g,收率88.18%。
步骤(10)10-溴-1-(叔丁基二甲基甲硅烷氧基)-癸烷的合成
取500mL三口瓶,称取10-溴癸醇(24g,101.19mmol,1eq),加入250 mL二氯甲烷,氩气保护。冰浴下,加入咪唑(13.78g,202.38mmol,2eq)。将叔丁基二甲基氯硅烷(TBSCl)(18.3g,121.43mmol,1.2eq)溶于二氯甲烷,冰浴条件下,用恒压滴液漏斗将叔丁基二甲基氯硅烷的二氯甲烷溶液缓慢滴入体系。缓慢恢复室温,反应过夜。点板检测,无原料点,加30mL水淬灭,水洗(100mL×3,即每次用100mL水洗涤,共洗涤3次),再用乙酸乙酯萃取(100mL×3,即每次用100mL乙酸乙酯萃取,共萃取3次),合并有机相,旋干,过柱。得到无色油状液体33.5g,收率94.2%。
步骤(11)1-(叔丁基二甲基甲硅烷氧基)-癸基三苯基溴化膦的合成取500mL单口瓶,称取10-溴-1-(叔丁基二甲基甲硅烷氧基)-癸烷 (32g,91.05mmol,1eq),加入250mL甲苯,加入三苯基膦(25.08g,95.61 mmol,1.05eq)。加热回流反应24h。先旋干溶剂,再加入乙醚重结晶,抽滤,用乙醚多次洗涤滤饼,收率86.17%。
步骤(12)(S,E)-13-甲基-10-烯-1-叔丁基二甲基甲硅烷氧基十七烷的合成
250mL三口瓶,称取1-(叔丁基二甲基甲硅烷氧基)-癸基三苯基溴化膦(4.79g,7.8mmol,2eq),氩气保护,加入125mL无水四氢呋喃。-30 ℃下,缓慢滴加n-BuLi(1.95mL,4.87mmol,1.25eq,c=2.5M),室温搅拌 1~2h。-30℃下,缓慢滴加(S)-3-甲基-1-庚醛(0.5g,3.9mmol,1eq),缓慢恢复室温,搅拌过夜。点板检测无醛,用饱和NH4Cl溶液淬灭。乙酸乙酯萃取(50mL×3,即每次用50mL乙酸乙酯萃取,共萃取3次),无水硫酸镁干燥,过滤,旋干,柱层析。得到无色油状液体1.16g,收率77.72%。
步骤(13)(S)-13-甲基-1-叔丁基二甲基甲硅烷氧基十七烷的合成
250mL单口瓶,称取(S,E)-13-甲基-10-烯-1-叔丁基二甲基甲硅烷氧基十七烷(2.5g,6.53mmol,1eq),加入150mL甲醇将其完全溶解,然后加入Pt/C(底物质量的10%)做催化剂,将容器内充满氢气,在内部加压下搅拌,45℃下反应12h。点板检测,待体系中原料反应完全,抽滤,旋蒸浓缩滤液,柱层析。得到无色油状液体2.1g,收率83.56%。
步骤(14)(S)-13-甲基-1-十七烷醇的合成
称取(S)-13-甲基-1-叔丁基二甲基甲硅烷氧基十七烷(1g,2.6mmol,1 eq)于125mL单口瓶中,加入无水四氢呋喃80mL。冰浴条件下滴加缓慢滴加四丁基氟化铵(3.12mL,3.12mmol,1.2eq,c=1M),缓慢恢复至室温搅拌 4h。点板检测,无原料点,用少量饱和氯化铵溶液淬灭,加入少量硅胶,旋干过柱,得到无色油状液体0.6g,收率85.34%。
步骤(15)(S)-13-甲基-1-十七烷醛的合成
取125mL三口瓶,称取(S)-13-甲基-1-十七烷醛(0.4g,1.48mmol,1 eq),加入80mL二氯甲烷,加入0.4g硅胶,氩气保护。冰浴下,加入重铬酸吡啶嗡盐(0.38mg,1.77mmol,1.2eq)。缓慢恢复室温,反应5h。点板检测,无原料点直接旋干过柱。得到无色油状液体0.35g,收率88.16%。
步骤(16)(S)-14-甲基-1-十八碳烯的合成
称取甲基三苯基溴化膦季鏻盐(1.8g,5.03mmol,1.5eq)于125mL三口瓶中,氩气保护。加入80mL无水四氢呋喃,在-30℃下,缓慢滴加 NaHMDS(2.1mL,4.19mmol,c=2M,1.25eq),在室温下搅拌3h。-30℃冰浴下,缓慢滴加用四氢呋喃溶解的(S)-13-甲基-1-十七烷醛(0.9g,3.35 mmol,1eq),滴加完毕后,缓慢恢复室温并搅拌过夜。点板检测无醛,用饱和氯化铵溶液淬灭。乙酸乙酯萃取(30mL×3,即每次用30mL乙酸乙酯萃取,共萃取3次),无水硫酸镁干燥,过滤,旋蒸,过硅胶柱进行纯化。得到无色油状液体0.76g,收率85.07%。
显然,上述实施例仅仅是为清楚地说明所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本专利申请权利要求的保护范围之中。
Claims (10)
1.一种鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,其特征在于,包括如下步骤:
(1)以γ-丁内酯为原料,先开环,后与氯化苄反应生成4-苄氧基丁酸;
(2)4-苄氧基丁酸与(S)-4-苄基-2-噁唑烷酮反应生成(S)-4-苄基-3-(4-(苄氧基)丁酰基)-2-噁唑烷酮;
(3)在有机碱作用下(S)-4-苄基-3-(4-(苄氧基)丁酰基)-2-噁唑烷酮与碘甲烷反应生成(S)-4-苄基-3-((S)-4-(苄氧基)-2-甲基丁酰基)-2-噁唑烷酮;
(4)(S)-4-苄基-3-((S)-4-(苄氧基)-2-甲基丁酰基)-2-噁唑烷酮在四氢铝锂作用下被还原成(S)-4-(苄氧基)-2-甲基-1-丁醇;
(5)(S)-4-(苄氧基)-2-甲基-1-丁醇经过氧化剂氧化得到(S)-4-(苄氧基)-2-甲基-1-丁醛;
(6)(S)-4-(苄氧基)-2-甲基-1-丁醛与三苯基丙基溴化膦在有机碱的作用下发生wittig反应得到(S,E)-3-甲基-1-苄氧基-4-庚烯;
(7)(S,E)-3-甲基-1-苄氧基-4-庚烯先在Pt/C做催化剂条件下,催化加氢消去双键,后在Pd/C做催化剂条件下脱去苄氧基生成(S)-3-甲基-1-庚醇;
(8)(S)-3-甲基-1-庚醇经过氧化剂氧化得到(S)-3-甲基-1-庚醛;
(9)1,10-癸二醇经过单溴代反应得到10-溴癸醇;
(10)10-溴癸醇在碱做催化剂条件下与TBSCl经过单保护反应得到10-溴-1-(叔丁基二甲基甲硅烷氧基)-癸烷;
(11)10-溴-1-(叔丁基二甲基甲硅烷氧基)-癸烷与三苯基膦反应,得到1-(叔丁基二甲基甲硅烷氧基)-癸基三苯基溴化膦;
(12)1-(叔丁基二甲基甲硅烷氧基)-癸基三苯基溴化膦与(S)-3-甲基-1-庚醛在有机碱的作用下发生wittig反应得到(S,E) - 13-甲基-10-烯-1-叔丁基二甲基甲硅烷氧基十七烷;
(13)(S,E) - 13-甲基-10-烯-1-叔丁基二甲基甲硅烷氧基十七烷在Pt/C做催化剂条件下,催化加氢消去双键得到(S)-13-甲基-1-叔丁基二甲基甲硅烷氧基十七烷;
(14)(S)-13-甲基-1-叔丁基二甲基甲硅烷氧基十七烷在有机碱催化剂四丁基氟化铵作用下,脱去TBS官能团保护,得到(S)-13-甲基-1-十七烷醇;
(15)(S)-13-甲基-1-十七烷醇经过氧化剂氧化得到(S)-13-甲基-1-十七烷醛;
(16)(S)-13-甲基-1-十七烷醛与甲基三苯基季鏻盐在有机碱作用下发生wittig反应得到目标产物桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯。
2.根据权利要求1所述的鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,其特征在于,在步骤(1)中,反应在溶剂甲苯中进行,并加入固体氢氧化钠;在步骤(2)中,反应在溶剂四氢呋喃中进行,(S)-4-苄基-2-噁唑烷酮为Evans模板,4-苄氧基丁酸与溶剂四氢呋喃THF的质量体积比为1:20 g/mL。
3.根据权利要求1所述的鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,其特征在于,在步骤(3)中,(S)-4-苄基-3-(4-(苄氧基)丁酰基)-2-噁唑烷酮与碘甲烷的当量比为1:(4-5) eq,所述有机碱为三乙胺。
4.根据权利要求1所述的鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,其特征在于,在步骤(4)中,(S)-4-苄基-3-((S)-4-(苄氧基)-2-甲基丁酰基)-2-噁唑烷酮与四氢铝锂的当量比为1:4 eq。
5.根据权利要求1所述的鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,其特征在于,在步骤(5)、步骤(8)和步骤(15)中,所述氧化剂为戴斯-马丁氧化剂、氯铬酸吡啶嗡盐或重铬酸吡啶嗡盐。
6.根据权利要求1所述的鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,其特征在于,在步骤(6)中,wittig反应所用的有机碱为双(三甲基硅基)氨基钠NaHMDS,双(三甲基硅基)氨基钠NaHMDS与三苯基丙基溴化膦的当量比为1.25:1.5 eq;在步骤(12)和步骤(16)中,wittig反应的有机碱为双(三甲基硅基)氨基钠NaHMDS或正丁基锂,滴加有机碱时的温度为-30~-20℃,在步骤(12)中:有机碱与1-(叔丁基二甲基甲硅烷氧基)-癸基三苯基溴化膦的当量比为1.25:1.5 eq;在步骤(16)中:有机碱与甲基三苯基溴化膦的当量比为1.25:1.5 eq;步骤(6)、(12)和(16)中:滴加有机碱时的温度为-30~-20℃。
7.根据权利要求1所述的鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,其特征在于,在步骤(2)、(3)、(4)、(5)、(6)、(8)、(10)、(12)、(15)和(16)的反应体系都为惰性气体保护体系,惰性气体为氮气或氩气。
8.根据权利要求1所述的鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,其特征在于,在步骤(7)和步骤(13)中,反应在溶剂甲醇中进行,反应体系温度为25-45℃,催化剂的加入量为反应底物的5-10wt%。
9.根据权利要求1所述的鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,其特征在于,在步骤(1)、(9)和(11)中,反应在溶剂甲苯中进行;在步骤(2)、(3)、(4)、(6)、(12)、(14)和(16)中,反应在溶剂四氢呋喃中进行;在步骤(5)、(8)和(15)中,反应在溶剂二氯甲烷中进行。
10.根据权利要求2、8或9所述的鳞翅目害虫桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯的合成方法,其特征在于,在步骤(1)-(16)中,当反应溶剂为二氯甲烷时,产物用二氯甲烷进行萃取;当反应溶剂为其它溶剂时,产物用乙酸乙酯进行萃取;在步骤(16)中:所得目标产物桃潜叶蛾性信息素(S)-14-甲基-1-十八碳烯先用乙酸乙酯进行萃取,用无水硫酸镁干燥后用柱层析的方法进行纯化。
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