CN1117061C - 一种制备环丙烷羧酸及其中间体的方法 - Google Patents
一种制备环丙烷羧酸及其中间体的方法 Download PDFInfo
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Classifications
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/16—Unsaturated compounds
- C07C61/35—Unsaturated compounds having unsaturation outside the rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/16—Unsaturated compounds
- C07C61/40—Unsaturated compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C62/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C62/02—Saturated compounds containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered
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Abstract
化合物3-(2,2-二氯-3,3,3-三氟-1-羟丙基)-2,2-二甲基-(1R,3R)一环丙烷羧酸,顺式-3-(2,2-二氯-3,3,3-三氟-1-羟丙基)-2,2-二甲基-环丙烷羧酸及(1R,5S)-4-(1,1-二氯-2,2,2-三氟乙基)-6,6-二甲基-3-氧杂双环〔3.1.0〕己-2-酮作为制备杀昆虫活性的环丙烷羧酸酯方法的中间体,该方法以6,6-二甲基-4-羟基-3-氧杂双环〔3.1.0〕己-2-酮(Biocartol)作为起始物质,于锌存在下与化合物CF3-CClX2(X=卤素)进行反应。
Description
本发明涉及制备环丙烷羧酸酯时可以作为中间体的化合物,且本发明还涉及制备该类化合物的方法。
环丙烷羧酸酯为杀昆虫的有效化合物,以“拟除虫菊酯”为人所知,且由于具有对哺乳动物极低毒性及非常良好的杀虫性质,因此相当受重视。业已作了多种努力以发现经济上有利的途径以制备环丙烷羧酸酯及其重要的中间产物。Ia:1R,顺式,ZIb:1RS,顺式,Z
一类显示高度活性的拟除虫菊酯化合物具有通式I,其中碳原子1及3为非对称性的碳原子,及R′选自已知对分子的杀虫活性极重要的基团,如RS-α-氰基-3-苯氧苄基或S-α-氰基-3-苯氧苄基或2-甲基联苯基-3-基甲基或2,3,5,6-四氟-4-甲苄基。
下文中的上标1、2等代表与本发明最后所列参考资料的来源。
已知该酯Ia的酸基团的立体异构体的构型应为1R,顺式,Z以获得最大的杀昆虫活性1,即在碳原子1的绝对构形为R,在碳原子1及3处的两个氢原子处在顺式位置,且氯原子及环丙烷基在碳-碳双键的同一侧。
因此,以技术上及经济上有吸引力的方式来制备I的活性异构体,并且在农作物,植被等方面减少有效物质(杀虫剂)的施用份量是十分重要的。
因此,若制备式Ia的化合物,则需提供立体选择性的化学合成途径或用物理分离技术由外消旋混合物中分离所需的立体异构体。后者方法通常较为昂贵且鲜用于工业规模。
已知,如下式II的Biocartol可与卤化的一碳化合物如CHBr3、CHCl3、CHClF2等在强碱存在下反应以获得环丙烷羧酸衍生物2。
已知式IVb的外消旋化合物可由将4-重氮乙酰氧基-5,5-二氯-6,6,6-三氟-2-甲基-2-己烷在乙酰基丙酮酸铜(II)盐于沸腾二噁烷悬浮液中环化来制备,其中环丙烷环在反应过程中的最后阶段来形成3。
同时。业已建议如下式IVb的外消旋化合物可由顺式-3-甲酰基-2,2-二甲基-环丙烷羧酸酯及1,1,1-三氯-2,2,2-三氟乙烷于锌存在下反应来形成3。
现在已发现一种途径来合成具有商业重要性的式I化合物,即使用物质Biocartol(式II)来作为起始物质,Biocartol由自然界存在的物质(+)-3-皆烯4,5,6能够以旋光纯形式的IIa或以由菊酸或其衍生物3的臭氧分解所得的外消旋形式的IIb容易地制得。反式-3-(二甲氧基甲基)-2,2-二甲基-环丙烷羧酸甲基酯(可购自例如A1drich-Chemie)可经由水解及差向立体异构-内酯化作用成为IIb的来源。
就产物的立体异构性而言此合成途径相当特殊,使得IIa的几何异构体可再次地于Ia产物中发现。除非能避免形成异构体,否则以此方式会损失昂贵的外消旋析分溶液及产量。IIa:1R,顺式 IIIIb:IRS,顺式在此描述数种自Biocartol IIa合成拟除虫菊酯式Ia(R′=H)的(IR顺式,Z)酸基团的新合成方式(见反应式),即通过本发明新颖的中间体IIIa及/或IVa来进行。此合成方法亦可以相同方式由Biocartol IIb经新颖中间体IIIb来制备拟除虫菊酯式Ib(R′=H)的(IRS,顺式,Z)酸基团。
在此亦描述由II至1(R′=H)的一釜法的合成路径,其中中间体并未分离但由GC确认及鉴定。此合成方法可用于自IIa合成Ia及自IIb合成Ib。
反应式
本发明也涉及通式III或通式IV的化合物,其中X代表卤素,特别是氯。
通式III的优选化合物为顺式-3-(2,2-二氯-3,3,3-三氟-1-羟丙基)-2,2-二甲基环丙烷羧酸(IIIb,X=Cl)、及3-(2,2-二氯-3,3,3-三氟-1-羟丙基)-2,2-二甲基(1R,3S)-环丙烷羧酸(IIIa,X=Cl)。
化合物IIIb(X=Cl)及IIIa,(X=Cl)是理想且新颖的起始物质,用以分别合成IVb(X=Cl)及IVa(X=Cl)以及最后分别得到Ib(R′=H)及Ia(R′=H)。这也可以通过连续添加反应物由II一釜法合成I的方式,其中III及IV为中间体。
化合物IVa(X=Cl)的特征是可以作为合成Ia(R′=H)的理想及新颖的起始物质,事实上还意外地发现进一步的反应几乎排除了I的Z异构体。由于邻近CXCl基的不对称碳原子及该CXCl基(对于X≠Cl)的不对称碳原子,化合物IIIa及IVa(且类似地IIIb及IVb)可存在多种异构体形式且不需为相等份量。其比例可用GC及NMR测定。所有此异构体产生相同的最终产物Ia(Ib)。
最终产物Ia及Ib的NMR及GC分析显示其有利地生成游离的Z-异构体。通常为包括多于90%的Z-异构体,且粗产物可容易地纯化成超过99%的Z-异构体。
本发明涉及制备通式I的化合物(其中R′代表H,且于环丙烷环上的两个氢原子处于彼此的顺式位置)的方法,即将通式II的化合物与CF3-CClX2(其中X代表卤原子,特别为氯及溴)于惰性介质如DMF中,在例如过量金属锌存在下,且温度介于0-150℃间,优选在20-100间进行反应。于一段时间后,当反应混合物的GC分析显示起始化合物II已被消耗,中间体III及IV业已形成且最终产物I也已少量形成后,加入一脱水剂,优选为醋酸酐,立即可将中间体III转变成中间体IV,用GC分析确认。进一步经过一段时间后,中间体IV完全被转变成最终产物I,若未反应的金属锌还存在的话,绝大多数为Z-异构体,是旋光纯物且是外消旋物形式。
当金属试剂用于上述情况中时,此试剂能以催化量的于反应期间用电化学方法再生的相同金属来取代。
本发明进一步用下述实施例说明。产量及纯度由气相及/或液相色谱法,以及NMR光谱来测定。
实施例1
由Biocartol IIa制备3-(2,2-二氯-3,3,3-三氟-1-羟基丙基)-2,2-二甲基-(1R,3S)-环丙烷羧酸(IIIa,X=Cl)。
往0.02摩尔的IIa(2.84克)及0.022摩尔的1,1-二氯-2,2,2-三氟乙烷(3.36克)于5克干燥DMF及25毫升的干燥THF混合物中的搅拌着的溶液中经外源冷却至-70℃,将27毫升的叔丁醇钾缓慢地加入,以使反应混合物的温度保持低于-55℃下。在相同温度下将反应继续30分钟,且然后将反应混合物用计算量的浓HCl来淬灭。在自发性热至室温后将反应溶液倾倒至水-甲基叔丁基醚混合物中。将水相及有机相分离,且水相用2×25毫升的甲基叔丁基醚(MTBE)来萃取。将有机相合并后,用Na2SO4脱水且于减压下挥发。获得1.1克的粗产物,以气相色谱测定具有60%纯度。将粗产物用己烷结晶纯化且分离出0.4克的IIIa(28%的理论值),具有熔点126-9℃(分解)及根据NMR纯度为>95%。比旋光度:[α]D 25=-11°(1.28克/100毫升,THF)。1H NMR(250MHz,CDCl3+CD3OD):由主要异构体得,1.21ppm(s,3H);1.31ppm(s,3H),1.7ppm(m,2H);4.51ppm(d,J=8.8Hz,1H);4.8ppm(宽单峰,2H)。由次要异构体得,1.27ppm(s,3H);1.39ppm(s,3H)。13C-NMR(63MHz,CDCl3+CD3OD):16.1ppm(q);28.4ppm(s);28.6ppm(q);29.5ppm(d);35.8ppm(d);71.4ppm(d);88.9ppm(qs,32Hz);122.9ppm(qs,282Hz);174.8ppm(s)。
以类似的方式由IIb制备顺式-3-(2,2-二氯-3,3,3-三氟-1-羟基丙基)-2,2-二甲基-环丙烷羧酸(IIIb,X=Cl)。熔点127-30℃。1H NMR(250MHzm,CDCl3):1.24ppm(s,3H);1.31ppm(s,3H),1.8ppm(m,2H);4.50ppm(d,8.6Hz,1H)。13C-NMR(63MHz,CDCl3):15.4ppm(q);28.1ppm(q);29.0ppm(d);29.2ppm(s);35.7ppm(d);71.0ppm(d);87.5ppm(qs,39Hz);121.9ppm(qs,277Hz);177.4ppm(s)。
实施例2
由Biocartol IIa制备3-(2,2-二氯-3,3,3-三氟-1-羟基丙基)-2,2-二甲基-(1R,3S)-环丙烷羧酸(IIIa,X=Cl)。
将13毫升1M叔丁醇钾(13毫摩尔)于THF中干燥氮气氛下冷却至约-70℃。往其中滴加入5毫摩尔IIa(0.7克),8毫摩尔的1,1-二氯-2,2,2-三氟乙烷(1.22克),1.0克干燥DMF或5毫升干燥THF的混合物,同时予与冷却及搅拌使温度不超过-55℃。90分钟后再加入2毫升叔丁醇钾(2毫摩尔),且立即加入2毫摩尔1,1-二氯-2,2,2-三氟乙烷(10.31克)。以相同间隔时间,再重复上述步骤两次。总共已加入19毫升叔丁醇钾及14毫摩尔的1,1-二氯-2,2,2-三氟乙烷。经6小时反应时间后,于继续冷却至<-55℃下加入4毫升浓HCl,然后使反应混合物静置,使自发性升至室温。将反应混合物如实施例1处理。产量为0.9克的粉末IIIa(61%理论值),以NMR分析纯度为>95%。
以类似方法从IIb制备顺式-3-(2,2-二氯-3,3,3-三氟-1-羟丙烷)-2,2-二甲基-环丙烷羧酸(IIIb,X=Cl)。
实施例3
由IIIa制备(1R,5S)-4-(1,1-二氯-2,2,2-三氟乙基)-6,6-二甲基-3-氧杂双环〔3.1.0〕己-2-酮(IVa,X=Cl)。
将溶于10毫升乙酸酐的IIIa(0.005摩尔;1.52克)于85℃下搅拌2小时15分钟,冷却至室温,用NaHCO3水溶液处理用MTBE萃取两次,用NaSO4脱水且挥发。结果分离出1.35克产物,经二氧化硅(CH2Cl2)色谱纯化,分离出1.23克IVa(GC测定纯度为93.4;83%产率)。自10毫升正己烷中重结晶0.51克的此产物,产生0.31克无色针状物,纯度高于95%(NMR分析),熔点91-93℃。比旋光度:[α]D 25=+5°(1.27克/100毫升,CHCl3)。
1H-NMR(250MHz,CDCl3):1.25ppm(s,3H);1.26ppm(s,
3H);2.13ppm(d,J=5.9Hz,1H);2.38ppm(d,J=5.9Hz,
1H);4.63ppm(s,1H).
13C-NMR(63MHz,CDCl3):15.1ppm(q);23.4ppm(s);25.3
ppm(q);30.0ppm(d);31.6ppm(d);77.6ppm(d);85.1ppm
(qs,34Hz);121.5(qs,284Hz);171.9ppm(s).
重结晶产物IVa的X-光结晶图检测显示如下结晶构造:结晶形式:单斜晶:空间群(space group):P 2/1a=9.3871(17);b==10.6301(51);c=6.2997(12);α=90°;β=110.505(12)°;γ=90°单胞体积=588.79(33)3单胞分子数目,Z=+′2计数密度=1.5627mg/m3F(000)=280.0000Mo K=α放射性=0.71073;μ=5.717cm-1;298K单胞中每个原子的坐标示于下表:
ATOM X Y Z
C11 0.3223(2) 0.7909 0.2218(3)
C12 0.3155(2) 0.7445(4) 0.6668(3)
F1 0.5513(4) 0.6180(7) 0.5499(10)
F2 0.4148(6) 0.5328(7) 0.2415(12)
F3 0.3865(7) 0.4839(9) 0.5457(18)
O1 -0.0170(6) 0.5798(7) -0.2696(7)
O2 0.1060(5) 0.5573(5) 0.0998(6)
C1 -0.0700(6) 0.7212(8) -0.0046(9)
C2 0.0025(7) 0.6177(8) -0.0841(9)
C3 0.1273(6) 0.6236(7) 0.3045(9)
C4 0.0086(6) 0.7265(8) 0.2502(9)
C5 -0.1548(6) 0.6869(7) 0.1514(9)
C6 -0.2043(7) 0.5552(10) 0.1695(10)
C7 -0.2674(8) 0.7845(12) 0.1647(15)
C8 0.2905(6) 0.6752(7) 0.3986(8)
C9 0.4102(8) 0.5711(13) 0.4301(19)
H1 -0.1052(76) 0.8094(88) -0.108(11)
H3 0.1286(54) 0.5547(63) 0.4182(78)
H4 0.0299(61) 0.8053(72) 0.3330(83)
H6a -0.2554 0.5325 0.2692
H6b -0.1131 0.5042 0.2146
H6c -0.2669 0.5305 0.0223
H7a -0.3201 0.7626 0.2682
H7b -0.3404 0.7966 0.0219
H7c -0.2142 0.8607 0.2216以类似方法由IIIb制备4-(1,1-二氯-2,2,2-三氟乙基)-6,6-二甲基-3-氧杂双环〔3.1.0〕己-2-酮(IVb,X=Cl)1H-NMR 250MHz,CDCl3):1.25ppm(s,3H);1.26ppm(s,3H);2.13ppm(dd,J=0.8和5.9Hz,1H);2.38ppm(d,J=5.9Hz,1H);4.63ppm(d,J=0.8Hz,1H).13C-NMR(63MHz,CDCl3):15.1ppm(q);23.4ppm(s);25.3ppm(q);30.1ppm(d);31.7ppm(d);77.6ppm(d);85.1ppm(qs,34Hz);121.5ppm(qs,284Hz);171.9ppm(s).
实施例4
由Biocartol IIb制备顺式-3-(2-溴-2-氯-3,3,3-三氟-1-羟基丙基)-2,2-二甲基-环丙烷羧酸
如实施例2,但以1-溴-1-氯-2,2,2-三氟乙烷取代1,1-二氯-2,2,2-三氟乙烷。由甲苯中重结晶产生白色粉末(IIIb),熔点170-2℃,纯度>95%(NMR,所有异构体的总和)。
1H-NMR(250MHz,DMSO-d6):1.14ppm(s,3H);1.24ppm(s
3H);1.53ppm(dd,9.1Hz and 9,6Hz,1H);1.65ppm(d,9.1
Hz,1H);4.17ppm(d,9.6Hz,1H);6.2ppm(宽s,1H);
11.9ppm(宽s,1H).
13C-NMR(63MHz,DMSO-d6):15.7(q);27.2ppm(s);27.8ppm
(q);28.3ppm(d);35.8ppm(d);69.8ppm(d);79.5ppm
(qs,30Hz);122.3(qs,282Hz);172.0ppm(s).
光谱数据由主要异构体得到。
实施例5
从IIb制备Z-顺-3-(2-氯-3,3,3-三氟-1-丙基)-2,2-二甲基-环丙烷羧酸(Ib)
将Zn粉末(0.03mol;1.96g)悬浮于IIb(0.005mol;0.71g)和1,1,1-三氯三氟乙烷(0.015mol;2.81g)于10ml无水DMF中,于65℃下回流搅拌约4小时,直至GC分析显示所有IIb已转变成IIIb及IVb的及微量Ib的混合物。加入醋酸酐(0.01mol;1.02g),且于60℃下持续搅拌约5小时,长时间保持未反应Zn粉存在于反应混合物中。加入HCl水溶液,用MTBE萃取反应混合物,分离产物,将MTBE相以Na2SO4脱水且挥发。Ib产率为0.57g(>95%纯度,47%理论值),由正庚烷重结晶得到产物,熔点106-8℃(文献7报道Ib为108-10℃)。
实施例6
由IVa制备Z-3-(2-氯-3,3,3-三氟-1-丙烯基)-2,2-二甲基(1R,3R)-环丙烷羧酸(Ia)
锌粉(0.004摩尔;0.26克)悬浮在IVa(0.026摩尔;0.72克)于3毫升DMF的溶液中,于60℃下搅拌7小时,且于冷却至室温后洳入10毫升水及5毫升浓HCl。混合物以MTBE萃取三次,以Na2SO4脱水且蒸发。产生0.62克结晶,依GC分析为几乎100%纯度。产率约100%。以10毫升正庚烷重结晶产生0.21克白色结晶,熔点105-8℃。比旋光度:[α]D 25=+47℃(1.14克/100毫升,CHCl3)。1H NMR(250MHz,CDCl3):1.32ppm(s,2×3H);1.99ppm(d,J=8.3Hz,1H);2.23ppm(dd,J=9.3和8.3Hz,1H);6.87ppm(d,J=9.3Hz,1H);10.8ppm(宽,1H)于6.58ppm(d,J=9.6Hz),的信号可能是相当于约5%E-异构体,当物质重结晶时完全消失。
13C-NMR(63MHz,CDCl3):14.9ppm(q);28.6ppm(q);29.5
ppm(s);31.6ppm(d);32.7ppm(d);120.5ppm(qs,38Hz);
122.1ppm(qs,271Hz);129.7ppm(qd,5Hz);176.6ppm
(s).
将微量Ia与过量亚硫酰氯及进一步与过量甲醇反应会产生Ia的甲基酯。将此酯置于手性GC柱分析显示其旋光纯度为>95%对映体过量值(enantiomeric excess)。
实施例7
由IVa制备Z-3-(2-氯-3,3,3-三氟-1-丙烯基)-2,2-二甲基-(1R,3R)-环丙烷羧酸(Ia)
使用具有铅阴极及石墨阳极的电子微流室(Electro Micro FlowCell)(来自Electrocell AB公司,Sweden),电极面积为10平方厘米。离子筛选膜制自SelemionCMV,而阳离子筛选膜来自日本AsahiGlass公司。将10毫升浓硫酸小心地溶于300毫升甲醇中,将150毫升倒入该电子微流室以作为阴极电解液且另150毫升倒入以作为阳极电解液。启动循环泵,且当温度保持在50℃时,加入IVa(0.0072摩尔;2.00克)于10毫升甲醇中的溶液至阴极电解液中。
将电极导线固定,开始供应电流且将稳定电压调整至4.0伏特。当时间为0时电流为0.30安培。每隔30分钟取样一次且至270分钟后才停止。将电流切断且移出导线。在实验结束时电流为0.2安培。
取出阴极电解液,加入水后在旋转蒸发器上于50℃及100mmHg下处理,以蒸出甲醇。而后将水相以甲基叔丁基醚萃取且干燥及蒸发。获得1.68克的油状物,然后与10毫升的2N NaOH(水溶液)混合且搅拌放置2小时。将水相用浓HCl(水溶液)酸化且以甲基叔丁基醚萃取,而后干燥及蒸发。可获得1.33克结晶,根据GC分析其为>95%纯度。产量约75%。
实施例8
自IIa制备Z-3-(2-氯-3,3,3-三氟-1-丙烯基)-2,2-二甲基-(1R,3R)环丙烷羧酸(Ia)
Zn粉末(0.045摩尔;2.94克)悬浮于IIa(0.015摩尔;2.13克)及1,1,1-三氯-三氟乙烷(0.038摩尔;7.12克)于25毫升无水DMF溶液中,于50毫升内衬特氟隆的压热器内于50℃下搅拌约2小时,开启压热器,GC分析显示所有IIa已被转变为IIIa及IVa的混合物,并含有微量Ia。加入醋酸酐(0.018摩尔,1.84克),关闭压热器,于50℃下加热15分钟且再开启。GC分析显示所有IIIa已转变成IVa。加入锌粉(0.018摩尔,1.18克),再次关闭压热器且于70℃下搅拌放置约2小时。将压热器打开,加入HCl水溶液至反应混合物中,以MTBE萃取反应混合物以分离产物。MTBE相以Na2SO4干燥且挥发。产率为Ia:2.48克(>95%纯度,68%理论值)。由正庚烷重结晶产生熔点为106-7℃的产物。
参考资料1 英国专利第2 000 764号(1977年3月23日),ICI2 丹麦专利申请案第2849/78(1978年6月26日),Roussel-Uclat,S.A.3 M.Fujita,K.Kondo和T.Hiyama,四面体通讯(TetrahedronLetters),27,2139-2142(1986)日本化学会公报(Bull.Chem.Soc.Jpn.)60,4385-4394(1987)4 Arun K.Mandal等人,四面体,42,5715(1986)5 D.Bakshi,V.K.Mahindroo,R.Soman,S.Dev,四面体(Tetrahedron)45,767-774(1989)6 丹麦专利申请案DK 5633/78(1978年12月14日),ShellInternationale Research Maatschappij B.V.7 U.S.P 4333950(1982年6月8日),FMC Corporation。
Claims (6)
1.一种制备通式I化合物的方法其中R′代表H,且处于环丙烷环上的两个氢原子彼此为顺式,该方法包括通式II的化合物与化合物CF3-CClX2于一惰性介质中,于Zn存在下,且于0至150℃间进行反应,其中X代表卤原子,在该反应期间,产生未经分离的作为中间体的化合物III及IV经一段时间后,分析显示起始化合物II基本上已被消耗,上述中间体III及IV已形成,且已产生微量的最终产物I,加入-脱水剂,可立即将中间体III转变成中间体IV,且经更长一段时间,则将中间体IV实质上完全转变成最终产物I,其中多于90%的产物为Z-异构体,是旋光纯及外消旋形式,特别注意未反应的金属锌应继续存在。
2.按照权利要求1的方法,其中惰性介质为DMF。
3.按照权利要求1或2的方法,其中脱水剂为醋酸酐。
4.按照权利要求1或2的方法,其中部分或全部金属试剂用电化学生成的金属物质所代替。
5.按照权利要求3的方法,其中部分或全部金属试剂用电化学生成的金属物质所代替。
6.化合物(1R,5S)-4-(1,1-二氯-2,2,2-三氟乙基)-6,6-二甲基-3-氧杂双环〔3.1.0〕己-2-酮。
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DK174698B1 (da) * | 1998-02-18 | 2003-09-22 | Cheminova Agro As | Fremgangsmåde til fremstilling af cyclopropancarboxylsyrer |
GB9808619D0 (en) * | 1998-04-22 | 1998-06-24 | Zeneca Ltd | Chemical process |
CN100500307C (zh) * | 2007-04-02 | 2009-06-17 | 浙江工业大学 | 一种基于连续输送的条烟异步分拣法 |
AR097362A1 (es) | 2013-08-16 | 2016-03-09 | Cheminova As | Combinación de 2-metilbifenil-3-ilmetil (z)-(1r)-cis-3-(2-cloro-3,3,3-trifluorprop-1-enil)-2, 2-dimetilciclopropanocarboxilato con por lo menos un insecticida, acaricida, nematicida y/o fungicida |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4281182A (en) * | 1977-06-27 | 1981-07-28 | Roussel Uclaf | Novel lactones of cis 2,2-dimethyl-cyclopropane-1-carboxylic acid and their use |
Family Cites Families (4)
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GB2000764B (en) * | 1977-03-23 | 1982-04-28 | Ici Ltd | Halogenated esters |
CA1146581A (en) * | 1977-12-16 | 1983-05-17 | Pieter A. Verbrugge | Intermediates in the preparation of cyclopropylcarboxylate esters and process for their manufacture |
US4333950A (en) * | 1979-05-24 | 1982-06-08 | Fmc Corporation | (+)-4-Substituted-2-indanol insecticidal ester derivatives |
FR2607133B1 (fr) * | 1986-11-20 | 1989-05-05 | Roussel Uclaf | Nouveaux derives de l'acide 2,2-dimethyl cyclopropane carboxylique portant en 3 une chaine halogenee saturee, leur procede de preparation et leur application comme pesticides |
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Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US4281182A (en) * | 1977-06-27 | 1981-07-28 | Roussel Uclaf | Novel lactones of cis 2,2-dimethyl-cyclopropane-1-carboxylic acid and their use |
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