JP5051775B2 - Perfume-releasing substance or odorant-releasing substance derivatized with a photolabile protecting group - Google Patents

Description

  The present invention relates to a fragrance-releasing substance or odorous substance-releasing substance derivatized with a photolabile protecting group and a method for generating a fragrance or odorous substance locally.

  As a system for generating a fragrance material locally, a system that encloses a fragrance material in a capsule and breaks the capsule to release the fragrance material is described in Patent Document 1, and a scent suitable for an image is supplied. It is disclosed.

  Patent Documents 2 to 6 are known for releasing a fragrance or a fragrance substance by light irradiation.

Furthermore, Patent Document 7 discloses a physiologically active peptide having a photosensitive group that can be removed by ultraviolet irradiation.
JP 09-327506 Special table 2004-513217 Special table 2005-502768 JP2001-303091 JP2002-20783 Special Table 2004-537520 Japanese Patent No.2863834

  An object of the present invention is to provide a technique for generating an aroma component when necessary.

  When the present inventor introduced a photolabile protecting group into a fragrance substance (fragrance, odor substance), a substance in which the odor of the fragrance substance was suppressed was obtained. It was clarified that when this was irradiated with light, the odor of the aromatic substance was recovered and the odor could be controlled by light.

The present invention provides the following perfume-releasing substance or odorant-releasing substance and a method for generating a perfume locally.
Item 1. Substance for releasing aldehyde or ketone perfume represented by general formula (I):

(Wherein R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, an amino group, a halogen atom, a hydroxyl group or a cyano group, or R ¹ , R ² and Any two of R ³ together represent a methylenedioxy group, Y ¹ is a divalent group in which Y ¹ ═O represents an aldehyde or ketone fragrance.)
Item 2. Substance for releasing amine or thiol odorant represented by general formula (II)

(In the formula, X represents OCO. N represents 0 or 1.

Z is a group in which Z-H represents a fragrance or an amine or thiol odor substance, and R ¹ , R ² and R ³ are the same or different and are a hydrogen atom, a lower alkyl group, a lower alkoxy group, an amino group,
Represents a halogen atom, a hydroxyl group or a cyano group, or any one of R ¹ , R ² and R ³
Together represent a methylenedioxy group. R represents a hydrogen atom or a methyl group. )
Item 3. A method for generating a fragrance locally, which comprises irradiating a compound of the following general formula (I) with light:

(Wherein R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, an amino group, a halogen atom, a hydroxyl group or a cyano group, or R ¹ , R ² and Any two of R ³ together represent a methylenedioxy group, Y ¹ is a divalent group in which Y ¹ ═O represents an aldehyde or ketone fragrance.)
Item 4. A method for locally generating an odorous substance, which comprises irradiating a compound of the following general formula (II) with light:

(In the formula, X represents OCO. N represents 0 or 1.

Z is a group in which ZH represents a fragrance or an amine or thiol odor substance, and R ¹ , R ²
, R ³ are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, an amino group,
Represents a halogen atom, a hydroxyl group or a cyano group, or any one of R ¹ , R ² and R ³
Together represent a methylenedioxy group. R represents a hydrogen atom or a methyl group. )

Specifically, the present invention provides a fragrance-releasing substance or odorant-releasing substance that can be used for the following applications, and a method for locally generating a fragrance / odorant:
・ Odor display (smells corresponding to the screen appear from the display of TV / PC etc. in cooking programs)
・ Scented e-mail (a signal is sent from a computer to generate a smell)
・ Environmental fragrances and desk mats at workplaces and toilets (light is irradiated when necessary)
-Crime ball spray (Smell occurs continuously. Easy tracking by police dogs)
・ Air freshener for events 1 (A large number of people can feel the smell at the same time by a wide range of light irradiation)
・ Event fragrance 2 (smell changes instantly by light irradiation over a wide area)
・ Notepaper (Odor substance is retained before opening)
・ Ink (printed on the package of sweets)
・ Sunburn warning sheet (A is attached to the top of the eaves of the hat, B is attached to the bottom, and the odor type is changed from A to warning, B to alarm)
・ Ultraviolet sensor (notifies dangerous ultraviolet rays by smell)
・ Quality control (examine UV exposure history)
・ Tool for odor determination test (light is irradiated when necessary)
・ Research reagents for olfactory research (light irradiation when necessary)
Also, play equipment such as game machines, video games, laptop computers, desktop computers, televisions, radios, mobile phones, portable music players, or medical equipment measuring devices that measure blood pressure, brain waves, pulse, pulse waves, body temperature, etc. In cooperation, specific fragrances or odorous substances can be released depending on the situation.

  In the present invention, by irradiating light according to the surrounding situation or according to the image or sound (music) or information, a scent suitable for the situation of the place is generated, or the scent that affects the human physical condition, emotion, or mood Can be released.

  Specifically, the fragrance release substance or odor substance release substance obtained by derivatizing the fragrance or odor substance with a photocleavable group is irradiated with light to release the fragrance or odor substance.

  In the present invention, the photocleavable group has any structure of an optionally substituted o-nitrobenzyl group, an optionally substituted o-nitrobenzyloxy group, and an o-nitrobenzyloxycarbonyl group, It has an o-nitrobenzyl moiety in common. Further, it may be bonded to a carrier via a substituent of an o-nitrobenzyl moiety (photolabile linker) (FIG. 1).

In the present invention, a caged compound is used as a fragrance-releasing substance or an odorous substance-releasing substance. The caged compound means a compound in which a photolabile protecting group is bonded to any one of the hydroxyl group, thiol group, amino group, carbonyl group (aldehyde or ketone), or carboxyl group of the fragrance compound / odor substance. Examples of the perfume-releasing substance of the present invention include compounds of the following formulas (I) and (II):

(Wherein R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, an amino group, a halogen atom, a hydroxyl group or a cyano group, or R ¹ , R ² and Any two of R ³ together represent a methylenedioxy group, Y ¹ is a divalent group in which Y ¹ ═O represents an aldehyde or ketone fragrance.)

(In the formula, X represents OCO. N represents 0 or 1.
Z is a group in which Z-H represents a fragrance or an amine or thiol odor substance, and R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, an amino group, a halogen atom It represents an atom, a hydroxyl group or a cyano group, or any ^{two of} R ¹ , R ² and R ³ together represent a methylenedioxy group. R represents a hydrogen atom or a methyl group. ) Is represented.

In the general formulas (I) and (II), examples of the lower alkyl group represented by R ¹ , R ² , and R ³ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert -C1-C4 linear or branched alkyl groups, such as butyl, are mentioned.

Examples of the lower alkoxy group include linear or branched alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy and the like. .
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In a preferred embodiment of the present invention, Z is bonded to X or CH via a heteroatom such as O, N, S or the like of the fragrance material when ZH is a fragrance material, and is an amine odor material. Is bonded to X or CH through the nitrogen atom of the amine, and in the case of a thiol-based odor substance, it is bonded to X or CH through the sulfur atom of the thiol, and any one of R ¹ , R ² and R ³ is It may be fixed to a carrier.

Preferred groups of the formulas (I) and (II) are such that any ^{two of} R ¹ , R ² and R ³ are hydrogen atoms, the remaining one is a hydrogen atom, a lower alkyl group or a lower alkoxy group, and R is a hydrogen atom. , N is 0 or 1, and Z is a group in which Z-H represents a fragrance or an amine or thiol odor substance.
1) Outline of synthesis of fragrance-releasing substance or odorous substance-releasing substance By introducing a photolabile protecting group into the hydroxyl group, carboxyl group, thiol group or amino group of the fragrance compound or odorous substance, the intended fragrance-releasing substance Substances or substances for releasing odorous substances (caged compounds) can be synthesized.

In Scheme 1, the reaction is carried out using an excess amount of diol of formula (IA) from 0.3 mol to 1 mol of ketone or aldehyde-based fragrance, and optionally in the presence of a catalyst and a solvent at 0 ° C to 100 ° C.
The reaction proceeds advantageously by reacting at about 10 ° C. for about 10 minutes to 24 hours. As a catalyst, the catalyst normally used for manufacture of acetals and ketals, such as p-toluenesulfonic acid and methanesulfonic acid, can be used. Examples of the solvent include benzene, toluene, hexane, chloroform, methylene chloride, ethyl acetate, acetonitrile and the like.

In Scheme 2, the reaction consists of 1 compound of formula (IIA) per mole of fragrance or odorant.
The reaction proceeds advantageously by using an excess amount from a mole and reacting at a temperature of about 0 ° C. to 100 ° C. for about 10 minutes to 24 hours.

  Examples of the leaving group include a halogen atom, a tosyl group, and a mesyl group.

In the fragrance-releasing substance or odorous substance-releasing substance of the present invention, the photolabile protecting group of the formula (II) is eliminated by irradiation with ultraviolet rays to produce a fragrance compound or odorous substance. As the wavelength of ultraviolet rays,
280-400 nm is mentioned. Since a fragrance compound is generated as long as light of this wavelength is contained, the ultraviolet light source may be a light source for ultraviolet irradiation such as a UV lamp, a high-pressure mercury lamp, and a low-pressure mercury lamp. Even light containing a large amount of visible light can be used for elimination of a photolabile protecting group as long as ultraviolet light is contained.

  The method for locally generating a fragrance or odor substance of the present invention will be described. First, at least one fragrance-releasing substance or odorous substance-releasing substance is applied or carried on the surface of a support such as a card, disk, floor, ceiling, wall (wallpaper) having a predetermined size. The support may be included in the support, and the substance for releasing the fragrance or the substance for releasing the odorant is adsorbed on powder, particles, beads, etc. of silica, alumina, activated carbon, polymer, etc., and this carrier is adsorbed on the support. Fix by bonding or kneading into polymer. A perfume-releasing substance or odorous substance-releasing substance may be covalently bound as part of the polymer.

  As a material for the support, synthetic polymers such as synthetic resins are mainly used, but natural polymers, metals, cardboard, woven fabrics, non-woven fabrics, wood, or composite materials thereof can be used as necessary. Application on the support may be performed by adsorption or by a binder. Alternatively, a sheet / film carrying a fragrance-releasing substance or an odorous substance-releasing substance may be affixed on a support or may be a component of a coating film.

  Light irradiation to the fragrance-releasing substance or odorous substance-releasing substance may be performed by moving the light of the light source to irradiate ultraviolet rays at a specific position on the support. Or the position on the support where the light source reaches may be changed by moving the optical element (slit, lens, etc.) of the light from the light source.

  Only one perfume releasing substance or odor substance releasing substance may be applied on the support, but two or more fragrance releasing substances or odor substance releasing substances may be used alone or as a mixture. Applying above, it is preferable to change the type of odor generated by changing the position of light irradiation. On the support, a mixture of two or more, for example, several to several tens or hundreds of fragrance source materials can be applied, and the scent can be arbitrarily changed depending on the position of light irradiation. As a mixture of a fragrance-releasing substance or a odorous substance-releasing substance, the fragrance compound produced by light irradiation is used to create an environment such as forest scent, grassy scent, soil scent, sea scent, water scent, and flower scent. Or a scent related to foods and cosmetics such as spices, various foods, and various flavors.

  Light irradiation is controlled to convert information sent by radio waves, microwaves, etc. from the Internet, mobile phones, TVs, radios, etc. into electrical signals, and thereby irradiate light at specific positions on the support. The position of light irradiation can be controlled via the mechanism. Alternatively, in an event venue or the like, light may be irradiated over a wide range according to the atmosphere of the place.

  As an electric signal input means for controlling the position of light irradiation, manual switching may be used, but operation of keyboards or buttons of game machines, video games, personal computers, mobile phones, special symbols such as pictograms, It is preferable to systematize so that light irradiation can be automatically controlled based on character information in digital television.

  The scent generated by the light irradiation may be diffused as it is, but it is preferable to release the scent generated by the blower or the heat generating device at the light irradiation position so that the scent is immediately felt. You may change the kind of fragrance by irradiating light simultaneously to two or more places.

Hereinafter, the present invention will be described in more detail based on examples.
Example 1) Synthesis of caged cinnamaldehyde In an eggplant flask (100 mL), 0.66 g (5 mmol) of cinnamaldehyde, 1.83 g (10 mmol) of 1- (2-nitrophenyl) ethane-1,2-diol, 0.075 g (0.39 mmol) of paratoluenesulfonic acid monohydrate and 50 mL of benzene were added, and the mixture was heated to reflux for 24 hours while dehydrating the reflux solvent. After allowing to cool, the solvent was distilled off, and fractions containing the desired product were collected by GPC. Yield 45% (calculated from GPC peak area). White waxy solid. ¹ H-NMR (CDCl ₃ , 500 MHz); δ: 3.87 (1H, d, O—CH—O), δ: 4.68 (1H, t, OC H —CH ₂ ), δ: 5.74 (2H, d, OC H ₂ -CH), δ: 6.35 (1H, m, CH = C H -CH),
δ: 6.90 (1H, d, Ar-C H = CH), δ: 7.30-8.13 (9H, m, Ar-H). MS (ESI) [Found M + H +, 298.00. C 17 H 15 NO 4 + H +, 298.10].
Reaction formula

Example 2) Synthesis of caged vanillin 1.52 g (10 mmol) 4-hydroxy-3-methoxybenzaldehyde, 0.92 g (5 mmol) 1- (2-nitrophenyl) ethane-1 in an eggplant flask (100 mL) , 2-diol, 0.075 g (0.39 mmol) of paratoluenesulfonic acid monohydrate and 50 mL of benzene were added, and the mixture was heated to reflux for 24 hours while dehydrating the reflux solvent. After allowing to cool, the solvent was distilled off, and fractions containing the desired product were collected by GPC. Yield 24% (calculated from GPC peak area). Black brown solid. ¹ H-NMR (CDCl ₃ , 500 MHz); δ: 1.60 (1H, br, —OH), δ: 3.94 (3H, s, —O—CH ₃ ), δ: 4.66 (1H, t, CH ₂ —C H -O), δ: 5.76 (2H, d, -CH _2- ),
δ: 5.93 (1H, s, O—CH—O), δ: 6.95 to 7.16 (3H, m, Ar—H), δ: 7.48-8.15 (4H, m, NO ₂ —Ar—H). MS (ESI) [Found M + H ⁺ , 318.13. C ₁₆ H ₁₅ NO ₆ + H ⁺ , 318.09].
Reaction formula

Example 3) Synthesis of caged menthone In an eggplant flask (100 mL) 0.77 g (5 mmol) menthone, 1.83 g (10 mmol) 1- (2-nitrophenyl) ethane-1,2-diol, 0.075 g (0.39 mmol) of paratoluenesulfonic acid monohydrate and 50 mL of benzene were added, and the mixture was heated to reflux for 24 hours while dehydrating the reflux solvent. After cooling, the solvent was distilled off and GPC
The fraction containing the target product was fractionated. Yield 47% (calculated from weight). Pale green waxy solid. ¹ H-NMR (CDCl ₃ , 500 MHz); δ: 0.88 (6H, d, C H ₃ —CH—C H ₃ ), δ: 0.95 (3H, d,> CH—C H ₃ ), δ: 1.18- 2.47 (9H, m, C H ₂ -C H -C H ₂ -C H ₂ -C H- , CH ₃ -C H -CH ₃ ), δ: 3.48-4.62 (2H, m, OC H ₂ ), δ: 5.51 (1H, t, CH 2 -C H -O), δ: 7.46-8.07 (4H, m, Ar-H). MS (ESI) [Found M + H ⁺ , 320.13. C ₁₈ H ₂₅ NO ₄ + H ⁺ , 320.18].
Reaction formula

Example 4) Synthesis of caged octadecyl mercaptan 0.29 g (1 mmol) octadecyl mercaptan, 1.08 g (5 mmol) 2-nitrobenzyl bromide, 0.212 g (2 mmol) sodium carbonate, 50 mL in an eggplant flask (100 mL) Of dry acetonitrile was added and heated to reflux for 24 hours. After cooling, the solid was filtered and the solvent was distilled off. Fractions containing the desired product were collected by GPC. Crude yield 81% (100% reaction rate of octadecyl mercaptan
As calculated from the GPC peak area). Black brown solid. ¹ H-NMR (CDCl ₃ , 500 MHz); δ: 0.88 (3H, t, CH ₃ ), δ: 1.25-1.31 (28H, br, -CH _2- ), δ: 1.49-1.56 (2H, br,- C H ₂ CH ₂ S), δ: 2.43 (2H, t, -CH ₂ S-), δ: 4.05 (2H, s, Ar-CH ₂ ), δ: 7.39-7.96 (4H, m, Ar-H ). MS (EI) [Found M ⁺ , 421.30. C ₂₅ H ₄₃ NO ₂ S, 421.30]
Reaction formula

Example 5) Synthesis of caged ethyl mercaptan 0.31 g (5 mmol) of ethyl mercaptan, 0.28 g (1 mmol) of 4,5-dimethoxy-2-nitrobenzyl chloroformate, 0.32 g in an eggplant flask (100 mL) (3 mmol) sodium carbonate and 50 mL of dry acetonitrile were added and stirred at room temperature for 12 hours. Thereafter, the mixture was heated to reflux for 0.5 hours, allowed to cool, and then the solvent was distilled off. Fractions containing the desired product were collected by GPC. Yield 70% (calculated from GPC peak area: Chloroformate standard). Pale yellow solid. ¹ H-NMR (CDCl ₃ , 500 MHz);
δ: 1.34 (3H, t, CH ₃ ), δ: 2.92 (2H, q, -CH ₂ S-), δ: 3.96 (3H, s, OCH ₃ ), δ: 3.99 (3H, s, OCH ₃ ) , δ: 5.67 (2H, s, Ar—CH ₂ —), δ: 7.01 (1H, s, Ar—H), δ: 7.74 (1H, s, Ar—H). ^{MS (EI) [Found M +} , 301.06. C 12 H 15 NO 6 S, 301.06].
Reaction formula

Example 6) Synthesis of caged piperidine (MNF) 0.43 g (5 mmol) piperidine, 0.28 g (1 mmol) 4,5-dimethoxy-2-nitrobenzyl chloroformate, 50 mL in an eggplant flask (100 mL) Of dry acetonitrile and stirred for 12 hours at room temperature. Thereafter, the mixture was heated to reflux for 0.5 hours, allowed to cool, and then the solvent was distilled off. Fractions containing the desired product were collected by GPC. Crude yield 100% (calculated from GPC peak area: chloroformate basis). Yellow crystalline solid. ¹ H-NMR (CDCl ₃ , 500 MHz); δ: 1.54-1.65 (6H, m, —CH ₂ —CH ₂ —CH ₂ —), δ: 3.48 (4H, s, —CH ₂ N—), δ: 3.96 (3H, s, OCH ₃ ), δ: 3.97 (3H, s, OCH ₃ ), δ: 5.53 (2H, s, Ar-CH _2- ), δ: 6.99 (1H, s, Ar-H), δ: 7.70 (1H, s, Ar-H). MS (ESI) [Found M + H ⁺ , 325.00. C ₁₅ H ₂₀ N ₂ O ₆ + H ⁺ , 325.13].
Reaction formula

Example 7) Synthesis of caged piperidine (NB) 1.7 g (20 mmol) of piperidine, 1.2 g (5 mmol) of 2-nitrobenzyl bromide and 50 mL of dry acetonitrile were placed in an eggplant flask (100 mL) for 24 hours. Heated to reflux. After allowing to cool, the solvent was distilled off, and fractions containing the desired product were collected by GPC. Yield 48% (calculated from GPC peak area: benzyl bromide standard). Yellow viscous liquid. ¹ H-NMR (CDCl ₃ , 500 MHz); δ: 1.44-1.60 (6H, m, —CH ₂ —CH ₂ —CH ₂ —), δ: 2.44 (4H, s, —CH ₂ N—), δ: 3.82 (2H, s, Ar—CH ₂ —), δ: 7.28-7.83 (4H, m, Ar—H). MS (ESI) [Found M + H ⁺ , 221.20. C ₁₂ H ₁₆ N ₂ O ₂ + H ⁺ , 221.12].
Reaction formula

Example 8) Synthesis of caged benzaldehyde 3.18g (30mmoL) benzaldehyde, 1.83g (10mmoL) 1- (2-nitrophenyl) ethane-1,2-diol, 0.075g in eggplant flask (100mL) (0.39 mmoL) of paratoluenesulfonic acid monohydrate and 50 mL of benzene were added, and the mixture was heated to reflux for 24 hours while dehydrating the reflux solvent. After allowing to cool, the solvent was distilled off, and fractions containing the desired product were collected by GPC. Yield 40% (calculated from GPC peak area). Pale yellow waxy solid. ¹ H-NMR (CDCl ₃ , 500 MHz); δ: 3.77 (1H, dd, O—CH ₂ —), δ
: 3.97 (1H, dd, O-CH _2- ), δ: 5.66 (1H, t, Ar-C H -CH ₂ ), δ: 5.90 (1H, s, O-CH-O), δ
: 7.34-8.04 (9H, m, Ar-H). MS (EI) [Found (M-1) ⁺ , 270.08. C ₁₇ H ₁₅ NO ₄ -H ⁺ , 270.08]. Reaction formula

Example 9) Synthesis of ethyl caged glycolate Into an eggplant flask (100 mL), 1.53 g (10 mmol) of 2-nitrobenzyl alcohol and 50 mL of dry hexane were added, and 0.5 g (21.7 mmol) of metallic sodium chopped while stirring was added. . The suspension was stirred for 3 hours at room temperature, and a solution obtained by dissolving 1.67 g (10 mmol) of ethyl bromoacetate in 10 mL of dehydrated hexane was added dropwise to the suspension. The solution was heated to reflux for 12 hours, allowed to cool, and the solid was filtered off. The filtrate was collected and the solvent was distilled off. After dissolving in chloroform, the fraction containing the desired product was collected by GPC. Yield 77% (calculated from GPC peak area). Colorless liquid. ¹ H-NMR (CDCl ₃ , 500 MHz); δ
: 1.30 (3H, t, -CH ₃ ), δ: 4.25 (2H, q, OC H ₂ -CH ₃ ), δ: 4.25 (2H, s, O-CH ₂ -CO), δ: 5.02 (2H, _{s, Ar-CH 2 -)} , δ: 7.32-8.08 (4H, m, Ar-H). MS (ESI) [Found M + Na ⁺ , 262.27.
_{C 11 H 13 NO 5 + Na} +, 262.07].
Reaction formula

Example 10) Sensory test A 6 mm diameter filter paper was impregnated with the sample chloroform solution (9 types), placed in a separate sample bottle (10 mL), and then air-dried.
2. The sample bottle containing the filter paper was smelled, and the odor intensity was evaluated in four stages (−, ±, +, ++).
3. Using an ultraviolet irradiation device, ultraviolet rays having a wavelength of 365 nm were irradiated from about 5 cm above the sample bottle for 30 seconds. *
4). Again, the smell of the sample bottle containing the filter paper was sniffed, and the odor intensity was evaluated in four levels. 5. Along with changes in odor intensity, we also examined changes in odor itself. The results are shown in Table 1.
* The intensity of the UV light applied to the sample is about 30 times the amount of UV light in a clear daytime.

Experimental Example 1) Light irradiation experiment 1- (2-Nitrophenyl) ethane-1,2-diol was added to caged benzaldehyde in chloroform as an internal standard, and the same amount was dispensed into three sample bottles A, B and C.
2. The solution in sample bottle A was analyzed by GPC (exclusion molecular weight 2000).
3. Using an ultraviolet irradiation device, a wavelength of 365 nm for 5 minutes from about 5 cm above sample bottle B
The ultraviolet rays were irradiated. The solution after irradiation was similarly analyzed by GPC.
4). Using an ultraviolet irradiation device, a wavelength of 365 nm for 10 minutes from about 5 cm above sample bottle C
The ultraviolet rays were irradiated. The solution after irradiation was similarly analyzed by GPC.
5. The results of GPC analysis of A to C were normalized with the peak area of the internal standard, and compared with the results of GPC analysis of benzaldehyde preparations.

From this light irradiation experiment, the formation of benzaldehyde was confirmed by irradiating the caged benzaldehyde with light (FIG. 2).
* The intensity of the UV light irradiated on the sample is approximately 30 times the amount of UV light on a clear day.

Odor substance is immobilized on a polymer carrier via a photolabile linker (linker having o-nitrobenzyl moiety) Light irradiation experiment of caged benzaldehyde. Vertical axis: absorbance (a.u.). Horizontal axis: Retention time (minutes).

Claims (4)

Substance for releasing aldehyde or ketone perfume represented by general formula (I):

(Wherein R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, an amino group, a halogen atom, a hydroxyl group or a cyano group, or R ¹ , R ² and Any two of R ³ together represent a methylenedioxy group, Y ¹ is a divalent group in which Y ¹ ═O represents an aldehyde or ketone fragrance.) Perfume represented by general formula (II) or amine or thiol odor substance releasing substance

(In the formula, X represents OCO. N represents 0 or 1.
Z is a group in which Z-H represents a fragrance or an amine or thiol odor substance, and R ¹ , R ² and R ³ are the same or different and are a hydrogen atom, a lower alkyl group, a lower alkoxy group, an amino group,
Represents a halogen atom, a hydroxyl group or a cyano group, or any one of R ¹ , R ² and R ³
Together represent a methylenedioxy group. R represents a hydrogen atom or a methyl group. ) A method for generating a fragrance locally, which comprises irradiating a compound of the following general formula (I) with light:

(Wherein R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, an amino group, a halogen atom, a hydroxyl group or a cyano group, or R ¹ , R ² and Any two of R ³ together represent a methylenedioxy group, Y ¹ is a divalent group in which Y ¹ ═O represents an aldehyde or ketone fragrance.) A method for locally generating an odorous substance, which comprises irradiating a compound of the following general formula (II) with light:

(In the formula, X represents OCO. N represents 0 or 1.
Z is a group in which Z-H represents a fragrance or an amine or thiol odor substance, and R ¹ , R ² and R ³ are the same or different and are a hydrogen atom, a lower alkyl group, a lower alkoxy group, an amino group,
Represents a halogen atom, a hydroxyl group or a cyano group, or any one of R ¹ , R ² and R ³
Together represent a methylenedioxy group. R represents a hydrogen atom or a methyl group. )

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