CN113912537A - 2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-diketone compound and preparation method and application thereof - Google Patents
2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-diketone compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN113912537A CN113912537A CN202110993556.5A CN202110993556A CN113912537A CN 113912537 A CN113912537 A CN 113912537A CN 202110993556 A CN202110993556 A CN 202110993556A CN 113912537 A CN113912537 A CN 113912537A
- Authority
- CN
- China
- Prior art keywords
- cyclohexane
- carbonyl
- quinolin
- preparation
- diones
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- -1 quinoline-8-yl Chemical group 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 241000192043 Echinochloa Species 0.000 claims abstract description 23
- 239000004009 herbicide Substances 0.000 claims abstract description 20
- 230000002363 herbicidal effect Effects 0.000 claims abstract description 13
- 230000032050 esterification Effects 0.000 claims abstract description 10
- 238000005886 esterification reaction Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000012265 solid product Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000012320 chlorinating reagent Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract description 3
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000004821 distillation Methods 0.000 claims abstract description 3
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical class C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- PVIULYUKOOLVPU-UHFFFAOYSA-N 2-(quinoline-8-carbonyl)cyclohexane-1,3-dione Chemical class N1=CC=CC2=CC=CC(=C12)C(=O)C1C(CCCC1=O)=O PVIULYUKOOLVPU-UHFFFAOYSA-N 0.000 claims description 14
- 239000004480 active ingredient Substances 0.000 claims description 14
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 4
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000005083 alkoxyalkoxy group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 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
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- 125000006677 (C1-C3) haloalkoxy group Chemical group 0.000 claims description 2
- 125000004768 (C1-C4) alkylsulfinyl group Chemical group 0.000 claims description 2
- 125000004769 (C1-C4) alkylsulfonyl group Chemical group 0.000 claims description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 2
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims description 2
- 125000006766 (C2-C6) alkynyloxy group Chemical group 0.000 claims description 2
- VMEHOTODTPXCKT-UHFFFAOYSA-N 2-hydroxy-2-methylbutanenitrile Chemical compound CCC(C)(O)C#N VMEHOTODTPXCKT-UHFFFAOYSA-N 0.000 claims description 2
- 125000003320 C2-C6 alkenyloxy group Chemical group 0.000 claims description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000004448 alkyl carbonyl group Chemical group 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
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 150000007530 organic bases Chemical class 0.000 claims 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 16
- 235000007164 Oryza sativa Nutrition 0.000 abstract description 12
- 235000009566 rice Nutrition 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 8
- 230000006378 damage Effects 0.000 abstract description 5
- 240000007594 Oryza sativa Species 0.000 abstract 1
- 230000017105 transposition Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 241000209094 Oryza Species 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000009472 formulation Methods 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- ZVBYXDPJZZRSOL-UHFFFAOYSA-N 3,7-dichloro-5-methylsulfonylquinoline-8-carboxylic acid Chemical compound CS(=O)(=O)C1=CC(=C(C2=C1C=C(C=N2)Cl)C(=O)O)Cl ZVBYXDPJZZRSOL-UHFFFAOYSA-N 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical compound O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- 239000005592 Penoxsulam Substances 0.000 description 3
- SYJGKVOENHZYMQ-UHFFFAOYSA-N Penoxsulam Chemical compound N1=C2C(OC)=CN=C(OC)N2N=C1NS(=O)(=O)C1=C(OCC(F)F)C=CC=C1C(F)(F)F SYJGKVOENHZYMQ-UHFFFAOYSA-N 0.000 description 3
- ZOMSMJKLGFBRBS-UHFFFAOYSA-N bentazone Chemical compound C1=CC=C2NS(=O)(=O)N(C(C)C)C(=O)C2=C1 ZOMSMJKLGFBRBS-UHFFFAOYSA-N 0.000 description 3
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- OVXMBIVWNJDDSM-UHFFFAOYSA-N (benzhydrylideneamino) 2,6-bis[(4,6-dimethoxypyrimidin-2-yl)oxy]benzoate Chemical compound COC1=CC(OC)=NC(OC=2C(=C(OC=3N=C(OC)C=C(OC)N=3)C=CC=2)C(=O)ON=C(C=2C=CC=CC=2)C=2C=CC=CC=2)=N1 OVXMBIVWNJDDSM-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 2
- 239000005476 Bentazone Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- CNBGNNVCVSKAQZ-UHFFFAOYSA-N benzidamine Natural products C12=CC=CC=C2C(OCCCN(C)C)=NN1CC1=CC=CC=C1 CNBGNNVCVSKAQZ-UHFFFAOYSA-N 0.000 description 2
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- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 2
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
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- 235000011151 potassium sulphates Nutrition 0.000 description 1
- LFULEKSKNZEWOE-UHFFFAOYSA-N propanil Chemical compound CCC(=O)NC1=CC=C(Cl)C(Cl)=C1 LFULEKSKNZEWOE-UHFFFAOYSA-N 0.000 description 1
- NQLVQOSNDJXLKG-UHFFFAOYSA-N prosulfocarb Chemical compound CCCN(CCC)C(=O)SCC1=CC=CC=C1 NQLVQOSNDJXLKG-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- FFSSWMQPCJRCRV-UHFFFAOYSA-N quinclorac Chemical compound ClC1=CN=C2C(C(=O)O)=C(Cl)C=CC2=C1 FFSSWMQPCJRCRV-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- MGLWZSOBALDPEK-UHFFFAOYSA-N simetryn Chemical compound CCNC1=NC(NCC)=NC(SC)=N1 MGLWZSOBALDPEK-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910002029 synthetic silica gel Inorganic materials 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- AHTPATJNIAFOLR-UHFFFAOYSA-N thifensulfuron-methyl Chemical group S1C=CC(S(=O)(=O)NC(=O)NC=2N=C(OC)N=C(C)N=2)=C1C(=O)OC AHTPATJNIAFOLR-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/36—Sulfur 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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
- A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
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)
Abstract
The invention provides a 2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-diketone compound and a preparation method and application thereof. During preparation, substituted quinolinecarboxylic acid is used as a raw material, a chlorinating agent is added into a solvent, and the mixture reacts at the temperature of 0-100 ℃ to obtain an acyl chloride solution; cooling to room temperature, adding 1, 3-cyclohexanedione, adding alkali at 0-100 ℃, reacting to obtain an esterification solution, adding a transposition agent into the esterification solution, continuously stirring overnight at room temperature, and removing the solvent by distillation to obtain a yellow solid product. The compound of the invention has high activity as herbicide for treating rice stem leaves and has special effect on barnyard grass, thereby effectively controlling the harm of the barnyard grass.
Description
Technical Field
The invention belongs to the technical field of compound synthesis, and relates to a 2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-diketone compound and a preparation method and application thereof.
Background
Barnyard grass, Latin school name: echinochloa crusgalli (L.) Beauv, an annual herbaceous plant, has a very similar appearance to barnyard grass and rice. Barnyard grass grows in rice fields, swamps, near ditches and in low-lying wastelands. The shape is similar to rice but the leaves are rough and astringent and the color is lighter. The barnyard grass and the rice absorb the nutrients in the rice field together, so the barnyard grass is a malignant weed in the rice field. It was reported that barnyard grass grown for one week per square meter reduced yield by 2%, about 10% for 5 weeks, about 19% for 10 weeks, and about 35% for 20 weeks. The barnyard grass in the existing paddy field weeds is still the biggest problem.
Although herbicides have been disclosed in the prior art, for example, CN102249996A discloses a compound represented by formula (3) wherein R1 and R2 are selected from methyl, halogen, nitro or methylsulfonyl. A compound represented by the following formula (4) is disclosed in EP0186118, a compound represented by the following formula (5) is disclosed in EP 1117639, and a compound represented by the following formula (6) is disclosed in JP 0625144.
Wherein the compound (4) and the compound (5) are corn field herbicides; although the compound (3) and the compound (6) are herbicides for paddy fields, the compound (3) is used in an amount of 50g or more per mu of land and has a narrow herbicidal spectrum, and the compound (6) has no good effect on barnyard grass. The development of herbicides capable of controlling barnyard grass is an urgent need in the agricultural field.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a 2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-diketone compound and a synthesis method and application thereof.
The purpose of the invention is realized by the following technical scheme:
2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones of the formula:
wherein R1 and R2 are any one of hydrogen base, benzyl, phenyl, trifluoromethyl, halogen, C1-C6 alkyl, C1-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C3 haloalkyl, C1-C3 haloalkoxy, C2-C4 alkoxyalkoxy, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C3 alkoxycarbonyl and C1-C3 alkylcarbonyl;
r3 is any one of C1-C6 alkyl, benzyl, phenyl, trifluoromethyl, C1-C6 cycloalkyl, C1-C3 haloalkyl, C2-C4 alkoxyalkoxy, C2-C6 alkenyl and C2-C6 alkynyl.
Preferably, said R1, R2 are halogen; r3 is C1-C3 alkyl.
Preferably, the preparation method of the 2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-diketone compound comprises the following steps:
s1, taking substituted quinolinecarboxylic acid as a raw material, adding a chlorinating agent into a solvent, and reacting at the temperature of 0-100 ℃ to obtain an acyl chloride solution;
s2, cooling to room temperature, adding 1, 3-cyclohexanedione, adding alkali at 0-100 ℃, and reacting to obtain an esterification solution;
and S3, adding a translocating agent into the esterification solution obtained in the S2, continuously stirring at room temperature overnight, then adding water, and removing the solvent through distillation at normal pressure to obtain a yellow solid product.
The above reaction formula is shown below:
preferably, the solvent in S1 is one or more of tetrahydrofuran, ethyl acetate, acetonitrile, toluene, xylene, hexane, dichloromethane, dichloroethane, and carbon tetrachloride.
Preferably, the chlorinating agent in S1 is one or a combination of more than one of thionyl chloride, phosgene, diphosgene, triphosgene, oxalyl chloride, phosphorus trichloride, phosphorus oxychloride and phosphorus pentachloride.
Preferably, the base in S2 is one or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, triethylammonium, pyridine, and the like.
Preferably, the transfer agent in S3 is one or more of acetone cyanohydrin, butanone cyanohydrin, and sodium cyanide.
Preferably, the use of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones as herbicides to control barnyard grass growth.
Preferably, the herbicide contains 0.1-99 wt% of active ingredients, and the active ingredients are 2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-diketone compounds.
Preferably, the herbicide also comprises 0.1 to 20 weight percent of surfactant or 0 to 99.9 weight percent of solid or liquid diluent.
The invention has the beneficial effects that: the compound of the invention has high activity as herbicide for treating rice stem leaves and has special effect on barnyard grass, thereby effectively controlling the harm of the barnyard grass.
Detailed Description
The following examples are provided to illustrate the present invention and disclose 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones of the formula:
the R1-R3 of the compound in the structural formula are selected from the groups shown in the table 1:
table 1: R1-R3 in the structural formula.
R1 | R2 | R3 | |
1 | Cl | Cl | SO2CH3 |
2 | Br | Cl | SO2CH3 |
3 | F | Cl | SO2CH3 |
4 | Br | Br | SO2CH3 |
5 | F | F | SO2CH3 |
6 | CH3 | Cl | SO2CH3 |
7 | Cl | Cl | SO2CH2CH3 |
8 | Br | Cl | SO2CH2CH3 |
9 | F | Cl | SO2CH2CH3 |
10 | Br | Br | SO2CH2CH3 |
11 | F | F | SO2CH2CH3 |
12 | CH3 | Cl | SO2CH2CH3 |
The preparation of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones is described below with reference to the examples.
Example 1:
160g of 3, 7-dichloro-5-methanesulfonyl-8-quinolinecarboxylic acid, 400ml of dichloroethane, and 75g of thionyl chloride, were heated to 78 ℃ for reflux reaction for 2 hours to obtain an acid chloride solution. And then cooling to room temperature, adding 52g of cyclohexanedione, dropwise adding 60g of triethylamine at 20-25 ℃, and reacting for 1 hour after the addition is finished to obtain an esterification solution.
3g of acetone cyanohydrin was added and the stirring was continued overnight at room temperature to obtain the product. Then 400ml of water is added to the mixture and the mixture is distilled to about 100 ℃ under normal pressure to obtain a yellow solid product.
13C NMR:δ20.0(1C,s),42.0(2C,s),44.3(1C,s),80.8(1C,s), 126.5(1C,s),126.8(1C,s),127.0(1C,s),128.0(1C,s),129.0(1C,s), 132.7(1C,s),142.6(1C,s),146.9(1C,s),156.0(1C,s),197.7(1C,s), 211.6(2C,s).
Example 2:
160g of 3, 7-dichloro-5-methanesulfonyl-8-quinolinecarboxylic acid, 400ml of toluene and 75g of thionyl chloride are heated to 78 ℃ for reflux reaction for 2 hours to obtain an acyl chloride solution. And then cooling to room temperature, adding 52g of cyclohexanedione, dropwise adding 60g of triethylamine at 20-25 ℃, and reacting for 1 hour after the addition is finished to obtain an esterification solution.
3g of acetone cyanohydrin was added and the stirring was continued overnight at room temperature to obtain the product. Then 400ml of water is added, and the mixture is distilled to about 110 ℃ under normal pressure to obtain a yellow solid product.
13C NMR:δ20.0(1C,s),42.0(2C,s),44.3(1C,s),80.8(1C,s), 126.5(1C,s),126.8(1C,s),127.0(1C,s),128.0(1C,s),129.0(1C,s), 132.7(1C,s),142.6(1C,s),146.9(1C,s),156.0(1C,s),197.7(1C,s), 211.6(2C,s).
Example 3:
160g of 3, 7-dichloro-5-methanesulfonyl-8-quinolinecarboxylic acid, 400ml of dichloroethane, and 75g of thionyl chloride were heated to 70 ℃ to carry out a reflux reaction for 4 hours, thereby obtaining an acid chloride solution. Then, the temperature is reduced to room temperature, 52g of cyclohexanedione is added, 60g of triethylamine is added dropwise at the temperature of 10-15 ℃, and the esterification solution is obtained after the addition of the triethylamine is finished and the reaction is carried out for 1 hour.
3g of acetone cyanohydrin was added and the stirring was continued overnight at room temperature to obtain the product. Then 400ml of water is added to the mixture and the mixture is distilled to about 100 ℃ under normal pressure to obtain a yellow solid product.
13C NMR:δ20.0(1C,s),42.0(2C,s),44.3(1C,s),80.8(1C,s), 126.5(1C,s),126.8(1C,s),127.0(1C,s),128.0(1C,s),129.0(1C,s), 132.7(1C,s),142.6(1C,s),146.9(1C,s),156.0(1C,s),197.7(1C,s), 211.6(2C,s).
Example 4:
160g of 3, 7-dichloro-5-methanesulfonyl-8-quinolinecarboxylic acid, 400ml of xylene and 75g of thionyl chloride are heated to 70 ℃ for reflux reaction for 4 hours to obtain an acid chloride solution. Then, the temperature is reduced to room temperature, 52g of cyclohexanedione is added, 60g of triethylamine is added dropwise at the temperature of 10-15 ℃, and the esterification solution is obtained after the addition of the triethylamine is finished and the reaction is carried out for 1 hour.
3g of acetone cyanohydrin was added and the stirring was continued overnight at room temperature to obtain the product. Then 400ml of water is added to the mixture and the mixture is distilled to about 120 ℃ under normal pressure to obtain a yellow solid product.
13C NMR:δ20.0(1C,s),42.0(2C,s),44.3(1C,s),80.8(1C,s), 126.5(1C,s),126.8(1C,s),127.0(1C,s),128.0(1C,s),129.0(1C,s), 132.7(1C,s),142.6(1C,s),146.9(1C,s),156.0(1C,s),197.7(1C,s), 211.6(2C,s).
The following examples are given to illustrate specific applications of the present 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones.
For the use of the compounds of the invention as herbicides, they are formulated by combining them with carriers, surfactants, dispersants or adjuvants of suitable type, for example wettable powders, emulsions, granules, suspensions and solvents. The compound is used as it is or after dilution with a suitable medium, as required. The furnish may be prepared from spray volumes of several hundred liters per acre to several thousand liters per acre. The formulations may optionally contain from about 0.1% to about 99% by weight of the active ingredient, with the addition of from 0.1% to about 20% surfactant or from 0% to about 99.9% solid or liquid diluent being suggested. The formulations will contain the corresponding active ingredients in the proportions shown in table 2.
Table 2: formulation composition
The specific ratio of active ingredients depends on the desired use. High ratios of surfactant to active ingredient are sometimes desirable and are achieved by incorporation into the formulation or mixing in a tank.
Solid diluents with high adsorptivity are preferred for wettable powders. The liquid diluent and solvent are preferably stable to phase separation at 0 ℃. All formulations may contain small amounts of additives to prevent the formation, clumping, corrosion and growth of microorganisms.
According to conventional methods for preparing compositions, solutions can be mixed by merely pulverizing the ingredients and fine solids by blending and powdering with a hammer mill. Suspensions can be made by wet milling and granules can be made by spraying the active ingredient onto a particulate carrier.
The following description of typical ingredients is given in conjunction with specific preparation examples.
1, preparing materials: wettable powders
The components are mixed thoroughly, the liquid surfactant sprayed onto the solid ingredients is then mixed and hammer milled until substantially all solids are less than 100 μm.
Active ingredient (Compound 1 in Table 1) | 20% by weight |
Dodecyl phenol polyglycol ether | 2% by weight |
Lignosulfonic acid sodium salt | 4% by weight |
Sodium aluminosilicate | 6% by weight |
Montmorillonite clay | 68% by weight |
And (3) preparing a material 2: wettable powders
The components are mixed, hammer milled until substantially all solids are less than 25 μm, and packaged.
Active ingredient (Compound 1 in Table 1) | 80% by weight |
Sodium alkyl naphthalene sulfonate | 2% by weight |
Lignosulfonic acid sodium salt | 2% by weight |
Synthetic amorphous silica | 3% by weight |
Kaolin clay | 13% by weight |
And (3) preparing materials: emulsion and method of making
The components were mixed and dissolved uniformly to give an emulsion.
Active ingredient (Compound 1 in Table 1) | 30% by weight |
Cyclohexanone | 20% by weight |
Polyoxyethylene alkylaryl ethers | 11% by weight |
Alkyl calcium benzene sulfonate | 4% by weight |
Methylnaphthalene | 35% by weight |
And (4) preparing materials: granules
The components were mixed well and 20 parts by weight of water were added to 100 parts by weight of the component mixture.
The component mixture was granulated to a size of 14 to 32 mesh with an extrusion granulator and dried.
Active ingredient (Compound 1 in Table 1) | 5% by weight |
Ammonium lauryl sulfonate | 2% by weight |
Sodium lignosulfonate | 5% by weight |
Carboxymethyl cellulose | 2% by weight |
Potassium sulfate | 16% by weight |
Gypsum plaster | 70% by weight |
The formulations according to the invention are sprayed and diluted to a certain concentration.
The compound of the invention has high activity as herbicide for treating rice stem leaves and has special effect on barnyard grass, thereby effectively controlling the harm of the barnyard grass.
The dosage of the active ingredients can be 2 g/mu to 100 g/mu, preferably 5 g/mu to 45 g/mu. The amount of the compound of the present invention used depends on the age of the weeds. The herbicides of the present invention may be used alone or in combination with other herbicides, insecticides or fungicides. In particular, it is necessary to add one or more agents selected from the following: bentazone, quinclorac, propanil, simetryn, MCPA, fenpyr, flumetsulam, bentazon, prosulfocarb, bensulfuron-methyl, pyrazosulfuron-ethyl, metsulfuron-methyl, thifensulfuron-methyl, bentazone, penoxsulam, cyhalofop-butyl, metamifop and fluroxypyr.
The herbicidal effect of the compounds of the present invention was examined, and the test was as follows.
Test example 1: stem and leaf treatment test
The method comprises the steps of placing seeds of rice, wheat and barnyard grass (seeds of the barnyard grass are collected from Lujiang Anhui, and are detected to generate drug resistance to penoxsulam, bispyribac and pyribenzoxim), digitaria sanguinalis, eleusine indica, setaria viridis and gynura bicolor in a plastic basin filled with soil, then covering the plastic basin with 0.5-2 cm of soil to enable the seeds to grow in a good greenhouse environment, treating test plants in a 4-5 leaf stage after sowing for 2-3 weeks, respectively dissolving a tested compound with DMF (dimethyl formamide) in the test solution, then adding Tween 80, diluting the solution with certain water into a solution with a certain concentration, and spraying the solution onto the plants by using a spray tower. The concentration of the spray is chosen such that a specific amount of active compound is desired. After a further 14 days of treatment, the plants were evaluated for the degree of damage, expressed as% damage, relative to the untreated control sample.
In the tests, the active compounds according to the invention have excellent selectivity for plants and herbicidal activity against weeds. Among the compounds of the present invention, some of the compounds in Table 1 have herbicidal activity as shown in Table 3.
Table 3: herbicidal activity of the compounds
These test results show that the compounds of the present invention have excellent selectivity for rice and excellent herbicidal activity against barnyard grass. Echinochloa crusgalli in paddy fields has become more and more resistant to drugs with the use of ALS inhibitor (penoxsulam, pyribenzoxim, bispyribac-sodium and the like) herbicides in the next year, and great challenges are created in China, southeast Asia and the like. Currently, the mainstream herbicides are ALS inhibitors, so that the search for medicaments with different mechanisms brings new choices, and has great social value and commercial value. Through long-term screening, we surprisingly found that the compound of the invention can have excellent control effect on barnyard grass which is resistant to ALS inhibitors and is from Anhui Lujiang county in China, and has good selectivity on rice.
There are, of course, many other specific embodiments of the invention and these are not to be considered as limiting. All technical solutions formed by adopting equivalent replacement or equivalent transformation are within the scope of the invention claimed by the invention.
Claims (10)
- A 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-dione compound, characterized in that: the compound has the following structural formula:wherein R1 and R2 are any one of hydrogen, benzyl, phenyl, trifluoromethyl, halogen, C1-C6 alkyl, C1-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C3 haloalkyl, C1-C3 haloalkoxy, C2-C4 alkoxyalkoxy, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C3 alkoxycarbonyl, and C1-C3 alkylcarbonyl;r3 is any one of C1-C6 alkyl, benzyl, phenyl, trifluoromethyl, C1-C6 cycloalkyl, C1-C3 haloalkyl, C2-C4 alkoxyalkoxy, C2-C6 alkenyl and C2-C6 alkynyl.
- 2. 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones according to claim 1, wherein: r1, R2 are halogen; r3 is C1-C3 alkyl.
- 3. A process for the preparation of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones according to claim 1, wherein: the method comprises the following steps:s1, taking substituted quinolinecarboxylic acid as a raw material, adding a chlorinating agent into a solvent, and reacting at the temperature of 0-100 ℃ to obtain an acyl chloride solution;s2, cooling to room temperature, adding 1, 3-cyclohexanedione, dropwise adding organic base at 0-100 ℃, and reacting to obtain an esterification solution;and S3, adding a translocating agent into the esterification solution obtained in the S2, continuously stirring at room temperature overnight, then adding water, and removing the solvent by distillation at normal pressure to obtain a yellow solid product.
- 4. A process for the preparation of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones according to claim 3, wherein: the solvent in the S1 is one or more of tetrahydrofuran, ethyl acetate, acetonitrile, toluene, xylene, hexane, dichloromethane, dichloroethane and carbon tetrachloride.
- 5. A process for the preparation of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones according to claim 3, wherein: and the chlorinating agent in the S1 is one or the combination of more than one of thionyl chloride, phosgene, diphosgene, triphosgene, oxalyl chloride, phosphorus trichloride, phosphorus oxychloride and phosphorus pentachloride.
- 6. A process for the preparation of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones according to claim 3, wherein: the S2 medium alkali is one or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, triethylamine, pyridine and the like.
- 7. A process for the preparation of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones according to claim 3, wherein: the transfer agent in the S3 is one or more of acetone cyanohydrin, butanone cyanohydrin, sodium cyanide, potassium cyanide and the like.
- Use of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones as herbicides to control barnyard grass growth.
- 9. Use of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones as claimed in claim 8 as herbicides for controlling barnyard grass growth, characterized in that: the herbicide contains 0.1-99 wt% of active ingredients, and the active ingredients are 2- (quinoline-8-yl) carbonyl-cyclohexane-1, 3-diketone compounds.
- 10. Use of 2- (quinolin-8-yl) carbonyl-cyclohexane-1, 3-diones as claimed in claim 9 as herbicides for controlling barnyard grass growth, characterized in that: the herbicide also comprises 0.1-20 wt% of a surfactant or 0-99.9 wt% of a solid or liquid diluent.
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