CN107721876A - Binol diform contracting amino acids schiff bases and its synthetic method and application - Google Patents
Binol diform contracting amino acids schiff bases and its synthetic method and application Download PDFInfo
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Abstract
Binol diform aldehyde contracting amino acids schiff bases and its synthetic method and application, it is related to a kind of dicarbaldehyde contracting amino acids schiff bases of 1,1 ' dinaphthalene of 2,2 ' dihydroxy 3,3 ' and its synthetic method and application.It is that the schiff bases that the naphthal amino acid of 2 hydroxyl of planar structure 1 to be solved obtains does not have the problem of recognition capability to metal.The structural formula of the dicarbaldehyde contracting amino acids schiff bases of 2,2 ' dihydroxy of the invention, 1,1 ' dinaphthalene 3,3 '.Method：First, amino acid and KOH are dissolved in organic solvent, add Binol diform reactions, obtain crude product；2nd, ethyl acetate is dissolved in after crude product is concentrated, is filtered, is concentrated, recrystallization, is produced.Compared with the analog with planar structure, its fluorescence identifying ability of synthesized schiff bases is remarkably reinforced.The present invention is used for the detection of micro cerium ion.
Description
Technical field
The present invention relates to a kind of 2,2 '-dihydroxy -1,1 '-dinaphthalene -3,3 '-dicarbaldehyde contracting amino acids schiff bases and its conjunction
Into method and application.
Background technology
Rare earth element is valuable strategic resource, and the reserves in China occupy first place in the world.In recent years, with rare earth demand
The a large amount of exploitations for increasing rare earth mineral reserve year by year, result in increasing rare earth element and move in environment, cause serious
Ecological disruption and problem of environmental pollution, make cultivated land degradation, grain drop in production in addition have no harvest.In addition, research shows, long-term low dose
Take in rare earth metal all has damage to brain, liver, bone, endocrine and immunologic function etc..Cerium (Ce) is content highest in the earth's crust
Rare earth metal, it is significant that qualitative and quantitative detection is carried out to it.
Metal ion inspection common at present includes atomic absorption spectrography (AAS), atomic emission spectrometry, chromatography of ions
Method, colorimetric method, fluorescent spectrometry etc..Wherein, fluorescent spectrometry due to its cost it is cheap, it is simple to operate, good selectivity with
And the characteristic such as real non-destructive detection in situ, it is of great interest.Adjacent hydroxy aldehyde contracting amino acids schiff bases is because in its structure
Simultaneously containing three kinds of carboxyl, carbon-to-nitrogen double bon, hydroxyl functional groups, the cyclic structure with stabilization can be quickly formed during metal complex, because
This this kind of compound attracts wide attention in fluorescence probe field.But find that there is planar structure 2- hydroxyls in research process
The schiff bases that base -1- naphthal amino acid obtains does not embody recognition capability to metal, and its structural formula is as follows：
The content of the invention
The schiff bases obtained the present invention is to solve planar structure 2- hydroxyl -1- naphthal amino acid does not identify to metal
The problem of ability, there is provided Binol-diform contracting amino acids schiff bases and its synthetic method and application.
The structural formula of Binol-diform contractings amino acids Schiff bases fluorescent probe compounds of the present invention is as follows：
Wherein R isOr
The synthetic method of above-mentioned Binol-diform contractings amino acids schiff bases, comprises the following steps：
First, amino acid and KOH are dissolved in organic solvent, add Binol-diform (2,2 '-dihydroxy -1,1 ' -
Join -3,3 '-two naphthaldehydes), 2~3h is reacted, obtains yellow liquid, i.e., 2,2 '-dihydroxy -1, -3,3 '-two naphthal ammonia of 1 '-connection
Base acids schiff bases crude product；
2nd, second will be dissolved in after 2,2 '-dihydroxy-the 1,1 '-naphthal amino acids schiff bases of connection -3,3 '-two crude product concentration
Acetoacetic ester, insoluble potassium amino acid being filtered to remove, be concentrated to give bright yellow solid, organic solvent recrystallization, obtained sterling is 2,
2 '-dihydroxy-the 1,1 '-naphthal amino acids schiff bases of connection -3,3 '-two；Amino acid and KOH mol ratio wherein in step 1
For 1:The mol ratio of 1~1.7, Binol-diform and amino acid is 1:2~3.
Further, amino acid is Valine, L-phenylalanine, L-Leu or ILE in step 1.
Further, organic solvent is methanol or ethanol in step 1.
The reaction equation of the present invention is as follows：
Wherein R isOr
The complexation reaction of 2,2 '-dihydroxy -1,1 '-naphthal amino acids schiff bases of connection -3,3 '-two and cerium ion：
Take 2 that the above method is prepared, 2 '-dihydroxy -1, -3,3 '-two naphthal amino acids schiff bases of 1 '-connection,
Methanol dissolving is added, then the cerium ion aqueous solution is added dropwise into methanol solution, reacts 2~3h at room temperature, is filtered, concentration, is obtained pale yellow
Color solid-like cerium ion complex compound crude product, crude product is washed 3~5 times, organic solvent washing (PE twice:EtOAc=5:1), i.e.,
Cerium complex is obtained, the cerium complex prepared is light yellow solid at room temperature.Wherein 2,2 '-dihydroxy -1,1 '-connection -3,
The mol ratio of 3 '-two naphthal amino acids schiff bases and cerium ion is 1:2.
Cerium complex is prepared, and determines complex compound and probe 2 respectively, 2 '-dihydroxy -1, -3,3 '-two naphthals of 1 '-connection
The fluorescence intensity of amino acids schiff bases, be in order to compare cerium complex and the fluorescence intensity of schiff bases probe between the two, with
It is easy to investigate whether probe has preferable recognition capability to cerium ion.
Above-mentioned Binol-diform contractings amino acids schiff bases is as fluorescence probe in rare earth ion Ce3+It is qualitative and
Application in quantitative analysis.
Rare earth ion Ce3+Qualitative and quantitative specific method be：
Take 10 μ g/mL's to contain Ce3+Solution, and be diluted to the Ce of various concentrations3+Solution, add Ce3+1 times of concentration
2,2 '-dihydroxy -1, the tetrahydrofuran solution of -3,3 '-two naphthal amino acids schiff bases of 1 '-connection, react at room temperature
10min, and the fluorescence intensity of solution is determined, the standard curve of draw calculation cerium ion concentration.
Further, 2,2 '-dihydroxy -1, -3,3 '-two naphthal amino acids schiff bases of 1 '-connection and cerium ion rub
You are than being 1:1~3.
The further cerium ion concentration is 0.2 μ g/mL, 0.4 μ g/mL, 0.6 μ g/mL, 0.8 μ g/mL or 1 μ g/mL.
Beneficial effects of the present invention：
The present invention is 2,2 '-dihydroxy -1,1 '-connection -3,3 '-two using Binol-diform and amino acid as Material synthesis
Naphthal amino acids schiff bases, the detection of micro cerium ion is used for as fluorescence probe, detectability to be 0.11 μ g/L.We
Method reaction carries out thorough, and yield is up to 82.1%~91%.
The inventive method be prepared 2,2 '-dihydroxy -1,1 '-connection -3,3 '-two naphthal amino acids schiff bases,
Due to the three-dimensional-structure of crossings on different level, excellent fluorescence property is shown.Test result indicates that with the similar of planar structure
Thing is compared, and synthesized 2,2 '-dihydroxy -1, naphthal amino acids schiff bases its fluorescence identifying ability of 1 '-connection -3,3 '-two
It is remarkably reinforced.
The inventive method be prepared 2,2 '-dihydroxy -1,1 '-connection -3,3 '-two naphthal amino acids schiff bases,
It can be used for the detection of micro cerium ion, detecting cerium ion field for fluorescence probe provides a kind of new approaches.
Brief description of the drawings
Fig. 1 is product prepared by embodiment 11H H NMR spectroscopies；
Fig. 2 is product prepared by embodiment 113C H NMR spectroscopies；
Fig. 3 is the INFRARED SPECTRUM of product prepared by embodiment 1；
Fig. 4 is the fluorescence Spectra of product 1 and probe prepared by embodiment 1；
Fig. 5 is the fluorescence Spectra of product 2 and probe prepared by embodiment 1；
Fig. 6 is the standard curve spectrum of product 1 prepared by embodiment 1.
Embodiment
Technical solution of the present invention is not limited to act embodiment set forth below, in addition between each embodiment
Any combination.
Embodiment one：Present embodiment Binol-diform contracting amino acids Schiff bases fluorescent probe compounds
Structural formula it is as follows：
Wherein R isOr
Embodiment two：The synthetic method of present embodiment Binol-diform contracting amino acids schiff bases, including
Following steps：
First, amino acid and KOH are dissolved in organic solvent, add Binol-diform, reacted 2~3h, obtain Huang
Color liquid, i.e., 2,2 '-dihydroxy -1, -3,3 '-two naphthal amino acids schiff bases crude products of 1 '-connection；
2nd, second will be dissolved in after 2,2 '-dihydroxy-the 1,1 '-naphthal amino acids schiff bases of connection -3,3 '-two crude product concentration
Acetoacetic ester, insoluble potassium amino acid being filtered to remove, be concentrated to give bright yellow solid, organic solvent recrystallization, obtained sterling is 2,
2 '-dihydroxy-the 1,1 '-naphthal amino acids schiff bases of connection -3,3 '-two；Amino acid and KOH mol ratio wherein in step 1
For 1:The mol ratio of 1~1.7, Binol-diform and amino acid is 1:2~3.
Binol-diform described in step 1 is 2,2 '-dihydroxy -1,1 '-naphthaldehyde of connection -3,3 '-two.
Embodiment three：Present embodiment is unlike embodiment two：Amino acid is L- in step 1
Valine, L-phenylalanine, L-Leu or ILE.It is other identical with embodiment two.
Embodiment four：Present embodiment is unlike embodiment two or three：It is organic molten in step 1
Agent is methanol or ethanol.It is other identical with embodiment two or three.
Embodiment five：Present embodiment 2,2 '-dihydroxy-the 1,1 '-naphthal amino acids seat of connection -3,3 '-two
Husband's alkali is as fluorescence probe in rare earth ion Ce3+Qualitative and quantitative analysis in application.
Embodiment six：Present embodiment is unlike embodiment five：Rare earth ion Ce3+Determine
Property and quantitative specific method are：
Take 10 μ g/mL's to contain Ce3+Solution, and be diluted to the Ce of various concentrations3+Solution, add Ce3+1 times of concentration
2,2 '-dihydroxy -1, the tetrahydrofuran solution of -3,3 '-two naphthal amino acids schiff bases of 1 '-connection, react at room temperature
10min, and the fluorescence intensity of solution is determined, the standard curve of draw calculation cerium ion concentration.Other and embodiment five
It is identical.
Embodiment seven：Present embodiment is unlike embodiment six：2,2 '-dihydroxy -1,1 ' -
The mol ratio for joining -3,3 '-two naphthal amino acids schiff bases and cerium ion is 1:1~3.It is other with the phase of embodiment six
Together.
Embodiment eight：Present embodiment is unlike embodiment six：The cerium ion concentration is 0.2
μ g/mL, 0.4 μ g/mL, 0.6 μ g/mL, 0.8 μ g/mL or 1 μ g/mL.It is other identical with embodiment six.
Embodiments of the invention are elaborated below, following examples are entered under premised on technical solution of the present invention
Row is implemented, and gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following realities
Apply example.
Embodiment one：
The present embodiment 2,2 '-dihydroxy -1, the preparation method of -3,3 '-two naphthal amino acids schiff bases of 1 '-connection, bag
Include following steps：
Take L-Leu (1.24g, 9.5mmoL) to be dissolved in methanol, add KOH (0.64g, 11.4mmoL), it is anti-at 50 DEG C
30min is answered, adds Binol-diform (1.50g, 4.4mmoL) afterwards, continuing reaction 2h makes raw material fully react.This reaction knot
Beam, the crude product of yellow liquid is obtained, be concentrated to give clear yellow viscous solid, then dissolved with ethyl acetate, has been filtered to remove insoluble
Leucine sylvite, then it is concentrated to give bright yellow solid, methanol solvate recrystallization.Finally filter to obtain yellow solid Binol-
Diform-Le-schiff (2.1g, 3.4mmoL), is product 1, yield 82.1%.
The structure of 2,2 '-dihydroxy -1,1 ' manufactured in the present embodiment-naphthal leucin potassium schiff bases of connection -3,3 '-two
Formula is as follows：
2,2 '-dihydroxy -1,1 ' manufactured in the present embodiment-naphthal leucin potassium schiff bases of connection -3,3 '-two1H
NMR(300MHz,CD3Cl, δ) (as shown in Figure 1):0.925-0.960(d,12H,4CH3),1.634-1.719(m,2H,2CH),
1.787-1.834(d,4H,2CH2),4.016-4.074(m,2H,2CH),7.069-8.129(m,10H),8.719(s,1H,-
HC=N)
13C NMR(75MHz,CD3Cl) (as shown in Figure 2):18.46,18.50,19.35,19.39,31.75,31.79,
31,31.95,52.07,76.59,78.51,78.61,78.65,78.71,116.72,116.75,120.75,120.79,
120.81,123.42,124.99,127.58,128.51,128.54,128.85,128.88,128.92,134.15,134.21,
135.55,154.52,154.55,154.57,166.88,166.94,171.19,171.21,171.40.
IR (KBr) (as shown in Figure 3) ν:3390,2963,1642,1617,1506,1388,1300,748,618.
From data above, the structure of product 1 is correct, is 2,2 '-dihydroxy -1, -3,3 '-two bright ammonia of naphthal of 1 '-connection
Base acid potassium schiff bases.
Weigh respectively probe Binol-diform-Le-schiff (0.19g, 0.30mmoL) and cerium chloride (0.28g,
0.75mmoL), in 100mL beaker, 20mL methanol dissolving Binol-diform-Le-schiff is added, cerium chloride is used
30mL distilled water dissolving, the aqueous solution of cerium ion is slowly dropped in the methanol solution of probe, discovery has light yellow immediately
Floccule generates, and 2h is stirred at room temperature, and filters, washing three times, organic solvent washing (PE twice:EtOAc=5:1), last vacuum
Dry, obtain light yellow solid (0.25g, 0.26mmoL), as cerium ion complex compound, yield 90.2%.IR(KBr)ν:
3381,3056,2955,2869,1640,1614,1580,1451,1300,1256,1120,951,748.
0.188g cerium ion complex compound is weighed in 100mL volumetric flask, adds ethyl acetate to dissolve constant volume, obtains concentration
For 2 × 10-3M cerium ion solution, pipettes 0.1mL and puts in 100mL volumetric flask, obtains concentration as 2 × 10-6M cerium ion network
Polymer solution, then the probe Binol-diform-Le-schiff for weighing 0.133g add acetic acid second in 100mL volumetric flask
Ester dissolves constant volume, obtains 2 × 10-3M probe solution, 0.1mL probe solution is pipetted into 100mL volumetric flask, acetic acid second
Ester dilution is settled to scale, obtains concentration as 2 × 10-6M probe solution, the fluorescence of cerium ion complex compound and probe is determined respectively
Intensity is (as shown in figure 4,1 be Ce in Fig. 43+Complex compound, 2 be probe).Condition determination is：EX=265nm, slit width EX=
5nm, EM=10nm.As shown in Figure 4, the fluorescence intensity of cerium complex is 3.6 times of probe, shows probe manufactured in the present embodiment
Compound (Binol-diform-Le-schiff) has preferable recognition capability to cerium ion.
Contrast test：
Take L-Leu (0.9g, 7.0mmoL) to be dissolved in methanol, KOH solution (0.30g, 5.0mmoL) is added, at 55 DEG C
30min is reacted, adds the methanol solution (1.00g, 5.8mmoL) of 2- hydroxyls-naphthaldehyde afterwards, continuing reaction 2h makes raw material fully anti-
Should, this reaction terminates.The crude product of yellow liquid has been obtained, has then been concentrated to give clear yellow viscous solid, then has been dissolved with ethyl acetate,
Insoluble leucine sylvite is filtered to remove, is then concentrated to give bright yellow solid, methanol solvate recrystallization.Finally filter yellow is consolidated
Body 2- hydroxyl -1- naphthal leucine potassium schiff bases (2-Hydroxy-1-naphth-Le-schiff, 1.5g, 4.7mmoL), it is
Product 2, yield 83.3%.
The structural formula of 2- hydroxyls -1- naphthals leucine potassium schiff bases manufactured in the present embodiment is as follows：
2- hydroxyls -1- naphthals leucine potassium schiff bases manufactured in the present embodiment1H NMR(300MHz,CD3OH, unit：
ppm):1.006-1.060(m,3H,CH3),1.148-1.194(m,3H,CH3),1.262-1.315(m,2H,CH2),1.700-
2.150 (m, H, CH), 4.055 (s, H, CH) 6.765-7.989 (m, 6H), 8.865 (s, 1H, HC=N)13C NMR(75MHz,
CD3OD, unit：ppm):10.7,15.12,24.26,38.4,46.78,47.06,47.35,47.63,47.91,48.20,
48.48,65.48,71.35,105.79,117.79,122.10,125.42,125.66,127.95,128.69,134.73,
138.23,157.39,174.90,179.99.IR(KBr)ν:3481,3021,2951,1724,1624,1432,1259,834,
755,701cm-1.
From data above, the structure of product 2 is correct, is 2-Hydroxy-1-naphth-Le-schiff.
0.170g cerium ion complex compound is weighed in 100mL volumetric flask, adds ethyl acetate to dissolve constant volume, obtains concentration
For 2 × 10-3M cerium ion solution, pipettes 0.1mL and puts in 100mL volumetric flask, obtains concentration as 2 × 10-6M cerium ion network
Polymer solution, then the probe 2-Hydroxy-1-naphth-Le-schiff for weighing 0.152g are added in 100mL volumetric flask
Ethyl acetate dissolves constant volume, obtains 2 × 10-3M probe solution, 0.1mL probe solution is pipetted into 100mL volumetric flask,
Ethyl acetate dilution is settled to scale, obtains concentration as 2 × 10-6M probe solution, cerium ion complex compound and probe are determined respectively
Fluorescence intensity (as shown in figure 5,1 being Ce in Fig. 53+Complex compound, 2 be probe).Condition determination is：EX=365nm, slit width
EX=5nm, EM=10nm.As shown in Figure 5, the fluorescence intensity of cerium complex and the fluorescence intensity difference of probe are little, show this
Probe compound 2 (2-Hydroxy-1-naphth-Le-schiff) prepared by embodiment does not have to identify energy substantially to cerium ion
Power.
0.020g cerium chlorides are weighed in 200mL volumetric flask, dissolve constant volume with distilled water, it is 100 μ g/mL to obtain concentration
Cerium ion storing solution, pipette 1 respectively with pipette, 0.8,0.6,0.4,0.2mL cerium ion storing solution put 5 100mL's
In volumetric flask, obtained cerium ion concentration is respectively 1,0.8,0.6,0.4,0.2 μ g/mL.Weigh 0.020g Binol-
Diform-Le-schiff dissolves constant volume in 200mL volumetric flask, with ethyl acetate, obtains the probe that concentration is 100 μ g/mL
Storing solution, the probe storing solution that 1mL is pipetted with pipette are put in 100mL volumetric flask, and obtained concentration and probe concentration is 1 μ g/mL.Point
The cerium ion solution 9mL that concentration is 1,0.8,0.6,0.4,0.2 μ g/mL is not taken then to divide in 5 beakers in each beaker
Not Jia Ru 5mL concentration be 1 μ g/mL probe solution.At room temperature, 2h is reacted, is extracted twice, is concentrated into 10mL ethyl acetate
5mL, 5mL is settled to, finally detects the fluorescence intensity of ethyl acetate solution.It was found that cerium ion concentration is in 0.2-1 μ g/mL, fluorescence
Intensity shows good linear relationship, wherein, calibration curve equation F=512.34I0+ 406.92, R2=0.990 (such as Fig. 6
It is shown).Condition determination is：EX=265nm, slit width EX=5nm, EM=10nm.It will be appreciated from fig. 6 that testing result be with
The increase of cerium ion concentration, fluorescence intensity also constantly strengthen, and cerium ion concentration shows well in 0.2-1 μ g/mL, fluorescence intensity
Linear relationship, wherein, calibration curve equation F=512.34I0+ 406.92, R2=0.990.The fluorescence for measuring No. 5 probes is strong
Degree, calculates to obtain standard deviation S=1.8%, detectability is 0.11 μ g/L.
Embodiment two：
The present embodiment 2,2 '-dihydroxy -1, the preparation method of -3,3 '-two naphthal amino acids schiff bases of 1 '-connection, bag
Include following steps：
All experiment conditions of the present embodiment and processing method are identical with embodiment one, and raw material L-Leu simply is changed into L-
Valine, addition are (1.24g, 15mmoL), final to obtain yellow solid 2,2 '-dihydroxy -1, -3,3 '-two naphthals of 1 '-connection
Figured silk fabrics potassium amino acid schiff bases (Binol-diform-Val-schiff), yield 91.0%.
Binol-diform-Val-schiff manufactured in the present embodiment structural formula is as follows：
Binol-diform-Val-schiff's1H NMR(300MHz,CD3Cl, unit：ppm):0.948-0.981(d,
12H,4CH3),2.269-2.382(m,2H,2CH),3.760-3.807(m,2H,2CH),7.182-7.997(m,10H),
8.592 (s, 1H ,-HC=N)13C NMR(75MHz,CD3Cl, unit：ppm):17.50,17.80,18.00,19.37,
19.60,31.75,31.79,31.92,31.95,52.07,76.59,78.51,78.61,78.65,78.71,116.72,
116.75,120.75,120.79,120.81,123.42,124.99,127.58,128.51,128.54,128.85,128.88,
128.92,134.15,134.21,135.55,154.52,154.55,154.57,166.88,166.94,171.06,171.21,
171.36.IR(KBr)ν:3444,3055,2961,2871,1739,1574,1505,1436,1253,980,935,749cm-1.
From data above, product structure is correct, is 2,2 '-dihydroxy -1, -3,3 '-two naphthal figured silk fabrics amino of 1 '-connection
Sour potassium schiff bases.
Embodiment three：
The present embodiment 2,2 '-dihydroxy -1, the preparation method of -3,3 '-two naphthal amino acids schiff bases of 1 '-connection, bag
Include following steps：
All experiment conditions of the present embodiment and processing method are identical with embodiment one, and raw material L-Leu simply is changed into L-
Phenylalanine, addition are (1.36g, 15mmoL), final to obtain yellow solid 2,2 '-dihydroxy -1, -3,3 '-two naphthaldehydes of 1 '-connection
Contracting phenylpropyl alcohol potassium amino acid schiff bases (Binol-diform-Phe-schiff), yield 90.3%.
Binol-diform-Phe-schiff manufactured in the present embodiment structural formula is as follows：
Binol-diform-Phe-schiff's1H NMR(300MHz,CD3Cl, unit：ppm):3.024-3.131(m,
2H,CH2),3.346-3.391(m,2H,CH2), 4.208-4.281 (m, 2H, 2CH), 7.173-7.840 (m, 20H), 8.302
(s, 2H, 2HC=N), 12.661-12.743 (s, 2H, OH)13C NMR(75MHz,CD3Cl, unit：ppm):25.62,
39.89,39.96,52.44,52.47,679.98,73.56,73.63,76.60,116.67,120.56,120,62,123.43,
124.79,124.88,126.88,126.95,127.49,127.54,128.50,128.61,128.63,128.90,128.95,
129.01,129.55,129.62,134.14,134.22,135.51,135.55,136.67,136.76,154.37,154.42,
154.47,167.16,170.93,171.08.IR(KBr)ν:3448.4,3026.69,2949.76,1739.87,1638.41,
1502.61,1254.15,934.47,748.96,699.75cm-1.
From data above, product structure is correct, is 2,2 '-dihydroxy -1, -3,3 '-two naphthal phenylpropyl alcohol ammonia of 1 '-connection
Base acid potassium schiff bases.
Example IV：
The present embodiment 2,2 '-dihydroxy -1, the preparation method of -3,3 '-two naphthal amino acids schiff bases of 1 '-connection, bag
Include following steps：
All experiment conditions of the present embodiment and processing method are identical with embodiment one, and raw material L-Leu simply is changed into L-
Isoleucine, addition are (1.36g, 15mmoL), final to obtain yellow solid 2,2 '-dihydroxy -1, -3,3 '-two naphthaldehydes of 1 '-connection
Contract different leucin potassium schiff bases (Binol-diform-Ile-schiff), yield 90.0%.
Binol-diform-Ile-schiff manufactured in the present embodiment structural formula is as follows：
Binol-diform-Ile-schiff's1H NMR(300MHz,CD3Cl, unit：ppm):0.925-0.936(d,
6H,2CH3),0.940-0.984(d,6H,2CH3),2.269-2.382(m,4H,2CH2),3.712(m,2H,2CH),3.760-
3.807(m,4H,2CH2), 7.114-8.021 (m, 10H), 8.589 (s, 1H ,-HC=N)13C NMR(75MHz,CD3Cl, it is single
Position：ppm):18.46,18.50,18.55,19.35,19.39,20.12,20.35,31.75,31.79,31.92,31.95,
52.07,76.59,78.51,78.61,78.65,78.71,116.72,116.75,120.75,120.79,120.81,
123.42,124.99,127.58,128.51,128.54,128.85,128.88,128.92,134.15,134.21,135.55,
154.52,154.55,154.57,166.88,166.94,171.19,171.21,171.40.IR(KBr)ν:3390,2963,
1642,1617,1506,1427,1388,1337,1300,748,618cm-1.
From data above, product structure is correct, is 2,2 '-dihydroxy -1,1 '-connection different bright ammonia of -3,3 '-two naphthals
Base acid potassium schiff bases.
Claims (8)
1.Binol-diform contracting amino acids schiff bases, it is characterised in that Binol-diform aldehyde contracting amino acids schiff bases
Structural formula is as follows：
Wherein R is
2. the synthetic method of Binol-diform contractings amino acids schiff bases as claimed in claim 1, it is characterised in that this method
Comprise the following steps：
First, amino acid and KOH are dissolved in organic solvent, add Binol-diform, reacted 2~3h, obtain yellow liquid
Body, i.e., 2,2 '-dihydroxy -1, -3,3 '-two naphthal amino acids schiff bases crude products of 1 '-connection；
2nd, acetic acid second will be dissolved in after 2,2 '-dihydroxy-the 1,1 '-naphthal amino acids schiff bases of connection -3,3 '-two crude product concentration
Ester, filtering, bright yellow solid, organic solvent recrystallization being concentrated to give, obtained sterling is 2,2 '-dihydroxy -1,1 '-connection -3,3 ' -
Two naphthal amino acids schiff bases；Amino acid and KOH mol ratio are 1 wherein in step 1:1~1.7, Binol-diform
Mol ratio with amino acid is 1:2~3.
3. the synthetic method of Binol-diform contractings amino acids schiff bases according to claim 2, it is characterised in that step
Amino acid is Valine, L-phenylalanine, L-Leu or ILE in rapid one.
4. the synthetic method of Binol-diform contractings amino acids schiff bases according to claim 2, it is characterised in that step
Organic solvent is methanol or ethanol in rapid one.
5. Binol-diform contractings amino acids schiff bases described in claim 1 is as fluorescence probe in rare earth ion Ce3+
Qualitative and quantitative analysis in application.
6. application according to claim 5, it is characterised in that rare earth ion Ce3+Qualitative and quantitative specific method
For：
Take 10 μ g/mL's to contain Ce3+Solution, and be diluted to the Ce of various concentrations3+Solution, add Ce3+The 2,2 ' of 1 times of concentration-
Dihydroxy -1, the tetrahydrofuran solution of -3,3 '-two naphthal amino acids schiff bases of 1 '-connection, reacts 10min, and survey at room temperature
Determine the fluorescence intensity of solution, the standard curve of draw calculation cerium ion concentration.
7. application according to claim 6, it is characterised in that 2,2 '-dihydroxy -1, -3,3 '-two naphthal amino of 1 '-connection
The mol ratio of acids schiff bases and cerium ion is 1:1~3.
8. application according to claim 6, it is characterised in that the cerium ion concentration is 0.2 μ g/mL, 0.4 μ g/mL, 0.6
μ g/mL, 0.8 μ g/mL or 1 μ g/mL.
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