CN106632239B - A kind of isolonglifolane ketone group hexahydro quinazoline -2- amine schiff's base type fluorescent material and its synthetic method and application - Google Patents
A kind of isolonglifolane ketone group hexahydro quinazoline -2- amine schiff's base type fluorescent material and its synthetic method and application Download PDFInfo
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Abstract
The invention discloses a kind of isolonglifolane ketone group hexahydro quinazoline -2- amine schiff's base type fluorescent material and its synthetic method and applications.The present invention comes into leaves ene derivative isolongitolanone using natural reproducible resource as raw material and the condensation of 2- pyridine carboxaldehyde, obtains 7- (2 '-pyridinylmethylene) isolongitolanone；7- (2 '-pyridinylmethylene) isolongitolanone carries out condensation and cyclization with guanidine hydrochloride again, obtains 6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] quinazoline -2- amine；1- (((6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5 is condensed to yield with 2- hydroxyl-1-naphthalene Formaldehyde again, 7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinolyl) imido grpup) methyl) Betanaphthol.The compound is glassy yellow in the sunlight, the capable of emitting bright orange green fluorescence under 365nm ultraviolet light.
Description
Technical field
The invention belongs to Minute Organic Synthesis technical fields, are related to a kind of isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff
Alkaline fluorescent material and its synthetic method and application.
Background technique
In luminescent material, the research of small organic molecule luminescent material is increasingly subject to the concern of people, many kinds of, color
It is color relatively abundanter, and since its structure is simple, it is easy to adjust, research is also increasingly extensive, organic compared with phosphor
Small molecule material has higher luminous efficiency and broader luminescent color range, is frequently utilized for optical electron device, photochemistry
Sensor, DNA dyeing, cell dyeing, dyestuff etc..But the most small organic molecule luminescent materials being currently known all hold
Fluorescence-quenching easily occurs under solid conditions, so this, which allows for small molecule emitter material, is typically used to optochemical sensor
Device, and rarely used as fluorescent dye.
Fluorescent dye is a kind of new dye that developed recently gets up, as functional material by more and more
Concern, small organic molecule fluorescent dye have high stability, high dyeing efficiency, cell compared to other kinds of fluorescent dye
The advantages that penetration capacity is strong, and dissolubility is good in cell, small to organism side effect, can be used for fluorescent marker, cell imaging
Etc..
Occur in recent years some for the synthesis of small organic molecule fluorescent dye and its research of optical property, aza-
Novel BODIPY flourescent dye, salicylide azine fluorescent dye etc., but hexahydro quinazoline -2- amine schiff bases are not used for fluorescence dye
Report in terms of color.
Summary of the invention
Goal of the invention: the deficiencies in the prior art are directed to, the purpose of the present invention is to provide a kind of isolongitolanones
Base hexahydro quinazoline -2- amine schiff's base type fluorescent material meets the use demand as fluorescent dye.Another object of the present invention
It is to provide a kind of synthetic method of above-mentioned isolonglifolane ketone group hexahydro quinazoline -2- amine schiff's base type fluorescent material.The present invention is also
There is a purpose to be to provide a kind of application of isolonglifolane ketone group hexahydro quinazoline -2- amine schiff's base type fluorescent material.
Technical solution: for achieving the above object, the technical solution adopted by the present invention are as follows:
A kind of isolonglifolane ketone group hexahydro quinazoline -2- amine schiff's base type fluorescent material, the compound be 1- (((6,6,
10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinoline
Base) imido grpup) methyl) Betanaphthol, structural formula are as follows:
The synthetic method of the isolonglifolane ketone group hexahydro quinazoline -2- amine schiff's base type fluorescent material, including it is following
Step:
1) isolongitolanone and 2- pyridine carboxaldehyde carry out aldol condensation, obtain 7- (2 '-pyridinylmethylene) isolonglifolane
Ketone；
2) 7- (2 '-pyridinylmethylene) isolongitolanone and guanidine hydrochloride carry out condensation reaction, obtain 6,6,10,10- tetra-
Methyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] quinazoline -2- amine；
3) 6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group
Benzo [h] quinazoline -2- amine and 2- hydroxyl-1-naphthalene Formaldehyde are condensed to yield 1- (((6,6,10,10- tetramethyl -4- (2 '-pyridines
Base) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinolyl) imido grpup) methyl) Betanaphthol.
Isolongitolanone and 2- pyridine carboxaldehyde carry out aldol condensation and obtain 7- (2 '-pyridinylmethylene) different length in step 1)
Leaf alkanone, detailed process are as follows:
(1) by 0.8mol isolongitolanone, 0.8~1.0mol 2- pyridine carboxaldehyde, 0.75~1.0mol sodium ethoxide and 1.5
~3L ethyl alcohol sequentially adds in the three-necked flask equipped with blender, thermometer and reflux condenser, carries out at 80-90 DEG C anti-
It answers；
(2) reactant is extracted 3 times with 4L-4.5L ethyl acetate, merges organic phase, for several times with saturated common salt water washing, directly
To neutrality；Organic phase is dried over anhydrous sodium sulfate, filters, concentration and recovery solvent, obtains that 7- (2 '-pyridinylmethylene) is different to come into leaves
Alkanone crude product；
(3) 7- (2 '-pyridinylmethylene) isolongitolanone crude product is recrystallized with EtOH-EtOAc, is obtained
7- (2 '-pyridinylmethylene) isolongitolanone sterling.
In step 2), under sodium ethoxide catalysis, 7- (2 '-pyridinylmethylene) isolongitolanone is reacted with guanidine hydrochloride, is obtained
To 6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h]
Quinazoline -2- amine, detailed process are as follows:
(1) by 0.5mol 7- (2 '-pyridinylmethylene) isolongitolanone, 0.5~0.8mol guanidine hydrochloride, 0.5~
1.0mol sodium ethoxide, 1L-1.5L ethyl alcohol sequentially add in the three-necked flask equipped with blender, thermometer and reflux condenser, add
Hot back flow reaction 8h, with GC tracing detection, until 7- (2 '-pyridinylmethylene) isolongitolanone conversion ratio terminates after reaching 95%
Reaction；
(2) reactant is extracted 3 times with 1L-1.5L ethyl acetate, merges organic phase, for several times with saturated common salt water washing, directly
To neutrality；Organic phase is dried over anhydrous sodium sulfate, filters, concentration and recovery solvent, obtains 6,6,10,10- tetramethyl -4- (2 '-pyrroles
Piperidinyl) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] quinazoline -2- amine crude product；
(3) 6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- bridge methylene
Base benzo [h] quinazoline -2- amine crude product is recrystallized with EtOH-EtOAc, obtains colorless and transparent 6,6,10,10-
Tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] quinazoline -2- amine is brilliant
Body.
In step 3), under acetic acid catalysis, 6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α -
Hexahydro -6H-6 α, 9- endo-methylene group benzo [h] quinazoline -2- amine is condensed with 2- hydroxyl-1-naphthalene Formaldehyde, obtains isolonglifolane
Ketone group hexahydro quinazoline -2- amine schiff's base type fluorescent material 1- (((6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,
9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinolyl) imido grpup) methyl) Betanaphthol, detailed process
Are as follows:
(1) by 0.01mol 6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6
α, 9- endo-methylene group benzo [h] quinazoline -2- amine, 0.01~0.02mol 2- hydroxyl-1-naphthalene Formaldehyde, 0.005~0.01mol second
Acid, 40~100mL ethyl alcohol sequentially add in the three-necked flask equipped with blender, thermometer and reflux condenser, are heated to reflux anti-
Answer 24-36h；
(2) reaction solution is cooled to room temperature, and light yellow sheet output 1- (((6,6,10,10- tetramethyl -4- (2 '-pyrroles are precipitated
Piperidinyl) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinolyl) imido grpup) methyl) naphthalene -2-
Phenol；
(3) the light yellow sheet output of gained is recrystallized in methylene chloride-methanol, obtains the 1- of light yellow sheet
(((6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo
[h] -2- quinolyl) imido grpup) methyl) Betanaphthol product.
Application of the isolonglifolane ketone group hexahydro quinazoline -2- amine schiff's base type fluorescent material as fluorescent dye.
The compound has good fluorescence intensity in the solid state, is in the sunlight glassy yellow, under fluorescence irradiation
Capable of emitting bright orange green fluorescence.
The utility model has the advantages that compared with prior art, the present invention is come into leaves using natural reproducible resource, and ene derivative is different to come into leaves
Alkanone is raw material, is prepared for a kind of isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff bases compound；The compound is in solid
There is good fluorescence intensity under state, be in the sunlight glassy yellow, the capable of emitting bright orange green fluorescence under fluorescence irradiation can be glimmering
Photoinitiator dye uses.
Detailed description of the invention
Fig. 1 is 1- (((6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9-
Endo-methylene group benzo [h] -2- quinolyl) imido grpup) methyl) and Betanaphthol solid luminescent result figure；
Fig. 2 is 1- (((6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9-
Endo-methylene group benzo [h] -2- quinolyl) imido grpup) methyl) and Betanaphthol liquid shine and its be used for paper, the fluorescence of gauze
Coloration result figure.
Specific embodiment
The present invention is described further combined with specific embodiments below.
Embodiment 1
The synthetic method of isolonglifolane ketone group hexahydro quinazoline -2- amine schiff base compounds, synthesis process are as follows:
Specific step is as follows:
1) preparation of 7- (2 '-pyridinylmethylene) isolongitolanone:
2.2g isolongitolanone, 1.07g pyridine 2- formaldehyde, 0.51g sodium ethoxide and 30mL ethyl alcohol are sequentially added to be 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 4h or so
To isolongitolanone conversion ratio up to 95% or more (GC tracing detection).Reactant is extracted 3 times with 20mL ethyl acetate, is merged organic
Phase, for several times with saturated common salt water washing, until neutral；Organic phase is dried over anhydrous sodium sulfate, filters, concentration and recovery solvent, obtains
To 7- (2 '-pyridinylmethylene) isolongitolanone crude product, is recrystallized, obtained colorless and transparent with EtOH-EtOAc
7- (2 '-pyridinylmethylene) isolongitolanone crystal, yield 88.1%, purity 98.1%.
2) 6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group
The preparation of benzo [h] quinazoline -2- amine:
By 1.545g 7- (2 '-pyridinylmethylene) isolongitolanone, 1.91g guanidine hydrochloride, 1.7g sodium ethoxide, 60mL second
Alcohol sequentially adds in the three-necked flask equipped with blender, thermometer and reflux condenser pipe, is heated to flowing back at 80-90 DEG C
Row reaction, reaction 18h or so to 7- (2 '-pyridinylmethylene) 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, for several times with saturated common salt water washing, until neutral；Organic phase warp
Anhydrous sodium sulfate is dry, filters, concentration and recovery solvent, obtains 6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,
10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] quinazoline -2- amine crude product, then weight is carried out with EtOH-EtOAc
Crystallization, obtains colorless and transparent 6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α,
9- endo-methylene group benzo [h] quinazoline -2- amine crystal, yield 86.1%, purity 98.3%.
Characterization of The Products data are as follows: ν: 3488,3266,3141 (v of FT-IR (KBr)N-H,NH2),2962(vas C-H,CH3),
2935(vas C-H,CH2),2872(vs C-H,CH3),1618(vC=N),1555(δN-H,NH2), 1506,1471,1401 (vC=C,
The stretching vibration of phenyl ring C=C ring), 1382,1330 (vC-N), 1243,1090 (δC-H, aromatic ring C-H out-of-plane bending vibration), 798,
748,713 (δC-H, aromatic ring C-H out-of-plane bending vibration)；HRMS(m/z):calcd for C22H28N4 348.2314found
349.2420[M+H+]；1H NMR(300MHz,DMSO-d6) δ: 0.61 (s, 3H), 0.72 (s, 3H), 0.91 (s, 3H), 1.06~
1.09 (m, 1H), 1.17 (d, J=9Hz, 1H), 1.32 (s, 3H), 1.46~1.50 (m, 2H, 1H), 1.59 (d, J=12Hz,
1H), 1.69 (s, 2H), 1.82 (s, 1H), 2.21~2.29 (m, 2H), 2.79 (d, J=15Hz, 1H), 3.34 (s, 1H), 6.19
(s, 2H), 7.41 (t, J=6Hz, 1H), 7.78 (d, J=6Hz, 1H), 7.89 (t, J=6Hz, 1H), 8.63 (d, J=3Hz,
1H)；13C NMR(75MHz,DMSO-d6) δ: 22.88,24.32,25.20,25.52,28.06,29.68,31.74,36.69,
43.67,47.41,54.57,57.10,114.66,123.36,123.31,136.49,148.05,157.17,160.68,
162.72,168.81。
3) 1- (((6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- bridge
Methylene benzo [h] -2- quinolyl) imido grpup) methyl) and Betanaphthol preparation:
By 0.348g 6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9-
Endo-methylene group benzo [h] quinazoline -2- amine, 0.206g 2- hydroxyl-1-naphthalene Formaldehyde, 0.30g acetic acid and 30mL ethyl alcohol, successively plus
Enter in the three-necked flask equipped with blender, thermometer and reflux condenser, heating reflux reaction 36h is then cooled to room temperature, analysis
Light yellow sheet output out, then recrystallized in methylene chloride-methanol, obtain light yellow sheet 1- (((6,6,10,
10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinolyl)
Imido grpup) methyl) Betanaphthol product, yield 43%.
Characterization of The Products data are as follows: IR (KBr, cm-1): 746,844,978,1162,1210,1254,1293,1401,1442,
1532,1629,2964,3113,3459,3573；1H NMR(CDCl3,400MHz):0.74(s,3H),0.82(s,3H),1.09
(s, 3H), 1.24~1.28 (m, 1H), 1.54 (s, 3H), 1.60~1.63 (m, 1H), 1.73~1.78 (m, 1H), 1.86~
1.88 (m, 2H), 2.01 (t, J=8,1H), 2.58 (d, J=12,2H), 3.15 (d, J=12,1H), 6.80 (d, J=8,1H),
7.47~7.51 (m, 2H), 7.55 (d, J=4,1H), 7.68 (d, J=4,1H), 7.98 (t, J=4,2H), 8.07 (d, J=4,
1H), 8.80 (s, 1H), 9.70 (d, J=4,1H), 14.40 (s, 1H)13C NMR(CDCl3,100MHz),23.23,24.76,
25.40,26.24,28.55,30.17,32.39,37.39,39.54,44.71,48.12,55.08,58.14,108.59,
118.84,123.71,123.86,124.10,124.77,126.83,127.04,128.70,129.39,134.47,136.71,
140.78,145.77,148.48,154.35,156.62,163.52,171.51,184.53:EI-MS:calcd for
C33H34N4O 502.66found503.7[M+H+]。
Embodiment 2
By a certain amount of 1- (((6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-
6 α, 9- endo-methylene group benzo [h] -2- quinolyl) imido grpup) methyl) Betanaphthol is placed on filter paper, observe that sample is thin
If the light yellow solid of shredded paper shape is placed under 365nm ultraviolet lamp for the fluorescence property for further looking at sample, discovery
Sample issues very strong yellow-green fluorescence, as shown in Figure 1, a: the photo of compound under sunshine；B: the chemical combination under 365nm ultraviolet lamp
The photo of object；Illustrate 1- (((6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9-
Endo-methylene group benzo [h] -2- quinolyl) imido grpup) methyl) and Betanaphthol solid have good fluorescence property, can be used as glimmering
The use of photoinitiator dye.
Embodiment 3
By a certain amount of 1- (((6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-
6 α, 9- endo-methylene group benzo [h] -2- quinolyl) imido grpup) methyl) Betanaphthol is dissolved in the ethanol-water solution of certain volume,
Then gauze, filter paper will be impregnated wherein respectively, after coming into full contact with profit bubble, filter paper and gauze will be dried, and be placed in 365nm purple
Under outer lamp, as shown in Fig. 2, a: the filter paper after compound dip dyeing；B: the gauze after compound dip dyeing；C: the ethyl alcohol-of compound
Aqueous solution observes that soaking filter paper later and gauze issue very strong nearly green fluorescence, and its liquid condition also has
Good fluorescence intensity illustrates 1- (((6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -
6H-6 α, 9- endo-methylene group benzo [h] -2- quinolyl) imido grpup) methyl) and Betanaphthol can be used as fluorescent dye use, have very
Good fluorescence property.
Claims (6)
1. a kind of isolonglifolane ketone group hexahydro quinazoline -2- amine schiff's base type fluorescent material, which is characterized in that the compound is 1-
(((6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo
[h] -2- quinazolyl) imido grpup) methyl) Betanaphthol, structural formula are as follows:
2. the synthetic method of isolonglifolane ketone group hexahydro quinazoline -2- amine schiff's base type fluorescent material described in claim 1,
It is characterized in that, comprising the following steps:
1) isolongitolanone and 2- pyridine carboxaldehyde carry out aldol condensation, obtain 7- (2 '-pyridinylmethylene) isolongitolanone；
2) 7- (2 '-pyridinylmethylene) isolongitolanone and guanidine hydrochloride carry out condensation reaction, obtain 6,6,10,10- tetramethyls-
4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] quinazoline -2- amine；
3) 6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo
[h] quinazoline -2- amine and 2- hydroxyl-1-naphthalene Formaldehyde be condensed to yield 1- (((6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,
7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinazolyl) imido grpup) methyl) Betanaphthol；
The structural formula of isolongitolanone used is as follows:
3. the synthesis side of isolonglifolane ketone group hexahydro quinazoline -2- amine schiff's base type fluorescent material according to claim 2
Method, which is characterized in that isolongitolanone and 2- pyridine carboxaldehyde carry out aldol condensation and obtain 7- (2 '-pyridyl group methylenes in step 1)
Base) isolongitolanone, detailed process are as follows:
(1) by 0.8mol isolongitolanone, 0.8~1.0mol 2- pyridine carboxaldehyde, 0.75~1.0mol sodium ethoxide and 1.5~3L
Ethyl alcohol sequentially adds in the three-necked flask equipped with blender, thermometer and reflux condenser, is reacted at 80-90 DEG C；
(2) reactant is extracted 3 times with 4L-4.5L ethyl acetate, merges organic phase, for several times with saturated common salt water washing, until in
Property；Organic phase is dried over anhydrous sodium sulfate, filters, concentration and recovery solvent, obtains 7- (2 '-pyridinylmethylene) isolongitolanone
Crude product；
(3) 7- (2 '-pyridinylmethylene) isolongitolanone crude product is recrystallized with EtOH-EtOAc, obtains 7-
(2 '-pyridinylmethylene) isolongitolanone sterling.
4. the synthesis side of isolonglifolane ketone group hexahydro quinazoline -2- amine schiff's base type fluorescent material according to claim 2
Method, which is characterized in that in step 2), under sodium ethoxide catalysis, 7- (2 '-pyridinylmethylene) isolongitolanone and guanidine hydrochloride are anti-
It answers, obtains 6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzene
And [h] quinazoline -2- amine, detailed process are as follows:
(1) by 0.5mol 7- (2 '-pyridinylmethylene) isolongitolanone, 0.5~0.8mol guanidine hydrochloride, 0.5~1.0mol second
Sodium alkoxide, 1L-1.5L ethyl alcohol sequentially add in the three-necked flask equipped with blender, thermometer and reflux condenser, are heated to reflux anti-
8h is answered, with GC tracing detection, is reacted until 7- (2 '-pyridinylmethylene) isolongitolanone conversion ratio terminates after reaching 95%；
(2) reactant is extracted 3 times with 1L-1.5L ethyl acetate, merges organic phase, for several times with saturated common salt water washing, until in
Property；Organic phase is dried over anhydrous sodium sulfate, filters, concentration and recovery solvent, obtains 6,6,10,10- tetramethyl -4- (2 '-pyridines
Base) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] quinazoline -2- amine crude product；
(3) 6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzene
And [h] quinazoline -2- amine crude product is recrystallized with EtOH-EtOAc, obtains colorless and transparent 6,6,10,10- tetramethyls
Base -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] quinazoline -2- amine crystal.
5. the synthesis side of isolonglifolane ketone group hexahydro quinazoline -2- amine schiff's base type fluorescent material according to claim 2
Method, which is characterized in that in step 3), under acetic acid catalysis, 6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,
10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] quinazoline -2- amine is condensed with 2- hydroxyl-1-naphthalene Formaldehyde, is obtained
Isolonglifolane ketone group hexahydro quinazoline -2- amine schiff's base type fluorescent material 1- (((6,6,10,10- tetramethyl -4- (2 '-pyridines
Base) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinazolyl) imido grpup) methyl) naphthalene -2-
Phenol, detailed process are as follows:
(1) by 0.01mol 6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9-
Endo-methylene group benzo [h] quinazoline -2- amine, 0.01~0.02mol 2- hydroxyl-1-naphthalene Formaldehyde, 0.005~0.01mol acetic acid,
40~100mL ethyl alcohol sequentially adds in the three-necked flask equipped with blender, thermometer and reflux condenser, heating reflux reaction
24-36h；
(2) reaction solution is cooled to room temperature, and light yellow sheet output 1- (((6,6,10,10- tetramethyl -4- (2 '-pyridines are precipitated
Base) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinazolyl) imido grpup) methyl) naphthalene -2-
Phenol；
(3) the light yellow sheet output of gained is recrystallized in methylene chloride-methanol, obtains the 1- of light yellow sheet
(((6,6,10,10- tetramethyl -4- (2 '-pyridyl group) -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo
[h] -2- quinazolyl) imido grpup) methyl) Betanaphthol product.
6. isolonglifolane ketone group hexahydro quinazoline -2- amine schiff's base type fluorescent material described in claim 1 is as fluorescent dye
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| Title |
|---|
| "A Stereospecific Approach to Diterpene Alkaloids with a Bridge Across Ring B";K.WIESNER等;《EXPERIENTIA》;19721231;第28卷(第7期);766-767页 |
| "Isolongifolanone-based molecular fluorescence marker for imaging endogenous Zn2+ in vivo";WANG Zhonglong等;《Tetrahedron》;20170821;第73卷(第40期);5912-5919页 |
| "异长叶烷酮合成新型喹唑啉衍生物的研究";芮坚等;《林产化学与工业》;20160831;第36卷(第4期);121-127页 |
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