AU678826B2

AU678826B2 - Dimethylfurancarboxanilide derivative

Info

Publication number: AU678826B2
Application number: AU65131/94A
Authority: AU
Inventors: Kiyoshi Konishi; Akio Saito; Toshiaki Yanai
Original assignee: Sankyo Co Ltd
Current assignee: Sankyo Lifetech Co Ltd
Priority date: 1993-10-15
Filing date: 1994-04-15
Publication date: 1997-06-12
Anticipated expiration: 2014-04-15
Also published as: WO1995010511A1; NZ263884A; AU6513194A

Description

LT- C 1 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, s ~1 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.

O

J.R (I I)

CH

3 0

CH

3 [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 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 -L I~s pM II I 3 observed and a wood preservative composition can be prepared.

The compounds of the present invention are the dimethylfurancarboxyanilide derivatives represented by the general formula 0 ,-R 1

CH

3 0

CH

3 [In this formula, R 1 and R 2 are the same or different and each represents 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 alkoxylkylene 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

V

7 rf" 0~ I -L SL~S I~ -4b~ LI II 4 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 moi and having from 2 to 5 carbon atoms in the alkenylene moiety; and R 1 and R 2 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. 1 show the minimum inhibitory concentrations (ppm) of Compound of Example 1 in combination with various wood preservatives. Fig. 2 show the minimum inhibitory concentrations (ppm) of Compound of Example 2 in combination with various wood preservatives.

[The best mode for working of the invention] In the general formula above, as an alkyl group having from 2 to 6 carbon atoms, which is included in the definitions for R 1 and R 2 there may be mentioned a straight or branched chain alkyl group such as ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, a

~I~C_

5 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 above, as a cycloalkyl group having from 3 to 6 carbon atoms, which is included 1 2 in the definitions for R and R 2 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 above, as an alkenyl group having from 3 to 6 carbon atoms, which is included in the 1 2 definitions for R 1 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 above, as an alkynyl group having from 2 to 6 carbon atoms, which is included in the 1 2 definitions for R and R 2 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 above, as a halogenoalkyl group having from 1 to 3 carbon atoms, which is included apr IL b s~,u 6 1 2 in the definitions for R and R 2 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 1 to 2 carbon atoms; and more preferably trifluoromethyl.

In the general formula above, as an alkoxy group having from 2 to 6 carbon atoms, which is included in the definitions for R 1 and R 2 there may be 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 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 1 to 6 carbon atoms in the alkyl moiety, which is included in the definitions for

R

1 and R 2 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 carbon atoms; and more preferably an alkoxy group having from 1 to 3 carbon atoms or having 5 carbon atoms.

In the general formula above, as an alkylene group S IIP%~l I plB1 I 7 contained in an alkoxyalkylene group having from 1 to 6 carbon atoms in the alkoxy moiety and from 1 to 6 carbon atoms in the alkylene moiety which is included in the definitions for R and R 2 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 above, as a substituted amide group, which is included in the definitions for R 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 above, as an alkoxycarbonyl group having from 1 to 6 carbon atoms in the alkoxy I C ~P Id~ Ld

TI

8 moiety, which is included in the definitions for R 1 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 1 to 6 carbon atoms in the alkoxy moiety and having from 1 to 6 carbon atoms in the 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 1 to 3 carbon atoms in the alkoxy moiety.

In the general formula 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 2 there may be mentioned an optionally substituted benzoyl group such as benzoyl, 2-chlorobenzoyl, 2,4-dichlorobenzoyl, :-methylbenzoyl, 2,4-dimethylbenzoyl, 4-ethylbenzoyl or 4-methoxybenzoyl; preferably benzoyl.

In the general formula above, as a benzoylamino group which may have optionally from 1 to 2 substituents, 1 2 which is included in the definitions for R 1 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, ~l-1 M 9 2,4-dichlorobenzoylamino, 2,4-dimethylbenzoylamiiio, 4-methylbenzoylamino, 4-ethylbenzoylairtino or 4-methoxybenzoylamino; preferably benzoylamino.

In the general formula above, as an alkanoylamino group having from 2 to 6 carbon atoms, which is included 1 2 in the definitions for R and R2, there may be mentioned acbcylamino, propionylamino, butyrylamino, isobutyrylamino, valerylamino, isovalerylamino, caproylamino or isocaproylamino; preferably acetylamino.

In the general formula 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 R2, there may be mentioned cyclopropylcarbonylamino, cyclobutylcarbonylamino, cyclopentylcarbonylamino or cyclohexylcarbonylamino; preferably cyclohexylcarbonylamino.

In the general formul 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-inethoxybenzyl or 4-ethoxybenzyl; preferably benzyl.

In the general formula 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 T1 tJ 71O ~I P141R~ T

Y

10 1 2 definitions for R 1 and R there may be mentioned methoxycarbonylvinylene, ethoxycarbonyl-2-propenylene, methoxycarbonyl-2-butenylene or ethoxycarbonyl-2-pentenylene; preferably methoxycarbonylvinylene.

Preferred compounds having the general formula (I) above include ones in which:

R

1 and R 2 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 1 to 6 carbon atoms in the alkoxy moiety and having from 1 to 2 carbon atoms in the alkylene 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 1 to 2 substituents; a benzyl group which may have optionally fronm 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 atoms in the alkenylene moiety; and R 1 and R 2 do not represent hydrogen atoms at the same time. More preferred ones include those in which: Jig 11

R

1 and R 2 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 1 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 1 substituent; 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; and R1 and R 2 do not represent hydrogen atoms at the same time. Particularly preferred ones include those in which:

R

1 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

R

2 is a hydrogen atom.

I -ql II 12 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.

Benzyl Butyl H Hexyl Methyl Phenyl Piperidyl Pentyl Propyl secondary tertiary Table 1 Compound No. RlR 2 1. 3-CF 3

H

2 4-CF 3

H

3 3-CH 2 OMe H 4 4-CH 2 OMe H 2-Et H 6 3-Et H 7 4-Et H 8 3-C=-CH H 9 4-C=-CH H 3-CH 2 OEt H 11 4-CH 2 OEt H 12 2-Et 3 -Et 13 2-Et 4 -Et 14 2-Et 5 -Et 2-Et 6-Et 16 3-Et 4-Et 17 3-Et 5 -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 £4)1 24 3 -cPr H 4-cPr H 26 3-CH 2 OPr H 27 3-CH 2 OiPr H 28 4-CH 2 OiPr H 29 3-CH 2

C=CH

2

H

4-CH 2

C=CH

2

H

31 3-CH 2 C=-CH H 32 4-CH 2 C=-CH H 33 3-Pr 4-Pr 34 2-iPr 4-iPr 3-iPr 36 3-CH 2 OBu H 37 4-CH 2 0Bu H 38 3-CH 2 ~iBu H 39 4-CH 2 OiBu H 3-CH 2 0SBU H 41 4-CH 2 0SBU H 42 3-Bu H 43 4-Bu H 44 3-iBu H 3-sBu H 46 3-cBu H 47, 4-cBu H 48 3-t~u H 49 3-CH 2 CH=CH~e H z 14- L0I 3-CH 2 C=-CMe H 51. 3-CH 2 IMeCH=CH 2

H

52 4-CH 2 MeCH=CH 2

H

53 3-Pn H 54 4-Pn H 3-iPn H 56 3-cPn H 57 3-neoPn H 58 3-CH 2 OPn H 59 3-CH 2 0neo-Pn H 3-Hx H 61 3-iHx H 62 3-cHx H 63 3-CN H 64 3-aEt H 3-OiPr H 66 3-CONHMe H 67 3-(CO-1-Pip) H 68 3-CONHPh H 69 3-COOMe H 3-COQEt H 71 3-COOPr H 72 3-COOiPr H 73 3-COOBu H 74 3-CQOtBu H 3-COPh H 15 16 76 3 -CO (2 -MePh) H 77 3-NHCOPh H 78 3-NIICOMe H 79 3-NHCOBu H 3-NHCOcPn H 81 3-NHCOcHx H 82 3-Bz H 83 3-(4-MeOBz) H 84 3-(4-MeBz) H 3-CH=CIlCOOMe H 86 3-Ph H 87 3-(2-MePh) H Among the compounds above, Compound Nos. 3, 4, 5, 6, 7, 8, 19, 20, 21, 22, 23, 24, 25, 26, 36, 38, 40, 42, 43, 44, 45, 46, 56, 57, 58, 59, 60, 61, 62, 81, 82, 83 and 85; and more Compound Nos. 3, 6, 10, 19, 22, 38, 40, 42, 44, 45, 46, 48, 53, and preferred jn,, include 27, 28, 29, 31, 33, 48, 49, 50, 51, 53, 54, 64, 69, 70, 71, 72, preferred ones include 24, 26, 27, 33, 35, 36, 55, 60, 61, 69, 70, 81, 83

I

The compounds of the said general formula may be prepare. according to the procedure summarized in either the fo-1c-,ing Method A or Method B.

Method A 0 X+ H 2 N I

CH

3 0C3A2 Step Al (111) (1 V)

C

3 0 OH 3 Method B 2

OH

3 0 CH 3 Step BI.

(III)(V)

H N R 1, Mg X,1

OH

3

CH

3 Pd(dppf)C1 2 (V 1) Step 32

CH

3 0 CH 3 (1a I~ 18 In the above formulae, R 1 and R 2 are as defined above. R represents a C 1

-C

6 alkyl, C 3

-C

6 cycloalkyl or benzyl group which may optionally have 1 or 2 substituents. The compound of formula (Ia) is that of a general formula in which R 1 is R1 and R 2 signifies a hydrogen atom. The compound of formula 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 Al consists of the preparation of a compound of general formula 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.

i I 19 Examples of the inert solvents used include, for example, ethers such as ether, isopropyl ether, tetrahydrofuran or dioxane; aromatic h.ydrocarbons 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 solvent, the reaction is carried out at a cemperature of 0 C to reflux temperature of the solvent used, preferably from room temperature to 100 0 C. The time required for the reaction takes generally from minuts to 5 hours, preferably from 30 minutes to 2 hours.

Step 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 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 3^< no ql 20 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 (Ia) by reacting a compound having general formula (VI) with a Grignard reagent having 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 [1,1'-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: 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 0 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.

~1 21 The compounds having th-, said general formula in according with the inventiou 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 a 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, too. 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 1 3'-Acetylamino-2,5-dimethylfuran-3-carboxanilide 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 mnit'.ure was stirred at room cemperature for hours followed by heating under reflux for 4.5 hours.

s After the reaction mixture was cooled, it was diluted by ~s~ir 22 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 recrystallized from ethyl acetate to give 0.51 g of the desired compound as white crystals in a 59.4% yield.

172.0-172.5°C :H NMR (CDC1 3 DMSO) 6 ppm: 8.4 (1H, 7.95 (1H, 7.88 (1H, 7.4 (1H, in. 7.32 (1H, 7.25 (1H, t, J=8Hz), 6.25 (1H, 2.55 (3H, 2.25 (3H, 2.15 (3H, s) -1 IR (KBr) cm 3306, 1672, 1651, 1086, 781 oElemental analysis Calc'd for C 5

H

16

N

2 0 3 C, 66.16; H, 5.92; N, 10.29. Found: C, 66.30; H, 5.98; N, 10.32.

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

Example 2 3'-(N-methylcarbamoyl)-2,5-dimethylfuran-3-carboxanilide Yield: 42.0% 23 in.p.: 212.0-213.0 0

C

HNMR (CDCl 3 DMSO) 8 ppm: (1H, 8.05 (1H, in), 7.88 (1H, in), 7.52 (1H, in), 7.38 (1H, t, J=8Hz), 6.8 (1H, 6.35 2.95 (3H, d, J=J..4Hz), 2.55 (3H, s), 2.25 (3H, s).

IR (KBr) cm- I: 3293, 1638, 1581, 2074, 689 Elemental analysis Calc'd foc C 15

H

16

N

2 0 3 C, 66.16; H, 5.92; N, 10.29. Found: C, 66.08; H, 6.20; N, 10.28.

Example 3 (l-PiT3eridylcarbonyl) -2.5 -dimethvlfuran-3 1-c.arboxalilide Yield: 50.0?c 183.0-185.0 0

C

H NM spectrumr 8C~ ppm: 7.68 (1H, in), 7.55 (2H, in), 7.35 (lH, t, J=8Hz), 7.1 (lH, mn), 6.15 (iH, 3.7 (2H, 3.35 (2H, 2.55 (3H, 2.2E (3H, 2.75-1.4 (6H, in) IR (KBr) cm 1 3302, 1663, 1615, 1065, 808 Elemental analysis Calc'd for C 19H 22N 2C C, 69.92; H, 6.79; N, 8.58. Found: C, 69.52; H, 6.88; N, 8.48.

Example 4 (N-Thenylcarbanoyl) 5-dimethylfuran-3-carboxanilide 0&e 24 Yield: 53.5% 182.5-184.0 0

C

1H NMR (CDC1 3 DMSO) 6 ppm: 8.48 (1H, 8.2 (1H, 8.1 (1H, 7.95 (1H, 7.7 (2H, d, T=8Hz), 7.65 (1H, d, J=8Hz), 7.45 (1H, t, J=8Hz), 7.35 (2H, t, J=8Hz), 7.15 (1H, t, J=8Hz), 6.28 (1H, 2.55 (3H, 2.25 (3H, s) -1 IR (KBr) cm- 1 3282, 1646, 1080, 755, 691 Elemental analysis Calc'd for C20H18N203 C, 71.84; H, 5.43; N, 8.38. Found: C, 71.87; H, 5.64; N, 8.34.

Example o 3' -Tert-butoxvcarbonyl -2,5-dimethylfuran-3-carboxanilide Yield: 92.0% 117.0-11.00 :H NMR (CDCl 3 6 ppm: 8.05 (1H, 7.88 (1H, 7.75 (1H, 7.4 (1H, t, J=8Hz), 7.35 (1H, 6.1 (1H, 2.55 Se (3H, 2.25 (3H, 1.65 (9H, s) IR (KBr) cm 1 3362, 1687, 1672, 1067, 757 Elemental analysis Calc'd for C 8H21NO 4

C,

68.55; H, 6.71; N, 4.44. Found: C, 68.04; H, 7.00; N, 4.40.

Example 6 25 3'-Methoxvcarbonvl-2. 5-dimethvlfuran-3 -carboxanlilide Yield: 77.1% 104.0-106.0 0

C

1NH NR (CDC 3 5 ppm: 8.05 (1H, in), 7.98 (lE, ri), 7.8 (1H, in), 7.42 (l1H, t, J=8Hz), 7.38 (1H, 6.1 (1H, 3.92 (3H, s) 2.55 (3H, s) 2.25 (3H, s) IR (KBr) cm- 3437, 1704, 1675, 1070, 759 Elemental analysis Calc'd for C 5H 15NO 4:C, 65.92; H, 5.53; N, 5.13. Found: C, 66.02; H, 5.60; N, 5.08.

Example 7 3' -Benzovl-2,.5-dimethylfuran-3-carboxanilide Yield: 69.1% 137.0-139.0 0 c HND4R (CDC 3 5 PPM: 5 8.05 (1H, in), 7.85-7.7 (3H, in), 7.6 (1H, in), 7.55-7.35 (5H, in), 6.1 (1H, 2.55 (3H, s), No". 2.25 (3H, s) IR (KBr) cm 1 3386, 1672, 1647, 1069, 707 Elemental analysis Calc'd for C 20H 17NO 3:C, 75.22; H, 5.37; N, 4.39. Found: C, 75.38; H, 5.43; N, 4.38.

I

26 Example 8 3' -Benzovlamirio-2,.5-dimethylfuran-3 -carboxanilide Yield: 46.0?k 194.5-195.0 0

C

1 H NMR (CDC1 3 DMSO) 5 ppm: 8. 7 (1H, b) 8. 1 (1H, mn), 7. 95 (1H, b) 7. 9 (2 H, in), 7.6-7.4 (5H, in), 7.3 (1H, t, J=8Hz) 6.25 (1H, s) 2.55 (3H, s) 2.25 (3H, s) IR (KBr) cm- 1 3283, 1642, 1074, 791, 705 Elemental analysis (%:Calc'd for C 20

H

18

N

1 0 3 C, 71.84; H, 5.43; N, 8.38. Found: C, 71.96; H, 5.53; N, 8.28.

Example 9 3' -Valerylamino-2,.5-dimethylfuran-3-carboxanilide Yield: 70.3? a: 104.0-105.0 C 1 1 H NMR (CDC 3 6 ppm: 7.9 (1H, 7.45-7.1 (SH, mn), 6.1 (iN, 2.55 (3H, 2.35 (2H, t, J=7Hz), 2.25 (3H, 1.7 (2H, in), 1.4 (2H, mn), 0.95 (1H, t, J=7Hz) IR (KBr) cm- 1 3250, 1660, 1644, 1074, 781 Elemental analysis Calc'd for C 18H 22N 203 C, 68.77; H, 7.05; N, 8.91. Found: C, 68.73; H, 7.17; N, 8.90.

27 Example 3' -Cyclohexylcarbonvlanino -2.5 -dimethylfuran- 3- carboxanilide Yield: 45.1t 212.5-213.0 0

C

H NMR (CDCl 3 6 ppm: 7.92 (1H, 7.88 (1H, 7.45-7.35 (2H, in), 7.25 (1H, t, J=BHz), 6.22 (1H, 2.55 (3H, s), 2.25 (3H, 2.25-2.2 (1H, in), 2.0-1.2 (10H, m) IR (KBr) cm': 3238, 1651, 1639, 1076, 781 Elemental analysis Calc'd for C 20

H

4

N

2 0 C, 70.57; H, 7.11; N, 8.23. Found:C, 70.56; H, 7.26; N, 8.16 Example 11 3' -Methoxymethyl-2. 5-dimethylfuran-3-carboxanilide :Yield: 73.3% 102.5-103.5 C ~H NMR (CDCl 3 8 ppm: 7.55 (lE, mn), 7.52 (1H, d, J=8Hz), 7.32 (1H, t, J=8Hz), 7.32 (1H, 6.9 d, J=8Hz), 6.1 (1H, S) 4. 45 (2 H, s) 3. 4 (3 H, s) 2. 55 (3 H, s) 2.25 i 3H, s) IR (KBr) cma 3278, 1645, 1237, 1107, 784 Elemental analysis Calc'd for C 15H 17NO 3 C, 69.48; H, 6.61; N, 5.40. Found: C, 69.22; H, 7.02; N, 5.37.

28 Example 12 3' -Ethoxymethyl-2.5 -dimethvlfuran-3-carboxanilide Yield: 64.40- 85.0-85.5 0

C.

HNMR (CDCl 3 6 ppm: 7.65-7.55 (2H, in), 7.38 (lH, t, J=8Hz), 7.35 (1H, 7.15 (lH, d, J=8Hz), 6.15 (1H, 4.55 (2H, 3.58 (2H, q, J=8Hz), 2.55 (3H, 2.25 (3H, s) 1. 3 (3H, t, J=8Hz) IR (KBr) cm- 3279, 1646, 1115, 785 **Elemental analysis Calc'd for C 16H1 NO 3:C *70.31; H, 7.01; N, 5.12. Found: C, 70.14; H, 7.27; N, 5.06.

Example 13 3'-Isoproovloxymethyl-2,.5-dimethvlfuran-3-carboxanilide S Yield: 92.7W m.p. 68.0-69.5 ~C HNMF. (CDCl 3 7.55 (1H, d, J=8Hz), 7.5 (1H, in), 7.3 (1H, t, J=8Hz), 7.3 (1H, 7.12 (1H, d, J=8Hz), 6.1 (1H1, 4.5 (2H, 3.7 (1H, mn), 2.55 (3H, s), 2.25 (3H, 1.25 (6H, d, J=7Hz) IR (Liquid f ilm) cm 1 I: 3321, 1651, 1072, 785 29 Elemental analysis Calc'd for C 17H 21W I C, 71.06; H, 7.37; N, 4.87. Found: C, 70.35; H, 7.14; N, 4.91.

Example 14 3' -(4-Methoxybenzyl) S-dimethylfuran-3 -carboxanilide Yield: 86. 8! 100.0-102.50 HNNR (CDC 3 6 ppm: 7.45 (lH, in), 7.35 (1H, in), 7.25 (1H, t, J=8Hz), 7.25 (1H, 7.1 (2H, d, J=8Hz), 6.92 (1H, d, J=8Hz), 6.88-6.75 (1H, in), 6.82 (2H, d, J=BHz), 6.05 (1H, 3.9 (2H, 3.75 (3H, 2.55 (3H, s) 2.25 (3H, s) as-1 IR (KBr) cm- 3345, 1656, 1246, 1074, 694 Elemental analysis Calc'd for C 21

H

21 NO: C, 75.20; H, 6.31; N, 4.18. Found: 75.28; H, 6.32; N, 4.21.

safe a* 9 Examnple 3' -Methoxycarbonylvinyl) -2,5 -dimethylfuran- 3- carboxanilide Yield: 63.3% 159.7--161.5 0

C

1HNMR (CDC1 3 6 ppmi: 30 7.82 (1H, in), 7.7 (1H, d, J=l5Hz), 7.58 ClH, m), 7. 38 (1H, 7.35 (1H, t, J=8Hz), 7.28 (1H, m), 6. 48 (1H, d, J=l5Hz) 6.12 (1H, s) 3.82 (3H, s) 2.55 (3H, 2.25 (3H, s) IR (KBr) cm 1 I: 3387, 1685, 1670, 1068, 800 Elemental analysis Calc'd for C 17 H17 0O4 C, 68.22; H, 5.72; N, 4.68. Found: C, 67.55; H, 5.64; N, 4.62.

Example 16 Phenyl-2. 5-dimethylfuran- 3-carboxanilide Yield: m.p. 90.0-92.00 9. 1 H NMR (CDCl 3 8 ppm: 7.82 (1H, 7.6 (2H, d, J=8Hz), 7.55 (1H, d, J=8Hz), 6.48-6.3 (6H, mn), 6.12 (1H, 2.55 (3H, 2.25 (3H, s) *IR (KBr) cm 3367, 1646, 1074, 755 Elemental analysis Calc'd for C 19H 17NO 2C, 783;H, 5.88; N, 4.81. Found:,C, 78.17; H, 6.00; N, 4. 72.

Example 17 3' -Neopentyloxymethyl -2.5 -dimethylfuran- 3- carboxanilide Yield: 50.0% 95.5-97.0 0 31 Hi NM (CDC 3 8 ppm.: 7.48 (2H, in), 7.32 (1K, t, J=8HZ), 7.3 (1H, b), 7.12 (11K, d, J=8Hz), 4.52 (2H, 3.12 (2H, s), 2.55 (3H, s) 2.25 (3H, s) 0. 95 (9H, s) IR (KBr) cm- 3324, 1646, 1091, 700 Elemental analysis Calc'd for C 19H 25NO 3:C, 72.35; H, 7.99; N, 4.44. Found: C, 72.38; H, 8.03; N, 4.20.

Example 18 3' -IsoTropeny1-2,.5-diiethvlfuran-3-carboxanilide V, Yield: 50.0k6 1 HK NM4R (CDCl 3 8 ppm: 7.65 (1K, in), 7.5 (1K, mn), 7.3 (1K, 7.3 (1K, t, J=8Kz), 7.22 (1H, in), 6.12 (1K, 5.4 (1K, 5.1 (1H, 2.6 (3K, 2.55 (3K, 2.25 (3K, s) sees IR (KBr) cm- 3275, 1641, 1580, 1078, 790 Elemental analysis Calc'd for C H NO :C, 16 17 2' 75.27; K, 6.71; N, 5.49. Found: C, 75.29; H, 6.88; N, 5.48.

Example 2.9 3' -Ethyvnyl-2,.5-dimrethvlfuran-3 -carboxanilide Yield: 50.0%6 32 83.0-84.0 0

C

HNNR (CDC 3 8 ppm: 7.7 (1H, mn), 7.6 (lH, in), 7.32-7.2 (3H, mn), 6.1 (1H, 3.05 2.55 (3H, 2.25 (3H, s) IR (KBr) cm 1 I: 3245, 1644, 1079, 796 Elemental analysis Calc'd for C 15H 13NO C, 75.30; H, 5.48; N, 5.85. Found: C, 75.50; H, 5.46; N, 5.96.

Example eas*:3' -Ethyl-2,.5-dimethvlfuran-3-carboxanilide Yield: 91.0%k *Vgo 113-1150 Mass 243 (M 12 .7594 HNMR (CDC 3 6 ppm: 557.47-6.95 (4H, in), 6.1 (1H, 2.66 (3H, q), :2.60 (3H, 2.29 (3H, 1.25 (3H, t) 0

S

0:004: Example 21 loco 3' -Isopropvyl-2. 5-diiethvlfuran-3-carboxanilide Yield: 84.0% 79-80 0 Mass 257 (M 14j.135 1H NNR (CDC 3 8 ppm: 7.47-6.98 (4H, in), 6.11 (lH, 2.91 (1H, q,q), 2.60 (3H, 2.29 (3H, s),*1.26 6H) 33 Example 22 2',6'-Diethyl-2,5-dimethylfuran-3-carboxanilide Yield: 85.2% 128.0-131.0°C Mass 271 242.228 H NMR (CDC13) 6 ppm: 7.28-7.12 (3H, 6.82 (1H, 6.16 (1H, s), 2.63 (4H, 2.58 (3H, 2.31 (3H, 1.20 (6H, t) Example 23 3'-Hexyl-2,5-dimethylfuran-3-carboxanilide (Step 1) To a solution of 3.95 g of 2,5-dimethylfuran-3-carbonyl chloride in 60 ml of dichlcromethane 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 hours. After the reaction mixture was cooled, it was diluted by adding 50 ml of dichloromethane. The diluted *0**00 S" mixture was successively washed with 1 N sodium hydroxide, 1 N hydrochloric acid and a saturated aqueous solution of 0* 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-iodoanilide) as pale-yellow fF S, T y 7A^ )Vr 0 1- 34 crystals in a 89.9% yield.

(Step 2) To a solution of 0.68 g of the crystals obtained in Step 1 in 8 ml of diethyl ether were added 29.3 mg of [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) chloride and 11 ml of 1 M hexylmagnesium bromide, prepared from hexyl bromide and magnesium, divided into six equal parts, and the resulting mixture was stirred at room temperature for 47 hours. 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 .i was purified by chromatography through silica gel and then D-ODS-5, YMC-packed column to give 316 mg of the desired compound as white crystals in a 52.8% yield.

71.5-72.0°C H NMR (CDC13) 6 ppm: 7.45 (1H, 7.35 (1H, 7.25 (1H, 7.22 (1H, t, J=8Hz), 6.95 (1H, d, J=8Hz), 6.1 (1H, s), 2.65-2.5 (2H, 2.55 (3H, 2.25 (3H, s), 1.7-1.5 (2H, 1.4-1.2 (6H, 0.85 (3H, t, J=7Hz) IR (KBr) cm- 1 3310, 1643, 1077, 788 Y b-P3 35 Elemental analysis Calc'd for C 1 9 2 5

N

2

C,

76.22; H, 8.42; N, 4.68. Found: C, 76.15; H, 8.54; N, 4.55 Following the similar procedure as above, but using an appropriate Grignard reagent instead of hexylmagnesium bromide, there were obtained the following compounds.

Example 24 3' -Butvl-2. 5-dimethylfuran-3-carboxanilide Yield: 36.4!k m.p. 77.0-80.00C H NMR (CDC 3 8 ppm: 7.45 (1H, in), 7.35 (lIH, in), 7.25 (1H, 7.22 (1H, t, J=8Hz), 6.95 (l1H, d, J=8Hz), 6.1 (lH, s), 2.65-2.55 (2H, in), 2.55 (3H, 2.25 (3H, E), IR 1.6 (2H, in), 1.35 (2H, mn), 0.92 (1H, t, J=7Hz) I(KBR) cm- 3285, 1646, 1075, 702 :Elemental analysis Calc'd for C 17

H

21 N0 2

C,

:75.25; H, 7.80; N, 5.16. Found: C, 75.13; H, 7.87; N, 0 5.13 Example 3' -Sec-butyl-2. 5-dimethvlfuran-3 -carboxanilide Yield: 38.1*1 8'0.0-81.0 0

C

1HNNR 6 ppm: 36 7.4 (1H, in), 7.38 (1H, in), 7.25 (1H, b) 7.22 (1H, t, J=8Hz) 6.95 (1H, d, J=8Hz) 6.1 (1H, S), 2.65-2.5 (1K, in), 2.55 (3H, s) 2.25 (3H, s), 1.68-1.5 (2H, mn), 1. 25 (3H, J=7Hz) 0. 85 (3H, t, J=79z) IR (KBr) cm- 1: 3255, 1647, 1078, 791 Elemental analysis Calc'd for C 17H 21NO2:C 75.25; H, 7.80; N, 5.16. Found: C, 75.19; H, 7.68; N, .14 Example 26 3' -Pentyl-2,.5-dimethylfuran-3 -carboxanilide Yield: 18.3% C. CC 0 C 97.0-97.5 C 1H NNR (CDC1 3 8 ppm: 7.45 (1H, mn), 7.35 (1H, mn), 7.28 (1H, 7.25 2.65-2.5 (2H, mn), 2.55 (3H, 2.25 (3H, s), 1.7-1.5 (2H, mn), 1.4-1.2 (4H, in), 0.88 (3H, t, J=7Kz) -1 IR (KBr) cm :3304, 1644, 1077, 710 *Elemental analysis Cal~c'd for C H NO :C, C18 23 2 75.76; H, 8.12; N, 4.91. Found: C, 75.77; 11, 8.18; N, 5.06 Example 27 37 3' CYclohexyl-2,5-dinethlfuran-3-carboxanilide Yield: 52.7% 113.0-114.5 0

C

1NMR (CDCl 3 8 ppm: 7.48 (1H, 7.35 (iH,I 7.28 (lI, b),7.25 (1H, t, J=8Hz), 6.98 (1H, d, J=8Hz), 6.1 (1H, s), 2.55 (3H, 2.55-2.45 (1H, 2.25 (3H, s), 1.95-1.68 (5H, 1.55-1.15 (5H, m) IR (KBr) cm 1 3324, 1646, 1230, 1074, 791 Elemental analysis Calc'd for C19H23 N C 76,74; H, 7.80; N, 4.71. Found: C, 76.62; H, 7.78; N, 4.67 Example 28 3'-Cvclo~enty-2,5-diiethlfuran-3-carboxanilide Yield: 35.9% 92.0-93.00 H NNR (CDCl 3 6 ppm: 7.45 (1H, 7.35 (1H, 7.25 (1H, 7.22 (1H, t, J=8Hz), 7.00 (1H, d, J=8Hz), 6.1 (1H, s;, 3.08-2.9 (1H, in), 2.55 2.25 (3H, s), 2.15-1.95 (2H, 1.9-1.5 (6H, m) .(KBr) cm 3322, 1647, 1232, 1076, 700 Elemental analysis Calc'd for C 1 8

H

2 1 N 2 C 1 76.30; H, 7.47; N, 4.94. Found: C, 76.21; H, 7.56; N, 4.93 'p 38 Example 29 3'-Benzyl-2,5-dimethylfuran-3-carboxanilide Yield: 59.8% 123.0-125.0 0

C

1H NMR (CDC13) 6 ppm: 7.45 (1H, 7.38 (1H, 7.35-7.15 (7H, m), 6.95 (1H, d, J=8Hz), 3.98 (2H, 2.55 (3H, s), 2.25 (3H, s) -1 IR (KBr) cm 3314, 1640, 1078, 777, 701 Elemental analysis Calc'd for C21H19NO2 C, 78.66; H, 6.27; N, 4.59. Found: C, 77.76; H, 6.28; N, S..4.55 Referential Example 1 i Ethyl 2,5-dimethylfuran-3-carboxylate 0 0 To a suspension of 2.4 g of sodium hydride dispersion in mineral oil) in 10 ml of N,N-dimethylformamide (hereinafter, abbreviated as DMF) a solution of 6.5 ml of ethyl acetoacetate in 5 ml of DMF 0 i 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 39 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 0 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 .'cetate 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-carboxylic acid A mixture of 3.2 g of ethyl 2,5-dimethylfuran-3-carboxylate, 35 ml of ethanol and ml of 2 N sodium hydroxide was stirred at room temperature 4 40 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.

'I 41 The compound having the general formula mentioned above and the composition containing the compound 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, flowable, 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 I q 42 bis-(2,3,3,3-tetrachlorpropyl) 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 1 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 emulsifiable 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

II--

S43 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 2 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 1, 20 parts of Barite dust, 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 3, 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.

Test examples of wood preservation The effectiveness of the wood preservative of the

R__

a II 44 present invention will be explained concretely by the following examples.

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 (2 x 2 x 1) 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 The test material was placed on the flora of SerPula lacrymans which had been previously grown on a quartz sand medium (malt extract glucose peptone 0.3% and yeast 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 ehc.n in Table 2 are the mean values calculated from 9 ksamples.

-IMOMM~rl 45 Table 2 Sample drugs Impregnant Mean weight decrease concentration by decay Compound No. 20 0.01 0 0.005 0.1 Compound No. 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 prevented decay of the wood samples due to wood-rotting fungi to a significant extent 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, 2 x 2 x 0.5 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 0 C. After dry air sterilization, the test samples were prepared.

The test materials were placed on the flora of Coriolus versicolor which is a lignin-decomposing fungus, 46 and of Tyromyces palustris 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 glucose 1% and peptone 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 Compound No. 1 Compound No. 2 I I M IPCI -C 47 Compound No. 3 Compound No. 4 Compound No. Compound No. 6 Compound No. 7 Compound No. 8 Compound No. 9 Compound No. 10 Compound No. 11 Compound No. 12 Compound No. 13 Compound No. 14 Compound No. 15 Compound No. 20 Compound No. 21 Compound No. 23 Compound No. 24 Compound No. 25 Compound No. 26 Control compound 2 Without treatment Control compound 2: 3-Bromo-2,3-diiodo-2propenylethylcarbonate Product of Sankyo Co., Ltd.: Sanplas When the composition of the present invention is desired to be employed, the combination ratio may be icj^R ,J (9a^ I- I 48 suitably selected depending on the kind of wood and the kind of wood material to be treated with the wood preservative, or the means for treatment (for extple, coating, dipping, dispersal, impregnation, mixing and mixing with an adhesive). Usually, the combination ratio of dimethylfurancarboxyanilide and any other wood preservative may be from 240:1 to 1:35, preferably from 30:1 to 1:10, and more preferably from 5:1 to The content of the composition of the present invention may be changed within a wide range depending on the formulation. In general, the content may be from 0.1 to 95%, preferably from 0.2 to 60%, in the formulation.

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.

Formulation examples of the wood preservative composition Formulation Example 1 Emulsifiable concentrate Ten parts of Compound 1 were dissolved in 30 parts of Sanplas and 50 parts of xylene, 10 parts of polyoxyethylene nonyl phenyl ether were then added and mixed enough to obtain the emulsifiable concentrate.

Thus obtained emulsifiable concentrate is diluted with a suitable amount of water at the time of use, and can be applied to a wood material to be treated by coating, p 49 dipping or 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 2 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 3, 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 glucose agar prepared to contain certain concentrations of a test sample, flora (about 4 mm in diameter) of wood rotting fungi, Coriolus versicolor and Tyromyces palustris, which had been cultured previously on 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 9, 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 show the results obtained by combination of Compound 20 with each of Sanplas, Troysan and IF-1000.

Table 4-1 MIC (ppm) of Compound No. 1 combined with several other active agents (Combined ratio) Test Compd. Compd. No. 1 A Compd. No.l:A fungus No. 1 A 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 1) 40.0 +14.0 1) S51 Table 4-2 MIC (ppm) of Compound No. 1 several other active agents combined with (Combined ratio) Test Compd. Compd. No. 1 B Compd. No.l:B fungus No. 1 B 25 1.25 5.0 1 4) Coriolus Versicolor 0.8 7.5 1 9.4) 0.4 +12. 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) of Compound No. 1 combined with several other active agents (Combined ratio) Test Compd. Compd. No. 1 C Compd. No.l:C fungus No. 1 C 6 1.25 1.2 1) Coriolus Versicolor 0.8 1.8 1 2.3) 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) A: Sanplas B: Troysan C: IF-1000 zi I, I o ya~sn~rra~CIIII-r- 52 Then, the same test as above was carried out for Compound 2. Table 5 and Figures 2 show the result.

Table 5-1 MIC (ppm) of Cornound No. 2 several other active agents combined with Test Compd.

fungus No. 2 (Combined ratio) Compd. No.2:A Compd. No. 2 A 10.0 15 6.0 3.0 2 1) Coriolus Versicolor 3.5 5.0 1 :1.4) 8.0 1 4) 200 25 120.0 5.0 (24 1) Tyromyces Palustris 75.0 9.0 8.3: 1) 40.0 +15.0 2.7: 1) Table 5-2 MIC (ppm) of Compound No. 2 combined with several other active agents (Combined ratio) Test Compd. Compd. No. 2 B Compd. No.2:B fungus No. 2 B 10.0 25 5.5 5.0 (1.1 1) Coriolus Versicolor 3.0 8.0 (1 2.7) +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) 53 Table 5-3 MIC (ppm) of Compound No. 2 combined with several other active agents (Combined ratio) Test Compd. Compd. No. 2 C Compd. No.2:C fungus No. 2 C 10.0 6 6.0 1.6 (3.6 1) Coriolus Versicolor 4.0 2.4 (1.7 1) 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.

Claims

1. Dimethylfurancarboxyanilide derivatives represented by the general formula o R 1 CH 3 CH 3 wherein R 1 and R 2 are the same or different and each 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; e an alkoxy group having from 2 to 6 carbon atoms; an alkoxyalkyl group having from 1 to 6 carbon atoms in the oo.* alkoxy moiety and from 1 to 6 carbon atoms in the alkyl 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 0'!0 substituents; 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; a phenyl group which has from 1 to 2 substituents; 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: 0 R 1 and R 2 do not both represent hydrogen atoms; (ii) one of R 1 and R 2 does not represent an unsubstituted phenyl group when the other represents a hydrogen atom; and (iii) one of R1 and R 2 does not represent, in the ortho position on the aniline ring, an alkyl group having from 2 to 6 carbon atoms, a cycloalkyl group having from 3 to 6 carbon atoms or an alkoxy group having from 2 to 6 carbon atoms when the other is a hydrogen atom.

2. A wood preservative composition containing the dimethylfurancarboxyanilide derivative of Claim 1 as the active ingredient.

3. A method of preserving wood comprising applying to the wood a composition comprising an effective amount of a compound having the general formula 0 RI C 6 R 2 CH3 C H 3 wherein R and R 2 are the same or different and each 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 *:fee: atoms; an alkynyl group having from 2 to 6 carbon atoms; a halogenoalkyl group having from 1 to 3 carnon 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 6 carbon atoms in the alkyl 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 benzylamino group which may have optionally from 1 to 2 substituents; an alkanoylamino group having from 2 to 6 s/ carbon atoms; a cycloalkylcarbonylamino group having c -56- from 3 to 6 carbon atoms in the cycloalkyl 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 from 2 to 5 carbon atoms in the alkenylene moiety; PROVIDED THAT R 1 and R 2 do not both represent hydrogen atoms.

4. A wood preservative composition wherein at least one compound selected from the dimethylfurancarboxyanilide derivatives as defined in Claim 3 is combined with at least one compound selected from 3-bromo-2,3-diiodo- 2-propenylethylcarbamate (Sanplas), 3-iodo-2- propynylbutylcarbamate (Troysan) and 4-chlorophenyl- 3-iodopropargylformal (IF-1000).

*5 S S ooo *s **Dated this 19th day of November 1996 Sankyo Company Limited By its Patent Attorneys S Davies Collison Cave 0 Abstract Dimethylfurancarboxyanilide derivatives represented by the general formula (I) 0 R 1 J R2 (i) CH3 0 CH 3 [In this formula, R 1 and R 2 are the same or different and each represents hydrogen atom; a (C 2 -C 6 )-alkyl group; a (C 3 -C 6 )-cycloalkyl group; a (C 3 -C 6 )-alkenyl group; a (C 2 -C 6 )-alkynyl group; a (C 1 -C 3 )-halogenoalkyl group; a (C 2 -C 6 )-alkoxy group; a (C -C 6 )-alkoxy-(C 1 -C 6 )-alkyl group; a cyano group; a substituted amide group; a (C 1 -C 6 )-alkoxy-carbonyl group; a benzoyl group which may have optionally from 1 to 2 substituents; a benzoylamino group which may have optionally from 1 to 2 substituents; a (C2-C 6 )-alkanoylamino group; a (C 3 -C 6 )-cycloalkylcarbonylamino group; a benzyl group which may have optionally from 1 to 2 substituent; a phenyl group which may have optionally from 1 to 2 substituent; or a (C 1 -C 6 )-alkoxycarbonyl- 1 2 (C 2 -C 5 )-alkenylene group; and R and R do not represent hydrogen atoms at the same time]; a wood preservative containing the dimethylfurancarboxyanilide derivative as the active ingredient, and a wood VPservative composition in which s the dimethylfurancarboxyanilide derivative as the active ingredient is combined with any other commercially available wood preservative the effect of which has been confirmed. The wood preservatives above show an excellent wood preservative effect at a low concentration.