1-bromo-2,2,3,3-tetramethyl-1-(1-propynyl)cyclopropane | 138777-60-3

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机溴化物
• 英文名称: 1-bromo-2,2,3,3-tetramethyl-1-(1-propynyl)cyclopropane
• 英文别名: Cyclopropane, 1-bromo-2,2,3,3-tetramethyl-1-prop-1-ynyl-；1-bromo-2,2,3,3-tetramethyl-1-prop-1-ynylcyclopropane
• CAS: 138777-60-3
• 化学式: C₁₀H₁₅Br
• 分子量: 215.133
• InChiKey: NIGPDTPDUAQPHA-UHFFFAOYSA-N

物化性质

• 沸点：
  192.1±19.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  2,3-二甲基-2-丁烯 、 1,1-dibromobut-2-yne 在 potassium tert-butylate 作用下， 以 正戊烷 为溶剂， 以44%的产率得到1-bromo-2,2,3,3-tetramethyl-1-(1-propynyl)cyclopropane
  参考文献：
  名称：

  Alkynylhalocarbenes 1. Generation of alkynylchloro- and alkynylbromocarbenes from alkynylchlorobromo- and alkynyldibromomethanes, their multiplicity and philicity

  摘要：

  The action of t-BuOK on alkynyldihalomethanes RC=CCHBrX (I, R = Me, t-Bu, Ph; X = Br, Cl) in pentane at -20 to 0-degrees-C generates the corresponding alkynylhalocarbenes RC=CCX (II; X = Br, Cl) which in the presence of olefins give alkynylhalocyclopropanes (V) in 26-70% yield. It has been shown for the example of the reaction of (methylethynyl-) and (tert-butylethynyl)bromocarbenes with cis-butene-2 that the cycloaddition is fully stereospecific. The selectivity index for (methylethynyl)bromocarbene was experimentally determined as 0.48 which is evident for electrophilic character in this carbene.

  DOI：

  10.1007/bf00961044

文献信息

• ——
  作者：K. N. Shavrin、V. D. Gvozdev、O. M. Nefedov

  DOI：10.1023/a:1020952513679

  日期：——

  When treated with KOH under phase-transfer catalysis or with (BuOK)-O-t, 3-substituted (alkyl or phenyl) 1, 1, 3-tribromo-1-fluoropropanes 1a-c exclusively generate previously unknown (alk-1-ynyl)fluorocarbenes 5a-c, which react with olefins to give 1-(alk-1-ynyl)-1-fluorocyclopropanes 6a-h in 12-69% yields. Under analogous conditions, 3-alkyl- and 3-aryl-3-bromo-1, 1, 1-trichloropropanes 2a-c selectively afford (alk-1-ynyl)chlorocarbenes 7a-c, which are trapped by olefins to form the corresponding 1-(alk-1-ynyl)-1-chlorocyclopropanes 8a-k in 35-70% yields. (Phenylethynyl)chlorocarbene 7a is also selectively generated from 1, 1, 1, 3-tetrachloro-3-phenylpropane (3a) upon its treatment with (BuOK)-O-t. With an excess of 2,3-dimethylbut-2-ene or 2-methylpropene, carbene 7a yields 1-chloro-1-(phenylethynyl)cyclopropanes 8a or 8c, respectively. In contrast, 1, 1, 1, 3-tetrachloroheptane 3b and 3-alkyl- and 3-phenyl-1, 1, 1, 3-tetrabromopropanes 4a,c,f react with bases in the presence of olefins to give, along with the corresponding 1-(alk-1-ynyl)-1-halocyclopropanes 8a,c,d and 11a-f, vinylidenecyclopropanes 12a,c-g, which suggests the generation, under these conditions; both (alk-1-ynyl)halocarbenes 7b and 9a-c and vinylidenecarbenes 10 and 11a-c. The composition and structures of intermediate products in the reactions of tetrahalides 1b, 2a, 2b, 3a, and 3b with (BuOK)-O-t were determined and the mechanisms for carbene generation in these reactions were proposed.
• Shavrin, Konstantin N.; Krylova, Irina V.; Shvedova, Inna B., Journal of the Chemical Society. Perkin transactions II, 1991, # 12, p. 1875 - 1882
  作者：Shavrin, Konstantin N.、Krylova, Irina V.、Shvedova, Inna B.、Okonnishnikova, Galina P.、Dolgy, Igor E.、Nefedov, Oleg M.

  DOI：——

  日期：——
• Alkynylhalocarbenes 1. Generation of alkynylchloro- and alkynylbromocarbenes from alkynylchlorobromo- and alkynyldibromomethanes, their multiplicity and philicity
  作者：K. N. Shavrin、I. B. Shvedova、O. M. Nefedov

  DOI：10.1007/bf00961044

  日期：1991.11

  The action of t-BuOK on alkynyldihalomethanes RC=CCHBrX (I, R = Me, t-Bu, Ph; X = Br, Cl) in pentane at -20 to 0-degrees-C generates the corresponding alkynylhalocarbenes RC=CCX (II; X = Br, Cl) which in the presence of olefins give alkynylhalocyclopropanes (V) in 26-70% yield. It has been shown for the example of the reaction of (methylethynyl-) and (tert-butylethynyl)bromocarbenes with cis-butene-2 that the cycloaddition is fully stereospecific. The selectivity index for (methylethynyl)bromocarbene was experimentally determined as 0.48 which is evident for electrophilic character in this carbene.