CN107434801B - 4 '-pyridyl-pyrimidine class compounds of one kind and its synthetic method and application - Google Patents

4 '-pyridyl-pyrimidine class compounds of one kind and its synthetic method and application Download PDF

Info

Publication number
CN107434801B
CN107434801B CN201710186766.7A CN201710186766A CN107434801B CN 107434801 B CN107434801 B CN 107434801B CN 201710186766 A CN201710186766 A CN 201710186766A CN 107434801 B CN107434801 B CN 107434801B
Authority
CN
China
Prior art keywords
pyridine
isolongitolanone
methylene
base
pyridyl
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
Application number
CN201710186766.7A
Other languages
Chinese (zh)
Other versions
CN107434801A (en
Inventor
王石发
王忠龙
谷文
徐徐
杨益琴
徐海军
匡红波
杨丽娟
姜倩
张燕
刘艳芳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Forestry University
Original Assignee
Nanjing Forestry University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nanjing Forestry University filed Critical Nanjing Forestry University
Priority to CN201710186766.7A priority Critical patent/CN107434801B/en
Publication of CN107434801A publication Critical patent/CN107434801A/en
Application granted granted Critical
Publication of CN107434801B publication Critical patent/CN107434801B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C09K11/07—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials having chemically interreactive components, e.g. reactive chemiluminescent compositions
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432—Quenching

Abstract

The invention discloses a kind of 4-pyridyl-pyrimidine class compounds and its synthetic method and applications.The present invention is raw material using the terebinthine derivative isolongitolanone of natural reproducible resource, prepares 4-novel pyridyl-pyrimidine class compounds.Isolongitolanone and 4- pyridine carboxaldehyde are condensed, and generate 7- (pyridine-4-base-methylene) isolongitolanone；7- (pyridine-4-base-methylene) isolongitolanone carries out condensation and cyclization with guanidine hydrochloride again, obtains 4-pyridyl-pyrimidine class compounds 6,6,10,10- tetramethyl-4- (pyridine-4-yl)-5,7,8,9,10,10a- hexahydro-6H-6a, 9- endo-methylene group benzo-2- quinazoline amine, the compound can specificity identification copper ion, can specificity and Cu2+Ion complexation generates the quenching of blue-fluorescence, therefore the compound can be used as the fluorescence probe of detection copper ion, have good practicability.

Description

4 '-pyridyl-pyrimidine class compounds of one kind and its synthetic method and application
Technical field
The invention belongs to Minute Organic Synthesis technical field, be related to 4 '-pyridyl-pyrimidine fluorescence probes and preparation method thereof with And the fluorescence detection for copper ion.More particularly to 4 '-pyridyl-pyrimidine class compounds and its synthetic method and application.
Background technique
Cu2+It is one of the essential trace elements of the human body, it exists usually in the form of cuprein in human body.Its one kind is non- Often important biocatalyst, and it all plays very in the hemoposieis of human body, angiomalacia and hormone secretion Important role.The intake and enrichment of excessive copper ion can then make human body slow poisoning, and the organs such as liver are badly damaged.Past Conventional analyzing detecting method cannot carry out effectively the intracorporal copper ion of biology due to the disadvantages of sensitivity is low and complicated for operation Timely detect, fluorescence analysis by the selectivity, height of height sensitivity, quick responsiveness the advantages that gradually It has become a hot topic of research.
In recent years there is the study on the synthesis of many small organic molecule fluorescence probes and it is used for Cu2+The report of detection, Such as: 1- (2- hydroxy phenyl) -4- (9- anthryl) -3- benzothiazolyl pyrazoline, (E) -4- (4- (double picolyl amine) styrene Base) cyano benzene etc..But 4 '-pyridyl-pyrimidine compounds are synthesized not yet and it is used for Cu2+The relevant report of ion detection.
Summary of the invention
Goal of the invention: being directed to the deficiencies in the prior art, and the purpose of the present invention is to provide a kind of 4 '-pyridyl groups are phonetic Pyridine class compound, satisfies the use demand.It is a further object of the present invention to provide a kind of conjunctions of above-mentioned 4 '-pyridyl-pyrimidine compound At method.Further object of the present invention is to provide the application of the compound.
Technical solution: for achieving the above object, the technical solution adopted by the present invention are as follows:
4 '-pyridyl-pyrimidine class compounds are 6,6,10,10- tetramethyl -4- (pyridine -4 '-yl) -5,7,8,9,10, 10a- hexahydro -6H-6a, 9- endo-methylene group benzo -2- quinazoline amine, structural formula are as follows:
Described 4 '-pyridyl-pyrimidine class compound synthesis method, comprises the technical steps that:
1) isolongitolanone and 4- pyridine carboxaldehyde carry out aldol condensation, obtain that 7- (pyridine -4 '-base-methylene) is different to come into leaves Alkanone.
2) 7- (pyridine -4 '-base-methylene) isolongitolanone and guanidine hydrochloride carry out condensation reaction, obtain 6,6,10,10- Tetramethyl -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydro -6H-6a, 9- methylene bridge benzo -2- quinazoline amine.
In step 1), isolongitolanone and 4- pyridine carboxaldehyde carry out aldol condensation and obtain 7- (pyridine -4 '-base-methylene) Isolongitolanone, specific preparation method include:
(1) by 0.1mol isolongitolanone, the 4- pyridine carboxaldehyde of 0.1~0.15mol, 0.2~0.3mol sodium ethoxide and 0.1 ~0.3L ethyl alcohol sequentially adds in the three-necked flask equipped with blender, thermometer and reflux condenser, under nitrogen protection 0~ It is reacted within the scope of 100 DEG C.
(2) reactant is extracted 3 times with 0.4L-0.6L ethyl acetate, merges organic phase, then uses saturated common salt water washing again For several times, until neutral, organic phase is dry with anhydrous sodium sulfate；Filtering and concentrating recycling design obtains 7- (pyridine -4 '-base-methylene Base) isolongitolanone.
(3) 7- (pyridine -4 '-base-methylene) isolongitolanone crude product is recrystallized with EtOH-EtOAc, is obtained To the very high 7- of purity (pyridine -4 '-base-methylene) isolongitolanone.
In step 2), 7- (pyridine -4 '-base-methylene) isolongitolanone is reacted with guanidine hydrochloride under sodium ethoxide effect, is obtained To 6,6,10,10- tetramethyl -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydro -6H-6a, 9- methylene bridge benzo -2- Quinazoline amine, specific preparation method include:
(1) by 0.1mol 7- (pyridine -4 '-base-methylene) isolongitolanone, 0.3~0.5mol guanidine hydrochloride, 0.1~ 1.0mol sodium ethoxide, 0.1-0.5L ethyl alcohol sequentially add in the three-necked flask equipped with blender, thermometer and reflux condenser, Heating reflux reaction 8h under nitrogen protection, with GC tracing detection, until 7- (pyridine -4 '-base-methylene) isolongitolanone conversion ratio Reaction is terminated after reaching 95%.
(2) reactant is extracted 3 times with 0.1-0.3L ethyl acetate, merges organic phase, then uses saturated common salt water washing again For several times, until neutral, organic phase is dry with anhydrous sodium sulfate；Filtering and concentrating recycling design obtains 6,6,10,10- tetramethyl -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydro -6H-6a, 9- methylene bridge benzo -2- quinazoline amine crude product.
(3) 6,6,10,10- tetramethyl -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydro -6H-6a, 9- methylene Bridge benzo -2- quinazoline amine crude product is recrystallized with EtOH-EtOAc, obtains purer 6,6,10,10- tetramethyls - - 5,7,8,9,10,10a- hexahydro -6H-6a, 9- methylene bridge benzo -2- quinazoline amine of 4- (pyridine -4 '-yl), is white needles Crystal.
Described 4 '-pyridyl-pyrimidine class compound is in detection Cu2+In application.
Application of the described 4 '-pyridyl-pyrimidine class compound as fluorescence probe.
Described 4 '-pyridyl-pyrimidine class compound is as fluorescence probe in detection Cu2+In application.
The present invention is raw material with the terebinthine derivative isolongitolanone of natural reproducible resource-, anti-with 4- pyridine carboxaldehyde 7- (pyridine -4 '-base-methylene) isolongitolanone should be generated；7- (pyridine -4 '-base-methylene) isolongitolanone again with hydrochloric acid Guanidine carries out condensation reaction and obtains 6,6,10,10- tetramethyl -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydro -6H-6a, 9- methylene bridge benzo -2- quinazoline amine；It was found that the identification copper ion of compound energy specificity, can be used as detection copper ion Fluorescence probe.
The utility model has the advantages that compared with prior art, of the invention utilizes the different length of the terebinthine derivative of natural reproducible resource- Leaf alkanone is that raw material prepares 4 '-novel pyridyl-pyrimidine class compounds；The identification copper ion of energy specificity, energy specificity With Cu2+Ion complexation generates the quenching of blue-fluorescence, therefore the compound can be used as the fluorescence probe of detection copper ion, have Good practicability.
Detailed description of the invention
Fig. 1 is 6,6,10,10- tetramethyl -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydro -6H-6a, 9- methylene The fluorescence intensity results figure of the copper ion of base bridge benzo -2- quinazoline amine and various concentration complexing.
Fig. 2 is 6,6,10,10- tetramethyl -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydro -6H-6a, 9- methylene The result figure of base bridge benzo -2- quinazoline amine and different metal ions complexing front and back change in fluorescence；In figure, compound under a- sunshine Compound under the front and back photo b-360nm ultraviolet lamp of different metal ions is added, photo before and after different metal ions is added.
Fig. 3 is 6,6,10,10- tetramethyl -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydro -6H-6a, 9- methylene The interference figure of base bridge benzo -2- quinazoline amine and other metal ions of copper ion quenching.
Specific embodiment
The present invention is described further combined with specific embodiments below.
Embodiment 1
The synthetic method of 4 '-pyridyl-pyrimidine class compounds, synthesis process are as follows:
Specific step is as follows:
1) preparation of 7- (pyridine -4 '-base-methylene) isolongitolanone:
8mmol isolongitolanone, 12mmol 4- pyridine carboxaldehyde, 16mmol sodium ethoxide and 30mL ethyl alcohol are successively furnished with and stirred In the three-necked flask for mixing device, thermometer and reflux condenser, it is heated to reflux at 80-90 DEG C and is reacted, reaction 5h or so To isolongitolanone conversion ratio up to 95% or more (GC tracing detection).Reactant is extracted 3 times with 25mL ethyl acetate, is merged organic Then phase uses saturated common salt water washing for several times again, until neutral, organic phase is dry with anhydrous sodium sulfate；Filtering and concentrating recycling is molten Agent obtains 7- (pyridine -4 '-base-methylene) isolongitolanone；It is recrystallized, is obtained colorless and transparent with EtOH-EtOAc 7- (pyridine -4 '-base-methylene) isolongitolanone, yield 86.9%, purity 98.2%, fusing point 88.5-88.6 ℃；FT-IR(KBr,cm-1)ν:2965,2933,2874,1672,1588,1467,1411,1364,1233,1186,957,814, 787；1H NMR(400MHz,CDCl3) δ: 0.85 (s, 3H), 0.87 (s, 3H), 0.95~1.01 (m, 1H), 1.06 (s, 3H), 1.24 (s, 3H), 1.32 (d, J=4Hz, 1H), 1.50~1.57 (m, 1H), 1.63~1.70 (m, 1H), 1.79~1.88 (m, 3H), 2.00 (d, J=4Hz, 1H), 2.56 (d, J=16Hz, 1H), 2.82~2.87 (m, 1H), 7.30 (d, J=8Hz, 2H), 7.39 (s, 1H), 8.63 (d, J=8Hz, 2H)；13C NMR(100MHz,CDCl3)δ:23.99,24.49,25.40,25.49, 28.13,30.19,31.59,37.52,41.33,44.80,47.95,55.46,62.88,124.10,133.12,134.25, 139.16,143.30,149.73,149.95,202.04；EIMS m/z (%): 309 (M+,100),294(52),280(12), 266(37),252(63),238(50),135(37),93(63)；HRMS(m/z):[M+H]+calcd for C21H27NO+H+, 310.2171；found,310.2171.
2) 6,6,10,10- tetramethyl -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydro -6H-6a, 9- bridge methylene The preparation of base benzo -2- quinazoline amine:
By 5mmol 7- (pyridine -4 '-base-methylene) isolongitolanone, 20mmol guanidine hydrochloride, 30mol sodium ethoxide, 60mL Ethyl alcohol sequentially adds in the three-necked flask equipped with blender, thermometer and reflux condenser, is heated to flowing back at 80-90 DEG C Row reaction, reaction 20h or so to 7- (pyridine -4 '-base-methylene) isolongitolanone conversion ratio is up to 95% or more (GC tracking inspection It surveys).Reactant is extracted with ethyl acetate 3 times, merges organic phase, then uses saturated common salt water washing for several times again, until it is neutral, have Machine is mutually dry with anhydrous sodium sulfate；Filtering and concentrating recycling design obtains 6,6,10,10- tetramethyl -4- (pyridine -4 '-yl) -5,7, 8,9,10,10a- hexahydro -6H-6a, 9- endo-methylene group benzo -2- quinazoline amine crude products, then weight is carried out with EtOH-EtOAc Crystallization, obtains -5,7,8,9,10,10a- hexahydro -6H- of 6,6,10,10- tetramethyl -4- of white needle-like crystals (pyridine -4 '-yl) 6a, 9- endo-methylene group benzo -2- quinazoline amine, yield 84.7%, purity 97.6%, fusing point are 272.2-272.4 DEG C；FT- IR(KBr,cm-1)ν:3327,3156,2960,2925,2872,1647,1567,1544,1465,1407,1386,1213,998, 825,793；1H NMR(400MHz,CDCl3)δ:0.65(s,3H),0.77(s,3H),0.97(s,3H),1.12(s,1H),1.24 (s, 3H), 1.36 (s, 3H), 1.49~1.56 (m, 1H), 1.61~1.65 (m, 1H), 1.71 (d, J=8Hz, 1H), 1.76 (s, 1H), 1.90 (t, J=8Hz, 1H), 2.07~2.13 (m, 1H), 2.31 (s, 1H), 2.69 (d, J=16Hz, 1H), 4.98 (s, 2H), 7.42 (d, J=4Hz, 2H), 8.70 (d, J=8Hz, 2H)；13C NMR(100MHz,CDCl3)δ:23.16,24.34, 24.95,25.59,26.10,28.56,29.88,30.33,32.86,37.46,39.32,44.63,48.20,55.45, 58.13,116.38,123.59,146.56,150.04,160.65,163.57,170.86；EIMS m/z (%): 348 (M+, 100),333(17),319(30),266(76),251(14),237(10),105(7),78(6)；HRMS(m/z):[M+H]+ calcd for C22H28N4+H+,349.2392；found,349.2393.
Embodiment 2
6,6,10,10- tetramethyl -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydro-that embodiment 1 is obtained 6H-6a, 9- endo-methylene group benzo -2- quinazoline amine are configured to 1 × 10-5HEPES buffer solution (20mM, the pH=7.2,80% of M (v/v)C2H5OH), by Cu2+It is 0.1~1.0 × 10 that ion, which is made into concentration with identical HEPES buffer solution,-4The solution of M.It measures The Cu of various concentration2+Ion pair 6,6,10,10- tetramethyl -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydro -6H-6a, Then the fluorescence intensity of 9- endo-methylene group benzo -2- quinazoline amine carries out linear fit to the fluorescence intensity at 450nm, obtains Straight line as shown in Figure 1 is further calculated the compound by formula and limits the detection of copper ion down to 4 × 10-8M。
Embodiment 3
By 6,6,10,10- tetramethyl -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydro -6H-6a, 9- bridge methylene Base benzo -2- quinazoline amine is dissolved in straight alcohol, and being configured to concentration is 1 × 10-5The solution of M, solution are nothing under fluorescent light The transparent state of color, with 1.5 × 10-4The addition of the different metal ions of M, solution colour there is no significantly changing, Then it is observed under 365nm ultraviolet lamp, as shown in Fig. 2, Cu is added2+Its blue-fluorescence of the solution of ion has disappeared, and passes through Other metal ions of equivalent, such as Hg is added2+,Al3+,Ag+,La3+,Pb2+,Fe3+,Fe2+,Cr3+,Co2+,Zn2+Plasma pair Than the fluorescence of compound illustrates that compound can be used as a kind of effectively identification Cu there is no significantly changing2+The fluorescence of ion Probe.
Embodiment 4
In configured 6,6,10,10- tetramethyl -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydro -6H-6a, 9- endo-methylene group benzo -2- quinazoline amine (1 × 10-5M HEPES buffer solution (20mM, pH=7.2,80% (v/v) C)2H5OH) In, it is 1 × 10 that concentration, which is added,-4The Cu of M2+HEPES buffer solution, is then respectively adding and Cu2+Other metal ions of equimolar amounts Hg2+,Al3+,Ag+,La3+,Pb2+,Fe3+,Fe2+,Cr3+,Co2+,Zn2+Its fluorescence intensity is tested, as a result as shown in figure 3, other are golden The addition for belonging to ion will not influence the Fluorescence quenching effect of copper ion.

Claims (4)

1.4-pyridyl-pyrimidine class compounds, which is characterized in that it is 6,6,10,10- tetramethyl-4- (pyridine-4-yl)-5,7, 8,9,10,10a- hexahydro -6H-6a, 9- endo-methylene group benzo -2- quinazoline amine, structural formula are as follows:
。
2. the synthetic method of 4-pyridyl-pyrimidine class compound described in claim 1, which comprises the steps of:
1) isolongitolanone and 4- pyridine carboxaldehyde carry out aldol condensation, obtain 7- (pyridine-4-base-methylene) isolongitolanone；
2) 7- (pyridine-4-base-methylene) isolongitolanone and guanidine hydrochloride carry out condensation reaction, obtain 6,6,10,10- tetramethyls Base-4- (pyridine-4-yl)-5,7,8,9,10,10a- hexahydro-6H-6a, 9- endo-methylene group benzo-2- quinazoline amine；
Specific reaction equation is as follows:
。
3. the synthetic method of 4-pyridyl-pyrimidine class compound according to claim 2, which is characterized in that in step 1), Isolongitolanone and 4- pyridine carboxaldehyde carry out aldol condensation, obtain 7- (pyridine-4-base-methylene) isolongitolanone, specifically Preparation method includes:
(1) by 0.1mol isolongitolanone, 0.1 ~ 0.15 mol 4- pyridine carboxaldehyde, 0.2 ~ 0.3mol sodium ethoxide and 0.1 ~ 0.3L Ethyl alcohol sequentially adds in the three-necked flask equipped with blender, thermometer and reflux condenser, under nitrogen protection in 0 ~ 100 DEG C of model Enclose interior reacted；
(2) reactant is extracted 3 times with 0.4L-0.6L ethyl acetate, merges organic phase, then uses saturated common salt water washing number again Secondary, until neutral, organic phase is dry with anhydrous sodium sulfate；Filtering and concentrating recycling design obtains 7- (pyridine-4-base-methylene) Isolongitolanone；
(3) 7- (pyridine-4-base-methylene) isolongitolanone crude product is recrystallized with EtOH-EtOAc, is obtained pure Spend very high 7- (pyridine-4-base-methylene) isolongitolanone.
4. the synthetic method of 4-pyridyl-pyrimidine class compound according to claim 2, which is characterized in that in step 2, 7- (pyridine-4-base-methylene) isolongitolanone is reacted with guanidine hydrochloride under sodium ethoxide effect, obtains 6,6,10,10- tetramethyls - 5,7,8,9,10,10a- hexahydro-6H-6a, 9- endo-methylene group benzo-2- quinazoline amine of base-4- (pyridine-4-yl), specifically Preparation method includes:
(1) by 0.1mol 7- (pyridine-4-base-methylene) isolongitolanone, 0.3 ~ 0.5mol guanidine hydrochloride, 0.1 ~ 1.0mol second Sodium alkoxide, 0.1-0.5L ethyl alcohol sequentially add in the three-necked flask equipped with blender, thermometer and reflux condenser, in nitrogen protection Lower 8 h of heating reflux reaction, with GC tracing detection, until 7- (pyridine-4-base-methylene) isolongitolanone conversion ratio reaches 95% Reaction is terminated afterwards；
(2) reactant is extracted 3 times with 0.1-0.3L ethyl acetate, merges organic phase, then uses saturated common salt water washing for several times again, Until neutral, organic phase is dry with anhydrous sodium sulfate；Filtering and concentrating recycling design obtains 6,6,10,10- tetramethyl -4- (pyrroles Pyridine-4-yl)-5,7,8,9,10,10a- hexahydro-6H-6a, 9- endo-methylene group benzo-2- quinazoline amine crude product；
(3) 6,6,10,10- tetramethyl-4- (pyridine-4-yl)-5,7,8,9,10,10a- hexahydro-6H-6a, 9- endo-methylene group Benzo -2- quinazoline amine crude product is recrystallized with EtOH-EtOAc, obtains purer 6,6,10,10- tetramethyl -4- (pyridine-4-yl)-5,7,8,9,10,10a- hexahydro-6H-6a, 9- endo-methylene group benzo-2- quinazoline amine, is white needles Crystal.
CN201710186766.7A 2017-03-27 2017-03-27 4 '-pyridyl-pyrimidine class compounds of one kind and its synthetic method and application Expired - Fee Related CN107434801B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710186766.7A CN107434801B (en) 2017-03-27 2017-03-27 4 '-pyridyl-pyrimidine class compounds of one kind and its synthetic method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710186766.7A CN107434801B (en) 2017-03-27 2017-03-27 4 '-pyridyl-pyrimidine class compounds of one kind and its synthetic method and application

Publications (2)

Publication Number Publication Date
CN107434801A CN107434801A (en) 2017-12-05
CN107434801B true CN107434801B (en) 2019-08-27

Family

ID=60458544

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710186766.7A Expired - Fee Related CN107434801B (en) 2017-03-27 2017-03-27 4 '-pyridyl-pyrimidine class compounds of one kind and its synthetic method and application

Country Status (1)

Country Link
CN (1) CN107434801B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108586361B (en) * 2018-04-03 2021-03-12 南京林业大学 Isolongifolane dihydro-pyrimidine thioketone compound and preparation method and application thereof
CN109761917B (en) * 2019-02-15 2022-02-08 南京林业大学 Isolongifolanone-2-aminopyrimidine boron trifluoride fluorescent probe and synthetic method and application thereof
CN109776492B (en) * 2019-03-04 2021-04-30 南京林业大学 Reaction type fluorescent probe for detecting hydrazine with high selectivity as well as preparation method and application thereof
CN112480071B (en) * 2020-11-30 2021-09-07 南京林业大学 Isolongifolane ratio type fluorescent probe for detecting hydrazine and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996010181A1 (en) * 1994-09-29 1996-04-04 Merck & Co., Inc. Compounds and methods for identifying activated platelets

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104892543B (en) * 2015-06-03 2017-02-22 南京林业大学 Thiazole compounds, as well as synthesis method and application thereof
CN105541795B (en) * 2016-02-22 2018-01-19 南京林业大学 Pyridyl-pyrimidine class compound and its synthetic method and application
CN105669565B (en) * 2016-03-21 2017-07-11 南京林业大学 Isolonglifolane yl pyrimidines class compound and preparation method and application

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996010181A1 (en) * 1994-09-29 1996-04-04 Merck & Co., Inc. Compounds and methods for identifying activated platelets

Also Published As

Publication number Publication date
CN107434801A (en) 2017-12-05

Similar Documents

Publication Publication Date Title
CN107434801B (en) 4 '-pyridyl-pyrimidine class compounds of one kind and its synthetic method and application
CN103320118B (en) Schiff base cooper ion fluorescence probe and preparation method thereof
CN106632084B (en) Isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff bases zinc ion fluorescent and its preparation method and application
CN103013495B (en) Copper ion fluorescence probe and synthetic method thereof
CN109867611B (en) Water-soluble two-photon hydrogen sulfide fluorescent probe for detecting red wine and hydrogen sulfide in vivo and preparation method and application thereof
CN105669644B (en) A kind of benzimidazole quinoline, preparation method and applications
CN105504860B (en) The synthesis and its application of a kind of pyranoquinoline fluorochrome
CN104845612A (en) Polystyrene mercury ion fluorescence recognition materials and preparation method thereof
CN102911111A (en) Carbazole benzaldehyde-p-phenylenediamine bi-schiff base and preparation method thereof
CN105524055A (en) Preparation and application of fluorescent probe capable of being used for distinguishing cysteine/homocysteine and glutathione
CN103012372A (en) Naphthalimide derivatives and applications thereof
CN108658838B (en) Heptamethine indocyanine-based formaldehyde fluorescent probe and preparation method and use method thereof
CN108424393A (en) A kind of hypochlorous acid fluorescence probe and its preparation method and application
CN106800548B (en) 8- benzimidazole quinoline Ratio-type pH probe and its preparation method and application
CN104151325B (en) Fluorescent probe with rhodamine fluorophore as matrix and preparation method of fluorescent probe with rhodamine fluorophore as matrix
CN107892654B (en) Isolongifolane-based fluorescent acid-base indicator and synthetic method and application thereof
CN105968098B (en) A kind of quinoline substituted containing carbazole, benzimidazole and its preparation method and application
Zhao et al. A highly selective and easy-to-synthesize Zn (II) fluorescent probe based on 6-methoxyquinolin
CN103304548B (en) N'-(2-aminopyridine)-7-lignocaine-3-formamide-coumarin as well as preparation method and application thereof
CN110590664A (en) Preparation method of fluorescent probe and application of fluorescent probe
CN107831165B (en) Double-channel copper ion detection test paper and preparation method thereof
CN106967025B (en) A kind of preparation and its application of the chloro- 3- of 6- [(2- hydroxyl -4- diethylin benzylidene) amino] cumarin
CN108623575B (en) Simple and effective fluorescent probe for detecting sulfite
CN107098852A (en) The amine-modified pyrene derivatives fluorescence probe of two (2 picolines) and its synthetic method and application
CN109651336B (en) Fluorescent probe for detecting hydrogen sulfide based on drug molecules and preparation method thereof

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
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20190827

Termination date: 20200327