4494-16-0Relevant academic research and scientific papers
Chain Multiplication of Fatty Acids to Precise Telechelic Polyethylene
Witt, Timo,H?u?ler, Manuel,Kulpa, Stefanie,Mecking, Stefan
supporting information, p. 7589 - 7594 (2017/06/13)
Starting from common monounsaturated fatty acids, a strategy is revealed that provides ultra-long aliphatic α,ω-difunctional building blocks by a sequence of two scalable catalytic steps that virtually double the chain length of the starting materials. The central double bond of the α,ω-dicarboxylic fatty acid self-metathesis products is shifted selectively to the statistically much-disfavored α,β-position in a catalytic dynamic isomerizing crystallization approach. “Chain doubling” by a subsequent catalytic olefin metathesis step, which overcomes the low reactivity of this substrates by using waste internal olefins as recyclable co-reagents, yields ultra-long-chain α,ω-difunctional building blocks of a precise chain length, as demonstrated up to a C48 chain. The unique nature of these structures is reflected by unrivaled melting points (Tm=120 °C) of aliphatic polyesters generated from these telechelic monomers, and by their self-assembly to polyethylene-like single crystals.
COMBINED SYNTHESIS OF A NITRILE-ESTER/ACID AND OF A DIESTER/DIACID
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Paragraph 0137-0138, (2016/03/13)
A method for the combined synthesis of a mono-unsaturated nitrile-ester(acid) and of a bi-functional carbonyl compound, wherein it includes a step including the cross metathesis mc1 of an unsaturated fatty acid/ester compound with an unsaturated nitrile compound, in which mc1 is performed with partial conversion such as to obtain and recover, separately, at least the following products: a mono-unsaturated nitrile-ester/acid and a symmetrical compound, diester or diacid respectively including a double bond located in the middle of the molecular chain of compound, and subsequently a step including the oxidation cleavage cp2 of the double bond of compound, such as to form a single type of carbonyl compound having formula R2-(CH2)n-COR′, in which R′ is H or OH, depending on the operating conditions selected for the oxidation cleavage cp2. Also, the production of monomers for the polymer industry.
METHOD FOR SYNTHESISING BIOBASED UNSATURATED ACIDS
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Paragraph 0071-0081, (2015/12/07)
The invention relates to a method for preparing a compound of formula (I), wherein n is an integer from 1 to 21,said method comprises reacting a light olefin fraction, in the presence of a metathesis catalyst, with a compound having from 10 to 24 carbon atoms, of the following formula (II): wherein, n is an integer from 1 to 21,R corresponds to a hydrogen atom or an alkyl or alkenyl chain from 1 to20 carbon atoms optionally substituted by at least one hydroxyl group, said compound of formula (II) being used alone or in a mixture of compounds of formula (II).
TRIACYLGLYCEROL OLIGOMERS
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Paragraph 0050, (2015/11/27)
This application relates to triacylglycerol oligomers derived from the metathesis of natural oils. These oligomers are structure controlled dimers and quatrimers, and the effect of saturation, molecular size, and positional isomerization are also described herein.
Synthesis of bio-based monomer from vegetable oil fatty acids and design of functionalized greener polyester
Abd. Rahim, Noor Farisha,Ariffin, Hidayah,Hassan, Mohd Ali,Watanabe, Kohtaro,Andou, Yoshito,Shirai, Yoshihito
supporting information, p. 1517 - 1519 (2014/12/11)
In order to design sustainable materials from vegetable oilbased fatty acids, we propose herewith a method to obtain unsaturated dicarboxylic acids as a polymerizable monomer through metathesis reaction of oleic and linoleic acids with the 2nd generation Grubbs catalyst. Subsequently, functional green polyester was produced from dicarboxylic acids and aromatic diol. Dicarboxylic acid having similar structure i.e., octadec-9-enedioic acid was successfully obtained from metathesis of both oleic and linoleic acids. Condensation polymerization of octadec-9-enedioic acid with 1,6-hexanediol and 4,4′-biphenol was carried out and it was shown that polymer with aromatic backbone had higher glass-transition temperature than aliphatic polyester.
Synthesis of a series of hydroxycarboxylic acids as standards for oxidation of nonanoic acid
Rajabi, Mehdi,Lanfranchi, Moreno,Campo, Federica,Panza, Luigi
supporting information, p. 1149 - 1154 (2014/04/03)
The synthesis of a series of nonanoic acids hydroxylated in terminal,ω-1,ω-2,ω-3 positions is described. These compounds will be employed as useful standards for the study of enzymatic and microbiological oxidation of nonanoic acid.
Isomerizing olefin metathesis as a strategy to access defined distributions of unsaturated compounds from fatty acids
Ohlmann, Dominik M.,Tschauder, Nicole,Stockis, Jean-Pierre,Gooben, Kaethe,Dierker, Markus,Gooben, Lukas J.
experimental part, p. 13716 - 13729 (2012/10/08)
The dimeric palladium(I) complex [Pd(μ-Br)tBu 3P]2 was found to possess unique activity for the catalytic double-bond migration within unsaturated compounds. This isomerization catalyst is fully compatible with state-of-the-art olefin metathesis catalysts. In the presence of bifunctional catalyst systems consisting of [Pd(μ-Br)tBu3P]2 and NHC-indylidene ruthenium complexes, unsaturated compounds are continuously converted into equilibrium mixtures of double-bond isomers, which concurrently undergo catalytic olefin metathesis. Using such highly active catalyst systems, the isomerizing olefin metathesis becomes an efficient way to access defined distributions of unsaturated compounds from olefinic substrates. Computational models were designed to predict the outcome of such reactions. The synthetic utility of isomerizing metatheses is demonstrated by various new applications. Thus, the isomerizing self-metathesis of oleic and other fatty acids and esters provides olefins along with unsaturated mono- and dicarboxylates in distributions with adjustable widths. The cross-metathesis of two olefins with different chain lengths leads to regular distributions with a mean chain length that depends on the chain length of both starting materials and their ratio. The cross-metathesis of oleic acid with ethylene serves to access olefin blends with mean chain lengths below 18 carbons, while its analogous reaction with hex-3-enedioic acid gives unsaturated dicarboxylic acids with adjustable mean chain lengths as major products. Overall, the concept of isomerizing metatheses promises to open up new synthetic opportunities for the incorporation of oleochemicals as renewable feedstocks into the chemical value chain.
Method for Synthesizing an Omega-Amino Acid or Ester from a Monounsaturated Fatty Acid or Ester
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Page/Page column 7, (2011/12/14)
The invention relates to a method for synthesizing ω-aminoalkanoic acids or esters thereof from unsaturated natural fatty acids, passing through a monounsaturated dinitrile intermediate compound. The method of the invention is simple to carry out and, compared to other known methods, avoids the environmental constraints and economic disadvantages due to reaction by-products.
METHOD FOR SYNTHESISING 9-AMINONONANOIC ACID OR THE ESTERS THEREOF FROM NATURAL UNSATURATED FATTY ACIDS
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, (2011/05/08)
The invention relates to a method for synthesizing 9-aminononanoic acid or the esters thereof from natural unsaturated fatty acids, comprising at least one step of metathesis of the natural fatty acid and an oxidation step by oxidative cleaving. Said synthetic method uses widely available renewable starting materials and hence economical.
The cross-metathesis of methyl oleate with c/s-2-butene-1,4-diyl diacetate and the influence of protecting groups
Behr, Arno,Gomes, Jessica Perez
scheme or table, p. 1 - 8 (2011/03/22)
Background: α,ω-Difunctional substrates are useful intermediates for polymer synthesis. An attractive, sustainable and selective (but as yet unused) method in the chemical industry is the oleochemical cross-metathesis with preferably symmetric functionalised substrates. The current study explores the cross-metathesis of methyl oleate (1) with cis-2-butene-1,4-diyl diacetate (2) starting from renewable resources and quite inexpensive base chemicals. Results: This cross-metathesis reaction was carried out with several phosphine and N-heterocyclic carbene ruthenium catalysts. The reaction conditions were optimised for high conversions in combination with high cross-metathesis selectivity. The influence of protecting groups present in the substrates on the necessary catalyst loading was also investigated. Conclusions: The value-added methyl 11-acetoxyundec-9-enoate (3) and undec-2-enyl acetate (4) are accessed with nearly quantitative oleochemical conversions and high cross-metathesis selectivity under mild reaction conditions. These two cross-metathesis products can be potentially used as functional monomers for diverse sustainable polymers.
