CN106866579B - The synthetic method of herbicide flufenacet thiadiazoles intermediate - Google Patents
The synthetic method of herbicide flufenacet thiadiazoles intermediate Download PDFInfo
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 17
- 239000005531 Flufenacet Substances 0.000 title description 18
- -1 flufenacet thiadiazoles Chemical class 0.000 title description 11
- 230000002363 herbicidal effect Effects 0.000 title description 5
- 239000004009 herbicide Substances 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- KEHNEEAKQRXDOB-UHFFFAOYSA-N CC1=NN=C(C(F)(F)F)[S+]1S Chemical class CC1=NN=C(C(F)(F)F)[S+]1S KEHNEEAKQRXDOB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims description 22
- 238000003786 synthesis reaction Methods 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 238000003541 multi-stage reaction Methods 0.000 claims description 13
- 230000004044 response Effects 0.000 claims description 13
- 239000000543 intermediate Substances 0.000 claims description 12
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 8
- 229960002218 sodium chlorite Drugs 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 20
- 230000035484 reaction time Effects 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 8
- SQLPTSMJAQPVKR-UHFFFAOYSA-N 2-methylsulfonyl-5-(trifluoromethyl)-1,3,4-thiadiazole Chemical class CS(=O)(=O)C1=NN=C(C(F)(F)F)S1 SQLPTSMJAQPVKR-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- IANUJLZYFUDJIH-UHFFFAOYSA-N flufenacet Chemical compound C=1C=C(F)C=CC=1N(C(C)C)C(=O)COC1=NN=C(C(F)(F)F)S1 IANUJLZYFUDJIH-UHFFFAOYSA-N 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 14
- 150000004867 thiadiazoles Chemical class 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002440 hydroxy compounds Chemical class 0.000 description 4
- 238000006053 organic reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000005507 Diflufenican Substances 0.000 description 2
- 239000005582 Metosulam Substances 0.000 description 2
- VGHPMIFEKOFHHQ-UHFFFAOYSA-N Metosulam Chemical compound N1=C2N=C(OC)C=C(OC)N2N=C1S(=O)(=O)NC1=C(Cl)C=CC(C)=C1Cl VGHPMIFEKOFHHQ-UHFFFAOYSA-N 0.000 description 2
- 239000005583 Metribuzin Substances 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- BDKZHNJTLHOSDW-UHFFFAOYSA-N [Na].CC(O)=O Chemical compound [Na].CC(O)=O BDKZHNJTLHOSDW-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- WYEHFWKAOXOVJD-UHFFFAOYSA-N diflufenican Chemical compound FC1=CC(F)=CC=C1NC(=O)C1=CC=CN=C1OC1=CC=CC(C(F)(F)F)=C1 WYEHFWKAOXOVJD-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- XIGAUIHYSDTJHW-UHFFFAOYSA-N mefenacet Chemical compound N=1C2=CC=CC=C2SC=1OCC(=O)N(C)C1=CC=CC=C1 XIGAUIHYSDTJHW-UHFFFAOYSA-N 0.000 description 2
- FOXFZRUHNHCZPX-UHFFFAOYSA-N metribuzin Chemical compound CSC1=NN=C(C(C)(C)C)C(=O)N1N FOXFZRUHNHCZPX-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- OYVABZRZDZPVQD-UHFFFAOYSA-N [F].C=1C=CSC=1 Chemical compound [F].C=1C=CSC=1 OYVABZRZDZPVQD-UHFFFAOYSA-N 0.000 description 1
- GLCYMSPOJRDUEE-UHFFFAOYSA-N [N+](=O)([O-])C1=CC=CC=C1.[F] Chemical compound [N+](=O)([O-])C1=CC=CC=C1.[F] GLCYMSPOJRDUEE-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000003375 sulfoxide group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003583 thiosemicarbazides Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
- C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
Abstract
The invention discloses a kind of using microwave ultrasonic wave promotion by 2- methyl mercapto -5- Trifluoromethyl-1,3,4- thiadiazoles oxidation preparation 2- methylsulfonyl -5- Trifluoromethyl-1,3,4- thiadiazoles synthetic method.Compared with existing public technology, the present invention, which has, saves the reaction time, improves equipment and space utilization rate；Not only reaction efficiency is improved, but also increases technique essential safety.
Description
Technical field
The present invention relates to sulfone compound synthetic method, especially a kind of sulfone compound microwave ultrasonic wave assists synthesis side
Method.
Background technique
Flufenacet, English name: N- (4-fluorophenyl)-N- (1-me- thylethyl) -2- [[5-
(trifluoromethyl) -1,3,4- thiadiazol-2-yl] oxy] acetamide, No. CAS: 142459-58-3, point
Minor: C14H13F4N3O2S, molecular weight: 363.3, relative density: 1.312 (25).Physicochemical property: white to brown solid, fusing point
75~77 DEG C.Flufenacet system oxygen acetanil class herbicide, Bayer A.G's exploitation in 1988, test code number
BAYFOE5043, common name Flufenact, trade name Axiom, Herald, Terano, Epic, Arist.Flufenacet is
Bayer A.G's another oxygen acetanil class herbicide after successfully developing mefenacet, it is main by inhibiting cell point
It splits and plays a role.A large amount of field trial has been done in the U.S., Europe, South Africa, Asia, South America within 1988 to 1994, tested
Show that the kind is handled with 120 ~ 200g/ha, can effectively prevent and kill off before the bud of annual gramineous weed and broadleaf weeds and after bud
In early days, main weeds are prevented and kill off suitable for the big beans ﹑ cotton ﹑ rice of beautiful rice ﹑ and other crops, flufenacet can with prevent and kill off broadleaf weeds
Herbicide metribuzin (metribuzin), metosulam (metosulam), Diflufenican (diflufenican) etc. it is multiple
Match, expands degrass spectrum.Compared with mefenacet, flufenacet has higher activity, is suitable for more crop managements of weeds.
Synthetic method document report about flufenacet and its intermediate is more, but its synthetic route mainly has following two
Kind route.Route one: para-fluoroaniline is reacted with 2 cbloropropane isopropyl chloride first, is then reacted with chloracetyl chloride；Again with acetic acid sodium reaction, and
Hydrolysis becomes hydroxy compounds (N- (4- fluorophenyl)-N- isopropyl -2- hydroxymethyl acetamide)；Meanwhile trifluoroacetic acid and amino
Thiocarbamide is that thiadiazoles amino-compound is made in raw material, and thiadiazoles amino-compound obtains intermediate thiadiazoles chlorine by chlorination
Compound；Last thiadiazoles chloride and aforementioned hydroxy compound intermediate be condensed up to target product flufenacet (bibliography:
Jiang Yutian, Chen Tongming etc., the synthesis of flufenacet, " pesticide ", 2007, volume 46,11 phases, P734-736).Route two: to fluorine
Nitrobenzene and acetone generate N- isopropyl para-fluoroaniline through catalytic hydrogenation, then with acetic acid sodium reaction, and hydrolyze and become hydroxy compound
Object (N- (4- fluorophenyl)-N- isopropyl -2- hydroxymethyl acetamide)；Intermediate is made using trifluoroacetic acid and thiosemicarbazides as raw material
2- methyl mercapto -5- Trifluoromethyl-1,3,4- thiadiazoles；2- methyl mercapto -5- Trifluoromethyl-1,3,4- thiadiazoles pass through further oxygen
Change reaction and obtains 2- methylsulfonyl -5- Trifluoromethyl-1,3,4- thiadiazoles；Last 2- methylsulfonyl -5- Trifluoromethyl-1,3,4- thiophene two
Azoles and aforementioned hydroxy compound intermediate are condensed up to target product flufenacet (bibliography: Li Yusheng, Zhou Guidong, Shen Yi
Congruence, the synthesis of flufenacet, " modern ", 2002, the 2nd phase, P8-10).Due to one thiadiazoles amino-compound of route
Intermediate thiadiazoles chloride and final step reaction thiadiazoles chloride and aforementioned hydroxy chemical combination are obtained by chlorination
Object intermediate condensation is up to target product flufenacet, this two-step reaction yield is lower, and by-product is more, therefore practical fluorine thiophene at present
95% or more manufacturer is all to select route two as synthetic route in careless amine industrial production.
It is found that 2- methylsulfonyl -5- Trifluoromethyl-1,3,4- thiadiazoles (abbreviation TDA- sulfone from the narration of aforementioned alignment analysis；
Formula 1) it is the important intermediate that flufenacet synthesizes.2- methylsulfonyl -5- Trifluoromethyl-1 is studied, the synthesis of 3,4- thiadiazoles has weight
Big practical application value, synthesis technology are worth with potential major application.
Document (Li Yusheng, Zhou Guidong, Shen Yi congruence, the synthesis of flufenacet, " modern ", and 2002, the 2nd phase,
P8-10), document (Jiang Yutian, Chen Tongming etc., the synthesis of flufenacet, " pesticide ", 2007, volume 46,11 phases, P734-736),
United States Patent (USP) (US5856499, patent filing date 1999.1.5), European patent (EP0926143A1, patent filing date
1998.1.12), United States Patent (USP) (US6031108, patent filing date 2000.2.29) etc. is all referred to by 2- methyl mercapto -5- trifluoro
Methyl-1,3,4- thiadiazoles prepare 2- methylsulfonyl -5- Trifluoromethyl-1, the synthetic method of 3,4- thiadiazoles through peroxidization.
But many defects exist in the prior art, such as there are sulfoxide by-product 2- first sulfoxide group -5- fluoroforms for reaction
Base -1,3,4- thiadiazoles (abbreviation TDA- sulfoxide；Formula 2), and be difficult to remove in the follow-up process；Reaction time it is longer (for example,
Embodiment 1 in the United States Patent (USP) US6031108(patent), the method needs 11 of report are more than hour；Li Yusheng, Zhou Guidong,
Shen Yi congruence, the synthesis of flufenacet, " modern ", 2002, the 2nd phase, P8-10, the method for report need 9 hours with
On；Jiang Yutian, Chen Tongming etc., the synthesis of flufenacet, " pesticide ", and 2007, volume 46,11 phases, P734-736, the method for report
Need 9 more than hour)；The defects of still reaction largely uses hydrogen peroxide, and safety is uncontrollable.Therefore, there is demand in this field
Develop a kind of synthesis 2- methylsulfonyl -5- Trifluoromethyl-1, the method for 3,4- thiadiazoles, this method is quickly not elapsed time
's；This method is that raw material cost is low, and technique essence is safer.
Microwave organic synthetic chemistry is sent out on the basis of people further investigate the characteristic of substance in microwave field and variation
The emerging forward position cross discipline that exhibition is got up.Microwave organic synthetic chemistry is to be existed using modern microwave technology to study substance
The a science of physics and chemical behavior under microwave action.The research of organic microwave reaction starts from 1986 earliest.1986
Canadian Lauventian university chemistry system Gedye professor and colleague have studied the esterification of microwave acceleration, this is microwave
Synthetic Organic Chemistry starts beautiful.The toluene oxidation that the discovery of Gedye study group carries out in micro-wave oven seal pipe is benzoic acid
Reaction, use permanganate for oxidant, the reaction than conventional heating reflux it is fast 5 times.Hair is further studied by Gedye study group
Existing, benzyl chlorine reacts 1240 times faster than conventional heating mode at ester with 4- cyano phenates.Microwave current organic synthesis
Have evolved into a spectacular uncharted field.The more traditional heating means of organic reaction speed under microwave assisted are fast
Several times even thousands of times, and have the characteristics that easy to operate and easy purification of products.Therefore the organic synthesis development of microwave assisted is fast
Speed has been directed to the every aspect of compound synthesis, is applied successfully to various organic reactions, and before illustrating wide application
Scape.The compound synthesis of microwave assisted will continue directly to synthesize to the microwave of chipal compounds, labyrinth natural products, microwave
Continue to develop in the fields such as synthesis is engineered, microwave is combined with other new technologies.Present microwave assisted organic synthesis type is non-
It often extensively, almost include all reaction types, or even have been introduced into asymmetric reaction field and continue to answer microwave technology
It is grinding with theory significance and practical application value for there is the research of the organic synthesis of industrialization practical value
Study carefully direction.
Ultrasonic cavitation effect promotes organic synthesis dominant mechanism to refer under intense ultrasonic wave effect, in reaction liquid
A large amount of gas micro-bubble can be generated, minute bubbles will be grown into and increase with ultrasonic vibration, the relatively atmosphere then formed
Bubble is again unexpected to vanish and divides, and the bubble after division is again continuous to be grown and vanish.It is main the reason is that: these minute bubbles rapidly collapse
Produce high temperature and pressure in bubble when bursting, and the liquid at high speed around bubble due to pour bubble in the liquid near bubble
Produce strong local shock, also form local high temperature and pressure, be equivalent in reaction system have it is countless miniature
Blender and countless micro- heating device promote the progress of organic reaction, so that producing ultrasonic wave promotes organic reaction
The final effect of progress.Ultrasonic wave has been applied to oxidation, reduction, addition, polycondensation and hydrolysis etc. in organic chemistry, several
It is related to the every field of organic chemistry, sonochemistry method is considered as Green Chemistry.Ultrasonic wave is as a kind of new energy
Form is used for organic chemical reactions, not only make it is many not can be carried out or be difficult in the past the reaction carried out smooth, but also
It is significantly better than traditional stirring, external heating method as a kind of convenience, synthetic technology rapidly, effectively, safe.
Summary of the invention
It is an object of the invention to be directed to current 2- methylsulfonyl -5- Trifluoromethyl-1, in 3,4- thiadiazoles synthetic method
Defect, it is safer, quickly to provide a kind of technique essence, low-cost synthetic method.
The technical solution adopted by the invention is as follows:
The present invention provide it is a kind of using microwave ultrasonic wave promote by 2- methyl mercapto -5- Trifluoromethyl-1,3,4- thiadiazoles
(abbreviation TDA；Formula 3) oxidation preparation 2- methylsulfonyl -5- Trifluoromethyl-1,3,4- thiadiazoles synthetic method (formula 4).
Project team personnel of the present invention are it is discovered by experiment that by 2- methyl mercapto -5- Trifluoromethyl-1,3,4- thiadiazoles (TDA)
It is oxidized to 2- methylsulfonyl -5- Trifluoromethyl-1, the presence of 3,4- thiadiazoles (TDA- sulfone) typically carries out process (formula 5) step by step,
It is further found by theoretical calculation (Gauss 09, version Gauss view 5.0) and many experiments: being aoxidized and formed by TDA
TDA- sulfoxide (first step) is easier to carry out thorough；However, forming TDA- sulfone (second step) by TDA- sulfoxide oxidation, but it is difficult
It carries out complete.Because the transition state energy of second step reaction is much higher than the transition state energy of first step reaction.Therefore, second step is anti-
It should be at aoxidizing the rate controlling step (or committed step) for forming TDA- sulfone by TDA.
According to theoretical calculation and experimental result and analysis, the needs of combined process essential safety, we adopt two-step reaction
It is carried out with differential responses condition.The first step uses ultrasonic wave and common heating, and second step uses microwave ultrasonic wave composite reaction side
Formula (formula 6).
Above-mentioned 2- methylsulfonyl -5- Trifluoromethyl-1, the synthesis specific process step of 3,4- thiadiazoles are as follows:
Solvent, starting original are added in the three-necked bottle that reflux condensing tube, constant pressure funnel, microwave special-purpose thermometer are housed
Expect 2- methyl mercapto -5- Trifluoromethyl-1,3,4- thiadiazoles (TDA), sodium chlorite combine oxidation catalyst, 35% pair with sodium tungstate
Oxygen water.Ultrasonic response section is carried out first, certain ultrasonic power is set, and supersonic range temperature is carried out accurate by external heat exchanger
Control, heat-exchange system is equipped with two sets, and (high and low temperature is each a set of, can remove heat when reacting very exothermic；Reaction needs to heat
When can be rapidly achieved set temperature), heat transferring medium is atoleine；Promote organic synthesis anti-using ultrasonic cavitation effect
It answers, first by 2- methyl mercapto -5- Trifluoromethyl-1,3,4- thiadiazoles (TDA) convert completely, and what is mainly generated is 2- methyl mercapto -
5- Trifluoromethyl-1,3,4- thiadiazoles (TDA- sulfoxide), while having a small amount of 2- methylsulfonyl -5- Trifluoromethyl-1,3,4- thiadiazoles
(TDA- sulfone) is formed.Then, a certain amount of 70% hydrogen peroxide is supplemented, reaction solution is directly carried out to microwave ultrasonic wave composite reaction section again,
And certain ultrasonic power and microwave reaction power is respectively set, until TDA- sulfoxide intermediates content is lower than 1%, end is anti-
It answers, carries out popular response post-processing.Reaction solution ice-water bath crystallisation by cooling, suction filtration obtain target product 2- methylsulfonyl -5- trifluoro
Methyl-1, the sterling of 3,4- thiadiazoles (TDA- sulfone), white flakes shape crystal, mother liquor concentrations recrystallization, merging yield 90~
96%, by-product TDA- sulfoxide content is lower than 0.5%) in liquid content 95~99.9%(product.If necessary, further using molten
Agent recrystallization.Organic solvent recycles in reaction solution, and catalyst recycling utilizes after purification process.
In the processing step, sodium chlorite combines oxidation catalyst 6~0.5:1 of weight ratio with sodium tungstate, preferably 3~
1:1。
In the processing step, ultrasonic response section heat exchange medium temperature is 20~80 DEG C, preferably 50~60 DEG C.
In the processing step, microwave ultrasonic wave composite reaction section temperature is 70~120 DEG C, preferably 100 DEG C.
In the processing step, microwave ultrasonic wave composite reaction section ultrasonic power be 300~1000W, preferably 500~
900W。
In the processing step, microwave ultrasonic wave composite reaction section microwave power be 400~1200W, preferably 600~
1000W。
In the processing step, ultrasonic response section change the reaction time be 5-10 minutes；Microwave ultrasonic wave composite reaction section
Reaction time is 2-10 minutes.
Compared with existing public technology, the present invention has the advantage that
1, according to reacting quintessence, combined process essential safety needs, and reaction substep is carried out, reaction efficiency is not only improved, but also
Increase technique essential safety.
2, it using novel sodium chlorite and sodium tungstate combination catalyst, effectively facilitates reaction and carries out.
3, microwave ultrasonic wave suites of measure promotes reaction, greatlys save the reaction time, improves equipment and space utilization rate.
4, reaction yield is high (90~95%).
5, by 2- methyl mercapto -5- Trifluoromethyl-1,3,4- thiadiazoles (abbreviation TDA) oxidation preparation 2- methylsulfonyl -5- trifluoro
Methyl-1,3,4- thiadiazoles traditional handicraft reaction time need 9-11 hours, and the reaction time of the invention is within 20 minutes.
6, good reaction selectivity, TDA- sulfoxide by-products content is lower than 0.5% in product.
Therefore, of the invention with good economic efficiency and social benefit in summary.
Specific embodiment by the following examples is again described in further detail above content of the invention.But
The range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to following instance.The above-mentioned technical idea feelings of the present invention are not being departed from
Under condition, the various replacements or change made according to ordinary skill knowledge and customary means, should all include of the invention
In range.
Specific embodiment
Embodiment 1
In the 500 mL three-necked bottle (XO-SM100 that reflux condensing tube, constant pressure * dropping funel, microwave special-purpose thermometer are housed
The straight three-necked bottle of ultrasonic microwave composite reaction system support) in be added 150 mL of solvent toluene, content 99.5% 2- first sulphur
Base -5- Trifluoromethyl-1,50 grams, 0.3 gram sodium chlorite of 3,4- thiadiazoles (TDA) combined with 0.1 gram of sodium tungstate oxidation catalyst,
35% 40 grams of hydrogen peroxide.Carrying out ultrasonic response section first, (ultrasound reactor model YCFS201-1500, Hangzhou is far at ultrasound
The production of wave Science and Technology Ltd.), ultrasonic power 800W is set, and ultrasonic response section temperature setting is 60 DEG C, and temperature fluctuation is small
It in 3 DEG C, is accurately controlled by external heat exchanger, heat-exchange system is equipped with two sets, and (high and low temperature is each a set of, and high temperature heat-exchange system is set
It is set to 60 DEG C；Low-temperature heat exchange system is set as 5 DEG C；Low-temperature heat exchange system injection cryogenic liquid can be used when reacting very exothermic
Paraffin removes heat；Reaction can be used the heating of high temperature heat-exchange system and be rapidly achieved set temperature when needing to heat), heat exchange is situated between
Matter is atoleine；Reaction time 8 minutes.Then, slightly cold, 20 gram of 70% hydrogen peroxide is slowly added into three neck reaction flasks, by three
Neck reaction flask directly carries out microwave ultrasonic wave composite reaction section (XO-SM100 ultrasonic microwave composite reaction system, Nanjing elder generation Europe
The manufacture of instrument manufacturing Co., Ltd), and ultrasonic power 600W and microwave reaction power 800W is respectively set, reaction is in reflux shape
State, 10 minutes reaction time, (reaction was completed, and liquid-phase chromatographic analysis TDA- sulfoxide intermediates content is 0.4%), to carry out conventional anti-
It should post-process.Reaction solution ice-water bath crystallisation by cooling, suction filtration obtain target product 2- methylsulfonyl -5- Trifluoromethyl-1,3,4- thiophenes
The sterling of diazole (TDA- sulfone), white flakes shape crystal, mother liquor concentrations recrystallization merge crystalline product, obtain 2- methylsulfonyl -5-
Trifluoromethyl-1,55.1 grams of 3,4- thiadiazoles (TDA- sulfone), yield 95%, by-product TDA- is sub- in liquid content 99.6%(product
Sulfone content 0.07%).
Embodiment 2
In the 500 mL three-necked bottles equipped with reflux condensing tube, constant pressure funnel, microwave special-purpose thermometer, (XO-SM100 is super
The matched straight three-necked bottle of sound wave microwave combination reaction system) in be added 150 mL of solvent toluene, content 99.5% 2- methyl mercapto-
5- Trifluoromethyl-1,50 grams, 0.3 gram sodium chlorite of 3,4- thiadiazoles (TDA) combine oxidation catalyst, 35% with 0.1 gram of sodium tungstate
40 grams of hydrogen peroxide.Carrying out ultrasonic response section first, (ultrasound reactor model YCFS201-1500, Hangzhou is far at ultrasonic wave section
The production of skill Co., Ltd), ultrasonic power 800W is set, and ultrasonic response section temperature setting is 60 DEG C, and temperature fluctuation is less than 3
DEG C, it is accurately controlled by external heat exchanger, heat-exchange system is equipped with two sets, and (high and low temperature is each a set of, and high temperature heat-exchange system is set as
60℃；Low-temperature heat exchange system is set as 5 DEG C；Low-temperature heat exchange system injection cryogenic liquid paraffin can be used when reacting very exothermic
Heat is removed；Reaction can be used the heating of high temperature heat-exchange system and be rapidly achieved set temperature when needing to heat), heat transferring medium is
Atoleine；Reaction time 8 minutes.Then, slightly cold, 20 gram of 70% hydrogen peroxide is slowly added into three neck reaction flasks, and (second step is anti-
Microwave ultrasonic wave composite reaction mode should not be used, and uses conventional mechanical stirring, oil bath heating mode), reaction solution is being stirred
It mixes, under oil bath heating counterflow condition, 20 minutes reaction time, (reaction was completed, and liquid-phase chromatographic analysis TDA- sulfoxide intermediate product contains
Amount is 22.7%), to carry out popular response post-processing.Reaction solution ice-water bath crystallisation by cooling, suction filtration obtain target product 2- methyl sulfone
Base -5- Trifluoromethyl-1, the product of 3,4- thiadiazoles (TDA- sulfone), mother liquor concentrations recrystallization merge crystalline product, due to TDA-
Sulfoxide content is high, is recrystallized twice using toluene, obtains 2- methylsulfonyl -5- Trifluoromethyl-1,3,4- thiadiazoles (TDA-
Sulfone) 32.6 grams, yield 56.3%, by-product TDA- sulfoxide content 2.9% in liquid content 96.8%(product).
Embodiment 3
In reaction described in embodiment 1,0.4 gram of sodium tungstate 0.3 gram of sodium chlorite of substitution combines oxidation with 0.1 gram of sodium tungstate and urges
Agent, other operations are the same as embodiment 1.
It is operated according to embodiment 1, and last products obtained therefrom is once recrystallized using toluene, finally obtain 2-
Methylsulfonyl -5- Trifluoromethyl-1,50.6 grams of 3,4- thiadiazoles (TDA- sulfone), yield 87.2% are secondary in liquid content 98.1%(product
Product TDA- sulfoxide content 1.7%).
Embodiment 4
Described in embodiment 1 reaction in, the first step after reaction, by former embodiment " it is then, slightly cold, to three neck reaction flasks
In be slowly added to 20 gram of 70% hydrogen peroxide " operation change be " it is then, slightly cold, 40 grams 35% pair is slowly added into three neck reaction flasks
Oxygen water ", other operations are the same as embodiment 1.
It is operated according to embodiment 1, and last products obtained therefrom is once recrystallized using toluene, finally obtain 2-
Methylsulfonyl -5- Trifluoromethyl-1,48.5 grams of 3,4- thiadiazoles (TDA- sulfone), yield 83.6% are secondary in liquid content 97.2%(product
Product TDA- sulfoxide content 2.3%).
Claims (6)
1.2- methylsulfonyl -5- Trifluoromethyl-1, the synthetic method of 3,4- thiadiazoles, it is characterised in that with 2- methyl mercapto -5- trifluoro
Methyl-1,3,4- thiadiazoles are predominant starting material, promote the synthetic method of target product using microwave ultrasonic wave combination,
Chemical reaction process is as follows:
Specific synthetic method are as follows: be added in the three-necked bottle that reflux condensing tube, constant pressure funnel, microwave special-purpose thermometer are housed
Solvent, starting material 2- methyl mercapto -5- Trifluoromethyl-1,3,4- thiadiazoles, sodium chlorite combined with sodium tungstate oxidation catalyst,
35% hydrogen peroxide；Carry out ultrasonic response section first, certain ultrasonic power be set, supersonic range temperature by external heat exchanger into
The accurate control of row, heat-exchange system are equipped with two sets, and heat transferring medium is atoleine；Promote organic synthesis using ultrasonic cavitation effect
Reaction, first by 2- methyl mercapto -5- Trifluoromethyl-1,3,4- thiadiazoles convert completely, and what is mainly generated is TDA- sulfoxide, simultaneously
There is a small amount of TDA- sulfone to be formed；Then, a certain amount of 70% hydrogen peroxide is supplemented, it is anti-that reaction solution is directly carried out to microwave ultrasonic wave combination again
Answer section, and certain ultrasonic power and microwave reaction power be respectively set, until TDA- sulfoxide intermediates content be lower than 1%, knot
Shu Fanying carries out popular response post-processing；Reaction solution ice-water bath crystallisation by cooling, suction filtration obtain target product 2- methylsulfonyl -5-
Trifluoromethyl-1, the sterling of 3,4- thiadiazoles, white flakes shape crystal, mother liquor concentrations recrystallization merge yield 90~96%, liquid
Phase content 95~99.9%；If necessary, further being recrystallized using solvent；Organic solvent recycles in reaction solution, urges
Agent recycling, utilizes after purification process.
2. in synthetic method described in claim 1, it is characterized in that sodium chlorite combines oxidation catalyst weight ratio 3 with sodium tungstate
~1:1.
3. in synthetic method described in claim 1, it is characterized in that ultrasonic response section temperature is 50~60 DEG C.
4. in synthetic method described in claim 1, it is characterized in that microwave ultrasonic wave composite reaction section temperature is 70~120 DEG C.
5. in synthetic method described in claim 1, it is characterized in that microwave ultrasonic wave composite reaction section ultrasonic power be 500~
900W。
6. in synthetic method described in claim 1, it is characterized in that microwave ultrasonic wave composite reaction section microwave power be 600~
1000W。
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| CN1162413C (en) * | 1998-09-16 | 2004-08-18 | 美国拜尔公司 | Improved method for conversion of TDA into TDA sulfone |
| CN103664824A (en) * | 2013-11-19 | 2014-03-26 | 泸州东方农化有限公司 | Preparation method of thiadiazole carboxamide compounds |
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| CN1162413C (en) * | 1998-09-16 | 2004-08-18 | 美国拜尔公司 | Improved method for conversion of TDA into TDA sulfone |
| CN103664824A (en) * | 2013-11-19 | 2014-03-26 | 泸州东方农化有限公司 | Preparation method of thiadiazole carboxamide compounds |
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