Methyl chlorine

Imidazole, 2,4,5-trichloro-1-methyl-chlorination, 5, 398 Imidazole, 2,4,5-trideutero-iodination, 5, 401 Imidazole, 1-trifiuoroacetyl-reactions, 5, 451-452 Imidazole, 2-trifiuoromethyl-hydrolysis, 5, 432 Imidazole, 2,4,5-triiodo-nitration, 5, 396 synthesis, 5, 400 Imidazole, 1,2,4-trimethyl-photolysis, 5, 377 rearrangement, 5, 378 Imidazole, 1,2,5-trimethyl-photochemical rearrangement, 5, 377 rearrangement, 5, 378 Imidazole, 1,4,5-trimethyl-bromination, 5, 399 3-oxide... 

Pyrazine, 2-methoxy-3-sulfanilamido-plasma half-life, 1, 162 Pyrazine, methyl-chlorination, 3, 168 oxidation, 3, 168 reactions... 

The formal addition of a methane molecule to a ft-pyrrolic C — C double bond can be achieved when bishydroxytin(IV) octaethylporphyrin 17 is first treated with a chloroform/aluminum tribromide mixture to give 18 which can subsequently be reduced with sodium borohydride and dcmctalated with acid to give the methylated chlorin 19.23... 

Sometimes lateral chlorination can occur on a methyl or alkylthio substituent, especially when phosphorus pentachloride or its mixtures with phosphoryl chloride are used (91JHC1549). Reactions of 2-methyl-4(I//)-quinoline (67) exemplify this behavior (81CPB1069) (Scheme 31) 2-chloro-3- and -4-methyquinolines are also subject to methyl chlorinations by similar reagents (91JHC1549). Sulfuryl chloride and NCS are also likely to induce a proportion of lateral chlorination (83KFZ1055 86S835). 

We find, as described below, that these methyl + chlorine monolayers are active in forming methylchlorosilanes. Furthermore, studies of samples with and without promoters show changes in activity and selectivity which parallel those found over real catalysts, and the results are beginning to show how these additives influence the catalytic process. 

Figure 1. Relative rates of methyl chlorosilane formation from a methyl + chlorine monolayer on a CusSi surface. The Cu3Si surface was prepared by ion bombardment at 330 K, and a 1 1 ratio of methyl groups and chlorine atoms were reacted in these studies.

Figure 2. Comparison of the relative yields of methylchlorosilanes from methyl + chlorine monolayers on Cu3Si and doped CuaSi samples with typical yields for the catalytic Rochow process.

A methyl radical abstracts a This step produces a molecule of methyl chlorine atom from a chloride and a cholrine atom. The chlorine chlorine molecule. atom can now cause a repetition of Step 2. 

Summary Tri- butylstannane is a valuable reagent for partial conversion of Si-Cl into Si-H functions. Now it is possible to obtain disilanes containing methyl, chlorine and hydrogen simultaneously by treatment of methylchlorodisilanes with Bu3SnH in the presence of a catalyst. 

The pKa of the methylene protons of 7 is close to that of cyanacetic ester. Thus, it was interesting to compare the reactions of these two species. We found that 7 can be acylated by various carboxylic acid halides, leading to compound 11. According to IR and NMR data 11 exists mostly as the enol-form, due to the influence of the carboranyl substituent, which strongly stabilizes conjugated double bonds.13 Compound 11 is a useful synthon for the preparation of heterocyclic compounds. It can be methylated, chlorinated and acylated twice ( compound 13). Compound 13 gives an adduct with phenylhydrazine (scheme 6). 

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