Acetals allylations

With higher alkenes, three kinds of products, namely alkenyl acetates, allylic acetates and dioxygenated products are obtained[142]. The reaction of propylene gives two propenyl acetates (119 and 120) and allyl acetate (121) by the nucleophilic substitution and allylic oxidation. The chemoselective formation of allyl acetate takes place by the gas-phase reaction with the supported Pd(II) and Cu(II) catalyst. Allyl acetate (121) is produced commercially by this method[143]. Methallyl acetate (122) and 2-methylene-1,3-diacetoxypropane (123) are obtained in good yields by the gas-phase oxidation of isobutylene with the supported Pd catalyst[144]. 

Benzene, propyl acetate, allyl acetate, 1-pentanol, cyclohexanone, cyclohexanol, dicyclohexyl ether, cyclohexyl valerate, butyric acid, valeric acid, caproic acid, 1,5-pentanediol, dicyclohexyl succinate, and dicyclohexyl glutarate 30 m DB-FFAP column, 60-200° at 67min. 

Show how organoborane intermediates can be used to synthesize the gypsy moth pheromone E, Z-CH3C02(CH2)4CH=CH(CH2)2CH=CH(CH2)3CH3 from hept-6-ynyl acetate, allyl bromide, and 1-hexyne. 

Another route to the diol monomer is provided by hydroformylation of allyl alcohol or allyl acetate. Allyl acetate can be produced easily by the palladium-catalyzed oxidation of propylene in the presence of acetic acid in a process similar to commercial vinyl acetate production. Both cobalt-and rhodium-catalyzed hydroformylations have received much attention in recent patent literature (83-86). Hydroformylation with cobalt carbonyl at 140°C and 180-200 atm H2/CO (83) gave a mixture of three aldehydes in 85-99% total yield. 

In the 1952 paper mentioned above [3], Gilman reported on the formation of lithium dimethylcuprate from polymeric methylcopper and methyllithium. These so-called Gilman cuprates were later used for substitution reactions on both saturated [6] and unsaturated [7, 8, 9] substrates. The first example of a cuprate substitution on an allylic acetate (allylic ester) was reported in 1969 [8], while Schlosser reported the corresponding copper-catalyzed reaction between an allylic acetate and a Grignard reagent (Eq. 2) a few years later [10]. 

The time for optimized conversion has been determined by GLC for all olefins. It is crucial for all reactions to be stopped at optimum conversion, because slow decomposition of the allylic product occurs during the reaction. To obtain optimum yields one should follow the reaction by GLC. Optimized conversion is defined as allylic acetate/allylic acetate plus remaining olefin. 

Acetate Allyl Chloro-difluoro-F.I0b2, 224f. (Educt)... 

Allyl Acetate. Allyl acetate is produced mostly for manufacturing allyl alcohol. 

Property Allyl chloride Allyl acetate Allyl methacrylate AGE Allyl amine DMAA1... 

Alkyl groups attached to aromatic rings are oxidized more readily than the ring in alkaline media. Complete oxidation to benzoic adds usually occurs with nonspecific oxidants such as KMn04, but activated tertiary carbon atoms can be oxidized to the corresponding alcohols (R. Stewart, 1965 D. Arndt, 1975). With mercury(II) acetate, allylic and benzylic oxidations are also possible. It is most widely used in the mild dehydrogenation of tertiary amines to give, enamines or heteroarenes (M. Shamma, 1970 H. Arzoumanian, 1971 A. Friedrich, 1975). 

Thus a synthesis of M based on this retrosynthetic analysis would start with edryl acetate, allyl bromide, and 3-phenyl-l-propanol. 

In another study several simple silenes RR Si=CH2 (R, R = Me, Vinyl etc.) were formed by laser-powered pyrolysis and were found to form linear polymers, in contrast to the usual behavior of silenes which yield cyclodimers when formed by conventional thermolysis techniques16. Reactions of the silenes in the presence of several monomers such as vinyl acetate, allyl methyl ether and methyl acrylate were also studied. Laser-induced decomposition of silacyclobutane and 1,3-disilacyclobutane gave rise to silenes and other oxygen-sensitive deposits17,18. 

The in situ regeneration of Pd(II) from Pd(0) should not be counted as being an easy process, and the appropriate solvents, reaction conditions, and oxidants should be selected to carry out smooth catalytic reactions. In many cases, an efficient catalytic cycle is not easy to achieve, and stoichiometric reactions are tolerable only for the synthesis of rather expensive organic compounds in limited quantities. This is a serious limitation of synthetic applications of oxidation reactions involving Pd(II). However it should be pointed out that some Pd(II)-promoted reactions have been developed as commercial processes, in which supported Pd catalysts are used. For example, vinyl acetate, allyl acetate and 1,4-diacetoxy-2-butene are commercially produced by oxidative acetoxylation of ethylene, propylene and butadiene in gas or liquid phases using Pd supported on silica. It is likely that Pd(OAc)2 is generated on the surface of the catalyst by the oxidation of Pd with AcOH and 02, and reacts with alkenes. 

Tandem acetalization-allylation reaction of aldehydes with allylsilanes provides a convenient route to homoallyl ethers.82 Under catalysis by Sc(OTf)3, various aldehydes can be converted into homoallyl ethers by treatment with... 

From what we have discussed in (b"), it follows that when the two sets of D(Cj) data derived from sorption experiments and permeation experiments do not agree with one another within the expected limits of accuracy, the sorption values of D are incorrect and the measured sorption processes are non-Fickian. This method of examining whether sorption is Fickian or not is particularly useful when the experimental sorption curve has a shape equivalent to the true Fickian curve. Meares (1958a) demonstrated that the D values for the system polyvinyl acetate-allyl chloride at 40° C. determined from steady-state permeation data in-... 

Nielson GD, Bakbo JC, Holst E. 1984. Sensory irritation and pulmonary irritation by airborne allyl acetate, allyl alcohol and allyl ether compared to acrolein. Acta Pharmacol Toxicol 54 292- 298. 

Acetaldehyde Diethyl Acetal 2-Acetyl Thiazole Allyl Phenoxy Acetate Allyl Propionate Borneol... 

Hydrogenolysis of allylic acetates. Allylic acetates (or carbonates or chlorides) are converted into terminal alkenes by ammonium formate using a Pd(ll) catalyst com-plexed with a trialkylphosphine, particularly P(n-Bu),. 

That mercury(ll) acetate allylic oxidatimi can be a usrful reaction in the case of complex and sensitive substrates is demonstrated by the oxidation of avomectin A2a (38). The reaction, carried out in anhydrous toluene at 100 C for 40 min, was mnaikably selective, allylic oxidation occurring exclusively at the 3,4-double bond with rearrangement to give (39) in up to 73% yield (equation 17). 

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