Chloromethyl radical

Chloromethane Chlorine atom Chloromethyl radical Hydrogen chloride... 

Chloromethyl radical Chlorine Dichloromethane Chlorine atom... 

Electronic states and photodissociation dynamics of chloromethyl radical have been studied recently.114-117 Because of the chlorine substitution, there are several low-lying valence excited states (such as l2Ai and 22Bi, which mainly involve the orbitals on the CC1 bond) in addition to the 3s Rydberg state (22Ai), and more dissociation channels are available. 

Chloromethyl radical reacts with Cl2in the next propagation step. 

The etherification stage entails only the substitution of chlorine atoms which are situated directly at the silicon atom, forming methyl(chloromethyl)diethoxysilane (the chlorine in the chloromethyl radical is not affected) ... 

At the stage of methyl(phenylaminomethyl)diethoxysilane amidation with aniline, the chlorine atoms in the chloromethyl radical are replaced with a phenylamine group, which forms... 

The C—Cl bond in the lowest singlet state of chlorocarbene of 169.61(25) pm is by about 9 pm shorter than that in chloromethane and this shortening is very similar to that in the fluorinated analogues [130.5(6) vs 139.1(1) pm]. Again, the biradical is strongly bent with a C1CH angle of 101.4°. A similarly short C—Cl bond has been determined for the chloromethyl radical [169.1(4) pm]. 

H. Loss of a chloromethyl radical from metastable ions ... 

Fig. 25. The mechanism for the reaction of a pyridinyl radical with bromochloromethane. The initial, rate-limiting, solvent-insaisitive step involves transfer of the bromine atom to tl pyridinyl radical, forming one or more bromodihydropyhdines and a chloromethyl radical. The latter reacts rapidly with another pyridinyl radical to yield two isomeric dihydropyridines, while the former dissociates to a pyridinium bromide...

The chlorine radical has abstracted a hydrogen atom from the chloromethane to form the chloromethyl radical, and this may go on to react to form the disubstituted product. This, in turn, may react with more chlorine radicals and so on. It is this lack of control over which product is formed that makes this reaction not very useful synthetically. 

The diphenylmercury is added to effect utilization of both (CH3)3SiCCl2 groups. When heated to higher temperatures the reagent gives rise to the trimethylsilyldi-chloromethyl radical. 

Chloromethyl radical CHCl-H 102.1 2.5 427.2 10.5 Derived This volume... 

Precise description of the pyramidal structures would also require that the bond angles be specified. The EPR spectrum of the methyl radical leads to the conclusion that its structure could be either planar or a very shallow pyramid. The IR spectrum of methyl radical has been recorded at very low temperatures in frozen inert gas. ° Under these conditions, a relatively high concentration of reactive species can be obtained, since chemical reactions are prevented by the inertness of the surrounding matrix. The IR spectrum puts a maximum of 5° on the deviation from planarity. Similar studies have suggested a planar arrangement for the mono-chloromethyl radical, although the trichloromethyl radical is found to be pyramidal. Both EPR and IR studies lead to the conclusion that the trifluoromethyl radical is nonplanar. ... 

Tedder and his co-workers have studied some further additions of tri-chloromethyl radicals (from the photolysis of bromotrichloromethane) to mainly chlorine-containing olefins and have suggested that the ratios of attack at either end of a variety of olefins (at 150 are as follows ... 

---