4,8-bis(1,1-dimethylethyl)-6-[2-(1,1-di-methylethyl)-4-methoxyphenoxy]-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin

• 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: 4,8-bis(1,1-dimethylethyl)-6-[2-(1,1-di-methylethyl)-4-methoxyphenoxy]-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin
• 英文别名: 4,8-Ditert-butyl-6-(2-tert-butyl-4-methoxyphenoxy)-2,10-dimethoxybenzo[d][1,3,2]benzodioxaphosphepine
• 化学式: C₃₃H₄₃O₆P
• 分子量: 566.675
• InChiKey: RAMUVMFXEBADSF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.2
• 重原子数：
  40
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4,8-bis(1,1-dimethylethyl)-6-[2-(1,1-di-methylethyl)-4-methoxyphenoxy]-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin 在 水 作用下， 以 1,4-二氧六环 为溶剂， 反应 6.0h， 生成 亚磷酸 、 、 O,O'-3,3'-di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl phosphonate
  参考文献：
  名称：

  用于修饰Rh催化的n-区域选择性烯烃氢甲酰化的双齿亚磷酸酯的水解稳定性

  摘要：

  配体和催化剂的稳定性在均相催化中是几乎被忽略的问题，但对于在技术规模上成功应用该方法至关重要。我们已经研究了水对亚磷酸酯的影响，亚磷酸酯是烯烃在n-区域选择性均相Rh催化加氢甲酰化中应用最广泛的助催化剂。双齿不对称二亚磷酸酯L1以及其两个单亚磷酸酯成分L2和L3的稳定性通过原位NMR光谱法在类似于工业上应用的条件下研究了向水解反应中的H 2 O 3的水解。阐明了水解途径，中间体和动力学。DFT计算用于支持实验发现的数据。与水以非选择性方式反应的酰基亚磷酸酯单元L2被证明比酚亚磷酸酯L3不稳定得多。因此，双齿配体L1的稳定性主要归因于其酚亚磷酸酯部分。相对于亚磷酸酯，过量的水对L1和L2以及它们的Rh复合物的水解作用是一级的。出人意料的是，与Rh的配位显着稳定了单齿配体L2与此相反，二齿配体L1在Rh络合物中分解得更快。NMR光谱提供了亚磷酸盐分解产生的物种的证据，亚磷酸盐也可以作为金属的配

  DOI：

  10.1021/acscatal.6b02185

文献信息

• Stabilization of phosphite ligands in hydroformylation process
  申请人：UNION CARBIDE CHEMICALS & PLASTICS TECHNOLOGY CORPORATION

  公开号：EP0697391A1

  公开（公告）日：1996-02-21

  The present invention provides a hydroformylation process comprising: (1) forming a reaction mixture containing: (a) an olefinic compound, (b) hydrogen, (c) carbon monoxide, (d) a phosphite in which each phosphorus atom is bonded to three oxygen atoms and at least one such oxygen atom is bonded to a carbon atom of an aromatic ring that is adjacent to another carbon atom of said ring having a pendant monovalent group having a steric hindrance at least as great as the steric hindrance of the isopropyl group, (e) a catalytic amount of rhodium, and (f) a Group VIII metal (other than a rhodium) in an amount sufficient to reduce the rhodium-catalyzed decomposition of the phosphite during the hydroformylation process; and (2) maintaining the reaction mixture under conditions at which the olefinic compound reacts with the hydrogen and carbon monoxide to form an aldehyde.

  本发明提供了一种加氢甲酰化工艺，包括：(1) 形成一种反应混合物，其中含有(a) 烯烃化合物，(b) 氢气，(c) 一氧化碳，(d) 亚磷酸酯，其中每个磷原子与三个氧原子键合，且至少一个氧原子与一个芳香环的碳原子键合，该芳香环的碳原子与所述芳香环的另一个碳原子相邻，该芳香环的另一个碳原子上有一个单价基团，该单价基团具有至少与异丙基基团的立体阻碍相同的立体阻碍、(e) 催化量的铑，以及 (f) VIII 族金属（铑除外），其用量足以在氢甲酰化过程中减少亚磷酸酯在铑催化下的分解；(2) 将反应混合物保持在烯烃化合物与氢气和一氧化碳反应生成醛的条件下。
• Process for producing aldehyde acids or salts thereof
  申请人：UNION CARBIDE CHEMICALS & PLASTICS TECHNOLOGY CORPORATION

  公开号：EP0872469A1

  公开（公告）日：1998-10-21

  This invention relates in part to processes for producing one or more substituted or unsubstituted aldehyde acids or salts, e.g., 5-formylvaleric acid or salt, which comprises subjecting one or more substituted or unsubstituted alkadienes, e.g., butadiene, to hydroxycarbonylation in the presence of a hydroxycarbonylation catalyst, e.g., a metal-organophosphorus ligand complex catalyst, and optionally neutralization with a base to produce one or more substituted or unsubstituted unsaturated acids or salts, e.g., pentenoic acid or salt, and subjecting said one or more substituted or unsubstituted unsaturated acids or salts to hydroformylation in the presence of a hydroformylation catalyst, e.g., a metal-organophosphorus ligand complex catalyst, to produce said one or more substituted or unsubstituted aldehyde acids or salts and/or one or more substituted or unsubstituted epsilon caprolactam precursors. This invention also relates in part to reaction mixtures containing one or more substituted or unsubstituted aldehyde acids or salts as the principal product(s) of reaction.

  本发明部分涉及生产一种或多种取代或未取代的醛酸或盐，例如 5-甲酰基戊酸或盐的工艺，其中包括将一种或多种取代或未取代的烯烃，例如丁二烯，在羟基羰基化催化剂，例如金属有机磷配位体络合物催化剂存在下进行羟基羰基化，并可选择地用碱中和、丁二烯，在羟基羰基化催化剂（如金属有机磷配位体络合物催化剂）存在下进行羟基羰基化，并可选择用碱中和，以生成一种或多种取代或未取代的不饱和酸或盐，如戊烯酸或盐，并使所述一种或多种取代或未取代的不饱和酸或盐在氢甲酰化催化剂（如金属有机磷配位体络合物催化剂）存在下进行氢甲酰化反应，以生成所述一种或多种取代或未取代的醛酸或盐和/或一种或多种取代或未取代的epsilon己内酰胺前体。本发明还部分涉及含有一种或多种取代或未取代醛酸或盐作为主要反应产物的反应混合物。
• Process for producing epsilon caprolactones from penten-1-ols
  申请人：UNION CARBIDE CHEMICALS & PLASTICS TECHNOLOGY CORPORATION

  公开号：EP0872483A1

  公开（公告）日：1998-10-21

  This invention relates in part to processes for producing one or more substituted or unsubstituted epsilon caprolactones and/or hydrates and/or esters thereof which comprise subjecting one or more substituted or unsubstituted penten-1-ols to carbonylation in the presence of a carbonylation catalyst, e.g., a metal-organophosphorus ligand complex catalyst, to produce said one or more substituted or unsubstituted epsilon caprolactones and/or hydrates and/or esters thereof. The substituted and unsubstituted epsilon caprolactones and/or hydrates and/or esters thereof produced by the processes of this invention can undergo further reaction(s) to afford desired derivatives thereof, e.g., epsilon caprolactam. This invention also relates in part to reaction mixtures containing one or more substituted or unsubstituted epsilon caprolactones and/or hydrates and/or esters thereof as principal product(s) of reaction.

  本发明部分涉及生产一种或多种取代或未取代的epsilon己内酯和/或其水合物和/或酯的工艺，该工艺包括在羰基化催化剂（如金属-有机磷配位体络合物催化剂）存在下，将一种或多种取代或未取代的戊烯-1-醇进行羰基化，以生产所述一种或多种取代或未取代的epsilon己内酯和/或其水合物和/或酯。通过本发明工艺生产的取代和未取代的epsilon己内酯和/或其水合物和/或酯类可通过进一步反应得到所需的衍生物，如epsilon己内酰胺。本发明还部分涉及含有一种或多种取代或未取代的epsilon己内酯和/或其水合物和/或酯作为主要反应产物的反应混合物。
• Improved metal-ligand complex catalyzed processes
  申请人：UNION CARBIDE CHEMICALS & PLASTICS

  公开号：EP1108707A1

  公开（公告）日：2001-06-20

  This invention relates to a person for separating one or more phosphorus acidic compounds from a reaction product fluid containing said one or more phosphorus acidic compounds, a metal-organophosphite ligand complex catalyst and optionally free organophosphite ligand which process comprises (a) treating said reaction product fluid with water sufficient to remove at least some amount of said one or more phosphorus acidic compounds from said reaction product fluid and (b) treating the water which contains phosphorus acidic compounds removed from said reaction product fluid with an acid removal substance sufficient to remove at least some amount of said one or more phosphorus acidic compounds from said water.

  本发明涉及一种从含有一种或多种磷酸性化合物的反应产物流体中分离一种或多种磷酸性化合物的方法、本发明涉及一种从含有一种或多种磷酸性化合物的反应产物流体中分离出一种或多种磷酸性化合物的工艺，该工艺包括：(a) 用足以从反应产物流体中去除至少一定量的所述一种或多种磷酸性化合物的水处理所述反应产物流体；(b) 用足以从所述水中去除至少一定量的所述一种或多种磷酸性化合物的脱酸物质处理从所述反应产物流体中去除的含有磷酸性化合物的水。
• Hydroformylation process
  申请人：Dow Technology Investments LLC

  公开号：US10023516B2

  公开（公告）日：2018-07-17

  Catalytic metal loss when using a hydroformylation catalyst comprising an organophosphite ligand is ameliorated by adding CO to a strip gas vaporizer.

  通过在带状气体蒸发器中加入一氧化碳，可改善使用包含有机膦配体的加氢甲酰化催化剂时的催化金属损失。