CN1342405A - Anticorrosion composition for wood - Google Patents
Anticorrosion composition for wood Download PDFInfo
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- CN1342405A CN1342405A CN 00127086 CN00127086A CN1342405A CN 1342405 A CN1342405 A CN 1342405A CN 00127086 CN00127086 CN 00127086 CN 00127086 A CN00127086 A CN 00127086A CN 1342405 A CN1342405 A CN 1342405A
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Abstract
An antiseptic composition for wood contains carrier, dimethy furoylphenylamine derivative as active component, and at least one of 3-bromo-2,3-diido-2-acrylethyl aminoformate, 3-iodo-2-propynylbutyl aminoformate, and 4-chlorophenyl-3-iodopropargyl formal through mixing them.
Description
The application submitted, is entitled as the dividing an application of PCT/JP94/00631 application for a patent for invention of " Dimethylfurancarboxaderivative derivative " on April 15th, 1994, and original application obtains Chinese patent application number 94195129.4 (notice of accepting that Patent Office sends is not listed as the date that enters the China national stage).
The present invention relates to have new Dimethylfurancarboxaderivative (dimethylqurancarboxyanilide) derivative of good anticorrosion activity, be the wood preservative of active ingredient and this Dimethylfurancarboxaderivative derivative is engaged in timber antiseptic composition in the commercially available wood preservative that present affirmation produced effect as one of active ingredient with this Dimethylfurancarboxaderivative derivative for timber.
Past, in order to prevent because various wood-decaying fungus rotten to timber used various inorganic or organic compounds 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 concentration 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 disease 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.
The object of the present invention is to provide safety higher, at low 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 anil, 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 active ingredient this furoyl anil 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; C
1-C
6Alcoxyl C
1-C
6Alkyl; Cyano group; Substituted amido; C
1-C
6Alkoxy carbonyl group; 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
6Alkoxy carbonyl group 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 active ingredient and with the timber anticorrosive composite.
Fig. 1 (a)～(f) is the figure of the minimum growth inhibitory concentration of binary (ppm) of compound+various compounding ingredients of expression embodiment 1.
Fig. 2 (a)～(f) is the figure of the minimum growth inhibitory concentration of binary (ppm) of compound+various compounding ingredients of expression embodiment 2.
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), R1And R2Defined C3-C
6Thiazolinyl is the thiazolinyl of pi-allyl, isopropenyl, methylallyl, 2-cyclobutenyl, 3-cyclobutenyl, 1,3-butadiene base, 2-pentenyl, 2-hexene base class, preferably C3-C
4Acrylic, more preferably isopropenyl.
In the above-mentioned general formula (1), R
1And R
2Defined C
2-C
6Alkynyl is the alkynyl of acetenyl, propargyl, 2-butynyl, 4-pentynyl, 2-hexin base class, preferably C
2-C
4Alkynyl, more preferably acetenyl.
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 is the alkoxyl of the straight or branched of ethyoxyl, propoxyl group, isopropoxy, butoxy, amoxy, own oxygen base class, preferably C
2-C
4Alkoxyl, more preferably C
2-C
3Alkoxyl.
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 is the alkoxyl of the straight or branched of methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, amoxy, neopentyl oxygen, own oxygen base class, preferably C
1-C
5Alkoxyl, more preferably C
1-C
3Alkoxyl or C
5Alkoxyl.
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 methylene, ethylidene, 1,2-propylidene, 1, the alkylidene of the straight or branched of 3-propylidene, butylidene, pentylidene, hexylidene class, preferably C
1-C
2Alkylidene, more preferably methylene.
In the above-mentioned general formula (1), R
1And R
2Defined replacement acylamino-is an alkyl amido of formamide, acetamide, Isopropamide, butyramide, secondary butyryl amine; Diformamide, diacetayl amide, diisopropyl amide, two butyramides, di-secondary butyramide, Methylethyl acid amides, isopropyl methyl acid amides, methyl butyl acid amides, methyl sec-butyl acid amides, ethyl isopropyl acid amides, isopropyl butyl amide, pyrrolidinyl acid amides, the dialkyl group acylamino-of piperidyl amide class, benzamide, 2-chlorobenzamide, 2,4-dichloro-benzenes acid amides, 2-methylbenzene acid amides, 2-ethylo benzene acid amides, 4-methoxybenzene amide-type have substituent benzoyl amino, preferably an acylamino-of formamide, piperidyl amide or benzamide.
In the above-mentioned general formula (1), R
1And R
2Defined C
1-C
6Alkoxy carbonyl group is the above-mentioned " C of methoxycarbonyl group, carbethoxyl group, 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 combines with carbonyl and the base that constitutes ", C preferably
1-C
3Alkoxy carbonyl group.
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-methoxybenzoyl base 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 acetylamino, propionamido, butyrylamino, isobutyryl amino, valeryl amino, isovaleryl amino, hexanoyl amino, dissident's acylamino-, acetylamino 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, cyclopenta 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
6Alkoxy carbonyl group C
2-C
5Alkenylene is methoxycarbonyl group ethenylidene, carbethoxyl group 2-allylidene, methoxycarbonyl group 2-butenylidene, carbethoxyl group 2-inferior pentenyl, preferably methoxycarbonyl group ethenylidene.
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
6Alkoxy carbonyl group, C
1-C
6Alcoxyl C
1-C
2Alkylidene, C
3-C
6Cycloalkyl carbonyl amino, C
2-C
4Alkoxyl, can have 1 to 2 substituent benzoyl, can have 1 to 2 substituent benzyl or C
1-C
6Alkoxy carbonyl group 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
3Alkoxy carbonyl group, C
1-C
6Alcoxyl methylene, C
4-C
6Cycloalkyl carbonyl amino, benzoyl, can have 1 substituent benzyl or C
1-C
3Alkoxy carbonyl group 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
3Alkoxy carbonyl group) base, 3-(C
1-C
3The alcoxyl methylene) base, C
4-C
6The cycloalkyl carbonyl amino, can have the substituent benzyl of methoxyl group, benzoyl or C
1-C
3Alkoxy carbonyl group C
2-C
3The compound of alkenylene,
(4) R
2It is the compound of hydrogen atom.
Constitute the new Dimethylfurancarboxaderivative derivative of wood preservative active ingredient of the present invention.Shown in following table.
In the following table 1, used following contracted notation
The Bz benzyl
The Bu butyl
The Et ethyl
The Hx hexyl
The Me methyl
The Ph phenyl
The Pip piperidyl
The Pn amyl group
The Pr propyl group
I is different
S second month in a season
Uncle t
The c ring
Table 1 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 H 10 3-CH
2OEt H 11 4-CH
2OEt H 12 2-Et 3-Et 13 2-Et 4-Et 14 2-Et 5-Et 15 2-Et 6-Et 16 3-Et 4-Et 17 3-Et 5-Et 18 3-Et 6-Et 19 3-Pr H 20 4-Pr H 21 2-iPr H 22 3-iPr H 23 4-iPr H 24 3-cPr H 25 4-cPr H
26?????????3-CH
2OPr?????????H
27?????????3-CH
2OiPr????????H
28?????????4-CH
2OiPr????????H
29?????????3-CH
2C＝CH
2?????H
30?????????4-CH
2C＝CH
2?????H
31?????????3-CH
2C≡CH???????H
32?????????4-CH
2C≡CH???????H
33?????????3-Pr???????????4-Pr
34?????????2-iPr?????????4-iPr
35?????????3-iPr?????????5-iPr
36?????????3-CH
2OBu?????????H
37?????????4-CH
2OBu?????????H
38?????????3-CH
2OiBu????????H
39?????????4-CH
2OiBu????????H
40?????????3-CH
2OsBu????????H
41?????????4-CH
2OsBu????????H
42?????????3-Bu??????????????H
43?????????4-Bu??????????????H
44?????????3-iBu?????????????H
45?????????3-sBu?????????????H
46?????????3-cBu?????????????H
47?????????4-cBu?????????????H
48?????????3-tBu?????????????H
49?????????3-CH
2CH＝CHMe????H
50?????????3-CH
2C≡CMe??????H
51?????????3-CH
2MeCH＝CH
2??H
52?????????4-CH
2MeCH＝CH
2??H
53?????????3-Pn??????????????H
54?????????4-Pn??????????????H
55???????????3-iPn????????????????H
56???????????3-cPn????????????????H
57???????????3-neoPn??????????????H
58???????????3-CH
2OPn????????????H
59???????????3-CH
2Oneo-Pn????????H
60???????????3-Hx?????????????????H
61???????????3-iHx????????????????H
62???????????3-cHx????????????????H
63???????????3-CN?????????????????H
64???????????3-OEt????????????????H
65???????????3-OiPr???????????????H
66???????????3-CONHMe?????????????H
67???????????3-(CO-1-Pip)?????????H
68???????????3-CONHPh?????????????H
69???????????3-COOMe??????????????H
70???????????3-COOEt??????????????H
71???????????3-COOPr??????????????H
72???????????3-COOiPr?????????????H
73???????????3-COOBu??????????????H
74???????????3-COOtBu?????????????H
75???????????3-COPh???????????????H
76???????????3-CO(2-MePh)?????????H
77???????????3-NHCOPh?????????????H
78???????????3-NHCOMe?????????????H
79???????????3-NHCOBu?????????????H
80???????????3-NHCOcPn????????????H
81???????????3-NHCOcHx????????????H
82???????????3-Bz?????????????????H
83???????????3-(4-MeOBz)??????????H
84??????????????3-(4-MeBz)?????????????????H
85??????????????3-CH＝CHCOOMe??????????????H
86??????????????3-Ph???????????????????????H
87??????????????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 atent 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 chlroacetone and the ethyl acetoacetate 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 atent solvent that uses is the ethers of ether, isopropyl ether, oxolane, diox etc., arene, carrene, chloroform, the halogenated hydrocarbon of carbon tetrachloride 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 atent solvent, in the presence of dehydrohalogenating agent, the compound of (III) that has general formula and compound with general 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 atent 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, oxolane, dioxane as atent solvent, specially suitable is ether.
Catalyzer, particularly preferred being to use (1,1 '-two (diphenylphosphine)-ferrocene) palladium (II) chloride.
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.
Reaction temperature is generally 0 ℃ to 50 ℃, preferably room temperature.Reaction time is different according to solvent and reagent, but normally 10 hours to 10 days.
Compound with general formula (1) of the present invention and known wood preservative relatively can demonstrate good activity under low 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 low 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
3 '-acetylaminohydroxyphenylarsonic acid 2,5-dimethyl furan-3-formailide
With 2,5-dimethyl furan-3-carbonyl chlorine (0.50g) is dissolved in the carrene (10ml), adds triethylamine (0.44ml) down ice-cold, and 3-acetylaminoaniline (0.47g), stirs 2.5 hours under the room temperature, then adds hot reflux 4.5 hours.Behind the cooling reactant liquor, add carrene (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 residue of silica gel chromatograph, then, obtain the title compound 0.51g (yield 59.4%) of white crystals shape with behind the ethyl acetate 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(1H，t，J＝8H2)，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
Elementary analysis value: C
15H
16N
2O
3Calculated value (%) C66.16 H5.92 N10.29
Assay value (%) C66.30 H5.98 N10.32
Carry out same operation, use suitable anil to replace the 3-acetylaminoaniline, can obtain following compound.
3 '-(N-methylamino formoxyl)-2,5-dimethyl furan-3-formailide
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
Elementary analysis value: C
15H
16N
2O
3Calculated value (%) C86.16 H5.92 N10.29
Assay value (%) C66.08 H6.20 N10.28
Embodiment 3
3 '-(1-pyridine radicals carbonyl)-2,5-dimethyl furan-3-formailide
Yield: 50.0%
Fusing point: 183.0-185.0 ℃
1HNMR(CDCl
3)δppm：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
Elementary analysis value: C
19H
22N
2O
3Calculated value (%) C69.92 H6.79 N8.58
Assay value (%) C69.52 H6.88 N8.48
Embodiment 4
3 '-(N-phenyl amino formoxyl)-2,5-dimethyl furan-3-formailide
Yield: 53.5%
Fusing point: 182.5-184.0 ℃
1HNMR(CDCl
3+DMSO)δppm：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
Elementary analysis value: C
20H
18N
2O
3Calculated value (%) C71.84 H5.43 N8.38
Embodiment 5
Assay value (%) C71.87 H5.64 N8.34
3 '-tertbutyloxycarbonyl-2,5-dimethyl furan-3-formailide
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
Elementary analysis value: C
18H
21NO
4Calculated value (%) C68.55 H6.71 N4.44
Assay value (%) C68.04 H7.00 N4.40
3 '-methoxycarbonyl group-2,5-dimethyl furan-3-formailide
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
Elementary analysis value: C
15H
15NO
4Calculated value (%) C65.92 H5.53 N5.13
Assay value (%) C66.02 H5.60 N5.08
Embodiment 7
3 '-benzoyl-2,5-dimethyl furan-3-formailide
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
Elementary analysis value: C
20H
17NO
3Calculated value (%) C75.22 H5.37 N4.39
Assay value (%) C75.38 H5.43 N4.38
Embodiment 8
3 '-benzamido-2,5-dimethyl furan-3-formailide
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 elementary analysis value: C
20H
18N
1O
3Calculated value (%) C71.84 H5.43 N8.38
Assay value (%) C71.96 H5.53 N8.28
Embodiment 9
3 '-valeryl amino-2,5-dimethyl furan-3-formailide
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 elementary analysis value: C
18H
22N
2O
3Calculated value (%) C68.77 H7.05 N8.91
Assay value (%) C68.73 H7.17 N8.90
3 '-cyclohexyl carbonyl amino-2,5-dimethyl furan-3-formailide
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 elementary analysis value: C
20H
24N
2O
3Calculated value (%) C70.57 H7.11 N8.23
Assay value (%) C70.56 H7.26 N8.16
Embodiment 11
3 '-methoxyl methyl-2,5-dimethyl furan-3-formailide
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)
1R (KBr) cm
-1: 3278,1645,1237,1107,784 elementary analysis value: C
15H
17NO
3Calculated value (%) C69.48 H6.61 N5.40
Assay value (%) C69.22 H7.02 N5.37
Embodiment 12
3 '-ethoxymethyl-2,5-dimethyl furan-3-formailide
Yield: 64.4%
Fusing point: 85.0-85.5 ℃
1HNMR(CDCl
3)δppm：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 elementary analysis value: C
16H
19NO
3Calculated value (%) C70.31 H7.01 N5.12
Embodiment 13
Assay value (%) C70.14 H7.27 N5.06
3 '-the different third oxygen methyl-2,5-dimethyl furan-3-formailide
Yield: 92.7%
Fusing point: 68.0-69.5 ℃
1HNMR(CDCl
3)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 film): cm-1 3321,1651,1072,785 elementary analysis value: C
17H
21NO
3Calculated value (%) C71.06 H7.37 N4.87
Assay value (%) C70.35 H7.14 N4.91
Embodiment 14
3 '-(4-methoxybenzyl)-2,5-dimethyl furan-3-formailide
Yield: 86.8%
Fusing point: 100.0-102.5 ℃
1HNMR(CDCl
3)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 elementary analysis value: C
21H
21NO
3Calculated value (%) C75.20 H6.31 N4.18
Assay value (%) C75.28 H6.32 N4.21
Embodiment 15
3 '-(2-methoxy carbonyl vinyl)-2,5-dimethyl furan-3-formailide
Yield: 63.3%
Fusing point: 159.5-161.5 ℃
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: 3387,1685,1670,1068,800 elementary analysis value: C
17H
17NO
4Calculated value (%) C68.22 H5.72 N4.68
Assay value (%) C67.55 H5.64 N4.62
Embodiment 16
3 '-phenyl-2,5-dimethyl furan-3-formailide
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
Elementary analysis value: C
19H
17NO
2Calculated value (%) C78.33 H5.88 N4.81
Assay value (%) C78.17 H6.00 N4.72
Embodiment 17
3 '-neopentyl oxygen methyl-2,5-dimethyl furan-3-formailide
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 elementary analysis value: C
19H
25NO
3Calculated value (%) C72.35 H7.99 N4.44
Embodiment 18
Assay value (%) C72.38 H8.03 N4.20
3 '-isopropenyl-2,5-dimethyl furan-3-formailide
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 elementary analysis value: C
16H
17NO
2Calculated value (%) C75.27 H6.71 N5.49
Assay value (%) C75.29 H6.88 N5.48
Embodiment 19
3 '-acetenyl-2,5-dimethyl furan-3-formailide
Yield: 50.0%
Fusing point: 83.0-84.0 ℃
1HNMTR(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 elementary analysis value: C
15H
13NO
2Calculated value (%) C75.30 H5.48 N5.85
Assay value (%) C75.50 H5.46 N5.96
Embodiment 20
3 '-ethyl-2,5-dimethyl furan-3-formailide
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
3 '-isopropyl-2,5-dimethyl furan-3-formailide
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 22
2 ', 6 '-diethyl-2,5-dimethyl furan-3-formailide
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
3 '-hexyl-2,5-dimethyl furan-3-formailide
Step 1), with 2,5-dimethyl furan-3-carbonyl chlorine (3.95g) is dissolved in the carrene (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 reactant liquor, add carrene (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 residue, obtain 2 of faint yellow crystallization, 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) chloride (29.3mg) and prepare by hexyl bromide and magnesium, 11ml), at room temperature stir 47 hours.Add 2N hydrochloric acid in reactant liquor, the elimination catalyzer is used extracted with diethyl ether.After extract 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 residue.
Fusing point: 71.5-72.0 ℃
1HNMR (CDCl
3) δ ppm: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), and 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 elementary analysis value: C
19H
25NO
2Calculated value (%) C76.22 H8.42 N4.68
Assay 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
3 '-butyl-2,5-dimethyl furan-3-formailide
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 elementary analysis value: C
17H
21NO
2Calculated value (%) C75.25 H7.80 N5.16
Assay value (%) C75.13 H7.87 N5.13
3 '-sec-butyl-2,5-dimethyl furan-3-formailide
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)，5.95(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 elementary analysis value: C
17H
21NO
2Calculated value (%) C75.25 H7.80 N5.16
Assay value (%) C75.19 H7.68 N5.14
Embodiment 26
3 '-amyl group-2,5-dimethyl furan-3-formailide
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 elementary analysis value: C
18H
23NO
2Calculated value (%) C75.76 H8.12 N4.91
Assay value (%) C75.77 H8.18 N5.06
Embodiment 273 '-cyclohexyl-2,5-dimethyl furan-3-formailide
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
Elementary analysis value: C
19H
23NO
2Calculated value (%) C76.74 H7.80 N4.71
Assay value (%) C76.62 H7.78 N4.67
Embodiment 28
3 '-cyclopenta-2,5-dimethyl furan-3-formailide
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 elementary analysis value: C
18H
21NO
2Calculated value (%) C76.30 H7.47 N4.94
Assay value (%) C76.21 H7.56 N4.93
Embodiment 29
3 '-benzyl-2,5-dimethyl furan-3-formailide
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
Elementary analysis value: C
21H
19NO
2Calculated value (%) C78.66 H6.27 N4.59
Assay value (%) C77.76 H6.28 N4.55
Reference example 1
2,5-dimethyl furan-3-carboxylic acid, ethyl ester
Ice-cold, the DMF5ml drips of solution of ethyl acetoacetate 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 chlroacetone 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 extract, use anhydrous sodium sulfate drying.Steam ethyl acetate under the decompression, behind the bottoms, obtain α-acetonyl-ethyl acetoacetate 8.01g (yield 86%) under the vacuum.Boiling point: 105 ℃/2mmHg.
The ester that obtains is dissolved in the 20ml ethanol, in this solution, behind the adding 2g p-methyl benzenesulfonic acid, added hot reflux 2 hours.Reaction mixture steams solvent under the decompression after room temperature.Add ethyl acetate in the residue, after the saturated common salt water washing, use anhydrous magnesium sulfate drying.Steam ethyl acetate under the decompression, the residue that obtains is added on the silica gel chromatograph, obtain 2 by mixed solvent wash-out, 5-dimethyl furan-3-carboxylic acid, ethyl ester 5.14g (yield 71%) with n-hexane/ethyl acetate=10/1.
Reference example 2
2,5-dimethyl furan-3-carboxylic acid
With 3.2g 2, after the mixed solution of 5-dimethyl furan-3-carboxylic acid, ethyl ester, 35ml ethanol, 20ml 2N sodium hydrate aqueous solution at room temperature stirs 1.5 hours, added hot reflux 1 hour.Behind the reactant mixture cool to room temperature, decompression concentrates down.Residue is dissolved in the water, is adjusted to acidity with dilute sulfuric acid.Filter and collect the crystallization of separating out, washing after the drying, obtains 2.27g2,5-dimethyl furan-3-carboxylic acid (yield 85%).
It is the composition of active ingredient that above-mentioned formula (1) compound that the present invention relates to reaches with this compound, can reach the adjuvant that mixes other in case of necessity by mixed carrier, can be modulated into common operable preparation form as preservative, for example but finish, emulsion solvation, paste, hydrating agents, trickling agent, dry type trickling agent, spray, coating etc. use with known treating of wood method.For proterties, the raising antiseptic power that improves preparation, as spendable suitable adjuvant, can enumerate for example lyophobic dusts such as various macromolecular compounds such as anionic property, cationic, non-ionic tenside and methylcellulose, vinyl acetate resin etc., organic silicone oil, paraffin.Can certainly be also with following effectiveness reinforcing agent, further improve effect, these render a service reinforcing agent 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-Le) etc., thiabendazole, the wood preservation of Euparen and quaternary ammonium salt based compound etc., mould inhibitor and other bactericide, perhaps cross the first spirit, ethrel, super first spirit (サ イ パ-メ ス リ Application), the anti-sweet smell of hila, the pyrethroid based compound of special Lip river first spirit class, chlopyrifos, Phoxim, organic phosphor based compound and other insecticides and two (2 such as imide chloride 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, adjuvant can have very big change certainly.(" part " in the literary composition is all represented " weight portion ").
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 after fully 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, hardboard 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
10 parts of embodiment 1 compounds, 20 parts of barites, 10 parts of vinyls, 25 parts of rosin and 35 parts of dimethylbenzene are evenly obtained coating after the mixing.
Formulation example 4 hydrating agents
40 parts of embodiment 3 compounds, 56 parts of carclazytes, 3 parts of lauryl alcohol sodium sulfonates and 1 part of polyvinyl alcohol are evenly mixed in mixer, 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 antiseptic effect test method(s) [JISA-9201 (the 1991)] standard of the wood preservative of JIS regulation, each compound is made the methanol solution of normal concentration, decompression is injected among test body China fir sapwood (2 * 2 * 1) cm, after air-dry, 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 medium (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 slip 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 average weight slip (%) 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 18.6 non-processor, 184 comparative compound 1:4-chlorphenyls-3-iodine propargyl formal
Long rapids industry (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 quantity delivered) 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 hot air sterilization, modulation test body.
This test body is arranged in advance agar medium (Fructus Hordei Germinatus leaching juice 2%, glucose 1%, peptone 0.5%) at the sterilization culture dish goes up growth, on the flora as the lignin decomposer Coriolus versicolor (Coriolus versicolor) of wood preservation effect test organism and cellulose decomposition bacteria 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 antiseptic 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 3 compounds--
Embodiment 4 compounds--
Embodiment 5 compounds--
Embodiment 7 compounds+-
Embodiment 8 compounds ±-
Embodiment 9 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 26 compounds++
Non-processor--comparative compound 2:3-bromo-2,3-two iodo-2-acrylic ethyl carbonate esters, three altogether
(strain) system: Sang Pu Lars
Match ratio when using the present composition is according to selecting as the kind of the seeds of preservative treatment object and wood materials or processing means (for example be coated with, flood, distribution, injection, mixing, adhesive sneak into) etc., but the match ratio of Dimethylfurancarboxaderivative 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, adjuvant 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 after fully 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 adhesives such as plywood, fiber laminate, hardboard 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
15 parts of embodiment 3 compounds, 25 parts of IF-1000 products, 56 parts of carclazytes, 3 parts of lauryl alcohol sodium sulfonates and polyvinyl alcohol are evenly mixed in mixer for 1 part, obtain hydrating agents after pulverizing with hammer-mill.
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 medium: potato leachate end 0.4%, glucose 2%, agar 1.5%) on each sterilising medium that is adjusted to normal concentration medicament inoculation grows in advance and the flora (about 4mm diameter) of quarter butt junket bacterium (Tyromyces palustris) on same medium, 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 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 anil to obtain multiplying each other.
The minimum growth inhibitory concentration (ppm) of the binary of table 4 embodiment 1 compound+various compounding ingredients
| Embodiment 1 is for examination bacterium compound | (match ratio) embodiment 1 embodiment 1 A compound+A compound: A | (match ratio) embodiment 1 embodiment 1 B compound+B compound: B | (match ratio) 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 junket bacterium | ??25??110.0+5.0?????(22∶1) ???????70.0+9.0?????(1.8∶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) |
A: Sang Pu Lars
B: special Lip river one mulberry
C：IF-1000
The minimum growth inhibitory concentration (ppm) of the binary of table 5 embodiment 2 compounds+various compounding ingredients
| Embodiment 2 is for examination bacterium compound | (match ratio) embodiment 2 embodiment 2 A compound+A compound: A | (match ratio) embodiment 2 embodiment 2 B compound+B compound: B | (match ratio) embodiment 2 embodiment 2 C compound+C compound: C |
| Assorted 10.0 looks leather covers bacterium | ??15????6.0+3.0?????(2∶1) ????????3.5+5.0?????(1∶1.4) ????????2.0+8.0?????(1∶4) | ?25????5.5+5.0?????????(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) |
| Quarter butt 200 junket bacterium | ??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) |
A: Sang Pu Lars
B: special Lip river one mulberry
C：IF-1000
Claims (3)
1. anticorrosion composition for wood, contain carrier and mix with it, as the Dimethylfurancarboxaderivative derivative of the following general formula (I) that makes the effective anticorrosion amount of timber of active component,
Wherein, R
1Expression
3-alkyl with 2-6 carbon atom;
The 3-alkoxy carbonyl that partly has 1-3 carbon atom at alkoxyl;
The 3-alkoxy methyl that partly has 1-3 carbon atom at alkoxyl;
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; And R
2The expression hydrogen atom, described composition also comprises at least a following compound that is selected from: 3-bromo-2,3-two iodo-2-acrylic ethyl carbamates, 3-iodo-2-propynyl butyl carbamate and 4-chlorphenyl-3-iodine propargyl formal.
2. according to the anticorrosion composition for wood of claim 1, wherein said Dimethylfurancarboxaderivative derivative is 3 '-isopropyl-2,5-dimethyl furan-3-formailide.
3. make the method for wood preservation, comprise that the composition with claim 1 or 2 imposes on the timber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00127086 CN1342405A (en) | 2000-09-08 | 2000-09-08 | Anticorrosion composition for wood |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00127086 CN1342405A (en) | 2000-09-08 | 2000-09-08 | Anticorrosion composition for wood |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94195129A Division CN1076350C (en) | 1994-04-15 | 1994-04-15 | Dimethylfurancarboxanilide derivative |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106994725A (en) * | 2017-05-27 | 2017-08-01 | 江苏农林职业技术学院 | It is a kind of to be used to impregnate rosin furans preservative of poplar and its preparation method and application |
| CN110627767A (en) * | 2019-09-05 | 2019-12-31 | 中国药科大学 | Selective butyrylcholinesterase inhibitor or pharmaceutically acceptable salt thereof, preparation method and application thereof |
| TWI743976B (en) * | 2020-09-04 | 2021-10-21 | 國立中興大學 | Pest control composition |
-
2000
- 2000-09-08 CN CN 00127086 patent/CN1342405A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106994725A (en) * | 2017-05-27 | 2017-08-01 | 江苏农林职业技术学院 | It is a kind of to be used to impregnate rosin furans preservative of poplar and its preparation method and application |
| CN106994725B (en) * | 2017-05-27 | 2018-08-21 | 江苏农林职业技术学院 | It is a kind of to be used to impregnate rosin furans preservative of poplar and its preparation method and application |
| CN110627767A (en) * | 2019-09-05 | 2019-12-31 | 中国药科大学 | Selective butyrylcholinesterase inhibitor or pharmaceutically acceptable salt thereof, preparation method and application thereof |
| CN110627767B (en) * | 2019-09-05 | 2020-08-25 | 中国药科大学 | Selective butyrylcholinesterase inhibitor or pharmaceutically acceptable salt thereof, preparation method and application thereof |
| TWI743976B (en) * | 2020-09-04 | 2021-10-21 | 國立中興大學 | Pest control composition |
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