CN102796025A - Synthesis method for stable isotope labeled malachite green - Google Patents
Synthesis method for stable isotope labeled malachite green Download PDFInfo
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- CN102796025A CN102796025A CN201210313832XA CN201210313832A CN102796025A CN 102796025 A CN102796025 A CN 102796025A CN 201210313832X A CN201210313832X A CN 201210313832XA CN 201210313832 A CN201210313832 A CN 201210313832A CN 102796025 A CN102796025 A CN 102796025A
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Abstract
The invention relates to a synthesis method for stable isotope labeled malachite green. The stable isotope labeled malachite green is obtained by the steps of reacting stable isotope labeled N, N-dimethylaniline with a coupling agent and benzaldehyde, introducing mixed gas of NO and NO2, and separating and purifying after the reaction is finished. Compared with the prior art, after the stable isotope labeled malachite green prepared by the method is separated and purified, the chemical purity reaches over 99 percent and the isotope abundance is over 98 percent atom.
Description
Technical field
The present invention relates to the isotopic labeling field, especially relate to the compound method of mark detection reagent cold labeling malachite green in a kind of isotropic substance.
Background technology
Malachite green once was widely used in the Fish culture industry as sterilant.Chemical functional group tritane in the malachite green can be carcinogenic, and a lot of countries forbid, but still have the fisherman when control fish fungal infection, to use, and also has the forwarding agent to be used as sterilizing agent, to prolong the survival time of fish in long-distance traffic.For preventing the residual entering food chain of Synthesis of diaminodiphenyl such as malachite green, culturist and supervision department of government need a kind of can be fast, accurately also very sensitive technology detects it.
The main detection technique that is used for detecting this type Synthesis of diaminodiphenyl has HPLC, tlc, spectrophotometry and using high performance liquid chromatography tandem mass spectrum method.HPLC highly sensitive, but this method is loaded down with trivial details, so this method is seldom used.Tlc is simple and efficient to handle, but can not detect malachite green and procrypsis malachite green simultaneously.The detectability of spectrophotometry is very high, but the sensitivity that detects is lower, and accuracy is very poor.And mass spectrum is used in all kinds of residue detection and is popularized gradually as present detection technique with fastest developing speed, becomes the indispensable detecting instrument in analysis and confirmatory test chamber.Because mass spectrum can provide qualitative and quantitative information simultaneously, so developed country detects with mass spectroscopy for residual all requirement the in food, the feed, and the 2002/657/EC instruction of detailed regulation such as European Union has been carried out in relevant criterion.
Stable isotope dilution mass spectrometry IDMS (Isotope Dilution Mass Spectrometry) adopts the compound of cold labeling that has the same molecular structure with measured matter as internal standard substance matter; Detect with high resolution liquid chromatography one GC-MS (LC/MS), measure the ionic ratio of respective quality number and reach accurate quantitative purpose with the odds ratio of standard through mass spectrograph.Adopt the interior mark of isotropic substance can effectively eliminate sample caused recovery difference in the pre-treatment step of chemistry and physics, thereby avoid because the deviation that the loss of sample preparation process causes detected result.
This specific character of target combines with the highly sensitive of LC/MS and the ability of dealing with complicated sample in the stable isotope, makes chromatogram/isotopic dilution mass-spectrometric technique be acknowledged as a kind of pedestal method of measuring trace and trace organic substance.And the succeeding in developing of cold labeling Synthesis of diaminodiphenyl cold labeling procrypsis malachite green, malachite green; To standard reagent be provided for detection by quantitative procrypsis malachite green, malachite green more accurately, thereby be China's food safety field detection of veterinary drugs in food service effectively.
Summary of the invention
The object of the invention is exactly for the defective that overcomes above-mentioned prior art existence the compound method that a kind of process is simple, separate the easy cold labeling malachite green of purifying to be provided.
The object of the invention can be realized through following technical scheme:
The compound method of cold labeling malachite green is utilized the N of cold labeling, accelerine and coupler, phenyl aldehyde reaction, and the back feeds NO and NO
2Mixed gas, reaction finishes to obtain the malachite green of cold labeling after separate, purify.
The N of described cold labeling, accelerine are N, accelerine-
15N, N, accelerine-
13C
2Or N, accelerine-D
6
N, accelerine-
15The malachite green of N mark-
15N
2Molecular structure be:
N, accelerine-
13C
2The malachite green of mark-
13C
4Molecular structure be:
N, accelerine-D
6Malachite green-the D of mark
12Molecular structure be:
The synthetic of malachite green specifically may further comprise the steps: with the N of cold labeling; Accelerine mixes by the certain mol proportion example with coupler, phenyl aldehyde; Place liquid phase environment, under catalyst action, under certain pressure; Control reaction temperature reaction certain hour, after feed NO and NO again
2Mixed gas, reaction solution obtains the malachite green of cold labeling after separate purifying.
The N of described cold labeling, the mol ratio of accelerine and coupler is 2: 1～4: 1; The N of said cold labeling, accelerine and phenyl aldehyde are 1: 1～3: 1 in molar ratio; Described coupler comprises urea, Paraformaldehyde 96 or FORMAMIDINE ACETATE; Described liquid phase environment is one or more in hydrochloric acid, acetate, diacetyl oxide, acetone, acetonitrile or the dioxane; Described catalyzer is selected from one or more in tri-n-octyl methyl ammonium chloride, DTAC, benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride or the 4-butyl ammonium hydrogen sulfate; The N of catalyzer and cold labeling, the weight ratio of accelerine is 0.01: 1～0.2: 1; Reaction pressure is 0～5MPa; Temperature of reaction is 10～190 ℃; Reaction times is 2～16h.
The N of described cold labeling, a kind of in preferred 2: 1,3: 1 or 4: 1 of the mol ratio of accelerine and coupler; A kind of among the N of said cold labeling, preferred in molar ratio 1: 1,2: 1 or 3: 1 of accelerine and phenyl aldehyde; Preferred urea of described coupler or Paraformaldehyde 96; In the preferred hydrochloric acid of described liquid phase environment, acetate, diacetyl oxide, acetone or the acetonitrile one or more; The preferred DTAC of described catalyzer, benzyltriethylammoinium chloride, Tetrabutyl amonium bromide or tetrabutylammonium chloride; The N of catalyzer and cold labeling, preferred 0.04: 1～0.1: 1 of the weight ratio of accelerine; Preferred 30～160 ℃ of temperature of reaction; Preferred 4～12h of reaction times.
Compared with prior art, the present invention has the following advantages:
(1) the present invention adopts procedure simple, and the stable isotope atom utilization is high;
(2) the easily separated purification of product of the present invention, product chemical purity are more than 99%, and isotopic abundance can fully satisfy the demand of food safety field detection of veterinary drugs in food more than 98%atom;
(3) the present invention has good economy and use value.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated.
Embodiment 1
A kind of isotropic substance
13The compound method of C mark malachite green, this method specifically may further comprise the steps:
With isotropic substance
13The N of C mark, accelerine-
13C
2Be 1: 1 in molar ratio, mixed in 2: 1 in molar ratio in the mixing solutions that is placed on acetate and diacetyl oxide with phenyl aldehyde, add DTAC with urea, DTAC with
13The weight ratio of the procrypsis malachite green of C mark is 0.04: 1, and control reaction temperature is 120 ℃, stirring reaction 4h, after feed NO and NO again
2Mixed gas, stirring reaction 8h obtains
13The malachite green of C mark is product, and the products obtained therefrom chemical purity reaches 99.0%, and isotopic abundance is 99.0%atom.
Embodiment 2
A kind of isotropic substance
13The compound method of C mark malachite green, this method specifically may further comprise the steps:
With isotropic substance
13The N of C mark, accelerine-
13C
2Be 3: 1 in molar ratio with phenyl aldehyde, mixed in 4: 1 in molar ratio with urea and be placed in the hydrochloric acid soln, add tetrabutylammonium chloride, tetrabutylammonium chloride with
13The weight ratio of the procrypsis malachite green of C mark is 0.1: 1, and control reaction temperature is 160 ℃, stirring reaction 2h, after feed NO and NO again
2Mixed gas, stirring reaction 4h obtains
13The malachite green of C mark is product, and the products obtained therefrom chemical purity reaches 99.1%, and isotopic abundance is 99.4%atom.
Embodiment 3
A kind of isotropic substance
15The compound method of N mark malachite green, this method specifically may further comprise the steps:
With isotropic substance
15The N of N mark, accelerine-
15N is 2: 1 with phenyl aldehyde in molar ratio, mixed in 3: 1 in molar ratio with urea and be placed in the acetonitrile solution, adds Tetrabutyl amonium bromide, Tetrabutyl amonium bromide with
15The weight ratio of the procrypsis malachite green of N mark is 0.06: 1, and control reaction temperature is 90 ℃, stirring reaction 4h, after feed NO and NO again
2Mixed gas, stirring reaction 6h obtains
15The malachite green of N mark is product, and the products obtained therefrom chemical purity reaches 99.2%, and isotopic abundance is 99.2%atom.
Embodiment 4
A kind of isotropic substance
15The compound method of N mark malachite green, this method specifically may further comprise the steps:
With isotropic substance
15The N of N mark, accelerine-
15N is 1: 1 with phenyl aldehyde in molar ratio, mixed in 2: 1 in molar ratio with urea and be placed in the acetone soln, adds benzyltriethylammoinium chloride, the tetrabenzyl triethyl ammonium chloride with
15The weight ratio of the procrypsis malachite green of N mark is 0.08: 1, and control reaction temperature is 60 ℃, stirring reaction 6h, after feed NO and NO again
2Mixed gas, stirring reaction 6h obtains
15The malachite green of N mark is product, and the products obtained therefrom chemical purity reaches 99.1%, and isotopic abundance is 99.2%atom.
Embodiment 5
A kind of compound method of isotope D mark malachite green, this method specifically may further comprise the steps:
With the N of isotope D mark, accelerine-D
6Be 3: 1 in molar ratio with phenyl aldehyde, mixed in 2: 1 in molar ratio with urea and be placed in the dioxane solution; Add tetrabutylammonium chloride, the weight ratio of the procrypsis malachite green of tetrabutylammonium chloride and D mark is 0.1: 1, and control reaction temperature is 30 ℃; Stirring reaction 8h, after feed NO and NO again
2Mixed gas, stirring reaction 4h obtains the malachite green of D mark, is product, the products obtained therefrom chemical purity reaches 99.5%, isotopic abundance is 99.0%atom.
Embodiment 6
A kind of compound method of isotope D mark malachite green, this method specifically may further comprise the steps:
With the N of isotope D mark, accelerine-D
6Be 2: 1 in molar ratio with phenyl aldehyde, mixed in 4: 1 in molar ratio with urea and be placed in the acetonitrile solution; Add Tetrabutyl amonium bromide, the weight ratio of the procrypsis malachite green of Tetrabutyl amonium bromide and D mark is 0.04: 1, and control reaction temperature is 100 ℃; Stirring reaction 4h, after feed NO and NO again
2Mixed gas, stirring reaction 6h obtains the malachite green of D mark, is product, the products obtained therefrom chemical purity reaches 99.4%, isotopic abundance is 99.2%atom.
Embodiment 7
With isotropic substance
13The N of C mark, accelerine-
13C
2Mix to place liquid phase environment acetate with coupler Paraformaldehyde 96, phenyl aldehyde, wherein, N, accelerine-
13C
2With the mol ratio of coupler be 2: 1, N, accelerine-
13C
2With phenyl aldehyde be 1: 1 in molar ratio, add tri-n-octyl methyl ammonium chloride and DTAC as catalyzer, catalyzer and N, accelerine-
13C
2Weight ratio be 0.01: 1, the control reaction pressure is 0MPa, control reaction temperature is 10 ℃ of reaction 16h, in reaction system, feeds NO and NO again
2Mixed gas, reaction solution obtains N after separate purifying, accelerine-
13C
2The malachite green of mark-
13C
4, its molecular structure is:
Embodiment 8
With isotropic substance
15The N of N mark, accelerine-
15N mixes with coupler urea, phenyl aldehyde and places liquid phase environment acetone, wherein, N, accelerine-
15The mol ratio of N and coupler is 2: 1, N, and accelerine-
15N and phenyl aldehyde are 2: 1 in molar ratio, add Tetrabutyl amonium bromide as catalyzer, catalyzer and N, and accelerine-
15The weight ratio of N is 0.04: 1, and the control reaction pressure is 2MPa, and control reaction temperature is 30 ℃ of reaction 12h, in reaction system, feeds NO and NO again
2Mixed gas, reaction solution obtains N after separate purifying, accelerine-
15The malachite green of N mark-
15N
2, molecular structure is:
Embodiment 9
With the N of isotope D mark, accelerine-D
6Mix to place the liquid phase environment dioxane with coupler FORMAMIDINE ACETATE, phenyl aldehyde, wherein, N, accelerine-D
6With the mol ratio of coupler be 4: 1, N, accelerine-D
6With phenyl aldehyde be 3: 1 in molar ratio, add 4-butyl ammonium hydrogen sulfate as catalyzer, catalyzer and N, accelerine-D
6Weight ratio be 0.2: 1, the control reaction pressure is 5MPa, control reaction temperature is 190 ℃ of reaction 2h, in reaction system, feeds NO and NO again
2Mixed gas,, reaction solution obtains N, accelerine-D after separate purifying
6Malachite green-the D of mark
12, molecular structure is:
Claims (6)
1. the compound method of cold labeling malachite green is characterized in that, this method is utilized the N of cold labeling, and accelerine mixes with coupler, phenyl aldehyde, adds catalyzer, reaction for some time, feeds NO and NO
2Mixed gas, reaction finishes to obtain the malachite green of cold labeling after separate, purify, and is product.
2. the compound method of a kind of cold labeling malachite green according to claim 1 is characterized in that, the N of described cold labeling, accelerine are N, accelerine-
15N, N, accelerine-
13C
2Or N, accelerine-D
6
3. the compound method of a kind of cold labeling malachite green according to claim 2 is characterized in that,
N, accelerine-
15The malachite green of N mark-
15N
2Molecular structure be:
N, accelerine-
13C
2The malachite green of mark-
13C
4Molecular structure be:
N, accelerine-D
6Malachite green-the D of mark
12Molecular structure be:
4. the compound method of a kind of cold labeling malachite green according to claim 1 is characterized in that, the synthetic of malachite green specifically may further comprise the steps: with the N of cold labeling; Accelerine mixes by the certain mol proportion example with coupler, phenyl aldehyde; Place liquid phase environment, under catalyst action, under certain pressure; Control reaction temperature reaction certain hour, after feed NO and NO again
2Mixed gas, reaction solution obtains the malachite green of cold labeling after separate purifying.
5. the compound method of a kind of cold labeling malachite green according to claim 4 is characterized in that, the N of described cold labeling, and the mol ratio of accelerine and coupler is 2: 1～4: 1; The N of said cold labeling, accelerine and phenyl aldehyde are 1: 1～3: 1 in molar ratio; Described coupler comprises urea, Paraformaldehyde 96 or FORMAMIDINE ACETATE; Described liquid phase environment is one or more in hydrochloric acid, acetate, diacetyl oxide, acetone, acetonitrile or the dioxane; Described catalyzer is selected from one or more in tri-n-octyl methyl ammonium chloride, DTAC, benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride or the 4-butyl ammonium hydrogen sulfate; The N of catalyzer and cold labeling, the weight ratio of accelerine is 0.01: 1～0.2: 1; Reaction pressure is 0～5MPa; Temperature of reaction is 10～190 ℃; Reaction times is 2～16h.
6. the compound method of a kind of cold labeling malachite green according to claim 5 is characterized in that, the N of described cold labeling, a kind of in preferred 2: 1,3: 1 or 4: 1 of the mol ratio of accelerine and coupler; A kind of among the N of said cold labeling, preferred in molar ratio 1: 1,2: 1 or 3: 1 of accelerine and phenyl aldehyde; Preferred urea of described coupler or Paraformaldehyde 96; In the preferred hydrochloric acid of described liquid phase environment, acetate, diacetyl oxide, acetone or the acetonitrile one or more; The preferred DTAC of described catalyzer, benzyltriethylammoinium chloride, Tetrabutyl amonium bromide or tetrabutylammonium chloride; The N of catalyzer and cold labeling, preferred 0.04: 1～0.1: 1 of the weight ratio of accelerine; Preferred 30～160 ℃ of temperature of reaction; Preferred 4～12h of reaction times.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104945277A (en) * | 2015-06-23 | 2015-09-30 | 上海化工研究院 | Stable isotope labeling alkaline bright yellow O and synthetic method thereof |
| CN105199423A (en) * | 2015-08-25 | 2015-12-30 | 上海化工研究院 | Synthesizing method for prohibited pigment labeled by stable isotope |
| CN108623477A (en) * | 2017-03-21 | 2018-10-09 | 上海安谱实验科技股份有限公司 | A kind of leucogentian violet and its synthetic method of stable isotope labeling |
| CN113512304A (en) * | 2021-06-16 | 2021-10-19 | 丰城三友制笔科技有限公司 | Preparation process of environment-friendly alkaline green dye |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945277A (en) * | 2015-06-23 | 2015-09-30 | 上海化工研究院 | Stable isotope labeling alkaline bright yellow O and synthetic method thereof |
| CN105199423A (en) * | 2015-08-25 | 2015-12-30 | 上海化工研究院 | Synthesizing method for prohibited pigment labeled by stable isotope |
| CN108623477A (en) * | 2017-03-21 | 2018-10-09 | 上海安谱实验科技股份有限公司 | A kind of leucogentian violet and its synthetic method of stable isotope labeling |
| CN113512304A (en) * | 2021-06-16 | 2021-10-19 | 丰城三友制笔科技有限公司 | Preparation process of environment-friendly alkaline green dye |
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Address after: 200062 Shanghai city Putuo District Yunling Road No. 345 Patentee after: Shanghai Chemical Research Institute Co., Ltd. Address before: 200062 Shanghai city Putuo District Yunling Road No. 345 Patentee before: Shanghai Research Institute of Chemical Industry |