3-benzyloxymethylcyclohexanone | 108743-93-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-benzyloxymethylcyclohexanone
• 英文别名: 3-<(benzyloxy)methyl>cyclohexan-1-one；3-[(Benzyloxy)methyl]cyclohexanone；3-(phenylmethoxymethyl)cyclohexan-1-one
• CAS: 108743-93-7
• 化学式: C₁₄H₁₈O₂
• 分子量: 218.296
• InChiKey: HQYNKMFMUGOJEZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-benzyloxymethylcyclohexanone 在 盐酸羟胺 、 sodium acetate 作用下， 以 乙醇 为溶剂， 生成 3-benzyloxymethylcyclohexanone oxime
  参考文献：
  名称：

  Imide derivatives, and their production and use

  摘要：

  公式为：##STR1## 其中 Z 是一个具有以下结构的基团：##STR2## 在其中，取代基在此处定义，n 是 0 到 1 的整数；D 是一个具有以下结构的基团：--(CH.sub.2).sub.p --A--(CH.sub.2).sub.q -- 其中 A 是一个非芳香烃环，可选择地与较低的烷基链或氧原子桥接，所述非芳香烃环和所述较低的烷基链各自可选择地取代至少一个较低的烷基，p 和 q 各自是 0、1 或 2 的整数；Ar 是一个芳香基团，一个杂环芳香基团，一个苯甲酰基团，一个苯氧基团或一个苯硫基团，G 是 >N--，>CH-- 或 >COH-- 或 Ar 是一个联苯甲基亚基团，G 是 >C.dbd.，上述所有基团均可选择地取代至少一个较低烷基、较低烷氧基和卤素；以及其酸盐，作为抗精神病药物。

  公开号：

  US05532372A1
• 作为产物：
  描述：

  3-环己烯-1-甲醇 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 3-benzyloxymethylcyclohexanone
  参考文献：
  名称：

  Regiochemical control of the ring-opening of 1,2-epoxides by means of chelating processes. 2. Synthesis and reactions of the cis- and trans-oxides of 4-[(benzyloxy)methyl]cyclohexene, 3-cyclohexenemethanol, and methyl 3-cyclohexenecarboxylate

  摘要：

  The synthesis of the diastereoisomeric epoxides cis-1b-d and trans-2b-d and the products of their ring-opening by various nucleophiles are described. The results of the ring-openings of the trans-epoxides 2b-d can be rationalized by combining stereoelectronic and conformational arguments. However, the regioselectivity of the ring-openings of the cis-epoxides 1b-d can, in principle, be influenced by the chelation of a metal ion by the oxygen atom of the epoxy group and that of the substituent on the 4-position. The results of the reactions of the cis-epoxides 1b-d indicate that, to some degree, chelation is indeed a factor. How important a factor it is is dependent both on the reaction conditions and on the concentration and nature of the metal ion. In the ring-openings of the cis-epoxides 1b and 1d, chelation seems to be a larger factor than it is in the ring-openings of cis-epoxide 1c. However, in no case is chelation as large a factor as it was in the ring-openings of the cis-epoxide 1a, which was studied earlier. On the other hand, the autocatalyzed methanolysis, under neutral conditions, of epoxy acid 1e, followed by CH2N2 methylation of the crude product, afforded a mixture of the two regioisomeric hydroxy ethers in which the C-2-type compound predominates. This result suggests that intramolecular hydrogen bonding may determine the reactive conformation of 1e.

  DOI：

  10.1021/jo00031a018

文献信息

• Regiochemical Control of the Ring Opening of 1,2-Epoxides by Means of Chelating Processes. Part 14: Regioselectivity of the Opening Reactions with MeOH of Remote O-Substituted 1,2-Epoxycyclohexanes under Gas-Phase Operating Conditions
  作者：Paolo Crotti、Valeria Di Bussolo、Lucilla Favero、Mauro Pineschi、Francesco Marianucci、Gabriele Renzi、Giuseppina Amici、Graziella Roselli

  DOI：10.1016/s0040-4020(00)00643-8

  日期：2000.9

  was determined in the gas-phase in opening reactions with MeOH, using a gaseous acid (D3+, CnH5+, Me2F+) as the promoting agent. The results obtained indicate the incursion in the opening process in the gas phase of H+(or D+)-mediated chelated bidentate species completely absent in the corresponding reactions (methanolysis) carried out in the condensed phase.

  使用气态酸（D 3 +，C n H 5 +，Me 2 F +）作为促进剂，在与MeOH进行开环反应的气相中，确定了具有远距离O-官能度的环己烯氧化物的区域化学行为。所获得的结果表明，在缩合相中进行的相应反应（甲烷分解）中完全不存在H +（或D +）介导的螯合双齿物质在气相中的打开过程。
• Carbonyl 1,2-transposition through triflate-mediated α-amination
  作者：Zhao Wu、Xiaolong Xu、Jianchun Wang、Guangbin Dong

  DOI：10.1126/science.abl7854

  日期：2021.11.5

  Chemists devote tremendous effort to the precise placement of oxygens in molecular frameworks. Wu et al . report a convenient method to shift the oxygen in a carbonyl group to an adjacent carbon center. After activation of the oxygen to an alkenyl triflate, cooperative catalysis by palladium and norbornene adds nitrogen to the neighboring carbon while displacing the triflate with hydride. Hydrolysis then produces the desired shifted ketone. The protocol is well suited to late-stage variation of complex molecules during drug optimization. —JSY

  标题：酮转移的谨慎编排 化学家们致力于在分子框架中精确放置氧原子。吴等人报告了一种方便的方法，将羰基中的氧转移到相邻的碳中心。在将氧活化为烯基三氟乙酸酯后，钯和环辛烯的协同催化作用在邻近碳上加入氮，同时用氢化物取代三氟乙酸酯。然后水解产生所需的转移酮。该协议非常适合在药物优化期间对复杂分子进行后期变异。 —JSY
• METHOD FOR SYNTHESIZING OPTICALLY ACTIVE CARBONYL COMPOUNDS
  申请人：BASF SE

  公开号：US20180057437A1

  公开（公告）日：2018-03-01

  The present invention relates to a process for the preparation of an optically active carbonyl compound by asymmetric hydrogenation of a prochiral α,β-unsaturated carbonyl compound with hydrogen in the presence of at least one optically active transition metal catalyst that is soluble in the reaction mixture and which has rhodium as catalytically active transition metal and a chiral, bidentate bisphosphine ligand, wherein the reaction mixture during the hydrogenation of the prochiral α,β-unsaturated carbonyl compound additionally comprises at least one compound of the general formula (I): in which R 1 , R 2 : are identical or different and are C 6 - to C 10 -aryl which is unsubstituted or carries one or more, e.g. 1, 2, 3, 4 or 5, substituents which are selected from C 1 - to C 6 -alkyl, C 3 - to C 6 -cycloalkyl, C 6 - to C 10 -aryl, C 1 - to C 6 -alkoxy and amino; Z is a group CHR 3 R 4 or aryl which is unsubstituted or carries one or more, e.g. 1, 2, 3, 4 or 5, substituents which are selected from C 1 - to C 6 -alkyl, C 3 - to C 6 -cycloalkyl, C 6 - to C 10 -aryl, C 1 - to C 6 -alkoxy and amino, wherein R 3 and R 4 are as defined in the claims and the description.

  本发明涉及一种通过在至少一种可溶于反应混合物中的光学活性过渡金属催化剂的存在下，将可溶性光学活性过渡金属铑和手性双膦配体作为催化活性过渡金属的α，β-不对称氢化的可半手性α，β-不饱和羰基化合物与氢气反应制备光学活性羰基化合物的方法。在氢化可半手性α，β-不饱和羰基化合物的过程中，反应混合物中还包括至少一种符合一般式（I）的化合物：其中 R1、R2：相同或不同，为未取代或带有一个或多个（例如1、2、3、4或5个）C6到C10芳基取代基的化合物，所述取代基选自C1到C6烷基、C3到C6环烷基、C6到C10芳基、C1到C6烷氧基和氨基；Z是一种基团CHR3R4或未取代或带有一个或多个（例如1、2、3、4或5个）取代基的芳基，所述取代基选自C1到C6烷基、C3到C6环烷基、C6到C10芳基、C1到C6烷氧基和氨基，其中R3和R4如权利要求和说明书中定义。
• Method for the Production of Optically Active Carbonyl
  申请人：Jakel Christoph

  公开号：US20080269528A1

  公开（公告）日：2008-10-30

  The present invention relates to a process for preparing optically active carbonyl compounds by asymmetrically hydrogenating α,β-unsaturated carbonyl compounds in the presence of optically active transition metal catalysts which are soluble in the reaction mixture and have at least one carbon monoxide ligand. The present invention especially relates to a process for preparing optically active aldehydes or ketones, in particular citronellal, by asymmetrically hydrogenating the corresponding optically active α,β-unsaturated aldehydes or ketones.

  本发明涉及一种通过在存在可溶于反应混合物中并具有至少一个一氧化碳配体的光学活性过渡金属催化剂的情况下，对α，β-不饱和羰基化合物进行不对称氢化的方法。本发明特别涉及一种通过对相应的光学活性α，β-不饱和醛或酮进行不对称氢化而制备光学活性醛或酮的方法，特别是柠檬醛。
• Imide derivatives and their production and use
  申请人：Sumitomo Pharmaceuticals Company, Limited

  公开号：US05780632A1

  公开（公告）日：1998-07-14

  An imide compound of the formula: ##STR1## wherein Z is a group of the formula: ##STR2## in which B is a carbonyl group or a sulfonyl group, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each a hydrogen atom or a lower alkyl group, or R.sup.1 and R.sup.2 or R.sup.1 and R.sup.3 may be combined together to make a non-aromatic hydrocarbon ring or R.sup.1 and R.sup.3 may be combined together to make an aromatic ring, said non-aromatic hydrocarbon ring being optionally bridged with a lower alkylene group or an oxygen atom therein and said aromatic ring, said non-aromatic hydrocarbon ring and said lower alkylene group being each optionally substituted with at least one lower alkyl, and n is an integer of 0 or 1; D is a group of the formula: --(CH.sub.2).sub.p --A--(CH.sub.2).sub.q -- in which A is a non-aromatic hydrocarbon ring optionally bridged with a lower alkylene group or an oxygen atom, said non-aromatic hydrocarbon ring and said lower alkylene group being each optionally substituted with at least one lower alkyl, and p and q are each an integer of 0, 1 or 2; and Ar is an aromatic group, a heterocyclic aromatic group, a benzoyl group, a phenoxy group or a phenylthio group and G is ##STR3## or Ar is a biphenylmethylidene group and G is ##STR4## all of the above groups being each optionally substituted with at least one of lower alkyl, lower alkoxy and halogen; and its acid addition salts, useful as an antipsycotic agent.

  化合物的imide公式：##STR1## 其中Z是公式的一个基团：##STR2## 其中B是一个羰基或磺酰基，R.sup.1、R.sup.2、R.sup.3和R.sup.4分别是氢原子或较低的烷基基团，或R.sup.1和R.sup.2或R.sup.1和R.sup.3可以结合在一起形成非芳香烃环，或R.sup.1和R.sup.3可以结合在一起形成芳香环，所述的非芳香烃环可以选择地与较低的烷基烷基或其中的氧原子桥接，所述的芳香环、非芳香烃环和较低的烷基烷基可以选择地被至少一个较低的烷基取代，n是0或1的整数；D是公式的一个基团：--(CH.sub.2).sub.p --A--(CH.sub.2).sub.q -- 其中A是一个非芳香烃环，可以选择地与较低的烷基烷基或其中的氧原子桥接，所述的非芳香烃环和较低的烷基烷基可以选择地被至少一个较低的烷基取代，p和q均为0、1或2的整数；Ar是一个芳香基团、杂环芳香基团、苯甲酰基、苯氧基或苯基硫基，G是##STR3## 或Ar是一个联苯甲基亚基，G是##STR4## 所有上述基团均可以选择地被至少一个较低的烷基、较低的烷氧基和卤素取代；以及其酸加成盐，用作抗精神病药物。