Reactions with allyl chloride

Even more impoitandy, these lead to reduction by-products in the commercial hydrosdylation reaction with allyl chloride. 

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. 

Less extended investigations have been carried out for the stereochemistry of further substitution reactions, which mostly proceed with lower regioselectivities a-carboxylation (inversion) reaction with methyl chloroformate in the a-position (inversion) a-acylation by 2,2-dimethylpropanoyl chloride (inversion)" y-methylation by methyl iodide (anti-S g) and methyl triflate syn-S f° , intramolecular reactions with allyl chlorides (a, inversion or y, awh -S see Section IV.C.3). 

The 3-phenylthieno[2,3-d]pyrimidine-2,4-diones 3b and the corresponding -4-one-2-thiones 4b were converted into the respective 2-allyloxy 139a and 2-allylthio 139b derivatives by reaction with allyl chloride in base (89KGS347). 

The data in Table II demonstrate that the effectiveness for poly (vinyl chloride) stabilization of dibutyltin salts of maleic acid or monoesters of maleic acid is caused by a high rate of reaction with allylic chloride moieties. Thus, it is not necessary to postulate, as has been done several times in the literature, that these compounds are effective because they are dieneophiles and therefore capable of disrupting the long chains of unsaturation responsible for color formation. It is gratifying that the performance of the maleate stabilizers is consistent with the Frye-Horst substitution hypothesis. 

Therefore, the isomerization reaction was also performed starting from the a-substituted enol ether 119 (Scheme 52). By using the tandem allylic C-H activation-elimination reactions, Z-120c is initially formed and by a transmetalation reaction into organocopper with a stoichiometric amount of CuCI/ 2LiCl, followed by heating at +50 °C for 1 h and reaction with allyl chloride, the resulting ( , )-diene 122 is obtained with an isomeric ratio of 90 10 but in a low 40% yield as described in Scheme 52. 

OSHA PEL TWA 1 mg(Fe)/m3 ACGIH TLV TWA 1 mg(Fe)/m3 DOT CLASSIFICATION 8 Label Corrosive SAFETY PROFILE Poison by ingestion and intravenous routes. Experimental reproductive effects. Corrosive. Probably an eye, skin, and mucous membrane irritant. Mutation data reported. Reacts with water to produce toxic and corrosive fumes. Catalyzes potentially explosive polymerization of ethylene oxide, chlorine + monomers (e.g., styrene). Forms shock-sensitive explosive mixtures with some metals (e.g., potassium, sodium). Violent reaction with allyl chloride. When heated to decomposition it emits highly toxic fumes of HCl. 

BORON FLUORIDE (7637-07-2) Reacts with moist air, water, steam, producing hydrogen fluoride, boric acid, and fluoboric acid. Violent reaction with allyl chloride, alkyl nitrate, benzyl nitrate, calcium oxide, ethyl ether, iodine, magnesium tetrahydroaluminate, active metals (except magnesium). Used as a polymerization catalyst contact with monomers may cause explosions. Corrodes most metals in the presence of moisture. 

Platinum vapour also has been observed to react with unsaturated compounds [286]. With propene and but-l-ene, compounds of undetermined structure are produced. Reaction with 1,5-cyclooctadiene produces b/s(l,5-cyclooctadiene) platinum(O), while reaction with allyl chloride yields the tetranuclear complex [PtCl(C3Hs)] 4. 

Reaction with allyl chlorides 14, 10.3.4.2.1 Reaction with Group IllB halides 14,... 

Reaction with allyl chloride 14, 10.3.3.LI Reaction with Group IVB halides 14, 10.3.3.1.1... 

Precaution DOT Corrosive catalyzes potentially explosive polymerization of ethylene oxide, chlorine + monomers violent reaction with allyl chloride reacts violently with water to form toxic and corrosive fumes reacts with moisture in air to form pungent hydrogen chloride... 

The yields of reactions with allyl chloride and/or bromide are quite good except for those cases where precipitates are formed. 

Allyl halides add to the more reactive d complexes. Both a- and w-allyl complexes are found, occasionally both in the same system. An example of this reaction with allyl chloride is that of 7r-cyclopentadienylcobalt dicarbonyl discovered by Fischer 58) and reinvestigated by Heck (66). Both cationic (XLI I) and neutral complexes (XLIII) are formed, depending on the conditions. The cationic sr-allyl complex (XLII) is interesting in that this is another example of the stepwise addition of an electrophile to a live-coordinate rf complex. The reader should remember that the formation of the TTrallyl group entails the loss of an additional neutral ligand. 

Draw the products of the reaction of 2-methylcylopentanone with LDA by reaction with allyl chloride. 

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