Ketones, diallyl

Ketones can be prepared by trapping (transmetallation) the acyl palladium intermediate 402 with organometallic reagents. The allylic chloride 400 is car-bonylated to give the mixed diallylic ketone 403 in the presence of allyltri-butylstannane (401) in moderate yields[256]. Alkenyl- and arylstannanes are also used for ketone synthesis from allylic chlorides[257,258]. Total syntheses of dendrolasin (404)f258] and manoalide[259] have been carried out employing this reaction. Similarly, formation of the ketone 406 takes place with the alkylzinc reagent 405[260],... 

Goure Wright Davis Labadie Slille J. Am. Chem. Soc. 1984,106, 6417. For a similar preparation of diallyl ketones, see Merrifield Godschalx Slille Organometallics 1984, 3, 1108. 

The reactions of allyliron tricarbonyl halides with donor molecules were studied. Triphenylphosphine substituted only one carbonyl, that trans-oriented with respect to the halogen of the form (XIX) [432). The phosphine derivatives of (XX) were not isolated as pure compounds. The complexes were decomposed entirely by dimethyl sulfoxide, giving [(0113)280] jFeX2 [435). Thermal decomposition of C3H5Fe(CO)3X depended on the medium and gave either diallyl, or diallyl ketone, together with propene, allyl ether, Fe(CO)5, and FeX2 [436). 

Meerifield, J. H., Godschal, J. P., Stille, J. K. Synthesis of unsymmetrical diallyl ketones the palladium-catalyzed coupling of allyl halides with allyltin reagents in the presence of carbon monoxide. Organometallics 3, 1108-1112. 

The Norrish Type I reaction usually leads to decarbonylation. This is the case with dicyclopropyl ketone on irradiation at 193 nm. Decarbonylation, however, is a second step and this is preceded by ring opening of the cyclopropyl moieties to diallyl ketone. Calculations have shown that decarbonylation of cyclobutanone occurs from the nji triplet state. The resultant triplet trimethylene biradical undergoes ISC to the ground state before formation of cyclopropane. On the other hand, the cycloelimination reaction to yield ketene and ethene arises from the singlet excited state.Irradiation of cyclopentanone in aqueous and frozen aqueous solutions has been examined and the influence of applied magnetic fields assessed. Photodecarbonylation in the crystalline phase of the ketone (3) at 310 nm takes place stereospecifically with the formation of the cyclopentane derivative (4). The latter can be readily transformed into racemic herbertenolide (5). ... 

Palladium catalyses the coupling of vinylstannanes to vinyl iodide/co, to give divlnyl ketones (diallyl ketones prepared... 

Dialkoxytitanium phosphinates, preparation of, 251 Diallyldiethylammonium bromide, cyclopolymerization of, 32 Diallyl ketones,... 

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]. 

The ketones 47-49 can be made in good yield (55-95%) by RCM of the appropriate diallyl compounds using 8 as catalyst234. If the spacing between the two C=C bonds in the reactant is increased to ten bonds, then ADMET polymerization is the preferred reaction at normal concentrations. However, by working at 10-3 M it is possible to favour the RCM of oleon (50), equation 35, to give civetone (51) (musk odour) with a yield of up to 14%235. This method of preparation of 51 has the advantage that the metathesis reaction... 

The Pd enolates also undergo the intramolecular Michael addition when the allyl / -keto carboxylate or diallyl malonate 450, in which an enone is present at a suitable position, is treated with Pd(0) catalyst [190], The main product is the saturated ketone 451, and the allylated product 452 is obtained as a byproduct. 

Diallyl phthalate, diallyl isophthalate Acetone, methyl ethyl ketone Abrasion. Grit or vapor blast or 100-grit emery cloth followed by solvent degreasing. Steel wool may be used for abrasion... 

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... 

The more reactive ft -carbon atom of ketone a,/ -dianions can be regiospecifically coupled with alkyl halides to give first lithium enolates, which are then trapped by more reactive carbon electrophiles such as allylic halides. The first example shown in Table 8 deals with the sequential /1-alkylation and ce-allylation of a ketone a,/1-dianion1 13. Thus, the dianion underwent regioselective alkylation at the ft carbon with //-pentyl bromide and then allylation with allyl bromide at the a carbon. When an excess of allyl bromide is reacted with the a, ft -dianion, the diallylated product is obtained in a good yield, whereas a threefold excess of pentyl bromide only resulted in the formation of the ft-alkylation product. Similar consecutive alkyl/allyl-type reactions are also possible for ketone a,5-dianions14. 

The preparation of a-selenoketones, esters, nitriles and related compounds can easily be performed via alkylation of the corresponding enolates or stabilized carbanions [21]. These compounds have found many synthetic applications in radical chemistry. In Eq. (9), a typical example involving a ketone is depicted [22]. The stability of a-selenoketones such as 41 is remarkable. Similar reactions with lactones have been performed. For instance, this approach has been applied to the stereoselective synthesis of oxygen-containing rings to either faces of a bicyclic structure [23]. The approach based on a-selenenylation/radical allyla-tion compares favorably with classical enolate allylation procedures, which usually leads to mixture of mono- and diallylated compounds. Furthermore, this strategy is excellent for the preparation of quaternary carbon centers [24] as shown by the conversion of 43 to 45, a key intermediate for the synthesis of fredericamycin A, [Eq. (10)] [25]. Similar reactions with sulfoxides [26] and phosphonates [27] have also been reported. 

A,A-Disubstituted amides can be converted to alkynyl ketones by treatment with alkynylboranes RCONR2 + (R C=C)3B RCOC=CR. Lactams react with triallylborane to give cyclic 2,2-diallyl amines after treatment with methanol, and then aqueous hydroxide. Triallylborane reacts with the carbonyl group of lactams, and after treatment with methanol and then aqueous NaOH gives the... 

CO2. CHj, CO. H . propene. isobutene, dimethyl ketene. acrolein, diallyl ether, allyl methacrylate monomer and dimer, chain fragments including anhydnde structures from side-group cydization. and an aliphatic ketone in the vidnity of unsaturation CO , SO , phenol, bisphenol S, hydroquinone. fragments of backbone, benzene sulfonic acid... 

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