Double bond oxidation of unsaturated fatty acids

Zaldman, B.; Kisilev, A.; Sasson, Yoel; Garti, Nissim

doi:10.1007/bf02540689

Cited by 48 publications

(26 citation statements)

References 4 publications

(2 reference statements)

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“…4). This was inspired by classical methods of extraction [21], previously used for separation of dicarboxylic from monocarboxylic acids [22], and also applied in the specific case of the azelaic and pelargonic couple [23].…”

Section: Oxidative Cleavage In a Single Step (B)mentioning

confidence: 99%

Sustainable Process for Production of Azelaic Acid Through Oxidative Cleavage of Oleic Acid

Benessere

Cucciolito

Santis

et al. 2015

J Americ Oil Chem Soc

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relevant role. They can be transformed into methyl esters for production of biodiesel or functionalized to produce surfactants, plasticizers, monomers, and new solvents [2,3]. These include cis-9-octadecenoic acid (oleic acid, OA in Scheme 1), which is a very interesting raw material, since it is renewable, inexpensive, and available in different geographical areas.Its most common transformations are epoxidation, hydroxylation, and oxidative cleavage of the double bond. The latter reaction is particularly interesting because it selectively produces azelaic acid (AA) and pelargonic acid (PA) (Scheme 1).Azelaic acid has important applications in textiles (polyesters and polyamides) and pharmaceuticals (antiacne). Industrially, oxidative cleavage of the double bond is carried out by ozonolysis [4]. However, use of ozone and molecular oxygen at high temperatures represents a serious drawback of this process, since these oxidants present combustion hazards. It is therefore required to find new processes that meet the standards of sustainability.A valid alternative is hydrogen peroxide, because it is capable of oxidizing with excellent atom economy and is safer than gaseous reactants [5]. Many of the known strategies couple H 2 O 2 with catalytic systems such as RuO 2 , Na 3 PO 4 {[WO(O 2 ) 2 ]}, H 2 WO 4 /Co(OAc) 2 , and Re 2 O 7 [6][7][8][9][10][11][12][13][14][15][16]. These synthetic routes (path i of Scheme 1) typically include a first step of dihydroxylation that gives 9,10-dihydroxystearic acid (DSA). In a second step (ii) a new catalyst is introduced, either in the same reaction environment [14] or on the purified diol [15], for oxidative cleavage of the CH(OH)-CH(OH) bond.Recently, an efficient one-pot strategy (iii in Scheme 1) was proposed with a catalyst based on the quaternary ammonium salt Q 3 {PO 4 [WO(O 2 ) 2 ] 4 } [17]. Even in this case, there are some disadvantages, namely high catalyst Abstract This work describes two sustainable methods for production and purification of azelaic acid (AA) to replace the current process of ozonolysis of oleic acid (OA). The first proceeds in two steps, coupling smooth oxidation of OA to 9,10-dihydroxystearic acid (DSA) with subsequent oxidative cleavage by sodium hypochlorite. An alternative methodology is also proposed, using a chemocatalytic system consisting of H 2 O 2 /H 2 WO 4 for direct oxidative cleavage of the double bond of OA at 373 K. A convenient technique for separation and purification of azelaic acid is also proposed.

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Section: Oxidative Cleavage In a Single Step (B)mentioning

confidence: 99%

Sustainable Process for Production of Azelaic Acid Through Oxidative Cleavage of Oleic Acid

Benessere

Cucciolito

Santis

et al. 2015

J Americ Oil Chem Soc

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“…[1][2][3] This conversion is nowadays mostly performed with second-and third-row transition-metal catalysts based on Os, [4][5][6][7][8][9][10][11][12] Ru, [13][14][15][16][17][18] or W, [19][20][21][22][23][24][25] on the lab scale, or with ozone in an industrial process. [3,26] More benign methods for these processes are clearly desired. Recently, we reported on the nonmetal-mediated oxidative cleavage of internal alkenes and unsaturated fatty acids into carboxylic acids with a combination of the oxidants oxone and sodium periodate.…”

Section: Introductionmentioning

confidence: 99%

Fe‐Catalyzed One‐Pot Oxidative Cleavage of Unsaturated Fatty Acids into Aldehydes with Hydrogen Peroxide and Sodium Periodate

Spannring

Yazerski

Bruijnincx

et al. 2013

Chemistry A European J

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A one-pot method has been developed for the oxidative cleavage of internal alkenes into aldehydes by using 0.5 mol% of the nonheme iron complex [Fe(OTf)2(mix-bpbp)] (bpbp=N,N'-bis(2-picolyl)-2,2'-bipyrrolidine) as catalyst and 1.5 equivalents of hydrogen peroxide and 1 equivalent of sodium periodate as oxidants. A mixture of diastereomers of the chiral bpbp ligand can be used, thereby omitting the need for resolution of its optically active components. The cleavage reaction can be performed in one pot within 20 h and under ambient conditions. Addition of water after the epoxidation, acidification and subsequent pH neutralization are crucial to perform the epoxidation, hydrolysis, and subsequent diol cleavage in one pot. High aldehyde yields can be obtained for the cleavage of internal aliphatic double bonds with cis and trans configuration (86-98%) and unsaturated fatty acids and esters (69-96%). Good aldehyde yields are obtained in reactions of trisubstituted and terminal alkenes (62-63%). The products can be easily isolated by a simple extraction step with an organic solvent. The presented protocol involves a lower catalyst loading than conventional methods based on Ru or Os. Also, hydrogen peroxide can be used as the oxidant in this case, which is often disproportionated by second- and third-row metals. By using only mild oxidants, overoxidation of the aldehyde to the carboxylic acid is prevented.

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“…The oxidation of oleic acid in neutral oil in water emulsion resulted in the formation of dihydroxy, ketohydroxy, and diketo acids along with azelaic and pelargonic acids. Zaldman et al (11) used sodium hypochlorite as an oxidizing agent for the oxidation of oleic acid. The results showed that oxidation of oleic acid in an emulsion system consisting of sodium hypochlorite, surface-active agents, and ruthenium chloride as catalysts could be achieved with higher conversion and reduced reaction time compared with the nonemulsified (heterogeneous) systems.…”

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confidence: 99%

Liquid‐phase catalytic oxidation of unsaturated fatty acids

Noureddini

Kanabur

1999

J Americ Oil Chem Soc

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Liquid‐phase catalytic oxidation of oleic acid with hydrogen peroxide in the presence of various transition metal/metal oxide catalysts was studied in a batch autoclave reactor. Azelaic and pelargonic acids are the major reaction products. Tungsten and tantalum and their oxides in supported and unsupported forms were used as catalysts. Alumina pellets and Kieselguhr powder were used as supports for the catalysts. Tungsten, tantalum, molybdenum, zirconium, and niobium were also examined as catalysts. Tertiary butanol was used as solvent. Experimental results concluded that tungsten and tungstic oxide are more suitable catalysts in terms of their activity and selectivity. The rate of reaction observed in the case of supported catalysts appears to be comparable or superior to that of unsupported catalysts. In pure form, tungsten, tantalum, and molybdenum showed strong catalytic activity in the oxidation reaction; however, except for tantalum the other two were determined to be economically unfeasible. Zirconium and niobium showed very little catalytic activity. Based on the experimental observations, tungstic oxide supported on silica is the most suitable catalyst for the oxidation of oleic acid with 85% of the starting oleic acid converted to the oxidation products in 60 min of reaction with high selectivity for azelaic acid.

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Double bond oxidation of unsaturated fatty acids

Cited by 48 publications

References 4 publications

Sustainable Process for Production of Azelaic Acid Through Oxidative Cleavage of Oleic Acid

Sustainable Process for Production of Azelaic Acid Through Oxidative Cleavage of Oleic Acid

Fe‐Catalyzed One‐Pot Oxidative Cleavage of Unsaturated Fatty Acids into Aldehydes with Hydrogen Peroxide and Sodium Periodate

Liquid‐phase catalytic oxidation of unsaturated fatty acids

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