Allyl alcohol chloroformate

The reagent, b.p. 127-130°, is prepared by reaction of allyl alcohol in ether with methyl chloroformate and pyridine (86% yield). 

The chemistry and procedures for modification of the - CO2H groups of PAA hyperbranched grafts on PE powder were analogous to those used for PAA grafts on PE or PP films and wafers. For example, a 90% yield in ester formation was possible using acid-catalyzed Fisher esterification. Likewise, quantitative reduction (ethyl chloroformate activation, borane-dimethyl sulfide reduction) to hyperbranched poly(allyl alcohol)s and amidation all could be carried out using procedures like those used for PAA/Au surfaces. 

Oxidative stress Glutathione depletion (e.g., acetaminophen, bromoben-zene, chloroform, allyl alcohol) redox cyclers (see oxidative phosphorylation) reactive metabolites... 

As shown in Figure 12, the treatment of (1 mol equiv.) with allyl alcohol (2 mol equiv.) in the presence of anhydrous ferric chloride (1.5 mol equiv.) in dlchloromethane (Kiso and Anderson, 6) gave which was converted into m.p. 109° [a]j) -29.6° (chloroform) (87% yield from as described for the synthesis of Compound is a useful, common intermediate for... 

The most commonly used diallyl monomer is diallyl diethylene glycol carbonate, DADC or CR 39, developed for preparing clear, colorless, abrasion- and heat-resistant polymers (Table 2.29). DADC is obtained by reaction of diethylene glycol bis(chloroformate) with allyl alcohol, or allyl-chloroformate and diethylene glycol. 

The cyclohexene 121, which was readily accessible from the Diels-Alder reaction of methyl hexa-3,5-dienoate and 3,4-methylenedioxy-(3-nitrostyrene (108), served as the starting point for another formal total synthesis of ( )-lycorine (1) (Scheme 11) (113). In the event dissolving metal reduction of 121 with zinc followed by reduction of the intermediate cyclic hydroxamic acid with lithium diethoxyaluminum hydride provided the secondary amine 122. Transformation of 122 to the tetracyclic lactam 123 was achieved by sequential treatment with ethyl chloroformate and Bischler-Napieralski cyclization of the resulting carbamate with phosphorus oxychloride. Since attempts to effect cleanly the direct allylic oxidation of 123 to provide an intermediate suitable for subsequent elaboration to ( )-lycorine (1) were unsuccessful, a stepwise protocol was devised. Namely, addition of phenylselenyl bromide to 123 in acetic acid followed by hydrolysis of the intermediate acetates gave a mixture of two hydroxy se-lenides. Oxidative elimination of phenylselenous acid from the minor product afforded the allylic alcohol 124, whereas the major hydroxy selenide was resistant to oxidation and elimination. When 124 was treated with a small amount of acetic anhydride and sulfuric acid in acetic acid, the main product was the rearranged acetate 67, which had been previously converted to ( )-lycorine (108). 

Note Nonpolar solvent soluble in alcohols, ethers, chloroform, benzene, and most fixed and volatile oils insoluble in water nonflammable extremely toxic by inhalation, ingestion, or skin absorption carcinogenic incompatible with allyl alcohol, silanes, triethyldialuminum, and many metals (e.g., sodium). Synonyms tetrachloromethane, perchloromethane, methane tetrachloride, Halon-104. 

The addition product obtained from allyl alcohol and tellurium tetrachloride in refluxing chloroform, probably 3-chloro-2-hydroxypropyl tellurium trichloride, reacted with acetyl chloride or benzoyl chloride. 3-Chloro-2-acyloxypropyl tellurium trichlorides were isolated3. 

Studies of allyl ether migrations in this system have stemmed solely from the efforts of Makisumi.23,24 By reacting 5-methyl-7-chloro-s-triazolo-(l,5-a)pyrimidine with sodium allyloxide in allyl alcohol at room temperature, the corresponding 7-allyloxy derivative was obtained. When this was rearranged at 150°, during 30 minutes, seven different products were obtained. These were separated into chloroform-soluble and chloroform-insoluble material. Out of the latter, by fractional crystallization two products were isolated. One of these was... 

The chiral acetals of a,p-enals derived from (H,R)-( -I-)-N,N,N, N -tetramethyltartaric acid diamide (9, 47-48) undergo either 1,4- or I. . .-addition of R,AI with high asymmetric induction. The course of reaction can be controlled by the choice of solvent. 1,4-Addition is favored in 1,2-dichloroethane (or toluene) 1,2 addition is the main or only reaction in chloroform. The adducts can be converted into optically active p-alkyl aldehydes or allylic alcohols (Chart I). ... 

Oxidation. This mild oxidizing reagent can be used for selective oxidation of benzylic and allylic alcohols. Complete conversnm requires 3 equiv. of oxidant. Primary and secondary alcohols are oxidized slowly in refluxing chloroform, but require a large excess of oxidant. An example is the selective oxidation of 1-phenyl-1,3-propanediol to 3-hydroxy-1-phenyl-1-propanone (52% yield). 

In dilute solutions of aprotic solvents (hexane, chloroform) allylic hydroperoxides undergo a [2,3] sigmatropic rearrangement to form either an equilibrium mixture of allylic isomers or the thermodynamically more stable allylic hydroperoxides1 -3. The allylic alcohols were obtained by reduction of the hydroperoxides [P(C6H5)3, LiAlH4 see also Section D.4.9.]. 

In the steroid series tetrasubstituted double bonds are hydrogenated with difficulty or not at all, but they nevertheless consume perbenzoic acid. The product isolated, however, is not an epoxide but an allylic alcohol or a conjugated diene. The first case was encountered by Windaus and Luttringhaus, but a better documented example was reported by Windaus, Linsert, and Eckhardt. Reaction of A -cholesteryl acetate (1) with perbenzoic acid in chloroform afforded an unsaturated 98 17 CaH,. 

Allylic alcohols Dimethylacetamide diethyl acetal. p-PhenylsuIfonylbenzoylchloride. Amines Carbobenzoxy chloride. Cholesteryl chloroformate. 2,4-Dinitrobenzaldehyde. Di-p-toluyl-D-tartrate. Ethylene sulfide. N-Hydroxymethylphthalamide. Oxalic acid. 

The reaction of allyl alcohol with dichlorocarbene, generated from bromodichloro-methyl(phenyl)mercury/heat or chloroform/base/phase-transfer catalyst, does not afford the corresponding cyclopropane derivative. In the first case, allyl chloride, allyl formate and chloroform were formed and in the second case, tris(allyloxy)ethane (20%), l,l-dichloro-2-... 

Cyclic allylic alcohols fairly easily cycloadd dichlorocarbene, particularly if generated under chloroform/base/phase-transfer catalyst conditions. Five- and six-membered-ring allylic alcohols form a mixture of cis- and fran.v-isomers, while those of larger rings form only the trans-isomer. In contrast with the phase-transfer catalysis method, dichlorocarbene generated from bromodichloromethyl(phenyl)mercury did not add to cyclohex-3-en-1 -ol, while cyclonon-3-en-l-ol yielded exo-10,10-dichlorobicyclo[7.1.0]decan-2-ol (28 /o), which could not be purified. Examples of dichlorocarbene adducts to cyclic allylic alcohols are presented in Table 19. 

Acrylic acid and its fumes have a pungent, unpleasant odor and are a strong irritant. It is miscible with water, alcohol, chloroform and ether. It polymerizes easily in the presence of oxygen and has a boiling point of 141°C. Acrylic acid is obtained from the oxidation of allyl alcohol or acrylaldehyde. 

The oxidation can also be carried out in toluene or, in the case of very reactive alcohols (allylic or benzylic), in chloroform or methylene chloride. Allylic alcohols can be selectively oxidized in acetone. 

ALLYL CHLOROCARBONATE or ALLYL CHLOROFORMATE (2937-50-0) C4H5CIO1 Forms explosive mixture with air (flash point 88°F/31°C Fire Rating 3). Decomposes in water, forming chloroformic acid and allyl alcohol. Incompatible with strong oxidizers acids, alkali, caustics. 

---