allyl 2,3-dimethylbut-2-yl ether

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: allyl 2,3-dimethylbut-2-yl ether
• 英文别名: 2,3-Dimethyl-2-prop-2-enoxybutane
• 化学式: C₉H₁₈O
• 分子量: 142.241
• InChiKey: OLTVJCQXYUZMPU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  2,3-二甲基-2-丁烯 以52.1%的产率得到allyl 2,3-dimethylbut-2-yl ether
  参考文献：
  名称：

  Production of butane-1,4-diol

  摘要：

  丁二醇是通过将烯丙醇转化为通式的烯丙基t-烷基或-环烷基醚而生产的：其中R.sub.1和R.sub.2各自独立地代表C.sub.1至C.sub.4烷基基团，R.sub.3和R.sub.4各自独立地代表氢原子或C.sub.1至C.sub.3烷基基团，或其中R.sub.1代表C.sub.1至C.sub.4烷基基团，R.sub.2和R.sub.3与它们附着的碳原子一起形成5-成员或6-成员环脂环，R.sub.4代表氢原子或C.sub.1至C.sub.3烷基基团，然后在加氢甲酰化催化剂存在下，以碳一氧化物和氢反应生成通式的相应醛醚：减少通式的相应醛醚以形成通式的相应羟基醚：并裂解得到的通式的羟基醚以给出丁二醇。通常情况下，R.sub.1和R.sub.2各代表一个甲基基团，而R.sub.3和R.sub.4各代表一个氢原子。在裂解通式(II)的羟基醚时释放的通式的烯烃可以回收用于与进一步的烯丙醇反应以形成通式(III)的进一步数量的醚。

  公开号：

  US04503275A1

文献信息

• Aldehyde-ethers
  申请人：Davy McKee (Oil & Chemicals) Limited

  公开号：US04383125A1

  公开（公告）日：1983-05-10

  Aldehyde ethers of the general formula ##STR1## wherein R.sub.1 and R.sub.2 each, independently of the other, represent a C.sub.1 to C.sub.4 alkyl radical, and R.sub.3 and R.sub.4 each, independently of the other, represent a hydrogen atom or a C.sub.1 to C.sub.3 alkyl radical, or wherein R.sub.1 represents a C.sub.1 to C.sub.4 alkyl radical, R.sub.2 and R.sub.3 together with the carbon atoms to which they are attached form a 5-membered or 6-membered cycloaliphatic ring, and R.sub.4 represents a hydrogen atom or a C.sub.1 to C.sub.3 alkyl radical, and wherein Y represents --CH.sub.2 --CH.sub.2 --C.sub.2 or --CH.sub.2 --CH (CH.sub.3)--, are prepared by hydroformylation of a corresponding compound of formula: ##STR2## by reaction with hydrogen and carbon monoxide in the presence of a hydroformylation catalyst, e.g. a rhodium complex catalyst. Preferred compounds include 4-t-butoxybutyraldehyde and 3-t-butoxy-2-methylpropionaldehyde. The compounds are useful chemical intermediates in the production of, for example, butane-1,4-diol, butyrolactone and tetrahydrofuran.

  通式为##STR1##的醛醚，其中R.sub.1和R.sub.2各自独立地表示C.sub.1至C.sub.4烷基基团，而R.sub.3和R.sub.4各自独立地表示氢原子或C.sub.1至C.sub.3烷基基团，或者其中R.sub.1表示C.sub.1至C.sub.4烷基基团，R.sub.2和R.sub.3与它们连接的碳原子一起形成5元环或6元环脂环，R.sub.4表示氢原子或C.sub.1至C.sub.3烷基基团，Y表示--CH.sub.2 --CH.sub.2 --C.sub.2或--CH.sub.2 --CH (CH.sub.3)--，通过与氢气和一氧化碳在存在氢甲酰化催化剂的条件下反应，例如铑配合物催化剂，通过将通式为##STR2##的相应化合物进行氢甲酰化制备而得到。首选化合物包括4-t-丁氧基丁醛和3-t-丁氧基-2-甲基丙醛。这些化合物在生产丁二醇，丁内酯和四氢呋喃等化学中间体中有用。
• Production of tetrahydrofuran
  申请人：Davy McKee (Oil & Chemicals) Limited

  公开号：US04287127A1

  公开（公告）日：1981-09-01

  Tetrahydrofuran is produced by converting allyl alcohol to an allyl t-alkyl or -cycloalkyl ether of the general formula: ##STR1## wherein R.sub.1 and R.sub.2 each, independently of the other, represent a C.sub.1 to C.sub.4 alkyl radical, and R.sub.3 and R.sub.4 each, independently of the other, represent a hydrogen atom or a C.sub.1 to C.sub.3 alkyl radical, or wherein R.sub.1 represents a C.sub.1 to C.sub.4 alkyl radical, R.sub.2 and R.sub.3 together with the carbon atoms to which they are attached form a 5-membered or 6-membered cycloaliphatic ring, and R.sub.4 represents a hydrogen atom or a C.sub.1 to C.sub.3 alkyl radical, followed by reacting resulting compound of formula (III) under hydroformylation conditions with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst to form a corresponding aldehyde-ether of the general formula: ##STR2## reducing resulting aldehyde-ether of the general formula (I) a corresponding hydroxy-ether of the general formula: ##STR3## and cleaving resulting hydroxy-ether of the general formula (II) under dehydrating conditions to produce tetrahydrofuran. Typically R.sub.1 and R.sub.2 each represent a methyl group while R.sub.3 and R.sub.4 each represent a hydrogen atom. The alkene of the general formula: ##STR4## released upon cleavage of the hydroxy-ether of formula (II) can be recycled for reaction with further allyl alcohol to form a further quantity of the ether of the general formula (III).

  四氢呋喃是通过将烯丙醇转化为通式为：其中R.sub.1和R.sub.2各自独立地代表一个C.sub.1到C.sub.4烷基基团，R.sub.3和R.sub.4各自独立地代表一个氢原子或一个C.sub.1到C.sub.3烷基基团，或其中R.sub.1代表一个C.sub.1到C.sub.4烷基基团，R.sub.2和R.sub.3与它们连接的碳原子一起形成一个5-或6-环脂环，R.sub.4代表一个氢原子或一个C.sub.1到C.sub.3烷基基团，然后在加氢甲酰化催化剂的存在下，将通式为（III）的产物在加氢甲酰化条件下与一氧化碳和氢反应，形成通式为：将通式为（I）的产物还原为相应的羟基醚通式为：并在脱水条件下裂解通式为（II）的产物，以生成四氢呋喃。通常R.sub.1和R.sub.2各代表一个甲基基团，而R.sub.3和R.sub.4各代表一个氢原子。在脱水-醚通式（II）裂解时释放的通式为：的烯烃可以回收用于与进一步的烯丙醇反应，形成通式为（III）的进一步数量的醚。
• Production of butyrolactone
  申请人：DAVY McKEE (LONDON) LIMITED

  公开号：EP0018162A1

  公开（公告）日：1980-10-29

  Butyrolactone is produced by oxidizing an aldehyde-ether of the general formula: wherein R, and R2 each, independently of the other, represent a C, to C4 alkyl radical, and R3 and R4 each, independently of the other, represent a hydrogen atom or a C, to C3 alkyl radical, or wherein R, represents a C, to C4 alkyl radical, R2 and R3 together with the carbon atoms to which they are attached form a 5-membered or 6-membered cycloaliphatic ring, and R4 represents a hydrogen atom or a C, to C3 alkyl radical, to form an acid ether of the general formula: followed by deetherification, dehydration and cyclization. Oxidation can be carried out with e.g. gaseous oxygen. Deetherification can be accomplished by contact with an acid catalyst, whilst cyclization may occur spontaneously. A cyclic process is described in which allyl alcohol is converted by reaction with a suitable olefin, e.g. iso-butylene, to an allyl ether of a tertiary alcohol, e.g. allyl t-butyl ether, which is then hydroformylated to form the compound of formula (I), whilst the olefin, e.g. iso-butylene, released on deetherification of the acid ether of formula (II), is recycled to the allyl ether formation step.

  丁内酯是通过氧化通式如下的醛醚而制得的： 其中 R 和 R2 各自独立地代表一个 C 至 C4 烷基，R3 和 R4 各自独立地代表一个氢原子或一个 C 至 C3 烷基，或其中 R 代表一个 C 至 C4 烷基，R2 和 R3 与它们所连接的碳原子一起形成一个 5 元或 6 元环脂族环，R4 代表一个氢原子或一个 C 至 C3 烷基，形成通式的酸醚： 然后进行脱醚、脱水和环化反应。氧化作用可以用气态氧气等进行。脱醚可以通过与酸催化剂接触来完成，而环化则可能自发发生。描述了一种循环工艺，其中烯丙基醇通过与合适的烯烃（如异丁烯）反应转化为叔醇的烯丙基醚（如烯丙基叔丁基醚），然后进行氢甲酰化反应生成式（I）化合物，而式（II）酸醚脱醚反应释放的烯烃（如异丁烯）被回收至烯丙基醚形成步骤。
• Process for removing hydroperoxides and aldehydes from allyl-alkyl ether
  申请人：UNION CARBIDE CORPORATION

  公开号：EP0060523A1

  公开（公告）日：1982-09-22

  Described herein is a process for the conversion of hydroperoxides, present in allyl-alkyl ethers to products including α,β-unsaturated aldehydes and for reducing such α,β-unsaturated aldehydes to alcohols prior to the use of the ether as a feedstock in a hydroformylation reaction to produce the corresponding ether aldehyde. The process involves contacting the ether with a metal hydride, either in aqueous solution and/or by means of an ion exchange resin. Such treatment decomposes the hydroperoxides and then reduces their α,β-unsaturated aldehyde decomposition products, thereby reducing the catalyst inhibition period present in the hydroformylation reaction which is observed when such α,β-unsaturated aldehyde impurities are present.

  本文介绍了一种将烯丙基烷基醚中的氢过氧化物转化为包括α，β-不饱和醛在内的产品的工艺，以及在使用醚作为加氢甲酰化反应的原料以生产相应的醚醛之前，将这种α，β-不饱和醛还原为醇的工艺。该工艺包括在水溶液中和/或通过离子交换树脂使醚与金属氢化物接触。这种处理方法可使氢过氧化物分解，然后减少其 α、β-不饱和醛分解产物，从而缩短加氢甲酰化反应中的催化剂抑制期。
• Aldehyde-ethers and process for their production
  申请人：DAVY McKEE (LONDON) LIMITED

  公开号：EP0018161B1

  公开（公告）日：1983-05-25