Formation of 1,6-hexanedial via hydroformylation of 1,3-butadiene

Ohgomori, Yuji; Suzuki, Naoki; Sumitani, Naoko

doi:10.1016/s1381-1169(98)00129-0

Cited by 29 publications

(34 citation statements)

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“…4-Methylpent-4-enal 4 was isolated as a mixture with 3methylpent-3-enal by preparative GC and identified by 1 H-NMR and MS: 1 H-NMR (400 MHz, CDCl 3 ): d = 1.62 (s, 3H, C-CH 3 ), 2.28-2.30 (m, 2H, C(O)H-CH 2 ), 2.54 (t, 2H, C-CH 2 ), 9.54 (dt, 1H, C(O)H); m/z 98 (M+, 3%), 83 (18), 79 (9), 77 (2), 70 (54), 69 (35), 67 (7), 55 (68), 53 (24), 41 (100), 39 (81). (16), 80 (5), 70 (14), 69 (33), 67 (7), 55 (40), 53 (20), 51 (10), 41 (100), 39 (52).…”

Section: Analyticsmentioning

confidence: 99%

Selective hydroformylation-hydrogenation tandem reaction of isoprene to 3-methylpentanal

2011

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The hydroformylation of isoprene catalysed by rhodium phosphine complexes usually yields a broad mixture of the monoaldehydes, the isomeric methylpentenals, as well as the dialdehyde 3-methyl-1,6-hexandial. Under usual reaction conditions the products of a consecutive hydrogenation are only formed as minor by-products. Surprisingly we discovered now a selective auto-tandem reaction consisting of a hydroformylation and a hydrogenation step if a rhodium complex with the chelate ligand bis(diphenylphosphino)ethane is used as catalyst. If branched aromatic solvents like cumene are applied the conversion of isoprene is nearly quantitatively and the yield of the tandem product 3-methylpentanal amounts to 85%.

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Section: Analyticsmentioning

confidence: 99%

Selective hydroformylation-hydrogenation tandem reaction of isoprene to 3-methylpentanal

2011

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“…The results are generally in agreement with those reported in earlier studies. Ohgomori et al 7 report that pent-3-enal selectivity varies between 53%− 67% and that the sum of pent-4-enal plus adipaldehyde selectivities varies between 33%−37%. Results from the current work confirm that the selectivity toward pent-3-enal is dominant (50%−62%) at all conditions studied and that the adipaldehyde selectivity ranges from 18% to 32%.…”

Section: Industrial and Engineering Chemistry Researchmentioning

confidence: 99%

Rh-Catalyzed Hydroformylation of 1,3-Butadiene and Pent-4-enal to Adipaldehyde in CO₂-Expanded Media

Tenorio

Chaudhari

Subramaniam

2019

Ind. Eng. Chem. Res.

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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 CO 2 -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 CO 2 -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 CO 2 . The beneficial effects of CO 2 -expanded media are attributed to the facile tunability of the H 2 /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 1,3butadiene hydroformylation) to pent-4-enal (the preferred isomer).

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“…However, by using 1,3‐dienes, such as butadiene, various very interesting products can be formed under typical hydroformylation reaction conditions. (E/Z)‐3‐pentenal and 4‐pentenal are attractive intermediates for the production of valuable C6 compounds such as adipic acid, hexamethylenediamine and 1,6‐hexanediol via the selective conversion of 1,6‐hexanedial (adipaldehyde) as a central intermediate (Figure ) …”

Section: C4 Moleculesmentioning

confidence: 99%

“…Many research groups investigated hydroformylation of butadiene experimentally. In recent decades, however, the selectivity for adipic aldehyde has been low, which has led to further research . The highest reported selectivities to adipaldehyde in butadiene hydroformylation so far is 50 % .…”

Section: C4 Moleculesmentioning

confidence: 99%

“…However, a tandem catalytic system for directly converting butadiene into adipic aldehyde, although of very high industrial interest, has not been established in the chemical industry. BASF reports on a 60 % selectivity to the desired dialdehyde and the corresponding diol via a two‐step approach and researchers at Mitsubishi on a selectivity of up to 37 % for the direct tandem catalysis. In addition, UCC has put effort in achieving this reaction economically.…”

Section: C4 Moleculesmentioning

confidence: 99%

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Homogeneously Catalyzed 1,3‐Diene Functionalization – A Success Story from Laboratory to Miniplant Scale

et al. 2018

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For many years, the efficient use of resources has been a major and permanent challenge for the chemical industry. The implementation of alternative resources such as renewables and carbon dioxide has been a subject of considerable discussion, but also the more efficient use of long known bulk chemicals is of great interest. Among them, 1,3‐dienes such as 1,3‐butadiene from the C4 cut of the naphtha cracker as well as isoprene, piperylene and cyclopentadiene from the corresponding C5 section are important substrates. These dienes are presently employed in various markets, with the greatest importance being in the production of polymers and copolymers. However, homogeneous transition metal catalysis has proven to be a versatile tool to functionalize these important 1,3‐dienes to low molecular weight fine chemicals by introducing, for example, nitrogen, oxygen or silicon. Hence, an upgraded use of the corresponding products as agrochemicals, pharmaceuticals, fragrances or special detergents is close at hand. The main approaches in the topic of homogeneous functionalization reactions of the industrially relevant 1,3‐dienes will be summarized and discussed within the present article. Besides that, novel applications including renewable 1,3‐dienes, for example β‐myrcene and β‐farnesene, as well as the application of CO2 in telomerization, will be critically discussed.

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Formation of 1,6-hexanedial via hydroformylation of 1,3-butadiene

Cited by 29 publications

References 6 publications

Selective hydroformylation-hydrogenation tandem reaction of isoprene to 3-methylpentanal

Selective hydroformylation-hydrogenation tandem reaction of isoprene to 3-methylpentanal

Rh-Catalyzed Hydroformylation of 1,3-Butadiene and Pent-4-enal to Adipaldehyde in CO₂-Expanded Media

Homogeneously Catalyzed 1,3‐Diene Functionalization – A Success Story from Laboratory to Miniplant Scale

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Formation of 1,6-hexanedial via hydroformylation of 1,3-butadiene

Cited by 29 publications

References 6 publications

Selective hydroformylation-hydrogenation tandem reaction of isoprene to 3-methylpentanal

Selective hydroformylation-hydrogenation tandem reaction of isoprene to 3-methylpentanal

Rh-Catalyzed Hydroformylation of 1,3-Butadiene and Pent-4-enal to Adipaldehyde in CO2-Expanded Media

Homogeneously Catalyzed 1,3‐Diene Functionalization – A Success Story from Laboratory to Miniplant Scale

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Rh-Catalyzed Hydroformylation of 1,3-Butadiene and Pent-4-enal to Adipaldehyde in CO₂-Expanded Media