CN104292156A - Boscalid homologs and uncoupling synthesis method thereof as well as application of boscalid homologs in preparing medicines for preventing and treating pathogenic bacteria - Google Patents

Boscalid homologs and uncoupling synthesis method thereof as well as application of boscalid homologs in preparing medicines for preventing and treating pathogenic bacteria Download PDF

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CN104292156A
CN104292156A CN201410546424.8A CN201410546424A CN104292156A CN 104292156 A CN104292156 A CN 104292156A CN 201410546424 A CN201410546424 A CN 201410546424A CN 104292156 A CN104292156 A CN 104292156A
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etme
boscalid
etso
meso
acid
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于康平
李泽方
徐韶康
罗志会
李惠
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JIANGSU GENGYUN CHEMICAL CO Ltd
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JIANGSU GENGYUN CHEMICAL CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C07C17/266—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of hydrocarbons and halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups

Abstract

The invention provides boscalid homologs and an uncoupling synthesis method thereof as well as the application of the boscalid homologs in preparing medicines for preventing and treating pathogenic bacteria. The general formula I of the structures of the boscalid homologs is as shown in the specification; in the formula I, Q is selected from N and CH; R1 is a tertiary alkyl having a relatively large space volume; R2 is selected from hydrogen atom, single substituent or multiple substituent halogens, nitryl, cyano, alkyl sulphanyl and sulfonyl. The boscalid homologs are capable of effectively controlling harmful pathogenic bacteria by a tiny dosage (the content of the active ingredients in a common formula is 10%-30%). The uncoupling synthesis method of the boscalid homologs is simple in process, and easy to popularize and utilize.

Description

Boscalid amine homologue, its non-coupled method synthetic method and the application in preparation control germ medicine thereof
Technical field
The invention belongs to disinfectant use in agriculture field, relate to a class boscalid amine homologue, its non-coupled method synthetic method and the application in preparation control germ medicine thereof particularly.
Background technology
Boscalid amine is the disinfectant use in agriculture that BASF Aktiengesellschaft developed in 1992, is succsinic acid ubiquinone reductase inhibitor in mitochondrial respiratory chain, by suppressing the breathing of the oxygen of succsinic acid matrix, thus hinders the energy metabolism of pathogenic bacteria to present fungicidal activity.The crops such as grass poison, tomato, eggplant, cucumber, French beans, red bean, onion, grape, watermelon, muskmelon, lettuce, wild cabbage can be widely used in, prevent and treat Powdery Mildew, gray mold, sclerotium disease and various cankers etc.The synthesis of current boscalid amine and analogue thereof substantially all adopts coupling method to synthesize key intermediate p-diaminodiphenyl, and owing to needing to use expensive benzene feedstock boric acid and noble metal catalyst, synthesis cost is higher.
Summary of the invention
The object of the present invention is to provide a kind of boscalid amine homologue, its non-coupled method synthetic method and the application in preparation control germ medicine thereof.Boscalid amine homologue provided by the invention, just effectively can control harmful levels of pathogens at very low doses.
The technical scheme completing the present application task is as follows:
The invention provides a kind of boscalid amine homologue, its structure is as shown in general formula I:
In formula:
Q is selected from N or CH; R 1be selected from the tertiary alkyl that spatial volume is larger, as the tertiary butyl, tert-pentyl, R 2be selected from hydrogen atom, monosubstituted or polysubstituted halogen, nitro, cyano group, alkylthio or alkylsulfonyl;
In the definition of the compound of Formula I provided, collect term general proxy used as given a definition above:
Halogen: refer to fluorine, chlorine, bromine or iodine; Polysubstituted finger 2,4-dichloro, 3,4=difluoros, 3,4,5-trifluoros;
Alkylthio: refer to the alkylthio that straight or branched alkyl replaces, such as, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl or tert-pentyl;
Alkylsulfonyl: nail alkylsulfonyl, methanesulfinyl, ethylsulfonyl or second sulfinyl.
Further optimization of the present invention, scheme is:
In formula:
Q is selected from N or CH; R 1be selected from the tertiary alkyl that spatial volume is larger, as the tertiary butyl, tert-pentyl, R 2be selected from hydrogen atom, monosubstituted or polysubstituted halogen, nitro, cyano group, alkylthio or alkylsulfonyl;
Halogen: refer to fluorine, chlorine, bromine or iodine; Polysubstituted finger 2,4-dichloro, 3,4=difluoros, 3,4,5-trifluoros;
Alkylthio: refer to the alkylthio that straight or branched alkyl replaces, such as, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl or tert-pentyl;
Alkylsulfonyl: nail alkylsulfonyl, methanesulfinyl, ethylsulfonyl or second sulfinyl.
Can be used in particular compound cited by table 1 the present invention is described, but not limit the present invention.
Table 1
Numbering Q R 1 R 2 Mp(℃) Numbering Q R 1 R 2 Mp(℃)
1 CH H Cl 138-140 41 N H Cl 140-142
2 CH H 2,4-2Cl 150-152 42 N H 2,4-2Cl 158-160
3 CH H 3,4,5-3F 134-136 43 N H 3,4,5-3F 144-146
4 CH H MeS 130-132 44 N H MeS 142-144
5 CH H NO 2 137-139 45 N H NO 2 138-140
6 CH H CN 136-138 46 N H CN 141-143
7 CH H MeSO 2 142-144 47 N H MeSO 2 146-148
8 CH H MeSO 138-140 48 N H MeSO 144-146
9 CH H EtSO 2 151-153 49 N H EtSO 2 162-164
10 CH H EtSO 142-144 50 N H EtSO 152-154
11 CH Me 3C Cl 167-168 51 N Me 3C Cl 139-141
12 CH Me 3C 2,4-2Cl 169-171 52 N Me 3C 2,4-2Cl 179-181
13 CH Me 3C 3,4,5-3F 162-164 53 N Me 3C 3,4,5-3F 168-170
14 CH Me 3C MeS 160-162 54 N Me 3C MeS 169-171
15 CH Me 3C NO 2 170-172 55 N Me 3C NO 2 180-182
16 CH Me 3C CN 167-169 56 N Me 3C CN 175-177
17 CH Me 3C MeSO 2 168-170 57 N Me 3C MeSO 2 172-174
18 CH Me 3C MeSO 159-161 58 N Me 3C MeSO 167-169
19 CH Me 3C EtSO 2 174-176 59 N Me 3C EtSO 2 176-178
20 CH Me 3C EtSO 170-172 60 N Me 3C EtSO 178-180
21 CH EtMe 2C Cl 166-168 61 N EtMe 2C Cl 174-176
22 CH EtMe 2C 2,4-2Cl 172-174 62 N EtMe 2C 2,4-2Cl 180-182
23 CH EtMe 2C 3,4,5-3F 165-167 63 N EtMe 2C 3,4,5-3F 172-174
24 CH EtMe 2C MeS 157-159 64 N EtMe 2C MeS 167-169
25 CH EtMe 2C NO 2 173-175 65 N EtMe 2C NO 2 181-183
26 CH EtMe 2C CN 170-172 66 N EtMe 2C CN 177-179
27 CH EtMe 2C MeSO 2 173-175 67 N EtMe 2C MeSO 2 183-185
28 CH EtMe 2C MeSO 169-171 68 N EtMe 2C MeSO 176-178
29 CH EtMe 2C EtSO 2 177-179 69 N EtMe 2C EtSO 2 188-190
30 CH EtMe 2C EtSO 170-172 70 N EtMe 2C EtSO 174-176
31 CH H Br 142-144 71 N H Br 152-154
32 CH H F 132-134 72 N H F 140-142
33 CH H I 142-144 73 N H I 150-152
34 CH H H 122-124 74 N H H 132-134
35 CH Me 3C Br 177-179 75 N Me 3C Br 189-191
36 CH Me 3C F 165-167 76 N Me 3C F 176-178
37 CH Me 3C I 176-178 77 N Me 3C I 184-188
38 CH EtMe 2C Br 177-179 78 N EtMe 2C Br 189-191
39 CH EtMe 2C F 168-170 79 N EtMe 2C F 176-178
40 CH EtMe 2C I 180-182 80 N EtMe 2C I 188-190
Further restriction, boscalid amine homologue of the present invention refers to: except Q=N, R1=H, R2=Cl (compound 41) compound outward in table 1.Preferably, refer in particular to Q=N, R1=H, R2=SMe, CN, SO 2the compound of Me etc.
The technical scheme completing the application's second goal of the invention is: the non-coupled method synthetic method of above-mentioned boscalid amine homologue: it is characterized in that, step is as follows:
Wherein Q, R 1and R 2definition identical with upper.
(1) substituted biphenyl II and alkylating reagent RX is under protonic acid or Louis acid catalysis, in suitable solvent and carry out alkylated reaction at suitable temperature and obtain compound shown in general formula III.Described alkylating reagent RX is the trimethyl carbinol, tertiary amyl alcohol, methyl tertiary butyl ether, tert-butyl chloride, tert-bromo butane, the tertiary pentane of chloro or 2-bromoisopentane; Described protonic acid is the vitriol oil, phosphoric acid, tosic acid or trifluoromethanesulfonic acid, and described Lewis acid is aluminum chloride, boron trifluoride or zirconium tetrachloride;
React and carry out in suitable solvent.Suitable solvent can be selected from methylene dichloride, chlorobenzene etc.;
Suitable temperature of reaction is 40 ~ 120 DEG C, is generally 40 ~ 80 DEG C;
(2) compound shown in general formula III is nitrated with nitration mixture selective action under optimal temperature obtains nitration product IV.Suitable temperature of reaction is 0 ~ 80 DEG C, is generally 20 ~ 40 DEG C.Suitable solvent is selected from diacetyl oxide, acetic acid or ethyl acetate;
(3) compound shown in general formula I V in suitable solvent under certain hydrogen pressure catalytic hydrogenation or use reductive agent reduction obtain reduzate V.The catalyzer of described catalytic hydrogenation is Raney Ni or 5%Pd/C, and described hydrogen pressure is 1 ~ 20 normal atmosphere, and suitable reaction solvent is selected from methyl alcohol or ethanol; Described reductive agent is SnCl 2, hydrazine hydrate or Fe/HCl; Suitable temperature of reaction is 20 ~ 80 DEG C;
(4) in suitable solvent, compound shown in general formula V generates acid amides I (R ≠ H) with acyl chlorides VI condensation under acid binding agent exists, and described acid binding agent is salt of wormwood, sodium carbonate, cesium carbonate, potassium hydroxide, triethylamine, pyridine or Dimethylamino pyridine; Suitable solvent is selected from methylene dichloride, toluene, dimethylbenzene or purified petroleum benzin; Suitable temperature of reaction is 25 ~ 130 DEG C, is generally 80 ~ 100 DEG C;
(5) compound shown in general formula I (R ≠ H) obtains dealkylation compound I (R=H) with alkyl receptor acting under Lewis acid effect, and described alkyl acceptor is benzene, and described Lewis acid is selected from aluminum chloride, zirconium tetrachloride.
The technical scheme completing the application's the 3rd invention task is, the application of above-mentioned boscalid amine homologue in preparation control germ medicine.
Compound shown in general formula I shows high reactivity to the harmful levels of pathogens in agricultural technology field, and therefore another technical scheme of the present invention relates to the application that compound shown in general formula I prevents and treats germ in other fields such as agricultural, gardening.Especially the kind of compound of Formula I to following section has activity: Powdery Mildew, anthrax, damping-off, blight, gray mold, sclerotium disease, various canker, brown heart and root rot etc.
Meanwhile, compound shown in general formula I has hypotoxicity to the insect of environmental beneficial, Mammals, bird and fish etc., and does not have toxicity to plant.
Due to the characteristic that it is positive, compound of Formula I can be used for the injury of the staple crop in protecting agriculture and gardening from harmful levels of pathogens.The compound dosage of per hectare 20-500 gram can provide effectively preventing.
In order to opportunity is effectively applied to agricultural, use the composition of one or more compound of Formula I normally useful.
Therefore, another kind of technical scheme of the present invention also comprises one group of Bactericide composition, and containing as the compound of Formula I of active ingredient and agriculturally acceptable carrier, in composition, the weight percent of activeconstituents is 1%-99%.
The type of service of composition can be wettable powder, missible oil, microemulsion or suspension agent etc., and its type selecting depends on the needs of embody rule.
Composition is prepared in known manner.The specific configuration method of several formulation is exemplified below:
The preparation of wettable powder: by recipe requirements, by composition mixing such as active ingredient, various tensio-active agent and solid diluents (as clay, silicate), after ultra-fine pulverizer disintegrating, namely obtain the wettable powder product of predetermined content (such as 10%-50%).
The preparation of suspension agent: in common prescription, the content of activeconstituents is 10%-30%.With water or Chinese wax for medium, active ingredient, dispersion agent, suspending agent and antifreezing agent etc. are joined in sand mill and grinds, make suspension agent.
Boscalid amine homologue provided by the invention just effectively can control harmful levels of pathogens (in common prescription, the content of activeconstituents is 10%-30%) at very low doses.Its non-coupled method synthetic method craft is simple, is easy to apply.
Embodiment
Following specific embodiment is used for further illustrating the present invention, but the present invention is not limited only to these examples.
The preparation of embodiment 1.2-(2-chIorobenzoyIamino)-4 '-chlordiphenyl (compound 1)
(1) preparation of the 4-tertiary butyl-4 '-chlordiphenyl
Be dissolved in by 5.66g4'-chlordiphenyl in 50mL methylene dichloride, then add 10.5g zirconium tetrachloride, stir lower dropping 4g methyl tertiary butyl ether, control temperature is no more than 40 DEG C, adds rear continuation reaction 8h.Cooling, is poured in frozen water at leisure by reaction solution.With dichloromethane extraction (3 × 20mL), extraction liquid uses water, aqueous sodium carbonate and water washing to neutral successively, anhydrous sodium sulfate drying, filter, obtain white thick product after filtrate decompression precipitation, obtain pure product with after 95% ethyl alcohol recrystallization, yield 64%, fusing point 146-148 DEG C 1h-NMR (CDCl 3, δ ppm): 1.35 (s, 9H), 7.25-7.52 (m, 8H).
(2) preparation of the 2-nitro-4-tertiary butyl-4 '-chlordiphenyl
By the 1.11g4-tertiary butyl-4 '-chlordiphenyl is dissolved in 15mL diacetyl oxide, and water-bath cooling is lower to be dripped 5mL acetic acid and 3mL and to be fuming HNO 3mixed solution, control temperature not higher than 20 DEG C, add rear continuation reaction 4h.In reaction solution, add 25mL water and stir, having light yellow solid to separate out, suction filtration, be washed to neutrality, 95% ethyl alcohol recrystallization obtains light yellow product, yield 90%, fusing point: 95-96 DEG C, 1h-NMR (CDCl 3, δ ppm): 1.39 (s, 9H), 7.22-7.87 (m, 7H).
(3) preparation of the 2-amino-4-tertiary butyl-4 '-chlordiphenyl
0.054mol2-nitro-4-the tertiary butyl-4 '-chlordiphenyl is dissolved in 120mL ethanol, adds 0.24mol SnCl 2with 60mL hydrochloric acid, back flow reaction 4h.Cooling, with 3 times of water dilutions, filter the ammonium salt of separating out, be then added in KOH solution by much filtrate, stir 4h, suction filtration, is washed to neutrality, and dry, recrystallization obtains white powder 4a, yield 85%, fusing point 99-100 DEG C, 1h-NMR (CDCl 3, δ ppm): 1.41 (s, 9H), 7.22-7.87 (m, 7H), 3.71 (s, 2H).
(4) preparation of 2-(2-the chIorobenzoyIamino)-4-tertiary butyl-4 '-chlordiphenyl
2.6g2-amino-4-the tertiary butyl-4 '-chlordiphenyl is dissolved in 40mL methylene dichloride, adds the 2-Benzoyl chloride of 1.8g and a small amount of DMAP, stirring at room temperature 8h.In reaction solution, add saturated sodium bicarbonate solution adjusts pH to neutral, organic phases washed with water three times, and anhydrous sodium sulfate drying is concentrated, obtains white solid, obtains white needle-like crystals, yield 92%, fusing point 167-169 DEG C after recrystallization, 1h-NMR (CDCl 3, δ ppm): 1.41 (s, 9H), 7.17-7.84 (m, 7H), 8.14 (d, 1H).
(5) preparation of 2-(2-chloro-benzoyl amino)-4 '-chlordiphenyl (compound 1)
3.98g2-(2-the chIorobenzoyIamino)-4-tertiary butyl-4 '-chlordiphenyl is dissolved in 100mL benzene, adds the anhydrous AlCl3 of 6.7g, stirring reaction 40h at 45 DEG C.Poured into by reactant in frozen water, add hydrochloric acid while stirring, be then extracted with ethyl acetate, extraction liquid washes with water to neutrality, anhydrous sodium sulfate drying, uses ethyl acetate-light petrol recrystallization, obtain white powder after precipitation, yield 32%, fusing point 138-140 DEG C, 1h-NMR (CDCl 3, δ ppm): 7.26-7.46 (m, 8H), 8.16-8.46 (m, 3H), 8.46 (d, J=1.8Hz, 1H).
The synthesis of embodiment 2.2-(2-chloropyridine-3-formamido-)-4 '-methylsulfonyl biphenyl (compound 47)
(1) preparation of 4-methylsulfonyl biphenyl
50g4-methylthio group biphenyl is dissolved in 250mL glacial acetic acid, adds 2.5g sodium wolframate, be warming up to 95 DEG C, stir the lower hydrogen peroxide dripping 86g30%, add follow-up continuous insulation reaction 6 hours.Be down to room temperature, have a large amount of solid to separate out, filter, washing, dry, obtain white crystal 52g, yield 89.7%, fusing point 138-140 DEG C. 1H-NMR(CDCl 3,δppm)：3.42(s,3H),7.41-7.52(m,5H),7.88-7.92(m,4H)。
(2) preparation of the 4-tertiary butyl-4 '-methylsulfonyl biphenyl
Be dissolved in 50mL methylene dichloride by 4.64g4-methylsulfonyl biphenyl, then add 11.2g aluminum trichloride (anhydrous), stir lower dropping 4g methyl tertiary butyl ether, control temperature is no more than 40 DEG C, adds rear continuation reaction 8h.Cooling, is poured in frozen water at leisure by reaction solution.With dichloromethane extraction (3 × 20mL), extraction liquid uses water, aqueous sodium carbonate and water washing to neutral successively, anhydrous sodium sulfate drying, filter, obtain white thick product after filtrate decompression precipitation, obtain pure product with after 95% ethyl alcohol recrystallization, yield 72%, fusing point 127-129 DEG C 1h-NMR (CDCl 3, δ ppm): 1.32 (s, 9H), 3.31 (s, 3H), 7.37-7.42 (m, 4H), 7.82-7.90 (m, 4H).
(3) preparation of the 4-tertiary butyl-2-nitro-4 '-methylsulfonyl biphenyl
By the 2.88g4-tertiary butyl-4 '-methylsulfonyl biphenyl is dissolved in 30mL diacetyl oxide, and water-bath cooling is lower to be dripped 10mL acetic acid and 6mL and to be fuming HNO 3mixed solution, control temperature not higher than 20 DEG C, add rear continuation reaction 4h.In reaction solution, add 50mL water and stir, having light yellow solid to separate out, suction filtration, be washed to neutrality, 95% ethyl alcohol recrystallization obtains light yellow product, yield 91%, fusing point: 159-161 DEG C, 1h-NMR (CDCl 3, δ ppm): 1.39 (s, 9H), 3.36 (s, 3H), 7.37-7.42 (m, 3H), 7.82-7.90 (m, 5H).
(4) preparation of amino-4 '-methylsulfonyl biphenyl of the 4-tertiary butyl-2-
6.66g2-nitro-4-the tertiary butyl-4 '-methylsulfonyl biphenyl is dissolved in 60mL ethanol, adds 11.4g SnCl 2with 60mL hydrochloric acid, back flow reaction 4h.Cooling, with 3 times of water dilutions, filter the ammonium salt of separating out, be then added in KOH solution by much filtrate, stir 4h, suction filtration, is washed to neutrality, and dry, recrystallization obtains white powder, yield 77%, fusing point 131-133 DEG C, 1h-NMR (CDCl 3, δ ppm): 1.33 (s, 9H), 3.35 (s, 3H), 4.01 (bs, 2H), 7.36-7.48 (m, 5H), 7.72-7.84 (m, 2H).
(5) preparation of the 4-tertiary butyl-2-(2-chloropyridine-3-formamido-)-4 '-methylsulfonyl biphenyl (compound 57)
3.03g2-amino-4-the tertiary butyl-4 '-methylsulfonyl biphenyl is dissolved in 40mL methylene dichloride, adds 1.93g2-chloronicotinoyl chloride and a small amount of DMAP, stirring at room temperature 6h.In reaction solution, add saturated sodium bicarbonate solution adjusts pH to neutral, organic phases washed with water three times, and anhydrous sodium sulfate drying is concentrated, obtains white solid, obtains white needle-like crystals, yield 96%, fusing point 172-174 DEG C after recrystallization, 1h-NMR (CDCl 3, δ ppm): 1.43 (s, 9H), 3.46 (s, 3H), 7.27-7.84 (m, 7H), 8.14 (d, 1H), 8.20 (d, 1H), 8.60 (s, 1H).
(6) preparation of 2-(2-chloropyridine-3-formamido-)-4 '-methylsulfonyl biphenyl (compound 47)
4.42g2-(2-chloropyridine-3-the formamido-)-4-tertiary butyl-4 '-chlordiphenyl is dissolved in 100mL benzene, adds the anhydrous AlCl of 6.7g 3, stirring reaction 40h at 60 DEG C.Poured into by reactant in frozen water, add hydrochloric acid while stirring, be then extracted with ethyl acetate, extraction liquid washes with water to neutrality, anhydrous sodium sulfate drying, uses ethyl acetate-light petrol recrystallization, obtain white powder after precipitation, yield 46%, fusing point 146-148 DEG C, 1h-NMR (CDCl 3, δ ppm): 7.26-7.46 (m, 8H), 8.16-8.46 (m, 3H), 8.46 (d, J=1.8Hz, 1H).
Embodiment 3.50% compound 41 wettable powder
After each component fully being mixed, through ultra-fine pulverizer disintegrating, obtain the wettable powder of 50%
Embodiment 4.20% compound 35 suspension agent
The in vitro fungicidal activity of embodiment 5. measures
Adopt growth rate method.In super clean bench, for picking one piece in examination strain tube be put in the large culture dish containing PDA substratum with the substratum fritter of object bacteria, cover culture dish rapidly, be tamping with strip of paper used for sealing, cultivate in constant incubator with inoculating needle.After bacterium colony is evenly distributed in culture dish for examination bacterium, is the punching of 0.70cm sampler with internal diameter, obtains the bacterium cake that diameter is 0.70cm.To diameter be 10cm culture dish in inject 1mL liquid to be measured, then injecting 9mL (temperature 85 ~ 90 DEG C) substratum wherein, super clean bench shaking up, is paved into a uniform planar.Preliminary survey test setting concentration is former medicine 50 μ g/mL.By the bacterium cake made, be placed on band medicine substratum, in every culture dish, put into 1 bacterium cake; Repeat twice.Culture dish is put into incubator cultivate, after 24 ~ 48 hours, according to target bacterium colony expansion situation check result, and at the colony diameter that each bacterium cake of suitable timing is expanded.Inhibiting rate is calculated according to bacterium colony expansion diameter and blank diameter.
Mycelial growth inhibition rate (%)=[(contrast colony diameter-chemicals treatment colony diameter)/contrast colony diameter] × 100%.
The sterilization effect of part of compounds is in table 2.
The fungicidal activity (inhibiting rate %, 50 μ g/mL) of table 2. Compound I
"-" represents active not obvious.
Industrial application:
The invention provides general structure such as formula the 2-amido compounds of biphenyl shown in I and non-coupled preparation method thereof and application, this compound is that the present inventor is through extensively investigating and appropriate design, by the screening to large quantization compound, the preferred fungicidal activity of a class filtered out is high, and preparation method is easy, the actual application value of this compound is improved greatly.
Fungicidal activity experiment shows, shown in formula (I), biphenyl 2-amido compounds has very high preventive effect to Plant diseasess such as cotton standing dead, cucumber anthrax, rape sclerotium and tomato gray moulds, can be used as disinfectant use in agriculture and uses.
Formula (I).
Embodiment 6, substantially identical with above embodiment, but in general formula wherein: Q is selected from N; R 1be selected from the tertiary alkyl that spatial volume is larger; R 2be selected from hydrogen atom.
Embodiment 7, substantially identical with above embodiment, but in general formula wherein: Q is selected from CH; R 1be selected from the tertiary alkyl that spatial volume is larger; R 2be selected from monosubstituted halogen.
Embodiment 8, substantially identical with above embodiment, but in general formula wherein: R 2be selected from polysubstituted halogen.
Embodiment 9, substantially identical with above embodiment, but R in general formula wherein 2be selected from nitro.
Embodiment 10, substantially identical with above embodiment, but in general formula wherein: R 2be selected from cyano group.
Embodiment 11, substantially identical with above embodiment, but in general formula wherein: R 2be selected from alkylthio or alkylsulfonyl.
Embodiment 12, substantially identical with above embodiment, but in general formula wherein: R 2be selected from alkylsulfonyl.
Embodiment 13, substantially identical with above embodiment, but the larger tertiary alkyl of wherein said spatial volume is the tertiary butyl; The alkylthio that described straight or branched alkyl replaces is: methyl; Described halogen is: fluorine; Described alkylthio is: the alkylthio that straight chain replaces; Described alkylsulfonyl is: methylsulfonyl.
Embodiment 14, substantially identical with above embodiment, but the larger tertiary alkyl of wherein said spatial volume is tert-pentyl; The alkylthio that described straight or branched alkyl replaces is: ethyl; Described halogen is: chlorine; Described alkylthio is: the alkylthio that branched-chain alkyl replaces; Described alkylsulfonyl is: methanesulfinyl.
Embodiment 15, substantially identical with above embodiment, but the alkylthio that wherein said straight or branched alkyl replaces is: n-propyl; Described halogen is: bromine; Described alkylsulfonyl is: ethylsulfonyl.
Embodiment 16, substantially identical with above embodiment, but the alkylthio that wherein said straight or branched alkyl replaces is: sec.-propyl; Described halogen is iodine; Described alkylsulfonyl is: second sulfinyl.
Embodiment 17, substantially identical with above embodiment, but the alkylthio that wherein said straight or branched alkyl replaces is: normal-butyl; Described polysubstituted halogen is: 2,4-dichloro.
Embodiment 18, substantially identical with above embodiment, but the alkylthio that wherein said straight or branched alkyl replaces is: sec-butyl; Described polysubstituted halogen is: 3,4=difluoro.
Embodiment 19, substantially identical with above embodiment, but the alkylthio that wherein said straight or branched alkyl replaces is: isobutyl-; Described polysubstituted halogen is: 3,4,5-trifluoro.
Embodiment 20, substantially identical with above embodiment, but the alkylthio that wherein said straight or branched alkyl replaces is: the tertiary butyl.
Embodiment 21, substantially identical with above embodiment, but the alkylthio that wherein said straight or branched alkyl replaces is: n-pentyl.
Embodiment 22, substantially identical with above embodiment, but the alkylthio that wherein said straight or branched alkyl replaces is: isopentyl.
Embodiment 23, substantially identical with above embodiment, but the alkylthio that wherein said straight or branched alkyl replaces is: sec.-amyl sec-pentyl secondary amyl.

Claims (10)

1. a boscalid amine homologue, is characterized in that, its structure is as shown in general formula I:
In formula:
Q is selected from N or CH;
R 1be selected from the tertiary alkyl that spatial volume is larger;
R 2be selected from hydrogen atom, monosubstituted or polysubstituted halogen, nitro, cyano group, alkylthio or alkylsulfonyl.
2. boscalid amine homologue according to claim 1, is characterized in that,
The tertiary alkyl that described spatial volume is larger is the tertiary butyl or tert-pentyl;
The alkylthio that described straight or branched alkyl replaces is: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl or tert-pentyl;
Described halogen is: fluorine, chlorine, bromine or iodine;
Described polysubstituted halogen is: 2,4-dichloro, 3,4=difluoros, 3,4,5-trifluoros;
Described alkylthio is: the alkylthio that straight or branched alkyl replaces;
Described alkylsulfonyl is: methylsulfonyl, methanesulfinyl, ethylsulfonyl or second sulfinyl.
3. boscalid amine homologue according to claim 1 and 2, is characterized in that, in formula:
Q is selected from N or CH; R 1be selected from the tertiary butyl, tert-pentyl, R 2be selected from hydrogen atom, monosubstituted or polysubstituted halogen, nitro, cyano group, alkylthio or alkylsulfonyl;
Halogen is selected from: fluorine, chlorine, bromine or iodine; Polysubstituted halogen is selected from: 2,4-dichloro, 3,4=difluoros or 3,4,5-trifluoro;
Alkylthio is selected from: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl or tert-pentyl;
Alkylsulfonyl is selected from: methylsulfonyl, methanesulfinyl, ethylsulfonyl or second sulfinyl.
4. boscalid amine homologue according to claim 3, is characterized in that,
Described boscalid amine homologue refers to the particular compound cited by table 1,
Table 1
Numbering Q R 1 R 2 Mp(℃) Numbering Q R 1 R 2 Mp(℃) 1 CH H Cl 138-140 41 N H Cl 140-142 2 CH H 2,4-2Cl 150-152 42 N H 2,4-2Cl 158-160 3 CH H 3,4,5-3F 134-136 43 N H 3,4,5-3F 144-146 4 CH H MeS 130-132 44 N H MeS 142-144 5 CH H NO 2 137-139 45 N H NO 2 138-140 6 CH H CN 136-138 46 N H CN 141-143 7 CH H MeSO 2 142-144 47 N H MeSO 2 146-148 8 CH H MeSO 138-140 48 N H MeSO 144-146 9 CH H EtSO 2 151-153 49 N H EtSO 2 162-164 10 CH H EtSO 142-144 50 N H EtSO 152-154 11 CH Me 3C Cl 167-168 51 N Me 3C Cl 139-141 12 CH Me 3C 2,4-2Cl 169-171 52 N Me 3C 2,4-2Cl 179-181 13 CH Me 3C 3,4,5-3F 162-164 53 N Me 3C 3,4,5-3F 168-170 14 CH Me 3C MeS 160-162 54 N Me 3C MeS 169-171 15 CH Me 3C NO 2 170-172 55 N Me 3C NO 2 180-182 16 CH Me 3C CN 167-169 56 N Me 3C CN 175-177 17 CH Me 3C MeSO 2 168-170 57 N Me 3C MeSO 2 172-174 18 CH Me 3C MeSO 159-161 58 N Me 3C MeSO 167-169 19 CH Me 3C EtSO 2 174-176 59 N Me 3C EtSO 2 176-178 20 CH Me 3C EtSO 170-172 60 N Me 3C EtSO 178-180 21 CH EtMe 2C Cl 166-168 61 N EtMe 2C Cl 174-176 22 CH EtMe 2C 2,4-2Cl 172-174 62 N EtMe 2C 2,4-2Cl 180-182 23 CH EtMe 2C 3,4,5-3F 165-167 63 N EtMe 2C 3,4,5-3F 172-174 24 CH EtMe 2C MeS 157-159 64 N EtMe 2C MeS 167-169 25 CH EtMe 2C NO 2 173-175 65 N EtMe 2C NO 2 181-183 26 CH EtMe 2C CN 170-172 66 N EtMe 2C CN 177-179 27 CH EtMe 2C MeSO 2 173-175 67 N EtMe 2C MeSO 2 183-185 28 CH EtMe 2C MeSO 169-171 68 N EtMe 2C MeSO 176-178 29 CH EtMe 2C EtSO 2 177-179 69 N EtMe 2C EtSO 2 188-190 30 CH EtMe 2C EtSO 170-172 70 N EtMe 2C EtSO 174-176 31 CH H Br 142-144 71 N H Br 152-154 32 CH H F 132-134 72 N H F 140-142 33 CH H I 142-144 73 N H I 150-152 34 CH H H 122-124 74 N H H 132-134 35 CH Me 3C Br 177-179 75 N Me 3C Br 189-191 36 CH Me 3C F 165-167 76 N Me 3C F 176-178 37 CH Me 3C I 176-178 77 N Me 3C I 184-188 38 CH EtMe 2C Br 177-179 78 N EtMe 2C Br 189-191 39 CH EtMe 2C F 168-170 79 N EtMe 2C F 176-178 40 CH EtMe 2C I 180-182 80 N EtMe 2C I 188-190
5. boscalid amine homologue according to claim 4, is characterized in that,
Described boscalid amine homologue refers to: Q=N, R1=H, R2=SMe, CN, SO 2the compound of Me.
6. the non-coupled method synthetic method of boscalid amine homologue described in claim 1: it is characterized in that, step is as follows:
In formula:
Q is selected from N or CH;
R 1be selected from the tertiary alkyl that spatial volume is larger;
R 2be selected from hydrogen atom, monosubstituted or polysubstituted halogen, nitro, cyano group, alkylthio or alkylsulfonyl;
Concrete steps are:
(1) substituted biphenyl II and alkylating reagent RX is under protonic acid or Louis acid catalysis, in suitable solvent and carry out alkylated reaction at suitable temperature and obtain compound shown in general formula III; Described alkylating reagent RX is the trimethyl carbinol, tertiary amyl alcohol, methyl tertiary butyl ether, tert-butyl chloride, tert-bromo butane, the tertiary pentane of chloro or 2-bromoisopentane; Described protonic acid is the vitriol oil, phosphoric acid, tosic acid or trifluoromethanesulfonic acid, and described Lewis acid is aluminum chloride, boron trifluoride or zirconium tetrachloride;
React and carry out in suitable solvent, this suitable solvent is selected from methylene dichloride or chlorobenzene;
Suitable temperature of reaction is 40 ~ 120 DEG C, is generally 40 ~ 80 DEG C;
(2) compound shown in general formula III is nitrated with nitration mixture selective action under optimal temperature obtains nitration product IV; This suitable temperature of reaction is 0 ~ 80 DEG C, and solvent is selected from diacetyl oxide, acetic acid or ethyl acetate;
(3) compound shown in general formula I V in suitable solvent under certain hydrogen pressure catalytic hydrogenation or use reductive agent reduction obtain reduzate V; The catalyzer of described catalytic hydrogenation is Raney Ni or 5%Pd/C, and described hydrogen pressure is 1 ~ 20 normal atmosphere; Described suitable reaction solvent is selected from methyl alcohol or ethanol; Described reductive agent is SnCl 2, hydrazine hydrate or Fe/HCl; Described suitable temperature of reaction is 20 ~ 80 DEG C;
(4) in suitable solvent, compound shown in general formula V generates acid amides I (R ≠ H) with acyl chlorides VI condensation under acid binding agent exists, and described acid binding agent is salt of wormwood, sodium carbonate, cesium carbonate, potassium hydroxide, triethylamine, pyridine or Dimethylamino pyridine; Described suitable solvent is selected from methylene dichloride, toluene, dimethylbenzene or purified petroleum benzin; Described suitable temperature of reaction is 25 ~ 130 DEG C, is generally 80 ~ 100 DEG C;
(5) compound shown in general formula I (R ≠ H) obtains dealkylation compound I (R=H) with alkyl receptor acting under Lewis acid effect, and described alkyl acceptor is benzene, and described Lewis acid is selected from aluminum chloride, zirconium tetrachloride.
7. the non-coupled method synthetic method of boscalid amine homologue according to claim 6: it is characterized in that,
Temperature of reaction suitable described in step (1) is 40 ~ 80 DEG C;
Temperature of reaction suitable described in step (2) is 20 ~ 40 DEG C;
Temperature of reaction suitable described in step (4) is 80 ~ 100 DEG C.
8. the application of boscalid amine homologue described in claim 1 in preparation control germ medicine.
9. the application of boscalid amine homologue according to claim 8 in preparation control germ medicine, it is characterized in that, described control germ medicine refers to the following illness of control: Powdery Mildew, anthrax, damping-off, blight, gray mold, sclerotium disease, various canker, brown heart and root rot.
10. the boscalid amine homologue according to claim 8 or claim 9 application in preparation control germ medicine, it is characterized in that, described control dosage is: the boscalid amine homologue compound of per hectare 20-500 gram; Or,
Sterilant adopt containing as active ingredient compound of Formula I and agriculturally acceptable carrier formation composition, in said composition, the weight percent of activeconstituents is 1%-99%.
CN201410546424.8A 2014-10-15 2014-10-15 Boscalid homologs and uncoupling synthesis method thereof as well as application of boscalid homologs in preparing medicines for preventing and treating pathogenic bacteria Pending CN104292156A (en)

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