(1R,4R)-(3,4,5,5-tetramethyl-2-cyclopentenyl)methyl isobutyrate | 1224178-84-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1R,4R)-(3,4,5,5-tetramethyl-2-cyclopentenyl)methyl isobutyrate
• 英文别名: isobutyric acid 3,4,5,5-tetramethylcyclopent-2-enylmethyl ester；α-necrodyl isobutyrate；trans-(3,4,5,5-Tetramethyl-2-cyclopentenyl)methyl isobutyrate；[(1R,4R)-3,4,5,5-tetramethylcyclopent-2-en-1-yl]methyl 2-methylpropanoate
• CAS: 1224178-84-0
• 化学式: C₁₄H₂₄O₂
• 分子量: 224.343
• InChiKey: GBPIVQULIDDYBQ-NEPJUHHUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,4R)-(3,4,5,5-tetramethyl-2-cyclopentenyl)methyl isobutyrate 在 对甲苯磺酸 作用下， 以 甲苯 为溶剂， 反应 5.0h， 以75%的产率得到(R)-(2,2,3,4-tetramethyl-3-cyclopentenyl)methyl isobutyrate
  参考文献：
  名称：

  KINETIC RESOLUTION REACTION OF A (1RS,2SR)-(2-HYDROXY-3,5,5-TRIMETHYL-3-CYCLOPENTENYL)METHYL CARBOXYLATE COMPOUND, A PROCESS FOR PREPARING OPTICALLY ACTIVE TRANS-alpha-NECRODYL ISOBUTYRATE, AND A PROCESS FOR PREPARING OPTICALLY ACTIVE gamma-NECRODYL ISOBUTYRATE

  摘要：

  本发明涉及一种制备以下通式（S，R）-（2）的（1S，2R）-（2-羟基-3,5,5-三甲基-3-环戊烯基）甲酸酯化合物的方法，其中R1表示具有1至6个碳原子的一价烃基，粗体楔头线代表绝对构型，以及以下通式（R，S）-（3）的（1R，2S）-（2-乙酰氧基-3,5,5-三甲基-3-环戊烯基）甲酸酯化合物，其中R1如上定义，哈希楔头线代表绝对构型，Ac代表乙酰基，该方法包括：将以下通式（RS，SR）-（2）的（1RS，2SR）-（2-羟基-3,5,5-三甲基-3-环戊烯基）甲酸酯化合物，其中R1如上定义，哈希未楔头线代表相对构型，与脂肪酶在乙酸乙烯酯存在下进行动力学分辨反应，以获取（1S，2R）-（2-羟基-3,5,5-三甲基-3-环戊烯基）甲酸酯化合物（（S，R）-（2））和（1R，2S）-（2-乙酰氧基-3,5,5-三甲基-3-环戊烯基）甲酸酯化合物（（R，S）-（3））。

  公开号：

  US20220234983A1
• 作为产物：
  描述：

  ethyl (1R,3S,4S)-4-hydroxy-2,2,3-trimethylcyclopentane carboxylate 在 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 草酰氯 、 四氯化钛 、 lithium 、 二甲基亚砜 、 乙二胺 、 三乙胺 、 锌 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 3.15h， 生成 (1R,4R)-(3,4,5,5-tetramethyl-2-cyclopentenyl)methyl isobutyrate
  参考文献：
  名称：

  Synthesis and Bioassay of Racemic and Chiral trans-α-Necrodyl Isobutyrate, the Sex Pheromone of the Grape Mealybug Pseudococcus maritimus

  摘要：

  A concise synthesis of the racemic form of the female-produced pheromone of the grape mealybug was developed. The synthesis was readily adapted to production of both enantiomers of the pheromone via lipase-catalyzed kinetic resolution of an intermediate in the synthesis. Replicated field trials revealed that, contrary to a preliminary report, the (R,R)- rather than the (S,S)-enantiomer is the attractive stereoisomer. Lithium aluminum hydride reduction of the insect-produced compound to a-necrodol followed by analysis on a chiral stationary phase GC column showed that the insect-produced material was actually an 85:15 mixture of the (R,R)- and (S,S)-enantiomers. The racemic form of the pheromone was highly attractive to male mealybugs, and in one of two field bioassays, the racemic material was significantly more attractive than the pure (R,R)-enantiomer, suggesting that the (S,S)-enantiomer might act synergistically.

  DOI：

  10.1021/jf904452v

文献信息

• KINETIC RESOLUTION REACTION OF A (1RS,2SR)-(2-HYDROXY-3,5,5-TRIMETHYL-3-CYCLOPENTENYL)METHYL CARBOXYLATE COMPOUND, A PROCESS FOR PREPARING OPTICALLY ACTIVE TRANS-alpha-NECRODYL ISOBUTYRATE, AND A PROCESS FOR PREPARING OPTICALLY ACTIVE gamma-NECRODYL ISOBUTYRATE
  申请人：Shin-Etsu Chemical Co., Ltd.

  公开号：US20220234983A1

  公开（公告）日：2022-07-28

  The present invention relates to a process for preparing a (1S,2R)-(2-hydroxy-3,5,5-trimethyl-3-cyclopentenyl)methyl carboxylate compound of the following general formula (S,R)-(2), wherein R 1 represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a bold wedged bond represents the absolute configuration, and a (1R,2S)-(2-acetoxy-3,5,5-trimethyl-3-cyclopentenyl)methyl carboxylate compound of the following general formula (R,S)-(3), wherein R 1 is as defined above, a hashed wedged bond represents the absolute configuration, and Ac represents an acetyl group, the process comprising: subjecting a (1RS,2SR)-(2-hydroxy-3,5,5-trimethyl-3-cyclopentenyl)methyl carboxylate compound of the following general formula (RS,SR)-(2), wherein R 1 is as defined above, and a hashed unwedged bond represents a relative configuration, to a kinetic resolution reaction with a lipase in the presence of vinyl acetate to obtain the (1S,2R)-(2-hydroxy-3,5,5-trimethyl-3-cyclopentenyl)methyl carboxylate compound ((S,R)-(2)) and the (1R,2S)-(2-acetoxy-3,5,5-trimethyl-3-cyclopentenyl)methyl carboxylate compound ((R,S)-(3)).

  本发明涉及一种制备以下通式（S，R）-（2）的（1S，2R）-（2-羟基-3,5,5-三甲基-3-环戊烯基）甲酸酯化合物的方法，其中R1表示具有1至6个碳原子的一价烃基，粗体楔头线代表绝对构型，以及以下通式（R，S）-（3）的（1R，2S）-（2-乙酰氧基-3,5,5-三甲基-3-环戊烯基）甲酸酯化合物，其中R1如上定义，哈希楔头线代表绝对构型，Ac代表乙酰基，该方法包括：将以下通式（RS，SR）-（2）的（1RS，2SR）-（2-羟基-3,5,5-三甲基-3-环戊烯基）甲酸酯化合物，其中R1如上定义，哈希未楔头线代表相对构型，与脂肪酶在乙酸乙烯酯存在下进行动力学分辨反应，以获取（1S，2R）-（2-羟基-3,5,5-三甲基-3-环戊烯基）甲酸酯化合物（（S，R）-（2））和（1R，2S）-（2-乙酰氧基-3,5,5-三甲基-3-环戊烯基）甲酸酯化合物（（R，S）-（3））。
• METHOD FOR EFFECTIVELY CONTROLLING COCCOIDEA INSECT PESTS
  申请人：Ecologia Y Proteccion Agricola, S.L.

  公开号：EP3732964A1

  公开（公告）日：2020-11-04

  The present invention relates to a method for determining the effective flow rate of at least one semiochemical for controlling at least one coccoid insect pest using an artificial semiochemical matrix, and use of the effective flow rate for effectively controlling at least one coccoid insect pest through the diffusion of at least one semiochemical.

  本发明涉及一种利用人工半化学物质基质确定至少一种半化学物质的有效流速以控制至少一种茧翅目害虫的方法，以及利用该有效流速通过至少一种半化学物质的扩散有效控制至少一种茧翅目害虫的方法。
• Processes for preparing alpha-necrodyl compounds and processes for preparing gamma-necrodyl compounds
  申请人：Shin-Etsu Chemical Co., Ltd.

  公开号：US11370741B2

  公开（公告）日：2022-06-28

  The present invention provides processes for preparing an α-necrodyl compound of the following general formula (3): wherein R2 represents a monovalent hydrocarbon group having 1 to 9 carbon atoms, the process comprising: subjecting a 3, 5, 5-trimethyl-3-cyclopentene compound of the following general formula (1): wherein R2 is as defined above, and X represents a leaving group, to a nucleophilic substitution reaction with a methylating agent of the following general formula (2): wherein M represents Li, MgZ1, ZnZ1, Cu, CuZ1, or CuLiZ1, and Z1 represents a halogen atom or a methyl group, to form the α-necrodyl compound (3). The present invention further provides processes for preparing γ-necrodyl compounds of the following general formula (4): wherein R2 represents a monovalent hydrocarbon group having 1 to 9 carbon atoms, the process comprising: subjecting the α-necrodyl compound (3) thus obtained to a positional isomerization reaction at the double bond to form the γ-necrodyl compound (4).

  本发明提供了制备以下通式（3）的α-癸基化合物的工艺： 其中 R2 代表具有 1 至 9 个碳原子的一价烃基，该工艺包括：将以下通式（1）的 3，5，5-三甲基-3-环戊烯化合物：其中 R2 如上定义，且 X 代表离去基团，与下式通式（2）的甲基化剂进行亲核取代反应： 其中 M 代表 Li、MgZ1、ZnZ1、Cu、CuZ1 或 CuLiZ1，且 Z1 代表卤原子或甲基，以形成 α-十一烷基化合物（3）。本发明进一步提供了制备以下通式（4）的γ-癸二基化合物的工艺： 其中 R2 代表具有 1 至 9 个碳原子的一价烃基，该工艺包括：将由此获得的 α-癸二基化合物（3）在双键处进行位置异构化反应，以形成γ-癸二基化合物 （4）。
• METHOD FOR EFFECTIVELY CONTROLLING COCCOID INSECT PESTS
  申请人：Ecología y Protección Agrícola, S.L.

  公开号：US20210059246A1

  公开（公告）日：2021-03-04

  The present invention relates to a method for determining the effective flow rate of at least one semiochemical for controlling at least one coccoid insect pest using an artificial semiochemical matrix, and use of the effective flow rate for effectively controlling at least one coccoid insect pest through the diffusion of at least one semiochemical.
• Synthesis of the Grape Mealybug Pheromone trans-alpha-Necrodyl Isobutyrate
  申请人：Trécé Inc.

  公开号：US20210206711A1

  公开（公告）日：2021-07-08

  Methods are provided for synthesizing the grape mealybug pheromone, trans-α-necrodyl isobutyrate, starting with essential plant oils that contain trans-α-necrodyl acetate. The synthesis method, in two steps, converts the trans-α-necrodyl acetate to trans-α-necrodol and then converts the trans-α-necrodol to the desired trans-α-necrodyl isobutyrate. The first step can be achieved by either of a hydrolysis reaction or a reduction reaction. In the hydrolysis reaction, the essential oil is mixed in an alcohol solvent with a hydroxide base, or by mixing the essential oil in an aqueous acid. A reduction reaction can instead by performed in an organic solvent in the presence of a reducing agent. The trans-α-necrodol is converted to the desired trans-α-necrodyl isobutyrate by an esterification reaction with a carboxylic acid, an acyl halide, or an acid anhydride.