United States Patent (19) 11) 4,283,565 Bernhardt Et Al

United States Patent (19) 11) 4,283,565 Bernhardt et al. 45) Aug. 11, 1981

54). PROCESS FOR PREPARING 3,931,290 1/1976 Bourgau et al...... 560/236 BENZYLALCOHOLS 3,993,699 11/1976 Maeda et al...... 568/715 4,117,251 9/1978 Kaufhold et al. ... 560/236 75 Inventors: Ginther Bernhardt, St. Augustin; 4,134,925 l/1979 Petersen et al...... 568/638 X Gerhard Daum, Cologne, both of Fed. Rep. of Germany FOREIGN PATENT DOCUMENTS 2024948 1/1971 Fed. Rep. of Germany ...... 560/230 73) Assignee: Dynamit Nobel AG, Troisdorf, Fed. 2534209 2/1977 Fed. Rep. of Germany . Rep. of Germany 51-48626 4/1976 Japan ...... 560/236 21 Appl. No.: 974,468 51-65725 6/1976 Japan ...... 560/236 875999 8/1961 United Kingdom ...... 56O/236 22 Filed: Dec. 29, 1978 Primary Examiner-Bernard Helfin (30) Foreign Application Priority Data Attorney, Agent, or Firm-Sprung, Felfe, Horn, Lynch Dec. 31, 1977 DE Fed. Rep. of Germany ...... 2759168 & Kramer Jun. 9, 1978 DE Fed. Rep. of Germany ...... 2825.364 57 ABSTRACT 51) Int. Cl...... CO7C 29/128 There is described an essentially two step process for 52 U.S. C...... 568/648; 568/584; the preparation of benzylalcohols including those ben 568/587; 568/588; 568/637; 568/638; 568/649; zylalcohols having substituents on the benzyene ring by 568/650, 568/651; 568/652; 568/705; 568/706; reaction of a substituted or unsubstituted benzyl halide 568/709;568/710; 568/711; 568/713; 568/715; with a formate typically an alkali or alkaline earth metal 568/764; 568/811; 568/812; 560/234; 560/236; formate to form the corresponding substituted or unsub 260/465 F; 260/465 H; 260/465 G stituted benzyl formate. In the second step of the pro (58) Field of Search ...... 568/764, 715, 638, 584, cess the benzyl formate is contacted with an alcohol 568/587, 588,705, 706, 709, 710, 711, 713, 637, whereby the same is converted into the desired ben 648, 649, 650, 651, 652, 812, 811; 560/234, 236; zylalcohol. Both steps can be performed employing 260/465 F, 465 H, 465 G catalysts. Described in the specification is the realiza tion of the desired product in exceptionally high yields (56) References Cited in a short period of time whereby the process is charac U.S. PATENT DOCUMENTS terized by high space-time yields. 3,098,093 7/1963 Hagemeyer et al...... 560/234 3,328,439 6/1967 Hamilton ...... 560/234 X 48 Claims, No Drawings 4,283,565 1. 2 tion-medium, decreasing the utilization capacity of the PROCESS FOR PREPARING BENZYLALCOHOLS reactor. Saponification has been suggested under increased BACKGROUND OF THE INVENTION temperatures and pressure (U.S. Pat. No. 2,939,886), with addition of emulsifiers (U.S. Pat. No. 2,819,319) or FIELD OF THE INVENTION saponification under heavy shear agitation (DE-AS No. This invention relates to the preparation of substi 16 18530). tuted or unsubstituted benzyl alcohols by reaction of Consequently, all of these measures increase the rate benzyl halides with alkali metal or alkaline earth metal of saponification, but do not stop the formation of di formates at an elevated temperature in the presence of a 10 benzyl ether or resin-like by-products. In order to keep benzyl formate to the corresponding benzyl alcohol by the resin content in the reaction product to a minimum, contacting the benzyl formate with an alcohol suitably working in dilute solutions is necessary. Therefore, for in the presence of an esterification catalyst. This inven example, only xylylenedichloride concentrations of a tion is concerned with a commercially feasible process maximum of 5 to 8 weight percent within the aqueous which provides high yields of desired substituted or 15 reaction solutions are possible. Therefore, it follows, unsubstituted benzyl alcohols at high space-time yields. that after completed saponification heavily dilute Benzyl alcohols, especially the ones substituted in the xylyleneglycol solutions result which must be concen benzene ring, are valuable intermediates for organic trated to a gylcol content of 15 weight percent or, in the syntheses, i.e., starting substances for the manufacture case of easily water soluble glycols, must be evaporated of the corresponding benzoic aldehydes. Xylyleneg 20 until complete dryness in order to isolate the glycols by lycols and nuclear substituted xylyleneglycols are, for crystallization or extraction. The evaporation of such example, starting materials for the manufacture of poly large amounts of water is economically unsound and esters and polyurethanes. constitutes a disadvantage of the procedure. Starting from benzylhalides, such as benzylchlorides According to the process of U.S. Pat. No. 2,939,886, or -bromides or xylylenedichlorides, two general meth 25 the conversion of xylylenedichloride with alkali ace ods for the preparation of benzyl alcohols or xylyleneg tates is carried out in water at increased temperatures lycols are used: and elevated pressure. The separation of xylyleneglycol (a) The direct saponification of benzylhalides or is achieved through saponification of its bisacetate. This xylylenedichlorides with dilute aqueous alkali metal procedure has the disadvantage of an exceptionally long 30 reaction-time of 11 hours until the completion of the hydroxide-and-carbonate-solutions, and first reaction step, and of low glycol-yields after saponi (b) a two-step process consisting of a conversion of fication during the second reaction-step. In addition, an benzylhalides as well as xylylenedichloride with alkali autoclave is necessary for the implementation of the metal- or alkaline earth acetates to benzyl acetates as conversion. well as xylyleneglycolbisacetates which afterwards are 35 According to another process (U.S. Pat. No. saponified to the corresponding benzyl alcohols as well 3,993,699) in which these disadvantages are said to be as glycols. eliminated, xylylenedichloride is reacted with an alkali The method of direct saponification mentioned under metal or alkaline earth acetate to xylyleneglycolbisace (a) has the advantage of being a one-step process. On tate in the presence of an aromatic hydrocarbon as the other hand, considerable quantities of dibenzyl ether 40 adjuvant and a tertiary amine as catalyst. This bisacetate occur generally as by-products, as well as polymers of is saponified with aqueous alkaline lye to xylyleneg xylylenedichlorides. Therefore, up to 20% of dibenzyl lycol. After separation of the adjuvant and the catalyst, ether may form during alkaline hydrolysis. (Ullmann, xylyleneglycol is extracted from the aqueous solution. volume 4, page 310.) This particular procedure shows decisive disadvan According to this procedure, benzyl chlorides, i.e., 45 tages also. The conversion to xyleneglycolbisacetate dimethylbenzylchloride or methoxybenzylchloride sub progresses in a satisfactory way only in the presence of stituted in the benzene nucleus by one or more methyl an adjuvant. By using large amounts of the adjuvant, groups or another electronegative group, do not pro valuable utilization space within the reactor is lost. The duce the desired alcohol as principal product, but the starting concentration of xylylenedichloride in the reac corresponding dibenzyl ether (German Pat. No. Pll 08 50 tion mixture amounts to only 25 to 40 weight percent. 677). In this German patent, a two-step process is de In addition, through the dilution effect of the adjuvant, scribed. the reaction time is considerably lengthened. Another One procedes in such a way that one heats up benzyl disadvantage resides in that after saponification, only halides or xylyenedihalides, preferably chlorides with heavily dilute xylyleneglycol solutions are present with alkali metal or alkaline earth acetate in a concentrated 55 a maximum 16 weight percent glycol as well as an addi aqueous solution until all halogenmethyl groups are tional 20 weight percent sodium acetate as by-product. changed to acetoxymethyl groups, and, afterwards, In order to isolate the xylyleneglycol by means of ex benzyl alcohols or xylyleneglycols are freed through traction, a multi-fold amount of the aqueous solution as saponification with alkali metal or alkaline earth metal extraction medium is necessary, and, in order to regain hydroxides. 60 the sodium acetate from the aqueous solution free of There is no doubt that the formation of dibenzyl glycol, large amounts of water must be evaporated. ethers or resin-like products is prevented, but the disad Therefore, the economical feasability of this process is vantage of this procedure resides in that it takes long unsatisfactory. reaction-times for the formation of acetates in the first Furthermore, a process has been described, wherein reaction-step. It is also disadvantageous that high so 65 benzylbenzoate is formed through conversion of ben dium acetate surpluses must be used, amounting up to zylchloride and sodiumbenzoate in large quantities in six-fold the required quantity, restricting the economy the presence of tertiary amine used as catalyst. Yet, the very heavily. Besides, a solvent must be used as a reac literature does not mention anything about the prepara 4,283,565 3 4. tion of xylyleneglycolbisbenzoate of the corresponding According to the invention, unsubstituted as well as glycol. substituted benzyl chlorides and/or -bromides in singu As shown in the comparative example, transferring lar or multiple form (also nuclearly-substituted) are this reaction to xylylenedichloride is impossible, since a suitable for the conversion with alkali- and/or alkaline reaction mixture consisting of one mol xylylenechloride 5 earth formates. and 2 mols sodiumbenzoate can not be stirred. The For example, nuclear-substituted benzylhalides are preparation of xylyleneglycol through bisbenzoate such as shown in the general formula would be economically unsound, since only 40 weight percent of the mol mass consists of the xylyleneglycol Y. Ac component. O Within the DE-OS No. 2 731 259 the preparation of CH2-X substituted benzylformate in o-position through elec tron-attracting radicals, such as nitro-, cyane- or halo W Zb gen-, is discussed, but no reference is given to the prepa ration of benzyl alcohols. The disadvantage of this well 15 where the substituents represent are: known process residues in that the formation of benzyl Y= halogen, especially Cl or Br and/or alkyl groups, formates derived from benzylhalide and sodium for (n = 0 to 5, preferably 0 to 2), mate requires large amounts of solvents, such as di W=CH2-X, (a-0 to 5, preferably 0 to 2) methyl sulfoxide, dimethyl formamide or hexamethyl Z= OH and/or alkoxy and/or phenoxy groups (b=0 phosphoric acid triamide and that the benzylformates to 3, preferably 0 to 2), have to be separated from the solvents through the A = nitro groups and/or nitrile groups (c = 0 to 2) addition of large amounts of water. In this way, the whereby a + b --n + c = 1 to 5, preferably 1 to 3 and space-time- yield diminishes with the presence of large where X represents chlorine or bromide. amounts of solvents. In order to regain the expensive Considered as alkyl groups or alkoxy groups are 25 those with from 1 to 8, preferably 1 to 4 C- atoms, in a solvents which are soluble with water in unlimited straight or branched chain, especially methyl- or me amounts, large quantities of water have to be evapo thoxy groups. rated, making the process complicated and economi The phenoxy groups can contain substituents, such as cally unsound. Cl- or Br- or the above mentioned substituents, such as The presented invention is addressed to the problem alkyl groups. The substituents of the benzene ring of the of supplying an economically improved procedure for phenoxy group can be similar or different to the substit the preparation of benzyl alcohols and benzyl alcohols uents of the benzene ring shown in the formula. substituted in the benzene ring, for example xylyleneg In particular, the following benzylhalides are consid lycols, which can be carried out from a commercial ered nuclearly substituted: benzylchlorides and/or -bro point of view without large structural apparatus and 35 mides, showing an extra -CH2-X substituent in o-, m which provides good yields within short reaction times. or p- position, i.e., p-, m-, or o- xylylenedichloride and SUMMARY OF THE INVENTION /or -dibromide. Furthermore, there are such which show in addition to the -CH2-X-substituent one or The foregoing objects are fulfilled in accordance more substituents in the benzene ring, i.e., Cl- or Br with the invention by contacting a benzylhalide espe 40 substituents, such as tetrachloroxylylenedichloride, the cially where the halide is chlorine and/or bromine or a corresponding monochloro-dichloro-and trichlorox substituted benzylhalide such as xylylenedihalide with ylylenedichlorides as well as the corresponding dibro an alkali metal or alkaline earth metal formate and sub mides, alkyl-substituted xylylenedihalides, as i.e., C1 to jecting the resultant benzyl formate so formed to trans C4-dialkyl-substituted xylylenedihalides, such as di esterification in order to form benzyl alcohols or 45 methyl- or diethylxylylenedihalides as well as the corre xylyleneglycols, as the case may be. sponding hydroxy-substituted xylylenedihalide like Fundamentally, the conversion to benzyl formate as mono- and dihydroxy-xylylenedihalides. well as substituted benzyl formates can be achieved Other nuclear-substituted chlorides or bromides ca without the use of an inert solvent for the substituted or pable of being reacted according to the invention are unsubstituted benzylhalide and/or the admixed alkali 50 benzylhalides which in o- and/or m- and/or p- position metal or alkaline earth formate. in reference to the -CH2-X group contain Cl- or Br The conversion without the use of a solvent takes substituents and/or alkyl groups, like methyl- or alkoxy place in an advantageous manner, namely, in the heter groups, like methoxy. In particular, there should be ogenous phase whereby the alkali metal and/or alkaline named: o- or m- or p-methylbenzylchloride, o- or m- or earth metal formate constitute the solid phase and the 55 p- phenoxybenzylchloride, o- or m- or p-chlorobenzyl benzylhalide or xylylenehalide constitute the liquid chloride, o- or m- or p-bromobenzylchloride, 2,4-dime phase. thylbenzylchloride, o- or m- or p-hydroxybenzylchlo The conversion occurs at or above the melting point ride, o- or m- or p-methoxybenzylchloride, o- or m- or of the admixed halide, but below the disintegration p-nitrobenzylchloride or o-, or m- or p-cyanobenzyl temperature of the developing or admixed formates or 60 chloride, trichloro- or tribromo benzylchloride, tetra admixed halides and below the melting points of the chlorobenzylchloride, tetrabromobenzylchloride, pen alkali metal and/or alkaline earth metal formates. In tabromobenzylchloride, pentachlorobenzylchloride general, during preparation of benzyl formates or etc., as well as the corresponding bromides of the men xylyleneglycolbisformates one works with tempera tioned compounds. tures in the area of 100 to 250 C., preferably between 65 The alkali metal and alkaline earth formates to be 110 and 200 C. Depending on the reaction compo used according to the invention are namely sodium nents, temperatures may range below or above the formate, potassium formate, magnesium formate, cal range mentioned above. cium formate, while in principle the formates of all 4,283,565 5 6 other alkali metal) or alkaline earth metals can be em Suitable phosphines with aromatic radicals are tri ployed as reactants. Sodium formate is preferred. phenylphosphine, tri-(4-methyl-phenyl)- phosphine, According to the inventive process, the conversion of dimethyl-phenyl-phosphine, isopropyl-diphenylphos the formate with the benzyl chloride occurs in the het phine, carbethoxymethyl-diphenyl-phosphine, triben erogenous phase. The formate should not be used in too 5 zylphosphine, l-phenyl-phospholane and 1-phenyl coarse a form, since this would decrease the speed of phosphorinane. conversion. Excessively fine grained formate may pro Especially suitable for the execution of the present duce filtration difficulties when the resulting inorganic invention are tertiary phosphines with aliphatic radicals halide should be separated in solid form from the devel up to C4, i.e. triethylphosphine or dibutylphosphine or oped benzyl formate after the conversion with benzyl 10 others with aromatic radicals like triphenylphosphine halide. Suitable grain size ranges are i.e. 0.025 to 0.5 and tribenzylphosphine. Tribenzylphosphine is pre Inn. ferred, The alkali metal and alkaline earth metal formates are For the execution of the procedure according to the employed in the quantity of 1 stoichiometric equivalent presented invention, all ammonium-halides derived per equivalent benzylhalide stoichiometrically required 15 through quaternization of the above-mentioned tertiary for the complete process of the reaction. Perferably, amines and tertiary phosphines with aliphatic C1 up to one works with surplus quantities of the formate. The C4-alkylhalides or benzylhalides can be used as quater stoichiometric equivalent portion of benzylhalide to nary ammonium salts or phosphonium salts. alkali metal, as well as alkaline earth formate, is gener Tetracethylammoniumchloride, methyl-tricaprylam ally 1:1-1.5. Preferably, one works with a slight stoi 20 moniumchloride, tetrabutylammoniumchloride, trime chiometric excess represented by 1:) 1 to 1:1. 1. thylbenzylammoniumchloride, triethylbenzylammoni Suitable catalysts for the reaction of benzylhalide umchloride, N-benzylpyridiniumchloride, triphenylme with the formate are tertiary amines, tertiary phos thylphosphoniumbromide and triphenylethylphos phines, quaternary ammonium salts and quaternary phoniumbromide have been found especially suitable. phosphonium Salts. 25 Fundamentally, mixtures of the above-mentioned Homogeneous and heterogeneous tertiary amines are tertiary amines, tertiary phosphines quaternary ammo suitable with aliphatic, cycloaliphatic or aromatic radi nium slats and quaternary phosphonium salts are suit cals or heterocyclic tertiary amines. able catalysts for the conversion. Suitable tertiary amines with aliphatic radicals are, Tertiary amines, phosphines ammonium- or phospho i.e., trimethylamine, triethylamine, tripropylamine, 30 nium salts used as catalysts are admixed in quantities of triisopropylamine, tri-prim.-n-butylamine, as well as 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by their isomers, monoethyldiisopropylamine, N,N,N'N'- weight per 100 parts by weight of benzylhalide. tetramethylethylenediamine, for instance, substituted In general, the conversion takes place within a tem tertiary, aliphatic diamine, like tri-((3-ethoxyethyl) perature range of 100 to 250° C., preferably between -amine. dimethyl- aminoacetonitrile, N,N-Di-n-butyl 35 110 and 200 C. aminoacetonitrile, N,N-diisopropyl aminoacetonitrile, Preferably, the conversion is carried out at normal N-n-butyl-N-methyl aminoacetonitrile, N,N-diisobutyl pressure, while, basically, one could work at elevated aminopropionitrile, {3-dimethyl aminopropionitrile, p pressure, i.e., in an autoclave. N,N-dimethylaminobenzonitrile. The trans-esterification of the benzylformate is car For example, an amine with cycloaliphatic radical is 40 ried out at elevated temperatures. Preferably, one dimethylcyclohexylamine. works at boiling temperature of the reaction mixture, Suitable amines with aromatic radicals are, i.e., N,N- preferably in such a way that the formic acid ester de dialkylaniline (N,N-dimethylaniline, N,N-diethylani veloped from the admixed alcohol is continuously dis line, etc.), benzyldimethylamine, p-nitrophenyl-di-n- tilled from the reaction mixture during the trans-esterifi butylamine, N,N,N'-tetramethyl benzidine etc. 45 cation process. Generally the trans-esterification can Suitable heterocyclic tertiary amines are the follow take place at temperatures between 30 and 250 C., ling: preferably 50 to 200° C. hexamethylene tetramine, N-alkyl- as well as N-aryl Primary or secondary aliphatic or cyclophatic univa morpholine, like N-n-butylmorpholine, N-phenylmor lent alcohols are admixed for esterification of the benzyl pholine, N-(p-methylphenyl-) morpholine, morpholino 50 formate, i.e., C1-up to C3 alcohols. acetic acid-morpholide, N-aryl or N-alkyl-tetrahy Univalent alcohols are: methanol, ethanol, n droquinoline, or -tetrahydroisoquinoline, like N-n- propanol-, n-butanol, amylalcohol, isopropanol, and propyltetrahydrozuinoline, N-phenyl-tetrahy cyclohexanol. droisoquinoline, i.e. N-alkyl- and N-arylpyrrolidine and Primary or secondary aliphatic alcohols are favored, their derivatives, i.e., N-methylpyrrolidine, N-n-butyl 55 with preference given to those which have a low molec pyrrolidine, N-phenylpyrrolidine etc. Other aromatic ular weight, because at equal molar ratio of benzyl tertiary amines are pyridine, isoquinoline, pyrazine, formate and alcohol, the higher is the weight concentra Oxazine, quinazoline, oxazol, oxdiazol, etc. tion of benzyl formate in the reaction mixture, the lower Especially suitable for the execution of the presented is the molar weight of the alcohol. After complete trans invention are tertiary amines with aliphatic radicals up 60 esterification, the weight concentration of the devel to C4, i.e., triethylamine, tributylamine triethylenedi oped benzyl alcohol rises accordingly. Preferred for use amine, as well as hexamethylenetetramine, dimethylani are methanol, or ethanol or n-prim, butanol is isopropa line, N-methylmorpholine. Triethylamine is preferred. nol, especially methanol. Tertiary aliphatic phosphines are i.e., trimethylphos The alcohols are admixed at the least in the stoichio phine, triethylphosphine, tributylphosphine, trioctyl 65 metrically necessary amount of 1 equivalent per for phosphine, triisopropylphosphine. moxymethyl group, preferably in excess thereof. In Tricyclohexylphosphine is a phosphine with cycloali general, the equivalent ratio 1:1 to 1:25, preferably 1:125 phatic radicals. to 1:12 is used. 4,283,565 7 During trans-esterification, formic acid esters de ric ratio of preferably 1:> 1 to 1.1 and, in a given in velop as valuable by-products, which are used as com stance, after melting the benzylhalide, the reaction mix mercial solvents and as intermediates in synthesis. ture is vehemently agitated, generally by stirring in Such According to the inventive process, acidic, basic or a way that suspension of the formate occurs within the neutral compounds are admixed as esterification cata liquid benzylhalide. lysts. The catalyst is introduced in portions into the Suspen All mineral acids, e.g., oxo-acids, such as nitric acid, sion which is heated appropriately but not substantially Sulfuric acid, phosphoric acid, or hydrochloric acid are above the melting point of the benzylhalide. In the case suitable as acidic catalysts, as well as carboxylic acids, where lightly volatile amines like triethylamine are especially formic acid and acetic acid. Mineral acids as O used, the reactor should be equipped with a reflux well as carboxylic acids are admixed preferably as acque cooler when working under normal pressure, in order ous Solutions of a concentration of, for example, 20 to prevent the escape of amine. weight percent to 60 weight percent. In general, the conversion to benzyl formate takes When using acidic esterification catalysts, the alco place in the temperature range of 100 to 250 C., pref hols used for trans-esterification can contain water, erably between 11 O' and 200 C. which partially affects the trans-esterification in a favor The quantitative extent of conversion during the able way. The water content of the trans-esterification process can be easily determined by extracting crystal mixture ranges between 2 to 80 volume percent, prefer line portions from the hot suspension, and determining ably between 5 to 50 volume percent. their residual formate portion through inanganometric AS basic or neutral esterification catalysts one can use titration according to Blackadder (F. P. Tradwell, organo-oxy compounds, especially those of elements of Handbook for Analytical Chemistry, 1949, pg. 536). the first, second and third group, as well as the fourth During the conversion, special protective gases are, and fifth subordinate group of the Periodic System apparently, unnecessary. Their absence does not affect preferably of the elements Na, K, Mg, Ca, Al, Ti, Zr. V. reaction-speed, conversion or product quality. According to the invention, alcoholates of primary, 25 After completing the reaction, a suspension of inor secondary, or tertiary aliphatic, cycloaliphatic or arali ganic halide occurs in the benzyl formate from which phatic univalent or bivalent alcohols, especially C1 up the inorganic halide is separated through filtration or to C& alcohols, or phenolates wherein the metal compo hydroextraction at temperatures above the solidifica nent consists of a metal from the first to third group of tion point of the benzyl formate. the Periodic Systern can be used. The preferred metal 30 The separation of the inorganic halide can be component is sodium or potassium. achieved in an advantageous manner, for instance, by The preferred alcohol component corresponding to using a submersible suction strainer or through hydro an alcoholate is an univalent C1 to C4 alcohol, prefera extraction in a heated filtration centrifuge. bly a primary or secondary alcohol, such as methanol, The complete separation of benzyl formate without ethanol, propanoi, isopropanol, or one of the isomeric 35 filtration or centrifugal residues is done by washing the primary or secondary butanols. same with organic soivents, such as acetone, methyliso The alcoholates are preferably those based on the butylketone or alcohols. It is advantageous to use alco alcohols which are used for the esterification of benzyl hols which are intended to be used for the following formate. The alcoholates of benzyl alcohol and of the trans-esterification of the benzy formate. xylyleneglycols are also quite suitable with bivalent 40 Benzy formates or-bisformates obtained in Such a alcoholis, mono-as well as di-aikali metal glycolates can way may be admixed as such for the trans-esterification. be employed. Suitable phenolates are, e.g., those of the In some instances, they are distilled for purification phenyl, cresol, salicyclic aldehyde or hydroxybenzoic before esterification takes place, appropriately under acids. vacuum. In general, purifying the benzy formate before Neutral catalysts useful in the invention are the esters 45 trans-esterification is not an absolutely necessary nea of metailic acids of the elements of the fourth and fifth S. subordinate group of the Periodic System, especially Preferably, the trans-esterification of the benzyl for that of titanium. Especially suitable is tetra-n- prim. - mates with primary and secondary alcohols is carried butyltitanate. out at the boiling point of each corresponding reaction Acidic and basic esterification catalysts are admixed 50 mixture, whereby the developed formic acid ester of the in quantities of 0.01 to 10 parts by weight, preferably admixed alcohol is continuously distilled off, so thai, 0.05 to 5 parts by weight. Neutral catalysts are admixed after complete trans-esterification, the benzyl alcohols in quantities of 0.01 to 5 parts by weight, preferably 0.02 are found in solid form or in highly concentrated aco to 3 parts by weight per hundred parts by weight of holic solutions, from which benzyl alcohols can be benzyl formate. 55 separated through distillation of the alcoholic Solutions. When using alcoholates, phenolates or metallic acid The boiling points of the formic acid esters formed esters as esterification catalysts, the univalent primary during esterification with the univalient primary or Sec or secondary alcohols admixed to the trans-esterifica ondary alcohols are lower than the boiling points of the tion reaction must be free of water or substantially free corresponding alcohols. Appropriately, the vaporiza of water so that the same is not present in an amount of 60 tion of the formic acid ester developed during trans more than 8 weight percent. Appropriately, the water esterification takes place in a heated cooler whose cool content of the trans-esterification mixture should not ing temperatures is regulated in such a way that the low exceed 4 weight percent. boiling ester is distilled from the reactor, while the Preferred esterification catalysts are the alkali metal desired high boiling alcohol remains inside. alcoholates especially sodium methylate. 65 If one commences the trans-esterification with puri The process of the invertion is carried out as follows: fied benzyl formates, the corresponding benzyl alcohols the benzylhalide and the alkali metal or alkaline earth or glycols occur in high purity when the dissolved metal formate are placed into a reactor of stoichiomet catalytic quantities of alcoholates or phenolates are 4,283,565 10 neutralized with moist carbon dioxide and mineral acid of solvent. In this way, a high volume-time-yield can be catalysts are neutralized with basic agents, i.e., alkali achieved, and smaller reactors can be used. metal hydroxides or carbonates, and, when the resulting 5. During esterification, commercially valuable for inorganic salts are sucked off, before evaporating the mic acid esters are obtained as by products which are alcoholic solutions. The metallic acid esters used as 5 catalysts become hydrolyzed and the inorganic hydrol used as solvents, insecticides and intermediate products ysis-products are separated in mechanical manner. for syntheses. Volatile acids used as catalysts, such as formic acid or In order to more fully illustrate the nature of the acetic acid can be distilled from benzyl alcohol solu invention and in a manner of practicing the same, the tions together with the excess alcohol. 10 following examples are presented: According to the invention, the purification of the benzyl alcohols takes place preferably after the final EXAMPLE 1 phase of conversion, meaning after completion of esteri 140.5 g p-methylbenzylchloride (1 mol) and 74.8 g fication of benzyl formate and after evaporation of the sodium formate (1.1 mols) were placed into a four residual alcohol. 15 necked column, equipped with a reflux cooler, ther Purification can be achieved through transcrystalliza mometer, dropping funnel and agitator; the mixture was tion or distillation; distillation is the preferred method. Before purification by distillation, is effected, acidic heated to 80° C. and 1.7 g (0.017 mols) of triethylamine components of the reaction mixture must be taken up by was dripped into the reaction mixture during agitation, neutralization with a basic agent, i.e., an alkali metal 20 whereby the temperature of the column content was hydroxide, carbonates or bicarbonates, in order to pre raised to 150° C. vent the formation of benzyl ethers or condensation After two hours, the content of the column was products. cooled down to 50 C., the liquid phase was separated Especially suitable for the purification of benzyl alco from the solid phase by filtration via a submersible suc hols is the method of vacuum distillation. 25 tion strainer, the filtration residue was washed twice According to the invention, alcohol yields of up to with 100 ml acetone each, the solvent was distilled off 99% can be obtained when using benzyl chlorides. the washing solution and the vaporization residues were When using benzyl bromides the yields are lower. combined with the filtrate, which amounted to 151 g of The inventive process can also be carried out as "one pot' process where the mixture of benzyl formate and 30 the above reaction product. halide is not separated after the first conversion step, but By determining the residual formate content in the is directly connected with the trans-esterification and filtration residue (according to Blackadder) a formate only after completion of the second processing step is consumption of 0.99 mols had occured, corresponding separation of inorganic halide from the alcoholic benzyl 35 to a p-methylbenzylchloride conversion of 99%. alcohol solution carried out. 151 g of the oily reaction product were heated under According to the invention, the separation of benzyl reflux with 150 ml methanol (3.7 mols) containing 1 g alcohols is carried out in a manner described above. sodium methylate (0.019 mol). The temperature of the According to the invention, the preferred form of cooling water was regulated at 32° C. The methyl for carrying out the invention resides in effecting the sepa 40 ration of inorganic halide after completing of the reac mate was distilled off overhead from the cooler (boil tion of benzylhalide with alkali metal or alkaline earth ing-point: 32° C) and was led via a mounted distillation formate. bridge through an intensive cooler and collected in a According to the invention, the admixed benzylha receiver. lides can be produced either through chlorine or bro 45 After 35 minutes, the distillation was completed. For mine ethylation of benzene (compare, i.e., R. C. Fuson the separation of the remaining methyl formate, the and C. H. McKeever, Org. Reactions I (1947) page 63) cooling-water temperature of the reflux cooler was or through side chain chlorination or -bromination of raised to 42° C. The distillate weighed 64 g and con toluene or toluenes substituted in the benzene ring sisted of 96% methyl formate, which was obtained (compare, i.e., Houben-Weyl, Method of Organic 50 through distillation in pure form. Chemistry, vol. V/3 (1962) page 736 and vol. V/4 From the content which remained in the reaction (1960). Compared to other syntheses, the inventive process flask, methanol was distilled off and the residue was has the following advantages: subjected to another distillation under reduced pres 1. The conversion of the benzylhalides with an alkali 55 Sure, or alkaline earth formate takes place directly in mass, 115.9 g p-methylbenzyl alcohol were distilled at whereby the available reaction space of the reactor is 103.5-105 C. and 12 mm, which amounts to a yield of used to its optimum. 95%, in response top-methylbenzylchloride. The melt 2. As shown in the examples, the conversion takes ing point ranged between 58-59 C. place under normal pressure within a short time span 60 and with high yields of benzyl formates. EXAMPLE 2a to 2c 3. The inorganic halide developed as by product is easily separated from the benzyl formates. Procedures were used as in Example 1, with the ex 4. When trans-esterifying benzyl formates with alco ception that instead of using triethylamine as a catalyst hols, the benzyl alcohols are obtained in substantial 65 for the conversion of p-methylbenzylchloride and so quantities or as concentrated alcoholic solutions. The dium formate, catalysts mentioned in Table 1 were used. benzyl alcohols can be isolated without expensive ex Yields for p-methylbenzylchloride and p-methylben traction procedures by evaporation of large quantities zyl alcohol are shown in Table 1. 4,283,565 11 12 TABLE 1 a yield of 93%, based on the reacted p-methylbenzyl chloride. p Mety EXAMPLES 4a to 4 enzyl Re- chloride p-Methylbenzyl- 5 According to Example 1, each l mol of the benzylha action- con- alcohol yield lide substituted in the benzene ring in Table 2 and 74.8 lvs tre werson - Engpo- g sodium formate were reacted in the presence of a Ex. Catalyst Mols (h) (%) (g/%) (C.) catalyst to the corresponding formates which were 2a trimethyl 0.2O 2 99. 117.1/ 58-59 distilled off under reduced pressure, and, according to Whium. 96 10 Example 1, were esterified to the corresponding benzyl chloride alcohol employing methanol and an esterification cata 2b triphenyl- O.O3 4. 98.3 14.7/ 57.5. lyst. TABLE 2 Benzylalcohol Ex- Benzylhalogenide Catalyst Formiate Methanol Esterification Yied Met. Pt. Boil. Pt. ample Chem. term (g) (Mol) % (m/Mole) catalyst (Mol) (g/%) (C.) (C.) 4 a m-Methyl- 40.5 TMBAC 97.3 81/2 K-tert.- O.O25 In-Methyl- (20 104-05 benzylchloride (0.017) Butylate 14.8/94. (12 mm) 4 b o-Methyl- 40.5 TMBAC: 96.9 162A. K-tert.- 0.015 o-Methyl- 35- O5.0 benzylchloride (0.02O) Butylate 15.9/95.0 36 (12 mm) 4 c m-Phenoxy- 28.5 TMBAC. 94.3 101/2.5 Mg- 0.05 m-Phenoxy- <20 142-144 benzylchloride (0.021) ) ethylate 82.4/912 (0.6 mm) 4 d o-Chlor- 16 TEA* * 940 61/15 o-Chlor- 67- 14-16 benzylchloride (O.O41) 29.2/91.O 68 (13 mirn) 4 e p-Nitro- 1715 TEA 95.5 81/2 Al-iso- O.OO p-Nitro- 93 84-85 benzylchloride (0.035) propylate 40.9/92.1 (12 mm) 4 f 2,4-Dimethyl- 1555 PP+ 4 + 97.3 101/2.5 Butyl- O.O. 1 2,4-Dimethyl- 28- 120-12 benzylchloride (O.O32) titanate 126.8/93.2 29 (13 mm) 4 g p-Hydroxy- 142.5 TMBAC 96.5 202AS Na-Phenolate 0.031 p-Hydroxy- 124 benzylchloride (O.O2O) 6.9/94.3 4 h p-Methyl- 40.5 TEA* * 97.5 2O2A5 Na-p-Methyl- p-Methyl- 58.5. 107-08 benzylchloride (0.024) benzylate 115.9/95.0 59.5 (14 mm) 4 i p-Cyan- 1515 TMBAC 93.8 2O2/5 K-tert. 0.031 p-Cyan- 32.5 -m benzylchloride (0.025) Butylate 20.4/90.5 34 TMBAC = Trimethylbenzylannonium chloride **TEA = Triethylamine ***TPP = Triphenylphosphine

phosphine 94 58.5 2c triphenyl- 0.02 2.5 98.5 115.9/ 58-59 EXAMPLES 5a to Sd ethvi-Shiphonium. 95 According to Example 1, 562 g p-methylbenzylchlo bromide ride (4 mols) were reacted with 299.2 g sodium formate 0 (4.4 mols) in the presence of 11.2 g hexamethylenetetra mine (0.08 mols) at 140 C. After 3 hours reaction time, EXAMPLE 3 the methylbenzylchloride conversion amounted to 99.3%. Analogous to the conversion carried out in Example The quantity of the reaction product freed from so l, potassium formate was used instead of sodium for 45 nate. dium chloride and excess sodium formate amounted to In the presence of 2.0 g (0.02 mol) triethylamine, 600.5 g. Each 150.1 of this product was esterified with 140.5g p-methylbenzylchloride was reacted with 92.5g 4 mols of alcohols listed in Table 3, in the presence of 0.025 mols of the corresponding sodium alcoholate. The potassium formate (1.1 mols) at 150° C. After 2.5 hours, trans-esterification time amounted to 1.25 hours. The the p-methylbenzylchloride conversion amounted to SO 99.5%. formic acid esters which had developed in the mean Through esterification of the resulting p-methylben time were purified through distillation. TABLE 3 Formic acid p-Methyl Boiling Cooling estet benzyl point Quantity wate CP Yield Melting Example alcohol (°C.) (ml) temp. ("C.) (%) Yield point 5a methanol 65 162 32 32 98 95. 58.559 Sb ethanol 78.5 234 53 54 97 96. 57-58 5c n-prim.- 7.7 366 O6 97 97: 94.5 57.5-58.5 butanol 5d iso- 82.3 30 7 71 96 95.0 57.5-58.5 propanol in azeotrope with butanol

65 zyl formate with 90 ml methanol in the presence of 1 g EXAMPLE 6 sodium methylate, l 13.5g p-methylbenzyl alcohol were According to Example l, 140.5 g p-methylbenzyl received at a melting point of 58 C., corresponding to chloride (1 mol) were reacted with 74.8 g. sodium for 4,283,565 13 14 mate (1.1 mols) and 4g trimethylbenzylammoniumchlo After complete fusion of the p-xylylenedichloride, ride (0.22 mols) at 140 C. the agitator was turned on, 1.7 g (0.017 mols) triethyl After two hours of reaction time, the conversion amine was dripped into the reaction mixture and the amounted to 99.5%. The reaction product, separated entire column content was heated to 150 C. under from the sodium chloride, was distilled under a water 5 heavy agitation. jet vacuum. At 12 mm and 97 to 98° C. 145.5g p-meth After 1.5 hours, the flask content was cooled to 115 ylbenzyl formate were recovered corresponding to a C., the liquid phase was separated from the solid phase yield of 97%. through filtration over a submersible suction filter 145.5 g p-methylbenzyl formate were heated for 2 strainer, the filtration residue were washed twice with hours under reflux with 166 ml methanol, 50 ml water 10 100 ml methylisobutylketone each, the solvent was and 10 ml formic acid while maintaining the colling evaporated from the washing solution and the evapori water temperature at 32 C. whereby methyl formate zation radicals were combined with the filtrate which was distilled off. The condensate weighed 62 g. 56 g amounted to 195.5 g. The product has a melting point of methyl formate corresponding to a yield of 96.2% were 82 to 84 C. obtained through distillation. 15 Through determination of the residual formate con Methanol and water were distilled off from the me tent in the filtration residue (according to Blackadder) a thanol/water-p-methylbenzyl alcohol which had re formate consumption of 1.98 mols resulted, correspond mained in the reaction flask. The colorless product had ing to a p-xylylenedichloride conversion of 99.0%. a melting point of 58-59 C. and weighed 115.3 g, 20 The product, melting around 83 to 84 C., was corresponding to a yield of 94.5% based on the admixed heated with 150 ml methanol (3.7 mols) which con p-methylbenzylchloride. tained 0.54 g sodium methylate (0.01 mols), whereby EXAMPLE 7 the temperature of the cooling water was regulated at 32 C. According to Example 1, 175 go-xylylenedichloride 25 Methyl formate (boiling point 32° C) was distilled off (1 mol) were reacted with 149.6 g sodium formate (2.2 overhead of the cooler, and was led via an attached mols) and 3.5 g triethylamine (0.035 mol) at 150 C. distillation bridge through an intensive-cooler and col After 2.5 hours reaction time, the conversion of o lected in a receiver. xylylenedichloride amounted to 99.3%. The conversion After 0.5 hours, the distillation was completed. In product, freed of sodium chloride, was subjected to a 30 order to extract the remaining methyl formate, the tem vacuum distillation. At 0.2 mm, 187.2 g o-xylyleneg perature of the cooled reflux unit was raised for a short lycolbisformate were recovered at a temperature of time to 40 C. 99°-103° C., corresponding to a yield of 96.5%. 187.2g The distillate weighed 128.2 g and consisted of 96% o-xylyleneglycolbisformate were heated with 317 ml methyl formate which was obtained in pure form methanol and 2.2 g sodium methylate under reflux for 2 35 through a Vigreux column. : hours and at a temperature of 32° C., whereby methyl The excess methanol was evaporated from the con formate was distilled off. The condensate weighed 125 tents which had remained in the reaction flask, and the g. 112 g methyl formate were obtained through distilla residue was subjected to distillation under reduced pres tion corresponding to a yield of 97%. sure. 134.4 g p-xylyleneglycol distilled at 0.5 Torr and Methanol was distilled off from a mixture of metha 40 nol and o-xylyleneglycol which had remained in the 140 to 142 C. which corresponds to a yield of 97.4%, reaction flask. The remaining residue was dried over based on p-xylylenedichloride. calcium oxide (burnt lime). The colorless product had a EXAMPLES 10 and 11 melting point of 63-64 C. and weighed 130.4 g, corre sponding to a yield of 94.5%, based on the admixed Procedures were carried out as in Example 9 with the o-xylylenedichloride. 45 exception that instead of using triethylamine as catalyst for the conversion of p-xylylenedichloride and sodium EXAMPLE 8 formate, 3.5 g tri-n-prim.-butylamine (0.02 mol) and 2.8 According to Example l, 244 g of 2,5-dichloro-1, g (0.02 mol) hexamethylenetetramine were admixed. 4-bis-chloro-methylbenzene (1 mol) were reacted with 50 Xylylenedichloride conversion and xylyleneglycol 149.6 g sodium formate and 4.5 g trimethylbenzylam yields can be read in Table 1. moniumchloride (0.024 mol) at a temperature of 150° C. TABLE After 3 hours reaction time, the conversion amounted Xylylene- Re- Xylylene- Melting to 99.6%. Tert, dichloride action glycol Point The reaction products was trans-esterified with 200 55 Ex. Amine conversion time yield g/% °C. ml methanol in the presence of 1.5 g sodium methylate. 10 tri-n-prim. 94.3 25 128.1/ 115-116 After transcrystallization, 190.4 g of 2,5-dichloro-1,4- butylamine 92.8 bis-hydroxymethylbenzene were obtained at a flame hexa- 96.3 1.75 131.0/ 114.5-115.5 point of 201-202 C., corresponding to a yield of 92%, methylene 94.9 based on the admixed 2,5-dichloro-1,4-bis-chlorometh 60 ylbenzene. EXAMPLE 12 EXAMPLE 9 Analogous to the conversion carried out in Example 175.1 g p-xylylenedichloride (1 mol) and 146.2 g so 9, potassium formate was used instead of sodium for dium formate (2.15 mols) free of water and in powder 65 nate. form were placed into a 4 necked column, equipped In the presence of 1 g triethylamine, 88.6 g (98.8%) with reflux cooler, thermometer, dropping funnel and p-xylylenedichloride (0.5 mols) were reacted with 92.5 agitator, and the mixture was heated to 110° C. g potassium formate (1.1 mols) at 140 C. After 2 hours, 4,283,565 15 16 the p-xylylenedichloride conversion amounted to Each 194.3 g of this product was trans-esterified with 99.2%. 5 mols of the alcohols listed in Table 3 in the presence Through trans-esterification of the obtained p of 0.01 mol of the corresponding sodium alcoholate. xylyleneglycol-bis-formate (melting point: 83.5'-84.5 The esterification time amounted to 1.5 hours. The C.) with 90 ml methanol in the presence of 0.27 g Na 5 developed formic acid esters were purified by distilla methylate, 66.3 g xylyleneglycol resulted in a yield of tion. TABLE 3 Formic Cooling acid ester Xylylene Boiling Quantity water BP yield glycol Melting Example Alcohol point C. ml temp. C. C. % yield Point 14a methanol 65 202 32 32 98 96.1 15 I6 4b. ethanol 78.5 292 53 54 97 95.5 15.5- 116.5 14c n-prim.- 17.7 458 106 97 97. 95.8 115 butanol 116 14-d iso- 82.3 383 71 71 98 94.9 115 propanol 16 "in azeotrope with butanol

96% (based( on admixed p-xylylenedichloride).p-xyly ) The EXAMPLE 1.5 melting point ranged between 115 and 116 C. According to Example 9, 350.2 g p-xylylenedichlo EXAMPLES 13a through 13h 25 ride (2 mols) were reacted with 299.2 g sodium formate According to Example 9, 1.424 kg p-xylylenedichlo (4.4 mols) in the presence of 4.3 g triethylamine (0.04 ride (8 mols) and 1.156 kg sodium formate (17 mois) mol) at 146° C. After 2 hours reaction time, the p were reacted in the presence of 26.6 g (0.26 mols) trieth xylylenedichloride conversion amounted to 99.0%. ylamine at 150 C. After 2 hours reaction time, the The developed sodium chloride was separated by p-xylylenedichloride conversion amounted to 99.5%. 30 filtration from the reaction mixture which was cooled The reaction product, freed from sodium chloride down to 110° C., and the filtration residue was washed and excess sodium formate weighed 1.576 kg. twice each with 200 ml methylisobutylketone, after Each 197.9 g of this product was esterified with meth vaporization of the solvent from the washed solution, anol in the presence of catalysts listed in Table 2. The the evaporated residues were combined with the filtrate trans-esterification time was 1 hour. 35 and the entire mixture subjected to a distillation under reduced pressure. TABLE 2 At 1.4 mm and 123 to 124° C., 380.2 g p-xylyleneg Xylylene- Melting Methanol Moles of glycol Point lycol-bis formate distilled off, corresponding to a yield Ex. ml/Mols Catalyst catalyst yield (%) °C. of 98.0%. The melting point was 85 C. 40 13a 161.5/4 aluminum 0.02 95.5 115-116 380 g p-xylyleneglycol-bis formate (1.96 mols) were isopropylate heated for 2 hours under reflux with 323 ml methanol 13b. 182A4.5 sodium 0.015 96.3 114.5- and 100 ml water (8 mols) in the presence of 10 ml phenolate 115.5 formic acid at a cooling water temperature of 32 C., 13c 150/3.7 magnesium 0.020 94.8 15-116 methylate whereby methyl formate distilled off. The condensate 13d 150/3.7 potassium 0.05 96.1 115-16 45 weighed 261.1 g and contained 8% methanol. Through tert, butylate distillation over a Vigreux-column, 235.3 g pure methyl 13e 323.0/8.0 n-prim.- 0.002 93.0 114.5- formate were obtained, corresponding to a yield of tetrabutyl- 5.5 98.0%. titanate 13f 161.5/4 sodium 0.02 96.8 115-116 Water and residual formic acid were distilled off from benzylate 50 the aqueous methanolic p-xylyleneglycol solution 13g 150.0/3.7 disodium- 0.018 96.6 115-116 which had remained in the reaction flask, and the resi p-xylylene glycolate dues were dried in a vacuum at 80 C. The completely 13h 182.0/4.5 mono- 0.025 95.8 115-16 colorless product exhibited a melting point of 115-116 sodium C. and weighed 265.5 g, corresponding to a yield of p-xylylene 55 96.2%. glycolate EXAMPLE 16 According to Example 9, 645g m-xylylenedichloride EXAMPLES 14a to 14d (3.68 mols) were reacted with 550 g sodium formate (8.1 According to Example 9, 700.4 g p-xylylenedichlo 60 mois) in the presence of 12.9 g triethylamine at 148 C. ride (4 mols) were reacted with 598.4 g sodium formate After 2 hours reaction time, the conversion of m (8.8 mols) in the presence of 11.2 g hexamethylenetetra xylylenedichloride amounted to 98.5%. mine (0.08 mol) at 150° C. The conversion product, separated from the sodium After 2 hours reaction time, the p-xylylenedichloride chloride and excess sodium formate, weighed 709 g and conversion amounted to 98.3%. 65 had a melting point of 32 C. The quantity of the reaction product, freed from The m-xylyleneglycol-bis formate was heated for 1.5 sodium chloride and from excess sodium formate, hours under reflux at a cooling water temperature of 32 amounted to 777.0 g. C. together with 742 ml methanol (18.4 mols) in which 4,283,565 17 18 0.45 g sodium were dissolved, whereby methyl formate stirred. After admixing 1.7 g triethylamine, the reaction distilled off. The condensate weighed 481 g and con mixture was heated for 2 hours at 130 C. and was then sisted of 92% methyl formate. stirred into water. According to analysis, the resulting Methanol was evaporized from the methanolic m solid oil consisted of 73% p-xylylenedichloride incapa xylyleneglycol solution left over in the reaction flask, 5 ble of being reacted. and the residue was distilled under reduced pressure. What is claimed is: At 0.22 Torr and 124-126 C., 492.1 g m-xylyleneg 1. A process for preparing benzylalcohol or benzylal lycol was obtained, corresponding to a yield of 97.4%. cohol having a substituent on the benzene ring which Its melting point was 55 to 56' C. comprises: 10 A. Contacting a benzylchloride and/or bromide or a EXAMPLE 17 benzylchloride and/or bromide singularly or multi According to Example 1, 87.5 g m-xylylenedichlo ply substituted on the benzene ring which com ride (0.5 mols) were reacted with 71.6 g calcium for pound has the formula mate (0.55 mols) in the presence of 0.9 g triethylamine for 1.5 hours at 152 C. 15 After this amount of time had passed, the conversion Yn Ac of m-xylylenedichloride amounted to 98.6%, The reaction product, separated from the calcium CH2-X chloride and the excess calcium formate, weighed 97.2 W Zb g. 20 The m-xylyleneglycol-bis formate was heated for one wherein hour under reflux at a cooling water temperature of 54 Y=halogen and/or alkyl C. with 175 ml ethanol (3 mols) containing 0.5g calcium n = 0 to 5 ethylate, whereby ethyl formate mixed with ethanol W = -CH2-X distilled off. 83.2 g condensate were weighed out, con 25 a = 0 to 5 taining 11% ethanol. By means of fractional distillation, Z=hydroxy or alkoxy 72.2 g ethyl formate were obtained, corresponding to a b=0 to 3 yield of 97.5%. A = nitro and/or nitrile The solvent was distilled off from the solution of c=o to 2 and a-i-b--n--c = 1 to 5, and X represents m-xylyleneglycol remaining in the reaction flask, and 30 chlorine or bromine the residues were subjected to a distillation under re at a temperature of 100' to 250 C. with an alkali duced pressure. metal or alkaline earth metal formate such that said At 0.2 Torr, 66.5 g distilled off, corresponding to a benzylchloride and/or bromide reacted is in the yield of 96.4%. Its melting point was around 55° to 56 heterogeneous phase in the presence of a catalyst C. 35 selected from the group consisting of tertiary EXAMPLE 1.8 amines, tertiary phosphines, quaternary ammonium In a four-necked column, equipped with reflux salts and quaternary phosphonium salts and in the cooler, themometer, dropping funnel and agitator, 175.1 absence of a solvent to form benzylformate or a g p-xylylenedichloride (1 mol) and 142.8 g. sodium for 40 benzylformate which contains a substituent on the mate (2.1 mols) were reacted in the presence of 2.1 g benzene ring; and triethylamine at 146 C. and under heavy agitation. B. Thereafter converting the so formed benzylfor After 2 hours of reaction time, the reaction mixture was mate or substituted benzylformate by means of a cooled down to 90° C. and 350 ml water were added transesterification step to the corresponding alco under continued agitation at 90° C. 45 hol by contacting the same with an alcohol in the After separation of the aqueous solution containing presence of an esterification catalyst. sodium chloride, the hot oil at 90° C. washed free of 2. A process according to claim 1 wherein Y=halo chlorides twice with 50 ml water of 90° C. The remain gen and/or alkyl of 1 to 4 carbon atoms, n is 0 to 2, a =0 ing oil solidified at 84 C. to 2, Z=hydroxy or C1 to C4 alkoxy b–0 to 2. After drying the disintegrated material under vacuum 50 3. A process according to claim 1 wherein the benzyl at 80 C., the weigh-out same amounted to 188.2g. chloride and/or bromide reactant is a chloro, dichloro, 202 ml (5 mols) of methanol were heated under reflux bromo, methyl, dimethyl, methoxy, hydroxy or ni at a cooling water temperature of 32 C. in the presence trobenzylchloride and/or bromide or an ortho, meta or of 0.65 g sodium methylate, whereby methyl formate para xylylenedichloride and/or xylylenedibromide. distilled off. The condensate weighed 134.5 g and con 55 4. A process according to claim 1 wherein the stoi tained 12% methanol. chiometric molar ratio of halogen methyl groups of the Excess methanol was evaporated from the methano benzyl chloride and/or bromide reactant to formate is lic p-xylyleneglycol solution remaining in the reaction in the range of 1:1 to 1.5. flask, and the residues were distilled under reduced 5. A process according to claim 4 wherein said stoi pressure. 60 chiometric ratio is 1:d 1 than to 1.1. At 0.5 Torr and 140°-142° C., 184.7 g xylyleneglycol 6. A process according to claim 1 wherein said for distilled off, corresponding to a yield of 95.2%. The mate is sodium formate. melting point was between 115.5 and 116.5 C. 7. A process according to claim 1 wherein the benzyl chloride and/or bromide is reacted with the formate at COMPARATIVE EXAMPLE 65 a temperature in the range of 110' to 200 C. 87.5 g p-xylylenedichloride (0.5 mols) were mixed 8. A process according to claim 1 wherein the cata with 158.4 g sodium benzoate (1.1 mols). After heating lyst employed for reaction of the benzyl chloride and to 110° C., a mixture developed incapable of being /or bromide with the formate is a tertiary amine. 4,283,565 19 20 9. A process according to claim 8 wherein said ter 27. A process according to claim 21 wherein the acid tiary amine is triethylamine, tripropylamine, a tributyl catalyst is nitric acid, sulphuric acid, phosphoric acid, amine, dimethylaniline, N-methyl-morpholine, hexa hydrochloric acid, formic acid or acetic acid. methylenetetramine or triethylenediamine. 28. A process according to claim 27 wherein said acid 10. A process according to claim 9 wherein said ter is in the form of an aqueous solution. tiary amine is triethylamine. 29. A process according to claim 1 wherein the esteri 11. A process according to claim 1 wherein the cata fication of step B takes place in the presence of an al lyst for the reaction of the benzyl chloride and/or bro coholate. mide with the formate is a tertiary phosphine. 30. A process according to claim 29 wherein the 12. A process according to claim 11 wherein said 10 alcohol component of the alcoholate is derived from a tertiary phosphine is triethylphosphine, tributylphos primary, secondary or tertiary alcohol. phine, triphenylphosphine or tribenzylphosphine. 31. A process according to claim 30 wherein the 13. A process according to claim 12 wherein said alcohol component of the alcoholate, is methanol, etha tertiary phosphine is triphenylphosphine. nol, propanol, isopropanol or one of the isomeric butyl 14. A process according to claim 1 wherein the cata 15 alcohols. lyst employed for the reaction of the benzyl or chloride 32. A process according to claim 1 wherein the trans and/or bromide with the formate is a quaternary ammo esterification of step B takes place in the presence of a nium salt. phenolate. 15. A process according to claim 14 wherein said 33. A process according to claim 32 wherein said quaternary ammonium salt is methyltricaprylylam 20 phenolate is derived from phenol, an ortho, meta or monium chloride, a tetrabutylammonium chloride, para cresol, salicylic aldehyde or an ortho, meta or para trimethylbenzylammonium chloride or triethylben hydroxybenzoic acid ester. zylammonium chloride. 34. A process according to claim 1 wherein the trans 16. A process according to claim 1 wherein the cata esterification of step B is carried out in the presence of lyst employed for reaction of the benzyl chloride and 25 an alcoholate or phenolate of an alkali metal, alkaline /or bromide with the formate is a quaternary phospho earth metal or aluminium. nium salt. 35. A process according to claim 34 wherein said 17. A process according to claim 16 wherein the alcoholate or phenolate is an alcoholate or phenolate of quaternary phosphonium salt is triphenylmethylphos sodium, potassium, calcium or magnesium. 30 36. A process according to claim 1 wherein the cata phonium bromide or triphenylethylphosphonium bro lyst employed in the trans-esterification step B is em mide. ployed in an amount of 0.01 to 10 weight percent based 18. A process according to claim 1 wherein the cata upon the amount of benzyl formate in the reaction mix lyst employed in the reaction of the benzyl chloride ture. and/or bromide with the formate is employed in an 35 37. A process according to claim 1 wherein the esteri amount of 0.1 to 10 parts by weight per 100 parts of fication catalyst is present in an amount of 0.05 to 5 benzylchloride and/or bromide reactant. weight percent. 19. A process according to claim 18 wherein said 38. A process according to claim 1 wherein the trans catalyst is employed in an amount of 0.5 to 5 parts by esterification takes place in the presence of a metallic weight per 100 parts of benzylchloride and/or bromide 40 acid ester. reactant. 39. A process according to claim 38 wherein said 20. A process according to claim 11 wherein in step metallic acid ester is a titanic acid ester. B, the stoichiometric proportion of formoxymethyl 40. A process according to claim 39 wherein said groups to alcohol employed for the esterification is in titanic acid ester is a tetrabutyltitanate. the range of 1:1.2 to 25. 45 41. A process according to claim 40 wherein said 21. A process according to claim 20 wherein the tetrabutyltitanate is tetra-n-prim.-butyltitanate. stoichiometric proportion of formoxymethyl groups of 42. A process according to claim 38 wherein said the formate so formed in step A to alcohol employed in metallic acid ester is employed in an amount of 0.01 to step B is in the range of 1:1.25 to 12. 5 weight percent, based upon the amount of benzylfor 22. A process according to claim 1 wherein the alco 50 mate in the reaction mixture. hol employed for trans-esterification in step B is a pri 43. A process according to claim 42 wherein said mary of secondary univalent alcohol. metallic acid ester is present in an amount of 0.02 to 3 23. A process according to claim 22 wherein said weight percent, based upon the amount of benzylfor alcohol is methanol, ethanol, n-propanol, n-butanol, mate in the reaction mixture. isobutanol, isopropanol or secondary butanol. 55 44. A process according to claim 26 wherein the 24. A process according to claim 1 wherein the trans trans-esterification is carried out in an aqueous alcoholic esterification of the benzyl formate or xylyleneglcolbis medium. formate formed according to step A with the alcohol in 45. A process according to claim 44 wherein the step B is carried out at the boiling temperature of the amount of water in the aqueous alcoholic medium is 2 to reaction mixture. 60 80 volume percent. 25. A process according to claim 1 wherein the for 46. A process according to claim 45 wherein the mic acid ester which forms as a result of contacting the amount of water in the aqueous alcoholic medium is 5 to formate formed in step A with alcohol according to step 50 volume percent. B is continuously distilled off from the trans-esterifica 47. A process for preparing benzylalcohol or a ben tion reaction mixture. 65 Zylalcohol having a substituent on the benzyl ring 26. A process according to claim 1 wherein the esteri which comprises: fication of step B is carried out in the presence of an acid A. Contacting a benzylchloride and/or bromide or a catalyst. benzylchloride and/or bromide singularly or multi 4,283,565 21 22 ply substituted on the benzene ring which com A. Contacting a benzylchloride and/or bromide or a pound has the formula benzylchloride and/or bromide singularly or multi ply substituted on the benzene ring which com Yn A. pound has the formula 5 CH2-X Yn Ac W Zb CH2-X

wherein 10 W Zb Y= halogen and/or alkyl n = 0 wherein W = -CH2-X Y=halogen and/or alkyl a = 0 to 5 n = 0 to 2 Z= hydroxy, alkoxy or phenoxy 15 W = -CH2-X b = 0 to 3 a=0 to 5 A = nitro and/or nitrile Z=hydroxy or alkoxy c=0 a+b+n+ c = 1 to 5, and X represents chlo- b=0 to 3 rine or bromine A = nitro and/or nitrile at a temperature of 100' to 250 C. with an alkali 20 c=0 to 2 and a-b--n + c = 1 to 5, and X represents metal or alkaline earth metal formate such that said chlorine or bromine benzylchloride and/or bromide reacted is in the at a temperature of 100 to 250 C. with an alkali heterogeneous phase in the presence of a catalyst metal or alkaline earth metal formate such that said selected from the group consisting of tertiary benzylchloride and/or bromide reacted is the het amines, tertiary phosphines, quaternary ammonium 25 erogeneous phase in the presence of a catalyst se salts and quaternary phosphonium salts and in the lected from the group consisting of tertiary amines, absence of a solvent to form benzylformate or a tertiary phosphines, quaternary ammonium salts benzylformate which contains a substituent on the and quaternary phosphonium salts and in the ab benzene ring; and sence of a solvent to form benzylformate or a ben B. Thereafter converting the so formed benzylfor- 30 zylformate which contains a substituent on the mate or substituted benzylformate by means of a benzene ring; and transesterification step to the corresponding alco B. Thereafter converting the so formed benzylfor hol by contacting the same with an alcohol in the mate or substituted benzylformate by means of a presence of an esterification catalyst. transesterification step to the corresponding alco 48. A process for preparing benzylalcohol or a ben- 35 hol by contacting the same with an alcohol in the Zylalcohol having a substituent on the benzene ring presence of an esterification catalyst. which comprises: k k k : :