CN108570041A - A kind of preparation method of the compound of uracil containing isoxazoline - Google Patents
A kind of preparation method of the compound of uracil containing isoxazoline Download PDFInfo
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- CN108570041A CN108570041A CN201710149117.XA CN201710149117A CN108570041A CN 108570041 A CN108570041 A CN 108570041A CN 201710149117 A CN201710149117 A CN 201710149117A CN 108570041 A CN108570041 A CN 108570041A
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- compound
- alkyl
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- carbonyl
- hydrogen
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 68
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- WEQPBCSPRXFQQS-UHFFFAOYSA-N 4,5-dihydro-1,2-oxazole Chemical compound C1CC=NO1 WEQPBCSPRXFQQS-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229940035893 uracil Drugs 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims abstract description 27
- -1 dimethyl methyl acyl chloride Chemical class 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 9
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 claims abstract 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 52
- 229910052739 hydrogen Inorganic materials 0.000 claims description 43
- 239000001257 hydrogen Substances 0.000 claims description 43
- 150000002431 hydrogen Chemical class 0.000 claims description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 238000007363 ring formation reaction Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000012312 sodium hydride Substances 0.000 claims description 6
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229940113088 dimethylacetamide Drugs 0.000 claims description 4
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-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
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 4
- 125000006559 (C1-C3) alkylamino group Chemical group 0.000 claims description 3
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 125000006603 (C1-C3) alkylaminosulfonyl group Chemical group 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 2
- 125000006254 cycloalkyl carbonyl group Chemical group 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 125000004001 thioalkyl group Chemical group 0.000 claims description 2
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 claims 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims 1
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 230000001035 methylating effect Effects 0.000 abstract 1
- 239000002574 poison Substances 0.000 abstract 1
- 231100000614 poison Toxicity 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 11
- OBTZDIRUQWFRFZ-UHFFFAOYSA-N 2-(5-methylfuran-2-yl)-n-(4-methylphenyl)quinoline-4-carboxamide Chemical compound O1C(C)=CC=C1C1=CC(C(=O)NC=2C=CC(C)=CC=2)=C(C=CC=C2)C2=N1 OBTZDIRUQWFRFZ-UHFFFAOYSA-N 0.000 description 9
- 230000006837 decompression Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000004519 grease Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WQMAANNAZKNUDL-UHFFFAOYSA-N 2-dimethylaminoethyl chloride Chemical compound CN(C)CCCl WQMAANNAZKNUDL-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 3
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 3
- 230000002363 herbicidal effect Effects 0.000 description 3
- 125000004674 methylcarbonyl group Chemical group CC(=O)* 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- RLKBOGLIOLFMEK-NSCUHMNNSA-N amino (e)-but-2-enoate Chemical compound C\C=C\C(=O)ON RLKBOGLIOLFMEK-NSCUHMNNSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- PFBUKDPBVNJDEW-UHFFFAOYSA-N dichlorocarbene Chemical group Cl[C]Cl PFBUKDPBVNJDEW-UHFFFAOYSA-N 0.000 description 2
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000009333 weeding Methods 0.000 description 2
- 240000006995 Abutilon theophrasti Species 0.000 description 1
- 244000237956 Amaranthus retroflexus Species 0.000 description 1
- 235000013479 Amaranthus retroflexus Nutrition 0.000 description 1
- 241000772998 Arthraxon Species 0.000 description 1
- 0 CCC(N(C(N(*)C(C(F)(F)F)=C1)OC)C1=O)=CC=C(/C(/*)=I(\C)/C=C)C1=NOC(*)(*)C1(C)* Chemical compound CCC(N(C(N(*)C(C(F)(F)F)=C1)OC)C1=O)=CC=C(/C(/*)=I(\C)/C=C)C1=NOC(*)(*)C1(C)* 0.000 description 1
- VHRRNUXFOJNMOZ-IHWYPQMZSA-N CN/C(=C\C(F)(F)F)/C(=O)O Chemical compound CN/C(=C\C(F)(F)F)/C(=O)O VHRRNUXFOJNMOZ-IHWYPQMZSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 244000037364 Cinnamomum aromaticum Species 0.000 description 1
- 235000014489 Cinnamomum aromaticum Nutrition 0.000 description 1
- 244000150195 Cyperus longus Species 0.000 description 1
- 235000018109 Cyperus longus Nutrition 0.000 description 1
- 244000058871 Echinochloa crus-galli Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 235000001047 Hibiscus trionum Nutrition 0.000 description 1
- 241001075721 Hibiscus trionum Species 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 244000234609 Portulaca oleracea Species 0.000 description 1
- 235000001855 Portulaca oleracea Nutrition 0.000 description 1
- 235000010086 Setaria viridis var. viridis Nutrition 0.000 description 1
- 235000002594 Solanum nigrum Nutrition 0.000 description 1
- 240000002307 Solanum ptychanthum Species 0.000 description 1
- 241001251949 Xanthium sibiricum Species 0.000 description 1
- 240000003307 Zinnia violacea Species 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- YKYMGFHOJJOSEB-UHFFFAOYSA-N butan-1-ol;potassium Chemical compound [K].CCCCO YKYMGFHOJJOSEB-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 244000230342 green foxtail Species 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention belongs to organic synthesis fields, and the present invention provides a kind of preparation methods of the compound of uracil containing isoxazoline：It is reacted first with alkali in organic solvent including compound IV, N is then added, N dimethyl methyl acyl chloride reactions obtain compound III, subsequent compound III and compound II and target compound I is obtained by the reaction in acid.Reaction equation is as follows：
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of preparation side of the compound of uracil containing isoxazoline
Method.
Background technology
Patent WO2016095768 reports the compound of uracil containing isoxazoline as shown in general formula I：
Compound of Formula I has good activity of weeding, can efficiently control barnyard grass, green bristlegrass, difformed galingale herb, water Sha
The weeds such as grass, lady's-grass, hispid arthraxon, piemarker, youth-and-old-age, Amaranthus retroflexus, purslane, Siberian cocklebur, black nightshade, Cassia, flowerofanhour root or herb, Wild soybean,
It is obtained with good herbicidal effect under low dosage, agriculturally can be used as herbicide.It is somebody's turn to do though referring to prepare in patent
The method of class compound, but such as dichloromethylene alkyl dimethyl ammonium chloride of cyclization reagent used in the preparation method, it is not industrial
Change large-scale production and it is expensive, cause compound shown in general formula I to be not easy to industrialized production；Simultaneously in preparation process first
Cyclization methylates again, and needs column chromatography, is not easy to industrialize.
In recent years, even if the compound of uracil containing isoxazoline shown in general formula I has good activity of weeding, but it is existing
Some preparation methods cannot meet the requirement of industrialized production, thus hinder the popularization and application of the compound.For this purpose, existing be badly in need of
A kind of new preparation method does not have industrialized and expensive dichloromethylene alkyl dimethyl ammonium chloride to avoid using, with
Reaching reduces cost, so that compound industry metaplasia shown in general formula I is produced.
Invention content
Present invention aims at provide a kind of preparation method of the compound of uracil containing isoxazoline.
To achieve the above object, the invention adopts a technical scheme as：
A kind of preparation method of the compound of uracil containing isoxazoline, it is characterised in that：Reaction equation is as follows：
Compound III is carried out cyclization under acid condition with compound II to react, obtains target compound I；
In formula,
R1Selected from hydrogen, C1-C4Alkyl or C1-C4Halogenated alkyl；
R2、R3It may be the same or different, be respectively selected from hydrogen, fluorine, chlorine or methyl；
R4Selected from hydrogen or C1-C4Alkyl；
R5Selected from hydrogen, C1-C4Alkyl, CO2R8Or CH2OR9；
R6Selected from hydrogen, cyano, C1-C4Alkyl, C1-C4Halogenated alkyl, CO2R8Or CH2OR9；
R7Selected from hydrogen, C1-C4Alkyl or C1-C4Halogenated alkyl；
R8Selected from hydrogen, C1-C4Alkyl, C1-C4Halogenated alkyl, C3-C4Alkenyl, C3-C4Alkynyl, C1-C4Alkoxy C1-C4Alkane
Base, C1-C4Alkyl carbonyl oxygroup C2-C3Alkyl, it is unsubstituted or benzyl, the furans Asia that following group replace are independently selected from by 1-4
Methyl or tetrahydrofuran methylene：Halogen, CN, NO2、C1-C4Alkyl or C1-C4Halogenated alkyl；
R9Selected from hydrogen, C1-C4Alkyl, C1-C4Halogenated alkyl, C1-C4Alkoxy carbonyl, C1-C4Alkyl-carbonyl, C1-C4It is halogenated
Alkyl-carbonyl, C3-C6Naphthene base carbonyl, C3-C6Halogenated cycloalkyl carbonyl, C1-C4Alkyl sulphonyl, C1-C4Halogenated alkyl sulphonyl
Base, C1-C3Alkyl amino sulfonyl, two (C1-C3) alkyl amino sulfonyl, C1-C3Alkyl amino-carbonyl, two (C1-C3) alkyl ammonia
Base carbonyl, two (C1-C3) thio-alkyl amino-carbonyl, C1-C2Alkylthio group C2-C4Alkyl-carbonyl, it is unsubstituted or independent by 1-4
Phenyl C selected from the substitution of following group1-C2Alkyl, phenylcarbonyl group, phenyl C1-C2Alkyl-carbonyl, phenyl C2-C4Alkenyl carbonyl, benzene
Oxygroup C1-C2Alkyl-carbonyl, thiophenecarbonyl groups, pyrazoles carbonyl, quinolinecarbonyl：Halogen, CN, NO2、C1-C4Alkyl, C1-C4Alkyl halide
Base, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkoxy carbonyl, C1-C4Alkylthio group, C1-C4Alkyl sulphonyl or by 1-
4 halogens, CN, NO2、C1-C4Alkyl, C1-C4Halogenated alkyl, C1-C4Alkoxy or C1-C4The benzene that halogenated alkoxy independently replaces
Oxygroup.
The preferred embodiment of prepare compound I is：By compound III and compound II under acid condition, in 25-150 DEG C
Cyclization reaction is carried out, target compound I is obtained；
The acid is acetic acid or hydrochloric acid；The dosage of acid is 1-20 times of compound III weight；The throwing of compound II and III
Expect that molar ratio is 1:1-1:1.5.
The further preferred scheme of prepare compound I is：The progress cyclization reaction is under the conditions of acetic acid, in 100-120
It DEG C carries out, sour dosage is 1-10 times of compound III weight；The molar ratio of compound II and III are 1:1-1:1.2；
The compound III be compound IV under alkaline condition with N, N- dimethyl methyls acyl chlorides in organic solvent, in
It reacts and obtains at a temperature of 0-120 DEG C；Wherein, R in compound IV formulas1Selected from hydrogen, C1-C4Alkyl or C1-C4Halogenated alkyl.
The organic solvent is atent solvent, and the dosage of organic solvent is 1-20 times of compound IV weight.
The preferred embodiment of prepare compound III is：The compound III be compound IV under alkaline condition with N, N- bis-
Methyl formyl chloride in organic solvent, is reacted at a temperature of 0-80 DEG C and is obtained；
Wherein organic solvent is benzene, toluene, tetrahydrofuran, dioxane, N,N-dimethylformamide (DMF), N, N- bis-
The dosage of methylacetamide (DMA), dimethyl sulfoxide (DMSO) (DMSO) or hexamethylphosphoramide (HMPA), organic solvent is compound
2-10 times of IV weight；Alkali is sodium hydroxide, potassium hydroxide, sodium hydride, Sodamide, sodium methoxide, potassium carbonate, potassium tert-butoxide or three
The molar ratio of ethamine, compound IV and alkali is 1:1-1:3；Compound IV and N, the molar ratio of N- dimethyl methyl acyl chlorides
It is 1:1-1:3.
The further preferred scheme of prepare compound III is：The reaction temperature is 0-30 DEG C；Solvent is N, N- dimethyl
Formamide (DMF), DMAC N,N' dimethyl acetamide (DMA) or dimethyl sulfoxide (DMSO) (DMSO)；The alkali is sodium hydride, Sodamide or uncle
Butanol potassium；The molar ratio of compound IV and alkali is 1:1-1:2；Compound IV and N, N- dimethyl methyl acyl chlorides feed intake mole
Than being 1:1-1:1.5.
The preparation method of the compound of uracil containing isoxazoline further includes：With compound III and compound II in
After carrying out the obtained target compound I of cyclization reaction under acid condition, the step of compound I is purified is carried out to the preparation.
The preparation method of the compound of uracil containing isoxazoline further includes：After the compound III is made, and
Before compound III is reacted with compound II, the step of purifying to the compound IIII.
The step of purifying is to be purified simultaneously using silica gel or diatomite, preferred substituent group in above-mentioned reaction equation
For：
R1Selected from hydrogen, C1-C4Alkyl；
R2、R3It may be the same or different, be respectively selected from hydrogen, fluorine or chlorine；
R4、R5It is selected from hydrogen；
R6Selected from hydrogen, cyano, C1-C4Alkyl, C1-C4Halogenated alkyl, CO2R8Or CH2OR9；
R7Selected from hydrogen, C1-C4Alkyl or C1-C4Halogenated alkyl；
R8Selected from hydrogen, C1-C4Alkyl, C1-C4Halogenated alkyl, C3-C4Alkenyl, C3-C4Alkynyl, C1-C4Alkoxy C1-C4Alkane
Base, C1-C4Alkyl carbonyl oxygroup C2-C3Alkyl or tetrahydrofuran methylene；
R9Selected from hydrogen, C1-C4Alkyl, C1-C4Halogenated alkyl or C1-C4Alkyl-carbonyl；
The further preferred substituent group of reaction equation is：
R1Selected from hydrogen, methyl；
R2、R3It may be the same or different, be respectively selected from hydrogen, fluorine or chlorine；
R4、R5It is selected from hydrogen；
R6Selected from hydrogen, C1-C4Alkyl, CO2R8Or CH2OR9；
R7Selected from hydrogen, methyl, ethyl, tertiary butyl or trifluoromethyl；
R8Selected from hydrogen, methyl, ethyl, n-propyl, normal-butyl, isopropyl, isobutyl group, tertiary butyl, trifluoroethyl, allyl
Base, propargyl, methoxy ethyl, ethoxyethyl group, methyl carbonyl oxygroup ethyl, 2- tetrahydrofurans methylene or 3- tetrahydrofurans
Methylene；
R9Selected from acetyl group；
The substituent group of reaction equation still more preferably is：
R1Selected from hydrogen, methyl；
R2、R3It may be the same or different, be respectively selected from hydrogen, fluorine or chlorine；
R4、R5It is selected from hydrogen；
R6Selected from hydrogen, cyano, methyl, ethyl, n-propyl, normal-butyl, isopropyl, isobutyl group, tertiary butyl, trifluoroethyl,
Trifluoromethyl or CO2R8；
R7Selected from hydrogen, methyl, ethyl, tertiary butyl or trifluoromethyl；
R8Selected from hydrogen, methyl, ethyl, n-propyl, normal-butyl, isopropyl, isobutyl group, tertiary butyl, trifluoroethyl, allyl
Base, propargyl, methoxy ethyl, ethoxyethyl group, methyl carbonyl oxygroup ethyl, 2- tetrahydrofurans methylene or 3- tetrahydrofurans
Methylene；
The most preferred substituent group of reaction equation is：
R1Selected from hydrogen, methyl；
R2、R3It may be the same or different, be respectively selected from hydrogen, fluorine or chlorine；
R4、R5It is selected from hydrogen；
R6Selected from hydrogen, cyano, methyl, ethyl, n-propyl, normal-butyl, isopropyl, isobutyl group, tertiary butyl, trifluoroethyl,
Trifluoromethyl or CO2R8；
R7Selected from hydrogen, methyl, ethyl, tertiary butyl or trifluoromethyl；
R8Selected from hydrogen, methyl, ethyl, n-propyl, normal-butyl, isopropyl, isobutyl group, tertiary butyl, trifluoroethyl, allyl
Base, propargyl, methoxy ethyl, ethoxyethyl group, methyl carbonyl oxygroup ethyl, 2- tetrahydrofurans methylene or 3- tetrahydrofurans
Methylene.
External standard method is used with high performance liquid chromatography for the content of product in above-mentioned preparation process；And the change obtained
Conjunction is to prepare the important intermediate (WO2016095768) of high herbicidal reactive compound.
In addition, raw material N of the present invention, N- dimethyl methyls acyl chlorides can be by being commercially available.Compound IV can be with
It is prepared by the method reported in commercially available or bibliography US20030216594 or WO2002053518, compound II references
Patent WO2016095768 synthesis.
Advantage for present invention：
The raw material of preparation method provided by the present invention, use is easy to get, of low cost, can effectively reduce process costs；And
And this method concise in technology can be obtained by the direct cyclization of compound II and III compared to existing preparation process, save first
Base, and without column chromatography, to effectively reduce technological operation difficulty；In addition, providing preparation process using the present invention
During progress, compound III and I can be used silica gel or diatomite and carry out purification process to it, with DNA purity, high yield
Product, the process is simple and efficient, is easy to industrialized production, can meet industrialization production requirements.
Specific implementation mode
Following specific examples is used for further illustrating the present invention, but the present invention is by no means limited to these examples；Under and
It is mass percent, such as content, purity to state percentage involved in embodiment.
The synthesis (1) of 1 compound I-1 of embodiment
Sodium hydride (60%, 80g, 2mol) is added in 500mL DMF, trifluoro aminocrotonate is added dropwise under ice bath and (changes
Close object IV-1,98%, 186g, 1mol) and 120mL DMF mixed solution, be added dropwise through 1.5 hours, be warmed to room temperature (20-
25 DEG C) it stirs 1 hour, dimethylaminoethyl chloride (97%, 166g, 1.5mol) is added dropwise under condition of ice bath, stirs 3~4 at room temperature
Hour, the reaction was complete for TLC monitorings.Decompression steam most DMF, pour into 500mL saturated sodium bicarbonate aqueous solutions, be used in combination according to
It is secondary to be extracted twice with 600mL ethyl acetate, combined ethyl acetate phase, after the filtering of 100g diatomite is added in Buchner funnel, decompression
It is compound III-1, purity 96.7% (HPLC normalizings content), yield 90.6% that distillation, which obtains 238g grease,.
Successively by 238g compounds III-1 (96.7%, 0.906mol) and 274g compound II-1 (references
WO2016095768 is synthesized, and 90%, 0.82mol) it is added in the reaction bulb equipped with 680ml acetic acid, 110 DEG C of reactions are warming up to,
Form dark solution, be kept at this temperature reaction 4h, decompression it is whole go out 500mL or so acetic acid, pour into 500mL water, room temperature
Stirring filters to obtain crude product after 30 minutes, obtains white solid 285g, as compound I-1 through ethyl alcohol recrystallization, content 94.5% is received
Rate, 70.9%, 105.2 DEG C of fusing point.1H-NMR (300MHz, internal standard TMS, solvent C DCl3)δ(ppm):1.33 (t, 3H), 1.71
(s, 3H), 3.34 (d, 1H), 3.89 (d, 1H), 4.27 (m, 2H), 6.21 (s, 1H), 7.36 (d, 1H), 7.71 (d, 1H).
The synthesis (2) of 2 compound I-1 of embodiment
Potassium tert-butoxide (98%, 172g, 1.5mol) is added in 650mL DMF, trifluoro aminocrotonate is then added
(compound IV-1,98%, 186g, 1mol), (20-25 DEG C) of room temperature stir 1 hour, dropwise addition dimethylaminoethyl chloride (97%,
166g, 1.5mol), it stirs 5 hours at room temperature, the reaction was complete for TLC monitorings.Decompression steams most DMF, pours into 500mL water
In, it is used in combination and is extracted twice successively with 600mL ethyl acetate, 100g diatomite mistakes are added in Buchner funnel for combined ethyl acetate phase
After filter, it is compound III-1, purity 95% (HPLC normalizings content), yield 85.3% that vacuum distillation, which obtains 228g grease,.
Successively by 228g compounds III-1 (96.7%, 0.853mol) and 270g compound II-1 (references
WO2016095768 is synthesized, and 90%, 0.81mol) it is added in the reaction bulb equipped with 600ml acetic acid, 110 DEG C of reactions are warming up to,
Form dark solution, be kept at this temperature reaction 4h, decompression it is whole go out 500mL or so acetic acid, pour into 500mL water, room temperature
Stirring filters to obtain crude product after 30 minutes, and light yellow solid 245g, as compound I-1 are obtained through ethyl alcohol recrystallization, content 95.2%,
Yield 62%, 103.8 DEG C of fusing point.
The synthesis (1) of 3 compound I-2 of embodiment
Sodium hydride (60%, 80g, 2mol) is added in 500mL DMF, fluoroform aminocrotonate is added dropwise under ice bath
The mixed solution of (compound IV-2,97%, 203g, 1mol) and 120mL DMF, were added dropwise through 1.5 hours, are warmed to room temperature
(20-25 DEG C) is stirred 1 hour, and dimethylaminoethyl chloride (97%, 166g, 1.5mol) is added dropwise under condition of ice bath, stirs 3 at room temperature
~4 hours, the reaction was complete for TLC monitorings.Decompression steams most DMF, pours into 500mL saturated sodium bicarbonate aqueous solutions, and
With being extracted twice successively with 600mL ethyl acetate, combined ethyl acetate phase, after the filtering of 100g diatomite is added in Buchner funnel,
It is compound III-2, purity 97.2% (HPLC normalizings content), yield 91.8% that vacuum distillation, which obtains 253g grease,.
Successively by 253g compounds III-2 (97.2%, 0.918mol) and 274g compound II-1 (references
WO2016095768 is synthesized, and 90%, 0.82mol) it is added in the reaction bulb equipped with 680ml acetic acid, 110 DEG C of reactions are warming up to,
Dark solution is formed, reaction 8h is kept at this temperature, decompression steams all acetic acid, and 800mL ethyl acetate is added, uses 500mL
Saturated sodium bicarbonate aqueous solution is washed twice, is washed once with 500mL saturated common salts, and 150g diatomite is added in Buchner funnel and filters second
After acetoacetic ester phase, it is compound I-2, content 92.1%, yield 77.1% to be evaporated under reduced pressure to grease 328g.1H-NMR
(300MHz, internal standard TMS, solvent C DCl3)δ(ppm):1.35 (t, 3H), 1.68 (s, 3H), 3.38 (d, 1H), 3.60 (s, 3H),
3.90 (d, 1H), 4.30 (m, 2H), 6.25 (s, 1H), 7.38 (d, 1H), 7.79 (d, 1H).
The synthesis (2) of 4 compound I-2 of embodiment
Potassium tert-butoxide (98%, 172g, 1.5mol) is added in 650mL DMF, trifluoro methylamino crotonic acid is then added
Ester (compound IV-2,97%, 203g, 1mol), (20-25 DEG C) of room temperature stir 1 hour, dropwise addition dimethylaminoethyl chloride (97%,
166g, 1.5mol), it stirs 5 hours at room temperature, the reaction was complete for TLC monitorings.Decompression steams most DMF, pours into 500mL water
In, it is used in combination and is extracted twice successively with 600mL ethyl acetate, 100g diatomite mistakes are added in Buchner funnel for combined ethyl acetate phase
After filter, it is compound III-2, purity 95.8% (HPLC normalizings content), yield that vacuum distillation, which obtains 246g grease,
87.9%.
Successively by 246g compounds III-1 (95.8%, 0.879mol) and 267g compound II-1 (references
WO2016095768 is synthesized, and 90%, 0.80mol) it is added in the reaction bulb equipped with 620ml acetic acid, 110 DEG C of reactions are warming up to,
Dark solution is formed, reaction 8h is kept at this temperature, decompression steams all acetic acid, and 700mL ethyl acetate is added, uses 500mL
Saturated sodium bicarbonate aqueous solution is washed twice, is washed once with 500mL saturated common salts, and 150g diatomite is added in Buchner funnel and filters second
After acetoacetic ester phase, it is compound I-2, content 91.5%, yield 79.5% to be evaporated under reduced pressure to grease 332g.
The following table 1 describes in the way of described in embodiment 1,2,3,4, and prepared removes compound I-1 and compound
Other belong to Formulas I compound represented and the nuclear magnetic data of these compounds other than I-2, specific as follows：
Table 1
In addition, by the different substituents by feed change in reaction equation, and according to the record of above-mentioned preparation process, may be used also
To obtain compound of formula I shown in different substituents, this also shows the popularity of the method for the present invention application.
Claims (10)
1. a kind of preparation method of the compound of uracil containing isoxazoline, it is characterised in that：Reaction equation is as follows：
Compound III is carried out cyclization under acid condition with compound II to react, obtains target compound I；
In formula,
R1Selected from hydrogen, C1-C4Alkyl or C1-C4Halogenated alkyl；
R2、R3It may be the same or different, be respectively selected from hydrogen, fluorine, chlorine or methyl；
R4Selected from hydrogen or C1-C4Alkyl；
R5Selected from hydrogen, C1-C4Alkyl, CO2R8Or CH2OR9；
R6Selected from hydrogen, cyano, C1-C4Alkyl, C1-C4Halogenated alkyl, CO2R8Or CH2OR9；
R7Selected from hydrogen, C1-C4Alkyl or C1-C4Halogenated alkyl；
R8Selected from hydrogen, C1-C4Alkyl, C1-C4Halogenated alkyl, C3-C4Alkenyl, C3-C4Alkynyl, C1-C4Alkoxy C1-C4Alkyl, C1-
C4Alkyl carbonyl oxygroup C2-C3Alkyl, it is unsubstituted or by 1-4 be independently selected from benzyl, fural that following group replaces or
Tetrahydrofuran methylene：Halogen, CN, NO2、C1-C4Alkyl or C1-C4Halogenated alkyl；
R9Selected from hydrogen, C1-C4Alkyl, C1-C4Halogenated alkyl, C1-C4Alkoxy carbonyl, C1-C4Alkyl-carbonyl, C1-C4Halogenated alkyl
Carbonyl, C3-C6Naphthene base carbonyl, C3-C6Halogenated cycloalkyl carbonyl, C1-C4Alkyl sulphonyl, C1-C4Halogenated alkyl sulfonyl, C1-
C3Alkyl amino sulfonyl, two (C1-C3) alkyl amino sulfonyl, C1-C3Alkyl amino-carbonyl, two (C1-C3) alkyl amino carbonyl
Base, two (C1-C3) thio-alkyl amino-carbonyl, C1-C2Alkylthio group C2-C4Alkyl-carbonyl, it is unsubstituted or be independently selected from by 1-4
The phenyl C of following group substitution1-C2Alkyl, phenylcarbonyl group, phenyl C1-C2Alkyl-carbonyl, phenyl C2-C4Alkenyl carbonyl, phenoxy group
C1-C2Alkyl-carbonyl, thiophenecarbonyl groups, pyrazoles carbonyl, quinolinecarbonyl：Halogen, CN, NO2、C1-C4Alkyl, C1-C4Halogenated alkyl, C1-
C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkoxy carbonyl, C1-C4Alkylthio group, C1-C4Alkyl sulphonyl or by 1-4 halogen
Element, CN, NO2、C1-C4Alkyl, C1-C4Halogenated alkyl, C1-C4Alkoxy or C1-C4The phenoxy group that halogenated alkoxy independently replaces.
2. the preparation method of the compound of uracil containing isoxazoline as described in claim 1, it is characterised in that：By compound
III and compound II carries out cyclization reaction under acid condition, in 25-150 DEG C, obtains target compound I；
The acid is acetic acid or hydrochloric acid；The dosage of acid is 1-20 times of compound III weight；Feeding intake for compound II and III rubs
You are than being 1:1-1:1.5.
3. the preparation method of the compound of uracil containing isoxazoline as described in claim 2, it is characterised in that：The progress
Cyclization is reacted under the conditions of acetic acid, and in 100-120 DEG C of progress, sour dosage is 1-10 times of compound III weight；Compound II
Molar ratio with III is 1:1-1:1.2.
4. the preparation method of the compound of uracil containing isoxazoline as described in claim 1, it is characterised in that：The chemical combination
Object III is compound IV under alkaline condition with N, and N- dimethyl methyls acyl chlorides in organic solvent, reacts at a temperature of 0-120 DEG C
It obtains；Wherein, R in compound IV formulas1Selected from hydrogen, C1-C4Alkyl or C1-C4Halogenated alkyl.
5. the preparation method of the compound of uracil containing isoxazoline as described in claim 4, it is characterised in that：It is described organic
Solvent is atent solvent, and the dosage of organic solvent is 1-20 times of compound IV weight.
6. by the preparation method of the compound of uracil containing isoxazoline described in claim 4 or 5, it is characterised in that：
The compound III be compound IV under alkaline condition with N, N- dimethyl methyls acyl chlorides in organic solvent, in 0-80
It reacts and obtains at a temperature of DEG C；
Wherein organic solvent is benzene, toluene, tetrahydrofuran, dioxane, N,N-dimethylformamide (DMF), N, N- dimethyl
The dosage of acetamide (DMA), dimethyl sulfoxide (DMSO) (DMSO) or hexamethylphosphoramide (HMPA), organic solvent is compound IV weights
2-10 times of amount；Alkali is sodium hydroxide, potassium hydroxide, sodium hydride, Sodamide, sodium methoxide, potassium carbonate, potassium tert-butoxide or three second
The molar ratio of amine, compound IV and alkali is 1:1-1:3；Compound IV and N, the molar ratio of N- dimethyl methyl acyl chlorides are
1:1-1:3。
7. the preparation method of the compound of uracil containing isoxazoline as described in claim 6, it is characterised in that：Described in preparation
The temperature of compound III reactions is 0-30 DEG C；Solvent is N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMA)
Or dimethyl sulfoxide (DMSO) (DMSO)；The alkali is sodium hydride, Sodamide or potassium tert-butoxide；The molar ratio of compound IV and alkali is
1:1-1:2；The molar ratio of compound IV and N, N- dimethyl methyl acyl chlorides are 1:1-1:1.5.
8. the preparation method of the compound of uracil containing isoxazoline as described in claim 1, it is characterised in that：It is described containing different
The preparation method of oxazoline uracil compound further includes：It is closed under acid condition with compound III and compound II
After target compound I is made in ring reaction, the step of compound I is purified is carried out to the preparation.
9. the preparation method of the compound of uracil containing isoxazoline as described in claim 4, it is characterised in that：It is described containing different
The preparation method of oxazoline uracil compound further includes：After the compound III is made, and compound III and chemical combination
Before object II reactions, the step of purifying to the compound IIII.
10. by claim 8 or the preparation method of 9 compounds of uracil containing isoxazoline, it is characterised in that：It is described pure
The step of change is to be purified using silica gel or diatomite.
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| WO2021088856A1 (en) * | 2019-11-07 | 2021-05-14 | 青岛清原化合物有限公司 | Substituted-isoxazoline-containing aromatic compound, preparation method therefor, herbicidal composition and use thereof |
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