CN102942528A - 2-sulfo hydantoin derivative, its preparation method and application - Google Patents
2-sulfo hydantoin derivative, its preparation method and application Download PDFInfo
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Abstract
The invention discloses a 2-sulfo hydantoin derivative of the formula (I), its preparation method and application. The preparation method is characterized by adding amino acid methyl ester and isorhodanate to a mixed solution of tetrahydrofuran and triethylamine, wherein the molar ratio of amino acid methyl ester to isorhodanate is 1:1.05-1.5, and the volume ratio of tetrahydrofuran to triethylamine is 10:1-0.5; reacting at room temperature for 12-24h, conducting distillation under reduced pressure to remove the solvent, using a silicagel column in an eluate to purify to obtain the residual solids, wherein the eluate comprises ethyl acetate and hexane with the volume ratio of 1:1-4, and each gram of amino acid methyl ester and isorhodanate is added in 8-15ml of the mixed solution of tetrahydrofuran and triethylamine. According to the invention, 2-sulfo hydantoin has anion identification performance, can be used for detecting fluorinion.
Description
Technical field
Sulphur substituted heterocyclic compound of the present invention particularly relates to and is specifically related to a kind of 2-thiohydantoin derivatives and preparation method thereof and application.The preparation method makes by phenylthioisocyanate ester derivative and amino acid methyl ester reaction, and this 2-thiohydantoin derivatives has the Anion Recognition performance, can be applied as the fluorion chemical sensor.
Background technology
Anion Recognition refers to acceptor (main body) selectivity and anion binding, and produce the process of certain specific function, in fields such as life science, pharmacy, Journal of Molecular Catalysis and environmental sciences very important effect is arranged, be particularly useful for metabolic process such as the aspects such as specific dna sequence identification, molecule transport of organism.Research take Anion Recognition as the chemical sensitisation system on basis becomes the supramolecular chemistry study hotspot gradually.The benzamido urea that contains urea groups has been synthesized in the designs such as Nie Li, acetonitrile solution at this benzene carbon amide adds fluorion, absorption spectrum generation considerable change, thereby realize the highly selective identification response (Nie Li of fluorion, Li Aifang, Jiang Yunbao. the synthetic and Anion Recognition of benzamido urea. chemical journal, 2009,67(6): 564-568).Thiosemicarbazone has been synthesized in the designs such as Zhang Youming, in the acetonitrile solution of above-mentioned thiosemicarbazone, add fluorion, acetate ion, butanic acid radical ion, solution is by the colourless yellow that becomes, thereby bore hole identification (Zhang Youming, Xu Weixia, the Zhou Yanqing of these three kinds of negatively charged ion have been realized, Yao Hong, Wei hooligan. the synthetic and Anion Recognition research of thiosemicarbazone derivative acceptor. chemical journal, 2006,64(1): 79-84).But above-mentioned Anion Recognition reagent must at first be prepared into solution, then could realize ion identification with the negatively charged ion effect.
Summary of the invention
First purpose of the present invention provides a kind of improved 2-thiohydantoin derivatives, and this compound can be used for detecting fluorion, is particularly useful for preparing the test paper of rapid detection fluorion.
The technical solution used in the present invention is:
A kind of 2-thiohydantoin derivatives, its chemical structure be as shown in the formula (I):
R is hydrogen, nitro, cyano group, methoxyl group, butyl or trifluoromethyl; R ' is methyl, benzyl, sec.-propyl, 2-methyl-propyl group or 1-methyl-propyl group.
Following compound is one of compound shown in the formula (I):
R is hydrogen, and compound shown in chemical formula when R ' is methyl (I), its chemical name are 4-methyl 1-phenyl-2-thiohydantoin;
R is hydrogen, and compound shown in chemical formula when R ' is benzyl (I), its chemical name are 4-benzyl 1-phenyl-2-thiohydantoin;
R is hydrogen, and compound shown in chemical formula when R ' is sec.-propyl (I), its chemical name are 4-sec.-propyl 1-phenyl-2-thiohydantoin;
R is hydrogen, compound shown in the chemical formula (I) when R ' is 2-methyl-propyl group, and its chemical name is 4-(2 '-methyl-propyl group) 1-phenyl-2-thiohydantoin;
R is hydrogen, compound shown in the chemical formula (I) when R ' is 1-methyl-propyl group, and its chemical name is 4-(1 '-methyl-propyl group) 1-phenyl-2-thiohydantoin;
R is nitro, and compound shown in chemical formula when R ' is methyl (I), its chemical name are 4-methyl 1-(4 '-nitrophenyl)-the 2-thiohydantoin;
R is nitro, and compound shown in chemical formula when R ' is benzyl (I), its chemical name are 4-benzyl 1-(4 '-nitrophenyl)-the 2-thiohydantoin;
R is nitro, and compound shown in chemical formula when R ' is sec.-propyl (I), its chemical name are 4-sec.-propyl 1-(4 '-nitrophenyl)-the 2-thiohydantoin;
R is nitro, compound shown in the chemical formula (I) when R ' is 2-methyl-propyl group, its chemical name is 4-(2 '-methyl-propyl group) 1-(4 '-nitrophenyl)-the 2-thiohydantoin;
R is nitro, compound shown in the chemical formula (I) when R ' is 1-methyl-propyl group, its chemical name is 4-(1 '-methyl-propyl group) 1-(4 '-nitrophenyl)-the 2-thiohydantoin;
R is cyano group, and compound shown in chemical formula when R ' is methyl (I), its chemical name are 4-methyl 1-(4 '-cyano-phenyl)-the 2-thiohydantoin;
R is cyano group, and compound shown in chemical formula when R ' is benzyl (I), its chemical name are 4-benzyl 1-(4 '-cyano-phenyl)-the 2-thiohydantoin;
R is cyano group, and compound shown in chemical formula when R ' is sec.-propyl (I), its chemical name are 4-sec.-propyl 1-(4 '-cyano-phenyl)-the 2-thiohydantoin;
R is cyano group, compound shown in the chemical formula (I) when R ' is 2-methyl-propyl group, its chemical name is 4-(2 '-methyl-propyl group) 1-(4 '-cyano-phenyl)-the 2-thiohydantoin;
R is cyano group, compound shown in the chemical formula (I) when R ' is 1-methyl-propyl group, its chemical name is 4-(1 '-methyl-propyl group) 1-(4 '-cyano-phenyl)-the 2-thiohydantoin;
R is methoxyl group, and compound shown in chemical formula when R ' is methyl (I), its chemical name are 4-methyl 1-(4 '-p-methoxy-phenyl)-the 2-thiohydantoin;
R is methoxyl group, and compound shown in chemical formula when R ' is benzyl (I), its chemical name are 4-benzyl 1-(4 '-p-methoxy-phenyl)-the 2-thiohydantoin;
R is methoxyl group, and compound shown in chemical formula when R ' is sec.-propyl (I), its chemical name are 4-sec.-propyl 1-(4 '-p-methoxy-phenyl)-the 2-thiohydantoin;
R is methoxyl group, compound shown in the chemical formula (I) when R ' is 2-methyl-propyl group, its chemical name is 4-(2 '-methyl-propyl group) 1-(4 '-p-methoxy-phenyl)-the 2-thiohydantoin;
R is methoxyl group, compound shown in the chemical formula (I) when R ' is 1-methyl-propyl group, its chemical name is 4-(1 '-methyl-propyl group) 1-(4 '-p-methoxy-phenyl)-the 2-thiohydantoin;
R is butyl, and compound shown in chemical formula when R ' is methyl (I), its chemical name are 4-methyl 1-(4 '-butyl phenyl)-the 2-thiohydantoin;
R is butyl, and compound shown in chemical formula when R ' is benzyl (I), its chemical name are 4-benzyl 1-(4 '-butyl phenyl)-the 2-thiohydantoin;
R is butyl, and compound shown in chemical formula when R ' is sec.-propyl (I), its chemical name are 4-sec.-propyl 1-(4 '-butyl phenyl)-the 2-thiohydantoin;
R is butyl, compound shown in the chemical formula (I) when R ' is 2-methyl-propyl group, its chemical name is 4-(2 '-methyl-propyl group) 1-(4 '-butyl phenyl)-the 2-thiohydantoin;
R is butyl, compound shown in the chemical formula (I) when R ' is 1-methyl-propyl group, its chemical name is 4-(1 '-methyl-propyl group) 1-(4 '-butyl phenyl)-the 2-thiohydantoin;
R is trifluoromethyl, and compound shown in chemical formula when R ' is methyl (I), its chemical name are 4-methyl 1-(4 '-trifluoromethyl)-the 2-thiohydantoin;
R is trifluoromethyl, and compound shown in chemical formula when R ' is benzyl (I), its chemical name are 4-benzyl 1-(4 '-trifluoromethyl)-the 2-thiohydantoin;
R is trifluoromethyl, and compound shown in chemical formula when R ' is sec.-propyl (I), its chemical name are 4-sec.-propyl 1-(4 '-trifluoromethyl)-the 2-thiohydantoin;
R is trifluoromethyl, compound shown in the chemical formula (I) when R ' is 2-methyl-propyl group, its chemical name is 4-(2 '-methyl-propyl group) 1-(4 '-trifluoromethyl)-the 2-thiohydantoin;
R is trifluoromethyl, compound shown in the chemical formula (I) when R ' is 1-methyl-propyl group, its chemical name is 4-(1 '-methyl-propyl group) 1-(4 '-trifluoromethyl)-the 2-thiohydantoin.
Second purpose of the present invention provides the preparation method of above-mentioned 2-thiohydantoin derivatives.Adopt following technical measures:
The preparation method of described 2-thiohydantoin derivatives: be that 1:1.05-1.5 adds in the mixing solutions of tetrahydrofuran (THF) and triethylamine according to mol ratio with amino acid methyl ester and lsothiocyanates; The volume ratio 10:1-0.5 of tetrahydrofuran (THF) and triethylamine; React under the room temperature after 12-24 hour, the underpressure distillation desolventizing, residual solids obtains at the elutriant purifying with silicagel column; Described elutriant group is that ethyl acetate and the normal hexane of 1:1-4 forms by volume ratio; Every gram amino acid methyl ester and lsothiocyanates add the mixing solutions 20-40ml of tetrahydrofuran (THF) and triethylamine.
The preparation method of 2-thiohydantoin derivatives is that the reaction formula II represents,
In the reaction formula, R is hydrogen, nitro, and cyano group, methoxyl group, butyl and trifluoromethyl are wherein a kind of; R ' is methyl, benzyl, and sec.-propyl, 2-methyl-propyl group and 1-methyl-propyl group are wherein a kind of.
The 3rd purpose of the present invention provides the application of above-mentioned 2-thiohydantoin derivatives in the test paper that detects fluorion and preparation detection fluorion.
Described test paper is to be prepared by following methods: first described 2-thiohydantoin derivatives is dissolved in acetonitrile, THF, acetone or the methylene dichloride to get solution, then filter paper is immersed in the described solution, soak into and take out filter paper behind the 1-10min and dry and get final product.
2-thiohydantoin derivatives of the present invention is combined with fluorion, makes the solution or the test paper generation colour-change that contain 2 thio-hydantoins.Wherein, make the method for the solution generation colour-change that contains the 2-thiohydantoin derivatives be, described 2-thiohydantoin derivatives is dissolved in the easy volatile solvent such as acetonitrile, THF, acetone or methylene dichloride, then drip detected sample, whether observe solution colour changes, if solution colour changes, then contain fluorion in the interpret sample;
Make the method for the test paper generation colour-change that contains the 2-thiohydantoin derivatives be, detected sample is dripped on test paper, observe the Test paper color and whether change; If the test paper color becomes purple from white, then contain fluorion in the interpret sample; The preparation method of above-mentioned test paper is: described 2-thiohydantoin derivatives is dissolved in the hydrophilic solvents such as acetonitrile, THF, DMF or DMSO, then filter paper is immersed in the solution of preparing, soak into rear taking-up filter paper and dry and get final product.
The present invention has the following advantages with respect to prior art:
(1) preparation of 2-thiohydantoin derivatives of the present invention and method of purification are simple, and productive rate is high;
(2) the NH group on the 2-thiohydantoin derivatives molecular structure of the present invention and negatively charged ion particularly fluorion pass through hydrogen bonded, can change fast 2-thiohydantoin derivatives the color of the solution, therefore needn't pass through spectral instrument, and directly bore hole can be identified fluorion, has easily and efficiently advantage;
(3) 2-thiohydantoin derivatives of the present invention can be prepared into the test paper that detects fluorion, and is not only easy to carry, and testing process is quick.
Description of drawings
Fig. 1 is 4-(1 '-methyl-propyl group) 1-(4 '-nitrophenyl)-the ultraviolet-visible spectrum of the interpolation different anions of 2-thiohydantoin acetonitrile solution.4-(1 '-methyl-propyl group) 1-(4 '-nitrophenyl wherein)-and 2-thiohydantoin concentration is 1mM, fluorinion concentration is 10mM.
Embodiment
For understanding better the present invention, the invention will be further described below in conjunction with drawings and Examples, but embodiments of the present invention are not limit so.
Relevant Characterization of The Products Apparatus and method for is as follows among the following embodiment:
NMR (Nuclear Magnetic Resonance) spectrum [
1H (400MHz) and
13C (100MHz) NMR]: adopt Bruker Avance/DMX 400-MHz nuclear magnetic resonance spectrometer to measure, adopt CH
3CN – d
3Or THF-d
8Be solvent, tetramethylsilane is internal standard substance.
Infrared spectra: adopt the FTIR-8100 of Shimadzu company (shimadzu) infrared spectrometer.
Fusing point (mp): adopt the little melting point apparatus of Yanaco.
Mass spectrum (MS): adopt GCT Premier CAB 048 mass spectrograph, operation (CI) under the chemi-ionization pattern.
Ultimate analysis: adopt Eager 300 elemental analysers.
Ultraviolet-visible spectrum (UV-vis): adopt JASCO J-820 ultraviolet-visible spectrometer.
Embodiment 1:4-(1 '-methyl-propyl group) 1-(4 '-nitrophenyl)-the 2-thiohydantoin
(1.4-1 '-methyl-propyl group) 1-(4 '-nitrophenyl)-preparation of 2-thiohydantoin
In the 100mL flask, add 2.86g Isoleucine methyl esters (20mmol) and 3.60g p-nitrophenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 5.05g.Productive rate 86%.
(2.4-2 '-methyl-propyl group) 1-(4 '-nitrophenyl)-sign of 2-thiohydantoin
Mp?214～215℃
1H?NMR(400MHz,CDCl
3):δ0.83～1.01(m,6H,2CH3),1.58～1.96(m,3H,CH2CH),4.24(s,1H,CH),7.22(s,1H,NH),7.44～7.59(d,2H,Ar),8.19～8.37(d,2H,Ar).
13C?NMR(100MHz,CDCl
3):δ20.60,23.01,24.82,40.51,58.53,124.18,129.31,138.32,147.46,173.67,182.07.
IR(cm
-1,KBr):3263,3014,2362,2106,1588,1525,1409,1334,1251,1179,1013,930,843,735,698.
Anal.Calcd?for?C
13H
15N
3O
3S:C,53.23;H,5.15;N,14.32;O,16.36;S,10.93.Found:C,53.27;H,5.13;N,14.29.
found?ES+,m/z:=293.3,[M-H]+;292.1.
Above-mentioned detected result confirms that the compound of preparation is 4-(2 '-methyl-propyl group) 1-(4 '-nitrophenyl)-the 2-thiohydantoin.
(3.4-1 '-methyl-propyl group) 1-(4 '-nitrophenyl)-the Anion Recognition performance of 2-thiohydantoin
(3.1.4-1 '-methyl-propyl group) 1-(4 '-nitrophenyl)-the ion identification selectivity of 2-thiohydantoin
In order to detect 4-(1 '-methyl-propyl group) 1-(4 '-nitrophenyl)-the Fluoride recognition ability of 2-thiohydantoin, at first compound concentration is 4-(1 '-methyl-propyl group) 1-(4 '-nitrophenyl of 1.0mM)-2-thiohydantoin acetonitrile solution, then add tetra-n-butyl ammonium nitrate, bromination tetra-n-butyl ammonium, chlorination tetra-n-butyl ammonium, tetra-n-butyl ammonium sulfur hydrogen salt, wherein the concentration of tetra-n-butyl ammonium salt is 10mM; Observing at last solution colour changes.
Observation as can be known, 4-(1 '-methyl-propyl group) 1-(4 '-nitrophenyl)-the acetonitrile solution color of 2-thiohydantoin is colourless, solution became yellow look after the tetra-n-butyl ammonium was fluoridized in adding, and adding tetra-n-butyl ammonium nitrate, bromination tetra-n-butyl ammonium, chlorination tetra-n-butyl ammonium, solution colour does not change behind the tetra-n-butyl ammonium sulfur hydrogen salt.Therefore 4-(1 '-methyl-propyl group) 1-(4 '-nitrophenyl)-the 2-thiohydantoin demonstrates selectivity and bore hole recognition capability to fluorion.
Detect the ultraviolet-visible of mentioned solution as shown in Figure 1, add and fluoridize the tetra-n-butyl ammonium, the absorption spectrum of solution is from the 316nm red shift to 432nm, and adding tetra-n-butyl ammonium nitrate, bromination tetra-n-butyl ammonium, chlorination tetra-n-butyl ammonium, the absorption spectrum of tetra-n-butyl ammonium sulfur hydrogen salt solution changes less.4-(1 '-methyl-propyl group) 1-(4 '-nitrophenyl)-2 thiohydantoins demonstrate good selectivity to fluorion.
4. detect the effect experiment of fluorion test paper
4.1. the preparation of Test paper
At first prepare 20mg/ml with 4-(1 '-methyl-propyl group) 1-(4 '-nitrophenyl)-the 2-thiohydantoin is dissolved in respectively in THF and the acetonitrile, obtain 4-(1 '-methyl-propyl group) 1-(4 '-nitrophenyl)-2-thiohydantoin THF solution and acetonitrile solution, then filter paper is immersed in respectively in THF solution and the acetonitrile solution, soaks into after 1 minute and to take out filter paper and dry and obtain two kinds of Test papers.
The preparation fluorinion concentration is the testing sample of 300 μ g/mL and 50 μ g/mL.
4.2. detection paper fluorion
Get detected sample and drip on Test paper, observe the Test paper color change, can find, when Test paper dropping concentration was the testing sample of 300 μ g/mL, the test paper color was by white yellowing; Be the testing sample of 50 μ g/mL and not during the testing sample of fluoride ion when Test paper drips concentration, the test paper color does not change.Therefore the Test paper of the present invention's preparation can rapid sensitive detects testing sample and whether contains fluorion.
5. contain the detection paper fluorion that contrasts acceptor
5.1. the preparation of contrast acceptor
Contrast acceptor 1:N-nitro-N-(2,6-dinitrobenzene-4-trifluoromethyl)-N '-(4-chloro-phenyl-) urea
Contrast acceptor 2:N-nitro-N-(2,6-dinitrobenzene-4-trifluoromethyl)-N '-(4-aminomethyl phenyl) urea.
Wherein contrast acceptor 1 and contrast acceptor 2 preparation method's reference (Jiang Hong, Ma Xuhong, Fang Li, the synthetic and Anion Recognition research of Wei Qing benefit .N-nitro ureas. Chinese Journal of Inorganic Chemistry, 2008,24 (7): 1073-1078)
5.2. the preparation of Test paper
At first prepare the contrast acceptor 1 of 20mg/mL or the THF solution of contrast acceptor 2.Filter paper is immersed in mentioned solution, and taking-up filter paper dries and obtains Test paper.
5.3. detection paper fluorion
The preparation fluorinion concentration is the testing sample of 300 μ g/mL and 50 μ g/mL.Get detected sample and drip on the Test paper that contains contrast acceptor 1 or contrast acceptor 2, find that the test paper hue preserving is yellow, do not change.
Therefore 4-of the present invention (1 '-methyl-propyl group) 1-(4 '-nitrophenyl)-and the 2-thiohydantoin can be used for preparation and detect the fluorion test paper, and whether this Test paper contains fluorion in the test sample quickly and easily.
Embodiment 2:4-(1 '-methyl-propyl group) 1-phenyl-2-thiohydantoin
The preparation of (1.4-1 '-methyl-propyl group) 1-phenyl-2-thiohydantoin
In the 100mL flask, add 2.86g Isoleucine methyl esters and 2.70g PITC, then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 24 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:4(v/v) lower purifying obtains white solid 4.02g.Productive rate 81%.
The sign of (2.4-1 '-methyl-propyl group) 1-phenyl-2-thiohydantoin
Mp?201.1～202.5℃.
1H?NMR(400MHz,CDCl
3):δ0.85～1.02(m,6H,2CH3),1.60～1.85(m,3H,CH2CH),4.20(s,1H,CH),7.15～7.28(d,2H,Ar),7.35～7.48(m,3H,Ar),8.39(s,1H,NH).
13C?NMR(100MHz,CDCl
3):δ21.49,23.09,25.12,40.47,58.52,128.29,129.19,129.30,132.66,174.04,183.71.
IR(cm
-1,KBr):3263,3014,2362,2106,1588,1525,1409,1334,1251,1179,1013,930,843,735,698.
Anal.Calcd?for?C
13H
16N
2O
2S:C,62.87;H,6.49;N,11.28;O,6.44;S,12.91.Found:C,62.92;H,6.46;N,11.26.
found?ES+,m/z:=248.3,[M-H]+;247.6.
Above-mentioned detected result confirms that the compound of preparation is 4-(1 '-methyl-propyl group) 1-phenyl-2-thiohydantoin.
3. detect the effect experiment of fluorion test paper
3.1. the preparation of Test paper
The preparation method is with embodiment 1.
The preparation fluorinion concentration is the testing sample of 360 μ g/mL and 50 μ g/mL.
3.2. detection paper fluorion
Detection method is with embodiment 1.
Observe the test paper colour-change, can find that the test paper color is by white yellowing when Test paper dropping concentration is the testing sample of 360 μ g/mL; Be the testing sample of 50 μ g/mL and not during the testing sample of fluoride ion when Test paper drips concentration, the test paper color does not change.Therefore the Test paper of the present invention's preparation can rapid sensitive detects testing sample and whether contains fluorion.
Embodiment 3:4-(1 '-methyl-propyl group) 1-(4 '-cyano-phenyl)-the 2-thiohydantoin
(1.4-1 '-methyl-propyl group) 1-(4 '-cyano-phenyl)-preparation of 2-thiohydantoin
In the 100mL flask, add 2.86g Isoleucine methyl esters (20mmol) and 3.20g to cyano-phenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:2(v/v) lower purifying obtains white solid 4.54g.Productive rate 83%.
(2.4-1 '-methyl-propyl group) 1-(4 '-cyano-phenyl)-sign of 2-thiohydantoin
1H?NMR(400MHz,CDCl
3):δ0.78～1.07(m,6H,2CH3),1.62～2.06(m,3H,CH2CH),4.31(s,1H,CH),7.44～7.56(d,2H,Ar),7.71～7.84(m,2H,Ar),9.78(s,1H,NH).
13C?NMR(100MHz,CDCl
3):δ21.63,23.02,24.67,40.50,58.59,112.53,118.08,129.24,132.71,136.86,173.87,182.08.
IR(cm
-1,KBr):3263,3014,2362,2106,1588,1525,1409,1334,1251,1179,1013,930,843,735,698.
Anal.Calcd?for?C
13H
16N
2O
2S:C,61.51;H,5.53;N,15.37;O,5.85;S,11.73.Found:C,61.54;H,5.51;N,15.34.
found?ES+,m/z:=273.4,[M-H]+;272.5.
Above-mentioned detected result confirms that the compound of preparation is 4-(1 '-methyl-propyl group) 1-(4 '-cyano-phenyl)-the 2-thiohydantoin.
3. detect the effect experiment of fluorion test paper
3.1. the preparation of Test paper
The preparation method is with embodiment 1.
The preparation fluorinion concentration is the testing sample of 320 μ g/mL and 50 μ g/mL.
3.2. detection paper fluorion
Detection method is with embodiment 1.
Observe the test paper colour-change, can find that the test paper color is by white yellowing when Test paper dropping concentration is the testing sample of 320 μ g/mL; Be the testing sample of 50 μ g/mL and not during the testing sample of fluoride ion when Test paper drips concentration, the test paper color does not change.Therefore the Test paper of the present invention's preparation can rapid sensitive detects testing sample and whether contains fluorion.
Embodiment 4:4-(1 '-methyl-propyl group) 1-(4 '-trifluoromethyl)-the 2-thiohydantoin
(1.4-1 '-methyl-propyl group) 1-(4 '-trifluoromethyl)-preparation of 2-thiohydantoin
In the 100mL flask, add 2.86g Isoleucine methyl esters (20mmol) and 4.06g p-trifluoromethyl phenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 18 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:3(v/v) lower purifying obtains white solid 5.50g.Productive rate 87%.
(2.4-1 '-methyl-propyl group) 1-(4 '-trifluoromethyl)-sign of 2-thiohydantoin
1H?NMR(400MHz,CDCl
3):δ0.68～0.97(m,6H,2CH
3),1.51～1.97(m,3H,CH
2CH),4.44(s,1H,CH),7.28～7.37(d,2H,Ar),7.61～7.77(m,2H,Ar),10.08(s,1H,NH).
13C?NMR(100MHz,CDCl
3):δ21.52,23.14,24.27,40.01,62.29,112.77,117.88,129.04,132.66,135.98,174.07,179.82.
Above-mentioned detected result confirms that the compound of preparation is 4-(1 '-methyl-propyl group) 1-(4 '-trifluoromethyl)-the 2-thiohydantoin.
3. detect the effect experiment of fluorion test paper
3.1. the preparation of Test paper
The preparation method is with embodiment 1.
The preparation fluorinion concentration is the testing sample of 350 μ g/mL and 50 μ g/mL.
3.2. detection paper fluorion
Detection method is with embodiment 1.
Observe the test paper colour-change, can find that the test paper color is by white yellowing when Test paper dropping concentration is the testing sample of 350 μ g/mL; Be the testing sample of 50 μ g/mL and not during the testing sample of fluoride ion when Test paper drips concentration, the test paper color does not change.Therefore the Test paper of the present invention's preparation can rapid sensitive detects testing sample and whether contains fluorion.
Embodiment 5:4-(1 '-methyl-propyl group) 1-(4 '-p-methoxy-phenyl)-the 2-thiohydantoin
(1.4-1 '-methyl-propyl group) 1-(4 '-p-methoxy-phenyl)-preparation of 2-thiohydantoin
In the 100mL flask, add 2.86g Isoleucine methyl esters (20mmol) and 3.30g p-methoxyphenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 4.73g.Productive rate 85%.
(2.4-1 '-methyl-propyl group) 1-(4 '-p-methoxy-phenyl)-sign of 2-thiohydantoin
1H?NMR(400MHz,CDCl
3):δ0.61～0.92(m,6H,2CH3),1.77～2.34(m,3H,CH2CH),5.01(s,1H,CH),5.34～5.57(m,3H,CH3O),7.08～7.27(d,2H,Ar),7.87～8.02(m,2H,Ar),9.78(s,1H,NH).
13C?NMR(100MHz,CDCl
3):δ20.52,22.57,23.82,43.45,57.42,60.12,112.87,117.68,129.15,132.78,136.14,175.22,181.12.
Above-mentioned detected result confirms that the compound of preparation is 4-(1 '-methyl-propyl group) 1-(4 '-p-methoxy-phenyl)-2 thiohydantoins.
3. detect the effect experiment of fluorion test paper
3.1. the preparation of Test paper
The preparation method is with embodiment 1.
The preparation fluorinion concentration is the testing sample of 330 μ g/mL and 50 μ g/mL.
3.2. detection paper fluorion
Detection method is with embodiment 1.
Observe the test paper colour-change, can find that the test paper color is by white yellowing when Test paper dropping concentration is the testing sample of 330 μ g/mL; Be the testing sample of 50 μ g/mL and not during the testing sample of fluoride ion when Test paper drips concentration, the test paper color does not change.Therefore the Test paper of the present invention's preparation can rapid sensitive detects testing sample and whether contains fluorion.
Embodiment 6:4-(1 '-methyl-propyl group) 1-(4 '-butyl phenyl)-the 2-thiohydantoin
In the 100mL flask, add 2.86g Isoleucine methyl esters (20mmol) and 3.83g to butyl phenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 5.11g.Productive rate 84%.
Embodiment 7:4-methyl isophthalic acid-phenyl-2-thiohydantoin
1.4-the preparation of methyl isophthalic acid-phenyl-2-thiohydantoin
In the 100mL flask, add 2.02g alanine methyl ester (20mmol) and 2.70g PITC (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 3.34g.Productive rate 81%.
2.4-methyl isophthalic acid-phenyl-2-thiohydantoin characterizes
1H?NMR(400MHz,CDCl
3):δ0.87～1.21(m,H,CH3),5.02(s,1H,CH),7.01～7.18(d,2H,Ar),7.54～7.68(m,3H,Ar),8.02(s,1H,NH).
13C?NMR(100MHz,CDCl
3):δ20.09,63.51,128.55,129.42,129.87,133.26,174.64,181.01.
Above-mentioned detected result confirms that the compound of preparation is 4-methyl isophthalic acid-phenyl-2-thiohydantoin.
Embodiment 8:4-methyl 1-(4 '-nitrophenyl)-the 2-thiohydantoin
1.4-methyl 1-(4 '-nitrophenyl)-preparation of 2-thiohydantoin
In the 100mL flask, add 2.02g alanine methyl ester (20mmol) and 3.60g p-nitrophenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 4.17g.Productive rate 83%.
2.4-the sign of methyl isophthalic acid-(4 '-nitrophenyl)-2-thiohydantoin
1H?NMR(400MHz,CDCl
3):δ1.24～1.52(m,3H,CH3),4.53(s,1H,CH),7.01(s,1H,NH),7.32～7.49(d,2H,Ar),8.12～8.30(d,2H,Ar).
13C?NMR(100MHz,CDCl
3):δ20.14,61.53,124.44,129.07,137.82,147.55,174.17,180.27.
Above-mentioned detected result confirms that the compound of preparation is 4-methyl isophthalic acid-(4 '-nitrophenyl)-2-thiohydantoin.
Embodiment 9:4-methyl 1-(4 '-cyano-phenyl)-the 2-thiohydantoin
1.4-methyl 1-(4 '-cyano-phenyl)-preparation of 2-thiohydantoin
In the 100mL flask, add 2.02g alanine methyl ester (20mmol) and 3.20g to cyano-phenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 4.07g.Productive rate 88%.
2.4-the sign of methyl isophthalic acid-(4 '-cyano-phenyl)-2-thiohydantoin
1H?NMR(400MHz,CDCl
3):δ1.15～1.34(m,3H,CH3),4.12(s,1H,CH),7.32～7.43(d,2H,Ar),7.65～7.74(m,3H,Ar),9.87(s,1H,NH).
13C?NMR(100MHz,CDCl
3):δ19.47,62.19,112.75,118.22,129.79,131.91,136.06,174.27,181.28.
Above-mentioned detected result confirms that the compound of preparation is 4-methyl isophthalic acid-(4 '-cyano-phenyl)-2 thiohydantoin.
3. detect the effect experiment of fluorion test paper
3.1. the preparation of Test paper
The preparation method is with embodiment 1.
The preparation fluorinion concentration is the testing sample of 400 μ g/mL and 50 μ g/mL.
3.2. detection paper fluorion
Detection method is with embodiment 1.
When Test paper dropping concentration was the testing sample of 400 μ g/mL, the test paper color was by white yellowing; Be the testing sample of 50 μ g/mL and not during the testing sample of fluoride ion when Test paper drips concentration, the test paper color does not change.Therefore the Test paper of the present invention's preparation can rapid sensitive detects testing sample and whether contains fluorion.
Embodiment 10:4-methyl 1-(4 '-p-methoxy-phenyl)-the 2-thiohydantoin
1.4-the preparation of methyl isophthalic acid-(4 '-p-methoxy-phenyl)-2-thiohydantoin
In the 100mL flask, add 2.02g alanine methyl ester (20mmol) and 3.30g p-methoxyphenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 3.97g.Productive rate 84%.
2.4-the sign of methyl isophthalic acid-(4 '-p-methoxy-phenyl)-2-thiohydantoin
1H?NMR(400MHz,CDCl
3):δ0.94～1.24(m,3H,CH3),4.67～4.83(m,3H,CH3O),5.14(s,1H,CH),6.98～7.11(d,2H,Ar),7.74～7.91(m,2H,Ar),10.02(s,1H,NH).
13C?NMR(100MHz,CDCl
3):δ20.05,56.11,64.52,112.55,117.08,129.75,132.18,136.87,177.12,183.51.
Above-mentioned detected result confirms that the compound of preparation is 4-methyl 1-(4 '-p-methoxy-phenyl)-the 2-thiohydantoin.
3. detect the effect experiment of fluorion test paper
3.1. the preparation of Test paper
The preparation method is with embodiment 1.
The preparation fluorinion concentration is the testing sample of 400 μ g/mL and 50 μ g/mL.
3.2. detection paper fluorion
Detection method is with embodiment 1.
When Test paper dropping concentration was the testing sample of 400 μ g/mL, the test paper color was by white yellowing; Be the testing sample of 50 μ g/mL and not during the testing sample of fluoride ion when Test paper drips concentration, the test paper color does not change.Therefore the Test paper of the present invention's preparation can rapid sensitive detects testing sample and whether contains fluorion.
Embodiment 11:4-methyl isophthalic acid-(4 '-butyl phenyl)-2-thiohydantoin
In the 100mL flask, add 2.02g alanine methyl ester (20mmol) and 3.83g to butyl phenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 4.51g.Productive rate 86%.
Embodiment 12:4-methyl isophthalic acid-(4 '-trifluoromethyl)-2 thiohydantoin
In the 100mL flask, add 2.02g alanine methyl ester (20mmol) and 4.06g p-trifluoromethyl phenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 4.50g.Productive rate 82%.
Embodiment 13:4-benzyl 1-phenyl-2-thiohydantoin
In the 100mL flask, add 3.54g phenylalanine methyl ester (20mmol) and 2.70g PITC (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 4.35g.Productive rate 81%.
Embodiment 14:4-benzyl 1-(4 '-nitrophenyl)-the 2-thiohydantoin
In the 100mL flask, add 3.54g phenylalanine methyl ester (20mmol) and 3.60g p-nitrophenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 5.20g.Productive rate 83%.
Embodiment 15:4-benzyl-1-(4 '-cyano-phenyl)-the 2-thiohydantoin
In the 100mL flask, add 3.54g phenylalanine methyl ester (20mmol) and 3.20g to cyano-phenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 4.99g.Productive rate 85%.
Embodiment 16:4-benzyl-1-(4 '-p-methoxy-phenyl)-the 2-thiohydantoin
In the 100mL flask, add 3.54g phenylalanine methyl ester (20mmol) and 3.30g p-methoxyphenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 4.89g.Productive rate 82%.
Embodiment 17:4-benzyl-1-(4 '-butyl phenyl)-the 2-thiohydantoin
In the 100mL flask, add 3.54g phenylalanine methyl ester (20mmol) and 3.83g to butyl phenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 5.39g.Productive rate 83%.
Execute routine 18:4-benzyl-1-(4 '-trifluoromethyl)-the 2-thiohydantoin
In the 100mL flask, add 3.54g phenylalanine methyl ester (20mmol) and 4.06g p-trifluoromethyl phenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 5.78g.Productive rate 86%.
Embodiment 19:4-sec.-propyl-1-phenyl-2-thiohydantoin
In the 100mL flask, add 2.58g valine methyl ester (20mmol) and 2.70g PITC (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 3.80g.Productive rate 81%.
Embodiment 20:4-sec.-propyl 1-(4 '-nitrophenyl)-the 2-thiohydantoin
1.4-sec.-propyl 1-(4 '-nitrophenyl)-preparation of 2-thiohydantoin
In the 100mL flask, add 2.58g valine methyl ester (20mmol) and 3.60g p-nitrophenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 4.75g.Productive rate 85%.
2.4-sec.-propyl 1-(4 '-nitrophenyl)-sign of 2-thiohydantoin
1H?NMR(400MHz,CDCl
3):δ0.71～0.94(m,6H,2CH3),1.85(s,H,（CH
3)
2CH),485(s,1H,CH),7.02～7.29(d,2H,Ar),7.89～8.01(d,2H,Ar)8.67(s,1H,NH),.
13C?NMR(100MHz,CDCl
3):δ20.52,38.41，,62.44,124.74,129.08,139.12,146.86,174.17,181.25.
Above-mentioned detected result confirms that the compound of preparation is 4-sec.-propyl 1-(4 '-nitrophenyl)-the 2-thiohydantoin.
3. detect the effect experiment of fluorion test paper
3.1. the preparation of Test paper
The preparation method is with embodiment 1.
The preparation fluorinion concentration is the testing sample of 400 μ g/mL and 50 μ g/mL.
3.2. detection paper fluorion
Detection method is with embodiment 1.
When Test paper dropping concentration was the testing sample of 400 μ g/mL, the test paper color was by white yellowing; Be the testing sample of 50 μ g/mL and not during the testing sample of fluoride ion when Test paper drips concentration, the test paper color does not change.Therefore the Test paper of the present invention's preparation can rapid sensitive detects testing sample and whether contains fluorion.
Embodiment 21:4-sec.-propyl-1-(4 '-cyano-phenyl)-the 2-thiohydantoin
In the 100mL flask, add 2.58g valine methyl ester (20mmol) and 3.20g to cyano-phenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 4.30g.Productive rate 83%.
Embodiment 22:4-sec.-propyl 1-(4 '-p-methoxy-phenyl)-the 2-thiohydantoin
In the 100mL flask, add 2.58g valine methyl ester (20mmol) and 3.30g p-methoxyphenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 4.23g.Productive rate 80%.
Embodiment 23:4-sec.-propyl 1-(4 '-butyl phenyl)-the 2-thiohydantoin
In the 100mL flask, add 2.58g valine methyl ester (20mmol) and 3.83g to butyl phenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 4.70g.Productive rate 81%.
Embodiment 24:4-sec.-propyl 1-(4 '-trifluoromethyl)-the 2-thiohydantoin
In the 100mL flask, add 2.58g valine methyl ester (20mmol) and 4.06g p-trifluoromethyl phenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 5.08g.Productive rate 84%.
Embodiment 25:4-(2 '-methyl-propyl group) preparation of 1-phenyl-2-thiohydantoin
In the 100mL flask, add 2.86g leucine methyl esters (20mmol) and 2.70g PITC (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 4.22g.Productive rate 85%.
Embodiment 26:4-(2 '-methyl-propyl group) 1-(4 '-nitrophenyl)-preparation of 2-thiohydantoin
In the 100mL flask, add 2.86g leucine methyl esters (20mmol) and 3.60g p-nitrophenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 4.69g.Productive rate 80%.
Embodiment 27:4-(2 '-methyl-propyl group) 1-(4 '-cyano-phenyl)-preparation of 2-thiohydantoin
In the 100mL flask, add 2.86g leucine methyl esters (20mmol) and 3.20g to cyano-phenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 4.76g.Productive rate 87%.
Embodiment 28:4-(2 '-methyl-propyl group) 1-(4 '-p-methoxy-phenyl)-the 2-thiohydantoin
In the 100mL flask, add 2.86g leucine methyl esters (20mmol) and 3.30g p-methoxyphenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 4.68g.Productive rate 84%.
Embodiment 29:4-(2 '-methyl-propyl group) 1-(4 '-butyl phenyl)-the 2-thiohydantoin
In the 100mL flask, add 2.86g leucine methyl esters (20mmol) and 3.83g to butyl phenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 5.24g.Productive rate 86%.
Embodiment 30:4-(2 '-methyl-propyl group) 1-(4 '-trifluoromethyl)-the 2-thiohydantoin
In the 100mL flask, add 2.86g leucine methyl esters (20mmol) and 4.06g p-trifluoromethyl phenyl lsothiocyanates (20mmol), then add 30mL tetrahydrofuran (THF) and 10mL triethylamine.React under the room temperature after 12 hours, the underpressure distillation desolventizing, residual solids is ethyl acetate with silicagel column at eluent components: normal hexane=1:1(v/v) lower purifying obtains white solid 5.19g.Productive rate 82%.
Claims (6)
1. 2-thiohydantoin derivatives is characterized in that: its chemical structure as shown in the formula (I):
R is hydrogen, nitro, cyano group, methoxyl group, butyl or trifluoromethyl; R ' is methyl, benzyl, sec.-propyl, 2-methyl-propyl group or 1-methyl-propyl group.
2. 2-thiohydantoin derivatives according to claim 1 is characterized in that: R is nitro in the described formula (I), and R ' is methyl, benzyl or sec.-propyl.
3. the preparation method of claim 1 or 2 described 2-thiohydantoin derivatives is characterized in that: be that 1:1.05-1.5 adds in the mixing solutions of tetrahydrofuran (THF) and triethylamine with amino acid methyl ester and lsothiocyanates according to mol ratio; The volume ratio 10:1-0.5 of tetrahydrofuran (THF) and triethylamine; React under the room temperature after 12-24 hour, the underpressure distillation desolventizing, residual solids obtains at the elutriant purifying with silicagel column; Described elutriant group is that ethyl acetate and the normal hexane of 1:1-4 forms by volume ratio; Every gram amino acid methyl ester and lsothiocyanates add the mixing solutions 20-40ml of tetrahydrofuran (THF) and triethylamine.
4. claim 1 or the 2 described 2-thiohydantoin derivatives application in detecting fluorion.
5. claim 1 or the 2 described 2-thiohydantoin derivatives application in the test paper of preparation detection fluorion.
6. application according to claim 5, it is characterized in that, described test paper is to be prepared by following methods: described 2-thiohydantoin derivatives is dissolved in gets solution in acetonitrile, THF, acetone or the methylene dichloride first, then filter paper is immersed in the described solution, soaks into and take out filter paper behind the 1-10min and dry and get final product.
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| CN110983309B (en) * | 2019-12-26 | 2023-01-03 | 广东东硕科技有限公司 | Application of 2-thiohydantoin compound or salt thereof |
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