Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B9/00—Essential oils; Perfumes
  • C11B9/0069—Heterocyclic compounds
  • C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
  • C11B9/008—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing six atoms

Definitions

• the process of this invention comprises treating alkynylcyclopentanone with certain unsubstituted aliphatic percarboxylic acids at temperatures in the range of from about to about 50 C. to form the alkynyl 6-lactone.
• the alkynylcyclopentanones treated according to the present invention include 2-(pentyn-2-yl) cyclopentanone. It is preferred that the starting material be relatively pure to avoid the formation of unwanted byproducts and to facilitate purification of the desired lactone.
• Such alkynylcyclopentanones can readily be prepared by treating cyclopentanone with a secondary amine such as pyrrolidine or piperidine under acidic conditions to form the corresponding enamine such as 1-pyrrolidylcyclopentene-1 and subsequently alkylating the enamine so obtained with l-bromopentyne-2.
• percarboxylic acid is most important in obtaining any significant yield of the desired product from the reaction, and accordingly aliphatic percarboxylic acids are used.
• the lower aliphatic percarboxylic acids having up to about four carbon atoms are most desirable, and performic, peracetic, and perpropionic acids are preferred. The best results are generally obtained with peracetic acid.
• the term aliphatic as used herein to describe the percarboxylic acids utilized in the practice of this process will be taken to exclude substituted percarboxylic acids such as monoor polyfluoro-, hydroxy-, methoxy-, and amino-substituted acids and the like.
• the yield of alkynyl lactone can be improved or the rate of reaction can be increased by incorporating catalytic amounts of certain strong protonic acids into the reaction system.
• These protonic acids may be added directly into the system or may first be mixed with the peracid material. When such protonic acids are used, only small amounts are required, that is, up to about 0.5% of the percarboxylic acid.
• the yield of the reaction is also affected by the amount of aliphatic percarboxylic acid present in the reaction mixture. If too small a quantity of the percarboxylic acid is present the yields are lower and the alkynylcyclopentanone starting material must be recovered. On the other hand, the use of too much percarboxylic acid causes side reactions which lower the yield. It is accordingly desirable to utilize an approximately equimolar quantity of the percarboxylic acid, and slight excesses of the per carboxylic acid up to about 40 molar percent are preferred.
• reaction can be carried out in the presence of an inert atmosphere such as nitrogen although this is not generally necessary or advantageous.
• an inert vehicle for example an aromatic material such as toluene and the like, can also be incorporated in the reaction mixture.
• the time of the reaction varies according to the temperature at which the reaction is carried out, the purity of the ingredients, the completeness of reaction desired, the presence of inert vehicle, if any, and the agitation utilized. It is desirable to conduct the reaction for times ranging from about two to about ten hours, shorter times producing lower yields and longer times giving no further advantage in the production of the desired lactone.
• the reaction is conveniently carried out by adding the percarboxylic acid slowly over a period of time and then holding the reaction mixture under agitation until the desired completeness of reaction is obtained.
• the progress of the reaction can be readily followed by analyzing small quantities of the reaction mixture, for example, by gas-liquid chromatography (GLC).
• the alkynylacetone is extracted with water-benzene mixture to remove water-soluble impurities, and the organic layer so obtained is washed with an alkaline material, preferably the salt of a strong base and a weak acid, for excess acid removal.
• the material can then be washed with salt solution for further purification. It can thereafter be dried, filtered, and stripped of the benzene or other solvent.
• the alkynyllactone product can further be treated, as by hydrogenation, or it can be purified by conventional techniques such as selective extraction, fractional distillation, and the like.
• the alkynyllacetone produced can be selectively hydrogenated in high yield to produce the corresponding alkenyllactone.
• the hydrogenation reaction is carried out in the presence of Lindlar catalysts such as palladium on calcium carbonate and the like, which are selective in maximizing the yield of alkenyl material and minimizing the yield of other hydrogenation products such as alkane-lactone and transalkenyllactones.
• Suitable pressures are in the range of from about 2 to about 50 p.s.i.g.
• the temperatures suitable in carrying out the reaction are in the range of from about 25 C. to about 60 C.
• the cis-alkenyllactone obtained by hydrogenation is filtered to remove the hydrogenation catalyst and can be washed or further treated as desired to provide a substantially pure material.
• the decenoic acid fi-lactone produced according to the present invention has a pronounced jasmin fragrance and is suitable for use as a fragrance material itself, as a component of fragrance compositions, or as a component of perfume compositions.
• the materials of this invention are useful as olfactory agents and fragrances.
• perfume composition is used herein to mean a mixture of compounds, including, for example, natural oils, synthetic oils, alcohols, aldehydes, ketones, esters, other lactones, and frequently hydrocarbons which are admixed so that the combined odors of the individual components produce a pleasant and desired fragrance.
• perfume compositions usually contain: (a) the main note (the bouquet or foundation-stone) of the composition; (b) modifiers which round off and accompany the main note; (c) fixatives including odorous substances which lend a particular note to the perfume throughout all stages of evaporation and substances which retard evaporation; and (d) top-notes which are usually lowboiling fresh-smelling materials.
• Such perfume compositions or the materials of this invention can be used in conjunction with carriers, vehicles, solvents, dispersants, emulsifiers, surface-active agents, aerosol propellants, and the like.
• perfume compositions the individual components contribute their particular olfactory characteristics, but the overall effect of the perfume composition can be more than the sum of the effect of each ingredient.
• the individual compounds of this invention, or mixtures thereof may be used to alter the aroma characteristics of a perfume composition, for example, by high-lighting or moderating the olfactory contribution of another ingredient in the composition.
• perfume compositions The amount of the compounds obtained according to this invention which will be effective in perfume compositions depends on many factors, including the other ingredients, their amounts, and the effects which are desired. It has been found that perfume compositions containing as little as 0.5% by weight of the compounds produced according to the process of this invention, or even less, can be used to impart a jasmin odor to soaps, cosmetics and similar products. The amount employed will depend on considerations of cost, nature of the end product, the effect desired on the finished product and the particular fragrance sought.
• the materials disclosed herein can be used alone, in a fragrance-modifying composition, or in a perfume composition as olfactory components in detergents and soaps; space deodorants; perfumes; colognes; bath preparations such as bath oil and bath salts; hair preparations such as lacquers, brilliantines, pomades, and shampoos; cosmetic preparations such as cremes, deodorants, hand lotions, and sun screens; powders such as talcs, dusting powders, and face powders; and the like.
• EXAMPLE I Preparation of alkynyllactone A 50 ml. Erlenmeyer flask is fitted with a stirrer, a thermometer, and cooling means, and 15 g. (0.1 mol) of pentynylcyclopentanone as prepared above is introduced into the flask. The flask is cooled to maintain a temperature of 2025 C. while 21 g. (0.11 mol) of 40% peracetic acid containing about 1% sulfuric acid is added over a 45-minute period. The mass is then maintained under agitation for three hours, at which point the GLC monitoring indicates formation of the desired product with a small amount of the original starting material still present. Accordingly, 7 g. (0.037 mol) of 40% peracetic acid is added, and the mixture is stirred for an additional one hour.
• the reaction mixture is transferred to a separatory funnel, and an equal volume of water and 50 ml. of benzene are added.
• the upper organic layer is separated from the aqueous layer and washed three times with 50 ml. of 5% aqueous sodium bicarbonate.
• the organic layer is further washed twice with 50 ml. of aqueous saturated sodium chloride, dried over anhydrous magnesium sulfate and filtered.
• the benzene is then removed on a rotary evaporator.
• reaction mixtures are stirred for approximately five hours, while the course of the reaction is monitored by GLC analysis of the reaction mixture.
• This material is substantially the pure a-lactone of 5-hydroxy-7-decynoic acid.
• the lactone prepared above in the amount of 27.5 g. is then placed in a Parr reaction vessel with 20 g. of isopropanol and 0.3 g. of a palladium on calcium carbonate catalyst.
• the mixture is hydrogenated with 0.15 mol of hydrogen at 27-55 C. with a pressure falling from 49 to 36 p.s.i.g. over the reaction period.
• Example III The procedure of Example II is repeated with 40% peracetic acid containing no sulfuric acid. Substantially the same yields are obtained, and the reaction velocity appears to be somewhat lower.
• reaction mixture is then treated with 250 ml. of ether and 250 ml. of 50% saturated sodium chloride solution, washed, and settled to separate the organic layer.
• the organic layer is washed five more times with 250 ml. of 50% saturated sodium chloride solution and then twice with 250 ml. of saturated sodium chloride solution.
• the washed material is dried over magnesium sulfate and filtered, and the solvent is stripped off with a rotary evaporator.
• the mixture is then distilled at 159-186 C. at 0.8-
• the percarboxylic acid can be formed in situ from an aliphatic earboxylic acid and a, peroxygen compound such as hydrogen peroxide and the like.
• This technique can be used to obtain any of the percarboxylic acids according to the present invention and it is especially useful when the aliphatic percarboxylic acid is not readily available or when the percarboxylic acid is rela- EXAMPLE V Lactone preparation with carboxylic acid and peroxide mixture
• a 200 ml. reaction flask is equipped with a stirrer, dropping funnel, and thermometer, and 15 g. (0.1 mol) of pentynylcyclopentanone and 50 g. of formic acid are introduced into the flask.
• the flask and its contents are then cooled to 20 C. and 7.8 g. of 50% hydrogen peroxide is added to the cooled contents during a forty-five minute period.
• the temperature of the reaction mixture is then allowed to rise to 35 C., and the contents are stirred for an additional 2.5 hours.
• Instrumental analysis shows the formation of substantial quantities of the a-lactone of 5 hydroxy 7 decynoic acid.
• a process for the production of an unsaturated lactone which comprises reacting 2(pentyne 2' yl)cycl0- pentanone with a lower alkyl percarboxylic acid at a temperature of from about 10 C. to about 50 C. to obtain the fi-lactone of 5-hydroxy-7-decynoic acid.
• percarboxylic acid is performic acid, peracetic acid, or perpropionic acid.

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• Chemical & Material Sciences (AREA)
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• Engineering & Computer Science (AREA)
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• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Pyrane Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Fats And Perfumes (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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Citations (1)

• 1967
  • 1967-10-16 US US675292A patent/US3531501A/en not_active Expired - Lifetime
• 1968
  • 1968-08-29 ES ES357649A patent/ES357649A1/es not_active Expired
  • 1968-09-06 GB GB42559/68A patent/GB1205159A/en not_active Expired
  • 1968-09-20 BE BE721164D patent/BE721164A/xx unknown
  • 1968-09-23 FR FR1582339D patent/FR1582339A/fr not_active Expired
  • 1968-10-04 NL NL6814210A patent/NL6814210A/xx unknown
  • 1968-10-16 CH CH1549468A patent/CH507230A/de not_active IP Right Cessation

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