Patent GB-926412-A (GB)
Title: Halogenated organic compounds
IPC: C07B39/00
Filed: 1959-05-13
Abstract: The invention comprises a process for the preparation of telomeric fluorine-containing 1,1-dihydro acyl compounds comprising reacting a halosulphate of the formula R(CH2CF2)mOSO2X with a compound containing at least one reactive hydrogen atom responsive to the Zerewitinoff reaction, R representing a perfluoro, perchloro, perfluorochloro, perfluorohydro, perchlorohydro or perfluorochlorohydro radical, or such a radical containing a -CX2OSO2X radical, or representing a -CX2OSO2X radical, X is fluorine or chlorine and m is an integer of at least 2, for example 3 to 20. The active hydrogen reactant may be a hydrolysing agent, a mono- or poly-hydric alcohol, a mono- or poly-amine, ammonia or a mono- or poly-thiol, and the resulting carboxylic acids and their salts, amides, esters and thiol esters are claimed per se.  In all these reactions, the groups -CF2OSO2X and -CX2OSO2X are replaced by the group -CO.B where B is the residue of the active hydrogen reactant BH; an acyl fluoride is formed as an intermediate which may sometimes be isolated. The carboxylic acids may be obtained by heating with water (salts being obtained on neutralizing, e.g. an aluminium salt), or with aqueous alkali followed by acidification.  The acids can be converted into their anhydrides by treatment with P2O5 and/or H2SO4. Esters and thiol-esters and amides may be prepared by reacting the halosulphates with excess of the appropriate hydroxy, thiol or nitrogenous reactant.  The reaction of polyfunctional active hydrogen compounds with polyhalosulphates as above defined yields polymeric condensation products.  The carboxylic acids and their esters and amides may be reduced to yield alcohols and amines which can be reacted with the above specified mono- and poly-halosulphates to yield esters and amides including polymeric products.  The various esters and amides are useful as lubricants and hydraulic fluids.  The carboxy and thiol esters are plasticizers for halogen containing resins, for example homopolymers of CH2=CF2 and its copolymers with ethylene and substituted ethylenes, and sulphur containing resins respectively.  The amides have pesticidal properties.  Typical examples describe: (1)  CF3CF2(CF3)(CH2CF2)2CH2 COOH and its sodium salt, amide, ethyl ester, di-ester of 1:5-pentanediol, di-ester of ethylene glycol, di-ester of the diol. HOCH2(CH2CF2)3CH2CH2OH, and its di-thiol ester of pentamethylene dimercaptan, which are prepared by reacting CF3CF2CF(CF3)(CH2CF2)3OSO 2X with water, aqueous NaHCO3, NH3, ethanol, pentanediol, ethylene glycol, the named fluorodiol and pentamethylene dimercaptan respectively; the ethyl ester is reduced to the alcohol C2F5CF(CF3)(CH2CF2)2CH2 CH2OH which may be esterified with a dicarboxylic acid p  chloride, e.g. sebacyl chloride, or a fluorinecontaining di-halosulphate, e.g. C1SO2OCF2(CH2CF2)4OSO2Cl to give a diester; the amide may be reduced with lithium aluminium hydride to form an amine; (2) CF2ClCF(CF3)(CH2CF2)3,5CH2CO and the free carboxylic acid by hydrolysis of the appropriate chlorosulphate, the acyl fluoride being reacted with NH3 to form the amide; (3) the di-ester. CH3OCO(CH2CF2)3CH2CO.OCH3, from methanol and the appropriate di-chlorosulphate, the ester then being reduced to the corresponding diol which may be esterified with mono- or di-carboxylic acid chlorides, e.g. adipyl or terephthallyl chloride, or fluorinecontaining di-halosulphates yielding monomers or polymers; (4) a polyester from ClSO2OCF2(CH2CF2)4OSO2Cl and trimethylene glycol or the diol HOCH2(CH2CF2)3CH2CH2OH; (5) a polyamide from the di-halosulphate of (4) and hexamethylene diamine.  Numerous other analogous products are referred to including polymers containing the recurring unit -[SCO(CH2CF2)3CH2COS(CH2)5] -n.  The halosulphates used as starting materials are prepared as described in Specification 926,411.  A disclaimer refers to Specification 824,229.ALSO:The invention comprises a process for the preparation of fluorine-containing 1,1-dihydro acyl compounds comprising reacting a halosulphate of the formula R(CH2CF2)mOSO2X with a compound containing at least one reactive hydrogen atom responsive to the Zerewitinoff reaction, R representing a perfluoro, perchloro, perfluorochloro, perfluorohydro, perchlorohydro or perfluorochlorohydro radical, or such a radical containing a -CX2OSO2X radical, or representing a -CX2OSO2X radical, X is fluorine or chlorine and m is an integer of at least 2, for example, 3 to 20. The active hydrogen reactant may be a hydrolysing agent, a mono- or poly-hydric alcohol, a mono- or poly-amine, ammonia, or a mono- or poly-thiol, and the resulting carboxylic acids and their salts, amides, esters and thiol esters are claimed per se.  In all these reactions, the groups -CF2OSO2X and -CX2OSO2X are replaced by the group -CO.B where B is the residue of the active hydrogen reactant BH; an acyl fluoride is formed as an intermediate which may sometimes be isolated. The carboxylic acids may be obtained by heating with water (salts being obtained on neutralising, e.g., an aluminium salt), or with aqueous alkali followed by acidification.  The acids can be converted into their anhydrides by treatment with P2O5 and/or H2SO4.  Esters and thiol-esters and amides may be prepared by reacting the halo-sulphates with excess of the appropriate hydroxy, thiol or nitrogenous reactant.  The reaction of polyfunctional active hydrogen compounds with poly-halosulphates as above defined yields polymeric condensation products (see Group IV(a)).  The carboxylic acids and their esters and amides may be reduced to yield alcohols and amines which can be reacted with the above specified mono- and poly-halosulphates to yield esters and amides including polymeric products.  The various esters and amides are useful as lubricants and hydraulic fluids.  The carboxy and thiol esters are plasticizers for halogen containing resins, for example homopolymers of CH2=CF2 and its copolymers with ethylene and substituted ethylenes, and sulphur containing resins respectively.  The amides have pesticidal properties.  Typical examples describe: (1) <FORM:0926412/IV(a)/1> and its sodium salt, amide, ethyl ester, di-ester of 1 : 5-pentanediol, di-ester of ethylene glycol, di-ester of the diol HOCH2(CH2CF2)3CH2 CH2OH, and its di-thiol ester of pentamethylene dimercaptan, which are prepared by reacting <FORM:0926412/IV(a)/2> with water, aqueous NaHCO3, NH3, ethanol, pentanediol, ethylene glycol, the named fluorodiol and pentamethylene dimercaptan respectively; the ethyl ester is reduced to the alcohol <FORM:0926412/IV(a)/3> which may be esterified with a dicarboxylic acid chloride, e.g., sebacyl chloride or a fluorine-containing di-halosulphate, e.g. ClSO2 OCF2(CH2CF2)OSO2Cl to give a diester; the amide may be reduced with lithium aluminium hydride to form an amine; (2) CF2ClCF(CF3)(CH2CF2)3,5CH2COF and the free carboxylic acid by hydrolysis of the appropriate chlorosulphate, the acyl fluoride being reacted with NH3 to form the amide; (3) the di-ester CH3OCO(CH2CF2)3CH2CO.  OCH3, from methanol and the appropriate di-chlorosulphate, the ester then being reduced to the corresponding diol which may be esterified with mono-carboxylic acid chlorides. Numerous other analogous products are referred to.  The halosulphates used as starting materials are prepared as described in Specification 926,411.  A disclaimer refers to Specification 824,229.