Synthesis of hydroxyfatty esters by sequential epoxidation-hydrogenolysis: Solvent effects

Dorado, Vicente; Herrerı́as, Clara I.; Fraile, José M.

doi:10.1016/j.apcata.2021.118270

Cited by 5 publications

(5 citation statements)

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“…The substrate for this study was a mixture of methyl 9-hydroxy-and 10-hydroxystearate (1a + 1b, represented as methyl 9(10)-hydroxystearate), obtained from the hydrogenolysis of methyl 9,10-epoxystearate as previously described [7]. First of all, the homogeneous method was tested using two sulfonic acids of different strengths, namely p-toluenesulfonic acid (p-TosOH, pK a ≈ −2.8 [25]) and triflic (trifluoromethanesulfonic) acid (TfOH, pK a = −5.9 [25]), under conditions analogous to those described in the literature [24]: room temperature, 24 h, CH 2 Cl 2 /H 2 O (9:1) as solvent, 1.5 eq 60% H 2 O 2 , 20 mol% KBr, and 20 mol% (p-TosOH) or 10 mol% (TfOH) of acid.…”

Section: Resultsmentioning

confidence: 99%

“…Methyl 9(10)-hydroxystearate (1a + 1b) was prepared via sequential epoxidationhydrogenolysis [7]: methyl oleate was epoxidized with tert-butyl hydroperoxide (TBHP) in trifluorotoluene (TFT) at 120 • C using a Ti-SiO 2 catalyst (prepared from Merck silica and Cp 2 TiCl 2 as previously described [6]). The catalyst was filtered and washed with CH 2 Cl 2 , and the filtrate was evaporated under reduced pressure.…”

Section: Methodsmentioning

confidence: 99%

“…Hence, the development of new sustainable methods for their transformation, or the adaptation of existing ones to the particularities of fatty acid derivatives, is an important objective in sustainable chemistry [4,5]. Our group has been working on methods that include heterogeneous catalysts for the transformation of fatty esters, starting from unsaturated ones, through a first epoxidation step and the further conversion of the epoxide via rearrangement [6], hydrogenolysis [7], hydrolysis [8] or oxidative cleavage [9].…”

Section: Introductionmentioning

confidence: 99%

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Sulfonic Resins as Catalysts for the Oxidation of Alcohols with H2O2/KBr

Dorado,

Herrerías,

Fraile

2024

Catalysts

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Sulfonic resins can replace homogeneous sulfonic acids in the oxidation of alcohols with the H2O2/KBr system. The performance of different resins was tested with methyl 9(10)-hydroxystearate, a secondary fatty alcohol. The structural features of the resin were more important than the acid strength for the catalytic performance of this reaction. The optimization of the reaction conditions allows the recovery of the resin, although regeneration is required due to the active role of KBr, and a significant loss of sulfonic groups can be detected after nine runs. In the case of primary fatty alcohols, the oxidation leads to carboxylic acids, which are esterified with the starting alcohol under the acidic conditions. For cyclic secondary alcohols, the steric hindrance around the hydroxyl group seems to be important for the efficiency of the oxidation to ketone.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Sulfonic Resins as Catalysts for the Oxidation of Alcohols with H2O2/KBr

Dorado,

Herrerías,

Fraile

2024

Catalysts

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“…of NaO t Bu at room temperature [27] . Similarly metal‐free homogeneous oxidative cleavage of 1,2‐diols are also known in literature using stoichiometric amount of oxidants or base [30–32] . Therefore, development of a new and versatile method for selective cleavage of C−C(OH) bond of alcohols with oxygen as an oxidizing agent is highly desired (Scheme 1A).…”

Section: Introductionmentioning

confidence: 99%

Metal‐Free Visible‐Light Induced Oxidative Cleavage of C(sp³)−C, and C(sp³)−N Bonds of Nitriles, Alcohols, and Amines

Borthakur,

Joshi,

Kumari

et al. 2024

Chemistry A European J

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Selective cleavage of unstrained (sp3) C‐C/ C‐N bonds under mild conditions is highly challenging due to the higher bond dissociation energy. A visible light mediated metal free oxidative dehomologation of aryl acetonitriles, primary alcohols and diols to carboxylic acids via organophotocatalysed C(sp3)‐CN, C(sp3)‐C(OH) bond cleavage is reported. Notably, this methodology was further extended towards selective synthesis of aldehydes via deamination of both primary as well as secondary amines. This mild protocol features wide array of substrate variation with excellent functional group tolerance, preparative‐scale synthesis, and operational simplicity. Possible mechanisms for these transformations were demonstrated through a series of control experiments.

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“…Another example entails catalytic hydrogenation of EMO with a Ni catalyst at 110°C to yield methyl 9(10)‐hydroxystearate, which was subsequently transesterified with 1,6‐hexanediol to generate polyester polyols for polymerization with diisocyanates to give thermoplastic PU elastomers (Yemul & Petrovic, 2014). Also reported is tandem epoxidation using TBHP and hydrogenation with Pd on carbon (Pd/C) of methyl oleate to give methyl 9(10)‐hydroxystearate (Dorado et al, 2021). Diving into the older literature reveals a couple of the earliest examples of catalytic hydrogenation of EMO, conducted at atmospheric temperature and pressure with 10% Pd/C in glacial acetic acid, to synthesize methyl 9(10)‐hydroxystearate (Howton & Kaiser Jr, 1964; Mack & Bickford, 1953).…”

Section: Introductionmentioning

confidence: 99%

A review of fatty epoxide ring opening reactions: Chemistry, recent advances, and applications

Moser

Cermak

Doll

et al. 2022

J Americ Oil Chem Soc

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Fatty epoxides are produced from the corresponding alkenes by oxidation in the presence of peracids or other oxidants. The classic method is the Prilezhaev epoxidation in which peracids are generated by in situ oxidation of formic or acetic acids with hydrogen peroxide. Epoxidized vegetable oils and esters are used directly as biobased plasticizers and stabilizers for poly(vinyl chloride) or as important platform chemicals for the oleochemical industry. Nucleophilic attack at the oxirane moiety affords a variety of ring opened monomeric or polymeric products, which in many cases undergo further synthetic modification to yield finished products. The most common nucleophiles include water, alcohols, carboxylic acids, acid anhydrides, and amines, although numerous others can also lead to valuable functionalized fatty derivatives. This review summarizes the chemistry of fatty epoxide ring opening reactions as well as applications of the resultant products. Literature from the last 20 years will be emphasized, although older publications of particular significance will be included. Important applications include biobased lubricants as well as polyols for subsequent production of polyurethanes. In addition, ring-opening reactions hitherto unreported on fatty oxiranes will be suggested to facilitate further advancements in the chemistry and utility of fatty epoxides. Finally, interest in fatty epoxides and their consequent products will continue to grow due to the simplicity, efficiency, and versatility of oxirane formation and ring opening as well as the continued societal transition away from petroleum to a sustainable, circular, low-carbon, and biobased economy.

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Synthesis of hydroxyfatty esters by sequential epoxidation-hydrogenolysis: Solvent effects

Cited by 5 publications

References 45 publications

Sulfonic Resins as Catalysts for the Oxidation of Alcohols with H2O2/KBr

Sulfonic Resins as Catalysts for the Oxidation of Alcohols with H2O2/KBr

Metal‐Free Visible‐Light Induced Oxidative Cleavage of C(sp³)−C, and C(sp³)−N Bonds of Nitriles, Alcohols, and Amines

A review of fatty epoxide ring opening reactions: Chemistry, recent advances, and applications

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Synthesis of hydroxyfatty esters by sequential epoxidation-hydrogenolysis: Solvent effects

Cited by 5 publications

References 45 publications

Sulfonic Resins as Catalysts for the Oxidation of Alcohols with H2O2/KBr

Sulfonic Resins as Catalysts for the Oxidation of Alcohols with H2O2/KBr

Metal‐Free Visible‐Light Induced Oxidative Cleavage of C(sp3)−C, and C(sp3)−N Bonds of Nitriles, Alcohols, and Amines

A review of fatty epoxide ring opening reactions: Chemistry, recent advances, and applications

Contact Info

Product

Resources

About

Metal‐Free Visible‐Light Induced Oxidative Cleavage of C(sp³)−C, and C(sp³)−N Bonds of Nitriles, Alcohols, and Amines