JP5517540B2 - Indicator substance for judgment of raw dry odor - Google Patents

Description

  The present invention relates to an indicator substance used for determining a raw dry odor generated from a textile product such as clothing by drying the room, a method for evaluating a raw dry odor using the indicator substance, and a simulated raw dry odor composition.

  "Dry odor" generated from textiles such as clothing, towels, bedding, etc. means that these textiles are dried after washing, especially in rainy season or in a closed room, etc. Is an unpleasant odor that is likely to occur when left untreated for a long time. In recent years, due to changes in lifestyles such as an increase in double-working households and high airtightness of houses, it is considered that an environment in which a dry odor of textile products tends to occur is becoming more likely.

  Conventionally, as a method for judging a raw dry odor of a textile product and an evaluation of the effectiveness of a treating agent for textile products that prevents the occurrence of the raw dry odor, it has relied on a sensory evaluation test that actually judges the smell of clothing by smelling it.

  This freshly dried odor (room-dried odor) is “smell-like odor” such as medium chain aldehyde, medium chain alcohol, and ketone, “sour odor” such as short chain fatty acid and medium chain fatty acid, and “raw odor” such as nitrogen compounds. It is reported that the contribution of medium-chain fatty acids is particularly large (Non-patent Document 1).

Sugawara, Sonoda, “Detergents that Control Room Drying Odors”, Fragrance, September 2004, No.223, p.109-116

  In Non-Patent Document 1, it is estimated that the key component of a raw dry odor is “a mixture of fatty acids containing 7 to 9 carbon atoms and containing unsaturation”, and these are also included in odors such as sweat. In other words, Non-Patent Document 1 does not suggest any existence of a component peculiar to a raw dry odor.

  Moreover, in the sensory evaluation test in which the odor of the clothing is actually smelled as described above, there is a large room for the evaluator's subjective judgment, so that there is a problem that quantitative judgment is difficult and objectivity is lacking. .

  An object of the present invention is to provide an indicator substance capable of objectively and quantitatively determining a raw dry odor, a method for determining a raw dry odor using the same, and a pseudo raw dry odor composition suitable for evaluation of a raw dry odor masking effect, etc. To provide things.

  The present inventors have studied the causative components of clothing having a strong raw dry odor. As a result, three types of methylhexenoic acid having a specific structure contribute greatly to the raw dry odor and have a quantifiable concentration. It has been found that a group of compounds having a structure close to those of these compounds can be used as an objective index for quantitatively determining the degree of raw dry odor.

  The present invention relates to determination of a raw dry odor containing at least one selected from the group consisting of a carboxylic acid represented by the general formula (1) and a carboxylic acid derivative obtained by introducing an atom or an atomic group into the carboxy group of the carboxylic acid. It provides an indicator substance for use.

[Wherein, R ¹ and R ² each represent a hydrogen atom or a methyl group, and a broken line indicates that it may be a double bond, at least one of which is a double bond. ]

  The present invention also provides a raw dry odor determination method using the carboxylic acid or a derivative thereof as an index.

  Moreover, this invention provides the pseudo-raw dry odor composition containing the said carboxylic acid.

  Furthermore, this invention provides the effectiveness determination method with respect to the raw dry odor of the processing agent for textiles using the said indicator substance.

  The carboxylic acid represented by the general formula (1) (hereinafter referred to as carboxylic acid (1)) has an odor very close to the odor of a raw fiber product, and is useful as an indicator substance for determining the raw odor. . Therefore, the strength of the raw dry odor can be objectively and quantitatively evaluated based on the abundance of the compound.

It is a figure which shows the gas chromatography-mass spectrometry result about the odor concentrate obtained from the jeans which generate | occur | produce a raw dry smell. It is a figure which shows the relationship between sensory intensity and the detection amount of 4-methyl-3- hexenoic acid.

● Indicator substance for odor determination [Carboxylic acid (1)]
The indicator substance for judging the dry odor of the present invention contains at least one selected from the group consisting of a carboxylic acid (1) and a carboxylic acid derivative obtained by introducing an atom or an atomic group into its carboxy group.

Among the compounds included in the carboxylic acid (1), the causative substance of the raw dry odor found by the present inventors is 5-methyl-2-hexenoic acid represented by the following formula (1a), the following formula (1b) And 5-methyl-4-hexenoic acid represented by the following formula (1c ₁ ) or (1c ₂ ), both of which have an odor very close to a raw dry odor .

5-Methyl-2-hexenoic acid (1a) is known as a compound contained in tobacco (Phytochemistry, 12 (4), 835-47 (1973)), and 5-methyl-4-hexenoic acid (1b) Is a compound used as an intermediate of pharmaceuticals and the like [Bioorganic & Medicinal Chemistry Letters, 15 (23), 5284-5287, (2005)]. In addition, 4-methyl-3-hexenoic acid (1c ₁ ) and (1c ₂ ) have been detected from hop aroma components (Journal of agricultural and food chemistry, 26 (6), 1426-1430, (1978) ]. However, none has been reported as a component of a raw dry odor.

5-Methyl-2-hexenoic acid (1a), 5-methyl-4-hexenoic acid (1b), 4-methyl-3-hexenoic acid (1c ₁ ) or (1c ₂ ) are all causes of conventional dry odor. Although the quality of isovaleric acid known as a substance is different from that of odors, it has an odor that is not inferior to that of odor and that is more like a dry odor. In addition, 5-methyl-2-hexenoic acid (1a), 5-methyl-4-hexenoic acid (1b), 4-methyl-3-hexenoic acid (1c ₁ ) or (1c ₂ ) But it is comparable to or more than isovaleric acid.

In particular, 4-methyl-3-hexenoic acid (1c ₁ ) and (1c ₂ ) give a strong odor even in a very small amount, and if 1 ng is contained in 10 g of fabric, a dry odor is felt, and 1 μg is contained in 10 g of fabric. Everyone has a strong odor so that everyone feels a dry odor. Furthermore, the quality of odor is very close to the actual raw dry odor compared to other compounds. 4-Methyl-3-hexenoic acid has the same odor both in the cis form of the formula (1c ₁ ) and in the trans form of the formula (1c ₂ ). Hereinafter, the cis form and the trans form are not distinguished and treated as 4-methyl-3-hexenoic acid.

  Since 5-methyl-2-hexenoic acid, 5-methyl-4-hexenoic acid, and 4-methyl-3-hexenoic acid have the following characteristics, the abundance and state of presence in clothing with a raw dry odor It is considered to indicate the degree of raw odor.

(I) Clothing that does not detect any of 5-methyl-2-hexenoic acid, 5-methyl-4-hexenoic acid, and 4-methyl-3-hexenoic acid does not generate a dry odor, The clothes in which any one or more compounds of methyl-2-hexenoic acid, 5-methyl-4-hexenoic acid and 4-methyl-3-hexenoic acid are detected have a clear dry odor. That is, the above three compounds exist specifically in the raw dry odor.

(B) Clothing that has a higher amount of 5-methyl-2-hexenoic acid, 5-methyl-4-hexenoic acid and 4-methyl-3-hexenoic acid contained in clothing has a stronger odor.

  From the above, among the carboxylic acids (1), 5-methyl-2-hexenoic acid, 5-methyl-4-hexenoic acid, and 4-methyl-3-hexenoic acid are particularly useful as indicator substances for judgment of a live-dry odor. Is preferred.

  When these carboxylic acids (1) are used as an indicator substance, they may be used alone or as a mixture composed of a plurality of carboxylic acids. Moreover, although the purity is so preferable that it is high, it may contain impurities as long as it does not affect the odor.

[Synthesis Method of Carboxylic Acid (1)]
Carboxylic acid (1) can be synthesized by a known method, and is also an indicator substance in that it can objectively evaluate and determine a dry odor regardless of time and place by stably supplying a synthetic product of constant quality. Suitable as

For example, among the carboxylic acids (1), 2-ene type compounds typified by 5-methyl-2-hexenoic acid are represented by Horner- as shown in the following reaction formula A (R ¹ and R ² are the same as described above). It can be synthesized by the Wadsworth-Emmons reaction [DJ Schauer, P, Helquist; Synthesis, 21, 3654-3660, (2006)].

Of the carboxylic acids (1), 4-ene type compounds represented by 5-methyl-4-hexenoic acid are represented by Johnson-Claisen as shown in Reaction Formula B (R ¹ and R ² are the same as above). It can be synthesized by rearrangement [S. Menon, D. Sinha-Mahapatra, and JW Herndon; Tetrahedron, 63, 8788-8793 (2007)].

  4-Methyl-3-hexenoic acid can be synthesized by the reaction of 2-methylbutyraldehyde and malonic acid as shown in Reaction Formula C.

(Derivatives of carboxylic acid (1))
Carboxylic acid (1) may be used after chemical modification, that is, by introducing an atom or an atomic group into a carboxy group, as long as the detection function as an indicator compound is not lost. For example, to improve analytical sensitivity in instrumental analysis, acylation, esterification, trimethylsilylation, amidation, carboxylation of the carboxy group, or coloration of the carboxy group to enable visualization of the indicator substance You can also introduce teams.

  Derivatizing reagents include UV reagents such as O- (p-nitrobenzyl) -N, N'-diisopropylisourea (PNBDI) and p-bromophenacyl bromide (PBPB), 4-bromomethyl-7-methoxycoumarin Fluorating reagents such as (Br-MmC), silylating agents such as N-trimethylsilylimidazole (TMSI) and N, O-bis (trimethylsilyl) acetamide (BSA), acylating agents such as trifluoroacetic anhydride and trifluoroacetylimidazole Etc. can be used.

  When a chromophore in the visible region is used as the labeling compound for carboxylic acid (1), a concentration-coloring standard sample of the labeling compound is prepared, and the odorant extract collected from the sample is colored with the same reagent. It is also possible to judge the degree of raw dry odor visually.

As a method of determining the presence or amount of carboxylic acid (1) using a color reaction,
i) Method of introducing a chromophore directly into the carboxy group of carboxylic acid (1)
ii) Method of introducing a chromophore into the derivative after converting the carboxylic acid (1) into the derivative
iii) A method of introducing a chromophore into the decomposed product after decomposing the carboxylic acid (1).

  As a color reagent used in the method of i) for introducing a chromophore directly into the carboxy group of the carboxylic acid (1), a reagent that introduces a carboxylic acid into a chromogenic acid hydrazide in the presence of a condensing agent to cause coloration; There are a reagent for introducing a carboxylic acid into a chromogenic ester to cause coloration, a reagent for introducing a carboxylic acid into a chromogenic amide for coloring, and the like.

  Reagents that lead carboxylic acid to chromogenic acid hydrazide for coloration include 2-nitrophenylhydrazine, 6,7-dimethoxy-1-methyl-2 (1H) -quinoxalinone-3-propionylcarboxylic acid hydrazide (DMEQ- H), p- (4,5-diphenyl-1H-imidazol-2-yl) -benzohydrazide, p- (1-methyl-1H-phenanthro- [9,10-imidazol-2-yl) -benzohydrazide, and p- (5,6-dimethoxy-2-benzothiazoyl) -benzohydrazide.

  Reagents for introducing a carboxylic acid into a chromogenic ester to cause coloration include 9-anthryldiazomethane, 1-naphthyldiazomethane, 1- (2-naphthyl) diazoethane, 1-pyrenyldiazomethane, 4-diazomethyl-7-methoxy. Coumarin, 4-bromomethyl-7-methoxycoumarin, 3-bromomethyl-6,7-dimethoxy-1-methyl-2 (1H) -quinoxalinone, 9-bromomethylacridine, 4-bromomethyl-6,7-methylenedioxycoumarin N- (9-acridinyl) -bromoacetamide, 2- (2,3-naphthylimino) ethyl trifluoromethanesulfonate, 2- (phthalimino) ethyl trifluoromethanesulfonate, N-chloromethylphthalimide, N-chloromethyl-4-nitro Examples include phthalimide, N-chloromethyl isatin, O- (p-nitrobenzyl) -N, N′-diisopropylisourea and the like.

  Examples of the reagent that introduces a carboxylic acid into a chromogenic amide to cause coloration include monodansylcadaverine, 2- (p-aminomethylphenyl) -N, N′-dimethyl-2H-benzotriazol-5-amine, and the like. .

  In the method of converting the carboxylic acid of ii) to a derivative and then introducing a chromophore into the derivative, examples of the carboxylic acid derivative that can be used for the color reaction include inorganic salts and acid chlorides.

  Carboxylic acid inorganic salts can be reacted with aromatic halogens to give chromogenic esters and acid chlorides to chromogenic amides.

  Examples of the method for converting the carboxylic acid into an inorganic salt include a method in which the carboxylic acid is mixed with an alkaline substance such as a sodium hydrogen carbonate solution, a sodium carbonate solution, a sodium hydroxide solution, a potassium hydroxide solution and neutralized. Aromatic halogens that can be converted to chromogenic esters by reacting with inorganic salts of hydroxycarboxylic acids include p-nitrobenzyl bromide, phenacyl bromide, p-chlorophenacyl bromide, p-bromophenacyl bromide, p-iodo Examples include phenacyl bromide, p-nitrophenacyl bromide, p-phenylphenacyl bromide, p-phenylazophenacyl bromide, N, N'-dimethyl-p-aminobenzeneazophenacyl chloride.

  Examples of the method for converting carboxylic acid to acid chloride include a method of reacting carboxylic acid with oxalyl chloride. Examples of the method for converting the acid chloride to a color-forming amide include a method of reacting with 9-aminophenanthrene in the presence of triethylamine.

  After degrading the carboxylic acid of iii), a chromophore can be introduced into the degradation product by acyl-CoA synthetase in the presence of adenosine triphosphate (ATP) and coenzyme CoA in the carboxylic acid. To produce acyl-CoA, then treated with acyl-CoA oxidase to produce enoyl-CoA and hydrogen peroxide, which is further treated with catalase to formaldehyde. There is a method in which a color reagent, 4-amino-3-hydrazino-5-mercapto-1,2,3-triazole (AHMT), is reacted to colorize the resulting purple color.

  Thus, in the present invention, the reagent used for the color reaction of the carboxylic acid is not particularly limited as long as it reacts with any of carboxylic acid, a carboxylic acid derivative, and a carboxylic acid decomposition product to develop a color.

  The raw dry odor detection reagent that colors carboxylic acid (1) can reliably, quickly and easily determine the degree of raw dry odor without using expensive analytical instruments such as gas chromatography and liquid chromatography. Since it is possible, it can be used when determining in an environment where there is no special analytical instrument.

● Raw dry odor determination method According to the present invention, it is possible to quantitatively determine the degree of raw dry odor using these indicator substances.

  The method of using the carboxylic acid (1) or its derivative as an indicator substance for determining a dry odor is not particularly limited, and may be used in accordance with various known evaluation methods.

  For example, when measuring the content of carboxylic acid (1) contained in clothing with a dry odor by GC-MS, use carboxylic acid (1) or its derivative as a standard substance (standard) to create a calibration curve To do. The calibration curve may be used to identify the peak of carboxylic acid (1) contained in the collected clothing and measure the amount.

  When performing sensory evaluation, the carboxylic acid (1) is diluted in several stages to prepare odor standard samples of various concentrations. Then, the odor of the evaluation sample prepared from the clothing having a raw dry odor is checked against the standard sample, and the amount of the carboxylic acid (1) contained in the clothing may be determined by sensory evaluation.

  In addition, if there is a large amount of carboxylic acid (1) produced in clothing but it has no odor such as salt or has changed to a weak derivative, there must be a latent state of raw dry odor. However, even if sensory evaluation is performed in such a case, the latent state of the raw dry odor may not be accurately evaluated. In contrast, in the present invention, by measuring the carboxylic acid (1) or a derivative thereof that can be analyzed by a necessary chemical treatment, whether or not the evaluation sample is a sample that may generate a raw dry odor, that is, Potential evaluation can be performed.

  As described above, the index substance of the present invention can be used for any of chemical analysis, instrumental analysis, sensory evaluation, etc. and can be quantitatively determined with high objectivity. By expressing the value as the abundance of carboxylic acid (1), it is possible to exclude subjectivity from the determination result.

  Furthermore, in the present invention, the effectiveness of a treating agent for textile products targeting a raw dry odor can be objectively and quantitatively determined using an indicator substance containing carboxylic acid (1) or a derivative thereof.

  In the method for determining the effectiveness of the treating agent for textile products, the indicator substance may be used as a simple substance, other components such as a solvent for dissolution or dilution, a stabilizer, an antibacterial agent, an antibacterial agent, Additives such as surfactants, antioxidants, fragrances, plant extracts and the like may be blended to prepare a composition suitable for practical use such as storage and use in judgment tests.

  A treatment for textile products that targets a raw dry odor is a type that disinfects bacteria attached to clothing and prevents the decomposition of sweat, sebum, etc. remaining on clothing, and a type that decomposes or changes to a derivative that does not smell odor components Alternatively, any type of mechanism of action may be used, such as a type that masks odors. The method of using the carboxylic acid (1) or a derivative thereof as an index substance for determining the effectiveness of the fiber product treatment agent is not particularly limited, and may be used according to the mechanism of action and the evaluation method of the fiber product treatment agent. .

  For example, carboxylic acid (1) or a derivative thereof as an active ingredient, preferably 5-methyl-2-hexenoic acid, 5-methyl-4-hexenoic acid, 4-methyl-3-hexenoic acid or a derivative thereof at a predetermined concentration. The effectiveness of the textile agent treatment agent is determined by attaching the indicator substance to the fiber such as clothing, adding a predetermined amount of textile agent treatment agent sample, and quantifying the change state of the indicator substance by an appropriate method. Can be determined objectively and quantitatively.

  As a method for quantifying the change state of the indicator substance, if the treatment sample for textile products is of the type that degrades carboxylic acid (1) or induces it to another compound to reduce odor, the indicator substance calibration curve May be prepared in advance, and an instrumental analysis may be performed using this calibration curve, or a changed or unchanged substance of the indicator substance may be quantified by chemical analysis such as titration or extraction. If the treatment sample for textile products is of the type that masks the raw dry odor, the indicator substance is diluted in several stages to prepare odor standard samples of each concentration, and the indicator substance to which the treatment sample for textile products is added. The odor is checked against a standard sample, and the masking effect may be determined by sensory evaluation.

-Simulated Live-Dry Odor Composition Furthermore, the present invention provides a simulated live-dry odor composition which contains carboxylic acid (1) and can be used for deodorizing the live-dry odor and evaluating the masking effect. By using this simulated raw dry odor composition, the screening of the deodorant base and the deodorizing effect of the raw dry odor of the deodorant composition can be evaluated accurately and with good reproducibility.

  When this carboxylic acid (1) is used for judgment of raw odor in sensory evaluation etc., known raw dry odor components are mixed in an appropriate ratio to reproduce the raw dry odor close to the actual situation, and simulated raw dry It can also be used as an odor composition.

  That is, the simulated raw dry odor composition of the present invention contains carboxylic acid (1) as component (A) from the viewpoint of more accurately reproducing the raw dry odor, which is a composite odor containing various odors, and is shown below. It is preferable to appropriately contain the components (B), (C) and (D).

  Component (B) is a lower fatty acid having 2 to 5 carbon chains, and it is preferable to add these compounds to the composition from the viewpoint of reproducing a sweat-like sour odor from a raw dry odor that is a complex odor. Examples of component (B) include acetic acid, propionic acid, butyric acid, valeric acid, and isovaleric acid, with isovaleric acid being particularly preferred. Any of these may be used alone or in combinations of two or more.

  In the present invention, the ratio (mass ratio) of the component (B) to the component (A) is preferably in the range of (B) / (A) from 0.01 to 10,000, more preferably from (B) / (A) from 0.1. A range of 1000, particularly preferably (B) / (A) is in the range of 1 to 100.

  Ingredient (C) is a saturated and unsaturated linear aldehyde having 6 to 14 carbon chains, and adding these compounds to the composition has a dusty and worn-out characteristic of textile products among raw dry odors that are complex odors. This is preferable in terms of reproducing the old-fashioned blue-smelling odor. Examples of the component (C) include hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal, tetradecanal, 2-hexenal, 2-heptenal, 2-octenal, 2-nonenal, and 2-decenal. , 2-undecenal, 2-dodecenal and the like, and any of them can be used alone or in combination of two or more.

  In the present invention, the ratio (mass ratio) of component (C) to component (A) is preferably in the range of 0.001 to 100 for (C) / (A), more preferably from 0.01 to (C) / (A). The range is 10.

  Ingredient (D) is a saturated fatty acid having 6 to 12 carbon chains detected from human sebum and sweat. Adding these compounds to the composition is a sweet odor peculiar to human-derived odors among the raw dry odors that are complex odors. This is preferable in that it reproduces an acid odor like a whisper. Examples of the component (D) include hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid and the like, and any of them can be used alone or in combination of two or more. .

  In the present invention, the ratio (mass ratio) of component (D) to component (A) is preferably in the range of 0.01 to 1000 for (D) / (A), more preferably from 0.1 to (D) / (A). The range is 100.

  Compounds other than these (A) to (D) may be used as the simulated raw dry odor composition, such as compounds derived from mold odor such as pyrazines, pyridines, dimethyl disulfide, dimethyl trisulfide, myristic acid, palmitic acid. When higher fatty acids such as palmitoyl acid, stearic acid, oleic acid, and linoleic acid are added, it can be brought closer to an actual raw dry odor.

  In addition, the simulated raw dry odor composition of the present invention contains a diluent such as water, diethyl phthalate, dipropylene glycol, propylene glycol, triethyl citrate, butyl diglycol or a solvent such as ethanol, if necessary. Can be made. The amount can be appropriately determined according to the intended use, intended purpose, etc. of the composition of the present invention.

  These compositions include deodorants that target mixed odor deodorization, nursing odor deodorization, indoor deodorants, clothing cleaning agents, clothing deodorants, and residential cleaning agents. It may be applied to the development of

Example 1
100 g of jeans that gave a strong, dry odor (dry room odor) were cut, and the odor components were extracted and concentrated with dichloromethane. Furthermore, according to a conventional method, only the acidic component was selectively extracted and concentrated, and if necessary, the odor component was concentrated using a Presative Fraction Collector (PFC) apparatus manufactured by Gerstel. The obtained odor concentrate was analyzed using a gas chromatography-mass spectrometer (GC-MS). The important ingredients that generate raw odors were identified by odor sniffing gas chromatography (sniffing GC).
When various odor components extracted from clothes having a raw dry odor were examined, GC-MS analysis (FIG. 1) confirmed a compound peak that was not found so far, along with a saturated fatty acid that had been confirmed so far. This elution component is 4-methyl-3-hexenoic acid, 5-methyl-2-hexenoic acid, and 5-methyl-4-hexenoic acid, which have a strong odor that is very similar to a dry-smelling odor in smell sniffing gas chromatography. I understood.
These fatty acids have never been reported as odor components of clothing, but were detected at each site from the sample clothing detected this time.

Example 2
Nine garments that had a dry odor in ordinary households were collected, and the sensory strength and instrumental analysis were conducted to examine the relationship between the sensory strength and 4-methyl-3-hexenoic acid.

(Evaluation of sensory strength)
In a room maintained at room temperature (25 ° C.) and humidity of 65%, 5 expert panelists sniffed the odors of the clothes, and the odor intensity was determined in the following 6 stages by discussion of 5 persons.
5: Smells very strongly 4: Smells strongly 3: Smells clearly 2: Smells slightly 1: Slightly smells 0: Does not smell

(Instrument analysis)
The odor component was extracted in the same manner as in Example 1, concentrated and subjected to GC-MS analysis, and the amount of 4-methyl-3-hexenoic acid contained in the clothing was examined.

  The results of sensory strength evaluation and instrumental analysis are shown in Table 1 and FIG. From these results, there was a correlation between the sensory strength and the detected amount of 4-methyl-3-hexenoic acid, and there was a tendency that the stronger the odor, the higher the detected amount of these fatty acids.

Production Example 1 Synthesis of 4-methyl-3-hexenoic acid
2-methylbutyraldehyde (Tokyo Kasei Kogyo) 2.68 mL, malonic acid (Wako Pure Chemical Industries) 2.86 g and triethylamine (Wako Pure Chemical Industries) 3.84 mL were added to a 50 mL eggplant flask, and the mixture was heated and stirred at 90 ° C. for 7 hours. After completion of the reaction, an appropriate amount of 1N sulfuric acid was added and extracted with dichloromethane. The extracted organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure to obtain 2.3 g of a crude product. The resulting crude product was purified by column chromatography to obtain 1.5 g (yield 47%) of the desired 4-methyl-3-hexenoic acid. The geometric isomer ratio of the obtained 4-methyl-3-hexenoic acid was E: Z = 63: 37.

Production Example 2 Synthesis of 5-methyl-2-hexenoic acid
5-Methyl-2-hexenoic acid was synthesized according to the method described in DJ Schauer, Paul Helquist; Synthesis, 21, 3654-3660, (2006).
Under a nitrogen atmosphere, in a three-necked flask, 2.4 g of zinc trifluoromethanesulfonate (Wako Pure Chemical Industries), (diethoxyphosphinoyl) acetic acid (Wako Pure Chemical Industries) 0.48 mL, N, N, N ', N'-Tetra Methylethylenediamine (Wako Pure Chemical Industries) 0.5 mL, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) (Wako Pure Chemical Industries) 1.79 mL and anhydrous THF (Wako Pure Chemical Industries) 25 mL were added. Thereafter, 0.35 mL of isovaleraldehyde (Tokyo Chemical Industry) was added dropwise and stirred for 20 hours. The reaction was then terminated with 1N hydrochloric acid, extracted with 50 mL × 2 dichloromethane, washed with 50 mL × 2 water, dried over magnesium sulfate, and the solvent was distilled off to give 0.42 g of 5-methyl-2-hexenoic acid (yield). 99%).

Production Example 3 Synthesis of 5-methyl-4-hexenoic acid
5-Methyl-4-hexenoic acid was synthesized according to the method described in S. Menon et al, Tetrahedron, 63, 8788-8793, (2007).
A cooling tube is attached to the eggplant flask, and 1.82 mL of 2-methyl-3-buten-2-ol (Wako Pure Chemical Industries), 29.8 mL of triethylorthoacetic acid (Aldrich) and 0.16 g of 2-nitrophenol (Tokyo Chemical Industry) And heated to reflux for 36 hours. After returning to room temperature, 25 mL of a mixture of methanol: water = 1: 1 was added and acidified with 5N hydrochloric acid. Thereafter, extraction was performed with 100 mL of diethyl ether, and after washing with 100 mL of water, the organic layer solution was concentrated under reduced pressure.
Next, the concentrated organic layer was transferred to an eggplant flask equipped with a condenser, and 1.25 g of sodium hydroxide, 30 mL of ethanol and 5.5 mL of water were added, and the mixture was heated to reflux for 24 hours. The obtained solution was returned to room temperature, acidified with 5N hydrochloric acid, extracted with 100 mL of diethyl ether, washed with 100 mL of water, and dried over magnesium sulfate. The solution was distilled off under reduced pressure to obtain 1.67 g (yield 67%) of 5-methyl-4-hexenoic acid.

Example 3
The olfactory thresholds of the synthesized medium chain fatty acids (carboxylic acid (1) and isovaleric acid) were measured, and their odor intensity was objectively evaluated.
(Threshold measurement method)
H. Boelens et al. (H. Boelens et al; Perfumer & Flavoerist, 8 (1983), 71-74
), The headspace threshold value of the concentration in the solution was measured.
Specifically, 250 mL each of a sample with a specific concentration is put into three glasses, and the presence or absence of odor is determined by smelling this by a plurality of specialized panelists. An expert panelist determines the odor of samples at several concentrations, and measures the relationship between the concentration and the concentration of panelists who determine that there is odor. At this time, a concentration at which more than half of the samples are judged to have odor was determined as a threshold value.
As a result, as shown in Table 2, carboxylic acid (1) has a low odor threshold equivalent to or higher than that of isovaleric acid used as a comparative control, and it can be seen that odor is strongly felt even at low concentrations. It was.

Example 4
In order to confirm how much carboxylic acid (1) was actually attached to clothing and how much it was recognized as odor, the following experiment was conducted.
A 10 g piece of towel was provided with 1 mL of a medium-chain fatty acid (carboxylic acid (1) or isovaleric acid) diluted with acetone having a constant concentration, and then dried at room temperature for 10 minutes to dry only the acetone. Then, about these medium chain fatty acid impregnation towels, three special panelists judged odor intensity | strength by sensory evaluation. The sensory evaluation is performed in the following six stages, and the average value is shown in Table 3.

5: Smells very strongly 4: Smells strongly 3: Smells clearly 2: Smells slightly 1: Slightly smells 0: Does not smell

  As a result of the evaluation, 4-methyl-3-hexenoic acid having the strongest odor intensity was recognizable as odor at 100 ppt (concentration in towel) or more, and very strong odor was felt at about 1 ppb.

Example 5
To evaluate how much the odor quality of carboxylic acid (1) is reminiscent of a dry odor, we prepared a towel containing 10ppm medium chain fatty acid (carboxylic acid (1) or isovaleric acid) in the cloth and sensory evaluation did. Production of a medium chain fatty acid impregnated towel was carried out in accordance with Example 4 (10 g towel pieces were impregnated with 1 mL of a 100 ppm acetone solution of medium chain fatty acid and dried at room temperature for 10 minutes to evaporate acetone). After that, three expert panelists evaluated the towel pieces. The sensory evaluation was performed in the following 6 stages, and the average value was taken. At the same time, the quality of odor was evaluated. These results are shown in Table 4.

5: Extremely strong, feels a dry odor 4: Strongly feels a dry odor 3: Feels a clear odor, 2: Feels a little dry odor 1: Feels a little odor, 0: Does not feel a odor

  As a result of evaluation, each of the products of the present invention as a single compound was reminiscent of a raw dry odor, and 4-methyl-3-hexenoic acid had the strongest odor of raw dry odor. In addition, 4-methyl-3-hexenoic acid was further recognized as an odor of raw dry odor by mixing an equal amount of isovaleric acid.

Examples 6 to 9 and Comparative Example 1
The simulated raw dry odor (room-dried odor) composition shown in Table 5 was prepared, and sensory evaluation was performed based on the following evaluation method. The content of each component in Table 5 is mass%.

(Evaluation method)
In a room kept at room temperature (25 ° C) and humidity of 65%, each simulated fresh dry odor composition was diluted 1000 times with ion-exchanged water into a 5 x 5 cm unused towel (made of cotton). 0.1 mL was applied. About how close the smell of this towel is to the dry-smelling odor, 10 expert evaluations (10: very dry-smelling odors to 1: not dry-smelling odors) were performed by 4 expert evaluators, and the average The values are shown in Table 5.

Claims (2)

A group consisting of a carboxylic acid derivative obtained by extracting a raw odor component from a textile product and introducing an atom or an atomic group into the carboxy group of the carboxylic acid represented by the following general formula (1) contained in the extract. raw dry odor determining how to analyze at least one of an amount selected from.

[Wherein, R ¹ and R ² each represent a hydrogen atom or a methyl group, and a broken line indicates that it may be a double bond, at least one of which is a double bond. ] Use at least one selected from the following formulas (1) consisting of carboxylic acids and carboxylic acid derivatives into a carboxy group obtained by introducing an atom or atomic group of the carboxylic acid represented by the group, the textile treating agent Effectiveness judgment method for raw dry odor.

[Wherein, R ¹ and R ² each represent a hydrogen atom or a methyl group, and a broken line indicates that it may be a double bond, at least one of which is a double bond. ]

Images