CN112574128B - Quinazoline diketone compound, preparation method and application thereof, and herbicide - Google Patents
Quinazoline diketone compound, preparation method and application thereof, and herbicide Download PDFInfo
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- CN112574128B CN112574128B CN201910935457.4A CN201910935457A CN112574128B CN 112574128 B CN112574128 B CN 112574128B CN 201910935457 A CN201910935457 A CN 201910935457A CN 112574128 B CN112574128 B CN 112574128B
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- herbicide
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- 239000004009 herbicide Substances 0.000 title claims abstract description 43
- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 37
- -1 Quinazoline diketone compound Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 241000196324 Embryophyta Species 0.000 claims abstract description 65
- 235000021307 Triticum Nutrition 0.000 claims abstract description 24
- 244000105624 Arachis hypogaea Species 0.000 claims abstract description 17
- 235000020232 peanut Nutrition 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims description 107
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 125000000217 alkyl group Chemical group 0.000 claims description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 125000005843 halogen group Chemical group 0.000 claims description 15
- 125000000304 alkynyl group Chemical group 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 125000003342 alkenyl group Chemical group 0.000 claims description 11
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 10
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 10
- 235000018262 Arachis monticola Nutrition 0.000 claims description 10
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 10
- 150000008515 quinazolinediones Chemical class 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000004480 active ingredient Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical group 0.000 claims description 7
- 125000001174 sulfone group Chemical group 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 6
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 241001573870 Alopecurus japonicus Species 0.000 claims description 5
- 229940125782 compound 2 Drugs 0.000 claims description 5
- 229940126214 compound 3 Drugs 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 5
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 4
- 125000004455 (C1-C3) alkylthio group Chemical group 0.000 claims description 4
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 claims description 4
- 241000219144 Abutilon Species 0.000 claims description 4
- 241000209200 Bromus Species 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000006462 rearrangement reaction Methods 0.000 claims description 4
- 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 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000005658 halogenation reaction Methods 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 3
- UAOUIVVJBYDFKD-XKCDOFEDSA-N (1R,9R,10S,11R,12R,15S,18S,21R)-10,11,21-trihydroxy-8,8-dimethyl-14-methylidene-4-(prop-2-enylamino)-20-oxa-5-thia-3-azahexacyclo[9.7.2.112,15.01,9.02,6.012,18]henicosa-2(6),3-dien-13-one Chemical compound C([C@@H]1[C@@H](O)[C@@]23C(C1=C)=O)C[C@H]2[C@]12C(N=C(NCC=C)S4)=C4CC(C)(C)[C@H]1[C@H](O)[C@]3(O)OC2 UAOUIVVJBYDFKD-XKCDOFEDSA-N 0.000 claims description 2
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 claims description 2
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 claims 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 claims description 2
- 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 claims description 2
- WWTBZEKOSBFBEM-SPWPXUSOSA-N (2s)-2-[[2-benzyl-3-[hydroxy-[(1r)-2-phenyl-1-(phenylmethoxycarbonylamino)ethyl]phosphoryl]propanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound N([C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)O)C(=O)C(CP(O)(=O)[C@H](CC=1C=CC=CC=1)NC(=O)OCC=1C=CC=CC=1)CC1=CC=CC=C1 WWTBZEKOSBFBEM-SPWPXUSOSA-N 0.000 claims description 2
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 claims description 2
- 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 claims description 2
- 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 claims description 2
- YSUIQYOGTINQIN-UZFYAQMZSA-N 2-amino-9-[(1S,6R,8R,9S,10R,15R,17R,18R)-8-(6-aminopurin-9-yl)-9,18-difluoro-3,12-dihydroxy-3,12-bis(sulfanylidene)-2,4,7,11,13,16-hexaoxa-3lambda5,12lambda5-diphosphatricyclo[13.2.1.06,10]octadecan-17-yl]-1H-purin-6-one Chemical compound NC1=NC2=C(N=CN2[C@@H]2O[C@@H]3COP(S)(=O)O[C@@H]4[C@@H](COP(S)(=O)O[C@@H]2[C@@H]3F)O[C@H]([C@H]4F)N2C=NC3=C2N=CN=C3N)C(=O)N1 YSUIQYOGTINQIN-UZFYAQMZSA-N 0.000 claims description 2
- TVTJUIAKQFIXCE-HUKYDQBMSA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynyl-1H-purine-6,8-dione Chemical compound NC=1NC(C=2N(C(N(C=2N=1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C)=O TVTJUIAKQFIXCE-HUKYDQBMSA-N 0.000 claims description 2
- QBWKPGNFQQJGFY-QLFBSQMISA-N 3-[(1r)-1-[(2r,6s)-2,6-dimethylmorpholin-4-yl]ethyl]-n-[6-methyl-3-(1h-pyrazol-4-yl)imidazo[1,2-a]pyrazin-8-yl]-1,2-thiazol-5-amine Chemical compound N1([C@H](C)C2=NSC(NC=3C4=NC=C(N4C=C(C)N=3)C3=CNN=C3)=C2)C[C@H](C)O[C@H](C)C1 QBWKPGNFQQJGFY-QLFBSQMISA-N 0.000 claims description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 2
- 229940126657 Compound 17 Drugs 0.000 claims description 2
- 240000005702 Galium aparine Species 0.000 claims description 2
- 235000014820 Galium aparine Nutrition 0.000 claims description 2
- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 claims description 2
- 240000005592 Veronica officinalis Species 0.000 claims description 2
- LJOOWESTVASNOG-UFJKPHDISA-N [(1s,3r,4ar,7s,8s,8as)-3-hydroxy-8-[2-[(4r)-4-hydroxy-6-oxooxan-2-yl]ethyl]-7-methyl-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1-yl] (2s)-2-methylbutanoate Chemical compound C([C@H]1[C@@H](C)C=C[C@H]2C[C@@H](O)C[C@@H]([C@H]12)OC(=O)[C@@H](C)CC)CC1C[C@@H](O)CC(=O)O1 LJOOWESTVASNOG-UFJKPHDISA-N 0.000 claims description 2
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
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- KGNDCEVUMONOKF-UGPLYTSKSA-N benzyl n-[(2r)-1-[(2s,4r)-2-[[(2s)-6-amino-1-(1,3-benzoxazol-2-yl)-1,1-dihydroxyhexan-2-yl]carbamoyl]-4-[(4-methylphenyl)methoxy]pyrrolidin-1-yl]-1-oxo-4-phenylbutan-2-yl]carbamate Chemical compound C1=CC(C)=CC=C1CO[C@H]1CN(C(=O)[C@@H](CCC=2C=CC=CC=2)NC(=O)OCC=2C=CC=CC=2)[C@H](C(=O)N[C@@H](CCCCN)C(O)(O)C=2OC3=CC=CC=C3N=2)C1 KGNDCEVUMONOKF-UGPLYTSKSA-N 0.000 claims description 2
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- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
- C07D239/72—Quinazolines; Hydrogenated quinazolines
- C07D239/95—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in positions 2 and 4
- C07D239/96—Two oxygen atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention relates to the field of pesticide herbicides, and discloses a quinazoline diketone compound, a preparation method and application thereof, and a herbicide. The quinazoline diketone compound provided by the invention can be used as an HPPD herbicide for preventing and removing gramineous weeds, and has good control effect on various gramineous weeds and part of broadleaf weeds which harm the growth of wheat and/or peanuts.
Description
Technical Field
The invention relates to the field of pesticide herbicides, and in particular relates to a quinazoline diketone compound, a preparation method and application thereof, and a herbicide containing the quinazoline diketone compound.
Background
The explosive growth of weed drug resistance has become a key challenge for the sustainable development of modern agriculture, and the creation of novel ultra-high-efficiency herbicides is a fundamental way to solve the challenge.
At present, more than 40 kinds of resistant weeds are officially reported in China, and the resistant weeds are one of five countries with the most serious harm to the resistant weeds in the world. Particularly, in several important crop fields in China, the problem of weed drug resistance has shown a more and more serious trend. For example, resistant populations of main weeds such as descurainia sophia, shepherd's purse, alopecurus japonicus, brome, jieji wheat, wild oat and the like in wheat fields have been developed into dominant weeds, so that the herbicide dosage of wheat fields in part of provincial and urban areas is continuously increased, the prevention and treatment cost is increased, and the occurrence of phytotoxicity events and the standard exceeding of pesticide residues are caused.
Therefore, under the large background that 'reduction synergism and green development' are vigorously advocated in the current country, the ultra-high-efficiency herbicide with a novel action mechanism is created to replace the traditional herbicide, and the herbicide is a fundamental way for preventing and treating resistant weeds and realizing reduction synergism and green development.
Herbicides targeting p-hydroxyphenylpyruvate dioxygenase (HPPD) are widely used due to their high efficacy, low toxicity, environmental friendliness and low risk of resistance.
Up to now, as many as tens of herbicides have been developed successfully targeting HPPDs, roughly classified into three major groups by structural classification: 1. triketones represented by Mesotrione (Mesotrione); 2. pyrazoles represented by Topramezone; 3. isoxazoles represented by isoxachlorotole (Isoxachlortole).
Through the research of pesticide market sales, the time of the HPPD inhibiting herbicide entering the market is later than that of AHAS-, PPO-and ACCase-inhibiting herbicides, but does not hinder the rapid occupation of the market by the star molecule, especially the triketone herbicide mesotrione (also known as mesotrione) developed by the Prondoda company continuously occupies the first five years of the herbicide sales. Mesotrione has gradually replaced other types of herbicides in corn fields with high numbers of resistant weeds as the most widely and most effective herbicide in corn fields.
However, mesotrione still has some inherent disadvantages, such as poor safety to other bulk crops and commercial crops, such as wheat, rice, peanut, soybean, rape and the like, poor control effect of mesotrione to various grassy weeds (such as common weeds, green bristlegrass, green-turning phenomenon and the like) and reports in literature that the weeds are easy to turn green after the mesotrione is used. The bicyclopyrone created by Qingyuan agricultural crown company is the first wheat field HPPD herbicide in China (as disclosed in CN 105218449A), can effectively prevent and kill gramineous weeds and part of broadleaf weeds such as resistant and multi-resistant alopecurus maiden, alopecurus japonicus and the like, and provides more choices for the use of the herbicide in wheat fields. However, the bicyclopyrone is not ideal for preventing various gramineous weeds which harm the growth of wheat, such as brome, wild oat, arthroncus and the like. In addition, the specific structure of the bicyclopyrone is as follows:
in view of the fact that no HPPD herbicide which has broad-spectrum and ultra-high-efficiency weeding activity and is used for wheat fields exists in the agricultural production practice of China, particularly a herbicide which has excellent control effect on various gramineous weeds which harm the growth of wheat, such as brome, wild oat, arthroncus, and the like. In addition, for economic crops of peanuts, currently, the HPPD inhibiting herbicides which can be used for controlling grassy weeds such as barnyard grass, crab grass and green bristlegrass in peanut fields are still lacking. Therefore, the novel super-efficient HPPD herbicide safe to wheat and peanuts is created to meet the practical requirements in agricultural production in China, and has very important significance.
Disclosure of Invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and to provide an HPPD herbicide which can be used on wheat and/or peanut crops.
The invention also aims to provide the quinazoline diketone compound with good control effect on various gramineous weeds and part of broadleaf weeds which harm the growth of wheat and/or peanuts, such as barnyard grass, crab grass, green bristlegrass, brome, wild oat, arthroncus, and the like.
In order to achieve the above object, a first aspect of the present invention provides a quinazolinedione compound having a structure represented by formula (I),
wherein, in the formula (I),
R 1 is n-propyl or cyclopentyl;
R 2 selected from H, C 1-6 Alkyl of (2), C substituted by 1 to 6 halogen atoms 1-3 Alkyl of (C) 2-6 Alkynyl of (a), C substituted by trimethylsilyl 5-8 Alkynyl of (A), C 2-6 Alkenyl of (a), C substituted by 1 to 6 halogen atoms 2-6 Alkenyl of (a);
x is selected from hydroxyl, halogen and C 1-3 Alkylthio, phenylthio, C 1-3 Alkyl sulfone group, phenyl sulfone group;
R 3 、R 4 、R 5 、R 6 and R 7 Each independently selected from H and C 1-3 Alkyl group of (1).
The inventor of the invention discovers in research that the quinazoline diketone compound with the general structure shown in the formula (I) has high crop safety and has better control effect on various gramineous weeds and part of broadleaf weeds which harm wheat and/or peanut growth, such as brome, wild oat, arthroncus, and the like, compared with the compounds in the prior art.
A second aspect of the present invention provides a method for producing the aforementioned quinazolinedione compounds, which comprises:
(1) reacting the compound with the structure shown in the formula (II-1) with thionyl chloride and the compound with the structure shown in the formula (II-2) in sequence to obtain the compound with the structure shown in the formula (II-3);
(2) under the rearrangement reaction condition, the compound with the structure shown in the formula (II-3) is contacted with a catalyst in the presence of alkali and a solvent to obtain a compound with the structure shown in the formula (II-4);
optionally, the method further comprises 1,2 or 3 of the following steps in sequence:
(a) carrying out halogenation reaction on the compound with the structure shown in the formula (II-4) to obtain a compound with the structure shown in the formula (II-5);
(b) reacting the compound with the structure shown in the formula (II-5) with sodium mercaptide with the structure shown in the formula (II-6) to obtain a compound with the structure shown in the formula (II-7);
(c) carrying out oxidation reaction on the compound with the structure shown in the formula (II-7) in the presence of peroxide with the structure shown in the formula (II-8) to obtain the compound with the structure shown in the formula (II-9);
wherein,
x in the Compound having the Structure represented by the formula (II-5) 1 Is halogen;
x in the compound of the formula (II-6), the compound of the formula (II-7) and the compound of the formula (II-9) 2 Is selected from C 1-3 Alkyl, phenyl of (a);
further, the remaining substituents referred to in the formula (II-1), the formula (II-2), the formula (II-3), the formula (II-4), the formula (II-5), the formula (II-7) and the formula (II-9) correspond to the same substituents as those of the aforementioned compounds of the present invention.
The third aspect of the invention provides the application of the quinazoline diketone compound in the first aspect in weed control.
In a fourth aspect, the present invention provides a herbicide, which comprises an active ingredient and an adjuvant, wherein the active ingredient comprises at least one of the quinazolinedione compounds according to the first aspect of the present invention.
The quinazoline diketone compound provided by the invention can be used as an HPPD herbicide for wheat and/or peanut crops, and has good control effect on various gramineous weeds and part of broadleaf weeds which harm the growth of wheat and/or peanut such as barnyard grass, crab grass, green bristlegrass, bromus, wild oat, arthroncus and the like, and has high safety on crops.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As mentioned above, the first aspect of the present invention provides a quinazoline diketone compound having a structure represented by the formula (I),
wherein, in the formula (I),
R 1 is n-propyl or cyclopentyl;
R 2 selected from H, C 1-6 Alkyl of (2), C substituted by 1 to 6 halogen atoms 1-3 Alkyl of (C) 2-6 Alkynyl of (a), C substituted by trimethylsilyl 5-8 Alkynyl of (A), C 2-6 Alkenyl of (a), C substituted by 1 to 6 halogen atoms 2-6 Alkenyl of (a);
x is selected from hydroxyl, halogen and C 1-3 Alkylthio, phenylthio, C 1-3 Alkyl sulfone group, phenyl sulfone group;
R 3 、R 4 、R 5 、R 6 and R 7 Each independently selected from H and C 1-3 The alkyl group of (1).
“C 1-6 The "alkyl group" of (b) represents an alkyl group having a total number of carbon atoms of 1 to 6, including straight-chain alkyl groups, branched-chain alkyl groups and cyclic alkyl groups, for example, straight-chain alkyl groups, branched-chain alkyl groups and cyclic alkyl groups which may be 1,2, 3, 4, 5 or 6 in total carbon atoms, and may be, for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl and the like.
“C 1-3 The alkyl group of (1) represents an alkyl group having 1 to 3 carbon atoms in total, and includes a straight-chain alkyl group, a branched-chain alkyl group and a cyclic alkyl group, and may be, for example, a straight-chain alkyl group, a branched-chain alkyl group and a cyclic alkyl group having 1,2 or 3 carbon atoms in total, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group or a cyclopropyl group.
"C substituted by 1 to 6 halogen atoms 1-3 The alkyl group of (A) represents a carbon atomAlkyl groups having a total number of 1 to 3, including straight-chain alkyl, branched-chain alkyl and cyclic alkyl groups, for example straight-chain alkyl, branched-chain alkyl and cyclic alkyl groups which may have a total number of carbon atoms of 1,2 or 3, and 1 to 6H's on the alkyl group being substituted with a halogen atom, for example 1,2, 3, 4, 5 or 6H's may be substituted with at least one halogen atom selected from fluorine, chlorine, bromine, iodine.
“C 2-6 The alkynyl group "of (a) represents an alkynyl group having 2 to 6 carbon atoms in total, and may be, for example, an ethynyl group, propynyl group, butynyl group or the like.
"C substituted by trimethylsilyl 5-8 The alkynyl group of (a) represents an alkynyl group having 5 to 8 carbon atoms in total, and at least one H of the alkynyl group is substituted with a trimethylsilyl group.
“C 2-6 The alkenyl group of (1) represents an alkenyl group having 2 to 6 carbon atoms in total, and may be, for example, an ethenyl group, a propenyl group, a butenyl group, or the like. "C substituted by 1 to 6 halogen atoms 2-6 Definition of "alkenyl" of (1) and "C 2-6 The definition of "alkenyl" is similar except that "C substituted by 1 to 6 halogen atoms 2-6 The alkenyl group "in (1) to (6) is substituted with a halogen atom, and for example, 1,2, 3, 4, 5 or 6 of the hydrogens may be substituted with at least one halogen atom selected from fluorine, chlorine, bromine and iodine.
“C 1-3 By alkylthio is meant a sulfur atom having one end attached to the parent nucleus and the other end attached to C 1-3 Alkyl group of (1). "Phenylthio" means a sulfur atom attached at one end to the parent nucleus and at the other end to a phenyl group. "C 1-3 The "alkyl sulfone group" represents a sulfone group respectively bonded to the parent nucleus and C 1-3 To an alkyl group of (a). "phenylsulfonyl" means a sulfone group attached to the parent nucleus and phenyl group, respectively.
According to a preferred embodiment, in formula (I),
R 1 is n-propyl or cyclopentyl;
R 2 selected from H, C 1-3 Alkyl of (2), C substituted by 1 to 3 halogen atoms 1-3 Alkyl of (C) 3-6 Alkynyl of (a), C substituted by trimethylsilyl 6-8 Alkynyl of (A), C 3-6 Alkenyl of (a), C substituted by 1 to 3 halogen atoms 3-6 Alkenyl of (a);
x is selected from hydroxyl, halogen and C 1-3 Alkylthio, phenylthio, C 1-3 Alkyl sulfone group, phenyl sulfone group;
R 3 、R 4 、R 5 、R 6 each independently selected from H and C 1-3 Alkyl groups of (a);
R 7 is H.
According to another preferred embodiment, in formula (I),
R 1 is n-propyl or cyclopentyl;
R 2 selected from H, methyl, ethyl, monofluoromethyl, difluoromethyl, monofluoroethyl, difluoroethyl, trifluoromethyl, trifluoroethyl,
X is selected from-OH, -F, -Cl, -Br, CH 3 -S-、CH 3 CH 2 -S-、CH 3 CH 2 CH 2 -S-、
R 3 、R 4 、R 5 、R 6 Each is independently selected from H, methyl, ethyl, n-propyl, and isopropyl;
R 7 is H.
According to a particularly preferred embodiment, the compound of formula (I) is selected from at least one of the following:
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:
compound 17:
compound 18:
compound 19:
compound 20:
compound 21:
compound 22:
compound 23:
compound 24:
compound 25:
compound 26:
compound 27:
compound 28:
compound 29:
compound 30:
the quinazoline diketone compound provided by the invention can be used as an HPPD herbicide for crops such as wheat and/or peanuts, has good control effect on various gramineous weeds and part of broadleaf weeds which are harmful to the growth of crops such as barnyard grass, crab grass, green bristlegrass, bromus, wild oat and arthroncus, and has excellent crop safety for wheat and peanuts.
The invention is not particularly limited to the specific method for obtaining the above quinazoline dione compound, and those skilled in the art can obtain a suitable method for preparing the quinazoline dione compound by combining the synthetic method in the field of organic synthesis according to the specific structure of the quinazoline dione compound provided by the invention.
However, in order to increase the yield of the quinazolinedione compounds obtained, as described above, the second aspect of the present invention provides a method for preparing the quinazolinedione compounds of the first aspect, the method comprising:
(1) reacting the compound with the structure shown in the formula (II-1) with thionyl chloride and the compound with the structure shown in the formula (II-2) in sequence to obtain the compound with the structure shown in the formula (II-3);
(2) under the rearrangement reaction condition, the compound with the structure shown in the formula (II-3) is contacted with a catalyst in the presence of alkali and a solvent to obtain a compound with the structure shown in the formula (II-4);
optionally, the method further comprises 1,2 or 3 of the following steps in sequence:
(a) carrying out halogenation reaction on the compound with the structure shown in the formula (II-4) to obtain a compound with the structure shown in the formula (II-5);
(b) reacting the compound with the structure shown in the formula (II-5) with sodium mercaptide with the structure shown in the formula (II-6) to obtain a compound with the structure shown in the formula (II-7);
(c) carrying out oxidation reaction on the compound with the structure shown in the formula (II-7) in the presence of peroxide with the structure shown in the formula (II-8) to obtain the compound with the structure shown in the formula (II-9);
wherein,
x in the Compound having the Structure represented by the formula (II-5) 1 Is halogen;
x in the compound of the formula (II-6), the compound of the formula (II-7) and the compound of the formula (II-9) 2 Is selected from C 1-3 Alkyl, phenyl of (a);
and the remaining substituents referred to in the formula (II-1), the formula (II-2), the formula (II-3), the formula (II-4), the formula (II-5), the formula (II-7) and the formula (II-9) are the same as those of the compound described in the aforementioned first aspect of the present invention.
According to the method for preparing the quinazoline diketone compound with the structure shown in the formula (I) in the invention, a person skilled in the art can contact the compound with the structure shown in the formula (II-3) and a catalyst in the presence of a base and a solvent according to the conventional conditions and operations of a rearrangement reaction.
Preferably, the molar ratio of the compound having the structure represented by the formula (II-3) to the catalyst and the base is 1: (0.01-1): (0.5-4); more preferably, the molar ratio of the compound of the structure represented by formula (II-3) to the catalyst and the base is 1: (0.05-1): (1-3).
Preferably, in step (2), the contacting conditions include: the reaction temperature is 0-100 ℃; the reaction time is 0.5-36 h; more preferably, in step (2), the contacting conditions include: the reaction temperature is 20-40 ℃; the reaction time is 5-30 h.
It will be understood by those skilled in the art that the method of the present invention may further include a step of purifying the obtained product, and there is no particular requirement for the purification method, and various purification methods conventionally used by those skilled in the art may be employed, for example, extraction with an extractant, drying with a drying agent, and removal of impurities by column chromatography or the like may be employed.
In the preparation method of the invention, the compound with the structure shown in the formula (II-1) can be prepared by adopting conventional reactions in the field.
Illustratively, the compound having the structure shown in formula (II-1) can be prepared by the following synthetic route:
specifically, a compound represented by the formula A is reacted with iodine chloride to obtain a compound represented by the formula B, and further reacted with a compound represented by the formula C to obtain a compound represented by the formula D, and then the compound represented by the formula D is reacted with a halide (R) in the presence of a base 2 I or R 2 Br) to obtain a compound shown in a formula E, further reacting with cuprous cyanide to obtain a compound shown in a formula F, and further hydrolyzing under an acidic condition to obtain a compound shown in a formula (II-1).
In the above synthetic routes, the definitions of the substituents mentioned are the same as the corresponding definitions in the preceding text, unless otherwise specified.
The examples section of this invention exemplifies the specific operating conditions of the above synthetic routes and those skilled in the art should not be construed as limiting the invention.
Preferably, in the step (2), the catalyst is at least one selected from the group consisting of sodium cyanide, potassium cyanide, acetone cyanohydrin, trimethylcyanosilane, 1,2, 4-triazole and benzo 1,2, 4-triazole.
Preferably, in the step (2), the base is selected from at least one of potassium carbonate, sodium carbonate, cesium carbonate, triethylamine and pyridine.
Preferably, in step (2), the solvent is selected from at least one of dichloromethane, chloroform, dichloroethane, acetonitrile, toluene, tetrahydrofuran and benzene.
As mentioned above, the third aspect of the present invention provides the use of the quinazolinedione compounds of the first aspect for controlling weeds.
The weeds of the present invention are plants that grow in a place that is harmful to human survival and activity, and may be non-cultivated wild plants or plants that are not useful to humans. For example, various wild plants in the field in which the crop is planted may be used.
In the aforementioned use of the invention, the weeds may be broadleaf weeds and/or grassy weeds.
Preferably, the weeds are wheat field weeds and/or peanut field weeds.
According to a preferred embodiment, the weeds are at least one of barnyard grass, green bristlegrass, crabgrass, amaranth, li, abutilon, jiejai, wild oats, brome, alopecurus japonicus, stiff grass, club grass, syzis, and cleavers, caraway, speedwell, trimmings, polygonum cuspidatum, bromus, and vetch.
Preferably, in the aforementioned use of the present invention, the quinazoline diones are used in an amount of 10 to 400 grams per hectare.
In the application of the quinazoline dione compound provided by the invention, the quinazoline dione compound is dissolved and diluted by a solvent, and the concentration of the dissolved and diluted quinazoline dione compound is preferably 0.05-0.4 g/L. The solvent for dissolving the quinazoline dione compound may include N, N-dimethylformamide, dimethylsulfoxide, etc., and the agent for dilution may be water, etc. containing conventional additives. Preferably, one or more additives commonly used in herbicides in the art, such as surfactants, emulsifiers, etc., may also be added to the solution in which the quinazolinedione compounds are dissolved. The diluted quinazolinedione compounds of the present invention may be sprayed onto the stems and/or leaves of plants by methods conventional in the art.
As mentioned above, the fourth aspect of the present invention provides a herbicide, which comprises an active ingredient and an adjuvant, wherein the active ingredient comprises at least one of the quinazolinedione compounds according to the first aspect of the present invention.
Preferably, the content of the active ingredient is 1 to 99.9% by weight.
The auxiliary materials of the invention are various additives commonly used in various formulations for preparing herbicides in the field.
Preferably, the formulation of the herbicide of the present invention is selected from at least one of emulsifiable concentrate, suspension, wettable powder, dust, granule, aqueous solution, mother liquor and mother powder.
The present invention will be described in detail below by way of examples. In the following examples, the various starting materials used in the present examples are commercially available and are of analytical grade, unless otherwise specified.
Unless otherwise specified, the room temperature below indicates 25 ℃. + -. 3 ℃.
Preparation example 1: preparation of Compound having the Structure represented by the formula (II-4-1)
75.5g of the compound represented by A was put into a 1L reaction flask at room temperature, 300mL of glacial acetic acid was added with stirring, 81g of ICl was dissolved in 200mL of glacial acetic acid, and the solution was added dropwise to the reaction system with stirring within 30min, and after completion of the dropwise addition, the reaction was continued with stirring for about 2.5 hours. After the reaction is finished, carrying out vacuum filtration on the reaction liquid, washing the obtained solid with 200mL of acetonitrile and 200mL of glacial acetic acid respectively, and drying to obtain an intermediate B with the yield of 95%; melting point: 186 ℃ and 188 ℃. 1 H NMR(600MHz,DMSO-d 6 )：δ8.97(brs,3H),7.72(d,J＝8.4Hz,1H),6.75(d,J＝7.8Hz,1H),2.40(s,3H)。
Adding 8.31g of intermediate BInto a 200mL two-necked flask, 80mL of pyridine was added, and 2.55g of N-N-propyl isocyanate represented by C-1 was slowly added to the system with stirring. Heating the reaction solution to 100 ℃ for overnight reaction, after the reaction is finished, distilling under reduced pressure to remove pyridine, dissolving the obtained solid with acetone, stirring the sample, and passing through a column to obtain an intermediate D-1. The yield is 78%; melting point: 295 ℃ and 296 ℃. 1 H NMR(600MHz,CDCl 3 )δ9.67(s,1H),8.14(d,J＝7.8Hz,1H),7.40(d,J＝7.8Hz,1H),3.45(t,J＝7.2Hz,2H),2.34(s,3H),1.72–1.32(m,2H),0.85(t,J＝7.2Hz,3H).
7.91g of intermediate D-1 was charged into a 200mL single-necked flask, 50mL of DMF was added, and 14.95g of Cs was added with stirring 2 CO 3 The reaction was continued with stirring for about 30 min. Mixing 6.49g of CH 3 And I, slowly dropwise adding the mixture into the reaction system, and stirring at room temperature to react overnight after the dropwise adding. After the reaction is finished, the system is poured into 200mL of water, and a large amount of solid is separated out to obtain an intermediate E-1. The yield is 95%; melting point: 208-210 ℃. 1 H NMR(600MHz,CDCl 3 )δ8.14(d,J＝7.8Hz,1H),7.40(d,J＝7.8Hz,1H),3.89(s,3H),3.45(t,J＝7.8Hz,2H),2.34(s,3H),1.54(dd,J＝14.4,7.8Hz,2H),0.85(t,J＝6.6Hz,3H).
7.82g of intermediate E-1, 3.89g of CuCN was charged to a 200mL two-necked flask, and 100mL of dry DMF was added. And (3) refluxing for 12h, distilling under reduced pressure to remove DMF after the reaction is finished, adding 100mL of acetone into the reaction bottle after cooling, stirring vigorously for 20min, and filtering to remove unreacted CuCN. The filtrate is dried to obtain an intermediate F-1. Yield 88%, melting point: 210 ℃ and 211 ℃. 1 H NMR(600MHz,CDCl 3 )δ7.91(d,J＝7.8Hz,1H),7.36(d,J＝7.8Hz,1H),3.92(s,3H),3.48(t,J＝7.8Hz,2H),2.38(s,3H),1.64(dd,J＝14.4,7.8Hz,2H),0.95(t,J＝6.6Hz,3H).
4.88g of intermediate F-1 was charged into a 200mL reaction flask, and 30mL of glacial acetic acid, 30mL of water, and 30mL of concentrated sulfuric acid were added with stirring. Heating to 120 ℃ for reaction for 12h, cooling to room temperature after the reaction is finished, pouring the reaction system into a beaker with 200mL of ice water, adding 100mL of ethyl acetate into the beaker, extracting and separating an organic layer, extracting an aqueous layer for 2 times by using 100mL of ethyl acetate, combining the organic layers after the extraction is finished, extracting the organic layer for 3 times by using 50 weight percent sodium hydroxide solution 30mL each time, combining the aqueous layer, acidifying the aqueous layer to the pH value of about 1 by using concentrated hydrochloric acid, standing to precipitate a large amount of solid (namely intermediate II-1-1), carrying out suction filtration, and directly putting the dried solid into the next reaction.
1.38g of intermediate II-1-1 was added to a 100mL single-necked flask, 20mL of dry THF was added, and 1.18g of SOCl was slowly added dropwise at room temperature 2 And after the dropwise addition is finished, refluxing and reacting at 75 ℃ for about 1.5h, tracking the reaction process by TLC, and removing the solvent after the reaction is finished. 20mL of dried CHCl was added 3 1.12g of the Compound represented by the formula II-2-1, 1.01g of Et 3 N, reacting for about 0.5h, and tracking by TLC until the acyl chloride disappears. After the reaction, the reaction mixture was washed once with 100mL of water, 2 times with 30mL of 1 mol/L HCl and 2 times with 30mL of saturated NaHCO 3 Washing for 2 times with anhydrous Na 2 SO 4 Drying and passing through a column to obtain an intermediate II-3-1. The yield is 80%; melting point: 177 ℃ and 178 ℃. 1 H NMR(600MHz,CDCl 3 )δ8.25(d,J＝9.0Hz,1H),7.82(d,J＝9.0Hz,1H),5.87(t,J＝1.8Hz,1H),3.89(s,3H),3.45(t,J＝7.2Hz,2H),3.16(t,J＝7.2Hz,2H),2.48(td,J＝6.6,1.8Hz,2H),2.34(s,3H),1.74–1.31(m,4H),0.85(t,J＝6.6Hz,3H).
1.48g of intermediate II-3-1 was charged into a 50mL two-necked flask, and 20mL of anhydrous acetonitrile, N 2 Et 0.81g was added under protection 3 N, 34mg of acetone cyanohydrin. The reaction was carried out at room temperature for 8h, and TLC followed until the starting material disappeared. After the reaction was complete, the acetonitrile was removed and about 30mL of CHCl was added 3 . The organic layer was washed three times with 10mL of 1 mol/L HCl each time, 3 times with 10mL of saturated sodium chloride each time, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to give a pale yellow oily substance, and the obtained oily substance was recrystallized from 20mL of methanol to give the compound represented by II-4-1 (white solid). The yield is 77%; melting point: 155 ℃ and 156 ℃. 1 H NMR(400MHz,CDCl 3 )δ17.65(s,1H),7.32(d,J＝8.8Hz,1H),7.09(d,J＝8.8Hz,1H),4.05–3.96(m,2H),3.58(s,3H),2.80(t,J＝6.4Hz,2H),2.70(s,3H),2.43(t,J＝6.4Hz,2H),2.05(p,J＝6.4Hz,2H),1.69(h,J＝7.6Hz,2H),0.97(t,J＝7.2Hz,3H).
Preparation example 2: preparation of Compound 2
0.925g of the compound represented by II-4-1 was charged in a 50mL two-necked flask, 15mL of anhydrous dichloromethane was added, and 0.945g of oxalyl chloride was slowly added to the system. The reaction was carried out at room temperature for 15h, and TLC followed until the starting material disappeared. After the reaction was completed, the organic phase was washed three times with saturated sodium bicarbonate, and the organic layers were combined and dried over anhydrous sodium sulfate. And removing the solvent under reduced pressure to obtain a white solid, namely the compound 2.
Preparation example 3: preparation of Compound 3
0.31g of Compound 2 was added to a 50mL two-necked flask, 15mL of anhydrous dichloromethane, and 0.112g of sodium thiomethoxide. The reaction was carried out at room temperature for 30h, and TLC followed until the starting material disappeared. After the reaction is finished, directly mixing the sample and carrying out column chromatography to obtain the compound 3.
Preparation example 4: preparation of Compound 7
0.2g of Compound 3 was charged into a 50mL two-necked flask, added to 15mL of anhydrous dichloromethane, and 0.171g of m-chloroperoxybenzoic acid (m-CPBA). The reaction was carried out at room temperature for 10h, and TLC was followed until the starting material disappeared. After the reaction is finished, directly mixing the sample and carrying out column chromatography to obtain the compound 7.
Preparation example 5: preparation of Compound having the Structure represented by the formula (II-4-2)
8.31g of intermediate B was charged into a 200mL two-necked flask, 80mL of pyridine was added, and 3.33g of cyclopentyl isocyanate represented by C-2 was slowly added to the system with stirring. The reaction solution was heated to 100 ℃ to react overnight,after the reaction is finished, pyridine is removed by reduced pressure distillation, the obtained solid is dissolved by acetone, and the mixture is stirred and passed through a column to obtain an intermediate D-2. The yield is 80%; melting point: 307 ℃ and 308 ℃. 1 H NMR(600MHz,CDCl 3 )δ9.63(s,1H),8.09(d,J＝8.4Hz,1H),7.36(d,J＝8.4Hz,1H),5.96–5.71(m,1H),2.33(s,3H),2.06–1.83(m,2H),1.81–1.50(m,6H).
8.88g of intermediate D-2 was charged into a 200mL single-necked flask, 50mL of DMF was added, and 15.6g of Cs was added with stirring 2 CO 3 The reaction was continued with stirring for about 30 min. 6.77g of CH 3 And I, slowly dropwise adding the mixture into the reaction system, and stirring at room temperature to react overnight after the dropwise adding. After the reaction is finished, the system is poured into 200mL of water, and a large amount of solid is separated out to obtain an intermediate E-2. The yield is 95%; melting point: 220 ℃ and 221 ℃. 1 H NMR(600MHz,CDCl 3 )δ8.12(d,J＝7.8Hz,1H),7.38(d,J＝7.8Hz,1H),4.12–4.08(m,1H),3.89(s,3H),2.34(s,3H),2.09–1.83(m,2H),1.87–1.43(m,6H).
8.755g of intermediate E-2, 4.06g of CuCN were charged into a 200mL two-necked flask, and 100mL of dry DMF was added. And (3) refluxing for 12h, distilling under reduced pressure to remove DMF after the reaction is finished, adding 100mL of acetone into the reaction bottle after cooling, stirring vigorously for 20min, and filtering to remove unreacted CuCN. The filtrate is dried to obtain an intermediate F-2. The yield is 86%; melting point: 232 ℃ and 233 ℃. 1 H NMR(600MHz,CDCl 3 )δ7.92(d,J＝7.8Hz,1H),7.37(d,J＝7.8Hz,1H),4.20–4.12(m,1H),3.92(s,3H),2.42(s,3H),2.15–1.99(m,2H),1.90–1.46(m,6H).
5.54g of intermediate F-2 was charged into a 200mL reaction flask, and 30mL of glacial acetic acid, 30mL of water, and 30mL of concentrated sulfuric acid were added with stirring. Heating to 120 ℃ for reaction for 12h, cooling to room temperature after the reaction is finished, pouring the reaction system into a beaker with 200mL of ice water, adding 100mL of ethyl acetate into the beaker, extracting and separating an organic layer, extracting an aqueous layer for 2 times by using 100mL of ethyl acetate, combining the organic layers after the extraction is finished, extracting the organic layer for 3 times by using 50 weight percent sodium hydroxide solution for 30mL each time, combining the aqueous layer, acidifying the aqueous layer to the pH value of about 1 by using concentrated hydrochloric acid, standing to precipitate a large amount of solid (namely intermediate II-1-2), carrying out suction filtration, and directly putting the dried solid into the next reaction.
Will 151g of intermediate II-1-2 was added to a 100mL single-necked flask, 25mL of dry THF was added, and 1.18g of SOCl was slowly added dropwise at room temperature 2 And after the dropwise addition is finished, refluxing and reacting at 75 ℃ for about 1.5h, tracking the reaction process by TLC, and removing the solvent after the reaction is finished. 20mL of dried CHCl was added 3 1.12g of the Compound represented by the formula II-2-1, 1.01g of Et 3 N, reacting for about 0.5h, and tracking by TLC until the acyl chloride disappears. After the reaction, the reaction mixture was washed once with 100mL of water, 2 times with 30mL of 1 mol/L HCl and 2 times with 30mL of saturated NaHCO 3 Washing for 2 times with anhydrous Na 2 SO 4 Drying and passing through a column to obtain an intermediate II-3-2. The yield is 70%; melting point: 180 ℃ and 181 ℃. 1 H NMR(600MHz,CDCl 3 )δ8.25(d,J＝8.4Hz,1H),7.82(d,J＝8.4Hz,1H),5.85(s,1H),4.31–4.05(m,1H),3.89(s,3H),3.16(t,J＝7.8Hz,2H),2.51(td,J＝6.6,1.8Hz,2H),2.34(s,3H),2.02–1.87(m,2H),1.83–1.60(m,6H),1.54(p,J＝6.6Hz,2H).
1.38g of intermediate II-3-2 was added to a 50mL two-necked flask, 25mL of anhydrous acetonitrile, N 2 Et 0.71g was added under protection 3 N, 30mg of acetone cyanohydrin. The reaction was carried out at room temperature for 10h, and TLC was followed until the starting material disappeared. After the reaction was complete, the acetonitrile was removed and about 30mL of CHCl was added 3 . The organic layer was washed three times with 10mL of 1 mol/L HCl each time, 3 times with 10mL of saturated sodium chloride each time, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to give a pale yellow oily substance, and the obtained oily substance was recrystallized from 20mL of methanol to give the compound represented by II-4-2 (white solid). The yield is 78%; melting point: 185 ℃ and 186 ℃. 1 H NMR(400MHz,CDCl 3 )δ17.66(s,1H),7.31(d,J＝6.0Hz,1H),7.07(d,J＝6.8Hz,1H),5.42(p,J＝8.8Hz,1H),3.57(s,3H),2.80(t,J＝6.4Hz,2H),2.69(s,3H),2.44(t,J＝6.4Hz,2H),2.21–2.12(m,2H),2.09–1.96(m,4H),1.93–1.81(m,2H),1.68–1.60(m,2H).
The remaining compounds of the present invention were prepared by the methods described in preparation examples 1 to 5. Wherein the characterization data for some specific compounds in the general structure of the present invention are listed in table 1:
TABLE 1
Test example 1
This test example is intended to illustrate the herbicidal activity inhibition (%) of a part of specific compounds among the compounds having the structure represented by the formula (I) and a comparative compound D1, wherein the structural formula of the comparative compound D1 (the comparative compound D1 is a specific compound disclosed in CN104557739A, and CN104557739A is the same as the main inventors of the present invention) is:
preliminary screening test (potting method): the test targets are cockspur grass, green bristlegrass, crab grass, amaranth, chenopodium album and abutilon, and the stem and leaf spray after seedling: taking a paper cup with the inner diameter of 7cm, filling composite soil (vegetable garden soil: seedling culture medium, 1: 2, v/v) to 3/4 positions, directly sowing weeds, covering soil of 0.2cm, and waiting until the leaf grows to 4-5 stages for later use. The compound of the present invention and the aforementioned comparative compound D1 were applied at a dose of 150g.a.i/ha (g/ha) in an automatic spray tower, and after the crop foliage liquid was dried, the solution was transferred to a greenhouse for cultivation (humidity 70%), and the results were investigated after 30 days.
The growth inhibition rate evaluation method was a visual method, and specifically, the evaluation was performed according to the conditions shown in table 2, and the test results are shown in table 3.
TABLE 2
| Growth inhibition ratio (%) | Evaluation (inhibition, abnormality, whitening, etc.) | Rank of |
| 0 | Has no influence on the growth of weeds or crops and no drug effect symptom. | Grade 0 (same as blank control) |
| 1-19 | Has slight influence on the growth of weeds or crops and has no obvious drug effect symptom. | Level 1 |
| 20-49 | Has obvious effect on the growth of weeds or crops. | Stage 2 |
| 50-79 | Weeds or crops are severely inhibited from growing. | Grade 3 |
| 80-99 | The weeds or crops die. | 4 stage |
| 100 | Complete death of weeds or cropsAnd (7) death. | Grade 5 |
TABLE 3
Test example 2
The reduced dose of partial compounds was re-screened in the same manner as in test example 1, and the test results are shown in Table 4.
TABLE 4
From the results shown above, it can be seen that:
in a primary screening weeding activity experiment, most of the compounds of the invention show very excellent weeding and control effects on 6 common gramineae and broadleaf weeds such as cockspur grass, green bristlegrass, crab grass, amaranth, chenopodium album and abutilon, and have the activity equivalent to or obviously better than that of the compound D1.
Further, in the double-screening test of reduced concentration, the herbicidal activity of the compound of the present invention on 3 kinds of weeds such as barnyard grass, green bristlegrass and crab grass is still equivalent to or even better than that of D1, while for the grassy weeds such as arthroncus, wild oat, brome, alopecurus, and alopecurus japonicus, the compounds 10, 11, 12 and 14 of the present invention still maintain good herbicidal activity on the above-mentioned weeds in the three application modes, while the control agent D1 shows almost no herbicidal activity on the above-mentioned weeds.
It is thus found that the compound of the present invention can be used as a broad-spectrum herbicide for controlling grassy weeds and some broadleaf weeds.
Test example 3
The crop safety was measured on the partial compounds in the same manner as in test example 1, and the results are shown in Table 5.
TABLE 5
From the results shown above, it can be seen that:
the compound 11 has only slight inhibition effect on wheat under three drug application concentrations, but does not influence the growth of wheat, and has excellent crop safety. While compounds 12 and 14 also have a higher safety profile for wheat at low concentrations. Therefore, the compound of the invention is suitable for being applied as a wheat field herbicide and has great commercial value.
In addition, the partial compounds 11 and 12 in the invention are also very safe to peanuts, so that the compounds can be used for controlling gramineous weeds and partial broadleaf weeds in peanut fields, and no HPPD inhibiting herbicide for controlling weeds in peanut fields is available in the market at present.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (16)
1. A quinazoline diketone compound has a structure shown in a formula (I),
wherein, in the formula (I),
R 1 is n-propyl or cyclopentyl;
R 2 selected from H, C 1-6 Alkyl of (2), C substituted by 1 to 3 halogen atoms 1-3 Alkyl of (C) 3-6 Alkynyl of (a), C substituted by trimethylsilyl 6-8 Alkynyl of (A), C 3-6 Alkenyl of (a), C substituted by 1 to 3 halogen atoms 3-6 An alkenyl group of,
X is selected from hydroxyl, halogen and C 1-3 Alkylthio, phenylthio, C 1-3 Alkyl sulfone group, phenyl sulfone group;
R 3 、R 4 、R 5 、R 6 each independently selected from H and C 1-3 Alkyl groups of (a);
R 7 is H.
2. The compound according to claim 1, wherein, in formula (I),
R 1 is n-propyl or cyclopentyl;
R 2 selected from H, methyl, ethyl, monofluoromethyl, difluoromethyl, monofluoroethyl, difluoroethyl, trifluoromethyl, trifluoroethyl,
X is selected from-OH, -F, -Cl, -Br, CH 3 -S-、CH 3 CH 2 -S-、CH 3 CH 2 CH 2 -S-、
R 3 、R 4 、R 5 、R 6 Each is independently selected from H, methyl, ethyl, n-propyl, and isopropyl;
R 7 is H.
3. The compound according to claim 1 or 2, wherein the compound of formula (I) is selected from at least one of the following:
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:
compound 17:
compound 18:
compound 19:
compound 20:
compound 21:
compound 22:
compound 23:
compound 24:
compound 25:
compound 26:
compound 27:
compound 28:
compound 29:
compound 30:
4. a process for the preparation of a quinazolinedione compound of any one of claims 1-3, comprising:
(1) reacting the compound with the structure shown in the formula (II-1) with thionyl chloride and the compound with the structure shown in the formula (II-2) in sequence to obtain the compound with the structure shown in the formula (II-3);
(2) under the rearrangement reaction condition, the compound with the structure shown in the formula (II-3) is contacted with a catalyst in the presence of alkali and a solvent to obtain a compound with the structure shown in the formula (II-4);
optionally, the method further comprises 1,2 or 3 of the following steps in sequence:
(a) carrying out halogenation reaction on the compound with the structure shown in the formula (II-4) to obtain a compound with the structure shown in the formula (II-5);
(b) reacting the compound with the structure shown in the formula (II-5) with sodium mercaptide with the structure shown in the formula (II-6) to obtain a compound with the structure shown in the formula (II-7);
(c) carrying out oxidation reaction on the compound with the structure shown in the formula (II-7) in the presence of peroxide with the structure shown in the formula (II-8) to obtain the compound with the structure shown in the formula (II-9);
wherein,
x in the Compound having the Structure represented by the formula (II-5) 1 Is halogen;
x in the compound of the formula (II-6), the compound of the formula (II-7) and the compound of the formula (II-9) 2 Is selected from C 1-3 Alkyl, phenyl of (a);
and the remaining substituents referred to in the formula (II-1), the formula (II-2), the formula (II-3), the formula (II-4), the formula (II-5), the formula (II-7) and the formula (II-9) are the same as the substituents of the compound according to any one of claims 1 to 3.
5. The method of claim 4, wherein in step (2), the conditions of the contacting comprise: the reaction temperature is 0-100 ℃; the reaction time is 0.5-36 h.
6. The method according to claim 4 or 5, wherein, in the step (2), the catalyst is selected from at least one of sodium cyanide, potassium cyanide, acetone cyanohydrin, trimethylcyanosilane, 1,2, 4-triazole and benzo 1,2, 4-triazole.
7. The process according to claim 4 or 5, wherein, in step (2), the base is selected from at least one of potassium carbonate, sodium carbonate, cesium carbonate, triethylamine and pyridine.
8. The method according to claim 4 or 5, wherein, in step (2), the solvent is selected from at least one of dichloromethane, trichloromethane, dichloroethane, acetonitrile, toluene, tetrahydrofuran and benzene.
9. Use of quinazolinedione compounds according to any one of claims 1 to 3 for controlling weeds.
10. Use according to claim 9, wherein the weeds are wheat field weeds and/or peanut field weeds.
11. The use as claimed in claim 9, wherein the weeds are at least one of Echinochloa crusgalli, Setaria viridis, Digitaria sanguinea, Amaranthus, Ricini, Abutilon, Arthropoda avenae, Bromus alata, alopecurus japonicus, Harpagophytum, Syzigachx, and Galium aparine, Caragana, Veronica, zizyphus quinata, Polygonum hydropiper, Broussonetia and Gynura.
12. Use according to any one of claims 9 to 11, wherein the quinazolinedione compound is used in an amount of 10 to 400 g/ha.
13. A herbicide which consists of an active ingredient and an auxiliary material, wherein the active ingredient comprises at least one quinazoline diketone compound as defined in any one of claims 1 to 3.
14. A herbicide as claimed in claim 13, wherein the active ingredient is present in an amount of 1 to 99.9% by weight, based on the total weight of the herbicide.
15. The herbicide of claim 13, wherein the herbicide is in a form selected from at least one of emulsifiable concentrate, suspension, powder, granules, aqueous solution, and mother liquor.
16. The herbicide according to claim 15, wherein the dust is at least one selected from wettable powder and mother powder.
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| CN115960049A (en) * | 2021-10-09 | 2023-04-14 | 山东先达农化股份有限公司 | Triketone-benzimidazolone compound, preparation method and application thereof, and herbicide |
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| CN117624136A (en) * | 2022-09-01 | 2024-03-01 | 山东先达农化股份有限公司 | Compound containing pyrazole-quinazoline dione structure, herbicide and application |
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| WO2017140612A1 (en) * | 2016-02-18 | 2017-08-24 | Bayer Cropscience Aktiengesellschaft | Quinazolinedione-6-carbonyl derivatives and their use as herbicides |
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| WO2017140612A1 (en) * | 2016-02-18 | 2017-08-24 | Bayer Cropscience Aktiengesellschaft | Quinazolinedione-6-carbonyl derivatives and their use as herbicides |
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