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United States Patent [191 [11] 3,943,181 Fleischer Et Al

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United States Patent [191 [11] 3,943,181 Fleischer Et Al United States Patent [191 [11] 3,943,181 Fleischer et al. , [45] Mar. 9, 1976 [54] SEPARATING OPTICALLY PURE d- AND 397,212 8/1933 United Kingdom ........... .. 260/631 R l-ISOMERS 0F MENTHOL, NEOMENTHOL AND ISOMENTHOL " OTHER PUBLICATIONS [75] Inventors: Jiirgen Fleischer, Cologne; Kurt Gilman Ed., Organic Chemistry, Wiley, N.Y., 1943, p. Bauer; Ruldolf Hopp, both of 254. Holzminden, all of Germany Reed et al_, J. Chem. Soc., pp. 167-173 (1933). [73] Assignee: Haarmann & Reimer Gesellschaft mit beschrankter Haftung Primary Examiner-Be1‘nard l-lel?n Assistant Examiner-James H. Reamer [22] Filed: Sept. 3, 1974 Attorney, Agent, or Firm—Burgess, Dinklage & [21] Appl. No.: 503,004 Sprung Related US. Application Data [63] Continuation of Ser. No. 229,109, Feb. 24, 1972, [57] ABSTRACT ' abandoned. A process for the separation of optically active d— and [30] Foreign Application Priority Data l-isomers of a compound selected from the group con sisting of menthol, neomenthol and isomenthol, which Feb. 27, 1971 Germany .......................... .. 2109456 comprises esterifying a d,l-isomeric mixture of the Feb. 2, 1972 Germany .......................... .. 2204771 compound with an acid selected from the group con sisting of benzoic acid optionally carrying at least one [52] US. Cl...... 260/631 R; 260/473 R; 260/471 R; substituent on the benzene ring and hexahydrobenzoic 260/468 R; 260/476 R acid; forming a supersaturated solution or a super [51] Int. Cl.2 ........................................ .. C07C 35/12 cooled melt of the dJ-ester; inoculating the solution or [58] Field of Search ................... .. 260/631 R, 631 H melt with crystals of the d- or l-form of the ester to effect selective crystallization of one of the two [56] References Cited optical isomers; separating the crystals and subjecting UNITED STATES PATENTS them to hydrolysis to yield the corresponding enantio 2,120,131 6/1938 Harris ........................... .. 260/631 H morph of the starting compound. FOREIGN PATENTS OR APPLICATIONS 5 Claims, 1 Drawing Figure 568,085 1/1933 Germany ...................... .. 260/631 H US. Patent March 9, 1976 3,943,181 3,943,181 1 2 such cases the carbocyclic nucleus may contain as SEPARATING OPTICALLY PURE d- AND substituents: alkoxy groups, preferably lower alkoxy l-ISOMERS OF MENTHOL, NEOMENTHOL AND groups containing up to 4 carbon atoms; nitro groups; ISOMENTHOL halogen atoms such as ?uorine, chlorine, bromine; or This is a continuation of application Ser. No. alkyl groups, preferably lower alkyl groups containing 229,109, ?led Feb. 24, 1972, now abandoned. up to 4 carbon atoms which may be substituted by This application relates to separating optically pure halogen atoms, such as trichloromethyl or tri?uoro d- and l-isomers of menthol, neomenthol and isomen methyl groups. p thol. ‘ The d,l-esters of benzoic acid, hexahydrobenzoic Processes for the synthetic production of menthol, acid, 4-methylbenzoic acid, 3,5-dinitrobenzoic acid neomenthol and isomenthol are known. Unfortunately, 4-methoxy-and 4-ethoxybenzoic acid are preferably the products obtained are mixtures of the d- and l-form used for the process according to the invention. and are inferior in their properties to the optically pure It has proven to be of particular advantage for carry isomers. For example, a mixture of d- and l-menthol is ing out the separation by the process according to the distinctly inferior to the l-menthol which occurs natu invention to use the d,l-ester of benzoic acid,_hexahy rally in peppermint oil because of the dcontent. Ac drobenzoic acid, 4-methylbenzoic acid, 3,5-dinitroben cordingly, there is considerable interest in processes for zoic acid or of 4-ethoxybenzoic acid for menthol, and separating the d- and l-isomers of menthol, neomenthol the d,l-ester of 4-methylbenzoic acid, 3,5-dinitroben and isomenthol. zoic acid or of 4-methoxybenzoic acid for neomenthol. The separation of these optical isomers can be car 20 The separation of isomenthol by the process according ried out for example by fractional crystallization of the to the invention is best carried out through its esters salts of optically active amines such as cinchonine, with 4-methoxybenzoic acid or 3,5-dinitrobenzoic acid. brucine, strychnine, ephedrine and l~( a-naphthyl) The d,l-isomer mixturev can be esteri?ed by any ethyl amine, with d,l-menthyl hydrogen phthalate or known method, for example in accordance with the hydrogen succinate or the corresponding d,l-neoment 25 description in Beilstein’s Handbuch der Organischen hyl derivatives. The separation process as a whole in Chemie, 4th Edition, Vol. 9 (1926) on page 1 15 for the cludes formation of a salt with the optically active preparation of benzoic acid-l-menthyl ester or ibid., amine; separation of the two diastereomeric semi ester Vol. 9 (Suppl. 3) (1970) on page 408 for the prepara salts by crystallization; splitting the d- and l-semi ester tion of benzoic acid-d-neomenthyl ester. salt into the optically active esters and ?nally hydrolyz 30 The process according to the invention can be car ing these into the d- and l-forms. In addition to the fact ried out by initially preparing a saturated solution of that the described process is a multi-stage process the d,l-ester at temperatures below the melting point of which uses optically active bases, which are themselves the racemate, preferably at temperatures of from 0° to extremely difficult to prepare, the physiologically 20°C. Examples of suitable solvents include hydrocar harmful bases used during splitting must be very care 35 bons, such as light petrol, cleaning spirit, hexane, cy fully removed in view of the use of l-menthol for exam clohexane, or toluene; ethe‘rs such as diethyl ether, ple in foodstuffs, confectionary and body-care prepara diisopropyl ether, dioxane or tetrahydrofuran; ketones, tions. such as acetone, methylethyl ketone, diethyl ketone, Because of the dif?culties mentioned above, natu methylpropyl ketone, methylbutyl ketone, di-n-propyl rally occurring starting materials must always be used 40 ketone or methylisopropyl ketone; or alcohols, such as in the largescale production of optically pure isomers methanol, ethanol, n-propanol, isopropanol, butanol, of menthol, neomenthol and isomenthol, for example linear or branched-chain amyl alcohols or hexanols, in'the recovery of l-menthol or neomenthol, pepper benzyl alcohol or cyclohexanol and mixtures of the mint oil which contains the l-menthol or d-neomenthol aforementioned solvents. Preferred solvents are petrol, itself, or optically active citronella recovered from oil 45 methanol, ethanol or acetone. The saturated solution of citronella may be used. Unfortunately, these natural separated from the sediment is heated by about 2° C., starting materials ?uctuate both in quality and in com as a result of which any crystal seeds still present disap position, depending upon their origin. Accordingly, it pear, and is divided into two, equal parts. The solutions would constitute a major technical stepforward if a are then adjusted to a slightlysupersaturated state in synthetically obtained isomer mixture could be used as 50 which there is still no spontaneous seed formation, by starting material in the large-scale production of the cooling to about 1° to 3° C. below the saturation tem aforementioned compounds. perature. If one batch is then inoculated with crystals of It has now been found that the optically active d- and the l-form and the other with crystals of the d-form only l-isomers of menthol, neomenthol and of isomenthol that menthyl ester corresponding to the form of the can be recovered by esterifying the d,l-isomer mixture 55 optically active seed crystals crystallizes out of the of the corresponding compound with benzoic acid supersaturated solution. The crystallizates of both which optionally contains one or more substituents on batches can be separated from the mother liquor in the the benzene ring, or with hexahydrobenzoic acid; inoc usual ways, for example by ?ltration or by centrifuging. ulating a supersaturated solution or a supercooled melt After they have been combined and reheated, the of the resulting d,l-ester with crystals of the d- or l-form 60 mother liquors are used to dissolve more racemate and of the ester and, in this way, selectively crystallizing the thus resaturated solution may again be used for the one of the two optical enantiomorphs, and hydrolyzing process according to the invention. the resulting ester of the d- or l-form by methods known Separation can of course, also be carried out by inoc per se. ulating a melt supercooled by about 1 to 3° C. with Apart from the esters of benzoic acid or of hexahy 6.5. crystals of l- or d-menthyl ester. In general, however, drobenzoic acid themselves, the esters of monosubsti separation is carried out using a solvent. tuted or polysubstituted benzoic acids are also prefera The separation of d,l-methyl esters can be carried out bly used for the process according to the invention. In either continuously or in batches. For example, contin 3,943,181 3 4 uous separation can be carried out as shown in the accompanying drawing, which is a schematic ?ow sheet EXAMPLE 1 of a suitable apparatus. 220 liters of petrol are cooled to +3°C in a vessel A saturated solution of the d,l-menthyl ester is pre equipped with stirring mechanism and cooling coils. pared in a 500 liter vessel 1 equipped with a stirring Solid d,l-methyl benzoate is added with stirring in a mechanism and cooling coils 2. This solution is ?ltered suf?cient quantity (about 350kg) to leave behind a off under suction of two metering pumps 4 and 5 small undissolved residue. The solution thus saturated at +3°C is ?ltered off from the undissolved menthyl through a wire basket 3 which retains most of the benzoate and heated to approximately +5“ C.
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