Phase-Transfer Catalytic Alkylation of Hydroperoxides: A Convenient Route to Mixed Dialkyl Peroxides

Moulines, J.; Bougeois, M.-J.; Campagnole, Monique; Lamidey, Anne‐Marie; Maillard, B.; Montaudon, E.

doi:10.1080/00397919008052775

Cited by 22 publications

(7 citation statements)

References 5 publications

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“…Mp 69-72 ЊC (from dichloromethane). 29 Column chromatography on Florisil using n-hexane as eluent gave the pure product (yield 47%). 1 H NMR (CDCl 3 ): δ 1.25 (9 H, s, C(CH 3 ) 3 ), 3.77 (3 H, s, OCH 3 ), 4.13 (2 H, s, CH 2 ), 6.79-6.90 (4 H, m, Ar).…”

Section: -(4-methoxyphenoxy)[11-2 H 2 ]Ethanol (14)mentioning

confidence: 98%

Oxidation of non-phenolic β-O-aryl-lignin model dimers catalysed by lignin peroxidase. Comparison with the oxidation induced by potassium 12-tungstocobalt(III)ate

Baciocchi

Bietti

Gerini

et al. 2001

J. Chem. Soc., Perkin Trans. 2

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The H 2 O 2 -promoted oxidations of the non-phenolic β-O-aryl-lignin model dimers 1-(3,4-dimethoxyphenyl)-2-phenoxyethanol (1) and 2-(4-methoxyphenoxy)-1-phenylethanol (2) catalysed by LiP at pH = 4.0 have been studied. The oxidation of 1 mainly leads to the corresponding ketone, indicating that the prevailing reaction of the intermediate radical cation 1 ϩؒ is Cα-H deprotonation. The oxidation of 2 forms 2-(4-methoxyphenoxy)-2-phenylethanol (7, an isomer of 2), 2-phenyl-1,4-dioxaspiro[4.5]deca-6,9-dien-8-one ( 8) and products coming from the cleavage of the C-C bond γ to the more electron rich ring. The formation of all these products can be rationalised by assuming that the main reaction of the intermediate 2 ϩؒ is a nucleophilic attack of the alcoholic OH group on the ring bearing the positive charge. This leads to a spirocyclohexadienyl radical, which either is then oxidised to the dioxaspirodecadienone 8 or undergoes ring opening to give an alkoxyl radical from which the isomer of 2 and the C-C bond cleavage products may form. Support for this mechanism has been provided by a study of the oxidation of 4-MeOC 6 H 4 OCH 2 CD 2 OH and by comparing the results with those obtained when the alkoxyl radical 4-MeOC 6 H 4 OCH 2 CD 2 O ؒ was generated from 4-MeOC 6 H 4 OCH 2 CD 2 OOt-Bu. The oxidation of 1 induced by the genuine one-electron oxidant potassium 12-tungstocobalt()ate at pH = 4.0 confirms the results obtained with LiP. However, under the same conditions, no fragmentation products were observed in the oxidation of 2, probably due to a fast oxidation, by potassium 12-tungstocobalt()ate, of the spirocyclohexadienyl radical.

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Section: -(4-methoxyphenoxy)[11-2 H 2 ]Ethanol (14)mentioning

confidence: 98%

Oxidation of non-phenolic β-O-aryl-lignin model dimers catalysed by lignin peroxidase. Comparison with the oxidation induced by potassium 12-tungstocobalt(III)ate

Baciocchi

Bietti

Gerini

et al. 2001

J. Chem. Soc., Perkin Trans. 2

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“…The most simple is the tert-butyl allyl peroxide (tBAP) synthesized by a phase-transfer catalysis (PTC) process. [8] The effects of numerous factors on the yield of the hydrosilylation of tBAP reaction were described. The thiol-ene reaction study was divided into two parts: first, the reaction of tBAP with mercaptopropylsilane monomer (DM3PSi) affords a functionalized monomer (BP3DM2Si).…”

Section: Introductionmentioning

confidence: 99%

“…The first step was the synthesis of a workable molecule bearing a peroxide function and an unsaturation. The most simple is the tert‐ butyl allyl peroxide ( t BAP ) synthesized by a phase‐transfer catalysis (PTC) process 8. The effects of numerous factors on the yield of the hydrosilylation of t BAP reaction were described.…”

Section: Introductionmentioning

confidence: 99%

Peroxide‐Grafted PDMS: Hydrosilylation Reaction and Thiol‐Ene Chemistry as an Alternative Pathway

Lucas¹,

Fleury²,

Estur³

et al. 2009

Macro Chemistry & Physics

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Peroxide‐containing PDMS was synthesized according to a new pathway. Although hydrosilylation is one of the main reactions carried out in silicone chemistry, the catalysts used are very sensitive to the chemical nature of the reactants and remained inefficient to graft allylic peroxide. Radical catalyzed thiol‐ene chemistry was involved for the first time to yield an initiator group containing polymer. The peroxide‐grafted polysiloxane structure and decomposition were characterized using 1H, 13C and 29Si NMR, FT‐IR and Raman spectroscopies, SEC and DSC. These macroinitiators can be used to obtain polysiloxane able to undergo crosslinking.

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“…(iii) Peroxydes 11s sont synthCtisCs par action de l'hydroperoxyde correspondant, en milieu basique, sur le mtsylate de l'alcool convenable (prCparC selon la rCfCrence 13) ou sur le 1-bromopentane (pour P3b), selon des mkthodes mises au point au laboratoire (14)(15)(16). Leurs caracteristiques physiques et spectroscopiques sont rassemblCes dans le tableau 6.…”

Section: Techniques Re'actionnellesunclassified

Déplacements homolytiques intramoléculaires. 19. Stéréochimie de la décomposition induite de peroxydes insaturés conduisant à la formation d'hétérocycles à trois et quatre chaînons

Lubeigt¹,

Flies²,

Bourgeois³

et al. 1991

Can. J. Chem.

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Homolytic decomposition induced by addition of dichloromethyl radicals to P-and y-unsaturated peroxides having a substituent on the chain linking the unsaturation and the peroxide function was studied. The stereochemistry of the heterocycles produced was determined by I3C NMR and the stereoselectivity of intramolecular homolytic substitution on the peroxidic bond discussed. Key words: unsaturated peroxides, homolytic intramolecular substitutions, radical additions, oxygenated heterocycles.Depuis plusieurs anntes nous avons abordt l'ttude de la CH2=CH-CH-CH2-OOR P1 dtcomposition induite de composts peroxydiques insaturts et montrt llinttr&t synthttique de cette rtaction pour l'obtentionNous avons, au cours de travaux prtctdents (I), dttermint les lirnites d'application de cette kaction. Nous venons d'aborder l'ttude de la sttrtochimie des substitutions homolytiques intramoltculaires p e radicaux alkyle sur des liaisons peroxydiques.Cette analyse a Ctt rtaliste 9 partir des additions radicalaires du chlomre de mtthylkne 9 des composts peroxydiques insaturts comportant un substituant sur la chaine liant les deux fonctions rtactives que sont la double liaison et la liaison 0-0. Nous avons ainsi mis en tvidence l'existence d'une certaine sttrtoselectivitt dans la formation d'htttrocycles B cinq chainons (2). La prtdominance de l'isornkre cis ou trans dtpend tout d'abord de la position relative des substituants et est influencte notamment par leur taille et celle du radical oxyle partant; par contre le volume du radical Z attaquant la double liaison et la temptrature 9 laquelle est effectute la rtaction n'ont que peu d'influence sur la sttrtostlectivitt.Ayant vu prtctdemment (3, 4) que les peroxydes P-et y-insaturts subissent une dtcomposition hornolytique induite pour conduire 9 des oxiranes et des oxttanes, nous avons voulu compltter le travail prtctdent par l'ttude de la sttrtochimie des htttrocycles susceptibles de se former par addition radicalaire du chlomre de rntthylkne aux peroxydes modkles suivants :1. Auteurs a qui adresser toute correspondance. I CH3 Identification des ethers cycliques

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Phase-Transfer Catalytic Alkylation of Hydroperoxides: A Convenient Route to Mixed Dialkyl Peroxides

Cited by 22 publications

References 5 publications

Oxidation of non-phenolic β-O-aryl-lignin model dimers catalysed by lignin peroxidase. Comparison with the oxidation induced by potassium 12-tungstocobalt(III)ate

Oxidation of non-phenolic β-O-aryl-lignin model dimers catalysed by lignin peroxidase. Comparison with the oxidation induced by potassium 12-tungstocobalt(III)ate

Peroxide‐Grafted PDMS: Hydrosilylation Reaction and Thiol‐Ene Chemistry as an Alternative Pathway

Déplacements homolytiques intramoléculaires. 19. Stéréochimie de la décomposition induite de peroxydes insaturés conduisant à la formation d'hétérocycles à trois et quatre chaînons

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