CN105418448B - A kind of biamide structure compound and preparation method and application - Google Patents

A kind of biamide structure compound and preparation method and application Download PDF

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Publication number
CN105418448B
CN105418448B CN201510920623.5A CN201510920623A CN105418448B CN 105418448 B CN105418448 B CN 105418448B CN 201510920623 A CN201510920623 A CN 201510920623A CN 105418448 B CN105418448 B CN 105418448B
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intermediate product
cau
structure compound
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CN105418448A (en
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张建军
孙国绍
董燕红
金淑惠
王道全
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China Agricultural University
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China Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
    • C07C233/46—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/47—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12—Powders or granules
    • A01N25/14—Powders or granules wettable
    • 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
    • A01N37/34—Nitriles
    • 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
    • A01N37/44—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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/46—N-acyl derivatives
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
    • C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
    • 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

Abstract

The invention discloses a kind of biamide structure compound for belonging to agriculture chemistry technical field and preparation method and application.Using malonic acid monomethyl ester acyl chlorides as raw material, reacted in anhydrous methylene chloride with arylamine, obtain intermediate product III；Intermediate product III first reacts, then react to obtain intermediate product IV with oxalyl chloride in tetrahydrofuran with lithium hydroxide；Again with 2,6 dimethylanilines for raw material, react to obtain intermediate product VI with 2 methyl bromide cs；Last intermediate product IV and intermediate product VI reacts the amide structure compound obtained shown in final product I in toluene solution.The compounds of this invention and its preparation have good bactericidal activity, good suppression growth is respectively provided with to P. capsici, tomato early blight bacterium, Rhizoctonia solani Kuhn, cotton rhizoctonia solani, Phytophthora infestans germ, botrytis cinerea, there is very high pesticide research to be worth.

Description

A kind of biamide structure compound and preparation method and application
Technical field
The invention belongs to agriculture chemistry technical field, more particularly to a kind of biamide structure compound and preparation method thereof with Using.
Background technology
Amides compound is wide concerned chemical constitution in the research fields such as medicine, agricultural chemicals and veterinary drug, is often had Unique desinsection, mite killing, sterilization, weeding and coordinate plant growth isoreactivity.Amides compound there are about 50 as bactericide Year history, occupies significant proportion in bactericide, and the kind for having novel structure always is reported, flourishing long time.
Present amide-type Fungicidal compounds account for a quarter of existing bactericidal activity agricultural chemical compound sum, such as contain N- The M 9834, furalaxyl, the zarilamid containing aroyl acetyl amine and cyano group etc. of (2,6- xylyl) methyl lactamine structure are all It is the representative in acid amide fungicides；In addition, the propanil containing propionamido- is the contact killing type herbicide of high selectivity； New acid amides insecticides such as fipronil bisamide, Rynaxypyr etc. using ryanodine receptor as target have good desinsection Activity.
Because the development of pesticide resistance is, it is necessary to further research and develop the novel pesticide with independent intellectual property right to ensure China Grain security.
The content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of amide structure compound and its system Preparation Method and application.
To achieve these goals, the technical scheme that the present invention takes is as follows：
A kind of amide structure compound, the general structure of the compound are as follows：
Wherein, R is rubigan, adjacent cyano-phenyl, m-trifluoromethylphenyl, phenyl, 4- methyl -3- chlorphenyls, 2- first Base -3- fluoro-phenyls, the bromo- phenyl of 3- trifluoromethyls -4-, the chloro- phenyl of 2- trifluoromethyls -4-, the trifluoromethyl-phenyls of 2,5- bis-, neighbour Methoxyphenyl, p-methylphenyl, m-methoxyphenyl, to ethoxyl phenenyl or the chloro- biphenyl -2- bases of 4'-.
A kind of preparation method of amide structure compound, it is characterised in that the synthetic route of the preparation method is：
Comprise the steps：
1) using malonic acid monomethyl ester acyl chlorides as raw material, react, obtain shown in formula III with arylamine in anhydrous methylene chloride Compound；
2) compound shown in formula III is in tetrahydrofuran, is first reacted with lithium hydroxide, then reacts with oxalyl chloride to obtain formula IV Shown compound；
3) again with 2,6- dimethylanilines for raw material, react to obtain compound shown in Formula IV with 2 bromopropionic acid methyl esters；
4) compound shown in compound shown in Formula IV and formula IV is reacted to the acid amides knot obtained shown in Formulas I in toluene solution Structure compound.
A kind of application of amide structure compound in terms of bactericide is prepared.
Described bactericide is used to kill P. capsici, tomato early blight bacterium, Rhizoctonia solani Kuhn, cotton seedling blight One or more in bacterium, Sclerotinia sclerotiorum, Phytophthora infestans germ, botrytis cinerea and cotton-wilt fusarium.
A kind of bactericide, the active component of the bactericide is the amide structure compound described in claim 1.
One kind sterilization agent emulsifiable solution, the mass percent of the sterilization agent emulsifiable solution each component are：1-10% amide structure The solvent of compound, 5-15% emulsifying agent, 0.1-1% bleeding agents and surplus.
Described a kind of sterilization agent emulsifiable solution, it is characterised in that described emulsifying agent is agriculture breast 0208, GFC, 0203B, OP- 10 or Tween-60；Described solvent is toluene or dimethylbenzene.
A kind of bactericide wettable powder, the mass percent of described bactericide wettable powder each component are：15- 50% amide structure compound, 10-20% surfactants and 30-75% White Carbon blacks.
Described a kind of bactericide wettable powder, it is characterised in that described surfactant is NNO.
A kind of microbicide compositions, the active component of the microbicide compositions is by two kinds of material compositions of a and b；
Wherein, a is the amide structure compound described in claim 1；B is one in Bravo, iprodione and carbendazim Kind or more than one.
The mass ratio of two kinds of materials of a and b is (1-90)：(10-99).
The formulation of described microbicide compositions is missible oil or wettable powder.
Beneficial effects of the present invention：Raw material needed for amide structure compound (CAU-BA) prepared by the present invention is cheap, instead Answer route simple, product has good bactericidal activity.Bactericidal activity measurement result shows, CAU-BA to P. capsici, Tomato early blight bacterium, Rhizoctonia solani Kuhn, cotton rhizoctonia solani, Phytophthora infestans germ, botrytis cinerea are respectively provided with good Suppress growth, there is very high pesticide research to be worth.
Brief description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of CAU-BA-3 in amide structure compound (CAU-BA).
Fig. 2 is the carbon-13 nmr spectra figure of CAU-BA-3 in amide structure compound (CAU-BA).
Fig. 3 is the high resolution mass spectrum figure of CAU-BA-3 in amide structure compound (CAU-BA).
Embodiment
Below by specific embodiment, the present invention is further described.It should be noted that description given here and implementation Example makes technical staff be easier to understand the present invention, does not limit this hair just for the sake of the embodiment of the description present invention Bright protection domain.
Experimental method described in following embodiments, it is conventional method unless otherwise specified；The reagent and material, such as Without specified otherwise, commercially obtain.
Embodiment 1：CAU-BA-3 (R=phenyl) preparation and Structural Identification in amide structure compound (CAU-BA).
(1) 1.86g (20mmol) aniline, 30ml anhydrous methylene chlorides dissolving, in ice are added in 250ml round-bottomed flask Under bath and nitrogen protective condition, 5.06g (50mmol) triethylamine is added dropwise, 3.28g (24mmol) malonic acid is slowly added dropwise after 5min Mono-methyl acyl chlorides, continue to react 3h after dripping off, add water quenching to go out, extracted with dichloromethane, 1N hydrochloric acid 30ml × 2, saturated sodium-chloride Organic phase is washed in solution 30ml × 2, boils off anhydrous methylene chloride after anhydrous sodium sulfate drying, column chromatography purifies to obtain malonyl benzene Amine methyl esters white solid 3.63g, yield 94%.
(2) products therefrom 1.93g (10mmol) couplers methyl esters in step (1) is taken, is dissolved with 20ml tetrahydrofurans Afterwards, 20ml mono- hydronium(ion) lithia (0.84g, 20mmol) aqueous solution is added, after reacting 2h, adds watery hydrochloric acid to be adjusted to acidity, acetic acid Ethyl ester and water extraction, organic phase are concentrated after drying, and white solid 1.63g, yield are recrystallized to obtain with ethyl acetate and petroleum ether 91%.
(3) 1.21g (10mmol) 2,6- dimethylanilines, 1.00g (12mmol) carbonic acid are added in 250ml round-bottomed flasks Hydrogen sodium, 5.01g (30mmol) 2 bromopropionic acid methyl esters, overnight, TLC detection reactions are complete, filtering, concentrate rear pillar layer for 122 DEG C of reactions Analysis Analyze ＆ separate obtains brown liquid 1.96g, yield 95%.
(4) in 250ml round-bottomed flasks, 1.79g steps (2) products therefrom, 20ml dry methylene chlorides, 3 drops are added DMF, under ice bath and nitrogen protective condition, 1.27g (10mmol) oxalyl chloride is added dropwise, after being added dropwise, room temperature reaction is overnight； Under ice bath and nitrogen protective condition, 1.26g (15mmol) sodium acid carbonate is added, is added dropwise obtained by 2.07g (10mmol) step (3) and produces Thing, after 2h, TLC detection reactions are complete, and dichloromethane and water extraction, organic phase are dried, after concentration column chromatography obtain CAU-BA-3 without Color solid 3.39g, yield 92%.
(5) Structural Identification：The structure of the CAU-BA-3 solids of acquisition identify, CAU-BA-3 nuclear magnetic resonance Hydrogen spectrogram is as shown in Figure 1；CAU-BA-3 carbon-13 nmr spectra figure is as shown in Figure 2；CAU-BA-3 high resolution mass spectrum figure such as Fig. 3 It is shown.As can be seen from Figure 3, the Mass Spectrometric Identification result of CAU-BA-3 mass-to-charge ratioes (m/z) is 369.1812, and its calculated value is 369.1809, difference is only -0.66, illustrates that the structure of the CAU-BA-3 compounds of acquisition is accurate.
Structural identification data is：
1H NMR(CDCl3,300MHz)δ:9.87 (s, 1H, NH), 7.54 (d, J=7.6Hz, 2H, ArH), 7.25-7.32 (m, 2H, ArH), 7.05~7.22 (m, 4H, ArH), 4.51 (q, J=7.4Hz, 1H, CHCO), 3.82 (s, 3H, COOCH3), 3.06 (dd, J=17.7,28.8Hz, 2H, COCH2), CO 2.14,2.43 (2s, 6H, 2 × ArMe), 1.05 (d, J=7.4Hz, 3H,CHCH3)；
13C NMR(75MHz,CD3DH)δ:
172.52,170.07,168.64,138.16,137.76,136.91,136.24,129.65,129.36, 129.01,128.84,124.25,120.20,55.85,52.40,40.55,18.52,18.24,15.01；HRMS(ESI) calcd for C21H25N2O4(M+H)+369.1809,found 369.1812.
Other formulas are that CAU-BA series compound is prepared according to the method described above.Their compound number, R Corresponding substituted radical, physicochemical data are shown in Table 1, and the proton nmr spectra of Structural Identification, mass spectrometric data are shown in Table 2.
Table 1:Formula is the numbering of CAU-BA series compound, substituted radical, physicochemical data
Note：Me:Methyl
Table 2:Formula is CAU-BA series compounds proton nmr spectra, mass spectrometric data
Note：Pos：The positive ion mode of mass spectroscopy；Neg：The negative ion mode of mass spectroscopy
Embodiment 2：The preparation of CAU-BA-3 (R=phenyl) preparation in amide structure compound (CAU-BA).
(1) missible oil：1-10g, compound CAU-BA-3,5-15g emulsifying agent are added in 100mL volumetric flasks, 0.1-1g oozes Saturating agent, then obtain the missible oil that CAU-BA-3 mass fractions are 1-10% with solvent (such as toluene, dimethylbenzene etc.) constant volume.
Other formulas are that the missible oil of CAU-BA series compound can be prepared according to the method described above.
(2) wettable powder：Take 15-50g compounds CAU-BA-3,10-20g surfactant, 30-75g White Carbon blacks, warp The wettable powder that CAU-BA-3 mass fractions are 15-50% is obtained after co-grinding.
Other formulas are that the wettable powder of CAU-BA series compound can be prepared according to the method described above.
Embodiment 3：Formula is the bactericidal activity measure of CAU-BA series compound.
Assay method：Using Activities, i.e., the decoction of various concentrations is mixed with the culture medium melted, be made Band poison culture base plane, is inoculated with pathogen, the size of medicament virulence is judged with the speed of pathogen growth speed in the plane.It is logical Formula is that the bactericidal activity of CAU-BA compound is shown in Table 3 and table 4.
Table 3:To the growth inhibition ratio (%) of eight kinds of phytopathogens under CAU-BA series compound 50mg/L concentration
Note：Comparison medicament M 9834 and sample are 50mg/L
Table 4:To the growth inhibition ratio (%) of eight kinds of phytopathogens under CAU-BA series compound 50mg/L concentration
Note：Comparison medicament M 9834 and sample are 50mg/L
From table 3 and table 4 as can be seen that compound CAU-BA-4 and CAU-BA-11 to Phytophthora capsici disease, rice sheath blight disease, Cotton seedling blight has good bactericidal activity, and is above comparison medicament M 9834, and CAU-BA-4 (50mg/L) is to tomato The growth inhibition ratio of early blight shows that compound involved by the application has good bactericidal activity up to 84.3%.
Source for trying target：
(1) cotton rhizoctonia solani, cause of disease [Rhizoctonia solani Kuhn] (high super Shandong agricultural sciences forever .2006,6,44.)
(2) Sclerotinia sclerotiorum, cause of disease [Sclerotinia sclerotiorum (Lib.) de Bary] (Li, J.J.J.Agric.Food.Chem.2010,58,2659.)
(3) botrytis cinerea, cause of disease [Botrytis cinerea Pers] (Li, J.J.J.Agric.Food.Chem.2010,58,2659.)
(4) cotton-wilt fusarium, cause of disease [Fsarium oxysporum f.sp.vasinfectum (Atk.) Synderand Hanen](Li,X.H.J.Agric.Food.Chem.2005,53,2202.)
(5) P. capsici, cause of disease [Phytophthora capsici leon] (blue extra large Hubei plant protection .2008,1, 16.)
(6) tomato early blight bacterium, cause of disease [Alternaria solani] (dawn Pesticide Science journals .2008,10,41.)
(7) Phytophthora infestans germ, cause of disease [Phtophthora infestans (Mont.) De Bary] (red plants of Yang Yu Protect journal .2003,30,57.)
(8) Rhizoctonia solani Kuhn, cause of disease [Rhizoctonia solani K ü hn] (Tang Zhenghe plant protection .2012, 38,158.)
Above-mentioned 8 kinds of germs can obtain from China Agricultural University.

Claims (1)

  1. A kind of 1. preparation method of amide structure compound, it is characterised in that the system of the amide structure compound CAU-BA-3 Standby process is as follows：
    (1) add 1.86g (20mmol) aniline in 250ml round-bottomed flask, the dissolving of 30ml anhydrous methylene chlorides, in ice bath and Under nitrogen protective condition, 5.06g (50mmol) triethylamine is added dropwise, 3.28g (24mmol) malonic acid list first is slowly added dropwise after 5min Ester acyl chlorides, continue to react 3h after dripping off, add water quenching to go out, extracted with dichloromethane, 1N hydrochloric acid 30ml × 2, saturated nacl aqueous solution Organic phase is washed in 30ml × 2, boils off anhydrous methylene chloride after anhydrous sodium sulfate drying, column chromatography purifies to obtain couplers first Ester white solid 3.63g, yield 94%；
    (2) products therefrom 1.93g (10mmol) couplers methyl esters in step (1) is taken, after being dissolved with 20ml tetrahydrofurans, is added Enter 20ml mono- hydronium(ion) lithia (0.84g, 20mmol) aqueous solution, after reacting 2h, add watery hydrochloric acid to be adjusted to acidity, ethyl acetate and Water is extracted, and organic phase is concentrated after drying, and white solid 1.63g, yield 91% are recrystallized to obtain with ethyl acetate and petroleum ether；
    (3) 1.21g (10mmol) 2,6- dimethylanilines, 1.00g (12mmol) bicarbonate are added in 250ml round-bottomed flasks Sodium, 5.01g (30mmol) 2 bromopropionic acid methyl esters, overnight, TLC detection reactions are complete, filtering, column chromatography after concentration for 122 DEG C of reactions Analyze ＆ separate obtains brown liquid 1.96g, yield 95%；
    (4) in 250ml round-bottomed flasks, 1.79g steps (2) products therefrom is added, 20ml dry methylene chlorides, 3 drip DMF, Under ice bath and nitrogen protective condition, 1.27g (10mmol) oxalyl chloride is added dropwise, after being added dropwise, room temperature reaction is overnight；In ice bath and Under nitrogen protective condition, 1.26g (15mmol) sodium acid carbonate is added, 2.07g (10mmol) step (3) products therefrom, 2h is added dropwise Afterwards, TLC detections reaction is complete, and dichloromethane and water extraction, organic phase are dried, and column chromatography obtains CAU-BA-3 colorless solids after concentration 3.39g, yield 92%.
CN201510920623.5A 2015-12-11 2015-12-11 A kind of biamide structure compound and preparation method and application Expired - Fee Related CN105418448B (en)

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