United States Patent (19) (11) 4,341,905 Strege 45) Jul. 27, 1982

(54) INORGANIC HALIDE CATALYSTS (56) References Cited FOR HYDROXYALKYLATION OF U.S. PATENT DOCUMENTS PHENOLS OR THOPHENOLS

2,075,018 3/1937 Bruson et al...... 568/648 75) Inventor: Paul E. Strege, Midland, Mich. 2,448,767 9/1948 Carlson ...... 568/648 X 73) Assignee: The Dow Chemical Company, 3,354,227 11/1967 Katzschmann ...... 568/648 X Midland, Mich. OTHER PUBLICATIONS (21) Appl. No.: 179,129 Levin et al., Chem. Abs., vol. 59, (1965), 7338(d). Yoshino et al., Bull. Chem. Soc. Japan 47 (1973), (22 Filed: Aug. 18, 1980 553-556. Related U.S. Application Data Shapiro et al., J. of Chem., USSR5, (1968), 200-203. I63 Continuation-in-part of Ser. No. 58,705, Jul. 18, 1979, Primary Examiner-Bernard Helfin abandoned. Attorney, Agent, or Firm-Douglas N. Deline 51 Int. Cl...... C07C 41/16 57 ABSTRACT 52 U.S.C...... 568/45; 568/27; Hydroxyalkylphenyl ether or thioether compounds are 568/48; 568/49; 568/55; 568/644; 568/648; prepared by reaction of cyclic organic carbonate com 568/649; 568/656; 568/642; 568/584; 568/640; 568/608; 546/134 pounds with phenols or thiophenols in the presence of 58) Field of Search ...... 568/648, 608, 55, 27, an halide catalyst. 568/48, 49, 45, 644, 649, 656, 642, 584, 640; 54.6/34 9 Claims, No Drawings 4,341,905 1. 2 NORGANIC HALDE SALT CATALYSTS FOR DETAILED DESCRIPTION OF THE HYDROXYALKYLATION OF PHENOLS OR INVENTION THOPHENOLS This invention lies in the discovery that certain alkali 5 metal halide act as effective catalysts in the reac CROSS-REFERENCE TO RELATED tion of cyclic organic carbonate compounds with phe APPLICATION nols or thiophenols. The particular compounds useful as catalysts accord This is a continuation-in-part of parent application ing to this invention include: the monofluoride salts of Ser. No. 058,705, filed July 18, 1979 and now aban 10 , , and cesium; the monochloride doned. salts of , , potassium, rubidium, and ce sium; and the monobromide salts of lithium, sodium and BACKGROUND OF THE INVENTION potassium. The preferred catalysts for use according to The present invention relates to a process for the this invention are the monochloride salts of lithium, preparation of hydroxyalkylphenyl ether or thioether 15 sodium, potassium, rubidium and cesium, and the mono compounds. More particularly, the present invention is fluoride salts of cesium, potassium, and rubidium. Most concerned with improved catalysts for use in the prepa preferred catalysts are the monofluoride salts of cesium, ration of compounds by the reaction of cyclic organic potassium and rubidium. carbonate compounds with phenols and thiophenols. The amount of alkali metal halide salt catalyst re Carlson disclosed in U.S. Pat. No. 2,448,767 a method 20 quired to effectively catalyze the hydroxyalkylation of hydroxyethylation wherein ethylene carbonate or reaction according to the present invention may vary ethylene sulfite was reacted with certain organic com compared to total reactant weight from about 0.1 per pounds including phenols and alcohols. The reaction cent to about 10.0 percent depending on the particular could be carried out in the presence or in the absence of catalyst. It is preferred to employ the catalyst in a suitable solvent, and in the presence or in the absence 25 amounts from about 0.5 percent to about 2.0 percent by of a suitable catalyst. Catalysts that were disclosed in weight. The weight ratios of those halide salts that form cluded an acid (concentrated sulfuric acid or an alkyl hydrates, e.g., KF.2H2O, refer to the dehydrated halide ester of sulfuric acid), a base (alkali carbonates), or the salt weight. alkali salt of a phenol. The preferred catalyst was an The catalyst of this invention may be used by them alkali carbonate or alkali salt of a phenol. U.S. Pat. No. 30 selves or in combination with other known hydrox 3,283,030 disclosed use of potassium carbonate as a yalkylation catalysts. The catalysts may also be em basic catalyst in the reaction of ethylene carbonate with ployed in an unsupported state or supported by attach certain substituted phenols. ment to inert supportive means such as particles of Alkali metal hydrides disclosed by U.S. Pat. No. alumina, silica gel, diatomaecous earths, porous glasses, 2,987,555 and alkali metal hydroxides disclosed by U.S. 35 zeolites, and the like. By the term zeolites is included Pat. No. 2,967,892 have also been found to be effective modern synthetic resin zeolites useful as ion-exchangers catalysts for hydroxyalkylation reactions of ethylene as well as the well-known naturally occurring mineral formations that may be used with or without modifica carbonate with phenols and chloromethylethylene car tion as ion-exchangers. Attachment of the catalysts to bonate with phenols respectively. such materials is known, one such method described in One disadvantage associated with prior art processes more detail in the following examples, having been using acidic or basic catalysts has been the occurrence disclosed by J. H. Clark in J.C.S. Chem. Comm., 789 of secondary reactions between the hydroxyalkylphe (1978). nyl ether product and the carbonate reactant forming The phenol- or thiophenol-containing compounds quantities of undesirable side-products. A further disad 45 that may be hydroxyalkylated by organic carbonate vantage of known prior art processes is the inability to compounds according to this invention are extremely use certain modified phenolic or thiophenolic com varied. Carlson in U.S. Pat. No. 2,448,767 discloses a pounds that are unstable under acidic or basic reaction wide variety of reactive hydrogen-containing aromatic conditions. compounds including phenol, thiophenol, alkaline salts SUMMARY OF THE INVENTION 50 of phenol, 3-naphthol, and 8-hydroxyquinoline that are capable of undergoing hydroxyalkylation with alkyl This invention comprises an improved process for the carbonate compounds. Additionally Carlson taught that hydroxyalkylation of phenols or thiophenols providing all such compounds tested responded to the hydrox high yields with good selectivity. In particular the in yalkylation reaction and it was believed all such com vention comprises the use of certain alkali metal halide 55 pounds would be responsive. salts as reaction catalysts for the reaction of phenols or Davis in U.S. Pat. No. 2,987,555 discloses an addi thiophenols and cyclic organic carbonate compounds. tional number of phenols that may be hydroxyalkylated The ability to operate at a neutral pH according to the by reaction with alkylene carbonates including: pp'- invention allows the reaction to be run under relatively biphenol, p,p'-sec-butylidene diphenol, 4,4'-iso mild conditions thereby allowing utilization of reactants propylidenebis(o-cresol), 4,4'-isopropylidenebis(2- having a greater variety of functionality than has been phenylphenol), o-chlorophenol, o-cresol, p-propyl possible under prior known methods. It is also possible phenol, p-bis(o-cresol) and the like. utilizing the invented process to attain reaction condi I have found that nearly any phenol- or thiophenol tions conducive to exclusive monohydroxyalkylation of containing reactant is suitable for use according to this the phenol or thiophenol reactant. The hydroxyalkyl 65 invention. Included are: phenol, thiophenol and phenol phenyl ether or thioether products formed according to or thiophenol compounds substituted with one or more this invention are used as solvents and in certain coat hydroxy, mercapto, alkyl, aryl, alkaryl, aralkyl, halo or ings as well as in additional industrial applications. sulfonyl substituents, or mixtures thereof. 4,341,905 3 4. However, Tsuruya disclosed in J. Polymer Sci., Part about five hours is sufficient. The evolution of carbon B, 7, 709 (1969) that 2,4,6-tribromophenol, preferably dioxide is a convenient indicator of the progress of the forms polymers through debromination when reacted reaction. with organic carbonate compounds. This compound The reaction may be run either accompanied by me therefore is not considered to be suitable for use accord chanical or magnetic stirring or without stirring. To ing to the present invention. avoid liquid entrapment during the evolution of carbon The cyclic organic carbonates used in the hydrox dioxide it is also advantageous to employ a condenser yalkylation reactions according to this invention may according to well-known techniques in the art. likewise be varied. In addition to ethylene carbonate, The product, a corresponding hydroxyalkyl ether or Davis in U.S. Pat. No. 2,987,555 disclosed that any 10 thioether derivative may be easily recovered from the cyclic alkylene carbonate having the appropriate car reaction mixture, for example, by distillation if a liquid, bonate moiety attached at adjacent positions was capa or by recrystallization if a solid. ble of undergoing hydroxyalkylation with phenolic While the invention has been described as useful in a compounds. Specifically mentioned carbonate com batch process reaction, it may be utilized equally advan pounds were propylene carbonate, 1,2- or 2,3-butylene 15 carbonate and phenylethylene carbonate. For said dis tageously in a continuous reaction process. closure I do incorporate this teaching by reference. SPECIFIC EMBOOMENTS OF THE In addition, ethers of alkylene carbonates of the for INVENTION mula Having described the invention the following exatin 20 ples are given merely as illustrative of the present inven tion and are not to be considered as limiting. o-C. D., EXAMPLE 1. Ethylene carbonate (89.9 g, 1.02 mole), phenol (94.1 wherein R is C1-20 alkoxy, alkoxyalkylene, or (poly)al 25 g, 1.0 mole) and (1 g, 0.5 percent of koxyalkylene may be used. total reactant weight) were placed in a 500 in round As previously mentioned, use of the alkali metal hal bottomed flask equipped with a condenser and gas bub ide salts as catalysts at a neutral pH in the practice of bler. A magnetic stirrer provided agitation. The mixture this invention instead of acidic or basic catalysts advan was heated to 160 C.E.2 C. in an oil bath. After 2.5 tageously permits the use of reactants containing 30 greater functionality. The catalysts and milder reaction hours the reaction vessel was removed from the oil conditions additionally allow greater selectivity in bath, cooled and the contents removed. Purification of product formation including the exclusive formation of the product by distillation gave 137 g of 2-phenoxye the monohydroxyalkylated product without concomi thanol (99 percent conversion based on phenol limiting tant formation of secondary reaction products. 35 reagent). The reaction may take place in the presence or ab EXAMPLES 2-13 sence of an inert solvent. In the preferred embodiment the cyclic carbonate reactant is a suitable solvent. The reaction conditions of Example 1 were repeated The reactants may be combined in nearly any molar using a variety of halide salts as catalysts. All catalysts ratio since some product is produced under nearly all were present in a 2 weight percent concentration based conditions. It is preferred however, to combine the on the combined weight of phenol and ethylene carbon reactants in a stoichiometric ratio thereby eliminating ate. The reaction temperature was maintained between the need to remove excess reactants from the finished about 160 C. and about 165 C. Table shows the product in a subsequent purification step. reaction time and indicated extent of reaction. Sorne The reaction may be carried out in any vessel suitably 45 results in Table I are the average of more than one run. designed to contain the reactants and products and be unreactive under the conditions of the invention. Rep TABLE I resentative of suitable reaction vessels are those made of Reaction Time glass, stainless steel or other unreactive material. Example Catalyst (hours) % Completion 50 The reaction may be run in the practice of this inven 2 CSF .5-2 98 tion at any suitable temperature from about 100° C. to 3 KF 1.75-2.25 98 about 210 C. Faster reaction rates are observed at 4 Rbf 3 95 higher temperatures but decomposition of reactants and 5 NaCl 3 94. products is likely to occur at the higher temperatures. 6 RbCl 4. 94. 55 7 KCl 4.25 94. The optimum temperature for particular reactants al 8 CsC 4 92 lowing fast reaction rates, but minimizing decomposi 9 LiCl 5 94. tion side-products may be easily determined according 10 NaBr 7 93 to ordinary techniques of experimentation. The pre KBr 4.25 1g ferred operating temperature for most phenolic and 12 LiBir 7 74. carbonate reactants is from about 150° C. to about 170 13 No Catalyst > 6.0 <20 C. Heating the reaction vessel to the operating tempera ture may conveniently be occasioned by any usual means such as a heat lamp, heating mantle, oil bath, etc. EXAMPLE 14 The time for the reaction to proceed to substantial The reaction apparatus used in Example 1 was completion will vary depending on various factors such 65 charged with 4-methylphenol (54 grams), ethylene car as the particular phenol- or thiophenol-containing reac bonate (45 grams) and a small amount of KF (0.5 grains, tant, cyclic organic carbonate reactant, the catalyst and 0.5 percent). After thorough mixing the flask was in temperature selected. Generally about two hours to mersed in an oil bath and the temperature adjusted to 4,341,905 5 6 160" C.-H2. After a reaction time of 1.1 hours, CO2 detail below. Excess water was then removed by evapo evolution ceased and the product, 4-(2-hydroxyethoxy)- ration to yield the desired supported catalyst. methylbenzene (71 grams, 94 percent yield) was recov ered and purified by recrystallization from acetone. Example Support Wt. 2 KF EXAMPLES 15-29 30 silica gel 2.5 31 silica gel 11.1 The reaction conditions of Example 14 were repeated 32 alumina 1.1 using phenol reactants more specifically identified in 33 *zeolite 11.1 Table II below. The catalyst was KF present in the "The zeolite used a strongly basic, macroporous, styrene-divinylbenzene copoly indicated weight percent. The product in Examples 10 meric resin in the MSA-1 ion-exchange form sold commercially as Dowex MSA-1 15-29 in each case was the corresponding 2-hydrox ion-exchange resin. yethyl ether derivative of the initial phenol reactant. TABLE II EXAMPLE 34 Ethyl 15 Ethylene carbonate (44.0 g, 0.5 mole), phenol (47.1 g, ele Carbon- Cata 0.5 mole) and 4.5g of the supported catalyst prepared in Exam- Amount ate wt. lyst Time Yield Example 30 consisting of 0.56 g KF catalyst were com ple Phenol (g) (g) % (hrs) % bined in a 250 ml round-bottom flask equipped with a 15 2-methyl- 54 45 0.5 2.0 91 condenser and gas bubbler. Agitation was provided by phenol 20 a magnetic stirrer. The reaction was conducted in an oil 16 1-methyl- 54 45 0.5 1.5 87 bath maintained at 160 C.E.2. After 2 hours heating phenol 17 4-methoxy- 62 45 0.5 1.8 92 was discontinued and the product remaining in the flask phenol was allowed to cool. Filtration to remove the catalyst i8 4-chloro- 64 45 0.5 1.5 95 gave 69.0 g (100 percent yield) of a slightly yellow phenol 25 liquid shown by vapor phase chromatography and in 19 3-chloro- 64 45 0.5 3.5 90 phenol frared spectroscopy to be phenoxyethanol of 98 percent 20 2-chloro- 64 45 0.5 1.0 92 purity. phenol 21 4-nitro- 70 45 0.4 15 71 EXAMPLE 35-38 phenol 22 3-nitro- 59 38 0.5 8 79 30 The reaction conditions of Example 34 were repeated phenol using the supported and unsupported catalysts more 23 2-nitro- 70 45 0.4 8 86 fully described in the following chart. Approximate phenol reaction times required to produce 95 percent yield are 24 2,4,6- 45 30 0.4 3.3 78 trimethyl taken as an indication of the effectiveness of the sup phenol 35 ported catalyst. 25 4-tert- 75 45 0.4 3 92 butyl phenol Approx. time to 26 4-phenyl- 85 45 0.4 2.7 97 produce 95% phenol Example Catalyst yield (min.) 27 2-phenyl- 85 45 0.4 1.5 95 unsupported phenol 35 KF.2H2O (0.5 g) 58 28 2,2'-thio- 10 4.9 0.9 72 80 36 Example 31 (4.5 g) 72 bis(4- 37 Example 32 (4.5 g) 105 phenyl 38 Example 33 (4.5 g) 60 phenol) 29 4-bromo- 86 44 0,4 3.5 93 phenol 45 EXAMPLES 39-42 Phenol was combined with the following ethers of EXAMPLES 30-33 alkylene carbonates and KF catalyst in a 25 ml round Supported potassium fluoride catalysts were pre 50 bottomed flask. The flask was then placed in an oil bath pared by combining as an aqueous slurry potassium maintained at 160° C.--2 C. After the specified time fluoride and the supportive material described in more the identified product was recovered in the yield indi cated. All amounts are by weight.

% Time Example Catalyst (hr) Carbonate Product Yield (%) 39. 0.54 i ethylene carbonate db-OC2H5OH 98

40 0.28 20 db-OCH2CH(OH)CH2OCH(CH3)2 86

O O \/CHOCH(CH3), 4. 1.29 6 R db-OCH2CH(OH)CH2OC(CH3)3 84

O O. 4,341,905 7 3 -continued % Time Example Catalyst (hr) Carbonate Product Yield (%)

42 0.67 6 db-OCH2CH(OH)CHO-d 86

O O \-/CHO-d db = phenyl ium chloride, cesium chloride, , sodium EXAMPLES 43-50 bromide and . The reaction conditions of Examples 39-42 were 2. The process of claim 1 wherein the phenol- or repeated using KF catalyst and thiophenol and 4- 15 thiophenol-containing compound and organic carbon methylthiophenol reactants. ate compound are combined in substantially stoichic

% Time Thiophenol % Example Catalyst (hr) Reactant Carbonate Product Yield 43 1.11 0.5 dBSH ethylene carbonate -SC2H4OH 84 44 0.82 0.25 ' db-SCH2CH(OH)OH2OCH(CH3)2 96

O O. \-/CHOCH(CH3), 45 0.77 0.33 '' db-SCH2CH(OH)CH2CC(CH3)3 95 /N O O \/CH2OC(CH3)3 46 0.72 18 '' db-SCH2CH(OH)CH2Odb 70 /N O. O. \-/CHOb 47 1.16 15 4-methyl- ethylene carbonate p-tolyl-SCH2CH2OH 90 thio phenol 48 0.88 15 4-methyl- O p-toly- 99 phenolthio- /N SCH2CH(OH)CH2OCH(CH3)2 O O \/CHOCH(CH3), 49 0.83 15 4-methyl- Q p-tolyl- 94. phenolthio- /N SCH2CH(OH)CH2O(CH3)3 O. O. V/CH2OC(CH3)3 50 0.78 15 4-methyl- O p-tolyl- 95 thio-phenol /N SCH2CHOH)CH2O-d O O \/CH-O-b db = phenyl What is claimed is: metric quantity. 1. In the method of hydroxyalkylation wherein phe- 3. The process of claim 1 wherein the carbonate con nol- or thiophenol-containing compounds are reacted 60 pound is ethylene carbonate. with cyclic organic carbonate compounds in the pres- 4. The process of claim 1 wherein the reaction is ence of a catalyst followed by recovery of the hydrox- carried out at a temperature from about 100° C. to about yalkylaryl ether or thioether formed, the improvement 21O C. wherein the reaction is conducted without addition of 5. The process of claim 1 wherein the quantity of strong acid or base and the catalyst is an inorganic hal- 65 catalyst present based on total reactant weight is from ide salt selected from a group consisting of potassium about 0.1 to about 10 weight percent. fluoride, , cesium fluoride, lithium 6. The process of claim 1 wherein the catalyst is se chloride, , , rubid- lected from a group consisting of potassium fluoride, 4,341,905 9 10 rubidium fluoride, cesium fluoride, , 8. The process of claim 1 wherein the catalyst is at sodium chloride, potassium chloride, tached to an inert supportive means. and cesium chloride. 9. The process of claim 8 wherein the inert supportive 7. The process of claim 1 wherein the catalyst is se- means are particles of alumina, silica gel, diatomaceous lected from a group consisting of potassium fluoride, 5 earths, porous glasses or zeolites. rubidium fluoride and cesium fluoride. k g : it

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65 UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. : 4341,905 DATED July 27, 1982 INVENTOR(S) : Paul E. Strege It is Certified that error appears in the above-identified patent and that said Letters Patent is hereby Corrected as shown below: Column 2, line 34, "diatomaecous" should read -- diatomaceous -- . Column 6, line 9, "used a " should read -- used was a -- . Column 6, line lo, "in the MSA-l ion-exchange form" should read -- in the chloride form --. eigned and scaled this Eighteenth Day of January 1983 SEAL Attest:

GERALD J. MOSSINGHOFF Attesting Officer Commissioner of Patents and Trademarks