CN100500665C - Triazolo-pyrimido-thioacetamide compounds, preparation method and uses - Google Patents
Triazolo-pyrimido-thioacetamide compounds, preparation method and uses Download PDFInfo
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- CN100500665C CN100500665C CNB2006101549562A CN200610154956A CN100500665C CN 100500665 C CN100500665 C CN 100500665C CN B2006101549562 A CNB2006101549562 A CN B2006101549562A CN 200610154956 A CN200610154956 A CN 200610154956A CN 100500665 C CN100500665 C CN 100500665C
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- pyrimidine
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- 238000002360 preparation method Methods 0.000 title description 7
- 230000002363 herbicidal effect Effects 0.000 claims abstract description 4
- 239000004009 herbicide Substances 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 38
- 241000196324 Embryophyta Species 0.000 claims description 13
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 20
- 238000009333 weeding Methods 0.000 abstract description 13
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- -1 triazole pyrimidine thioacetamide compound Chemical class 0.000 abstract description 4
- 239000003085 diluting agent Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 41
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 19
- 239000007787 solid Substances 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000013019 agitation Methods 0.000 description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 description 9
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 244000237956 Amaranthus retroflexus Species 0.000 description 2
- 235000013479 Amaranthus retroflexus Nutrition 0.000 description 2
- 244000178993 Brassica juncea Species 0.000 description 2
- 235000005855 Brassica juncea var. subintegrifolia Nutrition 0.000 description 2
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical class ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 150000003869 acetamides Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N aminomethyl benzene Natural products NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 150000003939 benzylamines Chemical class 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000008141 laxative Substances 0.000 description 2
- 230000002475 laxative effect Effects 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 1
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
- WTLNOANVTIKPEE-UHFFFAOYSA-N 2-acetyloxypropanoic acid Chemical compound OC(=O)C(C)OC(C)=O WTLNOANVTIKPEE-UHFFFAOYSA-N 0.000 description 1
- WZUUZPAYWFIBDF-UHFFFAOYSA-N 5-amino-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound NC1=NNC(S)=N1 WZUUZPAYWFIBDF-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OJRUSAPKCPIVBY-KQYNXXCUSA-N C1=NC2=C(N=C(N=C2N1[C@H]3[C@@H]([C@@H]([C@H](O3)COP(=O)(CP(=O)(O)O)O)O)O)I)N Chemical compound C1=NC2=C(N=C(N=C2N1[C@H]3[C@@H]([C@@H]([C@H](O3)COP(=O)(CP(=O)(O)O)O)O)O)I)N OJRUSAPKCPIVBY-KQYNXXCUSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 244000201986 Cassia tora Species 0.000 description 1
- 235000014552 Cassia tora Nutrition 0.000 description 1
- 240000006122 Chenopodium album Species 0.000 description 1
- 235000009344 Chenopodium album Nutrition 0.000 description 1
- 244000058871 Echinochloa crus-galli Species 0.000 description 1
- RXCPQSJAVKGONC-UHFFFAOYSA-N Flumetsulam Chemical compound N1=C2N=C(C)C=CN2N=C1S(=O)(=O)NC1=C(F)C=CC=C1F RXCPQSJAVKGONC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001101025 Lilaeopsis Species 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 244000234609 Portulaca oleracea Species 0.000 description 1
- 235000001855 Portulaca oleracea Nutrition 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940125797 compound 12 Drugs 0.000 description 1
- 229940126543 compound 14 Drugs 0.000 description 1
- 229940125758 compound 15 Drugs 0.000 description 1
- 229940126142 compound 16 Drugs 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012362 glacial acetic acid Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses a triazole pyrimidine thioacetamide compound and preparing method and application with formula as (I) or (II), which is characterized by the following: blending with carrier or diluent as herbicide. The real obtaining compound4 is N-(4'-chlorobenzene ethyl-1-radical)-2-(5, 7-dimethyl-1, 2, 4-triazole [1,5-a] pyrimidine-2-thio) acetamide, which possesses excellent weeding activity selectively.
Description
(1) technical field
The present invention relates to a kind of triazolo-pyrimido-thioacetamide compounds with and preparation method thereof and application in weedicide.
(2) background technology
Heterogeneous ring compound has been the main flow of novel pesticide development, and in heterogeneous ring compound, again based on nitrogen heterocyclic ring.The triazolo pyrimidine heterocyclic compounds is owing to contain triazole and the important active structure unit of pyrimidine two classes simultaneously in its molecular structure, thereby shown the biological activity of wide spectrum, that has now succeeded in developing has novel acetolactate synthestase (ALS) inhibitor class ultra-high efficiency weedicide DE498 (Flumetsulam), DE511 pesticide species such as (metosulams); Still very active to the composition optimizes and the bioactivity research of triazolopyrimidines in recent years.
When the contriver studies, found a kind of new triazolo-pyrimido-thioacetamide compounds in this area, found that it has selective herbicidal activity preferably, as yet not relevant for the report of this compound.
(3) summary of the invention
The objective of the invention is to seek and more have the triazolo-pyrimido-thioacetamide compounds of weeding activity preferably.
The technical solution used in the present invention is as follows:
A kind of triazolo-pyrimido-thioacetamide compounds, described compound be suc as formula (I) or (II),
In formula (I), the formula (II), described X
1, X
2, X
3Independent separately is alkyl, phenyl or the substituted-phenyl of hydrogen, C1～C4; Described R is the alkyl of C1～C4, R
1, R
2, R
3, R
4, R
5Independent separately is the alkyl of hydrogen, halogen, C1～C4 or the alkoxyl group of C1～C4, R
1, R
2, R
3, R
4, R
5In have one at least for halogen or alkoxyl group; Described halogen is chlorine, bromine or fluorine, works as R
2During for halogen, R
1, R
3, R
4, R
5Have at least one not to be hydrogen, work as R
3During for fluorine, R
1R
2, R
4, R
5Have at least one not to be hydrogen; Ar represents 2-trifluoromethyl-5-chloro-phenyl-(2-CF in the formula (I)
3-5 '-ClC
6H
3), 3, the 5-difluorophenyl (3 ', 5-F
2C
6H
3), 2-p-methoxy-phenyl (2-CH
3OC
6H
4), 2,4, the 6-trichlorophenyl (2 ', 4, ' 6 '-Cl
3C
6H
2), the 4-Phenoxyphenyl (4 '-C
6H
5OC
6H
4), 5-nitrobenzene thiazole-2-base
5,6-dichlorobenzothiazole-2-base
Deng.
Described triazolo-pyrimido-thioacetamide compounds is preferably:
Compound 1:
Compound 2:
Compound 3:
Compound 4:
Compound 5:
Compound 6:
Compound 7:
Compound 8:
Compound 9:
Compound 10:
Compound 11:
Compound 12:
Compound 13:
Compound 14:
Compound 15:
Compound 16:
What wherein have the best selective weeding activity is compound 4:N-(4 ' chlorobenzene ethyl-1-yl)-2-(5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine-2-sulfo-) ethanamide.
The present invention prepares the method for described triazolo-pyrimido-thioacetamide compounds: with suc as formula the 2-sulfydryl-5 shown in (III), 7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine with suc as formula the N-aryl chloride ethanamide shown in (IV) or with the replacement 2-sulfydryl-1 shown in formula V, 2,4-triazole [1,5-a] pyrimidine is with (chlor(o)acetamide of 1-alkyl substituted benzene methyl isophthalic acid-yl) is under the acid binding agent effect suc as formula the N-shown in (VI), in the miscible fluid of water and water-soluble organic solvent A arbitrary proportion, carrying out condensation reaction under 0～30 ℃ of condition, aftertreatment promptly gets (II) product shown in product shown in the formula (I) or the formula, the amount of substance that feeds intake is than being compound shown in the formula (III): formula (IV) compound: acid binding agent be 1: 1.0～1.3: 0.5～2.0 or formula V shown in compound: formula (VI) compound: acid binding agent is 1: 1.0～1.3: 0.5～2.0, the consumption of the miscible fluid of described water and water-soluble organic solvent A is 30～50 times of compound quality shown in compound shown in the formula (III) or the formula V, formula (IV), (V), (VI) Ar in, X
1, X
2, X
3, R
1, R
2, R
3, R
4, R
5As defined above, described acid binding agent is sodium hydroxide, potassium hydroxide, alkaline carbonate or supercarbonate, triethylamine or pyridine, preferred sodium hydroxide or yellow soda ash.
Water-soluble organic solvent A of the present invention is one of following or two or more: methyl alcohol, ethanol, dimethyl formamide, tetrahydrofuran (THF).The time of described condensation reaction is recommended as 0.5～3 hour, and the volume ratio of described water and water-soluble organic solvent A is 5: 1～25.
When described acetamides suc as formula shown in (I), preparation method: with suc as formula the 2-sulfydryl-5 shown in (III), 7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine with suc as formula the N-aryl chloride ethanamide shown in (IV) under the acid binding agent effect, in the miscible fluid of water and water-soluble organic solvent A, carry out condensation reaction at 15～20 ℃, aftertreatment promptly gets product (I), and the amount of substance that feeds intake ratio is formula (III) compound: formula (IV) compound: acid binding agent is 1: 1.0～1.1: 0.5～1.0; Described acid binding agent is sodium hydroxide or yellow soda ash.Described organic solvent A is the mixture of one of following two or more solvent arbitrary proportions: methyl alcohol, ethanol, dimethyl formamide (DMF), tetrahydrofuran (THF).
When described acetamides suc as formula shown in (II), preparation method: with the replacement 2-sulfydryl-1 shown in formula V, 2,4-triazole [1,5-a] pyrimidine is with (chlor(o)acetamide of 1-alkyl substituted benzene methyl isophthalic acid-yl) is under the acid binding agent effect suc as formula the N-shown in (VI), in the miscible fluid of water and water-soluble organic solvent A, carry out condensation reaction at 15～20 ℃, aftertreatment promptly gets formula (II) compound, described formula V: formula (VI): the amount of substance ratio that feeds intake of acid binding agent is 1: 1.0～1.1: 0.5～1.0; Described acid binding agent is sodium hydroxide or yellow soda ash.Described organic solvent A is the mixture of one of following two or more solvent arbitrary proportions: methyl alcohol, ethanol, dimethyl formamide (DMF), tetrahydrofuran (THF).
The present invention recommends the preparation method of described triazolo-pyrimido-thioacetamide compounds, compound can prepare by laxative remedy shown in described formula (III) or the formula V: 5-amino-3-sulfydryl-1,2,4-triazole and beta-dicarbonyl compound back flow reaction 4～20 hours in organic solvent B, the amount of substance that feeds intake is than being 5-amino-3-sulfydryl-1,2, the 4-triazole: beta-dicarbonyl compound is 1: 1.0～2.0, described organic solvent B is methyl alcohol, ethanol, glacial acetic acid or acetonitrile, consumption is 5-amino-3-sulfydryl-1,2,30～50 times of 4-triazole quality.
The present invention recommends the preparation method of described triazolo-pyrimido-thioacetamide compounds, described formula (IV) or formula (VI) compound can prepare by laxative remedy: substituted aromatic amines or alpha substituted benzylamine and chloroacetyl chloride react 0.5h～3h in 0 ℃～30 ℃ under the acid binding agent effect in organic solvent C, and the amount of substance that feeds intake is than being substituted aromatic amines/alpha substituted benzylamine: chloroacetyl chloride: acid binding agent is 1: 1.0～1.2: 1.0～2.0; Described organic solvent C is DMF or toluene, and consumption is 10～30 times of amine quality, and described acid binding agent is triethylamine or pyridine.
Triazolo-pyrimido-thioacetamide compounds has good application as weedicide.
When compound of the present invention uses as weedicide, can be with carrier or the mixing diluents that allows in compound of the present invention and other plant protection, whereby with the normally used various formulations of its furnishing, wait as pulvis, granule or aqueous emulsion and to use.
Also can mix and use or also use simultaneously with other weedicide.
The present invention compared with prior art, its beneficial effect is embodied in:
Described part triazolo-pyrimido-thioacetamide compounds is given birth to survey portion by country southern agricultural chemicals initiative base, Zhejiang, center and is carried out the weeding activity test.Test result shows, under 37.5gai/ha～150gai/ha effective dose, part Gramineae and broadleaf weeds are shown weeding activity efficiently, useful as herbicides, the compound 4:N-that the embodiment of the invention 4 makes (4 ' chlorobenzene ethyl-1-yl)-2-(5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine-2-sulfo-) ethanamide has extraordinary selective herbicidal activity, and broadleaf weeds is had higher weeding activity.
(4) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Synthesizing of embodiment 1N-(2-trifluoromethyl-5-chloro-phenyl-)-2-(5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine-2-sulfo-) ethanamide
In the 50mL there-necked flask, add 0.72g (0.004mol) 2-sulfydryl-5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine, 0.16g (0.004mol) sodium hydroxide, 20mL water, magnetic agitation dissolving, at room temperature splash into (0.004mol) 2-chloro-N-(2-trifluoromethyl-5-chloro-phenyl-) ethanamide the 5mL aqueous ethanolic solution (water: ethanol=1: 4, V/V), approximately 0.5h drips off, the adularescent solid generates, and stirs 0.5h behind the adding 10mL water, and suction filtration gets pale solid, respectively with 3% aqueous hydrochloric acid and the washing of 5% sodium bicarbonate aqueous solution, wash with water more for several times,, get white needles solid chemical compound 1 with ethanol-sherwood oil recrystallization, yield 85.0%, 187 ℃～189 ℃ of fusing points.
1(interior mark TMS, solvent are CDCl to H NMR
3): δ ppm
2.65(s，3H，5-CH
3)，2.74(s，3H，7-CH
3)，4.09(s，2H，SCH
2)，6.80(s，1H，6-H)，7.48～8.05(m，3H，C
6H
3)，9.42(s，1H，NH)
IR(V
(HNC＝0)/cm
-1)：3060，1678
MS(m/e)：[M
+]415
Synthesizing of embodiment 2N-(3, the 5-difluorophenyl)-2-(5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine-2-sulfo-) ethanamide
In the 100mL there-necked flask, add 0.72g (0.004mol) 2-sulfydryl-5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine, 0.40g (0.004mol) triethylamine, 20mL water, the magnetic agitation dissolving at room temperature splashes into (0.004mol) 2-chloro-N-(3, the 5-difluorophenyl) the 12mL methanol aqueous solution of ethanamide, (water: methyl alcohol=1: 5, v/v) approximately 0.5h drips off, and the adularescent solid generates, stir 0.5h after adding 20mL water, suction filtration gets white solid, with 3% aqueous hydrochloric acid and the washing of 5% sodium bicarbonate aqueous solution, washes with water more for several times respectively, with ethanol-sherwood oil recrystallization, get white needle-like crystals compound 2, yield 88.2%, 183 ℃～185 ℃ of fusing points.
1(interior mark TMS, solvent are CDCl to H NMR
3): δ ppm
2.71(s，3H，5-CH
3)，2.77(s，3H，7-CH
3)，3.94(s，2H，SCH
2)，6.87(s，1H，6-H)，6.48～7.20(m，3H，C
6H
3)，10.49(s，1H，NH)
IR(V
(HNC＝0)/cm
-1)：3063，1688
MS(m/e)：[M
+]349
Synthesizing of embodiment 3N-(2-p-methoxy-phenyl)-2-(5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine-2-sulfo-) ethanamide
In the 50mL there-necked flask, add 0.72g (0.004mol) 2-sulfydryl-5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine, 0.21g (0.002mol) yellow soda ash, 20mL water, magnetic agitation dissolving, at room temperature splash into (0.004mol) 2-chloro-N-(2-p-methoxy-phenyl) ethanamide the 5mLDMF aqueous solution (water: DMF=1: 4, v/v), approximately 0.5h drips off, the adularescent solid generates, and stirs 0.5h behind the adding 10mL water, and suction filtration gets white solid, respectively with 3% aqueous hydrochloric acid and the washing of 5% sodium bicarbonate aqueous solution, wash with water more for several times,, get white needle-like crystals compound 3 with ethanol-sherwood oil recrystallization, yield 90.5%, 189 ℃～191 ℃ of fusing points.
1(interior mark TMS, solvent are CDCl to H NMR
3): δ ppm
2.67(s，3H，5-CH
3)，2.74(s，3H，7-CH
3)，3.80(s，3H，OCH
3)，4.08(s，2H，SCH
2)，6.79(s，1H，6-H)，6.81～7.01(m，3H，C
6H
3)，8.38～8.40(d，1H，3-C
6H
3)，9.72(s，1H，NH)
IR(V
(HNC＝0)/cm
-1)：2921，1685
MS(m/e)：[M
+]343
Embodiment 4N-(4 ' chlorobenzene ethyl-1-yl)-2-(5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine-2-sulfo-) ethanamide synthetic
In the 50mL there-necked flask, add 0.72g (0.004mol) 2-sulfydryl-5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine, 0.16g (0.004mol) sodium hydroxide, 20mL water, magnetic agitation dissolving, at room temperature splash into (0.004mol) 2-chloro-N-(4 ' chlorobenzene ethyl-1-yl) ethanamide the 5mLDMF aqueous solution (water: DMF=1: 4, v/v), approximately 0.5h drips off, the adularescent solid generates, and stirs 0.5h behind the adding 10mL water, and suction filtration gets white solid, respectively with 3% aqueous hydrochloric acid and the washing of 5% sodium bicarbonate aqueous solution, wash with water more for several times,, get white needle-like crystals compound 4 with ethanol-sherwood oil recrystallization, yield 92.8%, 154 ℃～155 ℃ of fusing points.
1(interior mark TMS, solvent are CDCl to H NMR
3): δ ppm
1.41～1.42(d，3H，C-CH
3)，2.65(s，3H，5-CH
3)，2.67(s，3H，7-CH
3)，3.79～3.91(m，2H，SCH
2)，5.01～5.05(m，1H，-CH)，6.79(s，1H，6-H)，
7.07～7.13(m，4H，C
6H
4)，7.78～7.79(d，1H，NH)
IR(V
(HNC＝0)/cm
-1)：3069，1644
MS(m/e)：[M
+]375
Synthesizing of embodiment 5N-(5-nitrobenzene thiazole-2-yl)-2-(5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine-2-sulfo-) ethanamide
In the 50mL there-necked flask, add 0.72g (0.004mol) 2-sulfydryl-5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine, 0.28g (0.002mol) salt of wormwood, 20mL water, the magnetic agitation dissolving, at room temperature splash into the 5mLDMF of (0.004mol) 2-chloro-N-(5-nitrobenzene thiazole-2-yl) ethanamide the aqueous solution (water: DMF=1: 4, v/v), approximately 0.5h drips off, the adularescent solid generates, stir 0.5h after adding 10mL water, suction filtration gets white solid, respectively with 3% aqueous hydrochloric acid and the washing of 5% sodium bicarbonate aqueous solution, wash with water more for several times, get white crystal compound 5, yield 94.5%, 243 ℃～245 ℃ of fusing points.
1(interior mark TMS, solvent are DMSO-d to H NMR
6): δ ppm
2.52(s，3H，5-CH
3)，2.62(s，3H，7-CH
3)，
4.43(s，2H，SCH
2)，7.10(s，1H，6-H)，
7.92～7.94(d，1H，4-H)，8.28～8.30(d，1H，5-H)，9.05(s，1H，7-H)，13.17(s，1H，NH)
IR(V
(HNC＝0)/cm
-1)：2924，1704
MS(m/e)：[M
+]415
Synthesizing of embodiment 6N-(5,6-dichlorobenzothiazole-2-yl)-2-(5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine-2-sulfo-) ethanamide
In the 50mL there-necked flask, add 0.72g (0.004mol) 2-sulfydryl-5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine, 0.48g (0.006mol) pyridine, 20mL water, magnetic agitation is dissolved, and at room temperature splashes into the aqueous solution (water: DMF=1: 4 of the 5mL DMF of (0.004mol) 2-chloro-N-(5,6-dichlorobenzothiazole-2-yl) ethanamide, v/v), approximately 0.5h drips off, and the adularescent solid generates, and stirs 0.5h behind the adding 10mL water, suction filtration gets white solid, with 3% aqueous hydrochloric acid and the washing of 5% sodium bicarbonate aqueous solution, wash with water more for several times respectively, get white crystal compound 6, yield 86.5%, 192 ℃～194 ℃ of fusing points.
1(interior mark TMS, solvent are DMSO-d to H NMR
6): δ ppm
2.53(s，3H，5-CH
3)，2.62(s，3H，7-CH
3)，4.40(s，2H，SCH
2)，7.10(s，1H，6-H)，8.05～8.34(d，2H，4、7-H)，13.01(s，1H，NH)
IR(V
(HNC＝0)/cm
-1)：2924，1699
MS(m/e)：[M
+]439
Synthesizing of embodiment 7N-(2,4, the 6-trichlorophenyl)-2-(5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine-2-sulfo-) ethanamide
In the 50mL there-necked flask, add 0.72g (0.004mol) 2-sulfydryl-5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine, 0.40g (0.004mol) saleratus, 20mL water, the magnetic agitation dissolving at room temperature splashes into (0.004mol) 2-chloro-N-(2,4, the 6-trichlorophenyl) the 5mL tetrahydrofuran aqueous solution of ethanamide (water: tetrahydrofuran (THF)=1: 4, v/v), approximately 0.5h drips off, the adularescent solid generates, stir 0.5h after adding 10mL water, suction filtration gets white solid, respectively with 3% aqueous hydrochloric acid and the washing of 5% sodium bicarbonate aqueous solution, wash with water more for several times, get white crystal compound 7, yield 90.2%, 233 ℃～234 ℃ of fusing points.
1(interior mark TMS, solvent are CDC l to H NMR
3): δ ppm
2.66(s，3H，5-CH
3)，2.77(s，3H，7-CH
3)，4.06(s，2H，SCH
2)，6.83(，1H，6-H)，7.33(s，2H，C
6H
2)，9.63(s，1H，NH)
IR(V
(HNC＝0)/cm
-1)：3064，1689
MS(m/e)：[M
+]416
Synthesizing of embodiment 8N-(4-Phenoxyphenyl)-2-(5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine-2-sulfo-) ethanamide
In the 50mL there-necked flask, add 0.72g (0.004mol) 2-sulfydryl-5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine, 0.33g (0.004mol) sodium bicarbonate, 20mL water, the magnetic agitation dissolving, at room temperature splash into the 5mL DMF of (0.004mol) 2-chloro-N-(4-Phenoxyphenyl) ethanamide the aqueous solution (water: DMF=1: 4, v/v), approximately 0.5h drips off, the adularescent solid generates, stir 0.5h after adding 10mL water, suction filtration gets white solid, respectively with 3% aqueous hydrochloric acid and the washing of 5% sodium bicarbonate aqueous solution, wash with water more for several times, get white crystal compound 8, yield 95.0%, 233 ℃～234 ℃ of fusing points.
1(interior mark TMS, solvent are CDCl to H NMR
3): δ ppm
2.68(s，3H，5-CH
3)，2.76(s，3H，7-CH
3)，3.98(s，2H，SCH
2)，6.83(s，1H，6-H)，6.94～7.54(m，9H，-C
6H
40C
6H
3)，9.96(s，1H，NH)
IR(V
(HNC＝0)/cm
-1)：3050，1655
MS(m/e)：[M
+]405
Synthesizing of embodiment 9N-(4-Phenoxyphenyl)-2-(5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine-2-sulfo-) ethanamide
In the 50mL there-necked flask, add 0.72g (0.004mol) 2-sulfydryl-5,7-dimethyl-1,2,4-triazole [1,5-a] pyrimidine, 0.66g (0.008mol) sodium bicarbonate, 20mL water, the magnetic agitation dissolving, at room temperature splash into the 5mL DMF of (0.0052mol) 2-chloro-N-(4-Phenoxyphenyl) ethanamide the aqueous solution (water: DMF=5: 1, v/v), approximately 0.5h drips off, the adularescent solid generates, stir 0.5h after adding 10mL water, suction filtration gets white solid, respectively with 3% aqueous hydrochloric acid and the washing of 5% sodium bicarbonate aqueous solution, wash with water more for several times, get white crystal compound 8, yield 45.0%, 233 ℃～234 ℃ of fusing points.
1(interior mark TMS, solvent are CDCl to H NMR
3): δ ppm
2.68(s，3H，5-CH
3)，2.76(s，3H，7-CH
3)，3.98(s，2H，SCH
2)，6.83(s，1H，6-H)，6.94～7.54(m，9H，-C
6H
40C
6H
3)，9.96(s，1H，NH)
IR(V
(HNC＝0)/cm
-1)：3050，1655
MS(m/e)：[M
+]405
Adopt above-mentioned similar approach can prepare other compound equally.Compound 1～16 is institute of the present invention synthetic part of compounds.
The test of embodiment 10 weeding activity
At effective dose 75gai/ha, formulation is a 5%DMF solution, adopts the greenhouse pot culture spray method, under the single dose 6 kinds of weeds targets are carried out bud before, spraying is handled behind the bud, the target weeds are 3 kinds of gramineous weedss: barnyard grass grass, lady's-grass, Herba Setariae Viridis; Three kinds of broadleaf weedss: leaf mustard, Amaranthus retroflexus, lamb's-quarters.The bud aftertreatment time: 2～2.5 leaf phases of gramineous weeds, broadleaf weeds is a leaf period; Every processing was established once and was repeated at 10～12h after planting the bud pre-treatment time, and other establishes blank.5,10,20,25d observation at interval plant reflection symptom, the comprehensive weeding activity of appearance method evaluation, judgement criteria sees Table 1, the weeding activity test result sees Table 2.Activity has been carried out further screening, 6 kinds of broadleaf weedss after choosing 4 pairs of 6 kinds of broadleaf weeds buds of compound especially: leaf mustard, Cassia tora, sweet wine intestines, Amaranthus retroflexus, grasswort, purslane, and effective dose 37.5gai/ha, method is the same, the results are shown in Table 3.
Table 1 greenhouse pot culture weeding activity judgement criteria
The general sieve test of table 2 weeding activity % data
Table 3 compound 4 primary dcreening operations test weeding activity % data
By top test as can be seen, there is certain activity formula of the present invention (I), (II) compound (1)～(8) to gramineous weeds, and broadleaf weeds is had very high activity, can be used as weedicide and use.It is to be noted that especially compound (4) is to the selective weeding activity of broadleaf weeds.
Claims (2)
1. triazolo-pyrimido-thioacetamide compounds is characterized in that described compound is a compound 4:
2. a triazolo-pyrimido-thioacetamide compounds as claimed in claim 1 is as the application of broadleaf weed herbicide.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4983772A (en) * | 1983-11-14 | 1991-01-08 | The Dow Chemical Company | 2,6-disubstituted anilines |
| CN1331080A (en) * | 2000-06-22 | 2002-01-16 | 华中师范大学 | Syntehsis and activity of triazolo-pyrimido-thioacetyl hydrazone compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4983772A (en) * | 1983-11-14 | 1991-01-08 | The Dow Chemical Company | 2,6-disubstituted anilines |
| CN1331080A (en) * | 2000-06-22 | 2002-01-16 | 华中师范大学 | Syntehsis and activity of triazolo-pyrimido-thioacetyl hydrazone compounds |
Non-Patent Citations (1)
| Title |
|---|
| 新型三唑并嘧啶类衍生物的合成及生物活性（I）. 徐莉等.华中师范大学学报（自然科学版），第34卷第1期. 2000 * |
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