- Chain Multiplication of Fatty Acids to Precise Telechelic Polyethylene
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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.
- Witt, Timo,H?u?ler, Manuel,Kulpa, Stefanie,Mecking, Stefan
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supporting information
p. 7589 - 7594
(2017/06/13)
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- COMBINED SYNTHESIS OF A NITRILE-ESTER/ACID AND OF A DIESTER/DIACID
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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.
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Paragraph 0137-0138
(2016/03/13)
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- METHOD FOR SYNTHESISING BIOBASED UNSATURATED ACIDS
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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).
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Paragraph 0071-0081
(2015/12/07)
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- TRIACYLGLYCEROL OLIGOMERS
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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.
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Paragraph 0050
(2015/11/27)
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- Synthesis of bio-based monomer from vegetable oil fatty acids and design of functionalized greener polyester
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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.
- Abd. Rahim, Noor Farisha,Ariffin, Hidayah,Hassan, Mohd Ali,Watanabe, Kohtaro,Andou, Yoshito,Shirai, Yoshihito
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supporting information
p. 1517 - 1519
(2014/12/11)
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- Synthesis of a series of hydroxycarboxylic acids as standards for oxidation of nonanoic acid
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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.
- Rajabi, Mehdi,Lanfranchi, Moreno,Campo, Federica,Panza, Luigi
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supporting information
p. 1149 - 1154
(2014/04/03)
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- Isomerizing olefin metathesis as a strategy to access defined distributions of unsaturated compounds from fatty acids
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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.
- Ohlmann, Dominik M.,Tschauder, Nicole,Stockis, Jean-Pierre,Gooben, Kaethe,Dierker, Markus,Gooben, Lukas J.
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experimental part
p. 13716 - 13729
(2012/10/08)
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- METHOD FOR SYNTHESISING 9-AMINONONANOIC ACID OR THE ESTERS THEREOF FROM NATURAL UNSATURATED FATTY ACIDS
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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.
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- Method for Synthesizing an Omega-Amino Acid or Ester from a Monounsaturated Fatty Acid or Ester
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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.
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Page/Page column 7
(2011/12/14)
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- The cross-metathesis of methyl oleate with c/s-2-butene-1,4-diyl diacetate and the influence of protecting groups
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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.
- Behr, Arno,Gomes, Jessica Perez
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scheme or table
p. 1 - 8
(2011/03/22)
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- Method of producing dicarboxylic acids
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A method of producing dicarboxylic acids (e.g., α,ω dicarboxylic acids) by reacting a compound having a terminal COOH (e.g., unsaturated fatty acid such as oleic acid) and containing at least one carbon-carbon double bond with a second generation Grubbs catalyst in the absence of solvent to produce dicarboxylic acids. The method is conducted in an inert atmosphere (e.g., argon, nitrogen). The process also works well with mixed unsaturated fatty acids obtained from soybean, rapeseed, tall, and linseed oils.
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Page/Page column Sheet 2/6; 6-8; 16; 18
(2009/05/29)
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- METHOD FOR THE MANUFACTURE OF OLIGO- AND POLYESTERS FROM A MIXTURE OF CARBOXYLIC ACIDS OBTAINED FROM SUBERIN AND/OR CUTIN AND THE USE THEREOF
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The invention relates to a method for processing mixtures of carboxylic acids obtained as hydrolysis products of suberin and cutin, particularly suberin and cutin isolated from birch bark, to give oligo- and polyesters, or corresponding ester-ethers, as well as the use of the products thus obtained as lubricants, fuel components, plasticizers, surface active agents, environmentally friendly agents for modifying wood, binders in coatings, adhesives, printing inks and composites, further in various cosmetic applications.
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Page/Page column 17-18
(2008/06/13)
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- Metathesis of unsaturated fatty acids: Synthesis of long-chain unsaturated-α,ω-dicarboxylic acids
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The self-metathesis of readily available monounsaturated FA has the potential of being an important pathway for the synthesis of symmetrical long-chain unsaturated-α,ω-dicarboxylic acids (C18-C 26). Previous studies on the self-metathesis of monounsaturated FA esters using ruthenium catalysts in solution, however, suffered from low conversions as a result of the thermodynamic control of the reaction. We have found that the secondgeneration Grubbs catalyst can effectively catalyze the solventfree self-metathesis of monounsaturated FA of varying purity (from 90 to 99%) to afford two important products-monounsaturated dicarboxylic acids and hydrocarbons-in very high molar conversions (>80%). This solvent-free self-metathesis reaction also works for monounsaturated FA containing additional functional groups. Reactions were conducted at catalyst loadings as low as 0.005 mol%, and turnover numbers as high as 10,800 could be obtained. This discovery represents an attractive approach to the large-scale production of useful monounsaturated-α,ω-dicarboxylic acids and long-chain unsaturated hydrocarbons by means of this solvent-free ruthenium-catalyzed self-metathesis of readily available monounsaturated FA. Copyright
- Ngo, Helen L.,Jones, Kerby,Foglia, Thomas A.
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p. 629 - 634
(2007/10/03)
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- High activity ruthenium or osmium metal carbene complexes for olefin metathesis reactions and synthesis thereof
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A method of preparing a catalyst of the formula comprising:reacting a compound of the formula (XX1MLnL1m)p with a phosphorane of the formula wherein:M is Os or Ru;R and R1 are either the same or different and are(a) hydrogen,(b) a group selected from C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkyl, aryl, C1-C20 carboxylate, C2-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl, or C1-C20 alkylsulfinyl, or(c) one of the groups listed in (b) substituted with C1-C5 alkyl, halogen, C1-C5 alkoxy, unsubstituted phenyl, halogen substituted phenyl, C1-C5 alkyl substituted phenyl, or C1-C5 alkoxy substituted phenyl;R4, R5, and R6 are either the same or different and are each unsubstituted or substituted hydrocarbon wherein the hydrocarbon is selected from the group consisting of aryl, C1-C6 alkyl, C1-C6 alkoxy, and phenoxy and the hydrocarbon substitution is selected from the group consisting of halogen, C1-C3 alkyl, C1-C3 alkoxy, unsubstituted phenyl, halogen substituted phenyl, C1-C5 alkyl substituted phenyl, and C1-C5 alkoxy substituted phenyl;X and X1 are either the same or different and are any anionic ligand;L is any neutral electron donor;L1 is a trialkylphosphine ligand where at least one of the alkyl groups is a secondary alkyl or a cycloalkyl;n and m are independently 0-4, provided n+m=2, 3 or 4; andp is an integer equal to or greater than 1.
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