CN1210262A - 2-nitryl-4-benzyl chloride chromatographic derivative reagent and preparation thereof - Google Patents
2-nitryl-4-benzyl chloride chromatographic derivative reagent and preparation thereof Download PDFInfo
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- CN1210262A CN1210262A CN 98117772 CN98117772A CN1210262A CN 1210262 A CN1210262 A CN 1210262A CN 98117772 CN98117772 CN 98117772 CN 98117772 A CN98117772 A CN 98117772A CN 1210262 A CN1210262 A CN 1210262A
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Abstract
A liquid-phase chromatographic derivative reagent, amidohydroxy acylchlorine, for high-sensitivity ultraviolet and fluorescence detection is prepared through condensating phthalic aldehyde and 2-nitro-4-aminobenzoic acid in ether medium to obtain 2-nitro-4-(2-phthaloyl) benzoic acid, acylchlorinating with thionyl chloride in chloroform medium to obtain coarse product, separation and purifying to obtain colorless acicular product with output rate of 4.5%. The product has long storage period cover 3 years under the ordinary temp and dry condition.
Description
The present invention relates to a kind of high sensitivity liquid chromatography derivative reagent 2-nitryl-4-benzyl chloride and preparation technology thereof; this kind derivative reagent chemical name is 2-nitro-4-(2-phthalyl) chlorobenzoyl chloride, is applicable to the liquid chromatography column front derivation ultraviolet and the fluoroscopic examination of amido, hydroxyl and amino acids.
Liquid chromatography technology has become the widely used a kind of means of scientific research and technical appraisement department, can assemble UV, visible light, differential refraction, fluorescence, galvanochemistry and chemiluminescence detector usually.But up to now, also there is not a kind of universal highly sensitive detecting device can finish the qualitative, quantitative task of all kinds of materials.The very little compound of response also can be detected on these detecting devices in order to make, development in recent years multiple derivatization method.Make and have amino (NH
2), hydroxyl (OH), carbonyl (＞C=O) and carboxyl (compound COOH) and amino acid, by with all kinds of derivatization reagent phase reactions that have chromophoric group, the derivatization product that ultraviolet or fluorescent absorption are arranged that generates just can detect with existing these several high sensitivity detectors.In addition, by test compound can with specific derivatization reagent phase reaction, also help differentiating the structure of these compounds.Therefore, the derivatization method in the liquid chromatography has obtained using widely, and new derivatization reagent constantly occurs.
2,4-dinitrofluorobenzene (UV350nm) is applicable to deriving of secondary amine, paranitrobenzoyl chloride (UV254nm) is applicable to deriving of primary amine and secondary amine, triketohydrindene hydrate (VS570nm) is applicable to amino acid whose deriving, these derivative reagents belong to UV, visible light class derivative reagent, and are highly sensitive not as good as fluorescence class derivative reagent in general.Common fluorescence class derivative reagent has o-phthalaldehyde(OPA), fluorescamine, dansyl chloride, fluorenes for methoxyl acyl chlorides, Vitamin B6, dansylhydrazine and 4-bromomethyl-ayapanin.The o-phthalaldehyde(OPA) temperature of reaction is low, the time short, can reach 10 to primary amine and amino acid whose detectability
-12～10
-15, make auxiliary reagent but in reaction, need to add mercaptan, and hydroxyl compound do not responded.Dansyl chloride is another kind of most widely used fluorescent derivatizing agent, be applicable to the detection of amino acid, amine and phenolic compound reaction, but its storage life is shorter.
The present invention is a primary raw material with o-phthalaldehyde(OPA) and 2-nitro-4-aminobenzoic acid, synthetic in two steps 2-nitryl-4-benzyl chloride.2-nitryl-4-benzyl chloride is colourless fine acicular crystal, molecular weight 316, molecular formula C
15H
9N
2O
4Cl, structural formula:
2-nitryl-4-benzyl chloride belongs to the acyl chloride compound, has stronger reactivity for amido, hydroxyl and amino acids.In the 2-nitryl-4-benzyl chloride molecule, exist the big molecular conjugation system of 22 centers, 25 electronics, help absorbing ultraviolet light and launch fluorescence.Experiment finds that 2-nitryl-4-benzyl chloride has strong absorption feature for the 300nm ultraviolet light, and can produce hyperfluorescence.After deriving with detected material, because the increase of molecular structure, its uv absorption wavelength will produce red shift in various degree.
Dansyl chloride is a kind of derivative reagent commonly used, is applicable to the trace detection of amino acid and phenolic compound, but its reaction velocity with primary amine and secondary amine is slower, and it is that the fluid preservation phase is shorter.Compare with dansyl chloride, 2-nitryl-4-benzyl chloride is not only applicable to the trace detection of amino acid, amine and phenolic compound, and its reactivity and detection sensitivity are all greater than dansyl chloride.2-nitryl-4-benzyl chloride is a solid reagent, can preserve more than 3 years under the drying at room temperature condition.
Major technique content of the present invention is:
1 under the magnetic agitation condition, and o-phthalaldehyde(OPA) and 2-nitro-4-aminobenzoic acid are condensed into 2-nitro-4-(2-phthalyl) benzoic acid in the ether medium.This operates in the room temperature temperature lucifuge environment and carries out, and with sodium metal as dewatering agent and antioxidant.
The 2 2-nitro-4-with above-mentioned gained (2-phthalyl) benzoic acid is air-dry, stirs into suspension with the chloroform give medium, is heated to boiling, carries out chloride with thionyl chloride.Return and heated up in a steamer 30 minutes, get the 2-nitryl-4-benzyl chloride crude product.
3 remove blackish green impurity with chloroform washing, and the orange impurity of charcoal absorption carries out recrystallization with benzene as solvent and gets colourless fine acicular crystal.Synthetic yield 41.5%, product seal preservation in exsiccator.
Synthetic example
In the brown reagent bottle of 500ml, add 500ml ether (little air in the bottle can alleviate the oxidation subsidiary reaction), 6.8g 2-nitro-4-aminobenzoic acid successively, the iron staff of three of sodium metals and the long 2cm of diameter 3mm, magnetic agitation adds o-phthalaldehyde(OPA) 5.0g to all dissolvings, seals.Under 20 ℃ of conditions, lucifuge stirs 1h.Filter, reclaim ether from filtrate, filter residue is air-dry, gently press white powder.
Above-mentioned gained white powder is placed 250ml ground conical flask, add ferrometer, several broken ceramics and chloroform 200ml, magnetic agitation becomes suspension, is heated to boiling, returns and heats up in a steamer thionyl chloride 20ml.Return and heated up in a steamer 30 minutes.The color of reaction will be by dark yellow, through purple, dark blue become green brown.To return distillation unit and change distilling apparatus into, and steam chloroform and reclaim.Carefully be distilled to the solution thickness, natural cooling gets the 2-nitryl-4-benzyl chloride crude product.
Thick product is washed (each 10ml) 3 times with chloroform, present lavender to crystal, add 100ml benzene, heating for dissolving is adjusted benzene consumption to crystal and is just dissolved, and adds activated charcoal 1g, little 5min that boils, with 4G sand core funnel suction filtration (preheating sand core funnel in baking oven in advance) while hot, pale yellow solution, promptly have precipitation to separate out after cold slightly.The heating for dissolving precipitation is adjusted the benzene consumption to just dissolving of precipitation, and naturally cooling to room temperature then has crystal to separate out.Extract mother liquor out, carry out recrystallization, can get colourless fine acicular crystal 4 .9g.Synthetic yield 41.5% seals preservation with product in exsiccator.
One of application example
The detection of trace polyamines in the urine: polyamines refers generally to putrescine, essence is narrowed and spermine, and it is not only important metabolic regulation thing, and very close with the tumour relation.
Get urine 50 μ L, add 250 μ L 2-nitryl-4-benzyl chloride acetonitrile solutions (5 * 10
-3Mol/L), 50 μ L sodium bicarbonate (0.25mol/L) solution, jolting was carried out derivatization reaction in 1 minute under room temperature, got 8 μ L solution and carried out efficient liquid phase chromatographic analysis.With acetonitrile/water (54/46, v/v) be moving phase, flow set 0.8ml/min, selected fluorescence exciting wavelength 300nm, emission wavelength 420nm uses ODS post (12.5 * 0.46), and above-mentioned derivative products can obtain good separation on the LC-10A high performance liquid chromatograph of Tianjin, island.Good quantitative linearity relation is arranged in the 0.4-80ng scope, detect and be limited to 1.2ng/g.
Two of application example
The detection of trace Atrazine in the soil: Atrazine belongs to compound in triazine class, is applicable to the corn field weeding, application Swiss Patent in 1958, and nineteen fifty-nine is dropped into commodity production, and from the nineties, this herbicide is used widely in China.Find that Atrazine can make the hamster ovary cell chromosome break this year, be listed in possible human carcinogenic substance.Therefore, the retention analysis of Atrazine receives people's concern in the soil.
The earth sample 100.00 that fetches earth restrains (40 order), adds methyl alcohol 100mL, and ultrasonic oscillation 10 minutes, suction filtration, concentrated extract add 2-nitryl-4-benzyl chloride acetonitrile liquid (5 * 10 to 1mL
-3Mol/L) 1mL, 10 μ L sample introduction analyses are got in jolting 20 minutes.With methanol (80/20, v/v) be moving phase, flow set 0.8ml/min, selected fluorescence exciting wavelength 312nm, emission wavelength 420nm uses ODS post (12.5 * 0.46), and above-mentioned derivative products can obtain good separation on the LC-10A high performance liquid chromatograph of Tianjin, island.Good quantitative linearity relation is arranged in the 0.12-100ng scope, detect and be limited to 1.0ng/g.
Three of application example
The detection of phenol and halogenated phenols in the water body: phenol and halogenated phenols are widely used in the production of chemical products such as phenolics, agricultural chemicals, plastics, dyestuff, germifuge.Entering environment parameter constantly increases.Slowly reach in the water body characteristics such as probability of occurrence is big and be listed in the priority pollutants " blacklist " because of it has bio-toxicity, degradation speed.
With water sample G4# sintered filter funnel and 0.45 μ m membrane filtration.Get 50 μ L and filter the back water sample, add 250 μ L 2-nitryl-4-benzyl chloride acetonitrile solutions (5 * 10
-3Mol/L), jolting 1 minute adds 50 μ L sodium bicarbonate solutions (0.25mol/L) subsequently, and 10 μ L sample introduction analyses are got in jolting 2 minutes.With acetonitrile/water (71/29, v/v) be moving phase, flow set 1.0ml/min, selected fluorescence exciting wavelength 310nm, emission wavelength 410nm uses ODS post (12.5 * 0.46), phenol, orthomonochlorphenol, m-Chlorophenol, 2,4-two chlorophenols, 2,4, six kinds of derivative products of 5-trichlorophenol and pentachloro-phenol can obtain good separation on the LC-10A high performance liquid chromatograph of Tianjin, island.Good quantitative linearity relation is arranged in the 2.0-120pg scope, detect and be limited to 15pg/g.
Application example four
The detection of phenmethylol and saligenin in the tealeaves: phenmethylol and saligenin are the deodorant tunes that not only can be used as in the spices, but also are good fixastive.One of standard of its quality discrimination that how much can be used as of phenmethylol and saligenin content in the tealeaves.
With the tealeaves porphyrize, cross 40 mesh sieves, get 1.000 grams, add the 5.0mL acetonitrile, ultrasonic oscillation 15 minutes, centrifuging.Get centrifugal clear liquid 1.0mL, add 1.0mL 2-nitryl-4-benzyl chloride acetonitrile solution (5 * 10
-3Mol/L), 10 μ L sample introduction analyses are got in jolting 5 minutes.With acetonitrile/water (49/51, v/v) be moving phase, flow set 1.0ml/min, selected uv absorption wavelength 300nm, use ODS post (12.5 * 0.46), the derivative products of phenmethylol and saligenin can obtain good separation on the LC-10A high performance liquid chromatograph of Tianjin, island.Good quantitative linearity relation is arranged in the 0.5-110ng scope, detect and be limited to 2.0ng/g.
The detected material in above-mentioned sample, 2-nitryl-4-benzyl chloride also can be used for the detection of deriving of nitrosamine, fatty amine, aromatic amine, fatty alcohol, aromatic alcohol and several amino acids.
In sum, the 2-nitryl-4-benzyl chloride reagent that the present invention is prepared has had good reactivity and detection sensitivity, is applicable to the liquid chromatography column front derivation ultraviolet and the fluoroscopic examination of amido, hydroxyl and amino acids, and preparation technology is easy, and product is easy to preserve.
Claims (5)
1 one kinds of high sensitivity ultraviolets, fluoroscopic examination liquid chromatography derivatization reagent-2-nitryl-4-benzyl chloride and preparation technologies thereof.It is characterized in that the chemical name of 2-nitryl-4-benzyl chloride is: 2-nitro-4-(2-phthalyl) chlorobenzoyl chloride, colourless fine acicular crystal, molecular weight: 316, molecular formula: C
15H
9N
2O
4Cl.Structural formula:
The preparation technology of 2-nitryl-4-benzyl chloride comprises: the first step, o-phthalaldehyde(OPA) and 2-nitro-4-aminobenzoic acid are condensed into 2-nitro-4-(2-phthalyl) benzoic acid; In second step, carry out chloride with thionyl chloride and get thick product; In the 3rd step, obtain colourless fine acicular 2-nitryl-4-benzyl chloride product through separating to purify.
2 according to the described preparation technology of claim 1; be condensed in the benzoic reaction of 2-nitro-4-(2-phthalyl) in first step o-phthalaldehyde(OPA) and 2-nitro-4-aminobenzoic acid; reaction conditions is: ether is made reaction medium; 20 ℃ of temperature of reaction; 1 hour reaction time; lucifuge, stirring, and with sodium metal as water absorbing agent and antioxidant.
3 according to the described preparation technology of claim 1, carries out in the reaction of chloride with thionyl chloride in second step, and with the chloroform give medium, thionyl chloride dropwise adds and returns and heated up in a steamer 30 minutes.
4 according to the described preparation technology of claim 1, in the 3rd step process for separating and purifying, with the chloroform washing, uses activated carbon decolorizing more earlier, uses the benzene recrystallization at last.
The 5 2-nitryl-4-benzyl chloride reagent according to right 1～4 described preparation are used for the liquid chromatography column front derivation ultraviolet and the fluoroscopic examination of trace amido, hydroxyl and amino acids.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98117772 CN1210262A (en) | 1998-09-18 | 1998-09-18 | 2-nitryl-4-benzyl chloride chromatographic derivative reagent and preparation thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98117772 CN1210262A (en) | 1998-09-18 | 1998-09-18 | 2-nitryl-4-benzyl chloride chromatographic derivative reagent and preparation thereof |
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| CN1210262A true CN1210262A (en) | 1999-03-10 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105866303A (en) * | 2016-06-24 | 2016-08-17 | 曲阜师范大学 | Detecting method for determining various neurotransmitters on the basis of in situ derivation |
| CN110057944A (en) * | 2019-05-24 | 2019-07-26 | 广东中烟工业有限责任公司 | A kind of amino acid derivatization method and its application |
| CN111693633A (en) * | 2020-07-29 | 2020-09-22 | 珠海润都制药股份有限公司 | Method for detecting 3,4-dimethoxy benzoyl chloride in itopride hydrochloride |
-
1998
- 1998-09-18 CN CN 98117772 patent/CN1210262A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105866303A (en) * | 2016-06-24 | 2016-08-17 | 曲阜师范大学 | Detecting method for determining various neurotransmitters on the basis of in situ derivation |
| CN105866303B (en) * | 2016-06-24 | 2018-05-25 | 曲阜师范大学 | A kind of detection method based on derivative measure various neurotransmitters in situ |
| CN110057944A (en) * | 2019-05-24 | 2019-07-26 | 广东中烟工业有限责任公司 | A kind of amino acid derivatization method and its application |
| CN111693633A (en) * | 2020-07-29 | 2020-09-22 | 珠海润都制药股份有限公司 | Method for detecting 3,4-dimethoxy benzoyl chloride in itopride hydrochloride |
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