RU2120442C1 - Dimethylfurancarboxyanilide, protecting composition for wood (variants), and method of protection of wood - Google Patents

Abstract

FIELD: wood-working industry. SUBSTANCE: present invention concerns dimethyl furancarboxyanilide of general formula:

wherein R¹ and R² are the same or different and are hydrogen, (C₂-C₆) alkyl, (C₃-C₆) cycloalkyl, (C₃-C₆) alkenyl, (C₂-C₆) alkynyl, (C₁-C₃) halogenalkyl, benzoyl containing substituents, benzoylamino which also containing one or two substituents, (C₂-C₆) alkanoylamino, (C₃-C₆) cycloalkyl carbonylamino, benzyl which contains substituents, phenyl with optional substituents and also other substituents provided that R¹ and R² are not hydrogen atoms, and second condition is that one of R¹ and R² is not unsubstituted phenyl, whereas the other is hydrogen atom, and third condition is that one of R¹ and R² is ortho-position is not aniline ring, (C₂-C₆) alkyl, (C₃-C₆) cycloalkyl or (C₂-C₆) alkoxy, whereas the other is hydrogen atom. The present invention concerns protecting composition for wood comprising, as active ingredient, effective amount of said compound. The present invention describes method of protection of wood which comprises applying onto wood composition comprising effective amount of composition comprising effective amount of compound defined by the formula given above. The present invention concerns protecting composition for wood, which comprises mixture of at least one compound derivative of the formula given above and at least one compound selected from 3-bromo-2,3-diiodo-2-propenylethyl carbamate, 3-iodo-2-propylbutyl carbamate and 4- chlorophenyl-3-iodopropargylformal. The present invention makes it possible to make novel antiseptic for wood. Use of said antiseptic is safer and is more effective at low concentrations. Cost if antiseptic is low. EFFECT: more effective activity of the protecting composition. 5 cl, 2 dwg, 36 ex, 9 tbl

Description

Technical field
The present invention relates to new dimethylfurancarboxyanilide derivatives exhibiting excellent antimicrobial effects, to a wood preservative containing a dimethylfurancarboxyanilide derivative as an active component, and to a wood protective composition in which a dimethylfurancarboxyanilide derivative as one of the active components is combined with any other commercially offset wood preservative, the effect of which has already been confirmed.

State of the art
To protect timber from rotting due to a variety of fungi causing rotting of wood, various types of inorganic and organic compounds were previously used. However, these drugs have drawbacks, such as the effect on the human body due to their high toxicity, visible environmental pollution, the need for their high concentration during use and high cost.

 Regarding the compounds related to the dimethylfurancarboxyanilide derivatives of the present invention, the compounds represented by the following formula have been described in Japanese Patent Kokai Application Sho 50-10376 as chemical preparations preventing plant damage; in which, however, the radical R is limited to phenyl, 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 about other derivatives, and the activity of these compounds against wood-destroying fungi has not been described.

Сущность изобретения
Целью настоящего изобретения является создание нового антисептика для древесины, который более безопасен и который может быть более эффективно использован в низких концентрациях и/или при этом стоимость его должна быть невысокой.

SUMMARY OF THE INVENTION
The aim of the present invention is to provide a new wood preservative that is safer and which can be more effectively used in low concentrations and / or at the same time its cost should be low.

 Given the similar situation mentioned above, the authors of the present invention examined derivatives of furancarboxyanilide and intensively studied them. The result of the applicants' studies was that the new dimethylfurancarboxyanilide derivatives represented by the following formula I are very useful as wood preservatives, and moreover, if the dimethylfurancarboxyanilide derivative as an active component f is combined with any other commercially available wood preservative, an effect of enhancement can be observed , and can be made of a protective composition for wood.

В этой формуле R¹ и R² одинаковы или различны и каждый представляет собой атом водорода; алкильную группу, содержащую от 2 до 6 атомов углерода; циклоалкильную группу, содержащую от 3 до 6 атомов углерода; алкенильную группу, содержащую от 3 до 6 атомов углерода; алкинильную группу, содержащую от 2 до 6 атомов углерода; галогеналкильную группу, содержащую от 1 до 3 атомов углерода; алкоксигруппу, содержащую от 2 до 6 атомов углерода; алкоксиалкиленовую группу, содержащую от 1 до 6 атомов углерода в алкоксисоставляющей части и содержащую от 1 до 6 атомов углерода в алкиленовой составляющей части; цианогруппу; замещенную амидную группу; алкоксикарбонильную группу, содержащую от 1 до 6 атомов углерода в алкокси части; бензоильную группу, которая может, необязательно, содержать от 1 до 2 заместителей; бензоиламиногруппу, которая может, необязательно, содержать от 1 до 2 заместителей; алканоил-аминогруппу, содержащую от 2 до 6 атомов углерода; циклоалкилкарбониламиногруппу, содержащую от 3 до 6 атомов углерода в циклоалкильной части; бензильную группу, которая может, необязательно, содержать от 1 до 2 заместителей; фенильную группу, которая может, необязательно, содержать от 1 до 2 заместителей; или алкоксикарбонилалкениленовую группу, содержащую от 1 до 6 атомов углерода в алкокси части и содержащую от 2 до 5 атомов углерода в алкениленовой части; причем R¹ и R² одновременно не являются атомами водорода.The compounds of the present invention are dimethylfurancarboxyanilide derivatives represented by the general formula

In this formula, R ¹ and R ^{2 are the} same or different and each represents a hydrogen atom; an alkyl group containing from 2 to 6 carbon atoms; cycloalkyl group containing from 3 to 6 carbon atoms; an alkenyl group containing from 3 to 6 carbon atoms; alkynyl group containing from 2 to 6 carbon atoms; haloalkyl group containing from 1 to 3 carbon atoms; alkoxy group containing from 2 to 6 carbon atoms; alkoxyalkylene group containing from 1 to 6 carbon atoms in the alkoxy moiety and containing from 1 to 6 carbon atoms in the alkylene moiety; cyano group; substituted amide group; alkoxycarbonyl group containing from 1 to 6 carbon atoms in the alkoxy part; a benzoyl group, which may optionally contain from 1 to 2 substituents; benzoylamino group, which may optionally contain from 1 to 2 substituents; alkanoyl amino group containing from 2 to 6 carbon atoms; cycloalkylcarbonylamino group containing from 3 to 6 carbon atoms in the cycloalkyl part; a benzyl group, which may optionally contain from 1 to 2 substituents; a phenyl group, which may optionally contain from 1 to 2 substituents; or an alkoxycarbonylalkenylene group containing from 1 to 6 carbon atoms in the alkoxy part and containing from 2 to 5 carbon atoms in the alkenylene part; moreover, R ¹ and R ² at the same time are not hydrogen atoms.

 The present invention relates to the above compounds, an antiseptic for wood and an antiseptic composition for wood containing a dimethylfurancarboxyanilide derivative as an active component.

Brief Description of the Drawings
In FIG. 1 (a) - (e) show the minimum inhibitory concentrations (in ppm - mn ^-1) of the compound of Example 1 in combination with various wood preservatives. In FIG. 2 (a) - (e) show the minimum inhibitory concentrations (mn ^-1) of the compound of Example 2 in combination with various wood preservatives.

The best way to use the invention
In the indicated general formula I, as an alkyl group containing from 2 to 6 carbon atoms, which is included in the definitions for R ¹ and R ² , a linear or branched chain alkyl group such as ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl or sec-hexyl; particularly preferably, an alkyl group containing from 2 to 6 carbon atoms.

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

In the indicated general formula I, an alkenyl group such as allyl, isopropenyl, metal, 2-butenyl, 3-butenyl may be indicated as an alkenyl group containing from 3 to 6 carbon atoms, which is included in the definitions for R ¹ and R ² 1,3-butanedienyl, 2-pentenyl or 2-hexenyl; preferably an alkenyl group containing from 3 to 4 carbon atoms; and more preferably isopropenyl.

In the general formula I as an alkynyl group containing from 2 to 6 carbon atoms, which is included in the definitions for R ¹ and R ^2, an alkynyl group can be specified, such as ethynyl, propargyl, 2-butynyl, 4-pentynyl or 2 hexynyl; preferably an alkynyl group containing from 2 to 4 carbon atoms; and more preferably ethinyl.

In said general formula I, a haloalkyl group such as trifluoromethyl, trichloromethyl, pentafluoroethyl, 2,2,2-trichloroethyl may be indicated as a haloalkyl group containing from 1 to 3 carbon atoms, which is included in the definitions for R ¹ and R ² or 2,4-dichloropropyl; preferably a haloalkyl group containing from 1 to 2 carbon atoms; and more preferably trifluoromethyl.

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

In the specified general formula I, as containing from 1 to 6 carbon atoms, an alkoxy group included in the alkoxyalkyl group containing from 1 to 6 carbon atoms in the alkoxy part and containing from 1 to 6 carbon atoms in the alkyl part, which is included in the definitions for R ¹ and R ² , a straight or branched chain alkoxy group may be indicated, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentoxy, neopentoxy or hexyloxy; preferably an alkoxy group containing from 1 to 5 carbon atoms; and, more preferably, an alkoxy group containing from 1 to 3 carbon atoms or containing 5 carbon atoms.

In the indicated general formula I, as the alkylene group of the alkoxyalkylene group containing from 1 to 6 carbon atoms in the alkoxy part and from 1 to 6 carbon atoms in the alkylene part, which is included in the definitions for R ¹ and R ² a linear or branched chain alkylene group such as methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene or hexamethylene is indicated; preferably an alkylene group containing from 1 to 2 carbon atoms; and more preferably methylene.

In the indicated general formula I, a monoalkylamide group such as methylamide, ethylamide, isopropylamide, butylamide, sec-butylamide may be indicated as a substituted amide group, which is included in the definitions for R ¹ and R ² ; a dialkylamide group such as dimethylamide, diethylamide, diisopropylamide, dibutylamide, di-sec-butylamide, methylethylamide, methylisopropylamide, methylbutylamide, methyl sec-butylamide, ethyl isopropylamide, isopropylbutylamide, pyrrolidylamide or piperidylamide; optionally substituted phenylamide such as phenylamide, 2-chlorophenylamide, 2,4-dichlorophenylamide, 2-methylphenylamide, 2-ethylphenylamide or 4-methoxyphenylamide; preferably methylamide, piperidylamide or phenylamide.

In said general formula I, as an alkoxycarbonyl group containing from 1 to 6 carbon atoms in the alkoxy part, which is included in the definitions for R ¹ and R ² , a group which is formed by the aforementioned alkoxy group containing from 1 to 6 carbon atoms may be indicated, part of an alkoxyalkyl group containing from 1 to 6 carbon atoms in the alkoxy part and containing from 1 to 6 carbon atoms in the alkyl part and a carbonyl group such as methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, sec utoksikarbonil tert -butoxy-carbonyl, pentyloxycarbonyl, or hexyloxycarbonyl; preferably an alkoxycarbonyl group containing from 1 to 3 carbon atoms in the alkoxy part.

In the general formula I as a benzyl group which may optionally contain from 1 to 2 substituents, which is included in the definitions for R ¹ and R ^2, there may be mentioned 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 indicated general formula I, an optionally substituted benzoylamino group which is formed by substitution in the amino group (s) with the above benzene group may be indicated as a benzoylamino group, which may optionally contain from 1 to 2 substituents, which is included in the definitions for R ¹ and R ² which may optionally contain from 1 to 2 substituents, such as benzoylamino, 2-chlorobenzoylamino, 2,4-dichlorobenzoylamino, 2,4-dimethylbenzoylamino, 4-methylbenzoylamino, 4-ethylbenzoylamino or 4-methoxybenzoylamino; preferably benzoylamino.

In the indicated general formula I, an alkanoylamino group containing from 2 to 6 carbon atoms, which is included in the definitions for R ¹ and R ² , may include an acetylamino group, a propionylamino group, a butyrylamino group, an isobutyrylamino group, a valerylamino group, an isovalerylamino group, a caproylamino group or an isocapro; preferably an acetylamino group.

In said general formula I, as a cycloalkylcarbonylamino group containing from 3 to 6 carbon atoms in the cycloalkyl part, which is included in the definitions for R ¹ and R ² , the group cyclopropylcarbonylamino, cyclobutylcarbonylamino, cyclopentylcarbonylamino or cyclohexylcarbonylamino; preferably cyclohexylcarbonylamino.

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

In said general formula I, as an alkoxycarbonylalkenylene group containing from 1 to 6 carbon atoms in the alkoxy part and containing from 2 to 5 carbon atoms in the alkenylene part, which is included in the definitions for R ¹ and R ² , methoxycarbonylvinylene, ethoxycarbonyl- 2-propenylene, methoxycarbonyl-2-butenylene or ethoxycarbonyl-2-pentenylene; preferably methoxycarbonylvinyl.

Preferred compounds corresponding to the specified formula I include compounds in which R ¹ and R ^{2 are the} same or different, each of them represents a hydrogen atom; an alkyl group containing from 2 to 6 carbon atoms; an alkenyl group containing from 3 to 4 carbon atoms; alkynyl group containing from 2 to 4 carbon atoms; cycloalkyl group containing from 3 to 6 carbon atoms; alkoxycarbonyl group containing from 1 to 6 carbon atoms in the alkoxy part; alkoxyalkylene group containing from 1 to 6 carbon atoms in the alkoxy part and containing from 1 to 2 carbon atoms in the alkylene part; cycloalkylcarbonylamino group containing from 3 to 6 carbon atoms in the cycloalkyl part; alkoxy group containing from 2 to 4 carbon atoms; a benzoyl group, which may optionally contain from 1 to 2 substituents; a benzyl group, which may optionally contain from 1 to 2 substituents; or an alkoxycarbonylalkenylene group containing from 1 to 6 carbon atoms in the alkoxy part and containing from 2 to 5 carbon atoms in the alkenylene part; moreover, R ¹ and R ² at the same time do not represent hydrogen atoms. More preferred, said compounds include those in which: (2) R ¹ and R ^{2 are the} same or different, and each of them represents a hydrogen atom; an alkyl group containing from 2 to 6 carbon atoms; an alkenyl group containing from 3 to 4 carbon atoms; cycloalkyl group containing from 5 to 6 carbon atoms; alkoxycarbonyl group containing from 1 to 3 carbon atoms in the alkoxy part; alkoxymethylene group containing from 1 to 6 carbon atoms in the alkoxy part; cycloalkylcarbonylamino group containing from 4 to 6 carbon atoms in the cycloalkyl part; benzoyl group; a benzyl group, which may optionally contain 1 substituent; or an alkoxycarbonylalkenylene group containing from 1 to 3 carbon atoms in the alkoxy part and containing from 2 to 4 carbon atoms in the alkenylene part; moreover, R ¹ and R ² at the same time do not represent hydrogen atoms. Particularly preferred said compounds include those in which:
(3) R ¹ represents a 3-alkyl group containing from 2 to 6 carbon atoms; 3-alkoxycarbonyl group containing from 1 to 3 carbon atoms in the alkoxy part; 3-alkoxymethylene group containing from 1 to 3 carbon atoms in the alkoxy part; cycloalkylcarbonylamino group containing from 4 to 6 carbon atoms in the cycloalkyl part; a benzyl group which may be substituted with a methoxy group; benzoyl group; or an alkoxycarbonylalkenylene group containing from 1 to 3 carbon atoms in the alkoxy part and containing from 2 to 3 carbon atoms in the alkenylene part; and
(4) R ² represents a hydrogen atom.

 Examples of new derivatives of dimethylfurancarboxyanilide that can be used as the active component of the wood preservative of the present invention are presented in the following table.

In the table. 1 the following abbreviations are used:
Bz - benzyl
Bu - butyl
Et - ethyl
Hx - Hexyl
Me - methyl
Ph - phenyl
Pip - piperidyl
Pn - pentyl
Pr - cut
Among the above compounds, preferred are compounds N 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 most preferred are compounds NN 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.

 Compounds according to the specified General formula I can be obtained by the method represented either by the following method A, or method B.

Способ B

В приведенных формулах R¹ и R² определены как указано выше. R¹ представляет собой C₁-C₆ алкильную группу, C₃-C₆ циклоалкильную группу или бензильную группу, которая может, необязательно, содержать 1 или 2 заместителя. Соединение формулы Ia представляет собой соединение общей формулы I, в котором R² представляет собой R¹, а R¹ обозначает атом водорода. Соединение формулы V является иодзамещенным анилином. X обозначает атом галогена, такой как хлор, бром или йод, предпочтительно хлор. X обозначает атом галогена, такой как хлор, бром или йод, предпочтительно, бром или йод.Method A

Method B

In the above formulas, R ¹ and R ^{2 are} defined as described above. R ¹ represents a C ₁ -C ₆ alkyl group, a C ₃ -C ₆ cycloalkyl group or a benzyl group, which may optionally contain 1 or 2 substituents. The compound of formula Ia is a compound of general formula I, in which R ² represents R ¹ and R ¹ represents a hydrogen atom. The compound of formula V is iodo-substituted aniline. X represents a halogen atom such as chlorine, bromine or iodine, preferably chlorine. X represents a halogen atom such as chlorine, bromine or iodine, preferably bromine or iodine.

 Compounds of the present invention can be obtained by well-known methods.

 Step A1 involves preparing 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.

 The compound of formula III used as a starting material in this step can be obtained by hydrolysis of 2,5-dimethylfuran-3-carboxylate, which can be obtained by condensation of chloroacetone with acetoacetate and subsequent halogenation.

 The compound of formula IV used as a starting material in this step is an aniline derivative that is commercially available or can be prepared using well-known methods.

 Examples of 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 (especially 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 smoothly carry out the reaction using a solvent, the reaction is carried out at a temperature of from 0 ^° C. to the boiling point of the solvent used, preferably from room temperature to 100 ^° C. The time required for the reaction is generally from 30 minutes to 5 hours, preferably from 30 minutes to 2 hours.

 Step B1 involves preparing a compound having the general formula (VI) by reacting a compound having the general formula III with a compound having the general formula V in an inert solvent in the presence of a dehydrohalogenating agent.

 The compound of formula V used as a starting material in this step is an aniline derivative that is commercially available or can be prepared using well-known methods.

 The reaction conditions used in this step are similar to those used in step A1.

Step B2 involves preparing a compound having the general formula Ia by reacting a compound having the general formula VI with a Grignard reagent having the general formula:
R ^{1 ′} 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, [1,1'-bis (diphenylphosphino) -ferrocene] palladium (II) chloride (Pd (dppf) Cl ₂ ) can be used.

(где R^1′ и X' определены как указано выше) в соответствии с хорошо известными способами.The Grignard reagents used in this process are commercially available or can be obtained by reacting magnesium with an alkyl halide represented by the formula

(where R ^{1 ′} and X ′ are defined as described above) in accordance with well-known methods.

The reaction is usually carried out at a temperature of from 0 ^o C to 50 ^o C, preferably at room temperature. Although the time required for this reaction varies depending on the nature of the solvent and reagent that are used, usually the reaction is complete in a time ranging from 10 hours to 10 days.

 Compounds having the specified general formula I in accordance with the present invention have strong antiseptic activity against wood at a low concentration, compared with the activity exhibited by existing wood preservatives. A composition consisting of a combination of the aforementioned compound I with a known wood preservative gives a synergistic effect and lower concentrations are required than might be expected based on the activity exerted by each component individually, so that the wood exhibits effective antiseptic activity against wood at low concentration. Therefore, the new derivatives of dimethylfurancarboxyanilide are extremely effective as antiseptics for wood in low concentration, which solves one of the problems of improving the quality of life.

 The following examples illustrate the preparation of compounds of the present invention and the preparation of compositions based on them in more detail. These examples cannot be construed as limiting the scope of the present invention.

Example 1
3'-Acetylamino-2,5-dimethylfuran-3-carboxyanilide
To a solution of 0.50 g of 2.5 dimethylfuran-3-carbonyl chloride in 10 ml of dichloromethane was added 0.44 ml of triethylamine and 0.47 g of 3-acetylaminoaniline under ice cooling, and the resulting mixture was stirred at room temperature for 2.5 hours, after which it was heated under reflux for 4.5 hours. After the reaction mixture was cooled, it was diluted by adding 10 ml of dichloromethane. The diluted mixture was washed successively with 1N. sodium hydroxide, 1 N. hydrochloric acid and saturated aqueous sodium chloride and dried over sodium sulfate, after which the solvent was distilled off. The residue was purified by silica gel column chromatography and the desired fractions were recrystallized from ethyl acetate to obtain 0.51 g of the desired compound as white crystals in 59.4% yield.

Mp: 172.0 - 172.5 ^o C
¹ H NMR (CDCl ₃ + DMCO) δ mn ^-1: 8,4 (1H, br.), 7,95 (1H, br.), 7,88 (1H, m), 7,4 (1H, m ), 7.32 (1H, m), 7.25 (1H, t, J = 8 Hz), 6.25 (1H, s), 3.55 (3H, s), 2.25 (3H, s ), 2.15 (3H, s).

IR (KBr) cm ^-1 : 3306, 1672, 1651, 1086, 781.

Elemental analysis (%): Calculated for C ₁₅ H ₁₆ N ₂ O ₃ : C, 66.16; H, 5.92; N, 10.29. Found: C, 66.30; H, 5.98; N, 10.32.

 Following a procedure similar to that described above, but using a suitable aniline derivative instead of 3-acetylaminoaniline, the following compounds were obtained.

Example 2
3 '- (N-methylcarbamoyl) -2,5-dimethylfuran-3-carboxyanilide
Yield: 42.0%
T. pl .: 212.0 - 213.0 ^o C
¹ H NMR (CDCl ₃ + DMCO) δ mn ^-1: 8,5 (1H, br.), 8,05 (1H, m), 7,88 (1H, m), 7,52 (1H, m) , 7.38 (1H, t, J = 8 Hz), 6.8 (1H, broad), 6.35 (1H, s), 2.95 (3H, d, J = 1.4 Hz), 2.55 (3H, s); 2.25 (3H, s).

IR (KBr) cm ^-1 : 3293, 1638, 1581, 1074, 689.

Elemental analysis (%): Calculated for C ₁₅ H ₁₆ N ₂ O ₃ : C, 66.16; H, 5.92; N, 10.29. Found: C, 66.08; H, 6.20; N, 10.28.

Example 3
3 '- (1-piperidylcarbonyl) -2,5-dimethylfuran-3-carboxyanilide
Yield: 50.0% T. mp: 183.0 - 185.0 ^o C
¹ H NMR (CDCl ₃₎ δ mn ^-1: 7,68 (1H, m), 7,55 (2H, m), 7,35 (1H, t, J = 8 Hz), 7,1 (1H, m), 6.15 (1H, s), 3.7 (2H, broad), 3.35 (2H, broad), 2.55 (3H, s), 2.25 (3H, s), 2.75-1.4 (6H, m).

IR (KBr) cm ^-1 : 3302, 1663, 1615, 1065, 808.

Elemental analysis (%): Calculated for C ₁₉ H ₂₂ N ₂ O ₃ : C, 69.92; H, 6.79; N, 8.58. Found: C, 69.52; H, 6.88; N, 8.48.

Example 4
3 '- (N-phenylcarbamoyl) -2,5-dimethylfuran-3-carboxyanilide
Yield: 53.5%
Mp: 182.5 - 184.0 ^o C
¹ H NMR (CDCl ₃ + DMCO) δ mn ^-1: 8,48 (1H, br.), 8,2 (1H, br.), 8,1 (1H, c), 7,95 (1H, m ), 7.7 (2H, d, J = 8 Hz), 7.65 (1H, d, J = 8 Hz), 7.45 (1H, t, J = 8 Hz), 7.35 (2H, t, J = 8 Hz), 7.15 (1H, t, J = 8 Hz), 6.28 (1H, s), 2.55 (3H, s), 2.25 (3H, s).

IR (KBr) cm ^-1 : 3282, 1646, 1080, 755, 691
Elemental analysis (%): Calculated for C ₂₀ H ₁₈ N ₂ O ₃ : C, 71.84; H, 5.43; N, 8.38. Found: C, 71.87; H, 5.64; N, 8.34.

Example 5
3'-Tert-butoxycarbonyl-2,5-dimethylfuran-3-carboxyanilide
Yield: 92.0%
T. pl .: 117.0 - 118.0 ^o C
¹ H NMR (CDCl ₃₎ δ mn ^-1: 8,05 (1H, m), 7,88 (1H, m), 7,75 (1H, m), 7,4 (1H, t, J = 8 Hz), 7.35 (1H, broad), 6.1 (1H, s), 2.55 (3H, s), 2.25 (3H, s), 1.65 (9H, s).

IR (KBr) cm ^-1 : 3362, 1687, 1672, 1067, 757.

Elemental analysis (%): Calculated for C ₁₈ H ₂₁ HO ₄ : C, 68.55; H, 6.71; N, 4.44. Found: C, 68.04; H, 7.00; N, 4.40.

Example 6
3'Metoxycarbonyl-2,5-dimethylfuran-3-carboxyanilide
Yield: 77.1%
T. pl. 104.0 - 106.0 ^o C
¹ H NMR (CDCl ₃₎ δ mn ^-1: 8,05 (1H, m), 7,98 (1H, m), 7,8 (1H, m), 7,42 (1H, t, J = 8 Hz), 7.38 (1H, broad), 6.1 (1H, s), 3.92 (3H, s), 2.55 (3H, s), 2.25 (3H, s).

IR (KBr) cm ^-1 : 3437, 1704, 1675, 1070, 759.

Elemental analysis (%): Calculated for C ₁₅ H ₁₅ NO ₄ : C, 65.92; H, 5.53; N, 5.13. Found: C, 66.02; H, 5.60; N, 5.08.

Example 7
3'-Benzoyl-2,5-dimethylfuran-3-carboxyanilide
Yield: 69.1%
Mp: 137.0 - 139.0 ^o C
¹ H NMR (CDCl ₃₎ δ mn ^-1: 8,05 (1H, m), 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, s).

IR (KBr) cm ^-1 : 3386, 1672, 1647, 1069, 707.

Elemental analysis (%): Calculated for C ₂₀ H ₁₇ NO ₃ : C, 75.22; H, 5.37; N, 4.39. Found: C, 75.38; H, 5.43; N, 4.38.

Example 8
3'-Benzoylamino-2,5-dimethylfuran-3-carboxyanilide
Yield: 46.0%
T. pl .: 194.5 - 195.0 ^o C
¹ H NMR (CDCl ₃ + DMCO) δ mn ^-1: 8,7 (1H, br.), 8,1 (1H, m), 7,95 (1H, br.), 7,9 (2H, m ), 7.6 - 7.4 (5H, m), 7.3 (1H, t, J = 8 Hz), 6.25 (1H, s), 2.55 (3H, s), 2.25 (3H, s).

IR (KBr) cm ^-1 : 3283, 1642, 1074, 791, 705
Elemental analysis (%): Calculated for C ₂₀ H ₁₈ N ₁ O 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-carboxyanilide
Yield: 70.3%
T. pl.: 104.0 - 105.0 ^o C
¹ H NMR (CDCl ₃₎ δ mn ^-1: 7,9 (1H, br.), 7,45 - 7,1 (5H , m), 6,1 (1H, c), 2,55 (3H, s), 2.35 (2H, t, J = 7 Hz), 2.25 (3H, s), 1.7 (2H, m), 1.4 (2H, m), 0.95 (1H, t, J = 7 Hz).

IR (KBr) cm ^-1 : 3250, 1660, 1644, 1074, 781
Elemental analysis (%): Calculated for C ₁₈ H ₂₂ N ₂ O ₃ : C, 68.77; H, 7.05; N, 8.91. Found: C, 68.73; H, 7.17; N, 8.90.

Example 10
3'-Cyclohexylcarbonylamino-2,5-dimethylfuran-3-carboxyanilide
Yield: 45.1%
Mp: 212.5 - 213.0 ^o C
¹ H NMR (CDCl ₃ + DMCO) δ mn ^-1: 7,92 (1H, br.), 7,88 (1H, br.), 7,45 - 7,35 (2H , m), 7.25 (1H, t, J = 8 Hz), 6.22 (1H, s), 2.55 (3H, s), 2.25 (3H, s), 2.25 - 2.2 (1H, m) 2.0-1.2 (10H, m).

IR (KBr) cm ^-1 : 3238, 1651, 1639, 1076, 781.

Elemental analysis (%): Calculated for C ₂₀ H ₂₄ N ₂ O ₃ : C, 70.57; H, 7.11; N, 8.23. Found: C, 70.56; H, 7.26; N, 8.16.

Example 11
2,5-Dimethylfuran-3-carboxy (3-methoxymethylanilide)
Yield: 73.3%
Mp: 102.5 - 103.5 ^o C
¹ H NMR (CDCl ₃₎ δ mn ^-1: 7,55 (1H, m), 7,52 (1H, d, J = 8Hz), 7,32 (1H, t, J = 8Hz), 7 32 (1H, broad), 6.9 (1H, d, J = 8 Hz), 6.1 (1H, s), 4.45 (2H, s), 3.4 (3H, s), 2.55 (3H, s); 2.25 (3H, s).

IR (KBr) cm ^-1 : 3278, 1645, 1237, 1107, 784.

Elemental analysis (%): Calculated for C ₁₅ H ₁₇ NO ₃ : C, 69.48; H, 6.61; N, 5.40. Found: C, 69.22; H, 7.02; N, 5.37.

Example 12
3'-Ethoxymethyl-2,5-dimethylfuran-3-carboxyanilide
Yield: 64.4%
Mp: 85.0 - 85.5 ^o C
¹ H NMR (CDCl ₃₎ δ mn ^-1: 7,65 - 7,55 (2H, m), 7,38 (1H, t, J = 8Hz), 7,35 (1H, br.), 7 15 (1H, d, J = 8 Hz), 6.15 (1H, s), 4.55 (2H, s), 3.58 (2H, q, J = 8 Hz), 2.55 (3H , s), 2.25 (3H, s), 1.3 (3H, t, J = 8 Hz).

IR (KBr) cm ^-1 : 3279, 1646, 1115, 785.

Elemental analysis (%): Calculated for C ₁₆ H ₁₉ NO ₃ : C, 70.31; H, 7.01; N, 5.12. Found: C, 70.14; H, 7.27; N, 5.06.

Example 13
3'-Isopropyloxymethyl-2,5-dimethylfuran-3-carboxyanilide
Yield: 92.7%
Mp: 68.0 - 69.5 ^o C
¹ H NMR (CDCl ₃₎ δ mn ^-1: 7,55 (1H, d, J = 8 Hz), 7,5 (1H, m), 7,3 (1H, t, J = 8Hz), 7 , 3 (1H, broad), 7.12 (1H, d, J = 8 Hz), 6.1 (1H, s), 4.5 (2H, s), 3.7 (1H, m), 2.55 (3H, s), 2.25 (3H, s), 1.25 (6H, d, J = 7 Hz).

IR (liquid film) cm ^-1 : 3321, 1651, 1072, 785.

Elemental analysis (%): Calculated for C ₁₇ H ₂₁ NO ₃ : C, 71.06; H, 7.37; N, 4.87. Found: C, 70.35; H, 7.14; N, 4.91.

Example 14
3 '- (4-Methoxybenzyl) -2,5-dimethylfuran-3-carboxyanilide
Yield: 86.8%
Mp: 100.0 - 102.5 ^o C
¹ H NMR (CDCl ₃₎ δ mn ^-1: 7,45 (1H, m), 7,35 (1H, m), 7,25 (1H, t, J = 8Hz), 7,25 (1H, broad), 7.1 (2H, d, J = 8 Hz), 6.92 (1H, d, J = 8 Hz), 6.88 - 6.75 (1H, m), 6.82 (2H d, J = 8 Hz), 6.05 (1H, s), 3.9 (2H, s), 3.75 (3H, s), 2.55 (3H, s), 2.25 (3H , from).

IR (KBr) cm ^-1 : 3345, 1656, 1246, 1074, 694.

Elemental analysis (%): Calculated for C ₂₁ H ₂₁ NO ₃ : C, 75.20; H, 6.31; N, 4.18. Found: C, 75.28; H, 6.32; N, 4.21.

Example 15
3 '- (2-Methoxycarbonylvinyl) -2,5-dimethylfuran-3-carboxyanilide
Yield: 63.3%
Mp: 159.5 - 161.5 ^o C
¹ H NMR (CDCl ₃₎ δ mn ^-1: 7,82 (1H, m), 7,7 (1H, d, J = 15Hz), 7,58 (1H, m), 7,38 (1H, broad), 7.35 (1H, t, J = 8 Hz), 7.28 (1H, m), 6.48 (1H, d, J = 15 Hz), 6.12 (1H, s), 3.82 (3H, s), 2.55 (3H, s), 2.25 (3H, s)
IR (KBr) cm ^-1 : 3387, 1685, 1670, 1068, 800.

Elemental analysis (%): Calculated for C ₁₇ H ₁₇ NO ₄ : C, 68.22; H, 5.72; N, 4.68. Found: C, 67.55; H, 5.64; N, 4.62.

Example 16
3'-Phenyl-2,5-dimethylfuran-3-carboxyanilide
Yield: 50.0%
Mp: 90.0 - 92.0 ^o C
¹ H NMR (CDCl ₃₎ δ mn ^-1: 7,82 (1H, c), 7,6 (2H, d, J = 8Hz), 7,55 (1H, d, J = 8 Hz), 6 48 - 6.3 (6H, m), 6.12 (1H, s), 2.55 (3H, s), 2.25 (3H, s).

IR (KBr) cm ^-1 : 3367, 1646, 1074, 755.

Elemental analysis (%): Calculated for C ₁₉ H ₁₇ NO ₂ : C, 78.33; H, 5.88; N, 4.81. Found: C, 78.17; H, 6.00; N, 4.72.

Example 17
3'-Neopentyloxymethyl-2,5-dimethylfuran-3-carboxyanilide
Yield: 50.0%
Mp: 95.5 - 97.0 ^o C
¹ H NMR (CDCl ₃₎ δ mn ^-1: 7,48 (2H, m), 7,32 (1H, t, J = 8 Hz), 7,3 (1H, br.), 7,12 (1H d, J = 8 Hz), 4.52 (2H, s), 3.12 (2H, s), 2.55 (3H, s), 2.25 (3H, s), 0.95 (9H , from).

IR (KBr) cm ^-1 : 3324, 1646, 1091, 700.

Elemental analysis (%): Calculated for C ₁₉ H ₂₅ NO ₃ : C, 72.35; H, 7.99; N, 4.44. Found: C, 72.38; H, 8.03; N, 4.20.

Example 18
3'-Isopropenyl-2,5-dimethylfuran-3-carboxyanilide
Yield: 50.0%
Mp: 71.0 - 72.0 ^o C
¹ H NMR (CDCL ₃₎ δ mn ^-1: 7,65 (1H, m), 7,5 (1H, m), 7,3 (1H, br.), 7,3 (1H, t, J = 8 Hz), 7.22 (1H, s), 6.12 (1H, s), 5.4 (1H, s), 5.1 (1H, s), 2.6 (3H, s), 2 55 (3H, s); 2.25 (3H, s).

IR (KBr) cm ^-1 : 3275, 1641, 1580, 1078, 790.

Elemental analysis (%): Calculated for C ₁₆ H ₁₇ NO ₂ : C, 75.27; H, 6.71; N, 5.49. Found: C, 75.29; H, 6.88; N, 5.48.

Example 19
3'-Ethinyl-2,5-dimethylfuran-3-carboxyanilide
Yield: 50.0%
Mp: 83.0 - 84.0 ^o C
¹ H NMR (CDCl ₃₎ δ mn ^-1: 7,7 (1H, m), 7,6 (1H, m), 7,32 - 7,2 (3H, m), 6,1 (1H, with ), 3.05 (1H, s), 2.55 (3H, s), 2.25 (3H, s).

IR (KBr) cm ^-1 : 3245, 1644, 1079, 796.

Elemental analysis (%): Calculated for C ₁₅ H ₁₃ NO: C, 75.30; H, 5.48; N, 5.85. Found: C, 75.50; H, 5.46; N, 5.96.

Example 20
3'-Ethyl-2,5-dimethylfuran-3-carboxyanilide
Yield: 91.0%
Mp: 113.0 - 115.0 ^o C
Mass spectrometry (m / z): 243 (M ⁺ ), 123.94
¹ H NMR (CDCL ₃₎ δ mn ^-1: 7,47 - 6,95 (4H, m), 6,1 (1H, c), 2,66 (3H, q), 2,60 (3H, c ), 2.29 (3H, C), 1.25 (3H, t).

Example 21
3'-Isopropyl-2,5-dimethylfuran-3-carboxyanilide
Yield: 84.0%
Mp: 79 - 80 ^o C
Mass spectrometry (m / z): 257 (M ⁺ ), 149.135
¹ H NMR (CDCl ₃₎ δ mn ^-1: 7,47 - 6,98 (4H, m), 6,11 (1H, c), 2,91 (H, q, q), 2,60 (3H , s), 2.29 (3H, s), 1.26 (d, 6H).

Example 22
2'-6'-Diethyl-2,5-dimethylfuran-3-carboxyanilide
Yield: 85.2%
Mp: 128.0 - 131.0 ^o C
Mass spectrometry (m / z): 271 (M ⁺ ), 242.228
¹ H NMR (CDCl ₃₎ δ mn ^-1: 7,28 - 7,12 (3H, m), 6,82 (1H, br.), 6,16 (1H, c), 2,63 (4H, q), 2.58 (3H, s), 2.31 (3H, s), 1.20 (6H, t).

Example 23
3'-Hexyl-2,5-dimethylfuran-3-carboxyanilide
(Step 1) To a solution of 3.95 g of 2,5-dimethylfuran-3-carbonyl chloride in 60 ml of chloromethane was added 3.45 ml of triethylamine and 2.99 ml of m-iodaniline under ice-cooling, and the resulting mixture was stirred at room temperature.

 (Step 1) To a solution of 3.95 g of 2,5-dimethylfuran-3-carbonyl chloride in 60 ml of chloromethane was added 3.45 ml of triethylamine and 2.99 ml of m-iodaniline under ice-cooling, and the resulting mixture was stirred at room temperature for 6.5 hours. After the reaction mixture was cooled, it was diluted by adding 50 ml of dichloromethane. The diluted mixture was washed successively with 1N. sodium hydroxide, 1 N. hydrochloric acid and saturated aqueous sodium chloride and dried over sodium sulfate, after which the solvent was distilled off. The residue was purified by silica gel column chromatography to obtain 7.64 g of 2,5-dimethylfuran-3-carboxy (3-iodanilide) as pale yellow crystals, which corresponded to a yield of 89.9%.

 (Step 2) To a solution of 0.68 of the crystals obtained in Step 1 in 8 ml of diethyl ether was added 29.3 mg of [1,1'-bis (diphenylphosphino) ferrocene] palladium II chloride and 11 ml of 1 M hexyl magnesium bromide obtained from hexyl bromide and magnesium, divided into 6 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 washed successively 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 was purified by silica gel column chromatography and then on a column filled with D-ODS-5, YMC to obtain 316 mg of the desired compound as white crystals, which corresponds to a yield of 52.8%.

Mp: 71.5 - 72.0 ^o C
¹ H NMR (CDCl ₃₎ δ mn ^-1: 7,45 (1H, m), 7,35 (1H, m), 7,25 (1H, br.), 7,22 (1H, t, J = 8 Hz), 6.95 (1H, d, J = 8 Hz), 6.1 (1H, s), 2.65 - 2.5 (2H, m), 2.55 (3H, s), 2 25 (3H, s), 1.7-1.5 (2H, m), 1.4-1.2 (6H, m), 0.85 (3H, t, J = 7 Hz).

IR (KBr) cm ^-1 : 3310, 1643, 1077, 788.

Elemental analysis (%): Calculated for C ₁₉ H ₂₅ NO ₂ : C, 76.22; H, 8.42; N, 4.68. Found: C, 76.15; H, 8.54; N, 4.55.

 Following a procedure similar to that described above, but using a suitable Grignard reagent instead of hexyl magnesium bromide, the following compounds were obtained.

Example 24
3'-Butyl-2,5-dimethylfuran-3-carboxy (anilide)
Yield: 36.4%
Mp: 77.0 - 80.0 ^o C
¹ H NMR (CDCL ₃₎ δ mn ^-1: 7,45 (1H, m), 7,35 (1H, m), 7,25 (1H, br.), 7,22 (1H, t, J = 8 Hz), 6.95 (1H, d, J = 8 Hz), 6.1 (1H, s), 2.65 - 2.55 (2H, m), 2.55 (3H, s), 2 25 (3H, s), 1.6 (2H, m), 1.35 (2H, m), 0.92 (1H, t, J = 7 Hz).

IR (KBr) cm ^-1 : 3285, 1646, 1075, 702.

Elemental analysis (%): Calculated for C ₁₇ H ₂₁ NO ₂ : C, 75.25; H, 7.80; N, 5.16. Found: C, 75.13; H, 7.87; N, 5.13.

Example 25
3'-sec-butyl-2,5-dimethylfuran-3-carboxyanilide
Yield: 38.1%.

Mp: 80.0 - 81.0 ^o C
¹ H NMR (CDCl ₃₎ δ mn ^-1: 7,4 (1H, m), 7,38 (1H, m), 7,25 (1H, br.), 7,22 (1H, t, J = 8 Hz), 6.95 (1H, d, J = 8 Hz), 6.1 (1H, s), 2.65-2.5 (1H, m), 2.55 (3H, s), 2 25 (3H, s), 1.68-1.5 (1H, m), 1.25 (3H, d, J = 7 Hz), 0.85 (3H, t, J = 7 Hz).

IR (KBr) cm ^-1 : 3255, 1647, 1078, 791.

Elemental analysis (%): Calculated for C ₁₇ H ₂₁ NO ₂ : C, 75.25; H, 7.80; N, 5.16. Found: C, 75.19; H, 7.68; N, 5.14.

Example 26
3'-Pentyl-2,5-dimethylfuran-3-carboxyanilide
Yield: 18.3%
Mp: 97.0 - 97.5 ^o C
¹ H NMR (CDCl ₃ + DMCO) δ mn ^-1: 7,45 (1H, m), 7,35 (1H, m), 7,28 (1H, br.), 7,25 (1H, t, J = 8 Hz), 6.95 (1H, d, J = 8 Hz), 6.1 (1H, s), 2.65-2.5 (2H, m), 2.55 (3H, s) 2.25 (3H, s), 1.7-1.5 (2H, m), 1.4-1.2 (4H, m), 0.88 (3H, t, J = 7 Hz).

IR (KBr) cm ^-1 : 3304, 1644, 1077, 710.

Elemental analysis (%): Calculated for C ₁₈ H ₂₃ NO ₂ : C, 75.76; H, 8.12; N, 4.91. Found: C, 75.77; H, 8.18; N, 5.06.

Example 27
3'-Cyclohexyl-2,5-dimethylfuran-3-carboxyanilide
Yield: 52.7%.

Mp: 113.0 - 114.5 ^o C
¹ H NMR (CDCl ₃₎ δ mn ^-1: 7,48 (1H, m), 7,35 (1H, m), 7,28 (1H, br.), 7,25 (1H, t, J = 8 Hz), 6.98 (1H, d, J = 8 Hz), 6.1 (1H, s), 2.55 (3H, s), 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 (%): Calculated for C ₁₉ H ₂₃ NO ₂ : C, 76.74; H, 7.80; N, 4.71. Found: C, 76.62; H, 7.78; N, 4.67.

Example 28
3'-cyclopentyl-2,5-dimethylfuran-3-carboxyanilide
Yield: 35.9%.

Mp: 92.0 - 93.0 ^o C
¹ H NMR (CDCl ₃₎ δ mn ^-1: 7,45 (1H, m), 7,35 (1H, m), 7,25 (1H, br.), 7,22 (1H, t, J = 8 Hz), 7.00 (1H, d, J = 8 (Hz), 6.1 (1H, s), 3.08-2.9 (1H, m), 2.55 (3H, s), 2.25 (3H, s), 2.15-1.95 (2H, m), 1.9-1.5 (6H, m).

IR (KBr) cm ^-1 : 3322, 1647, 1232, 1076, 700.

Elemental analysis (%): Calculated for C ₁₈ H ₂₁ NO ₂ : C, 76.30; H, 7.47; N, 4.94. Found: C, 76.21; H, 7.56; N, 4.93.

Example 29
3'-Benzyl-2,5-dimethylfuran-3-carboxyanilide
Yield: 59.8%.

Mp: 123.0 - 125.0 ^o C
¹ H NMR (CDCl ₃ δ mn ^-1: 7,45 (1H, m), 7,38 (1H, m), 7,35-7,15 (7H, m), 6,95 (1H, d, J = 8 Hz), 3.98 (2H, s), 2.55 (3H, s), 2.25 (3H, s).

IR (KBr) cm ^-1 : 3314, 1640, 1078, 777, 701.

Elemental analysis (%): Calculated for C ₂₁ H ₁₉ NO ₂ : C, 78.66; H, 6.27; N, 4.59. Found: C, 77.76; H, 6.28; N, 4.55.

Reference Example 1
Ethyl (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 as DMF) was added dropwise a solution of 6.5 ml of ethyl acetoacetate in 5 ml of DMF under stirring under ice cooling and 5.7 ml of chloroacetone was added dropwise to this mixture with stirring and under ice-cooling. After stirring at room temperature for 3 hours, the reaction mixture was poured into water and extraction was carried out from the aqueous mixture with ethyl acetate. The extract was washed with 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 obtain 8.01 g of ethyl (α-acetonitrile acetate) having a mp of 105 ^o C / 266.6 PA, which corresponds to a yield of 86%.

 To a solution of the ester thus obtained in 20 ml of ethanol was 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, and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography using a 10: 1 mixture of n-hexane and ethyl acetate as an eluent, to obtain 5.14 g of ethyl (2,5-dimethylfuran-3-carboxylate), which corresponds to a yield of 71%.

Reference 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 20 ml of 2 N. sodium hydroxide was stirred at room temperature for 1.5 hours, after which it was heated under reflux for one hour. After the reaction mixture was allowed to cool to room temperature, it was evaporated under reduced pressure. The residue was dissolved in water and acidified with dilute sulfuric acid. The precipitated crystals were collected by filtration, washed with water and dried to obtain 2.27 g of 2,5-dimethylfuran-3-carboxylic acid, which corresponds to a yield of 85%.

 A compound having the general formula I mentioned above and a composition containing compound I as an active ingredient, which the present invention relates to, can be used by mixing with carriers or, if necessary, with other additives, followed by the preparation of commonly used compositions, such as oil solution, emulsifiable concentrate, solubilizer, paste, wettable powder, flowable composition, dry flowable composition, spray and paint, and then the composition can be used according to known methods obama treatment of wood preservatives. As additives that are suitably used to improve the properties of the composition and enhance the preservative effect on wood, cationic, anionic and nonionic surfactants, various high molecular weight polymers such as methyl cellulose and vinyl acetate polymer, and water repellent additives can be mentioned, such as silicone oil and paraffin. Needless to say, combined use with other wood preservatives, fungicides and bactericides, including organic iodine compounds such as Sanplas, IF-1000 and Troysan, azole compounds such as Propiconazole and Tebuconazole, Thiabendazole, Dichlofluanid (dichlorofluanide), and quaternary ammonium salts; with insecticides, including pyrethroids such as Permethrin (permethrin), Etofenprox, Cypermethrin (cypermethrin), Silaneophen, Tralomethrin, organophosphorus compounds such as Chloropyrifos, Phoxin and Propetamphos, and Imidacroprid; and with potentiating agents such as bis (2,3,3,3-tetrachloropropyl) ether. With combined use in this way, an improved effect can be expected. In practical use, although the content of the compound of the present invention can vary widely depending on the composition or object, it can usually be suitable in the range of 0.1 to 95 percent by weight, preferably 0.2 to 60 percent by weight. These compositions are applicable to conventional wood processing methods: for example, coating, spraying, dipping, mixing, impregnating, or mixing treatment simultaneously with glue.

 Some examples of compositions with the compounds of the present invention will be shown below, for which there is no need to say that the ratio in which the components are combined and the type of additives can vary widely (in the descriptions given below, “part” in all cases means “part by weight ").

Examples of compositions with wood preservatives
Formulation Example 1 Emulsifiable Concentrate
Twenty parts of compound 1 were dissolved in 70 parts of xylene, and then 10 parts of polyoxyethylenenonylphenyl ether was added and mixed sufficiently to give an emulsifiable concentrate.

 The emulsifiable concentrate thus obtained is diluted with a suitable amount of water immediately before use and can be applied to wood materials that need to be coated, dipped or sprayed, and, in addition, can be used by mixing with adhesives that are used for plywood, chipboards and solid fiberboards.

Formulation Example 2. Oil Solution
Two parts of compound 2 were added to 98 parts of kerosene to obtain an oil solution.

 The oil solution thus obtained can be used for wood-based materials that need to be sprayed, coated, dipped or impregnated.

Formulation Example 3. Coating Composition
Ten parts of compound 1, 20 parts of barite dust, 10 parts of vinyl polymer, 25 parts of pine resin and 35 parts of xylene were mixed until uniform to obtain a coating composition.

Formulation Example 4. Wettable Powder
Twelve parts of compound 3, 56 parts of clay, 3 parts of sodium sulfonate - lauryl alcohol and 1 part of polyvinyl alcohol were mixed until homogeneous in a mixer, and then crushed using a hammer mill to obtain a wettable powder.

Wood Protection Test Examples
The effectiveness of wood preservatives of the present invention will be specifically explained using the following examples.

(1) According to the wood protection test method described in Japan Industrial Standards [Japan Industrial, Standarts JIS A-9201 (1991)], each of the test compounds was dissolved to a specific concentration in methanol. The solution was injected under reduced pressure into the Sugi (Japanese cedar) sapwood (2 x 2 x 1) cm, and then dried in air. The weathering test, in which one treatment cycle was stirred in water for 8 hours and then heated for 16 hours at 60 ^° C., was repeated 10 times. The test material was placed on the Serpula lacrymans flora, which was previously grown on quartz sand medium (malt extract 2%, glucose 1%, peptone 0.3% and yeast 0.2%) and subjected to forced decomposition at 20 ^o C for 12 weeks. From the difference between the dry weight of the test product before the test and its dry weight after the test, the degree of weight reduction was obtained. The results are shown in table. 2. The test was carried out by using 9 samples for each variant of the test conditions, and the values shown in the table. 2 are the average values calculated from the data for 9 samples.

Control compound 1: 4-chlorophenyl-3-iodopropargyl formal
Product of Nagase Co., Ltd .: IF-1000
According to the data presented, compounds having the general formula (I) significantly prevented rotting of wood samples caused by wood-decomposing fungi.

(2) Each of the solutions of the compound of the present invention in methanol with a concentration of 0.1% in terms of weight to volume and the control preparation were injected into the test material [sapwood Sugi (Japanese cedar), 2 x 2 x 0.5 cm] under reduced pressure and then air dried. The weathering test, in which one treatment cycle consisted of washing (flow rate of about 2 liters per minute) with water for 5 hours and then heating for 19 hours at 60 ^° C., was repeated twice. After sterilization with dry air, test samples were obtained.

The test material was placed on the flora of Coriolus Versicolor, which is a lignin-degrading fungus, and Tyromyces palustris, which is a cellulose-degrading fungus, and which are both established species of sample fungi on the protective effect of wood preservatives. Both fungi were pre-grown on agar medium (malt extract 2%, glucose 1% and peptone 0.5%). After the wood samples underwent forced fracture at 26 ^° C. for 3 weeks, the efficiency was determined by the degree of hyphae growth on the test material and the presence or absence of a reduced maximum crush strength. The results are shown in table. 3.

 The effectiveness of wood protection was evaluated according to the following criteria.

 +: No hyphae growth was observed on the test material, and no differences were found with intact wood samples for maximum crush strength.

 +: A slight increase in hyphae was observed on the test material, or a slight decrease in maximum crush strength was detected.

 -: Hyphal growth was observed on the test material, or a clear decrease in maximum crush strength was detected.

 -: Hyphal growth was observed on the test material, or a clear decrease in maximum crush strength was detected.

Control compound 2: 3-Bromo-2,3-diiod-2-propenylethylcarbonate
Product of Sankyo Co., LTD .: Sanplas
When it is necessary to apply the composition of the present invention, the ratio in which the combination is made can be appropriately selected depending on the type of wood and the type of wood material to be treated with a wood preservative, or the treatment method (e.g., coating, dipping, spraying, impregnation, mixing or mixing together with glue). Typically, the ratio in which the combination of dimethylfurancarboxyanilide and any other wood preservative is made can be from 240: 1 to 1:35, preferably from 30: 1 to 1:10, and more preferably from 5: 1 to 1: 5.

 The content of the composition of the present invention can vary over a wide range depending on the composition. In general, the content in the composition may be from 0.1 to 95%, preferably from 0.2 to 60%.

 Some examples of compositions comprising the compounds of the present invention will be shown below, for which there is no need to say that the ratio in which the components are combined and the type of additives can vary widely.

Examples of compositions with wood preservatives
Formulation Example 1 Emulsifiable Concentrate
Ten parts of compound 1 were dissolved in 30 parts of Sanplas and 50 parts of xylene, then 10 parts of polyoxyethylene nonylphenyl ether was added and mixed sufficiently to give an emulsifiable concentrate.

 The emulsifiable concentrate thus obtained was diluted with a suitable amount of water immediately before use and can be used for wood materials that need to be coated, dipped or sprayed, and, in addition, can be used by mixing with adhesives that are used for plywood, chipboards and solid fiberboards.

Formulation Example 2 Oil Solution
Two parts of compound 2 and 1 part of the troysan preparation were dissolved in 96 parts of kerosene to obtain an 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 sulfonate - lauryl alcohol and 1 part of polyvinyl alcohol were mixed until homogeneous in a mixer, and then crushed using a hammer mill to obtain a wettable powder.

 The effect of the wood impregnation protective compositions of the present invention will be specifically explained by the following examples.

Test examples for wood preservatives
Minimum inhibitory concentration assay using agar dilution method.

In accordance with the method of agar dilution, sterilized medium (about 4 mm in diameter) of wood-destroying fungi, Coriolus Versicolor and Tyromyces palustris, which was previously cultivated on the same type of medium. After culturing at 25 ^° C. for 5 days, the growth of hyphae was monitored to determine the minimum inhibitory concentration.

 The determination of whether there is any enhancement of action or not is described in C. Kull et al., Applied Microbiology 9, 538-541 (1961). Tests were performed according to a commonly used method.

 In the table. 4-6 and Figures 1 (a) - (e) show the results obtained by combining compound 1 with each of the Sanplas, Troysan, and IF-1000 preparations.

 Then the same test, as described, was carried out for compound 2. The results are shown in table. 7 - 9 and in figures 2 (a) - (e).

 Each of the minimum inhibitory concentration curves shown in Figures 1 and 2 lies below the diagonal line shown by the dashed line.

 These data show that the dimethylfurancarboxyanilide derivative enhances the action of each of Sanplas, Troysan, and IF-1000 when combined with them.

Claims (4)

1. Derivatives of dimethylfurancarboxyanilide of the general formula I

where R ¹ and R ² are the same or different, each represents a hydrogen atom, C ₂ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₃ -haloalkyl, C ₂ -C ₆ -alkoxy, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, substituted amide group, C ₁ -C ₆ -alkoxycarbonyl, benzoyl group, which may contain one or two substituents, benzoylamino group which may have one or two substituents, C ₂ -C ₆ alkanoylamino, C ₃ -C ₆ - cycloalkylcarbonylamino group, a benzyl group which may contain one or two substituents, a phenyl group Which can contain one or two substituents or C ₁ -C ₆ -alkoxycarbonyl-C ₂ -C ₅ alkenylene group, provided that (1) R ¹ and R ² are not simultaneously hydrogen atoms, (2) one of R ¹ and R ^{2 is} not an unsubstituted phenyl group when the other one represents a hydrogen atom, (3) one of R ¹ and R ² in the ortho position does not represent an aniline ring, C ₂ -C ₆ alkyl, C ₃ -C ₆ - cycloalkyl or a C ₂ -C ₆ alkoxy group when the other one represents a hydrogen atom.  2. Protective composition for wood containing the active ingredient, characterized in that as the active ingredient it contains an effective amount of the dimethylfurancarboxyanilide derivative according to claim 1. 3. A method of protecting wood by applying to it a composition containing an active ingredient, characterized in that a composition containing an effective amount of a dimethylfurancarboxyanilide derivative of the general formula I is applied

where R ¹ and R ² are the same or different, each represents a hydrogen atom, C ₂ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₃ -haloalkyl, C ₂ -C ₆ -alkoxy, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, substituted amide group, C ₁ -C ₆ -alkoxycarbonyl, benzoyl group, which may contain one or two substituents, benzoyl, an amino group which may contain one or two substituents, C ₂ -C ₆ alkanoylamino, C ₃ -C ₆ -tsikloalkilkarbonilaminogruppu, a benzyl group which may contain one or two substituents, a phenyl group Which can contain one or two substituents or C ₁ -C ₆ -alkoxycarbonyl-C ₂ -C ₆ alkenylene group, provided that R ¹ and R ² do not simultaneously represent hydrogen atoms.  4. A protective composition for wood containing the active ingredient, characterized in that as the active ingredient it contains a mixture of at least one dimethylfurancarboxyanilide derivative indicated in claim 3 and at least one compound selected from 3-bromo-2,3- diiodo-2-propenylethylcarbamate, 3-iodo-2-propynylbutylcarbamate and 4-chloro-phenyl-3-iodopropargyl formaldehyde, taken in effective amounts.

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