2-(p-chlorophenyl)-4-diazo-4-phenyl-cis-2-butenenitrile | 253791-33-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: 2-(p-chlorophenyl)-4-diazo-4-phenyl-cis-2-butenenitrile
• 英文别名: (Z)-2-(4-chlorophenyl)-4-diazo-4-phenylbut-2-enenitrile
• CAS: 253791-33-2
• 化学式: C₁₆H₁₀ClN₃
• 分子量: 279.728
• InChiKey: ORGUIJQZXDCUAT-GXDHUFHOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(p-chlorophenyl)-4-diazo-4-phenyl-cis-2-butenenitrile 在 dirhodium tetraacetate 作用下， 以 1,1,2,2-四氯乙烷 、 苯 为溶剂， 生成 trans-2,3-di(p-chlorophenyl)-5-phenyl-2,3-dihydro-3-furancarbonitrile
  参考文献：
  名称：

  Reaction of vinylcarbenoids with aldehydes: formation of vinylcarbonyl ylides followed by ring closure to oxiranes and dihydrofurans

  摘要：

  Rh-2(OAc)(4)-catalyzed reaction of vinyldiazo compound 1 in the presence of benzaldehydes 2a-2c gave a mixture of isomeric vinyloxiranes 3 and 4, and sterically unstable (E)-dihydrofurans 5, but not stable (Z)-dihydrofurans 6. However, the reaction in the presence of maleic anhydride gave single 1,3-dipolar cycloadducts 15, indicating that onyl endo-aryl-endo-cyanostyryl carbonyl ylide 7 (8) is initially formed in the reaction of 1 with 2. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)02317-5
• 作为产物：
  描述：

  3-chloro-2-(p-chlorophenyl)propenenitrile 、 二氮杂甲苯 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 2-(p-chlorophenyl)-4-diazo-4-phenyl-cis-2-butenenitrile
  参考文献：
  名称：

  Reaction of Vinylcarbenoids with Benzaldehydes:  Formation of Vinylcarbonyl Ylides Followed by Ring Closure to Oxiranes and Dihydrofurans

  摘要：

  Rh-2(OAc)(4)-catalyzed reaction of vinyldiazo compound la in the presence of p-methoxybenz- 2a, mesit- 2b, and p-chlorobenzaldehyde 2c gave a mixture of isomeric vinyloxiranes 3a-c and 4a-c, and sterically unstable (E)-dihydrofurans 5a-c, but not stable (Z)-dihydrofurans 6. However, the reactions with p-nitro- 2d and 2,4-dinitrobenzaldehyde 2e gave (Z)-dihydrofurans 6d,e along with 3d, 4d, and 5d,e. The reaction in the presence of maleic anhydride and dimethyl fumarate gave single 1,3-dipolar cycloadducts 11 and 13, respectively, indicating that a single conformer, the sterically unstable endo-aryl-endo-cyanostyryl carbonyl ylide 14 (15), is initially formed in the reaction of I with 2. It was concluded that the endo-vinyl-exo-aryl vinylcarbonyl ylides 17a-c arising from 2a-c undergo disrotatory cylization to exlusively produce 5, whereas the ylides 17d,e arising from 2d,e undergo partly symmetry-forbidden conrotaory cyclization to sterically stable trans-diaryldihydrofurans 6d,e as well as the symmetry-allowed process to 5d,e.

  DOI：

  10.1021/jo015618l

文献信息

• Reaction of vinylcarbenoids with thioketones: formation of vinylthiocarbonyl ylides followed by ring closure to thiiranes and dihydrothiophenes
  作者：Masashi Hamaguchi、Nao Funakoshi、Takumi Oshima

  DOI：10.1016/s0040-4039(99)01716-5

  日期：1999.11

  Reactions were carried out on thioketones with vinylcarbenoids. Rh2(OAc)4-catalyzed reaction of vinyldiazo compounds 1a,b with xanthione 2 and thiochromone 3 gave thiiranes 4b and olefins 5 and 6, desulfurization products from thiiranes, while the reaction of 1c with 2 and 3 afforded dihydrothiophenes 7, 8 and 9.

  在硫酮上与乙烯基类化合物反应。的Rh 2（OAc）4 vinyldiazo化合物的催化的反应1A，B与xanthione 2和thiochromone 3给硫杂丙环4B和烯烃5和6，从硫杂丙环脱硫产物，而该反应1C与2个3，得到dihydrothiophenes 7,8和9。
• Surprising 1,7-cyclization of vinyl carbonyl ylides generated from reaction of indanetrione with vinyl diazo compounds
  作者：Masashi Hamaguchi、Kazuma Takahashi、Takumi Oshima、Hatsue Tamura

  DOI：10.1016/s0040-4039(03)00936-5

  日期：2003.6

  3-dione-2,2′-benzodihydrooxepin 7a,b,c, but not normal products oxirane and dihydrofuran derivatives expected from intermediate vinyl carbonyl ylides 4. Formation of 7 requires isomerization of vinyl carbonyl ylides 4 bearing a (Z)-cyanostyryl group to unstable (E)-form 5 and subsequent cyclization to oxepin 6 followed by a 1,5-hydrogen shift. However, reaction of 2 with six-membered cyclic tricarbonyl

  进行了三羰基化合物与乙烯基重氮化合物2的反应。1,2,3-茚满三酮与2a，b，c反应得到螺环1,3-二酮-2,2'-苯并二氢氧杂庚酸酯7a，b，c，但不是正常产物环氧乙烷和二氢呋喃衍生物，可从中间体乙烯基羰基化合物中获得叶利德4。7的形成需要将带有（Z）-氰基苯乙烯基的乙烯基羰基乙烯基化合物4异构化为不稳定的（E）-形式5，然后环化为oxepin 6然后是1,5-氢转移。然而，2与六元环状三羰基化合物1,2,3-三氧代-2,3-二氢苯并萘11和二甲基四氧六环13的反应分别得到二氧杂环戊烯12和二氢呋喃14，这是乙烯基羰基羰基化合物所期望的典型产物。
• Reaction of vinylcarbenoids with aldehydes: formation of vinylcarbonyl ylides followed by ring closure to oxiranes and dihydrofurans
  作者：Masashi Hamaguchi、Hiroshi Matsubara、Toshikazu Nagai

  DOI：10.1016/s0040-4039(99)02317-5

  日期：2000.2

  Rh-2(OAc)(4)-catalyzed reaction of vinyldiazo compound 1 in the presence of benzaldehydes 2a-2c gave a mixture of isomeric vinyloxiranes 3 and 4, and sterically unstable (E)-dihydrofurans 5, but not stable (Z)-dihydrofurans 6. However, the reaction in the presence of maleic anhydride gave single 1,3-dipolar cycloadducts 15, indicating that onyl endo-aryl-endo-cyanostyryl carbonyl ylide 7 (8) is initially formed in the reaction of 1 with 2. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Reaction of Vinylcarbenoids with Benzaldehydes:  Formation of Vinylcarbonyl Ylides Followed by Ring Closure to Oxiranes and Dihydrofurans
  作者：Masashi Hamaguchi、Hiroshi Matsubara、Toshikazu Nagai

  DOI：10.1021/jo015618l

  日期：2001.8.1

  Rh-2(OAc)(4)-catalyzed reaction of vinyldiazo compound la in the presence of p-methoxybenz- 2a, mesit- 2b, and p-chlorobenzaldehyde 2c gave a mixture of isomeric vinyloxiranes 3a-c and 4a-c, and sterically unstable (E)-dihydrofurans 5a-c, but not stable (Z)-dihydrofurans 6. However, the reactions with p-nitro- 2d and 2,4-dinitrobenzaldehyde 2e gave (Z)-dihydrofurans 6d,e along with 3d, 4d, and 5d,e. The reaction in the presence of maleic anhydride and dimethyl fumarate gave single 1,3-dipolar cycloadducts 11 and 13, respectively, indicating that a single conformer, the sterically unstable endo-aryl-endo-cyanostyryl carbonyl ylide 14 (15), is initially formed in the reaction of I with 2. It was concluded that the endo-vinyl-exo-aryl vinylcarbonyl ylides 17a-c arising from 2a-c undergo disrotatory cylization to exlusively produce 5, whereas the ylides 17d,e arising from 2d,e undergo partly symmetry-forbidden conrotaory cyclization to sterically stable trans-diaryldihydrofurans 6d,e as well as the symmetry-allowed process to 5d,e.