NZ263884A - Dimethylfurancarboxanilide derivatives and wood preservative compositions - Google Patents

Description

New Zealand No. 263884 international No. PCT/JP94/00631 TO BE ENTERED AFTER ACCEPTANCE AND PUBLICATION Priority dates: 15.10.1993; Complete Specification Filed: 15.04.1994 Classification:^) C07D307/68; B27K3/34 Publication date: 28 July 1998 Journal No.: 1430 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION Title of Invention: Dimethylfurancarboxanilide derivative Name, address and nationality of applicant(s) as in international application form: SANKYO COMPANY LIMITED, 5-1, Nihonbashi Honcho 3-chome, Chuo-ku, Tokyo 103, Japan 263884 M&C Folio: P74780 (FP-9412) WANGDOC:2086i (09.10.96) Dimethylfurancarboxyanilide derivatives [Technological field] The present invention is concerned with novel dimethylfurancarboxyanilide derivatives exhibiting an excellent antimicrobial effect, a wood preservative containing the dimethylfurancarboxyanilide derivative as the active ingredient, and a wood preservative composition in which the dimethylfurancarboxyanilide derivative as one of the active ingredients is combined with any commercially available wood preservative the effect of which has been already confirmed.

[Background technology] Various kinds of inorganic or organic compounds have previously been employed to preserve timber against decay due to various wood-rotting fungi. However, these chemicals have faults such as affecting the human body because of their high toxicity, showing environmental \ polution, requiring a high concentration thereof when employed and being expensive.

As for compounds relating to the dimethylfurancarboxyanilide derivatives of the present invention, compounds represented by the formula below have been disclosed in Japanese Patent Kokai Application Sho 50-10376 as a chemical for preventing plant injury; in which, however, R is limited to phenyl, 2638 84 nitro-substituted phenyl, carboxy-substituted phenyl, phenyl-substituted phenyl, methyl-substituted phenyl, halogen-substituted phenyl or methoxy-substituted phenyl. In addition, this patent is silent on the other derivatives, and no activity of these compounds on wood-rotting fungi has been described.

[Process and constitution of Invention] The object of the present invention exists in providing a novel wood preservative which is safer, and is possible to use effectively at a low concentration and/or at a low price.

In consideration of such situation as mentioned above, the present inventors considered furancarboxyanilide derivatives, and studied eagerly. Our study resulted in finding that novel dimethylfurancarboxyanilide derivatives represented by the general formula (I) below are very useful as a wood preservative and furthermore, if the dimethylfurancarboxyanilide derivative as the active ingredient is combined with any other commercially available wood preservative, potentiation-effect can be 0 (II) 3 26 3 8 8 4 observed and a wood preservative composition can be prepared.

The compounds of the present invention are the dimethylfurancarboxyanilide derivatives represented by the general formula and each represents hydrogen atom; an «ilkyl group having from 2 to 6 carbon atoms; a cycloalkyl group having from 3 to 6 carbon atoms; an alkenyl group having from 3 to 6 carbon atoms; an alkynyl group having from 2 to 6 carbon atoms; a halogenoalkyl group having from 1 to 3 carbon atoms; an alkoxy group having from 2 to 6 carbon atoms; an alkoxyalkylene group having from 1 to 6 carbon atoms in the alkoxy moiety and having from 1 to 6 carbon atoms in the alkylene moiety; a cyano group; a substituted,amide group; an alkoxycarbonyl group having from 1 to 6 carbon atoms in the alkoxy moiety; a benzoyl group which may have optionally from 1 to 2 substituents; a benzoylamino group which may have optionally from 1 to 2 substituents; an alkanoylamino group having from 2 to 6 carbon atoms; a (I) 1 2 [In this formula, R and R are the same or different v> cycloalkylcarbonylamino group having from 3 to 6 carbon atoms in the cycloakyl moiety; a benzyl group which may have optionally from 1 to 2 substituents; a phenyl group which may have optionally from 1 to 2 substituents; or an alkoxycarbonylalkenylene group having from 1 to 6 carbon atoms in the alkoxy moiety and having from 2 to 5 carbon 1 2 atoms in the alkenylene moiety; and R and R do not represent hydrogen atoms at the same time]. The present invention concerns the compounds mentioned above, a wood preservative and a wood preservative composition each containing the dimethylfurancarboxyanilide derivative as the active ingredient.

[Brief explanation of the figures] Fig. l (a)-(f) show the minimum inhibitory concentrations (ppm) of Compound of Example 20 in combination with various wood preservatives. Fig. 2 (a)-(f) show the minimum inhibitory concentrations (ppm) of Compound of Example 21 in combination with various wood preservatives.

[The best mode for working of the invention] In the general formula (I) above, as an alkyl group having from 2 to 6 carbon atoms, which is included in the 1 2 definitions for R and R , there may be mentioned a straight or branched chain alkyl group such as ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, INTaiECTUALPROPEnTY OF N1. 0 3 JUN 1998 2 6 3 8 8 4 pentyl, isopentyl, neo-pentyl, hexyl, isohexyl or sec-hexyl; particularly preferably an alkyl group having from 2 to 6 carbon atoms.

In the general formula (I) above, as a cycloalkyl group having from 3 to 6 carbon atoms, which is included 1 2 in the definitions for R and R , there may be mentioned a cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl; preferably a cycloalkyl group having from 3 to 6 carbon atoms; and more preferably a cycloalkyl group having from 5 to 6 carbon atoms.

In the general formula (I) above, as an alkenyl group having from 3 to 6 carbon atoms, which is included in the 1 2 definitions for R and R , there may be mentioned an alkenyl group such as allyl, isopropenyl, metallyl, 2-butenyl, 3-butenyl, 1,3-butandienyl, 2-pentenyl, or 2-hexenyl; preferably an alkenyl group having from 3 to 4 carbon atoms; and more preferably isopropenyl.

In the general formula (I) above, as an axkynyl group having from 2 to 6 carbon atoms, which is included in the l 2 definitions for R and R , there may be mentioned an alkynyl group such as ethynyl, propargyl, 2-butynyl, 4-pentynyl, or 2-hexynyl; preferably an alkynyl group having from 2 to 4 carbon atoms; and more preferably ethynyl.

In the general formula (I) above, as a halogenoalkyl group having from 1 to 3 carbon atoms, which is included 26 30 8 4 1 2 in the definitions for R and R , there may be mentioned a halogenoalkyl group such as trifluoromethyl, trichloromethyl, pentafluoroethyl, 2,2,2-trichloroethyl or 2,4-dichloropropyl; preferably a halogenoalkyl group having from l to 2 carbon atoms; and more preferably trifluoromethyl.

In the general formula (I) above, as an alkoxy group having from 2 to 6 carbon atoms, which is included in the 1 2 definitions for R and R , there may uq mentioned a straight or branched chain alkoxy group such as ethoxy, propoxy, isopropoxy, butoxy, pentoxy or hexyloxy; preferably an alkoxy group having from 2 to 4 carbon atoms; and more preferably an alkoxy group having from 2 to 3 carbon atoms.

In the general formula (I) above, as an alkoxy group having from 1 to 6 carbon atoms contained in an alkoxyalkyl group having from 1 to 6 carbon atoms in the alkoxy moiety and having from l to 6 carbon atoms in the alkyl moiety, which is included in the definitions for 1 2 R and R , there may be mentioned a straight or branched chain alkoxy group such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentoxy, neo-pentoxy or hexyloxy; preferably an alkoxy group having from 1 to 5 carbon atoms; and more preferably an alkoxy group having from l to 3 carbon atoms or having 5 carbon atoms.

In the general formula (I) above, as an alkylene group 7 2 6 3 0 8 4 contained in an alkoxyalkylene group having from l to 6 carbon atoms in the alkoxy moiety and from 1 to 6 carbon atoms in the alkylene moiety which is included in the 1 2 definitions for R and R , there may be mentioned a straight or branched chain alkylene group such as methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene or hexamethylene; preferably an alkylene group having from 1 to 2 carbon atoms; and more preferably methylene.

In the general formula (I) above, as a substituted amide group, which is included in the definitions for R1 k 2 and R , there may be mentioned a monoalkylamide group such as methylamide, ethylamide, isopropylamide, butylamide, sec-butylamide; a dialkylamide group such as dimethylamide, diethylamide, diisopropylamide, dibutylamide, di-sec-butylamide, methylethylamide, methylisopropylamide, methylbutylamide, methyl-sec-butylamide, ethylisopropylamide, isopropylbutylamide. pyrrolidylamide or piperidylamide; an optionally substituted phenylamide such as phenylamide, 2 -chlorophenylamide, 2,4-dichlorophenylamide, 2-methylphenylamide, 2 -ethylphenylamide or 4-methoxyphenylamide; preferably methylamide, piperidylamide or phenylamide.

In the general formula (I) above, as an alkoxycarbonyl group having from l to 6 carbon atoms in the alkoxy 8 26 3 0 moiety, which is included in the definitions for R1 and 2 R , there may be mentioned a group which is formed from the aforementioned alkoxy group having from 1 to 6 carbon atoms contained in an alkoxyalkyl group having from l to 6 carbon atoms in the alkoxy moiety and having from l to 6 carbon atoms in tfco alkyl moiety and from a carbonyl group, such as methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl or hexyloxycarbonyl; preferably an alkoxycarbonyl group having from l to 3 carbon atoms in the alkoxy moiety.

In the general formula (I) above, as a benzoyl group which may have optionally from 1 to 2 substituents, which 1 2 is included in the definitions for R and R , there may be mentioned an optionally substituted benzoyl group such as benzoyl, 2-chlorobenzoyl, 2,4-dichlorobenzoyl, 2-methylbenzoyl, 2,4-dimethylbenzoyl, 4-ethylbenzoyl or 4-methoxybenzoyl; preferably benzoyl.

In the general formula (I) above, as a benzoylamino group which may have optionally from 1 to 2 substituents, 1 2 which is included in the definitions for R and R , there may be mentioned an optionally substituted benzoylamino group which is formed by substitution of amino group(s) to the aforementioned benzoyl group which may have optionally from 1 to 2 substituents such as benzoylamino, 2 -chlorobenzoylamino, 9 2 6 3 0 2,4-dichlorobenzoylamino, 2,4-dimethylbenzoylamino, 4-methylbenzoylamino, 4-ethylbenzoylamino or 4-methoxybenzoylamino; preferably benzoylamino.

In the general formula (I) above, as an alkanoylamino group having from 2 to 6 carbon atoms, which is included 1 2 in the definitions for R and R , there may be mentioned acetylamino, propionylamino, butyrylamino, isobutyrylamino, valerylamino, isovalerylamino, caproylamino or isocaproylamino; preferably acetylamino.

In the general formula (I) above, as a cycloalkylcarbonylamino group having from 3 to 6 carbon atoms in the cycloalkyl moiety, which is included in the 1 2 definitions for R and R , there may be mentioned cyclopropylcarbonylamino, cyclobutylcarbonylamino, cyclopentylcarbonylamino or cyclohexylcarbonylamino; preferably cyclohexylcarbonylamino.

In the general formul (I) above, as a benzyl group which may have optionally from 1 to 2 substituents, which 1 2 is included in the definitions for R and R , there may be mentioned benzyl, 2-methylbenzyl, 2,4-dimethylbenzyl, 2-chlorobenzyl, 4-methoxybenzyl or 4-ethoxybenzyl; preferably benzyl.

In the general formula (I) above, as an alkoxycarbonylalkenylene group having from 1 to 6 carbon atoms in the alkoxy moiety and having from 2 to 5 carbon atoms in the alkenylene moiety, which is included in the 2 6 o C 8 1 2 definitions for R and R , there may be mentioned methoxycarbonylvinylene, ethoxycarbonyl-2-propenylene, methoxycarbonyl-2-butenylene or othoxycarbonyl-2-pentenylene; preferably methoxycarbonylvinylene.

Preferred compounds having the general formula (I) above include ones in which: 1 2 (1) R and R are the same or different and each represents a hydrogen atom; an alkyl group having from 2 to 6 carbon atoms; an alkenyl group having from 3 to 4 carbon atoms; an alkynyl group having from 2 to 4 carbon atoms; a cycloalkyl group having from 3 to 6 carbon atoms; an alkoxycarbonyl group having from 1 to 6 carbon atoms in the alkoxy moiety; an alkoxyalkylene group having from l to 6 carbon atoms in w.he alkoxy moiety and having from l to 2 carbon atoms in the alkylene moiety; a cycloalkylcarbonylamino group having from 3 to S carbon atoms in the cycloalkyl moiety; an alkoxy group having from 2 to 4 carbon atoms; a benzoyl group which may have optionally from 1 to 2 substituents; a benzyl group which may have optionally from 1 to 2 substituents; or an alkoxycarbonylalkenylene group having from 1 to 6 carbon atoms in the alkoxy moiety and having from 2 to 5 carbon 1 2 atoms in the alkenylene moiety; and R and R do not represent hydrogen atoms at the same time. More preferred ones include those in which: 11 2 C 3 C 1 2 (2) R and R are the same or different and each represents a hydrogen atom; an alkyl group having from 2 to 6 carbon atoms; an alkenyl group having from 3 to 4 carbon atoms; a cycloalkyl group having from 5 to 6 carbon atoms; an alkoxycarbonyl group having from 1 to 3 carbon atoms in the alkoxy moiety; an alkoxymethylene group having from l to 6 carbon atoms in the alkoxy moiety; a cycloalkylcarbonylamino group having from 4 to 6 carbon atoms in the cycloalkyl moiety; a benzoyl group; a benzyl group which may have optionally l substituent; or an alkoxycarbonylalkenylene group having from l to 3 carbon atoms in the alkoxy moiety and having from 2 to 4 carbon 1 2 atoms in the alkenylene moiety; and R and R do not represent hydrogen atoms at the same time. Particularly preferred ones include those in which: (3) R1 is a 3-alkyl group having from 2 to 6 carbon atoms; a 3-alkoxycarbonyl group having from 1 to 3 carbon atoms in the alkoxy moiety; a 3-alkoxymethylene group having from 1 to 3 carbon atoms in the alkoxy moiety; a cycloalkylcarbonylamino group having from 4 to 6 carbon atoms in the cycloalkyl moiety; a benzyl group which may be substituted by a methoxy group; a benzoyl group; or an alkoxycarbonylalkenylene group having from 1 to 3 carbon atoms in the alkoxy moiety and having from 2 to 3 carbon atoms in the alkenylene moiety; and 2 (4) R is a hydrogen atom. 12 2 6 3 0 8 4 Novel dimethylfurancarboxyanilide derivatives which may be used as an active ingredient of the wood preservative of the present invention are exemplified in the following table.

In Table 1 below, abbreviations are used as follows.

Bz Benzyl Bu Butyl Et Ethyl Hx Hexyl Me Methyl Ph Phenyl Pip Piperidyl.

Pn Pentyl Pr Propyl 1 iso a secondary & tertiary £ cyclo Table 1 2 6 3 8 8 4 Compound No. R1 R2 1 3-CF3 H 2 4-CF3 H 3 3-CH20Me H 4 4-CH2OMe H 2-Et H 6 3-Et H 7 4-Et H 8 3-C*CH H 9 4-C«CH H 3-CH2OEt H 11 4-CH2OEt H 12 2-Et 3-Et 13 2-Et 4-Et 14 2-Et -Et 2-Et 6-Et 16 3-Et 4-Et 17 3-Et -Et 18 3-Et 6-Et 19 3-Pr H 4-Pr H 21 2-iPr H 22 3-iPr H 23 4-iPr H 26 30 8 4 24 3-cPr H 4-cPr H 26 3-CH2OPr H 27 3-CH20iPr H 28 4-CH20iPr H 29 3-CH2C-CH2 H 4-CH2C-CH2 H 31 3-CH2C«CH H 32 4-CH2C»CH H 33 3-Pr 4-Pr 34 2-iPr 4-iPr 3-iPr -iPr 36 3-CH2OBu h 37 4-CH2OBu H 38 3-CH20iBU H 39 4-CH20iBu H 40 3-CH2OSBU H 41 4-CH20sBu H 42 3-Bu H 43 4-Bu H 44 3-iBu H 45 3-sBu H 46 3-cBu H 47 4-cBu H 48 3-tBu H 49 3-CH2 CH"CHMe H 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 3-CH2C*CMe 3-CH2MeCH»CH2 4-CH2MeCH«CH2 3-Pn 4-Pn 3-iPn 3-cPn 3-neoPn ?-CH20Pn 3-CHoOngo-Pn 3-HX 3-iHX 3-cHx 3-CN 3-OEt 3-0iPr 3-CONHK® 3-(C0-l-Pip) 3-COMHPh 3-COOMe 3-COOEt 3-COOPr 3-COOiPr 3-COOBU 3-COOtBU 3-COPh 16 ?r 3 3 8 '/6 3 - CO (2-MePh) H 77 3-NHCOPh H 78 3 -NHCOMe H 79 3 -NHCOBu H 80 3-NHCOfiPn H 81 3-NHCOfiHx H 82 3-Bz H 83 3-(4-MfiOBz) H 84 3 -(4-MeBz) H 85 3 -CH-CHCOOMe H 86 3-Ph H 87 3 -(2-MePh) H Among the compounds above, preferred ones include Compound Nos. 3, 4, 5, 6, 7, 8, 10, 11, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 31, 33, 35, 36, 38, 40, 42, 43, 44, 45, 46, 48, 49, 50, 51, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 64, 69, 70, 71, 72, 75, 80, 81, 82, 83 and 85; and more preferred ones include Compound Nos. 3, 6, 10, 19, 22, 24, 26, 27, 33, 35, 36, 38, 40, 42, 44, 45, 46, 48, 53, 55, 60, 61, 69, 70, 81, 83 and 85. 263884 The compounds off the said general formula (I) may be prepared according to the procedure summarized in either the following Method A or Method B.

Method A — ► Step A1 < i) o rt* + CHj 0 CHj ^=^R2 (III) (IV) Method b O CH3 0 CHj ' ^ scwB1 (III) (V) RrMgX' chj^o ch3 Pd(dppf)ci2 (vi) Step b2 jnc"'HN"@'Rl ch3ao ch3 (i*) 26 30 8 4 1 2 In the above formulae, R and R are as defined above. R represents a C^-Cg alkyl, C3*Cg cycloalkyl or benzyl group which may optionally have 1 or 2 substituents. The compound of formula (la) is that of a 1 1' 2 general formula (I), in which R is R and R signifies a hydrogen atom. The compound of formula (V) is iodine-substituted aniline. X signifies a halogen atom such as chlorine, bromine or iodine, preferably chlorine.

X' signifies a halogen atom such as a chlorine, bromine or iodine, preferably bromine or iodine.

The compounds of the present invention may be prepared by well-known procedure.

Step A1 consists of the preparation of a compound of general formula (I) by reacting a compound of general formula (III) with a compound of general formula (IV) in an inert solvent in the presence of a dehydrohalogenating agent.

A compound of formula (III) used as a starting material in this step may be prepared by hydrolyzing 2,5-dimethylfuran-3-carboxylate, which may be prepared by condensing chloroacetone with acetoacetate, followed by halogenation.

A compound of formula (IV) used as a starting material in this step is an aniline derivative which is commercially available or may be prepared by well-known methods. 26 3 8 8 4 Examples of the inert solvents used include, for example, ethers such as ether, isopropyl ether, tetrahydrofuran or dioxane; aromatic hydrocarbons such as benzene, toluene or xylene; halogenated hydrocarbons such as dichloromethane, chloroform or carbon tetrachloride; and mixtures of two or more of these solvents; preferably aromatic hydrocarbons (particularly toluene).

Examples of dehydrohalogenating agents used include, for example, tertiary amines such as triethylamine, N,N-dimethylaminopyridine or the like and pyridines. This reaction can be carried out in the presence or absence of a solvent. In order to perform the reaction smoothly, using a sclvent, the reaction is carried out at a temperature of 0°C to reflux temperature of the solvent used, preferably from room temperature to 100°C. The time required for the reaction takes generally from 30 minutfj to 5 hours*, preferably from 30 minutes to 2 hours.

'Jtep B1 consists of the preparation of a compound having general formula (VI) by reacting a compound having general formula (III) with a compound having general formula (V) in an inert solvent in the presence of a dehydrohalogenating agent.

A compound of formula (IV) used as a starting material in this step is an aniline derivative which is commercially available or may be prepared by 26 38 8 4 well-known methods.

The reaction conditions employed in this step are similar to those employed in Step Al.

Step B2 consists of the preparation of a compound having general formula (la) by reacting a compound having general formula (VI) with a Grignard reagent having i» general formula: R MgX' in an inert solvent in the presence of a catalyst.

Examples of preferred inert solvents used include, for example, ethers such as diethyl ether, isopropyl ether, tetrahydrofuran or dioxane; particularly preferably diethyl ether.

As a particularly preferred catalyst there may be used [l, l'-bis(diphenylphosphino)ferrocene]palladium(II) chloride.

The Grignard reagents used in this process are commercially available or can be prepared by reacting magnesium with an alkyl halide represented by formula: l' ' . l' R X (wherein R and X' are as defined above) according to well-known methods.

The reaction is normally carried out at a temperature of 0°C to 50°C, preferably at room temperature.

Although the time required for the reaction varies depending upon the nature of the solvent and reagent to be used, the reaction is normally complete within a period of hours to 10 days. 263884 The compounds having the said general formula (I) in according with the invention have potent wood preservative activity at low concentration, compared with the activity shown by existing wood preservatives. A composition consisting of a combination of the foregoing compound (I) with a known wood preservative gives & synergistic effect, lower concentrations of each compound being required than would be expected from the activity shown by each singly, such that the composition shows efficient wood preservative activity at a low concentration. Therefore, novel dimethylfurancarboxyanilide derivatives are extremely effective as a wood preservative in low concentration so as to solve one of the problems in the quality of life.

The following Examples illustrate the preparation and the formulation of the compound of the invention in more detail. Such examples are not to be construed as being limitative of the scope of the invention.

Example l 3'-Acetylamino-2.5-dimethylfuran-3 -carhoxanilide To a solution of 0.50 g of 2,5-dimethylfuran-3-carbonyl chloride in 10 ml of dichloromethane were added 0.44 ml of triethylamine and 0,47 g of 3-acetylaminoaniline under ice-cooling, and the resulting mixture was stirred at roan temperature f^r 2.5 hours followed by heating under reflux for 4.5 ^our*. After the reaction mixture was cooled, it was diluted by I* 7 t f " I l 22 263884 adding 10 ml of dichloromethane. The diluted mixture was successively washed with 1 N sodium hydroxide, 1 N hydrochloric acid and a saturated aqueous solution of sodium chloride and dried over sodium sulfate followed by distilling off the solvent. The residue was purified by column chromatography through silica gel and the desired fractions were recryetallized from ethyl acetate to give 0.51 g of the deaired compound as white crystals in a 59.4% yield. m.p.: 172.0-172.5°C XH NMR <CDC13 + DMSO) 6 ppm: 0.4 (1H, b) , 7.95 (1H, b) , 7.88 (1H, m) , 7.4 11H, m), 7.32 (IK, m), 7.25 (1H, t, J-0HZ), 6.25 (1H, a), 2.55 (3H, s), 2.25 (3H, s), 2.15 (3K, s) IR (KBr) cm"1: 3306, 1672, 16S1, 1086, 781 Elemental analysis (%) : Calc'd for C, 66.16; H, 5.92; N, 10.29. Pound: C, 66.30; H, 5.98; N, 10.32.

Following the similar procedure as above, but using an appropriate aniline derivative instead of 3-acecylaminoaniline, there were obtained the following compounds.

Example 2 3 * -(N-methvlcarbamoyl)-2.5-dimethvlfuran-3 -carboxanilIda Yield: 42.0% [n r L 23 263884 m.p.: 212.0-213. 0°C NMR (CDC13 + DMSO) 6 ppm: 8.5 (1H, b) . (3.05 (1H| m) , 7.88 (1H, m) . 7.52 (1H, ffl), 7.38 (1H, t, J-8Hz), 6.8 (1H, b) , 6.35 (1H, 0), 2.95 (3H, d, J-1.4Hz), 2.55 (3H, 8), 2.25 (3K, 8).

IR (KBr) cm"1: 3293, 1638, 1581, 1074, 689 Elemental analysis (%): Calc'd for C15H16N2°3: C, 66.16; H, 5.92; N. 10.29. Found: C, 66.08) H, 6.20; N, 10.28.

Example 3 3 ' - (1 - Piperidvlcarbonyl 1 - 2 . 5-dimethylfuran- 3 - carboxanillde Yield: 50.0% m.p.: 183.0-185.0°C 1H NMR spectrum (CDC13) t> ppm: 7.68 (1H, m), 7.55 (2H, m) , 7.35 (1H, t, J-BHz), 7.1 {1H, m) , 6.15 (1H, 8), 3.7 (2H, b), 3.35 (2H. b), 2.55 (3H, 8), 2.25 (3H, 8). 2.75-1.4 (6H, m) IR (KBr) cm"1: 3302, 1663, 1615, 1065, 808 Elemental analysis (%): Calc'd for Cl5H22N203: C, 69.92; H, 6.79; N, 8.58. Found: C, 69.52; H, 6.88; N, 8.48.

Example 4 3'-(N-Phenvlcarbaraavl\-2.5-dimethylf iiran-lrc*rhoxanil ide 24 26 3 8 Yield: 53.5% m.p.: 182.5 -184.0°C ^ NMR (CDC13 + DMSO) h ppm: 0.48 (1H, b) , 0.2 (1H, b), 8.1 (1H, 8), 7.95 (1H, m) , 7.7 (2H, d, J-8HZ), 7.65 (1H, d, J«8Hz) , 7.45 (1H, C, J-8HZ), 7.35 (2K, t, J-8HZ), 7.15 (1H, t, J-8Hz) , 6.28 (1H, a), 2.55 <3H, fl) , 2.25 OH, a) IR (KBr) cm"1: 3282, 1646, 1080, 7S5, 691 Elemental analysis (%): Calc'd for C20HxaN2°3; C, 71.84; H, 5.43; N, 8.38. Pound: C, 71.87; H, 5.64; N, 8.34.

Example 5 3'-Tert-butoxvcarbonvl-2.5-dimathvlCuran-3 -carboxanillde Yield: 92.0% m.p.: 117,0-110.0°C XH NMR (CDC13) 8 ppm: 8.05 (1H, m) , 7.88 (1H, m) , 7.75 (1H, m), 7.4 <1H, t, J-8HZ). 7.35 (1H. b). 6.1 <1H. s), 2.55 (3H, e), 2.25 (3H, 8), 1-65 (9H, 8) IR (KBr) cm"1: 3362, 1687, 1672, 1067, 757 Elemental analysis (%): Calc'd for ci0H2iNO4: C| 68.S5; H, 6.71; N, 4.44. Pound: C, 68.04; H, 7.00; N 4.40.

Example 6 26388 3' -Methoxyr-arbonvl- 2 .5 »dimethvlguran-3 -carbQJttnllidfl Yield: 77.1% NMR (CDC13) 6 ppm: 8.05 (1H, m) , 7.98 {1H, m) , 7.8 (1H, m), 7.42 (1H, t, J-8H«), 7.38 (1H, b> , 6.1 (1H, s) , 3.92 (3H, 8), 2.55 (3H, a), 2.25 (3H, s) IR (KBr) cm"1: 3437, 1704, lS^S, 1070, 759 Elemental analysis (%): Calc'd for C15H15N04! C' 65.92; H, 5.53; N, 5.13. Pound: C, 66.02; H, 5.60; N, 5-08.

Bxample 7 3' - Benzoyl -2.5- dlmethvlfuran- 3 - carbmcaniT i d*> Yield: 69.1% m.p.: 137.0-139.0°C NMR (CDC13) 6 ppm: 8.05 (1H, til), 7.85-7.7 (3H, m) , 7.6 (1H, m) , 7.55-7.35 (5H, m) , 6.1 (1H, s), 2.55 (3H, s) , 2.25 (3H, 9) IR (KBr) cm"1: 3386, 1672, 1647, 1069, 707 Elemental analysis (%): Calc'd for CaoH17N03: C, 75.22; H, 5.37; N, 4.39. Found: C, 7S.38; H, S.43; N, 4.38. m.p.: 104.0-106.0°C NGV 1396 I - 26 26388 Example 8 1 *.Benzoylamino-2.5-dlmethylfu^an-3 -carboxanilidfl Yield: 46.0% m.p.: 194.5-195.0°C lH NMR. (CDC13 + DMSO) & ppm: 8.7 (1H, b), 8.1 (1H, m), 7.95 {1H. b) , 7.9 (2H, m) , 7.6-7.4 (5H, m) , 7.3 (1H, t, J-8Hz) , 6.25 (1H, 8), 2.55 (3H, 8), 2.25 (3K, 8) IR (KBr) cm"1 3283, 1642, 1074, 791, 705 Elemental analysis (%) : Calc'd Cor C2oHi8Ni°3; C, 71.84; H, 5.43; N, 8.38. Pound: C, 71.96; H, S.53-N, 8.28.

Example 9 3' -Valervlantl io-2 .5 - dimethylfuran.3 -carboxanillde Yield: 70.3% m.p.: 104.0-105.0°C NMR (CDC13) 5 ppm; 7.9 (1H, b), 7.45-7.1 (5H, m), 6.1 (1H, a), 2.55 (3H, s), 2.35 (2H, t, J-7Hs), 2.25 (3H, s), 1.7 (2H, m), 1.4 (2H, m), 0.95 (1H, t, J-7Hz) IR (KBr) cm"1; 3250, 1660, 1644, 1074, 701 Elemental analysis (%): Calc'd for ^ia^22^2^3: C, 68.77; H, 7.05; N, 8.91. Pound: C, 66.73; H, 7.17 N, 8.90. 27 26o 8b'4 Example 10 3 ' -Cyclohexvlcarbonvlamino-2 . 5-dlmethvlfuran-3- carboxanillde Yield: 45.1* m.p.: 212.5-213.0°C XH NMR (CDC13) 6 ppm: 7.92 (1H, b), 7.00 (1H, b), 7.45-7.35 (2H, m) , 7.25 (1H, t, J»0Hz), 6.22 (1H, 8), 2.55 <3H, s), 2.25 (3H, a), 2.25-2.2 (1H, m) , 2.0-1.2 (10H, in) IR (KBr) cm"1: 3230, 1651, 1639, 1076, 701 Elemental analysis (%): Calc'd for C20H24N2°3: C, 70.57; H, 7.11; N, 0.23. Found:C, 70.56; H, 7.26; N, 8.16 Example 11 3'-Methoxvmethvl'2.5-dimathvlfuran-3-carboxanillde Yield: 73.3% m.p.: 102.5-103.5°C XH NMR (CDC13) 6 ppm: 7.55 (1H, m), 7.52 (1H, d, J-8HZ), 7.32 (1H, t, J-8Hz), 7.32 (1H, to), 6.9 (1H, d, J-8H«), 6.1 (1H, 8), 4.45 <2H, a), 3.4 (3H, 8), 2.55 (3H, 8), 2.25 (3H, 0) IR (KBr) cm"1: 3270, 1645, 1237, 1107, 704 Elemental analysis (%): Calc'd for Cl5Hl7NOjj C, 69.48; H, 6.61; N, 5.40. Found: C, 69.22; H, 7.02; N, 5.37. 28 263384 Example 12 3 ' • Ethoxvmethvl -2.5- dimethylfuran- 3 - carhoxanilide Yield: 64.4% m.p.: 85.0-85.S°C. 1H NMR (CDC13) * ppm: 7.65-7.55 (2H, m) , 7.38 (lH, t, J-8Hz), 7.35 (1H, b) . 7.15 (1H, d, J-8Hz), 6.15 (lH, S) , 4.55 (2H, s), 3.58 (2H, q, J«8Hz), 2.55 (3K, s) , 2.25 (3H, S). 1.3 (3H, t, J-8HZ) IR (KBr) cm"1: 3279, 1646, 1115, 785 Elemental analysis (%) : Calc'd for C^H^NC^: C. 70.31; H, 7.01; N, 5.12. Found: C, 70.14; H, t .7; N, 5.06 .

Example 13 3 - - IgQpropvlQxvmethvl - 2 . 5- Almothvlfuran- 3 - carboxaialllde Yield: 92.7% m.p.: 68.0-69.5°C ^ NMR (CDC13) 5 ppm: 7.55 (1H, d, J-8H2) , 7.5 (lH, tn) , 7.3 (1H, t, J-8HZ), 7.3 (1H, b) , 7.12 (1H, d, J«8Hz), 6.1 (1H, s), 4.5 (2H, 0), 3.7 (1H, m) , 2.55 (3H, s) , 2.25 (3H, S), 1.25 (6H, d, J«7Hz) IR (Liquid film) cm"1: 3321, 1651, 1072, 785 r\ r., , 26 0^84 Elemental analyaia (%) : Calc'd for ci7H2iN°3: C' 71.06; H, 7.37; N, 4.87. Found: C, 70.35; H, 7.14? N, 4.91.

Example 14 -V - (4 -Methoxvhangvll - 2 .5. aimethvlfuran- 3 - carboxanillde Yield: 86.8% m.p.: 100.0-102.5°C hi NMR (CDC13) 6 ppm: 7.45 <1H, m), 7.35 (1H, ta) , 7.25 (lH. t, J«8Hz) , 7.25 (1H, b), 7.1 (2H, <5, J-8Hz) , 6.92 (1H, d, J-8Hz), 6.88-6.75 (1H, m) , 6.82 (2H, d. J-8Hz) , 6.05 (1H, 8), 3.9 (2H, 9), 3.75 (3H, e), 2.55 (3H, 3), 2.25 (3H, 8) IR (KBr) cm"1: 3345, 1656, 1246, 1074, 694 Elemental analysis (%): Calc'd for C2lH21N03: c' 75.20; H, 6.31; N, 4.18. Found: C, 75.28; H, 6.32; N, 4.21.

Example 15 3' - (2 -MethoxvcarhanvIvinv 1) - 2. S - dimethyl furan - 3 - rnrhnxaTi i 1 ^ rt* Yield: 63.3% m.p.: 159.5-161.5°C XH NMR (CDC13) 6 ppm: •5 ^ " . 1335 ^•13 #4 7.82 (1H, m), 7.7 (1H, d, J-15Hz), 7.58 (1H, m) , 7.38 (1H. b). 7.35 (lH, t, J-8HZ) , 7.28 (1H, m) , 6.48 (1H, d, J-15HZ), 6.12 (1H, a), 3.82 <3H, a), 2.55 (3H, a), 2.25 (3H, a) IR (KBr) cm"1: 3387, 1685, 1670, 1068, 000 Elemental analyaia (%): calc'd Cor C17»17N04! C' 68.22; H, 5.72; N, 4.68. Pound: C, 67.55; H, 5.64; N, 4.62.

Example 16 3' -Phanvl-2. 5-dimgfchvlfiira.Ti.3-eagho3eatiill<la Yield: 50.0% m.p.: 90.0-92,0°C XH NMR (CDC13) 6 ppm: 7.82 (1H, a), 7.6 (2H, d, J-8HZ), 7.55 (1H, d. J-8Hz) , 6.48-6.3 (6H, Hi), 6.12 (IK, 9), 2.55 (3H. m) , 2.25 (3H, a) IR (KBr) cm'1: 3367, 1646, 1074, 755 Elemental analyaia (%): Calc'd for C19H17N02: C, 78.33; H, 5.88; N, 4.81. Found: C, 78.17; H, 6.00; N, 4.72.

Example 17 3' - Neopentvloxvmftthvl - 2.5 - dimethylfuran- 3 - carboxanillde Yield: 50.0% m.p.: 95.S-97.0°C - - 31 - 26388 lH NMR (CDClj) 6 ppm: 7.48 (2H, m), 7.32 (1H, t. J-8Ha), 7.3 (1H, b) , 7.12 (1H, d, J«8Hz), 4.52 (2H, a), 3.12 (2H, a), 2.55 (3H, B), 2.25 (3Hr 8), 0.95 (9H, a) IR (KBr) cm"1: 3324, 1646, 1091, 700 Elemental analysis (%) : Calc'd for cj>gH25N03: c» 72.35; H, 7.99; N, 4.44. Found: C, 72.38; tt, 0.03; N, 4.20.

Example 18 3 ' -Igopropanvl -2 . 5-flimethvlfuran-3 -r.arboxanlllde Yield: 50.0* m.p.: 71.1-72.0°C.

NMR (CDC13) 8 ppm: 7.65 (1H, m) , 7.5 (1H, m). 7.3 (1H, b), 7.3 (1H, t, J-8HZ) , 7.22 (1H, tn) , 6.12 (1H, 8), 5.4 (1H, 8), 5.1 (1H, 8), 2.6 (3H, a), 2.55 (3H, 8), 2.25 (3H, 8) IR (KBr) cm"1: 3275, 1641, 1580, 1078, 790 Elemental analysis (*): Calc'd for C, 75.27; H, 6.71; N, 5.49. Found: C. 75.29; H, 6.88; N, 5.48.

Example 19 1'■Erhvnvl■2.S-dimathvlfuran-3-carboxanilIda "Xield: 50.0% 2638 m.p.; 83.0-84.0°C XH NMR (CDC13) 6 ppm: 7.7 (1H, nO , 7.6 (1H, m), 7.32-7.2 (3H, m), 6.1 (1H, 0), 3.05 (IK, 0), 2.55 (3H, 0), 2.25 (3H. 0) IR (KBr) cm"1: 3245, 1644, 1079, 796 Elemental analy0i0 (%): Calc'd Cor ci5Hi3N02! C/ 75.30; H, 5.48; N, 5.85. Found: C, 75 50; H, 5.46; N, 5.96.

Bxaznple 20 3; -Btfayl-a.5-dimethylCuran-3 -carboxani11flti Yield: 91.0% m.p.: 113-115°C Maee (m/z) : 243 (M+), 123.94 NMR (CDCl^) h ppm: 7.47-6.95 (4H, m) , 6.1 UH, 0), 2.66 (3H, q) , 2.60 (3H, 0), 2.29 (3H, 0), 1.25 OH, t) Example 2i 3' - laopropvl -2.5- dlmethvl furan- 3. carfc»-»™n < n Yield: 84.0% m.p.: 79-80°C Maee (m/z)j 257 (M4*), 149.135 XH NMR (CDC13) b ppm: 7.47-6.98 (4H, m), 6.11 (1H, «), 2.91 (1H, q.q), 2.60 (3H, 8), 2.29 (3H, 0). 1.26 id, 6H) 263884 Bxample 22 .6' -pi»thvi-a. s-dimethyl furan-VcarhniMnUitte Yield: 85.2% m.p.: 128.U-131.0°C Mass (m/2): 271 (M+), 242.229 1H NMR (CDClj) 6 ppm: 7.28-7.12 (3H/ m), 6.82 (1H, b) , 6.16 (1H, 8), 2.63 (4H, q), 2.58 <3H, s) , 2.31 (3H, 8), 1.20 <6H, t) Bxample 23 3'-Httxyl-2,5 -dimethylEurta-3 -car^wxanl Urte (Step l) To a solution of. 3.95 g of 2,5-dimethylfuran-3-carbonyl chloride in 60 ml of dichloromethane were added 3.45 ml of triethylamine and 2.99 ml of m-iodoaniline under ice-cooling, and the resulting mixture was stirred at room temperature for 6.S hours. After the reaction mixture was cooled, it was diluted by adding 50 ml of dichloromethane. The diluted mixture was successively washed with 1 N sodium hydroxide, l N hydrochloric acid and a saturated aqueous solution of sodium chloride and dried over sodium sulfate followed by distilling off the solvent. The residue was subjected to column chromatography through silica gel to give 7.64 g of 2,5-dimethylfuran-3-carboxy(3-iodo&nilide) as pale-yellow 263884 crystals in a 39.9% yield.

(Step 2) To & solution of 0.60 g o£ the crystals obtained in Step l in 6 ml of diethyl ether were added 29.3 mg of [l,l'-bis(diphenylphoaphino)ferrocene]palladium(II) chloride and 11 ml of 1 M hexylmagnesium bromide, prepared from hexyl bromide and magnesium, divided into aix equal parta, and the resulting mixture was stirred at room temperature for 47 houra. After adding 2 N hydrochloric acid to the reaction mixture, the catalyst was filtered off and the filtrate was extracted with diethyl ether. The extract was successively washed with an aqueous solution of sodium bicarbonate and a saturated aqueous solution of sodium chloride and dried over sodium sulfate. After distilling off the solvent, the residue waa purified by chromatography through ailica gel and then D-ODS-5, YMC-pacJced column to give 316 mg of the desired compound as white crystals in a 52.8% yield. m.p.: 71.5 - 72.0°C 1H NMR (CDClj) I ppm: 7.45 (1H, m), 7.35 (1H, m), 7.25 (1H. b), 7.22 (1H, t» J-8HZ), 6.95 (1H, d, J-8Ht), 6.1 (1H, a), 2.65-2.5 (2H, m), 2.55 (3H, s), 2.25 (3H, a). 1.7-1.5 (2H, m), 1.4-1.2 (6H, m) , 0.85 (3H, t, J-7H2) IR (KBr) cm"1: 3310, 1643, 1077, 788 - 263884 Elemental analysis (%): Calc'd for CigH25N02: C, 76.22; H, 8.42; N, 4.68. Pound: C, 76.15; H, 8.54; N, 4.55 Following the similar procedure as above, but using an appropriate Grignard reagent instead of hexylmagneaium bromide, there were obtained the following compounds.

Bxample 24 3' -Butvl-2 . S -dimethylfuran-^-narbciatanilide Yield: 36.4% m.p.: 77.0-80.0°C XH NMR (CDClj) 6 ppm: 7.45 (1H, m), 7.35 <1H, m), 7.25 <1H, b) , 7.22 (1H, t, J-BHz), 6.95 (1H, d, , 6.1 (1H, s), 2.6b-2.55 (2H. m). 2.55 (3H, 8), 2.25 (3H, 8), 1.6 (2H, m), 1.35 (2H, m) , 0.92 (lH, t, J-7H*) IR (KBR) cm"1: 3285, 1646, 1075, 702 Elemental analysis t%): Calc'd for C17 75.25; H, 7.80; N, 5.16. Pound: C, 75.13; H, 7.87; N, 5.13 Example 25 V -figc-butvl-2 .S-dlmafKylfuran-^-earftn^iirll Yield: 28.1% m.p.: 80.0-81.0°C XH NMR (CDC13) 8 ppm: 26388 7.4 (1H, m) , 7.38 (1H, m) , 7.25 (1H, b), 7.22 (1H, t, J-8HZ), 6.95 (1H, d, J-8Hl), 6.1 (1H. a), 2.65-2.5 (1H, m), 2.55 (3H, a), 2.25 (3H, a), 1.68-1.5 (2H, m), 1.25 (3H, d, J-7HZ), 0.85 (3H, t, J-7Hz) XR (KBr) cm-1: 3255, 1647, 1078, 791 Elemental analyaia (%) : Calc'd for C^H^NOjt C, 75.25; H, 7.80; N, 5.16. Pound: C. 75.19; H, 7.68; N, 5.14 Bxample 26 3 ' - Pant vl -2.5- dims fchvl furan - 3 - carbmtanl 11 da Yield: 18.3% m.p.: 97.0-97.5°C 2H NMR (CDC13) 6 ppm: 7.45 (1H, m), 7.35 (1H, m), 7.28 (1H, b) , 7.25 (1H, t, J«8Hz), 6.95 (1H, d, J«8Hz), 6.1 (1H, a), 2.65-2.5 (2H, m) , 2.55 (3H, a), 2.25 (3K, 0), 1.7-1.5 (2H, in), 1.4-1.2 (4H, m) , 0.88 (3H, t, J-7HZ) IR (KBr) cm"1: 3304, 1644, 1077, 710 Elemental analyaia (%) : Calc'd for C^H^NOj: C, 75.76; H, 8.12; N, 4.91. Found: C, 75.77; H, 8.18; N, 5.06 Example 27 - 5 NO" 1S55 r i r 2038^4 3' - cyclohaxyl -2.5-flimathylturan-3 - carboxanUIfle Yield: 52.7% m.p,: 113.0-114.5°C 1H NMR (CDClj) h ppm: 7.48 (1H, m), 7.35 <1H, m), 7.28 (1H. b),7.25 (1H, t, J-BHz), 6.98 (1H, d, J-8Hz>, 6.1 (lH, ■), 2.55 (3H, a), 2.55*2.45 (1H,' m) , 2.25 (3H, s) , 1.95-1.68 (5H, m), 1.55-1.15 (5H, m) IR (KBr) cm*1: 3324, 1646, 1230, 1074, 791 Elemental analysis (%): Calc'd for C19H23N02! C' 76.74 j H, 7.80; N, 4.71. Found: C, 76.62; H, 7.78; N, 4.67 Example 2 8 3'-CvclQpentvl-2.5-dlmethvlfuran-3 -carboxaailide Yield: 35.9% m.p.: 92.0-93.0°C 1H NMR (CDC13) « ppm: 7.45 (1H, m) , 7.35 (1H, m) , 7.25 (1H, To), 7.22 (1H. t, J»8Hz), 7.00 (1H, d, J*8Hz), 6.1 (1H, S), 3.08-2.9 (1H, m), 2.55 (3H, B), 2.25 (3H, 8), 2.15-1.95 (2H, m), 1.9-1.5 (6H, m) IR (KBr) cm"1: 3322, 1647, 1232, 1076, 700 Elemental analysis (%): Calc'd Cor C18H21N02: C, 76.30; H, 7.47; N, 4.94. Found: C, 76.21; H, 7.56; N, 4.93 • 38 26 3 8 <3 Example 29 3'-Banzvl-2.5-dimethylfuran-3 -carboxanillde Yield: 59.8% m.p.: 123.0-125.0°C 1H NMR (CDC13) 6 ppm: 7.45 (1H, m), 7.38 (1H, m), 7.35-7.15 (7H, m) , 6.95 (1H, d, J-8HZ), 3.98 (2H, a), 2.55 (3H, 8). 2.25 OH, 8) Elemental analysis (%); Calc'd for C21H19M02: C' 78.66; H, 6.27; N, 4.59. Found: C. 77.76; H, 6.28; N, 4.55 Referential Example l Ethvl 2.5-dimethylfuran-3 -carboxylate To a suspension of 2.4 g of sodium hydride (60% dispersion in mineral oil) in 10 ml of N,N~dimethylformamide (hereinafter, abbreviated ae DMF) & solution of 6.5 ml of • ethyl acetoacitate in 5 ml of DMF was added dropwise with stirring under ice-cooling, and 5.97 ml of chloroacetone were added dropwise thereto with stirring under ice-cooling. After stirring at room temperature for 3 hours, the reaction mixture was poured into water and the aqueous mixture was extracted with ethyl acetate. The extract was washed with IR (KBr) cm"1: 3314, 1640. 1070, 777, 701 263884 a saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was distilled in vacuo to give 8.01 g of ethyl aacetonitrile-acetoacetate having b.p. 105°C/2 mmHg in a 86% yield.

To a solution of the ester thus obtained in 20 ml of ethanol were added 2 g of p-toluenesulfonic acid, and the resulting mixture was heated under reflux for 2 hours. The reaction mixture was allowed to cool to room temperature and the solvent was distilled off under reduced pressure. The residue was dissolved in ethyl acetate and the solution was washed with a saturated aqueous solution of sodium chloride followed by drying over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the residue was purified by column chromatography through silica gel using a 10:1 mixture of n-hexane and ethyl acetate as an eluent to give 5.14 g of ethyl 2,5-dimethylfuran-3-carboxylate in a 71% yield.

Referential Example 2 2.5-Dimethylfuran-3-carboxvlic acid A mixture of 3.2 g of ethyl 2,5-dimethylfuran-3-carboxylate, 35 ml of ethanol and 20 ml of 2 N sodium hydroxide was stirred at room temperature 263884 for 1.5 hours followed by heating under reflux for an hour. After the reaction mixture was allowed to cool to room temperature, it was concentrated under reduced pressure. The residue was dissolved in water and acidified with diluted sulfuric acid. Precipitated crystals were collected by filtration, washed with water and dried to give 2.27 g of 2,5-dimethylfuran-3-carboxylic acid in a 85% yield. 26 38 8 4 The compound having the general formula (I) mentioned above and the composition containing the compound (I) as the active ingredient, with which the present invention are concerned, can be employed by mixing with carriers or, if necessary, with any other additives, followed by the preparation of formulations usually employed such as oil solution, emulsifiable concentrate, solubilizer, paste, wettable powder, flowabie, dry flowable, spray and paint, and then the formulation can be used according to any known method for wood preservative treatment. As the additives which are employed suitably to improve the property of the formulation and to strengthen the wood preserving effect, there may be mentioned cationic, anionic and non-ionic surfactants, various high polymer compounds such as methylcellulose and vinyl acetate resin and water-repellents such as silicon oil and paraffin. It is needless to say that combined use may be possible with other wood preservatives, fungicides and bacteriocides including organic iodine compounds such as Sanplas, IF-1000 and Troysan, azole compounds such as Propiconazole and Tebuconazole, Thiabendazole, Dichlofluanid and quaternary ammonium salt compounds; with insecticides including pyrethroids such as Permethrin, Etofenprox, Cypermethrin, Silaneophen, Tralomethrin, organic phosphor compounds such as Chloropyrifos, Phoxim and Propetamphos, and Imidacroprid; and with potentiators such as <?, 42 ^ V \J , : ^ C- bia-(2,3,3,3-cecrachlorpropyl) ether. An increased effect can be expected by combined use in this manner. In a real case of application, though the content of the compound of the present invention can be changed within a wide range depending on the formulation or on the object, it may usually be suitable to use from 0.1 to 95 weight percent, preferably from 0.2 to 60 weight percent. These formulations are employable in usual methods for wood treatment: for example, coating, dispersal, dipping treatment, mixing, impreganation, or mixing treatment with an adhesive.

Several formulation examples of the compound of the present invention will be shown below, in which it is needless to say that the combination ratio and the kind of additives can be changed widely (in the descriptions below, part means weight part in all cases).

Formulation examples of the wood preservatives Formulation Example 1 Emulsifiable concentrate Twenty parts of Compound of Example 20 were dissolved in 70 parts of xylene, and then 10 parts of polyoxyethylene nonyl phenyl ether were added and mixed enough to obtain the emulsifiable concentrate.

Thus obtained entulsifiable concentrate is diluted with a suitable amount of water at use, and can be applied to a wood material to be treated by coating, dipping or INTELLECTUAL PROPERTY OFFICE OF NZ 0 3 JUN 1998 RECEIVED <6S.«. u & -f spraying, and in addition, employable by mixing with adhesives which are used for plywood, particle board and hardboard.

Formulation Example 2 Oil solution Two parts of Compound of Example 21 were added with 98 parts of kerosene oil to obtain the oil solution.

Thus obtained oil solution can be applied to a wood material to be treated by spraying, coating, dipping or impregantion.

Formulation Example 3 Coating formulation Ten parts of Compound of Example 20, 20 parts of Barite dust, 10 parts of vinyl resin, 25 parts of pine resin and 35 parts of xylene were mixed homogeneously to obtain the coating formulation.

Formulation Example 4 Wettable powder Forty parts of Compound of Example 22, 56 parts of clay, 3 parts of sodium lauryl alcohol sulfonate and 1 part of polyvinyl alcohol were mixed homogeneously in a mixer, and pulverized by use of a hammer-mi11 to obtain the wettable powder.

Test examples of wood preservation The effectiveness of the wood preservative of the INTELLECTUAL PROPERTY OFFICE OF N.Z 0 3 J'J!J 1998 RECEIVED 44 26 3 8 8 4 present invention will be explained concretely by the following examples. (1) According to the test method for wood preservation described in the Japan Industrial Standards [JIS A-9201 (1991)], each of the test compounds was dissolved to a defined concentration in methanol. The solution was impregnated under a reduced pressure into a Sugi (Japanese cedar) sapwood (2x2x1) cm and then air-dried. Weathering test was repeated 10 times in which one cycle of the treatment was stirring in water for 8 hours, and then heating for 16 hours at 60°C. The test material was placed on the flora of Serpula lacrym&ns which had been previously grown on a quartz sand medium (malt extract 2%, glucose 1%, peptone 0.3% and yeast 0.2%), and forcedly decayed at 20°C for 12 weeks. From the difference between the dry weight of the test material before the test and that after test, the degree of decrease in weight was obtained. Table 2 shows the results. The test was carried out by use of 9 samples for each condition, and the values shown in Table 2 are the mean values calculated from 9 samples. - 45 Table 2 Sample drugs Impregnant Mean weight decrease concentration (%) by decay (%) EXAMPLE 20 0.01 0 0.005 0.1 EXAMPLE 21 0.01 0 0.005 0 Control compound 1 0.01 9.7 0.005 18.6 Without treatment 18.4 Control compound 1: 4-Chlorophenyl-3 -iodopropargylformal Product of Nagase Co., Ltd.: IF-1000 From the data shown above, the compound having the general formula (I) prevented decay of the wood samples due to wood-rotting fungi to a significant extent . (2) Each of 0.1 w/v % methanol solutions of the compound of the present invention and the control drug was impregnated into the test material [a Sugi (Japanese cedar) sapwood, 2x2x0.5 cm] under a reduced pressure and then air-dried. Weathering test was repeated twice in which one cycle of the treatment was washing (about 2 liter per minute supply) with water for 5 hours, and then heating for 19 hours at 60°C. After dry air sterilization, the test samples were prepared.

The test materials were placed on the flora of Coriolua versicolor which is a lignin-decomposing fungus, INTELLECTUAL PROPERTY OFFICE OF N2. 0 3 JUN 1998 RECEIVED 46 and of Tvromyces palustria which is a cellulose-decomposing fungus, and both of which are designated fungal species for assay of wood preservating effect. Both fungi had been previously grown on an agar medium (malt extract 2%, glucose IV and peptone 0.5%). After the wood samples were forcedly deteriorated at 26°C for 3 weeks, the effectiveness was determined from the degree of hyphal growth on the test material and the presence or absence of lowered maximum crushing strength. Table 3 shows the result.

The wood preventive efficacy was judged by the following criteria.

+: No hyphal growth was observed on the test material, and no difference was found in the maximum crushing strength from the healthy wood sample.

+: A little hyphal growth was observed on the test material, or a little decrease was found in the maximum crushing strength.

-: Hyphal growth was observed on the test material, or clear decrease was found in the maximum crushing strength.

Table 3 Test drug Coriolus versicolor Tyromyces palustris EXAMPLE 1 + EXAMPLE 2 INTELLECTUAL PROPERTY OFFICE OF N2. 0 3 JUN 1998 RECEIVED 47 - EXAMPLE 3 EXAMPLE 4 EXAMPLE 5 EXAMPLE 6 EXAMPLE 7 EXAMPLE 8 EXAMPLE 9 EXAMPLE 10 EXAMPLE 11 EXAMPLE 12 EXAMPLE 13 EXAMPLE 14 EXAMPLE 15 EXAMPLE 2 0 EXAMPLE 21 EXAMPLE 23 EXAMPLE 24 EXAMPLE 2 5 EXAMPLE 26 Control compound 2 Without treatment 0&'e4 + + _+ ± + + + + + + + + + Control compound 2: 3-Bromo-2,3-diiodo-2- propenylethylcarbonate Product of Sankyo Co., Ltd.: Sanplas When the composition of the present invention is desired to be employed, the combination ratio may be •NTEUECTUAL PROPERTY OFFICE OFN1 0 3 JUN 1998 .RECEIVED 49 •J O " . \ \ dipping or spraying, and in addition, employable by mixing r" ' with adhesives which are used for plywood, particle board and hardboard.

Formulation Example 2 Oil solution Two parts of Compound of Example 21 and 1 part of troysan were dissolved in 96 parts of kerosene oil to obtain the oil solution.

Formulation Example 3 Wettable powder Fifteen parts of Compound of Example 22, 25 parts of IF-1000, 56 parts of clay, 3 parts of sodium lauryl alcohol sulfonate and 1 part of polyvinyl alcohol were mixed homogeneously in a mixer, and pulverized by use of a hammer-mill to obtain the wettable powder.

The effect of the wood preservative composition of the present invention will be explained concretely by the following examples.

Test Examples of wood preservative compositions Assay of minimum inhibitory concentration by the agar dilution method.

According to the agar dilution method, on sterilized media (potato dextrose agar medium; potato extract powder 0.4%, glucose 2%, agar 1.5%) prepared to contain certain concentrations of a test sample, flora (about 4 mm in diameter) of wood rotting fungi, Corlolus versicolor and Tvromvces palustris. which had been cultured previously on INTELLECTUAL PROPERTY OFFICE OF NZ 0 3 JUN 1998 50 the same kind of medium, were inoculated. After culture ^ ^ at 25°C for 5 days, hyphal growth was observed to determine the minimum inhibitory concentration.

Whether there is any potentiation or not has been described in Applied Microbiology 2, 538-541 (1961) by F. C. Kull et al. The assay was carried out according to the method usually employed.

Table 4 and Figures 1 (a)- (f) show the results obtained by combination of EXAMPLE 20 with each of Sanplas, Troysan and IF-1000. § 0 Table 4-1 MIC (ppm) of EXAMPLE 20 combined with several other active agents (Combined ratio) Test EXAMPLE 20 EXAMPLE 20 + A EXAMPLE 20 :A fungus 2.5 15 1.30 +3.0 ( 1 : 2.3) Coriolus Versicolor 0.8 +5.0 (1:6.3) 0.4 + 9.0 ( 1 : 22.5) 200 25 110.0 + 5.0 (22 : 1) Tyromyces Palustris 70.0 +9.0 (7.8: l) 40.0 +14.0 (2.9: 1) rfCTUAL PROPERTY OFFICE OF N1 0 3 JUN 1998 RECEIVED 51 2 ^ L Table 4-2 MIC (ppm) of EXAMPLE 20 _ combined with several other active agents Test EXAMPLE 20 EXAMPLE 20 + B fungus B (Combined ratio) EXAMPLE 2 0:B 2.5 25 1.25 + 5.0 (1:4) Coriolus Versicolor 0.8 +7.5 (1:9.4) 0.4 +12.5 ( 1 : 31.3) 200 2.5 120.0 + 0.6 (200: 1) Tyromyces Palustris 80.0 +1.0 ( 80: 1) 40.0 + 1.5 (26.7:1) Table 4-3 MIC (ppm) ot EXAMPLE 2 0 combined with several other active agents (Combined ratio) Test EXAMPLE 20 EXAMPLE 20 + C EXAMPLE 20 :C fungus C 2.5 6 1.25 + 1.2 (1.0: 1) Coriolus Versicolor 0.8 +1.8 (1:2.3) A: Sanplas B: Troysan C: IF-1000 0.5 +3.0 (1:6) 200 2 120.0 + 0.5 (240: 1) Tyromyces Palustris 80.0 + 0.8 (100: 1) 40.0 + 1.2 ( 33 :1) INTELLECTUAL PROPERTY OFFICE OF HI. 0 3 JUN 1998 RECEIVED 52 0 1 r) Then, the same test as above was carried out for (j fj EXAMPLE 21. Table 5 and Figures 2 (a)-(C) show the result.

Table 5-1 MIC (ppm) of EXAMPLE 21 combined with several other active agents Test EXAMPLE 21 fungus a EXAMPLE 21 + A (Combined ratio) EXAMPLE 21:A .0 Coriolus Versicolor 6.0 3.5 + 3.0 + 5.0 (2:1) ( 1 : 1.4) 2.0 + 8.0 ( 1:4) 200 Tyromyces Palustris 120.0 75.0 + 5.0 + 9.0 ( 24 : 1) ( 8.3: 1) 40.0 + 15.0 ( 2.7: 1) Table 5-2 MIC (ppm) of EXAMPLE 21 combined with several ether active agents (Combined ratio) Test EXAMPLE 21 EXAMPLE 21 t B EXAMPLE 21 :B fungus B .0 25 5.5 + 5.0 (1.1 : 1) Coriolus Versicolor 3.0 +8.0 (1 : 2.7) 1.5 +12.5 (1 : 8.3) 200 2.5 120.0 + 0.7 (171.4: 1) Tyromyces Palustris 90.0 + 1.0 (90 : 1) 40.0 + 1.75 ( 22.9: 1) INTELLECTUAL PROPERTY OFFICE OF HI. 0 3 JUN 1998 RECEIVED V , , J J Table 5-3 MIC (ppm) Of EXAMPLE 21 combined with several other active agents A' •T? (Combined ratio] Test EXAMPLE 21 EXAMPLE 21 + C EXAMPLE 21-C fungus C .0 6 6.0 + 1.6 (3.6 : 1) Coriolus Versicolor 4.0 + 2.4 (1.7 : l) 2.0 + 3.6 (1 : 1.8) 200 2 120.0 + 0.5 (240 : 1) Tyromyces Palustris 90.0 + 1.0 (90 : 1) 40.0 + 1.4 ( 28.6: 1) A: Sanplas B: Troysan C: IF-1000 Each of the minimum inhibitory concentration curves shown in Figs. 1 and 2 lies under the diagonal line shown by broken line.

This data exhibits that the furancarboxyanilide ' derivative potentiates the effect of each of Sanplas, Troysan and IF-1000 by combination.

INTELLECTUAL PROPERTY OFFICE OF N2. 0 3 JUN 1998 RECEIVED

Claims (10)

WHAT WE CLAIM IS:

1. Dimethylfurancarboxyanilide derivatives represented by the general formula (I): represents: a hydrogen atom; an alkyl group having from 2 to 6 carbon atoms; a cycloalkyl group having from 3 to 6 carbon atoms; an alkenyl group having from 3 to 6 carbon atoms; an alkynyl group having from 2 to 6 carbon atoms; a halogenoalkyl group having from 1 to 3 carbon atoms; an alkoxy group having from 2 to 6 carbon atoms; an alkoxyalkyl group having from i to 6 carbon atoms in the alkoxy moiety and from 1 to 6 carbon atoms in the alkyl moiety; a cyano group; an amide group substituted by one or two alkyl groups which may be the same or different and each has from 1 to 6 carbon atoms, a phenyl group which may be unsubstituted or substituted by at least one substituent selected from halogen atoms, alkyl groups having from 1 to 6 carbon atoms and alkoxy groups having from l to 6 carbon atoms, a pyrrolidyl group or a-piperidyl group; an alkoxycarbonyl group having from 1 to 6 carbon atoms in the alkoxy moiety; a benzoyl group which may have optionally 1 2 wherein R and R are the same or different and each 2r V. V. " ■ substituents selected from halogen atoms, alkyl groups having from l to 6 carbon atoms and alkoxy groups having from 1 to 6 carbon atoms; a benzoylamino group which may have optionally from 1 to 2 substituents selected from halogen atoms, alkyl groups having from 1 to 6 carbon atoms and alkoxy groups having from 1 to 6 carbon atoms; an alkanoylamino group having from 2 to 6 carbon atoms; a cycloalkylcarbonylamino group having from 3 to 6 carbon atoms in the cycloalkyl moiety; a benzyl group which may have optionally from l to 2 substituents selected from halogen atoms, alkyl groups having from 1 to 6 carbon atoms and alkoxy groups having from l to 6 carbon atoms; a phenyl group; or an alkoxycarbonylalkenylene group having from 1 to 6 carbon atoms in the alkoxy moiety and from 2 to 5 carbon atoms in the alkenylene moiety; PROVIDED THAT: 1 2 (i) R and R do not both represent hydrogen atoms; l 2 (ii) one of R and R does not represent an alkyl group having from 2 to 6 carbon atoms, an alkoxy group having from 2 to 6 carbon atoms, a halogenoalkyl group having from 1 to 3 carbon atoms or a phenyl group when the other represents a hydrogen atom; and 1 2 (iii) one of R and R does not represent, in the ortho position on the aniline ring, a cycloalkyl group having from 3 to 6 carbon atoms when the other is a hydrogen atom.

2. A dimethylfurancarboxyanilide derivative of general 1 2 formula (I) according to Claim 1 wherein R and R are the same or different and each represents: a hydrogen atom; an alkyl group having from 2 to 6 carbon atoms; an alkenyl group having from 3 to 4 carbon atoms; ifJTFi l FP.TUAL PROPERTY OFFICE or N2. 0 3 JUN 1998 RECEIVED 56 *-0 u o' 4 an alkynyl group having from 2 to 4 carbon atoms; a cycloalkyl group having from 3 to 6 carbon atoms; an alkoxycarbonyl group having from 1 to 6 carbon atoms in the alkoxy moiety; an alkoxyalkyl group having from 1 to 6 carbon atoms in the alkoxy moiety and having from 1 to 2 carbon atoms in the alkyl moiety; a cycloalkylcarbonylamino group having from 3 to 6 carbon atoms in the cycloalkyl moiety; an alkoxy group having from 2 to 4 carbon atoms; a benzoyl group which may have optionally from l to 2 substituents as defined in Claim 1; a benzyl group which may have optionally from 1 to 2 substituents as defined in Claim 1; or an alkoxycarbonylalkenylene group having from 1 to 6 carbon atoms in the alkoxy moiety and having from 2 to 5 carbon atoms in the alkenylene moiety.

3. A dimethylfurancarboxyanilide derivative of general 1 2 formula (I) according to Claim 1 wherein R and R are the same or different and each represents: a hydrogen atom; an alkyl group having from 2 to 6 carbon atoms; an alkenyl group having from 3 to 4 carbon atoms; a cycloalkyl group having from 5 to 6 carbon atoms; an alkoxycarbonyl group having from 1 to 3 carbon atoms in the alkoxy moiety; an alkoxymethylene group having from l to 6 carbon atoms in the alkoxy moiety; a cycloalkylcarbonylamino group having from 4 to 6 carbon atotis in the cycloalkyl moiety; a benzoyl group; a benzyl group which may have optionally 1 substituent as defined in Claim 1; or an alkoxycarbonylalkenylene group having from 1 to 3 carbon atoms in the alkoxy moiety and having from 2 to 4 carbon atoms in the alkenylene moiety INTELLECTUAL PROPERTY OFFICE OF MX 0 3 JUN 1998 IVED J* /■"> ' - 57 C, H < r: v u :■') j %,r 4

4. A dimethylfurancarboxyanilide derivative of general formula (I) according to Claim 1 wherein: R1 represents: a 3-alkoxycarbonyl group having from 1 to 3 carbon atoms in the alkoxy moiety; a 3-alkoxymethyl group having from 1 to 3 carbon atoms in the alkoxy moiety; a cycloalkylcarbonylamino group having from 4 to 6 carbon atoms in the cycloalkyl moiety; a benzyl group which may be substituted by a methoxy group; a benzoyl group; or an alkoxycarbonylalkenylene group having from l to 3 carbon atoms in the alkoxy moiety and having from 2 to 3 carbon atoms in the alkenylene moiety; and 2 R represents a hydrogen atom.

5. A dimethylfurancarboxyanilide derivative of general formula (I) according to Claim 1 wherein said derivative is 3'-benzyl-2,5-dimethylfuran-3-carboxyanilide.

6. A wood preservative composition containing an effective amount of a dimethylfurancarboxyanilide derivative of general formula (I') as defined below as the active ingredient: jntV®* * CH3^O^CH3 wherein R and R' each represents: a hydrogen atom; are the same or different and [Intellectual?ropers urni*] 0 3 J'JN 1998 RECEIVED, 58 *6 W an alkyl group having from 2 to 6 carbon atoms; a cycloalkyl group having from 3 to 6 carbon atoms; an alkenyl group having from 3 to 6 carbon atoms; an alkynyl group having from 2 to 6 carbon atoms; a halogenoalkyl group having from l to 3 carbon atoms; an alkoxy group having from 2 to 6 carbon atoms; an alkoxyalkyl group having from 1 to 6 carbon atoms in the alkoxy moiety and from 1 to G carbon atoms in the alkyl moiety; a cyano group; an amide group substituted by one or two alkyl groups which may be the same or different and each has from l to 6 carbon atoms, a phenyl group which may be unsubstituted or substituted by at least one substituent selected from halogen atoms, alkyl groups having from 1 to 6 carbon atoms and alkoxy groups having from 1 to 6 carbon atoms, a pyrrolidyl group or a piperidyl group; an alkoxycarbonyl group having from 1 to 6 carbon atoms in the alkoxy moiety; a benzoyl group which may have optionally from 1 to 2 substituents selected from halogen atoms, alkyl groups having from 1 to 6 carbon atoms and alkoxy groups having from 1 to 6 carbon atoms; a benzoylamino group which may have optionally from 1 to 2 substituents selected from halogen atoms, alkyl groups having from 1 to 6 carbon atoms and alkoxy groups having from 1 to 6 carbon atoms; an alkanoylamino group having from 2 to 6 carbon atoms; a cycloalkylcarbonylamino group having from 3 to 6 carbon atoms in the cycloalkyl moiety; a benzyl group which may have optionally from 1 to 2 substituents selected from halogen atoms, alkyl groups having from l to 6 carbon atoms and alkoxy groups having from 1 to 6 carbon atoms; a phenyl group; or an alkoxycarbonylaiKenylene group having from 1 to 6 carbon atoms in the alkoxy moiety and from 2 d 4 naasfcasap"0FRCE| j 3 1998 RECEIVED 59 c0 atoms in the alkenylene moiety; PROVIDED THAT R1 and do not both represent hydrogen atoms.

7. A wood preservative composition according to Claim 6 wherein said dimethylfurancarboxyanilide derivative is 3'-isopropyl-2,5-dimethylfuran-3-carboxyanilide.

8. A method of preserving wood comprising applying to the wood a composition comprising an effective amount of a dimethylfurancarboxyanilide derivative of general formula (I') as defined in Claim 6.

9. A method of preserving wood according to Claim 8 wherein said dimethylfurancarboxyanilide derivative is 3'-i sopropyl-2,5-dimethylfuran- 3 -carboxyani1ide.

10. A wood preservative composition wherein at least one dimethylfurancarboxyanilide derivative of general formula (I') as defined in Claim 6 is combined with at least one compound selected from 3-bromo-2,3-diiodo- 2-propenylethylcarbamate (Sanplas), 3-iodo-2-propynylbutylcarhamate (Troysan) and 4-chlorophenyl- 3-iodopropargylformal (IF-1000). i > , 1 W CUUks INTELLECTUAL PROPERTY OF N2. 0 3 J'JN 1998