(alphaS)-4-氟-alpha-羟基-3-苯氧基-苯乙腈 | 81496-30-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: (alphaS)-4-氟-alpha-羟基-3-苯氧基-苯乙腈
• 英文名称: (S)-alpha-cyano-4-fluoro-3-phenoxybenzyl alcohol
• 英文别名: (S) cyano-(4-fluoro-3-phenoxy-phenyl)-methanol；(S) α-cyano 4-fluoro 3-phenoxybenzyl alcohol；(S)-4-fluoro-3-phenoxybenzaldehyde cyanohydrin；(S)-4-Fluoro-3-phenoxybenzaldehyde-cyanhydrine；(2S)-2-(4-fluoro-3-phenoxyphenyl)-2-hydroxyacetonitrile
• CAS: 81496-30-2
• 化学式: C₁₄H₁₀FNO₂
• 分子量: 243.237
• InChiKey: FYIOXXUKFQPTJS-CYBMUJFWSA-N

物化性质

• 沸点：
  376.7±42.0 °C(Predicted)
• 密度：
  1.289±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  53.2
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-trimethylsilylethyl (1R,3R)-3-[(Z)-2-(4-chlorophenyl)-3,3,3-trifluoroprop-1-enyl]-2,2-dimethylcyclopropane-1-carboxylate 、 (alphaS)-4-氟-alpha-羟基-3-苯氧基-苯乙腈 生成 [(S)-cyano-(4-fluoro-3-phenoxyphenyl)methyl] (1R,3R)-3-[(Z)-2-(4-chlorophenyl)-3,3,3-trifluoroprop-1-enyl]-2,2-dimethylcyclopropane-1-carboxylate
  参考文献：
  名称：

  摘要：

  DOI：
• 作为产物：
  描述：

  (S)-(+)-1-氰基-1-(4-氟-3-苯氧基苯基)乙酸甲酯 在 乙醇 作用下， 以 异丙醚 为溶剂， 反应 6.0h， 生成 (alphaS)-4-氟-alpha-羟基-3-苯氧基-苯乙腈
  参考文献：
  名称：

  One-pot synthesis of optically active cyanohydrin acetates from aldehydes via lipase-catalyzed kinetic resolution coupled with in situ formation and racemization of cyanohydrins

  摘要：

  A novel one-pot synthesis of optically active cyanohydrin acetates from aldehydes has been accomplished by lipase-catalyzed kinetic resolution coupled with in situ formation and racemization of cyanohydrins in an organic solvent. Racemic cyanohydrins 2, generated from aldehydes 1 and acetone cyanohydrin in diisopropyl ether under the catalysis of basic anion-exchange resin (OH- form), were acetylated stereoselectively by a lipase from Pseudomonas cepacia (Amano) with isopropenyl acetate as an acylating reagent. The (S)-isomer of 2 was preferentially acetylated by the lipase, while the unreacted (R)-isomer was continuously racemized through reversible transhydrocyanation catalyzed by the resin. These processes thus enabled one-stage conversion of various aldehydes 1a-n into the corresponding (S)-cyanohydrin acetates 3a-n with up to 94% ee in 63-100% conversion yields. The racemization of the optically active cyanohydrin 2e by Amberlite IRA-904 (OH- form) was found to be much faster than the enzymatic acetylation, confirming the effective second-order asymmetric transformation. Enzymatic deacetylation of (S)-cyanohydrin acetates in an organic solvent and the synthesis of optically active pyrethroids are also described.

  DOI：

  10.1021/jo00047a016

文献信息

• Certain cyclopropyl dicarboxylates having pesticidal and insecticidal
  申请人：Roussel Uclaf

  公开号：US04732903A1

  公开（公告）日：1988-03-22

  Novel isomers and mixtures thereof of cyclopropane carboxylic acid derivatives with a 3-unsaturated side chain of the formula ##STR1## wherein A' is selected from the group consisting of wherein B is selected from the group consisting of --CH.sub.2 --, ##STR2## --O-- and --S--, R.sub.4 is selected from the group consisting of hydrogen, --CH.sub.3,--C.tbd.N--CONH.sub.2, --CSNH.sub.2 and --C.tbd.CH, n is an integer from 0, 1 or 2 and R.sub.5 is selected from the group consisting of halogen and --CH.sub.3 ##STR3## wherein R.sub.13 is selected from the group consisting of hydrogen and ##STR4## wherein R.sub.13 has the above definition and the benzoyl is in the 3- or 4-position, ##STR5## wherein R.sub.14 is selected from the group consisting of hydrogen, methyl, ethynyl and --CN and R.sub.15 and R.sub.16 are individually selected from the group consisting of hydrogen, bromine and fluorine and ##STR6## wherein R.sub.14 has the above definition, p is 0, 1 or 2, each R.sub.17 is selected from the group consisting of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms, --CF.sub.3, 3,4-methylenedioxy, chlorine, bromine and fluorine B' is selected from the group consisting of --O-- and --S-- and R is selected from the group consisting of alkyl of 1 to 18 carbon atoms substituted with one or more, optionally different functional groups, aryl of 6 to 14 carbon atoms optionally substituted with one or more optionally different functional groups, the double bond having Z or E geometry having insecticidal and nematocidal activity as well as plant and animal acaricidal activity and their preparation.

  环丙烷羧酸衍生物的新异构体和混合物，其具有式（I）的3-不饱和侧链，其中A'选择自下列组中的一种：其中B选择自下列组中的一种：--CH.sub.2 --，##STR2## --O--和--S--，R.sub.4选择自下列组中的一种：氢，--CH.sub.3，--C.tbd.N--CONH.sub.2，--CSNH.sub.2和--C.tbd.CH，n为0、1或2的整数，R.sub.5选择自下列组中的一种：卤素和--CH.sub.3 ##STR3##其中R.sub.13选择自下列组中的一种：氢和##STR4##其中R.sub.13具有上述定义，苯甲酰在3-或4-位，##STR5##其中R.sub.14选择自下列组中的一种：氢，甲基，乙炔基和--CN，R.sub.15和R.sub.16分别选择自下列组中的一种：氢、溴和氟，以及##STR6##其中R.sub.14具有上述定义，p为0、1或2，每个R.sub.17选择自下列组中的一种：1至4个碳原子的烷基，1至4个碳原子的烷氧基，1至4个碳原子的烷硫基，1至4个碳原子的烷基磺酰基，--CF.sub.3，3,4-亚甲二氧基，氯，溴和氟，B'选择自下列组中的一种：--O--和--S--，R选择自下列组中的一种：带有一个或多个、可选择不同的官能团的1至18个碳原子的烷基，6至14个碳原子的芳基，可选择不同的官能团进行取代，双键具有Z或E几何构型，具有杀虫、杀线虫活性以及植物和动物螨虫活性，以及它们的制备。
• Insecticidal esters
  申请人：Roussel Uclaf

  公开号：US04489093A1

  公开（公告）日：1984-12-18

  Novel esters in all possible isomeric forms of the formula ##STR1## wherein R is selected from the group consisting of (a) optionally unsaturated alkyl of 1 to 8 carbon atoms and optionally unsaturated cycloalkyl or cycloalkyl-alkyl of 3 to 8 carbon atoms optionally substituted with at least one member of the group consisting of halogen, ##STR2## aryl optionally substituted with at least one member of the group consisting of --OH, alkoxy of 1 to 8 carbon atoms, alkyl of 1 to 8 carbon atoms, halogen, ##STR3## R' is alkyl of 1 to 8 carbon atoms, R" and R"' are individually selected from the group consisting of hydrogen and alkyl of 1 to 8 carbon atoms, AlK.sub.1, AlK.sub.2 and AlK.sub.3 are individually alkyl of 1 to 18 carbon atoms (b) aryl of 6 to 14 carbon atoms optionally substituted with at least one substituent selected from the group consisting of --OH, alkoxy of 1 to 8 carbon atoms, alkyl of 1 to 8 carbon atoms, halogen, --OCF.sub.3, --CF.sub.3 and --SCF.sub.3 and (c) heterocycle optionally substituted with at least one member of the group consisting of --OH, alkoxy of 1 to 8 carbon atoms, alkyl of 1 to 8 carbon atoms, halogen, --CF.sub.3, --OCF.sub.3 and --SCF.sub.3, B is selected from the group consisting of optionally unsaturated alkyl of 1 to 18 carbon atoms, optionally unsaturated cycloalkyl of 3 to 18 carbon atoms and the remainder of an alcohol used in synthesis of pyrethrinoid esters, X is halogen and the ethylenic double bond may have Z or E geometry having parasitic activity, especially insecticidal acaricidal and nematocidal activity.

  公式为##STR1##的所有可能异构体的新酯，其中R选择自以下组：(a) 1到8个碳原子的可选不饱和烷基和可选不饱和3到8个碳原子的环烷基或环烷基烷基，可选用以下组的至少一种成员取代：卤素，##STR2##芳基，可选用以下组的至少一种成员取代：--OH、1到8个碳原子的烷氧基、1到8个碳原子的烷基、卤素、##STR3## R'是1到8个碳原子的烷基，R"和R"'分别选择自氢和1到8个碳原子的烷基组，AlK.sub.1、AlK.sub.2和AlK.sub.3分别为1到18个碳原子的烷基；(b) 6到14个碳原子的芳基，可选用以下组的至少一种取代基：--OH、1到8个碳原子的烷氧基、1到8个碳原子的烷基、卤素、--OCF.sub.3、--CF.sub.3和--SCF.sub.3；(c) 可选用以下组的至少一种成员取代的杂环：--OH、1到8个碳原子的烷氧基、1到8个碳原子的烷基、卤素、--CF.sub.3、--OCF.sub.3和--SCF.sub.3，B选择自以下组：1到18个碳原子的可选不饱和烷基、3到18个碳原子的可选不饱和环烷基和用于拟除虫菊酯酯合成的醇的剩余部分，X为卤素，乙烯双键可能具有Z或E几何形状，具有寄生活性，特别是杀虫剂、杀螨剂和杀线虫剂活性。
• Cyclopropane carboxylic esters and acids
  申请人：Roussel Uclaf

  公开号：US04808749A1

  公开（公告）日：1989-02-28

  Novel esters in all possible isomeric forms of the formula ##STR1## wherein R is selected from the group consisting of (a) optionally unsaturated alkyl of 1 to 8 carbon atoms and optionally unsaturated cycloalkyl or cycloalkyl-alkyl of 3 to 8 carbon atoms optionally substituted with at least one member of the group consisting of halogen, --OH, --SH, --OR', --SR', --NO.sub.2, ##STR2## --CN, --SO.sub.3 H, --PO.sub.4 H.sub.2, ##STR3## --SO.sub.2 AlK.sub.2, --SO.sub.3 AlK.sub.3, aryl optionally substituted with at least one member of the group consisting of --OH, alkoxy of 1 to 8 carbon atoms, alkyl of 1 to 8 carbon atoms, halogen, --CF.sub.3, --OCF.sub.3, --SCF.sub.3 and ##STR4## R' is alkyl of 1 to 8 carbon atoms, R" and R"' are individually selected from the group consisting of hydrogen and alkyl of 1 to 8 carbon atoms, AlK.sub.1, AlK.sub.2 and AlK.sub.3 are individually alkyl of 1 to 18 carbon atoms, (b) aryl of 6 to 14 carbon atoms optionally substituted with at least one substitutent selected from the group consisting of --OH, alkoxy of 1 to 8 carbon atoms, alkyl of 1 to 8 carbon atoms, halogen, --OCF.sub.3, --CF.sub.3 and --SCF.sub.3 and (c) heterocycle optionally substituted with at least one member of the group consisting of --OH, alkoxy of 1 to 8 carbon atoms, alkyl of 1 to 8 carbon atoms, halogen, --CF.sub.3, --OCF.sub.3 and --SCF.sub.3, B is selected from the group consisting of optionally unsaturated alkyl of 1 to 18 carbon atoms, optionally unsaturated cycloalkyl of 3 to 18 carbon atoms and the remainder of an alcohol used in synthesis of pyrethrinoid esters, X is halogen and the ethylenic double bond may have Z or E geometry having parasitic activity, especially insecticidal acaricidal and nematocidal activity.

  公式为##STR1##，其中R选自以下组合：(a) 选择1至8个碳原子的可选不饱和烷基和可选不饱和3至8个碳原子的环烷基或环烷基烷基，可选地被至少一种来自以下组合的成员置换：卤素，-OH，-SH，-OR'，-SR'，-NO.sub.2，##STR2##-CN，-SO.sub.3 H，-PO.sub.4 H.sub.2，##STR3##-SO.sub.2 AlK.sub.2，-SO.sub.3 AlK.sub.3，苯基，可选地被至少一种来自以下组合的成员置换：-OH，1至8个碳原子的烷氧基，1至8个碳原子的烷基，卤素，-CF.sub.3，-OCF.sub.3，-SCF.sub.3和##STR4##，R'是1至8个碳原子的烷基，R"和R"'分别选自氢和1至8个碳原子的烷基，AlK.sub.1，AlK.sub.2和AlK.sub.3分别为1至18个碳原子的烷基，(b) 选择6至14个碳原子的苯基，可选地被至少一种来自以下组合的取代基置换：-OH，1至8个碳原子的烷氧基，1至8个碳原子的烷基，卤素，-OCF.sub.3，-CF.sub.3和-SCF.sub.3，(c) 可选地被至少一种来自以下组合的取代基置换的杂环，-OH，1至8个碳原子的烷氧基，1至8个碳原子的烷基，卤素，-CF.sub.3，-OCF.sub.3和-SCF.sub.3，B选自以下组合：选择1至18个碳原子的可选不饱和烷基，可选不饱和3至18个碳原子的环烷基和用于拟除虫菊酯酯合成的酒精的剩余部分，X为卤素，乙烯双键可能具有寄生活性，特别是具有杀虫，杀螨和杀线虫的活性。
• Insecticidal cyclopropane carboxylic acid derivatives with
  申请人：Roussel Uclaf

  公开号：US04542142A1

  公开（公告）日：1985-09-17

  Novel isomers and mixtures thereof of cyclopropane carboxylic acid derivatives with a 3-unsaturated side chain of the formula ##STR1## The double bond having Z or E geometry and having insecticidal and nematocidal activity as well as plant and animal acaricidal activity.

  环丙烷羧酸衍生物的新异构体和混合物，其侧链为式子##STR1##的3-不饱和链，双键具有Z或E几何结构，具有杀虫和杀线虫活性，以及植物和动物的螨虫活性。
• Certain cyclopropanedicarboxylates with an unsaturated side chain having
  申请人：Roussel Uclaf

  公开号：US04883806A1

  公开（公告）日：1989-11-28

  Novel isomers and mixtures thereof of cyclopropane carboxylic acid derivatives with a 3-unsaturated side chain of the formula ##STR1## wherein A' is selected from the group consisting of (1) alkyl of 1 to 18 carbon atoms, (2) benzyl optionally substituted with at least one member of the group consisting of alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkenyloxy of 2 to 6 carbon atoms, alkadienyl of 4 to 8 carbon atoms, methylenedioxy or halogen, ##STR2## wherein R.sub.1 is selected from the group consisting of hydrogen and methyl and R.sub.2 is selected from the group consisting of --CH.sub.2 --C.tbd.CH and monocyclic aryl, ##STR3## wherein a is selected from the group consisting of hydrogen and methyl and R.sub.3 is an aliphatic group of 2 to 6 carbon atoms containing at least one carbon-carbon unsaturation ##STR4## wherein a and and R.sub.3 have the above definition and R.sub.1 ' and R.sub.2 ' are individually selected from the group consisting of hydrogen, halogen, alkyl of 1 to 6 carbon atoms, aryl of 6 to 10 carbon atoms, cyano and alkoxy carbonyl of 2 to 5 carbon atoms, (6) ##STR5## wherein B is selected from the group consisting of ##STR6## --O-- and --S--, R.sub.4 is selected from the group consisting of hydrogen, --CH.sub.3, --C.tbd.N--CONH.sub.2, --CSNH.sub.2 and --C.tbd.CH, n is an integer form 0, 1 or 2 and R.sub.5 is selected from the group consisting of halogen and --CH.sub.3 ##STR7## wherein R.sub.6, R.sub.7 , R.sub.8 and R.sub.9 are selected from the group consisting of hydrogen, chlorine and methyl and S/I symbolizes an aromatic ring or dihydro or tetrahydro ring, ##STR8## wherein R.sub.10 is selected from the group consisting of hydrogen and --CN, R.sub.12 is selected from the group consisting of --CH.sub.2 -- and --O-- and R.sub.11 is selected from the group consisting of thiazolyl and thiadiazolyl with the bond the bond to ##STR9## being in anyone of the positions, R.sub.12 being bonded to R.sub.11 by the carbon atom included between a sulfur atom and a nitrogen atom, ##STR10## wherein R.sub.13 is selected from the group consisting of hydrogen and --CN ##STR11## wherein R.sub.13 has the above definition and the benzoyl is in the 3- or 4-position; ##STR12## wherein R.sub.14 is; selected from the group consisting of hydrogen, methyl, ethynyl and --CN and R.sub.15 and R.sub.16 are individually selected from the group consisting of hydrogen, bromine and fluorine and ##STR13## wherein R.sub.14 has the above definition, p is 0, 1 or 2, each R.sub.17 is selected from the group consisting of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms, --CF.sub.3 3,4-methylenedioxy, chlorine, bromine and fluorine, B is selected from the group consisting of --O-- and --S-- and R is selected from the group consisting of alkyl of 1 to 18 carbon atoms substituted with one or more, optionally different functional groups, aryl of 6 to 14 carbon atoms optionally substituted with one or more optionally different functional groups, the double bond having Z or E geometry having insecticidal and nematocidal activity as well as plant and animal acaricidal activity and their preparation.

  环丙烷羧酸衍生物的新异构体和混合物，其具有式子##STR1##中的3-不饱和侧链，其中A'从以下组中选择：(1)1到18个碳原子的烷基，(2)苄基，可选择性地被1到4个碳原子的烷基，2到6个碳原子的烯基，2到6个碳原子的烯氧基，4到8个碳原子的烯二烯基，亚甲二氧基或卤素取代，##STR2##其中R.sub.1从氢和甲基的组中选择，R.sub.2从--CH.sub.2--C.tbd.CH和单环芳基的组中选择，##STR3##其中a从氢和甲基的组中选择，R.sub.3是一个含有至少一个碳-碳不饱和度的2到6个碳原子的脂肪基，##STR4##其中a和R.sub.3具有上述定义，R.sub.1'和R.sub.2'分别从氢，卤素，1到6个碳原子的烷基，6到10个碳原子的芳基，氰基和2到5个碳原子的烷氧基卡宾酰的组中选择，(6)##STR5##其中B从以下组中选择：##STR6##--O--和--S--，R.sub.4从氢，--CH.sub.3，--C.tbd.N--CONH.sub.2，--CSNH.sub.2和--C.tbd.CH的组中选择，n是0、1或2的整数，R.sub.5从卤素和--CH.sub.3的组中选择，##STR7##其中R.sub.6，R.sub.7，R.sub.8和R.sub.9从氢，氯和甲基的组中选择，S/I表示芳环或二氢或四氢环，##STR8##其中R.sub.10从氢和--CN的组中选择，R.sub.12从--CH.sub.2--和--O--的组中选择，R.sub.11从噻唑基和噻二唑基的组中选择，键与##STR9##中的任何一个位置相连，R.sub.12通过硫原子和氮原子之间包括的碳原子与R.sub.11相连，##STR10##其中R.sub.13从氢和--CN的组中选择，##STR11##其中R.sub.13具有上述定义，并且苯甲酰在3-或4-位置上；##STR12##其中R.sub.14从氢，甲基，乙炔基和--CN的组中选择，R.sub.15和R.sub.16分别从氢，溴和氟的组中选择，##STR13##其中R.sub.14具有上述定义，p为0、1或2，每个R.sub.17从1到4个碳原子的烷基，1到4个碳原子的烷氧基，1到4个碳原子的烷硫基，1到4个碳原子的烷基磺酰基，--CF.sub.3，3,4-亚甲二氧基，氯，溴和氟的组中选择，B从--O--和--S--的组中选择，R从1到18个碳原子的烷基中选择，被一个或多个，可选不同的官能团置换，6到14个碳原子的芳基，可选不同的官能团置换，双键具有映构体Z或E几何构型，具有杀虫和杀线虫活性以及植物和动物螨虫活性，以及它们的制备。