Patent GB-942130-A (GB)
Title: Method of preparing organic sulfates or sulfonates
IPC: C07F9/28
Filed: 1960-03-18
Abstract: 942,130. Organic sulphonates and sulphates. ESSO RESEARCH & ENGINEERING CO. March 18, 1960 [April 1, 1959(3); Dec. 24, 1959], No. 9655/60. Heading C2C. [Also in Division C3] Organic sulphates or sulphonated organic compounds are prepared by forming a complex of sulphur trioxide with an organic ester of an oxy-acid of phosphorus and then contacting the complex with an organic compound which is sulphonatable or sulphatable by the complex e.g. olefinic compounds, aromatic hydrocarbons, organic compounds containing active hydrogen and organo metallic compounds. The complex may be formed by contacting the ester with SO 3  itself as with chlorsuylphonic acid or oleum. The ester may be a phosphite, phosphinite, phosphinate, phosphate, phosphonate, phosphonite, pyrophosphate or metaphosphate, and numerous alkyl, aryl and aralkyl and partial phosphate, phosphite, metaphosphate and pyrophosphate esters are mentioned, some bearing chloro-, nitro- or sulpho-substituents. The complex is generally prepared using one or more moles of sulphur trioxide per phosphorus atom in the ester or a temperature of -20‹ to 100‹C. in the presence or absence of an inert solvent. Sulphatable organic compounds containing active hydrogen include primary, secondary and tertiary alcohols including methyl, lauryl, benzyl and furfuryl alcohols; polyhydric alcohols including glycol, glycerol and sugars; phenols e.g. resorcinol; non-tertiary amines e.g., dimethylamine, aniline, benzidine, ethyl glycinate, pyrrole and benzotriazole; amides including acetamide, urea, phthalimide and benzene sulphonamide; enolic compounds e.g., ethyl aceto acetate, reductase and ascorbic acid; oximes e.g. dimethyl glyoxime and heptaldoxime; hydrazones e.g. phenyl hydrazone and semicarbazones. Such compounds may be sulphated using one or more moles of SO 3 , in complexed form, per active hydrogen atom in the compound. Sulphonatable olefins include those of the general formulae R<SP>1</SP> RC=CH 2  and CH 2 =CR. CR<SP>1</SP> =CH 2  wherein R and R<SP>1</SP> represent hydrogen or alone or together form cyclic or acyclic aliphatic groups having up to 18 carbons, e.g., ethylene, butadiene and vinyl cyclohexane. Sulphonatable aromatic compounds specified include chloro- and bromobenzenes, isodurene, phenanthrene, naphthalene sulphonic acid, nonyl benzene, abietic acid, anisole, dimethyl aniline, vanillin and lignin. The sulphonation of olefines is preferably effected with complexes containing 1 mol of SO 3  per phosphorus atom. Desirably, sufficient of the complex is used to introduce two SO 3 groups into each double bond yielding a cyclic intermediate which on hydrolysis yields a hydroxy sulphonic acid. Sulphonation of the aromatic nucleus requires complexes containing more than one mole of SO 3 therein. Accordingly a 1:1- SO 3 /triethyl phosphate complex selectively sulphonates the vinyl group of styrene. Sulphonation of the aromatic nucleus may be effected with the appropriate complex together with excess SO  3  if desired. The sulphations and sulphonations are generally effected at from about -20‹C. to 100‹C. and inert solvents may be present. The organo metallic compounds which may be reacted with the complexes, are those of a C 2-30  acyclic or cyclic, saturated or unsaturated, hydrocarbon radical, which may be substituted by halogen or alkoxy, with an alkali metal, beryllium, magnesium, an alkaline earth metal, boron, aluminium, silicon, germanium, tin, lead or a metal having an atomic number of from 21 to 29. The complex used is suitably one containing 1-3 moles of SO 3. The reaction may be effected at -100‹ to +100‹C. and yields a sulphonic acid R SO  3  H where R corresponds to the organic component of the organo metallic reactant. Disulphonic acids may be obtained using a di-metallo organic reactant. In examples: (1) lauryl alcohol is sulphated using a complex obtained by adding SO  3  to a solution of triethyl phosphate in dichloroethane, the product being obtained as the sodium salt; the C 16  alcohol CH 3 . (CH 2 ) 7 CH (CH 2 OH). (CH 2 ) 5 CH 3  and octyl alcohol are similarly sulphated; lauryl alcohol is also sulphated using a complex formed from (5) SO 3 and tetrabutyl pyrophosphate, (6) chlorsulphonic acid and dipropyl hydrogen phosphate or (7) SO 3 and dimethyl phosphite; (14) octadecene-1 is sulphated as in (1); (16) ethyl benzene is sulphonated using a complex formed from triethyl phosphite and chloro sulphonic acid, or (17) from dimethyl hydrogen phosphite or (18) tetrabutyl pyrophosphate and SO 3 ; (19) dodecyl sulphonic acid is prepared by reacting tridodecyl aluminium with an SO 3-triethyl phosphate complex in dichloroethane and (20) phenyl ethane sulphonic acid is similarly prepared from tri-styryl aluminium. There is also described the sulphonation of polymeric material including protein, cellulose, starch and polyvinyl alcohol and polystyrene compounds (see Division C3). Specification 368,812 is referred to.