CN112125862A - Stable isotope labeled atrazine-d 5 and synthetic method thereof - Google Patents
Stable isotope labeled atrazine-d 5 and synthetic method thereof Download PDFInfo
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- CN112125862A CN112125862A CN201910552144.0A CN201910552144A CN112125862A CN 112125862 A CN112125862 A CN 112125862A CN 201910552144 A CN201910552144 A CN 201910552144A CN 112125862 A CN112125862 A CN 112125862A
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- 238000010189 synthetic method Methods 0.000 title claims description 5
- JDAPQMINSZDTBM-UHFFFAOYSA-N 4,6-dichloro-n-propan-2-yl-1,3,5-triazin-2-amine Chemical compound CC(C)NC1=NC(Cl)=NC(Cl)=N1 JDAPQMINSZDTBM-UHFFFAOYSA-N 0.000 claims abstract description 15
- XWBDWHCCBGMXKG-LUIAAVAXSA-N 1,1,2,2,2-pentadeuterioethanamine;hydrochloride Chemical compound Cl.[2H]C([2H])([2H])C([2H])([2H])N XWBDWHCCBGMXKG-LUIAAVAXSA-N 0.000 claims abstract description 12
- 238000001308 synthesis method Methods 0.000 claims abstract description 10
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001948 isotopic labelling Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000008213 purified water Substances 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 3
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 4
- 229910052805 deuterium Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- -1 atrazine compound Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 230000000155 isotopic effect Effects 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000000447 pesticide residue Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- 238000009333 weeding Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000004431 deuterium atom Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002124 endocrine Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000004750 isotope dilution mass spectroscopy Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000007430 reference method Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000008771 sex reversal Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/48—Two nitrogen atoms
- C07D251/50—Two nitrogen atoms with a halogen atom attached to the third ring carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/05—Isotopically modified compounds, e.g. labelled
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses stable isotope labeled atrazine and a synthesis method thereof, wherein stable isotope labeled ethyl-d 5-amine hydrochloride is used as a stable isotope labeling source, 2,4, 6-trichloro-1, 3, 5-triazine is firstly reacted with isopropylamine to obtain 2, 4-dichloro-6-isopropylamino-1, 3, 5-triazine, and then the obtained product is reacted with stable isotope labeled ethyl-d 5-amine hydrochloride to obtain a stable isotope labeled atrazine-d 5 product. The stable isotope labeling raw material used in the invention is ethyl-d 5-amine hydrochloride, the source is easy to obtain and the price is low, the synthesis process is simple, the product is easy to separate and purify, the chemical purity and the isotope abundance of the obtained product both reach more than 98 percent, and the related requirements of the product serving as a standard reagent for quantitatively detecting the content of the atrazine are met.
Description
Technical Field
The invention relates to the field of isotope labeling, in particular to atrazine-d 5 labeled by a stable isotope and a synthetic method thereof.
Background
Atrazine (also known as atrazine) is an artificially synthesized triazine herbicide. Since the market comes, the weeding composition quickly occupies the global market due to low production cost and good weeding effect. The atrazine has long residual life and is applied in large amount for a long time, so that the atrazine can be discharged through various ways, has good solubility, is easy to enter surface water and underground water to cause water body pollution, and further poses a threat to human health through a food chain. In addition, male amphibians exposed to atrazine undergo sex reversal, while interfering with endocrine secretion, adversely affecting human reproduction and development. The governments have therefore intensified the monitoring of this herbicide.
The stable isotope technology has the characteristics of high accuracy, no pollution, high sensitivity and the like, and is greatly developed and widely applied in recent years. The deuterium stable isotope analysis technology has been used for over 40 years, and the application of the deuterium stable isotope analysis technology in the aspects of determining the geographical sources of animal products, pesticide residues, veterinary drug residues and the like is more and more extensive. Particularly, the combination of mass spectrometry makes the chromatography/isotope dilution mass spectrometry technique recognized as a reference method for measuring trace and trace organic matters. The successful development of the stable isotope labeled atrazine compound provides a standard reagent for quantitative atrazine in the aspects of content application of pesticide residues, water body soil environment and the like, perfects a detection technology system of environment safety of pesticide products, soil, water quality and the like in China, meets the requirements of pesticide application and environment health development in China, and provides important technical support.
There is little disclosure of the current synthesis of stable isotope labeled atrazine-d 3. Therefore, a synthesis method which is simple in operation, high in yield and environment-friendly in process is needed to be found for the synthesis of stable isotope labeled atrazine-d 5.
Disclosure of Invention
The technical problem to be solved by the invention is to provide stable isotope labeled atrazine-d 5 and a synthetic method thereof, which can be used as a standard reagent for quantitatively detecting atrazine; and the preparation process is simple, the product is easy to separate and purify, and the obtained product has high chemical purity and deuterated purity.
The technical scheme adopted by the invention for solving the technical problems is to provide a synthesis method of stable isotope labeled atrazine-d 5, which comprises the following steps: s1: reacting 2,4, 6-trichloro-1, 3, 5-triazine with isopropylamine to obtain 2, 4-dichloro-6-isopropylamino-1, 3, 5-triazine; s2: 2, 4-dichloro-6-isopropylamino-1, 3, 5-triazine reacts with ethyl-d 5-amine hydrochloride which is marked by stable isotope to obtain atrazine-d 5 which is marked by stable isotope.
Further, the step S1 process is as follows: adding 0.9-1.2 parts by weight of 2,4, 6-trichloro-1, 3, 5-triazine and 5.0-6.0 parts by weight of tetrahydrofuran into a reaction vessel, adjusting the temperature to-10-0 ℃, dropwise adding 0.6-0.8 part by weight of isopropylamine at the temperature, after dropwise adding, heating to 20-30 ℃, reacting for 1-2 hours, after the reaction is finished, concentrating the tetrahydrofuran under reduced pressure, adding 7.0-8.0 parts by weight of purified water, extracting twice by using 7.0-8.0 parts by weight of ethyl acetate, and combining and concentrating organic phases to obtain white 2, 4-dichloro-6-isopropylamino-1, 3, 5-triazine.
Further, the step S2 process is as follows: adding 0.9-1.2 parts by weight of 2, 4-dichloro-6-isopropylamino-1, 3, 5-triazine into a reaction bottle, adding 2.0-4.0 parts by weight of toluene, adding 0.2-0.4 part by weight of sodium hydroxide and 1.0-2.0 parts by weight of purified water, controlling the temperature of a reaction solution to 10-20 ℃, adding 0.4-0.5 part by weight of ethyl-d 5-amine hydrochloride in batches, heating to 20-30 ℃, reacting at 20-30 ℃ for 1-2 hours, concentrating the toluene under reduced pressure after the reaction is finished, adding 20.0-25.0 parts by weight of purified water, and filtering to obtain a white solid crude product of atrazine-d 5.
Further, the step S2 further includes performing recrystallization purification on the crude white solid of atrazine-d 5 by using n-hexane and dichloromethane, so as to obtain a white solid product of atrazine-d 5 labeled with stable isotope.
The invention also provides a stable isotope labeled atrazine-d 5 prepared by the synthesis method for solving the technical problems, which has the following molecular structure:
the invention has the following beneficial effects: according to the stable isotope labeled atrazine and the synthesis method thereof, provided by the invention, ethyl-d 5-amine hydrochloride with isotope abundance of more than 99 atom% is used as an isotope labeling source, and the atrazine-d 5 is synthesized through a simple two-step reaction, so that deuterium atoms cannot fall off in the reaction process, and the utilization rate of stable isotope atoms is high; the synthetic process is simple, the product is easy to separate and purify, the chemical purity and the isotopic abundance of the obtained product reach more than 99 percent, and the requirement of the product as a standard reagent for quantitatively detecting the atrazine is met; high use value and good economical efficiency.
Drawings
FIG. 1 is a liquid chromatogram of atrazine-d 5 obtained in the example of the present invention.
FIG. 2 is a mass spectrum of atrazine-d 5 obtained in the example of the invention.
Detailed Description
The invention is further described in connection with the following figures and examples, which should not be construed as limiting the invention.
The invention utilizes 2H isotope labeling technology, utilizes ethyl-d 5-amine hydrochloride as a stable deuterium ribbon source, and synthesizes atrazine-d 5 through two-step reaction, thereby providing a method for simply and efficiently preparing the stable isotope labeled atrazine-d 5 compound.
The synthesis method of the stable isotope labeled atrazine provided by the invention comprises the following steps:
s1: reacting 2,4, 6-trichloro-1, 3, 5-triazine with isopropylamine to obtain 2, 4-dichloro-6-isopropylamino-1, 3, 5-triazine:
adding 0.9-1.2 parts of 2,4, 6-trichloro-1, 3, 5-triazine and 5.0-6.0 parts of tetrahydrofuran in a reaction container according to parts by weight (the amount is small, the stirring is not facilitated, the amount is large, the reaction rate is reduced, and the cost is increased); after the reaction is finished, concentrating tetrahydrofuran under reduced pressure, adding 7.0-8.0 parts of purified water, extracting twice by using 7.0-8.0 parts of ethyl acetate, combining organic phases, and concentrating the organic phases to obtain white 2, 4-dichloro-6-isopropylamino-1, 3, 5-triazine; the molecular structure is as follows:
s2: reacting 2, 4-dichloro-6-isopropylamino-1, 3, 5-triazine with stable isotope labeled ethyl-d 5-amine hydrochloride to obtain a stable isotope labeled atrazine-d 5 product:
adding 0.9-1.2 parts by weight of 2, 4-dichloro-6-isopropylamino-1, 3, 5-triazine into a reaction bottle, adding 2.0-4.0 parts by weight of toluene, adding 0.2-0.4 part by weight of sodium hydroxide and 1.0-2.0 parts by weight of purified water, controlling the temperature of a reaction solution to 10-20 ℃, and adding 0.4-0.5 part by weight of ethyl-d 5-amine hydrochloride in batches (the amount is less, the reaction is incomplete, the amount is more, the reaction purity is reduced, and the total cost is increased); after the reaction is finished, concentrating toluene under reduced pressure, adding 20.0-25.0 parts of purified water (the product is insoluble in water, the water amount can be properly increased, and the reaction is not greatly influenced), and filtering to obtain a white solid crude product of atrazine-d 5;
the adopted solvent can be dry anhydrous solvent; the stable isotope labeled atrazine-d 5 has a molecular structure as follows:
examples
The molecular structure of stable isotope labeled atrazine of this example is as follows:
the preparation method comprises the following synthetic steps:
s1, adding 5.0g of 2,4, 6-trichloro-1, 3, 5-triazine and 30ml of tetrahydrofuran into a reaction container, adjusting the temperature to-10-0 ℃ (the reaction is exothermic, the reaction rate is reduced when the temperature is too low, and the reaction purity is reduced when the temperature is too high), dropwise adding 3.2g of isopropylamine at the temperature, after dropwise adding, heating to 20-30 ℃, reacting for 1-2 hours, after the reaction is finished, concentrating the tetrahydrofuran under reduced pressure, adding 35g of purified water, extracting twice by using 35g of ethyl acetate, combining organic phases, and concentrating to obtain 5.2g of white 2, 4-dichloro-6-isopropylamino-1, 3, 5-triazine.
S2, adding 5.0g of 2, 4-dichloro-6-isopropylamino-1, 3, 5-triazine into a reaction container, adding 13g of toluene, 2.0g of sodium hydroxide and 5ml of purified water, controlling the temperature of a reaction solution to 10-20 ℃, adding 2.0g of ethyl-d 5-amine hydrochloride in batches, after the addition is finished, heating to 20-30 ℃, reacting at 20-30 ℃ for 1-2 hours, concentrating the toluene under reduced pressure after the reaction is finished, adding 100ml of purified water, and filtering to obtain a white solid crude product of atrazine-d 5. Recrystallization purification was performed using 50ml of n-hexane and 10ml of dichloromethane to obtain 3.7g of stable isotope-labeled atrazine-d 5 as a white solid product. The chemical purity and isotopic abundance of the pure atrazine-d 5 white solid can reach more than 98%.
The nuclear magnetic resonance hydrogen spectrum of the product obtained in the example was detected by a Bruke-400M nuclear magnetic resonance instrument with (CD3)2SO as to be a solvent. In H NMR (CDCl3), since 1.2 methyl hydrogen and 3.4 methylene hydrogen were substituted by deuterium, no peak was observed in the spectrum, and it was confirmed that the product was the isotope-stable marker atrazine-d 5.
Meanwhile, the product sample obtained in this example is dissolved in methanol (1 ppm) for purity and MS measurement, and the spectrogram is shown in FIG. 1 and FIG. 2. In the spectrogram 1, no obvious impurity peak is detected, and the chemical purity of the product of the atrazine-d 5 can reach more than 98 percent. In spectrum 2, the MS data showed LC-MS M/z 221.2[ M + H + ], so the MS data are correct (molecular weight of atrazine-d 5 is 220.7).
Although the present invention has been described with respect to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. A synthetic method of stable isotope labeled atrazine-d 5 is characterized by comprising the following steps:
s1: reacting 2,4, 6-trichloro-1, 3, 5-triazine with isopropylamine to obtain 2, 4-dichloro-6-isopropylamino-1, 3, 5-triazine;
s2: 2, 4-dichloro-6-isopropylamino-1, 3, 5-triazine reacts with ethyl-d 5-amine hydrochloride which is marked by stable isotope to obtain atrazine-d 5 which is marked by stable isotope.
2. The synthesis method according to claim 1, wherein the step S1 is as follows: adding 0.9-1.2 parts of 2,4, 6-trichloro-1, 3, 5-triazine and 5.0-6.0 parts of tetrahydrofuran in parts by weight into a reaction container, and adjusting the temperature to-10-0 ℃; dropwise adding 0.6-0.8 part of isopropylamine at the temperature, after dropwise adding, heating to 20-30 ℃, and reacting for 1-2 hours; after the reaction is finished, concentrating tetrahydrofuran under reduced pressure, adding 7.0-8.0 parts of purified water, extracting twice by using 7.0-8.0 parts of ethyl acetate, combining organic phases, and concentrating the organic phases to obtain white 2, 4-dichloro-6-isopropylamino-1, 3, 5-triazine.
3. The synthesis method according to claim 1, wherein the step S2 is as follows: adding 0.9-1.2 parts by weight of 2, 4-dichloro-6-isopropylamino-1, 3, 5-triazine into a reaction bottle, adding 2.0-4.0 parts by weight of toluene, adding 0.2-0.4 part by weight of sodium hydroxide and 1.0-2.0 parts by weight of purified water, controlling the temperature of a reaction solution to 10-20 ℃, adding 0.4-0.5 part by weight of ethyl-d 5-amine hydrochloride in batches, heating to 20-30 ℃, and reacting for 1-2 hours at 20-30 ℃; and after the reaction is finished, concentrating toluene under reduced pressure, adding 20.0-25.0 parts of purified water, and filtering to obtain a white solid crude product of atrazine-d 5.
4. The synthesis method according to claim 3, wherein the step S2 further comprises: and recrystallizing and purifying the white solid crude product of the atrazine-d 5 by using normal hexane and dichloromethane to obtain a white solid product of the atrazine-d 5 with stable isotope labeling.
5. A stable isotope labeled atrazine-d 5, characterized by having the following molecular structure, prepared by the synthesis method according to any one of claims 1 to 4:
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961700A (en) * | 2015-06-25 | 2015-10-07 | 南京工业大学 | Method for preparing atrazine by using micro-reaction device |
| CN107235924A (en) * | 2017-08-06 | 2017-10-10 | 河北诚信有限责任公司 | A kind of continuous production processes of Atrazine |
| US20180064717A1 (en) * | 2015-03-20 | 2018-03-08 | Anvyl, Llc | Deuterated analongs of etifoxine, their derivatives and uses thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180064717A1 (en) * | 2015-03-20 | 2018-03-08 | Anvyl, Llc | Deuterated analongs of etifoxine, their derivatives and uses thereof |
| CN104961700A (en) * | 2015-06-25 | 2015-10-07 | 南京工业大学 | Method for preparing atrazine by using micro-reaction device |
| CN107235924A (en) * | 2017-08-06 | 2017-10-10 | 河北诚信有限责任公司 | A kind of continuous production processes of Atrazine |
Non-Patent Citations (2)
| Title |
|---|
| BERG, MICHAEL: "Simultaneous Determination of Triazines Including Atrazine and Their Major Metabolites Hydroxyatrazine, Desethylatrazine, and Deisopropylatrazine in Natural Waters", 《ANALYTICAL CHEMISTRY》 * |
| ZHAO, HUA-PING: "Design, Synthesis, and Biological Activities of Arylmethylamine Substituted Chlorotriazine and Methylthiotriazine Compounds", 《OURNAL OF AGRICULTURAL AND FOOD CHEMISTRY》 * |
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