1,1-difluorodec-1-ene | 66291-71-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,1-difluorodec-1-ene
• CAS: 66291-71-2
• 化学式: C₁₀H₁₈F₂
• 分子量: 176.25
• InChiKey: BKZPWIFVSVSRGM-UHFFFAOYSA-N

物化性质

• 沸点：
  96 °C(Press: 74 Torr)
• 密度：
  0.890±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  12
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1,1-difluorodec-1-en-2-yl(dioctyl)borane 以84%的产率得到
  参考文献：
  名称：

  ICHIKAWA, JUNJI;SONODA, TAKAAKI;KOBAYASHI, HIROSHI, TETRAHEDRON LETT., 30,(1989) N3, C. 1641-1644

  摘要：

  DOI：

文献信息

• gem-Difluorovinyl Derivatives as Insecticides and Acaricides
  作者：Thomas Pitterna、Manfred Böger、Peter Maienfisch

  DOI：10.2533/000942904777678163

  日期：——

  The insecticidal lead 1,1-difluorododec-1-ene was optimised. This compound has attractive insecticidal activity against tobacco budworm (Heliothis virescens), banded cucumber beetle (Diabrotica balteata), pea aphid (Aphis cracciovora), brown planthopper (Nilaparvata lugens), and green rice leafhopper (Nephotettix cincticeps). Among different pharmacophore analogues, only 1,1-dichlorododec-1-ene and 1,1-difluoro-2-iodododec-1-ene showed weak insecticidal activity, whereas similar compounds such as 1-chloro-1-fluorododec-1-ene, 1-fluorododec-1-ene, and 1,1-difluoro-2-bromododec-1-ene were inactive. Only bridge analogues with even-numbered carbon chains were active, for example 1,1-difluorodec-1-ene and 1,1-difluorotetradec-1-ene. Odd-numbered analogues such as 1,1-difluoronon-1-ene, 1,1-difluoroundec-1-ene, 1,1-difluorotridec-1-ene, and 1,1-difluoro-pentadec-1-ene showed no activity. Modification of the tail group led to the analogues 12,12-difluorododec-11-enoic acid and its methyl ester, 12,12-difluorododec-11-en-1-ol, 1,1-difluoro-12-methoxydodec-1-ene, and 12,12-difluorododec-11-enylamine, all of which showed insecticidal activity. 12,12-difluorododec-11-enoic acid methyl ester, 12,12-difluorododec-11-enoic acid, and 12,12-difluorododec-11-en-1-ol were also active against spider mites (Tetranychus ssp). Thus, in a first optimisation cycle, broad activity against insect pests and mites was discovered. Two requirements, the gem-difluorovinyl pharmacophore and an even-numbered carbon chain, were found to be essential for activity. This latter requirement is in line with the proposed mode of action, which involves inhibition of the ? -oxidation of fatty acids in insect mitochondria. In a second optimisation cycle, it was found that 6,6-difluorohex-5-enoic acid and its derivatives, such as acids, amides, and hydrazides, possess even superior properties as insecticides and acaricides. This led to the discovery of 6,6-difluorohex-5-enoic acid 2-[4-(4-trifluoromethylbenzyloxy)-phenoxy]-ethyl ester (CGA 304'111). This compound showed excellent performance in field trials against a wide range of pests, as well as a more favourable toxicological profile than earlier derivatives. For a largescale synthesis of CGA 304'111, five different synthetic routes for 6,6-difluorohex-5-enoic acid were developed. The best route involved radical addition of CBrClF2 to pent-4-enoic acid. Removal of bromine by hydrogenation, elimination of chloride and hydrolysis of the ester concluded this most efficient sequence. Thus, a practical synthesis for CGA 304'111 was identified, which allowed the preparation of samples on a several 100 g scale.

  1,1-二氟十二烯是一种杀虫剂铅化合物，具有对烟草夜蛾、条纹黄瓜甲（Diabrotica balteata）、豌豆蚜虫（Aphis cracciovora）、褐飞虱（Nilaparvata lugens）和绿稻叶蝉（Nephotettix cincticeps）等昆虫的吸引力杀虫活性。在不同的药效团类似物中，只有1,1-二氯十二烯和1,1-二氟-2-碘十二烯表现出微弱的杀虫活性，而类似化合物如1-氯-1-氟十二烯、1-氟十二烯和1,1-二氟-2-溴十二烯则无活性。只有具有偶数碳链的桥接类似物才具有活性，例如1,1-二氟十烯和1,1-二氟十四烯。奇数碳链的类似物如1,1-二氟壬-1-烯、1,1-二氟十一-烯、1,1-二氟十三-烯和1,1-二氟十五-烯均没有活性。修改尾基导致类似物12,12-二氟十二-11-烯酸及其甲酯、12,12-二氟十二-11-烯-1-醇、1,1-二氟-12-甲氧基十二烯和12,12-二氟十二-11-烯基胺，均表现出杀虫活性。12,12-二氟十二-11-烯酸甲酯、12,12-二氟十二-11-烯酸和12,12-二氟十二-11-烯-1-醇也对蜘蛛螨（Tetranychus ssp）具有活性。因此，在第一个优化周期中，发现了对昆虫害虫和螨类广泛活性。两个要求，即gem-二氟乙烯药效团和偶数碳链，被发现是活性所必需的。后一个要求符合所提出的作用模式，涉及对昆虫线粒体中脂肪酸的β-氧化的抑制。在第二个优化周期中，发现6,6-二氟己-5-烯酸及其衍生物，如酸、酰胺和肼，具有更优越的杀虫剂和杀螨剂性能。这导致了6,6-二氟己-5-烯酸2-[4-(4-三氟甲基苄氧基)-苯氧基]-乙酯（CGA 304'111）的发现。这种化合物在田间试验中表现出对多种害虫的优异性能，且毒理学特性比早期衍生物更有利。为了大规模合成CGA 304'111，开发了六种不同的6,6-二氟己-5-烯酸合成路线。最佳路线涉及对戊-4-烯酸进行自由基加成反应。通过氢化去除溴，消除氯并水解酯结束了这个最有效的序列。因此，确定了CGA 304'111的实用合成方法，可以在数百克的规模上制备样品。
• Coupling of Trifluoroacetaldehyde <i>N</i>-Triftosylhydrazone with Organoboronic Acids for the Synthesis of <i>gem</i>-Difluoroalkenes
  作者：Yu Ma、Bhoomireddy Rajendra Prasad Reddy、Xihe Bi

  DOI：10.1021/acs.orglett.9b03740

  日期：2019.12.20

  synthesis of alkyl gem-difluoroalkenes remains a difficult task in organic synthesis. Here, we report a general and efficient approach for tackling this problem by gem-difluoroolefination of trifluoroacetaldehyde N-triftosylhydrazone with organoboronic acids. This protocol is operationally simple, free of transition metals, and suitable for a broad range of organoboronic acids. Moreover, the utility

  烷基宝石-二氟烯烃的合成在有机合成中仍然是一项艰巨的任务。在这里，我们报告了通过有机硼酸与三氟乙醛N-三氟甲yl的宝石二氟烯烃化反应来解决此问题的通用有效方法。该方案操作简单，不含过渡金属，适用于广泛的有机硼酸。此外，通过进一步转化宝石-二氟乙烯基，证明了产品的实用性。
• POLYISOCYANATE COMPOSITION AND ISOCYANATE POLYMER COMPOSITION
  申请人：Asahi Kasei Chemicals Corporation

  公开号：EP2915803A1

  公开（公告）日：2015-09-09

  The present invention relates to a polyisocyanate composition comprising, on the basis of the total mass of the polyisocyanate composition, 97 weight % or more of a polyisocyanate, and 2.0 mass ppm or more and 1.0×104 mass ppm or less of a compound having at least one unsaturated bond in which the compound is a different compound from the polyisocyanate, or 5.0 mass ppm or more and 2.0×104 mass ppm or less of at least one inactive compound selected from the group consisting of a hydrocarbon compound, an ether compound, a sulfide compound, a halogenated hydrocarbon compound, a Si-containing hydrocarbon compound, a Si-containing ether compound, and a Si-containing sulfide compound.

  本发明涉及一种多异氰酸酯组合物，以该多异氰酸酯组合物的总质量为基准，该组合物包含 97 重量％或以上的多异氰酸酯，以及 2.0 质量 ppm 或以上且 1.0×104 质量 ppm 或以下的至少具有一个不饱和键的化合物，其中该化合物是与多异氰酸酯不同的化合物，或 5.0 质量 ppm 或以上且 2.0×104 质量 ppm 或以下的至少一种非活性化合物，该化合物选 自烃化合物、醚化合物、硫化物化合物、卤代烃化合物、含硅烃化合物、含硅醚化合物和含硅硫 化物组成的组。
• ISOCYANATE COMPOSITION, PRODUCTION METHOD FOR ISOCYANATE COMPOSITION, AND PRODUCTION METHOD FOR ISOCYANATE POLYMER
  申请人：ASAHI KASEI KABUSHIKI KAISHA

  公开号：EP3527593A1

  公开（公告）日：2019-08-21

  An isocyanate composition according to the present invention contains an isocyanate compound of formula (1) and/or (2) (wherein R1 represents a hydrogen or a monovalent organic group, and R2 represents a monovalent organic group), and, relative to the total mass of the isocyanate compound in the composition, 1.0 ppm by mass to 10% by mass of a compound of formula (3): R13-(COO-R14)a (wherein R13 represents an organic group with a valence of a, R14 represents a monovalent organic group, and a represents an integer of 1 or 2), which is different from the isocyanate compound, and/or, 1.0 ppm by mass to 10% by mass of a compound having an UV absorption in an area of decamer or higher isocyanates in a measurement spectrum of gel permeation chromatography.

  根据本发明的异氰酸酯组合物含有式(1)和/或(2)的异氰酸酯化合物(其中 R1 代表氢或一价有机基团，R2 代表一价有机基团)，以及相对于组合物中异氰酸酯化合物的总质量，1.0ppm(质量)至 10%(质量)的式(3)化合物：R13-(COO-R14)a（其中 R13 代表价数为 a 的有机基团，R14 代表一价有机基团，a 代表 1 或 2 的整数），该化合物与异氰酸酯化合物不同，和/或，在凝胶渗透色谱法的测量光谱中，在十聚体或更高异氰酸酯区域具有紫外吸收的化合物的质量百分比为 1.0 ppm 至 10%。
• ISOCYANATE COMPOSITION AND PRODUCTION METHOD FOR ISOCYANATE POLYMER
  申请人：ASAHI KASEI KABUSHIKI KAISHA

  公开号：EP3527600A1

  公开（公告）日：2019-08-21

  An isocyanate composition according to the present invention contains: a difunctional or more-functional isocyanate compound; and 1.0 ppm by mass to 1.0 × 104 ppm by mass, based on the isocyanate compound, of a compound having at least one unsaturated bond excluding unsaturated bonds constituting an aromatic ring, the compound being different from the isocyanate.

  根据本发明的异氰酸酯组合物含有：双官能团或更多官能团的异氰酸酯化合物；以及以异氰酸酯化合物为基准，质量分数为 1.0 ppm 至 1.0 × 104 ppm 的化合物，该化合物具有至少一个不饱和键，不包括构成芳香环的不饱和键，该化合物不同于异氰酸酯。