CN107434801A - A kind of 4 ' pyridyl-pyrimidine class compounds and its synthetic method and application - Google Patents
A kind of 4 ' pyridyl-pyrimidine class compounds and its synthetic method and application Download PDFInfo
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Abstract
The invention discloses a kind of 4 pyridyl-pyrimidine class compounds and its synthetic method and application.The present invention is raw material using the terebinthine derivative isolongitolanone of natural reproducible resource, prepares 4 new pyridyl-pyrimidine class compounds.Isolongitolanone and 4 pyridine carboxaldehydes are condensed, and generate 7 (methylene of pyridine 4) isolongitolanones;7 (methylene of pyridine 4) isolongitolanones carry out condensation and cyclization with guanidine hydrochloride again, obtain 4 pyridyl-pyrimidine class compounds 6,6,10, (base of pyridine 4) 5,7,8 of 10 tetramethyl 4,9,10,10a hexahydro 6H 6a, the quinazoline amine of 9 endo-methylene group benzo 2, the compound can specific identification copper ion, can selectivity and Cu2+Ion complexation, the quenching of blue-fluorescence is produced, therefore the compound there can be good practicality as the fluorescence probe of detection copper ion.
Description
Technical field
The invention belongs to Minute Organic Synthesis technical field, be related to 4 '-pyridyl-pyrimidine fluorescence probe and preparation method thereof with
And the fluoroscopic examination for copper ion.More particularly to 4 '-pyridyl-pyrimidine class compound and its synthetic method and application.
Background technology
Cu2+It is one of the essential trace elements of the human body, it exists in human body generally in the form of cuprein.Its one kind is non-
Often important biocatalyst, and it all plays very in the hemoposieis of human body, angiomalacia and hormone secretion
Important effect.The intake and enrichment of excessive copper ion then can make the organs such as human body slow poisoning, liver be badly damaged.Past
Conventional analyzing detecting method is because sensitivity is low and the copper ion in organism can not be carried out effectively the shortcomings of complex operation
Timely detect, XRF by height selectivity, height sensitivity, quick response the advantages that it is gradual
As the focus of research.
In recent years there is the study on the synthesis of the organic molecule fluorescence probe of many and it is used for Cu2+The report of detection,
Such as:1- (2- hydroxy phenyls) -4- (9- anthryls) -3- benzothiazolyl pyrazolines, (E) -4- (4- (double picolyl amine) styrene
Base) cyano group benzene etc..But without synthesis 4 '-pyridyl-pyrimidine compound and it is also used for Cu2+The relevant report of ion detection.
The content of the invention
Goal of the invention:For the deficiencies in the prior art, it is an object of the invention to provide a kind of 4 '-pyridine radicals is phonetic
Pyridine class compound, meets use demand.It is a further object of the present invention to provide a kind of conjunction of above-mentioned 4 '-pyridyl-pyrimidine compound
Into method.Further object of the present invention is to provide the application of the compound.
Technical scheme:For achieving the above object, the technical solution adopted by the present invention is:
4 '-pyridyl-pyrimidine class compound, it is 6,6,10,10- tetramethyl -4- (pyridine -4 '-yl) -5,7,8,9,10,
10a- hexahydros -6H-6a, 9- endo-methylene group benzo -2- quinazoline amine, its structural formula are:
Described 4 '-pyridyl-pyrimidine class compound synthesis method, are comprised the technical steps that:
1) isolongitolanone and 4- pyridine carboxaldehydes carry out aldol condensation, obtain that 7- (pyridine -4 '-base-methylene) is different to come into leaves
Alkanone.
2) 7- (pyridine -4 '-base-methylene) isolongitolanones carry out condensation reaction with guanidine hydrochloride, obtain 6,6,10,10-
Tetramethyl -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydros -6H-6a, 9- methylene bridge benzo -2- quinazoline amine.
In step 1), isolongitolanone carries out aldol condensation with 4- pyridine carboxaldehydes and obtains 7- (pyridine -4 '-base-methylene)
Isolongitolanone, specific preparation method include:
(1) by 0.1mol isolongitolanones, 0.1~0.15mol 4- pyridine carboxaldehydes, 0.2~0.3mol caustic alcohols and 0.1
~0.3L ethanol is sequentially added in the three-necked flask equipped with agitator, thermometer and reflux condenser, under nitrogen protection 0~
Reacted in the range of 100 DEG C.
(2) reactant is extracted 3 times with 0.4L-0.6L ethyl acetate, is merged organic phase, is then used saturated common salt water washing again
For several times, it is until neutral, organic phase anhydrous sodium sulfate drying;Filtering and concentrating recycling design, obtain 7- (pyridines -4 '-base-methylene
Base) isolongitolanone.
(3) 7- (pyridine -4 '-base-methylene) isolongitolanone crude product is recrystallized with EtOH-EtOAc, obtained
To the very high 7- of purity (pyridine -4 '-base-methylene) isolongitolanone.
In step 2), 7- (pyridine -4 '-base-methylene) isolongitolanones react with guanidine hydrochloride under caustic alcohol effect, obtain
To 6,6,10,10- tetramethyls -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydros -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 hydrochlorides, 0.1~
1.0mol caustic alcohols, 0.1-0.5L ethanol are sequentially added in the three-necked flask equipped with agitator, thermometer and reflux condenser,
The lower heating reflux reaction 8h of nitrogen protection, with GC tracing detections, to 7- (pyridine -4 '-base-methylene) isolongitolanone conversion ratio
Terminating reaction after reaching 95%.
(2) reactant is extracted 3 times with 0.1-0.3L ethyl acetate, is merged organic phase, is then used saturated common salt water washing again
For several times, it is until neutral, organic phase anhydrous sodium sulfate drying;Filtering and concentrating recycling design, obtain 6,6,10,10- tetramethyl -4-
(pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydros -6H-6a, 9- methylene bridge benzo -2- quinazoline amine crude products.
(3) 6,6,10,10- tetramethyls -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydros -6H-6a, 9- methylene
Bridge benzo -2- quinazoline amine crude products are recrystallized with EtOH-EtOAc, obtain purer 6, and 6,10,10- tetramethyls -
Hexahydro -6H-6a, 9- the methylene bridge benzo -2- quinazoline amine of 4- (pyridine -4 '-yl) -5,7,8,9,10,10a-, is white needles
Crystal.
Described 4 '-pyridyl-pyrimidine class compound is in detection Cu2+In application.
Described 4 '-application of the 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 natural reproducible resource-terebinthine derivative isolongitolanone, anti-with 4- pyridine carboxaldehydes
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- tetramethyls -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 specific identification copper ion of compound energy, can be as detection copper ion
Fluorescence probe.
Beneficial effect:Compared with prior art, utilization natural reproducible resource-different length of terebinthine derivative of the invention
Leaf alkanone is that raw material prepares new 4 '-pyridyl-pyrimidine class compound;The specific identification copper ion of energy, energy selectivity
With Cu2+Ion complexation, the quenching of blue-fluorescence is produced, therefore the compound can have as the fluorescence probe of detection copper ion
Good practicality.
Brief description of the drawings
Fig. 1 is 6,6,10,10- tetramethyls -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydros -6H-6a, 9- methylene
The fluorescence intensity results figure of the copper ion of base bridge benzo -2- quinazolines amine and various concentrations complexing.
Fig. 2 is 6,6,10,10- tetramethyls -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydros -6H-6a, 9- methylene
Base bridge benzo -2- quinazolines amine and the result figure of change in fluorescence before and after different metal ions complexing;In figure, compound under a- sunshines
Add compound under the front and rear photo b-360nm uviol lamps of different metal ions and add photo before and after different metal ions.
Fig. 3 is 6,6,10,10- tetramethyls -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydros -6H-6a, 9- methylene
The interference figure of base bridge benzo -2- quinazolines amine and other metal ions of copper ion quenching.
Embodiment
With reference to specific embodiment, the present invention is described further.
Embodiment 1
The synthetic method of 4 '-pyridyl-pyrimidine class compound, building-up process are:
Comprise the following steps that:
1) preparation of 7- (pyridine -4 '-base-methylene) isolongitolanone:
8mmol isolongitolanones, 12mmol 4- pyridine carboxaldehydes, 16mmol caustic alcohols and 30mL ethanol are furnished with successively and stirred
In the three-necked flask for mixing device, thermometer and reflux condenser, at 80-90 DEG C being heated to backflow is reacted, reaction 5h or so
To isolongitolanone conversion ratio up to more than 95% (GC tracing detections).Reactant is extracted 3 times with 25mL ethyl acetate, is merged organic
Phase, then saturated common salt water washing is used for several times again, until neutral, organic phase anhydrous sodium sulfate drying;Filtering and concentrating recovery is molten
Agent, obtain 7- (pyridine -4 '-base-methylene) isolongitolanone;Recrystallized with EtOH-EtOAc, obtain water white transparency
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- tetramethyls -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydros -6H-6a, 9- bridge methylene
The preparation of base benzo -2- quinazoline amine:
By 5mmol 7- (pyridine -4 '-base-methylene) isolongitolanone, 20mmol guanidine hydrochlorides, 30mol caustic alcohols, 60mL
Ethanol is sequentially added in the three-necked flask equipped with agitator, 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 ratios is up to more than 95% (GC tracking inspections
Survey).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 mutually uses anhydrous sodium sulfate drying;Filtering and concentrating recycling design obtains 6,6,10,10- tetramethyls -4- (pyridine -4 '-yl) -5,7,
8,9,10,10a- hexahydro -6H-6a, 9- endo-methylene group benzo -2- quinazoline amine crude products, then carry out weight with EtOH-EtOAc
Crystallization, obtains the hexahydro -6H- of the tetramethyl -4- of white needle-like crystals 6,6,10,10- (pyridine -4 '-yl) -5,7,8,9,10,10a-
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- tetramethyls -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydros that embodiment 1 is obtained -
6H-6a, 9- endo-methylene group benzo -2- quinazoline amine are configured to 1 × 10-5M HEPES cushioning liquid (20mM, pH=7.2,80%
(v/v)C2H5OH), by Cu2+Ion is made into concentration as 0.1~1.0 × 10 with identical HEPES buffer solution-4M solution.Measure
The Cu of various concentrations2+Ion pair 6,6,10,10- tetramethyls -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydro -6H-6a,
The fluorescence intensity of 9- endo-methylene group benzo -2- quinazoline amine, linear fit then is carried out to the fluorescence intensity at 450nm, obtained
Straight line as shown in Figure 1, test limit as little as 4 × 10 of the compound to copper ion is further calculated by formula-8M。
Embodiment 3
By 6,6,10,10- tetramethyls -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydros -6H-6a, 9- bridge methylene
Base benzo -2- quinazoline amine is dissolved in straight alcohol, is configured to concentration as 1 × 10-5M solution, its solution are nothing under fluorescent light
The transparent state of color, with 1.5 × 10-4Obvious change does not occur for the addition of M different metal ions, solution colour,
Then observed under 365nm uviol lamps, as shown in Fig. 2 adding Cu2+Its blue-fluorescence of the solution of ion has disappeared, and passes through
Add other metal ions of equivalent, such as Hg2+,Al3+,Ag+,La3+,Pb2+,Fe3+,Fe2+,Cr3+,Co2+,Zn2+Plasma pair
Than obvious change does not occur for the fluorescence of compound, illustrates that compound can be used as a kind of effectively identification Cu2+The fluorescence of ion
Probe.
Embodiment 4
In 6,6,10,10- tetramethyls -4- (pyridine -4 '-the yl) -5,7,8,9,10,10a- hexahydro -6H-6a configured,
9- endo-methylene group benzo -2- quinazolines amine (1 × 10-5M HEPES buffer solution (20mM, pH=7.2,80% (v/v) C)2H5OH)
In, it is 1 × 10 to add concentration-4M Cu2+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 of category ion does not interfere with the Fluorescence quenching effect of copper ion.
Claims (7)
1.4 '-pyridyl-pyrimidine class compound, it is characterised 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, its structural formula are:
。
2. the synthetic method of 4 '-pyridyl-pyrimidine class compound described in claim 1, it is characterised in that comprise the following steps:
1) isolongitolanone carries out aldol condensation with 4- pyridine carboxaldehydes, obtains 7- (pyridine -4 '-base-methylene) isolongitolanone.
2) 7- (pyridine -4 '-base-methylene) isolongitolanones carry out condensation reaction with guanidine hydrochloride, obtain 6,6,10,10- tetramethyls
Base -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydros -6H-6a, 9- methylene bridge benzo -2- quinazoline amine.
3. the synthetic method of 4 '-pyridyl-pyrimidine class compound according to claim 2, it is characterised in that in step 1),
Isolongitolanone carries out aldol condensation with 4- pyridine carboxaldehydes, obtains 7- (pyridine -4 '-base-methylene) isolongitolanone, specifically
Preparation method includes:
(1) by 0.1mol isolongitolanones, 0.1~0.15mol 4- pyridine carboxaldehydes, 0.2~0.3mol caustic alcohols and 0.1~
0.3L ethanol is sequentially added in the three-necked flask equipped with agitator, thermometer and reflux condenser, under nitrogen protection 0~
Reacted in the range of 100 DEG C.
(2) reactant is extracted 3 times with 0.4L-0.6L ethyl acetate, is merged organic phase, is then used saturated common salt water washing number again
It is secondary, until neutral, organic phase anhydrous sodium sulfate drying;Filtering and concentrating recycling design, obtain 7- (pyridine -4 '-base-methylene)
Isolongitolanone.
(3) 7- (pyridine -4 '-base-methylene) isolongitolanone crude product is recrystallized with EtOH-EtOAc, obtained pure
Very high 7- (pyridine -4 '-base-methylene) isolongitolanone of degree.
4. the synthetic method of 4 '-pyridyl-pyrimidine class compound according to claim 2, it is characterised in that in step 2),
7- (pyridine -4 '-base-methylene) isolongitolanones react with guanidine hydrochloride under caustic alcohol effect, obtain 6,6,10,10- tetramethyls
Hexahydro -6H-6a, 9- the methylene bridge benzo -2- quinazoline amine of base -4- (pyridine -4 '-yl) -5,7,8,9,10,10a-, specifically
Preparation method includes:
(1) by 0.1mol 7- (pyridine -4 '-base-methylene) isolongitolanone, 0.3~0.5mol guanidine hydrochlorides, 0.1~1.0mol
Caustic alcohol, 0.1-0.5L ethanol are sequentially added in the three-necked flask equipped with agitator, thermometer and reflux condenser, are protected in nitrogen
The lower heating reflux reaction 8h of shield, with GC tracing detections, reaches to 7- (pyridine -4 '-base-methylene) isolongitolanone conversion ratio
Terminating reaction after 95%.
(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 anhydrous sodium sulfate drying;Filtering and concentrating recycling design, obtain 6,6,10,10- tetramethyl -4- (pyrroles
Pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydros -6H-6a, 9- methylene bridge benzo -2- quinazoline amine crude products.
(3) 6,6,10,10- tetramethyls -4- (pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydros -6H-6a, 9- methylene bridge benzene
And -2- quinazoline amine crude products are recrystallized with EtOH-EtOAc, purer 6,6,10,10- tetramethyl -4- (pyrroles are obtained
Pyridine -4 '-yl) -5,7,8,9,10,10a- hexahydro -6H-6a, 9- methylene bridge benzo -2- quinazoline amine are white needle-like crystals.
5. 4 '-pyridyl-pyrimidine class compound described in claim 1 is in detection Cu2+In application.
6. application of 4 '-pyridyl-pyrimidine class compound as fluorescence probe described in claim 1.
7. 4 '-pyridyl-pyrimidine class compound described in claim 1 is as fluorescence probe in detection Cu2+In application.
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CN109761917A (en) * | 2019-02-15 | 2019-05-17 | 南京林业大学 | Isolonglifolane ketone group -2- Aminopyrimidines boron trifluoride fluorescence probe and its synthetic method and application |
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CN108586361A (en) * | 2018-04-03 | 2018-09-28 | 南京林业大学 | Isolonglifolane base dihydro-pyrimidin thioketone and its preparation method and application |
CN109761917A (en) * | 2019-02-15 | 2019-05-17 | 南京林业大学 | Isolonglifolane ketone group -2- Aminopyrimidines boron trifluoride fluorescence probe and its synthetic method and application |
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CN109776492A (en) * | 2019-03-04 | 2019-05-21 | 南京林业大学 | A kind of fluorescence probe and the preparation method and application thereof of the highly selective detection hydrazine of response type |
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 |
CN112480071A (en) * | 2020-11-30 | 2021-03-12 | 南京林业大学 | Isolongifolane ratio type fluorescent probe for detecting hydrazine and preparation method 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 |
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