Allyl isocyanate

Condensation of allyl isocyanate with succinimide affords the cyclic diacylurea 39. Acid hydrolysis leads to ring opening of the succinimide (40). Oxymercuration of the terminal olefin bond with mercuric acetate in methanol solution affords the diuretic meralluride (41). ... 

The cyclized analog of meralluride is prepared by a similar synthesis. Thus, condensation of camphoric acid (42) (obtained by oxidation of camphor) with ammonia gives the bicyclic succinimide (44). Reaction with allyl isocyanate followed by ring opening and then reaction with mercuric acetate affords the mercury derivative (45) as the acetate rather than the hydroxide as above. Reaction with sodium chloride converts that acetate to the halide (46). Displacement on mercury with the disodium salt of thioglycollic acid affords the diuretic mercaptomerine (47). ... 

The [l,3]oxazino[4,3- ][l,3]oxazine 387 was obtained as the main product of a combined Asinger and Ugi multi-component reaction from MeOH, NH3, 2,2-dimethyl-3-hydroxypropanal, allyl isocyanate, and C02 in 40% yield. As shown by NMR spectroscopy and X-ray crystallography, 387 is formed as a single diastereomer <1998ACS107>. 

Reactions with Isocyanates. The reaction of alcohols with isocyanates to form carbamates is well known and similar reactions with poly(vinyl alcohol) would be expected. Until recently, the only available reaction conditions were to use a heterogeneous reaction mixture or to run the reaction in a poor solvent for poly(vinyl alcohol). The best poly(vinyl alcohol) solvents, water and formaide derivatives, react rapidly with isocyanates. Nevertheless, several such reactions have been run in the past and we will cite only a few of them. A potentially photosensitive polymer was made by the reaction of allyl isocyanate with poly(vinyl alcohol) (57) and several workers have crosslinked poly(vinyl alcohol) with hexamethylene diisocyanate (58.59). 

Although the crystalline poly(allyl isocyanate) polymers are reported to be stable, many of these polymers depolymerize upon heating to yield monomers and cyclic trimers. The level of temperature sensitivity is a strong function of the length of the side chain. Room temperature depolymerization occurs in polar solvents in the presence of an initiator. Interestingly, the solution properties of poly(alkyl isocyanates) display an unusual degree of chain stiffness which is attributed to their helical configuration (64). 

Seyferth reagents are ideal for the dihalocyclopropanation of deactivated or base sensitive substrates such as allyl halides, allyl isocyanates, polychloroalkenes, a, 3-unsaturated ketones, esters, nitriles and sulfones.19... 

Although there are many reports of reactants to achieve dimensional stabilization by ester bonding with hydroxyl groups of the wood components, an additional increase in biological resistance has been studied only for acetic anhydride [1-12] and several isocyanates [13-15] such as methyl isocyanate and allyl isocyanate. 

In the reaction of wood hydroxyls with isocyanates, a nitrogen-containing ester is formed. A limited reduction of fungal attack was reported earlier in beechwood modified with diisocyanate (13). Considerably more decay protection than acetylation has been shown in the methyl and allyl isocyanate modifications. Little decay was evident in methyl isocyanate-modified southern pine at WPGs between 14% and 19% in laboratory assay using G. trabeum. 

Allyl isothiocyanate treatment also gave a high decay resistance of wood comparable to methyl and allyl isocyanates, but the main reaction appaeared to be polymerization, which left isothiocyanate groups intact [15]. 

Overman, L. E., Kakimoto, M. Preparation of rearranged allylic isocyanates from the reaction of allylic alkoxides with cyanogen chloride. J. Org. Chem. 1978,43,4564-4567. 

In the patent specification [147] there data on the chemical attachment to hydridesilica surface in the presence of the Reney nickel, chloroplatinic acid or metallic platinum deposited on activated carbon as a catalyst of the following unsaturated functional compounds divinylbenzene, ethylene glycol diacrylate, acetylene, allyl alcohol, allyl glycidyl ether, allyl isocyanate, acrylic acid. The chemical reactions result in the transformation of Si-H bonds of hydridesilica surface into Si-C bonds. Such transformations may be also classified as processes of solid-phase catalytic hydrosilylation of functional olefins. 

Deprotonation of the 4-amino group in 4-(arylamino)nicotinic esters with sodium hydride and subsequent conversion to a urea with allyl isocyanate yields an intermediate urea, whose cyclization furnishes the corresponding l-aryl-3-allylpyrido[4,3-r/jpyrimidine-2,4(l//,3//)-dione 12.498... 

Other types of curing systems for allyl-terminated urethane polymers were described by Kehr and Wszolek (176). Polyether and polyester urethane-ene systems were prepared by reaction of polyester or polyether dlols with allyl isocyanate or by reaction of isocyanate-terminated prepolymers with allyl alcohol. These urethane-ene systems can be cured by branched monomeric polythiols such as pentaerythritol tetrakis(thioglycolate) C(CH20C0CH2SH)4. 

The autoxidation of triphenylphosphine and phosphorus esters has been studied kinetically. After a short induction period the reaction gave the corresponding quinquecovalent phosphorus compounds. The intermediate (55) is probably formed by the addition of oxygen to perfluoroacyl-diarylphosphines. Subsequent decomposition afforded diarylphosphinates (56). The oxadiazine (57) has been prepared from the reaction of carbon dioxide and allyl isocyanate in the presence of tributylphosphine. ... 

Cyclic diacylurea is prepared by the condensation of succinimide and allyl isocyanate which upon acid hydrolysis affords the eleavage of the ring of the succinimide. Oxymercuration of the terminal olefin bond in the presence of mercurie aeetate in methanol solution gives [3-[3-(3-caboxy-propionyl ureido]-2-methoxypropyl]-hydroxy mereury. This on eondensation with an equimolar portion of theophylline gives the official compound. 

Camphoric acid on condensation with ammonia and subsequent treatment with allyl isocyanate aflfords an intermediate which on reaction with mercuric acetate in methanol gives rise to the corresponding mercury derivative as acetate. This on treatment with sodium chloride followed by sodium thioglycollate in aqueous NaOH solution yields the offieial eompound which may be obtained either by evaporation or by preeipitation with an appropriate solvent. 

Allyl cyanates undergo a [3,3] sigmatropic rearrangement to allyl isocyanates, as depicted in reaction 36. ... 

Polyhydroxylated piperidines such as 16 are of interest as glucosidase inhibitors. Antoni Riera, also of the University of Barcelona, has developed J. Org. Chem. 2005. 70, 2325) a route to 16 from the readily-available enantiomerically-pure epoxide 11. Condensation with allyl isocyanate 12 followed by cyclization gave 13, which was further cyclized by a Grubb s catalyst (unspecified) to 14. Protection set the stage for face-selective dihydroxylation, to give 15. Several other piperidines having other polyhydroxylation patterns were also prepared from 14. 

Allyl isocyanate (isocyanic C3H5NCO acid allyl ester) [1476-23-9] 83.12... 

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