CN106543175B - Triaryl [1,2,4] triazole [1,5-a] pyridine derivate and preparation method thereof - Google Patents
Triaryl [1,2,4] triazole [1,5-a] pyridine derivate and preparation method thereof Download PDFInfo
- Publication number
- CN106543175B CN106543175B CN201610965720.0A CN201610965720A CN106543175B CN 106543175 B CN106543175 B CN 106543175B CN 201610965720 A CN201610965720 A CN 201610965720A CN 106543175 B CN106543175 B CN 106543175B
- Authority
- CN
- China
- Prior art keywords
- mmol
- triazole
- nmr
- mhz
- cdcl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The present invention relates to a kind of triaryl [1,2,4] triazole [1,5 a] pyridine derivates and preparation method thereof.The structural formula of the compound is：, wherein,.The derivative has triaryl structure and strong fluorescence, has been widely used in drug and material etc. tool.
Description
Technical field
The present invention relates to a kind of triaryl [1,2,4] triazole [1,5-a] pyridine derivates and preparation method thereof, such three
Aryl [1,2,4] triazole [1,5-a] pyridine derivate has good fluorescence property.
Technical background
Heterocyclic compound is current maximum organic chemistry branch, and is played in fields such as biology, drug, materials important
Effect.Wherein, nitrogenous compound in the application of medicine, pesticide and life science because with extensive bioactivity, having
Its only thick advantage is always the research emphasis of organic synthesis field.
So far, it has been found that many organic compounds have fluorescence phenomenon, and the new organic fluorescent material of specific function also obtains
To quick development and application.Fluorescent material is widely used in the fields such as science, material and industrial circle, such as fluorescent dye, light
Learn brightening agent, Organic Light Emitting Diode, bioluminescence label, fluorescence probe and pH fluorescent optical sensors etc..
1,2,4- triazole [1,5-a] pyridine structure is the important feature unit of many functional moleculars, pharmaceutical chemistry,
The fields such as material science are widely used.Traditional synthetic method is mostly on the basis of pyridine ring, then by anti-under different condition
Triazole ring should be closed.Such as J. Org. Chem. 2015, the method described in 80,7219-7225, N- aryl amidine class chemical combination
Object is in I2Single aryl 1,2,4- triazole [1,5-a] pyridine derivate is generated under the action of/IK, its main feature is that high yield itself
Ring-closure reaction；For another example J. Org. Chem. 2014, the method described in 79,4687-4693 are equally N- aryl amidine classes
The symphysis of object self loop is closed into single 1,2,4- triazole [1,5-a] pyridine derivate of aryl, feature is to use the efficiently quick oxygen of PIFA
Change forms N-N keys；For another example Eur. J. Org. Chem. 2005, the method described in 2005,3761-3765, using 2- pyrroles
The mode of piperidinyl amidine oxime itself cyclization, obtains monosubstituted 1,2,4- triazoles [1,5-a] pyridine derivate, and feature is at room temperature
It can carry out.But these methods all prepare more difficult there are raw material, and thinking is single, significantly limits expansion and the structure of substrate
The defects of derivatization.Nearest Synlett, 2013,24,1825-1829 report using the simple raw material one kettle way conjunction of multicomponent
Into two formyl carbomethoxy of diaryl 1,2,4- triazole [1,5-a] pyridine derivate, but can not be made of the present invention
Compound 3.It can be seen that it is always to the expansion of new [1,2,4] triazole [1,5-a] pyridine derivate and preparation method thereof
Hot spot in correlative study, particularly still without finding to use discovery using azine derivatives and alkene carbonitrile derivatives as raw material one kettle way
The method of triaryl [1,2,4] triazole [1,5-a] pyridine derivate is prepared.
The content of the invention
One of the objects of the present invention is to provide a kind of triaryl [1,2,4] triazole [1,5-a] pyridine derivates.
The second object of the present invention is the preparation method for providing the pyridine derivate.This method is with azine derivatives and alkene
Carbonitrile derivatives are raw material, are heated under the catalysis of the catalyst such as copper and react and obtain triaryl [1,2,4] triazole [1,5-a] pyrrole
The method of piperidine derivatives.
In order to achieve the above objectives, reaction equation of the invention is：
According to above-mentioned reactive mode, the present invention adopts the following technical scheme that：
A kind of [1,2,4] triazole [1,5-a] pyridine derivate with triaryl structure, it is characterised in that the derivative
Structural formula be：
In formula：
R1For：Hydrogen-based, C1-C18Alkyl, C1-C18Alkoxy, halogen or nitro；
R2For：Hydrogen-based, C1-C18Alkyl, C1-C18Alkoxy, halogen or trifluoromethyl；
R3For：Hydrogen-based or methyl.
A kind of method for preparing above-mentioned triaryl [1,2,4] triazole [1,5-a] pyridine derivate, it is characterised in that
This method concretely comprises the following steps：Compound 1 and compound 2 are pressed 1 with transition-metal catalyst：（1.5~2）：（0.2~0.5）
Molar ratio be dissolved in organic solvent, reacted at 80~120 DEG C 7~10 it is small when, the Molar number of solvent and compound it
Than for：10~30ml：1mmol；It is cooled and separated that obtain triaryl [1,2,4] triazole [1,5-a] after purification pyridine derived
Object；The structural formula of the compound 1 is：, wherein R4For：Hydrogen-based, methyl or second
Base, the structural formula of the compound 2 are：。
Above-mentioned catalyst is：Cu、Cu(OAc)2、Ag2O、MnO2、ZnO、FeCl3, CuCl, CuO, CuI or Zn (OAc)2。
Above-mentioned organic solvent is dimethyl sulfoxide (DMSO), N,N-dimethylformamide, 1,4- dioxane, glacial acetic acid or N- methyl
Pyrrolidones.
The preparation method of compound 1 refers to：Org. Lett., 2014, 16, 3532; J.
Electroanalytical Chem., 2015, 740, 105; Tetrahedron Lett., 2015, 56, 5512;
Synthesis, 2012, 44, 1501;Adv. Synth. Catal., 2013,355,2145. are prepared.
The preparation method of compound 2 refers to：Green Chem., 2012, 14, 2234; J. Mater. Chem.
A, 2015, 3, 17320; Tetrahedron Lett. 2014, 55, 4585; J. Saudi Chem. Soc.,
2014, 18, 541;New J. Chem., 2013,37,269. are prepared.
Triaryl [1,2,4] triazole [1,5-a] pyridine derivate maximum fluorescence in acetonitrile of present invention design synthesis
Emission wavelength works as R between 399-416nm1Or R2For alkoxy when the compound in acetonitrile maximum fluorescence emission wavelength send out
Raw red shift, in 455nm or so.
The compound fluorescence quantum yield of present invention design synthesis is higher, and phenyl ring is more in structure, in drug and material etc.
Aspect has potential application value.
Description of the drawings
Fig. 1 is compound 7- phenyl -2,5- two（4- methoxyphenyls）- [1,2,4] triazole [1,5-a] pyridine -8- first
Fluorescence excitation of the nitrile in acetonitrile（It is left）And transmitting（It is right）Spectrogram, sample concentration=3.7 × 10-8 Mol/L, λex/λem=274/452
Nm, 5/5 nm of slit.
Fig. 2 is compound 7- phenyl -2,5- two（4- trifluoromethyls）- [1,2,4] triazole [1,5-a] pyridine -8-
Fluorescence excitation of the formonitrile HCN in acetonitrile（It is left）And transmitting（It is right）Spectrogram, sample concentration=3.7 × 10-8 Mol/L, λex/λem=264/
398 nm, 5/5 nm of slit.
Fig. 3 is compound 7- phenyl -2,5- two（2- aminomethyl phenyls）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs
Fluorescence excitation in acetonitrile（It is left）And transmitting（It is right）Spectrogram, sample concentration=3.7 × 10-8 Mol/L, λex/λem=264/398
Nm, 5/5 nm of slit.
Fig. 4 is compound 7- phenyl -2,5- two（3- fluorophenyls）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs exist
Fluorescence excitation in acetonitrile（It is left）And transmitting（It is right）Spectrogram, sample concentration=3.7 × 10-8 Mol/L, λex/λem=264/398 nm,
5/5 nm of slit.
Fig. 5 is compound 2,5- diphenyl -7-（4- aminomethyl phenyls）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs
Fluorescence excitation in acetonitrile（It is left）And transmitting（It is right）Spectrogram, sample concentration=3.7 × 10-8 Mol/L, λex/λem=264/398
Nm, 5/5 nm of slit.
Fig. 6 is compound 2,5- diphenyl -7-（4- methoxyphenyls）- [1,2,4] triazole [1,5-a] pyridine -8- first
Fluorescence excitation of the nitrile in acetonitrile（It is left）And transmitting（It is right）Spectrogram, sample concentration=3.7 × 10-8 Mol/L, λex/λem=264/450
Nm, 5/5 nm of slit.
Specific embodiment
Embodiment one：(1E, 2E) -1,2- two (1- phenethyls) hydrazine 0.1180g (0.5 is added in dry round-bottomed flask
Mmol), 2- benzyls allyl dintrile 0.1540g (1.0 mmol), copper powder 0.0064g (0.1 mmol), are dissolved in 10mL dimethyl sulfoxides,
When 100 DEG C of reactions 8 are small, it is cooled and separated and obtains 2,5,7- triphenyl of target product-[1,2,4] triazole [1,5-a] after purification
Pyridine -8- formonitrile HCNs.White solid, yield：74%, 201.6-202.3 DEG C of fusing point.
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.41 – 8.34 (m, 2H), 8.13 (dd, J = 6.7, 3.0
Hz, 2H), 7.76 (dd, J = 7.8, 1.6 Hz, 2H), 7.65 – 7.60 (m, 3H), 7.60 – 7.53 (m,
3H), 7.52 – 7.45 (m, 3H), 7.27 (s, 1H)；
13C NMR (125 MHz, CDCl3) δ 165.61, 152.48, 149.18, 143.80, 135.85,
131.34, 130.96, 130.68, 130.29, 129.97, 129.51, 129.21, 128.80, 128.68,
128.64, 127.88, 114.74, 114.64, 96.61；
UV-vis (CHCl3) λmax /nm 264, 334; FT-IR ν/cm-1 (KBr): 3053, 2218,
1607, 1526, 1493, 1441, 1385, 1322, 1290, 1224, 767, 730, 692; MALDI-FTICR MSm/z Calcd for C25H16N4 M 372.1375, Found 372.1374。
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 334nm and 264nm, fluorescence emission peak 405nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.338.
Embodiment two：(1E, 2E) -1- benzylidenes -2- (1- phenethyls) hydrazine is added in dry round-bottomed flask
0.1110g (0.5 mmol), 2- benzyl allyl dintrile 0.1540g (1.0 mmol), copper powder 0.0064g (0.1 mmol), are dissolved in
10mL dimethyl sulfoxides when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 2,5,7- triphenyl-[1,2,4] after purification
Triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：65%, 201.6-202.3 DEG C of fusing point.
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.41 – 8.34 (m, 2H), 8.13 (dd, J = 6.7, 3.0
Hz, 2H), 7.76 (dd, J = 7.8, 1.6 Hz, 2H), 7.65 – 7.60 (m, 3H), 7.60 – 7.53 (m,
3H), 7.52 – 7.45 (m, 3H), 7.27 (s, 1H)；
13C NMR (125 MHz, CDCl3) δ 165.61, 152.48, 149.18, 143.80, 135.85,
131.34, 130.96, 130.68, 130.29, 129.97, 129.51, 129.21, 128.80, 128.68,
128.64, 127.88, 114.74, 114.64, 96.61；
UV-vis (CHCl3) λmax /nm 264, 334; FT-IR ν/cm-1 (KBr): 3053, 2218,
1607, 1526, 1493, 1441, 1385, 1322, 1290, 1224, 767, 730, 692; MALDI-FTICR MSm/z Calcd for C25H16N4 M 372.1375, Found 372.1374。
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 334nm and 264nm, fluorescence emission peak 405nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.338.
Embodiment three：(1E, 2E) -1,2- two (1- (4- methylbenzenes) ethylidene) hydrazine is added in dry round-bottomed flask
0.1320g (0.5 mmol), 2- benzyl allyl dintrile 0.1540g (1.0 mmol), copper powder 0.0064g (0.1 mmol), are dissolved in
10mL dimethyl sulfoxides when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 7- phenyl -2,5- bis- after purification（4- methyl
Phenyl）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：72%, 224.7-225.1 DEG C of fusing point.
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.26 (d, J = 8.1 Hz, 2H), 8.04 (d, J = 8.2
Hz, 2H), 7.75 (dt, J = 8.4, 2.2 Hz, 2H), 7.61 – 7.52 (m, 3H), 7.42 (d, J =
8.0 Hz, 2H), 7.29 (d, J = 7.9 Hz, 2H), 7.23 (s, 1H), 2.50 (s, 3H), 2.43 (s,
3H)；
13C NMR (125 MHz, CDCl3) δ 165.62, 152.50, 149.00, 143.84, 141.92,
140.87, 136.00, 130.18, 129.48, 129.44, 129.35, 129.16, 128.67, 128.13,
127.81, 127.24, 114.82, 114.19, 96.01, 21.64, 21.60；
UV-vis (CHCl3) λmax /nm 268, 339; FT-IR ν/cm-1 (KBr): 3024, 2908, 2858,
2216, 1607, 1498, 1445, 1377, 1282, 1176, 1114, 822, 754, 694; MALDI-FTICR MSm/z Calcd for C27H20N4 [M+H]+ 401.1761, Found 401.1767。
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 339nm and 268nm, fluorescence emission peak 416nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.316.
Example IV：(1E, 2E) -1,2- two (1- (4- methoxybenzenes) ethylidene) hydrazine is added in dry round-bottomed flask
0.1480g (0.5 mmol), 2- benzyl allyl dintrile 0.1540g (1.0 mmol), copper powder 0.0064g (0.1 mmol), are dissolved in
10mL dimethyl sulfoxides when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 7- phenyl -2,5- bis- after purification（4- methoxies
Base phenyl）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：76%, 221.9-222.1 DEG C of fusing point.
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.27 (d, J = 8.6 Hz, 2H), 8.12 (d, J = 8.7
Hz, 2H), 7.73 (d, J = 6.6 Hz, 2H), 7.54 (t, J = 6.8 Hz, 3H), 7.16 (s, 1H),
7.07 (d, J = 8.7 Hz, 2H), 6.96 (d, J = 8.6 Hz, 2H), 3.91 (s, 3H), 3.85 (s,
3H)；
13C NMR (125 MHz, CDCl3) δ 165.21, 161.93, 161.58, 152.56, 148.81,
143.32, 136.05, 131.20, 130.08, 129.34, 129.09, 128.64, 123.11, 122.59,
114.95, 114.11, 113.94, 113.50, 95.17, 55.53, 55.33；
UV-vis (CHCl3) λmax /nm 274, 350; FT-IR ν/cm-1 (KBr): 3050, 3004, 2220,
1606, 1501, 1450, 1295, 1250, 1171, 1117, 1014, 834, 763, 699 ; MALDI-FTICR
MS m/z Calcd for C27H20N4O2 M 432.1586, Found 432.1589.
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 350nm and 274nm, fluorescence emission peak 453nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.355.
Embodiment five：(1E, 2E) -1,2- two (1- (4- fluorobenzene) ethylidene) hydrazine is added in dry round-bottomed flask
0.1360g (0.5 mmol), 2- benzyl allyl dintrile 0.1540g (1.0 mmol), copper powder 0.0064g (0.1 mmol), are dissolved in
10mL dimethyl sulfoxides when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 7- phenyl -2,5- bis- after purification（4- fluorobenzene
Base）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：67%, 243.4-243.8 DEG C of fusing point.
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.36 (dd, J = 8.5, 5.5 Hz, 2H), 8.14 (dd, J
= 8.7, 5.3 Hz, 2H), 7.80 – 7.71 (m, 2H), 7.65 – 7.54 (m, 3H), 7.31 (t, J =
8.5 Hz, 2H), 7.25 (s, 1H), 7.18 (t, J= 8.6 Hz, 2H)；
19F NMR (470 MHz, DMSO) δ -108.49, -109.74; 13C NMR (125 MHz, DMSO) δ
164.15 (d, J FC = -240.7 Hz), 164.12 (d, J FC = -250.1 Hz), 163.61, 152.56,
149.68, 142.85, 135.95, 133.01 (d, J FC= 8.9 Hz), 130.79, 130.06 (d, J FC= 8.9
Hz), 129.49, 129.48, 127.50 (d, J FC = 3.3 Hz), 126.68 (d, J FC = 2.7 Hz),
116.62 (d, J FC = 21.9 Hz), 116.16 (d, J FC= 22.0 Hz), 115.78, 115.41, 96.02；
UV-vis (CHCl3) λmax /nm 264, 335; FT-IR ν/cm-1 (KBr): 3075, 2227, 1606,
1501, 1450, 1232, 1158, 840, 760, 695; MALDI-FTICR MS m/z Calcd for C25H14F2N4
[M+H]+ 409.1259, Found 409.1259.
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 335nm and 264nm, fluorescence emission peak 403nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.264.
Embodiment six：(1E, 2E) -1,2- two (1- (4- trifluoromethylbenzenes) ethylidene) is added in dry round-bottomed flask to join
Ammonia 0.1860g (0.5 mmol), 2- benzyl allyl dintrile 0.1540g (1.0 mmol), copper powder 0.0064g (0.1 mmol), it is molten
In 10mL dimethyl sulfoxides, when 100 DEG C of reactions 8 are small, it are cooled and separated and obtain target product 7- phenyl -2,5- bis- after purification（4- tri-
Trifluoromethylphenyl）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：54%, fusing point 230.6-231.0
℃。
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.47 (d, J = 8.1 Hz, 2H), 8.24 (d, J = 8.2
Hz, 2H), 7.90 (d, J = 8.2 Hz, 2H), 7.80 – 7.72 (m, 4H), 7.64 – 7.56 (m, 3H),
7.35 (s, 1H); 19F NMR (470 MHz, CDCl3) δ -62.80, -62.99；
13C NMR (125 MHz, CDCl3) δ 163.38, 151.36, 148.57, 141.24, 134.28,
133.05, 132.10 (q, J FC= 33.0 Hz), 132.04, 131.44 (q, J FC = 32.5 Hz), 129.63,
128.93, 128.90, 128.33, 127.61, 127.10, 124.83 (q, J FC = 3.8 Hz), 124.63 (q,J FC = 3.7 Hz), 122.90 (q, J FC = -272.4 Hz), 122.56 (q, J FC = -272.6 Hz),
114.64, 113.13, 96.82；
UV-vis (CHCl3) λmax /nm 263, 331; FT-IR ν/cm-1 (KBr): 3460, 2224, 1617,
1533, 1446, 1326, 1247, 1171, 1114, 1063, 1010, 846, 773, 700; MALDI-FTICR MSm/z Calcd for C27H14F6N4 M 508.1123, Found 508.1125.
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 331nm and 263nm, fluorescence emission peak 407nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.651.
Embodiment seven：(1E, 2E) -1,2- two (1- (4- methylbenzenes) propylidene) hydrazine is added in dry round-bottomed flask
0.1320g (0.5 mmol), 2- benzyl allyl dintrile 0.1540g (1.0 mmol), copper powder 0.0064g (0.1 mmol), are dissolved in
10mL dimethyl sulfoxides when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 6- methyl -2,5 after purification, and 7- triphenyls -
[1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：52%, 290.5-290.6 DEG C of fusing point.
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.29 – 8.21 (m, 2H), 7.67 – 7.50 (m, 8H),
7.46 – 7.39 (m, 5H), 2.03 (s, 3H)；
13C NMR (126 MHz, CDCl3) δ 164.94, 151.74, 149.81, 142.53, 135.92,
131.02, 130.38, 130.17, 130.12, 129.79, 129.47, 129.05, 128.80, 128.50,
128.48, 127.79, 120.98, 114.12, 99.71, 17.58；
UV-vis (CHCl3) λmax /nm 257, 326; FT-IR ν/cm-1 (KBr): 3056, 2963, 2852,
2223, 1607, 1519, 1481, 1439, 1327, 1261, 1011, 756, 745, 696; MALDI-FTICR MSm/z Calcd for C26H14N4 M 386.1531, Found 386.1535。
For sample in acetonitrile solution, ultraviolet characteristic absorption peak is 326nm and 257nm.
Embodiment eight：(1E, 2E) -1,2- two (1- (2- fluorobenzene) ethylidene) hydrazine is added in dry round-bottomed flask
0.1360g (0.5 mmol), 2- benzyl allyl dintrile 0.1540g (1.0 mmol), copper powder 0.0064g (0.1 mmol), are dissolved in
10mL dimethyl sulfoxides when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 7- phenyl -2,5- bis- after purification（2- fluorobenzene
Base）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：55%, 226.6-227.0 DEG C of fusing point.
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.32 (td, J = 7.6, 1.8 Hz, 1H), 7.98 (td, J
= 7.6, 1.7 Hz, 1H), 7.80 – 7.74 (m, 2H), 7.64 – 7.54 (m, 4H), 7.49 – 7.43 (m,
1H), 7.39 (td, J = 7.7, 1.0 Hz, 1H), 7.35 (d, J = 1.4 Hz, 1H), 7.34 – 7.30
(m, 1H), 7.28 (td, J= 7.8, 1.1 Hz, 1H), 7.23 – 7.17 (m, 1H)；
19F NMR (470 MHz, CDCl3) δ -110.59, -110.71；
13C NMR (125 MHz, CDCl3) δ 162.25 (d, J FC = 5.0 Hz), 160.94 (d, J FC =
257.0 Hz), 160.05 (d, J FC = 253.4 Hz), 151.44, 149.11, 138.58 (d, J FC = 1.2
Hz), 135.57, 133.15 (d, J FC = 8.7 Hz), 132.11 (d, J FC = 8.4 Hz), 131.46 (d, J FC
= 14.6 Hz), 131.45 (d, J FC = 13.9 Hz), 130.43, 129.25, 128.76, 124.36 (d, J FC
= 21.0 Hz), 124.33 (d, J FC = 21.1 Hz), 118.94 (d, J FC = 13.2 Hz), 118.21 (d,J FC = 11.2 Hz), 116.81 (d, J FC = 3.9 Hz), 116.63 (d, J FC = 21.4 Hz), 116.58 (d,J FC = 21.6 Hz), 114.34, 97.59; UV-vis (CHCl3) λmax/nm 258, 327；
FT-IR ν/cm-1 (KBr): 3070, 2224, 1614, 1579, 1530, 1598, 4181, 1316,
1227, 751, 698；
MALDI-FTICR MS m/z Calcd for C25H14F2N4 M 408.1187, Found 408.1176。
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 327nm and 258nm, fluorescence emission peak 399nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.286.
Embodiment nine：(1E, 2E) -1,2- two (1- (2- methylbenzenes) ethylidene) hydrazine is added in dry round-bottomed flask
0.1320g (0.5 mmol), 2- benzyl allyl dintrile 0.1540g (1.0 mmol), copper powder 0.0064g (0.1 mmol), are dissolved in
10mL dimethyl sulfoxides when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 7- phenyl -2,5- bis- after purification（2- methyl
Phenyl）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：62%, 182.7-183.1 DEG C of fusing point.
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.19 – 8.15 (m, 1H), 7.78 (dt, J = 8.5, 2.3
Hz, 2H), 7.61 – 7.55 (m, 3H), 7.49 (dd, J = 11.9, 4.5 Hz, 2H), 7.42 (d, J =
7.7 Hz, 1H), 7.37 (dd, J = 12.0, 4.4 Hz, 1H), 7.33 (dd, J = 7.4, 1.5 Hz, 1H),
7.29 (dd, J = 9.0, 7.6 Hz, 2H), 7.15 (d, J = 2.4 Hz, 1H), 2.64 (s, 3H), 2.29
(s, 3H)；
13C NMR (125 MHz, CDCl3) δ 166.80, 151.06, 148.93, 144.70, 138.20,
137.54, 135.76, 131.31, 131.23, 130.72, 130.68, 130.61, 130.31, 129.96,
129.76, 129.21, 129.17, 128.77, 126.04, 125.84, 115.70, 114.57, 96.94, 21.94,
20.11; UV-vis (CHCl3) λmax/nm 260, 325；
FT-IR ν/cm-1 (KBr); 3060, 2958, 2856, 2221, 1616, 1532, 1596, 1451,
1309, 1286, 768, 732, 699；
MALDI-FTICR MS m/z Calcd for C27H20N4 M 400.1688, Found 400.1679.
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 325nm and 260nm, fluorescence emission peak 403nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.469.
Embodiment ten：(1E, 2E) -1,2- two (1- (2- chlorobenzenes) ethylidene) hydrazine is added in dry round-bottomed flask
0.1520g (0.5 mmol), 2- benzyl allyl dintrile 0.1540g (1.0 mmol), copper powder 0.0064g (0.1 mmol), are dissolved in
10mL dimethyl sulfoxides when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 7- phenyl -2,5- bis- after purification（2- chlorobenzenes
Base）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：32%, 166.5-167.0 DEG C of fusing point.
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.04 (d, J = 6.6 Hz, 1H), 7.79 (d, J = 6.3
Hz, 2H), 7.69 (d, J = 7.2 Hz, 1H), 7.65 – 7.55 (m, 4H), 7.54 (t, J = 7.7 Hz,
1H), 7.49 (dd, J = 14.5, 7.7 Hz, 2H), 7.38 (dd, J = 9.4, 5.6 Hz, 2H), 7.31
(s, 1H)；
13C NMR (125 MHz, CDCl3) δ 164.33, 151.07, 149.08, 141.40, 135.52,
133.81, 133.68, 132.49, 132.07, 131.48, 131.05, 130.72, 130.48, 130.42,
130.12, 129.27, 128.80, 127.05, 126.73, 116.90, 114.23, 97.96; UV-vis (CHCl3)
λmax/nm 257, 321；
FT-IR ν/cm-1 (KBr): 3060, 2226, 1608, 1524, 1425, 1316, 1042, 746,
695；
MALDI-FTICR MS m/z Calcd for C25H14Cl2N4 M 440.0596, Found 400.0585。
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 321nm and 257nm, fluorescence emission peak 400nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.101.
Embodiment 11：(1E, 2E) -1,2- two (1- (3- fluorobenzene) ethylidene) hydrazine is added in dry round-bottomed flask
0.1360g (0.5 mmol), 2- benzyl allyl dintrile 0.1540g (1.0 mmol), copper powder 0.0064g (0.1 mmol), are dissolved in
10mL dimethyl sulfoxides when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 7- phenyl -2,5- bis- after purification（3- fluorobenzene
Base）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：54%, 232.6-232.7 DEG C of fusing point.
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.19 – 8.13 (m, 1H), 8.05 (ddd, J = 9.7,
2.5, 1.5 Hz, 1H), 7.93 – 7.85 (m, 2H), 7.79 – 7.73 (m, 2H), 7.64 – 7.54 (m,
4H), 7.47 (td, J = 8.0, 5.8 Hz, 1H), 7.34 (tdd, J = 8.4, 2.5, 0.8 Hz, 1H),
7.31 (s, 1H), 7.22 – 7.15 (m, 1H)；
19F NMR (470 MHz, CDCl3) δ -112.11, -113.23；
13C NMR (125 MHz, CD2Cl2) δ 164.37 (d, J FC = 3.1 Hz), 163.05 (d, J FC =
245.3 Hz), 162.54 (d, J FC = 246.7 Hz), 152.47, 149.55, 142.39 (d, J FC = 2.6
Hz), 135.69, 132.69 (d, J FC = 8.5 Hz), 132.18 (d, J FC= 8.5 Hz), 130.61 (d, J FC
= 8.3 Hz), 130.52 (d, J FC = 8.2 Hz), 130.46, 129.19, 128.71, 125.37 (d, J FC =
3.1 Hz), 123.49 (d, J FC = 3.0 Hz), 118.31 (d, J FC = 21.1 Hz), 117.60 (d, J FC =
21.2 Hz), 116.63 (d, J FC = 24.2 Hz), 115.48, 114.45 (d, J FC = 23.5 Hz),
114.38, 97.30；
UV-vis (CHCl3) λmax /nm 264, 332; FT-IR ν/cm-1 (KBr); 3062, 2226,
1613, 1583, 1527, 1468, 1431, 1377, 1318, 1240, 1205, 865, 791, 756, 689；
MALDI-FTICR MS m/z Calcd for C25H14F2N4 M 408.1187, Found 408.1177。
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 332nm and 264nm, fluorescence emission peak 401nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.663.
Embodiment 12：(1E, 2E) -1,2- two (1- (3- methoxybenzenes) ethylidene) is added in dry round-bottomed flask to join
Ammonia 0.1480g (0.5 mmol), 2- benzyl allyl dintrile 0.1540g (1.0 mmol), copper powder 0.0064g (0.1 mmol), it is molten
In 10mL dimethyl sulfoxides, when 100 DEG C of reactions 8 are small, it are cooled and separated and obtain target product 7- phenyl -2,5- bis- after purification（3- first
Phenyl）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：56%, fusing point 185.1-185.2
℃。
Structural formula：
1H NMR (500 MHz, CDCl3) δ 7.99 – 7.94 (m, 1H), 7.91 (dd, J = 2.5, 1.4
Hz, 1H), 7.79 – 7.73 (m, 2H), 7.73 – 7.70 (m, 1H), 7.67 – 7.62 (m, 1H), 7.62
– 7.55 (m, 3H), 7.51 (t, J = 8.0 Hz, 1H), 7.39 (t, J = 7.9 Hz, 1H), 7.28 (s,
1H), 7.15 (ddd, J = 8.3, 2.5, 0.8 Hz, 1H), 7.03 (ddd, J = 8.3, 2.6, 0.9 Hz,
1H), 3.92 (d, J= 2.5 Hz, 6H)；
13C NMR (125 MHz, CDCl3) δ 165.46, 159.85, 159.64, 152.45, 149.16,
143.59, 135.83, 132.06, 131.28, 130.31, 129.89, 129.74, 129.22, 128.69,
121.80, 120.34, 117.17, 117.12, 114.97, 114.81, 114.63, 112.48, 96.65, 55.57,
55.49；
UV-vis (CHCl3) λmax /nm 263, 338; FT-IR ν/cm-1 (KBr): 3050, 3004, 2936,
2840, 2220, 1610, 1501, 1450, 1384, 1495, 1250, 1171, 1117, 1024, 834, 763,
699；
MALDI-FTICR MS m/z Calcd for C27H20N4O2 M 432.1586, Found 432.1577.
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 338nm and 263nm, fluorescence emission peak 457nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.112.
Embodiment 13：(1E, 2E) -1,2- two (1- (3- bromobenzenes) ethylidene) hydrazine is added in dry round-bottomed flask
0.1960g (0.5 mmol), 2- benzyl allyl dintrile 0.1540g (1.0 mmol), copper powder 0.0064g (0.1 mmol), are dissolved in
10mL dimethyl sulfoxides when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 7- phenyl -2,5- bis- after purification（3- bromobenzenes
Base）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：55%, 257.5-257.6 DEG C of fusing point.
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.51 (t, J = 1.7 Hz, 1H), 8.32 – 8.28 (m,
1H), 8.19 (t, J = 1.8 Hz, 1H), 8.08 (ddd, J = 7.9, 1.7, 1.0 Hz, 1H), 7.79 –
7.74 (m, 3H), 7.64 – 7.57 (m, 4H), 7.52 (t, J = 8.0 Hz, 1H), 7.38 (t, J = 7.9
Hz, 1H), 7.29 (s, 1H)；
13C NMR (125 MHz, CD2Cl2) δ 164.12, 152.44, 149.61, 142.24, 135.66,
134.26, 133.69, 132.72, 132.22, 132.04, 130.48, 130.45, 130.39, 129.20,
128.71, 128.25, 126.35, 122.80, 122.64, 115.54, 114.36, 97.39；
UV-vis (CHCl3) λmax /nm 265, 333; FT-IR ν/cm-1 (KBr): 3069, 2229,
1617, 1559, 1520, 1460, 1323, 1290, 762, 689, 597, 513；
MALDI-FTICR MS m/z Calcd for C25H14Br2N4 M 527.9585, Found 527.9569。
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 333nm and 265nm, fluorescence emission peak 405nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.171.
Embodiment 14：(1E, 2E) -1,2- two (1- phenethyls) hydrazine 0.1180g is added in dry round-bottomed flask
(0.5 mmol)、2-（4- methyl benzylidenes）Malononitrile 0.1680g (1.0 mmol), copper powder 0.0064g (0.1 mmol),
10mL dimethyl sulfoxides are dissolved in, when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 2 after purification, 5- diphenyl -7-（4-
Aminomethyl phenyl）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：67%, fusing point 217.0-217.6
℃。
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.38 – 8.32 (m, 2H), 8.11 (dt, J = 8.1, 3.4
Hz, 2H), 7.66 (d, J = 8.1 Hz, 2H), 7.63 – 7.57 (m, 3H), 7.51 – 7.44 (m, 3H),
7.38 (d, J= 7.9 Hz, 2H), 7.25 (s, 1H), 2.46 (s, 3H)；
13C NMR (125 MHz, CDCl3) δ 165.47, 152.53, 149.21, 143.66, 140.71,
132.94, 131.26, 131.01, 130.61, 130.01, 129.90, 129.49, 128.76, 128.61,
128.58, 127.85, 114.82, 114.70, 96.27, 21.42；
UV-vis (CHCl3) λmax/nm 267, 335；
FT-IR ν/cm-1 (KBr):3067, 3032, 2225, 1611, 1527, 1440, 1286, 1228,
1027, 831, 767, 723, 686；
MALDI-FTICR MS m/z Calcd for C26H18N4 M 386.1531, Found 386.1536。
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 335nm and 267nm, fluorescence emission peak 408nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.711.
Embodiment 15：(1E, 2E) -1- benzylidenes -2- (1- phenethyls) hydrazine is added in dry round-bottomed flask
0.1110g (0.5 mmol)、2-（4- methyl benzylidenes）Malononitrile 0.1680g (1.0 mmol), copper powder 0.0064g
(0.1 mmol) is dissolved in 10mL dimethyl sulfoxides, when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 2,5- after purification
Diphenyl -7-（4- aminomethyl phenyls）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：65%, fusing point
217.0-217.6℃。
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.38 – 8.32 (m, 2H), 8.11 (dt, J = 8.1, 3.4
Hz, 2H), 7.66 (d, J = 8.1 Hz, 2H), 7.63 – 7.57 (m, 3H), 7.51 – 7.44 (m, 3H),
7.38 (d, J= 7.9 Hz, 2H), 7.25 (s, 1H), 2.46 (s, 3H)；
13C NMR (125 MHz, CDCl3) δ 165.47, 152.53, 149.21, 143.66, 140.71,
132.94, 131.26, 131.01, 130.61, 130.01, 129.90, 129.49, 128.76, 128.61,
128.58, 127.85, 114.82, 114.70, 96.27, 21.42；
UV-vis (CHCl3) λmax/nm 267, 335；
FT-IR ν/cm-1 (KBr):3067, 3032, 2225, 1611, 1527, 1440, 1286, 1228,
1027, 831, 767, 723, 686；
MALDI-FTICR MS m/z Calcd for C26H18N4 M 386.1531, Found 386.1536.
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 335nm and 267nm, fluorescence emission peak 408nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.711.
Embodiment 16：(1E, 2E) -1,2- two (1- phenethyls) hydrazine 0.1180g is added in dry round-bottomed flask
(0.5 mmol)、2-（4- methoxybenzylidenes）Malononitrile 0.1840g (1.0 mmol), copper powder 0.0064g (0.1
Mmol), 10mL dimethyl sulfoxides are dissolved in, when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 2 after purification, 5- hexichol
Base -7-（4- methoxyphenyls）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.Colorless solid, yield：59%, fusing point
251.0-251.3℃。
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.37 (dt, J = 8.9, 2.8 Hz, 2H), 8.15 – 8.08
(m, 2H), 7.77 – 7.71 (m, 2H), 7.65 – 7.58 (m, 3H), 7.52 – 7.46 (m, 3H), 7.25
(s, 1H), 7.12 – 7.07 (m, 2H), 3.91 (s, 3H)；
13C NMR (126 MHz, CDCl3) δ 165.50, 161.38, 152.66, 148.90, 143.65,
131.28, 131.09, 130.64, 130.24, 130.07, 129.52, 128.80, 128.65, 128.05,
127.89, 115.04, 114.71, 114.64, 95.87, 55.55；
UV-vis (CHCl3) λmax /nm 262, 340; FT-IR ν/cm-1 (KBr):3069, 2988, 2933,
2841, 2224, 1604, 1523, 1487, 1434, 1380, 1291, 1249, 1176, 1116, 1016, 837,
771, 724, 703, 686；
MALDI-FTICR MS m/z Calcd for C26H18N4O [M+H]+ 403.1553, Found
403.1554。
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 340nm and 262nm, fluorescence emission peak 452nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.430.
Embodiment 17：(1E, 2E) -1,2- two (1- phenethyls) hydrazine 0.1180g is added in dry round-bottomed flask
(0.5 mmol)、2-（4- ethoxybenzene methylene）Malononitrile 0.1980g (1.0 mmol), copper powder 0.0064g (0.1
Mmol), 10mL dimethyl sulfoxides are dissolved in, when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 2 after purification, 5- hexichol
Base -7-（4- ethoxyl phenenyls）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：62%, fusing point
226.1-226.6℃。
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.39 – 8.33 (m, 2H), 8.14 – 8.08 (m, 2H),
7.75 – 7.70 (m, 2H), 7.64 – 7.59 (m, 3H), 7.51 – 7.45 (m, 3H), 7.24 (s, 1H),
7.09 – 7.04 (m, 2H), 4.13 (q, J = 7.0 Hz, 2H), 1.47 (t, J= 7.0 Hz, 3H)；
13C NMR (125 MHz, CDCl3) δ 165.41, 160.76, 152.63, 148.89, 143.57,
131.23, 131.06, 130.58, 130.19, 130.05, 129.49, 128.75, 128.61, 127.84,
127.78, 115.12, 115.05, 114.63, 95.70, 63.78, 14.75；
UV-vis (CHCl3) λmax/nm 262, 341；
FT-IR ν/cm-1 (KBr): 3071, 3034, 2980, 2925, 2881, 2228, 1604, 1522,
1484, 1435, 1833, 1294, 1247, 1171, 1037, 841, 772, 724, 703, 687；
MALDI-FTICR MS m/z Calcd for C27H20N4O M 416.1634, Found 416.1631。
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 341nm and 262nm, fluorescence emission peak 455nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.439.
Embodiment 18：(1E, 2E) -1,2- two (1- phenethyls) hydrazine 0.1180g is added in dry round-bottomed flask
(0.5 mmol)、2-（4- bromobenzene methylene）Malononitrile 0.2320g (1.0 mmol), copper powder 0.0064g (0.1 mmol), it is molten
In 10mL dimethyl sulfoxides, when 100 DEG C of reactions 8 are small, it are cooled and separated and obtain target product 2 after purification, 5- diphenyl -7-（4- bromines
Phenyl）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：66%, 236.1-236.2 DEG C of fusing point.
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.39 – 8.33 (m, 2H), 8.15 – 8.08 (m, 2H),
7.76 – 7.69 (m, 2H), 7.67 – 7.60 (m, 5H), 7.53 – 7.46 (m, 3H), 7.22 (s, 1H)；
13C NMR (125 MHz, CDCl3) δ 165.72, 152.33, 147.79, 144.02, 134.65,
132.46, 131.46, 130.77, 130.75, 130.19, 129.82, 129.49, 128.82, 128.64,
127.86, 125.02, 114.42, 114.26, 96.47；
UV-vis (CHCl3) λmax/nm 268, 336；
FT-IR ν/cm-1 (KBr): 3078, 2223, 1612, 1527, 1484, 1438, 1388, 1289,
1224, 1065, 830, 766, 721, 688；
MALDI-FTICR MS m/z Calcd for C25H15BrN4 M 450.0480, Found 450.0486.
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 336nm and 268nm, fluorescence emission peak 408nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.143.
Embodiment 19：(1E, 2E) -1- benzylidenes -2- (1- phenethyls) hydrazine is added in dry round-bottomed flask
0.1110g (0.5 mmol)、2-（4- bromobenzene methylene）Malononitrile 0.2320g (1.0 mmol), copper powder 0.0064g (0.1
Mmol), 10mL dimethyl sulfoxides are dissolved in, when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 2 after purification, 5- hexichol
Base -7-（4- bromophenyls）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：63%, fusing point 236.1-
236.2℃。
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.39 – 8.33 (m, 2H), 8.15 – 8.08 (m, 2H),
7.76 – 7.69 (m, 2H), 7.67 – 7.60 (m, 5H), 7.53 – 7.46 (m, 3H), 7.22 (s, 1H)；
13C NMR (125 MHz, CDCl3) δ 165.72, 152.33, 147.79, 144.02, 134.65,
132.46, 131.46, 130.77, 130.75, 130.19, 129.82, 129.49, 128.82, 128.64,
127.86, 125.02, 114.42, 114.26, 96.47；
UV-vis (CHCl3) λmax /nm 268, 336; FT-IR ν/cm-1 (KBr): 3078, 2223,
1612, 1527, 1484, 1438, 1388, 1289, 1224, 1065, 830, 766, 721, 688；
MALDI-FTICR MS m/z Calcd for C25H15BrN4 M 450.0480, Found 450.0486。
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 336nm and 268nm, fluorescence emission peak 408nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.143.
Embodiment 20：(1E, 2E) -1,2- two (1- phenethyls) hydrazine 0.1180g is added in dry round-bottomed flask
(0.5 mmol)、2-（4- fluorobenzylidenes）Malononitrile 0.1720g (1.0 mmol), copper powder 0.0064g (0.1 mmol), it is molten
In 10mL dimethyl sulfoxides, when 100 DEG C of reactions 8 are small, it are cooled and separated and obtain target product 2 after purification, 5- diphenyl -7-（4- fluorine
Phenyl）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：71%, 237.2-237.8 DEG C of fusing point.
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.41 – 8.33 (m, 2H), 8.12 (dd, J = 6.5, 3.2
Hz, 2H), 7.80 – 7.71 (m, 2H), 7.68 – 7.58 (m, 3H), 7.53 – 7.46 (m, 3H), 7.29
(d, J= 8.5 Hz, 2H), 7.23 (s, 1H)；
19F NMR (470 MHz, CDCl3) δ -109.71; 13C NMR (125 MHz, CDCl3) δ 165.72,
163.94 (d, J = -251.8 Hz), 152.40, 148.04, 143.94, 131.91 (d, J = 3.4 Hz),
131.44, 130.85, 130.76 (d, J = 8.6 Hz), 130.75, 129.89, 129.51, 128.84,
128.67, 127.89, 116.45 (d, J = 22.0 Hz), 114.56, 114.52, 96.56; UV-vis
(CHCl3) λmax/nm 265, 335；
FT-IR ν/cm-1 (KBr): 3068, 2224, 1606, 1520, 1443, 1380, 1300, 1231,
1160, 1111, 841, 765, 723, 688；
MALDI-FTICR MS m/z Calcd for C25H15FN4 M 390.1283, Found 390.1285.
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 335nm and 265nm, fluorescence emission peak 404nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.269.
Embodiment 21：(1E, 2E) -1- benzylidenes -2- (1- phenethyls) hydrazine is added in dry round-bottomed flask
0.1110g (0.5 mmol)、2-（4- fluorobenzylidenes）Malononitrile 0.1720g (1.0 mmol), copper powder 0.0064g (0.1
Mmol), 10mL dimethyl sulfoxides are dissolved in, when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 2 after purification, 5- hexichol
Base -7-（4- fluorophenyls）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：61%, fusing point 237.2-
237.8℃。
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.41 – 8.33 (m, 2H), 8.12 (dd, J = 6.5, 3.2
Hz, 2H), 7.80 – 7.71 (m, 2H), 7.68 – 7.58 (m, 3H), 7.53 – 7.46 (m, 3H), 7.29
(d, J= 8.5 Hz, 2H), 7.23 (s, 1H)；
19F NMR (470 MHz, CDCl3) δ -109.71; 13C NMR (125 MHz, CDCl3) δ 165.72,
163.94 (d, J FC = -251.8 Hz), 152.40, 148.04, 143.94, 131.91 (d, J FC = 3.4 Hz),
131.44, 130.85, 130.76 (d, J FC = 8.6 Hz), 130.75, 129.89, 129.51, 128.84,
128.67, 127.89, 116.45 (d, J FC= 22.0 Hz), 114.56, 114.52, 96.56；
UV-vis (CHCl3) λmax/nm 265, 335；
FT-IR ν/cm-1 (KBr): 3068, 2224, 1606, 1520, 1443, 1380, 1300, 1231,
1160, 1111, 841, 765, 723, 688；
MALDI-FTICR MS m/z Calcd for C25H15FN4 M 390.1283, Found 390.1285.
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 335nm and 265nm, fluorescence emission peak 404nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.269.
Embodiment 22：(1E, 2E) -1,2- two (1- phenethyls) hydrazine 0.1180g is added in dry round-bottomed flask
(0.5 mmol)、2-（4- nitro benzylidenes）Malononitrile 0.1990g (1.0 mmol), copper powder 0.0064g (0.1 mmol),
10mL dimethyl sulfoxides are dissolved in, when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 2 after purification, 5- diphenyl -7-（4-
Nitrobenzophenone）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.Yellow solid, yield：54%, fusing point 296.8-297.1
℃。
Structural formula：
1H NMR (500 MHz, CD2Cl2) δ 8.45 (d, J = 8.7 Hz, 2H), 8.40 – 8.33 (m,
2H), 8.18 – 8.11 (m, 2H), 7.96 (d, J = 8.6 Hz, 2H), 7.66 (d, J = 5.4 Hz, 3H),
7.59 – 7.49 (m, 3H), 7.30 (s, 1H)；
13C NMR (125 MHz, CD2Cl2) δ 165.84, 152.25, 148.81, 146.65, 144.49,
142.03, 131.62, 130.94, 130.70, 129.99, 129.84, 129.56, 128.86, 128.81,
127.75, 124.26, 114.31, 114.06, 97.10；
UV-vis (CHCl3) λmax /nm 262, 339; FT-IR ν/cm-1 (KBr): 3062, 2227, 1605,
1523, 1440, 1343, 1303, 1209, 1109, 858, 748, 699; MALDI-FTICR MS m/z Calcd
for C25H15N5O2 [M+H]+ 418.1299, Found 418.1300。
For sample in acetonitrile solution, ultraviolet characteristic absorption peak is 339nm and 262nm.
Embodiment 23：(1E, 2E) -1,2- two (1- phenethyls) hydrazine 0.1180g is added in dry round-bottomed flask
(0.5 mmol)、2-（3- bromobenzene methylene）Malononitrile 0.2320g (1.0 mmol), copper powder 0.0064g (0.1 mmol), it is molten
In 10mL dimethyl sulfoxides, when 100 DEG C of reactions 8 are small, it are cooled and separated and obtain target product 2 after purification, 5- diphenyl -7-（3- bromines
Phenyl）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：59%, 205.7-205.8 DEG C of fusing point.
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.40 – 8.34 (m, 2H), 8.13 (dd, J = 6.5, 3.2
Hz, 2H), 7.84 (t, J = 1.8 Hz, 1H), 7.75 – 7.71 (m, 1H), 7.70 (ddd, J = 8.0,
1.8, 0.9 Hz, 1H), 7.66 – 7.60 (m, 3H), 7.52 – 7.48 (m, 3H), 7.47 (t, J = 7.9
Hz, 1H), 7.23 (s, 1H)；
13C NMR (125 MHz, CDCl3) δ 165.83, 152.30, 147.35, 144.11, 137.78,
133.27, 131.52, 131.45, 130.80, 130.75, 130.71, 129.83, 129.53, 128.86,
128.68, 127.92, 127.44, 123.23, 114.34, 114.22, 96.83；
UV-vis (CHCl3) λmax/nm 264, 335；
FT-IR ν/cm-1 (KBr): 3046, 2219, 1609, 1571, 1524, 1442, 1371, 1331,
1291, 1072, 791, 758, 686；
MALDI-FTICR MS m/z Calcd for C25H15BrN4 [M+H]+ 451.0553, Found
451.0553。
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 335nm and 264nm, fluorescence emission peak 410nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.246.
Embodiment 24：(1E, 2E) -1,2- two (1- phenethyls) hydrazine 0.1180g is added in dry round-bottomed flask
(0.5 mmol)、2-（2- nitro benzylidenes）Malononitrile 0.1990g (1.0 mmol), copper powder 0.0064g (0.1 mmol),
10mL dimethyl sulfoxides are dissolved in, when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 2 after purification, 5- diphenyl -7-（2-
Nitrobenzophenone）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.Yellow solid, yield：57%, fusing point 200.0-200.2
℃。
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.41 – 8.35 (m, 2H), 8.31 (dd, J = 8.3, 1.1
Hz, 1H), 8.13 – 8.06 (m, 2H), 7.85 (td, J = 7.6, 1.3 Hz, 1H), 7.79 – 7.73 (m,
1H), 7.64 – 7.62 (m, 1H), 7.61 (q, J = 2.8 Hz, 2H), 7.60 – 7.57 (m, 1H), 7.53
– 7.47 (m, 3H), 7.06 (s, 1H)；
13C NMR (125 MHz, CDCl3) δ 165.84, 151.70, 147.49, 146.60, 144.01,
134.03, 131.75, 131.55, 131.38, 131.10, 130.83, 130.58, 129.82, 129.62,
128.81, 128.70, 127.94, 125.61, 113.73, 113.51, 98.02；
UV-vis (CHCl3) λmax/nm 255, 332；
FT-IR ν/cm-1 (KBr): 3054, 2224, 1613, 1522, 1440, 1341, 1297, 1198,
1025, 754, 707, 691；
MALDI-FTICR MS m/z Calcd for C25H15N5O2 [M+H]+ 418.1299, Found
418.1292。
For sample in acetonitrile solution, ultraviolet characteristic absorption peak is 332nm and 255nm.
Embodiment 25：(1E, 2E) -1,2- two (1- phenethyls) hydrazine 0.1180g is added in dry round-bottomed flask
(0.5 mmol)、2-（3- methyl benzylidenes）Malononitrile 0.1680g (1.0 mmol), copper powder 0.0064g (0.1 mmol),
10mL dimethyl sulfoxides are dissolved in, when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 2 after purification, 5- diphenyl -7-（3-
Aminomethyl phenyl）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.Light yellow solid, yield：63%, fusing point 202.6-202.8
℃。
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.40 – 8.35 (m, 2H), 8.16 – 8.10 (m, 2H),
7.65 – 7.60 (m, 3H), 7.57 (d, J = 8.2 Hz, 1H), 7.55 (s, 1H), 7.51 – 7.44 (m,
4H), 7.37 (d, J= 7.6 Hz, 1H), 7.27 (s, 1H), 2.49 (s, 3H)；
13C NMR (125 MHz, CDCl3) δ 165.56, 152.49, 149.37, 143.69, 139.07,
135.83, 131.30, 131.04, 131.00, 130.65, 130.01, 129.51, 129.21, 129.10,
128.79, 128.63, 127.88, 125.83, 114.78, 114.65, 96.56, 21.50；
UV-vis (CHCl3) λmax/nm 265, 334；
FT-IR ν/cm-1 (KBr): 3065, 2916, 2849, 2216, 1607, 1523, 1492, 1438,
1332, 1293, 1258, 1027, 789, 764, 722, 691；
MALDI-FTICR MS m/z Calcd for C26H18N4 [M+H]+ 387.1604, Found 387.1604。
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 334nm and 265nm, fluorescence emission peak 407nm.With color
Propylhomoserin is standard, measures its quantum yield Φ=0.232.
Embodiment 26：(1E, 2E) -1,2- two (1- phenethyls) hydrazine 0.1180g is added in dry round-bottomed flask
(0.5 mmol)、2-（2- methoxybenzylidenes）Malononitrile 0.1840g (1.0 mmol), copper powder 0.0064g (0.1
Mmol), 10mL dimethyl sulfoxides are dissolved in, when 100 DEG C of reactions 8 are small, are cooled and separated and obtain target product 2 after purification, 5- hexichol
Base -7-（2- methoxyphenyls）- [1,2,4] triazole [1,5-a] pyridine -8- formonitrile HCNs.White solid, yield：70%, fusing point
201.4-201.5℃。
Structural formula：
1H NMR (500 MHz, CDCl3) δ 8.38 (dd, J = 6.5, 3.0 Hz, 2H), 8.12 (dd, J
= 6.6, 2.9 Hz, 2H), 7.64 – 7.58 (m, 3H), 7.55 – 7.50 (m, 1H), 7.49 (dd, J =
4.8, 1.6 Hz, 3H), 7.45 (dd, J = 7.5, 1.5 Hz, 1H), 7.25 (s, 1H), 7.14 (t, J =
7.5 Hz, 1H), 7.10 (d, J= 8.3 Hz, 1H), 3.91 (s, 3H)；
13C NMR (125 MHz, CDCl3) δ 165.31, 156.41, 152.20, 146.76, 143.21,
131.73, 131.16, 131.12, 130.60, 130.56, 130.13, 129.53, 128.72, 128.62,
127.87, 124.90, 121.08, 116.04, 114.52, 111.68, 99.06, 55.62；
UV-vis (CHCl3) λmax/nm 262, 336；
FT-IR ν/cm-1 (KBr): 3041, 2921, 2845, 2228, 1613, 1524, 1445, 1296,
1255, 1018, 747, 686；
MALDI-FTICR MS m/z Calcd for C26H18N4O [M+H]+ 403.1553, Found 403.1548.
Sample is in acetonitrile solution, and ultraviolet characteristic absorption peak is 336nm and 262nm, fluorescence emission peak 457nm.
Claims (3)
1. a kind of preparation method of [1,2,4] triazole [1,5-a] pyridine derivate with triaryl structure, the derivative
Structural formula is：
In formula：
R1For：Hydrogen-based, C1-C18Alkyl, C1-C18Alkoxy, halogen or nitro；
R2For：Hydrogen-based, C1-C18Alkyl, C1-C18Alkoxy, halogen or trifluoromethyl；
R3For：Hydrogen-based or methyl；
It is characterized in that this method concretely comprises the following steps：Compound 1 and compound 2 are pressed 1 with transition-metal catalyst：（1.5~
2）：（0.2~0.5）Molar ratio be dissolved in organic solvent, reacted at 80~120 DEG C 7~10 it is small when, solvent and compound
The ratio between Molar number be：10~30ml：1mmol；Be cooled and separated obtain after purification triaryl [1,2,4] triazole [1,
5-a] pyridine derivate；The structural formula of the compound 1 is：, wherein R4For：Hydrogen
Base, methyl or ethyl, the structural formula of the compound 2 are：。
2. according to the method described in claim 1, it is characterized in that the catalyst is：Cu、Cu(OAc)2、Ag2O、MnO2、
ZnO、FeCl3, CuCl, CuO, CuI or Zn (OAc)2。
3. according to the method described in claim 1, it is characterized in that the organic solvent for dimethyl sulfoxide (DMSO), N, N- dimethyl methyls
Amide, 1,4- dioxane, glacial acetic acid or N-Methyl pyrrolidone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610965720.0A CN106543175B (en) | 2016-10-28 | 2016-10-28 | Triaryl [1,2,4] triazole [1,5-a] pyridine derivate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610965720.0A CN106543175B (en) | 2016-10-28 | 2016-10-28 | Triaryl [1,2,4] triazole [1,5-a] pyridine derivate and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106543175A CN106543175A (en) | 2017-03-29 |
| CN106543175B true CN106543175B (en) | 2018-06-01 |
Family
ID=58394402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610965720.0A Expired - Fee Related CN106543175B (en) | 2016-10-28 | 2016-10-28 | Triaryl [1,2,4] triazole [1,5-a] pyridine derivate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106543175B (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3926770A1 (en) * | 1989-08-12 | 1991-02-14 | Basf Ag | (1,2,4) TRIAZOLO (1,5-A) PYRIDINE |
| US6355653B1 (en) * | 1999-09-06 | 2002-03-12 | Hoffmann-La Roche Inc. | Amino-triazolopyridine derivatives |
-
2016
- 2016-10-28 CN CN201610965720.0A patent/CN106543175B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN106543175A (en) | 2017-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Singh et al. | Advances of azide-alkyne cycloaddition-click chemistry over the recent decade | |
| Shatsauskas et al. | Synthesis and Photophysical Properties of 3-Amino-4-arylpyridin-2 (1Н)-ones | |
| Ashok et al. | Microwave-assisted synthesis and in vitro antiproliferative activity of some novel 1, 2, 3-triazole-based pyrazole aldehydes and their benzimidazole derivatives | |
| Levi et al. | Multicomponent syntheses of fluorophores initiated by metal catalysis | |
| Kumar et al. | Rh-Catalyzed regioselective C–H activation and C–C bond formation: synthesis and photophysical studies of indazolo [2, 3-a] quinolines | |
| Hasaninejad et al. | Eco-friendly polyethylene glycol (PEG-400): a green reaction medium for one-pot, four-component synthesis of novel asymmetrical bis-spirooxindole derivatives at room temperature | |
| Borah et al. | Recent advances in the microwave-and ultrasound-assisted green synthesis of coumarin-heterocycles | |
| Balijapalli et al. | CuO–CuAl2O4 and d-glucose catalyzed synthesis of a family of excited state intramolecular proton transfer imidazo [1, 2-a] pyridine analogues and their optical properties | |
| Sarkar et al. | Synthesis and photophysics of selective functionalized π-conjugated, blue light emitting, highly fluorescent C7-imidazo indolizine derivatives | |
| Sagirli | A new approach for the synthesis of fluorescent pyrido [1, 2-a] benzimidazoles | |
| JP6150297B2 (en) | Fluorescent color former, ion concentration sensor containing fluorescent color former, reagent containing fluorescent color former, reagent kit equipped with reagent, and method for synthesizing fluorescent color former | |
| Sharma et al. | La (OTf) 3-catalysed one-pot synthesis of pyrazole tethered imidazo [1, 2-a] azine derivatives and evaluation of their light emitting properties | |
| Bathula et al. | Microwave assisted synthesis of imidazolyl fluorescent dyes as antimicrobial agents | |
| Täuscher et al. | Bis (4-hydroxythiazoles): novel functional and switchable fluorophores | |
| Breuer et al. | Consecutive Alkynylation–Michael Addition–Cyclocondensation (AMAC) Multicomponent Syntheses of α-Pyrones and α-Pyridones | |
| CN106543175B (en) | Triaryl [1,2,4] triazole [1,5-a] pyridine derivate and preparation method thereof | |
| Brandner et al. | Multicomponent synthesis of chromophores–The one-pot approach to functional π-systems | |
| EL‐Mahdy et al. | Synthesis, characterization, and photophysical properties of some new thieno [2, 3‐b] pyridines bearing phenylethenyl moiety | |
| Nagaraj et al. | An Efficient Synthetic Protocol for Quinoxalinones, Benzoxazinones, and Benzothiazinones from 2‐Oxo‐2‐aryl‐acetyl Bromide Precursors | |
| Shaikh et al. | Electron-deficient molecules: photophysical, electrochemical, and thermal investigations of naphtho [2, 3-f] quinoxaline-7, 12-dione derivatives | |
| Hagimori et al. | 2-Pyridone-based fluorophores containing 4-dialkylamino-phenyl group: Synthesis and fluorescence properties in solutions and in solid state | |
| Yadav et al. | Synthesis of styryl-linked fused dihydropyridines by catalyst-free multicomponent reactions | |
| US5874587A (en) | Imidazolium cations, processes for their preparation, and uses therefor | |
| Bing et al. | Synthesis of efficient blue and red light emitting phenanthroline derivatives containing both hole and electron transporting properties | |
| KR101850607B1 (en) | Indolizino[3,2-c]quinolines based fluorescence probe |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180601 Termination date: 20201028 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |