CN109651146A - A kind of preparation method and application of 3- methyl -4- formaldoxime yl benzoic acid ethyl ester - Google Patents
A kind of preparation method and application of 3- methyl -4- formaldoxime yl benzoic acid ethyl ester Download PDFInfo
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Abstract
A kind of preparation method of 3- methyl -4- formaldoxime yl benzoic acid ethyl ester, comprising: 3- methyl -4- bromobenzoic acid S1, is dissolved in ethyl alcohol, adds chloride reagent to react 1-10h, obtains 3- methyl -4- bromobenzoic acid ethyl ester；S2, after dissolving 3- methyl -4- bromobenzoic acid ethyl ester in n,N-Dimethylformamide solvent, add cyanylation agent to react 5-72h, obtain 3- methyl -4- cyanobenzoic acid ethyl ester；S3,3- methyl -4- cyanobenzoic acid ethyl ester is dissolved with alcohols solvent, adds hydroxylamine hydrochloride, alkali and water, reacted 2-12h, obtain 3- methyl -4- formaldoxime yl benzoic acid ethyl ester.The application of 3- methyl -4- formaldoxime yl benzoic acid ethyl ester is detected heavy metal ion using 3- methyl -4- formaldoxime yl benzoic acid ethyl ester as ligand, can identify Cu (II), Fe (III) and Pb (II) well.
Description
Technical field
The present invention relates to Chemical metals to identify field, and in particular to a kind of 3- methyl -4- formaldoxime yl benzoic acid ethyl ester
Preparation method and application.
Background technique
Heavy metal refers to density not less than 4.5 g/cm3Metallic element, mainly include mercury, cadmium, lead, chromium, cobalt, copper, iron
Deng heavy metal has the characteristics that difficult to degrade, bio-toxicity is strong, great enriching, in empty gas and water, soil, living organism etc.
Carrier retain, be transferred to ecological environment and cause serious pollution, and by the enrichment of food chain by being passed to advanced life
In object, our human bodies are eventually entered into, our health is endangered, leads to the generation of various diseases.The environment as caused by heavy metal is dirty
Dye is known as heavy metal pollution, and it is super to refer mainly to the significant content of beary metal of the bio-toxicities such as lead, cadmium, chromium, mercury, thallium and metalloid arsenic
Normal range (NR) out causes environmental degradation, and many heavy metal elements are the essential trace elements of the human bodys, once lack certain or
Certain is several, human health will be made to be on the hazard, and influences the eubolism of body.For example, influencing fecundity, hindering
The normal development of embryo, the normal growth for influencing children, even if being the necessary heavy metal element of human body, tolerance of the human body to it
There is a threshold value, more than just causing damages to health after this threshold value.For example, cadmium can excessively lead to pulmonary edema blood pressure, it is poor
Blood, the diseases such as osteomalacia；Mercury can excessively make one to suffer from ephritis, and uremia injures the central nervous system of people；The excess of lead can be to kidney
Dirty, nervous system damages, and has higher toxicity to children, can also be carcinogenic.Therefore, it quickly, accurately and efficiently detects with much money
Belong to ion be it is highly important, the detection and analysis especially in environment measuring and biological field have become chemistry, life section
The important topic of the subjects such as, environmental science and medicine.
The detection of content of beary metal has become an importance of environmental monitoring, and its detection method is mostly by instrument
It analyzes (such as Atomic fluorophotometry), although heavy metal ion quantitatively can be detected, because inconvenient to carry, can not achieve
Live quickly detection.Therefore, the method for establishing heavy metal element in a kind of monitoring sewage quickly, easy, accomplish prevention with
It prevents and treats and combines, timely and effectively control and administer the pollution of heavy metal element bring, this is to improvement home for the survival of mankind
There is extremely important meaning with guarantee human health.The detection method of traditional heavy metal ion depends on instrument analysis such as
Spectrophotometry, electrochemical methods, atomic absorption spectrography (AAS) etc., these methods mostly require high, sensitivity to instrument and equipment
Low, detection and cannot achieve the purpose that real-time detection at limit for height.Fluorescence analysis has high sensitivity, and selectivity is good, easy to operate,
The advantages that sampling amount is few, has been widely used in the every field such as inorganic, organic, biochemical, medical and clinical examination.Many institute's weeks
Know, heavy metal ion is effective fluorescence quencher, the fluorescence quenching based on heavy metal ion and the ion sensor established
Method, obtained universal concern.Oxime compound contains-C=N-OH structure, and N atom therein has lone pair electrons,
Oxygen atom has a good coordination with great electronegativity and metal ion, and the oxime compound of aromatic structure its point
There is conjugatedπbond system in minor structure, and when the substituent group on aromatic ring is electron donating group (- CH3、-OCH3Deng) when, electron
N electron cloud on group is substantially parallel with the track on aromatic ring, expands the conjugated degree of system, so that compound fluorescence be made to increase
By force, the hetero atoms such as C, N, O on electron donating group can also enhance the coordination of ligand and metal ion by hydrogen bond.Oximes
Compound has good coordination ability, can form stable complex with metal ion, and property is stablized, and is readily synthesized, can
Excellent ligand as metal-ion fluorescent probe.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of easy to operate, high incomes, at low cost, fit
It closes industrialization large-scale production and there is the 3- methyl -4- formaldoxime yl benzoic acid ethyl ester ligand of fluorescence response to heavy metal ion
Preparation method.The ligand has preferable fluorescence response for Cu (II), Fe (III) and Pb (II) metal ion, for other
Metal-ion fluorescent response is very weak or does not have.
The purpose of the present invention is what is be accomplished by the following way:
A kind of preparation method of 3- methyl -4- formaldoxime yl benzoic acid ethyl ester, comprising the following steps:
S1,3- methyl -4- bromobenzoic acid is dissolved in ethyl alcohol, chloride reagent is then added and in 20-80 DEG C of reaction 1-10h, it is cold
But, then add it to saturated sodium carbonate aqueous wash medium wash after, be extracted with ethyl acetate, organic phase water and saturation chlorination
Sodium solution washing is concentrated under reduced pressure, and obtains the 3- methyl -4- bromobenzoic acid ethyl ester of brownish red；
S2, it after dissolving 3- methyl -4- bromobenzoic acid ethyl ester in n,N-Dimethylformamide solvent, is added thereto cyanalation
Reagent and after 40-180 DEG C of reaction 5-72h, is cooled to room temperature, then add it in saturated sodium carbonate solution, filters, filtrate
It is extracted with ethyl acetate, is concentrated, crystallize, filtering obtains white solid 3- methyl -4- cyanobenzoic acid ethyl ester；
S3,3- methyl -4- cyanobenzoic acid ethyl ester is dissolved with alcohols solvent, hydroxylamine hydrochloride, alkali and water is added, in 20-130 DEG C
2-12h is reacted, is concentrated under reduced pressure, filtering obtains white solid crude product, then tied again with ethyl acetate and petroleum ether mixed solvent
Crystalline substance obtains 3- methyl -4- formaldoxime yl benzoic acid ethyl ester white solid.
The chloride reagent is thionyl chloride, phosphorus trichloride, phosphorus pentachloride, any one in oxalyl chloride.
The cyanylation agent is cuprous cyanide, zinc cyanide, potassium ferrocyanide, Cymag, potassium cyanide, trimethyl cyano silicon
Any one in alkane.
The alcohols solvent is methanol, ethyl alcohol, propyl alcohol, any one in butanol；Methanol, ethyl alcohol, propyl alcohol, butanol difference
Corresponding reaction temperature is followed successively by 20-80 DEG C, 20-100 DEG C, 20-110 DEG C, 20-130 DEG C, and the corresponding reaction time is successively
For 2-12h, 2-10h, 2-8h, 2-6h.
Alkali described in S3 be sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, saleratus, ammonium hydrogen carbonate, sodium hydroxide,
Potassium hydroxide, ammonium hydroxide, triethylamine, pyridine, any one in piperidines.
The molar ratio of the chloride reagent and 3- methyl -4- bromobenzoic acid is (1-2): 1；The cyanylation agent and 3-
The molar ratio of methyl -4- bromobenzoic acid is (2-10): 1；The molar ratio of hydroxylamine hydrochloride, alkali and 3- methyl -4- bromobenzoic acid is (1-
1.8): (2-3.6): 1.
The application that 3- methyl -4- formaldoxime yl benzoic acid ethyl ester is responded as ligand counterweight metal-ion fluorescent, with 3- first
Base -4- formaldoxime yl benzoic acid ethyl ester detects heavy metal ion as ligand, and the heavy metal ion is Cu (II), Fe
(III), Pb (II), Fe (II), Mn (II), Cr (III), Co (II), Zn (II), Cd (II) and Ni (II).
Compared with prior art, the beneficial effects of the present invention are:
The present invention solves in original process that process route is long, and complicated for operation, severe reaction conditions, production safety risk is larger, receives
The disadvantages of rate is low, and quantity of three wastes is big and not easy to handle.Synthetic route of the present invention is shorter, and technological operation is simple, reaction condition milder,
Used raw material are cheap and easily-available, and the equal recoverable of solvent and by-product used, production cost is lower, more meets industry
Change production requirement.
The present invention replaces, finally and hydrochloric acid using 3- methyl -4- bromobenzoic acid as starting material through chloride, esterification, cyano
Azanol one-step method oximate obtains target product.Its advantage is that process route is short, method is easy to operate, and product yield is high, high-quality.
For Cu (II), Fe (III) and Pb (II) metal ion, the fluorescence emission spectral intensity of ligand is with metal ion
Increase regular reduction, the fluorescence of ligand completely disappears to the end, with concentration of metal ions in good within the scope of a certain concentration
Good linear relationship.For Fe (II), Mn (II), Cr (III) and Co (II), with the addition of metal ion, the fluorescence of ligand
Intensity decline, drops to a certain degree, with the addition of metal ion, the fluorescence of ligand is no longer changed.For Zn (II), Cd
(II) and Ni (II), with the addition of metal ion, the fluorescence intensity of ligand does not change substantially.Accordingly, one kind is established
The new method of fluorescent spectrometry analysis measurement heavy metal ion.
The fluorescence intensity of ligand constantly declines with the increase of metal ion ratio in system, and the decrease of fluorescence may be
Because energy is transferred to metal ion from ligand, and fluorescent quenching has occurred after liganded metal ions coordination.This show ligand L (after
Ligand L is 3- methyl -4- formaldoxime yl benzoic acid ethyl ester in text) coordination has occurred with metal ion, and ligand L is to Cu
(II), Fe (III) and Pb (II) has selectivity well.Fluorescence when especially Fe (III) is added to 40 equivalent to the end
It disappears substantially.It can illustrate that ligand has preferable selectivity to Fe (III).
Ligand can identify that Cu (II), Fe (III) with Pb (II) may be similar phenyl ring in ligand molecular structure well
The space size of molecule, shape can match with the radius size of Cu (II), Fe (III) and Pb (II), and other metals from
It is sub then cannot good match therewith, thus cannot be identified, this shows that ligand exists to metal ion in space size, shape matching
It plays an important role in molecular recognition.In addition, oxygen atom is as soft donor atom gold and soft category copper according to hsab theory
Having stronger affinity is also one of the power of ligand identification Cu (II).In this way, Cu (II), Fe (III) and Pb (II) and nitrogen, oxygen
It can be identified well by ligand under the synergistic effect of weak non-covalent bond such as pi-electron on the coordination and phenyl ring of atom.
Synthetic route of the present invention is as follows:
Detailed description of the invention
The nuclear magnetic resonance spectroscopy of Fig. 1 3- methyl -4- bromobenzoic acid ethyl ester；
The carbon-13 nmr spectra of Fig. 2 3- methyl -4- bromobenzoic acid ethyl ester；
The nuclear magnetic resonance spectroscopy of Fig. 3 3- methyl -4- cyanobenzoic acid ethyl ester；
The carbon-13 nmr spectra of Fig. 4 3- methyl -4- cyanobenzoic acid ethyl ester；
The nuclear magnetic resonance spectroscopy of Fig. 5 3- methyl -4- formaldoxime yl benzoic acid ethyl ester；
The carbon-13 nmr spectra of Fig. 6 3- methyl -4- formaldoxime yl benzoic acid ethyl ester；
The influence of Fig. 7 Cu (II) ion pair ligand L fluorescence；
The influence of Fig. 8 Fe (III) ion pair ligand L fluorescence；
The influence of Fig. 9 Pb (II) ion pair ligand L fluorescence；
The influence of Figure 10 Mn (II) ion pair ligand L fluorescence；
The influence of Figure 11 Fe (II) ion pair ligand L fluorescence；
The influence of Figure 12 Co (II) ion pair ligand L fluorescence；
The influence of Figure 13 Cr (III) ion pair ligand L fluorescence；
The influence of Figure 14 Ni (II) ion pair ligand fluorescence；
The influence of Figure 15 Zn (II) ion pair ligand L fluorescence；
The influence of Figure 16 Cd (II) ion pair ligand L fluorescence.
Specific embodiment
Embodiment
(1) preparation of 3- methyl -4- bromobenzoic acid ethyl ester: being dissolved in 30 ml ethyl alcohol for 5 g of 3- methyl -4- bromobenzoic acid, to
2 ml thionyl chlorides are wherein added, in 83 DEG C back flow reaction 6 hours, solution is cooled to room temperature, be added 30 ml saturated sodium carbonates it is molten
Liquid is sufficiently stirred, and 15 ml ' 3 are extracted with ethyl acetate, and 10 ml of 10 ml ' 2 and saturated salt solution is successively washed with water in organic layer
Washing, anhydrous magnesium sulfate dry, filter, and are concentrated under reduced pressure, and obtain the 2- methyl -4- bromobenzoic acid ethyl ester of brownish red, and 5.42 g are received
Rate 96%.
1H NMR (CDCl3, 400MHz): d (ppm) = 7.89-7.90 (d, 1H, Ar-H), 7.69-7.71
(dd, 1H, Ar-H), 7.58-7.60 (d, 1H, Ar-H), 4.34-4.39(q, 2H, -OCH2CH3), 2.44 (s,
3H, Ar-CH3), 1.37-1.41 (t, 3H, -OCH2CH3). 13CNMR (CDCl3, 100MHz): d (ppm) =
166.12 (COO-), 138.19 (Ar-C), 132.45 (Ar-C), 131.65 (Ar-C), 130.30 (Ar-C),
129.57 (Ar-C), 128.26 (Ar-C), 61.16 (-OCH2CH3), 22.88 (Ar-CH3), 14.31 (-
OCH2CH3).
(2) preparation of 3- methyl -4- cyanobenzoic acid ethyl ester: by 5.42 g of 3- methyl -4- bromobenzoic acid ethyl ester obtained by step (1)
After 20 ml DMF of middle addition dissolution, 7.37 g cuprous cyanides are added, are stirred, 150 DEG C is heated to and reacts 12 hours, be cooled to
Reaction solution is poured into 100 ml saturated sodium carbonate solutions by room temperature, there is yellow solid precipitation, filtering, filtrate acetic acid second
Ester extracts 25 ml ' 3, and 15 ml ' 2 and 15 ml of saturated salt solution washing is successively washed with water in organic layer, and anhydrous magnesium sulfate is dry,
Filtering is concentrated under reduced pressure, crystallisation by cooling, and filtering obtains 2.83 g of white solid 3- methyl -4- cyanobenzoic acid ethyl ester, yield
67%。
1H NMR (400 MHz, CDCl3): d (ppm) = 7.99 (s, 1H, Ar-H), 7.92-7.94(1H,
dd, Ar-H), 7.67-7.69 (1H, d, Ar-H),4.38-4.43 (q, 2H, -OCH2CH3), 2.61 (s, 3H,
Ar-CH3), 1.39-1.43 (t, 3H, -OCH2CH3).13C NMR (100MHz, CDCl3): d (ppm) = 165.24
(-COO-), 142.25 (Ar-C), 134.25 (Ar-C), 132.55 (Ar-C), 131.05 (Ar-C), 127.12
(Ar-C), 117.40 (Ar-C-CN), 116.65 (Ar-C-CN), 61.73 (-OCH2CH3), 20.92 (Ar-CH3),
14.26 (-OCH2CH3).
(3) preparation of 3- methyl -4- formaldoxime yl benzoic acid ethyl ester: by 3- methyl -4- cyanobenzoic acid ethyl ester obtained by step (2)
The dissolution of 20 ml methanol is added in 2.83 g, adds 1.25 g azanol hydrochloric acid and 3.25 g natrium carbonicum calcinatums, is eventually adding 20
Ml distilled water, in 60 DEG C back flow reaction 6 hours, be cooled to room temperature, be concentrated under reduced pressure, obtain crude product.With ethyl acetate and petroleum
Ether mixed solvent recrystallizes crude product, obtains
To White crystal target product 3- methyl -4- formaldoxime yl benzoic acid ethyl ester, 2.63 g, yield 85%.
1H NMR(CDCl3, 400MHz): d (ppm) = 7.88-7.92 (t, Ar-H, 2H), 7.49-7.52
(d, Ar-H, 1H), 7.65 (s, Ar-H, 1H), 5.75 (s, H-C=N+ N-O-H, 2H), 4.36-4.42 (q,
2H, -OCH2CH3), 2.54 (s, 3H, Ar-CH3), 1.39-1.43 (t, 3H, -OCH2CH3). 13C NMR
(CDCl3, 100MHz,): d (ppm) = 171.04 (COOCH3), 166.00 (H-C=N), 139.09 (Ar-C),
136.54 (Ar-C), 132.18 (Ar-C), 131.94 (Ar-C), 127.00 (Ar-C), 126.88 (Ar-C),
61.30 (-OCH2CH3), 19.83 (Ar-CH3), 14.31 (-OCH2CH3).
Fluorometric investigation condition: emission wavelength lambdaem=312.0 nm, excitation wavelength lambdaex=278.0 nm, fluorescent emission slit are wide
Degree is 5.0 nm, and exciting slit width is 2.5nm, solvent: CH3CN(analysis is pure).3 mL are separately added into quartz colorimetric utensil
10-5 Mol/L ligand L solution carries out fluorescence spectrum scanning.Ligand L is made into 10-5 The solution of mol/L, with Cu (OAc)2×
H2O is made into 10-2 The CH of mol/L3CN solution.3 ml of ligand L solution, 3 ml of metal ion solution are taken, guarantees the substance of the two
The ratio between amount is 1:1, and the amount of fixed ligands L gradually increases the volume progress fluorescence spectrum scanning of Cu (II).Other salt (Fe (NO3)3
×9H2O、PbCl2、Co(OAc)2×4H2O、Cr(NO3)3×6H2O、Cd(NO3)2×4H2O、(NH4)2Fe(SO4)2·6H2O、Mn
(OAc)2×4H2O、NiCl2、ZnCl2×6H2O the identification of the same Cu of identification experimental implementation (II)) is tested.
For Cu (II), Fe (III) and Pb (II) metal ion it can be seen from fluorescence spectra, the fluorescence of ligand L is sent out
Spectral intensity is penetrated with the regular reduction of increase of metal ion, the fluorescence of ligand completely disappears to the end, in a certain concentration model
With concentration of metal ions in good linear relationship in enclosing.For Fe (II), Mn (II), Cr (III) and Co (II), with metal
The addition of ion, the fluorescence intensity decline of ligand L, drops to a certain degree, with the addition of metal ion, the fluorescence of ligand is no longer
It changes.For Zn (II), Cd (II) and Ni (II), with the addition of metal ion, the fluorescence intensity of ligand is not sent out substantially
It is raw to change.Accordingly, a kind of new method of fluorescent spectrometry analysis measurement heavy metal ion is established.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, this
The preferred embodiment of invention is not intended to limit the invention, any person skilled in the art, is not departing from skill of the present invention
In the range of art scheme, according to the technical essence of the invention it is to the above embodiments it is any it is simple modification, equivalent variations with
Modification, all of which are still within the scope of the technical scheme of the invention.
Claims (7)
1. a kind of preparation method of 3- methyl -4- formaldoxime yl benzoic acid ethyl ester, which comprises the following steps:
S1,3- methyl -4- bromobenzoic acid is dissolved in ethyl alcohol, chloride reagent is then added and in 20-80 DEG C of reaction 1-10h, it is cold
But, then add it to saturated sodium carbonate aqueous wash medium wash after, be extracted with ethyl acetate, organic phase water and saturation chlorination
Sodium solution washing is concentrated under reduced pressure, and obtains the 3- methyl -4- bromobenzoic acid ethyl ester of brownish red；
S2, it after dissolving 3- methyl -4- bromobenzoic acid ethyl ester in n,N-Dimethylformamide solvent, is added thereto cyanalation
Reagent and after 40-180 DEG C of reaction 5-72h, is cooled to room temperature, then add it in saturated sodium carbonate solution, filters, filtrate
It is extracted with ethyl acetate, is concentrated, crystallize, filtering obtains white solid 3- methyl -4- cyanobenzoic acid ethyl ester；
S3,3- methyl -4- cyanobenzoic acid ethyl ester is dissolved with alcohols solvent, hydroxylamine hydrochloride, alkali and water is added, in 20-130 DEG C
2-12h is reacted, is concentrated under reduced pressure, filtering obtains white solid crude product, then tied again with ethyl acetate and petroleum ether mixed solvent
Crystalline substance obtains 3- methyl -4- formaldoxime yl benzoic acid ethyl ester white solid.
2. a kind of preparation method of 3- methyl -4- formaldoxime yl benzoic acid ethyl ester according to claim 1, it is characterised in that
The chloride reagent is thionyl chloride, phosphorus trichloride, phosphorus pentachloride, any one in oxalyl chloride.
3. a kind of preparation method of 3- methyl -4- formaldoxime yl benzoic acid ethyl ester according to claim 1, it is characterised in that
The cyanylation agent is cuprous cyanide, zinc cyanide, potassium ferrocyanide, Cymag, potassium cyanide, appointing in trimethyl cyanoalkysilane
It anticipates one kind.
4. a kind of preparation method of 3- methyl -4- formaldoxime yl benzoic acid ethyl ester according to claim 1, it is characterised in that
The alcohols solvent is methanol, ethyl alcohol, propyl alcohol, any one in butanol；Methanol, ethyl alcohol, propyl alcohol, butanol are corresponding anti-
Answer temperature to be followed successively by 20-80 DEG C, 20-100 DEG C, 20-110 DEG C, 20-130 DEG C, the corresponding reaction time be followed successively by 2-12h,
2-10h、2-8h、2-6h。
5. a kind of preparation method of 3- methyl -4- formaldoxime yl benzoic acid ethyl ester according to claim 1, it is characterised in that
Alkali described in S3 is sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, saleratus, ammonium hydrogen carbonate, sodium hydroxide, hydroxide
Potassium, ammonium hydroxide, triethylamine, pyridine, any one in piperidines.
6. a kind of preparation method of 3- methyl -4- formaldoxime yl benzoic acid ethyl ester according to claim 1, it is characterised in that
The molar ratio of the chloride reagent and 3- methyl -4- bromobenzoic acid is (1-2): 1；The cyanylation agent and 3- methyl -4-
The molar ratio of bromobenzoic acid is (2-10): 1；The molar ratio of hydroxylamine hydrochloride, alkali and 3- methyl -4- bromobenzoic acid is (1-1.8):
(2-3.6): 1.
The application that 7.3- methyl -4- formaldoxime yl benzoic acid ethyl ester is responded as ligand counterweight metal-ion fluorescent, feature exist
In detecting heavy metal ion as ligand using 3- methyl -4- formaldoxime yl benzoic acid ethyl ester, the heavy metal ion is Cu
(II), Fe (III), Pb (II), Fe (II), Mn (II), Cr (III), Co (II), Zn (II), Cd (II) and Ni (II).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201910079969.5A CN109651146A (en) | 2019-01-28 | 2019-01-28 | A kind of preparation method and application of 3- methyl -4- formaldoxime yl benzoic acid ethyl ester |
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| CN114534511A (en) * | 2022-02-17 | 2022-05-27 | 天津大学 | Intrinsic microporous polymeric membrane regulated and controlled by hydrogen bonding effect and preparation and application thereof |
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