CN102180875A - Preparation method of triazolopyridine derivative - Google Patents
Preparation method of triazolopyridine derivative Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 150000008523 triazolopyridines Chemical class 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 7
- 125000000547 substituted alkyl group Chemical group 0.000 claims abstract description 5
- 230000005855 radiation Effects 0.000 claims abstract description 3
- XAYCTBDPZIKHCW-UHFFFAOYSA-N (3-chloropyridin-2-yl)hydrazine Chemical compound NNC1=NC=CC=C1Cl XAYCTBDPZIKHCW-UHFFFAOYSA-N 0.000 claims description 24
- -1 substituted-phenyl Chemical group 0.000 claims description 18
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 claims description 6
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000001118 alkylidene group Chemical group 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 238000010572 single replacement reaction Methods 0.000 claims description 6
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 238000006392 deoxygenation reaction Methods 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 claims description 4
- UDEWPOVQBGFNGE-UHFFFAOYSA-N propyl benzoate Chemical compound CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 claims description 4
- SODPIMGUZLOIPE-UHFFFAOYSA-N (4-chlorophenoxy)acetic acid Chemical compound OC(=O)COC1=CC=C(Cl)C=C1 SODPIMGUZLOIPE-UHFFFAOYSA-N 0.000 claims description 3
- AFPHTEQTJZKQAQ-UHFFFAOYSA-N 3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1 AFPHTEQTJZKQAQ-UHFFFAOYSA-N 0.000 claims description 3
- 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
- BBYDXOIZLAWGSL-UHFFFAOYSA-N 4-fluorobenzoic acid Chemical compound OC(=O)C1=CC=C(F)C=C1 BBYDXOIZLAWGSL-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- ILUJQPXNXACGAN-UHFFFAOYSA-N O-methylsalicylic acid Chemical compound COC1=CC=CC=C1C(O)=O ILUJQPXNXACGAN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- CCMGSHLZTIQYKA-UHFFFAOYSA-N formic acid pentylbenzene Chemical compound C(=O)O.C(CCCC)C1=CC=CC=C1 CCMGSHLZTIQYKA-UHFFFAOYSA-N 0.000 claims description 3
- 229960003512 nicotinic acid Drugs 0.000 claims description 3
- 235000001968 nicotinic acid Nutrition 0.000 claims description 3
- 239000011664 nicotinic acid Substances 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- NSTREUWFTAOOKS-UHFFFAOYSA-N 2-fluorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1F NSTREUWFTAOOKS-UHFFFAOYSA-N 0.000 claims description 2
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 claims description 2
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 claims description 2
- FFMXLRXJGJMUDC-UHFFFAOYSA-N C(=O)O.ClC1=CC=CC(=C1)Cl Chemical compound C(=O)O.ClC1=CC=CC(=C1)Cl FFMXLRXJGJMUDC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 claims description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 claims description 2
- CKMXAIVXVKGGFM-UHFFFAOYSA-N p-cumic acid Chemical compound CC(C)C1=CC=C(C(O)=O)C=C1 CKMXAIVXVKGGFM-UHFFFAOYSA-N 0.000 claims description 2
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- AILWADBKBMRCKI-UHFFFAOYSA-N (1-chloro-2H-pyrimidin-2-yl)hydrazine Chemical compound N(N)C1N=CC=CN1Cl AILWADBKBMRCKI-UHFFFAOYSA-N 0.000 abstract 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 abstract 1
- 229910019213 POCl3 Inorganic materials 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 67
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 32
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 238000001953 recrystallisation Methods 0.000 description 21
- 239000013078 crystal Substances 0.000 description 19
- 229960000935 dehydrated alcohol Drugs 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- 230000002194 synthesizing effect Effects 0.000 description 19
- 239000012141 concentrate Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 239000000284 extract Substances 0.000 description 13
- 239000012044 organic layer Substances 0.000 description 13
- 150000003222 pyridines Chemical class 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 150000003852 triazoles Chemical group 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000575 pesticide Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000009333 weeding Methods 0.000 description 4
- 230000004071 biological effect Effects 0.000 description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 230000001093 anti-cancer Effects 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- FFSJPOPLSWBGQY-UHFFFAOYSA-N triazol-4-one Chemical compound O=C1C=NN=N1 FFSJPOPLSWBGQY-UHFFFAOYSA-N 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- 0 *c1nnc2[n]1cccc2Cl Chemical compound *c1nnc2[n]1cccc2Cl 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- KAWUBNUJMFOOOE-UHFFFAOYSA-N 3-amino-3-(3,5-dibromo-4-hydroxyphenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC(Br)=C(O)C(Br)=C1 KAWUBNUJMFOOOE-UHFFFAOYSA-N 0.000 description 1
- MXNBDFWNYRNIBH-UHFFFAOYSA-N 3-fluorobenzoic acid Chemical compound OC(=O)C1=CC=CC(F)=C1 MXNBDFWNYRNIBH-UHFFFAOYSA-N 0.000 description 1
- JFKUBRAOUZEZSL-UHFFFAOYSA-N 4-butylbenzoic acid Chemical compound CCCCC1=CC=C(C(O)=O)C=C1 JFKUBRAOUZEZSL-UHFFFAOYSA-N 0.000 description 1
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- YQEZLKZALYSWHR-UHFFFAOYSA-N Ketamine Chemical compound C=1C=CC=C(Cl)C=1C1(NC)CCCCC1=O YQEZLKZALYSWHR-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 239000002532 enzyme inhibitor Substances 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229960003299 ketamine Drugs 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- OVCXRBARSPBVMC-UHFFFAOYSA-N triazolopyridine Chemical compound C=1N2C(C(C)C)=NN=C2C=CC=1C=1OC=NC=1C1=CC=C(F)C=C1 OVCXRBARSPBVMC-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a preparation method of a triazolopyridine derivative as shown in a formula (I). The preparation method comprises the following steps: carrying out microwave radiation ring-closing reaction on 2-hydrazino-3-chloropyrimidine as shown in a formula (II) and acid as shown in a formula (III) in the presence of POCl3 at the temperature of 100-150 DEG C; and after fully reaction, post-treating a reaction liquid so as to obtain the product triazolopyridine derivative. In the formula (I) or (II), R represents H, C1-C10 alkyl, C1-C10 substituted alkyl, substituted phenyl, substituted phenoxy alkylidene, heterocyclic radical or substituted heterocyclic radical. The preparation method is simple to operate, the yield of the product is high, reaction time is short, used reagents in the reaction process are cheap, and the preparation method has a good application value.
Description
(1) technical field
The present invention relates to a kind of preparation method of triazolopyridine derivatives.
(2) background technology
In pesticide patent newly developed, nearly 90 percent pesticide species contains the heterocyclic compound, and nitrogen heterocyclic ring has occupied major part, and this has opened up wide development space for the development of agricultural chemicals.Nitrogen-containing heterocycle compound is very little to warm-blooded animal toxicity, and especially the toxicity to birds and fish is very low, and has excellent biological activity, as ultra-high efficiency weeding activity, insecticidal activity, fungicidal activity etc.In numerous nitrogen-containing heterocycle compounds, triazole ring, pyridine rings etc. are because of its particular structure feature, superior bioactive and to characteristics such as human body low toxicities, and are significant in novel pesticide initiative research, become one of research focus of current environment friendly agricultural.
Pyridine is the biological isostere of phenyl ring, to phenyl ring similar structure and character is arranged, because pyridine ring has interior preferably absorption, what the corresponding phenyl ring of its biological activity ratio replaced significantly improves, and toxicity reduces greatly.Thereby pyridine farm chemical has had significant progress after entering the nineties, has been penetrated in each application branch and structure type of agricultural chemicals.1,2, the compound of 4-triazole has broad-spectrum biological activity equally, as sterilization, weeding, coordinate plant growth, anticancer etc.From first triazole species efficient germicide triazolone
[5]Since the appearance, triazole class compounds is one of hot subject of pesticide research always, has developed the triazole bactericidal agent of tens kinds of efficient, low toxicities so far.
A plurality ofly heterocyclic fusedly in a part, often can realize its bioactive stack and widen drug effect spectrum that it is of common occurrence that this type of is reported in document.In Pesticide Science research, the triazole fused heterocyclic compound that contains pyridine structure is actually rare, simultaneously because unique physiologically active of triazole fused heterocyclic compound has obtained extensive concern, as sterilization, weeding, anticancer etc.Compound 1 as follows and 2 compounds are mainly by Du Pont, and rhone-poulenc and Schering Corp's development are the light requirement weedicide, and do not have commercial weedicide appearance; And compound 3-6 is according to ALS enzyme inhibitors triazolylsulfonamide compounds deutero-Triazolopyridine compounds, has excellent weeding activity under 5 gram/mus.
The existing several different methods report of synthetic Triazolopyridine.As:
1991, Chem Pharm Bull reported the method by imine intermediate pyridine synthesis and triazole:
2006, Tetrahedron Letters reported the synthetic method of two step pyridine synthesis and triazole:
2008, Bioorganic ﹠amp; Medicinal Chemistry Letters has reported the synthetic method of pyridine synthesis and triazole:
2010, Organic Letters reported the method for catalytic pyridine synthesis of a kind of palladium and triazole:
2010, Indian Journal of Chemistry, Section B reported a kind of under ketamine catalysis the microwave pyridine synthesis and the method for triazole.
(3) summary of the invention
The technical problem to be solved in the present invention provides a kind of easy method for preparing triazolopyridine derivatives.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of preparation method suc as formula the triazolopyridine derivatives shown in (I), comprise the steps: suc as formula the 2-diazanyl-3-chloropyridine shown in (II) with suc as formula the acid shown in (III) at POCl
3In carry out the microwave radiation ring closure reaction in 100～150 ℃, fully reaction back gained reaction solution promptly gets the product triazolopyridine derivatives through aftertreatment.
Reaction equation is as follows:
In formula (I) or the formula (III), R represents the alkyl of H, C1～C10, substituted alkyl or substituted-phenyl, substituent phenoxy alkylidene group, heterocyclic radical or the substituted heterocyclic radical of C1～C10; The substituting group number of the substituted alkyl of described C1～C10 is one or more, and described substituting group is a halogen; Be single replacement or polysubstituted on the phenyl ring of described substituted-phenyl, described substituting group independently is selected from the alkyl of C1～C10, alkoxyl group, halogen or the nitro of C1～C10 separately; It on the phenyl ring of described substituent phenoxy alkylidene group single replacement or polysubstituted, when the substituting group on the phenyl ring is 2 when above, other outer substituting groups of deoxygenation base alkylidene group independently are selected from the alkyl of C1～C10, alkoxyl group, halogen or the nitro of C1～C10 separately, and the carbon atom number of described alkylidene group is 1～4; Be single replacement or polysubstituted on the heterocycle of described substituted heterocyclic radical, described substituting group independently is selected from the alkyl of C1～C10, alkoxyl group, halogen or the nitro of C1～C10 separately.
Further, the substituting group of described substituted-phenyl independently is selected from one of following separately: methyl, nitro, methoxyl group, chlorine atom, fluorine atom; Substituting group on the phenyl ring of described substituent phenoxy alkylidene group is more than 2, and it is one of following that other outer substituting groups of deoxygenation base alkylidene group independently are selected from separately: methyl, nitro, methoxyl group, chlorine atom, fluorine atom; It is one of following that the substituting group of described substituted heterocyclic radical independently is selected from separately: methyl, nitro, methoxyl group, chlorine atom, fluorine atom.
Further, the preferred pyridyl of described heterocyclic radical, the preferred substituted pyridinyl of described substituted heterocycle.
Further, described acid is preferred one of following: m-methyl benzoic acid, M-NITROBENZOIC ACID, between fluorobenzoic acid, m-chlorobenzoic acid, o-methoxybenzoic acid, anisic acid is to amylbenzene formic acid, p-tert-butyl benzoic acid, the n-propyl benzoate, cuminic acid, p-chlorophenoxyacetic acid, p-nitrobenzoic acid, 2,4 dichloro benzene formic acid, o-toluic acid, p-methylbenzoic acid, 0-chloro-benzoic acid, parafluorobenzoic acid, formic acid, acetate, trifluoroacetic acid, propionic acid, the 2-chlorine apellagrin, nicotinic acid, Yi Yansuan.
Further, among the present invention, described 2-diazanyl-3-chloropyridine: acid: the molar ratio of phosphorus oxychloride is preferably 1: 1.0～and 1.5: 2～20.
Further, described ring closure reaction temperature is preferably 100-150 ℃, and the reaction times is preferably 10-20min.
Further, described ring closure reaction temperature is preferably 140 ℃, and the reaction times is preferably 15min.
The reaction solution that the present invention fully reacts the back gained can obtain target product through simple conventional aftertreatment, described post-treating method can be: reaction finishes, reaction solution directly concentrates and obtains resistates or reaction solution is poured in the water, extract with ethyl acetate again, merge organic layer, drying concentrates and to obtain resistates, and for example column chromatography or recrystallization method separate with purifying and obtain the target product triazolopyridine derivatives with currently known methods with the gained resistates then.Column chromatography or recrystallization solvent for use can be sherwood oil, ethyl acetate, normal hexane, ethanol or their mixed solution.
Compared with prior art, beneficial effect of the present invention is: preparation method of the present invention is simple to operate, and reagent used in product yield height, reaction times weak point, the reaction process is all less expensive, has excellent application value.
(4) embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further, but protection scope of the present invention is not limited to this.
Synthesizing of embodiment 1 8-chloro-[1,2,4] triazole [4,3, a] pyridine
2-diazanyl-3-chloropyridine (10mmol) and formic acid (50mmol) stir in microwave reactor.Reacted 10 minutes down at 100 ℃.Reaction finishes, and reaction solution is concentrated, and resistates dehydrated alcohol recrystallization obtains white crystal, i.e. 8-chloro-[1,2,4] triazole [4,3, a] pyridine.Fusing point 193-195 ℃, yield is 92.0%.
1H?NMR(400M，CDCl
3)：6.85(t，J＝6.86Hz，1H，Py)，7.35(d，J＝7.05Hz，1H，Py)，8.17(d，J＝6.73Hz，1H，Py)，8.94(s，1H，triazole-H).
Synthesizing of embodiment 2 8-chloro-3-methyl [1,2,4] triazole [4,3, a] pyridines
2-diazanyl-3-chloropyridine (10mmol) and acetate (50mmol) stir in microwave reactor.Reacted 15 minutes down at 140 ℃.Reaction finishes, and reaction solution is concentrated, and resistates dehydrated alcohol recrystallization obtains white crystal, i.e. 8-chloro-3-methyl [1,2,4] triazole [4,3, a] pyridine.Fusing point 180-182 ℃, yield is 97.0%.
1H?NMR(400M，CDCl
3)：2.77(s，3H，Me)，6.84(t，J＝7.00Hz，1H，Py)，7.30(d，J＝7.13Hz，1H，Py)，7.85(d，J＝6.89Hz，1H，Py).
Synthesizing of embodiment 38-chloro-3-ethyl [1,2,4] triazole [4,3, a] pyridine
2-diazanyl-3-chloropyridine (10mmol) and propionic acid (50mmol) stir in microwave reactor.Reacted 15 minutes down at 140 ℃.Reaction finishes, and reaction solution is concentrated, and resistates dehydrated alcohol recrystallization obtains white crystal, i.e. 8-chloro-3-ethyl [1,2,4] triazole [4,3, a] pyridine.Fusing point 133-135 ℃, yield is 95.0%.
1H?NMR(400M，CDCl
3)：1.50(t，J＝7.50Hz，3H，Me)，3.10(q，J＝7.56Hz，2H，CH
2)，6.81(t，J＝6.81Hz，1H，Py)，7.29(d，J＝7.04Hz，1H，Py)，7.85(d，J＝6.77Hz，1H，Py).
Synthesizing of embodiment 4 8-chloro-3-(3-aminomethyl phenyl) [1,2,4] triazole [4,3, a] pyridines
2-diazanyl-3-chloropyridine (10mmol) and 3-tolyl acid (10mmol) are dissolved in phosphorus oxychloride (10mL) and are placed in the microwave reactor, stir.Reacted 15 minutes down at 140 ℃.Reaction finishes, and reaction solution is poured in the water, extracts with ethyl acetate again, merges organic layer, and drying concentrates, and resistates dehydrated alcohol recrystallization obtains white crystal, i.e. 8-chloro-3-(3-aminomethyl phenyl) [1,2,4] triazole [4,3, a] pyridine.Fusing point 142-144 ℃, yield is 91.0%.
Synthesizing of embodiment 5 8-chloro-3-(4-isopropyl phenyl) [1,2,4] triazole [4,3, a] pyridines
2-diazanyl-3-chloropyridine (10mmol) and 4-isopropyl acid (10mmol) are dissolved in phosphorus oxychloride (10mL) and are placed in the microwave reactor, stir.Reacted 15 minutes down at 140 ℃.Reaction finishes, and reaction solution is poured in the water, extracts with ethyl acetate again, merges organic layer, and drying concentrates, and resistates dehydrated alcohol recrystallization obtains white crystal, i.e. 8-chloro-3-(4-isopropyl phenyl) [1,2,4] triazole [4,3, a] pyridine.Fusing point 142-145 ℃, yield is 93.0%.
Synthesizing of embodiment 6 8-chloro-3-(4-chloro-phenyl-) [1,2,4] triazole [4,3, a] pyridines
2-diazanyl-3-chloropyridine (10mmol) and 4-chloro-benzoic acid (10mmol) are dissolved in phosphorus oxychloride (10mL) and are placed in the microwave reactor, stir.Reacted 15 minutes down at 140 ℃.Reaction finishes, and reaction solution is poured in the water, extracts with ethyl acetate again, merges organic layer, and drying concentrates, and resistates dehydrated alcohol recrystallization obtains white crystal, i.e. 8-chloro-3-(4-chloro-phenyl-) [1,2,4] triazole [4,3, a] pyridine.Fusing point 164-165 ℃, yield is 92.0%.
Synthesizing of embodiment 7 8-chloro-3-(3-nitrophenyl) [1,2,4] triazole [4,3, a] pyridines
2-diazanyl-3-chloropyridine (10mmol) and 3-nitrobenzoic acid (10mmol) are dissolved in phosphorus oxychloride (10mL) and are placed in the microwave reactor, stir.Reacted 15 minutes down at 140 ℃.Reaction finishes, and reaction solution is poured in the water, extracts with ethyl acetate again, merges organic layer, and drying concentrates, and resistates dehydrated alcohol recrystallization obtains white crystal, i.e. 8-chloro-3-(3-nitrophenyl) [1,2,4] triazole [4,3, a] pyridine.Fusing point 266-269 ℃, yield is 93.0%.
1H?NMR(400M，CDCl
3)：7.08(t，J＝6.54Hz，1H，Py)，7.70(d，J＝6.70Hz，1H，Py)，7.94(t，J＝7.80Hz，1H，Ph)，8.35(d，J＝6.95Hz，1H，Py)，8.45(d，J＝7.44Hz，1H，Ph)，8.64(d，J＝6.42Hz，1H，Ph)，8.70(s，1H，Ph)，
Synthesizing of embodiment 8 8-chloro-3-(4-fluorophenyl) [1,2,4] triazole [4,3, a] pyridines
2-diazanyl-3-chloropyridine (10mmol) and 4-fluorobenzoic acid (10mmol) are dissolved in phosphorus oxychloride (10mL) and are placed in the microwave reactor, stir.Reacted 15 minutes down at 140 ℃.Reaction finishes, and reaction solution is poured in the water, extracts with ethyl acetate again, merges organic layer, and drying concentrates, and resistates dehydrated alcohol recrystallization obtains white crystal, i.e. 8-chloro-3-(4-fluorophenyl) [1,2,4] triazole [4,3, a] pyridine.Fusing point 240-243 ℃, yield is 95.0%.
1H?NMR(400M，CDCl
3)：6.85(t，J＝7.05Hz，1H，Py)，7.30(d，J＝8.62Hz，1H，Py)，7.36(d，J＝6.14Hz，2H，Ph)，7.81(d，J＝5.22Hz，2H，Ph)，8.15(d，J＝6.96Hz，1H，Py)
Synthesizing of embodiment 9 8-chloro-3-(4-aminomethyl phenyl) [1,2,4] triazole [4,3, a] pyridines
2-diazanyl-3-chloropyridine (10mmol) and 4-tolyl acid (10mmol) are dissolved in phosphorus oxychloride (10mL) and are placed in the microwave reactor, stir.Reacted 15 minutes down at 140 ℃.Reaction finishes, and reaction solution is poured in the water, extracts with ethyl acetate again, merges organic layer, and drying concentrates, and resistates dehydrated alcohol recrystallization obtains white crystal, i.e. 8-chloro-3-(4-aminomethyl phenyl) [1,2,4] triazole [4,3, a] pyridine.Fusing point 160-163 ℃, yield is 94.0%.
1H?NMR(400M，CDCl
3)：6.82(t，J＝7.05Hz，1H，Py)，7.32-7.38(m，2H，Ph)，7.46(t，J＝7.67Hz，1H，Ph)，7.57(d，J＝7.66Hz，1H，Py)，7.64(s，1H，Ph)，8.21(d，J＝7.00Hz，1H，Py)
Synthesizing of embodiment 10 8-chloro-3-(2-p-methoxy-phenyl) [1,2,4] triazole [4,3, a] pyridines
2-diazanyl-3-chloropyridine (10mmol) and O-Anisic Acid (10mmol) are dissolved in phosphorus oxychloride (10mL) and are placed in the microwave reactor, stir.Reacted 15 minutes down at 140 ℃.Reaction finishes, and reaction solution is poured in the water, extracts with ethyl acetate again, merges organic layer, and drying concentrates, and resistates dehydrated alcohol recrystallization obtains white crystal, i.e. 8-chloro-3-(2-p-methoxy-phenyl) [1,2,4] triazole [4,3, a] pyridine.Fusing point 132-134 ℃, yield is 89.0%.
1H?NMR(400M，CDCl
3)：3.81(s，3H，OMe)，6.77(t，J＝7.04Hz，1H，Py)，7.08(d，J＝8.32Hz，1H，Ph)，7.15(t，J＝7.49Hz，1H，Ph)，7.33(t，J＝7.10Hz，1H，Ph)，7.58(t，J＝8.41Hz，1H，Ph)，7.68(d，J＝6.09Hz，1H，Py)，7.74(d，J＝6.93Hz，1H，Py)
Synthesizing of embodiment 11 8-chloro-3-(3-fluorophenyl) [1,2,4] triazole [4,3, a] pyridines
2-diazanyl-3-chloropyridine (10mmol) and 3-fluorobenzoic acid (10mmol) are dissolved in phosphorus oxychloride (10mL) and are placed in the microwave reactor, stir.Reacted 15 minutes down at 140 ℃.Reaction finishes, and reaction solution is poured in the water, extracts with ethyl acetate again, merges organic layer, and drying concentrates, and resistates dehydrated alcohol recrystallization obtains white crystal, i.e. 8-chloro-3-(3-fluorophenyl) [1,2,4] triazole [4,3, a] pyridine.
1HNMR(400M，CDCl
3)：6.90(t，J＝7.08Hz，1H，Py)，7.31(t，J＝8.22Hz，1H，Ph)，7.39(d，J＝7.13Hz，1H，Py)，7.94(t，J＝7.80Hz，1H，Ph)，8.35(d，J＝6.95Hz，1H，Py)，8.45(d，J＝7.44Hz，1H，Ph)，8.64(d，J＝6.42Hz，1H，Ph)，8.70(s，1H，Ph)
Synthesizing of embodiment 12 8-chloro-3-(4-butyl phenyl) [1,2,4] triazole [4,3, a] pyridines
2-diazanyl-3-chloropyridine (10mmol) and 4-butylbenzoic acid (10mmol) are dissolved in phosphorus oxychloride (10mL) and are placed in the microwave reactor, stir.Reacted 15 minutes down at 140 ℃.Reaction finishes, and reaction solution is poured in the water, extracts with ethyl acetate again, merges organic layer, and drying concentrates, and resistates dehydrated alcohol recrystallization obtains white crystal, i.e. 8-chloro-3-(4-butyl phenyl) [1,2,4] triazole [4,3, a] pyridine.
1HNMR(400M，CDCl
3)：1.39(s，9H，t-Bu)，6.81(t，J＝7.05Hz，1H，Py)，7.33(d，J＝6.92Hz，1H，Py)，7.60(d，J＝8.14Hz，2H，Ph)，7.74(d，J＝8.14Hz，2H，Ph)，8.323(d，J＝6.98Hz，1H，Py)
Synthesizing of embodiment 13 8-chloro-3-(4-p-methoxy-phenyl) [1,2,4] triazole [4,3, a] pyridines
2-diazanyl-3-chloropyridine (10mmol) and 4-methoxybenzoic acid (10mmol) are dissolved in phosphorus oxychloride (10mL) and are placed in the microwave reactor, stir.Reacted 15 minutes down at 140 ℃.Reaction finishes, and reaction solution is poured in the water, extracts with ethyl acetate again, merges organic layer, and drying concentrates, and resistates dehydrated alcohol recrystallization obtains white crystal, i.e. 8-chloro-3-(4-p-methoxy-phenyl) [1,2,4] triazole [4,3, a] pyridine.Fusing point 179-182 ℃, yield is 91.0%.
1H?NMR(400M，CDCl
3)：3.91(s，3H，OMe)，6.82(t，J＝7.05Hz，1H，Py)，7.10(d，J＝8.71Hz，2H，Ph)，7.33(d，J＝7.09Hz，1H，Py)，7.74(d，J＝8.71Hz，2H，Ph)，8.17(d，J＝6.92Hz，1H，Py)
Synthesizing of embodiment 14 8-chloro-3-(4-amyl group phenyl) [1,2,4] triazoles [4,3, a] pyridine
2-diazanyl-3-chloropyridine (10mmol) and 4-amylbenzene formic acid (10mmol) are dissolved in phosphorus oxychloride (10mL) and are placed in the microwave reactor, stir.Reacted 15 minutes down at 140 ℃.Reaction finishes, and reaction solution is poured in the water, extracts with ethyl acetate again, merges organic layer, and drying concentrates, and resistates dehydrated alcohol recrystallization obtains white crystal, i.e. 8-chloro-3-(4-amyl group phenyl) [1,2,4] triazoles [4,3, a] pyridine.
1HNMR(400M，CDCl
3)：0.91(t，J＝6.81Hz，3H，Me)，1.32-1.37(m，4H，CH
2)，1.61-1.67(m，2H，CH
2)，2.71(t，J＝7.58Hz，2H，CH
2)，6.83(t，J＝7.05Hz，1H，Py)，7.28(d，J＝8.34Hz，1H，Ph)，7.36(d，J＝7.11Hz，1H，Py)，7.40(d，J＝8.04Hz，1H，Ph)，7.72(d，J＝8.06Hz，1H，Ph)，8.00(d，J＝8.16Hz，1H，Ph)，8.23(d，J＝6.96Hz，1H，Py)
Synthesizing of embodiment 15 8-chloro-3-(4-propyl group phenyl) [1,2,4] triazoles [4,3, a] pyridine
2-diazanyl-3-chloropyridine (10mmol) and 4-propylbenzoic acid (10mmol) are dissolved in phosphorus oxychloride (10mL) and are placed in the microwave reactor, stir.Reacted 15 minutes down at 140 ℃.Reaction finishes, and reaction solution is poured in the water, extracts with ethyl acetate again, merges organic layer, and drying concentrates, and resistates dehydrated alcohol recrystallization obtains white crystal, i.e. 8-chloro-3-(4-propyl group phenyl) [1,2,4] triazoles [4,3, a] pyridine.
1HNMR(400M，CDCl
3)：0.98(t，J＝7.33Hz，3H，Me)，1.64-1.75(m，2H，CH
2)，2.68(t，J＝7.45Hz，2H，CH
2)，6.82(t，J＝6.99Hz，1H，Py)，7.33(d，J＝7.05Hz，1H，Py)，7.40(d，J＝7.90Hz，2H，Ph)，7.72(d，J＝7.90Hz，2H，Ph)，8.21(d，J＝6.97Hz，1H，Py)
Synthesizing of embodiment 16 8-chloro-3-(4-chlorobenzene oxygen methylene radical) [1,2,4] triazole [4,3, a] pyridine
2-diazanyl-3-chloropyridine (10mmol) and p-chlorophenoxyacetic acid (50mmol) stir in microwave reactor.Reacted 15 minutes down at 140 ℃.Reaction finishes, and reaction solution is concentrated, and resistates dehydrated alcohol recrystallization obtains white crystal, i.e. 8-chloro-3-(4-chlorobenzene oxygen methylene radical) [1,2,4] triazole [4,3, a] pyridine.Fusing point 164-165 ℃, yield is 96.0%.
Synthesizing of embodiment 17 8-chloro-3-(2-chloropyridine base) [1,2,4] triazoles [4,3, a] pyridine
2-diazanyl-3-chloropyridine (10mmol) and 2-chlorine apellagrin (50mmol) stir in microwave reactor.Reacted 15 minutes down at 140 ℃.Reaction finishes, and reaction solution is concentrated, and resistates dehydrated alcohol recrystallization obtains white crystal, i.e. 8-chloro-3-(2-chloropyridine base) [1,2,4] triazoles [4,3, a] pyridine.Yield is 92.0%.
Synthesizing of embodiment 18 8-chloro-3-(3-pyridyl) [1,2,4] triazole [4,3, a] pyridines
2-diazanyl-3-chloropyridine (10mmol) and nicotinic acid (50mmol) stir in microwave reactor.Reacted 15 minutes down at 140 ℃.Reaction finishes, and reaction solution is concentrated, and resistates dehydrated alcohol recrystallization obtains white crystal, i.e. 8-chloro-3-(3-pyridyl) [1,2,4] triazole [4,3, a] pyridine.Yield is 91.0%.
Synthesizing of embodiment 19 8-chloro-3-(4-pyridyl) [1,2,4] triazole [4,3, a] pyridines
2-diazanyl-3-chloropyridine (10mmol) and Yi Yansuan (50mmol) stir in microwave reactor.Reacted 15 minutes down at 140 ℃.Reaction finishes, and reaction solution is concentrated, and resistates dehydrated alcohol recrystallization obtains white crystal, i.e. 8-chloro-3-(4-pyridyl) [1,2,4] triazole [4,3, a] pyridine.Yield is 93.0%.
Claims (6)
1. preparation method suc as formula the triazolopyridine derivatives shown in (I), it is characterized in that described preparation method comprise the steps: suc as formula the 2-diazanyl-3-chloropyridine shown in (II) with suc as formula the acid shown in (III) at POCl
3In carry out the microwave radiation ring closure reaction in 100～150 ℃, fully reaction back gained reaction solution promptly gets the product triazolopyridine derivatives through aftertreatment;
In formula (I) or the formula (III), R represents the alkyl of H, C1～C10, substituted alkyl, substituted-phenyl, substituent phenoxy alkylidene group, heterocyclic radical or the substituted heterocyclic radical of C1～C10; The substituting group number of the substituted alkyl of described C1～C10 is one or more, and described substituting group is a halogen; Be single replacement or polysubstituted on the phenyl ring of described substituted-phenyl, described substituting group independently is selected from the alkyl of C1～C10, alkoxyl group, halogen or the nitro of C1～C10 separately; It on the phenyl ring of described substituent phenoxy alkylidene group single replacement or polysubstituted, when substituting group is 2 when above, other outer substituting groups of deoxygenation base alkylidene group independently are selected from the alkyl of C1～C10, alkoxyl group, halogen or the nitro of C1～C10 separately, and the carbon atom number of described alkylidene group is 1～4; Be single replacement or polysubstituted on the heterocycle of described substituted heterocyclic radical, described substituting group independently is selected from the alkyl of C1～C10, alkoxyl group, halogen or the nitro of C1～C10 separately.
2. the preparation method of triazolopyridine derivatives as claimed in claim 1 is characterized in that: the substituting group of described substituted-phenyl independently is selected from one of following separately: methyl, nitro, methoxyl group, chlorine atom, fluorine atom; Substituting group on the phenyl ring of described substituent phenoxy alkylidene group is more than 2, and it is one of following that other outer substituting groups of deoxygenation base alkylidene group independently are selected from separately: methyl, nitro, methoxyl group, chlorine atom, fluorine atom; It is one of following that the substituting group of described substituted heterocyclic radical independently is selected from separately: methyl, nitro, methoxyl group, chlorine atom, fluorine atom.
3. the preparation method of triazolopyridine derivatives as claimed in claim 1, it is one of following to it is characterized in that described acid is selected from: m-methyl benzoic acid, M-NITROBENZOIC ACID, between fluorobenzoic acid, m-chlorobenzoic acid, o-methoxybenzoic acid, anisic acid is to amylbenzene formic acid, p-tert-butyl benzoic acid, the n-propyl benzoate, cuminic acid, p-chlorophenoxyacetic acid, p-nitrobenzoic acid, 2,4 dichloro benzene formic acid, o-toluic acid, p-methylbenzoic acid, 0-chloro-benzoic acid, parafluorobenzoic acid, formic acid, acetate, trifluoroacetic acid, propionic acid, the 2-chlorine apellagrin, nicotinic acid, Yi Yansuan.
4. the preparation method of triazolopyridine derivatives as claimed in claim 1, it is characterized in that described 2-diazanyl-3-chloropyridine: acid: the molar ratio of phosphorus oxychloride is 1: 1.0～1.5: 2～20.
5. the preparation method of triazolopyridine derivatives as claimed in claim 1 is characterized in that described ring closure reaction temperature is 100～150 ℃, and the reaction times is 10-20min.
6. the preparation method of triazolopyridine derivatives as claimed in claim 1 is characterized in that described ring closure reaction temperature is 140 ℃, and the reaction times is 15min.
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