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Home , Diose, Erythrulose, Threose

- 2,926,180 United States Patent Office Patented Feb. 23, 1960 2 cycloalkyl, etc. These substituents R and R' may also be substituted with various groupings such as carboxyl 2,926,180 groups, sulfo groups, halogen atoms, etc. Examples of CONDENSATION OF AROMATIC WITH compounds which are included within the scope of this AND RELATED MATER ALS 5 general formula are acetophenone, propiophenone, benzo Carl B. Linn, Riverside, Ill., assignor, by mesne assign phenone, acetomesitylene, phenylglyoxal, benzylaceto ments, to Universal Oil Products Company, Des phenone, dypnone, dibenzoylmethane, benzopinacolone, Plaines, Ill., a corporation of Delaware dimethylaminobenzophenone, acetonaphthalene, benzoyl No Drawing. Application June 18, 1957 naphthalene, acetonaphthacene, benzoylnaphthacene, ben 10 zil, benzilacetophenone, ortho-hydroxyacetophenone, para Serial No. 666,489 hydroxyacetophenone, ortho - hydroxy-para - methoxy 5 Claims. (C. 260-345.9) acetophenone, para-hydroxy-meta-methoxyacetophenone, zingerone, etc. This application is a continuation-in-part of my co Carbohydrates which are condensed with aromatic pending application Serial No. 401,068, filed December 5 ketones to form a compound selected from the group 29, 1953, now Patent No. 2,798,079. consisting of an acylaryl-desoxy-alditol and an acylaryl This invention relates to a process for interacting aro desoxy-ketitol include simple , their desoxy- and matic ketones with carbohydrates and materials closely omega-carboxy derivatives, compound sugars or oligo related to carbohydrates. The process relates more par saccharides, and . ticularly to the condensation of simple sugars, their 20 Simple sugars include , , , , desoxy- and their omega-carboxy derivatives, compound , , , , and decoses. Com sugars or , and polysaccharides with aro pound sugars include , , and matic ketones in the presence of a fluoride . Polysaccharides include polysaccharides catalyst. composed of only one type of residue, polysac | An object of this invention is to produce organic 25 charides composed of more than one type of sugar unit, materials suitable for use per se or as intermediates in polysaccharides composed of one type of uronic acid the manufacture of detergents, pharmaceuticals, explo unit, i.e., polyuronides, polysaccharides composed of sives, gelling agents, surface coatings, resins, and oxida ( or ) and uronic acid units, poly tion inhibitors by condensing aromatic ketones with saccharides containing hexose units esterified with an carbohydrates or with derivatives. 30 inorganic acid, and polysaccharides containing amino One embodiment of this invention relates to a process sugar units. which comprises condensing an aromatic with a Utilizable simple sugars include the , glycolalde carbohydrate in the presence of a hydrogen fluoride hyde; trioses, such as glycerylaldehyde and s-dihydroxy catalyst to produce a compound selected from the group acetone; tetroses, such as , , , consisting of an acylaryl-desoxy-alditol and an acylaryl 35 and apiose; the pentoses, such as , , , desoxy-ketitol, and recovering said resultant condensation , (a methylpentose), (a methyl product. pentose), rhodeose (a methylpentose), digitalose (a meth A specific embodiment of this invention relates to a oxymethylpentose), ketoxylose (a ketopentose), 2-desoxy process which comprises condensing acetophenone with ribose and 2-desoxy-methylpentose (digitoxose); hexoses, in the presence of a hydrogen fluoride catalyst 40 such as , glucose, , , , , to produce a 1-(acetophenyl)-1-desoxy-glucitol, and re , , , , and ; heptoses, covering said resultant condensation product. such as glucoheptose, mannoheptose, galactoheptose, I have found that useful water-insoluble condensation Sedoheptose, mannoketoheptose, glucoheptulose, and products and also water-soluble condensation products perseulose; octoses, such as glucooctose, mannooctose, are formed by reacting aromatic ketones with carbo 45 and galactooctose; nonoses, such as glucononose, and hydrates and related substances in the presence of a mannononose; and decoses such as glucodecose. Desoxy hydrogen fluoride catalyst. These reactions may be car derivatives of simple sugars are formed by the replace ried out in steel equipment or other suitable apparatus ment of a hydroxyl substituent in a sugar with hydrogen lined with silver, copper, and certain alloys such as thereby forming a methyl or methylene linkage. The Monel metal and the like. This treatment may be ef 50 desoxypentoses and desoxyhexoses are the most com fected at temperatures of from about -40 C. to about monly occurring of such compounds. The omega-car 100. C. and preferably at temperatures of from about boxy derivatives of simple sugars, which are suitable in -10 C. to about --50 C. The pressure at which the the process of the present invention include tartronic reaction is carried out will vary with the reaction tem semialdehyde or its tautomer, hydroxypyruvic acid; perature used and the mol fractions of reactants and 55 alpha-gamma-dihydroxyacetoacetic acid, threuronic acid, hydrogen fluoride catalyst present. While many of the 4-keto-2,3,5-trihydroxypentanoic acid, xyluronic acid, condensation reactions are carried out at substantially 5-keto-tetrahydroxyhexanoic acids such as 5-keto-allonic atmospheric pressure, it may be desirable in certain in acid, 5-keto-gluconic acid, 5-keto-mannonic acid, 5-keto stances and with certain reactants to carry out the re gulonic acid, and 5-keto-galactonic acid; uronic acids action at pressures up to about 100 atmospheres or more. 60 containing 6 atoms such as glucuronic acid, man It is convenient in most instances to operate the equip nuronic acid, and galacturonic acid, and the 6-keto-penta ment utilized at the pressure generated by the reaction hydroxyheptanoic acids. The simple sugars and their mixture and the catalyst contained therein. omega-carboxy derivatives, as starting materials for the Aromatic ketones which may be used as starting ma process of this invention, may be represented by the terials in the process of this invention may be represented 65 following general formula: by the following general formula: o 70 chor). in which R represents an aryl nucleus and R' is selected B - from the group consisting of alkyl, aryl, aralkyl, alkaryl, in which A equals H and CHOH, n equals an integer 3,926,180 3 4. from 1 to about 12 or so, and B equals H, CHOH, and and in some other instances it is most desirable to use COOH. As an example of the utility of this general anhydrous hydrogen fluoride as the catalyst. formula, when A=H, n=1, and B=H, the compound The process may be carried out by slowly adding a is ; when A=H, n=1, and B=CHOH, hydrogen fluoride catalyst to a stirred mixture of aro the compound is glycerylaldehyde; when A=H, n=1, matic ketone and carbohydrate or related material being and B=COOH, the compound is tartronic semialdehyde, subjected to reaction while maintaining the reaction tem a tautomer of hydroxypyruvic acid; when A=CH2OH, perature at from about -40 to about 100° C. by suit n=1, and B=H, the compound is s-; able cooling and/or heating means. It is often desirable when A=CH2OH, n=1, and B=CH2OH, the compound or advisable to commingle the reactants and catalyst at is erythrulose; when A=CHOH, na-1, and B-COOH, 0. relatively low temperatures such as from about -80 C. the compound is alpha-gamma-dihydroxyacetoacetic acid; to about -30 C. and then to permit the reaction mix when A=H, n=2, and B=CH2OH, the compound is ture to warm gradually while the reactants and catalyst - erythrose or threose; when A=H, n=2, and B-COOH, are stirred by suitable means such as a motor driven - the compound is threuronic acid; when A=CHOH, stirrer or other adequate mixing equipment. After the ins2, and B=CH2OH, the compound is riboketose or 5 reaction has reached the desired degree of completion, .xyloketose; when A=CHOH, n=2, and Bas-COOH, the the hydrogen fluoride catalyst is removed from the re compound is a 4-keto-2,3,5-trihydroxypentanoic acid; action mixture by distillation at atmospheric or lower ... when A=H, n=3, and B=CHOH, the compound is pressures, or by passing an inert gas through the reaction ribose, arabinose, xylose, or lyxose; when A=H, n=3, mixture while maintaining it at a relatively low tempera and B=COOH, the compound is a 5 carbon atom uronic 20 ture. Also the entire reaction mixture and catalyst may acid such as xyluronic acid; when A=CHOH, na-3, be mixed with water or may be added to ice in order and B2-CH2OH, the compound is psicose, fructose, to quench the activity of the hydrogen fluoride catalyst sorbose, or tagatose; when A=CHOH, n=3, and and to permit separation of the organic reaction products B-COOH, the compound is a 5-keto-tetrahydroxyhexa and unreacted starting materials from the catalyst. The noic acid; when A=H, n=4, and B=CHOH, the com 25 organic reaction products may also be separated from pound is allose, , glucose, mannose, gulose, idose, aqueous hydrogen fluoride by means of an organic sol galactose, or talose; when A=H, n=4, and B-COOH, vent such as ether, in which some of the organic material the compound is a 6 carbon atom uronic acid such as may be dissolved. Further means of isolating the re glucuronic acid, mannuronic acid, and galacturonic acid; action products are illustrated in the examples. Thus 'when A=CH2OH, n=4, and B=CHOH, the compounds 30 the product formed by reacting acetophenone with glu are heptoses; and when A=CHOH, n=4, and B-COOH, cose or in the presence of substantially anhy - the compounds are 6-keto-pentahydroxyheptanoic acids. drous hydrogen fluoride at 30° C. separated into an ether The utilizable oligosacchrides or compound sugars Soluble and water-insoluble product and an ether-insolu : include disaccharides such as the pentose-hexose disac ble and water-soluble product. charides including glucoapiose, vicianose and primeverose; 35 The process of this invention broadly emphasizes the - the methylpentose-hexose disaccharides including glycor reaction of carbohydrates including simple sugars, their hamnoside, and rutinose; and the dihexoses such as derivatives, compound sugars, and polysaccharides with , , , , gentiobiose, meli aromatic ketones using as a catalyst hydrogen fluoride. biose, , and . Other compound sugars The type of product obtained is markedly affected by are represented by trisaccharides such as the methyl 40 the length of time that the reactants are in contact with pentose-hexose saccharides including rhamninose and the hydrogen fluoride catalyst as well as the temperature robinose; the trihexose saccharides including , of the reaction. The reaction products of this process , and gentianose. An example of a suitable lead to materials having diversified uses. For example, is . Some of the reaction products can be used per se as sur Various polysaccharides are also utilizable in the proc 45 face coating materials as, for example, thermosetting ess of the present invention. These polysaccharides in resins which can be prepared simply by heating. Resins clude pentosans such as araban, methylpentosans such can also be made by heating the reaction products with as fucosan, and hexosans such as , cellulose, gly phenol, aniline, etc., and combinations of the above com cogen, , mannan, , lichenin, levan, , pounds. Nitration of many of the reaction products will and laminarin. Other polysaccharides which are com 50 give explosives. These explosives will contain nitro posed of more than one type of sugar unit such as pen groups attached to the aromatic rings as well as being tosans like araboxylan, and the hexosans like galacto nitric acid esters or nitroalcohol derivatives. Various mannan may be used. Other utilizable polysaccharides Teaction products are effective for gelling parafiinic or are represented by those composed of uronic acid units aromatic hydrocarbons. The products are useful inter and aldose units such as gum arabic, damson gum, gum 55 mediates in the preparation of other organic compounds, tragacanth, linseed mucilage, and , those com for example, metal deactivators may be prepared by the posed of uronic acid units such as pectic acid and alginic reaction of these compounds with a primary amine to acid, and those containing hexose units esterified with yield a Schiff's base. The nature of this invention is illus an inorganic acid such as certain sea weed polysaccharides trated further by the following examples, which however, like agar. 60 should not be construed to limit unduly the generally The hydrogen fluoride catalyst which is used in this broad scope of this invention. process may be used in anhydrous form or diluted with water to make a hydrofluoric acid of the desired con Example I centration. The hydrofluoric acid may also be further This example illustrates the reaction of an aromatic diluted with various inert diluents when it is desirable to 65 ketone, namely acetophenone, with a carbohydrate, operate the process of this invention with low hydrogen namely cellulose which is a containing fluoride concentrations. Suitable inert diluents include glucoside linkages. the perfluoro derivatives of n-paraffinic hydrocarbons - An an example of the manner of conducting these such as perfluoropropane, perfluoro-n-butane, perfluoro-n- experiments, the following detailed description is given: 70 In a one liter steel turbomixer autoclave is sealed 41 pentane, perfluoro-n-hexane, etc. Other suitable diluents grams of cellulose and 77 grams of acetophenone. With are well known to those skilled in the art, for example, stirring, the autoclave is then cooled to -78° C. and cycloparaffins such as cyclopentane or cyclohexane may about 220 grams of hydrogen fluoride is added. The tem be utilized. In some instances, hydrofluoric acida of from perature is allowed to rise to 0°C. and the reactants about 85 to about 100% HF concentration is desirable, 75 are then contacted at this temperature for 36 hours. 2,926,180 5 - 6 Then, a stream of nitrogen is passed through the reactor stirred. Then, while continuing the stirring a stream of at room temperature to remove most of the hydrogen nitrogen is passed through the autoclave for about 3 fluoride. A substantial amount of hydrogen fluoride re hours. The reaction product is washed with several por mains behind in the reaction mixture, although most of tions of cold water, and the cold water insoluble por it can be removed by prolonging the nitrogen purge. 5 tion thereof is dissolved in boiling water. The hot aque The autoclave is opened and the product is found to be ous solution is filtered and then set aside to cool. After a heavy fuming brown syrup. This is then poured into standing for about 24 hours at 0° C., crystals of a chemi a silver dish and depending upon the amount of hydro cal individual are recovered therefrom. This material gen fluoride remaining therein weighs from about 130 after recrystallization is found to have the following struc to about 150 grams. After standing for several days O tural formula: in a hood-draft the product solidifies. This mass is then mascerated with large quantities of cold water to remove unreacted carbohydrate, if any. During the process, the cellulose is broken down into glucose residues which become soluble in cold water. The cold water insoluble 5 portion of the product is treated with boiling water which after cooling and reduction in volume yields a chemical individual corresponding to 1,1 - di- (acetophenyl)-1- 0000 & HoH desoxy-glucitol of the following formula: (Hon O O 20 Hic- (-CH, (HotCBOE bH.oh. p d 25 Example IV & HoH In this example, starch is reacted with beta-acetonaph thalene. This experiment is carried out in a steel turbo & HoH mixer autoclave as described in Example I, the charge bHoH being 109 grams of beta-acetonaphthalene, 40 grams of bHoH 30 starch, and about 220 grams of hydrogen fluoride. The beta-acetonaphthalene and starch are sealed into the autoclave which is then cooled to about -40° C. at This product may be recrystallized from a 50% ethanol which temperature the hydrogen fluoride is added. The solution. temperature of the autoclave is then allowed to rise to Example II 35 room temperature and is kept there for 24 hours time This experiment again illustrates the reaction of a during which time the reaction mixture is stirred con carbohydrate, namely glucose, with an aromatic alde tinually. Then, a stream of nitrogen is passed through hyde. In this example 40 grams of glucose, 77 grams the autoclave for about 6 hours. The reaction product of acetophenone, and about 225 grams of hydrogen fluo is washed with several portions of water, then dissolved ride are utilized. The procedure utilized in this example 40 in boiling water. The hot aqueous solution is filtered, is the same as that described hereinabove in Example i cooled, and set aside at 0° C. From this cooled filtrate down through allowing the product to stand in a draft. a new chemical entity is recovered. After recrystalliza To this crude product is added one liter of ethyl ether tion from 50% ethanol a product is isolated of the follow and the mixture is allowed to stand for two days. The ing structural formula: ether is then decanted off and the residue is dissolved in 500 ml. of hot ethanol. The alcohol solution is filtered while hot, and is then allowed to stand at 0° C. The H3C-C C-Cls crystals which separate at this point are identified and correspond to the 1,1-di-(acetophenyl)-1-desoxy-glucitol H. described in Example I. -C- The more soluble part of the product is believed to 50 & Hoa contain a mono-acetophenyl-glucitol corresponding to the following structural formula: & Hon. g & Hoh C-C 55 bHoH CHOF claim as my invention: 1. A process which comprises reacting an aromatic ketone having the general formula 60

CHOH wherein R is an aryl nucleus and R' is selected from Example III the group consisting of alkyl, aryl, aralkyl, alkaryl and cycloalkyl, with a carbohydrate selected from the group In this example, glucose is reacted with benzophenone. consisting of , oligosaccharides, and poly The experiment is carried out in a steel turbomixer auto saccharides, in the presence of hydrogen fluoride cata clave as described in Example I, the charge being 117 lyst at a temperature of from about -40° C. to about grams of benzophenone, 40 grams of glucose, and about 100° C. 225 grams of hydrogen fluoride. The benzophenone and 70 2. A process which comprises reacting acetophenone glucose are sealed into the autoclave which is then cooled with cellulose in the presence of hydrogen fluoride cata to about -30° C. at which temperature the hydrogen lyst at a temperature of from about -40 C. to about fuoride is added. The temperature of the autoclave is 100° C. s allowed to rise to room temperature and is kept there 3. A process which comprises reacting acetophenone for 12 hours during which time the reaction mixture is 75 with glucose in the presence of hydrogen fluoride cata: 2,926,180 7 8 lyst at a temperature of from about -40 C. to about References Cited in the file of this patent 100° C. 4. A process which comprises reacting benzophenone UNITED STATES PATENTS with glucose in the presence of hydrogen fluoride cata- 2,252,725 Niederl ------Aug. 19, 1941 lyst at a temperature of from about -40° C. to about 5 2,798,079 Linn ------July 2, 1957 100° C. 5. A process which comprises reacting beta-aceto- OTHER REFERENCES naphthalene with starch in the presence of hydrogen fluo ride catalyst at a temperature of from about -40 to Hackh's Chem. Dictionary, p. 260, 3rd ed., The Blakis about 100 C. 10 ton Co., Philadelphia (1944).