Miscellaneous reactions alkylation

Sulphonylbenzofurans 638 a-Sulphonyl carbanions 760, 766, 767, 797, 813, 951, 961 acylation of 627-636 addition to unsaturated bonds 636-642 alkylation of 627-636, 781 halogenation of 1058-1060 Michael addition of 642-649 miscellaneous reactions of 653-655 Ramberg-Backlund reaction of 649-653, 1057, 1058... 

Miscellaneous Reactions. - Finn and co-workershave reported the one-pot double deoxygenation of simple alkyl- and polyether-tethered aromatic... 

Miscellaneous Reactions.- Excited state alkyl nitrites undergo competing nitrogen-oxygen bond homolysis and exchange by labelled... 

Miscellaneous reactions. The sulfides are oxidized by an excess of e.g. hydrogen peroxide or 3-chloroperoxybenzolc acid to the corresponding sulfones. A controlled addition of peroxide yields a mixture of sulfoxide and sulfone products. The use of nitronium hexafluorophosphate or tetrafluoroborate to oxidize dlalkyl, aryl alkyl or dlaryl sulfides yields only the corresponding sulfoxide under extremely mild conditions (224). Sulfoxides may be further oxidized to the corresponding sulfones In good yield by the nitronium salts as well (225). 

The use of organic halogen compounds as the starting products for the synthesis of other organic chemicals is too immense a field to do more than indicate some of the commercial applications. In his book I4S) on the chemistry of petroleum derivatives, Ellis includes a chapter on the production of alcohols and esters from alkyl halides, and also one on miscellaneous reactions of halo-paraffins and cycloparaffins. The manufacture of amyl alcohols and related products from the chlorides has been well covered 14 ) 1 )-A two-step process for the synthesis of cyclopropane by chlorinating propane from natural gas and dechlorinating with zinc dust was devised in 1936 152). A critical review of syntheses from l,3-dichloro-2-butene was published in Russia in 1950 (1-54). The products obtainable from the allylic chlorides are covered in a number of articles 14If 14 157). 

Miscellaneous Reactions.- Oxygen versus carbon alkylation of p-... 

Miscellaneous Reactions. - p-Toluenesulfonaraide undergoes Mitsunobu-type reactions in the presence of alcohols and cyanomethylenetriphenyl-phos-phorane (56) to give predominantly mono-N-alkylation products. This reaction has also been applied to the synthesis of cyclic ethers from diols and cyclic amines from amino alcohols and to carbon-carbon bond formation. Examples of cyclic amine synthesis include that of (+)-a-skytanthine (57). A comparative study of the reactions of active methine compounds (58) as nucleophiles using... 

Several selective cleavage reactions (classed as miscellaneous reactions in the introduction to this section) have been described. Thus, preferential 0-deacetylation of a phenyl acetate in the presence of an alkyl acetate occurred when 3-(4-acetoxy-3-methoxyphenyl)propylacetate was allowed to stand in pyrrolidine (or pyrrolidine in dichloromethane) at ambient temperature for 3 mins, followed by acidic quenching, to give 3-(3-methoxy-4-hydroxy)propylacetate in more than 80% yield (ref. 88). 

Hazardous properties, including toxicity, flammability, and explosive reactions of miscellaneous metal alkyls are presented in Table 32.2. 

Miscellaneous Reactions of Phosphines.- Theoretical treatments have appeared of a number of strained heterocyclic phosphine systems, notably phospha[3]radiaIene (148), triphospha[l, 1, l]propellane (149), and the tetraphosphacubane system (150). The reactivity of tetrakis-r-butyltetraphosphacubane has been studied in superacid media, with respect to protonation, alkylation, and alkynylation. Stable monophosphonium ions have been characterised. ... 

Miscellaneous Reactions. A study of the photodissociation of ketene under jet-cooled conditions in the 193-215 nm wavelength range has shown that bond fission to afford H atoms is a principal reaction.Acryloyl chloride undergoes C-Cl bond fission on irradiation at 193 nm. The photodecarbon-ylation of the cyclopropenones (54) occurs quantitatively on irradiation in methanol solution to yield the corresponding alkynes. The quantum yield for decarbonylation for the alkyl substituted derivatives is in the range 0.2-0.3, while for the aryl derivatives = 0.7. A determination of the reaction dynamics for the photodissociation of diphenylcyclopropenone has shown that the dissociation occurs from the So state. 

Miscellaneous Reactions. The reactions of the selenosulfon-ate with acyl derivatives of 7V-hydroxy-2-thiopyridone, alkyl, alkenyl, and alkynyl derivatives of tin and mercury triethylger-mane and diazomethane have also been reported, but the synthetic potential of these processes remains to be determined. 

Miscellaneous Reactions. Voelter and co-workers have observed the exclusive formation of the unexpected alkylation product 33, along with recovered starting material in their attempt to promote a [3 + 2] cycloaddition of 32 with Pd-TMM (eq 51). They speculated that either enolate formation or an electron-transfer process disrupt the expected [3 + 2] cycloaddition of 32 with Pd-TMM. 

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