4-(1'-but-3'-enyl)-2-cyclohex-2-en-1-one | 70436-08-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-(1'-but-3'-enyl)-2-cyclohex-2-en-1-one
• 英文别名: 4-(3-butenyl)-2-cyclohexenone；4-(3-Butenyl)-2-cyclohexen-1-one；4-(3-Butenyl)-2-cyclohexen-1-on；4-(But-3-en-1-yl)cyclohex-2-en-1-one；4-but-3-enylcyclohex-2-en-1-one
• CAS: 70436-08-7
• 化学式: C₁₀H₁₄O
• 分子量: 150.221
• InChiKey: WOHOFQIQRBIQOG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-(1'-but-3'-enyl)-2-cyclohex-2-en-1-one 在 palladium dichloride 六甲基磷酰三胺 、 正丁基锂 、 samarium diiodide 、 potassium tert-butylate 、 氧气 、 copper(l) chloride 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 32.28h， 生成 (1R*,6S*,9S*)-3-(hydroxymethyl)-9-methylbicyclo[4.3.0]-2-nonen-9-ol
  参考文献：
  名称：

  Samarium(II) Iodide-Mediated Reductive Annulations of Ketones Bearing a Distal Vinyl Epoxide Moiety

  摘要：

  Samarium(II) iodide in the presence of hexamethylphosphoramide (HMPA) efficiently promotes the intramolecular coupling of ketones with distal epoxy olefins. The reaction appears to proceed by a mechanism wherein a ketyl couples with the unsaturated epoxide. Subsequent fragmentation of the epoxide ring in compounds 1a-k yields carbocycles 2a-k with an allyl alcohol side chain in good yields, and often with high diastereoselectivity. When tetramethylguanidine was used as an additive instead of HMPA, the desired carbocycle was obtained in good yield, but the diastereoselectivity was diminished. A palladium(0)-catalyzed SmI2 reaction provided the expected product in modest yield, but the sense of diastereoselectivity was reversed. In the latter case, a different reaction mechanism may be involved. Thus, formation of an allylsamarium species may be invoked, with nucleophilic carbonyl addition leading to the observed facial selectivity.

  DOI：

  10.1021/jo960335s
• 作为产物：
  描述：

  (3-(but-3-enyl)cyclopent-1-enyloxy)trimethylsilane 在 diethylzinc 、 sodium acetate 、 三氯化铁 作用下， 以 乙醚 为溶剂， 生成 4-(1'-but-3'-enyl)-2-cyclohex-2-en-1-one
  参考文献：
  名称：

  A new 4-substituted-2-Cyclohexenone synthesis

  摘要：

  Conjugate addition of a variety of Grignard reagents to 2-cyclopentenone followed by cyclopropanation of the resulting enol ethers gave a range of substituted cyclopropyl silyl ethers in good yield. Treatment of these cyclopropyl silyl ethers with ferric chloride in DMF gave the one carbon ring expanded beta-chloro ketones which were eliminated to the corresponding 4- substituted-2-cyclohexenones.

  DOI：

  10.1016/s0040-4039(00)79311-7

文献信息

• Ring opening of cyclopropylketones induced by photochemical electron transfer
  作者：Janine Cossy、Nathalie Furet、Samir BouzBouz

  DOI：10.1016/0040-4020(95)00727-p

  日期：1995.10

  Depending on the substitution pattern of cyclopropylketones, the photochemically induced electron transfer of tertiary amines to cyclopropylketones leads either to the formation of 3-substituted cycloalkanones or to ring expanded products.

  根据环丙基酮的取代方式，光化学诱导的叔胺电子转移至环丙基酮会导致3-取代的环烷酮的形成或环扩产物。
• 3-[2-Hydroxy-4-(substituted)phenyl]-cycloalkanol analgesic agents
  申请人：Pfizer Inc.

  公开号：US04306097A1

  公开（公告）日：1981-12-15

  Cycloalkanones, cycloalkanols and unsaturated analogs thereof, each of which has at the 3-position a 2-hydroxy-4-substituted phenyl group wherein the 4-position substituent is alkyl which can have an oxygen atom as part of the chain, or aralkyl which can have an oxygen atom as part of the alkyl chain, their use for pharmacological and medicinal purposes, intermediates therefor and processes for their preparation.

  环烷酮、环烷醇及其不饱和类似物，每个在3位上具有一个2-羟基-4-取代苯基团，其中4位取代基是可以在链中具有氧原子的烷基，或者可以在烷基链中具有氧原子的芳基烷基，它们用于药理学和药用目的，以及其中间体和制备过程。
• 2-Hydroxy-4-(substituted) phenyl cycloalkanes and derivatives
  申请人：Pfizer Inc.

  公开号：US04371720A1

  公开（公告）日：1983-02-01

  Compounds having the formula ##STR1## R.sub.1 is hydrogen, benzyl or an ester moiety; Y is --CH(R.sub.2 ")CH(R.sub.2)-- or--CH(R.sub.3)CH.sub.2 --; R.sub.2 " is hydrogen or methyl; R.sub.2 is OH or X-substituted (C.sub.1-6)alkyl; R.sub.3 is OH, cyano or X-substituted (C.sub.1-3) alkyl; X is --OR.sub.6, --SR.sub.6, --S(O)R.sub.6, --S(O).sub.2 R.sub.6, --NR.sub.6 R.sub.7, --COOR.sub.7, --CONR.sub.7 R.sub.8 or oxo; with the proviso that when X is --NR.sub.6 R.sub.7, --COOR.sub.7 or --CONR.sub.7 R.sub.8, said group is located on the terminal carbon atom of R.sub.2 or R.sub.3 ; R.sub.6 is hydrogen, (C.sub.1-6)alkyl or acetyl; each of R.sub.7 and R.sub.8 is hydrogen or (C.sub.1-6)alkyl; s is an integer of 1 or 2; with the proviso that when R.sub.6 is acetyl, R.sub.7 is hydrogen and X is other than S(O)R.sub.6 or S(O).sub.2 R.sub.6 ; Z--W is alkyl, phenylalkyl or pyridylalkyl which can have an oxygen atom as part of the alkyl chain, and their use as CNS agents, antidiarrheals and antiemetics. Processes for their preparation and intermediates therefor are described.

  具有以下式的化合物 ##STR1## R.sub.1 为氢、苄基或酯基团；Y 为--CH(R.sub.2 ")CH(R.sub.2)-- 或--CH(R.sub.3)CH.sub.2 --；R.sub.2 " 为氢或甲基；R.sub.2 为羟基或取代的（C.sub.1-6）烷基；R.sub.3 为羟基、氰基或取代的（C.sub.1-3）烷基；X 为--OR.sub.6、--SR.sub.6、--S(O)R.sub.6、--S(O).sub.2 R.sub.6、--NR.sub.6 R.sub.7、--COOR.sub.7、--CONR.sub.7 R.sub.8 或氧代；但当 X 为--NR.sub.6 R.sub.7、--COOR.sub.7 或--CONR.sub.7 R.sub.8 时，该基团位于 R.sub.2 或 R.sub.3 的末端碳原子上；R.sub.6 为氢、（C.sub.1-6）烷基或乙酰基；R.sub.7 和 R.sub.8 中的每一个为氢或（C.sub.1-6）烷基；s 为 1 或 2 的整数；但当 R.sub.6 为乙酰基、R.sub.7 为氢且 X 不是 S(O)R.sub.6 或 S(O).sub.2 R.sub.6 时；Z--W 为烷基、苯基烷基或吡啶基烷基，其中烷基链中可能含有氧原子，并且它们作为中枢神经系统药物、止泻药和抗恶心药。描述了它们的制备过程和中间体。
• Intramolecular cyclizations of allyl- and propargylsilanes
  作者：Dieter Schinzer、Sándor Sólyom、Marion Becker

  DOI：10.1016/s0040-4039(00)94749-x

  日期：1985.1

  Allylsilanes of type 5 and propargylsilanes of type 13 undergo efficient cyclizations upon treatment with EtAlCl2 in toluene to afford stereoselectively functionalized hydrindanones of type 6 and spiro[4,5]decanes of type 14.

  在甲苯中用EtAlCl 2处理后，类型5的烯丙基硅烷和类型13的炔丙基硅烷会发生有效的环化反应，从而得到类型6的立体选择性官能化的氢化茚酮和类型14的螺[4,5]癸烷。
• Iron(III) mediated transformations of trimethylsilyloxy cyclopropyl ethers
  作者：Kevin I. Booker-Milburn、David F. Thompson

  DOI：10.1016/0040-4020(95)00817-r

  日期：1995.11

  Conjugate addition of a variety of Grignard reagents to 2-cyclopentenone gave a number of silyl enol ethers (1) which were Created with Et2Zn/CH2I2 to give the corresponding cyclopropyl silyl ethers (2) in good yield. Ferric chloride ring expansion followed by base elimination of the resulting β-chloro ketones gave the 4-substituted-2-cyclohexenones (4) in moderate to good overall yield. The overall

  在2-环戊烯酮中共轭添加各种格氏试剂，得到了许多甲硅烷基烯醇醚（1），它们由Et 2 Zn / CH 2 I 2生成，以高收率得到了相应的环丙基甲硅烷基醚（2）。氯化铁环膨胀，然后碱消除所得的β-氯代酮，以中等至良好的总收率得到4-取代的2-环己烯酮（4）。整个过程提供了从2-环戊烯酮到这些烯酮的方便的三步路线。