Hydroformylation of piperylene and efficient catalyst recycling in propylene carbonate

Neubert, Peter; Fuchs, Sarah; Behr, Arno

doi:10.1039/c5gc00020c

Cited by 32 publications

(11 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This corresponds to a turnover frequency (TOF) of over 739 mol mol −1 h −1 , which is the highest rate obtained to date for the hydroformylation of a 1,3‐diene. Similar hydroformylation reactions of conjugated linear dienes reached TOFs of 90 for myrcene, 600 for isoprene, 39 for 1,3‐piperylene, and 500 for 1,3‐butadiene (all TOFs were calculated as moles of carbonylation product per mole of Rh and hour at full conversion, given in mol mol −1 h −1 ). Reducing the catalyst concentration led to even higher TOFs but slowed the hydrogenation down significantly.…”

Section: Methodsmentioning

confidence: 94%

Renewable Surfactants through the Hydroaminomethylation of Terpenes

et al. 2017

Self Cite

View full text Add to dashboard Cite

A catalytic system was developed to enable the use of industrially available terpenes (e.g., β‐myrcene, β‐farnesene) in hydroaminomethylation to obtain renewable building blocks for surfactants in two steps. This homogeneously catalyzed tandem reaction includes both hydroformylation and enamine condensation steps, followed by hydrogenation. Under the optimized conditions, the Rh/1,2‐bis(diphenylphosphino)ethane catalytic system delivers products in high yields (70 %) after short reaction times (3 h) with unprecedentedly high turnover frequency (TOF) values for the hydroformylation of 1,3‐dienes of over 739 mol mol−1 h−1. This is the highest TOF reported to date for the hydroformylation of a 1,3‐diene. Furthermore, regioselectivities of 97 % and above were observed in the hydroformylation step, which is extraordinarily high for the conversion of 1,3‐dienes. The terpene‐derived amines obtained were further functionalized to quaternary ammonium compounds that were found to show surface activity quite similar to that of industrially available quaternary ammonium compounds. The hydroaminomethylation of terpenes achieves higher step efficiency than industrial means and makes use of an alternative, renewable feedstock to synthesize more environmentally friendly surfactants.

show abstract

Section: Methodsmentioning

confidence: 94%

Renewable Surfactants through the Hydroaminomethylation of Terpenes

et al. 2017

Self Cite

View full text Add to dashboard Cite

show abstract

“…Our working group achieved very promising yields of the unsaturated aldehyde by hydroformylation of piperylene in which the double bond is conjugated to the aldehyde moiety 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 ( Figure 33). [79] Further hydrogenation is prevented at this position. The use of a rhodium/Xantphos catalytic system in the green solvent propylene carbonate (PC) allows for both the recovery of the product fraction by distillation and the reuse of the catalyst-containing PC-phase for recycling at once.…”

Section: Carbonylationmentioning

confidence: 99%

“…Our working group achieved very promising yields of the unsaturated aldehyde by hydroformylation of piperylene in which the double bond is conjugated to the aldehyde moiety (Figure ) . Further hydrogenation is prevented at this position.…”

Section: C5 Moleculesmentioning

confidence: 99%

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

et al. 2018

Self Cite

View full text Add to dashboard Cite

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.

show abstract

“…The hydroformylation of 1,3-butadiene, isoprene and piperylene is useful for the synthesis of commodity products. [14][15][16][17][18] Also, 1,3-dienes moieties often occur in natural products, and their hydroformylation leads to aldehydes of interest for the fragrance industry. [19][20][21] However, hydroformylation of this kind of substrates is particularly difficult to achieve.…”

Section: Insert Schemementioning

confidence: 99%

Tandem hydroformylation/isomerization/hydrogenation of bio-derived 1-arylbutadienes for the regioselective synthesis of branched aldehydes

Vieira

Granato

Gusevskaya

et al. 2020

Applied Catalysis A: General

View full text Add to dashboard Cite

The rhodium-catalyzed hydroformylation of 1-arylbutadienes derived from lignocellulosic bio-resources has been carried out in toluene and green solvents. In the presence of DPPE and XANTPHOS ligands, a regioselective Markovnikov Rh-H insertion takes place resulting in branched aldehydes in high selectivity, which contrasts with previous results obtained from aliphatic conjugated dienes. Depending on the nature of the diphosphine ligand, conjugated enals or saturated aldehydes are obtained in good to excellent selectivity. The later have a potential interest for fragrance industry, as they are homologous to commercial fragrance ingredients.

show abstract

Hydroformylation of piperylene and efficient catalyst recycling in propylene carbonate

Cited by 32 publications

References 41 publications

Renewable Surfactants through the Hydroaminomethylation of Terpenes

Renewable Surfactants through the Hydroaminomethylation of Terpenes

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

Tandem hydroformylation/isomerization/hydrogenation of bio-derived 1-arylbutadienes for the regioselective synthesis of branched aldehydes

Contact Info

Product

Resources

About