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United States Patent Office - 2,837,570 United States Patent Office Patented June 3, 1958 2 thesis of l-carvone from d-limonene glycol are repre sented as follows, along with the structural formulae of 2,837,570 l-carvone, d-limonene and d-limonene monoxide. For purposes of illustration, the intermediate substitution METHOD OF PREPARNG CARVONE 5 product formed in the dehydration and hydrolysis of the Seymour M. Linder, Eggertsville, and Frank P. Green 1-hydroxyhydrocarvone is represented as the semicar span, Buffalo, N.Y., assignors to Food Machinery and . bazone derivative of that compound. Chemical Corporation, San Jose, Calif. (His GH, CE No Drawing. Application March 21, 1956 -o COH Serial No. 572,789 10 6 Claims. (C. 260-587) Hic bH, C bH, NHMC NH/ 5 This invention relates to a method for preparing 1-car S n vone, and particularly to a method for preparing 1-car C /'sCH HC /o CH vone from d-limonene and certain d-limonene deriva : - d-limonene monoxide d-limonene glycol - tives. (H, CH 1-Carvone, the levoratory form of carvone, by reason COE O of its minty odor and flavor has found wide acceptance 20 / in the prepartion of cosmetics and comestibles. Typi HaC Yo-NNENH cally, it is used as a flavoring and perfuming ingredient for toothpaste, mouth wash, chewing gum and mint can dies. 1-Carvone is expensive, presently being obtained 25 from principally from spearmint oil in which it occurs / Sn naturally. HC CH The high cost combined with the usefulness of 1-car -carvone vone offers a strong incentive to chemists to devise syn thetic methods for preparing the material. 1-Carvone The d-limonene glycol employed herein preferably is has been prepared from dextrorotatory limonene, i.e., 30 derived from d-limonene, which is obtained from orange d-limonene, which is readily obtainable as orange oil, oil. d-Limonene is treated with an epoxidizing agent to by converting the d-limonene into the nitrosochloride form d-limonene monoxide, and this compound is hy derivative of that compound and subsequently dehydro drolyzed to formid-limonene glycol. Typical epoxidiz chlorinating this derivative and hydrolyzing the product ing agents useful in the preparation of d-limonene oxide of dehydrochlorination to 1-carvone. This process, while 35 include the organic saturated aliphatic peracids, the aro useful, requires the use of nitrosyl chloride and liquid matic peracids, and the inorganic peracids. These per sulfur dioxide and for this reason is difficult to carry acids may be formed by well known techniques. out, and further requires the use of expensive apparatus The epoxidation preferably is carried out by reacting . capable of operating at sub-zero temperatures. This in together in a suitable solvent medium, approximately volved synthesis has been used, however, for the reason 40 equal molar quantities of an organic peracid and the that while many attempts have been made to devise d-limonene. When peracetic acid is employed, the re simpler and less hazardous methods for preparing l-car action is conducted with stirring, generally at a tempera vone from readily obtainable d-limonene, these attempts ture below 30, C. over a period of approximately one generally have been unsuccessful. Such failures are not half to one hour. Specific, reaction conditions and sol surprising when they are considered in the light of the vent media will vary with the particular peracid used. well known unpredictability of the reactions of terpene For example, in some instances it will be found neces chemicals, in which class d-limonene falls. sary to cool the reaction batch while in others it may be It is a feature of this invention to provide a method necessary to provide heat from an external source. The for preparing 1-carvone synthetically and from readily 50 d-limonene monoxide which results from the epoxida available raw materials. tion is separated from the reaction batch suitably by It is a further feature to provide a method for pre fractional distillation as the ingredient removed in the paring 1-carvone synthetically and with a minimum of boiling range 74-75.5 at 9.5 mm. of mercury. complicated apparatus. Hydrolysis of the d-limonene monoxide to d-limonene In accordance with the method of this invention, 55 glycol advantageously is effected with a dilute acid solu d-limonene glycol is oxidized with a selective oxidizing tion, for example 1% aqueous sulfuric acid solution, at agent, suitably chromic acid, chromium trioxide, or a a temperature of from 0° C. to room temperature over lower tertiary alkyl chromate, preferably tertiary butyl a period of approximately 24 hours. Use of higher tem or tertiary amyl chromate, to effect conversion of the peratures results in a reduction in the yield due to by limonene glycol to the ketol derivative of d-limonene 60 product formation, while at lower temperatures the mix glycol, 1-hydroxyhydrocarvone. This ketol then is de ture freezes and substantially no reaction occurs. As hydrated to form 1-carvone. The dehydration advan the reaction time is decreased, the yield decreases. - tageously is effected by reacting the ketol with a car The d-limonene glycol is separated from impurities, bonyl reagent which replaces the oxygen of the ketol for example by drying followed by fractional distilla carbonyl group with a radical the nature of which de 65 tion, being removed as the fraction boiling at 140-143 pends on the reagent used, and subsequently dehydrat C./10 mm. Hg. m ing and hydrolyzing the substitution product resulting Examples of alternate methods for preparing the limo from this reaction. In the dehydration and hydrolysis of nene glycol include the hydroxylation of d-limonene in the substitution product the carbonyl reagent radical is acid medium with a suitable peracid, the reaction of . replaced with oxygen with the result that the carbonyl 70 d-limonene with hydrogen peroxide in the presence of group is reformed, and further the ring unsaturation of tungsten oxide, and the auto-oxidation of d-limonene. 1-carvone is produced. The structural formulae of the Oxidation of d-limonene glycol to the ketol, 1-hydroxy starting and intermediate compounds in the present syn hydrocarvone involves selective oxidation of the sec 2,837,570 4 3 and hydrolyzed to form 1-carvone. The technique of re ondary hydroxyl group of the d-limonene glycol to a placing the carbonyl oxygen is carried out for the reason carbonyl group, that is, oxidation of the secondary hy that direct dehydration of the ketol has proved to be in droxyl group without attack on the tertiary hydroxyl effective. This is due perhaps to the presence in the group or on the exocyclic double bond. This selective ketol of hydrogen bonding between the ketol hydroxyl oxidation is accomplished by reacting the d-limoriene and carbonyl groups, and the hindering effect of such glycol with a hexavalent chromium compound from the hydrogen bonding on the dehydration. The carbonyl re group of chromic acid, its anhydride chromium trioxide, agent substitution product is believed to function herein or a lower tertiary alkyl chromate, preferably tertiary by eliminating this hydrogen bonding. butyl chromate or tertiary amyl chromate. Reaction of Carbonyl reagents are a recognized class of materials the d-limonene glycol with one of these oxidizing agents O which are used in organic analysis as agents for isolating results in the formation of oxidation products complexed and identifying aldehydes and ketones. They may be with the chromium. These products are worked up to described generally as derivatives of ammonia containing liberate the desired d-limonene glycol from these com free primary amino nitrogen. Specifically, free amine plex products in a form suitable for subsequent reaction, containing compounds in the class of hydroxylamine, sub by treatment with suitable alkaline or acid reagents. Ex 5 stituted hydroxylamines, hydrazine and the various sub amples of such reagents useful herein are sodium car stituted hydrazines such as the phenylhydrazines, semi bonate, or a mixture of a dilute acid such as sulfuric carbazide and its derivatives such as semi-carbazide hy acid with a reducing agent of the type of oxalic acid, drochloride, and the thio derivatives of these compounds, tartaric acid, or hydrazine sulfate. 20 are among known carbonyl reagents and are suitable for The tertiary butyl and amyl chromates are formable use herein. These reagents are believed to function by a by reaction of the appropriate alcohol with chromic acid condensation between the carbonyl oxygen and the amine or chromium trioxide, normally in an inert organic solvent hydrogen to form water and an unsaturated nitrogen medium, e. g., benzene or toluene. For purposes of containing derivative of the aldehyde or ketone. efficient operation in the oxidation process, the solution 25 Reaction conditions for the reaction between the ketol of the chromate ester as it is formed frequently is added and the carbonyl reagent are dependent on the particular directly to a solution of the d-limonene glycol in an inert reagent employed. Generally, the carbonyl reagent and organic solvent such as is referred to above. Preferably, the ketol are mixed in the presence of a suitable solvent, 1.3 to 2.0 moles of chromate ester per mole of d-limonene e.g., ethanol, and a small amount of acid such as hy glycol is employed for the oxidation, this amount of 30 drochloric acid is added to the solution. In some in chromate ester being approximately a 100 to 300% ex stances heat or cooling is required to effect a smooth cess over the stoichiometric amount required to oxidize reaction. the d-limonene glycol. This is for the reason that a por The derivative of the ketol contained in this reaction tion of the chromate ester is converted to complexes, mixture is dehydrated and hydrolyzed, whereby the l and in this form does not serve to oxidize the glycol.
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