JP2001039971A - Molecular compound containing tri-o-thymotides as constituent compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a molecular compound having new useful properties such as sustained release, decrease of skin irritation, chemical stability, involatity, powderization, selective separation of useful materials or the like other than inherent properties in effective components and useful as a germicide, an antibacterial agent, an insecticide, an insect repellent, a flavor, an antifoulant and a curing agent for epoxy resins. SOLUTION: This molecular compound is obtained by reacting tri-o- thymotides represented by the formula (R1 to R12 are each independently H or a 1-6C straight chain or branched alkyl group; and X is O or S) with a germicide, an antibacterial agent, an antifungal agent, an insecticide, an insect pest-repellent, a flavor, a deodorant, an antifoulant, a curing and accelerating agent for paints, resins and adhesives, a natural essential oil, an antioxidant or a vulcanization accelerator capable of forming a molecular compound with tri-o-thymotides.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel molecular compound containing tri-o-thymotide as a component compound, and more particularly to tri-o-thymotide, a fungicide, an antibacterial agent, and an antifungal agent. , Insecticides, insect repellents, fragrances, deodorants and deodorants, antifouling agents, curing agents and curing accelerators for paints, resins and adhesives, natural essential oils, antioxidants, vulcanization accelerators and other useful substances And a molecular compound having as a component compound.

[0002]

2. Description of the Related Art A molecular compound is a compound in which two or more compounds are bonded by a relatively weak interaction other than a covalent bond represented by a hydrogen bond, van der Waals force, or the like. Since it has the property of dissociating into each component compound, it is expected in recent years to be applied in technical fields such as selective separation of useful substances, chemical stabilization, non-volatization, sustained release, and powdering.

An example of a molecular compound having particularly excellent functions in these technical fields is an inclusion compound.
For example, JP-A-61-53201 discloses that 1,1,
6,6, -tetraphenyl-2,4-hexadiyne-
1,6-diol or 1,1-di (2,4-dimethylphenyl) -2-propyn-1-ol, JP-A-62-2
No. 2701 describes an inclusion compound of 1,1′-bis-2-naphthol and 5-chloro-2-methyl-4-isothiazolin-3-one, respectively. JP-A-3-279373 reports an inclusion compound of a bisphenol compound and an isothiazolone compound. JP-A-6-166646 discloses clathrates of tetrakisphenols with various organic compounds.

Further, Japanese Patent Application Laid-Open No. 11-12256 discloses a molecular compound containing a triazine derivative as a component compound.
JP-A-11-12257 discloses a molecular compound containing a cross-linked triazine derivative as a component compound.
No. 9501 discloses a molecular compound containing a tetrakisphenol derivative as a component compound.
JP-A-11-43448 and JP-A-11-189565 describe a molecular compound having a substituted hydroxydiphenylsulfone as a component compound, and a molecular compound having a phenol derivative as a component compound, respectively. .

On the other hand, for tri-o-thymotides,
Topics in Current Chemistry (Topics i
n Current Chemistry) 140,71 (1987), Journal of Chemical Science (J. Chem. Soc.) 2339 (19)
58), Journal of American Chemical Science (J. Am. Chem. Soc.) 105,4561 (1983), Advances in the Synthesiss and Reactivity of Solids (Advances in the Synthesis) an
d Reactivity of Solids) Vol.1, 81 (1991), “Comprehensive Supramolecular Chemistry“ Comprehe
nsive Supramolecular Chemistry ”” vol 6, Elsevier
Science, UK, 239-280 (1996) describes inclusion of an organic solvent and the like. However, it has not been known to form a molecular compound with a useful substance such as a bactericide, particularly a compound having a low hydrogen bonding property.

[0006]

The object of the present invention is to selectively separate useful substances such as bactericides, chemical stabilization, non-volatization,
It is an object of the present invention to provide a molecular compound having sufficiently satisfactory performance in sustained release, powdering, and the like.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object. As a result, when tri-o-thymotides are used as host compounds, useful substances such as fungicides, especially hydrogen bonding Completed the present invention by finding that a molecular compound formed by using a low compound as a guest compound has extremely excellent performance in selective separation of these useful substances, chemical stabilization, non-volatilization, sustained release, powdering, etc. I came to.

That is, the present invention provides a compound represented by the general formula (I)

Embedded image (Wherein, R ^{1 to} R ¹² are each independently a hydrogen atom, C ₁
Represents a straight-chain or branched alkyl group of -C ₆ , and X represents an oxygen atom or a sulfur atom. ) And a bactericide, an antibacterial agent, an antifungal agent, an insecticide, a pest repellent, a fragrance, a deodorant / deodorant which reacts with the tri-o-thymotide to form a molecular compound. Deodorants, antifouling agents, curing agents and curing accelerators for paints, resins and adhesives, natural essential oils, antioxidants,
The present invention relates to a molecular compound comprising a vulcanization accelerator as a component compound.

Further, the present invention provides a bactericide, antibacterial agent, antifungal agent, insecticide, insect repellent, fragrance, deodorant / deodorant, antifouling agent which reacts with tri-o-thymotides to form a molecular compound. Agents, curing agents and curing accelerators for paints, resins and adhesives, natural essential oils, antioxidants and vulcanization accelerators include, for example, 4-chlorophenyl- (3-iodo) propargyloxymethyl ether, 2,3,3 -Triiodoallyl alcohol, 2,
4,5,6-tetrachloroisophthalonitrile, 5-chloro-2,4,6-trifluoroisophthalonitrile,
3-iodopropargyl = N-butyl carbamate,
2,3,5,6-tetrachloro-4-methanesulfonylpyridine, 2,2-dithio-bis- (pyridine-1-oxide), 3,5-dichloro-1,2-dithiolane-
The present invention relates to the above molecular compound, comprising a compound having a low hydrogen bonding property such as 3-one.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The molecular compound of the present invention has the general formula (I) wherein R ^{1 to} R ¹² are each independently a hydrogen atom, a C _{1 to} C ₆ linear or branched alkyl. X represents a group
Represents an oxygen atom or a sulfur atom. ) Represented by
o-Timotides and fungicides, antibacterial agents, antifungal agents, insecticides, pest repellents, fragrances, deodorants / deodorants, antifouling agents which form molecular compounds by reacting with the tri-o-thymotides ,paint·
It is characterized in that a curing agent and a curing accelerator for resins and adhesives, a natural essential oil, an antioxidant, and a vulcanization accelerator are used as component compounds.

In the present invention, a molecular compound is a compound which can exist stably by itself when two or more kinds of component compounds are relatively weakly interacting other than a covalent bond represented by a hydrogen bond, van der Waals force, or the like. Means hydrates, solvates, adducts, clathrates and the like.

The tri-o-thymotide used in the present invention is represented by the above general formula (I), wherein R ^{1 to} R ¹²
Each independently represents a hydrogen atom, a C ₁ -C ₆ linear or branched alkyl group, and X represents an oxygen atom or a sulfur atom, and X represents a C ₁ -C ₆ linear or branched alkyl group. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert
-Butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, isohexyl, 1-methylpentyl, 2-methylpentyl and the like.

The tri-o-thymotides used in the present invention include, for example, Journal of Organic Chemicals.
It can be synthesized by the method described in Chemistry (J. Org. Chem.) 56, 4525-4529 (1991). Specifically, salicylic acid derivatives or o-mercaptobenzoic acid derivatives can be synthesized with POCl _3.
Can be produced by reacting in the presence of

Specific examples of the tri-o-thymotides represented by the general formula (I) thus obtained include the tri-o-thymotide, tri-o-carbaclotide, and tris-3 listed in Table 1. -(2-butyl) -6-methylsalicylide, tri-o-thiothymotide and the like can be mentioned. In Table 1, Me represents a methyl group, iPr represents an isopropyl group, and Bu represents a butyl group.

[0015]

[Table 1]

In the present invention, useful compounds found as substances forming molecular compounds with tri-o-thymotides include fungicides, antibacterial agents, antifungal agents, insecticides, insect repellents, fragrances, deodorants, etc. Deodorants, antifouling agents, curing agents and curing accelerators for paints, resins, adhesives, natural essential oils, antioxidants,
Vulcanization accelerators can be mentioned, and more specifically, the following substances can be mentioned.

As bactericides, 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2-
Alcohols such as nitroethanol and 2,3,3-triiodoallyl alcohol, 4-chlorophenyl = (3-
Ethers such as iodo) propargyl ether, 4-chlorophenyl = (3-iodo) propargyloxymethyl ether, ketones such as 2-bromo-4'-hydroxyacetophenone, 2,2-dibromomethylglutarnitrile, 2, Nitriles such as 4,5,6-tetrachloroisophthalonitrile, 5-chloro-2,4,6-trifluoroisophthalonitrile, 1,2-dibromo-2,4-dicyanobutane, dibromonitrilepropionamide Amides such as 2,2-dibromo-3-nitrilopropionamide, N, N-diethyl-m-toluamide, and 3-iodopropargyl = N-butylcarbamate;
Phenols such as -chloro-m-cresol, N, N-
Urea such as dimethyldichlorophenylurea, disulfides such as tetramethylthiuram disulfide, phenyl-
Sulfones such as (2-cyano-2-chlorovinyl) sulfone, hexabromodimethyl sulfone, diiodomethyl paratolylsulfone, thiocyanic acid and isothiocyanic acid such as methyl thiocyanate and methyl isothiocyanate, methylene bisthiocyanate, methylene Thiocyanates such as bisisothiocyanate and isothiocyanates, tris (hydroxymethyl)
Nitro compounds such as nitromethane, 2,3,5,6-tetrachloro-4-methanesulfonylpyridine, 2,2-
Dithio-bis- (pyridine-1-oxide), N-methylpyrrolidone, methyl 2-benzimidazolecarbamate, sodium 2-pyridinethiol-1-oxide, hexahydro-1,3,5-tris (2-hydroxyethyl) -S-triazine, hexahydro-1,3,
5-triethyl-s-triazine, 2-methylthio-4
-T-butylamino-6-cyclopropylamino-s-
Nitrogen-containing heterocyclic compounds such as triazine, N- (fluorodichloromethylthio) phthalimide, 1-bromo-3-chloro-5,5-dimethylhydantoin, 2-methoxycarbonylbenzimidazole, and 2,4,6-trichlorophenylmaleimide; 5-methyloxazolidine, 4-
Nitrogen-containing and oxygen-heterocyclic compounds such as (2-nitrobutyl) morpholine and 4,4 ′-(2-ethyl-2-nitrotrimethylene) dimorpholine; 3,3,4,4-tetrahydrothiophene-1,1-di Oxide, 4,5-dichloro-1,2-dithiolan-3-one, 5-chloro-4-
Phenyl-1,2-dithiolan-3-one, 3,3
4,4-tetrachlorotetrahydrothiophene-1,1
Sulfur-containing heterocyclic compounds such as -dioxide, 5-chloro-2
-Methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,5-dichloro-
3-n-octylisothiazolin-3-one, 2-octyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2-thiocyanomethylbenzothiazole, 2- (4-thiazolyl) benz Specific examples include nitrogen-containing and sulfur heterocyclic compounds such as imidazole and 2-thiocyanomethylbenzothiazole.

Examples of natural essential oils include steroids such as cholesterol, alkaloids such as brucine, quinine and theophylline, cineole, hinokitiol, menthol, terpineol, borneol, nopol, citral, citronellol, citronellal, geraniol, menthon, eugenol, linalool. , Dimethyloctanol, etc., as synthetic flavors,
Specific examples of jasmine, lemon and the like and vitamins and their related compounds include ascorbic acid, nicotinic acid, nicotinamide and the like.

Examples of curing agents and curing accelerators for paints, resins and adhesives include amines, imidazoles, amides, esters, alcohols, thiols, ethers, thioethers, phenols, phosphorus, and urea. And thiourea-based, acid anhydride-based, Lewis acid-based, onium salt-based, active silicon compound-aluminum complex-based compounds, and more specifically, the following compounds.

As the amine compound, ethylenediamine, trimethylenediamine, tetramethylenediamine,
Hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, dimethylaminopropylamine, diethylaminopropylamine, trimethylhexamethylenediamine, pentanediamine, bis (2-dimethylaminoethyl) ether, pentamethyldiethylenetriamine, Alkyl-t-monoamine, 1,4-diazabicyclo (2,2,2) octane (triethylenediamine), N, N, N ', N'-tetramethylhexamethylenediamine, N, N, N', N'- Fats such as tetramethylpropylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N-dimethylcyclohexylamine, dimethylaminoethoxyethoxyethanol, dimethylaminohexanol Amine or, piperidine, piperazine, menthane diamine, isophorone diamine, methylmorpholine, ethylmorpholine, N,
N ′, N ″ -tris (dimethylaminopropyl) hexahydro-s-triazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) undecane adduct, N -Aminoethylpiperazine, trimethylaminoethylpiperazine, bis (4
Alicyclic and heterocyclic amines such as -aminocyclohexyl) methane, N, N'-dimethylpiperazine and 1,8-diazabicyclo (4,5,0) undecene-7;
Phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, pyridine,
Aromatic amines such as picoline, modified polyamines such as epoxy compound-added polyamine, Michael-added polyamine, Mannich-added polyamine, thiourea-added polyamine, ketone-blocked polyamine, and others, dicyandiamide, guanidine, organic acid hydrazide, diaminomaleonitrile And amine imides, amines such as boron trifluoride-piperidine complex and boron trifluoride-monoethylamine complex.

Examples of the imidazole compounds include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-n-propylimidazole, 2-undecyl-1H-imidazole,
2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-1H-imidazole, 4-methyl-
2-phenyl-1H-imidazole, 2-phenyl-4
-Methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2 -Phenylimidazole, 1
-Cyanoethyl-2-ethyl-4-methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2
-Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]
-Ethyl-s-triazine, 2,4-diamino-6
(2′-undecylimidazolyl-)-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4
-Imidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole Isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct,
2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,
5-di (2-cyanoethoxy) methylimidazole, 1
Specific examples thereof include -dodecyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenylimidazole hydrochloride, 1-benzyl-2-phenylimidazolium trimellitate and the like.

Examples of the imidazoline compound include, for example, 2
-Methylimidazoline, 2-phenylimidazoline and the like; amide compounds such as polyamides obtained by condensation of dimer acid and polyamine; and ester compounds such as carboxylic acid aryl and thioaryl esters. Active carbonyl compounds and the like can be mentioned. Examples of phenol, alcohol, thiol, ether and thioether compounds include phenol novolak, cresol novolak, polyol, polymercaptan, polysulfide, and 2- (dimethylaminomethylphenol). ),
Examples thereof include 2,4,6-tris (dimethylaminomethyl) phenol and tri-2-ethylhexyl hydrochloride of 2,4,6-tris (dimethylaminomethyl) phenol.

The urea-based, thiourea-based, and Lewis-acid-based curing agents include, for example, butylated urea, butylated melamine, butylated thiourea, and boron trifluoride. Examples of the curing agent include alkyl phosphines such as ethyl phosphine and butyl phosphine; primary phosphines such as phenyl phosphine; dialkyl phosphines such as dimethyl phosphine and dipropyl phosphine;
Organic phosphine compounds such as a second phosphine such as diphenylphosphine and methylethylphosphine, and a third phosphine such as trimethylphosphine and triethylphosphine can be exemplified.

Further, examples of the acid anhydride-based curing agent include phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydroanhydride. Phthalic acid, maleic anhydride, tetramethylene maleic anhydride, trimellitic anhydride, chlorendic anhydride, pyromellitic anhydride, dodecenyl succinic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimellitate), methyl Cyclohexenetetracarboxylic anhydride, polyazellaic anhydride and the like can be mentioned,
Onium salt-based or active silicon compound-aluminum complex-based curing agents include aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, triphenylsilanol-aluminum complexes, triphenylmethoxysilane-aluminum complexes, and silyl peroxide-aluminum complexes. And triphenylsilanol-tris (salicylaldehyde) aluminum complex.

In the molecular compound of the present invention using tri-o-thymotides as a host compound, the above-mentioned bactericide, antibacterial agent, antifungal agent, insecticide, insect repellent, fragrance, deodorant / deodorant as the guest compound , Antifouling agents, hardeners and hardening accelerators for paints, resins and adhesives, natural essential oils, antioxidants, vulcanization accelerators, especially hydrogen bonding properties which have been difficult to encapsulate with conventionally known host compounds Useful compounds such as 4
-Chlorophenyl- (3-iodo) propargyloxymethyl ether, 2,3,3-triiodoallyl alcohol, 2,4,5,6-tetrachloroisophthalonitrile, 5-chloro-2,4,6-trifluoroyl Sophthalonitrile, 3-iodopropargyl = N-butylcarbamate, 2,3,5,6-tetrachloro-4-methanesulfonylpyridine, 2,2-dithio-bis- (pyridine-1-oxide), 3,5 -Dichloro-1,2-dithiolan-3-one and the like, even when these useful substances are selectively separated, chemically stabilized, non-volatile, controlled release,
It has extremely excellent performance in powdering and the like.

The molecular compound of the present invention can be obtained by directly mixing tri-o-thymotide with the useful substance forming a molecular compound with tri-o-thymotide or by mixing them in a solvent. Can be. In the case of a substance having a low boiling point or a substance having a high vapor pressure, a target molecular compound can be obtained by allowing the vapor of these substances to act on tri-o-thymotides. Furthermore, tri-o-
A molecular compound of interest can also be obtained by generating a molecular compound of thymotides and a specific useful substance, and reacting this molecular compound with another useful substance by the method described above.

The molecular compound of the present invention can change the composition of each of the component compounds constituting the molecular compound according to the conditions for its formation, and can react two or more kinds of useful substances with tri-o-thymotides. By doing so, a molecular compound consisting of three or more components can be obtained.

The fact that the substance obtained by these methods is a molecular compound can be confirmed by thermal analysis (TG and DTA), infrared absorption spectrum (IR), X-ray diffraction pattern, solid-state NMR
It can be confirmed by a spectrum or the like. The composition of the molecular compound can be confirmed by thermal analysis, ¹ H-NMR spectrum, high performance liquid chromatography (HPLC), elemental analysis and the like.

The molecular compound of the present invention is used for the purpose of selective separation of useful substances, chemical stabilization, non-volatilization, pulverization, and the like, and for the purpose of stably producing a molecular compound having a constant composition. It is preferably crystalline, and more preferably a crystalline inclusion compound. Although the same molecular compound may be in a polymorphic form, the crystallinity can be confirmed by, for example, examining an X-ray diffraction pattern.
The presence of the polymorph can be confirmed by MR or the like.
Here, an clathrate is a compound in which a three-dimensional structure formed by bonding atoms or molecules has pores of an appropriate size, in which other atoms or molecules have non-covalent interactions. Means a substance that has entered at a constant composition ratio, but as such a molecule, one of the component molecules forming the inclusion compound does not necessarily have to be a single molecule, and the inclusion compound is formed from two or more component compounds. It may be something.

The form of use of the molecular compound of the present invention is not particularly limited. For example, two or more kinds of molecular compounds each composed of different component compounds may be used in combination. The molecular compound of the present invention may be used in combination with other substances as long as the intended function is not impaired. It can be used in addition to resins, paints, and their raw materials and raw material compositions. Further, the molecular compound of the present invention can be used as it is as a raw material for organic synthesis, or the molecular compound can be used as a specific reaction field.

For example, using tri-o-thymotide as a host compound, a bactericide, an antibacterial / insecticidal / insect repellent, a fragrance, an antifouling agent,
Inclusion compounds that use a catalyst such as a curing agent for epoxy resins and a curing accelerator for epoxy resins as a guest compound, in addition to the action inherent in the guest compound, sustained release, reduced skin irritation, chemical stabilization, Functions such as non-volatilization, powderization, and selective separation of useful substances are newly added, and as catalysts such as disinfectants, antibacterial agents, insecticides / insect repellents, fragrances, antifouling agents, and curing agents for epoxy resins, which have new properties. Extremely useful.

[0032]

Next, the present invention will be described in more detail with reference to examples, but the technical scope of the present invention is not limited to these examples. Example 1 After heating and dissolving 150 mg (0.28 mmol) of tri-o-thymotide in 13 ml of methanol, 5-chloro-2 was added.
-Methyl-4-isothiazolin-3-one 0.28 mm
ol was added, and the mixture was heated and stirred to dissolve. Room temperature (10-20
) For 24 hours, and the precipitated crystals were collected by filtration, dried under reduced pressure at room temperature using a rotary vacuum pump for 5 hours, and tri-o-thymotide and 5-chloro-2-methyl-4-isothiazoline-3- A molecular compound having a composition ratio with ON of 1: 1 (molar ratio) was obtained. The molecular compound having the above composition was confirmed by thermal analysis (TG / DTA), ¹ H NMR and X-ray diffraction pattern. From the X-ray diffraction pattern, it was confirmed that the obtained molecular compound was clearly crystalline. The decomposition temperature of this molecular compound was 121.6 ° C. Thus, the molecular compound of the present invention has a low melting point of 5-chloro-2-methyl-4-isothiazoline-3-.
On (melting point = 51.3 ° C.) made the powder less volatile.

Example 2 After 150 mg (0.28 mmol) of tri-o-thymotide was dissolved under heating in 13 ml of methanol, 0.28 mmol of 4,5-dichloro-1,2-dithiolan-3-one was added, and the mixture was stirred with heating and dissolved. I let it. 2 at room temperature (10-20 ° C)
After standing for 4 hours, the precipitated crystals were collected by filtration, dried under reduced pressure at room temperature using a rotary vacuum pump for 5 hours, and tri-o-thymotide and 4,5-dichloro-1,2-dithiolane-3-
A molecular compound consisting of ON was obtained. Thermal analysis (TG / DTA), ¹ H NM
Performed by R and X-ray diffraction patterns. From the X-ray diffraction pattern, it was confirmed that the obtained molecular compound was clearly crystalline. The decomposition temperature of this molecular compound is 14
It was 1.8 ° C. Thus, the molecular compound of the present invention
4,5-dichloro-1,2-dithiolan-3- having a low melting point
On (melting point = 60-61.5 ° C.) made the powder less volatile.

Example 3 After 150 mg (0.28 mmol) of tri-o-thymotide was dissolved in 20 ml of isooctane by heating, 2-bromo-thymotide was dissolved in 20 ml of isooctane.
0.28 mmol of 2-nitropropane-1,3-diol
and heated and stirred to dissolve. Room temperature (10-20 ° C)
After leaving for 24 hours at room temperature, the precipitated crystals were collected by filtration, dried under reduced pressure at room temperature using a rotary vacuum pump for 5 hours, and tri-o
-Thymotide and 2-bromo-2-nitropropane-1,3
A molecular compound having a composition ratio with diol of 1: 0.5 (molar ratio) was obtained. The molecular compound having the above composition was confirmed by thermal analysis (TG / DTA), ¹ H NMR and X-ray diffraction pattern. From the X-ray diffraction pattern, it was confirmed that the obtained molecular compound was clearly a crystalline inclusion compound. The decomposition temperature of this molecular compound is 177.
It was 0 ° C.

Example 4 After 150 mg (0.28 mmol) of tri-o-thymotide was dissolved in 20 ml of isooctane by heating, 4-chlorophenyl (3-iodo) propargyl ether 0.28 was dissolved.
The solution was dissolved by stirring with heating. Room temperature (10-2
(0 ° C.) for 24 hours, and the precipitated crystals were collected by filtration, dried under reduced pressure at room temperature using a rotary vacuum pump for 5 hours, and tri-o-thymotide and 4-chlorophenyl = (3-iodo) propargyl = ether were added. A molecular compound having a composition ratio of 1: 0.5 (molar ratio) was obtained. Thermal analysis (TG / DTA), ¹ H NMR
And an X-ray diffraction pattern. The X-ray diffraction pattern confirmed that the molecular compound was clearly crystalline. The decomposition temperature of this molecular compound was 163.3 ° C. Thus, the molecular compound of the present invention has a low melting point of 4.
-Chlorophenyl = (3-iodo) propargyl = ether (melting point = 53-55 ° C.) was turned into a powder with low volatility.

Example 5 After dissolving 150 mg (0.28 mmol) of tri-o-thymotide in 20 ml of isooctane with heating, 0.28 mmol of dibromonitrilepropionamide was added, and the mixture was heated and stirred to dissolve. After standing at room temperature (10 to 20 ° C.) for 24 hours, the precipitated crystals are collected by filtration, dried under reduced pressure at room temperature using a rotary vacuum pump for 5 hours, and prepared from a molecule comprising tri-o-thymotide and dibromonitrilepropionamide. The compound was obtained. The fact that the obtained substance was a molecular compound was confirmed by thermal analysis (TG / DTA), ¹ H NMR and X-ray diffraction pattern. From the X-ray diffraction pattern, it was confirmed that the molecular compound was clearly a crystalline inclusion compound.
The decomposition temperature of this molecular compound was 173.0 ° C.

[0037]

Industrial Applicability The novel molecular compound of the present invention can be prepared by a simple operation and, in addition to the action inherent in the guest compound, sustained release, reduction of skin irritation, chemical stabilization, and non-volatilization. Newly added functions such as powdering, selective separation of useful substances, etc., and catalysts such as fungicides, antibacterial agents, insecticides / insect repellents, fragrances, antifouling agents, curing agents for epoxy resins, etc. which have new and useful properties Can be provided. In particular, useful compounds having a low hydrogen bonding property, which are difficult to include with conventional host compounds, can also be encapsulated, and can be used in a very wide range of useful substances.

Continued on the front page F term (reference) 4C022 NA01 4C055 AA01 AA17 BA02 BA03 BA39 BA47 CA01 CA03 CA39 DA01 DA21 DB15 4H011 AA01 AA02 AA03 AC01 AC06 BA04 BB03 BB04 BB06 BB10 BC06 DG03

Claims (3)

[Claims] 1. A compound of the general formula (I) (Wherein, R ^{1 to} R ¹² are each independently a hydrogen atom, C ₁
Represents a straight-chain or branched alkyl group of -C ₆ , and X represents an oxygen atom or a sulfur atom. ) And a bactericide, an antibacterial agent, an antifungal agent, an insecticide, a pest repellent, a fragrance, a deodorant / deodorant which reacts with the tri-o-thymotide to form a molecular compound. Deodorants, antifouling agents, curing agents and curing accelerators for paints, resins and adhesives, natural essential oils, antioxidants,
A molecular compound comprising a vulcanization accelerator and a component compound. 2. Fungicides, antibacterial agents, antifungal agents, insecticides, insect repellents, fragrances, deodorants / deodorants, antifouling agents, paints that react with tri-o-thymotides to form molecular compounds. ·resin·
The molecular compound according to claim 1, wherein the curing agent and the curing accelerator for the adhesive, the natural essential oil, the antioxidant, and the vulcanization accelerator comprise a compound having a low hydrogen bonding property. 3. The compound having a low hydrogen bonding property is 4-chlorophenyl- (3-iodo) propargyloxymethyl ether, 2,3,3-triiodoallyl alcohol,
4,5,6-tetrachloroisophthalonitrile, 5-chloro-2,4,6-trifluoroisophthalonitrile,
3-iodopropargyl = N-butyl carbamate,
2,3,5,6-tetrachloro-4-methanesulfonylpyridine, 2,2-dithio-bis- (pyridine-1-oxide), 3,5-dichloro-1,2-dithiolane-
The molecular compound according to claim 2, which is one or more compounds selected from 3-one.