CN106632084A - Iso-longitolanone based hexahydroquinazoline-2-amine Schiff base Zn<2+> fluorescent probe as well as preparation method and application thereof - Google Patents
Iso-longitolanone based hexahydroquinazoline-2-amine Schiff base Zn<2+> fluorescent probe as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN106632084A CN106632084A CN201610887565.5A CN201610887565A CN106632084A CN 106632084 A CN106632084 A CN 106632084A CN 201610887565 A CN201610887565 A CN 201610887565A CN 106632084 A CN106632084 A CN 106632084A
- Authority
- CN
- China
- Prior art keywords
- hexahydro
- phenyl
- endo
- amine
- tetramethyl
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
-
- 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
-
- 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"
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an iso-longitolanone based hexahydroquinazoline-2-amine Schiff base Zn<2+> fluorescent probe as well as a preparation method and an application thereof. The preparation method comprises steps as follows: iso-longitolanone which is a derivative of longifolene as a natural renewable resource is taken as a raw material and is subjected to condensation with benzaldehyde, and 7-benzylidene-iso-longitolanone is produced; 7-benzylidene-iso-longitolanone is subjected to condensation and cyclization with guanidine hydrochloride, and 6,6,10,10-tetramethyl-4-phenyl-5,7,8,9,10 alpha-hexahydro-6H-6 alpha,9-methano-benzo[h] quinazoline-2-amine is obtained and subjected to condensation with 2-hydroxy-1-naphthaldehyde, 1-(((6,6,10,10- tetramethyl-4-phenyl-5,7,8,9,10alpha-hexahydro-6H-6alpha,9-methano-benzo[h]-2-quinolyl) imidogen)methyl)naphthalene-2-phenol is obtained, the compound can only react with Zn<2+> to form a complex, and the complex emits green fluorescence under the irradiation of 365 nm ultraviolet light and can be taken as the fluorescent probe for Zn<2+>concentration detection.
Description
Technical field
The invention belongs to Minute Organic Synthesis technical field, is related to isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff bases
Zinc ion fluorescent and its preparation method and application.
Background technology
Zn2+It is one of trace element needed by human, it is widely distributed in the middle of the blood of human body and cell, in human body
Grow, hereditary reproduction, the aspect such as immunity of organism plays vital role.Free zinc ion even more almost divides
It is distributed in the middle of all important tissues of human body, but due to the special stable chemical constitution of zinc ion, conventional detection method is such as
The detection of the methods such as ultraviolet-visible spectrum, cyclic voltammetry and inapplicable zinc ion, and other traditional detection methods are as divided
The methods such as light luminosity, chemoluminescence method there is also the shortcoming more than comparison.The advantages of fluorescence probe method has quick, sensitivity is high is
It is used in the middle of the detection for zinc ion.
In recent years occur in that a certain amount of organic fluorescence probe study on the synthesis and its be used for Zn2+The report of detection, such as：6-
Hydroxyl -9- [4- (4,7,10- trimethyls-Isosorbide-5-Nitrae, 7,10- tetraazacyclododecanand bases)]-phenyl -3H- xanthene -3- ketone, quinoline
Derivative, 2- (N- (2- ethoxys)-N- ((pyridine -2- bases) methyl) amino)-N- (8- quinolyls) acetamide etc..But also do not have
There is synthesis hexahydro quinazoline -2- amine schiff base compound and it is used for Zn2+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 isolongitolanone
Base hexahydro quinazoline -2- amine Schiff bases zinc ion fluorescents, can selectivity and Zn2+Complexing, and issue in ultraviolet light
Go out specific fluorescence, for detecting Zn2+Concentration.It is a further object of the present invention to provide a kind of above-mentioned isolonglifolane ketone group hexahydro
The preparation method of quinazoline -2- amine Schiff bases zinc ion fluorescents.Further object of the present invention is to provide above-mentioned different come into leaves
The application of alkanone base hexahydro quinazoline -2- amine Schiff bases zinc ion fluorescents.
Technical scheme：For achieving the above object, the technical solution used in the present invention is：
Isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff bases zinc ion fluorescents, the compound name is：1-
(((6,6,10,10- tetramethyl -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinoline
Base) imido grpup) methyl) Betanaphthol；Structural formula is：
The preparation method of described isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff bases zinc ion fluorescents, bag
Include following steps：
1) isolongitolanone carries out aldol condensation with benzaldehyde, obtains 7- benzylidene isolongitolanones；
2) 7- benzylidenes isolongitolanone carries out condensation reaction with guanidine hydrochloride, obtains 6,6,10,10- tetramethyl -4- benzene
The α of base-5,7,8,9,10,10-hexahydro-6H-6 α, 9- endo-methylene group benzo [h] quinazoline-2- amine；
3) 6,6,10,10- tetramethyls -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- endo-methylene group benzos [h]
Quinazoline -2- amine and 2- hydroxyl-1-naphthalene Formaldehydes be condensed to yield 1- (((6,6,10,10- tetramethyl -4- phenyl -5,7,8,9,10,
10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinolyls) imido grpup) methyl) Betanaphthol.
Step 1) in, isolongitolanone carries out aldol condensation and obtains 7- benzylidene isolongitolanones with benzaldehyde, specifically
Preparation method it is as follows：
(1) by 0.8mol isolongitolanones, 0.8～1.0mol benzaldehydes, 0.75～1.0mol caustic alcohols and 1.5～3L second
Alcohol is sequentially added to be furnished with the there-necked flask of agitator, 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, with saturated common salt water washing for several times, directly
To neutrality；Organic phase Jing anhydrous sodium sulfate drying, filtration, concentration and recovery solvent, obtain 7- benzylidene isolongitolanones and slightly produce
Thing；
(3) 7- benzylidenes isolongitolanone crude product is recrystallized with EtOH-EtOAc, obtains 7- benzylidenes
Isolongitolanone sterling.
Step 2) in, under caustic alcohol catalysis, 7- benzylidenes isolongitolanone reacts with guanidine hydrochloride, obtains 6,6,10,
10- tetramethyl -4- phenyl -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] quinazoline -2- amine, specifically
Preparation method include：
(1) by 0.5mol 7- benzylidene isolongitolanones, 0.5～0.8mol guanidine hydrochlorides, 0.5～1.0mol caustic alcohols,
1L-1.5L ethanol is sequentially added to be furnished with the there-necked flask of agitator, thermometer and reflux condenser, heating reflux reaction 8h,
GC tracing detections are used, until terminating reaction after 7- benzylidene isolongitolanone conversion ratios reach 95%；
(2) reactant is extracted 3 times with 1L-1.5L ethyl acetate, merges organic phase, with saturated common salt water washing for several times, directly
To neutrality；Organic phase Jing anhydrous sodium sulfate drying, filtration, concentration and recovery solvent, obtain 6,6,10,10- tetramethyl -4- phenyl -
5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] quinazoline -2- amine crude products；
(3) 6,6,10,10- tetramethyls -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- endo-methylene group benzos
[h] quinazoline -2- amine crude products are recrystallized with EtOH-EtOAc, obtain the tetramethyl -4- of white cotton like 6,6,10,10-
The α of phenyl-5,7,8,9,10,10-hexahydro-6H-6 α, 9- endo-methylene group benzo [h] quinazoline-2- amine crystal.
Step 3) in, with acetic acid catalyst, 6,6,10,10- tetramethyl -4- phenyl -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 Formaldehydes, obtains 1- (((6,6,10,10-
Tetramethyl -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinolyls) imido grpup) first
Base) Betanaphthol；Specific preparation method includes：
(1) by 0.01mol 6,6,10,10- tetramethyl -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- bridges are sub-
Methyl benzo [h] quinazoline -2- amine, 0.01～0.02mol 2- hydroxyl-1-naphthalene Formaldehydes, 0.005～0.01mol acetic acid, 40～
100mL ethanol is sequentially added to be furnished with the there-necked flask of agitator, thermometer and reflux condenser, and heating reflux reaction 24～
36h；
(2) reactant is cooled to room temperature, separate out light yellow 1- (((6,6,10,10- tetramethyl -4- phenyl -5,7,8,9,
10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinolyls) imido grpup) methyl) Betanaphthol powder；
(3) gained buff powder is recrystallized in methylene chloride-methanol, obtain light yellow 1- (((6,6,10,
10- tetramethyl -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinolyls) imido grpup)
Methyl) Betanaphthol crystal.
Described isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff bases zinc ion fluorescents are in detection zinc ion
Application.
Described application, compound 1- (((6,6,10,10- tetramethyl -4- phenyl -5,7,8,9,10,10 α-hexahydro -6H-
6 α, 9- endo-methylene group benzo [h] -2- quinolyls) imido grpup) methyl) Betanaphthol is narrow spectrum and Zn2+Ion complexation,
Green fluorescence is sent under 365nm ultraviolet lights, zinc ion is detected.
The present invention natural reproducible resource ene derivative isolongitolanone that comes into leaves is raw material, and with benzaldehyde reaction 7- is generated
Benzylidene isolongitolanone；7- benzylidenes isolongitolanone carries out condensation reaction and obtains 6,6,10,10- tetra- with guanidine hydrochloride again
The α of methyl 4-phenyl-5,7,8,9,10,10-hexahydro-6H-6 α, 9- endo-methylene group benzo [h] quinazoline-2- amine；6,6,10,10-
Tetramethyl -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] quinazoline -2- amine again with 2- hydroxyls
Base -1- naphthaldehydes are condensed, and obtain new hexahydro quinazoline -2- amine schiff base compounds 1- (((6,6,10,10- tetra-
The α of methyl 4-phenyl-5,7,8,9,10,10-hexahydro-6H-6 α, 9- endo-methylene group benzo [h]-2- quinolyls) imido grpup) methyl)
Betanaphthol.It was found that the compound can narrow spectrum identification Zn2+Ion, can be used as detection Zn2+The fluorescence probe of ion.
Beneficial effect：Compared with existing achievement in research, the utilization natural reproducible resource of the present invention comes into leaves ene derivative
Isolongitolanone prepares isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff bases compounds for raw material；Can selectively and Zn2+
Ion complexation, and the fluorescence of green is sent, the compound can be used to detect Zn as selectivity fluorescence probe2+Ion.
Description of the drawings
Fig. 1 is 1- (((6,6,10,10- tetramethyl -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- bridge methylene
Base benzo [h] -2- quinolyls) imido grpup) methyl) and Betanaphthol and variable concentrations the ultra-violet absorption spectrum knot that is complexed of zinc ion
Fruit is schemed；
Fig. 2 is 1- (((6,6,10,10- tetramethyl -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- bridge methylene
Base benzo [h] -2- quinolyls) imido grpup) methyl) and Betanaphthol under sunshine and 365nm ultraviolet lights with zinc ion complexing before and after
Result figure.
Specific embodiment
With reference to specific embodiment, the present invention is described further.
Embodiment 1
The synthetic method of isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff bases compounds, building-up process is：
Comprise the following steps that：
1) preparation of 7- benzylidenes isolongitolanone：
2.2g isolongitolanones, 1.06g benzaldehydes, 0.51g caustic alcohols and 30mL ethanol are sequentially added be furnished with agitator,
In the there-necked flask of thermometer and reflux condenser, it is heated to backflow at 80-90 DEG C and is reacted, reaction 4h or so is to different length
Leaf alkanone conversion ratio is up to more than 95% (GC tracing detections).Reactant is extracted 3 times with 20mL ethyl acetate, merges organic phase, is used
Saturated common salt water washing for several times, until neutral；Organic phase Jing anhydrous sodium sulfate drying, filtration, concentration and recovery solvent, obtain 7- benzene
Methylene isolongitolanone crude product, is recrystallized with EtOH-EtOAc, obtains the different length of water white 7- benzylidenes
Leaf alkanone crystal, yield is 87.1%, and purity is 97.2%.
2) 6,6,10,10- tetramethyls -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- endo-methylene group benzos [h]
Quinazoline -2- amine：
1.540g 7- benzylidene isolongitolanones, 1.91g guanidine hydrochlorides, 1.7g caustic alcohols, 60mL ethanol are sequentially added
In being furnished with the there-necked flask of agitator, thermometer and reflux condenser, it is heated to backflow at 80-90 DEG C and is reacted, reacts
18h or so to 7- benzylidene isolongitolanone conversion ratios are up to more than 95% (GC tracing detections).Reactant is extracted with ethyl acetate
Take 3 times, merge organic phase, with saturated common salt water washing for several times, until neutral；It is organic phase Jing anhydrous sodium sulfate drying, filtration, dense
Contracting recycling design, obtains 6,6,10,10- tetramethyl -4- phenyl -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzene
And [h] quinazoline -2- amine crude products, recrystallized with EtOH-EtOAc, the 6 of white cotton like are obtained, 6,10,10- tetramethyls
Base -4- phenyl -5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] quinazoline -2- amine crystal, yield
85.3%, purity is 98.5%.
3) 1- (((6,6,10,10- tetramethyl -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- endo-methylene group benzene
And [h] -2- quinolyls) imido grpup) methyl) Betanaphthol：
By 0.347g 6,6,10,10- tetramethyl -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- endo-methylene groups
Benzo [h] quinazoline -2- amine, 0.206g 2- hydroxyl-1-naphthalene Formaldehydes, 0.30g acetic acid and 30mL ethanol are sequentially added to be furnished with and stirred
In mixing the there-necked flask of device, thermometer and reflux condenser, heating reflux reaction 36h is subsequently cooled to room temperature, separates out light yellow
Powder, then recrystallized with methylene chloride-methanol, obtain lurid 1- (((6,6,10,10- tetramethyl -4- phenyl -
5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinolyls) imido grpup) methyl) Betanaphthol crystal,
Yield is 41%.
Characterization of The Products data are：IR(KBr,cm-1):702,749,777,841,975,1135,1158,1207,1284,
1370,1400,1439,1458,1529,1594,1629,1654,2862,2964,3126,3420.1H NMR(CDCl3,
400MHz):0.43 (s, 3H), 0.55 (s, 3H), 0.78 (s, 3H), 0.95～0.96 (m, 1H), 1.07 (d, J=8,1H),
(1.25 s, 3H), 1.30～1.35 (m, 1H), 1.43～1.45 (m, 1H), 1.47～1.49 (m, 2H), 1.52 (d, J=4,
1H), 1.58 (s, 1H), 1.71～1.74 (m, 1H), 2.13 (d, J=12,1H), 2.29 (s, 1H), 2.62 (d, J=8,1H),
6.50 (d, J=8,1H), 700 (t, J=4,1H), 7.19 (t, J=4,1H), 7.24 (s, 1H), 7.38～7.43 (m, 3H),
7.67 (d, J=8,1H), 9.40 (d, J=8,1H), 14.07 (s, 1H).13C NMR(CDCl3,100MHz),184.93,
170.97,166.85,154.92,146.04,141.06,138.11,134.84,129.78,129.68,129.61,129.00,
128.55,128.28,127.43,127.13,126.99,124.39,122.57,119.21,108.89,58.44,55.51,
48.35,44.91,40.20,37.69,33.10,30.39,28.75,26.49,25.70,25.07,23.29:EI-MS:calcd
for C34H35N3O 501.66found 524.1[M+Na+]。
Embodiment 2
By a certain amount of 1- (((6,6,10,10- tetramethyl -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- bridges
Methylene benzo [h] -2- quinolyls) imido grpup) methyl) Betanaphthol is dissolved in HEPES cushioning liquid (1 × 10-5M), equally will
Zn2+Ion is dissolved in HEPES cushioning liquid and is made into concentration for 0～2.1 × 10-5The solution of M.Measure the Zn of variable concentrations2+Ion pair
1- (((6,6,10,10- tetramethyl -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinolines
Quinoline base) imido grpup) methyl) and Betanaphthol ultra-violet absorption spectrum, as shown in Figure 1.As a result show, compound is 320nm's or so
UV absorption is remarkably reinforced, and illustrates compound energy and Zn2+Ion is complexed.
Embodiment 3
By a certain amount of 1- (((6,6,10,10- tetramethyl -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- bridges
Methylene benzo [h] -2- quinolyls) imido grpup) methyl) Betanaphthol is dissolved in HEPES cushioning liquid (1 × 10-5M), its solution is in
Water white transparency state, with Zn2+Ion (1 × 10-5M addition), solution rapidly goes to glassy yellow, sees under 365nm uviol lamps
Examine, as shown in Fig. 2 a：Compound adds Zn under sunshine2+Product photo before and after ion；b：Compound adds Zn under 365nm uviol lamps2 +Photo before and after ion, adds Zn2+The solution of ion sends very strong green fluorescence, and passes through to add the K of equimolar amounts+, Na+,
Cu2+, Hg2+, Pb2+, Mg2+, Fe3+, Fe2+, Ni2+, Cd2+, Co2+, Mn2+Deng metal ion, then the increasing of compound fluorescence is not result in
By force, illustrate that the compound can be used as a kind of effectively identification Zn2+The fluorescence probe of ion.
Claims (7)
1. isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff bases zinc ion fluorescents, it is characterised in that the chemical combination name
Referred to as：1- (((6,6,10,10- tetramethyl -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- endo-methylene group benzos
[h] -2- quinolyls) imido grpup) methyl) Betanaphthol；Structural formula is：
2. the preparation of the isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff bases zinc ion fluorescents described in claim 1
Method, it is characterised in that comprise the following steps：
1) isolongitolanone carries out aldol condensation with benzaldehyde, obtains 7- benzylidene isolongitolanones；
2) 7- benzylidenes isolongitolanone carries out condensation reaction with guanidine hydrochloride, obtains 6,6,10,10- tetramethyl -4- phenyl -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- tetramethyls -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] quinoline azoles
Quinoline-2- amine and 2- hydroxyl-1-naphthalene Formaldehydes be condensed to yield 1- (((α of 6,6,10,10- tetramethyl-4- phenyl-5,7,8,9,10,10-
Hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinolyls) imido grpup) methyl) Betanaphthol.
3. isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff bases zinc ion fluorescents according to claim 2
Preparation method, it is characterised in that step 1) in, isolongitolanone carries out aldol condensation and obtains the different length of 7- benzylidenes with benzaldehyde
Leaf alkanone, specific preparation method is as follows：
(1) by 0.8mol isolongitolanones, 0.8～1.0mol benzaldehydes, 0.75～1.0mol caustic alcohols and 1.5～3L ethanol according to
Secondary addition is furnished with the there-necked flask of agitator, 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, with saturated common salt water washing for several times, until in
Property；Organic phase Jing anhydrous sodium sulfate drying, filtration, concentration and recovery solvent, obtain 7- benzylidene isolongitolanone crude products；
(3) 7- benzylidenes isolongitolanone crude product is recrystallized with EtOH-EtOAc, obtains the different length of 7- benzylidenes
Leaf alkanone sterling.
4. isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff bases zinc ion fluorescents according to claim 2
Preparation method, it is characterised in that step 2) in, under caustic alcohol catalysis, 7- benzylidenes isolongitolanone reacts with guanidine hydrochloride,
Obtain 6,6,10,10- tetramethyl -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] quinoline azoles
Quinoline -2- amine, specific preparation method includes：
(1) by 0.5mol 7- benzylidene isolongitolanones, 0.5～0.8mol guanidine hydrochlorides, 0.5～1.0mol caustic alcohols, 1L-
1.5L ethanol is sequentially added to be furnished with the there-necked flask of agitator, thermometer and reflux condenser, and heating reflux reaction 8h uses GC
Tracing detection, until terminating reaction after 7- benzylidene isolongitolanone conversion ratios reach 95%；
(2) reactant is extracted 3 times with 1L-1.5L ethyl acetate, merges organic phase, with saturated common salt water washing for several times, until in
Property；Organic phase Jing anhydrous sodium sulfate drying, filtration, concentration and recovery solvent, obtain 6,6,10,10- tetramethyl -4- phenyl -5, and 7,
8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] quinazoline -2- amine crude products；
(3) 6,6,10,10- tetramethyls -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] quinolines
Oxazoline -2- amine crude products are recrystallized with EtOH-EtOAc, obtain the tetramethyl -4- phenyl of white cotton like 6,6,10,10- -
5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] quinazoline -2- amine crystal.
5. isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff bases zinc ion fluorescents according to claim 2
Preparation method, it is characterised in that step 3) in, with acetic acid catalyst, 6,6,10,10- tetramethyl -4- phenyl -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 Formaldehydes, obtains 1-
(((6,6,10,10- tetramethyl -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinoline
Base) imido grpup) methyl) Betanaphthol；Specific preparation method includes：
(1) by 0.01mol 6,6,10,10- tetramethyl -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- endo-methylene groups
Benzo [h] quinazoline -2- amine, 0.01～0.02mol 2- hydroxyl-1-naphthalene Formaldehydes, 0.005～0.01mol acetic acid, 40～100mL
Ethanol is sequentially added to be furnished with the there-necked flask of agitator, thermometer and reflux condenser, 24～36h of heating reflux reaction；
(2) reactant is cooled to room temperature, separate out light yellow 1- (((6,6,10,10- tetramethyl -4- phenyl -5,7,8,9,10,10
α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinolyls) imido grpup) methyl) Betanaphthol powder；
(3) gained buff powder is recrystallized in methylene chloride-methanol, is obtained light yellow 1- (((6,6,10,10-
Tetramethyl -4- -5,7,8,9,10,10 α of phenyl-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinolyls) imido grpup) first
Base) Betanaphthol crystal.
6. the isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff bases zinc ion fluorescents described in claim 1 are in detection
Application in zinc ion.
7. application according to claim 6, it is characterised in that compound 1- (((6,6,10,10- tetramethyl -4- phenyl -
5,7,8,9,10,10 α-hexahydro -6H-6 α, 9- endo-methylene group benzo [h] -2- quinolyls) imido grpup) methyl) Betanaphthol is single-minded
Property and Zn2+Ion complexation, under 365nm ultraviolet lights green fluorescence is sent, and detects zinc ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610887565.5A CN106632084B (en) | 2016-10-10 | 2016-10-10 | Isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff bases zinc ion fluorescent and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610887565.5A CN106632084B (en) | 2016-10-10 | 2016-10-10 | Isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff bases zinc ion fluorescent and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106632084A true CN106632084A (en) | 2017-05-10 |
| CN106632084B CN106632084B (en) | 2019-01-04 |
Family
ID=58856034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610887565.5A Expired - Fee Related CN106632084B (en) | 2016-10-10 | 2016-10-10 | Isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff bases zinc ion fluorescent and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106632084B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459488A (en) * | 2017-09-04 | 2017-12-12 | 南京林业大学 | Isolonglifolane base and the amine Schiff bases fluorescent chemicals of pyrimidine 2 and preparation method thereof |
| CN107892654A (en) * | 2017-11-30 | 2018-04-10 | 南京林业大学 | A kind of isolonglifolane base fluorescent type acid-base indicator and its synthetic method and application |
| CN108424393A (en) * | 2018-03-13 | 2018-08-21 | 南京林业大学 | A kind of hypochlorous acid fluorescence probe 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 |
| 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 |
| CN111808109A (en) * | 2020-06-29 | 2020-10-23 | 南京林业大学 | Pyridazine quinoxaline diamine Schiff base cobalt ion fluorescent probe and preparation method 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1360324A (en) * | 2002-02-01 | 2002-07-24 | 厦门宏发电声有限公司 | Electromagnetic relay with well flexible moving reed |
| US20120277325A1 (en) * | 2011-02-15 | 2012-11-01 | Belko Robert P | Novel pyrimidine derivatives and their use in perfume compositions |
| CN105085413A (en) * | 2015-09-01 | 2015-11-25 | 南京林业大学 | Tetrahydroquinazoline-2-schiff base compounds as well as synthesis method and application thereof |
| CN105669565A (en) * | 2016-03-21 | 2016-06-15 | 南京林业大学 | Isolongifolanone pyrimidine compound, and preparation method and application thereof |
-
2016
- 2016-10-10 CN CN201610887565.5A patent/CN106632084B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1360324A (en) * | 2002-02-01 | 2002-07-24 | 厦门宏发电声有限公司 | Electromagnetic relay with well flexible moving reed |
| US20120277325A1 (en) * | 2011-02-15 | 2012-11-01 | Belko Robert P | Novel pyrimidine derivatives and their use in perfume compositions |
| CN105085413A (en) * | 2015-09-01 | 2015-11-25 | 南京林业大学 | Tetrahydroquinazoline-2-schiff base compounds as well as synthesis method and application thereof |
| CN105669565A (en) * | 2016-03-21 | 2016-06-15 | 南京林业大学 | Isolongifolanone pyrimidine compound, and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| WIESNER, K.，等: "Stereospecific approach to diterpene alkaloids with a bridge across ring B", 《EXPERIENTIA 》 * |
| ZHONGLONG WANG，等: "Isolongifolanone-based molecular fluorescence marker for imaging endogenous Zn2+ in vivo", 《TETRAHEDRON》 * |
| 芮坚，等: "异长叶烷酮合成新型喹唑啉衍生物的研究", 《林产化学与工业》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459488B (en) * | 2017-09-04 | 2019-05-07 | 南京林业大学 | Isolonglifolane base and pyrimidine -2- amine Schiff bases fluorescent chemicals and preparation method thereof |
| CN107459488A (en) * | 2017-09-04 | 2017-12-12 | 南京林业大学 | Isolonglifolane base and the amine Schiff bases fluorescent chemicals of pyrimidine 2 and preparation method thereof |
| CN107892654B (en) * | 2017-11-30 | 2020-02-14 | 南京林业大学 | Isolongifolane-based fluorescent acid-base indicator and synthetic method and application thereof |
| CN107892654A (en) * | 2017-11-30 | 2018-04-10 | 南京林业大学 | A kind of isolonglifolane base fluorescent type acid-base indicator and its synthetic method and application |
| CN108424393A (en) * | 2018-03-13 | 2018-08-21 | 南京林业大学 | A kind of hypochlorous acid fluorescence probe 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 |
| 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 |
| 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 |
| CN111808109A (en) * | 2020-06-29 | 2020-10-23 | 南京林业大学 | Pyridazine quinoxaline diamine Schiff base cobalt ion fluorescent probe and preparation method thereof |
| CN111808109B (en) * | 2020-06-29 | 2022-03-25 | 南京林业大学 | Pyridazine quinoxaline diamine Schiff base cobalt ion fluorescent probe and preparation method 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106632084B (en) | 2019-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106632084A (en) | Iso-longitolanone based hexahydroquinazoline-2-amine Schiff base Zn<2+> fluorescent probe as well as preparation method and application thereof | |
| CN109232444B (en) | Camphor-based fluorescent probe for detecting hydrazine and preparation method thereof | |
| CN108424393B (en) | Hypochlorous acid fluorescent probe and preparation method and application thereof | |
| CN105085413B (en) | Tetrahydroquinazoline-2-schiff base compounds as well as synthesis method and application thereof | |
| CN104845612A (en) | Polystyrene mercury ion fluorescence recognition materials and preparation method thereof | |
| CN110759871B (en) | Camphor synthesized quinazoline compound used as fluorescent probe for hypochlorous acid detection | |
| CN106632239B (en) | A kind of isolonglifolane ketone group hexahydro quinazoline -2- amine schiff's base type fluorescent material and its synthetic method and application | |
| CN108658838B (en) | Heptamethine indocyanine-based formaldehyde fluorescent probe and preparation method and use method thereof | |
| CN107434801A (en) | A kind of 4 ' pyridyl-pyrimidine class compounds and its synthetic method and application | |
| CN105504860A (en) | Synthesis and applications of pyranoquinoline fluorescent dye | |
| CN111825655A (en) | Hg detection method2+High-sensitivity fluorescent probe and preparation method and application thereof | |
| CN107892654B (en) | Isolongifolane-based fluorescent acid-base indicator and synthetic method and application thereof | |
| CN106478645B (en) | A kind of cyclosubstituted spiro indole diketopiperazine compound of virtue and its synthetic method | |
| CN111518128B (en) | Fluorescent probe for detecting fluorine ions and preparation method and application thereof | |
| CN107760298A (en) | A kind of fluorescence probe for detecting bisulfite and preparation method and application | |
| Kosower et al. | Some unsaturated imines | |
| CN109081784B (en) | Triphenylamine derivative and preparation method and application thereof | |
| CN109776492B (en) | Reaction type fluorescent probe for detecting hydrazine with high selectivity as well as preparation method and application thereof | |
| CN107267139B (en) | Multifunctional bis (benzimidazole) naphthalene fluorescence chemical sensor and application thereof | |
| CN110003049A (en) | A method of preparing 4- cyano -1- indone | |
| CN106349250B (en) | A kind of compound and its preparation method and application of Selective recognition mercury ion | |
| CN104292215A (en) | Method for preparing dabigatran etexilate hydrolysis impurity | |
| CN111763187B (en) | Coumarin-based hydrogen sulfide fluorescent probe and preparation method and application thereof | |
| CN109916874B (en) | Preparation method of fluorescent material for formaldehyde gas detection | |
| CN109761917B (en) | Isolongifolanone-2-aminopyrimidine boron trifluoride fluorescent probe and synthetic method and application 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 |
Granted publication date: 20190104 Termination date: 20211010 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |