Process for Manufacturing 1,4-Butanediol from Acrolein

Ichikawa, S.; Ohgomori, Yuji; Sumitani, Naoko; Hayashi, Hideto; Imanari, Makoto

doi:10.1021/ie00042a034

Cited by 9 publications

(6 citation statements)

References 2 publications

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“…[13] The Rh-PomPom system indeed showed high activity, yet with a regioselectivity in favor of the branched aldehyde ( % 65 %) somewhat decreased as compared to Rh-dppe systems (entries 2 and 3). Finally, different tridentate PCNCP R ligands [14] were investigated and shown to favor the formation of the branched aldehyde with good activities, but again the regioselectivities were similar (71-77 %) to those observed with the Rh-dppe system, with marginal influence of the R substituent on the central nitrogen atom (entries [4][5][6][7][8][9][10][11][12].…”

Section: Entrymentioning

confidence: 98%

“…However, reports in the open and patent literatures were only focused on the formation of BDO. Indeed, Ohgomori et al reported the hydroformylation of a variety of 2-vinyl-1,3-dioxane type compounds (i.e., acrolein acetals derived from 1,3-diols) in the presence of Rh-triarylphosphine [6] and Rh-diphosphine [7] catalysts. In all cases, hydroformylation followed by hydrolysis/hydrogenation over Ru and heteropolyacid catalysts supported on charcoal gave BDO in high yields (up to 79 %); the best hydroformylation selectivities toward the linear aldehydes (85 %) so far reported were achieved with a Rh-catalytic system based on the CHDIOP ligand.…”

Section: Introductionmentioning

confidence: 99%

“…In all cases, hydroformylation followed by hydrolysis/hydrogenation over Ru and heteropolyacid catalysts supported on charcoal gave BDO in high yields (up to 79 %); the best hydroformylation selectivities toward the linear aldehydes (85 %) so far reported were achieved with a Rh-catalytic system based on the CHDIOP ligand. [7] Several patents also described acrolein acetal hydroformylation processes for the preparation of BDO with a Rh-phosphite catalyst systems (phosphite = P(OMe) 3 ), which led to selectivity of up to 86 % in favor of the linear aldehyde. [7] Herein we report a detailed study of the hydroformylation of 2-vinyl-5-methyl-1,3-dioxane (VMD), the acetal obtained from acrolein and MPD.…”

Section: Introductionmentioning

confidence: 99%

“…[7] Several patents also described acrolein acetal hydroformylation processes for the preparation of BDO with a Rh-phosphite catalyst systems (phosphite = P(OMe) 3 ), which led to selectivity of up to 86 % in favor of the linear aldehyde. [7] Herein we report a detailed study of the hydroformylation of 2-vinyl-5-methyl-1,3-dioxane (VMD), the acetal obtained from acrolein and MPD. The reaction is performed under homogeneous and biphasic aqueous conditions with a variety of Rh-phosphane systems to possibly The rhodium-catalyzed hydroformylation of 2-vinyl-5-methyl-1,3-dioxane (VMD), the acetal derived from acrolein and 2methyl-1,3-propanediol, has been investigated.…”

Section: Introductionmentioning

confidence: 99%

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Rhodium‐Catalyzed Homogeneous and Aqueous Biphasic Hydroformylation of the Acrolein Acetal 2‐Vinyl‐5‐Methyl‐1,3‐Dioxane

Ternel¹,

Dubois²,

Couturier³

et al. 2013

ChemCatChem

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International audienceThe rhodium-catalyzed hydroformylation of 2-vinyl-5-methyl-1,3-dioxane (VMD), the acetal derived from acrolein and 2-methyl-1,3-propanediol, has been investigated. Under homogeneous conditions, phosphane-based catalysts afforded perfect chemoselectivity for the aldehydes. Catalysts based on diphosphine ligands with a narrow bite angle of approximately 85°, such as 1,2-bis(phenylphosphino)ethane, were found to favor the branched aldehyde 2, with selectivities of up to 78 %, whereas diphosphine ligands with a large bite angle of approximately 110°, such as xantphos, produce the linear aldehyde 1 with up to 91 % selectivity. Control of the 1/2 regioselectivity by means of the P[BOND]Rh[BOND]P bite angle was ascertained with a variety of ethylene-, hydrazino- and CNC-bridged diphosphines, irrespective of electronic factors induced by these ligands. Under aqueous biphasic conditions, chemoselective hydroformylation of VMD proved feasible only with disulfonated xantphos; in this case, remarkable activities (turnover frequencies of up to 1075 molaldehyde molRh−1 h−1 at 120 °C) were observed, with up to 82 % yield for the linear aldehyde. On the other hand, the catalyst based on tetrasulfonated dppe systematically induced the formation of very large amounts of the hydrogenated product

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Section: Entrymentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Rhodium‐Catalyzed Homogeneous and Aqueous Biphasic Hydroformylation of the Acrolein Acetal 2‐Vinyl‐5‐Methyl‐1,3‐Dioxane

Ternel¹,

Dubois²,

Couturier³

et al. 2013

ChemCatChem

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“…1,4-Butanediol was prepared from acrolein and 2-methyl 1,3-propanediol through a multistep process (Figure 30) by using a bifunctional catalyst consisting in 5 wt% Ru and 5 wt% SiW supported. It was found that this catalytic material was active and could also be used in four catalytic cycles, being in each reuse a little more active than in the preceding one, achieving 1,4-butanediol yield values greater than 96% 252 . Figure 30.…”

Section: 4-butanediolmentioning

confidence: 99%