CN110256308B - Synthesis process of mesotrione - Google Patents
Synthesis process of mesotrione Download PDFInfo
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- CN110256308B CN110256308B CN201910612878.3A CN201910612878A CN110256308B CN 110256308 B CN110256308 B CN 110256308B CN 201910612878 A CN201910612878 A CN 201910612878A CN 110256308 B CN110256308 B CN 110256308B
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- nitro
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- molecular sieve
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- KPUREKXXPHOJQT-UHFFFAOYSA-N mesotrione Chemical compound [O-][N+](=O)C1=CC(S(=O)(=O)C)=CC=C1C(=O)C1C(=O)CCCC1=O KPUREKXXPHOJQT-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000005578 Mesotrione Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000008569 process Effects 0.000 title claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 title claims description 24
- 238000003786 synthesis reaction Methods 0.000 title claims description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 68
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 52
- 239000002808 molecular sieve Substances 0.000 claims abstract description 39
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 125000002252 acyl group Chemical group 0.000 claims abstract description 34
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- QNOUABMNRMROSL-UHFFFAOYSA-N 110964-79-9 Chemical compound CS(=O)(=O)C1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 QNOUABMNRMROSL-UHFFFAOYSA-N 0.000 claims abstract description 25
- SKDDBIWRHFHMKM-UHFFFAOYSA-N 4-methylsulfonyl-2-nitrobenzoyl chloride Chemical compound CS(=O)(=O)C1=CC=C(C(Cl)=O)C([N+]([O-])=O)=C1 SKDDBIWRHFHMKM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- OXBDLEXAVKAJFD-UHFFFAOYSA-N 1-methyl-4-methylsulfonyl-2-nitrobenzene Chemical compound CC1=CC=C(S(C)(=O)=O)C=C1[N+]([O-])=O OXBDLEXAVKAJFD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000007670 refining Methods 0.000 claims abstract description 23
- -1 enol ester Chemical class 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 230000008707 rearrangement Effects 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 15
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 108
- 239000011964 heteropoly acid Substances 0.000 claims description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 21
- 238000004321 preservation Methods 0.000 claims description 19
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 17
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000000967 suction filtration Methods 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 10
- 238000010902 jet-milling Methods 0.000 claims description 10
- 239000012265 solid product Substances 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 9
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 7
- 229940011182 cobalt acetate Drugs 0.000 claims description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 7
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000010 aprotic solvent Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 150000003985 15-crown-5 derivatives Chemical group 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 231100000331 toxic Toxicity 0.000 abstract description 7
- 230000002588 toxic effect Effects 0.000 abstract description 7
- 238000006482 condensation reaction Methods 0.000 abstract description 5
- 230000002363 herbicidal effect Effects 0.000 abstract description 4
- 239000004009 herbicide Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- 229910001415 sodium ion Inorganic materials 0.000 description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 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 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000006462 rearrangement reaction Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- ZXOQKCSPENGHOG-UHFFFAOYSA-N 1-(bromomethyl)-4-methylsulfonyl-2-nitrobenzene Chemical compound CS(=O)(=O)C1=CC=C(CBr)C([N+]([O-])=O)=C1 ZXOQKCSPENGHOG-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- FKUYMLZIRPABFK-UHFFFAOYSA-N Plastoquinone 9 Natural products CC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCC1=CC(=O)C(C)=C(C)C1=O FKUYMLZIRPABFK-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- FKUYMLZIRPABFK-IQSNHBBHSA-N plastoquinone-9 Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC1=CC(=O)C(C)=C(C)C1=O FKUYMLZIRPABFK-IQSNHBBHSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HUGPVFHLSSCVSM-UHFFFAOYSA-N 4-methylsulfonyl-2-nitrobenzaldehyde Chemical compound CS(=O)(=O)C1=CC=C(C=O)C([N+]([O-])=O)=C1 HUGPVFHLSSCVSM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 102100033538 Clusterin-associated protein 1 Human genes 0.000 description 1
- 101000945057 Danio rerio Clusterin-associated protein 1 homolog Proteins 0.000 description 1
- 102000016680 Dioxygenases Human genes 0.000 description 1
- 108010028143 Dioxygenases Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 101000945060 Homo sapiens Clusterin-associated protein 1 Proteins 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 230000006696 biosynthetic metabolic pathway Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/06—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of herbicide technical preparation, and discloses a synthetic process of mesotrione, which comprises the following steps: (1) catalytic oxidation, namely generating 2-nitro-4-methylsulfonyl benzoic acid under the catalysis of manganese oxide octahedral molecular sieve loaded heteropoly acid-transition metal salt by taking 2-nitro-4-methylsulfonyl toluene as a raw material and oxygen as an oxidant; (2) performing acyl chlorination, namely performing acyl chlorination on 2-nitro-4-methylsulfonylbenzoic acid to generate 2-nitro-4-methylsulfonylbenzoyl chloride; (3) condensation, 2-nitro-4-methylsulfonyl benzoyl chloride and 1, 3-cyclohexanedione are subjected to condensation reaction to obtain enol ester intermediate reaction liquid; (4) rearranging, namely carrying out enol ester rearrangement on the enol ester intermediate under the catalysis of a rearrangement catalyst to obtain crude reaction liquid; (5) refining, and refining the crude reaction solution to obtain a finished product of mesotrione. The invention optimizes the reaction conditions, has high conversion rate of each step, high yield and purity of the product, does not relate to highly toxic materials in the whole production process, and has high safety.
Description
Technical Field
The invention belongs to the technical field of herbicide technical preparation, and particularly relates to a synthetic process of mesotrione.
Background
Mesotrione, also known as mesotrione and mesotrione, has the chemical name 2- (4-methanesulfonyl 2-nitro-benzoyl) -cyclohexane-1, 3-dione, and was manufactured by Syngenta and sold in Europe under the name gallisto (Miston) in 2001. Mesotrione can inhibit p-hydroxyphenylpyruvate dioxygenase (HPPD), ultimately affecting carotenoid biosynthesis. HPPD is a key enzyme in the plastoquinone and tocopherol biosynthesis pathway necessary for the normal growth of plants and can catalyze the biochemical process from tyrosine to plastoquinone in plants, and is one of the most important herbicide action targets at present. The mesotrione has the characteristics of wide weed control spectrum, high activity, strong miscibility, safety to succeeding crops, flexible use, strong environmental compatibility and the like, and has great development value and good popularization and application prospect in China in recent years.
More mesotrione is synthesized in the prior art, for example, Chinese patent with the publication number of CN103172549A discloses a preparation method of 2- (2-nitro-4-methylsulfonyl-benzoyl) cyclohexane-1, 3-dione, which takes 2-nitro-4-methylsulfonylbenzaldehyde and 1, 3-cyclohexanedione as raw materials and prepares high-purity 2- (2-nitro-4-methylsulfonyl-benzoyl) cyclohexane-1, 3-dione through reactions such as nucleophilic addition, oxidation and the like.
Chinese patent publication No. CN102174003A discloses a synthesis method of mesotrione, which comprises adding pyridine dropwise into 2-nitro-4-methylsulfonyl-benzoyl chloride, adding 1, 3-cyclohexanedione, adding rearrangement agent cyanide dropwise after the reaction is finished, and refining to obtain mesotrione after the rearrangement reaction is finished. The method adopts a large amount of toxic and malodorous harmful chemicals, such as pyridine and cyanide, and has high production cost, difficulty in raw material approval, purchase and operation and high production risk.
Yugang et al (Yugang, Guning, Qilin, Zhouyi. synthesis of mesotrione, a corn field herbicide [ J ]. Jiangsu agricultural science, 2007,23 (6): 661 one 662.) react 2-nitro-4-methylsulfonyl toluene with anhydrous bromine to generate 2-nitro-4-methylsulfonyl benzyl bromide, and then the 2-nitro-4-methylsulfonyl benzyl bromide reacts with 1, 3-cyclohexanedione under alkaline conditions to generate mesotrione. The method has the advantages of expensive materials, incomplete reaction, high reaction temperature, long production period and high cost, and is not suitable for large-scale industrial production.
Disclosure of Invention
In view of the above, the invention aims to provide a synthesis process of mesotrione, which optimizes reaction conditions, has high conversion rate of each step, high product yield and purity, does not involve highly toxic materials in the whole production process, and has high safety.
In order to achieve the above object, the technical scheme adopted by the invention is to provide a synthesis process of mesotrione, which comprises the following steps:
(1) performing catalytic oxidation, namely reacting 2-nitro-4-methylsulfonyl toluene serving as a raw material, oxygen serving as an oxidant and acetic acid serving as a solvent under the catalytic action of manganese oxide octahedral molecular sieve loaded heteropoly acid-transition metal salt in an oxidation reaction kettle at 0.1-4.5 MPa and 100-450 ℃ to generate 2-nitro-4-methylsulfonylbenzoic acid;
(2) acyl chlorination, namely adding an acyl chlorination reagent into an acyl chlorination reaction kettle, adding 2-nitro-4-methylsulfonylbenzoic acid and DMF, heating to 60-80 ℃, performing reflux reaction for 2-4 h, and distilling out a solvent to obtain 2-nitro-4-methylsulfonylbenzoyl chloride;
(3) condensing, namely adding an aprotic solvent into 2-nitro-4-methylsulfonylbenzoyl chloride, adding 1, 3-cyclohexanedione at the temperature of 30-40 ℃, dropwise adding an acid-binding agent, and reacting for 1-2 h under heat preservation after dropwise adding to obtain an enol ester intermediate reaction liquid;
(4) rearranging, namely adding a rearrangement catalyst into the intermediate reaction liquid, and carrying out heat preservation reaction for 2-5 h at the reaction temperature of 30-40 ℃ to obtain a crude product reaction liquid;
(5) refining, namely putting the crude reaction liquid into a refining reaction kettle while the crude reaction liquid is hot, stirring for 20-40 minutes at 50-55 ℃, discharging, carrying out suction filtration, taking a solid product, drying, and carrying out jet milling to obtain a mesotrione finished product.
Through the scheme, the heteropoly acid has stronger acidity than concentrated sulfuric acid, simultaneously has oxidation-reduction property, has the advantages of low-temperature high activity, thermal stability and the like, is easy to dissolve in an acute solvent, but a homogeneous catalysis system can cause the heteropoly acid to be difficult to recycle, and not only causes the loss of the heteropoly acid with high price but also causes environmental pollution. The manganese oxide octahedral molecular sieve is composed of octahedral MnO6The common edge and the common corner are connected to form a one-dimensional tunnel structure of about 2 multiplied by 2, and the tunnel structure has the characteristics of porous structure, mixed valence state manganese, mild surface acidity and alkalinity and the like. The manganese oxide octahedral molecular sieve has certain oxidation-reduction property and acidic surface, and hydroxyl on the surface is hydrogenated to form a complex with heteropoly acid anions, so that the active area of heteropoly acid can be increased, the acidity of the catalyst is increased, the capacity of catalyzing and oxidizing 2-nitro-4-methylsulfonyl toluene is improved by the synergistic effect of the manganese oxide octahedral molecular sieve and the heteropoly acid anions, the consumption of the heteropoly acid is reduced, and the catalyst is favorable for recycling and reusing.
Further, the manganese oxide octahedral molecular sieve supported heteropolyacid catalyst in the step (1) is prepared by the following steps:
(1) preparing a carrier, namely dripping a mixed solution of a manganese sulfate aqueous solution and concentrated nitric acid into an aqueous solution of potassium permanganate at a constant pressure, stirring and refluxing at a high speed for 12-24 hours at 100 ℃, taking out a slurry product after the reaction is finished, and performing suction filtration, washing and drying to obtain a manganese oxide octahedral molecular sieve;
(2) loading, namely soaking a certain weight of manganese oxide octahedral molecular sieve support in heteropoly acid solution at the soaking temperature of 45-65 ℃ for 2-6 h, heating and evaporating the mixed solution at 100 ℃ after soaking is finished, and drying in a vacuum drying oven at the temperature of 100-120 ℃ to obtain manganese oxide octahedral molecular sieve loaded heteropoly acid;
(3) activating, namely placing the manganese oxide octahedral molecular sieve supported heteropoly acid in a tubular furnace, and activating for 3-6 hours at 200-400 ℃ under the protection of nitrogen to obtain an activated manganese oxide octahedral molecular sieve supported heteropoly acid catalyst;
the heteropoly acid is phosphomolybdic acid or phosphotungstic acid; the weight ratio of the 2-nitro-4-methylsulfonyl toluene to the manganese oxide octahedral molecular sieve supported heteropolyacid catalyst is 1: 0.01-0.1.
Further, the transition metal salt in the step (1) is one or more of acetate, sulfate, chloride or carbonate, and the transition metal is one or more of cobalt, manganese, titanium, chromium, iron or molybdenum; the weight ratio of the 2-nitro-4-methylsulfonyltoluene to the transition metal salt is 1: 0.002 to 0.005.
Further, the transition metal salt is cobalt acetate and chromium acetate, and the molar ratio of cobalt to chromium is 2.0-5.0.
Further, the acyl chlorination reagent in the step (2) is one or more of thionyl chloride, tricarbonyl chloride and oxalyl chloride; the weight ratio of the 2-nitro-4-methylsulfonyltoluene to the acyl chlorination reagent is 1: 0.3-1.2.
Further, the acyl chloride reagent in the step (2) is tricarboxychloride.
By adopting the scheme, tricarbochlor is used as an acyl chlorination reagent, byproducts are hydrogen chloride and carbon dioxide which are insoluble in a reaction system and gasified and overflowed, and the hydrogen chloride can be absorbed by water to prepare hydrochloric acid without generating more toxic gases. In the production process, the using amount of the tricarboxychloride is less, and the cost of the produced materials is lower. Therefore, the tricarbochlor is used as the acyl chlorination reagent, and compared with the traditional acyl chlorination reagents of phosgene, phosphorus oxychloride and the like, the method has much less harm to the environment, so that green substitution of raw materials can be realized, and the reaction is safer and more environment-friendly.
Further, the acid-binding agent in the step (3) is a 15-crown-5/sodium hydroxide complex, and the weight ratio of the 2-nitro-4-methylsulfonyl toluene to the acid-binding agent is 1: 0.4 to 1.2; the aprotic solvent in the step (3) is at least one of ethyl acetate, dichloromethane, dichloroethane and chloroform.
Through the scheme, the 15-crown-5 is complexed with sodium ions in the sodium hydroxide, so that the sodium ions can be dissolved in the organic solvent, and meanwhile, negative ions opposite to the sodium ions enter the organic solvent along with the sodium ions, so that the diffusion of the sodium hydroxide in the organic phase is accelerated, the reaction activity of free or naked negative ions is high, the free or naked negative ions can rapidly react with hydrogen chloride generated in the synthetic process of the enol ester intermediate, the reaction is ensured to be carried out in the positive reaction direction, and the reaction efficiency of the whole condensation reaction is improved.
Further, the rearrangement catalyst is sodium hydroxide and tetramethylguanidine, and the weight ratio of the 2-nitro-4-methylsulfonyltoluene to the rearrangement catalyst is 1: 0.06 to 0.2.
According to the scheme, enol ester intermediate 2-nitro-4-methylsulfonylbenzoic acid- [3 '-carbonyl-1' -cyclohexenol ] -ester reaction liquid generated by condensation reaction is directly subjected to rearrangement reaction, and 2-nitro-4-methylsulfonylbenzoic acid- [3 '-carbonyl-1' -cyclohexenol ] -ester is subjected to rearrangement under the co-catalytic action of sodium hydroxide and tetramethylguanidine to obtain an acylated annular 1, 3-dicarbonyl compound, so that extremely toxic cyanide catalysts such as acetone cyanohydrin, potassium cyanide or sodium cyanide are avoided. The intermediate product is rearranged by adopting a composite catalytic system of sodium hydroxide and tetramethylguanidine, the reaction condition is mild, and the reaction time is short.
Further, the sodium hydroxide may form a complex with 15-crown-5 or 18-crown-6 together with the tetramethylguanidine as a rearrangement catalyst.
Through the scheme, the 15-crown-5 or 18-crown-6 is complexed with the sodium hydroxide, so that the diffusion of the sodium hydroxide in an organic phase can be accelerated, and the efficacy of the catalyst can be better exerted.
The invention has the following beneficial effects:
1. the synthesis process of mesotrione optimizes reaction conditions, has high conversion rate in each step, high product yield and purity, does not involve highly toxic materials in the whole production process, and has high safety.
2. According to the synthesis process of mesotrione, the manganese oxide octahedral molecular sieve has certain oxidation-reduction property and the surface of the octahedral molecular sieve is acidic, and hydroxyl on the surface of the octahedral molecular sieve is hydrogenated and then forms a complex with heteropoly acid anions, so that the active area of heteropoly acid can be increased, the acidity of a catalyst is increased, the capability of catalyzing and oxidizing 2-nitro-4-methylsulfonyl toluene is improved under the synergistic effect of the manganese oxide octahedral molecular sieve and the heteropoly acid anions, and the consumption of heteropoly acid is reduced; in addition, the heteropolyacid is loaded on the manganese oxide octahedral molecular sieve to form a heterogeneous catalysis system, which is beneficial to the recovery and the reuse of the catalyst.
3. The synthesis process of the mesotrione takes tricarbonyl chloride as an acyl chlorination reagent, byproducts are hydrogen chloride and carbon dioxide which are insoluble in a reaction system and gasified and overflow, and the hydrogen chloride can be absorbed by water to prepare hydrochloric acid without generating more toxic gases. In the production process, the using amount of the tricarboxychloride is less, and the cost of the produced materials is lower. Therefore, the tricarbochlor is used as the acyl chlorination reagent, and compared with the traditional acyl chlorination reagents of phosgene, phosphorus oxychloride and the like, the method has much less harm to the environment, so that green substitution of raw materials can be realized, and the reaction is safer and more environment-friendly.
4. According to the synthesis process of mesotrione, the 15-crown-5 is complexed with sodium ions in sodium hydroxide, so that the sodium ions can be dissolved in the organic solvent, and negative ions opposite to the sodium ions enter the organic solvent, so that the diffusion of the sodium hydroxide in the organic phase is accelerated, the reaction activity of free or naked negative ions is high, the free or naked negative ions can rapidly react with hydrogen chloride generated in the synthesis process of the enol ester intermediate, the reaction is ensured to be carried out in the positive and negative reaction directions, the reaction efficiency of the whole condensation reaction is improved, and the synthesis time of the whole mesotrione is shortened.
5. According to the synthesis process of mesotrione, enol ester intermediate 2-nitro-4-methylsulfonylbenzoic acid- [3 '-carbonyl-1' -cyclohexenol ] -ester reaction liquid generated by condensation reaction is directly subjected to rearrangement reaction, and 2-nitro-4-methylsulfonylbenzoic acid- [3 '-carbonyl-1' -cyclohexenol ] -ester is subjected to rearrangement under the co-catalysis of sodium hydroxide and tetramethylguanidine to obtain an acylated annular 1, 3-dicarbonyl compound, so that extremely toxic cyanide catalysts such as acetone cyanohydrin, potassium cyanide or sodium cyanide are avoided. The intermediate product is rearranged by adopting a composite catalytic system of sodium hydroxide and tetramethylguanidine, the reaction condition is mild, and the reaction time is short.
6. According to the synthesis process of mesotrione, the 15-crown-5 or 18-crown-6 is complexed with sodium hydroxide, so that the diffusion of the sodium hydroxide in an organic phase can be accelerated, the effect of the catalyst is better exerted, and the catalytic activity of the rearrangement catalyst is improved.
Detailed Description
The technical solutions in the examples will be clearly and completely described below. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Example 1
A process for the synthesis of mesotrione, comprising the steps of: (1) carrying out catalytic oxidation, namely reacting 100g of 2-nitro-4-methylsulfonyl toluene serving as a raw material, oxygen serving as an oxidant and acetic acid serving as a solvent under the catalytic action of manganese oxide octahedral molecular sieve loaded phosphotungstic acid 1g, cobalt acetate 0.1g and chromium sulfate 0.1g in an oxidation reaction kettle at 0.1MPa and 100 ℃ to generate 2-nitro-4-methylsulfonylbenzoic acid; (2) acyl chlorination, namely adding 30g of thionyl chloride into an acyl chlorination reaction kettle, adding 2-nitro-4-methylsulfonylbenzoic acid and DMF, heating to 60 ℃, carrying out reflux reaction for 2 hours, and distilling out a solvent to obtain 2-nitro-4-methylsulfonylbenzoyl chloride; (3) condensing, adding ethyl acetate into 2-nitro-4-methylsulfonylbenzoyl chloride, adding 1, 3-cyclohexanedione at 30 ℃, dropwise adding 40g of 15-crown-5/sodium hydroxide complex, and reacting for 1h under heat preservation after dropwise adding to obtain an enol ester intermediate reaction liquid; (4) rearranging, adding 2.83g of sodium hydroxide and 0.17g of tetramethylguanidine into the intermediate reaction liquid, and carrying out heat preservation reaction for 2 hours at the reaction temperature of 30 ℃ to obtain a crude product reaction liquid; (5) refining, namely putting the crude reaction liquid into a refining reaction kettle while the reaction liquid is hot, stirring for 20 minutes at 50 ℃, discharging, carrying out suction filtration, taking a solid product, drying, and carrying out jet milling to obtain a mesotrione finished product.
The purity of the resulting mesotrione product was 96.56% and the yield was 87.79%.
Example 2
A process for the synthesis of mesotrione, comprising the steps of: (1) catalytic oxidation, namely reacting 100g of 2-nitro-4-methylsulfonyl toluene serving as a raw material, oxygen serving as an oxidant and acetic acid serving as a solvent under the catalytic action of manganese oxide octahedral molecular sieve loaded phosphomolybdic acid 10g, chromium acetate 0.2g and manganese carbonate 0.3g in an oxidation reaction kettle at 4.5MPa and 450 ℃ to generate 2-nitro-4-methylsulfonylbenzoic acid; (2) acyl chlorination, namely adding 120g of oxalyl chloride into an acyl chlorination reaction kettle, adding 2-nitro-4-methylsulfonylbenzoic acid and DMF, heating to 80 ℃, carrying out reflux reaction for 4 hours, and distilling out a solvent to obtain 2-nitro-4-methylsulfonylbenzoyl chloride; (3) condensing, namely adding dichloromethane into 2-nitro-4-methylsulfonylbenzoyl chloride, adding 1, 3-cyclohexanedione at 40 ℃, dropwise adding 120g of 15-crown-5/sodium hydroxide complex, and reacting for 2h under heat preservation after dropwise adding to obtain an enol ester intermediate reaction liquid; (4) rearranging, adding 13.3g of sodium hydroxide and 6.7g of tetramethylguanidine into the intermediate reaction liquid, and carrying out heat preservation reaction at the reaction temperature of 40 ℃ for 5 hours to obtain a crude product reaction liquid; (5) refining, namely putting the crude reaction liquid into a refining reaction kettle while the reaction liquid is hot, stirring for 40 minutes at 55 ℃, discharging, carrying out suction filtration, taking a solid product, drying, and carrying out jet milling to obtain a finished product of mesotrione.
The purity of the resulting mesotrione product was 95.98%, with a yield of 87.64%.
Example 3
A process for the synthesis of mesotrione, comprising the steps of: (1) catalytic oxidation, namely reacting 100g of 2-nitro-4-methylsulfonyl toluene serving as a raw material, oxygen serving as an oxidant and acetic acid serving as a solvent under the catalytic action of manganese oxide octahedral molecular sieve loaded phosphomolybdic acid 5g, cobalt acetate 0.2g and chromium acetate 0.15g in an oxidation reaction kettle at 2.5MPa and 300 ℃ to generate 2-nitro-4-methylsulfonylbenzoic acid; (2) acyl chlorination, namely adding 50g of tricarbonyl chloride into an acyl chlorination reaction kettle, adding 2-nitro-4-methylsulfonylbenzoic acid and DMF, heating to 70 ℃, carrying out reflux reaction for 3 hours, and distilling out a solvent to obtain 2-nitro-4-methylsulfonylbenzoyl chloride; (3) condensing, namely adding dichloroethane into 2-nitro-4-methylsulfonylbenzoyl chloride, adding 1, 3-cyclohexanedione at 35 ℃, dropwise adding 70g of 15-crown-5/sodium hydroxide complex, and reacting for 1.5h under heat preservation after dropwise adding to obtain an enol ester intermediate reaction liquid; (4) rearranging, adding 9.6g of sodium hydroxide and 2.4g of tetramethylguanidine into the intermediate reaction liquid, and carrying out heat preservation reaction at the reaction temperature of 35 ℃ for 3.5h to obtain a crude product reaction liquid; (5) refining, namely putting the crude reaction liquid into a refining reaction kettle while the reaction liquid is hot, stirring for 30 minutes at 52 ℃, discharging, carrying out suction filtration, taking a solid product, drying, and carrying out jet milling to obtain a mesotrione finished product.
The purity of the resulting mesotrione product was 96.89% with a yield of 88.14%.
Example 4
A process for the synthesis of mesotrione, comprising the steps of: (1) catalytic oxidation, namely reacting 100g of 2-nitro-4-methylsulfonyl toluene serving as a raw material, oxygen serving as an oxidant and acetic acid serving as a solvent under the catalytic action of manganese oxide octahedral molecular sieve loaded phosphomolybdic acid 4g, cobalt chloride 0.2g and ferric sulfate 0.15g in an oxidation reaction kettle at 2.5MPa and 300 ℃ to generate 2-nitro-4-methylsulfonylbenzoic acid; (2) acyl chlorination, namely adding 50g of tricarbonyl chloride into an acyl chlorination reaction kettle, adding 2-nitro-4-methylsulfonylbenzoic acid and DMF, heating to 70 ℃, carrying out reflux reaction for 3 hours, and distilling out a solvent to obtain 2-nitro-4-methylsulfonylbenzoyl chloride; (3) condensing, namely adding trichloromethane into 2-nitro-4-methylsulfonylbenzoyl chloride, adding 1, 3-cyclohexanedione at 35 ℃, dropwise adding 75g of 15-crown-5/sodium hydroxide complex, and reacting for 1.5h under heat preservation after dropwise adding to obtain an enol ester intermediate reaction liquid; (4) rearranging, adding 9.6g of sodium hydroxide and 2.4g of tetramethylguanidine into the intermediate reaction liquid, and carrying out heat preservation reaction at the reaction temperature of 35 ℃ for 3.5h to obtain a crude product reaction liquid; (5) refining, namely putting the crude reaction liquid into a refining reaction kettle while the reaction liquid is hot, stirring for 30 minutes at 52 ℃, discharging, carrying out suction filtration, taking a solid product, drying, and carrying out jet milling to obtain a mesotrione finished product.
The purity of the resulting mesotrione product was 95.73% with a yield of 87.32%.
Example 5
A process for the synthesis of mesotrione, comprising the steps of: (1) catalytic oxidation, namely reacting 100g of 2-nitro-4-methylsulfonyl toluene serving as a raw material, oxygen serving as an oxidant and acetic acid serving as a solvent under the catalytic action of manganese oxide octahedral molecular sieve loaded phosphomolybdic acid 4g, cobalt chloride 0.2g and ferric sulfate 0.15g in an oxidation reaction kettle at 2.5MPa and 300 ℃ to generate 2-nitro-4-methylsulfonylbenzoic acid; (2) acyl chlorination, namely adding 50g of tricarbonyl chloride into an acyl chlorination reaction kettle, adding 2-nitro-4-methylsulfonylbenzoic acid and DMF, heating to 70 ℃, carrying out reflux reaction for 3 hours, and distilling out a solvent to obtain 2-nitro-4-methylsulfonylbenzoyl chloride; (3) condensing, namely adding trichloromethane into 2-nitro-4-methylsulfonylbenzoyl chloride, adding 1, 3-cyclohexanedione at 35 ℃, dropwise adding 75g of 15-crown-5/sodium hydroxide complex, and reacting for 1.5h under heat preservation after dropwise adding to obtain an enol ester intermediate reaction liquid; (4) rearrangement, adding 15-crown-5/sodium hydroxide complex 12.5g and tetramethylguanidine 2.4g into the intermediate reaction solution, and reacting at 35 deg.C for 3.5h to obtain crude reaction solution; (5) refining, namely putting the crude reaction liquid into a refining reaction kettle while the reaction liquid is hot, stirring for 30 minutes at 52 ℃, discharging, carrying out suction filtration, taking a solid product, drying, and carrying out jet milling to obtain a mesotrione finished product.
The purity of the resulting mesotrione product was 97.43%, with a yield of 88.98%.
The preparation method of the manganese oxide octahedral molecular sieve supported heteropoly acid in any embodiment comprises the following steps: the method comprises the following steps:
(1) preparing a carrier, namely dripping a mixed solution of a manganese sulfate aqueous solution and concentrated nitric acid into an aqueous solution of potassium permanganate at a constant pressure, stirring and refluxing at a high speed for 12-24 hours at 100 ℃, taking out a slurry product after the reaction is finished, and performing suction filtration, washing and drying to obtain a manganese oxide octahedral molecular sieve;
(2) loading, namely soaking a certain weight of manganese oxide octahedral molecular sieve support in heteropoly acid solution at the soaking temperature of 45-65 ℃ for 2-6 h, heating and evaporating the mixed solution at 100 ℃ after soaking is finished, and drying the mixed solution in a vacuum drying oven at the temperature of 100-120 ℃ to obtain manganese oxide octahedral molecular sieve loaded heteropoly acid;
(3) and (3) activating, namely placing the manganese oxide octahedral molecular sieve supported heteropoly acid in a tubular furnace, and activating for 3-6 hours at 200-400 ℃ under the protection of nitrogen to obtain the activated manganese oxide octahedral molecular sieve supported heteropoly acid catalyst.
Comparative example 1
A process for the synthesis of mesotrione, comprising the steps of: (1) catalytic oxidation, namely reacting 100g of 2-nitro-4-methylsulfonyl toluene serving as a raw material, oxygen serving as an oxidant and acetic acid serving as a solvent under the catalytic action of 5g of phosphomolybdic acid, 0.2g of cobalt acetate and 0.15g of chromium acetate in an oxidation reaction kettle at 2.5MPa and 300 ℃ to generate 2-nitro-4-methylsulfonylbenzoic acid; (2) acyl chlorination, namely adding 50g of tricarbonyl chloride into an acyl chlorination reaction kettle, adding 2-nitro-4-methylsulfonylbenzoic acid and DMF, heating to 70 ℃, carrying out reflux reaction for 3 hours, and distilling out a solvent to obtain 2-nitro-4-methylsulfonylbenzoyl chloride; (3) condensing, namely adding dichloroethane into 2-nitro-4-methylsulfonylbenzoyl chloride, adding 1, 3-cyclohexanedione at 35 ℃, dropwise adding 70g of 15-crown-5/sodium hydroxide complex, and reacting for 1.5h under heat preservation after dropwise adding to obtain an enol ester intermediate reaction liquid; (4) rearranging, adding 9.6g of sodium hydroxide and 2.4g of tetramethylguanidine into the intermediate reaction liquid, and carrying out heat preservation reaction at the reaction temperature of 35 ℃ for 3.5h to obtain a crude product reaction liquid; (5) refining, namely putting the crude reaction liquid into a refining reaction kettle while the reaction liquid is hot, stirring for 30 minutes at 52 ℃, discharging, carrying out suction filtration, taking a solid product, drying, and carrying out jet milling to obtain a mesotrione finished product.
The purity of the resulting mesotrione product was 81.32% and the yield was 73.43%.
Comparative example 2
A process for the synthesis of mesotrione, comprising the steps of: (1) catalytic oxidation, namely reacting 100g of 2-nitro-4-methylsulfonyl toluene serving as a raw material, oxygen serving as an oxidant and acetic acid serving as a solvent under the catalytic action of manganese oxide octahedral molecular sieve loaded phosphomolybdic acid 5g, cobalt acetate 0.2g and chromium acetate 0.15g in an oxidation reaction kettle at 2.5MPa and 300 ℃ to generate 2-nitro-4-methylsulfonylbenzoic acid; (2) acyl chlorination, namely adding 50g of tricarbonyl chloride into an acyl chlorination reaction kettle, adding 2-nitro-4-methylsulfonylbenzoic acid and DMF, heating to 70 ℃, carrying out reflux reaction for 3 hours, and distilling out a solvent to obtain 2-nitro-4-methylsulfonylbenzoyl chloride; (3) condensing, namely adding dichloroethane into 2-nitro-4-methylsulfonylbenzoyl chloride, adding 1, 3-cyclohexanedione at 35 ℃, dropwise adding 50g of sodium hydroxide, and reacting for 1.5h under heat preservation after dropwise adding to obtain an enol ester intermediate reaction liquid; (4) rearranging, adding 9.6g of sodium hydroxide and 2.4g of tetramethylguanidine into the intermediate reaction liquid, and carrying out heat preservation reaction at the reaction temperature of 35 ℃ for 3.5h to obtain a crude product reaction liquid; (5) refining, namely putting the crude reaction liquid into a refining reaction kettle while the reaction liquid is hot, stirring for 30 minutes at 52 ℃, discharging, carrying out suction filtration, taking a solid product, drying, and carrying out jet milling to obtain a mesotrione finished product.
The purity of the resulting mesotrione product was 84.32% and the yield was 74.45%.
Comparative example 3
A process for the synthesis of mesotrione, comprising the steps of: (1) catalytic oxidation, namely reacting 100g of 2-nitro-4-methylsulfonyl toluene serving as a raw material, oxygen serving as an oxidant and acetic acid serving as a solvent under the catalytic action of manganese oxide octahedral molecular sieve loaded phosphomolybdic acid 5g, cobalt acetate 0.2g and chromium acetate 0.15g in an oxidation reaction kettle at 2.5MPa and 300 ℃ to generate 2-nitro-4-methylsulfonylbenzoic acid; (2) acyl chlorination, namely adding 50g of tricarbonyl chloride into an acyl chlorination reaction kettle, adding 2-nitro-4-methylsulfonylbenzoic acid and DMF, heating to 70 ℃, carrying out reflux reaction for 3 hours, and distilling out a solvent to obtain 2-nitro-4-methylsulfonylbenzoyl chloride; (3) condensing, namely adding dichloroethane into 2-nitro-4-methylsulfonylbenzoyl chloride, adding 1, 3-cyclohexanedione at 35 ℃, dropwise adding 50g of 15-crown-5/sodium hydroxide complex, and reacting for 1.5h under heat preservation after dropwise adding to obtain an enol ester intermediate reaction liquid; (4) rearranging, adding 15g of acetone cyanohydrin into the intermediate reaction liquid, and carrying out heat preservation reaction for 3.5h at the reaction temperature of 35 ℃ to obtain a crude product reaction liquid; and (5) refining, namely putting the crude reaction liquid into a refining reaction kettle while the crude reaction liquid is hot, stirring for 30 minutes at 52 ℃, discharging, carrying out suction filtration, taking a solid product, drying, and carrying out jet milling to obtain a mesotrione finished product.
The resulting mesotrione product was 87.32% pure with a yield of 73.45%.
The experimental results of the examples 1-5 and the comparative examples 1-3 show that the manganese oxide octahedral molecular sieve and the heteropoly acid have synergistic effect, so that the yield of the mesotrione can be effectively improved; in addition, the acid-binding agent 15-crown-5/sodium hydroxide complex can further improve the yield, effectively shorten the whole reaction time, has good catalytic effect of rearrangement catalyst sodium hydroxide and tetramethylguanidine and mild reaction conditions, and avoids using virulent cyanide catalysts such as acetone cyanohydrin, potassium cyanide or sodium cyanide. The synthesis process of the invention optimizes the reaction conditions, has high conversion rate of each step, high yield and purity of the product, no involvement of highly toxic materials in the whole production process and high safety.
Claims (2)
1. A process for synthesizing mesotrione, comprising the steps of:
(1) performing catalytic oxidation, namely reacting 2-nitro-4-methylsulfonyl toluene serving as a raw material, oxygen serving as an oxidant and acetic acid serving as a solvent under the catalytic action of manganese oxide octahedral molecular sieve loaded heteropoly acid-transition metal salt in an oxidation reaction kettle at 0.1-4.5 MPa and 100-450 ℃ to generate 2-nitro-4-methylsulfonylbenzoic acid; the weight ratio of the 2-nitro-4-methylsulfonyl toluene to the manganese oxide octahedral molecular sieve supported heteropolyacid catalyst is 1: 0.01-0.1; the weight ratio of the 2-nitro-4-methylsulfonyltoluene to the transition metal salt is 1: 0.002 to 0.005; the heteropoly acid is phosphomolybdic acid or phosphotungstic acid, the transition metal salt is cobalt acetate and chromium acetate, and the molar ratio of cobalt to chromium is 2.0-5.0;
(2) acyl chlorination, namely adding an acyl chlorination reagent into an acyl chlorination reaction kettle, adding 2-nitro-4-methylsulfonylbenzoic acid and DMF, heating to 60-80 ℃, performing reflux reaction for 2-4 h, and distilling out a solvent to obtain 2-nitro-4-methylsulfonylbenzoyl chloride; the acyl chlorination reagent is tricarbochlor, and the weight ratio of the 2-nitro-4-methylsulfonyl toluene to the acyl chlorination reagent is 1: 0.3-1.2;
(3) condensing, namely adding an aprotic solvent into 2-nitro-4-methylsulfonylbenzoyl chloride, adding 1, 3-cyclohexanedione at the temperature of 30-40 ℃, dropwise adding an acid-binding agent, and reacting for 1-2 h under heat preservation after dropwise adding to obtain an enol ester intermediate reaction liquid; the acid-binding agent is a 15-crown-5/sodium hydroxide complex, and the weight ratio of the 2-nitro-4-methylsulfonyl toluene to the acid-binding agent is 1: 0.4 to 1.2; the aprotic solvent is at least one of ethyl acetate, dichloromethane, dichloroethane and chloroform;
(4) rearranging, namely adding a rearrangement catalyst into the intermediate reaction liquid, and carrying out heat preservation reaction for 2-5 h at the reaction temperature of 30-40 ℃ to obtain a crude product reaction liquid; the rearrangement catalyst is sodium hydroxide and tetramethylguanidine, and the weight ratio of the sodium hydroxide to the tetramethylguanidine is 1: 0.03-0.5; the weight ratio of the 2-nitro-4-methylsulfonyl toluene to the rearrangement catalyst is 1: 0.06 to 0.2;
(5) refining, namely putting the crude reaction liquid into a refining reaction kettle while the crude reaction liquid is hot, stirring for 20-40 minutes at 50-55 ℃, discharging, carrying out suction filtration, taking a solid product, drying, and carrying out jet milling to obtain a mesotrione finished product;
the manganese oxide octahedral molecular sieve supported heteropolyacid catalyst in the step (1) is prepared by the following steps:
s1, preparing a carrier, namely dripping a mixed solution of a manganese sulfate aqueous solution and concentrated nitric acid into an aqueous solution of potassium permanganate at a constant pressure, stirring and refluxing at a high speed for 12-24 hours at 100 ℃, taking out a slurry product after the reaction is finished, and performing suction filtration, washing and drying to obtain the manganese oxide octahedral molecular sieve;
s2, loading, namely soaking a certain weight of manganese oxide octahedral molecular sieve support in heteropoly acid solution at the soaking temperature of 45-65 ℃ for 2-6 h, heating and evaporating the mixed solution at 100 ℃ after the soaking is finished, and drying the mixed solution in a vacuum drying oven at the temperature of 100-120 ℃ to obtain manganese oxide octahedral molecular sieve loaded heteropoly acid;
and S3, activating, namely placing the manganese oxide octahedral molecular sieve supported heteropoly acid in a tubular furnace, and activating for 3-6 hours at 200-400 ℃ under the protection of nitrogen to obtain the activated manganese oxide octahedral molecular sieve supported heteropoly acid catalyst.
2. The process for the synthesis of mesotrione as claimed in claim 1, wherein: the sodium hydroxide can form a complex with 15-crown-5 or 18-crown-6 together with the tetramethylguanidine as a rearrangement catalyst.
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