CN115974728A - Synthesis of phenyl semicarbazone and identification of hexavalent chromium ions by phenyl semicarbazone - Google Patents
Synthesis of phenyl semicarbazone and identification of hexavalent chromium ions by phenyl semicarbazone Download PDFInfo
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- AKGUXECGGCUDCV-POHAHGRESA-N [(z)-benzylideneamino]urea Chemical compound NC(=O)N\N=C/C1=CC=CC=C1 AKGUXECGGCUDCV-POHAHGRESA-N 0.000 title claims abstract description 59
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 8
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- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title claims abstract description 6
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- SHPPDRZENGVOOR-UHFFFAOYSA-N 1-butylbenzimidazole Chemical compound C1=CC=C2N(CCCC)C=NC2=C1 SHPPDRZENGVOOR-UHFFFAOYSA-N 0.000 claims abstract description 5
- UJTTUOLQLCQZEA-UHFFFAOYSA-N 9h-fluoren-9-ylmethyl n-(4-hydroxybutyl)carbamate Chemical compound C1=CC=C2C(COC(=O)NCCCCO)C3=CC=CC=C3C2=C1 UJTTUOLQLCQZEA-UHFFFAOYSA-N 0.000 claims abstract description 5
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- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 37
- 239000000243 solution Substances 0.000 description 37
- 238000010521 absorption reaction Methods 0.000 description 17
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- 230000000694 effects Effects 0.000 description 7
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- 239000003054 catalyst Substances 0.000 description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 6
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
Synthesis of phenyl semicarbazone and identification of hexavalent chromium ions thereof, adding N-butyl benzimidazole and proline into a reaction vessel, and reacting at 80 ℃ for 8 hours to obtain light yellow oily liquid, namely proline ionic liquid; and cooling to room temperature, then sequentially adding benzaldehyde and semicarbazide hydrochloride, carrying out reflux reaction, and monitoring by TLC until the reaction is complete. After the reaction is finished, cooling the reaction liquid to room temperature, adding water, extracting with diethyl ether, separating liquid, and evaporating the solvent by diethyl ether phase to obtain phenyl semicarbazone; and (3) after water in the water phase is distilled off, drying to obtain proline ionic liquid, and preparing the synthesized probe phenyl semicarbazone into a to-be-detected liquid by using a solvent. Adding different anions into the solution to be detected, and observing the change of the light absorption intensity of the compound through ultraviolet-visible absorption spectrum detection to realize the adjustment of Cr 2 O 7 2‑ And CrO 4 2‑ Selective identification of (2); at the same time, the probe pair Cr 2 O 7 2‑ And CrO 4 2‑ The detection has stronger anti-interference capability and sensitive response.
Description
Technical Field
The invention relates to the field of chemical synthesis and a probe taking benzaldehyde Schiff base as a recognition receptor, which can recognize Cr with high selectivity 2 O 7 2- And CrO 4 2- And has good anti-interference capability on other anions. In particular to a method for synthesizing benzaldehyde Schiff base and Cr pair thereof 2 O 7 2- And CrO 4 2- And (5) identifying.
Background
Chromate (CrO) 4 2- ) Is a heavy metal ion which is widely applied to agriculture and industrial production, but can cause serious damage to the environmental ecology if the heavy metal ion cannot be properly treated. Chromate ions in the environment are enriched in the human body if being absorbed by the human body, and the chromate ions have stimulation and corrosion effects on skin mucous membranes and damage the skin and respiratory tracts, so that diseases such as rhinitis, dermatitis, pharyngitis, perforation of nasal septum, ulcer and the like are caused. The resulting ulcers are both chromycosis, which can allow further passage of chromium toxins into the blood. Thus, the kidney function is damaged, and the patient can suffer from the symptoms of the kidney failure and die quickly if the patient is not treated in time. Dichromate thus belongs to the first category of carcinogens.
Dichromate ion (Cr) 2 O 7 2- ) Has wide application in the industrial field, and is often used in light industrial production such as metallurgy, wood preservation, pigment production, electroplating, leather tanning and the like. Hexavalent chromium (Cr (VI)) as a heavy metal contaminant, if not properly treated in industrial processes, can pose serious environmental and human hazards. It can enter human body through water, air and food, etc. to cause health hazard. It has strong oxidative properties that cause severe loss of DNA and makes it difficult to repair damaged DNA, and also has irreversible damage to the cytoskeleton of cells, which may even lead to death of liver cells, and prolonged exposure to high concentrations of Cr (VI) may also lead to increased probability of cancer. In order to avoid the harm of the pollution of chromate and dichromate ions to human health, the method for quickly, sensitively and simply detecting chromate and dichromate in the environment is developedThe detection method of root pollutants is a problem to be solved at present. At present, conventional means for detecting chromium element trace include an optical analysis method, an atomic spectrometry method and a chemical analysis method, and in addition, novel detection technologies such as a fluorescence analysis method, a test paper method, an electrochemical analysis method and an enzyme inhibition method are widely applied.
Disclosure of Invention
The invention aims to provide a synthesis method of phenyl semicarbazone and a p-hexavalent chromium ion (Cr) thereof 2 O 7 2- And CrO 4 2- ) Selective identification of Cr by UV-visible absorption spectroscopy 2 O 7 2- And CrO 4 2- 。
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for synthesizing a probe of phenyl semicarbazone comprises the following steps:
adding N-butyl benzimidazole and proline into a reaction container, and reacting at 80 ℃ for 8 hours to obtain light yellow oily liquid, namely proline ionic liquid; and cooling to room temperature, then adding benzaldehyde and semicarbazide in sequence, carrying out reflux reaction, and monitoring by TLC until the reaction is complete. After the reaction is finished, cooling the reaction liquid to room temperature, adding water, extracting with diethyl ether, separating liquid, and evaporating the solvent by diethyl ether phase to obtain phenyl semicarbazone; and after the water phase is distilled off, drying to obtain the proline ionic liquid which can be recycled for 5 times.
As shown in formula (1):
probe containing benzaldehyde Schiff base applied to Cr detection 2 O 7 2- And CrO 4 2- A method of ionizing, comprising the steps of:
step 1) preparation of phenyl semicarbazone to a concentration of 1X 10 -4 mol/L of solution to be detected;
step 2) preparation of 1X 10 -2 mol/L anion solution;
mixing the anionic solution withUniformly mixing the solution to be detected to obtain a detection solution, and detecting Cr by ultraviolet-visible spectrum 2 O 7 2- And CrO 4 2- 。
The anion is C 6 H 5 COO - ,HSO 3 - ,F - ,CH 3 COO - ,Br - ,Cr 2 O 7 2- ,CO 3 2- ,SO 4 2- ,S 2- ,S 2 O 8 2- ,C 2 O 4 2- ,SiO 3 2- ,H 2 PO 4 - ,I - ,CrO 4 2- ,Cl - 。
Step 3) mixing the anion solution and the solution to be detected uniformly, wherein the concentration of the solution to be detected is 1 multiplied by 10 -4 mol/L; the concentration of the cation solution is 1X 10 -2 mol/L。
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a preparation method of benzaldehyde Schiff base, which takes benzaldehyde and semicarbazide hydrochloride as raw materials and ionic liquid as a catalyst to synthesize phenyl semicarbazone through reflux reaction and can be used as Cr 2 O 7 2- And CrO 4 2- The high-selectivity ion probe for recognizing the receptor also has stronger anti-interference capability. The invention adopts the ionic liquid as the catalyst and adopts the reflux reaction for synthesis, thereby improving the product yield, shortening the required time, having complete reaction and being green and environment-friendly, and being a green, economic, simple, convenient and efficient method for synthesizing the phenyl semicarbazone.
Drawings
FIG. 1 is the FT-IR of a phenyl semicarbazone;
FIG. 2 is a UV-VIS absorption spectrum of phenyl semicarbazone with added anions;
FIG. 3 shows the addition of phenyl semicarbazone to CrO 4 2- Interference immunity of the ions;
FIG. 4 shows P-Cr addition of phenylsemicarbazone 2 O 7 2- The immunity of the ion;
FIG. 5 is a phenyl semicarbazone versus CrO 4 2- Quantitative testing of ions;
FIG. 6 shows phenylsemicarbazone vs. Cr 2 O 7 2- Quantitative testing of ions;
FIG. 7 is a graph showing pH vs. phenylsemicarbazones for CrO detection 4 2- The effect of the absorption intensity of the ions;
FIG. 8 is a graph showing the detection of Cr by pH vs. phenylsemicarbazones 2 O 7 2- The effect of the absorption intensity of the ions;
FIG. 9 depicts the time-dependent detection of CrO for phenylsemicarbazones 4 2- The influence of (a);
FIG. 10 is a graph of time vs. phenylsemicarbazone detection of CrO 4 2- The influence of (a);
FIG. 11 is a graph showing the effect of the number of times the carbon-based solid acid catalyst was reused on the yield of phenylsemicarbazone.
Detailed Description
The present invention will be described in further detail below with reference to specific examples thereof:
EXAMPLE 1 preparation of phenyl semicarbazone
Adding 1mmol of N-butyl benzimidazole and 30mL of absolute ethyl alcohol into a reaction container, stirring to dissolve, adding proline, slowly heating and refluxing for reaction for 8 hours to obtain light yellow oily liquid, namely proline ionic liquid. Adding 1.2mmol of benzaldehyde and 1mmol of semicarbazide hydrochloride, carrying out reflux reaction, and monitoring by TLC until the reaction is finished; after the reaction is finished, cooling the reaction liquid to room temperature, adding water, extracting with diethyl ether, separating liquid, and evaporating the solvent by diethyl ether phase to obtain phenyl semicarbazone;
recrystallizing to obtain pure product.
IR(KBr)υ：3261cm -1 、3072cm -1 、1690cm -1 、1600cm -1 、1428cm -1 、1520cm -1 、1646cm -1 、1609cm -1 、690cm -1 、758cm -1 、692cm -1 。
Example 2 Selective detection of anions by a phenylsemicarbazone
Dissolving phenyl semicarbazoneIn methanol H 2 O =5:5 prepared as a 1 × 10 concentration solution -4 Ultrasonically mixing the mol/L solution to be detected; will C 6 H 5 COONa,NaHSO 3 ,NaF,CH 3 COONa,NaBr,Na 2 Cr 2 O 7 ,Na 2 CO 3 ,Na 2 SO 4 ,Na 2 S,Na 2 S 2 O 8 ,Na 2 C 2 O 4 ,Na 2 SiO 3 ,NaH 2 PO 4 ,NaI,K 2 CrO 4 Anion salt such as NaCl is dissolved in ultrapure water to be prepared to a concentration of 1X 10 -2 mol/L of anion solution. Adding 3mL of the solution to be tested of the phenyl semicarbazone into each sample tube, preparing one sample tube as a blank reference sample, adding 30 mu L of the 16 anion solutions into the other 16 sample tubes respectively, carrying out ultrasonic treatment on the 17 groups of sample tubes, and measuring the ultraviolet-visible absorption spectrum after uniformly mixing. As can be seen from FIG. 2, when the solution to be tested and other 14 kinds of cations are added into the solution to be tested, an absorption peak appears at 275nm in the ultraviolet-visible absorption spectrum; and adding CrO 4 2- And Cr 2 O 7 2- The absorption peak at 275nm is blue-shifted to 270nm when the ion is excited, and the absorption intensity is obviously enhanced. And new absorption peaks appear at 368nm and 360nm, respectively. It can be easily seen from FIG. 2 that phenylsemicarbazone can selectively recognize CrO 4 2- And Cr 2 O 7 2- Ions.
Example 3 phenyl semicarbazone p-CrO 4 2- Interference immunity detection of
Dissolving phenyl semicarbazone in methanol H 2 O =5:5, prepared at a concentration of 1X 10 -4 Ultrasonically mixing mol/L solution to be detected; will C 6 H 5 COONa,NaHSO 3 ,NaF,CH 3 COONa,NaBr,Na 2 CO 3 ,Na 2 SO 4 ,Na 2 S,Na 2 S 2 O 8 ,Na 2 C 2 O 4 ,Na 2 SiO 3 ,NaH 2 PO 4 ,NaI,K 2 CrO 4 Anion salt such as NaCl is dissolved in ultrapure water to prepare a solution having a concentration of 1X 10 -2 Anion of mol/LA sub-solution. Adding 3mL of the solution to be tested of phenyl semicarbazone into each sample tube, preparing one sample tube as a blank control sample, adding 30 μ L of the 15 kinds of anion solutions into the other 15 sample tubes, and adding 30 μ L of LCrO into each sample tube 4 2- And (4) performing ultrasonic treatment on the 16 groups of sample tubes, uniformly mixing, and measuring the ultraviolet-visible absorption spectrum. As can be seen from FIG. 3, when 14 kinds of other anion solutions were added dropwise, the absorption intensity of the test solution was similar to that of the phenyl semicarbazone test solution, and only CrO was added 4 2- The light absorption intensity is obviously improved when ions are generated, which shows that the phenylsemicarbazone test solution can selectively identify CrO 4 2- Ions; adding CrO again after adding the anionic solution to the phenyl semicarbazone 4 2- Ionic solutions, it can be seen from fig. 3 that the absorption intensity of all solutions to be tested is significantly increased. Illustrating other anion pairs CrO 4 2- The selective recognition function of the ions is not interfered; phenyl semicarbazone p-CrO 4 2- The ions have good specificity recognition effect and can be applied to actual detection.
Example 4 phenyl semicarbazone p-Cr 2 O 7 2- Interference immunity detection of
Dissolving phenyl semicarbazone in methanol H 2 O =5:5, prepared at a concentration of 1 × 10 -4 Ultrasonically mixing the mol/L solution to be detected; c is to be 6 H 5 COONa,NaHSO 3 ,NaF,CH 3 COONa,NaBr,Na 2 Cr 2 O 7 ,Na 2 CO 3 ,Na 2 SO 4 ,Na 2 S,Na 2 S 2 O 8 ,Na 2 C 2 O 4 ,Na 2 SiO 3 ,NaH 2 PO 4 Anion salt such as NaI and NaCl is dissolved in ultrapure water to prepare a solution having a concentration of 1X 10 -2 mol/L of anion solution. Adding 3mL of the solution to be tested of phenyl semicarbazone into each sample tube, preparing one sample tube as a blank control sample, adding 30 μ L of the above 15 kinds of anion solution into the other 15 sample tubes, and adding 30 μ L of the solution to be tested into each sample tubeCr 2 O 7 2- And (4) carrying out ultrasonic treatment on the 16 groups of sample tubes, and measuring the ultraviolet-visible absorption spectrum of the sample tubes after uniformly mixing. As can be seen from FIG. 4, when 14 kinds of other anion solutions were added dropwise, the absorption intensity of the test solution was similar to that of the phenylsemicarbazone test solution, and only Cr was added 2 O 7 2- The light absorption intensity is obviously improved when ions are generated, which shows that the phenylsemicarbazone test solution can selectively identify Cr 2 O 7 2- Ions; adding Cr again after adding the anionic solution to the phenylsemicarbazone 2 O 7 2- The ionic solution, as can be seen from fig. 4, the light absorption intensity of all solutions to be tested is significantly increased. Description of other anion pairs Cr 2 O 7 2- The selective recognition function of the ions is not interfered; phenyl semicarbazone p-Cr 2 O 7 2- The ions have good specificity recognition function and can be applied to actual detection.
Example 5 phenylsemicarbazones vs. CrO 4 2- Quantitative test of
Identification of metal ion CrO 4 2- The results of the effect of (2) on the probe performance are shown in FIG. 5. With CrO 4 2- The concentration in the solution to be detected is increased continuously, and the absorption peak at 291nm is gradually reduced.
Example 6 phenyl semicarbazone p-Cr 2 O 7 2- Quantitative test of
Identification of metal ion Cr 2 O 7 2- The results of the effect of the concentration of (2) on the performance of the probe are shown in FIG. 6. With Cr 2 O 7 2- The concentration in the solution to be detected is increased continuously, and the absorption peak is gradually reduced at 290 nm.
Example 7 detection of CrO at different pH values for phenylsemicarbazones 4 2- Application study of
In addition, in order to investigate the practical applicability of phenyl semicarbazones at different pH, the absorbance intensity of phenyl semicarbazones at 347nm was investigated at different pH environments. As shown in FIG. 7, the absorbance intensity of phenyl semicarbazone was not increased in different pH environmentsObviously changing, adding CrO 4 2- Thereafter, it was substantially stabilized at pH =2.0 to 6.0 and pH =7.0 to 10.0. Adding CrO 4 2- The absorption intensity of the acidic solution after ionization is significantly lower than that of the alkaline solution. The result shows that the probe can effectively identify CrO in acid and alkaline environments 4 2- Ions.
Example 8 detection of Cr in phenylsemicarbazones at different pH values 2 O 7 2- Application study of
In addition, in order to investigate the practical applicability of phenyl semicarbazone at various pH, the phenyl semicarbazone was investigated at various pH environments at an absorption intensity of 360 nm. As shown in FIG. 8, the absorption intensity of the phenyl semicarbazone did not change significantly under different pH environments, and Cr was added 2 O 7 2- Thereafter, it was substantially stabilized at pH =2.0 to 6.0 and pH =7.0 to 12.0. In the presence of Cr 2 O 7 2- The absorption intensity of the acidic solution after ionization is significantly lower than that of the alkaline solution. The results show that the probe can effectively identify Cr in acidic and alkaline environments 2 O 7 2- Ions.
EXAMPLE 9 detection of CrO by time on phenylsemicarbazone 4 2- Influence of (2)
To verify whether phenylsemicarbazone could be put to practical use, the change in the absorption intensity of phenylsemicarbazone with time during the test was investigated at room temperature, as shown in FIG. 9, and phenylsemicarbazone ((methanol: H) 2 O＝5:5),1×10 -4 mol/L) is increased at 280nm within 0-80 min. Adding CrO 4 2- Then the light absorption intensity reaches the strongest value in 0-5 min, and the light absorption intensity slightly decreases in 5-80 min and finally tends to be stable. This result indicates that the probe can complete the reaction on CrO within 5min 4 2- Detection of (3).
EXAMPLE 10 time-to-time Cr detection with phenylsemicarbazones 2 O 7 2- Influence of (2)
To verify whether phenylsemicarbazones could be practically used, phenylsemicarbazones were investigated at room temperatureThe change in the absorption intensity with time during the measurement was shown in FIG. 10 for phenyl semicarbazone ((methanol: H) 2 O＝5:5),1×10 -4 mol/L) in 0-80 min, the absorbance at 280nm increases. Adding Cr 2 O 7 2- Then the light absorption intensity reaches the strongest value within 0-5 min, and the light absorption intensity is stable and unchanged within 5-80 min. This result indicates that the probe can complete the treatment of Cr within 5min 2 O 7 2- And is stable.
As can be seen from fig. 11, the use of an ionic liquid as a catalyst improves the reaction yield; the reaction time is reduced; the catalyst has good catalytic activity; after the reaction is finished, the ionic liquid is simple to recover and operate and can be directly reused. The result shows that the catalyst used in the invention can be directly reused, so that the synthesis has the advantages of low cost, green and environment-friendly method and the like.
Claims (10)
1. The synthesis of phenyl semicarbazone and the identification of hexavalent chromium ions thereof are characterized in that the synthesis of the phenyl semicarbazone is as shown in formula (1):
2. the method for synthesizing phenylsemicarbazone and identifying hexavalent chromium ions according to claim 1, wherein the solution to be tested for synthesizing phenylsemicarbazone comprises the following steps:
step 1) adding N-butyl benzimidazole and proline into a reaction container, and reacting for 8 hours at 80 ℃ to obtain light yellow oily liquid, namely proline ionic liquid;
step 2) sequentially adding benzaldehyde and semicarbazide hydrochloride, carrying out reflux reaction, monitoring by TLC (thin layer chromatography) until the reaction is complete, cooling the reaction solution to room temperature after the reaction is finished, adding water, extracting by using ether, separating, and evaporating the solvent by using the ether phase to obtain phenyl semicarbazone; after water in the water phase is removed by evaporation, the proline ionic liquid is obtained by drying, and can be recycled for 5 times;
and 3) preparing a phenyl semicarbazone solution with a certain concentration to obtain a solution to be detected.
3. The method for preparing phenyl semicarbazone according to claim 2, characterized in that the phenyl semicarbazone is obtained by a reflux reaction in an ionic liquid.
4. The method of claim 2, wherein the proline ionic liquid is N-butylbenzimidazole and proline.
5. The method for preparing phenyl semicarbazone according to claim 2, characterized in that the charge ratio of the benzaldehyde, the semicarbazide hydrochloride and the ionic liquid is (1-1.3) to 1 (0.05-0.3).
6. Probe containing benzaldehyde Schiff base applied to Cr detection 2 O 7 2- And CrO 4 2- The method is characterized by comprising the following steps:
1) Preparing benzaldehyde Schiff base into a solution to be detected;
2) Preparing an anion solution;
3) Mixing the anion solution and the solution to be detected to obtain a detection solution, and detecting Cr by ultraviolet-visible spectrum 2 O 7 2- And CrO 4 2- 。
7. The application of the benzaldehyde Schiff base-containing probe to Cr detection according to claim 6 2 O 7 2- And CrO 4 2- Characterized in that the anion is C 6 H 5 COO - ,HSO 3 - ,F - ,CH 3 COO - ,Br - ,Cr 2 O 7 2- ,CO 3 2- ,SO 4 2- ,S 2- ,S 2 O 8 2- ,C 2 O 4 2- ,SiO 3 2- ,H 2 PO 4 - ,I - ,CrO 4 2- ,Cl - 。
8. The application of the benzaldehyde Schiff base-containing probe to Cr detection according to claim 6 2 O 7 2- And CrO 4 2- The method is characterized in that the volume ratio of the mixed anion solution and the solution to be measured is 100:1; when the anion solution and the solution to be detected are mixed, the concentration of the solution to be detected is 1 multiplied by 10 -4 mol/L; the concentration of the anionic solution is 1X 10 -2 mol/L。
9. The application of the benzaldehyde Schiff base-containing probe to Cr detection according to claim 6 2 O 7 2- And CrO 4 2- When the solution to be detected contains Cr 2 O 7 2- Or CrO 4 2- When ionic, the absorbance of the solution system increases.
10. The application of the benzaldehyde Schiff base-containing probe of claim 6 in Cr detection 2 O 7 2- And CrO 4 2- Is characterized by, for C 6 H 5 COO - ,HSO 3 - ,F - ,CH 3 COO - ,Br - ,CO 3 2- ,SO 4 2- ,S 2- ,S 2 O 8 2- ,C 2 O 4 2- ,SiO 3 2- ,H 2 PO 4 - ,I - ,Cl - The plasma has anti-interference capability.
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