CN106117268A - α aminophosphonate compound with 2 amino 1,3,4 thiadiazoles structures and preparation method thereof and purposes - Google Patents
α aminophosphonate compound with 2 amino 1,3,4 thiadiazoles structures and preparation method thereof and purposes Download PDFInfo
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- CN106117268A CN106117268A CN201610550422.5A CN201610550422A CN106117268A CN 106117268 A CN106117268 A CN 106117268A CN 201610550422 A CN201610550422 A CN 201610550422A CN 106117268 A CN106117268 A CN 106117268A
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- thiadiazoles
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- 238000002360 preparation method Methods 0.000 title claims abstract description 63
- -1 aminophosphonate compound Chemical class 0.000 title claims abstract description 50
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 title abstract 5
- 238000006243 chemical reaction Methods 0.000 claims description 109
- 239000007787 solid Substances 0.000 claims description 45
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 37
- 239000002994 raw material Substances 0.000 claims description 30
- QUKGLNCXGVWCJX-UHFFFAOYSA-N 1,3,4-thiadiazol-2-amine Chemical group NC1=NN=CS1 QUKGLNCXGVWCJX-UHFFFAOYSA-N 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 21
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 150000003583 thiosemicarbazides Chemical class 0.000 claims description 18
- 238000004440 column chromatography Methods 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 17
- 230000006837 decompression Effects 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 230000000844 anti-bacterial effect Effects 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 claims description 3
- 239000002917 insecticide Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- MBIZXFATKUQOOA-UHFFFAOYSA-N 1,3,4-thiadiazole Chemical group C1=NN=CS1 MBIZXFATKUQOOA-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 230000000749 insecticidal effect Effects 0.000 abstract description 6
- 230000001954 sterilising effect Effects 0.000 abstract description 5
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 241000213004 Alternaria solani Species 0.000 abstract description 3
- 241000409991 Mythimna separata Species 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000575 pesticide Substances 0.000 abstract description 3
- 239000000645 desinfectant Substances 0.000 abstract description 2
- 150000004867 thiadiazoles Chemical group 0.000 abstract 2
- 229910052760 oxygen Inorganic materials 0.000 description 76
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 43
- 238000003756 stirring Methods 0.000 description 31
- 239000000047 product Substances 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 239000007788 liquid Substances 0.000 description 22
- 229910019142 PO4 Inorganic materials 0.000 description 20
- 239000010452 phosphate Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000009833 condensation Methods 0.000 description 15
- 230000005494 condensation Effects 0.000 description 15
- 239000013067 intermediate product Substances 0.000 description 15
- 238000010792 warming Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- 238000013019 agitation Methods 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 14
- 239000011521 glass Substances 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 14
- 238000001953 recrystallisation Methods 0.000 description 14
- 150000003851 azoles Chemical class 0.000 description 12
- XFDJMIHUAHSGKG-UHFFFAOYSA-N chlorethoxyfos Chemical compound CCOP(=S)(OCC)OC(Cl)C(Cl)(Cl)Cl XFDJMIHUAHSGKG-UHFFFAOYSA-N 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- NQMUGNMMFTYOHK-UHFFFAOYSA-N 1-methoxynaphthalene Chemical compound C1=CC=C2C(OC)=CC=CC2=C1 NQMUGNMMFTYOHK-UHFFFAOYSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- PHUAPJQOWVQEEB-UHFFFAOYSA-N pyridin-3-ylmethyl dihydrogen phosphate Chemical compound OP(O)(=O)OCC1=CC=CN=C1 PHUAPJQOWVQEEB-UHFFFAOYSA-N 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IHCCAYCGZOLTEU-UHFFFAOYSA-N 3-furoic acid Chemical compound OC(=O)C=1C=COC=1 IHCCAYCGZOLTEU-UHFFFAOYSA-N 0.000 description 2
- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 241000223218 Fusarium Species 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical group C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 1
- FBRJYBGLCHWYOE-UHFFFAOYSA-N 2-(trifluoromethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(F)(F)F FBRJYBGLCHWYOE-UHFFFAOYSA-N 0.000 description 1
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 1
- ZMJRUUBDMPKHJS-UHFFFAOYSA-N 2-phenyl-1,3,4-thiadiazole Chemical class S1C=NN=C1C1=CC=CC=C1 ZMJRUUBDMPKHJS-UHFFFAOYSA-N 0.000 description 1
- RBIGKSZIQCTIJF-UHFFFAOYSA-N 3-formylthiophene Chemical compound O=CC=1C=CSC=1 RBIGKSZIQCTIJF-UHFFFAOYSA-N 0.000 description 1
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 1
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- WZWIQYMTQZCSKI-UHFFFAOYSA-N 4-cyanobenzaldehyde Chemical compound O=CC1=CC=C(C#N)C=C1 WZWIQYMTQZCSKI-UHFFFAOYSA-N 0.000 description 1
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 description 1
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 description 1
- 241000223600 Alternaria Species 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- QJZUKDFHGGYHMC-UHFFFAOYSA-N pyridine-3-carbaldehyde Chemical compound O=CC1=CC=CN=C1 QJZUKDFHGGYHMC-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- QERYCTSHXKAMIS-UHFFFAOYSA-N thiophene-2-carboxylic acid Chemical compound OC(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-N 0.000 description 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6536—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and sulfur atoms with or without oxygen atoms, as the only ring hetero atoms
- C07F9/6539—Five-membered rings
- C07F9/65392—Five-membered rings containing two nitrogen atoms
- C07F9/65395—Five-membered rings containing two nitrogen atoms having the two nitrogen atoms in positions 1 and 2
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing heterocyclic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
- Lubricants (AREA)
Abstract
The invention discloses one and there are 2 amino 1,3, α aminophosphonate compound of 4 thiadiazoles structures and preparation method thereof and purposes, of the present invention have 2 amino 1,3, the α aminophosphonate compound of 4 thiadiazoles structures has the general character of α aminophosphonate compound sterilization, it is simultaneously introduced the insecticidal properties of 2 amino 1,3,4 thiadiazoles groups, both combine and make the purposes of compound more extensively, and sterilization and insecticidal effect are better.Preparation method step of the present invention is few, simple to operate, but yield and productivity are high, can save substantial amounts of time and cost in actual production, good in economic efficiency.2 amino 1,3,4 thiadiazoles of the present invention are inhibited to the growing multiplication of Alternaria solani, have Developing restraint effect to mythimna separata, can be applied to manufacture and the purposes of different disinfectant use in agriculture as pesticide intermediate.
Description
Technical field
The present invention relates to technical field of pesticide, a kind of alpha-amido with 2-amido-1,3,4-thiadiazoles structure
Phosphonate compound and preparation method thereof and purposes.
Background technology
In the research of α-aminophosphonicacid ester compounds, the synthetic method once reported is varied, wherein with Louis
Sour or bronsted acid catalysis aldehyde, amine, three components of phosphite ester, synthesize α-aminophosphonicacid esters by " treating different things alike " method
The method of compound is in the majority；2011, Chou Jikuan et al. reported the α-aminophosphonicacid esters derivative of a novel pyrazolyl containing of class
Synthesis；Thereafter, constantly having the synthesis of α-aminophosphonicacid esters derivative, 2013, Abdel-Rahman et al. reported logical
Cross and add boron trifluoride in para-fluoroaniline, single aldehyde (or dialdehyde) and three components of diethyl phosphite, carry out " one pot
Boil " reaction, synthesize fluorination α-aminophosphonicacid ester type compound and the sub-benzene of Isosorbide-5-Nitrae-two (α-aminophosphonicacid ester) of series of new
Based compound, is found by biological activity test, and all compounds are respectively provided with suppression alternaric bacteria (Alternaria
And the activity that grows of Fusarium spp. (Fusarium oxysporium), and improve the enzyme of cellobiose enzyme alternate)
Catalytic effect.2014, Subba Reddy G et al. reported with microwave irradiation, and under macroporous resin is catalyzed, synthesis one is
Row α-aminophosphonicacid ester type compound.But not yet find the alpha-amido phosphine about 2-amino-1,3,4-thiadiazoles structure at present
The report of ester compound and preparation method thereof and application thereof.
Summary of the invention
It is an object of the invention to solve at least the above or defect, and the advantage that at least will be described later is provided.
In order to realize according to object of the present invention and further advantage, it is provided that one has 2-amino-1,3,4-thiophenes
The α-aminophosphonicacid ester compounds of diazole structure, wherein, structural formula is as follows:
Preferably, in the described α-aminophosphonicacid ester compounds with 2-amido-1,3,4-thiadiazoles structure, described
R in structural formula is
The preparation method of a kind of α-aminophosphonicacid ester compounds with 2-amido-1,3,4-thiadiazoles structure, mainly wraps
Include:
1) from thiosemicarbazides, in acid condition through heating, dehydration, cyclization, obtain 2-amino-1,3,4-thiophenes two
Azoles,
2) described 2-amido-1,3,4-thiadiazoles is transformed, occur from diethyl phosphite and different aromatic aldehydes
Quasi-Mannich reaction, can obtain a class and have the α-aminophosphonicacid ester compounds of 2-amido-1,3,4-thiadiazoles structure.
Wherein, following steps are specifically included:
Step one, with thiosemicarbazides as raw material, mix with organic acid, heating, carry out cyclization and obtain 2-amino-1,3,
4-thiadiazole compound；
Step 2, the 2-amido-1,3,4-thiadiazoles compound of gained is dissolved in solvent, adds containing carboxaldehyde radicals dough
Compound and diethyl phosphite, in reaction bulb, 105-115 DEG C of back flow reaction 9-11 hour, then decompression boils off solvent and obtains
Residue；
The solid that step 3, the column chromatography for separation that carried out by the residue use chromatographic solution of gained obtain is described having
The α-aminophosphonicacid ester compounds of 2-amino-1,3,4-thiadiazoles structure；
Wherein, course of reaction is as follows:
Reagent and condition: a:HCl/NH3·H2O/HCOOH；b:Toluene；
Wherein, the R group in compound 3～17 is as follows:
Preferably, in the preparation method of the α-aminophosphonicacid ester compounds with 2-amido-1,3,4-thiadiazoles structure,
Described step one is also mixed with the concentrated hydrochloric acid of concentration 36-38%.
Preferably, in the preparation method of the α-aminophosphonicacid ester compounds with 2-amido-1,3,4-thiadiazoles structure,
Described organic acid is formic acid.
Preferably, in the preparation method of the α-aminophosphonicacid ester compounds with 2-amido-1,3,4-thiadiazoles structure,
Described solvent is toluene.
Preferably, in the preparation method of the α-aminophosphonicacid ester compounds with 2-amido-1,3,4-thiadiazoles structure,
In described chromatographic solution, the volume ratio of methanol and dichloromethane is 1:100.
A kind of have the α-aminophosphonicacid ester compounds of 2-amino-1,3,4-thiadiazoles structure as antibacterial and insecticide
Application.
The method have the advantages that the most of the present invention there is 2-amino-1,3,4-thiadiazoles structure
α-aminophosphonicacid ester compounds has the general character of α-aminophosphonicacid ester compounds sterilization, is simultaneously introduced 2-amino-1,3,4-thiophenes two
The insecticidal properties of oxazolyl group, both combinations make the purposes of compound more extensively, and sterilization and insecticidal effect are better.
Secondly, preparation method step of the present invention is few, simple to operate, but yield and productivity are high, in actual production
In can save substantial amounts of time and cost, good in economic efficiency.
Finally, from data it can be seen that the 2-amido-1,3,4-thiadiazoles of the present invention growing multiplication to Alternaria solani
Inhibited, mythimna separata is had Developing restraint effect, the system of different disinfectant use in agriculture can be applied to as pesticide intermediate
Make and purposes.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is elaborated, after making those of ordinary skill in the art refer to this specification
Can implement according to this.
Embodiment 1
The preparation of O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) benzyl phosphate ester:
Step 1, the preparation of intermediate product
Weigh 5.00g thiosemicarbazides, in the disposable addition 50mL three-neck flask with stirring magneton, add 5.00mL's
After formic acid, under condition of ice bath, pulp is reacted in stirring, re-uses constant pressure funnel and is slowly added dropwise 6.00mL concentrated hydrochloric acid.Dropping
After be placed in 107 DEG C of oil baths heating, and open agitating device, react 4.5～5.0h, TLC follows the tracks of reaction, and the disappearance of raw material point is then
Stopped reaction, is adjusted to system PH between 8～9 with strong aqua ammonia after room temperature cooling.Place refrigerator overnight, separate out white crystal, take out
Filter, washs three times with frozen water, and distilled water is recrystallized to give 4.96g white crystal 1, productivity about 90%, m.p.:198～201 DEG C.
Product structure is analyzed through IR, NMR and MS and is defined as 2-amino-1,3,4-thiadiazoles.
Step 2, O, the preparation of O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) benzyl phosphate ester
In the reaction bulb be connected with spherical condensation tube, 0.51g (5mmol) 2-amino-1,3,4-thiadiazoles is dissolved in 30mL first
In benzene, add 0.53g (5mmol) benzaldehyde and 0.64mL (5mmol) diethyl phosphite, be warming up to 110 DEG C of return stirrings anti-
10h, TLC is answered to follow the tracks of, complete to raw material reaction, stopped reaction, reduce pressure and steam major part solvent, column chromatography for separation (chromatographic solution:
VMethanol:VDichloromethane=1:100) obtain 0.74g faint yellow solid 3.Productivity 45%, m.p.:126～134 DEG C.Product structure through IR,
NMR and MS analyzes and is defined as O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) benzyl phosphate ester.
Embodiment 2
O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) preparation to benzyl phosphate ester (4):
Step 1, the preparation of intermediate product
Thiosemicarbazides 1.82g (0.02mol), 2-thiophenic acid 2.54g (0.02mol) and 20mL tri-is added in three-necked bottle
Chlorethoxyfos, is to slowly warm up to 65 DEG C under magnetic agitation, after reaction 2h, be continuously heating to 106 DEG C of back flow reaction 4h, and TLC tracks to
Point without raw material, stopped reaction.While be slowly poured in frozen water with Glass rod stirring limit, pH value is adjusted to be 8～9 by saturated NaOH solution,
There is Precipitation, centrifugal, remove upper liquid, combining solid, obtain 2.56g yellow solid 2, productivity with the ethyl alcohol recrystallization of 75%
70%, m.p.:200～204 DEG C.Product structure is analyzed through IR, NMR and MS and is defined as 2-amino-5-thiophene-1,3,4-thiophene two
Azoles.
Step 2, O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) preparation to benzyl phosphate ester (4)
In the reaction bulb be connected with spherical condensation tube, 0.51g (5mmol) 2-amino-1,3,4-thiadiazoles is dissolved in 50mL first
In benzene, add 0.54mL (5mmol) 4-fluorobenzaldehyde and 0.64mL (5mmol) diethyl phosphite, be warming up to 110 DEG C of backflows and stir
Mixing reaction 10h, TLC to follow the tracks of, complete to raw material reaction, stopped reaction, decompression steams major part solvent, column chromatography for separation (chromatography
Liquid: V methanol: V dichloromethane=1:100) obtain 0.64g faint yellow solid 4, productivity 37%, m.p.:116～128 DEG C.Through IR,
NMR and MS analyzes and determines that product structure is that O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) is to benzyl phosphate ester
(4)。
Embodiment 3
The preparation of O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) o-trifluoromethyl benzyl phosphate ester:
Step 1, the preparation of intermediate product
In three-necked bottle add thiosemicarbazides 0.91g (0.01mol), 2-(Trifluoromethyl)benzoic acid. 2.15g (0.01mol) and
20mL phosphorus oxychloride, is to slowly warm up to 65 DEG C under magnetic agitation, after reaction 2h, be continuously heating to 106 DEG C of back flow reaction 4h, TLC
Track to without raw material point, stopped reaction.While be slowly poured in frozen water with Glass rod stirring limit, with saturated NaOH solution tune pH value it is
8～9, there is Precipitation, centrifugal, remove upper liquid, combining solid, obtain 1.99g light green with the ethyl alcohol recrystallization of 75% solid
Body 3, productivity 81%, m.p.:215～221 DEG C.Product structure is analyzed through IR, NMR and MS and is defined as 2-amino-5-(fluoroform
Base) phenyl-1,3,4-thiadiazoles.
Step 2, O, the preparation of O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) o-trifluoromethyl benzyl phosphate ester
In the reaction bulb be connected with spherical condensation tube, 0.51g (5mmol) 2-amino-1,3,4-thiadiazoles is dissolved in 50mL first
In benzene, add 0.66mL (5mmol) 2-trifluoromethylated benzaldehyde and 0.64mL (5mmol) diethyl phosphite, be warming up to 110 DEG C
Return stirring reaction 10h, TLC follow the tracks of, complete to raw material reaction, stopped reaction, and decompression steams major part solvent, column chromatography for separation
(chromatographic solution: VMethanol:VDichloromethane=1:100) obtain 0.97g white solid 5, productivity 49%, m.p.:149～153 DEG C.Through IR, NMR
Analyze with MS and determine that product structure is O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) o-trifluoromethyl benzyl phosphoric acid
Ester (5).
Embodiment 4
O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) preparation to mehtoxybenzyl phosphate ester
Step 1, the preparation of intermediate product
Thiosemicarbazides 1.82g (0.02mol), 3-furancarboxylic acid 2.22g (0.02mol) and 20mL tri-is added in three-necked bottle
Chlorethoxyfos, is to slowly warm up to 65 DEG C under magnetic agitation, after reaction 2h, be continuously heating to 106 DEG C of back flow reaction 4h, and TLC tracks to
Point without raw material, stopped reaction.While be slowly poured in frozen water with Glass rod stirring limit, pH value is adjusted to be 8～9 by saturated NaOH solution,
There is Precipitation, centrifugal, remove upper liquid, combining solid, obtain 2.92g faint yellow solid 4 with the ethyl alcohol recrystallization of 75%, produce
Rate 87%, m.p.:197～208 DEG C.Product structure is analyzed through IR, NMR and MS and is defined as 2-amino-5-(3-furan)-1,3,4-
Thiadiazoles.
Step 2, O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) preparation to mehtoxybenzyl phosphate ester
In the reaction bulb be connected with spherical condensation tube, 0.51g (5mmol) 2-amino-1,3,4-thiadiazoles is dissolved in 50mL first
In benzene, add 0.66mL (5mmol) p-anisaldehyde and 0.64mL (5mmol) diethyl phosphite, be warming up to 110 DEG C of return stirrings
It is complete that reaction 10h, TLC track to raw material reaction, stopped reaction, reduces pressure and steams major part solvent, column chromatography for separation (chromatographic solution:
VMethanol:VDichloromethane=1:100) obtain 0.97g white solid 6, productivity 52%, m.p.:144～150 DEG C.Divide through IR, NMR and MS
Analysis determines that product structure is that O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) is to mehtoxybenzyl phosphate ester (6).
Embodiment 5
The preparation of O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles)-2-thenyl phosphate ester:
Step 1, the preparation of intermediate product
Thiosemicarbazides 1.82g (0.02mol), benzoic acid 2.44g (0.02mol) and 20mL trichlorine oxygen is added in three-necked bottle
Phosphorus, is to slowly warm up to 65 DEG C under magnetic agitation, after reaction 2h, be continuously heating to 106 DEG C of back flow reaction 4h, and TLC tracks to without former
Shots, stopped reaction.While be slowly poured in frozen water with Glass rod stirring limit, adjusting pH value to be 8～9 by saturated NaOH solution, there have to be heavy
Precipitation goes out, centrifugal, removes upper liquid, combining solid, obtains 2.26g white solid 5, productivity with the ethyl alcohol recrystallization of 75%
64%, m.p.:233～246 DEG C.Product structure is analyzed through IR, NMR and MS and is defined as 2-amino-5-phenyl-1,3,4-thiophene two
Azoles.
Step 2, O, the preparation of O'-diethyl-α-(2-amino-1,3,4-thiadiazoles)-2-thenyl phosphate ester
In the reaction bulb be connected with spherical condensation tube, 0.51g (5mmol) 2-amino-1,3,4-thiadiazoles is dissolved in 50mL first
In benzene, add 0.47mL (5mmol) 2 thiophene carboxaldehyde and 0.64mL (5mmol) diethyl phosphite, be warming up to 110 DEG C of backflows and stir
Mixing reaction 10h, TLC and track to raw material reaction completely, stopped reaction, decompression steams major part solvent, column chromatography for separation (chromatography
Liquid: VMethanol: VDichloromethane=1:100) obtain 0.94g white solid 7, productivity 51%, m.p.:102～109 DEG C.Through IR, NMR and MS
Analysis determines that product structure is O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles)-2-thenyl phosphate ester (7).
Embodiment 6
The preparation of O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles)-3-thenyl phosphate ester:
Step 1, the preparation of intermediate product
Thiosemicarbazides 1.82g (0.02mol), salicylic acid 2.76g (0.02mol) and 20mL trichlorine oxygen is added in three-necked bottle
Phosphorus, is to slowly warm up to 65 DEG C under magnetic agitation, after reaction 2h, be continuously heating to 106 DEG C of back flow reaction 4h, and TLC tracks to without former
Shots, stopped reaction.While be slowly poured in frozen water with Glass rod stirring limit, adjusting pH value to be 8～9 by saturated NaOH solution, there have to be heavy
Precipitation goes out, centrifugal, removes upper liquid, combining solid, obtains 2.75g yellow solid 6, productivity with the ethyl alcohol recrystallization of 75%
71%, m.p.:207～215 DEG C.Product structure is analyzed through IR, NMR and MS and is determined 2-amino-5-o-hydroxy-phenyl-1,3,4-thiophene
Diazole.
Step 2, O, the preparation of O'-diethyl-α-(2-amino-1,3,4-thiadiazoles)-3-thenyl phosphate ester
In the reaction bulb be connected with spherical condensation tube, 0.51g (5mmol) 2-amino-1,3,4-thiadiazoles is dissolved in 50mL first
In benzene, add 0.44mL (5mmol) 3-thiophenecarboxaldehyde and 0.64mL (5mmol) diethyl phosphite, be warming up to 110 DEG C of backflows and stir
Mixing reaction 10h, TLC and track to raw material reaction completely, stopped reaction, decompression steams major part solvent, column chromatography for separation (chromatography
Liquid: VMethanol: VDichloromethane=1:100) obtain 0.95g white solid 8, productivity 57%, m.p.:112～121 DEG C.Through IR, NMR and MS
Analysis determines that product structure is O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles)-3-thenyl phosphate ester (8).
Embodiment 7
O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) preparation to first sulfydryl benzyl phosphate ester:
Step 1, the preparation of intermediate product
Thiosemicarbazides 1.82g (0.02mol), 2-quinolinecarboxylic acid 3.44g (0.02mol) and 20mL tri-is added in three-necked bottle
Chlorethoxyfos, is to slowly warm up to 65 DEG C under magnetic agitation, after reaction 2h, be continuously heating to 106 DEG C of back flow reaction 4h, and TLC tracks to
Point without raw material, stopped reaction.While be slowly poured in frozen water with Glass rod stirring limit, pH value is adjusted to be 8～9 by saturated NaOH solution,
There is Precipitation, centrifugal, remove upper liquid, combining solid, obtain 3.14g yellow solid 7, productivity with the ethyl alcohol recrystallization of 75%
69%., m.p.:238～249 DEG C.Product structure is analyzed through IR, NMR and MS and is defined as 2-amino-5-quinoline-1,3,4-thiophene two
Azoles.
Step 2, O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) preparation to first sulfydryl benzyl phosphate ester
In the reaction bulb be connected with spherical condensation tube, 0.51g (5mmol) 2-amino-1,3,4-thiadiazoles is dissolved in 50mL
In toluene, add 0.67mL (5mmol) 4-first sulfydryl benzaldehyde and 0.64mL (5mmol) diethyl phosphite, be warming up to 110 DEG C
It is complete that return stirring reaction 10h, TLC track to raw material reaction, stopped reaction, and decompression steams major part solvent, column chromatography for separation
(chromatographic solution: VMethanol: VDichloromethane=1:100) obtain 1.19g white solid 9, productivity 64%, m.p.:108～113 DEG C.Product structure
Analyze through IR, NMR and MS and be defined as O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) to first sulfydryl benzyl phosphate ester
(9)。
Embodiment 8
O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) preparation to chlorophenylmethyl phosphate ester:
Step 1, the preparation of intermediate product
Thiosemicarbazides 1.82g (0.02mol), 2-quinolinecarboxylic acid 3.44g (0.02mol) and 20mL tri-is added in three-necked bottle
Chlorethoxyfos, is to slowly warm up to 65 DEG C under magnetic agitation, after reaction 2h, be continuously heating to 106 DEG C of back flow reaction 4h, and TLC tracks to
Point without raw material, stopped reaction.While be slowly poured in frozen water with Glass rod stirring limit, pH value is adjusted to be 8～9 by saturated NaOH solution,
There is Precipitation, centrifugal, remove upper liquid, combining solid, obtain 3.14g yellow solid 7, productivity with the ethyl alcohol recrystallization of 75%
69%., m.p.:238～249 DEG C.Product structure is analyzed through IR, NMR and MS and is defined as 2-amino-5-quinoline-1,3,4-thiophene two
Azoles.
Step 2, O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) preparation to chlorophenylmethyl phosphate ester
In the reaction bulb be connected with spherical condensation tube, 0.51g (5mmol) 2-amino-1,3,4-thiadiazoles is dissolved in 50mL first
In benzene, add 0.70g (5mmol) 4-chloro-benzaldehyde and 0.64mL (5mmol) diethyl phosphite, be warming up to 110 DEG C of backflows and stir
Mixing reaction 10h, TLC and track to raw material reaction completely, stopped reaction, decompression steams major part solvent, column chromatography for separation (chromatography
Liquid: VMethanol: VDichloromethane=1:100) obtain 1.01g yellow solid 10, productivity 53%, m.p.:106～118 DEG C.Through IR, NMR and MS
Analysis determines that product structure is that O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) is to chlorophenylmethyl phosphate ester (10).
Embodiment 9
O, O '-diethyl-α-(2-amino-1,3,4-thiadiazoles) preparation to cyanobenzyl phosphate ester:
Step 1, the preparation of intermediate product
Thiosemicarbazides 1.82g (0.02mol), 2-quinolinecarboxylic acid 3.44g (0.02mol) and 20mL tri-is added in three-necked bottle
Chlorethoxyfos, is to slowly warm up to 65 DEG C under magnetic agitation, after reaction 2h, be continuously heating to 106 DEG C of back flow reaction 4h, and TLC tracks to
Point without raw material, stopped reaction.While be slowly poured in frozen water with Glass rod stirring limit, pH value is adjusted to be 8～9 by saturated NaOH solution,
There is Precipitation, centrifugal, remove upper liquid, combining solid, obtain 3.14g yellow solid 7, productivity with the ethyl alcohol recrystallization of 75%
69%., m.p.:238～249 DEG C.Product structure is analyzed through IR, NMR and MS and is defined as 2-amino-5-quinoline-1,3,4-thiophene two
Azoles.
Step 2, O, O '-diethyl-α-(2-amino-1,3,4-thiadiazoles) preparation to cyanobenzyl phosphate ester
In the reaction bulb be connected with spherical condensation tube, 0.51g (5mmol) 2-amino-1,3,4-thiadiazoles is dissolved in 50mL first
In benzene, add 0.66g (5mmol) 4-cyanobenzaldehyde and 0.64mL (5mmol) diethyl phosphite, be warming up to 110 DEG C of backflows
It is complete that stirring reaction 10h, TLC track to raw material reaction, stopped reaction, and decompression steams major part solvent, column chromatography for separation (chromatography
Liquid: VMethanol: VDichloromethane=1:100) obtain 0.89g white solid 11, productivity 47%, m.p.:122～130 DEG C.Through IR, NMR and MS
Analysis determines that product structure is that O, O '-diethyl-α-(2-amino-1,3,4-thiadiazoles) is to cyanobenzyl phosphate ester (11).
Embodiment 10
The preparation of O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) menaphthyl phosphate ester:
Step 1, the preparation of intermediate product
Thiosemicarbazides 1.82g (0.02mol), 2-quinolinecarboxylic acid 3.44g (0.02mol) and 20mL tri-is added in three-necked bottle
Chlorethoxyfos, is to slowly warm up to 65 DEG C under magnetic agitation, after reaction 2h, be continuously heating to 106 DEG C of back flow reaction 4h, and TLC tracks to
Point without raw material, stopped reaction.While be slowly poured in frozen water with Glass rod stirring limit, pH value is adjusted to be 8～9 by saturated NaOH solution,
There is Precipitation, centrifugal, remove upper liquid, combining solid, obtain 3.14g yellow solid 7, productivity with the ethyl alcohol recrystallization of 75%
69%., m.p.:238～249 DEG C.Product structure is analyzed through IR, NMR and MS and is defined as 2-amino-5-quinoline-1,3,4-thiophene two
Azoles.
Step 2, O, the preparation of O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) menaphthyl phosphate ester
In the reaction bulb be connected with spherical condensation tube, 0.51g (5mmol) 2-amino-1,3,4-thiadiazoles is dissolved in 50mL first
In benzene, add 0.68mL (5mmol) 1-naphthaldehyde and 0.64mL (5mmol) diethyl phosphite, be warming up to 110 DEG C of return stirrings
It is complete that reaction 10h, TLC track to raw material reaction, stopped reaction, reduces pressure and steams major part solvent, column chromatography for separation (chromatographic solution:
VMethanol: VDichloromethane=1:100) obtain 1.24g yellow solid 12, productivity 66%, m.p.:175～180 DEG C.Divide through IR, NMR and MS
Analysis determines that product structure is O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) menaphthyl phosphate ester (12).
Embodiment 11
The preparation of O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles)-2-picolyl phosphoric acid easter:
Step 1, the preparation of intermediate product
Thiosemicarbazides 1.82g (0.02mol), 2-quinolinecarboxylic acid 3.44g (0.02mol) and 20mL tri-is added in three-necked bottle
Chlorethoxyfos, is to slowly warm up to 65 DEG C under magnetic agitation, after reaction 2h, be continuously heating to 106 DEG C of back flow reaction 4h, and TLC tracks to
Point without raw material, stopped reaction.While be slowly poured in frozen water with Glass rod stirring limit, pH value is adjusted to be 8～9 by saturated NaOH solution,
There is Precipitation, centrifugal, remove upper liquid, combining solid, obtain 3.14g yellow solid 7, productivity with the ethyl alcohol recrystallization of 75%
69%., m.p.:238～249 DEG C.Product structure is analyzed through IR, NMR and MS and is defined as 2-amino-5-quinoline-1,3,4-thiophene two
Azoles.
Step 2, O, the preparation of O'-diethyl-α-(2-amino-1,3,4-thiadiazoles)-2-picolyl phosphoric acid easter
In the reaction bulb be connected with spherical condensation tube, 0.51g (5mmol) 2-amino-1,3,4-thiadiazoles is dissolved in 50mL first
In benzene, add 0.54mL (5mmol) 2-pyridine carboxaldehyde and 0.64mL (5mmol) diethyl phosphite, be warming up to 110 DEG C of backflows and stir
Mixing reaction 10h, TLC and track to raw material reaction completely, stopped reaction, decompression steams major part solvent, column chromatography for separation (chromatography
Liquid: VMethanol: VDichloromethane=1:100) obtain 0.21g yellow solid 13, productivity 13%, m.p.:94～101 DEG C.Through IR, NMR and MS
Analysis determines that product structure is O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles)-2-picolyl phosphoric acid easter (13).
Embodiment 12
The preparation of O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) 3-picolyl phosphoric acid easter:
Step 1, the preparation of intermediate product
Thiosemicarbazides 1.82g (0.02mol), 2-quinolinecarboxylic acid 3.44g (0.02mol) and 20mL tri-is added in three-necked bottle
Chlorethoxyfos, is to slowly warm up to 65 DEG C under magnetic agitation, after reaction 2h, be continuously heating to 106 DEG C of back flow reaction 4h, and TLC tracks to
Point without raw material, stopped reaction.While be slowly poured in frozen water with Glass rod stirring limit, pH value is adjusted to be 8～9 by saturated NaOH solution,
There is Precipitation, centrifugal, remove upper liquid, combining solid, obtain 3.14g yellow solid 7, productivity with the ethyl alcohol recrystallization of 75%
69%., m.p.:238～249 DEG C.Product structure is analyzed through IR, NMR and MS and is defined as 2-amino-5-quinoline-1,3,4-thiophene two
Azoles.
Step 2, O, the preparation of O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) 3-picolyl phosphoric acid easter
In the reaction bulb be connected with spherical condensation tube, 0.51g (5mmol) 2-amino-1,3,4-thiadiazoles is dissolved in 50mL first
In benzene, add 0.54mL (5mmol) 3-pyridine carboxaldehyde and 0.64mL (5mmol) diethyl phosphite, be warming up to 110 DEG C of backflows and stir
Mixing reaction 10h, TLC and track to raw material reaction completely, stopped reaction, decompression steams major part solvent, column chromatography for separation (chromatography
Liquid: VMethanol: VDichloromethane=1:100) obtain 0.14g yellow solid 14, productivity 8%, m.p.:85～90 DEG C.Divide through IR, NMR and MS
Analysis determines that product structure is O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) 3-picolyl phosphoric acid easter (14).
Embodiment 13
The preparation of O, O'-diethyl-α-(1,3,4-thiadiazoles-2-base) amino-to methoxynaphthalene ylmethyl phosphate ester:
Step 1, the preparation of intermediate product
Thiosemicarbazides 1.82g (0.02mol), 2-quinolinecarboxylic acid 3.44g (0.02mol) and 20mL tri-is added in three-necked bottle
Chlorethoxyfos, is to slowly warm up to 65 DEG C under magnetic agitation, after reaction 2h, be continuously heating to 106 DEG C of back flow reaction 4h, and TLC tracks to
Point without raw material, stopped reaction.While be slowly poured in frozen water with Glass rod stirring limit, pH value is adjusted to be 8～9 by saturated NaOH solution,
There is Precipitation, centrifugal, remove upper liquid, combining solid, obtain 3.14g yellow solid 7, productivity with the ethyl alcohol recrystallization of 75%
69%., m.p.:238～249 DEG C.Product structure is analyzed through IR, NMR and MS and is defined as 2-amino-5-quinoline-1,3,4-thiophene two
Azoles.
Step 2, O, O'-diethyl-α-(1,3,4-thiadiazoles-2-base) amino-to methoxynaphthalene ylmethyl phosphate ester
Preparation
In the reaction bulb be connected with spherical condensation tube, 0.51g (5mmol) 2-amino-1,3,4-thiadiazoles is dissolved in 50mL first
In benzene, add 0.93mg (5mmol) 2-methoxyl group-2-naphthaldehyde and 0.64mL (5mmol) diethyl phosphite, be warming up to 110 DEG C
It is complete that return stirring reaction 10h, TLC track to raw material reaction, stopped reaction, and decompression steams major part solvent, column chromatography for separation
(chromatographic solution: VMethanol: VDichloromethane=1:100) obtain 0.55g faint yellow solid 15, productivity 27%, m.p.:142～152 DEG C.Through IR,
NMR and MS analyzes and determines that product structure is O, O'-diethyl-α-(1,3,4-thiadiazoles-2-base) amino-to methoxyl group naphthyl first
Base phosphate ester (15).
Embodiment 14
O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) preparation to Dimethylaminobenzene methyl phosphorodithioate:
Step 1, the preparation of intermediate product
Thiosemicarbazides 1.82g (0.02mol), 2-quinolinecarboxylic acid 3.44g (0.02mol) and 20mL tri-is added in three-necked bottle
Chlorethoxyfos, is to slowly warm up to 65 DEG C under magnetic agitation, after reaction 2h, be continuously heating to 106 DEG C of back flow reaction 4h, and TLC tracks to
Point without raw material, stopped reaction.While be slowly poured in frozen water with Glass rod stirring limit, pH value is adjusted to be 8～9 by saturated NaOH solution,
There is Precipitation, centrifugal, remove upper liquid, combining solid, obtain 3.14g yellow solid 7, productivity with the ethyl alcohol recrystallization of 75%
69%., m.p.:238～249 DEG C.Product structure is analyzed through IR, NMR and MS and is defined as 2-amino-5-quinoline-1,3,4-thiophene two
Azoles.
Step 2, O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) preparation to Dimethylaminobenzene methyl phosphorodithioate
In the reaction bulb be connected with spherical condensation tube, 0.51g (5mmol) 2-amino-1,3,4-thiadiazoles is dissolved in 50mL first
In benzene, add 0.75g (5mmol) 4-dimethylaminobenzaldehyde and 0.64mL (5mmol) diethyl phosphite, be warming up to 110 DEG C
It is complete that return stirring reaction 10h, TLC track to raw material reaction, stopped reaction, and decompression steams major part solvent, column chromatography for separation
(chromatographic solution: VMethanol: VDichloromethane=1:100) obtain 1.16g yellow solid 16, productivity 63%, m.p.:142～149 DEG C.Through IR,
NMR and MS analyzes and determines that product structure is that O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) is to dimethylamino benzyl
Phosphate ester (16).
Embodiment 15
The preparation of O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) furfuryl phosphate ester:
Step 1, the preparation of intermediate product
Thiosemicarbazides 1.82g (0.02mol), 2-quinolinecarboxylic acid 3.44g (0.02mol) and 20mL tri-is added in three-necked bottle
Chlorethoxyfos, is to slowly warm up to 65 DEG C under magnetic agitation, after reaction 2h, be continuously heating to 106 DEG C of back flow reaction 4h, and TLC tracks to
Point without raw material, stopped reaction.While be slowly poured in frozen water with Glass rod stirring limit, pH value is adjusted to be 8～9 by saturated NaOH solution,
There is Precipitation, centrifugal, remove upper liquid, combining solid, obtain 3.14g yellow solid 7, productivity with the ethyl alcohol recrystallization of 75%
69%., m.p.:238～249 DEG C.Product structure is analyzed through IR, NMR and MS and is defined as 2-amino-5-quinoline-1,3,4-thiophene two
Azoles.
Step 2, O, the preparation of O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) furfuryl phosphate ester
In the reaction bulb be connected with spherical condensation tube, 0.51g (5mmol) 2-amino-1,3,4-thiadiazoles is dissolved in 50mL first
In benzene, add 0.54mL (5mmol) 2 furan carboxyaldehyde and 0.64mL (5mmol) diethyl phosphite, be warming up to 110 DEG C of backflows and stir
Mixing reaction 10h, TLC and track to raw material reaction completely, stopped reaction, decompression steams major part solvent, column chromatography for separation (chromatography
Liquid: VMethanol: VDichloromethane=1:100) obtain 0.92g brown solid 17, productivity 58%, m.p.:112～123 DEG C.Through IR, NMR and MS
Analysis determines that product structure is O, O'-diethyl-α-(2-amino-1,3,4-thiadiazoles) furfuryl phosphate ester (17).
Experimental analysis
Use the α-aminophosphonicacid ester compounds described in embodiment of the present invention 1-15 that certain plants antibacterial and fungus are entered
Row bactericidal assay and certain plants disease and insect is carried out insecticidal test, find to have significantly suppression pathogen growth cultivation effect and
Insecticidal effect.The especially inhibitory action to Alternaria solani, and the inhibitory action to mythimna separata.Result is as shown in table 1 below:
The sterilization suppression ratio (%) (concentration is 50 μ g/mL) of table 1 compound
Although embodiment of the present invention are disclosed as above, but it is not restricted in description and embodiment listed
Using, it can be applied to various applicable the field of the invention completely, for those skilled in the art, and can be easily
Realizing other amendment, therefore under the general concept limited without departing substantially from claim and equivalency range, the present invention does not limit
In specific details.
Claims (8)
1. having a α-aminophosphonicacid ester compounds for 2-amido-1,3,4-thiadiazoles structure, wherein, structural formula is as follows:
There is the α-aminophosphonicacid ester compounds of 2-amido-1,3,4-thiadiazoles structure the most as claimed in claim 1, wherein,
R in described structural formula is
3. there is a preparation method for the α-aminophosphonicacid ester compounds of 2-amido-1,3,4-thiadiazoles structure, wherein, including
Following steps:
Step one, with thiosemicarbazides as raw material, mix with organic acid, heating, carry out cyclization and obtain 2-amino-1,3,4-thiophenes
Diazole compounds；
Step 2, the 2-amido-1,3,4-thiadiazoles compound of gained is dissolved in solvent, adds containing formaldehyde group compound
And diethyl phosphite, in reaction bulb, 105-115 DEG C of back flow reaction 9-11 hour, then decompression boils off solvent and is remained
Thing；
Step 3, the residue of gained uses chromatographic solution carry out solid that column chromatography for separation obtains are described has 2-ammonia
The α-aminophosphonicacid ester compounds of base-1,3,4-thiadiazoles structure.
There is the preparation of the α-aminophosphonicacid ester compounds of 2-amino-1,3,4-thiadiazoles structure the most as claimed in claim 3
Method, wherein, is also mixed with the concentrated hydrochloric acid of concentration 36-38% in described step one.
There is the preparation of the α-aminophosphonicacid ester compounds of 2-amino-1,3,4-thiadiazoles structure the most as claimed in claim 4
Method, wherein, described organic acid is formic acid.
There is the preparation of the α-aminophosphonicacid ester compounds of 2-amino-1,3,4-thiadiazoles structure the most as claimed in claim 5
Method, wherein, described solvent is toluene.
There is the preparation of the α-aminophosphonicacid ester compounds of 2-amino-1,3,4-thiadiazoles structure the most as claimed in claim 6
Method, wherein, in described chromatographic solution, the volume ratio of methanol and dichloromethane is 1:100.
8. one kind as described in claim 1-2 is arbitrary or the arbitrary preparation method of claim 3-7 obtains have 2-amino-
The α-aminophosphonicacid ester compounds of 1,3,4-thiadiazoles structure is as antibacterial and the application of insecticide.
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| CN113802201A (en) * | 2021-09-16 | 2021-12-17 | 成政 | Aromatic mosquito-proof fabric and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107232210A (en) * | 2017-05-04 | 2017-10-10 | 浙江大学 | Application of the thiadiazole compound on paddy bacterial rice shoot damping-off control medicament is prepared |
| CN110041368A (en) * | 2019-05-22 | 2019-07-23 | 西南大学 | Organic phosphine Clinafloxacin derivative and its preparation method and application |
| CN110041368B (en) * | 2019-05-22 | 2021-09-14 | 西南大学 | Organic phosphine clinafloxacin derivative and preparation method and application thereof |
| CN110229122A (en) * | 2019-07-25 | 2019-09-13 | 河南省化工研究所有限责任公司 | The reuse method of ammonia gas as byproduct in a kind of cationic blue X-BL production process |
| CN113802201A (en) * | 2021-09-16 | 2021-12-17 | 成政 | Aromatic mosquito-proof fabric and preparation method thereof |
| CN113802201B (en) * | 2021-09-16 | 2023-12-26 | 佛山市天天娃服饰有限公司 | Aromatic mosquito-proof fabric and preparation method thereof |
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