7,7-difluoronorcarane | 823-70-1

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氟化物
• 英文名称: 7,7-difluoronorcarane
• 英文别名: 7,7-difluornorcaran；7,7-Difluor-bicyclo<4.1.0>heptan；7,7-Difluorobicyclo[4.1.0]heptane
• CAS: 823-70-1
• 化学式: C₇H₁₀F₂
• 分子量: 132.153
• InChiKey: PWDGIWDIBFQZPD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  7,7-difluoronorcarane 生成 氟环庚烷
  参考文献：
  名称：

  ISOGAI KOJI; SAKAI JUN-ICHI, J. CHEM. SOC. JAP., CHEM. AND IND. CHEM.,(1986) N 5, 650-657

  摘要：

  DOI：
• 作为产物：
  描述：

  1-溴-2-(溴二氟甲基)环己烷 在 锌 作用下， 以 乙醚 为溶剂， 以19%的产率得到7,7-difluoronorcarane
  参考文献：
  名称：

  Mechanistic Studies on Zinc-Induced Addition of CF2Br2 to Olefins. A Novel Radical Reductive Cyclopropanation on the Zinc Surface

  摘要：

  The addition reaction of dibromodifluoromethane (1) to olefins induced by zinc in ethereal solvent differs surprisingly from addition reactions hitherto reported. Both cyclopropane derivatives and 1:1 addition products were obtained from this reaction. A free-radical chain addition reaction induced ; by single electron transfer (SET) is proposed. This reaction is inhibited by hydroquinone and completely quenched by p-dinitrobenzene. The nature of the 1:1 adducts formed revealed the character of a typical radical reaction. The nature of the cyclopropane derivatives formed was also much different from the usual cyclopropane adduct derived from carbene addition. When diallyl ether (15) and norbornadiene (16) were used as substrates, only rearranged 1:1 addition products could be obtained, and no cyclopropane product could be detected. The results of addition reactions with 4-octenes (27) showed also that the cyclopropanation reaction was not stereospecific. On the basis of the above-mentioned results, a novel reductive debromocyclopropanation reaction of the gamma-bromopropyl radical intermediate proceeding on the zinc metal surface is suggested.

  DOI：

  10.1021/jo00083a030

文献信息

• Synthetic and mechanistic aspects of halo-F-methylphosphonates
  作者：Richard M. Flynn、Donald J. Burton

  DOI：10.1016/j.jfluchem.2011.05.034

  日期：2011.10

  The synthesis of a variety of new halo-F-methylphosphonates has been achieved by a Michaelis–Arbuzov type reaction between a halo-F-methane and a trialkyl phosphite. This synthesis has proved to be of wide scope and utility for the high yield preparation of a number of heretofore unknown compounds. The 1H, 19F, 13C and 31P NMR spectroscopic properties are reported in detail. The mechanism for the formation

  卤代F-甲烷与亚磷酸三烷基酯之间的Michaelis-Arbuzov型反应已实现了多种新的卤代F-甲基膦酸酯的合成。已证明该合成对于高产率制备许多迄今未知的化合物具有广泛的范围和实用性。的1 H，19男，13 C和31种P NMR光谱性质报告于细节。溴二氟甲基膦酸酯的形成机理已证明是通过二氟卡宾：CF 2的中间体来进行的。已显示膦酸酯产物与多种试剂反应。氟化物和醇盐离子通过攻击在磷反应与碳-磷键的裂解和形成[：CF 2 ]从bromodifluoromethylphosphonates和CFBR 2 -从dibromofluoromethylphosphonates阴离子。碘离子和叔膦通过攻击酯碳反应生成稳定的膦酸酯盐。用50％的HCl水溶液水解膦酸酯，得到预期的膦酸。三甲基甲硅烷基溴化物侵蚀磷酰基氧，得到双（三甲基甲硅烷基）酯。
• (CF3)2Cd·D und (CF3)2Zn·D: neue reagenzien für difluorcarben-reaktionen [1]
  作者：Horst Lange、Dieter Naumann

  DOI：10.1016/s0022-1139(00)81310-x

  日期：1985.3

  thermal decomposition of (CF3)2Cd and (CF3)2Zn complexes primarily difluorocarbene is eliminated. The formation of CF2 is unambiguously proved by matrix i.r. spectroscopy. Both (CF3)2Cd·D and (CF3)2Zn·D are excellent CF2 sources, which can easily be prepared and handled, and which undergo CF2 reactions even at low temperature. CF2 insertion was found during the reaction of (CF3)2Te with (CH3)2Cd via the

  在（CF 3）2 Cd和（CF 3）2 Zn络合物的热分解过程中，主要消除了二氟卡宾。CF 2的形成已通过基质红外光谱法明确证实。（CF 3）2 Cd D和（CF 3）2 Zn D都是优异的CF 2源，可以容易地制备和处理，甚至在低温下也可以进行CF 2反应。在（CF 3）2 Te与（CH 3）2反应期间发现CF 2插入通过中间形成CF 3 Cd化合物形成Cd以形成CH 3 TeCF 2 CH 3。（CF 3）2 Cd·甘醇二甲醚与（CH 3）3 Si（OCOCF 3）反应成CF 3 Cd（OCOCF 3）·甘醇二甲醚；在该反应过程中，CF 2也被消除。
• Catalytic hydrogenolysis of cyclopropanes: Metal insertion into a saturated carbon—carbon bond as the key step
  作者：Yves Bessard、Manfred Schlosser

  DOI：10.1016/s0040-4020(01)86379-1

  日期：1991.1

  Hydrogenolytic ring cleavage of gem-difluorocydopropanes occurs exclusively at the carbon—carbon bond opposite to the halogen-bearing center and affords mainly gem-difluoroalkanes. The intermediacy of catalyst/cyclopropane derived adducts (e.g., palladacyclobutanes or 1,3-dipal]adiopropanes) is postulated in order to rationalize the formation of monofluorinated and halogen-free by-products and, in

  宝石-二氟环丙烷的氢解环裂解仅发生在与含卤素中心相反的碳-碳键处，并且主要提供宝石-二氟烷烃。假定催化剂/环丙烷衍生的加合物（例如，四环环丁烷或1,3-二棕榈二丙烷）的中间体是为了合理形成单氟化和无卤素的副产物，此外，还应解释对取代基的特定取代基效应。反应速度。
• Synthesis of gem-Difluorinated Cyclopropanes and Cyclopropenes: Trifluoromethyltrimethylsilane as a Difluorocarbene Source
  作者：Fei Wang、Tao Luo、Jinbo Hu、Ying Wang、Hema S. Krishnan、Parag V. Jog、Somesh K. Ganesh、G. K. Surya Prakash、George A. Olah

  DOI：10.1002/anie.201101691

  日期：2011.7.25

  Highly versatile: The Ruppert–Prakash reagent (Me3SiCF3) can be an efficient source of difluorocarbene. By varying the nonmetallic initiator that is used (F− at lower temperatures and I− at higher temperatures), a range of structurally diverse alkenes and alkynes can be converted into the corresponding gem‐difluorinated cyclopropanes and cyclopropenes in good yields (see scheme).

  用途广泛：Ruppert–Prakash试剂（Me 3 SiCF 3）可以是二氟卡宾的有效来源。通过改变所使用的非金属引发剂（F -在较低温度和我-在更高的温度），范围结构多样的烯烃和炔烃的可转化成相应的宝石-difluorinated以良好产率和环丙烷环丙烯（参见方案）。
• Synthesis of<i>gem</i>-Difluorocyclopropa(e)nes and O<i>-</i>, S<i>-</i>, N<i>-</i>, and P-Difluoromethylated Compounds with TMSCF₂Br
  作者：Lingchun Li、Fei Wang、Chuanfa Ni、Jinbo Hu

  DOI：10.1002/anie.201306703

  日期：2013.11.18

  Two-in-one: Me3 SiCF2 Br is an efficient difluorocarbene source and is compatible with both neutral and aqueous basic conditions. Bromide-ion-initiated [2+1] cycloaddition with alkenes/alkynes and hydroxide ion promoted α-addition with (thio)phenols, (thio)alcohols, sulfinates, heterocyclic amines, and H-phosphine oxides give the corresponding gem-difluorinated compounds with broad functional-group tolerance.