CN105503642B - N replaces 2 (2 hydroxybenzyl) glycyl amine compounds and its preparation and use - Google Patents

N replaces 2 (2 hydroxybenzyl) glycyl amine compounds and its preparation and use Download PDF

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CN105503642B
CN105503642B CN201510947214.4A CN201510947214A CN105503642B CN 105503642 B CN105503642 B CN 105503642B CN 201510947214 A CN201510947214 A CN 201510947214A CN 105503642 B CN105503642 B CN 105503642B
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hydroxybenzyls
phenyl
acetamide
benzyls
alkylidenes
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CN105503642A (en
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唐子龙
李新兴
齐永存
谭经照
张少伟
彭丽芬
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Hunan University of Science and Technology
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    • 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
    • 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
    • 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
    • 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
    • A01N37/24—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 containing at least one oxygen or sulfur atom being directly attached to the same aromatic ring system

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Abstract

The N aryl of logical formula (I) replaces 2 (2 hydroxybenzyl) glycyl amine compounds and preparation method thereof：Wherein R1It is phenyl, C1 C3 alkyl phenyls, C1 C3 alkoxyl phenyls, phenyl C1 C3 alkylidenes, C1 C3 alkyl phenyl C1 C3 alkylidenes, or C1 C3 alkoxyl phenyl C1 C3 alkylidenes.The compound has good bactericidal activity to corps diseases, is suitable as agricultural chemicals.

Description

N- substitutions -2- (2- hydroxybenzyls) glycyl amine compounds and its prepare and Purposes
Technical field
Lived the present invention relates to the synthesis of new N- substitutions -2- (2- hydroxybenzyls) glycyl amine compound and its sterilization Property, belong to pesticide field
Background technology
Amides compound is the very important active material of a class, shows to be widely applied in terms of agricultural bactericidal. Early in 1969, since favourable incoming road company of the U.S. develops acid amide fungicides carboxin, occupy in global agrochemical market Considerable status.In recent years, the research to acid amide fungicides is increasingly subject to extensive concern., the report such as Elebe in 2002 Substituted pyrazolecarboxylic amides compound is 94% to the preventive effect of apple powder mould, to the preventive effect of barley caryosphere bacterium up to 100%；2003 Hu Liming etc. reports pyridine -4- Carbox amides, and the suppression for showing it to Rhizoctonia solani Kuhn is tested through bactericidal activity Rate is up to 93%；Xu in 2009 et al. report a class thiazole -4-carboxamide class compound have to staphylococcus aureus it is preferable Inhibitory activity；The Double diamantane hydrocarbons base Carbox amide of Zhong in 2014 et al. report synthesis is to bacillus subtilis Minimum inhibitory concentration is 0.3 μ g/mL；Xiao in 2015 etc. has synthesized a series of similar thing of pyrazolecarboxamides, to tobacco mosaic disease Show powerful bioactivity.But have no that document report crosses N- substitutions -2- (2- hydroxybenzyls) glycyl amine chemical combination Thing.Therefore, the present invention has synthesized this kind of new N- substitutions -2- (2- hydroxybenzyls) glycyl amine compound, and have studied Its bactericidal activity.It is an object of the invention to provide new N- substitutions -2- (2- hydroxybenzyls) the amino second with bactericidal activity Amides compound.
The content of the invention
It is an object of the invention to provide N- substitutions -2- (2- hydroxybenzyls) glycyl amine with below general formula (I) Compound, or N- aryl substitutions -2- (2- hydroxybenzyls) glycyl amine compound：
Wherein R1It is phenyl, C1-C3 alkyl phenyls, C1-C3 alkoxyl phenyls, phenyl C1-C3 alkylidenes, C1-C3 alkyl Phenyl C1-C3 alkylidenes, or C1-C3 alkoxyl phenyl C1-C3 alkylidenes.
Preferably, R1It is phenyl, C1-C2 alkyl phenyls, C1-C2 alkoxyl phenyls, phenyl C1-C2 alkylidenes, C1-C2 Alkyl phenyl C1-C2 alkylidenes, or C1-C2 alkoxyl phenyl C1-C2 alkylidenes.
Preferably, R1It is：
C6H5, C6H5CH2, o-CH3C6H4CH2, m-CH3C6H4CH2, p-CH3C6H4CH2, o-CH3OC6H4CH2, m- CH3OC6H4CH2,p-CH3OC6H4CH2, o-CH3C6H4, m-CH3C6H4, p-CH3C6H4, o-CH3OC6H4, m-CH3OC6H4, or p- CH3OC6H4。
It is further preferred that the compound is selected from：
1) N- benzyls -2- (2- hydroxybenzylaminos) acetamide：
2) N- (2- methyl-benzyls) -2- (2- hydroxybenzyls) amino acetamide：
3) N- (4- methyl-benzyls) -2- (2- hydroxybenzyls) amino acetamide：
4) N- (2- methoxy-benzyls) -2- (2- hydroxybenzyls) amino acetamide：
5) N- (3- methoxy-benzyls) -2- (2- hydroxybenzyls) amino acetamide：
6) N- (4- methoxy-benzyls) -2- (2- hydroxybenzyls) amino acetamide：
7) N- phenyl -2- (2- hydroxybenzyls) amino acetamide：
8) N- (2- aminomethyl phenyls) -2- (2- hydroxybenzyls) amino acetamide：
9) N- (4- aminomethyl phenyls) -2- (2- hydroxybenzyls) amino acetamide：
10) N- (2- methoxyphenyls) -2- (2- hydroxybenzyls) amino acetamide：
11) N- (4- methoxyphenyls) -2- (2- hydroxybenzyls) amino acetamide：
The present invention also provides the method for preparing above-mentioned logical formula (I) compound, and this method includes：By the 2- (ammonia for leading to formula (II) Methyl) oxybenzene compound and the N- substitution -2- Haloacetamide compounds of logical formula (III) are reacted：
Wherein R1As defined above, X is chlorine, bromine or iodine.
Preferably, methods described includes：By leading to 2- (aminomethyl) oxybenzene compounds of formula (II) and the N- of logical formula (III) Substitution -2- Haloacetamide compounds with the addition of organic solvent (such as DMF of alkali carbonate (such as potassium carbonate or sodium carbonate) With THF according to 1:0.2-5, more preferably 1:The mixed solvent of 0.5-2 volume ratio) in reacted, separate, obtain lead to formula (I) Compound.
It is further preferred that methods described includes：By 2- (aminomethyl) oxybenzene compounds and logical formula (III) that lead to formula (II) N- substitution -2- Haloacetamide compounds with the addition of the organic solvent of alkali carbonate (such as potassium carbonate or sodium carbonate) (such as DMF and THF is according to 1:0.2-5, more preferably 1:The mixed solvent of 0.5-2 volume ratio) in reacted, depressurize slough solvent, Add water, then extract (being for example extracted with ethyl acetate (50mL × 3 time)), merge organic layer, gained organic layer successively with water, Saturated common salt water washing, by organic layer dries (such as with anhydrous sodium sulfate drying), suction filtration, be concentrated under reduced pressure to obtain crude product, then The compound of the logical formula (I) of white solid forms is obtained through column chromatography for separation.
The present invention also provides above-claimed cpd purposes as Fungicidal compounds in agriculture field or pesticide field.Want The bacterium of killing is gibberellic hypha, phytophthora germ, hyphal cluster germ, ash arrhizus bacteria, sheath blight fungus or Pyricularia oryzae.
The synthetic method of new N- substitutions -2- (2- hydroxybenzyls) glycyl amine compound of the present invention is such as Under：
In the 150mL round-bottomed flasks with reflux condensing tube and drier, N- substitution -2- acetbromamides, 2- (ammonia are added Methyl) phenol, Anhydrous potassium carbonate and 50mL DMF and THF mixed solvents (V:V=1:1) reactant, is heated to 65 DEG C and stirred Mix reaction 3h-5h.After having reacted, solvent is sloughed in decompression, adds 40mL water, (50mL × 3 time) are extracted with ethyl acetate, are associated with Machine layer, is washed with water (40mL × 2 time), saturated aqueous common salt (40mL × 2 time) successively, and anhydrous sodium sulfate drying, suction filtration, decompression are dense Contracted to obtain crude product, and white solid is obtained through column chromatography for separation.
Embodiment
The embodiment of form, does further specifically to the above of the invention by the following examples Bright, the present invention includes but is not limited to this preparation method.
Embodiment 1:The synthesis of N- benzyls -2- (2- hydroxybenzyls) amino acetamide.
In the 150mL round-bottomed flasks with reflux condensing tube and drier, N- benzyl -2- acetbromamides 4.560g is added (20mmol), 2- (aminomethyl) phenol 2.953g (24mmol), Anhydrous potassium carbonate 3.312g (24mmol), 50mL DMF and THF Mixed solvent (V:V=1:1) 65 DEG C of stirring reaction 3h, TLC plate tracing detections, are heated to.After having reacted, solvent is sloughed in decompression, 40mL water is added, is extracted with ethyl acetate (50mL × 3 time), merges organic layer, successively with water (40mL × 2 time), saturated common salt Water (40mL × 2 time) is washed, and anhydrous sodium sulfate drying, suction filtration, be concentrated under reduced pressure to obtain crude product, and it is solid to obtain white through column chromatography for separation Body；M.p.107.6-108.4 DEG C, yield 68.7%.
1H NMR(500MHz,CDCl3)δ:7.33-7.30 (m, 2H), 7.25-7.22 (m, 2H), 7.14 (t, J=7.5Hz, 1H), 6.93 (d, J=7.5Hz, 1H), 6.80-6.75 (m, 2H), 4.40 (d, J=5.5Hz, 2H), 3.90 (s, 2H), 3.22 (s,2H).
13C NMR(125MHz,CDCl3)δ:170.24,157.51,137.80,129.00(2C),128.78(2C), 127.78(2C),127.69,122.30,119.43,116.30,51.84,50.53,43.54.
IR(KBr,ν/cm-1):3322,3254,3081,2852,1633,1600,1456,1395,1259,1225,921, 747,697.
Embodiment 2：The synthesis of N- (2- methyl-benzyls) -2- (2- hydroxybenzyls) amino acetamide.
In the 150mL round-bottomed flasks with reflux condensing tube and drier, N- (2- methyl-benzyls) -2- acetyl bromides are added Amine 4.840g (20mmol), 2- (aminomethyl) phenol 2.953g (24mmol), Anhydrous potassium carbonate 3.312g (24mmol), 50mL DMF and THF mixed solvents (V:V=1:1) 65 DEG C of stirring reaction 3h, TLC plate tracing detections, are heated to.After having reacted, decompression is de- Remove solvent, add 40mL water, be extracted with ethyl acetate (50mL × 3 time), merge organic layer, successively with water (40mL × 2 time), full With saline solution (40mL × 2 time) washing, anhydrous sodium sulfate drying, suction filtration, be concentrated under reduced pressure to obtain crude product, is obtained through column chromatography for separation White solid；M.p.142.2-143.8 DEG C, yield 64.4%.
1H NMR(500MHz,CDCl3)δ:7.11 (t, J=7.2Hz, 4H), 6.91 (d, J=7.3Hz, 1H), 6.85 (t, J =4.8Hz, 1H), 6.73 (dd, J=16.2,8.0Hz, 2H), 6.00 (s, 1H), 4.32 (d, J=5.4Hz, 2H), 3.80 (s, 2H),3.16(s,2H),2.23(s,3H).
13C NMR(125MHz,CDCl3)δ:170.47,157.31,136.31,135.51,130.55,129.18, 129.10,129.01,128.84,128.31,127.84,126.23,122.61,119.45,116.21,51.49,50.36, 41.55,19.01.
IR(KBr,ν/cm-1):3331,3269,3097,2922,2862,1642,1580,1527,1488,1460, 1356,1238,1014,750,619.
Embodiment 3：The synthesis of N- (4- methyl-benzyls) -2- (2- hydroxybenzyls) amino acetamide.
In the 150mL round-bottomed flasks with reflux condensing tube and drier, N- (4- methyl-benzyls) -2- acetyl bromides are added Amine 4.840g (20mmol), 2- (aminomethyl) phenol 2.953g (24mmol), Anhydrous potassium carbonate 3.312g (24mmol), 50mL DMF and THF mixed solvents (V:V=1:1) 65 DEG C of stirring reaction 3h, TLC plate tracing detections, are heated to.After having reacted, decompression is de- Remove solvent, add 40mL water, be extracted with ethyl acetate (50mL × 3 time), merge organic layer, successively with water (40mL × 2 time), full With saline solution (40mL × 2 time) washing, anhydrous sodium sulfate drying, suction filtration, be concentrated under reduced pressure to obtain crude product, is obtained through column chromatography for separation White solid；M.p.122.6-123.5 DEG C, yield 67.2%.
1H NMR(500MHz,CDCl3)δ:7.28 (s, 1H), 7.18 (d, J=9.1Hz, 4H), 6.98 (d, J=7.3Hz, 1H), 6.85 (d, J=8.1Hz, 1H), 6.80 (t, J=7.3Hz, 1H), 5.90 (d, J=37.5Hz, 1H), 4.45 (d, J= 5.5Hz,2H),4.00(s,2H),3.30(s,2H),2.36(s,3H).
13C NMR(125MHz,CDCl3)δ:169.79,157.70,137.56,134.61,129.51(2C),129.06, 128.90,127.87(2C),119.38,116.41,52.04,50.52,43.44,21.15.
IR(KBr,ν/cm-1):3416,3323,3256,3070,2922,1637,1557,1455,1397,1266, 1013,931,748,590.
Embodiment 4：The synthesis of N- (2- methoxy-benzyls) -2- (2- hydroxybenzyls) amino acetamide.
In the 150mL round-bottomed flasks with reflux condensing tube and drier, N- (2- methoxy-benzyls) -2- bromine second is added Acid amides 5.160g (20mmol), 2- (aminomethyl) phenol 2.953g (24mmol), Anhydrous potassium carbonate 3.312g (24mmol), 50mL DMF and THF mixed solvents (V:V=1:1) 65 DEG C of stirring reaction 3h, TLC plate tracing detections, are heated to.After having reacted, decompression is de- Remove solvent, add 40mL water, be extracted with ethyl acetate (50mL × 3 time), merge organic layer, successively with water (40mL × 2 time), full With saline solution (40mL × 2 time) washing, anhydrous sodium sulfate drying, suction filtration, be concentrated under reduced pressure to obtain crude product, is obtained through column chromatography for separation White solid；M.p.104.7-105.1 DEG C, yield 62.1%.
1H NMR(500MHz,CDCl3)δ:7.13 (d, J=5.3Hz, 2H), 7.09-6.98 (m, 2H), 6.90 (s, 1H), 6.78 (d, J=5.2Hz, 2H), 6.68 (d, J=5.6Hz, 1H), 4.30 (s, 2H), 3.85 (s, 3H), 3.72 (s, 2H), 3.21 (s,2H).
13C NMR(125MHz,CDCl3)δ:169.43,158.08,156.63,129.45,128.23(2C),128.13, 127.89,121.91,118.31,115.28,113.12(2C),54.40,50.81,49.76,41.90.
IR(KBr,ν/cm-1):3301,3261,3069,2920,2861,1654,1600,1556,1489,1458, 1391,1248,1014,750,699.
Embodiment 5：The synthesis of N- (3- methoxy-benzyls) -2- (2- hydroxybenzyls) amino acetamide.
In the 150mL round-bottomed flasks with reflux condensing tube and drier, N- (3- methoxy-benzyls) -2- bromine second is added Acid amides 5.160g (20mmol), 2- (aminomethyl) phenol 2.953g (24mmol), Anhydrous potassium carbonate 3.312g (24mmol), 50mL DMF and THF mixed solvents (V:V=1:1) 65 DEG C of stirring reaction 3h, TLC plate tracing detections, are heated to.After having reacted, decompression is de- Remove solvent, add 40mL water, be extracted with ethyl acetate (50mL × 3 time), merge organic layer, successively with water (40mL × 2 time), full With saline solution (40mL × 2 time) washing, anhydrous sodium sulfate drying, suction filtration, be concentrated under reduced pressure to obtain crude product, is obtained through column chromatography for separation White solid；M.p.86.7-88.4 DEG C, yield 54.4%.
1H NMR(500MHz,CDCl3)δ:7.22 (d, J=5.3Hz, 2H), 7.17-7.07 (m, 2H), 6.99 (s, 1H), 6.87 (d, J=5.2Hz, 2H), 6.77 (d, J=5.6Hz, 1H), 4.39 (s, 2H), 3.94 (s, 3H), 3.81 (s, 2H), 3.30 (s,2H).
13C NMR(125MHz,CDCl3)δ:169.30,157.95,156.51,129.33,128.11(2C),128.01, 127.76,121.79,118.19,115.15,113.00(2C),54.28,50.69,49.64,41.78.
IR(KBr,ν/cm-1):3288,3053,2960,2872,1642,1611,1588,1542,1488,1458, 1359,1286,1047,783,696.
Embodiment 6：The synthesis of N- (4- methoxy-benzyls) -2- (2- hydroxybenzyls) amino acetamide.
In the 150mL round-bottomed flasks with reflux condensing tube and drier, N- (4- methoxy-benzyls) -2- bromine second is added Acid amides 5.160g (20mmol), 2- (aminomethyl) phenol 2.953g (24mmol), Anhydrous potassium carbonate 3.312g (24mmol), 50mL DMF and THF mixed solvents (V:V=1:1) 65 DEG C of stirring reaction 3h, TLC plate tracing detections, are heated to.After having reacted, decompression is de- Remove solvent, add 40mL water, be extracted with ethyl acetate (50mL × 3 time), merge organic layer, successively with water (40mL × 2 time), full With saline solution (40mL × 2 time) washing, anhydrous sodium sulfate drying, suction filtration, be concentrated under reduced pressure to obtain crude product, is obtained through column chromatography for separation White solid；M.p.142.4-143.6 DEG C, yield 58.6%.
1H NMR(500MHz,CDCl3)δ:7.21 (d, J=5.3Hz, 2H), 7.16-7.06 (m, 2H), 6.98 (s, 1H), 6.86 (d, J=5.2Hz, 2H), 6.76 (d, J=5.6Hz, 1H), 4.38 (s, 2H), 3.93 (s, 3H), 3.80 (s, 2H), 3.29 (s,2H).
13C NMR(125MHz,CDCl3)δ:169.31,157.96,156.52,129.34,128.12(2C),128.02, 127.77,121.80,118.20,115.16,113.01(2C),54.29,50.70,49.65,41.79.
IR(KBr,ν/cm-1):3452,3288,3057,2966,2840,1642,1596,1549,1496,1458, 1320,1251,1030,758.
Embodiment 7：The synthesis of N- phenyl -2- (2- hydroxybenzylaminos) acetamide.
In the 150mL round-bottomed flasks with reflux condensing tube and drier, N- phenyl -2- acetbromamides 4.260g is added (20mmol), 2- (aminomethyl) phenol 2.953g (24mmol), Anhydrous potassium carbonate 3.312g (24mmol), 50mL DMF and THF Mixed solvent (V:V=1:1) 65 DEG C of stirring reaction 3h, TLC plate tracing detections, are heated to.After having reacted, solvent is sloughed in decompression, 40mL water is added, is extracted with ethyl acetate (50mL × 3 time), merges organic layer, successively with water (40mL × 2 time), saturated common salt Water (40mL × 2 time) is washed, and anhydrous sodium sulfate drying, suction filtration, be concentrated under reduced pressure to obtain crude product, and it is solid to obtain white through column chromatography for separation Body, m.p.124.7-127.6 DEG C, yield is 71.1%.
1H NMR(500MHz,CDCl3)δ:8.48 (s, 1H), 7.50 (d, J=7.8Hz, 2H), 7.27 (t, J=7.6Hz, 2H), 7.12 (dt, J=25.3,7.3Hz, 2H), 6.98 (d, J=7.1Hz, 1H), 6.90-6.70 (m, 2H), 5.26 (s, 1H), 3.89(s,2H),3.31(s,2H).
13C NMR(125MHz,CDCl3)δ:169.08,157.00,137.33,129.34,129.12(2C),129.08 (2C),124.70,122.72,120.11,119.74,116.21,53.51,51.58,51.22.
IR(KBr,ν/cm-1):3421,3283,3063,2974,2848,1675,1599,1544,1492,1460, 1371,1246,1012,757.
Embodiment 8：N- (2- aminomethyl phenyls) -2- (2- hydroxybenzylaminos) acetamide.
In the 150mL round-bottomed flasks with reflux condensing tube and drier, N- (2- aminomethyl phenyls) -2- acetyl bromides are added Amine 4.560g (20mmol), 2- (aminomethyl) phenol 2.953g (24mmol), Anhydrous potassium carbonate 3.312g (24mmol), 50mL DMF and THF mixed solvents (V:V=1:1) 65 DEG C of stirring reaction 3h, TLC plate tracing detections, are heated to.After having reacted, decompression is de- Remove solvent, add 40mL water, be extracted with ethyl acetate (50mL × 3 time), merge organic layer, successively with water (40mL × 2 time), full With saline solution (40mL × 2 time) washing, anhydrous sodium sulfate drying, suction filtration, be concentrated under reduced pressure to obtain crude product, is obtained through column chromatography for separation White solid, m.p.111-113.6 DEG C, yield 61.2%.
1H NMR(500MHz,DMSO)δ:9.80 (s, 1H), 7.47 (d, J=7.8Hz, 1H), 7.32 (d, J=7.2Hz, 1H), 7.22 (dd, J=16.2,7.6Hz, 3H), 7.11 (t, J=7.3Hz, 1H), 6.92 (d, J=8.0Hz, 1H), 6.84 (t, J=7.4Hz, 1H), 4.09 (s, 2H), 3.77 (s, 2H), 2.21 (s, 3H)
13C NMR(125MHz,CDCl3)δ:169.02,157.09,135.06,130.62,129.48,129.27, 192.12,126.80,125.60,123.13,122.63,119.67,116.27,51.6451.32,17.78.
IR(KBr,ν/cm-1):3415,3299,3068,2914,2845,1693,1643,1588,1538,1492, 1454,1378,1244,1051,755.
Embodiment 9：N- (4- aminomethyl phenyls) -2- (2- hydroxybenzylaminos) acetamide.
In the 150mL round-bottomed flasks with reflux condensing tube and drier, N- (4- aminomethyl phenyls) -2- acetyl bromides are added Amine 4.560g (20mmol), 2- (aminomethyl) phenol 2.953g (24mmol), Anhydrous potassium carbonate 3.312g (24mmol), 50mL DMF and THF mixed solvents (V:V=1:1) 65 DEG C of stirring reaction 3h, TLC plate tracing detections, are heated to.After having reacted, decompression is de- Remove solvent, add 40mL water, be extracted with ethyl acetate (50mL × 3 time), merge organic layer, successively with water (40mL × 2 time), full With saline solution (40mL × 2 time) washing, anhydrous sodium sulfate drying, suction filtration, be concentrated under reduced pressure to obtain crude product, is obtained through column chromatography for separation White solid, m.p.127.0-128.8 DEG C, yield 67.1%.
1H NMR(500MHz,CDCl3)δ:8.24 (s, 1H), 7.39 (s, 2H), 7.12 (d, J=30.8Hz, 3H), 6.99 (s,1H),6.91–6.67(m,2H),3.91(s,2H),3.32(s,2H),2.29(s,3H).
13C NMR(125MHz,CDCl3)δ:168.93,157.11,134.72,134.38,129.58(2C),129.30, 129.10,122.65,120.15(2C),119.69,116.23,51.63,51.14,20.93.
IR(KBr,ν/cm-1):3399,3297,3070,2923,2833,1686,1632,1543,1510,1496, 1442,1374,1243,1052,751.
Embodiment 10：N- (2- methoxyphenyls) -2- (2- hydroxybenzylaminos) acetamide.
In the 150mL round-bottomed flasks with reflux condensing tube and drier, N- (2- methoxyphenyls) -2- bromine second is added Acid amides 4.880g (20mmol), 2- (aminomethyl) phenol 2.953g (24mmol), Anhydrous potassium carbonate 3.312g (24mmol), 50mL DMF and THF mixed solvents (V:V=1:1) 65 DEG C of stirring reaction 3h, TLC plate tracing detections, are heated to.After having reacted, decompression is de- Remove solvent, add 40mL water, be extracted with ethyl acetate (50mL × 3 time), merge organic layer, successively with water (40mL × 2 time), full With saline solution (40mL × 2 time) washing, anhydrous sodium sulfate drying, suction filtration, be concentrated under reduced pressure to obtain crude product, is obtained through column chromatography for separation White solid, m.p.100.6-103.5 DEG C, yield 68.3%.
1H NMR(500MHz,CDCl3)δ:8.36 (d, J=7.7Hz, 1H), 8.17 (s, 1H), 7.19 (t, J=7.4Hz, 1H), 7.09-7.03 (m, 1H), 7.01 (d, J=7.2Hz, 1H), 6.96 (t, J=7.5Hz, 1H), 6.91-6.83 (m, 2H), (s, the 2H) of 6.80 (t, J=7.2Hz, 1H), 4.00 (s, 2H), 3.85 (s, 3H), 3.45
13C NMR(125MHz,CDCl3)δ:168.27,157.62,147.94,129.13,129.08,126.96, 124.21,122.30,121.09,119.82,119.44,116.42,110.03,55.68,51.97,51.54.
IR(KBr,ν/cm-1):3334,3255,3012,2964,2846,1662,1599,1536,1484,1457, 1357,1248,1021,740.
Embodiment 11：N- (4- methoxyphenyls) -2- (2- hydroxybenzylaminos) acetamide.
In the 150mL round-bottomed flasks with reflux condensing tube and drier, N- (4- methoxyphenyls) -2- bromine second is added Acid amides 4.880g (20mmol), 2- (aminomethyl) phenol 2.953g (24mmol), Anhydrous potassium carbonate 3.312g (24mmol), 50mL DMF and THF mixed solvents (V:V=1:1) 65 DEG C of stirring reaction 3h, TLC plate tracing detections, are heated to.After having reacted, decompression is de- Remove solvent, add 40mL water, be extracted with ethyl acetate (50mL × 3 time), merge organic layer, successively with water (40mL × 2 time), full With saline solution (40mL × 2 time) washing, anhydrous sodium sulfate drying, suction filtration, be concentrated under reduced pressure to obtain crude product, is obtained through column chromatography for separation White solid, m.p.114.3-116.7 DEG C, yield 69.5%.
1H NMR(500MHz,CDCl3)δ:7.41 (d, J=8.9Hz, 2H), 7.21-7.13 (m, 1H), 6.98 (dd, J= 25.7,7.2Hz, 1H), 6.89-6.74 (m, 4H), 3.94 (d, J=8.8Hz, 2H), 3.77 (s, 3H), 3.34 (d, J= 6.4Hz,2H).
13C NMR(125MHz,CDCl3)δ:168.63,157.17,156.61,130.38,129.27,129.11, 122.59,121.90,121.87,119.66,116.25,114.19(2C),55.50,51.72,51.11.
IR(KBr,ν/cm-1):3271,3203,3044,2937,2837,1655,1606,1542,1512,1462, 1387,1247,1015,748.
Above-mentioned new 2- (fragrant amino ethylamino) the phenmethylol class compound of the present invention is experimentally confirmed to crops Disease there is good bactericidal activity.
Using in vitro method, to N- benzyls -2- (2- hydroxybenzylaminos) acetamide, N- (2- methyl-benzyls) -2- (2- hydroxyls Benzylamino) acetamide, N- (4- methyl-benzyls) -2- (2- hydroxybenzylaminos) acetamide, N- (2- methoxy-benzyls) -2- (2- hydroxybenzylaminos) acetamide, N- (3- methoxy-benzyls) -2- (2- hydroxybenzylaminos) acetamide, N- (4- methoxyl groups Benzyl) -2- (2- hydroxybenzylaminos) acetamide, N- phenyl -2- (2- hydroxybenzylaminos) acetamide, N- (2- methylbenzenes Base) -2- (2- hydroxybenzylaminos) acetamide, N- (4- aminomethyl phenyls) -2- (2- hydroxybenzylaminos) acetamide, N- (2- first Phenyl) -2- (2- hydroxybenzylaminos) acetamide, N- (4- methoxyphenyls) -2- (2- hydroxybenzylaminos) acetamide Bactericidal activity test is carried out.
With fusarium graminearum, botrytis cinerea pers, P. capsici, Sclerotinia sclerotiorum, Rhizoctonia solani Kuhn and The material to be tested that Pyricularia oryzae is tested as bactericidal activity, reagent agent is dissolved in acetone, then with 200 μ g/mL Sorporl-144 emulsifying agents are diluted to 500 μ g/mL decoctions.Under sterile operating condition, 1mL chemical combination is drawn with liquid-transfering gun Thing solution is added in sterilized plate, then the sterilizing PDA culture medium for adding 9mL with pipette mixes in plate, phase is made Answer the pastille flat board of concentration.By cultured pathogen, aseptically with a diameter of 4mm sterilization punchers, from bacterium colony Edge cuts bacteria cake, and after after culture medium solidifying, pure culture biscuits involvng inoculation is placed in into the training of preference temperature in pastille flat board center with inoculator Support in case and cultivate.Blank control is done with not adding medicine.Handle in being cultivated in 24 ± 1 DEG C of incubators, observed simultaneously after 72 hours by each Colony diameter is measured, each bacterium colony vertically measures diameter with crossing method respectively once, takes its average value.Growth inhibition ratio (%) =(control colony diameter-processing colony diameter) × 100/ (control colony diameter -4mm).Drug concentration is 50 μ g/mL.Sterilization Active testing the results are shown in Table one.It was found from table one, target compound for examination germ to having excellent inhibitory activity, wherein chemical combination Thing N- (2- methoxy-benzyls) -2- (2- hydroxybenzylaminos) acetamide is to P. capsici, Sclerotinia sclerotiorum and rice blast The inhibiting rate of germ is 100%；Compound N-(4- methoxyphenyls) -2- (2- hydroxybenzylaminos) acetamide is to Phytophthora capsici The inhibiting rate of germ, Sclerotinia sclerotiorum and ash arrhizus bacteria is 100%, and the inhibiting rate to Pyricularia oryzae is 94.4%；N- (2- first Phenyl) -2- (2- hydroxybenzylaminos) acetamides are 87.7% to the inhibiting rate of Sclerotinia sclerotiorum.
The bactericidal activity of table 1 N- substitutions -2- (2- hydroxybenzylaminos) acetamide

Claims (12)

1. N- substitutions -2- (2- hydroxybenzyls) glycyl amine compound with below general formula (I)：
Wherein R1It is phenyl, C1-C3 alkyl phenyls, C1-C3 alkoxyl phenyls, phenyl C1-C3 alkylidenes, C1-C3 alkyl phenyls C1-C3 alkylidenes, or C1-C3 alkoxyl phenyl C1-C3 alkylidenes.
2. compound according to claim 1, wherein R1It is phenyl, C1-C2 alkyl phenyls, C1-C2 alkoxyl phenyls, phenyl C1- C2 alkylidenes, C1-C2 alkyl phenyl C1-C2 alkylidenes, or C1-C2 alkoxyl phenyl C1-C2 alkylidenes.
3. compound according to claim 1 or 2, wherein R1It is：
C6H5, C6H5CH2, o-CH3C6H4CH2, m-CH3C6H4CH2, p-CH3C6H4CH2, o-CH3OC6H4CH2, m-CH3OC6H4CH2,p- CH3OC6H4CH2, o-CH3C6H4, m-CH3C6H4, p-CH3C6H4, o-CH3OC6H4, m-CH3OC6H4, or p-CH3OC6H4。
4. compound according to claim 1 or 2, it is selected from：
1) N- benzyls -2- (2- hydroxybenzylaminos) acetamide：
2) N- (2- methyl-benzyls) -2- (2- hydroxybenzyls) amino acetamide：
3) N- (4- methyl-benzyls) -2- (2- hydroxybenzyls) amino acetamide：
4) N- (2- methoxy-benzyls) -2- (2- hydroxybenzyls) amino acetamide：
5) N- (3- methoxy-benzyls) -2- (2- hydroxybenzyls) amino acetamide：
6) N- (4- methoxy-benzyls) -2- (2- hydroxybenzyls) amino acetamide：
7) N- phenyl -2- (2- hydroxybenzyls) amino acetamide：
8) N- (2- aminomethyl phenyls) -2- (2- hydroxybenzyls) amino acetamide：
9) N- (4- aminomethyl phenyls) -2- (2- hydroxybenzyls) amino acetamide：
10) N- (2- methoxyphenyls) -2- (2- hydroxybenzyls) amino acetamide：
Or
11) N- (4- methoxyphenyls) -2- (2- hydroxybenzyls) amino acetamide：
5. preparing the method for the logical formula (I) compound any one of claim 1-4, this method includes：By formula (II) 2- (aminomethyl) oxybenzene compounds and the N- substitution -2- Haloacetamide compounds of logical formula (III) are reacted：
Wherein R1As any one of claim 1-3 is defined, X is chlorine, bromine or iodine.
6. method according to claim 5, this method includes：By leading to 2- (aminomethyl) oxybenzene compounds of formula (II) with leading to N- substitution -2- the Haloacetamide compounds of formula (III) are reacted in the organic solvent for the addition of alkali carbonate, point From the compound of the logical formula (I) of acquisition.
7. method according to claim 6, this method includes：The alkali carbonate is potassium carbonate or sodium carbonate；Institute It is DMF and THF according to 1 to state organic solvent:The mixed solvent of 0.2-5 volume ratio.
8. method according to claim 7, this method includes：The organic solvent is DMF and THF according to 1:0.5-2's The mixed solvent of volume ratio.
9. method according to claim 5, this method includes：By leading to 2- (aminomethyl) oxybenzene compounds of formula (II) with leading to N- substitution -2- the Haloacetamide compounds of formula (III) are reacted in the organic solvent for the addition of alkali carbonate, are subtracted Solvent is removed in pressure-off, is added water, is then extracted, and merges organic layer, and gained organic layer is used water, saturated common salt water washing, will had successively Machine layer drying, suction filtration, be concentrated under reduced pressure to obtain crude product, and the change of the logical formula (I) of white solid forms is then obtained through column chromatography for separation Compound.
10. method according to claim 9, this method includes：The alkali carbonate is potassium carbonate or sodium carbonate；Institute It is DMF and THF according to 1 to state organic solvent:The mixed solvent of 0.2-5 volume ratio；The extraction is extracted with ethyl acetate；It is described Drying anhydrous sodium sulfate drying.
11. method according to claim 10, this method includes：The organic solvent is DMF and THF according to 1:0.5-2 Volume ratio mixed solvent.
12. N- substitutions -2- (2- hydroxybenzyls) glycyl amine compound conduct in agriculture field described in claim 1 The purposes of Fungicidal compounds.
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