Diallyl carbonate

Allylation of the 10-carborane 236 (pKa = 18-22) with diallyl carbonate is possible under neutral conditions to give 237[146], Allylation and rearrangement of the trialkylalkynylborane 238 affords the trisubstituted alkene 239 stereoselectively [ 147],... 

The slow oxidation of primary alcohols, particularly MeOH, is utilized for the oxidation of allylic or secondary alcohols with allyl methyl carbonate without forming carbonates of the alcohols to be oxidized. Allyl methyl carbonate (564) forms 7r-allylpalladium methoxide, then exchange of the methoxide with a secondary or allylic alcohol 563 present in the reaction medium takes place to form the 7r-allylpalladium alkoxide 565, which undergoes elimination of j3-hydrogen to give the ketone or aldehyde 566. The lactol 567 was oxidized selectively with diallyl carbonate to the lactone 568 without attacking the secondary alcohol in the synthesis of echinosporin[360]. 

Reaction of aHyl chloroformate and diethylene glycol in the presence of alkaU with cooling is another method of preparing the diallyl carbonate ester DADC. The properties of diallyl carbonate monomers are given in Table 1. 

Other allyl compounds described in the literature include diallyl carbonate, diallyl isophthalate and diallyl benzene phosphonate. 

Diallyl carbonate, Pd(OAc)2, PhjR Conventional methods failed to protect this hindered 12-a-hydroxycholestane derivative. ... 

A solution of Pd(OAc)2 (0.05 mmol) and bis(diphenylphosphino)ethane (0.05 mmol) in acetonitrile (1 ml) was heated gently to reflux, at which time a solution of the silyl enol ether (1 mmol) and diallyl carbonate (2 mmol) in MeCN (4 ml) was added in one portion. The mixture was heated under reflux for 1-3 h, the course of reaction being monitored by t.l.c. or g.l.c. analysis. On completion, the cooled reaction solution was filtered through fluorosil. The pure a/ -unsaturated compound was isolated by column chromatography on silica gel (70-95%). 

Scheme 4.19 Trost (—)-physostigmine synthesis plan (2006). (a) EtaN (72%) (b) (CH3)2SO (88%) (c) diallyl carbonate, LiOfBu, Mo, L (98%) (d) I/2OSO4, then Nal04 (92%) (e) recrystallization from iPrOH-cyclohexane (72%) (f) CH3NH2 HCI, then 1/2LiAlH4, 2H2O (88%) (g) BBra, 3H2O (79%) (h) Na, CH3N=C=0, then H2O (79%).

Diallyl ammonium monomers, 20 472 Diallyl ammomium polymers, 2 267 Diallyl carbonate... 

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. 

Primary alcohols have been successfully used as substrates for lipases. Monterde et. Al60 reported the resolution of the chiral auxiliary 2-methoxy-2-phenylethanol 1 via Candida antarctica lipase B (CAL-B)-catalyzed acylation using either vinyl acetate (R=H) or isopropenyl acetate (R= CH3) as acyl donor (cf. fig. 8) and the alkoxycarbonylation using diallyl carbonate as the alkoxycarbonylation agent in THF at 30 °C (cf. fig. 9). 

Here the Pd(0) complex reacts with diallyl carbonate to form a n-allyl palladium alkoxide that ligates to 16. The resulting intermediate then undergoes P-hydride elimination to produce the lactone and propene (Scheme 6.10). 

Diallyl ether and diallyl carbonate produced monoglycidyl and diglyddyl ethers in a ratio that depended on the conversion. Allyl methacrylate yielded the corresponding glycidyl methacrylate [5]. Ti-MWW, in acetonitrile and acetone solvents, was again reported to be more active and selective than TS-1 [100]. 

This process also avoids the use of methylene chloride as a solvent and the co-production of NaCl salt. Another well-established application of DMC in the field of polycarbonates relates to the production of poly[diethyleneglycol bis(allylcarbo-nate)], a thermosetting resin used in the production of optical glasses and lenses. The non-phosgene process involves the intermediate formation of diallyl carbonate from DMC - whereas the traditional process was based on the use of diethyleneglycol bis(chloroformate) that in turn was obtained from phosgene - and allows high flexibility in terms of customer-tailored products. 

The corresponding imide can be formed if the medium is hexane. Amines can be protected as their allyl carbamates by formation with diallyl carbonate and a lipase... 

There are several interesting polymerization schemes intermediate between a sequential IPN and an SIN. For example, in in situ prepared sequential IPNs, both monomers are polymerized via free radical reaction [He et ai, 1993 Rouf et ai, 1994]. The two monomers must have quite different reactivities towards the free radicals. This situation arises with vinyl or acrylic double bonds and aUylic double bonds. The allylic double bonds react about 100 times slower than acrylic or methacrylic bonds. Often, two initiators are used, one reacting at a lower temperature, and the other at a higher temperature. In one of the systems studied, based on methyl methacrylate and diallyl carbonate of bisphenol-A (DACBA), first, crosslinked PMMA was formed at moderate temperatures. Then, by just increasing the temperature after completion of the first polymerization, the synthesis of the allylic network followed. 

Unsaturated Aldehydes and Ketones. - Trimethylsilylenol ethers derived from either aldehydes or ketones are oxidised, in good yields, to enals or enones respectively, by treatment with diallyl carbonate in the presence of catalytic palladium(0). Acetonitrile is the required solvent if allylation is to be avoided... 

In this chapter, procedures for the polymerization of allyl acetate and related monocarboxylates of diallyl carbonate types, of diallyl phthalates, and of diallyl esters of other dicarboxylic acids are discussed. 

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