4-甲基戊-3-烯腈 | 4786-23-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: 4-甲基戊-3-烯腈
• 中文别名: 3-甲基-3-丙烯腈；4-甲基-3-戊腈
• 英文名称: 4-methyl-3-pentenenitrile
• 英文别名: 4-methylpent-3-enenitrile；4-Methyl-pent-3-ennitril；Brenzterebinsaeurenitril；γ-Methyl-β-butylen-α-carbonsaeurenitril
• CAS: 4786-23-6
• 化学式: C₆H₉N
• 分子量: 95.1442
• InChiKey: AYDNYRHVOPYCDZ-UHFFFAOYSA-N

物化性质

• 沸点：
  63 °C(Press: 14 Torr)
• 密度：
  0.8556 g/cm3(Temp: 18.8 °C)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2926909090
• 包装等级：
  III
• 危险类别：
  3,6.1
• 危险性防范说明：
  P501,P261,P270,P240,P210,P233,P243,P241,P242,P271,P264,P280,P370+P378,P337+P313,P305+P351+P338,P362+P364,P303+P361+P353,P332+P313,P301+P310+P330,P304+P340+P312,P403+P235,P405
• 危险品运输编号：
  1992
• 危险性描述：
  H301,H312+H332,H316,H320,H225

反应信息

• 作为反应物：
  描述：

  4-甲基戊-3-烯腈 在 吡啶 、 4-二甲氨基吡啶 、 sodium hydroxide 、 sodium tetrahydroborate 、 正丁基锂 、 ammonium cerium(IV) nitrate 、 四溴化碳 、 三乙胺 、 三苯基膦 、 叔丁醇 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 乙腈 为溶剂， 反应 18.24h， 生成 紫草素
  参考文献：
  名称：

  A New Efficient Route for Multigram Asymmetric Synthesis of Alkannin and Shikonin

  摘要：

  A short and convergent approach for the synthesis of alkannin, shikonin and shikalkin is presented. A Hauser-type annulation of cyanophthalide 26 with enone 7 affords the complete aromatic system in just one step with concomitant attachment of the entire side chain. Subsequent Corey's oxazaborolidine mediated asymmetric reduction of the above advanced intermediate, leads to the required isomer in high enantiomeric excess. Finally, a selective and high yielding deprotection protocol furnishes the title compounds as pure crystalline precipitates. Thus, a multigram synthesis of shikonin, alkannin and shikalkin is achieved in high yield and enantioselectivity.

  DOI：

  10.1002/1521-3765(20020415)8:8<1795::aid-chem1795>3.0.co;2-v
• 作为产物：
  描述：

  1-氯-3-甲基-2-丁烯 在 氰化钠 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 以64%的产率得到4-甲基戊-3-烯腈
  参考文献：
  名称：

  Trichodiene synthase. Synergistic inhibition by inorganic pyrophosphate and aza analogs of the bisabolyl cation.

  摘要：

  A series of aza analogs of the bisabolyl and alpha-terpinyl cations were tested as inhibitors of the sesquiterpene cyclase, trichodiene synthase. Both (R)- and (S)-16 and (R)- and (S)-13 as well as trimethylamine were only weak inhibitors when incubated alone. In the presence of inorganic pyrophosphate, itself a known competitive inhibitor of trichodiene synthase, all five amines showed strong cooperative competitive inhibition with an enhancement factor estimated to be 10-40. The apparent induced inhibition constant alpha-K(j) decreased in going from trimethylamine to the monoterpene analogs 13 and was strongest for the sesquiterpene analogs 16, indicating that both electrostatic and hydrophobic interactions are important in the binding of each intermediate analog. The cyclase showed little discrimination, however, between the individual enantiomers of each inhibitor.

  DOI：

  10.1021/jo00038a040

文献信息

• Die Solvoyse von 4-substituierten 2-Chlor-2-methylbutanen
  作者：Cyril A. Grob、Adrian Waldner

  DOI：10.1002/hlca.19790620614

  日期：1979.9.19

  The solvolysis of sixteen 4-substituted 2-chloro-2-methylbutanes in aqueous dioxane has been studied.

  已经研究了十六种4-取代的2-氯-2-甲基丁烷在二恶烷水溶液中的溶剂化作用。
• Manufacture of organic nitriles
  申请人：Imperial Chemical Industries Ltd.

  公开号：US03947487A1

  公开（公告）日：1976-03-30

  Olefins are converted to nitriles by reacting with hydrogen cyanide in the presence of an organic thiol or sulphide and a catalytic amount of a cuprous salt which is soluble therein; especially for making 3-pentene nitrile from butadiene.

  烯烃在有机硫醇或硫化物和可溶于其中的一种铜盐的催化作用下，与氢氰酸反应转化为腈类化合物；特别适用于从丁二烯制备3-戊烯腈。
• Efficient Amide-Directed Catalytic Asymmetric Hydroboration
  作者：Sean M. Smith、Nathan C. Thacker、James M. Takacs

  DOI：10.1021/ja710492q

  日期：2008.3.1

  (>95%) and enantioselective (93-99% ee) rhodium-catalyzed hydroboration with pinacolborane (PinBH) using simple chiral monophosphite or phosphoramidite ligands in combination with Rh(nbd)2BF4. The most effective ligands identified are phosphoramidite 4, derived from BINOL and N-methylaniline, and phosphite 5c, prepared from the (4'-tert-butyl)phenyl TADDOL analogue and phenol. For example, (E)-3-hexenoic

  使用简单的手性单亚磷酸酯或亚磷酰胺配体与频哪醇硼烷 (PinBH) 结合，一系列无环 β, γ-不饱和酰胺显示出高度区域 (>95%) 和对映选择性 (93-99% ee) 铑催化硼氢化反应Rh(nbd)2BF4。确定的最有效的配体是亚磷酰胺 4，衍生自 BINOL 和 N-甲基苯胺，以及亚磷酸酯 5c，由（4'-叔丁基）苯基 TADDOL 类似物和苯酚制备。例如，(E)-3-己烯酸苯基酰胺 ((E)-1) 与 PinBH (0.5 mol % Rh(nbd)2BF4，1.1 mol % BINOL 衍生的亚磷酰胺 4，THF，40 摄氏度进行铑催化硼氢化, 2 h) 得到中间体硼酸酯，在用碱性过氧化氢氧化后得到 β-羟基酰胺，(S)-3-羟基己酸苯酰胺 ((S)-3)，以良好的收率 (80%) 和高对映体纯度 (99% ee)。异构二取代 (E)- 和 (Z)- 烯烃产生几乎相同的结果，
• Synthesis of γ-hydroxy α,β-unsaturated amides by base-induced isomerization of epoxy amides
  作者：Peter B. Brooks、Charles M. Marson

  DOI：10.1016/s0040-4020(98)00519-5

  日期：1998.8

  Treatment of 3,4-epoxyamides with LDA affords γ-hydroxy-α,β-unsaturated amides, usually with high (E)-selectivity. The 3,4-epoxyamides were prepared by the epoxidation of β,γ-unsaturated amides with meta-chloroperbenzoic acid.

  用LDA处理3，4-环氧酰胺可得到γ-羟基-α，β-不饱和酰胺，通常具有高（E）选择性。通过将β，γ-不饱和酰胺与间-氯过苯甲酸环氧化制备3，4-环氧酰胺。
• Silylation of 2- or 3-Alkenenitriles with Iodosilanes/Triethylamine Affording 2- or 4-Silyl-2-alkenenitriles
  作者：Hiroshi Yamashita、N. Prabhakar Reddy、Masato Tanaka

  DOI：10.1246/bcsj.67.1510

  日期：1994.5

  2- or 3-Alkenenitriles, (R1R2HC)R3C=CHCN or R1R2C=CR3CH2CN (R1, R2, R3 = H, Me, etc.), react with iodosilanes, R4Me2SiI (R4 = Me, Me3Si), in the presence of Et3N to give 2-silyl-2-alkenenitriles, (R1R2HC)R3C=C(SiMe2R4)(CN), in good to moderate yields with high E selectivity (R3 = H). A 2-methylalkenenitrile, H2C=CHCHMe(CN) or MeCH=CMe(CN), is silylated with Me3SiI to provide a 4-silyl-2-alkenenitrile, Me3SiCH2CH=CMe(CN).

  2-或3-烯腈，（R1R2HC）R3C=CHCN或R1R2C=CR3CH2CN（R1，R2，R3 = H，Me等），在Et3N的存在下与碘硅烷R4Me2SiI（R4 = Me，Me3Si）反应，生成2-硅基-2-烯腈，（R1R2HC）R3C=C(SiMe2R4)(CN)，产率良好到中等，且具有高E选择性（R3 = H）。一种2-甲基烯腈H2C=CHCHMe(CN)或MeCH=CMe(CN)与Me3SiI反应，生成4-硅基-2-烯腈Me3SiCH2CH=CMe(CN)。

表征谱图