Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
  • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
  • C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
• • 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
  • C11B9/0007—Aliphatic compounds
  • C11B9/0015—Aliphatic compounds containing oxygen as the only heteroatom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/04—Systems containing only non-condensed rings with a four-membered ring
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/50—Perfumes

Definitions

• the present invention relates to an isobutyric acid ester compound having a normal-butyryloxy group at the ⁇ position, a fragrance composition, and use as a fragrance.
• isobutyric acid esters include compounds useful as fragrances.
• various isobutyric acid esters are mainly used as flavors. Specifically, sweet apricot-like methyl isobutyrate, pineapple-like heavy propyl isobutyrate, and butyl isobutylate are fresh apples.
• sweet apricot-like methyl isobutyrate, pineapple-like heavy propyl isobutyrate, and butyl isobutylate are fresh apples.
• “/Nana-like, isoamyl isobutyrate is sweet apricot and//“Inaapple-like” are all fruit flavor flavor materials.
• Patent Document 1 discloses that, as an isobutyric acid ester having a bond with oxygen at the position, a linear or branched alkyl ester having 4 to 12 carbon atoms of alkoxyisobutyric acid is useful as a fragrance. However, it is stated that normal-hexyl «-ethoxyisobutyrate has a lavender-like aroma.
• Patent Document 1 US Pat. No. 3,368,943
• Non-Patent Document 1 Synthetic fragrance chemistry and product knowledge augmented new edition, Chemical Industry Daily,
• the problem to be solved by the present invention is to provide an isobutyric acid ester compound having a normal-butyryloxy group at the position, which is useful as a perfume and a mixed perfume raw material.
• a further problem to be solved by the present invention is to provide a fragrance composition containing the above compound as an active ingredient, and use of the compound as a fragrance.
• the present inventors have synthesized various compounds and have studied the fragrance of them, and found that a specific ester compound of isobutyric acid having a normalptyryloxy group at the position is useful as a fragrance and a compounded fragrance material. I found that.
• the present invention is as follows.
• ⁇ 6> In formula (1), is an isopropyl group, and is described in ⁇ 1> or ⁇ 2>. ⁇ 2020/175 241 3 ⁇ (: 170? 2020 /006278
• ⁇ 11> The compound described in any one of ⁇ 3>, ⁇ 4>, and ⁇ 6> imparts a damascene-like fruity, floral, or woody scent. ⁇ 10> use.
• an isobutyric acid ester compound having a normal-butyryloxy group at the position which is useful as a perfume and a compounded perfume material.
• a fragrance composition containing the compound as an active ingredient, and use of the compound as a fragrance.
• the compound of the present invention is represented by the following formula (1).
• the compound represented by the following formula (1) is also referred to as “isobutyric acid ester of the present invention” or “compound of the present invention”.
• Examples of are specifically methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isoptyl group (2-methyl propyl group)
• the compound of the present invention may have only one of the optical isomers produced thereby, and may contain a plurality of optical isomers at any ratio. It may be a mixture.
• the compound represented by the formula (1) is a novel compound.
• the isobutyric acid ester of the present invention represented by the formula (1) is useful as a fragrance and a compounded fragrance material, and exhibits an aroma such as a floral tone, a green tone and a fruity tone.
• the compound represented by the formula (1) is represented by the following formula (1 — 1)
• a particularly preferable compound is a compound represented by any of the following formulas (1 — 1) to (1 — 6)
• the compound of the present invention includes a compound having excellent biodegradability, and from the viewpoint of biodegradability, is selected from the group consisting of a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normalptyl group, and an isoptyl group. It is preferred that it is
• the isobutyric acid ester of the present invention is useful as a fragrance because it has an excellent aroma as described below.
• the fragrance is generally not used as a single item, and a mixed fragrance that combines multiple fragrances according to the purpose (fragrance group ⁇ 2020/175 24 6 6 (: 170? 2020 /006278
• the isobutyric acid ester of the present invention is useful as a perfume (also referred to as a “prepared perfume raw material”) to be mixed with a prepared perfume (perfume composition).
• a perfume also referred to as a “prepared perfume raw material”
• a prepared perfume perfume composition
• the fragrance one kind of the compound represented by the above formula (1) may be used alone, or two or more kinds thereof may be used in combination.
• the compound of the present invention contains a small amount of impurities, by-products, impurities and the like within a range that does not impair the effects of the present invention.
• the isobutyric acid ester of the present invention represented by the formula (1) has an aroma such as a floral tone, a green tone and a fruity tone and is also excellent in diffusibility. Further, the isobutyric acid ester of the present invention represented by any one of the formulas (1 — 1), (1 — 2) and (1-4) has a Damascon-like fruity, floral or woody tone. It has an aroma and is excellent in diffusivity.
• the isobutyric acid ester of the present invention may be added as a fragrance alone to various cosmetics, health and hygiene materials, pharmaceuticals, daily sundries, foods, etc. to add fragrance, and the present invention may also be used.
• the isobutyric acid ester of 1) may be mixed with other mixed fragrance ingredients to prepare a fragrance composition (prepared fragrance) described later, and this may be mixed with various products to impart a fragrance.
• a fragrance composition prepared fragrance
• the fragrance composition (prepared fragrance) of the present invention contains the isobutyric acid ester of the present invention as an effective component.
• the isobutyric acid ester of the present invention is not particularly limited as long as it contains at least one isobutyric acid ester, and may contain two or more isobutyric acid esters of the present invention.
• fragrance composition of the present invention only needs to contain the isobutyric acid ester of the present invention as an active ingredient, and other ingredients are not particularly limited, but other compounded fragrance materials (hereinafter also referred to as “conventional fragrance”) .) is further contained.
• fragrance composition prepared fragrance means a composition that imparts a fragrance by adding the fragrance composition to various cosmetics, pharmaceuticals, foods, beverages, or the like. ⁇ 2020/175 241 7 ⁇ (: 170? 2020 /006278
• composition itself is used for perfumes and the like, and may contain an additive such as a solvent, if necessary, in addition to the conventional fragrance.
• the compounding amount of the isobutyric acid ester of the present invention varies depending on the kind of the isobutyric acid ester of the present invention, the kind of the target aroma, the intensity of the aroma, etc., but the isobutyric acid ester of the present invention represented by the formula (1) In the perfume composition as an amount of, preferably ⁇ .
• 0.01 mass% or more more preferably 0.01 mass% or more, further preferably 0.1 mass% or more, preferably 90 mass% or less, more preferably 70 mass% or less, further preferably Is 50% by mass or less.
• the conventional fragrance is not particularly limited as long as it is a conventionally known fragrance component, and a wide range of fragrances can be used. For example, one of the following may be used alone or two or more may be selected in any mixing ratio. And can be used.
• limonene "- pinene, / 3 - pinene, terpinene, cedrene, mouth Ngiforen, hydrocarbons such as valencene; linalool, citronellol, Geranio _ Le, Nero _ Le, Terupineo _ Le, dihydromyrcenol Seno _ le, ethyl Linalool, farnesol, nerolidol, cis-3-hexenol, cedrol, menthol, borneol, /3-phenyl ether, benzyl alcohol, phenylhexanol, 2,2,6-trimethylcyclohexyl 3-hexanol , 1-(2 _ 1: _Putylcyclohexyloxy) _ 2-butanol, 4-isopropylcyclohexanemethanol, 4 _ -Butylcyclohexanol, 4-methyl-2
• Urine geranyl acetate, neryl acetate, tervinyl acetate, nopyl acetate, bornyl acetate, isobornyl acetate, _ _ _ butyl cyclohexyl acetate, -Butylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, styrylyl acetate, cinnamyl acetate, dimethylbenzylcarbinyl acetate, 3-pentyltetrahydropyran-4-yl acetate, citronellyl propionate, tricyclodecenyl Probionate, Allylcyclohexylprobionate, Ethyl 2-cyclohexylprobionate, Benzylpropionate, Citronellyl butylate, Dimethylbenzylcarbinyl _butyrate, Tricyclodecenyl
• Lactones orange, lemon, bergamot, mandarin, peppermint, spearmint, lavender, chamomile, mouth mousse, eucalyptus, sage, basil, mouth mousse, geranium, jasmine, ylang ylang, anise, cloves, ginger, nutmeg , Cardamom, cedar, cypress, sandalwood, petiper, patchouli, labdanum and other natural essential oils and natural extracts; other fragrance substances such as synthetic fragrances.
• the fragrance composition comprises, as a constituent component other than the prepared fragrance material, a surfactant such as polyoxyethylene lauryl sulfate and the like; dipropylene glycol, diethyl phthalate, ethylene glycol, propylene glycol, methyl myristate, and triethyl ether.
• a solvent such as chill citrate; an antioxidant; a coloring agent and the like may also be included.
• the isobutyric acid ester of the present invention represented by the formula (1) has a floral tone and a green color. ⁇ 2020/175 241 10 boxes (: 170? 2020 /006278
• the isobutyric acid ester of the present invention represented by any one of the formulas (1 _ 1), (1 -2) and (1 -4) has a Damascon-like fruity, floral or woody aroma. Therefore, it is useful for giving an aroma by combining with a conventional fragrance.
• a perfume composition containing the isobutyric acid ester of the present invention represented by the formula (1) can be added to impart an aroma and to improve the aroma of an object to be blended.
• Health and hygiene materials miscellaneous goods, beverages, foods, quasi-drugs, pharmaceuticals, and other products.
• fragrance products such as perfumes and colognes; shampoos, rinses, hair nicks, hair creams.
• Cosmetics for hair, mousse, jewel, vomade, spray and other hair lotion, beauty essence, cream, milky lotion, pack, foundation, cosmetics for face, lipstick, make-up, etc.; dishwashing detergent, Laundry detergents, softeners, disinfecting detergents, deodorant detergents, indoor air fresheners, furniture care, glass cleaners, household cleaners, floor cleaners, disinfectants, insecticides, bleaches, disinfectants, repellents Agents, other various kinds of health and hygiene detergents; toothpaste, mouthwash, bath salts, antiperspirant products, quasi-drugs such as perm solution; miscellaneous goods such as toilet vapors, tissue vapors; pharmaceuticals; foods, etc. It can be used as an aroma component of.
• the blending amount of the flavor composition in the above-mentioned product is not particularly limited, and the blending amount of the flavor composition over a wide range depending on the kind of the product to be perfumed, the nature and the sensory effect. Can be selected. For example, 0.001% by mass or more, preferably 0.001% by mass or more, more preferably 0.001% by mass or more.
• a fragrance such as perfume
• the method for producing the isobutyric acid ester of the present invention represented by the formula (1) is not particularly limited, and may be appropriately selected from conventionally known methods and used.
• acylating a hydroxyl group at the ⁇ position by reacting ⁇ -hydroxyisobutyric acid ester with an acylating agent in the presence or absence of a catalyst.
• the acylating agent used include carboxylic acids such as butyric acid, carboxylic acid anhydrides such as butyric anhydride, carboxylic acid halides such as butyryl chloride and butyryl bromide, and ketene compounds such as ethyl ketene.
• carboxylic acids such as butyric acid
• carboxylic acid anhydrides such as butyric anhydride
• carboxylic acid halides such as butyryl chloride and butyryl bromide
• ketene compounds such as ethyl ketene.
• two or more acylating agents selected from these may be used in combination at any ratio.
• the target normal butyryloxyisobutyric acid ester can be produced by subjecting another type of normal butyryloxyisobutyric acid ester and an alcohol to a transesterification reaction in the presence of a catalyst.
• the anti reaction ⁇ 2020/175 241 12 boxes (: 170? 2020/006278
• Equation (5) Represents a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms.
• the catalyst, reaction method, reaction conditions, reaction apparatus, and the like used in these reactions may be any conventionally known catalyst, reaction method, reaction conditions, and reaction apparatus, and are not particularly limited. Further, as a method for purifying the obtained compound of the formula (1), a conventionally known purification method can be adopted without any limitation.
• Reaction yield (%) [(number of moles of ester formed in reaction solution) / (number of moles of raw material ester in feed solution)] X I 0%
• the ester was identified by 1 1 to 1 _ IV! measurement and 13 ⁇ _ IV! measurement.
• the measurement conditions are shown below.
• Minaha 500 product name, manufactured by JEOL Ltd.
• the compounds were also identified by measuring their molecular weights by measuring 001-1/13 (chemical ionization method [ ⁇ I10], high-resolution mass spectrometry [millimass]). The measurement conditions are shown below.
• Reagent gas isobutane ⁇ 2020/175 241 14 ⁇ (: 170? 2020/006278
• Kishiiso butyrate (Mitsubishi Gas Chemical Co., Ltd.) 20.0 9, (manufactured by Wako Pure Chemical Industries, Ltd.) butyric anhydride (Wako Pure Chemical Industries, Ltd.) 29.4 9, pyridine 1 3.6 9 4-dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, Ltd.) 2.19 was charged, and the mixture was stirred at room temperature to 40° for 24 hours for reaction. From the 0 (3 analysis of the reaction solution, the reaction with butyric anhydride completely consumed ⁇ -methyl hydroxyisobutyrate, and the reaction of the following formula (7) It was confirmed that methyl normaltylyloxyisobutyrate was obtained with a reaction yield of 93%.
• the ester exchange reaction was completed while the methanol produced by the reaction was removed from the system by distillation or azeotropic distillation with the reaction solvent under the reaction conditions, and the same separation operation as in Reference Example 1 was performed. Butyric acid esters were obtained respectively. The purity of the obtained isobutyric acid ester is also shown.
• Examples 3 to 6 Synthesis of Normal Butyryloxy Isobutyric Acid Ester> Using the same reaction apparatus as in Example 2, ⁇ _ hydroxyisobutyric acid ester, butyric anhydride (manufactured by Wako Pure Chemical Industries, Ltd.), pyridine prepared in Reference Examples 2 to 5 (Wako Pure Chemical Industries, Ltd.) and 4-dimethylaminopyridine (Wako Pure Chemical Industries, Ltd.) were used in appropriate amounts for the reaction. In the same manner as in Example 1, the following ⁇ -normal butyryloxyisobutyric acid esters were obtained by column chromatography. The resulting ester 0 (3 purity, Spectrum analysis and
• One of the methods for evaluating the biodegradability of a compound is the ⁇ 0 test guideline 3101, which is based on the biochemical oxygen demand and the actual oxygen consumption rate in an aqueous solution in which the compound and aerobic microorganisms coexist. It is possible to judge the biodegradability of the product.
• the probability of biodegradation of a compound according to this test method is determined by the chemical structure of the test substance.
• the calculation software called “B i ow in 5” and “B iowin 6” is known as a method to estimate easily and accurately.
• the software is a calculation software called "The Estimations Programs Interface for Windows version 4.1" created by the United States Environmental Protection Agency (EPA) for the purpose of evaluating the environmental impact of chemical substances. It has been distributed to the public as one of the modules of the Globally Harmonized System of Classification and Labeling of Chemicals (GHS), and is being used in the new chemical substance examination of the United States Environmental Protection Agency. This software was used to evaluate the difference in biodegradability between existing flavoring materials and the compounds of the invention.
• GCS Globally Harmonized System of Classification and Labeling of Chemicals
• the good degradability is 0 or more (the symbol “A” in the table), and the less than 0.5 is the poor degradability (the symbol “B” in the table).
• Similar existing flavoring materials (E) _ ⁇ 3 ⁇ 4_ Damascon, (E) _/3_ Damascenone show that the compound of the present invention can be expected to have good biodegradability.
• the compounds of the present invention tended to have less environmental impact by being easily biodegraded after being released as fragrance to the environment.
• Example 4 95.0 parts by weight of the fragrance composition having the composition shown in Table 4 was obtained in Example 4.
• a fragrance composition was prepared by adding 5.0 parts by mass of isopropyl normal butyryloxyisobutyrate.
• the fragrance composition having the composition shown in Table 4 was obtained.
• isopropyl normal butyryloxyisobutyrate mouth-like floral and fruity were added, and gorgeous sweetness and broad floral feeling were obtained.
• a more natural and fragrant miuge-like fragrance composition having a sweetness and fruitiness similar to that of the mouth was obtained.
• the fragrance of this fragrance composition seems to be suitable for perfuming shampoos, lotions, skin creams, emulsions, soft toners, soaps and the like.
• the isobutyric acid ester compound having a normalputyryloxy group at the ⁇ position of the present invention has an excellent fragrance, and is expected to be used as a fragrance itself, and at the same time, the compound is used as a fragrance material prepared. As a result, a fragrance composition having an excellent fragrance is obtained, and when it is mixed with various products, a desired fragrance property is emitted.
• the compounds obtained in the examples all have excellent biodegradability and low environmental load, and are suitable for use.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Fats And Perfumes (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=72238449

Family Applications (1)

Country Status (6)

Cited By (3)

Citations (5)

Family Cites Families (5)

• 2020
  • 2020-02-18 ES ES20762322T patent/ES2943559T3/es active Active
  • 2020-02-18 WO PCT/JP2020/006278 patent/WO2020175241A1/ja not_active Ceased
  • 2020-02-18 US US17/433,028 patent/US12162833B2/en active Active
  • 2020-02-18 JP JP2021502024A patent/JP7400800B2/ja active Active
  • 2020-02-18 EP EP20762322.4A patent/EP3932901B1/en active Active
  • 2020-02-18 CN CN202080016604.9A patent/CN113474324B/zh active Active

Patent Citations (5)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events