Allylic derivatives allyl chloride

Benzoic acid and naphthoic acid are formed by the oxidative carbonylation by use of Pd(OAc)2 in AcOH. t-Bu02H and allyl chloride are used as reoxidants. Addition of phenanthroline gives a favorable effect[360], Furan and thiophene are also carbonylated selectively at the 2-position[361,362]. fndole-3-carboxylic acid is prepared by the carboxylation of 1-acetylindole using Pd(OAc)2 and peroxodisulfate (Na2S208)[362aj. Benzoic acid derivatives are obtained by the reaction of benzene derivatives with sodium palladium mal-onate in refluxing AcOH[363]. 

Aldehydes can also be prepared by the carbonylation of aryl and alkenyl halides and triflate, and benzyl and allyl chlorides using tin hydride as a hydride source and Pd(PhjP)4 as a catalyst[377]. Hydrosilancs arc used as another hydride source[378]. The arenediazonium tetralluoroborate 515 is converted into a benzaldehyde derivative rapidly in a good yield by using Et ,SiH or PH MS as the hydride source[379]. 

Previous syntheses of terminal alkynes from aldehydes employed Wittig methodology with phosphonium ylides and phosphonates. 6 7 The DuPont procedure circumvents the use of phosphorus compounds by using lithiated dichloromethane as the source of the terminal carbon. The intermediate lithioalkyne 4 can be quenched with water to provide the terminal alkyne or with various electrophiles, as in the present case, to yield propargylic alcohols, alkynylsilanes, or internal alkynes. Enantioenriched terminal alkynylcarbinols can also be prepared from allylic alcohols by Sharpless epoxidation and subsequent basic elimination of the derived chloro- or bromomethyl epoxide (eq 5). A related method entails Sharpless asymmetric dihydroxylation of an allylic chloride and base treatment of the acetonide derivative.8 In these approaches the product and starting material contain the same number of carbons. 

After succeeding in the direct synthesis of allyidichlorosilane hy reacting elemental silicon with a mixture of allyl chloride and hydrogen chloride in 1993," Jung el cil. reinvestigated the Friedel-Crafts reactions of benzene derivatives with allyidichlorosilanes in detail (Eq. (2)). 

A crystal structure of the C02 derivative of (8), K[Co(salen)( 71-C02)], haso been reported in which the Co—C bond is 1.99 A, the C—O bonds are both equivalent at 1.22 A and the O-C-O angle is 132°.125 Carboxylation of benzylic and allylic chlorides with C02 in THF-HMPA was achieved with (8) electrogenerated by controlled-potential electrolysis,126 in addition to reductive coupling of methyl pyruvate, diethyl ketomalonate and / -tolylcarbodiimide via C—C bond formation. Methyl pyruvate is transformed into diastereomeric tartrates concomitant with oxidation to the divalent Co(salen) and a free-radical mechanism is proposed involving the homolytic cleavage of the Co—C bond. However, reaction with diphenylketene (DPK) suggests an alternative pathway for the reductive coupling of C02-like compounds. 

In contrast to ethyl diazoacetate, diethyl diazomalonate reacts with allyl bromide in the presence of Rh2(OAc)4 to give the ylide-derived diester favored by far over the cyclopropane (at 60 °C 93 7 ratio). This finding bespeaks the greater electrophilic selectivity of the carbenoid derived from ethyl diazomalonate. For reasons unknown, this property is not expressed, however, in the reaction with allyl chloride, as the carbenoids from both ethyl diazoacetate and diethyl diazomalonate exhibit a similarly high preference for cyclopropanation. 

Allyl acetals154). Allyl ethers give no or only trace amounts of ylide-derived products in the Rh2(OAc)4-catalyzed reaction with ethyl diazoacetate, thus paralleling the reactivity of allyl chloride. In contrast, cyclopropanation must give way to the ylide route when allyl acetals are the substrates and ethyl diazoacetate or dimethyl diazomalonate the carbenoid precursors. 

Ylide-derived products may be formed as minor by-products from propargylic chlorides or ethers this contrasts with the inertness of allylic chloride or ethers... 

Other protocols, such as iodocyclization of alkene or alkyne 345 affording 346 (Equation 60) <1996JA9073, 2000BML2015>, cyclization of allyl chloride derivative <1998EJO509>, or of mesylate <1998JOC5680> were used in order to access this class of products. 

Allylations of hydroquinone derivatives, 32 459-461 Allyl chloride oxidation, 41 305 thermal decomposition, 41 80 tl-Allyl complexes, 25 129-134 Allyl hydroperoxide, 27 187-189 Allylic alcohols, olefinic substitution of, 26 343-345... 

In the cases of a series of allyl chlorides derived from the antibiotic cephalosporin, reduction leads to a delocalised carbanion, which is protonated on die ester... 

The same strategy has been used by Williams (90JA808) in his synthesis of brevianamide B. The aldehyde (82), prepared enantioselectively from L-proline, was converted to the silyl ether. Acylation of this (BuLi, ClC02Me) gave the carbomethoxy derivative as a mixture of diastereo-mers, which was alkylated by gramine. As before, an enolate alkylation (Sn2 ) on an allyl chloride derived from the above gave the tricyclic compound, which could be transformed to brevianamide B (Scheme 24). 

Hydrolysis of Chlorinated Hydrocarbons. The production of oxygenated aliphatics by the hydrolysis of chlorinated hydrocarbons includes the synthetic glycerol process and the amyl alcohols process. Glycerol (7) is made from propylene via allyl chloride (CH2 CHCH2C1), and competes with glycerol made from fats and oils for use in dynamite and alkyd resins, as a tobacco humectant and cellophane plasticizer, in cosmetics and pharmaceuticals, and for other applications. Amyl alcohols have been made since 1926 by the alkali hydrolysis of a mixture of amyl chlorides, made by the chlorination of pentanes from natural gasoline. Production from this source far exceeds the supply from the fusel oil by-product of fermentation processes. Amyl alcohol and its derivatives are used mainly as solvents. 

Allyl chloride is used to make intermediates for downstream derivatives such as resins and polymers. Approximately 90% of allyl chloride production is used to synthesize epichlorohydrin, which is used as a basic building block for epoxy resins and in glycerol synthesis. Allyl chloride is also a starting material for allyl ethers of phenols, bisphenol A and phenolic resins, and for some allyl esters. Other compounds made from allyl chloride are quaternary amines used in chelating agents and quaternary ammonium salts, which are used in water clarification and sewage sludge flocculation (Kneupper Saathoff, 1993). 

ALLYL CHLORIDE. See Chlorinated Organics Allyl Alcohol and Monoallyl Derivatives. 

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