Patent GB-787531-A (GB)
Title: Improvements in or relating to hydrocarbon-carbohydrate derivatives
Inventor: LINN CARL BARNES
IPC: C08B37/14
Filed: 1955-10-28
Abstract: An isoparaffinic, naphthenic or aromatic hydrocarbon, free from other than aromatic unsaturation, is reacted with a simple sugar, a desoxy or omega-carboxy derivative thereof, a compound sugar or a polysaccharide, in the presence of hydrogen fluoride as catalyst, and the resultant hydrocarbon-carbohydrate derivatives recovered. Temperatures are about -40 DEG  to 100 DEG  C., preferably -10 DEG to 50 DEG  C., and pressures from atmospheric to 100 atm. or more, preferably sufficient to maintain the catalyst liquid. Specified hydrocarbons include isoalkanes from isobutane up to isododecanes; aromatics from benzene up to cumene, alkylates obtained from olefin polymers having up to 18 carbon atoms in the alkyl group, and di- or polyaryls or hydrocarbons with condensed benzene rings, e.g. diphenyl, diphenylmethane, fluorene, naphthalene, naphthacene; and naphthenes particularly of at least 5 carbon atoms in the ring and having a tertiary carbon atom, e.g. methyl- and phenyl-cyclopentane and cyclohexane. Carbohydrate-like materials include dioses, e.g. glycol aldehyde, trioses, e.g. glyceraldehyde and b -dihyceroxy acetone, tetroses up to decoses; desoxy-pentoses and hexoses; simple sugars or their omega-carboxy derivatives, e.g. tartronic semialdehyde, hydroxypyruvic acid and, generally, compounds of formula <FORM:0787531/IV (b)/1> where A=H or CH2OH, n=1 to about 12, B=H, CH2OH or COOH; di-, tri-, tetra- and poly-saccharides including pentosans, hexosans, e.g. starch, cellulose, pectic and alginic acids, gum arabic and tragacanth, linseed mucilage, pectins, and agar.  The hydrofluoric acid may be anhydrous or hydrous, e.g. 85 to about 100 per cent, or diluted with inert diluent ssuch as n-paraffins or their perfluo derivatives.  It may be added slowly to the mixed reactants, cooled if necessary, and finally removed by distillation or passing inert gas or quenched with water prior to separating the products.  These may contain both ether-soluble, water-insoluble components and vice versa.  Sulphonation or sulphation of some of the products gives compounds which may be converted into salts for use as detergents. Nonionic type detergents are obtained using, e.g., mono-alkylbenzenes and glucose.  Resins are made by heating some of the products with formaldehyde, urea, phenol or aniline. Nitration yields explosives which may be nitro-aromatic and nitro-alcohol derivatives.  In examples: (1) toluene in mol. ratios of 1 and above 2 is reacted with cellulose at temperatures of 0 DEG , -30 DEG  and +30 DEG  C. No reaction occurs at -30 DEG  C., or, if there is insufficient HF, at 0 DEG  C.  An excess of toluene at 0 DEG  C. yields 1,1 - di - p - tolyl - 1 - desoxy - D - glucitol. At 30 DEG  C. an ether-soluble product was obtained which was sulphonated to give a water-soluble, surface active material, and a water-soluble product of foaming tendencies and formula C13H18O5; (2) glucose is used with excess of toluene and the products separated according to water solubility giving di-tolyl-glucitol and unidentified products, one possibly mono-tolyl-glucitol; (3) the recovery of pure di-tolyl-glucitol by recrystallization from various solvents is described; (4) the use of lithium hydroxide to remove HF is described; (5), (6) the di-tolyl-glucitol is nitrated with nitric acid or a mixture thereof with sulphuric giving esters containing varying nitro content; (7) alkyd resins are obtained by heating the di-tolyl-glucitol with phthalic anhydride at 200-250 DEG  C.; (8) fructose reacts with toluene, the watersoluble fraction of the product yielding a compound <FORM:0787531/IV (b)/2> and the water-insoluble fraction a compound C20H24O3 of unknown structure but useful for gelling benzene and other hydrocarbons, together with more complex products; (9) l-sorbose and toluene yield similar products; (10) catalytic hydrogenation of the di-tolyl-glucitol at various conditions yields different products, one of which corresponds to hydrogenation of one tolyl ring; (11) glucose and isobutane give a solid product, a benzene-soluble fraction of which yields inter alia compounds derived from one butane and one glucose unit; (12) cellulose is reacted with dodecylbenzene obtained from benzene and propylene tetramer and a product separated agreeing with <FORM:0787531/IV (b)/3> used as a lub. oil additive.  It can be hydrogenated and nitrated; (13) the di-tolyl-glucitol is converted to the penta-acetate which is then nitrated; (14) properties of the products from glucose or cellulose and toluene are given; (15) sucrose or molasses reacts with toluene yielding the compounds obtained from glucose or fructose alone; (16) the properties of the pentanesoluble oil obtained from glucose or fructose and benzene, toluene, toluene and isobutane, or ethylbenzene are described. Products include di- and tri-phenylmethane, di- and tri-p-tolylmethane, tert. - butyltoluene, tert. - butyl - di - p - tolylmethane, di - p - ethylphenylmethane, and 1 - p - ethylphenyl - 1 - phenylethane; (17) alginic acid is reacted with toluene at 0 DEG C.ALSO:An isoparaffinic, naphthenic or aromatic hydrocarbon, free from other than aromatic unsaturation, is reacted with a simple sugar, a desoxy or omega-carboxy derivative thereof, a compound sugar or a polysaccharide, in the presence of hydrogen fluoride as catalyst, and the resultant hydrocarbon-carbohydrate derivatives are recovered.  They are used as lubricating oil additives and detergent aids.  Specified hydrocarbons include isoalkanes from isobutane up to isododecanes; aromatics from benzene up to cumene, alkylates obtained from olefin polymers having up to 18 carbon atoms, and di- or poly-aryls or hydrocarbons with condensed benzene rings, e.g. diphenyl, diphenylmethane, fluorene, naphthalene or naphthacene; and naphthenes, particularly of at least 5 carbon atoms in the ring and having a tertiary carbon atom, e.g. methyl- and phenyl-cyclopentane and cyclohexane. Carbohydrate-like materials include dioses, e.g. glycol aldehyde, trioses, e.g. glyceraldehyde and s-dhydroxy acetone, tetroses up to decoses; desoxy-pentoses and hexoses; simple sugars or their omega-carboxy derivatives, e.g. tartronic semi-aldehyde, hydroxypyruvic acid and, generally, compounds of the formula: <FORM:0787531/III/1> where A is H or CH2OH, n is 1 to about 12, B is H, CH2OH or COOH; di-, tri-, tetra- and polysaccharides including pentosans and hexosans, e.g. starch, cellulose, pectic and alginic acids, gum arabic and tragacanth, linseed mucilage, pectins and agar. Sulphonation or sulphation of some of the products gives compounds which may be converted into salts for use as detergents. Non-ionic type detergents are obtained using, e.g., mono-alkylbenzenes and glucose.  In examples: (1) toluene in mol. ratios of 1 and above 2 is reacted with cellulose at temperatures of 0, -30 and +30 DEG  C.  No reaction occurs at -30 or, if there is insufficient catalyst, at 0 DEG  C.  An excess of toluene at 0 DEG  C. yields 1,1-di-p-tolyl-1-desoxy-D-glucitol.  At 30 DEG  C. an ether-soluble product is obtained which is sulphonated to give a water-soluble, surface-active material, and a water-soluble product of foaming tendencies and formula C13H18O5; (2) glucose is used with excess of toluene and the products separated according to water solubility, giving di-tolyl-glucitol and unidentified products, one possibly mono-tolyl-glucitol; (12) cellulose is reacted with dodecylbenzene obtained from benzene and propylene tetramer and a product is separated agreeing with: <FORM:0787531/III/2> useful for enhancing the viscosity index of mineral lubricating oil; (14) the products from glucose or cellulose and toluene are soluble in mineral oil; (16) the pentane-soluble oil obtained from fructose and toluene is added to SAE 40 lubricating oil to reduce the V.I.ALSO:An isoparaffinic, naphthenic or aromatic hydrocarbon, free from other than aromatic unsaturation, is reacted with a simple sugar, a desoxy or omega-carboxy derivative thereof, a compound sugar or a polysaccharide, e.g. cellulose, in the presence of hydrogen fluoride as catalyst, and the resultant hydrocarbon-carbohydrate derivatives are recovered.  Temperatures applied are about -40 to 100, preferably -10 to 50 DEG  C., and pressures from atmospheric to 200 atm. or more, preferably sufficient to maintain the catalyst liquid.  Resins may be obtained by heating many of the products with formaldehyde, urea, phenol, aniline or mixtures thereof. Specified hydrocarbons include isoalkanes from isobutane up to isododecanes; aromatics from benzene up to cumene, alkylates obtained from olefin polymers having up to 18 carbon atoms, and di- or poly-aryls or hydrocarbons with condensed benzene rings, e.g. diphenyl, diphenylmethane, fluorene, naphthalene or naphthacene; and naphthenes, particularly of at least 5 carbon atoms in the ring and having a tertiary carbon atom, e.g. methyl- and phenyl-cyclopentane and cyclohexane. Carbohydrate-like materials include dioses, e.g. glycol aldehyde, trioses, e.g. glyceraldehyde and s-dihydroxy acetone, tetroses up to decoses; desoxy-pentoses and hexoses; simple sugars or their omega-carboxy derivatives, e.g. tartronic semialdehyde, hydroxypyruvic acid and, generally, compounds of the formula: <FORM:0787531/IV (a)/1> where A is H or CH2OH, n is 1 to about 12, B is H, CH2OH or COOH; di-, tri-, tetra- and polysaccharides including pentosans and hexosans, e.g. starch, cellulose, pectic and alginic acids, gum arabic and tragacanth, linseed mucilage, pectins and agar.  The hydrofluoric acid may be anhydrous or hydrous, e.g. 85 to about 100 per cent, or diluted with inert diluents such as n-paraffins or their perfluor derivatives.  It may be added slowly to the mixed reactants, cooled if necessary, and finally removed by distillation or by passing inert gas or quenched with water prior to separating the products.  These