1,1-difluorononene | 66794-17-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,1-difluorononene
• 英文别名: 1,1-Difluoronon-1-ene
• CAS: 66794-17-0
• 化学式: C₉H₁₆F₂
• 分子量: 162.223
• InChiKey: JSCRLHAXHUFQLN-UHFFFAOYSA-N

物化性质

• 沸点：
  157.5±8.0 °C(Predicted)
• 密度：
  0.894±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  11
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  triethyl(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)silane 、 1,1-difluorononene 在 iron(III)-acetylacetonate 、 1,3-双(二苯基膦)丙烷 、 sodium t-butanolate 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以72%的产率得到non-1-ene-1,1-diylbis(triethylsilane)
  参考文献：
  名称：

  铁催化未活化脂肪族宝石-二氟烯烃选择性和可控制的脱氟硅烷化的实验和计算研究

  摘要：

  首次开发了未活化的宝石二氟烯烃的铁催化脱氟甲硅烷基化反应，以极高的效率提供了宝石二甲硅烷基化的烯烃和（E）甲硅烷基化的烯烃。该方案具有良好的官能团相容性以及出色的区域和立体选择性，可实现生物学相关化合物的后期甲硅烷基化，从而为药物化学应用提供了良好的机会。初步的机理研究和DFT计算表明，第二个C-F键的亲核加成和消除可能参与了二甲硅烷基化催化体系，证明了铁催化的异常反应活性。

  DOI：

  10.1002/anie.202100049
• 作为产物：
  描述：

  2-bromo-1,1-difluoro-1-methylthiononane 在 HOF* CH₃CN 、 锌 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 0.17h， 生成 1,1-difluorononene
  参考文献：
  名称：

  From ketones, aldehydes or alkyl halides to terminal 1,1-difluoroolefins using BrF3

  摘要：

  Terminal difluoromethylenes were prepared by two different routes: (a) by treating ketones and aldehydes with bis(methylthio)methane, producing 2-alkyl-1,1-bis(methylthio)alkene (2) (b) reacting alkyl halides with tris(methylthio)methane forming 1-alkyl-1,1,1-tris(methylthio)alkane derivatives (7). The reaction of either 2 or 7 with BrF3, followed by oxidation with (HOFCH3CN)-C-. gave the difluorosulfonyl derivatives 4. Consecutive treatment with Zn led to the target difluoroolefins (5) in overall yields of 60-75%. (c) 2005 Elsevier B.V All rights reserved.

  DOI：

  10.1016/j.jfluchem.2005.06.003

文献信息

• Pd‐Catalyzed Selective Carbonylation of <i>gem</i> ‐Difluoroalkenes: A Practical Synthesis of Difluoromethylated Esters
  作者：Jiawang Liu、Ji Yang、Francesco Ferretti、Ralf Jackstell、Matthias Beller

  DOI：10.1002/anie.201813801

  日期：2019.3.26

  described. This novel catalytic transformation proceeds in the presence of Pd(acac)2/1,2‐bis((di‐tert‐butylphosphan‐yl)methyl)benzene (btbpx) (L4) and allows for an efficient and straightforward access to a range of difluoromethylated esters in high yields and regioselectivities. The synthetic utility of the protocol is showcased in the practical synthesis of a Cyclandelate analogue using this methodology

  描述了宝石二氟烯烃烷氧基羰基化的第一种催化剂。在Pd（acac）2 / 1,2-双（（二叔丁基膦基）甲基）苯（btbpx）（L4）的存在下进行这种新颖的催化转化过程，可以有效而直接地获得一系列二氟甲基化酯的高收率和区域选择性。使用该方法学作为关键步骤，在环戊酸酯类似物的实际合成中展示了该协议的综合用途。
• Highly Active Cross-Metathesis of Tetrafluoroethylene with a Seven-Membered N-Heterocyclic-Carbene–Ruthenium Catalyst
  作者：Kenta Mori、Midori Akiyama、Ko Inada、Yutaka Imamura、Yuichiro Ishibashi、Yusuke Takahira、Kyoko Nozaki、Takashi Okazoe

  DOI：10.1021/jacs.1c10574

  日期：2021.12.15

  A drastic increase in catalyst turnover number (TON) was accomplished in the cross-metathesis of tetrafluoroethylene (TFE) and vinyl ethers. Under a continuous flow of TFE, catalyst Ru7, which contains a seven-membered N-heterocyclic carbene (NHC) ligand, reached a TON of 4100; this is 2 orders of magnitude higher than the highest hitherto reported value. Mechanistic studies revealed that the expanded

  在四氟乙烯 (TFE) 和乙烯基醚的交叉复分解中实现了催化剂周转数 (TON) 的急剧增加。在 TFE 的连续流动下，含有七元 N-杂环卡宾 (NHC) 配体的催化剂Ru7的 TON 达到 4100；这比迄今为止报告的最高值高出 2 个数量级。机理研究表明，扩展的 NHC 成功地破坏了具有二氟卡宾结构的稳定中间体，从而强烈促进了反应。
• 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。
• Synthesis of Alkyl Aryl(heteroaryl)acetates from <i>N</i>-Oxides, 1,1-Difluorostyrenes, and Alcohols
  作者：Rafał Loska、Katarzyna Szachowicz、Dorota Szydlik

  DOI：10.1021/ol402735m

  日期：2013.11.15

  anes are formed from imidazole or thiazole N-oxide, 1,1-difluorostyrene, and an alcohol, amine, or water in a three-component reaction, which probably occurs via 1,3-dipolar cycloaddition. The whole process is a novel method for functionalization of a heterocyclic ring in a position originally occupied by hydrogen. Preliminary experiments show that it occurs for 6-membered N-oxides as well.

  芳基（杂芳基）乙酸或芳基（杂芳基）甲烷的衍生物是由咪唑或噻唑N-氧化物，1，1-二氟苯乙烯和醇，胺或水以三组分反应形成的，很可能是通过1 ，3-偶极环加成。整个过程是一种用于在最初被氢占据的位置上杂环官能化的新颖方法。初步实验表明，它也在6元N-氧化物中发生。
• 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。