CN105646386A - Substituted azole penta-heterocyclic derivatives and solvothermal one-pot synthesis method and application thereof - Google Patents

Substituted azole penta-heterocyclic derivatives and solvothermal one-pot synthesis method and application thereof Download PDF

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CN105646386A
CN105646386A CN201610058287.2A CN201610058287A CN105646386A CN 105646386 A CN105646386 A CN 105646386A CN 201610058287 A CN201610058287 A CN 201610058287A CN 105646386 A CN105646386 A CN 105646386A
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cyclizing agent
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substituted azole
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CN105646386B (en
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陈连清
万子露
牛雄雷
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South Central Minzu University
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South Central University for Nationalities
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Abstract

The invention belongs to the technical field of organic synthesis and particularly discloses a series of substituted azole penta-heterocyclic derivatives and a solvothermal one-pot synthesis method thereof. By the adoption of the solvothermal one-pot synthesis method for preparing the target product, reaction time is short, a solvent is not prone to volatilization in an airtight system, recycling can be realized, production cost is effectively reduced, the advantages of energy conservation and environment friendliness are achieved, operation is easy, yield is high, and the prepared substituted azole penta-heterocyclic derivatives have good anti-microbial biological activity and excellent photophysical properties such as electron conductivity, the fluorescence property and the ultraviolet property, thereby having very high development and application value.

Description

Substituted azole five-ring heterocycles derivant and solvent thermal one-pot synthesis thereof and application
Technical field
The present invention relates to technical field of organic synthesis, particularly relate to a kind of substituted azole five-ring heterocycles derivant and solvent thermal One-step Synthesis method thereof, further relate to the application of this compounds.
Background technology
Azole compounds is the nitrogenous five-membered heterocycles that a class is important, owing to it is easily formed hydrogen bond, coordinate bond etc., multiple non-covalent interaction can be played, there is the extensive uses such as antibacterial, antiviral, antiinflammatory in biological activity, new drug design is often taken as pharmacophoric group, and is widely used in the field such as medicine, pesticide; In photoelectric properties, some azole compounds has excellent electronic transmission performance due to it in electroluminescent device, can being applied to electroluminescent instrument as photosensitive macromolecular material, some azole derivative has photo-sensitive characteristic, can be used for producing fluorescent agent, scintillator etc. Multiformity with its structure of many uses due to azole five-ring heterocycles derivant, causes the great interest of people, has boundless research and development prospect.
The synthetic method that substituted azole five-ring heterocycles derivant is traditional is carrying out under oil bath heated reflux condition, there is the shortcomings such as energy consumption big, time length, productivity are low, post processing trouble, solvent volatilization, limit the application to substituted azole five-ring heterocycles derivant to a certain extent, the present invention is directed to these shortcomings and be optimized improvement.
Solvent-thermal method refers in special closed reaction vessel (autoclave), adopt different solvents as reaction medium, by reaction vessel is heated, create high temperature, a reaction under high pressure environment so that generally indissoluble or insoluble material dissolve and recrystallization. One-pot synthesis has selectivity efficient, high, mild condition, the feature such as easy and simple to handle, and it can also synthesize the object that some conventional methods are difficult to synthesize relatively easily. Current solvent-thermal method has very wide application on inorganic material synthesizes, but the application on organic synthesis rarely has report, experiment proves, solvent thermal one-pot synthesis has productivity height, the advantages such as the time is short, simple to operate, energy-conserving and environment-protective, being expected to become the new method efficiently preparing substituted azole five-ring heterocycles derivant, application prospect is by boundless.
Summary of the invention
For the deficiencies in the prior art, the present invention devises by N-(2-oxo) amide derivatives (Ia) or 1,4 '-bishydrazide derivant (Ib) is inner at closed reaction vessel (autoclave), adopt different solvents as reaction medium, by reaction vessel is heated, create high temperature, a reaction under high pressure environment, One-step Synthesis a series of substituted azole five-ring heterocycles derivant (II), (III) and (IV) type compound.
Based on considerations above, four goals of the invention of the present invention are:
First purpose: provide a kind of substituted azole five-ring heterocycles derivant, shown in its structural formula such as formula (A):
Wherein, M is-O-,-S-or-NH-;
When M is-O-, described formula (A) is for shown in following structure formula II:
When M is-S-, described formula (A) is for shown in following structure formula III:
When M is-NH-, described formula (A) is for shown in following structure formula IV:
In described structural formula (A), (II), (III), (IV), X is-CR3Or-N=;
When X is-CR3Time, described structure formula II, (III) and (IV) be 2,4,5 three replacement-1 respectively, 3-azoles (II a), 2,4,5 three replacement-1,3-thiazoles (III a) and 2,4,5 three replace-1,3-imidazoles (IV a) type compound, and its structural formula is as follows:
When X is-N=, described structural formula (III), (IV) and (V) is 2,5 two replacement-1,3 respectively, 4-diazole (II b), 2,5 two replace-1,3,4-thiadiazoles (III b) and 2,5 two replace-1,3,4-triazoles (IV b) type compound, its structural formula is as follows:
In above-mentioned each structural formula, R1��R2Be each independently selected from following group any one:
CH3-��CH3CH2-��CH3CH2CH2-��CH3(CH2)2CH2-��CH3(CH2)3CH2-��CH3(CH2)4CH2-��CH3(CH2)5CH2-��CH(CH3)2CH2CH2-��ClCH2-��ClCH2CH2-��Cl2CHCH2CH2-��Cl3CCH2CH2-�� And
Preferably, described R1��R2Be each independently selected from following group any one:
And
Best, described R1��R2Be independently chosen from following group respectively any one:
And
R3Any one in following group :-H,Substituted or unsubstituted phenyl;
Described 2,4,5 three replace-1, and 3-azoles (II a), 2,4,5 three replacement-1,3-thiazoles (III a) and 2,4,5 three replace-1, in 3-imidazoles (IV a) compound, work as R1During for substituted or unsubstituted phenyl, R2With R3It is connected to form six-membered ring structure;
Second purpose: a kind of synthetic method being prone to relatively low substituted azole five-ring heterocycles derivant (A) of efficient preparation, energy-conserving and environment-protective, production cost is provided.
The synthetic method of compound shown in a kind of structural formula such as formula (A):
By compound N-(2-oxo) amide derivatives (Ia) or 1,4 '-bishydrazide derivant (Ib) and cyclizing agent are inner in closed reaction vessel (autoclave) at solvent existent condition, reacting 2-14h by solvent-thermal method at 70��180 DEG C, one pot prepares compound shown in formula (A);
N-(2-oxo) amide derivatives (Ia) and Isosorbide-5-Nitrae ' structural formula of-bishydrazide derivant (Ib) is as follows:
Synthetic route is as follows:
Described solvent is selected from any one in cyclic ethers class, arene, chain ethers, amine and other solvents;
Further, described cyclic ether solvents includes oxolane and dioxane;
Described aromatic hydrocarbon solvent includes toluene, dimethylbenzene, sym-trimethylbenzene., chlorobenzene, bromobenzene and pyridine;
Described chain ether solvent includes ethylene glycol diethyl ether, butyl glycol ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether and dihydroxypropane single-ether;
Described amine solvent includes N,N-dimethylformamide and DMAC N,N' dimethyl acetamide;
Other kind solvents described include dimethyl sulfoxide and CHP;
Preferably, described solvent is any one in oxolane, dioxane, toluene, pyridine, chlorobenzene, dimethylbenzene, ethylene glycol diethyl ether, DMF, N,N-dimethylacetamide and CHP.
Best, described organic solvent is any one in oxolane, toluene, pyridine, chlorobenzene, ethylene glycol diethyl ether and DMF;
Described cyclizing agent is selected from one of three class cyclizing agents, first kind cyclizing agent is cyclizing agent used by synthesis substituted azole five-ring heterocycles derivant (II), Equations of The Second Kind cyclizing agent is cyclizing agent used by synthesis substituted azole five-ring heterocycles derivant (III), and the 3rd class cyclizing agent is cyclizing agent used by synthesis substituted azole five-ring heterocycles derivant (IV);
Any one in phosphorus pentoxide, polyphosphoric acids, phosphorus oxychloride, Phosphorous chloride., phosphorus pentachloride, chlorosulfonic acid and trim,ethylchlorosilane of described first kind cyclizing agent, it is preferable that any one in phosphorus pentoxide, phosphorus oxychloride, Phosphorous chloride., phosphorus pentachloride, chlorosulfonic acid and trim,ethylchlorosilane;
Described Equations of The Second Kind cyclizing agent is selected from any one in phosphorus pentasulfide, thiourea and 2-TGA, it is preferred to phosphorus pentasulfide or thiourea;
Described 3rd class cyclizing agent has the aminated compounds of hydrogen on ammonium salt or nitrogen, any one in ammonia, ammonium carbonate, ammonium hydrogen carbonate, ammonium nitrate, ammonium sulfate and ammonium hydrogen sulfate, it is preferred to any one in ammonium hydrogen carbonate, ammonium nitrate and ammonium sulfate;
Preferably, described solvent thermal reaction temperature is 100��170 DEG C, and the response time is 3��10h.
Best, described solvent thermal reaction temperature is 140��160 DEG C, and the response time is 4��8h.
Described compound N-(2-oxo) amide derivatives (Ia) or Isosorbide-5-Nitrae ' mol ratio of-bishydrazide derivant (Ib) and cyclizing agent is 1:1.2.
3rd purpose: the application in antibacterials of a kind of above-mentioned substituted azole five-ring heterocycles derivant is provided.
For realizing the 3rd purpose of the present invention, the substituted azole five-ring heterocycles derivant prepared is respectively used to anti-Staphylococcus aureus, colon bacillus and proteus vulgaris test by the present invention, achieves good antibacterial effect.
4th purpose: the application in luminescent material of a kind of above-mentioned substituted azole five-ring heterocycles derivant is provided.
For realizing the 4th purpose of the present invention, the substituted azole five-ring heterocycles derivant prepared is investigated from fluorescence emission spectrum and uv-visible absorption spectra two aspect by the present invention photophysical property of product, it is determined that it has good Photophysics.
Compared with prior art, advantages of the present invention and having the beneficial effect that:
The present invention adopts substituted azole five-ring heterocycles derivant (A) prepared by solvent thermal one-pot synthesis, and the response time is short, and solvent is not volatile in enclosed system, recoverable, significantly reduces production cost, the advantage with energy-conserving and environment-protective, and simple to operate, yield is higher.
Substituted azole five-ring heterocycles derivant (A) prepared has good biological activity, particularly shows high activity at antibiosis, and has excellent Photophysics, therefore has very big development and application values.
Accompanying drawing explanation
Fig. 1 is the fluorescence emission spectrogram that substituted azole five-ring heterocycles derivant is dissolved in dichloromethane solution.
Fig. 2 is the uv-visible absorption spectra figure that substituted azole five-ring heterocycles derivant is dissolved in dichloromethane solution.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, but the protection domain that these specific embodiments do not limit the present invention in any way.
Raw material used in following embodiment is known compound, is commercially available, or the synthesis of available methods known in the art.
The synthesis of embodiment 1,2,5 diphenyloxazole ((II) 1)
100mL reactor adds 25mL pyridine, 2.39gN-(2-oxygen-2-phenyl) ethyl benzamide and 1.7g phosphorus pentoxide, mix homogeneously, tighten sealing lid, put in electric drying oven with forced convection, reaction temperature 120 DEG C is heated to from room temperature, after isothermal reaction 6h, stop heating, naturally cool to room temperature, by mixture, with distilled water wash, dry, ethyl alcohol recrystallization, weigh, obtaining faint yellow solid 1.82g (II) 1, productivity is 82.3%.mp:180.1��183.6 DEG C .IR �� (cm-1): 3045,1584,1483,1443,1126,1062,1020,944,908,820,760,683;1H-NMR(CDCl3, 400MHz): 8.12 (dd, J=7.7,1.5Hz, 2H), 7.74 (dd, J=8.2,1.3Hz, 2H), 7.51 7.44 (m, 6H), 7.35 (t, J=7.5Hz, 1H);13C-NMR(125MHz,CDCl3): 161.5,151.7,130.8,129.4,129.3,128.9,128.4,127.9,126.7,12 4.6,123.9; HRMS (MALDI-FTMS) calcdforC15H12NO+[M+H]+222.0913,found222.0914.
Embodiment 2,2-indyl-5-phenyl azoles ((II) 2) synthesis
100mL reactor adds 25mL toluene, 2.78gN-(2-oxygen-2-phenyl) ethyl-1H-indole-3-Methanamide and 1.7g phosphorus pentoxide, mix homogeneously, tighten sealing lid, put in electric drying oven with forced convection, reaction temperature 150 DEG C is heated to from room temperature, after isothermal reaction 6h, stop heating, naturally cool to room temperature, by mixture, with distilled water wash, dry, ethyl alcohol recrystallization, weigh, obtaining pale white solid 2.31g (II) 2, productivity is 88.7%.IR �� (cm-1): 3413,3154,2919,1625,1602,1443,1361,1249,1120,914,767,726;1H-NMR(400MHz,DMSO-d6): 8.10 8.07 (m, 2H), 7.98 7.95 (m, 2H), 7.60 7.48 (m, 5H), 7.25 7.17 (m, 2H);13C-NMR(125MHz,DMSO-d6): 158.0,148.3,136.4,130.1,129.2,127.2,125.5,123.9,123.5,12 2.3,120.8,120.3,119.6,112.2,103.6; HRMS (MALDI-FTMS) calcdforC17H13N2O+[M+H]+261.1022,found261.1021.
Embodiment 3,2-indyl-5 pyridine radicals azoles ((II) 3) synthesis
100mL reactor adds 25mL dimethylbenzene, 2.78gN-(2-oxygen-2-pyridine radicals) ethyl-1H-indole-3-Methanamide and 1.7g phosphorus pentoxide, mix homogeneously, tighten sealing lid, put in electric drying oven with forced convection, reaction temperature 150 DEG C is heated to from room temperature, after isothermal reaction 6h, stop heating, naturally cool to room temperature, by mixture, with distilled water wash, dry, ethyl alcohol recrystallization, weigh, obtaining yellow solid 2.35g (II) 3, productivity is 90%.IR �� (cm-1): 3173,2919,1755,1628,1431,1331,1255,1120,1008,920,803,750,703,614;1H-NMR(400MHz,DMSO-d6): 9.27 (s, 1H), 8.69 (d, J=5.0Hz, 1H), 8.41 (d, J=6.7Hz, 1H), 8.01 (d, J=2.4Hz, 1H), 7.97 (d, J=7.9Hz, 1H), 7.67 (s, 1H), 7.59 (dd, J=7.9,5.0Hz, 1H), 7.49 (d, J=7.9Hz, 1H), 7.25 7.17 (m, 2H);13C-NMR(100MHz,DMSO-d6): 155.9,150.6,149.0,136.4,132.8,124.2,124.1,123.5,123.4,12 2.3,120.9,120.4,119.6,112.2,103.4; HRMS (MALDI-FTMS) calcdforC16H12N3O+[M+H]+262.0975,found262.0972.
Embodiment 4,2-(4-fluorophenyl)-5 thienyl azoles ((II) 4) synthesis
100mL reactor adds 25mLN, the fluoro-N-of dinethylformamide, 2.63g4-(2-oxygen-2-thiene-3-yl) ethyl benzamide and 1.7g phosphorus pentoxide, mix homogeneously, tighten sealing lid, put in electric drying oven with forced convection, heat to reaction temperature 150 DEG C from room temperature, after isothermal reaction 6h, stop heating, naturally cool to room temperature, by mixture, with distilled water wash, dry, ethyl alcohol recrystallization, weighing, obtain yellow solid 1.64g (II) 4, productivity is 67%.M.p.65��67.IR �� (cm-1):3100,1610,1600.1H-NMR(DMSO-d6, 400MHz): 7.2��8.3 (8H, m, CH, arom-H, thiophene-H) .HRMS (MALDI-FTMS) calcdforC13H8FNOS+[M+H]+222.0913, C, 63.66; H, 3.29; N, 5.71; S, 13.07.Found:222.0914, C, 63.57; H, 3.41; N, 5.82; S, 12.93.
Embodiment 5,2-phenyl-4,5,6,7-tetrahydro benzo [d] azoles ((II) 5) synthesis
100mL reactor adds 25mL pyridine, 2.17gN-(2-oxygen-cyclohexyl) Benzoylamide and 5mL phosphorus oxychloride, mix homogeneously, tightens sealing lid, put in electric drying oven with forced convection, heat to reaction temperature 80 DEG C from room temperature, after isothermal reaction 12h, stop heating, naturally cool to room temperature, by mixture, with distilled water wash, dry, ethyl alcohol recrystallization, weigh, obtaining white solid 1.3g (II) 5, productivity is 65%.IR �� (cm-1):2931,2837,1637,1542,1478,1443,1284,1055,920,767,709.1H-NMR(CDCl3, 400MHz): 8.07 (dd, J=8.1,1.2Hz, 2H), 7.52 7.45 (m, 3H), 2.78 2.67 (m, 4H), 2.00 1.89 (m, 4H).13C-NMR(100MHz,CDCl3): 159.7,146.9,135.0,129.6,128.6,128.0,125.8,23.1,23.0,22.9,21.9;HRMS (MALDI-FTMS) calcdforC13H14NO+[M+H]+200.1070,found200.1068.
Embodiment 6,1-benzyl group-5-(5-methyl isophthalic acid, 3,4 diazole-2-bases) nafoxidine-2-ketone ((II) 6) synthesis
100mL reactor adds 25mL toluene, 2.75gN-acetyl group-1-benzyl-2-carbohydrazide-5-oxygen-nafoxidine and 5mL phosphorus oxychloride, mix homogeneously, tightens sealing lid; put in electric drying oven with forced convection, heat to reaction temperature 150 DEG C from room temperature, after isothermal reaction 6h; stop heating, naturally cool to room temperature, by mixture; with distilled water wash; dry, ethyl alcohol recrystallization, weigh; obtaining white solid 2.18g (II) 6, productivity is 85%.Mp:86 DEG C of .IR �� (cm-1): 1680 (C=O), 1585-1565-1495 (C=C, C=N).1H-NMR(CDCl3, 400MHz): 2-2.9 (m, 4H), 2.36 (s, 3H), 4.24 (d, lH, J=14.4Hz), 4.65 (d, lH, J=14.4Hz), 4.7-5 (m, IH), 7.25 (s, 5H) .Anal.Calcd.forC14H15N3O2: C, 65.35; H, 5.88; N, 16.33.Found:C, 65.24; H, 5.98; N, 16.27.
Embodiment 7,2-(3,4,5-trimethoxyphenyl)-4-carboxymethyl-5-methyl azoles ((II) 7) synthesis
100mL reactor adds 25mL pyridine, 3.25g2-(3,4,5-trimethoxybenzoy) 3-oxy butyrate methyl ester and 5mL phosphorus oxychloride; mix homogeneously, tightens sealing lid, puts in electric drying oven with forced convection; heat to reaction temperature 150 DEG C from room temperature, after isothermal reaction 6h, stop heating; naturally cool to room temperature, by mixture, with distilled water wash; dry, ethyl alcohol recrystallization, weigh; obtaining white solid 2.2g (II) 7, productivity is 68%.mp:152-154 DEG C.1H-NMR(400MHz,CDCl3): 7.24 (s, 2H), 3.90 (s, 3H), 3.89 (s, 6H), 3.85 (s, 3H), 2.66 (s, 3H);13C-NMR(125MHz,CDCl3):162.7(C),159.4(C),156.1(C),153.3(C),140.3(C),128.4(C),121.7(C),103.7(CH),60.8(CH3),56.2(CH3),51.9(CH3),12.0(CH3); HRMS (EI) m/z:calcdforC15H17NO6:307.1056,found:307.1051.
The synthesis of embodiment 8,2,5 diphenylthiazol ((III) 1)
100mL reactor adds 25mL ethylene glycol diethyl ether, 2.39gN-(2-oxygen-2-phenyl) ethyl benzamide and 2.66g phosphorus pentasulfide, mix homogeneously, tighten sealing lid, put in electric drying oven with forced convection, reaction temperature 150 DEG C is heated to from room temperature, after isothermal reaction 6h, stop heating, naturally cool to room temperature, by mixture, with distilled water wash, dry, ethyl alcohol recrystallization, weigh, obtaining yellow solid 2.05g (III) 1, productivity is 86.7%.mp:180.1��183.6 DEG C .IR �� (cm-1): 3056,3021,2915,2833,1602,1488,1441,1306,1236,1171,1077,1 000,942,760,689,601;1H-NMR(CDCl3, 400MHz): 7.88 (dd, J=8.3,1.3Hz, 2H), 7.51 7.26 (m, 8H), 5.08 (dd, J=8.8,5.5Hz, 1H), 4.79 (dd, J=16.1,8.8Hz, 1H), 4.63 (dd, J=16.1,5.5Hz, 1H);13C-NMR(125MHz,CDCl3): 167.7,142.1,133.1,131.3,128.8,128.5,128.4,127.8,127.0,73 .2,54.5; HRMS (MALDI-FTMS) calcdforC15H12NS+[M+H]+240.0841,found240.0837.
Embodiment 9,2-indyl-5-phenyl thiazole ((III) 2) synthesis
100mL reactor adds 25mL toluene, 2.78gN-(2-oxygen-2-phenyl) ethyl benzamide and 2.66g phosphorus pentasulfide, mix homogeneously, tighten sealing lid, put in electric drying oven with forced convection, reaction temperature 150 DEG C is heated to from room temperature, after isothermal reaction 6h, stop heating, naturally cool to room temperature, by mixture, with distilled water wash, dry, ethyl alcohol recrystallization, weigh, obtain yellow solid 2.31g (III) 2, productivity is 83.6%.mp:180.1��183.6 DEG C .IR (film) �� max3399, 3170, 2912, 1562, 1487, 1452, 1421, 1337, 1245, 1120, 978, 911, 740, 689, 630cm 1,1HNMR (500MHz, CDCl3) �� 7.85 (m, 2H), 7.47 7.38 (m, 3H), 4.26 (dt, J=11.0,5.5Hz, 1H), 3.82 (dt, J=8.8,5.8Hz, 1H), 2.28 (m, 1H), 1.89 1.80 (m, 2H), 1.70 1.51 (m, 4H), 1.37 1.29 (m, 1H); 13CNMR (100MHz, CDCl3) �� 165.1,138.4,136.4,133.8,132.7,129.7,129.0,126.3,125.4,12 3.1,122.8,121.0,119.7,111.6,108.3; HRMS (MALDI-FTMS) calcdforC17H13N2S+[M+H]+277.0794,found277.0788.
Embodiment 10,2-(4-chlorphenyl)-5-thienyl thiazole ((III) 3) synthesis
100mL reactor adds 25mL toluene, 2.3g4-chlorine N-(2-oxygen-2-thienyl) ethyl benzamide and 2.66g phosphorus pentasulfide, mix homogeneously, tighten sealing lid, put in electric drying oven with forced convection, reaction temperature 150 DEG C is heated to from room temperature, after isothermal reaction 6h, stop heating, naturally cool to room temperature, by mixture, with distilled water wash, dry, ethyl alcohol recrystallization, weigh, obtaining white solid 1.68g (III) 3, productivity is 64%.M.p.143��144 DEG C .IR �� (cm-1):3100,1595.1H-NMR(DMSO-d6, 400MHz): 7.9��7.41 (4H, m, arom-H), 7.78 (1H, s, thiophene-H) 7.2��7.5 (3H, m, thiophene-H) .AnalcalcdforC13H8ClNOS2:C, 56.21; H, 2.90; N, 5.04; Cl, 12.76; S, 23.08.Found:C, 56.11; H, 2.84; N, 5.08; Cl, 12.99; S, 22.75.
Embodiment 11,2-phenyl-4,5,6,7-tetrahydro benzo [d] thiazole ((III) 4) synthesis
100mL reactor adds 25mL toluene, 2.17gN-(2-oxygen-cyclohexyl) Benzoylamide and 2.66g phosphorus pentasulfide, mix homogeneously, tightens sealing lid, put in electric drying oven with forced convection, heat to reaction temperature 150 DEG C from room temperature, after isothermal reaction 6h, stop heating, naturally cool to room temperature, by mixture, with distilled water wash, dry, ethyl alcohol recrystallization, weigh, obtaining white solid 1.5g (III) 4, productivity is 68%.IR �� (cm-1):3060,2919,2849,1572,1484,1443,1302,1243,1078,997,950,761,686,609.1H-NMR(CDCl3, 400MHz): 7.85 (m, 2H), 7.47 7.38 (m, 3H), 4.26 (dt, J=11.0,5.5Hz, 1H), 3.82 (dt, J=8.8,5.8Hz, 1H), 2.28 (m, 1H), 1.89 1.80 (m, 2H), 1.70 1.51 (m, 4H), 1.37 1.29 (m, 1H).13C-NMR(100MHz,CDCl3): 134.4,131.5,128.8,128.6,75.2,51.6,30.2,29.0,23.5,22.1; HRMS (MALDI-FTMS) calcdforC13H14NO+[M+H]+218.0998,found218.0997.
Embodiment 12,2,5-bis-(4-aminomethyl phenyl)-1,3,4-thiadiazoles ((III) 5) synthesis
100mL reactor adds 25mL oxolane, 2.67g4-methyl-N-(2-oxygen-2-(4-aminomethyl phenyl)) ethyl benzamide and 2.66g phosphorus pentasulfide, mix homogeneously, tighten sealing lid, put in electric drying oven with forced convection, reaction temperature 150 DEG C is heated to from room temperature, after isothermal reaction 6h, stop heating, naturally cool to room temperature, by mixture, with distilled water wash, dry, ethyl alcohol recrystallization, weigh, obtaining white solid 2.3g (III) 5, productivity is 87%.1H-NMR(CDCl3, 400MHz): 7.91 (d, J=8.2Hz, 4H, C6H5), 7.31 (d, J=8.1Hz, 4H, C6H5),2.44(s,6H,CH3);13C-NMR(125MHz,CDCl3):168.0,141.6,129.9,127.9,127.6,21.6.
Embodiment 13,2-(4-nitrobenzophenone)-4-carboxymethyl-5-methylthiazol ((III) 6) synthesis
100mL reactor adds 25mL oxolane, 2.8g2-(4-nitro benzoyl) 3-oxygen-methyl butyrate and 2.66g phosphorus pentasulfide; mix homogeneously; tighten sealing lid; put in electric drying oven with forced convection; reaction temperature 150 DEG C is heated to from room temperature; after isothermal reaction 6h; stop heating, naturally cool to room temperature, by mixture; with distilled water wash; dry, ethyl alcohol recrystallization, weigh; obtaining white solid 2.3g (III) 6, productivity is 83%.m.p.191��193 DEG C.1H-NMR(CDCl3, 400MHz): 8.27 (d, J=9.0Hz, 2H), 8.07 (d, J=9.0Hz, 2H), 3.97 (s, 3H), 2.84 (s, 3H);13C-NMR(125MHz,CDCl3):162.6(C),160.7(C),148.6(C),146.8(C),142.8(C),138.2(C),127.3(CH),124.2(CH),52.3(CH3),13.4(CH3); HRMS (EI) m/z:calcdforC12H10N2O4S:278.0361,found:278.0358.
The synthesis of embodiment 14,2,5 2 (4-hydroxy phenyl) imidazoles ((IV) 1)
100mL reactor adds 25mL pyridine, 2.71gN-(2-oxygen-2-(4-hydroxy phenyl)) ethyl benzamide and 1.15g ammonium carbonate, mix homogeneously, tightens sealing lid, put in electric drying oven with forced convection, heat to reaction temperature 150 DEG C from room temperature, after isothermal reaction 6h, stop heating, naturally cool to room temperature, by mixture, with distilled water wash, dry, ethyl alcohol recrystallization, weigh, obtain yellow solid 1.45g (IV) 1, productivity 57%. IR �� (cm-1): 2590,1645,1488,1114,841;1H-NMR(CD3OD, 400MHz): 7.83 (d, J=8.70Hz, 2H), 7.62 (d, J=8.70Hz, 2H), 7.60 (s, 1H), 7.03 (d, J=8.70Hz, 2H), 6.92 (d, J=8.70Hz, 2H);13C-NMR(125MHz,CD3OD): 131.30,129.15,120.15 (2C), 119.80 (2C), 115.55 (2C), 114.75 (2C), 114.30; MS (ESI): 253 (M+H)+; Anal.CalcdC15H12N2O2: C, 71.42; H, 4.79; N, 11.10.Found:C, 71.30; H, 4.52; N, 11.00.
Embodiment 15,2-(4-methoxyphenyl)-5-(3-methoxyphenyl) imidazoles ((IV) 2) synthesis
100mL reactor adds 25mL oxolane, 2.99gN-(2-oxygen-2-(4-methoxyphenyl)) ethyl benzamide and 1.15g ammonium carbonate, mix homogeneously, tightens sealing lid, put in electric drying oven with forced convection, heat to reaction temperature 100 DEG C from room temperature, after isothermal reaction 6h, stop heating, naturally cool to room temperature, by mixture, with distilled water wash, dry, ethyl alcohol recrystallization, weigh, obtain white solid 1.26g (IV) 2, productivity 45%. Mp:198 DEG C; IR �� (cm-1): 3070,2950,1578,1242,742;1H-NMR(CD3OD, 400MHz): 8.07 (d, J=2.50Hz, 1H), 7.98 (d, J=8.50Hz, 2H), 7.78 (d, J=8.50Hz, 1H), 7.57 (s, 1H), 7.37 (s, 1H), 7.12 7.08 (m, 2H), 6.75 (s, 1H), 3.83 (s, 3H, OMe), 3.82 (s, 3H, OMe);13C-NMR(125MHz,CD3OD): 162.10,160.85,151.40,137.50,128.65 (2C), 127.25,125.40,123.35,20.75,115.75 (2C), 113.70,56.80,56.50; MS (ESI): 281 (M+H)+.Anal.CalcdC21H12N2O2: C, 76.42; H, 3.79; N, 7.10.Found:C, 76.30; H, 3.52; N, 7.00.
Embodiment 16,5-methyl-2,4 diphenyl 1-H-imidazoles ((IV) 3) synthesis
100mL reactor adds 25mL toluene, 2.99gN-(1-phenyl-2-oxygen-propyl group) ethyl benzamide and 1.15g ammonium carbonate, mix homogeneously, tightens sealing lid, put in electric drying oven with forced convection, heat to reaction temperature 150 DEG C from room temperature, after isothermal reaction 6h, stop heating, naturally cool to room temperature, by mixture, with distilled water wash, dry, ethyl alcohol recrystallization, weigh, obtain white solid 1.26g (IV) 2, productivity 45%. IR �� (cm-1): 3020,2930,1568,1252,772;1H-NMR(CD3OD,400MHz):8.07-7.21(m,10H,Ar-H),3.82(s,3H,CH3);13C-NMR(125MHz,CD3OD): 161.10,158.85,151.40,133.50,124.65 (2C), 127.25,125.40,123.35,20.75,115.75 (2C), 113.70,55.80,53.50;
Embodiment 17,2-(4-methoxyphenyl)-5-phenyl-1H-1,2,4-triazole ((IV) 4) synthesis
100mL reactor adds 25mL chlorobenzene, 2.7gN`-benzoyl-4-methoxybenzoyl hydrazine and 1.15g ammonium carbonate, mix homogeneously, tightens sealing lid; put in electric drying oven with forced convection, heat to reaction temperature 150 DEG C from room temperature, after isothermal reaction 6h; stop heating, naturally cool to room temperature, by mixture; with distilled water wash; dry, ethyl alcohol recrystallization, weigh; obtain white solid 1.95g (IV) 3, productivity 78%.Mp:169.5-72.0 DEG C; IR �� (cm-1): 3500-2500 (broad), 1614,1508,1471,1441,1408,1394,1310,1304,1290,1278,1260,1 180,1142,1034,982,836,749,722;1H-NMR(400MHz,DMSO-d6): 3.84 (s, 3H), 7.10 (d, 2H, J=8.8Hz), 7.49-7.53 (m, 3H), 8.00-8.20 (m, 4H) ppm;13C-NMR(125MHz,DMSO-d6): 55.2,114.2,121.4,125.9,127.5,128.7,129.3,129.7,157.5,160 .3ppm; Analysis:Calc.forC15H13N3O:C, 71.70; H, 5.21; N, 16.72; O, 6.37.Found:C, 71.88; H, 5.41; N, 16.67.
Comparative example, 2,5 diphenyloxazoles ((II) 1) synthesis
Separately or concurrently changing the temperature of embodiment 1, response time and mode of heating, other are identical with embodiment 1, preparation 2,5 diphenyloxazoles ((II) 1), and the result of preparation result and embodiment 1 is listed in the table below in 1 simultaneously:
Under table 1. different condition (II) 1 synthesis and productivity
It can be seen that reaction temperature and response time all affect productivity comparative example 1��3, solvent-thermal method productivity compared with oil bath backflow is used to be obviously improved.
Embodiment 18, substituted azole five-ring heterocycles derivant (II), (III), (IV) solution preparation
Antibacterial dosage form prepared by the present embodiment is solution, test compound is dissolved in DMSO, it is made into the concentration of 0.1% (m/v) in advance, is then diluted to 10,1 with 1% (m/v) acetic acid distilled water solution, 0.1mg/L3 kind concentration is as test sample, positive control drug norfloxacin (NF), is directly configured to 10,1 with 1% (m/v) acetic acid distilled water, 0.1mg/L3 kind concentration, blank group is 1% (m/v) acetum.
Prepared dilute solution agent is ready for use on following embodiment.
Embodiment 19, antibacterial activity evaluation to staphylococcus aureus
The antibacterial activity evaluation of staphylococcus aureus is adopted plate test method determination, use the dilute solution agent of each compound of embodiment 18 preparation, using beef extract-peptone as culture medium, cultivate 24h in 37 DEG C after inoculation, observe, record inhibition zone size, and compared with positive control drug norfloxacin (NF), evaluate the bacteriostatic activity height of test compound according to this, ++ represent high activity ,+represent medium activity ,-represent that activity is more weak. Preliminary pharmacological tests is in Table 2.
The anti-Staphylococcus aureus activity of table 2. compound (III) 1��(V) 4
Embodiment 20, antibacterial activity evaluation to colon bacillus
The antibacterial activity evaluation of colon bacillus is adopted plate test method determination, use the dilute solution agent of each compound of embodiment 18 preparation, using beef extract-peptone as culture medium, cultivate 24h in 37 DEG C after inoculation, observe, record inhibition zone size, and compared with positive control drug norfloxacin (NF), evaluate the bacteriostatic activity height of test compound according to this, ++ represent high activity ,+represent medium activity ,-represent that activity is more weak. Preliminary pharmacological tests is in Table 3.
The anti-colon bacillus activity of table 3. compound (III) 1��(V) 4
Embodiment 21, antibacterial activity evaluation to proteus vulgaris
The antibacterial activity evaluation of proteus vulgaris is adopted plate test method determination, use the dilute solution agent of each compound of embodiment 18 preparation, using beef extract-peptone as culture medium, cultivate 24h in 37 DEG C after inoculation, observe, record inhibition zone size, and compared with positive control drug norfloxacin (NF), evaluate the bacteriostatic activity height of test compound according to this, ++ represent high activity ,+represent medium activity ,-represent that activity is more weak.Preliminary pharmacological tests is in Table 4.
The anti-proteus vulgaris activity of table 4. compound (III) 1��(V) 4
Embodiment 22, substituted azole five-ring heterocycles derivant Photophysics evaluation
Investigated the photophysical property of substituted azole five-ring heterocycles derivant from fluorescence emission spectrum and uv-visible absorption spectra two aspect, substituted azole five-ring heterocycles derivant is dissolved in the fluorescence emission spectrogram in dichloromethane solution and uv-visible absorption spectra figure is shown in Fig. 1, Fig. 2 respectively.
As shown in Figure 1, (II) 1 in nine compounds tested, (II) 5, (II) 6, (III) 2, (III) 3, (III) 5, (IV) 3 and (IV) 4 luminescence all at ultraviolet region, the luminescence of the compound (III) 6 that nitro replaces, in visibility region, all belongs to the pi-electron transition of conjugated system. Simultaneously it is also seen that, the substituent groups different on the phenyl ring impact on launching wavelength is different, methoxyl group and methyl are little on launching wavelength impact, and inhale by force electrical group, the electronics making excited state disperses, excited energy step-down, thus causing that fluorescence emission wavelengths is elongated, red has been moved to visibility region 422nm place.
As shown in Figure 2, nine compounds (II) 1 being tested, (II) 5, (II) 6, (III) 2, (III) (III) 3, (III) 5, (III) 6, (IV) 3 and (IV) 4 have absworption peak in ultra-violet (UV) band, eight compounds are had to have absworption peak at about 280nm, and the compound (III) 6 that nitro replaces has absworption peak at 317nm place, all belong to the pi-electron transition of conjugated system. Simultaneously it can also be seen that substituent groups different on phenyl ring is different on the impact of absorbing wavelength, methoxyl group and methyl are little on absorbing wavelength impact, and inhale by force electrical nitro, the electronics making excited state disperses more, and excited energy is lower, thus causing that ultraviolet-ray visible absorbing wavelength is elongated.

Claims (10)

1. a substituted azole five-ring heterocycles derivant, shown in its structural formula such as formula (A):
Wherein, M is-O-,-S-or-NH-;
When M is-O-, described formula (A) is for shown in following structure formula II:
When M is-S-, described formula (A) is for shown in following structure formula III:
When M is-NH-, described formula (A) is for shown in following structure formula IV:
In described structural formula (A), (II), (III), (IV), X is-CR3Or-N=;
In described structural formula (A), (II), (III), (IV), R1��R2Be each independently selected from following group any one:
CH3-��CH3CH2-��CH3CH2CH2-��CH3(CH2)2CH2-��CH3(CH2)3CH2-��CH3(CH2)4CH2-��CH3(CH2)5CH2-��CH(CH3)2CH2CH2-��ClCH2-��ClCH2CH2-�� Cl2CHCH2CH2-��Cl3CCH2CH2-��
R3Any one in following group :-H,Substituted or unsubstituted phenyl;
Or, R1��R2��R3Combine as follows:
When X is-CR3Time, and work as R1During for substituted or unsubstituted phenyl, R2With R3It is connected to form six-membered ring structure.
2. substituted azole five-ring heterocycles derivant according to claim 1, it is characterised in that: described R1��R2Be each independently selected from following group any one:
CH3-��
3. substituted azole five-ring heterocycles derivant according to claim 1, it is characterised in that: described R1��R2Be each independently selected from following group any one:
CH3-��
4. the synthetic method of arbitrary described substituted azole five-ring heterocycles derivant in a claim 1-3:
By compound N-(2-oxo) amide derivatives (Ia) or 1,4 '-bishydrazide derivant (Ib) and cyclizing agent at solvent existent condition in closed reaction vessel, reacting 2-14h by solvent-thermal method at 70��180 DEG C, one pot prepares;
Described N-(2-oxo) amide derivatives (Ia) and Isosorbide-5-Nitrae ' structural formula of-bishydrazide derivant (Ib) is as follows:
Described cyclizing agent is selected from one of three class cyclizing agents, first kind cyclizing agent is cyclizing agent used by compound shown in composite structure formula II, Equations of The Second Kind cyclizing agent is cyclizing agent used by compound shown in composite structure formula III, and the 3rd class cyclizing agent is cyclizing agent used by compound shown in composite structure formula IV;
Described first kind cyclizing agent is selected from any one in phosphorus pentoxide, polyphosphoric acids, phosphorus oxychloride, Phosphorous chloride., phosphorus pentachloride, chlorosulfonic acid and trim,ethylchlorosilane;
Described Equations of The Second Kind cyclizing agent is selected from any one in phosphorus pentasulfide, thiourea and 2-TGA;
Described 3rd class cyclizing agent has any one in the aminated compounds ammonia of hydrogen, ammonium carbonate, ammonium hydrogen carbonate, ammonium nitrate, ammonium sulfate and ammonium hydrogen sulfate on ammonium salt or nitrogen;
Described solvent is selected from any one in cyclic ethers class, arene, chain ethers, amine and other solvents;
Described cyclic ether solvents includes oxolane and dioxane;
Described aromatic hydrocarbon solvent includes toluene, dimethylbenzene, sym-trimethylbenzene., chlorobenzene, bromobenzene and pyridine;
Described chain ether solvent includes ethylene glycol diethyl ether, butyl glycol ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether and dihydroxypropane single-ether;
Described amine solvent includes N,N-dimethylformamide and DMAC N,N' dimethyl acetamide;
Other kind solvents described include dimethyl sulfoxide and CHP.
5. synthetic method according to claim 4, it is characterised in that: described first kind cyclizing agent is selected from any one in phosphorus pentoxide, phosphorus oxychloride, Phosphorous chloride., phosphorus pentachloride, chlorosulfonic acid and trim,ethylchlorosilane; Described Equations of The Second Kind cyclizing agent is selected from phosphorus pentasulfide or thiourea; Described 3rd class cyclizing agent is selected from any one in ammonium hydrogen carbonate, ammonium nitrate and ammonium sulfate.
6. the synthetic method according to claim 4 or 5, it is characterized in that: described solvent is oxolane, dioxane, toluene, pyridine, chlorobenzene, dimethylbenzene, ethylene glycol diethyl ether, N, any one in dinethylformamide, N,N-dimethylacetamide and CHP.
7. the synthetic method according to claim 4 or 5, it is characterised in that: described solvent is any one in oxolane, toluene, pyridine, chlorobenzene, ethylene glycol diethyl ether and DMF.
8. the synthetic method according to claim 4 or 5, it is characterised in that: described solvent thermal reaction temperature is 100��170 DEG C, and the response time is 3��10h.
9. arbitrary described substituted azole five-ring heterocycles derivant application in preparation antibacterials in claim 1-3.
10. arbitrary described substituted azole five-ring heterocycles derivant application in preparing luminescent material in claim 1-3.
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JUAN F. SANZ-CERVERA ET AL.: "Solution versus Fluorous versus Solid-Phase Synthesis of 2,5-Disubstituted 1,3-Azoles. Preliminary Antibacterial Activity Studies", 《 J. ORG. CHEM.》 *

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