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

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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)
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