4-(2-bromoethylidene)heptane | 10297-66-2

• 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: 4-(2-bromoethylidene)heptane
• 英文别名: 1-Bromo-3-propyl-2-hexen；1-Brom-3-n-propyl-2-hexen；1-Brom-3-propyl-2-hexen；1-bromo-3-propyl-hex-2-ene；1-Bromo-3-propyl-2-hexene
• CAS: 10297-66-2
• 化学式: C₉H₁₇Br
• 分子量: 205.138
• InChiKey: DHONOAPSAYTYAY-UHFFFAOYSA-N

物化性质

• 沸点：
  105 °C(Press: 40 Torr)
• 密度：
  1.116±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  4-(2-bromoethylidene)heptane 在 barium dihydroxide 、 sodium tetrahydroborate 、 氢溴酸 作用下， 以 甲醇 、 乙醇 、 水 为溶剂， 反应 17.0h， 生成 1-Brom-8-n-propyl-3.7-undecadien
  参考文献：
  名称：

  Rohela,L.C.; Anand,R.C., Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1978, vol. 16, p. 767 - 769

  摘要：

  DOI：
• 作为产物：
  描述：

  4-庚酮 在 三溴化磷 、 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 乙醚 、 甲苯 、 mineral oil 为溶剂， 反应 23.5h， 生成 4-(2-bromoethylidene)heptane
  参考文献：
  名称：

  铜（I）催化的具有亲核氢化物的烯丙基取代基

  摘要：

  容易获得的铜（I）/ N-杂环卡宾（NHC）络合物能够将区域选择性氢化物转移至烯丙基溴，从而实现烯丙基还原。得到的芳基和烷基取代的支链α-烯烃，是合成的重要组成部分，可以高收率和区域选择性地获得。使用可商购的硅烷（TMSO）2 Si（Me）H作为氢化物源。该协议为建立的碳催化亲核试剂催化的金属烯丙基取代提供了统一的替代方法，因为不需要使催化剂适应亲核试剂的性质。

  DOI：

  10.1021/acs.orglett.6b00941

文献信息

• Copper(I)-Catalyzed Allylic Substitutions with a Hydride Nucleophile
  作者：T. N. Thanh Nguyen、Niklas O. Thiel、Felix Pape、Johannes F. Teichert

  DOI：10.1021/acs.orglett.6b00941

  日期：2016.5.20

  easily accessible copper(I)/N-heterocyclic carbene (NHC) complex enables a regioselective hydride transfer to allylic bromides, an allylic reduction. The resulting aryl- and alkyl-substituted branched α-olefins, which are valuable building blocks for synthesis, are obtained in good yields and regioselectivity. A commercially available silane, (TMSO)2Si(Me)H, is employed as hydride source. This protocol

  容易获得的铜（I）/ N-杂环卡宾（NHC）络合物能够将区域选择性氢化物转移至烯丙基溴，从而实现烯丙基还原。得到的芳基和烷基取代的支链α-烯烃，是合成的重要组成部分，可以高收率和区域选择性地获得。使用可商购的硅烷（TMSO）2 Si（Me）H作为氢化物源。该协议为建立的碳催化亲核试剂催化的金属烯丙基取代提供了统一的替代方法，因为不需要使催化剂适应亲核试剂的性质。
• Cyclopropanecarboxylic acids and esters
  申请人：Roussel-UCLAF

  公开号：US03997586A1

  公开（公告）日：1976-12-14

  Novel cyclopropanecarboxylic acids and esters of the formula ##STR1## wherein Z.sub.1 and Z.sub.2 are selected from the group consisting of hydrogen, alkyl, aralkyl, aryl, alkenyl non-conjugated with the cyclopropane ring, alkenyl non-conjugated with the cyclopropane ring, cycloalkyl, cycloalkenyl and heterocyclic; R is selected from the group consisting of OH and OR' in which R' is selected from the group consisting of lower alkyl which may be substituted, benzyl which may be substituted on the phenyl or methylene portion, N-methylene-dicarboximide, (5-benzyl-furyl-3) methyl, and a cyclopentene of the formula ##STR2## WHEREIN R" is selected from the group consisting of alkyl, alkynyl, alkenyl, aryl, aralkyl, cycloalkyl, cycloalkenyl and heterocyclic; A is a bivalent alkyl radical selected from the group consisting of ##STR3## WHEREIN R.sub.1 is selected from the group consisting of hydrogen and lower alkyl, R.sub.2 and R.sub.3 are selected from the group consisting of alkyl, alkynyl, alkenyl, aryl, aralkyl, cycloalkyl, cycloalkenyl and heterocyclic and taken together with the carbon atom to which they are attached form a ring selected from the group consisting of carbon homo rings and unsaturated carbon homo rings of 3 to 7 carbon atoms and heterocyclic rings which may be substituted with lower alkyl or lower alkoxy and R.sub.2 and R.sub.3 may together form a polycyclic aromatic radical, R.sub.4 is lower alkyl, R.sub.5 is selected from the group consisting of hydrogen and lower alkyl and R.sub.4 and R.sub.5 together with the carbon atoms to which they are attached may form a saturated or unsaturated carbon homo ring or a heterocyclic ring, Y is selected from the group consisting of methylene and a saturated or unsaturated carbon chain and Y' is selected from the group consisting of methine and a saturated or unsaturated carbon chain with the proviso that when Z.sub.1 and Z.sub.2 are methyl and R.sub.1 is hydrogen, R.sub.2 is other than methyl and their preparation.

  化合物的名称为新型环丙烷羧酸和酯，其化学式为##STR1## 其中Z.sub.1和Z.sub.2的取值包括氢、烷基、芳基烷基、芳基、非与环丙烷环共轭的烯基、非与环丙烷环共轭的烯基、环烷基、环烯基和杂环基；R的取值包括OH和OR'，其中R'的取值包括可被取代的低烷基、苯甲基（苯环或亚甲基部分可被取代）、N-亚甲基双酰亚胺、（5-苯甲基呋喃-3）甲基和化学式为##STR2## 其中R"的取值包括烷基、炔基、烯基、芳基、芳基烷基、环烷基、环烯基和杂环基；A是一种二价烷基基团，其取值包括##STR3## 其中R.sub.1的取值包括氢和低烷基，R.sub.2和R.sub.3的取值包括烷基、炔基、烯基、芳基、芳基烷基、环烷基、环烯基和杂环基，并且它们与它们附着的碳原子一起形成3到7个碳原子的碳同族环和不饱和碳同族环和可被取代的杂环，R.sub.2和R.sub.3可以一起形成多环芳香基团，R.sub.4是低烷基，R.sub.5的取值包括氢和低烷基，R.sub.4和R.sub.5与它们附着的碳原子一起可以形成饱和或不饱和的碳同族环或杂环，Y的取值包括亚甲基和饱和或不饱和的碳链，Y'的取值包括亚甲基和饱和或不饱和的碳链，但当Z.sub.1和Z.sub.2为甲基且R.sub.1为氢时，R.sub.2不为甲基。
• Novel cyclopropanecarboxylic acids and esters
  申请人：Roussel Uclaf

  公开号：US04206140A1

  公开（公告）日：1980-06-03

  Novel cyclopropanecarboxylic acids and esters of the formula ##STR1## wherein Z.sub.1 and Z.sub.2 are selected from the group consisting of hydrogen, alkyl, aralkyl, aryl, alkenyl non-conjugated with the cyclopropane ring, alkynyl non-conjugated with the cyclopropane ring, cycloalkyl, cycloalkenyl and heterocyclic; R is selected from the group consisting of OH and OR' in which R' is selected from the group consisting of lower alkyl which may be substituted, benzyl which may be substituted on the phenyl or methylene portion, N-methylene-dicarboximide, (5-benzyl-furyl-3) methyl, and a cyclopentene of the formula ##STR2## wherein R" is selected from the group consisting of alkyl, alkynyl, alkenyl, aryl, aralkyl, cycloalkyl, cycloalkenyl and heterocyclic; A is a bivalent alkyl radical selected from the group consisting of ##STR3## wherein R.sub.1 is selected from the group consisting of hydrogen and lower alkyl, R.sub.2 and R.sub.3 are selected from the group consisting of alkyl, alkynyl, alkenyl, aryl, aralkyl, cycloalkyl, cycloalkenyl and heterocyclic and taken together with the carbon atom to which they are attached form a ring selected from the group consisting of carbon homo rings and unsaturated carbon homo rings of 3 to 7 carbon atoms and heterocyclic rings which may be substitued with lower alkyl or lower alkoxy and R.sub.2 and R.sub.3 may together form a polycyclic aromatic radical, R.sub.4 is lower alkyl, R.sub.5 is selected from the group consisting of hydrogen and lower alkyl and R.sub.4 and R.sub.5 together with the carbon atoms to which they are attached may form a saturated or unsaturated carbon homo ring or a heterocyclic ring, Y is selected from the group consisting of methylene and a saturated or unsaturated carbon chain and Y' is selected from the group consisting of methine and a saturated or unsaturated carbon chain with the proviso that when Z.sub.1 and Z.sub.2 are methyl and R.sub.1 is hydrogen, R.sub.2 is other than methyl and their preparation.

  化合物的名称为新型环丙烷羧酸和酯，其化学式为##STR1##其中Z.sub.1和Z.sub.2选择自氢、烷基、芳基烷基、芳基、不与环丙烷环共轭的烯基、不与环丙烷环共轭的炔基、环烷基、环烯基和杂环；R选择自OH和OR'，其中R'选择自可以被取代的低烷基、可以在苯环或亚甲基部分上被取代的苄基、N-亚甲基-二酰亚胺、(5-苄基呋喃-3)甲基和化学式为##STR2##其中R"选择自烷基、炔基、烯基、芳基、芳基烷基、环烷基、环烯基和杂环；A是一个双价烷基基团，选择自##STR3##其中R.sub.1选择自氢和低烷基，R.sub.2和R.sub.3选择自烷基、炔基、烯基、芳基、芳基烷基、环烷基、环烯基和杂环，并与它们附着的碳原子一起形成选择自碳同系环和不饱和碳同系环的3至7个碳原子和杂环环，该杂环环可以用低烷基或低烷氧基取代，R.sub.2和R.sub.3可以共同形成多环芳香基团，R.sub.4是低烷基，R.sub.5选择自氢和低烷基，R.sub.4和R.sub.5与它们附着的碳原子一起可以形成饱和或不饱和的碳同系环或杂环，Y选择自亚甲基和饱和或不饱和的碳链，Y'选择自亚甲基和饱和或不饱和的碳链，但是当Z.sub.1和Z.sub.2为甲基且R.sub.1为氢时，R.sub.2除了甲基外，还有其他基团。这些化合物的制备方法也在描述中提及。
• Cyclopropanecarboxylic acid chlorides
  申请人：Roussel Uclaf

  公开号：US04101574A1

  公开（公告）日：1978-07-18

  Novel cyclopropanecarboxylic acids and esters of the formula ##STR1## wherein Z.sub.1 and Z.sub.2 are selected from the group consisting of hydrogen, alkyl, aralkyl, aryl, alkenyl non-conjugated with the cyclopropane ring, alkynyl non-conjugated with the cyclopropane ring, cycloalkyl, cycloalkenyl and heterocyclic; R is selected from the group consisting of OH and OR' in which R' is selected from the group consisting of lower alkyl which may be substituted, benzyl which may be substituted on the phenyl or methylene portion, N-methylene-dicarboximide, (5-benzyl-furyl-3) methyl, and a cyclopentene of the formula ##STR2## WHEREIN R" is selected from the group consisting of alkyl, alkynyl, alkenyl, aryl, aralkyl, cycloalkyl, cycloalkenyl and heterocyclic; A is a bivalent alkyl radical selected from the group consisting of ##STR3## WHEREIN R.sub.1 is selected from the group consisting of hydrogen and lower alkyl, R.sub.2 and R.sub.3 are selected from the group consisting of alkyl, alkynyl, alkenyl, aryl, aralkyl, cycloalkyl, cycloalkenyl and heterocyclic and taken together with the carbon atom to which they are attached form a ring selected from the group consisting of carbon homo rings and unsaturated carbon homo rings of 3 to 7 carbon atoms and heterocyclic rings which may be substituted with lower alkyl or lower alkoxy and R.sub.2 and R.sub.3 may together form a polycyclic aromatic radical, R.sub.4 is lower alkyl, R.sub.5 is selected from the group consisting of hydrogen and lower alkyl and R.sub.4 and R.sub.5 together with the carbon atoms to which they are attached may form a saturated or unsaturated carbon homo ring or a heterocyclic ring, Y is selected from the group consisting of methylene and a saturated or unsaturated carbon chain and Y' is selected from the group consisting of methine and a saturated or unsaturated carbon chain with the proviso that when Z.sub.1 and Z.sub.2 are methyl and R.sub.1 is hydrogen, R.sub.2 is other than methyl and their preparation.

  新型环丙烷羧酸和酯的化学式为##STR1##其中Z.sub.1和Z.sub.2选自氢、烷基、芳基烷基、芳基、不与环丙烷环共轭的烯基、不与环丙烷环共轭的炔基、环烷基、环烯基和杂环基；R选自OH和OR'的群，其中R'选自下列群：可被取代的低烷基、苯甲基（可能在苯基或亚甲基部分上被取代）、N-亚甲基-二羧酐、（5-苯甲基呋喃-3）甲基和化学式为##STR2##其中R"选自烷基、炔基、烯基、芳基、芳基烷基、环烷基、环烯基和杂环基；A是二价烷基基团，选自下列群：##STR3##其中R.sub.1选自氢和低烷基，R.sub.2和R.sub.3选自烷基、炔基、烯基、芳基、芳基烷基、环烷基、环烯基和杂环基，并与它们所附着的碳原子一起形成选自下列群的环：含3至7个碳原子的碳同系环和不饱和碳同系环和杂环环，其中杂环环可能被低烷基或低烷氧基取代，R.sub.2和R.sub.3可以一起形成多环芳基基团，R.sub.4是低烷基，R.sub.5选自氢和低烷基，R.sub.4和R.sub.5与它们所附着的碳原子一起可以形成饱和或不饱和的碳同系环或杂环，Y选自亚甲基和饱和或不饱和的碳链，Y'选自甲基和饱和或不饱和的碳链，但当Z.sub.1和Z.sub.2为甲基，R.sub.1为氢，R.sub.2不为甲基时，不在此范围内。这些化合物的制备方法。
• Radical Addition-Enabled C–C σ-Bond Cleavage/Reconstruction to Access Functional Indanones: Total Synthesis of Carexane L
  作者：Cong Shi、Ruihua Liu、Zemin Wang、Xiaowei Li、Hongyun Qin、Leifeng Yuan、Wenlong Shan、Wenli Zhuang、Xiangqian Li、Dayong Shi

  DOI：10.1021/acs.orglett.4c00348

  日期：2024.4.19

  modification in synthetic chemistry but it remains a formidable challenge to perform on unstrained skeletons. Herein, we describe a radical addition-enabled C–C σ-bond cleavage/reconstruction reaction of unstrained allyl ketones to access various functional indanones bearing a benzylic quaternary center. The synthetic utility of this method has been showcased by the first total synthesis of carexane L, an indanone-based

  C-C σ 键断裂和重建是合成化学中结构修饰的重要工具，但在无应变骨架上进行仍然是一个巨大的挑战。在此，我们描述了无张力烯丙基酮的自由基加成C-C σ-键裂解/重建反应，以获得带有苄基四元中心的各种功能性茚满酮。该方法的合成实用性已通过茚满酮天然产物 Carexane L 的首次全合成得到展示。