CN102617393B - Bisamide type compound - Google Patents
Bisamide type compound Download PDFInfo
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- CN102617393B CN102617393B CN201210093985.8A CN201210093985A CN102617393B CN 102617393 B CN102617393 B CN 102617393B CN 201210093985 A CN201210093985 A CN 201210093985A CN 102617393 B CN102617393 B CN 102617393B
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- China
- Prior art keywords
- methyl
- kharophen
- butyramide
- phenyl
- styroyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical class CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 title abstract 3
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 48
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 claims description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 38
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 125000002252 acyl group Chemical group 0.000 claims description 26
- 229940095054 ammoniac Drugs 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- YOETUEMZNOLGDB-UHFFFAOYSA-N 2-methylpropyl carbonochloridate Chemical compound CC(C)COC(Cl)=O YOETUEMZNOLGDB-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 241000255967 Helicoverpa zea Species 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 241000255925 Diptera Species 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- 241001147398 Ostrinia nubilalis Species 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 201000010099 disease Diseases 0.000 claims description 4
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims description 4
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 3
- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 claims description 3
- 241000198596 Alternaria tomatophila Species 0.000 claims description 3
- 240000008067 Cucumis sativus Species 0.000 claims description 3
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 claims description 3
- 241000223218 Fusarium Species 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 241000233616 Phytophthora capsici Species 0.000 claims description 3
- 241000233622 Phytophthora infestans Species 0.000 claims description 3
- 206010039509 Scab Diseases 0.000 claims description 3
- 241000209140 Triticum Species 0.000 claims description 3
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003899 bactericide agent Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 2
- 239000002917 insecticide Substances 0.000 abstract 1
- 101150065749 Churc1 gene Proteins 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 13
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000005457 ice water Substances 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000003905 agrochemical Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RQEUFEKYXDPUSK-UHFFFAOYSA-N 1-phenylethylamine Chemical compound CC(N)C1=CC=CC=C1 RQEUFEKYXDPUSK-UHFFFAOYSA-N 0.000 description 4
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 4
- 101100391174 Dictyostelium discoideum forC gene Proteins 0.000 description 4
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 4
- 102100038239 Protein Churchill Human genes 0.000 description 4
- 230000000855 fungicidal effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XDEHMKQLKPZERH-BYPYZUCNSA-N (2s)-2-amino-3-methylbutanamide Chemical compound CC(C)[C@H](N)C(N)=O XDEHMKQLKPZERH-BYPYZUCNSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- KWLVWJPJKJMCSH-UHFFFAOYSA-N 2-(4-chlorophenyl)-N-{2-[3-methoxy-4-(prop-2-yn-1-yloxy)phenyl]ethyl}-2-(prop-2-yn-1-yloxy)acetamide Chemical compound C1=C(OCC#C)C(OC)=CC(CCNC(=O)C(OCC#C)C=2C=CC(Cl)=CC=2)=C1 KWLVWJPJKJMCSH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 0 CC(C)C(C(NC(C)c1ccc(*)cc1)=O)NC(Cc(cc1OC)ccc1O*)=O Chemical compound CC(C)C(C(NC(C)c1ccc(*)cc1)=O)NC(Cc(cc1OC)ccc1O*)=O 0.000 description 2
- 239000005804 Mandipropamid Substances 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- MAGPZHKLEZXLNU-UHFFFAOYSA-N mandelamide Chemical compound NC(=O)C(O)C1=CC=CC=C1 MAGPZHKLEZXLNU-UHFFFAOYSA-N 0.000 description 2
- 230000010534 mechanism of action Effects 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 235000010603 pastilles Nutrition 0.000 description 2
- SGQLGSKBIIHNBL-UHFFFAOYSA-N 2-(3-methoxy-4-propoxyphenyl)acetic acid Chemical compound CCCOC1=CC=C(CC(O)=O)C=C1OC SGQLGSKBIIHNBL-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- QVWUGOPTWQXCAJ-UHFFFAOYSA-N CC(C)C(C(O)=O)NC(Cc(cc1)cc(OC)c1OI)=O Chemical compound CC(C)C(C(O)=O)NC(Cc(cc1)cc(OC)c1OI)=O QVWUGOPTWQXCAJ-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 241000256113 Culicidae Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- UDSJPFPDKCMYBD-UHFFFAOYSA-N Metsulfovax Chemical compound S1C(C)=NC(C)=C1C(=O)NC1=CC=CC=C1 UDSJPFPDKCMYBD-UHFFFAOYSA-N 0.000 description 1
- 241000233654 Oomycetes Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000021405 artificial diet Nutrition 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229940054066 benzamide antipsychotics Drugs 0.000 description 1
- 150000003936 benzamides Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- -1 diamide compound Chemical class 0.000 description 1
- 150000001470 diamides Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000006916 nutrient agar Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- APEJMQOBVMLION-VOTSOKGWSA-N trans-cinnamamide Chemical compound NC(=O)\C=C\C1=CC=CC=C1 APEJMQOBVMLION-VOTSOKGWSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a bisamide type compound which is shown as a formula (I) and discloses a preparation method thereof. The bisamide type compound provided by the invention can be applied as an insecticide and a bactericide and has an obvious effect.
Description
(1) technical field
The preparation method who the present invention relates to a kind of pair of acyl ammoniac compounds is preparation method and the application of 2-(2-(the disubstituted phenyl of 3,4-) kharophen)-3-methyl-N-(4-substituted-phenyl) butyramide derivative.
(2) background technology
There is important effect the aspects such as life, grain-production and the environment protection of agricultural chemicals to the mankind; for improve the mankind life, improve the output of farm crop unit surfaces and prevent environmental degradation, just must exploitation initiative upgrade, more efficient, safer agrochemicals.Simultaneously, along with people use agricultural chemicals for a long time, resistance problem is more and more serious, and agricultural chemicals also increasingly sharpens to the seriousness of soil pollution problem, all needs urgently constantly to research and develop novel pesticide.
Carboxylic acid amide series bactericidal agent is the new type bactericide of developing in recent years, the three class acid amides that it comprises: cinnamide, valine amide amino formate and mandelamide type, can prevent and treat very efficiently Oomycete disease, and novel structure.These compounds are to produce at present the upper sterilant for alternative benzamides.Novel structure, high-efficient and lasting, mechanism of action uniqueness has researching value very much.
Valine amide series bactericidal agent is amino acids agricultural chemicals, can be decomposed by microorganism, does not cause residual contamination and decompose the advantage such as nutrition that the amino-acid, fatty-acid producing can improve soil the emphasis that becomes pesticide research.Simultaneously it or another carboxylic acid amide series bactericidal agent, there are similar fungicidal spectrum and bacteriostatic activity to mandipropamid, and between them, also there is the orthogonal transreactance property of medicine, this all illustrates that probably they have identical mechanism of action, and what have kind benzene metsulfovax of bibliographical information valine amide series bactericidal agent and mandipropamid effect should be same enzyme, and catastrophe point effect is similar.Therefore can design new molecule by modes such as pharmacophores, i.e. the diamide compound of α-amino-isovaleric acid.
But, there is not yet the bibliographical information of the synthetic and bioactivity research of relevant 2-(2-(the disubstituted phenyl of 3,4-) kharophen)-3-methyl-N-(4-substituted-phenyl) butyramide derivative.
(3) summary of the invention
The object of the invention is to provide a kind of preparation method of 2-(2-(the disubstituted phenyl of 3,4-) kharophen)-3-methyl-N-(4-substituted-phenyl) butyramide derivative with insecticidal activity and fungicidal activity.
The technical solution used in the present invention is:
A kind of suc as formula the two acyl ammoniac compounds shown in (I):
In formula (I), R
1for the alkynyl of alkyl, C2～C6 thiazolinyl or the C3～C6 of C1～C6; R
2for the alkyl of H or C1～C6.
Further, described R
1be preferably ethyl, propyl group, allyl group or propargyl, R
2be preferably methyl or hydrogen.
Most preferably described pair of acyl ammoniac compounds is 2-(2-(4-oxyethyl group-3-p-methoxy-phenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide, 2-(2-(4-propoxy--3-p-methoxy-phenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide, 2-(2-(3-methoxyl group-4-propoxy-) kharophen)-3-methyl-N-(1-(p-methylphenyl) ethyl) butyramide, 2-(2-(4-(propenyloxy group)-3-methoxyphenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide, 2-(2-(4-(allyloxy)-3-methoxyphenyl) kharophen)-3-methyl-N-(1-(p-methylphenyl) ethyl) butyramide, 2-(2-(3-methoxyl group-4-(propargyl alcoholate) phenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide or 2-(2-(3-methoxyl group-4-(propargyl alcoholate) phenyl) kharophen)-3-methyl-N-(1-(p-methylphenyl) ethyl) butyramide.
The present invention also provides the method for the two acyl ammoniac compounds shown in a kind of preparation formula (I), described method is: compound shown in formula (II) is added in organic solvent, at-20～-5 DEG C, be uniformly mixed, add basic catalyst and isobutyl chlorocarbonate, stirring reaction 1～2h at 0～5 DEG C, add again compound shown in formula (III), stirring reaction under room temperature, after reacting completely, reaction solution aftertreatment makes the two acyl ammoniac compounds shown in formula (I); Shown in compound shown in described formula (II), formula (III), the ratio of the amount of substance of compound, basic catalyst, isobutyl chlorocarbonate is 1: 1.0～1.5: 1.0～1.5: 1.0～1.5; Described organic solvent is one of following: methylene dichloride, chloroform or toluene, preferably methylene dichloride; Described basic catalyst is one of following: triethylamine, diisopropylethylamine or pyridine, preferably triethylamine;
In formula (II), R
1for the alkynyl of alkyl, C2～C6 thiazolinyl or the C3～C6 of C1～C6, be preferably ethyl, propyl group, allyl group or propargyl; In formula (III), R
2for the alkyl of H or C1～C6, be preferably methyl or hydrogen.
Further, the ratio of the amount of substance that shown in compound shown in described formula (II), formula (III), compound, basic catalyst, isobutyl chlorocarbonate feed intake is 1: 1.0～1.5: 1.0～1.5: 1.0～1.5, preferably 1: 1.0～1.1: 1.1～1.2: 1, described organic solvent volumetric usage was counted 4～10mL/mmol with the amount of substance of compound shown in formula (II).
Further, described in the method for the described two acyl ammoniac compounds of preparation, reaction solution post-treating method is: after reaction finishes, reaction solution is washed with dilute hydrochloric acid, then removes solvent under reduced pressure, and gained crude product ethyl alcohol recrystallization makes described two acyl ammoniac compounds.
Shown in formula of the present invention (II), compound can make by the following method:
Shown in formula (IV), compound is dissolved in methylene dichloride, be added dropwise in the oxalyl chloride of 0～5 DEG C of insulation, drip and finish rear room temperature reaction 24h, then the solvent in reaction solution and excessive oxalyl chloride steaming are removed, residual solution is added dropwise in the solution that α-amino-isovaleric acid is dissolved in 1mol/L aqueous sodium hydroxide solution, room temperature reaction 10h, it is 1～2 that acid adding is adjusted the pH of reaction solution, there is solid to separate out, suction filtration, filter cake is dried to obtain compound shown in formula (II), compound shown in described formula (IV), oxalyl chloride, α-amino-isovaleric acid, the ratio of the amount of substance of NaOH is 1: 1～1.5: 1～1.2: 2～2.4.This is to well known to a person skilled in the art preparation method.
Two acyl ammoniac compounds described in the present invention also provides are as the application of sterilant, concrete, can apply the sterilant as control mosquito, bollworm, Pyrausta nubilalis (Hubern)..Further, 2-(2-(4-oxyethyl group-3-p-methoxy-phenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide or 2-(2-(4-propoxy--3-p-methoxy-phenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide can be applied the sterilant as control mosquito, bollworm, Pyrausta nubilalis (Hubern)..
Two acyl ammoniac compounds described in the present invention also provides are as the application of sterilant, concrete, can apply the sterilant as early blight of tomato, wheat scab, Phytophthora capsici disease, the late blight of potato, cucumber fusarium axysporum, ring rot of apple.Further, 2-(2-(4-oxyethyl group-3-p-methoxy-phenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide, 2-(2-(4-propoxy--3-p-methoxy-phenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide, 2-(2-(3-methoxyl group-4-propoxy-) kharophen)-3-methyl-N-(1-(p-methylphenyl) ethyl) butyramide, 2-(2-(4-(propenyloxy group)-3-methoxyphenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide, 2-(2-(4-(allyloxy)-3-methoxyphenyl) kharophen)-3-methyl-N-(1-(p-methylphenyl) ethyl) butyramide, 2-(2-(3-methoxyl group-4-(propargyl alcoholate) phenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide or 2-(2-(3-methoxyl group-4-(propargyl alcoholate) phenyl) kharophen)-3-methyl-N-(1-(p-methylphenyl) ethyl) butyramide are applied as early blight of tomato, wheat scab, Phytophthora capsici disease, the late blight of potato, cucumber fusarium axysporum, the sterilant of ring rot of apple.
Compared with prior art, beneficial effect of the present invention is mainly reflected in: the invention provides a class and have the new compound of desinsection and fungicidal activity, for the research and development of novel pesticide provide the foundation.
(4) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Shown in formula II in the embodiment of the present invention, compound prepares by the following method:
With the example that is prepared as of IIa, by oxalyl chloride (2.86g, 22.5mmol), join in the mono-neck bottle of 50ml, under ice-water bath 4-oxyethyl group-3-methoxyphenylacetic acid IVa (3.15g, 15mmol is dissolved in the methylene dichloride of 20ml) be added drop-wise in reaction system, 30min drips complete, room temperature reaction 24h, then the solvent in reaction solution and excessive oxalyl chloride are screwed out, residual solution is for subsequent use, α-amino-isovaleric acid (2.11g, 18mmol) be dissolved in 36ml sodium hydroxide (1.44g, 36mmol) in solution, then the above-mentioned acyl chlorides residual solution preparing is slowly dripped, 4h drips complete, room temperature reaction 10h, adjust the pH of reaction solution to be about 1, there is solid to separate out, suction filtration, filter cake is dried to obtain white powder 2.98g.IIb, IIc, IId preparation method are similar, just the R in formula IV
1be respectively corresponding substituted radical, change respectively 4-propoxy--3-methoxyphenylacetic acid IVb (3.36g into by 4-oxyethyl group-3-methoxyphenylacetic acid IVa, 15mmol), 4-propenyloxy group-3-methoxyphenylacetic acid IVc (3.33g, 15mmol), 4-propargyl alcoholate-3-methoxyphenylacetic acid IVd (3.30g, 15mmol).The data that make product are as following table 1:
Table 1:
| No. | R 1 | Mp(℃) | Yield (%) | Proterties |
| IIa | -CH 2CH 3 | 97～98 | 84 | White solid |
| IIb | -CH 2CH 2CH 3 | 95～97 | 90 | White solid |
| IIc | -CH 2CH＝CH 2 | 117～119 | 50 | White solid |
| IId | -CH 2C≡CH | 103～105 | 81 | Brown solid |
Compound nuclear magnetic data is as follows:
IIa：
1H NMR(400MHz，DMSO)：δ8.19(d，J＝8.5Hz，1H，NH)，6.92(s，1H，Ar-H)，6.84(d，J＝8.1Hz，1H，Ar-H)，6.75(d，J＝8.2Hz，1H，Ar-H)，4.15-4.12(m，1H，NH
CHCOOH)，3.96(q，J＝6.9Hz，2H，O
CH 2 CH
3)，3.72(s，3H，OCH
3)，2.09-2.01(m，1H，(CH
3)
2 CH)，1.29(t，J＝6.9Hz，3H，OCH
2 CH 3 )，0.87(dd，J
1＝6.8Hz，J
2＝11.6Hz，6H，
(CH 3 ) 2 CH)
IIb：
1H NMR(400MHz，CDCl
3)：δ6.89(d，J＝7.5Hz，1H，Ar-H)，6.82(s，2H，Ar-H)，6.01(t，J＝8.5Hz，1H，NH)，4.56-4.54(m，1H，NH
CHCOOH)，4.00(t，J＝6.5Hz，2H，O
CH 2 CH
2CH
3)，3.88(s，3H，OCH
3)，3.61(s，2H，
CH 2 CO)，2.21-2.19(m，1H，(CH
3)
2 CH)，1.94-1.85(m，2H，OCH
2 CH 2 CH
3)，1.07(t，J＝7.3Hz，3H，OCH
2CH
2 CH 3 )，0.92(dd，J＝6.5Hz，3H，
(CH 3 ) 2 CH)，0.81(ddJ＝6.5Hz，3H，
(CH 3 ) 2 CH)
IIc：
1H NMR(400MHz，CDCl
3)：δ6.90-6.75(m，3H，Ar-H)，6.14-6.18(m，1H，OCH
2 CH＝CH
2)，6.00(d，J＝8.3Hz，1H，NH)，5.43(d，J＝17.3Hz，1H，OCH
2CH＝C
H a H
b)，5.32(d，J＝10.3Hz，1H，OCH
2CH＝CH
a H b )，4.64(s，2H，O
CH 2 CH＝CH
2)，4.55(t，J＝4.3Hz，1H，NH
CHCOOH)，3.89(s，3H，OCH
3)，3.61(s，2H，
CH 2 CO)，2.26-2.19(m，1H，(CH
3)
2 CH)，0.92(dd，J＝6.1Hz，3H，
(CH 3 ) 2 CH)，0.81(dd，J＝6.1Hz，3H，
(CH 3 ) 2 CH)
IId：
1H NMR(400MHz，CDCl
3)：δ6.94(d，J＝8.0Hz，1H，Ar-H)，6.81(s，1H，Ar-H)，6.76(d，J＝8.1Hz，1H，Ar-H)，6.37(d，J＝8.5Hz，1H，NH)，4.69(s，2H，O
CH 2 C≡CH)，4.50(dd，J
1＝4.3Hz，J
2＝7.9Hz，1H，NH
CHCOOH)，3.79(s，3H，OCH
3)，3.55(s，2H，
CH 2 CO)，2.49(s，1H，OCH
2C≡
CH)，0.84(d，J＝6.6Hz，3H，
(CH 3 ) 2 CH)，0.81(d，J＝6.7Hz，3H，
(CH 3 ) 2 CH)
Embodiment 1:2-(2-(4-oxyethyl group-3-p-methoxy-phenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide: (I-1) synthetic
2-(2-(4-oxyethyl group-3-p-methoxy-phenyl) kharophen)-3 Methylbutanoic acid (2.5mmol) is joined in the methylene dichloride that 10ml was dried, under cryosel bath condition, stir, control temperature at-15～-10 DEG C, add triethylamine (2.75mmol), then drip isobutyl chlorocarbonate (2.5mmol), under ice-water bath, stir 1h, still under this condition, drip 1-phenylethylamine (2.75mmol is dissolved in 10ml methylene dichloride), 15min drips complete, under room temperature, react 1h, wash with 10wt% dilute hydrochloric acid, be spin-dried for, crude product ethyl alcohol recrystallization, suction filtration obtains white solid, yield is 50%.
1H NMR(400MHz，CDCl
3)：δ7.39-7.25(m，5H，Ar-H)，6.87-6.73(m，3H，Ar-H)，6.21-5.67(m，2H，2NH)，5.12-5.03(m，1H，NH
CHCH
3)，4.18-4.11(m，3H，(CH
3)
2CH
CH，CH
3 CH 2 O)，3.85(s，3H，
CH 3 O)，3.56-3.52(m，2H，
CH 2 CO)，2.08-1.97(m，1H，(CH
3)
2 CHCH)，1.49(s，6H，NHCH
CH 3 ，
CH 3 CH
2O)，0.94-0.76(m，6H，
(CH 3 ) 2 CH).HRMS(ESI)m/z Calcd forC
24H
32N
2O
4Na
+[M+Na]
+435.2254，Found：435.2256.
Embodiment 2:2-(2-(4-propoxy--3-p-methoxy-phenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide: (I-2) synthetic
2-(2-(4-propoxy--3-p-methoxy-phenyl) kharophen)-3 Methylbutanoic acid (2.5mmol) is joined in the methylene dichloride that 10ml was dried, under cryosel bath condition, stir, control temperature at-15～-10 DEG C, add triethylamine (2.75mmol), then drip isobutyl chlorocarbonate (2.5mmol), under ice-water bath, stir 1h, still under this condition, drip 1-phenylethylamine (2.75mmol is dissolved in 10ml methylene dichloride), 15min drips complete, under room temperature, react 1h, wash with 10wt% dilute hydrochloric acid, be spin-dried for, crude product ethyl alcohol recrystallization, suction filtration obtains white solid, yield is 69%,
1h NMR (400MHz, CDCl
3): δ 7.36-7.25 (m, 5H, Ar-H), 6.86-6.73 (m, 3H, Ar-H), 6.54 (s, 1H, NH), 6.22 (d, J=22.8Hz, 1H, NH), 5.09-5.02 (m, 1H, NH
cHcH
3), 4.22 (t, J=7.6Hz, 1H, (CH
3)
2cH
cH), 3.99-3.95 (m, 2H, CH
3cH
2 cH 2 o), 3.83 (d, J=21.6Hz, 3H, O
cH 3), 3.58-3.50 (m, 2H,
cH 2 oC), 2.06-1.95 (m, 1H, (CH
3)
2 cHcH), 1.93-1.84 (m, 2H, CH
3 cH 2 cH
2o), 1.46 (dd, J
1=6.8Hz, J
2=10.8Hz, 3H, NHCH
cH 3 ), 1.05 (t, J=7.2Hz, 3H,
cH 3 cH
2cH
2o), 0.93-0.75 (m, 6H,
(CH 3 ) 2 cH) .HRMS (ESI) m/z Calcd for C
25h
34n
2o
4na
+[M+Na]
+449.2411, Found:449.2415.
Embodiment 3:2-(2-(3-methoxyl group-4-propoxy-) kharophen)-3-methyl-N-(1-(p-methylphenyl) ethyl) butyramide: (I-3) synthetic
2-(2-(4-propoxy--3-p-methoxy-phenyl) kharophen)-3 Methylbutanoic acid (2.5mmol) is joined in the methylene dichloride that 10ml was dried, under cryosel bath condition, stir, control temperature at-15～-10 DEG C, add triethylamine (2.75mmol), then drip isobutyl chlorocarbonate (2.5mmol), under ice-water bath, stir 1h, still under this condition, drip 1-(4-aminomethyl phenyl) ethamine (2.75mmol is dissolved in 10ml methylene dichloride), 15min drips complete, under room temperature, react 1h, wash with 10wt% dilute hydrochloric acid, be spin-dried for, crude product ethyl alcohol recrystallization, suction filtration obtains white solid, yield is 64%,
1hNMR (400MHz, CDCl
3): δ 7.20-7.12 (m, 4H, Ar-H), 6.86-6.73 (m, 3H, Ar-H), 6.45 (s, 1H, NH), 6.21 (s, 1H, NH), 5.05-4.99 (m, 1H, NH
cHcH
3), 4.22 (t, J=7.2Hz, 1H, (CH
3)
2cH
cH), 3.97 (t, J=6.8Hz, 2H, CH
3cH
2 cH 2 o), 3.83 (d, J=20.0Hz, 3H,
oCH 3 ), 3.58-3.46 (m, 2H,
cH 2 oC), 2.34 (s, 3H, p-
cH 3 ar), 2.05-1.94 (m, 1H, (CH
3)
2 cHcH), 1.93-1.84 (m, 2H, CH
3 cH 2 cH
2o), 1.44 (dd, J
1=7.2Hz, J
2=10.0Hz, 3H, NHCH
cH 3 ), 1.05 (t, J=7.6Hz, 3H,
cH 3 cH
2cH
2o), 0.92-0.75 (m, 6H,
(CH 3 ) 2 cH) .HRMS (ESI) m/z Calcd forC
26h
36n
2o
4na
+[M+Na]
+463.2567, Found:463.2564.
Embodiment 4:2-(2-(4-(propenyloxy group)-3-methoxyphenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide: (I-4) synthetic
2-(2-(4-propenyloxy group-3-p-methoxy-phenyl) kharophen)-3 Methylbutanoic acid (2.5mmol) is joined in the methylene dichloride that 10ml was dried, under cryosel bath condition, stir, control temperature at-15～-10 DEG C, add triethylamine (2.75mmol), then drip isobutyl chlorocarbonate (2.5mmol), under ice-water bath, stir 1h, still under this condition, drip 1-phenylethylamine (2.75mmol is dissolved in 10ml methylene dichloride), 15min drips complete, under room temperature, react 1h, wash with 10wt% dilute hydrochloric acid, be spin-dried for, crude product ethyl alcohol recrystallization, suction filtration obtains incarnadine solid, yield is 68%,
1h NMR (400MHz, CDCl
3): δ 7.36-7.25 (m, 5H, Ar-H), 6.86-6.71 (m, 3H, Ar-H), 6.51 (s, 1H, NH), 6.20 (d, J=24.0Hz, 1H, NH), 6.14-6.05 (m, 1H, CH
2=
cHcH
2o), 5.36 (dd, J
1=15.6Hz, J
2=48.0Hz, 2H,
cH 2 =CHCH
2o), 5.08-5.03 (m, 1H, NH
cHcH
3), 4.61 (s, 2H, CH
2=CH
cH 2 o), 4.22 (t, J=8.0Hz, 1H, (CH
3)
2cH
cH), 3.84 (t, J=22.0Hz, 3H, O
cH 3 ), 3.58-3.46 (m, 2H,
cH 2 oC), 2.07-1.93 (m, 1H, (CH
3)
2 cHcH), 1.46 (dd, J
1=6.8Hz, J
2=10.8Hz, 3H, NHCH
cH 3 ), 0.93-0.75 (m, 6H,
(CH 3 ) 2 cH) .HRMS (ESI) m/z Calcd forC
25h
32n
2o
4na
+[M+Na]
+447.2260, Found:447.2252.
Embodiment 5:2-(2-(4-(propenyloxy group)-3-methoxyphenyl) kharophen)-3-methyl-N-(1-(p-methylphenyl) ethyl) butyramide: (I-5) synthetic
2-(2-(4-propenyloxy group-3-p-methoxy-phenyl) kharophen)-3 Methylbutanoic acid (2.5mmol) is joined in the methylene dichloride that 10ml was dried, under cryosel bath condition, stir, control temperature at-15～-10 DEG C, add triethylamine (2.75mmol), then drip isobutyl chlorocarbonate (2.5mmol), under ice-water bath, stir 1h, still under this condition, drip 1-(4-aminomethyl phenyl) ethamine (2.75mmol is dissolved in 10ml methylene dichloride), 15min drips complete, under room temperature, react 1h, wash with 10wt% dilute hydrochloric acid, be spin-dried for, crude product ethyl alcohol recrystallization, suction filtration obtains incarnadine solid, yield is 65%,
1h NMR (400MHz, CDCl
3): δ 7.20-7.15 (m, 4H, Ar-H), 6.87-6.73 (m, 3H, Ar-H), 6.39 (s, 1H, NH), 6.21 (d, J=21.2Hz, 1H, NH), 6.14-6.06 (m, 1H, CH
2=
cHcH
2o), 5.36 (dd, J
1=17.2Hz, J
2=49.2Hz, 2H,
cH 2 =CHCH
2o), 5.04-5.00 (m, 1H, NH
cHcH
3), 4.61 (s, 2H, CH
2=CH
cH 2 o), 4.20 (t, J=5.6Hz, 1H, (CH
3)
2cH
cH), 3.85 (d, J=20.4Hz, 3H, O
cH 3 ), 3.53 (d, J=14Hz, 2H,
cH 2 oC), 2.34 (s, 3H, p-
cH 3 ar), 2.07-1.99 (m, 1H, (CH
3)
2 cHcH), 1.46 (t, J=7.6Hz, 3H, NHCH
cH 3 ), 0.93-0.76 (m, 6H,
(CH 3 ) 2 cH) .HRMS (ESI) m/zCalcd for C
26h
34n
2o
4h
+[M+H]
+439.2591, Found:439.2598.
Embodiment 6:2-(2-(3-methoxyl group-4-(propargyl alcoholate) phenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide: (I-6) synthetic
2-(2-(4-propargyl alcoholate-3-p-methoxy-phenyl) kharophen)-3 Methylbutanoic acid (2.5mmol) is joined in the methylene dichloride that 10ml was dried, under cryosel bath condition, stir, control temperature at-15～-10 DEG C, add triethylamine (2.75mmol), then drip isobutyl chlorocarbonate (2.5mmol), under ice-water bath, stir 1h, still under this condition, drip 1-phenylethylamine (2.75mmol is dissolved in 10ml methylene dichloride), 15min drips complete, under room temperature, react 1h, wash with 10wt% dilute hydrochloric acid, be spin-dried for, crude product ethyl alcohol recrystallization, suction filtration obtains light yellow solid, yield is 53%,
1h NMR (400MHz, CDCl
3): δ 7.37-7.26 (m, 5H, Ar-H), 7.01 (t, J=8.4Hz, 1H, Ar-H), 6.84-6.78 (m, 2H, Ar-H), 6.51 (s, 1H, NH), 6.26 (d, J=15.6Hz, 1H, NH), 5.10-5.03 (m, 1H, NH
cHcH
3), 4.77 (s, 2H, O
cH 2 c ≡ CH), 4.23 (t, J=6.4Hz, 1H, (CH
3)
2cH
cH), 3.85 (d, J=23.6Hz, 3H,
cH 3 o), 3.54 (d, J=16.0Hz, 2H,
cH 2 oC), 2.52 (s, 1H, OCH
2c ≡
cH), 2.08-2.00 (m, 1H, (CH
3)
2 cHcH), 1.48 (dd, J
1=7.2Hz, J
2=9.6Hz, 3H, NHCH
cH 3 ), 0.89 (dd, J
1=6.4Hz, J
2=32Hz, 3H,
(CH 3 ) 2 cH), 0.80 (dd, J
1=6.4Hz, J
2=14.8Hz, 3H,
(CH 3 ) 2 cH) .HRMS (ESI) m/zCalcd for C
25h
30n
2o
4h
+[M+H]
+423.2278, Found:423.2276.
Embodiment 7:2-(2-(3-methoxyl group-4-(propargyl alcoholate) phenyl) kharophen)-3-methyl-N-(1-(p-methylphenyl) ethyl) butyramide: (I-7) synthetic
2-(2-(4-propargyl alcoholate-3-p-methoxy-phenyl) kharophen)-3 Methylbutanoic acid (2.5mmol) is joined in the methylene dichloride that 10ml was dried, under cryosel bath condition, stir, control temperature at-15～-10 DEG C, add triethylamine (2.75mmol), then drip isobutyl chlorocarbonate (2.5mmol), under ice-water bath, stir 1h, still under this condition, drip 1-(4-aminomethyl phenyl) ethamine (2.75mmol is dissolved in 10ml methylene dichloride), 15min drips complete, under room temperature, react 1h, wash with 10wt% dilute hydrochloric acid, be spin-dried for, crude product ethyl alcohol recrystallization, suction filtration obtains light yellow solid, yield is 83%,
1h NMR (400MHz, CDCl
3): δ 7.19-7.15 (m, 4H, Ar-H), 7.00 (t, J=7.6Hz, 1H, Ar-H), 6.83-6.78 (m, 2H, Ar-H), 6.36 (s, 1H, NH), 6.22 (d, J=20.0Hz, 1H, NH), 5.08-5.00 (m, 1H, NH
cHcH
3), 4.77 (s, 2H, O
cH 2 c ≡ CH), 4.02 (d, J=6.0Hz, 1H, (CH
3)
2cH
cH), 3.84 (d, J=21.6Hz, 3H,
cH 3 o), 3.54 (d, J=13.6Hz, 2H,
cH 2 oC), 2.51 (s, 1H, OCH
2c ≡
cH), 2.34 (s, 3H, p-
cH 3 ar), 2.10-1.97 (m, 1H, (CH
3)
2 cHcH), 1.46 (t, J=8.0Hz, 3H, NHCH
cH 3 ), 0.93-0.77 (m, 3H,
(CH 3 ) 2 cH) .HRMS (ESI) m/z Calcd forC
26h
32n
2o
4h
+[M+H]
+437.2435, Found:437.2436.
Embodiment 8: two acyl ammoniac compounds kill mosquito active testing
Adopt immersion method, every kind of compound is mixed with to the mother liquor of concentration 200ppm with acetone solution, from mother liquor, draw a certain amount of solution and be made into suitable intermediate concentration, and then from then on draw a certain amount of solution in liquid and put into the beaker that contains 100mL dechlorination water (leaving standstill tap water more than 15 days), put 10 of mosquito larvaes to every beaker, 72 hours check results.Improved mortality formula is as follows:
Total borer population × 100% of mortality ratio=dead borer population/process
Gained mortality ratio the results are shown in Table 2.
Embodiment 9: two acyl ammoniac compounds kill bollworm active testing
Adopt the mixed medicine method of feed, the compound preparing is formulated as to solution with DMF, pipette in the bollworm artificial diet that 3mL adds 27g, thereby obtain diluting the desired concn of ten times.Medicament mixes rear pouring into uniformly in 24 clean orifice plates, and 24 bollworms of cool rear access of drying in the air, observe check result after 3 days.Improved mortality formula is with embodiment 8, and gained mortality ratio the results are shown in Table 2.
Embodiment 10: two acyl ammoniac compounds kill Pyrausta nubilalis (Hubern). active testing
Adopt immersion method (J.Agric.Food Chem., 2004,52 (22): 6737-6741), the compound preparing is prepared after desired concn with DMF, the maize leaf of diameter 5-6cm is soaked to into the liquid 5-6 second, take out, be placed on thieving paper and dry, be placed in the culture dish of appointment, access 10 3 instar larvaes, put into the insectary of 27 ± 1 degree and observe check result after 3 days.Improved mortality formula is with embodiment 8, and gained mortality ratio the results are shown in Table 2.
Table 2:
Embodiment 11: the fungicidal activity test of two acyl ammoniac compounds
Adopt biomass growth rate assay method (mycelium growth rate test), reagent agent is become to certain multiple with DMF solvent cut under aseptic condition, then respectively drawing 1mL liquid injects in culture dish, add respectively again 9mL nutrient agar, after shaking up, make 50ug/mL pastille flat board, do blank with the flat board that adds 1mL aqua sterilisa.Cut bacterium dish along mycelia outer rim with the punch tool of diameter 4mm, move on pastille flat board.Every processing in triplicate.Culture dish is placed in 24 ± 1 DEG C of constant incubators and is cultivated.Within 72 hours, " Invest, Then Investigate " is respectively processed bacterium dish expansion diameter, averages, and relatively calculates relative bacteriostasis rate with blank, the results are shown in Table 3.
Table 3: diamide compounds sterilization effect
Claims (10)
1. one kind suc as formula the two acyl ammoniac compounds shown in (I):
In formula (I), R
1for the alkynyl of alkyl, C2～C6 thiazolinyl or the C3～C6 of C1～C6; R
2for the alkyl of H or C1～C6.
2. as claimed in claim 1 pair of acyl ammoniac compounds, is characterized in that described R
1for ethyl, propyl group, allyl group or propargyl, R
2for methyl or hydrogen.
3. as claimed in claim 1 pair of acyl ammoniac compounds, it is characterized in that described pair of acyl ammoniac compounds is 2-(2-(4-oxyethyl group-3-p-methoxy-phenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide, 2-(2-(4-propoxy--3-p-methoxy-phenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide, 2-(2-(3-methoxyl group-4-propoxy-) kharophen)-3-methyl-N-(1-(p-methylphenyl) ethyl) butyramide, 2-(2-(4-(propenyloxy group)-3-methoxyphenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide, 2-(2-(4-(allyloxy)-3-methoxyphenyl) kharophen)-3-methyl-N-(1-(p-methylphenyl) ethyl) butyramide, 2-(2-(3-methoxyl group-4-(propargyl alcoholate) phenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide or 2-(2-(3-methoxyl group-4-(propargyl alcoholate) phenyl) kharophen)-3-methyl-N-(1-(p-methylphenyl) ethyl) butyramide.
4. the preparation method of as claimed in claim 1 pair of acyl ammoniac compounds, it is characterized in that described method is: compound shown in formula (II) is added in organic solvent, at-20～-5 DEG C, be uniformly mixed, add basic catalyst and isobutyl chlorocarbonate, stirring reaction 1～2h at 0～5 DEG C, then add compound shown in formula (III), stirring reaction under room temperature, after reacting completely, reaction solution aftertreatment makes the two acyl ammoniac compounds shown in formula (I); Shown in compound shown in described formula (II), formula (III), the ratio of the amount of substance of compound, basic catalyst, isobutyl chlorocarbonate is 1: 1.0～1.5: 1.0～1.5: 1.0～1.5; Described organic solvent is one of following: methylene dichloride, chloroform or toluene; Described basic catalyst is one of following: triethylamine, diisopropylethylamine or pyridine;
In formula (II), R
1for the alkynyl of alkyl, C2～C6 thiazolinyl or the C3～C6 of C1～C6; In formula (III), R
2for the alkyl of H or C1～C6.
5. the as claimed in claim 1 pair of acyl ammoniac compounds is as the application of sterilant.
6. application as claimed in claim 5, is characterized in that the application of described two acyl ammoniac compounds as the sterilant of control mosquito, bollworm, Pyrausta nubilalis (Hubern)..
7. application as claimed in claim 6, is characterized in that described two acyl ammoniac compounds are 2-(2-(4-oxyethyl group-3-p-methoxy-phenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide or 2-(2-(4-propoxy--3-p-methoxy-phenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide.
8. the as claimed in claim 1 pair of acyl ammoniac compounds is as the application of sterilant.
9. application as claimed in claim 8, is characterized in that the application of described two acyl ammoniac compounds as the sterilant of early blight of tomato, wheat scab, Phytophthora capsici disease, the late blight of potato, cucumber fusarium axysporum, ring rot of apple.
10. application as claimed in claim 9, it is characterized in that described two acyl ammoniac compounds are 2-(2-(4-oxyethyl group-3-p-methoxy-phenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide, 2-(2-(4-propoxy--3-p-methoxy-phenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide, 2-(2-(3-methoxyl group-4-propoxy-) kharophen)-3-methyl-N-(1-(p-methylphenyl) ethyl) butyramide, 2-(2-(4-(propenyloxy group)-3-methoxyphenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide, 2-(2-(4-(allyloxy)-3-methoxyphenyl) kharophen)-3-methyl-N-(1-(p-methylphenyl) ethyl) butyramide, 2-(2-(3-methoxyl group-4-(propargyl alcoholate) phenyl) kharophen)-3-methyl-N-(1-styroyl) butyramide or 2-(2-(3-methoxyl group-4-(propargyl alcoholate) phenyl) kharophen)-3-methyl-N-(1-(p-methylphenyl) ethyl) butyramide.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1108863A (en) * | 1993-04-28 | 1995-09-20 | 久美蓝化学工业株式会社 | Amino acid amide derivative, agrohorticultural bactericide, and production process |
| CN1226887A (en) * | 1996-08-02 | 1999-08-25 | 拜尔公司 | Process for preparing substituted valine amide derivatives |
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2012
- 2012-04-01 CN CN201210093985.8A patent/CN102617393B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1108863A (en) * | 1993-04-28 | 1995-09-20 | 久美蓝化学工业株式会社 | Amino acid amide derivative, agrohorticultural bactericide, and production process |
| CN1226887A (en) * | 1996-08-02 | 1999-08-25 | 拜尔公司 | Process for preparing substituted valine amide derivatives |
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