4-methylenenonan-5-one | 76919-90-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-methylenenonan-5-one
• 英文别名: 4-Methylen-5-nonanon；4-Methylidenenonan-5-one
• CAS: 76919-90-9
• 化学式: C₁₀H₁₈O
• 分子量: 154.252
• InChiKey: JFJVLLSQLBNXFP-UHFFFAOYSA-N

物化性质

• 沸点：
  219.0±9.0 °C(Predicted)
• 密度：
  0.831±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  11
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 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-methylenenonan-5-one 在 盐酸羟胺 、 sodium carbonate 作用下， 以 甲醇 为溶剂， 反应 1.0h， 生成
  参考文献：
  名称：

  Rh(III)-催化区域选择性合成由烯烃和α,β-不饱和肟酯合成吡啶

  摘要：

  α,β-不饱和的 O-新戊酰基肟通过 Rh(III) 催化与烯烃偶联，得到取代的吡啶。与活化烯烃的反应具有异常的区域选择性和高产率。机理研究表明，杂环的形成是通过可逆的 CH 活化、烯烃插入和 CN 键形成/NO 键裂解过程进行的。

  DOI：

  10.1021/ja3104389
• 作为产物：
  描述：

  4-[(Dimethylamino)methyl]nonan-5-one 在 sodium hydroxide 、 双氧水 、 potassium carbonate 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 24.0h， 生成 4-methylenenonan-5-one
  参考文献：
  名称：

  An Easy Transformation of Ketones into α,α-Epoxymethylketones by Hydrogen Peroxide Oxidation of Mannich Base Derivates

  摘要：

  DOI：

  10.1055/s-1980-29257

文献信息

• Rh(III)-Catalyzed Regioselective Synthesis of Pyridines from Alkenes and α,β-Unsaturated Oxime Esters
  作者：Jamie M. Neely、Tomislav Rovis

  DOI：10.1021/ja3104389

  日期：2013.1.9

  O-pivaloyl oximes are coupled to alkenes by Rh(III) catalysis to afford substituted pyridines. The reaction with activated alkenes is exceptionally regioselective and high-yielding. Mechanistic studies suggest that heterocycle formation proceeds via reversible C-H activation, alkene insertion, and a C-N bond formation/N-O bond cleavage process.

  α,β-不饱和的 O-新戊酰基肟通过 Rh(III) 催化与烯烃偶联，得到取代的吡啶。与活化烯烃的反应具有异常的区域选择性和高产率。机理研究表明，杂环的形成是通过可逆的 CH 活化、烯烃插入和 CN 键形成/NO 键裂解过程进行的。
• Asymmetric Sulfa-Michael Addition to α-Substituted Vinyl Ketones Catalyzed by Chiral Primary Amine
  作者：Niankai Fu、Long Zhang、Sanzhong Luo、Jin-Pei Cheng

  DOI：10.1021/ol5022178

  日期：2014.9.5

  effective example of asymmetric conjugate addition–protonation reactions of thiols to α-substituted vinyl ketones by chiral primary amine catalysis is reported. A simple chiral primary–tertiary diamine catalyst derived from l-phenylalanine was found to promote the sulfa-Michael addition–protonation reactions with good to excellent enantioselectivity.

  报道了通过手性伯胺催化硫醇与α-取代的乙烯基酮发生不对称共轭加-质子化反应的第一个有效实例。发现一种简单的衍生自1-苯丙氨酸的手性伯叔叔二胺催化剂可促进磺胺-迈克尔加成-质子化反应，并具有良好至优异的对映选择性。
• [EN] PROCESS FOR THE PRODUCTION OF 2-ALKYLALKANOL<br/>[FR] PROCÉDÉ DE PRODUCTION DE 2-ALKYLALCANOL
  申请人：JOHNSON MATTHEY DAVY TECHNOLOGIES LTD

  公开号：WO2018069714A1

  公开（公告）日：2018-04-19

  A process for the production of 2-alkylalkanol from an aldehyde is disclosed. The process comprises the steps of: feeding aldehyde to a reactor (42) operated under condensation and dehydration conditions such that reaction occurs and an unsaturated aldehyde is produced; recovering a stream from the reactor (42) comprising the unsaturated aldehyde and feeding said stream to a first hydrogenation reactor (45) operated under conditions such that at least some of the unsaturated aldehyde is converted to 2-alkylalkanol; recovering the stream from the first hydrogenation reactor (45) comprising the 2-alkylalkanol, one or more of unreacted acrolein, alkylalkenol and alkylalkanal and heavies; passing the stream recovered from the first hydrogenation reactor (45) to a first distillation zone (48) where at least some of the heavies are separated from the stream; recovering a stream from the first distillation zone (48) comprising the 2-alkylalkanol, one or more of unreacted acrolein, alkylalkenol and alkylalkanal, said stream having a reduced heavies content when compared to the stream fed to the first distillation zone (48), and feeding said stream to a second hydrogenation reactor (51) operated under conditions such that at least one of the unreacted acrolein, alkylalkenol and alkylalkanal are converted to 2-alkylalkanol; and recovering a stream from the second hydrogenation reactor (51) comprising an increased 2-alkylalkanol content compared to the stream fed to the second hydrogenation reactor (51).

  本发明公开了一种从醛生产2-烷基醇的方法。该方法包括以下步骤：将醛送入在缩合和脱水条件下操作的反应器（42），使反应发生并产生不饱和醛；从反应器（42）中回收包含不饱和醛的流，并将该流送入第一氢化反应器（45），在条件下操作，使至少一部分不饱和醛转化为2-烷基醇；从第一氢化反应器（45）中回收包含2-烷基醇、未反应的丙烯醛、烷基烯醇和烷基醛以及重质的流；将从第一氢化反应器（45）回收的流经过到第一蒸馏区（48），至少分离出一部分重质；从第一蒸馏区（48）中回收包含2-烷基醇、未反应的丙烯醛、烷基烯醇和烷基醛的流，与送入第一蒸馏区（48）的流相比，其重质含量降低，并将该流送入第二氢化反应器（51），在条件下操作，使未反应的丙烯醛、烷基烯醇和烷基醛之一转化为2-烷基醇；从第二氢化反应器（51）中回收包含比送入第二氢化反应器（51）的流更高的2-烷基醇含量的流。
• Adolisation-dehydration process
  申请人：Davy Process Technology Limited

  公开号：EP0751109A1

  公开（公告）日：1997-01-02

  An aldolisation-dehydration process is disclosed for converting an aldehyde, e.g. n-valeraldehyde, to a substituted acrolein, e.g. propyl butyl acrolein (2-propylhept-2-enal). Aldolisation and dehydration are effected in a stirred tank reactor (16;111) using an alkali catalyst, such as sodium hydroxide. A reaction product stream (23;113) containing both organic and aqueous phases is supplied to an intermediate section of a distillation zone (25;123) which further includes a higher temperature section below the intermediate section and a lower temperature distillation section. Decomposition aldols and "heaving" to regenerate aldehyde or aldehydes occurs in the higher temperature section of the distillation column so that aldehyde or aldehydes are recoverable from the top of the distillation section in a heterogeneous azeotrope containing water and aldehyde. On condensation and phase separation the lower water layer (34;150) can be discharged from the plant without the need for neutralisation. From the bottom of the distillation zone a mixture (36;157) of substituted acrolein and alkali catalyst solution is obtained. The substituted acrolein is recovered as product (45;173), while the catalyst solution (47;175) is recycled to the aldolisation reactor. Part (49;181) of the catalyst solution is purged to control the level of Cannizzaro reaction products.

  本发明公开了一种醛化脱水工艺，用于将醛（如正戊醛）转化为取代的丙烯醛（如丙基丁基丙烯醛（2-丙基庚-2-烯醛））。醛化和脱水在搅拌罐反应器 (16;111) 中使用碱催化剂（如氢氧化钠）进行。含有有机相和水相的反应产物流（23;113）被输送到蒸馏区（25;123）的中间段，该蒸馏区还包括中间段以下的高温段和低温蒸馏段。醛醇分解和 "翻腾 "再生醛或醛的过程发生在蒸馏塔的高温段，因此醛或醛可以从蒸馏段顶部的含水和醛的异质共沸物中回收。冷凝和相分离后，下部水层（34;150）无需中和即可排出设备。从蒸馏区底部可以得到取代丙烯醛和碱催化剂溶液的混合物（36;157）。取代的丙烯醛作为产品 (45;173) 被回收，而催化剂溶液 (47;175) 则被回收至醛化反应器。部分 (49;181) 催化剂溶液被净化，以控制坎尼扎罗反应产物的含量。
• Process for the production of 2-alkylalkanol
  申请人：JOHNSON MATTHEY DAVY TECHNOLOGIES LIMITED

  公开号：US10717692B2

  公开（公告）日：2020-07-21

  A process for the production of 2-alkylalkanol from an aldehyde is disclosed. The process comprises the steps of: feeding aldehyde to a reactor (42) operated under condensation and dehydration conditions such that reaction occurs and an unsaturated aldehyde is produced; recovering a stream from the reactor (42) comprising the unsaturated aldehyde and feeding said stream to a first hydrogenation reactor (45) operated under conditions such that at least some of the unsaturated aldehyde is converted to 2-alkylalkanol; recovering the stream from the first hydrogenation reactor (45) comprising the 2-alkylalkanol, one or more of unreacted acrolein, alkylalkenol and alkylalkanal and heavies; passing the stream recovered from the first hydrogenation reactor (45) to a first distillation zone (48) where at least some of the heavies are separated from the stream; recovering a stream from the first distillation zone (48) comprising the 2-alkylalkanol, one or more of unreacted acrolein, alkylalkenol and alkylalkanal, said stream having a reduced heavies content when compared to the stream fed to the first distillation zone (48), and feeding said stream to a second hydrogenation reactor (51) operated under conditions such that at least one of the unreacted acrolein, alkylalkenol and alkylalkanal are converted to 2-alkylalkanol; and recovering a stream from the second hydrogenation reactor (51) comprising an increased 2-alkylalkanol content compared to the stream fed to the second hydrogenation reactor (51).

  本发明公开了一种利用醛生产 2-烷基烷醇的工艺。该工艺包括以下步骤将醛送入在冷凝和脱水条件下运行的反应器（42），使其发生反应并生成不饱和醛；从反应器（42）中回收包含不饱和醛的气流，并将所述气流送入在至少部分不饱和醛转化为 2-烷基烷醇的条件下运行的第一氢化反应器（45）；从第一氢化反应器 (45) 中回收包含 2-烷基烷醇、一种或多种未反应的丙烯醛、烷基烯醇和烷基醛以及重质物的料流；将从第一氢化反应器 (45) 中回收的料流送入第一蒸馏区 (48)，在该区至少将部分重质物从料流中分离出来；从第一蒸馏区（48）回收包含 2-烷基烷醇、未反应的丙烯醛、烷基烯醇和烷基醛中的一种或多种的料流，与送入第一蒸馏区（48）的料流相比，所述料流的重质含量降低，并将所述料流送入第二氢化反应器（51），该反应器的运行条件是未反应的丙烯醛、烷基烯醇和烷基醛中的至少一种转化为 2-烷基烷醇；从第二氢化反应器 (51) 中回收与送入第二氢化反应器 (51) 的流体相比 2-烷基烷醇含量增加的流体。