Allyl chloride oxidation

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... 

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]. 

Quantitative Analysis of All llithium Initiator Solutions. Solutions of alkyUithium compounds frequentiy show turbidity associated with the formation of lithium alkoxides by oxidation reactions or lithium hydroxide by reaction with moisture. Although these species contribute to the total basicity of the solution as determined by simple acid titration, they do not react with allyhc and henzylic chlorides or ethylene dibromide rapidly in ether solvents. This difference is the basis for the double titration method of determining the amount of active carbon-bound lithium reagent in a given sample (55,56). Thus the amount of carbon-bound lithium is calculated from the difference between the total amount of base determined by acid titration and the amount of base remaining after the solution reacts with either benzyl chloride, allyl chloride, or ethylene dibromide. 

Metal oxides. Magnesium oxide is used to cure polychloroprene by converting its few active allylic chloride from 1,2 addition into ether cross-links. There is a synergistic effect when magnesium oxide is used in combination with t-butyl phenolic resins in solvent-borne polychloroprene adhesives. When solvent is removed, the phenolic group in the resin reacts with the magnesium oxide to cross-link [49]. 

Examples for necessary process improvements through catalyst research are the development of one-step processes for a number of bulk products like acetaldehyde and acetic acid (from ethane), phenol (from benzene), acrolein (from propane), or allyl alcohol (from acrolein). For example, allyl alcohol, a chemical which is used in the production of plasticizers, flame resistors and fungicides, can be manufactured via gas-phase acetoxylation of propene in the Hoechst [1] or Bayer process [2], isomerization of propene oxide (BASF-Wyandotte), or by technologies involving the alkaline hydrolysis of allyl chloride (Dow and Shell) thereby producing stoichiometric amounts of unavoidable by-products. However, if there is a catalyst... 

Later, Torii et al. found that the tin-aluminum-mediated allylation can be carried out with the less expensive allyl chloride, instead of allyl bromide, when a mixture of alcohol-water-acetic acid was used as the solvent.77 When combined with stoichiometric amounts of aluminum powder, both stoichiometric and catalytic amounts of tin are effective. As reported by Wu et al., higher temperatures can be used instead of aluminum powder.78 Under such a reaction condition, allyl quinones were obtained from 1,4-quinones, followed by oxidation with ferric chloride. Allylation reactions in water/organic solvent mixtures were also carried out electrochemically, with the advantage that the allyltin reagent could be recycled.79... 

ETHYLENE GLYCOL ETHYL MERCAPTAN DIMETHYL SULPHIDE ETHYL AMINE DIMETHYL AMIDE MONOETHANOLAMINE ETHYLENEDIAMINE ACRYLONITRILE PROPADIENE METHYL ACETYLENE ACROLEIN ACRYLIC ACID VINYL FORMATE ALLYL CHLORIDE 1 2 3-TRICHLOROPROPANE PROPIONITRILE CYCLOPROPANE PROPYLENE 1 2-DICHLOROPROPANE ACETONE ALLYL ALCOHOL PROPIONALDEHYDE PROPYLENE OXIDE VINYL METHYL ETHER PROPIONIC ACID ETHYL FORMATE METHYL ACETATE PROPYL CHLORIDE ISOPROPYL CHLORIDE PROPANE... 

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. 

T etrachloroethylene, 1,1,1 -Trichloroethane Chlorine oxides, see 1,1,1-Trichloroethane Chloroacetaldehyde, see Allyl chloride, 1,2-... 

Olefination of the Aldehyde 178 using a stabilized Wittig reagent followed by protecting group chemistry at the lower branch and reduction of the a,p-unsaturated ester afforded the allylic alcohol 179 (Scheme 29). The allylic alcohol 179 was then converted into an allylic chloride and the hydroxyl function at the lower branch was deprotected and subsequently oxidized to provide the corresponding aldehyde 161 [42]. The aldehyde 161 was treated with trimethylsilyl cyanide to afford the cyanohydrin that was transformed into the cyano acetal 180. The decisive intramolecular alkylation was realized by treatment of the cyano acetal 180 with sodium bis(trimethylsi-lyl)amide. Subsequent treatment of the alkylated cyano acetal 182 with acid (to 183) and base afforded the bicyclo[9.3.0]tetradecane 184. 

Subsequently to rhodium coordination with the enyne to form X, oxidative addition with the allyl chloride affords a rhodium-7r-allyl complex. Then isomerization... 

Epichlorohydrin (chloropropylene oxide) is used for the production of epoxy resins. It is produced by the dehydrochlorination of 2,3-dichloro-l-propanol (structure 17.23). The hydrin is produced by the chlorohydrination of allyl chloride. 

Activation of allyl chloride to genotoxic substances appears to involve aldehydes, since inhibition of aldehyde dehydrogenase by cyanamide increases the mutagenic activity in Salmonella typhimurium TAIOO on the other hand neither SKF525 nor 1,1,1-tri-chloropropene-2,3-oxide affect the mutagenicity, so that metabolic activation via an epoxide is unlikely (Neudecker Henschler, 1986). 

Since allyl chloride could be converted to glycerol by several routes, the synthesis of glycerol from propylene [115-07-1] became possible. Propylene can also be oxidized in high yields to acrolein [107-02-8]. Several routes for conversion of acrolein to glycerol are shown in Figure 1. 

With fumaronitrile and maleic anhydride, IR spectra, after adding olefin and HCN to NiL3, showed only the very stable (olefin)NiL2 complexes. In these cases the oxidative addition of HCN is evidently suppressed by the strongly electron withdrawing character of the olefins. Small amounts of the reduction products were detected by GC/MS after the solutions had stood for a day, however. The failure of allyl chloride to hydrocyanate is no doubt due... 

There are four processes for industrial production of allyl alcohol. One is alkaline hydrolysis of allyl chloride. A second process has two steps. The first step is oxidation of propylene to acrolein and the second step is reduction of acrolein to allyl alcohol by a hydrogen transfer reaction, using isopropyl alcohol. At present, neither of these two processes is being used industrially. Another process is isomerization of propylene oxide. Until 1984. all allyl alcohol manufacturers were using this process. Since 1985 Showa Denko K.K. has produced allyl alcohol industrially by a new process which they developed- This process, which was developed partly for the purpose of producing epichlorohydrin via allyl alcohol as the intermediate, has the potential to be the main process for production of allyl alcohol. The reaction scheme is as follows ... 

Addition of HBr in the presence of an oxidizing agent yields l-chloro-3-bromopropune. which is used to prepare cyclopropane. Allyl chloride is one of the most loxic of the chlorinated organics. 

The oxidations of C5-C8 olefins, allyl chloride, allyl alcohol, and allyl methacrylate with H202 give the corresponding epoxides. Data characterizing oxidations carried out in methanol solvent at an olefin concentration of 0.90 M, in the presence of TS-1 (6.2 g/L), are given in Table V. 

The oxidative carbonylation of arenes to aromatic acids is a useful reaction which can be performed in the presence of Wacker-type palladium catalysts (equation 176). The stoichiometric reaction of Pd(OAc)2 with various aromatic compounds such as benzene, toluene or anisole at 100 °C in the presence of CO gives aromatic acids in low to fair yields.446 This reaction is thought to proceed via CO insertion between a palladium-carbon (arene) allyl chloride, but substantial amounts of phenol and coupling by-products are formed.447... 

Replacement of ligands in C3H5MoCl(CO)2(NCMe)2 by isocyanides has given the substituted products C3H5MoC1(CO)2(CNR)2 (R = alkyl) and C3H5MoC1(CO)(CNBu )3, and the reduced products [MoC1(CNBu )4]2 and m-Mo(CO)2(CNR)4 (R = Me, Et). No rationale for the loss of allyl and allyl chloride in the latter two cases was proposed (206). These reactions are rare examples of the formation of low-oxidation state metal-isocyanide complexes via reductive elimination of allyl or allyl chloride from metal-allyl species. The potential applications of mono-, bis-, and tris-n-allylic systems as precursors to low-oxidation state compounds remain to be explored. Substitution and simultaneous reduction of Mo(SBu )4 also occurred on reaction with CNBu to give Mo(SBu )2(CNBu )4 (207) (see Section IV,D,2). 

No oxidation of the allylic alcohol occurs, because the intermediate activated alcohols evolve very quickly to the corresponding allylic chlorides. 

The use of moist DMSO causes the generation of adventitious HC1, that produces the transformation of the allylic alcohol into an allylic chloride. A properly performed Swern oxidation, under anhydrous conditions, allows the obtention of the desired dialdehyde in... 

N-Allyl-tetranitroaniline, C HTNS Og—not found in Beil or CA through 1956 Allylazide 3-Triazapropene or 3-Azida-l-propene, N3. CH,. CH CH, mw 83.09, N 50.57%. Mobile liq, bp 76.5°, d 0.924 at 25/25 decomp violently on adding of coned HjS04 its vapor explodes when heated. Was first prepd by heating an ale soln of allyl chloride with an aq soln of NaN3. Fridman (Ref 3) studied its oxidation reaction, Sheinker Syrkin (Ref 4) detd its vibrational spectra and Shott-L vova Syrkin (Ref 5) its dipole moments... 

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