T. D. Petrova

Polyfluoroarylcarbonimidoyl dichlorides and chlorides. A new method of obtaining such compounds from polyfluoroaromatic amines and compounds of the CCl3R-type in the presence of AlCl3

Abstract Reactions of some polyfluorinated amines of the benzene, diphenyl, naphthalene and pyridine series with CCl 4 in the presence of AlCl 3 have been Investigated. A new method is proposed for producing polyfluoroarylcarbonimidoyl dichlorides Ar f NCCl 2 . The reaction is shown to be sufficiently general and applicable in the series of polychlorinated anilines and low-base anilines of the hydrocarbon series as well. The possibility of involving other compounds of the type CCl 3 R and other Lewis acids in the reaction has been studied. The factors influencing the course of the reaction and the mechanism of formation of polyfluoroarylcarbonimidoyl dichlorides are discussed.

Reactions of polyfluoroaromatic imidoyl chloride derivatives with S-nucleophilic reagents

Abstract The interactions of N -pentafluorophenylcarbonimidoyl dichloride, N -pentafluorophenylbenzimidoyl chloride and N -pentafluorophenyl (C-pentafluorophenyl) imidoyl chloride with the S-nucleophilic reagents thiourea, sodium N,N -diethyldithiocarbamate, thiocarbonyl difluoride and bis(trifluoromethyl)trithiocarbonate in the presence of CsF or AgSCF 3 , or thiophenol and polyfluorinated thiophenols in the presence of anhydrous K 2 CO 3 , were studied. Reactions with charged S-nucleophiles and with S-nucleophiles in the presence of a base proceeded with preservation of the N-C multiple bond in the reaction products. By varying the reaction conditions in the case of N -pentafluorophenylcar-bonimidoyl dichloride it was possible to substitute one or two chlorines and obtain mono- or di-thioimidates. When C 6 F 5 or SC 6 F 5 groups were present at the C atom of the N-C multiple bond, preferential substitution of the para -fluorine atom occurred. Semiempirical PM3 calculation data were used to explain the direction of these reactions. N -Pentafluorophenylcarbonimidoyl dichloride reacted with sodium N , N -diethyldithiocarbamate or thiourea to give pentafluorophenylisothiocyanate. Depending on the conditions of the reactions of polyfluorinated benzimidoyl chlorides with thiourea, N -pentafluorophenylthioamides and 2-aryl-4,5,6,7-tetrafluorobenzothiazoles were formed. An attempt to produce SCF 3 derivatives from AgSCF 3 was unsuccessful.

Fluoro-organic sulphur-containing compounds. IV. Haloalkylation reactions of polyfluorinated thiophenols with CHal3R compounds in the presence of AlCl3: Synthesis and some reactions of polyfluorophenylthio derivatives of halomethanes

Abstract The haloalkylation of polyfluorothiophenols with CHal 3 R compounds (Hal=Cl, F; R=Cl, H, C 6 H 5 , C 6 F 5 ) in the presence of AlCl 3 has been investigated. The reactions of polyfluorothiophenols 4-XC 6 F 4 SH (X=F, H, CH 3 ) with CCl 4 and AlCl 3 lead to dichloromethane derivatives (4-XC 6 F 4 S) 2 CCl 2 . The reaction of pentafluorothiophenol with CHCl 3 in the presence of AlCl 3 gave (C 6 F 5 S) 2 CHCl and (C 6 F 5 S) 3 CH (ratio by GLC 8:1). In the reaction of pentafluorothiophenol with ArCX 3 (Ar=C 6 H 5 , C 6 F 5 ; X=Cl, F) compounds (C 6 F 5 S) 2 CClAr (Ar=C 6 H 5 , C 6 F 5 ) together with C 6 F 5 SCCl 2 Ar (Ar=C 6 H 5 , C 6 F 5 ) are formed. Peculiarities of these processes are considered. The hydrolysis of (C 6 F 5 S) 2 CCl 2 and C 6 F 5 SCCl 2 C 6 H 5 leads to bis(pentafluorophenyl)dithiocarbonate and the S -(pentafluorophenyl) ester of thiobenzoic acid, respectively. Compounds (C 6 F 5 S) 2 CF 2 and (C 6 F 5 S) 2 CClF were obtained from (C 6 F 5 S) 2 CCl 2 by the action of caesium fluoride. An attempt to produce these compounds through the action of antimony fluorides was unsuccessful. The compounds (C 6 F 5 S) 2 CCl 2 , (C 6 F 5 S) 2 CClF and (C 6 F 5 S) 2 CF 2 are stable to oxidation. The reactions of (C 6 F 5 S) 2 CF 2 and (C 6 F 5 S) 2 CClF with CrO 3 in acetic acid proceeded only with the formation of mono-sulphoxide. The conversion is low in the former case.

New route to fluorinated arylcarbonimidoyl chlorides: Interaction of polyfluoroaryl-amines with halomethanes in the presence of lewis acids

Abstract Recently we have described the preparation of polyfluoroarylcarbonimidoyl chlorides by high-temperature copyrolysis of polyfluoroaromatic amines with CCl 4 or pentafluorobenzotrichloride. In presented paper we wish to report a new and convenient route to carbonimidoyl chlorides by interaction of polyfluoroaromatic amines with CCl 4 or pentafluorobenzotrichloride in the presence of AlCl 3 at ordinary temperature. This method gives carbonimidoyl chlorides in high yields. Polyfluorinated carbonimidoyl chlorides of naphthalene can be also obtained. The possibility of synthesis of both nonfluorinated and polychlorinated arylcarbonimidoyl chlorides, as well as utilization of another halomethanes and Lewis acids will be discussed. Polyfluorinated carbonimidoyl chlorides can be transformed to N-trifluoromethylpolyfluoroanilines according to the following scheme: A number of reactions of polyfluoroarylcarbonimidoyl chlorides and the mechanistic details of the titled reactions will be considered.

Replacement of an oxygen atom by chlorine atoms in the reaction of pentafluorobenzaldehyde with CCl3-substituted compounds in the presence of AlCl3

The interaction of pentafluorobenzaldehyde with RCCl3 (R = Cl, Ph, C6F5) in the presence of threefold molar excess of AlCl3 proceeds with replacing the oxygen atom of the aldehyde group by two chlorine atoms from the CCl3 group and results in the formation of pentafluorobenzylidene chloride. The electrophilic mechanism of the reaction is proposed.

Reactions of pentafluoroaniline with aromatic trihalomethyl derivatives in the presence of AlCl3

The reactions of pentafluoroaniline with aromatic CX3-derivatives (X = F, Cl) in the presence of AlCl3 were studied. It was shown that compounds with a CF3 group can be used in reactions with polyfluoroaromatic amines instead of CCl3-derivatives for the synthesis of imidoyl chlorides. In the case of compounds with several CX3 groups, the formation of the imidoyl chloride moiety predominantly involves one of the CX3 groups under the conditions studied. The introduction of a second CX3 group can be carried out only under more drastic conditions.

Haloalkylation reaction of polyfluoroaromatic amino, hydroxy and thio derivatives with ArCCl3 or ArCF3in the presence of AlCl3. Synthesis of polyfluoroaromatic compounds of various classes.

Abstract A general haloalkylation reaction of polyfluoroaromatic amino, hydroxy and thio derivatives with compounds of the formula ArCCl 3 or ArCF 3 in the presence of AlCl 3 has been found. The reaction proceeds at heteroatom and leads to compounds of various classes. The products of the reactions of polyfluoroaromatic amines and AlCl 3 with benzotrichlorides or benzotrifluorides have been shown to be polyfluoroaromatic imidoyl chlorides. For compound containing several CF 3 or CCl 3 groups in a molecule only one trihalomethyl group is involved in formation of the imidoyl chloride group. Polyfluorinated phenols react with benzotrichlorides and benzotrifluorides in the presence of AlCl 3 to give polyfluorophenol esters of the respective carboxylic acids. The haloalkylation reaction of polyfluorinated thiophenols with CCl 4 /AlCl 3 leads to bis(arylthio)dichloromethanes. With benzotrichlorides or benzotrifluorides bis(arylthio)arylchloromethanes are formed. Peculiarities of these processes are discussed as well as routes of transformations.

Electrophilic reactions of polyfluoroaromatic imidoyl chloride derivatives in the presence of AlCl3

Abstract Previously we have worked out methods of synthesis of polyfluoroaromatic imidoyl chloride derivatives of the general formula ArfNCClR (including RCl), and studied their reactions with O- and N-nucleophilic agents. The present work examines electrophilic reactions of these compounds in the presence of AlCl3. Polyfluoroaromatic imidoyl chlorides have been found to react with aromatic compounds at the ring carbon or functional group heteroatom of the aromatic compound. The reactions of imidoyl chlorides with compounds containing the NC bond in the side chain yield heterocyclic derivatives. Reaction routes and mechanisms of these transformations are discussed.

New electrophilic alkenylating reagents based on polyfluoroaromatic carbonimidoyl dichlorides and imidoyl chlorides

Abstract The polyfluoroaromatic carbonimidoyl dichlorides and imidoyl chlorides have been shown to be efficient electrophilic alkenylating reagents in the presence of AlCl3. For example, the reaction of pentafluorophenylcarbonimidoyl dichloride with aromatic hydrocarbons (benzene, toluene,o-, m- and p-xylene, mesitylene) and AlCl3 allows easy introduction of the group into electron-donating reagent molecules to form stable compounds. Under mild conditions the reaction leads to imidoyl chlorides which further alkenylate another hydrocarbon molecule to give polyfluorinated azomethines. The structure of isomers and their ratio have been established. The tendencies and specific features of the reactions are discussed, as well as their mechanisms.

Synthesis of halogen-containing aza and diaza diene derivatives of polyfluoro aromatic compounds

Conclusions1.Halogen-containing aza diene derivatives of polyfluoro aromatic compounds were obtained by reactions of pentafluoroaniline with haloolefins containing a CCl3 group at the C-C bond in the presence of AlCl3.2.A mixture of cis and trans aza dienes is formed by pentafluoroaniline with cis-1-(pentafluorophenyl)-2-fluorotetrachloropropylene in the presence of AlCl3.3.1,6-Dichloro-4-(pentafluorophenyl)-2,3-diaza-1,3-butadiene is formed by pentafluorobenzaldehyde hydrazone with CCl4 in the presence of AlCl3.