Diallyl ether, oxidation

Real-Time FTIR. For our IR studies, we utilized a stoichiometrically equivalent amount of a trifunctional thiol, trimethylolpropane tris(2-mercaptoacetate), with a difunctional allyl, trimethylolpropane diallyl ether. The thiols were protected from oxidative polymerization by the addition of hydroquinone. The monomers and hydroquinone were purchased from Aldrich Chemicals and were used as received. This formulation was mixed for five minutes and then a commercial photoinitiator, Esacure TZT (Sartomer Inc.), which contained a blend of methyl benzophenones, was added at a level of 1.0% by weight of monomers to the formulation. Stirring was maintained for a further five minutes following the addition of the photoinitiator. The final formulation contained 2.0% by weight of hydroquinone. The samples were prepared prior to each experiment in order to ensure reproducibility of sample history. 

Failure to achieve the bicyclization of diallyl ether with nBu2ZrCp2 led to the unexpected discovery of the oxidative addition reaction,226 shown in Scheme 44. This reaction has been extensively used for developing synthetically useful reactions, also shown in Scheme 44 232 234>234a-234c Another breakthrough on this topic was made with alkenyl chloride,235 which led to more recent similar discoveries with alkenyl sulfides, sulfones, and ethers236,23611 237 (Scheme 45). 

The oxidation of butadiene, diallyl carbonate, or diallyl ether gives the products of monoepoxidation with selectivities of 85% and higher when the ratio diene/H202 is 2.5 (Table VIII). The diepoxides are formed in larger amounts when the diene/H202 ratio is 1. 

Whereas diallyl ethers do not readily undergo Zr-promoted cyclization due to competitive oxidative addition [23a], diallylamines have been shown to readily undergo Zr-promoted cyclization, even in cases where the corresponding all-C dienes fail to do so [231. Since the development of the Zr-catalyzed diene cyclization with n-butylmagnesiums. such as n-BuMgBr... 

This reaction is applicable to both homoallyl and diallyl ethers and results in multicyclic furanes. These products can be oxidized to novel butyrolactones.2 Examples ... 

In the experiments using El-dj- and 3,3-d2-allyl alcohol in the presence and absence of pyridine bases, the results (Table IV) show that reaction occurs on Bronsted acid sites (Scheme 8), which results in diallyl ether formation with scrambling of the deuterium label via carbonium ion formation, and also on oxidizing sites on which both 1-d- and 3,3-d2-acrolein form via the formation and interconversion of the two isomeric 1,1 -d2- and 3,3-d2-allyl molybdates (27). These mechanisms are supported by data (Table IV) that show the suppression of ether formation and reduction of deuterium scrambling in the presence of base, which has little effect on the acrolein yield. The oxidation of O-allyl alcohol to acrolein over MOO3, which... 

DIALLYL ETHER (557-40-4) Forms explosive mixture with air (flash point 20°F/—7°C oc). Forms explosive peroxides with air. Violent reaction with strong oxidizers, strong acids. Flow or agitation of substance may generate electrostatic charges due to low conductivity. 

Fission of aryl ethers can also be effected by metallic sodium or potassium. For instance, diphenyl ether, which is one of the most resistant ethers, is decomposed by liquid potassium-sodium alloy at room temperature.38 Weber and Sowa have cleaved 4,4 -disubstituted diphenyl ethers into benzene and phenol derivatives by sodium in liquid ammonia.39 Diallyl ether is converted by sodium dust at 35° into allylsodium and sodium allyl oxide, which provides a suitable method for preparation of allylsodium.3 7a Anisole, phenetole, benzyl phenyl ether, and diphenyl ether give the phenols in 90% yield, without by-products, when boiled with sodium or potassium in pyridine.40... 

Caustic potash Chloric acid Chlorine, dry Chloroacetic acid Chloroacetone Chloroform Chlorosilanes Chlorosulfonic acid Chromic acid Chromic chloride Chromic fluorides Chromic hydroxide Chromic nitrates Chromic oxides Chromic phosphate Chromic sulfate Coconut oil Cod liver oil Coke oven gas Copper carbonate Copper chloride Copper cyanide Copper nitrate Copper oxide Copper sulfate Corn oil Coconut oil Cresylic acid Crude oil Cutting oils Cyclohexane Cyclohexanol Cyclohexanone Cyclohexene Denatured alcohol Detergent solution Dex train Dextrose Diacetone Diallyl ether Diallyl phthalate Dichloroacetic acid Dichloroaniline o-Dichlorobenzene Dichloroethane Dichloroethylene Dichloromethane Dichlorophenol Diesel oil... 

That both C=C bonds participating in 2n + 2n photocycloadditions can be acyclic is evident from the photobicyclization reactions of simple diallyl ethers that deliver bicyclic tetrahydrofurans (eq 20). In conjunction with ruthenium(IV) oxide-catalyzed oxidation by sodium periodate, these CuOTf-catalyzed photo-bicyclizations provide a synthetic route to butyrolactones from diallyl ethers (eq 20), The synthetic method is applicable to the construction of multicyclic tetrahydrofurans and butyrolactones from diallyl ethers (eq 21 and eq 22) as well as from homoallyl vinyl ethers (eq 23). ... 

Copper(I)-catalyzed intramolecular [2 + 2]-photocycloaddition of diallyl ethers and homoallyl vinyl ethers provides a new route to 3-oxabicyclo- and 2-oxabicyclo[3.2.0]heptanes, respectively.Different structural variants of diallyl ethers have been investigated. UV irradiation of diaUyl ethers 77a-f in the presence of CuOTf catalyst produces 3-oxabicyclo[3.2.0]heptanes 78a-f in moderate to excellent yields (Scheme 22). The diallyl ethers 77c and 77d having alkyl substitution at the aUyhc position produce exclusively the 2-exo-alkyl-3-oxabicyclo [3.2.0] heptanes 78c and 78d, respectively. The observed stereoselectivity arises through photocycloaddition of the Cu(l)-diene complex 80, which is stericaUy less crowded than the complex 81 with an axial alkyl group. The bicychc ethers 78 can be oxidized smoothly to the lactones 79 with RuO. Cu(l)-catalyzed photocycloaddition of homoallyl vinyl ethers 82 also proceeds smoothly, producing 2-oxabicyclo[3.2.0]heptanes 83 (Scheme 22). 

Using the sequence of Cu(l)-catalyzed photocycloaddition of diallyl ethers or homoallyl vinyl ethers and RUO4 oxidation, a variety of novel multicyclic compounds such as 86 and 89 can be synthesized (Scheme 23) starting with the dienes 84 and 87, respectively. 

PB PBI PBMA PBO PBT(H) PBTP PC PCHMA PCTFE PDAP PDMS PE PEHD PELD PEMD PEC PEEK PEG PEI PEK PEN PEO PES PET PF PI PIB PMA PMMA PMI PMP POB POM PP PPE PPP PPPE PPQ PPS PPSU PS PSU PTFE PTMT PU PUR Poly(n.butylene) Poly(benzimidazole) Poly(n.butyl methacrylate) Poly(benzoxazole) Poly(benzthiazole) Poly(butylene glycol terephthalate) Polycarbonate Poly(cyclohexyl methacrylate) Poly(chloro-trifluoro ethylene) Poly(diallyl phthalate) Poly(dimethyl siloxane) Polyethylene High density polyethylene Low density polyethylene Medium density polyethylene Chlorinated polyethylene Poly-ether-ether ketone poly(ethylene glycol) Poly-ether-imide Poly-ether ketone Poly(ethylene-2,6-naphthalene dicarboxylate) Poly(ethylene oxide) Poly-ether sulfone Poly(ethylene terephthalate) Phenol formaldehyde resin Polyimide Polyisobutylene Poly(methyl acrylate) Poly(methyl methacrylate) Poly(methacryl imide) Poly(methylpentene) Poly(hydroxy-benzoate) Polyoxymethylene = polyacetal = polyformaldehyde Polypropylene Poly (2,6-dimethyl-l,4-phenylene ether) = Poly(phenylene oxide) Polyp araphenylene Poly(2,6-diphenyl-l,4-phenylene ether) Poly(phenyl quinoxaline) Polyphenylene sulfide, polysulfide Polyphenylene sulfone Polystyrene Polysulfone Poly(tetrafluoroethylene) Poly(tetramethylene terephthalate) Polyurethane Polyurethane rubber... 

Alkyl sulfides. Di-n-butyl sulfide and dibenzyl sulfide have been oxidized to the sulfoxides by prolonged shaking of a petroleum ether solution with active MnOj. Diallyl sulfoxide was obtained by this method in 13% yield. 

The formation of D-glucaric acid by platinum-catalysed oxidation of D-gluconic acid has been noted in the previous section. Mono- and per-allyl ether derivatives of xylaric and galactaric acids have been prepared by treating the aldaric acid with allyl alcohol in the presence of an appropriate acid catalyst. Diallyl 3-0-allyl-2,4-0-methylenexylarate was obtained in good yield when 2,4-0-methylenexylaric acid reacted with allyl bromide in the presence of alkali. The reaction of 2,3,4-tri-O-acetylxylaryl dichloride with diazomethane has been mentioned in Chapter 7. 

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