CN106008290A - Method for preparing tembotrions - Google Patents
Method for preparing tembotrions Download PDFInfo
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- CN106008290A CN106008290A CN201610321517.XA CN201610321517A CN106008290A CN 106008290 A CN106008290 A CN 106008290A CN 201610321517 A CN201610321517 A CN 201610321517A CN 106008290 A CN106008290 A CN 106008290A
- Authority
- CN
- China
- Prior art keywords
- chloro
- preparation
- ring sulphur
- sulphur ketone
- sulfosalicylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title abstract description 15
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 claims abstract description 7
- -1 sulphur ketone Chemical class 0.000 claims description 35
- 239000005864 Sulphur Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 10
- CVSXWGCKOPYBCT-UHFFFAOYSA-N 4-hydroxy-3-methoxycarbonylbenzenesulfonic acid Chemical compound COC(=O)C1=CC(S(O)(=O)=O)=CC=C1O CVSXWGCKOPYBCT-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 6
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 6
- YEDUAINPPJYDJZ-UHFFFAOYSA-N 2-hydroxybenzothiazole Chemical compound C1=CC=C2SC(O)=NC2=C1 YEDUAINPPJYDJZ-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical group C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 150000002148 esters Chemical class 0.000 abstract description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008707 rearrangement Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical class CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- JXHYCCGOZUGBFD-UHFFFAOYSA-N benzoic acid;hydrochloride Chemical compound Cl.OC(=O)C1=CC=CC=C1 JXHYCCGOZUGBFD-UHFFFAOYSA-N 0.000 abstract 2
- 230000007547 defect Effects 0.000 abstract 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 abstract 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 abstract 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 229940095102 methyl benzoate Drugs 0.000 abstract 1
- MZDGXTXYHXDWIM-UHFFFAOYSA-N methyl benzoate;hydrochloride Chemical compound Cl.COC(=O)C1=CC=CC=C1 MZDGXTXYHXDWIM-UHFFFAOYSA-N 0.000 abstract 1
- MSGMXYUAWZYTFC-UHFFFAOYSA-N sodium;2,2,2-trifluoroethanolate Chemical compound [Na+].[O-]CC(F)(F)F MSGMXYUAWZYTFC-UHFFFAOYSA-N 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 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 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 6
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 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 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- UQMQEGXOVRHYOV-UHFFFAOYSA-N sodium;2,2,2-trifluoroethanol Chemical compound [Na].OCC(F)(F)F UQMQEGXOVRHYOV-UHFFFAOYSA-N 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a method for preparing tembotrions, and belongs to the technical field of organic chemical industry. The method comprises the steps that sodium 2,2,2-trifluoroethanolate and 2-chloro-3-brooethyl-4-methylsulfonylpropyl methyl benzoate react, and generated 2-chloro-3-trifluoro-ethoxy methyl-4-methyl sulfone chloride benzoic acid and 1,3-cyclohexanedione are condensed and rearranged to prepare tembotrions. According to the method for preparing tembotrions, the defects that in a traditional method, 2-chloro-3-brooethyl-4-methyl sulfone chloride methyl benzoate, trifluoroethanol and potassium tert-butoxide are used for preparing 2-chloro-3-trifluoro-ethoxy methyl-4-methyl sulfone chloride benzoic acid, the yield is low, and a potassium tert-butoxide reagent is expensive are overcome, meanwhile, the defect that after carboxyl is acylate chlorinated into ester, a toxic catalyst acetone cyanohydrins is needed in a rearrangement method is overcome, the advantages of being high in yield, low in cost, easy to operate, low in pollution, safe, environmentally friendly and the like are achieved, and the method is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to field of chemical technology, be specifically related to the preparation method of a kind of ring sulphur ketone.
Background technology
Ring sulphur ketone is that activity is higher, consumption is less up to now, and a safest class herbicide, its
Industrial production process mainly trifluoroethanol, potassium tert-butoxide method prepare key intermediate 2-chloro-3-trifluoroethoxy
Rearrangement method after methyl-4-first sulfosalicylic acid then carboxyl acyl chlorides chemical conversion ester, and this kind of method acquisition finished product
Yield is relatively low, the expensive reagents used.Wherein, key intermediate 2-chloro-3-trifluoroethoxy methyl is being prepared
-4-first sulfosalicylic acid uses potassium tert-butoxide to do alkali, and yield is relatively low, expensive reagents；Carboxyl acyl chlorides chemical conversion ester
Rear rearrangement method poisonous reagent to be used .alpha.-hydroxyisobutyronitrile. is rearrangement catalyst, and needs to make acyl chlorides with thionyl chloride
Change reagent, and thionyl chloride has the biggest harm to environment.
To sum up, traditional method prepares ring sulphur ketone, and to be respectively provided with yield low, and cost is high, and containing play in production technology
The features such as poisonous substance matter, do not meet the requirement of large-scale industrial production.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that the preparation method of a kind of ring sulphur ketone,
Low to solve yield when tradition prepares ring sulphur ketone, cost is high, and containing technology such as extremely toxic substances in production technology
Problem.
The technical problem to be solved realizes by the following technical solutions:
The invention provides the preparation method of a kind of ring sulphur ketone, comprise the following steps:
Step a: with 2-chloro-3-bromomethyl-4-first sulfosalicylic acid methyl ester (compound I) and trifluoroethanol
Sodium is reaction substrate, adds MOH or M2CO3, reacts, it is thus achieved that 2-chloro-3-trifluoro in reaction dissolvent
Ethoxymethyl-4-first sulfosalicylic acid (compound II), shown in concrete chemical equation such as following formula (1):
Step b: with the compound II and 1 of step a, hydroresorcinol (compound III) is reaction substrate,
Under the effect of condensing agent and base catalyst, reaction dissolvent carries out condensation reaction, it is thus achieved that ring sulphur ketone (is changed
Compound IV), shown in concrete chemical equation such as following formula (2):
Wherein, in described step a, M is the one in Li, Na, K ion.
Further, in described step a, trifluoroethanol is 1.1-1.2:1 with the mol ratio of compound I.
Further, in described step a, the mol ratio of MOH/M2CO3 and compound I is 1-1.5:1.
Further, in described step a, reaction temperature is 0-5 DEG C, and the response time is 2-10 hour.
Further, in described step b, the mol ratio of compound III and compound II is 1-1.3:1；Institute
The mol ratio stating base catalyst and compound II is 1-3:1；Described condensing agent with the mol ratio of compound II is
1-2:1。
Further, in described step b, base catalyst selected from sodium carbonate, potassium carbonate, calcium hydroxide, three
One or more in ethamine, pyridine.
Further, in described step b, condensing agent one in CDI, HBTU, HOBT, DBU or
Multiple, wherein, CDI is N, N'-carbonyl dimidazoles, and HBTU is O-BTA-tetramethylurea hexafluoro phosphorus
Acid esters, HOBT is I-hydroxybenzotriazole, and DBU is 1,8-diazabicylo 11 carbon-7-alkene.
Further, in described step b, the temperature of condensation reaction is-10-30 DEG C, and the response time is
0.5-12h。
Further, described step a is or/and in step b, reaction dissolvent is hexane, hexamethylene, N, N-bis-
Methylformamide, benzene,toluene,xylene, dichloromethane, 1,2-dichloroethanes, chloroform, Isosorbide-5-Nitrae-
One or more in dioxane, ether, oxolane, acetonitrile.
Further, described reaction dissolvent is 2-8:1 with the weight ratio of compound I or compound II.
The present invention has the advantage that the preparation side that the invention provides a kind of ring sulphur ketone compared to existing technology
Method, the method, using trifluoroethanol as reactant, overcomes trifluoroethanol and potassium tert-butoxide preparation key
The shortcoming that intermediate 2-chloro-3-trifluoroethoxy methyl-4-first sulfosalicylic acid yield is low, cost is high, simultaneously
The shortcoming needing severe toxicity catalyst .alpha.-hydroxyisobutyronitrile. after also overcoming carboxyl acyl chlorides chemical conversion ester in rearrangement method, has
Reaction yield height, low cost, easily operation, pollute less, the advantage such as safety and environmental protection, be suitable for large-scale industry
Metaplasia is produced.
Detailed description of the invention
For the technological means making the present invention realize, creation characteristic, reach purpose and effect and be readily apparent from
Solve, below in conjunction with specific embodiment, the present invention is expanded on further.
Embodiment 1
The preparation method of a kind of ring sulphur ketone that the present embodiment provides, comprises the following steps:
Step a: take 1.1mol (134.2g) trifluoroethanol, 1.2mol (48g) sodium hydroxide, 1.0mol
(318g) 2-chloro-3-bromomethyl-4-first sulfosalicylic acid methyl ester (compound I), 1000mL N, N-diformazan
Base Methanamide joins in reactor, then 30 DEG C insulation 5 hours after, by the N in reactant liquor, N-dimethyl
After Methanamide removes under reduced pressure, being added by residual liquid in 300mL water, the hydrochloric acid tune pH with 35% is to faintly acid, cold
But crystallize, filter, washing, it is dried to obtain compound II, weigh to obtain 314.8g, yield 91%, wherein, N, N-
Dimethylformamide is as reaction dissolvent, it is also possible to hexane, hexamethylene, benzene,toluene,xylene,
Dichloromethane, 1,2-dichloroethanes, chloroform, Isosorbide-5-Nitrae-dioxane, ether, oxolane, acetonitrile
In one or more replace.
Step b: take the compound II of 1mol above-mentioned reaction gained, is dissolved in the 1 of 1000mL, 2-dichloroethanes
In, then under 5-10 DEG C of temperature conditions, add containing 1.2mol (117.6g) 1,3-hexamethylene two in half an hour
Ketone (compound III) and 1.2mol (194.6g) condensing agent CDI and 1.2mol (121.2g) triethylamine, then
Under 5-10 DEG C of temperature conditions stirring reaction 8 hours, be then passed through washing, concentrating under reduced pressure, add methanol pull an oar,
Filter, be dried to obtain finished product ring sulphur ketone (compound IV) 366.4g, purity 96.5%, yield 86.3%,
Wherein, 1,2-dichloroethanes is as reaction dissolvent, it is also possible to hexane, hexamethylene, N, N-dimethyl methyl
Amide, benzene,toluene,xylene, dichloromethane, chloroform, Isosorbide-5-Nitrae-dioxane, ether, tetrahydrochysene furan
Mutter, one or more in acetonitrile replace.
Embodiment 2
The preparation method of the another kind of ring sulphur ketone that the present embodiment provides, comprises the following steps:
Step a: take 1.2mol (146.4g) trifluoroethanol, 1.2mol (67.2g) potassium hydroxide,
1.0mol (318g) 2-chloro-3-bromomethyl-4-first sulfosalicylic acid methyl ester (compound I), 1000mL N, N-
Dimethylformamide joins in reactor, after then reacting 10 hours at 0 DEG C, by the N in reactant liquor, N-
After dimethylformamide removes under reduced pressure, being added by residual liquid in 300mL water, the hydrochloric acid with 35% adjusts pH to weak acid
Property, crystallisation by cooling, filter, washing, be dried to obtain compound II, weigh to obtain 321.7g, yield 93%.
Step b: take the compound II of 1mol above-mentioned reaction gained, be dissolved in the dichloromethane of 1000mL,
Then under 8-15 DEG C of temperature conditions, adding containing 1.3mol (145.6g) 1 in half an hour, hydroresorcinol (is changed
Compound III) and 2mol (758g) condensing agent HBTU and 2mol (212g) sodium carbonate, then 8-15 DEG C of temperature strip
Stirring reaction 9 hours under part, then washing, concentrating under reduced pressure, add methanol and pull an oar, filter, be dried to obtain into
Product ring sulphur ketone (compound IV) 362.5g, purity 95.8%, yield 86%.
Embodiment 3
The preparation method of the another kind of ring sulphur ketone that the present embodiment provides, comprises the following steps:
Step a: take 1.1mol (134.2g) trifluoroethanol, 1.2mol (129.6g) sodium carbonate,
1.0mol (318g) 2-chloro-3-bromomethyl-4-first sulfosalicylic acid methyl ester (compound I), 1000mL N, N-
Dimethylformamide joins in reactor, then 50 DEG C insulation 2 hours after, by the N in reactant liquor, N-bis-
After methylformamide removes under reduced pressure, residual liquid is added in 300mL water, with 35% hydrochloric acid adjust pH to faintly acid,
Crystallisation by cooling, filters, and washing is dried to obtain compound II, and weigh to obtain 311.4g, yield 90%.
Step b: take the compound II of 1mol above-mentioned reaction gained, be dissolved in the dichloroethanes of 1000mL,
Then under 15-20 DEG C of temperature conditions, adding containing 1.5mol (147g) 1 in half an hour, hydroresorcinol (is changed
Compound III) and 3mol (405g) condensing agent HOBT and 3mol (222g) calcium hydroxide, then 15-20 DEG C of temperature
Under the conditions of stirring reaction 8 hours, then washing, concentrating under reduced pressure adds first, alcohol and pulls an oar, filters, is dried to obtain
Finished product ring sulphur ketone (compound IV) 375.4g, purity 97.5%, yield 87.5%.
Embodiment 4
The preparation method of the another kind of ring sulphur ketone that the present embodiment provides, comprises the following steps:
Step a: take 1.1mol (134.2g) trifluoroethanol, 1.2mol (166.8g) potassium carbonate,
1.0mol (318g) 2-chloro-3-bromomethyl-4-first sulfosalicylic acid methyl ester (compound I), 1000mL N, N-
Dimethylformamide joins in reactor, then 30 DEG C insulation 5 hours after, by the N in reactant liquor, N-bis-
After methylformamide removes under reduced pressure, residual liquid is added in 300mL water, with 35% hydrochloric acid adjust pH to faintly acid,
Crystallisation by cooling, filters, and washing is dried to obtain compound II, and weigh to obtain 321.7g, yield 93%.
Step b: take the compound II of 1mol above-mentioned reaction gained, be dissolved in the hexamethylene of 1000mL, so
After under-10-8 DEG C of temperature conditions, add containing 1mol (98g) 1, hydroresorcinol (compound in half an hour
III) and 1mol (152g) condensing agent DBU and 1mol (152g) pyridine, then under-10-8 DEG C of temperature conditions
Stirring reaction 24 hours, is then passed through washing, concentrating under reduced pressure, adds methanol and pull an oar, filter, be dried to obtain
Finished product ring sulphur ketone (compound IV) 332.9g, purity 94.6%, yield 80.1%.
Embodiment 5
The preparation method of the another kind of ring sulphur ketone that the present embodiment provides, comprises the following steps:
Step a: take 1.1mol (134.2g) trifluoroethanol, 1.2mol (28.8g) Lithium hydrate,
1.0mol (318g) 2-chloro-3-bromomethyl-4-first sulfosalicylic acid methyl ester (compound I), 1000mL N, N-
Dimethylformamide joins in reactor, then 30 DEG C insulation 5 hours after, by the N in reactant liquor, N-bis-
After methylformamide removes under reduced pressure, residual liquid is added in 300mL water, with 35% hydrochloric acid adjust pH to faintly acid,
Crystallisation by cooling, filters, and washing is dried to obtain compound II, and weigh to obtain 318.3g, yield 92%.
Step b: take the compound II of 1mol above-mentioned reaction gained, be dissolved in the hexamethylene of 1000mL, so
After under 20-30 DEG C of temperature conditions, add in half an hour containing 1.1mol (106.7g) 1, hydroresorcinol (is changed
Compound III) and 1.8mol (291.6g) condensing agent CDI and 5mol (690g) potassium carbonate, then at 20-30 DEG C
Under temperature conditions stirring reaction 15 hours, be then passed through washing, concentrating under reduced pressure, add methanol making beating, filtration,
It is dried to obtain finished product ring sulphur ketone (compound IV) 355.5g, purity 96.3%, yield 83.9%.
The ultimate principle of the present invention and principal character and advantages of the present invention have more than been shown and described.This
Skilled person will appreciate that of industry, the present invention is not restricted to the described embodiments, above-described embodiment and saying
The principle that the present invention is simply described described in bright book, without departing from the spirit and scope of the present invention,
The present invention also has various changes and modifications, and these changes and improvements both fall within claimed invention model
In enclosing.Claimed scope is defined by appending claims and equivalent thereof.
Claims (10)
1. the invention provides the preparation method of a kind of ring sulphur ketone, it is characterised in that comprise the following steps:
Step a: with 2-chloro-3-bromomethyl-4-first sulfosalicylic acid methyl ester and trifluoroethanol for the reaction end
Thing, adds MOH or M2CO3, reacts, it is thus achieved that 2-chloro-3-trifluoroethoxy methyl-4-in reaction dissolvent
First sulfosalicylic acid, shown in concrete chemical equation such as following formula (1):
Step b: with 2-chloro-3-trifluoroethoxy methyl-4-first sulfosalicylic acid and the 1,3-hexamethylene two of step a
Ketone is reaction substrate, under the effect of condensing agent and base catalyst, carries out condensation reaction in reaction dissolvent,
Obtain ring sulphur ketone, shown in concrete chemical equation such as following formula (2):
Wherein, in described step a, M is the one in Li, Na, K ion.
The preparation method of a kind of ring sulphur ketone the most according to claim 1, it is characterised in that described step
In rapid a, the mol ratio of trifluoroethanol 3-chloro-with 2-bromomethyl-4-first sulfosalicylic acid methyl ester is
1.1-1.2:1.
The preparation method of a kind of ring sulphur ketone the most according to claim 1, it is characterised in that described step
In rapid a, the mol ratio of MOH/M2CO3 with 2-chloro-3-bromomethyl-4-first sulfosalicylic acid methyl ester is
1-1.5:1。
The preparation method of a kind of ring sulphur ketone the most according to claim 1, it is characterised in that described step
In rapid a, reaction temperature is 0-5 DEG C, and the response time is 2-10 hour.
The preparation method of a kind of ring sulphur ketone the most according to claim 1, it is characterised in that described step
In rapid b, 1, hydroresorcinol with the mol ratio of 2-chloro-3-trifluoroethoxy methyl-4-first sulfosalicylic acid is
1-1.3:1；Described base catalyst with the mol ratio of 2-chloro-3-trifluoroethoxy methyl-4-first sulfosalicylic acid is
1-3:1；Described condensing agent with the mol ratio of 2-chloro-3-trifluoroethoxy methyl-4-first sulfosalicylic acid is
1-2:1。
The preparation method of a kind of ring sulphur ketone the most according to claim 1, it is characterised in that described step
In rapid b, base catalyst one in sodium carbonate, potassium carbonate, calcium hydroxide, triethylamine, pyridine or
Multiple.
The preparation method of a kind of ring sulphur ketone the most according to claim 1, it is characterised in that described step
In rapid b, one or more in CDI, HBTU, HOBT, DBU of condensing agent, wherein, CDI is N, N'-
Carbonyl dimidazoles, HBTU is O-BTA-tetramethylurea hexafluorophosphoric acid ester, and HOBT is 1-hydroxy benzo
Triazole, DBU is 1,8-diazabicylo 11 carbon-7-alkene.
The preparation method of a kind of ring sulphur ketone the most according to claim 1, it is characterised in that described step
In rapid b, the temperature of condensation reaction is-10-30 DEG C, and the response time is 0.5-12h.
The preparation method of a kind of ring sulphur ketone the most according to claim 1, it is characterised in that described step
Rapid a or/and in step b, reaction dissolvent be hexane, hexamethylene, DMF, benzene, toluene,
Dimethylbenzene, dichloromethane, 1,2-dichloroethanes, chloroform, Isosorbide-5-Nitrae-dioxane, ether, tetrahydrochysene furan
Mutter, one or more in acetonitrile.
The preparation method of a kind of ring sulphur ketone the most according to claim 1, it is characterised in that described instead
Answer solvent and 2-chloro-3-bromomethyl-4-first sulfosalicylic acid methyl ester or 2-chloro-3-trifluoroethoxy methyl-4-first
The weight ratio of sulfosalicylic acid is 2-8:1.
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| CN109678767A (en) * | 2018-12-27 | 2019-04-26 | 浙江中山化工集团股份有限公司 | A kind of synthesis technology of herbicide tembotrions |
| CN110357797A (en) * | 2018-04-11 | 2019-10-22 | 江西天宇化工有限公司 | A kind of preparation method of 2- (the chloro- 3- chloromethyl -4- methylsulfonylbenzoyl of 2-)-hydroresorcinol |
| CN112645853A (en) * | 2019-10-10 | 2021-04-13 | 江西天宇化工有限公司 | Preparation method of 2-chloro-3-alkoxymethyl-4-methylsulfonylbenzoic acid |
| CN114560795A (en) * | 2021-06-25 | 2022-05-31 | 浙江先锋科技股份有限公司 | Method for preparing tembotrione |
| CN114621122A (en) * | 2020-12-14 | 2022-06-14 | 南通泰禾化工股份有限公司 | Process for the preparation of a cyclic sulphonone metabolite |
| CN116283680A (en) * | 2022-10-20 | 2023-06-23 | 安徽久易农业股份有限公司 | Preparation method of cyclosulfamide |
| WO2024109718A1 (en) * | 2022-11-22 | 2024-05-30 | 兰升生物科技集团股份有限公司 | Method for preparing cyclosulfonone, and intermediates |
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| CN110357797A (en) * | 2018-04-11 | 2019-10-22 | 江西天宇化工有限公司 | A kind of preparation method of 2- (the chloro- 3- chloromethyl -4- methylsulfonylbenzoyl of 2-)-hydroresorcinol |
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| CN112645853A (en) * | 2019-10-10 | 2021-04-13 | 江西天宇化工有限公司 | Preparation method of 2-chloro-3-alkoxymethyl-4-methylsulfonylbenzoic acid |
| CN114621122A (en) * | 2020-12-14 | 2022-06-14 | 南通泰禾化工股份有限公司 | Process for the preparation of a cyclic sulphonone metabolite |
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| CN114560795B (en) * | 2021-06-25 | 2024-04-05 | 浙江先锋科技股份有限公司 | Method for preparing cyclosulfamide |
| CN116283680A (en) * | 2022-10-20 | 2023-06-23 | 安徽久易农业股份有限公司 | Preparation method of cyclosulfamide |
| WO2024109718A1 (en) * | 2022-11-22 | 2024-05-30 | 兰升生物科技集团股份有限公司 | Method for preparing cyclosulfonone, and intermediates |
| WO2024109721A1 (en) * | 2022-11-22 | 2024-05-30 | 兰升生物科技集团股份有限公司 | Preparation method for hppd inhibitor herbicide, intermediate, preparation method for intermediate |
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