CN103172549B - Preparation method of 2-(2-nitryl-4-methyl sulfuryl-benzoyl) cyclohexane-1,3-diketone - Google Patents
Preparation method of 2-(2-nitryl-4-methyl sulfuryl-benzoyl) cyclohexane-1,3-diketone Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 methyl mesotrione Chemical compound 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 238000001953 recrystallisation Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- SQLJHMXKBLNJAO-UHFFFAOYSA-O azanium sulfuric acid nitrate Chemical compound [NH4+].[O-][N+]([O-])=O.OS(O)(=O)=O SQLJHMXKBLNJAO-UHFFFAOYSA-O 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 8
- 239000005578 Mesotrione Substances 0.000 abstract description 4
- 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 abstract description 3
- 238000005935 nucleophilic addition reaction Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- AKEZKSMCJJWKPX-UHFFFAOYSA-N 4-methyl-6-nitro-5-sulfonylcyclohexa-1,3-diene-1-carbaldehyde Chemical compound [N+](=O)([O-])C1C(C=O)=CC=C(C1=S(=O)=O)C AKEZKSMCJJWKPX-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000001117 sulphuric acid Substances 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- 238000007039 two-step reaction Methods 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000012790 confirmation Methods 0.000 description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- MIEHTLXLEUKOEU-UHFFFAOYSA-N 1-methyl-4-methylsulfanyl-2-nitrobenzene Chemical compound CSC1=CC=C(C)C([N+]([O-])=O)=C1 MIEHTLXLEUKOEU-UHFFFAOYSA-N 0.000 description 2
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QBKSWRVVCFFDOT-UHFFFAOYSA-N gossypol Chemical compound CC(C)C1=C(O)C(O)=C(C=O)C2=C(O)C(C=3C(O)=C4C(C=O)=C(O)C(O)=C(C4=CC=3C)C(C)C)=C(C)C=C21 QBKSWRVVCFFDOT-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960003053 thiamphenicol Drugs 0.000 description 2
- 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 description 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- GMVPRGQOIOIIMI-DODZYUBVSA-N 7-[(1R,2R,3R)-3-hydroxy-2-[(3S)-3-hydroxyoct-1-enyl]-5-oxocyclopentyl]heptanoic acid Chemical compound CCCCC[C@H](O)C=C[C@H]1[C@H](O)CC(=O)[C@@H]1CCCCCCC(O)=O GMVPRGQOIOIIMI-DODZYUBVSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 102000016680 Dioxygenases Human genes 0.000 description 1
- 108010028143 Dioxygenases Proteins 0.000 description 1
- RMFGNMMNUZWCRZ-UHFFFAOYSA-N Humulone Natural products CC(C)CC(=O)C1=C(O)C(O)(CC=C(C)C)C(O)=C(CC=C(C)C)C1=O RMFGNMMNUZWCRZ-UHFFFAOYSA-N 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
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QHOPXUFELLHKAS-UHFFFAOYSA-N Thespesin Natural products CC(C)c1c(O)c(O)c2C(O)Oc3c(c(C)cc1c23)-c1c2OC(O)c3c(O)c(O)c(C(C)C)c(cc1C)c23 QHOPXUFELLHKAS-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
- 238000007259 addition reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process 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
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229930000755 gossypol Natural products 0.000 description 1
- 229950005277 gossypol Drugs 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- VMSLCPKYRPDHLN-NRFANRHFSA-N humulone Chemical compound CC(C)CC(=O)C1=C(O)C(CC=C(C)C)=C(O)[C@@](O)(CC=C(C)C)C1=O VMSLCPKYRPDHLN-NRFANRHFSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
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- 238000003541 multi-stage reaction Methods 0.000 description 1
- ISRXMEYARGEVIU-UHFFFAOYSA-N n-methyl-n-propan-2-ylpropan-2-amine Chemical compound CC(C)N(C)C(C)C ISRXMEYARGEVIU-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 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 1
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- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of 2-(2-nitryl-4-methyl sulfuryl-benzoyl) cyclohexane-1,3-diketone (methyl mesotrione, mesotrione). The preparation method adopting 2-nitryl-4-methyl sulfuryl benzaldehyde and 1,3-cyclohexanedione as the materials comprises the following steps of: carrying out the reactions including nucleophilic addition, oxidation and the like to prepare the high-purity 2-(2-nitryl-4-methyl sulfuryl-benzoyl) cyclohexane-1,3-diketone. The preparation method disclosed by the invention is short in route; all steps are free of severe conditions, simple to operate, environment-friendly, remarkable in innovative significance and economic value and extensive in industrial production prospect.
Description
Technical field
The present invention relates to novel pesticide herbicide 2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1, preparation method and the production technique of 3-diketone (MST), method of the present invention is with 2-nitro-4-methylsulfonyl-phenyl aldehyde and 1, hydroresorcinol is raw material, through nucleophilic addition(Adn), 2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1 is prepared in the reactions such as oxidation, 3-diketone, product purity is greater than 99%, total recovery is more than 69%, it is brief that preparation method of the present invention has route, reaction conditions is gentle, operation is smooth, the features such as environmental protection, be expected to be applied to actual production.。
Background technology
2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1; 3-diketone (MST) has another name called mesotrione, nitre sulphur ketone; a three ketones weedicide kind of Shi You Switzerland Syngenta Co.,Ltd exploitation; it is the inhibitor to oxypyroracemic acid dioxygenase (HPPD), tyrosine can be converted into plastoquinone.Mesotrione is by modifying sulphur humulone structure, and its biological activity surpasses sulphur humulone more than 10 times, thereby has better exploitation potential quality and the market competitiveness.Novel systemic weedicide as a kind of corn field special use, it with broad weed-killing spectrum, activity is high, miscibility is strong, toxicity is low, environmentally friendly, to succession crop safely, use the feature such as flexible to obtain abroad immense success, in China, also have larger exploitation to be worth and to promote the use of preferably prospect.
It is raw material that the current synthetic report about MST substantially all adopts 2-nitryl-4-thiamphenicol benzoic acid/Benzoyl chloride and hydroresorcinol, and reaction process is as follows:
Wherein hydroresorcinol can be made by Resorcinol hydro-reduction, and 2-nitryl-4-thiamphenicol benzoic acid/Benzoyl chloride all has more synthetic schemes at home and abroad, and main route gathers as follows:
1) chloroacetic acid route: take chloroacetic acid as raw material, through nitrated, methyl oxidation two-step reaction synthetic (Jingxi Huagong Zhongjianti, 35 (2), 50-51,56,2005; Zhejiang Polytechnical University's journal, 35 (5), 493-494,2007; CN1995014).Raw materials used being easy to purchased, but in nitrifying process, needs to use the mixed acid system of concentrated nitric acid/vitriol oil, and quantity of three wastes is very large.
2) Ortho Nitro Toluene route: take Ortho Nitro Toluene as raw material, further can be divided into the method for MSMization oxidation and the method for sulfonating chlorinating → MSM → oxidation
The method steps of MSMization oxidation is more brief, but agents useful for same is comparatively special, and yield lower (47%), and practical application also needs to carry out a large amount of research work.(Russian?Journal?of?Organic?Chemistry(Translation?of?Zhurnal?Organicheskoi?Khimii),?34(11),?1573-1578,?1998)
Second method: the raw materials used price of sulfonating chlorinating method is easy to get, in production process, quantity of three wastes is less, but there is no at present document and directly synthesize the report of target compound with this route, can only be with reference to the pertinent literature of stepwise reaction and similar reaction, therefore this technique is still not mature enough, and reactions steps is more, still have a large amount of work of optimizing to need badly.(Bioorganic?&?Medicinal?Chemistry,?10(6),?1841-1854,?2002;?Nippom?Kagaku?Kaishi,?11,?1694-1697,?1977;?J.?Org.?Chem.,?56,?4974-4976,?1991)
3) 4-methyl-3-nitro thioanisole route: the 4-methyl-3-nitro thioanisole of take is raw material, synthetic through two-step oxidation reaction.This route there is no bibliographical information at present, just has theoretic possibility, and the raw materials used commercialized supply that not yet forms on market, does not temporarily possess practical value.
In addition, also having document to adopt 2-nitro-4-methylsulfonyltoluene and hydroresorcinol is raw material, through bromo, addition, oxidation three-step reaction synthetic (Jiangsu agricultural journal, 23 (6), 661-662,2006).This route has certain novelty, but in process, needs with expensive anhydrous bromine, and high expensive is only suitable for laboratory preparation sample in a small amount at present, and large-scale industrial production is lacked competitiveness.
Summary of the invention
The present invention is on the relative merits basis of serious analysis target compound synthetic method; designed with 2-nitro-4-methylsulfonyl phenyl aldehyde and 1; hydroresorcinol is that starting raw material is prepared 2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1; the method of 3-diketone (MST); this route is via nucleophilic addition(Adn), oxidation two-step reaction; the target product of the synthesis of high content of high yield; all steps are without severe condition; simple to operate; quantity of three wastes is few; there is original creation meaning, be applicable to suitability for industrialized production.
For achieving the above object, a kind of 2-provided by the invention (2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1, the synthetic method of 3-diketone (MST) comprises the following steps:
2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1, the structural formula of 3-diketone is as follows:
Its synthetic route is:
Concrete operation step is as follows:
Step 1: be under the condition of 5～45 ℃ in temperature, to 2-nitro-4-methylsulfonyl phenyl aldehyde and 1, the mixed solution and dripping alkaline solution of hydroresorcinol, note maintaining temperature of reaction, dropwise, continue insulation reaction 0.5～2 hour, stopped reaction, obtain intermediate 2-(2-nitro-4-methylsulfonyl-benzyl hydroxyl) hexanaphthene-1, the mixed solution of 3-diketone, can be directly used in next step reaction.
In step 1 of the present invention, solvent can be tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, DMF, methyl-sulphoxide, tetramethylene sulfone, ethylene dichloride, toluene etc., consumption be raw materials quality and 2～3 times, preferred toluene.
In step 1 of the present invention, alkaline solution can be mineral alkali, as aqueous sodium hydroxide solution (wt 15%), aqueous sodium carbonate (wt 15%), sodium bicarbonate aqueous solution (wt 20%) etc., also can be organic bases, as triethylamine, N, accelerine, N, N-dimethyl benzylamine, methyl Diisopropylamine, pyridine, 4-(N, N-dimethyl) pyridine, preferred N, N-dimethyl benzylamine.
In step 1 of the present invention, reaction can be carried out in the temperature range of 5～45 ℃, preferably 10～15 ℃.
Step 2: be, under the condition of 35～60 ℃, to 2-(2-nitro-4-methylsulfonyl-benzyl hydroxyl) hexanaphthene-1, to add oxygenant in the mixed solution of 3-diketone in temperature, continue to stir 1～3.5 hour, stop heating, reaction solution is bathed cooling with cryosel, filter, wash product with water to neutral.Crude product further recrystallization is purified.
In step 2 of the present invention, oxygenant can be PCC, CrO
3/ pyridine, ceric ammonium nitrate-sulfuric acid, aluminum isopropylate, Peracetic Acid, benzoyl hydroperoxide, hydrogen peroxide etc., preferably hydrogen peroxide.
In step 2 of the present invention, reaction can be carried out in the temperature range of 35～60 ℃, preferably 40～45 ℃.
In step 2 of the present invention, recrystallization solvent can be methylene dichloride, chloroform, 1,2-ethylene dichloride, methyl acetate, ethyl acetate etc., preferably 1,2-ethylene dichloride.
The invention relates to 2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1, the synthetic method of 3-diketone (MST), technical essential is:
(1) in intermediate 2-(2-nitro-4-methylsulfonyl-benzyl hydroxyl) hexanaphthene-1, in 3-diketone synthetic, select appropriate solvent, raw material and alkali are had to good miscible effect, be conducive to addition reaction;
(2) in intermediate 2-(2-nitro-4-methylsulfonyl-benzyl hydroxyl) hexanaphthene-1, in 3-diketone synthetic, select appropriate alkali, control temperature of reaction, suppress the dehydration reaction of intermediate, improved yield.
The present invention is with 2-nitro-4-methylsulfonyl phenyl aldehyde and 1; hydroresorcinol is starting raw material; explored a preparation 2-capable of being industrialized (2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1; the route of 3-diketone; its total recovery is more than 85%; product purity is greater than 99%, and this route institute, in steps without severe condition, simple to operate, environmentally friendly, has important actual application value.
Embodiment
In order to be illustrated more clearly in the present invention, hereinafter adopt indefiniteness embodiment to be described further.
Embodiment mono-:
(1) 2-(2-nitro-4-methylsulfonyl-benzyl hydroxyl) hexanaphthene-1,3-diketone (MST01) synthetic
In the four-hole boiling flask of 2L, add successively 2-nitro-4-methylsulfonyl phenyl aldehyde (114.5g/0.5mol), 1, hydroresorcinol (67.2g/0.6mol) and 400ml toluene, stirring and evenly mixing, control temperature of reaction system at 10～15 ℃, drip N, N-dimethyl benzylamine (94.5g/0.7mol), dropwise, continue insulation reaction 1.5h, stopped reaction, by dilute sulphuric acid (wt 20%) regulation system, to neutral, obtain the mixed solution of intermediate MST01, can be directly used in next step reaction.
(2) 2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1,3-diketone (MST) synthetic
Control the mixeding liquid temperature of MST01 at 40～45 ℃, add 30% hydrogen peroxide (62.33g/0.55mol), stirring and evenly mixing, drip 120ml dilute sulphuric acid (wt 20%), dropwise, continue insulation reaction 2h, stop heating, reaction solution is bathed and to be cooled to below 0 ℃ with cryosel, filter, filter cake with clear water drip washing until washings is neutrality, dry, obtain MST crude product 163.7g, content 95.7% (HPLC-outer marking quantitative), structure warp
1h-NMR, MS confirmation.Select the further recrystallization of ethylene dichloride to purify to content and be greater than 99% (HPLC-outer marking quantitative) MST product 153.7g.
Two-step reaction yield 86.8%.
Embodiment bis-:
(1) 2-(2-nitro-4-methylsulfonyl-benzyl hydroxyl) hexanaphthene-1,3-diketone (MST01) synthetic
In the four-hole boiling flask of 2L, add successively 2-nitro-4-methylsulfonyl phenyl aldehyde (114.5g/0.5mol), 1, hydroresorcinol (67.2g/0.6mol) and 400ml tetrahydrofuran (THF), stirring and evenly mixing, control temperature of reaction system at 35～40 ℃, drip 400ml aqueous sodium hydroxide solution (wt 5%), dropwise, continue insulation reaction 40min, stopped reaction, extremely neutral by dilute sulphuric acid (wt 20%) regulation system, obtain the mixed solution of intermediate MST01, can be directly used in next step reaction.
(2) 2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1,3-diketone (MST) synthetic
Control the mixeding liquid temperature of MST01 at 55～60 ℃, drip Peracetic Acid (41.5g/0.55mol), stirring and evenly mixing, dropwise, continue insulation reaction 1h, stop heating, reaction solution is bathed and is cooled to below 0 ℃ with cryosel, filter, filter cake, is dried until washings is neutral with clear water drip washing, obtains MST crude product 156.4g, content 93.9% (HPLC-outer marking quantitative), structure warp
1h-NMR, MS confirmation.Further methyl acetate recrystallization purifies to content and is greater than 99% (HPLC-outer marking quantitative) product 146.4g.
Two-step reaction yield 81.1%.
Embodiment tri-:
(1) 2-(2-nitro-4-methylsulfonyl-benzyl hydroxyl) hexanaphthene-1,3-diketone (MST01) synthetic
In the four-hole boiling flask of 2L, add successively 2-nitro-4-methylsulfonyl phenyl aldehyde (114.5g/0.5mol), 1, hydroresorcinol (67.2g/0.6mol) and 400ml tetramethylene sulfone, stirring and evenly mixing, control temperature of reaction system at 10～15 ℃, drip 300ml aqueous sodium carbonate (wt 15%), dropwise, continue insulation reaction 2h, stopped reaction, extremely neutral by dilute sulphuric acid (wt 20%) regulation system, obtain the mixed solution of intermediate MST01, can be directly used in next step reaction.
(2) 2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1,3-diketone (MST) synthetic
Under room temperature condition, to the mixed solution of MST01, add ceric ammonium nitrate (164.4g/0.3mol), stirring and evenly mixing, drip 50ml dilute sulphuric acid (wt 20%), dropwise, continue room temperature reaction 3h, stop heating, reaction solution is bathed and to be cooled to below 0 ℃ with cryosel, filter, filter cake with clear water drip washing until washings is neutrality, dry, obtain MST crude product 160.8g, content 96.1% (HPLC-outer marking quantitative), structure warp
1h-NMR, MS confirmation.Further Gossypol recrystallized from chloroform purifies to content and is greater than 99% (HPLC-outer marking quantitative) product 151.2g.
Two-step reaction yield 85.5%.
Claims (9)
1. a 2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1, the synthetic method of 3-diketone (MST), react as follows:
Described method comprises following two steps:
Step 1: be under the condition of 5～45 ℃ in temperature, to 2-nitro-4-methylsulfonyl phenyl aldehyde and 1, the mixed solution and dripping alkaline solution of hydroresorcinol, note maintaining temperature of reaction, dropwise, continue insulation reaction 0.5～2 hour, stopped reaction, obtain intermediate 2-(2-nitro-4-methylsulfonyl-benzyl hydroxyl) hexanaphthene-1, the mixed solution of 3-diketone, is directly used in next step reaction;
Step 2: be under the condition of 35～60 ℃ in temperature, to 2-(2-nitro-4-methylsulfonyl-benzyl hydroxyl) hexanaphthene-1, in the mixed solution of 3-diketone, add oxygenant, continue to stir 1～3.5 hour, stop heating, reaction solution is bathed cooling with cryosel, filter, wash product with water to neutral, crude product further recrystallization is purified.
2. according to the method for claim 1, in described step 1, solvent is tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, DMF, methyl-sulphoxide, tetramethylene sulfone, ethylene dichloride, toluene, consumption be raw materials quality and 2～3 times.
3. according to the method for claim 2, in described step 1, solvent is toluene.
4. according to the method for claim 1, it is characterized in that in described step 1, alkaline solution is 5wt% aqueous sodium hydroxide solution, 10wt% aqueous sodium hydroxide solution, 15wt% aqueous sodium hydroxide solution, 15wt% aqueous sodium carbonate, 20wt% sodium bicarbonate aqueous solution.
5. according to the method for claim 4, in described step 1, alkaline solution is 5wt% aqueous sodium hydroxide solution.
6. according to the method for claim 1, it is characterized in that in described step 2, oxygenant is PCC, CrO
3/ pyridine, ceric ammonium nitrate-sulfuric acid, aluminum isopropylate, Peracetic Acid, benzoyl hydroperoxide, hydrogen peroxide.
7. according to the method for claim 6, in described step 2, oxygenant is hydrogen peroxide.
8. according to the method for claim 1, it is characterized in that in described step 2, recrystallization solvent is methylene dichloride, chloroform, 1,2-ethylene dichloride, methyl acetate, ethyl acetate.
9. method according to Claim 8, in described step 2, recrystallization solvent is 1,2-ethylene dichloride.
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| CN1169140A (en) * | 1995-01-25 | 1997-12-31 | 曾尼卡有限公司 | Process for prodn. of 2-(substd. benzoyl)-1,3-cyclohexanediones |
| CN1169139A (en) * | 1995-01-25 | 1997-12-31 | 曾尼卡有限公司 | Process for prodn. of 2-(substd. Benzyl)-1,3-cyclohexanediones |
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| CN1169140A (en) * | 1995-01-25 | 1997-12-31 | 曾尼卡有限公司 | Process for prodn. of 2-(substd. benzoyl)-1,3-cyclohexanediones |
| CN1169139A (en) * | 1995-01-25 | 1997-12-31 | 曾尼卡有限公司 | Process for prodn. of 2-(substd. Benzyl)-1,3-cyclohexanediones |
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| 余刚，等.玉米田除草剂甲基磺草酮的合成.《江苏农业学报》.2007,第23卷(第6期),661-662. * |
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