CN1076350C - Dimethylfurancarboxanilide derivative - Google Patents
Dimethylfurancarboxanilide derivative Download PDFInfo
- Publication number
- CN1076350C CN1076350C CN94195129A CN94195129A CN1076350C CN 1076350 C CN1076350 C CN 1076350C CN 94195129 A CN94195129 A CN 94195129A CN 94195129 A CN94195129 A CN 94195129A CN 1076350 C CN1076350 C CN 1076350C
- Authority
- CN
- China
- Prior art keywords
- derivative
- compound
- carbon atom
- wood
- dimethylfurancarboxaderivative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
A formula (I) is disclosed in the specification. The present invention relates to a dimethylfurancarboxanilide derivative represented with the formula (I). In the formula (I), R<1> and R<2> equally or differently represent hydrogen atoms, C2 to C6 alkyl, C3 to C6 cycloalkyl, C3 to C6 alkenyl, C2 to C6 alkynyl, C1 to C3 halogenolalkyl, C2 to C6 alkoxyl, C1 to C6 alcoxyl, C1 to C6 alkoxyl, cyano, substituted amido, C1 to C6 alkoxycarbonyl, benzoyl which can have 1 to 2 substituent groups, C2 to C6 alkanol amino, C3 to C6 cycloalkyl carbonyl, phenyl which can have 1 to 2 substituent groups or C1 to C6 carbalkoxy, and C2 to C5 alkenylene. However, R<1> and R<2> can not be hydrogen atoms simultaneously. Wood preservative contains the dimethylfurancarboxanilide derivative as effective components. A wood anticorrosion composition adopts the dimethylfurancarboxanilide derivative as effective components and is matcehd with the wood preservative whose effect is determined, and the wood preservative is sold in a market.
Description
Technical field
The present invention relates to have good anticorrosion active new Dimethylfurancarboxaderivative (dimethylqurancarboxyanilide) derivative, be the wood preservative of effective constituent and this Dimethylfurancarboxaderivative derivative is engaged in timber antiseptic composition in the commercially available wood preservative that present affirmation produced effect as one of effective constituent with this Dimethylfurancarboxaderivative derivative for timber.
Background technology
Past, in order to prevent because various wood-decaying fungus rotten to timber used various inorganic or organic compound as wood preservative.These medicaments have following shortcoming, and promptly toxicity is big, and are harmful and to the contaminative of environment, and need high density when using and cost an arm and a leg.
In Japanese Patent Publication 50-10376, disclose as the Dimethylfurancarboxaderivative derivative involved in the present invention that removes the Plant diseases with medicament, and represented this compound with following general formula.But R wherein only is limited to phenyl, nitro substituted-phenyl, carboxyl substituted phenyl, phenyl substituted-phenyl, methyl substituted phenyl, halogen substituted phenyl, methoxyl group substituted-phenyl,
For other derivative without any disclose, in addition, these compounds are to the activity of wood-decaying fungus also not record fully.
Summary of the invention
The object of the present invention is to provide security higher, at lower concentration and be the new wood preservative that can efficiently use under the low price.
Present inventors In view of the foregoing are conceived to the furoyl anils, have carried out repeatedly research.Found that the new Dimethylfurancarboxaderivative derivative of representing with general formula (1) is exceedingly useful as wood preservative.When being engaged in commercially available wood preservative that present affirmation produced effect as effective constituent this furoyl anils in addition, can seeing the effect that multiplies each other, and can make the timber antiseptic composition.Compound of the present invention is the Dimethylfurancarboxaderivative derivative with formula (1) expression,
[R in the formula
1And R
2Represent hydrogen atom identical or differently; C
2-C
6Alkyl; C
3-C
6Cycloalkyl; C
3-C
6Thiazolinyl; C
2-C
6Alkynyl; C
1-C
3Haloalkyl; C
2-C
6Alkoxyl group; C
1-C
6Alcoxyl C
1-C
6Alkyl; Cyano group; Substituted amido; C
1-C
6Carbalkoxy; 1～2 substituent benzoyl can be arranged; 1～2 substituent benzamido can be arranged; C
2-C
6Alkyl amido; C
3-C
6The cycloalkyl carbonyl amino; 1～2 substituent benzyl can be arranged; 1～2 substituent phenyl can be arranged; Or C
1-C
6Carbalkoxy C
2-C
5Alkenylene, but R
1And R
2Can not be hydrogen atom simultaneously].The present invention relates to this Dimethylfurancarboxaderivative derivative as the wood preservative of effective constituent and with the timber anticorrosive composite.
The simple declaration of figure
Fig. 1 (a)～(f) is the figure of the minimum growth inhibitory concentration of binary (ppm) of compound+various Synergist S-421 95s of expression embodiment 1.
Fig. 2 (a)～(f) is the figure of the minimum growth inhibitory concentration of binary (ppm) of compound+various Synergist S-421 95s of expression embodiment 2.
Implement preferred plan of the present invention
In the above-mentioned general formula (1), R1And R2Defined C2-C
6Alkyl is the straight or branched alkyl of ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, isopentyl, neopentyl, hexyl, isohesyl, Sec-Hexyl class, particularly preferably is C2-C
6Alkyl.
In the above-mentioned general formula (1), R1And R2Defined C3-C
6Cycloalkyl is the cycloalkyl of cyclopropyl, cyclobutyl, cyclopenta, hexamethylene base class, preferably C3-C
6Cycloalkyl, more preferably C5-C
6Cycloalkyl.
In the above-mentioned general formula (1), R
1And R
2Defined C
3-C
6Thiazolinyl is the thiazolinyl of allyl group, pseudoallyl, methylallyl, crotyl, 3-butenyl, 1,3-butadiene base, pentenyl, 2-hexene base class, preferably C
3-C
4Propenyl, more preferably pseudoallyl.
In the above-mentioned general formula (1), R
1And R
2Defined C
2-C
6Alkynyl is the alkynyl of ethynyl, propargyl, 2-butyne base, 4-pentynyl, 2-hexin base class, preferably C
2-C
4Alkynyl, more preferably ethynyl.
In the above-mentioned general formula (1), R
1And R
2Defined C
1-C
3Haloalkyl is trifluoromethyl, trichloromethyl, pentafluoroethyl group, 2,2,2-three chloroethyls, 2, the haloalkyl of 4-two chloropropyl classes, preferably C
1-C
2Haloalkyl, more preferably trifluoromethyl.
In the above-mentioned general formula (1), R
1And R
2Defined C
2-C
6Alkoxyl group is the alkoxyl group of the straight or branched of oxyethyl group, propoxy-, isopropoxy, butoxy, pentyloxy, hexyloxy class, preferably C
2-C
4Alkoxyl group, more preferably C
2-C
3Alkoxyl group.
In the above-mentioned general formula (1), R
1And R
2Defined C
1-C
6Alcoxyl C
1-C
6C in the alkyl
1-C
6Alkoxyl group is the alkoxyl group of the straight or branched of methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, pentyloxy, neopentyl oxygen, hexyloxy class, preferably C
1-C
5Alkoxyl group, more preferably C
1-C
3Alkoxyl group or C
5Alkoxyl group.
In the above-mentioned general formula (1), R
1And R
2Defined C
1-C
6Alcoxyl C
1-C
6C in the alkyl
1-C
6Alkyl is the alkylidene group of the straight or branched of methylene radical, ethylidene, propylene, trimethylene, butylidene, pentylidene, hexylidene class, preferably C
1-C
2Alkylidene group, more preferably methylene radical.
In the above-mentioned general formula (1), R
1And R
2Defined replacement amido is an alkyl amido of methane amide, ethanamide, Isopropamide, butyramide, secondary butyryl amine; Diformamide, diethylamide, diisopropyl amide, two butyramides, di-secondary butyramide, methylethyl acid amides, isopropyl methyl acid amides, methyl butyl acid amides, methyl sec-butyl acid amides, ethyl sec.-propyl acid amides, sec.-propyl butyl amide, pyrrolidyl acid amides, the dialkyl group amido of piperidyl amide class, benzamide, 2-chlorobenzamide, 2,4-dichlorobenzene acid amides, 2-methylbenzene acid amides, 2-ethylbenzene acid amides, 4-anisole amides have substituent benzoyl amino, preferably an amido of methane amide, piperidyl amide or benzamide.
In the above-mentioned general formula (1), R
1And R
2Defined C
1-C
6Carbalkoxy is the above-mentioned " C of methoxycarbonyl, ethoxycarbonyl, the different third oxygen carbonyl, butoxy carbonyl, secondary butoxy carbonyl, tertbutyloxycarbonyl, penta oxygen carbonyl, own oxygen carbonyl class
1-C
6Alcoxyl C
1-C
6Alkyl " in " C
1-C
6Alkoxyl group combines with carbonyl and the base that constitutes ", C preferably
1-C
3Carbalkoxy.
In the above-mentioned general formula (1), R
1And R
2It is defined that to have 1 to 2 substituent benzoyl be benzoyl, 2-chlorobenzene formacyl, 2; 4-dichloro-benzoyl base, 2-methyl benzoyl, 2; 4-dimethylbenzoyl, 4-ethylamino benzonitrile acyl group, 4-anisoyl class have optional substituent benzoyl, preferably a benzoyl.
In the above-mentioned general formula (1), R
1And R
2It is defined that to have 1 to 2 substituent benzamido be that above-mentioned " can have 1 to 2 substituent benzoyl " is replaced to amino base; for example; benzamido, 2-chlorobenzoyl amino, 2; 4-dichloro-benzoyl amino, 2; the amino class of 4-dimethyl benzene formamido group, 4-toluyl amino, 4-ethylamino benzonitrile acyl group, 4-methoxybenzoyl have substituent benzamido, preferably a benzamido.
In the above-mentioned general formula (1), R
1And R
2Defined alkyl amido is kharophen, propionamido, butyrylamino, isobutyryl amino, valeryl amino, isovaleryl amino, hexanamido, dissident's amido, kharophen preferably.
In the above-mentioned general formula (1), R
1And R
2Defined C
3-C
6The cycloalkyl carbonyl amino is cyclopropyl carbonyl amino, cyclobutyl carbonyl amino, cyclopentyl carbonyl amino, cyclohexyl carbonyl amino.Cyclohexyl carbonyl amino preferably.
In the above-mentioned general formula (1), R
1And R
2Defined have 1 to 2 substituent benzyl and be meant benzyl, 2-methyl-benzyl, 2,4-dimethyl benzyl, 2-benzyl chloride base, 4-methoxy-benzyl, 4-ethoxy benzyl.Benzyl preferably.
In the above-mentioned general formula (1), R
1And R
2Defined C
1-C
6Carbalkoxy C
2-C
5Alkenylene is methoxycarbonyl vinylidene, ethoxycarbonyl 2-propenylidene, methoxycarbonyl 2-crotonylidene, ethoxycarbonyl 2-inferior pentenyl, preferably methoxycarbonyl vinylidene.
Have in the compound of above-mentioned general formula (1), preferred compound is as follows,
(1) R
1And R
2Identical or represent hydrogen atom, C unequally
2-C
6Alkyl, C
3-C
4Alkenyl, C
2-C
4Alkynyl, C
3-C
6Cycloalkyl, C
1-C
6Carbalkoxy, C
1-C
6Alcoxyl C
1-C
2Alkylidene group, C
3-C
6Cycloalkyl carbonyl amino, C
2-C
4Alkoxyl group, can have 1 to 2 substituent benzoyl, can have 1 to 2 substituent benzyl or C
1-C
6Carbalkoxy C
2-C
5The alkenylene compound, but R should do not had
1, R
2Be the compound of hydrogen atom simultaneously,
More preferably,
(2) R
1And R
2Identical or represent hydrogen atom, C unequally
2-C
6Alkyl, C
3-C
4Alkenyl, C
5-C
6Cycloalkyl, C
1-C
3Carbalkoxy, C
1-C
6Alcoxyl methylene radical, C
4-C
6Cycloalkyl carbonyl amino, benzoyl, can have 1 substituent benzyl or C
1-C
3Carbalkoxy C
2-C
4The compound of alkenylene, but R should do not had
1, R
2Be the compound of hydrogen atom simultaneously,
Most preferably
(3) R
1Be 3-(C
2-C
6Alkyl) base, 3-(C
1-C
3Carbalkoxy) base, 3-(C
1-C
3The alcoxyl methylene radical) base, C
4-C
6The cycloalkyl carbonyl amino, can have the substituent benzyl of methoxyl group, benzoyl or C
1-C
3Carbalkoxy C
2-C
3The compound of alkenylene,
(4) R
2It is the compound of hydrogen atom.
Constitute the new Dimethylfurancarboxaderivative derivative of wood preservative effective constituent of the present invention.Shown in following table.
In the following table 1, used the secondary uncle t c ring of the following different s of contracted notation Bz benzyl Bu butyl Et ethyl Hx hexyl Me methyl Ph phenyl Pip piperidyl Pn amyl group Pr propyl group i
Table I compound number R
1R
21 3-CF
3H 2 4-CF
3H 3 3-CH
2OMe H 4 4-CH
2OMe H 5 2-Et H 6 3-Et H 7 4-Et H 8 3-C ≡ CH H 9 4-C ≡ CH H10 3-CH
2OEt H11 4-CH
2OEt H12 2-Et 3-Et13 2-Et 4-Et14 2-Et 5-Et15 2-Et 6-Et16 3-Et 4-Et17 3-Et 5-Et18 3-Et 6-Et19 3-Pr H20 4-Pr H21 2-iPr H22 3-iPr H23 4-iPr H24 3-cPr H25 4-cPr H26 3-CH
2OPr H27 3-CH
2OiPr H28 4-CH
2OiPr H29 3-CH
2C=CH
2H30 4-CH
2C=CH
2H31 3-CH
2C ≡ CH H32 4-CH
2C ≡ CH H33 3-Pr 4-Pr34 2-iPr 4-iPr35 3-iPr 5-iPr36 3-CH
2OBu H37 4-CH
2OBu H38 3-CH
2OiBu H39 4-CH
2OiBu H40 3-CH
2OsBu H41 4-CH
2OsBu H42 3-Bu H43 4-Bu H44 3-iBu H45 3-sBu H46 3-cBu H47 4-cBu H48 3-tBu H49 3-CH
2CH=CHMe H50 3-CH
2C ≡ CMe H51 3-CH
2MeCH=CH
2H52 4-CH
2MeCH=CH
2H53 3-Pn H54 4-Pn H55 3-iPn H56 3-cPn H57 3-neoPn H58 3-CH
2OPn H59 3-CH
2Oneo-Pn H60 3-Hx H61 3-iHx H62 3-cHx H63 3-CN H64 3-OEt H65 3-OiPr H66 3-CONHMe H67 3-(CO-1-Pip) H68 3-CONHPh H69 3-COOMe H70 3-COOEt H71 3-COOPr H72 3-COOiPr H73 3-COOBu H74 3-COOtBu H75 3-COPh H76 3-CO (2-MePh) H77 3-NHCOPh H78 3-NHCOMe H79 3-NHCOBu H80 3-NHCOcPn H81 3-NHCOcHx H82 3-Bz H83 3-(4-MeOBz) H84 3-(4-MeBz) H85 3-CH＝CHCOOMe H86 3-Ph H87 3-(2-MePh) H
Preferred compound is numbered 3 in the above-claimed cpd, 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 No. 85, preferred compound be numbered 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 No. 85 compounds.
With the compound of above-mentioned general formula (1) expression, two kinds of method preparations of available following A method, B method.
The A method
The B method
In the above-mentioned formula, R
1And R
2The meaning identical with aforementioned expression.R
1Expression C
1-C
6Alkyl, C
3-C
6Cycloalkyl or have 1 to 2 substituent benzyl.(Ia) be in general formula (1), R
1Expression R
1 ', R
2The compound of expression hydrogen atom.(V) expression iodine substituted aniline.X represents the halogen atom of chlorine, bromine, iodine class, preferred chlorine atom.The halogen atom of X ' expression chlorine, bromine, iodine class, preferably bromine or iodine atom.
Compound of the present invention can prepare with known method.
The A1 step is to make to have the step of general formula (1) compound, is in inert solvent, in the presence of dehydrohalogenating agent, the compound of (III) that has general formula and compound with general formula (IV) is reacted finish.
Starting compound in this step (III) is by after monochloroacetone and the ethyl 3-oxobutanoate condensation, with obtain 2, behind 5-dimethyl furan-3-carboxyester hydrolysis, carry out halogenation again and obtain.
Starting compound in this step (IV) is commercially available phenyl amines, perhaps the known phenyl amines made from known method.
The inert solvent that uses is the ethers of ether, isopropyl ether, tetrahydrofuran (THF), diox etc., arene, methylene dichloride, chloroform, the halogenated hydrocarbon of tetracol phenixin class or the mixture of these solvents of benzene,toluene,xylene class, preferably arene particularly preferably is toluene.
The dehydrohalogenating agent that uses is a triethylamine, N, tertiary amines, the pyridines of N-dimethyl aminopyridine etc.This reaction can be carried out in the presence of solvent or under solvent-free, but successfully carry out in order to make reaction, preferably use solvent, at 0 ℃ in the temperature range of the boiling point of solvent, preferably under the temperature of room temperature～100 ℃, usually carried out preferably 30 minutes～2 hours reaction 30 minutes～5 hours.
The B1 step is that preparation has the step of general formula (VI) compound, in inert solvent, in the presence of dehydrohalogenating agent, the compound of (III) that has general formula and compound with logical formula V is reacted finish.
Starting compound (V) is commercially available phenyl amines, perhaps makes known phenyl amines with known method.
This step is carried out in the same manner with the A1 step.
The B2 step is to make to have the step of general formula (Ia) compound, and in inert solvent, catalyzer exists down, makes (VI) compound that has general formula and has general formula: R
1 'MGX ' Grignard reagent reacts to be finished.
Can enumerate the ethers of ether, isopropyl ether, tetrahydrofuran (THF), dioxane as inert solvent, specially suitable is ether.
Catalyzer, particularly preferred being to use (1,1 '-two (diphenylphosphine)-ferrocene) palladium (II) muriate.
The Grignard reagent class can be with commercially available reagent, perhaps with known method by magnesium with use formula R
1 'X ' (R
1 'And the implication of X ' is same as described above) the alkyl halide reaction of expression makes.
Temperature of reaction is generally 0 ℃ to 50 ℃, preferably room temperature.Reaction times is different according to solvent and reagent, but normally 10 hours to 10 days.
Compound and known wood preservative with general formula (1) of the present invention compares, and can demonstrate good activity under lower concentration.In addition, this compound (1) cooperated with known wood preservative and the composition that constitutes, compare when using separately, can under lower concentration, bring into play the good effect that multiplies each other, shown wood preservation activity efficiently with this compound (1).Therefore, new Dimethylfurancarboxaderivative derivative can reach the effect of using under the lower concentration of one of problem of the present invention, is exceedingly useful as wood preservative.
Below illustrate in greater detail the manufacturing and the preparation of The compounds of this invention with embodiment, but the present invention is not limited by these.
Embodiment 1
2,5-dimethyl furan-3-formyl-(3-acetylaminoaniline)
With 2,5-dimethyl furan-3-carbonyl chlorine (0.50g) is dissolved in the methylene dichloride (10ml), adds triethylamine (0.44ml) down ice-cold, and 3-acetylaminoaniline (0.47g), stirs 2.5 hours under the room temperature, and then reflux is 4.5 hours.Behind the cooling reaction solution, add methylene dichloride (10ml) dilution, then use 1N sodium hydroxide, 1N hydrochloric acid, saturated common salt water washing successively, use dried over sodium sulfate, concentrate.With the refining resistates of silica gel chromatography, then, obtain the title compound 0.51g (yield 59.4%) of white crystals shape with behind the vinyl acetic monomer recrystallization.
Fusing point: 172.0-172.5 ℃
1HNMR(CDCl
3＋DMSO)δppm：8.4(1H，b)，7.95(1H，b)，7.88(1H，m)，7.4(1H，m)， 7.32(1H，m)，7.25(IH，t，J＝8Hz)，6.25(1H，s)，2.55(3H，s)，2.25(3H，s)，2.15(3H，s)
IR (kBr) cm
-1: 3306,1672,1651,1086,781 ultimate analysis value: C
15H
16N
2O
3Calculated value (%) C66.16H5.92 N10.29
Analytical value (%) C66.30H5.98 N10.32
Carry out same operation, use suitable anils to replace the 3-acetylaminoaniline, can obtain following compound.
3 '-(N-methylamino formyl radical)-2,5-dimethyl furan-3-formylaniline
Yield: 42.0%
Fusing point: 212.0-213.0 ℃
1HNMR(CDCl
3＋DMSO)δppm：8.5(1H，b)，8.05(1H，m)，7.88(1H，m)，7.52(1H，m)，7.38(1H，t，J＝8Hz)，6.8(1H，b)，6.35(1H，s)，2.95(3H，d，J＝1.4Hz)，2.55(3H，s)，2.25(3H，s)
IR (KBr) cm
-1: 3293,1638,1581,1074,689 ultimate analysis value: C
15H
16N
2O
3Calculated value (%) C66.16 H5.92 N10.29
Analytical value (%) C66.08 H6.20 N10.28
Embodiment 3
3 '-(piperidino carbonyl)-2,5-dimethyl furan-3-formylaniline
Yield: 50.0
Fusing point: 183.0-185.0 ℃
1HNMR (CDCl
3) δ ppm:7.68 (1H, m), 7.55 (2H, m), 7.35 (1H, t, J=8Hz), 7.1 (1H, m), 6.15 (1H, s), 3.7 (2H, b), 3.35 (2H, b), 2.55 (3H, s), 2.25 (3H, s), 2.75-1.4 (6H, m) IR (KBr) cm
-1: 3302,1663,1615,1065,808 ultimate analysis value: C
19H
22N
2O
3Calculated value (%) C69.92 H6.79 N8.58
Analytical value (%) C69.52 H6.88 N8.48
Embodiment 4
3 '-(N-phenyl amino formyl radical)-2,5-dimethyl furan-3-formylaniline
Yield: 53.5%
Fusing point: 182.5-184.0 ℃
1HNMR (CDCl
3+ DMSO) δ ppm:8.48 (1H, b), 8.2 (1H, b), 8.1 (1H, s), 7.95 (1H, m), 7.7 (2H, d, J=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, s), 2.55 (3H, s), 2.25 (3H, s) IR (KBr) cm
-1: 3282,1646,1080,755,691 ultimate analysis value: C
20H
18N
2O
3Calculated value (%) C71.84 H5.43 N8.38
Analytical value (%) C71.87 H5.64 N8.34
Embodiment 5
3 '-tertbutyloxycarbonyl-2,5-dimethyl furan-3-formylaniline
Yield: 92.0%
Fusing point: 117.0-118.0 ℃
1HNMR(CDCl
3)δppm：8.05(1H，m)，7.88(1H，m)，7.75(1H，m)，7.4(1H，t，J＝8Hz)，7.35(1H，b)，6.1(1H，s)，2.55(3H，s)，2.25(3H，s)，1.65(9H，s)
IR (KBr) cm
-1: 3362,1687,1672,1067,757 ultimate analysis value: C
18H
21NO
4Calculated value (%) C68.55 H6.71 N4.44
Analytical value (%) C68.04 H7.00 N4.40
Embodiment 63 '-methoxycarbonyl-2,5-dimethyl furan-3-formylaniline
Yield: 77.1%
Fusing point: 104.0-106.0 ℃
1HNMR(CDCl
3)δppm：8.05(1H，m)，7.98(1H，m)，7.8(1H，m)，7.42(1H，t，J＝8Hz)，7.38(1H，b)，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 ultimate analysis value: C
15H
15NO
4Calculated value (%) C65.92 H5.53 N5.13
Analytical value (%) C66.02 H5.60 N5.08
Embodiment 72,5-dimethyl furan-3-formyl-(3-benzanilide)
Yield: 69.1%
Fusing point: 137.0-139.0 ℃
1HNMR(CDCl
3)δppm：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 ultimate analysis value: C
20H
17NO
3Calculated value (%) C75.22 H5.37 N4.39
Analytical value (%) C75.38H5.43 N4.38
Embodiment 82,5-dimethyl furan-3-formyl-(3-benzamido aniline)
Yield: 46.0%
Fusing point: 194.5-195.0 ℃
1HNMR(CDCl
3＋DMSO)δppm：8.7(1H，b)，8.1(1H，m)，7.95(1H，b)，7.9(2H，m)，7.6-7.4(5H，m)，7.3(1H，t，J＝8Hz)，6.25(1H，s)，2.55(3H，s)，2.25(3H，s)
IR (KBr) cm
-1: 3283,1642,1074,791,705 ultimate analysis value: C
20H
18N
1O
3Calculated value (%) C71.84 H5.43 N8.38
Analytical value (%) C71.96 H5.53 N8.28
Embodiment 92,5-dimethyl furan-3-formyl-(3-valeryl amino aniline)
Yield: 70.3%
Fusing point: 104.0-105.0 ℃
1HNMR(CDCl
3)δppm：7.9(1H，b)，7.45-7.1(5H，m)，6.1(1H，s)，2.55(3H，s)，2.35(2H，t，J＝7Hz)，2.25(3H，s)，1.7(2H，m)，1.4(2H，m)，0.95(1H，t，J＝7Hz)
IR (KBr) cm
-1: 3250,1660,1644,1074,781 ultimate analysis value: C
18H
22N
2O
3Calculated value (%) C68.77 H7.05 N8.91
Analytical value (%) C68.73 H7.17 N8.90
2,5-dimethyl furan-3-formyl-(3-cyclohexyl carbonyl amino aniline)
Yield: 45.1%
Fusing point: 212.5-213.0 ℃
1HNMR(CDCl
3)δppm：7.92(1H，b)，7.88(1H，b)，7.45-7.35(2H，m)，7.25(1H，t，J＝8Hz)，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 ultimate analysis value: C
20H
24N
2O
3Calculated value (%) C70.57 H7.11 N8.23
Analytical value (%) C70.56 H7.26 N8.16
Embodiment 11
2,5-dimethyl furan-3-formyl-(3-methoxyl methyl aniline)
Yield: 73.3%
Fusing point: 102.5-103.5 ℃
1HNMR(CDCl
3)δppm：7.55(1H，m)，7.52(1H，d，J＝8Hz)，7.32(1H，t，J＝8Hz)，7.32(1H，b)，6.9(1H，d，J＝8Hz)，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 ultimate analysis value: C
13H
17NO
3Calculated value (%) C69.48 H6.61 N5.40
Analytical value (%) C69.22 H7.02 N5.37
Embodiment 122,5-dimethyl furan-3-formyl-(3-ethoxymethyl aniline)
Yield: 64.4%
Fusing point: 85.0-85.5 ℃
1HNMR (CDCl
3) δ ppm:7.65-7.55 (2H, m), 7.38 (1H, t, J=8Hz), 7.35 (1H, b), 7.15 (1H, d, J=8Hz), 6.15 (1H, s), 4.55 (2H, s), 3.58 (2H, q, J=8Hz), 2.55 (3H, s), 2.25 (3H, s), 1.3 (3H, t, J=8Hz) IR (KBr) cm
-1: 3279,1646,1115,785 ultimate analysis value: C
18H
19NO
3Calculated value (%) C70.31 H7.01 N5.12
Analytical value (%) C70.14 H7.27 N5.06
Embodiment 132,5-dimethyl furan-3-formyl-(the different third oxygen monomethylaniline of 3-)
Yield: 92.7%
Fusing point: 68.0-69.5 ℃
1HNMR(CDCl3)δppm：7.55(1H，d，J＝8Hz)，7.5(1H，m)，7.3(1H，t，J＝8Hz)，7.3(1H，b)，7.12(1H，d，J＝8Hz)，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＝7Hz)
IR (liquid membrane): cm-1 3321,1651,1072,785 ultimate analysis value: C
17H
21NO
3Calculated value (%) C71.06 H7.37 N4.87
Analytical value (%) C70.35 H7.14 N4.91
Embodiment 142,5-dimethyl furan-3-formyl-[3-(4-methoxybenzyl) aniline]
Yield: 86.8%
Fusing point: 100.0-102.5 ℃
1HNMR(CDCl3)δppm：7.45(1H，m)，7.35(1H，m)，7.25(1H，t，J＝8Hz)，7.25(1H，b)，7.1(2H，d，J＝8Hz)，6.92(1H，d，J＝8Hz)，6.88-6.75(1H，m)，6.82(2H，d，J＝8Hz)，6.05(1H，s)，3.9(2H，s)，3.75(3H，s)，2.55(3H，s)，2.25(3H，s)
IR (KBr) cm
-1: 3345,1656,1246,1074,694 ultimate analysis value: C
21H
21NO
3Calculated value (%) C75.20 H6.31 N4.18
Analytical value (%) C75.28 H6.32 N4.21
Embodiment 152,5-dimethyl furan-3-formyl-[3-(2-methoxycarbonyl vinyl) aniline]
Yield: 63.3%
Fusing point: 159.5-181.5 ℃
1HNMR(CDCl
3)δppm：7.82(1H，m)，7.7(1H，d，J＝15Hz)，7.58(1H，m)，7.38(1H，b)，7.35(1H，t，J＝8Hz)，7.28(1H，m)，6.48(1H，d，J＝15Hz)，6.12(1H，s)，3.82(3H，s)，2.55(3H，s)，2.25(3H，s)
IR (KBr) cm
-1: 3387,1685,1870,1068,800 ultimate analysis value: C
17H
17NO
4Calculated value (%) C68.22 H5.72 N4.68
Analytical value (%) C67.55 H5.64 N4.62
Embodiment 162,5-dimethyl furan-3-formyl-(3-phenylaniline)
Yield: 50.0%
Fusing point: 90.0-92.0 ℃
1HNMR(CDCl
3)δppm：7.82(1H，s)，7.6(2H，d，J＝8Hz)，7.55(1H，d，J＝8Hz)，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 ultimate analysis value: C
19H
17NO
2Calculated value (%) C78.33 H5.88 N4.81
Analytical value (%) C78.17 H6.00 N4.72
Embodiment 172,5-dimethyl furan-3-formyl-(3-neopentyl oxygen monomethylaniline)
Yield: 50.0%
Fusing point: 95.5-97.0 ℃
1HNMR(CDCl
3)δppm：7.48(2H，m)，7.32(1H，t，J＝8Hz)，7.3(1H，b)，7.12(1H，d，J＝8Hz)，4.52(2H，s)，3.12(2H，s)，2.55(3H，s)，2.25(3H，s)，0.95(9H，s)
IR (KBr) cm
-1: 3324,1646,1091,700 ultimate analysis values: C19H25NO3 calculated value (%) C72.35 H7.99 N4.44
Analytical value (%) C72.38 H8.03 N4.20
Embodiment 182,5-dimethyl furan-3-formyl-(3-pseudoallyl aniline)
Yield: 50.0%
Fusing point: 71.0-72.0 ℃
1HNMR(CDCl
3)δppm：7.65(1H，m)，7.5(1H，m)，7.3(1H，b)，7.3(1H，t，J＝8Hz)，7.22(1H，m)，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 ultimate analysis value: C
16H
17NO
2Calculated value (%) C75.27 H6.71 N5.49
Analytical value (%) C75.29 H6.88 N5.48
Embodiment 192,5-dimethyl furan-3-formyl-(3-ethynyl aniline)
Yield: 50.0%
Fusing point: 83.0-84.0 ℃
1HNMR(CDCl
3)δppm：7.7(1H，m)，7.6(1H，m)，7.32-7.2(3H，m)，6.1(1H，s)，3.05(1H，s)，2.55(3H，s)，2.25(3H，s)
IR (KBr) cm
-1: 3245,1644,1079,796 ultimate analysis value: C
15H
13NO
2Calculated value (%) C75.30 H5.48 N5.85
Analytical value (%) C75.50 H5.46 N5.96
Embodiment 202,5-dimethyl furan-3-formyl-(3-ethylaniline)
Yield: 91.0%
Fusing point: 113-115.0 ℃
Mass(m/z)：243(M
+)123.94
1HNMR(CDCl
3)δppm：7.47-6.95(4H，m)，6.1(1H，s)，2.66(3H，q)，2.60(3H，s)，2.29(3H，s)，1.25(3H，t)
Embodiment 21
2,5-dimethyl furan-3-formyl-
(3-isopropyl aniline)
Yield: 84.0%
Fusing point: 79-80 ℃
Mass(m/z)：257(M
+)149.135
1HNMR(CDCl
3)δppm：7.47-6.98(4H，m)，6.11(1H，s)，2.91(1H，q，q)，2.60(3H，s)，2.29(3H，s)，1.26(d，6H)
Embodiment 222,5-dimethyl furan-3-formyl-(2, the 6-Diethyl Aniline)
Yield: 85.2%
Fusing point: 128.0-131.0 ℃
Mass(m/z)：271(M
+)242.228
1HNMR(CDCl
3)δppm：7.28-7.12(3H，m)6.82(1H，b)，6.16(1H，s)，2.63(4H，q)，2.58(3H，s)，2.31(3H，s)，1.20(6H，t)
Embodiment 23
2,5-dimethyl furan-3-formyl-(3-hexyl aniline)
Step 1), with 2,5-dimethyl furan-3-carbonyl chlorine (3.95g) is dissolved in the methylene dichloride (60ml), and under ice-cold, Iodoaniline (2.99ml) between adding triethylamine (3.45ml) reaches stirred 6.5 hours under the room temperature.Behind the cooling reaction solution, add methylene dichloride (50ml) dilution, use 1N sodium hydroxide, 1N hydrochloric acid, saturated common salt water washing then successively, use dried over sodium sulfate, concentrate.Use silica gel, behind the chromatographic refining resistates, obtain faint yellow crystalline 2,5-dimethyl furan-3-formyl-(3-Iodoaniline) 7.64g (yield 89.9%).
Step 2), in the crystallization (0.68g) that step 1) obtains, add ether (8ml), the bromination hexyl magnesium (1M that then divides 6 addings (1,1 '-two (diphenyl phosphine)-ferrocene) palladium (II) muriate (29.3mg) and prepare by hexyl bromide and magnesium, 11ml), at room temperature stir 47 hours.Add 2N hydrochloric acid in reaction solution, the elimination catalyzer is used extracted with diethyl ether.After extraction liquid sodium bicarbonate water, the saturated common salt water washing, use dried over sodium sulfate, concentrate.At first use silica gel,, obtain the purpose compound 316mg (yield 52.8%) of white crystals then with YMC packed column D-ODS-5 chromatographic refining resistates.
Fusing point: 71.5-72.0 ℃
1HNMR(CDCl
3)δppm：7.45(1H，m)，7.35(1H，m)，7.25(1H，b)，7.22(1H，t，J＝8Hz)，6.95(1H，d，J＝8Hz)，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＝7Hz)
IR (KBr) cm
-1: 3310,1643,1077,788 ultimate analysis value: C
19H
25NO
2Calculated value (%) C76.22 H8.42 N4.68
Analytical value (%) C76.15 H8.54 N4.55
Carry out same operation, use suitable Grignard reagent to replace bromination hexyl magnesium, can obtain following compound.
Embodiment 24
2,5-dimethyl furan-3-formyl-(3-butylaniline)
Yield: 36.4%
Fusing point: 77.0-80.0 ℃
1HNMR(CDCl
3)δppm：7.45(1H，m)，7.35(1H，m)，7.25(1H，b)，7.22(1H，t，J＝8Hz)，6.95(1H，d，J＝8Hz)，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＝7Hz)
IR (KBr) cm
-1: 3285,1646,1075,702 ultimate analysis value: C
17H
21NO
2Calculated value (%) C75.25 H7.80 N5.16
Analytical value (%) C75.13 H7.87 N5.13
Embodiment 252,5-dimethyl furan-3-formyl-(3-sec-butyl aniline)
Yield: 38.1%
Fusing point: 80.0-81.0 ℃
1HNMR(CDCl
3)δppm：7.4(1H，m)，7.38(1H，m)，7.25(1H，b)，7.22(1H，t，J＝8Hz)，6.95(1H，d，J＝8Hz)，6.1(1H，s)，2.65-2.5(1H，m)，2.55(3H，s)，2.25(3H，s)，1.68-1.5(2H，m)，1.25(3H，d，J＝7Hz)，0.85(3H，t，J＝7Hz)
IR (KBr) cm
-1: 3255,1647,1078,791 ultimate analysis value: C
17H
21NO
2Calculated value (%) C75.25 H7.80 N5.16
Analytical value (%) C75.19 H7.68 N5.14
Embodiment 262,5-dimethyl furan-3-formyl-(3-amyl aniline)
Yield: 18.3%
Fusing point: 97.0-97.5 ℃
1HNMR(CDCl
3)δppm：7.45(1H，m)，7.35(1H，m)，7.28(1H，b)，7.25(1H，t，J＝8Hz)，6.95(1H，d，J＝8Hz)，6.1(1H，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＝7Hz)
IR (KBr) cm
-1: 3304,1644,1077,710 ultimate analysis value: C
18H
23NO
2Calculated value (%) C75.76 H8.12 N4.91
Analytical value (%) C75.77 H8.18 N5.06
Embodiment 272,5-dimethyl furan-3-formyl-(3-cyclohexyl aniline)
Yield: 52.7%
Fusing point: 113.0-114.5 ℃
1HNMR(CDCl
3)δppm：7.48(1H，m)，7.35(1H，m)，7.28(1H，b)，7.25(1H，t，J＝8Hz)，6.98(1H，d，J＝8Hz)，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 ultimate analysis value: C
19H
23NO
2Calculated value (%) C76.74 H7.80 N4.71
Analytical value (%) C76.62 H7.78 N4.67
Embodiment 282,5-dimethyl furan-3-formyl-(3-cyclopentyl aniline)
Yield: 35.9%
Fusing point: 92.0-93.0 ℃
1HNMR(CDCl
3)δppm：7.45(1H，m)，7.35(1H，m)，7.25(1H，b)，7.22(1H，t，J＝8Hz)，7.00(1H，d，J＝8Hz)，6.1(1H，s)，3.08-2.9(1H，m)，2.55(3H，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 ultimate analysis value: C
18H
21NO
2Calculated value (%) C76.30 H7.47 N4.94
Analytical value (%) C76.21 H7.56 N4.93
Embodiment 29
2,5-dimethyl furan-3-formyl-(3-benzylaniline)
Yield: 59.8%
Fusing point: 123.0-125.0 ℃
1HNMR(CDCl
3)δppm：7.45(1H，m)，7.38(1H，m)，7.35-7.15(7H，m)，6.95(1H，d，J＝8Hz)，3.98(2H，s)，2.55(3H，s)，2.25(3H，s)
IR (KBr) cm-1:3314,1640,1078,777,701 ultimate analysis value: C
21H
19NO
2Calculated value (%) C78.66 H6.27 N4.59
Analytical value (%) C77.76 H6.28 N4.55
Reference example 1
2,5-dimethyl furan-3-carboxylic acid, ethyl ester
Ice-cold, the DMF 5ml drips of solution of ethyl 3-oxobutanoate 6.5ml is added to the N of the sodium hydride (60%, 2.4g) of 10ml under stirring, in dinethylformamide (the following abbreviation DMF) suspension.Stir down on one side ice-cold, to this mixture in drip monochloroacetone 5.97ml on one side.Under the room temperature, stir after 3 hours, be injected in the water, use ethyl acetate extraction, behind saturated common salt water washing extraction liquid, use anhydrous sodium sulfate drying.Steam vinyl acetic monomer under the decompression, behind the distillation residue, obtain α-acetonyl-ethyl 3-oxobutanoate 8.01g (yield 86%) under the vacuum.Boiling point: 105 ℃/2mmHg.
The ester that obtains is dissolved in the 20ml ethanol, in this solution, add the 2g tosic acid after, reflux 2 hours.Reaction mixture steams solvent under the decompression after room temperature.Add vinyl acetic monomer in the residue, after the saturated common salt water washing, use anhydrous magnesium sulfate drying.Steam vinyl acetic monomer under the decompression, the residue that obtains is added on the silica gel chromatography, obtain 2 by mixed solvent wash-out, 5-dimethyl furan-3-carboxylic acid, ethyl ester 5.14g (yield 71%) with normal hexane/vinyl acetic monomer=10/1.
Reference example 2
2,5-dimethyl furan-3-carboxylic acid
With 3.2g 2, after the mixing solutions of 5-dimethyl furan-3-carboxylic acid, ethyl ester, 35ml ethanol, 20ml 2N aqueous sodium hydroxide solution at room temperature stirs 1.5 hours, reflux 1 hour.Behind the reaction mixture cool to room temperature, decompression concentrates down.Residue is dissolved in the water, is adjusted to acidity with dilute sulphuric acid.Filter and collect the crystallization of separating out, washing after the drying, obtains 2.27g 2,5-dimethyl furan-3-carboxylic acid (yield 85%).
It is the composition of effective constituent that above-mentioned formula (1) compound that the present invention relates to reaches with this compound, can reach the auxiliary that mixes other in case of necessity by mixed carrier, can be modulated into common operable preparation form as sanitas, for example but finish, emulsion solvation, paste, hydrating agents, trickling agent, dry type trickling agent, sprays, coating etc. use with known treating of wood method.For proterties, the raising antiseptic power that improves preparation, as spendable suitable auxiliary, can enumerate for example lyophobic dusts such as various macromolecular compounds such as anionic property, cationic, non-ionic tenside and methylcellulose gum, vinyl acetate resin etc., organic silicone oil, paraffin.Can certainly be also with following effectiveness toughener, further improve effect, these render a service toughener the Sang Pu Lars, IF-1000, the organic iodine based compound of special Lip river one mulberry class, propyconazole, the azole series compound of ladder skin azoles (テ Block コ Na ゾ one Le) etc., Apl-Luster, the wood preservation of Pecudin and quaternary ammonium salt based compound etc., mould inhibitor and other sterilant, perhaps cross the first spirit, ethrel, super first spirit (サ イ パ one メ ス リ Application), the anti-sweet smell of hila, the pyrethroid based compound of special Lip river first spirit class, Chlorpyrifos 94, Phoxim, organophosphorus based compound and other sterilants and two (2 such as imino-choride such as propetanphos, 3,3,3-tetrachloro propyl group) ether etc.During practical application, can change the content of The compounds of this invention within a large range according to preparation form or application target, generally be 0.1～95 weight %, preferably 0.2～60 weight %.These preparations can use according to common Wood treatment method.For example can adopt coating, scatter, flood, mix, inject or sneak into methods such as adhesive treatment.
Below enumerate some formulation example of The compounds of this invention, the kind of use level, auxiliary can have very big change certainly.(" part " in the literary composition is all represented " weight part ").
The wood preservation formulation example
Formulation example 1 emulsion
20 parts of embodiment 1 compound dissolutions in 70 parts of dimethylbenzene, are added 10 parts of polyoxyethylene nonylplenyl ethers, obtain emulsion behind the thorough mixing.
The available in use suitable water gaging dilution of these emulsions except with the methods such as coating, dipping or spraying, also may be combined in the binding agent of plywood, fiber laminate, fiber board etc. and uses on processed wood materials.
Formulation example 2 finishes
In 2 parts of embodiment 2 compounds, add 98 parts of kerosene and obtain finish.
This finish, the method for available spraying, coating or dipping, injection is used on processed timber.
Formulation example 3 coating
To obtain coating behind 10 parts of embodiment 1 compounds, 20 parts of barites, 10 parts of ethenoid resins, 25 parts of rosin and 35 parts of dimethylbenzene uniform mixing.
Formulation example 4 hydrating agents
With 40 parts of embodiment 3 compounds, 56 parts of carclazytes, 3 parts of lauryl alcohol sodium sulfonates and 1 part of polyvinyl alcohol uniform mixing in mixing machine, obtain hydrating agents after in hammer mill, pulverizing.
Wood preservation test example
Below with the effect of testing routine specific description wood preservative of the present invention.
(1) according to preservative effect test method(s) [JISA-9201 (the 1991)] standard of the wood preservative of JIS regulation, each compound is made the methanol solution of normality, decompression is injected among test body China fir sapwood (2 * 2 * 1) cm, air-dry after.Carry out the weather operation in 1 cycle that was treated to of (stirring 8 hours → 60 ℃ in the water heated 16 hours down), carry out repeatedly 10 times.This test body is placed on the imperial cyprid that grows in advance in quartz sand substratum (Fructus Hordei Germinatus leaching liquid 2%, glucose 1%, peptone 0.3%, yeast 0.2%) belong on the flora of (Serpulalacrymans), after the pressure of carrying out for 12 weeks under 20 ℃ is rotten, the dry weight of test body before and after the test, measure the rotten weight decrement that causes owing to the test body, the result is as shown in table 2.In addition, for all using 9 test bodies under 1 condition, and obtain mean value.
Table 2 test medicine injects liquid concentration (%) because rotten weight in average decrement (%) embodiment 20 compounds 0.01 0
0.005 0.1 embodiment, 21 compounds 0.01 0
0.005 0 comparative compound 1 0.01 9.7
0.005 the long rapids industry of 18.6 non-processor, 18.4 comparative compound 1:4-chloro-phenyl-s-3-iodine propargyl formal (strain) system: IF-1000
Can find out significantly that from above result the compound of above-mentioned general formula (1) can prevent the deterioration of wood-decaying fungus to timber effectively.
(2) each the 0.1w/v methanol solution decompression with compound of the present invention and contrast medicament is injected into test body (China fir sapwood, in 2 * 2 * 0.5cm), after air-dry, washing (about 21/ minute of feed rate) 5 hours, heat the weather operation of handling in 19 hours as 1 cycle down at 60 ℃, repeatedly after 2 times, and then carry out dry sterilization, modulation test body.
This test body is arranged in advance nutrient agar (Fructus Hordei Germinatus leaching juice 2%, glucose 1%, peptone 0.5%) at the sterilization culture dish goes up growth, on the flora as the xylogen decomposer Coriolus versicolor (Coriolus versicolor) of wood preservation effect test organism and cellulose-decomposing bacterium quarter butt junket bacterium (Tyromyces palustris), under 26 ℃, after forcing rotten 3 weeks, judge its effect by testing the hyphal development degree on the body and having or not compressive strength to descend, its result is illustrated in the table 3.
In addition, with following symbolic representation preservative effect.
+: can't see the growth of mycelia on the test body fully, compressive strength and standard material do not have assorted
Difference.
±: only see that on the test body mycelial growth or the compressive strength of trace descend a little.
-: see mycelial growth on the test body, compressive strength obviously descends. table 3 test medicine Coriolus versicolor quarter butt junket bacterium embodiment 1 compound ±-embodiment 2 compounds--embodiment 3 compounds--embodiment 4 compounds--embodiment 5 compounds--embodiment 6 compounds++ embodiment 7 compounds+-embodiment 8 compounds ±-embodiment 9 compounds--embodiment 10 compounds+-embodiment 11 compounds+± embodiment 12 compounds ± ± embodiment 13 compounds++ embodiment 14 compounds++ embodiment 15 compounds+-embodiment 20 compounds++ embodiment 21 compounds++ embodiment 23 compounds++ embodiment 24 compounds++ embodiment 25 compounds++ embodiment 26 compounds++ comparative compound 2++ non-processor--comparative compound 2:3-bromo-2; 3-two iodo-2-acrylic ethyl carbonate esters, three altogether
(strain) system: Sang Pu Lars
Proportioning when using the present composition is according to selecting as the kind of the seeds of rotproofing object and wood materials or processing means (for example be coated with, flood, distribution, injection, mixing, tackiness agent sneak into) etc., but the proportioning of dimethyl furan formyl benzene peace derivative and other medicaments was 240: 1～1: 35 (weight ratio) scope usually, preferably 30: 1～1: 10, more preferably 5: 1～1: 5.
And during actual the use, the content of the present composition is that the form according to preparation changes in very wide scope, and generally content is 0.1～95% (weight) in preparation, preferably in 0.2～60% (weight) scope.
Below enumerate the some formulation example of timber of the present invention with anticorrosive composite, but the kind of use level, auxiliary can change significantly, this is self-evident.
Timber anticorrosive composite formulation example
Formulation example 1 emulsion
30 parts of 10 parts of embodiment 1 compounds and Sang Pu Lars are dissolved in 50 parts of the dimethylbenzene, add 10 parts of polyoxyethylene nonylplenyl ethers again, obtain emulsion behind the thorough mixing.
This emulsion in use, the dilution of available an amount of water except handling the wood materials with methods such as coating, dipping or sprayings, also may be combined in the tackiness agents such as plywood, fiber laminate, fiber board and uses.
Formulation example 2 finishes
1 part in 3 parts of embodiment 2 compounds and special Lip river one mulberry is dissolved in 96 parts of the kerosene, obtains finish.
Formulation example 3 hydrating agents
With 15 parts of embodiment 3 compounds, 25 parts of IF-1000 products, 56 parts of carclazytes, 3 parts of lauryl alcohol sodium sulfonates and 1 part of uniform mixing in mixing machine of polyvinyl alcohol, with obtaining hydrating agents after the hammer mill pulverizing.
Below with the effect of test example explanation timber of the present invention with anticorrosive composite.
Timber is routine with the anticorrosive composite test
With the minimum growth inhibitory concentration of the binary of agar dilution
Use agar dilution, containing wood-decaying fungus Coriolus versicolor (Coriolusversicolor) that (potato dextrose agar substratum: potato leach liquor end 0.4%, glucose 2%, agar 1.5%) on each sterilising medium that is adjusted to normality medicament inoculation grows in advance and the flora (about 4mm diameter) of quarter butt junket bacterium (Tyromyces palustris) on same substratum, obtaining the minimum inhibition of binary growth concentration from 25 ℃ of mycelial growth situations of cultivating down after 5 days.
In addition, about having or not synergism, people such as F.C. Ka Er are in applied microbiology, the 538th～541 page, 9 volumes (1961) (applied microbiology, people such as F.C.Kull, 538,9 (1961) go up on the books, now according to the general method research of using.
At first in embodiment 20 compounds, cooperate the result of Sang Pu Lars, special Lip river one mulberry and IF-1000 respectively, be illustrated among table 4 and Fig. 1 (a)～(f).
Then embodiment 21 compounds are carried out and above-mentioned same research, its result is illustrated among table 5 and Fig. 2 (a)-(f).
Fig. 1 and the 2 represented minimum growth inhibitory concentration curves of binary all are to be present in the diagonal lines below that dots.
This has just clearly illustrated Sang Pu Lars, special Lip river one mulberry and the IF-1000 effect by cooperating the furoyl anils to obtain multiplying each other.
The minimum growth inhibitory concentration (ppm) of the binary of table 4 embodiment 1 compound+various Synergist S-421 95s
A: Sang Pu Lars B: special Lip river one mulberry C:IF-1000
| Embodiment 1 is for examination bacterium compound | (proportioning) embodiment 1 embodiment 1 A compound+A compound: A | (proportioning) embodiment 1 embodiment 1 B compound+B compound: B | (proportioning) embodiment 1 embodiment 1 C compound+C compound: C |
| Assorted 2.5 looks leather covers bacterium | 15 1.30＋3.0 (1∶2.3) 0.8＋5.0 (1∶6.3) 0.4＋9.0 (1∶22.5) | 25 1.25＋5.0 (1∶4) 0.8＋7.5 (1∶9.4) 0.4＋12.5 (1∶31.3) | 6 1.25＋1.2 (1.0∶1) 0.8＋1.8 (1∶2.3) 0.5＋3.0 (1∶6) |
| Short 200 bar junket bacterium | 25 110.0＋5.0 (22∶1) 70.0＋9.0 (7.8∶1) 40.0＋14.0 (2.9∶1) | 2.5 120.0＋0.6 (200∶1) 80.0＋1.0 (80∶1) 40.0＋1.5 (26.7∶1) | 2 120.0＋0.5 (240∶1) 80.0＋0.8 (100∶1) 40.0＋1.2 (33∶1) |
The minimum growth inhibitory concentration (ppm) of the binary of table 5 embodiment 2 compounds+various Synergist S-421 95s
A: Sang Pu Lars B: special Lip river one mulberry C:IF-1000
| Embodiment |
| 2 is for examination bacterium compound | (proportioning) | (proportioning) | (proportioning) |
| Variegated 10.0 leather cover bacterium | 15 6.0＋3.0 (2∶1) 3.5＋5.0 (1∶1.4) 2.0＋8.0 (1∶4) | 25 5.5＋6.0 (1.1∶1) 3.0＋8.0 (1∶2.7) 1.5＋12.5 (1∶8.3) | 6 6.0＋1.6 (3.6∶1) 4.0＋2.4 (1.7∶1) 2.0＋3.6 (1∶1.8) |
| | 25 120.0＋5.0 (24∶1) 75.0＋9.0 (8.3∶1) 40.0＋15.0 (2.7∶1) | 2.5 120.0＋0.7 (171.4∶1) 90.0＋1.0 (90∶1) 40.0＋1.75 (22.9∶1) | 2 120.0＋0.5 (240∶1) 90.0＋1.0 (90∶1) 40.0＋1.4 (28.6∶1) |
Claims (6)
1. the Dimethylfurancarboxaderivative derivative of formula (1),
Wherein, R
1Expression
The 3-alkoxy carbonyl that partly has 1-3 carbon atom at alkoxyl group;
The 3-alkoxy methyl that partly has 1-3 carbon atom at alkoxyl group;
The cycloalkyl amino carbonyl that has 4-6 carbon atom at cycloalkyl moiety;
The benzyl that does not replace or on its phenyl ring, replaced by methoxyl group;
Benzoyl; Or
Partly have 1-3 carbon atom and have the alkoxy carbonyl thiazolinyl of 2-3 carbon atom at alkenyl part at alkoxyl group; And R
2The expression hydrogen atom.
2. according to the Dimethylfurancarboxaderivative derivative of the formula (1) of claim 1, wherein said derivative is 3 '-benzyl-2,5-dimethyl furan-3-formylaniline.
3. anticorrosion composition for wood, contain carrier and with it blended, as the Dimethylfurancarboxaderivative derivative of the following general formula (I) that makes the effective anticorrosion amount of timber of activeconstituents,
Wherein, R
1Expression
3-alkyl with 2-6 carbon atom;
The 3-alkoxy carbonyl that partly has 1-3 carbon atom at alkoxyl group;
The 3-alkoxy methyl that partly has 1-3 carbon atom at alkoxyl group;
The cycloalkyl amino carbonyl that has 4-6 carbon atom at cycloalkyl moiety;
The benzyl that does not replace or on its phenyl ring, replaced by methoxyl group;
Benzoyl; Or
Partly have 1-3 carbon atom and have the alkoxy carbonyl thiazolinyl of 2-3 carbon atom at alkenyl part at alkoxyl group; And R
2The expression hydrogen atom.
4. according to the anticorrosion composition for wood of claim 3, wherein said Dimethylfurancarboxaderivative derivative is 3 '-sec.-propyl-2,5-dimethyl furan-3-formylaniline.
5. make the method for wood preservation, comprise that the composition with the Dimethylfurancarboxaderivative derivative of the formula (I) of effective processing amount of wood of containing of claim 3 imposes on the timber.
6. according to the method that makes wood preservation of claim 5, wherein said Dimethylfurancarboxaderivative derivative is 3 '-sec.-propyl-2,5-dimethyl furan-3-formylaniline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94195129A CN1076350C (en) | 1994-04-15 | 1994-04-15 | Dimethylfurancarboxanilide derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94195129A CN1076350C (en) | 1994-04-15 | 1994-04-15 | Dimethylfurancarboxanilide derivative |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00127086 Division CN1342405A (en) | 2000-09-08 | 2000-09-08 | Anticorrosion composition for wood |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1152307A CN1152307A (en) | 1997-06-18 |
| CN1076350C true CN1076350C (en) | 2001-12-19 |
Family
ID=5039638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94195129A Expired - Fee Related CN1076350C (en) | 1994-04-15 | 1994-04-15 | Dimethylfurancarboxanilide derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1076350C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ565245A (en) * | 2005-06-21 | 2010-07-30 | Mitsui Chemicals Inc | Amide derivative and pesticide containing such compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05221994A (en) * | 1991-11-22 | 1993-08-31 | Basf Ag | Acid anilide derivative and method for preventing botrytis using same |
-
1994
- 1994-04-15 CN CN94195129A patent/CN1076350C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05221994A (en) * | 1991-11-22 | 1993-08-31 | Basf Ag | Acid anilide derivative and method for preventing botrytis using same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1152307A (en) | 1997-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1028713C (en) | Pyrazole derivatve, insechicidal or miticidal composition | |
| CN1291993C (en) | N-substituted benzothiazolyl-1-substituted phenyl-0,0-dialkyl-alpha-amino phosphonate ester derivatives preparation and application | |
| CN1036564C (en) | Herbicidal glutarmides | |
| CN1185216C (en) | Fungicidies | |
| CN86103514A (en) | The preparation method of the tetrazolinone that replaces | |
| CN1394202A (en) | Picolinic acid derivatives and their use as fungicides | |
| CN1133642C (en) | Nucleoside 5'-thiophosphoryl amino-acid ester compound | |
| CN101036457A (en) | Microemulsion | |
| CN86108936A (en) | Heterogeneous ring compound | |
| CN1020449C (en) | Insecticidal triffluormethyl alkane derivatives | |
| CN1150825C (en) | Mixed rotenone preparation | |
| CN1051556A (en) | Pyrimidine derivatives and preparation thereof and application | |
| CN100335481C (en) | Poly-substituted pyridino-[4,3d] pyramine with antibacterial and herbicide activity and its production thereof | |
| CN1147477C (en) | Novel allylthiopyridazine derivatives and process for preparing the same | |
| CN1037705A (en) | The preparation method of new pyrimidone derivatives | |
| CN86105901A (en) | Agricultural chemical compound | |
| CN1062530A (en) | Isonicotinic acid derivatives and corresponding spirocyclic compound thereof with herbicide effect | |
| CN1076350C (en) | Dimethylfurancarboxanilide derivative | |
| CN87106830A (en) | Tertiary amine compound | |
| CN1030913C (en) | Benzohyolroxymoylazole derivatives, method for producing same, and insecticide including same | |
| CN1029189C (en) | Isothiazolecarboxylic acid derivatives, rice blast control agents containing same as active ingredients, and rice blast control method applying control agents | |
| CN1568694A (en) | Weed removal combination | |
| CN87108356A (en) | Pyrimidine derivatives | |
| CN1061406A (en) | Fungicidal 3,3-1,1-bialkyl sulphide-2-pyridyl acrylic acid derivative | |
| CN87102121A (en) | Heterogeneous ring compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |