Rh-Catalyzed Hydroformylation of 1,3-Butadiene and Pent-4-enal to Adipaldehyde in CO2-Expanded Media,Industrial & Engineering Chemistry Research

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Rh-Catalyzed Hydroformylation of 1,3-Butadiene and Pent-4-enal to Adipaldehyde in CO2-Expanded Media
Industrial & Engineering Chemistry Research ( IF 3.8 ) Pub Date : 2019-11-08 , DOI: 10.1021/acs.iecr.9b05184
Maria-José Tenorio ₁ , Raghunath V. Chaudhari _{1,

2} , Bala Subramaniam _{1,

2}

Affiliation

The homogeneous hydroformylation of pent-4-enal, the preferred aldehyde intermediate from 1,3-butadiene hydroformylation, was systematically investigated with Rh catalyst complexes in neat and CO₂-expanded toluene media at 40–80 °C, syngas partial pressures ranging from 5–50 bar, and different ligand/Rh ratios. At similar operating conditions, the TOFs are generally greater with Rh/DIOP relative to a Rh/TPP catalyst. On both catalyst complexes, the chemoselectivity toward the dialdehydes ranges from 75%–100%, with the maximum adipaldehyde selectivity reaching approximately 75% (n/i ∼ 3) at 60 °C, 10 bar syngas, and molar DIOP/Rh ratio of 2.5. By using CO₂-expanded toluene, the regioselectivity toward the adipaldehyde (desired product), and therefore its yield, is significantly enhanced. Interestingly, even with the simple Rh/TPP catalyst complex, adipaldehyde selectivity of up to 85% (n/i ∼ 5.6) is achieved at 60 °C, 10 bar syngas, and 50 bar CO₂. The beneficial effects of CO₂-expanded media are attributed to the facile tunability of the H₂/CO ratio in such a phase with a fixed syngas feed composition. This approach to accelerate pent-4-enal hydroformylation to form adipaldehyde could also help in overcoming equilibrium limitations typically associated with the catalytic isomerization of pent-3-enal (the dominant product from 1,3-butadiene hydroformylation) to pent-4-enal (the preferred isomer).

中文翻译：

在CO ₂膨胀介质中Rh催化1,3-丁二烯和Pent-4-烯醛的羰基化为己二醛

在40-80°C的纯净和CO ₂膨胀的甲苯介质中，使用Rh催化剂配合物，在40-80°C，合成气分压范围为5–50 bar，以及不同的配体/ Rh比。在相似的操作条件下，相对于Rh / TPP催化剂，Rh / DIOP的TOF通常更大。在两种催化剂配合物上，对二醛的化学选择性范围为75％–100％，在60°C，10 bar合成气和DIOP / Rh摩尔比为60°C时，最大的己二醛选择性达到约75％（n / i〜3）。 2.5。通过使用CO ₂在甲苯膨胀后，对己二醛（所需产物）的区域选择性大大提高。有趣的是，即使使用简单的Rh / TPP催化剂配合物，在60°C，10 bar合成气和50 bar CO _{2的条件下}，对己二醛的选择性仍可达到85％（n / i〜5.6）。CO ₂膨胀介质的有益作用归因于H ₂的易调谐性具有固定的合成气进料组成的这样的相中的/ CO比。这种加速戊4-烯醛加氢甲酰化形成己二醛的方法还可以帮助克服通常与戊3-烯醛（1,3-丁二烯加氢甲酰化的主要产物）催化异构化为戊4-烯醛相关的平衡限制。（优选的异构体）。

更新日期：2019-11-08

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