N. V. Kruglova

Reduction of 1,1,1-trichloroethane and its addition to 1-heptene initiated by tert-butyl peroxide or Fe(CO)5 in the presence of triethylsilane

Conclusions1.1,1,1-Trichloroethane is reduced by triethylsilane with initiation by either tertbutyl peroxide or Fe(CO)5 to give 1,1-dichloroethane in high yield and high trichloroethane conversion.2.1,1,1-Trichloroethane reacts with 1-heptene in the presence of triethylsilane upon initiation either by tert-butyl peroxide or Fe(CO)5 to form 2,2-dichlorononane and 2,2,4-trichlorononane. The ratio of these products depends on the nature of the initiator. The major product with TBP as initiator is 2,2-dichlorononane while the major product with Fe(CO)5 as initiator is 2,2,4-trichlorononane.

Homolytic addition of polyhalomethanes to α-olefins containing CHCl2 and CCl2=CH groups in the ω-position to the C=C bond

1. The homolytic addition of some polyhalomethanes CXCl3(X=H, Cl, Br) to the α-olefins: CHCl2-(CH2)3CH=CH2 and CCl2=CH(CH2)nCH=CH2 (n=2,4, 6), was accomplished. The adducts were obtained in good yields. 2. The adduct from the diene with n=4 is formed only when an efficient carrier of the reaction chain (CCl3Br) is used.

Reaction ofα,α-dichloro-ω-bromoalkanes andα,α-dichloro-ω-bromoalkenes with benzylmagnesium and allylmagnesium halides

Theα,α-dichloro-ω-bromoalkanes andα,α-dichloro-ω-bromoalkenes react with the benzyl- and allylmagnesium halides in tetrahydrofuran solution to giveω,ω-dichloroalkyl(alkenyl)benzenes,ω,ω-dichloroalkadienes in high yields. For all practical purposes the reactions do not go in ether.

Infrared spectra, molecular volumes, and refractions of α,α,α,ω-tetrachloroalkanes and α,α,ω-trichloroalkenes, containing five to eleven carbon atoms

1. Pure C5-C11α,α,α,ω-tetrachloroalkanes andα,α,ω-trichloroalkenes, containing 98.8–99.8% of the basic substance according to the data of gas-liquid chromatography, were produced. 2. Their IR spectra were measured, and their physical constants were determined.

Reaction of γ,γ-dichloroallyl acetate with addends reacting at the C-H and C-Cl bonds

Conclusions1.Carbonyls of iron and manganese initiate addition of CHCl3. and CCl4, at the C-Cl bond to γ, γ-dichloroallyl acetate. The adduct-radicals formed [CCl2CH(R)CH2OCOCH3 (R= CHCl2, CCl3)] are stabilized mainly by H atom abstraction (from CHCl3 or the medium) with formation of the compounds HCCl2CH(R)CH2OCOCH3. The system Fe(CO)5+ nucleophilic coinitiator assists the transfer of chlorine by the adduct-radical.2.Under peroxide initiation only C6H5CH3 and CHCl3 add to γ,γ-dichloroallyl acetate, which reacts by C-H bond cleavage in the chain transfer stage.

Investigation of a rearrangement of ĊCl2CHX(CH2)3Y radicals with 1,5-hydrogen shift by ESR and chemical transformations of these radicals

Conclusions1.Using ESR and the spin trapping method for the first time the rearrangement of ĊCl2CH2CH2CH2CH2Y radicals (A) (Y=Me, Et, and OMe) to HCCl2CH2CH2CH2CHY with 1,5-hydrogen shift has been confirmed.2.During the reduction of CCl3CH2CH2CH2CH2OCH3 or addition of CCl4 to CCl2= CHCH2CH2CH2OCH3 the formed ĊCl2CH(X)CH2CH2CH2OCH3 radicals (X=H, CCl3) undergo isomerization with 1,5-hydrogen shift to HCCl2CH(X)CH2CH2CHOCH3 radicals which undergo oxidation to HCCl2CH(X)CH2CH2COOCH3.

Fe(CO)5-initiated reaction of CCl4 with 1,1-dichloro-5-cyano-1-pentene and 1,1,5-trichloro-1-pentene

Conclusions1.The reaction of CCl4 with 1,1-dichloro-5-cyano-1-pentene and 1,1,5-trichloro-1-pentene is initiated by iron coordination compounds (CC); tert-butyl peroxide initiates only the reaction with 1,1,5-trichloro-1-pentene.2.The main reaction products, namely 1,1,5-trichloro-2-trichloromethyl-5-cyanopentane and 1,1,5,5-tetrachloro-2-trichloromethylpentane, are respectively formed by the isomerization of the radical adducts CC12CH(CCl3) C2H4CH2X (X=CN, Cl), with 1,5-migration of the H atom.3.The radical addition of CCl4 to the CCl2=CH group, with chain transfer to the CCl4 and the formation of compounds of type CCl3CH(CCl3)R, was accomplished for the first time by initiation with iron coordination compounds.

Radical addition of polychloromethanes toα,α-dichlorovinyl compounds

The reaction of CCl4 and CHCl3 with CCl2=CHR, where R=(CH2)3H (I) and (CH2)3Cl (II), gives compounds of type HCCl2CH(CCl3)R, and the adducts HCCl2CH(CCl)2CH2CH2CH2Cl (V) from (I) and HCCl2CH·(CCl3)CH2CH2CHCl2 (VIII) from (II).

Action of magnesium on polyhaloalkanes and polyhaloalkenes and synthesis of 5, 5-dichloropentaneboronic acid

1. The bromides CHCl2(CH2)nCH2Br and CCl2=CH(CH2)nBr, where n=3 and 5, react with magnesium in ether to give ω,ω-dichloroalkyl (alkenyl)magnesium bromides, in yields of 40–50% for n=3, and 10–20% for n=5. The condensation products [CHCl2(CH2)nCH2-]2 and [CCl2=CH(CH2)n-]2 are also formed in 10–30% of the theoretical yields. 2. 5, 5-Dichloropentaneboronic acid, identified as the iminodiethyl ester, was synthesized from the Grignard reagent, obtained from 1, 1-dichloro-5-bromopentane and magnesium. 3. Bromides of the type CHCl2(CH2)nCH2Br and CC12=CH(CH2)nBr, where n=3 and 5, were obtained from the corresponding chlorides by exchange of the chlorine in the CH2Cl group by bromine.

Synthesis of some derivatives of α-phenylethyl- and α-phenylisopropylboronic acids

1. The synthesis of theα-phenylethyl- andα-phenylisopropylmagnesium chlorides in THF at 0 to − 10° was described. Whenα-phenylisopropylmagnesium chloride is synthesized in THF at 20–45° it reacts with the THF to yield 5-methyl-5-phenyl-1-hexanol. 2. When reacted with methyl borate, theα-phenylethyl- andα-phenylisopropylmagnesium chlorides give theα-phenylethyl- andα-phenylisopropylboronic acids. We also prepared the anhydride ofα-phenylethylboronic acid and the diethanolamine esters ofα-phenylethyl- andα-phenylisopropylboronic acid.α-Phenylethylmercury chloride was obtained from the and mercuric chloride.