[go: up one dir, main page]

CN103601610A - Synthesis method of C13-labelled DDT (Dichlorodiphenyl Trichloroethane), DDD (Dichlorodiphenyl Dichloroethane) and DDE (Dichlorodiphenyl Dichloroethene) - Google Patents

Synthesis method of C13-labelled DDT (Dichlorodiphenyl Trichloroethane), DDD (Dichlorodiphenyl Dichloroethane) and DDE (Dichlorodiphenyl Dichloroethene) Download PDF

Info

Publication number
CN103601610A
CN103601610A CN201310612782.XA CN201310612782A CN103601610A CN 103601610 A CN103601610 A CN 103601610A CN 201310612782 A CN201310612782 A CN 201310612782A CN 103601610 A CN103601610 A CN 103601610A
Authority
CN
China
Prior art keywords
ddt
dde
ddd
reaction
synthesis method
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201310612782.XA
Other languages
Chinese (zh)
Other versions
CN103601610B (en
Inventor
折冬梅
蒋志福
宁君
梅向东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Plant Protection of CAAS
Original Assignee
Institute of Plant Protection of CAAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Plant Protection of CAAS filed Critical Institute of Plant Protection of CAAS
Priority to CN201310612782.XA priority Critical patent/CN103601610B/en
Publication of CN103601610A publication Critical patent/CN103601610A/en
Application granted granted Critical
Publication of CN103601610B publication Critical patent/CN103601610B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明公开了属于同位素标记化合物合成技术领域，具体涉及一种碳13标记的DDT、DDD和DDE的合成方法。本发明方法以13C6-苯为原料，通过氧氯化得12C6-氯苯，再分别与三氯乙醛水合物与二氯乙醛水合物经酸催化缩合可制得13C12-DDT和13C12-DDD，而13C12-DDE通过相转移催化剂对13C12-DDT进行催化脱氯化氢法制得。通过一系列表征，证明产物是13C12-DDT、13C12-DDD和13C12-DDE，且化学纯度达到90%以上，稳定同位素丰度90%以上。The invention discloses the technical field of synthesis of isotope-labeled compounds, and in particular relates to a synthesis method of carbon-13-labeled DDT, DDD and DDE. The method of the present invention uses 13 C 6 -benzene as a raw material to obtain 12 C 6 -chlorobenzene through oxychlorination, and then respectively reacts with trichloroacetaldehyde hydrate and dichloroacetaldehyde hydrate through acid-catalyzed condensation to obtain 13 C 12 -DDT and 13 C 12 -DDD, while 13 C 12 -DDE is prepared by catalytic dehydrochlorination of 13 C 12 -DDT with a phase transfer catalyst. Through a series of characterizations, it was proved that the products were 13 C 12 -DDT, 13 C 12 -DDD and 13 C 12 -DDE, with a chemical purity of more than 90% and a stable isotope abundance of more than 90%.

Description

A kind of DDT, DDD of carbon 13 marks and the synthetic method of DDE
Technical field
The invention belongs to isotope-labeled compou nd synthesis technical field, be specifically related to a kind of DDT, DDD of carbon 13 marks and the synthetic method of DDE.
Technical background
Compound isotopically labelled, as tracer reagent, is widely used in the research fields such as pharmacology, biology, chemistry and environmentalism.This technology is that detectable radioactivity or nonradioactive isotope are inserted in chemistry, biology or physical system, and marker research material, to follow the trail of the scientific method of process, operation conditions or the research structure of matter etc. that occur.Isotopic tracer technique, by analyzing information and the data that obtain, is illustrated motion and the Changing Pattern of material in the various complex systems of nature.Have sensitive, accurately and resolving power is high and the feature such as somatometry.In agricultural and bio-science research, be the important means of direct or indirect acquired information and foundation, aspect some research, demonstrating the irreplaceable advantage of other technologies.The compound of cold labeling, in synthetic and use procedure, does not have radioactive ray to produce, not stricter to the requirement of shelter of experiment condition and experimentation, therefore uses extensive gradually.
DDTs, as a class persistence organochlorine contamination thing, even produces physiological action under ultra-trace concentration at trace, trace.International CCQM (CCQM) regulation: the unique authoritative measuring method of this compounds is isotopic dilution mass spectrometry (IDMS).Isotopic dilution method needs carbon stable isotope-13 or deuterated standard substance to detect as standard substance.Pesticide D-D T is one of organochlorine persistence organic pollutant that production and application is maximum, though completely forbidden use, but at present dichlorodiphenyl trichloroethane and major metabolite dichloro-diphenyl-dichlorothane and drip her and still exist in a large number in environment.Utilize the DDTs of cold labeling can disclose toxicity, degraded, the distribution of this class persistence organochlorine contamination thing, transfer ability and people and the exposed amount of wildlife to DDTs of long distance.
Stable isotope is as interior mark, is mainly to compose or liquid spectrum detects with high resolution mass spec is online by gas.As standard control thing, the carbonatoms of mark is more, detects Vietnamese side just, and tolerance range is better, and sensitivity is higher.For accurately checking, science the invention provides the pollution situation of DDT in environment and metabolite DDD, DDE a kind of synthetic 13c 6the method of the generally labelled DDT of-phenyl ring, DDD and DDE, promotes the research aspect persistence organic pollutant inspection.
The document of the synthetic DDTs of cold labeling at home and abroad not yet appears in the newspapers.Therefore the present invention intends by mark synthesizing mean, and the mark that utilizes stable isotope to carry out DDTs synthesizes.
Summary of the invention
The object of the present invention is to provide a kind of DDT, DDD of carbon 13 marks and the synthetic method of DDE, the molecular structure of its above-claimed cpd is as follows:
Figure BDA0000423290440000021
DDT, the DDD of carbon 13 marks and a synthetic method of DDE, comprise that step is as follows:
(1) with 13c 6-benzene is raw material, by oxi-chlorination, obtains 12c 6-chlorobenzene, then under catalyst action, carry out condensation reaction with trichoro-aldehyde hydrate or dichloro acetaldehyde hydrate respectively and make 13c 12-DDT or 13c 12-DDD;
(2) 13c 12-DDT makes by dehydrochlorination under phase-transfer catalyst effect 13c 12-DDE.
Described in step (1), the condition of oxi-chlorination is: chlorizating agent is chlorine, hydrochloric acid or sulfuryl chloride, oxygenant is more than one in phosphorus pentachloride, sulfur oxychloride, hydrogen peroxide, and catalyzer is bromination Shi six alkyl San Ding Ji Phosphonium, methyl tricapryl ammonium chloride, Tetrabutyl amonium bromide, polyoxyethylene glycol or polyglycol ether.
In described oxi-chlorination 13c 6the mol ratio of-benzene, chlorizating agent, oxygenant, catalyzer is 1～10:2～8:0.1～2.0:0.1～1; Temperature of reaction is 1～180 ℃, and the reaction times is 5～140 minutes.
Described in step (1), catalyzer is phosphoric acid, sulfuric acid, hydrochloric acid, formic acid or acetic acid.
Described in step (1), the temperature of condensation reaction is 0～50 ℃, and the reaction times is 0.5～4 hour.Trichoro-aldehyde hydrate or dichloro acetaldehyde hydrate with 12c 6the mol ratio of-chlorobenzene is 1～1.5:2.
Synthetic product in step (1) 13c 12-DDT and 13c 12the purification process of-DDD is: use CH 2cl 2extract product, extract 3 times, organic layer anhydrous sodium sulfate drying, concentrates to obtain primary products, and the ethanol that is 2:1 through volume ratio and methylene dichloride mixed solvent recrystallization obtain sterling.
Described in step (2), phase-transfer catalyst is cetyl trimethylammonium bromide, benzyl triethyl ammonium bromide or Polyethylene Glycol-600, and catalyst levels accounts for 13c 121～10% of-DDT total amount.
Dehydrochlorination reaction condition described in step (2) is, acid binding agent is sodium hydroxide, potassium hydroxide, triethylamine, diethylamine or ammoniacal liquor, acid binding agent with 13c 12mol ratio 1～2:1 of-DDT, temperature of reaction is 0～210 ℃, reaction times 1～15h.
Product described in step (2) 13c 12the purification process of-DDE: 40～60 ℃ of hot washes, are dried to obtain head product, the ethanol that is 5:1 through volume ratio: methylene dichloride mixed solvent recrystallization obtains sterling.
Method of the present invention with 13c 6-benzene is raw material, by oxychlorination, obtains 12c 6-chlorobenzene, then can make through acid catalysis condensation with trichoro-aldehyde hydrate and dichloro acetaldehyde hydrate respectively 13c 12-DDT and 13c 12-DDD, and 13c 12-DDE is by phase-transfer catalyst pair 13c 12-DDT carries out catalysis dechlorination hydrogen method and makes.By nucleus magnetic hydrogen spectrum, high resolution mass spectrum, characterize, prove that product is 13c 12-DDT, 13c 12-DDD and 13c 12-DDE, and chemical purity reaches more than 90%, and stable isotope abundance is more than 90%.
Embodiment
Embodiment 1
13c 6synthesizing of-monochloro-benzene
In 100mL reaction flask, add 1.00g (11.9mmol) 13c 6-benzene, 8.12g (71.4mmol) hydrochloric acid and 0.38g Shi six alkyl San Ding Ji Phosphonium, stir in 10 ℃, slowly drips 1.52g sulfuryl chloride within half an hour, continues at this temperature, to react 10 minutes.Reaction solution is cooled to room temperature, separatory, and anhydrous magnesium sulfate drying, distillation (normal pressure, 132 ℃) obtains product 1.21g (86%).
Embodiment 2
2,2-pair (4-chloro-phenyl-- 13c 6)-1，1，1-trichloroethane ( 13c 12-DDT)
In 50mL two-mouth bottle, add 0.46g (3.88mmol) 13c 6-chlorobenzene, 0.32g (1.94mmol) trichoro-aldehyde hydrate and 1.9mL sulfuric acid, stir 5 hours in 30 ℃, then adds 9 grams of shrends reaction of going out, and uses 5mL CH at every turn 2cl 2extract product, extract 3 times, organic layer anhydrous sodium sulfate drying, concentrates to obtain primary products, through ethanol and methylene dichloride (V:V=2:1) recrystallization, obtains sterling 0.52g (chemical yield 73%, isotropic substance yield 63%). 1H?NMR(CDCl 3,300MHz)δ：7.56-7.45(m,4H)，7.33-7.25(m,4H)，5.02(m,1H)；HRMS(EI,positive,m/z)：calcd?mass?for 12C 2 13C 12H 9 35Cl 4 37Cl，[M] +：365.9520。Found:365.9513。
Embodiment 3
2,2-pair (4-chloro-phenyl-- 13c 6)-1,1-ethylene dichloride ( 13c 12-DDD)
In 50mL two-mouth bottle, add 0.23g (1.94mmol) 13c 6-chlorobenzene, 0.13g (0.97mmol) dichloro acetaldehyde hydrate and 0.9mL phosphoric acid, stir 8 hours in 30 ℃, then adds the 4.6 shrends reaction of going out, and uses 5mL CH at every turn 2cl 2extract product, extract 3 times, organic layer anhydrous sodium sulfate drying, concentrates to obtain primary products, through ethanol and methylene dichloride (V:V=2:1) recrystallization, obtains sterling 0.23g (70%, isotropic substance yield 60%). 1H?NMR(CDCl 3,300MHz)δ：7.46-7.19(m,8H)，6.29(d,J=7.9Hz,1H)，4.56-4.53(m,1H)；HRMS(EI,positive,m/z)：calcd?mass?for 12C 2 13C 12H 10 35Cl 3 37Cl，[M] +：331.9910。Found:331.9914。
Embodiment 4
2,2-pair (4-chloro-phenyl-- 13c 6)-vinylidene chloride ( 13c 12-DDE)
In 50mL two-mouth bottle, add 0.13g (0.34mmol) 13c 12-DDT and 1.5mg polyoxyethylene glycol-600, slowly dripped 4g30% potassium hydroxide aqueous solution, in 10 ℃ of stirring reactions 8 hours, be cooled to room temperature, hot wash, is dried to obtain head product, through ethanol and methylene dichloride (V:V=5:1) recrystallization, obtain sterling 0.11g (96%, isotropic substance yield 60%). 1H?NMR(CDCl 3,300MHz)δ：7.47-7.12(m,8H)；HRMS(EI,positive,m/z)：calcd?mass?for 12C 2 13C 12H 8 35Cl 3 37Cl，[M] +：329.9753。Found:329.9757。
Embodiment 5
2,2-pair (4-chloro-phenyl-- 13c 6)-1，1，1-trichloroethane ( 13c 12-DDT)
In 50mL two-mouth bottle, add 0.46g (3.88mmol) 13c 6-chlorobenzene, 0.32g (1.94mmol) trichoro-aldehyde hydrate and 1.5mL phosphoric acid, stir 3 hours in 60 ℃, then adds 9 grams of shrends reaction of going out, and uses 5mL CH at every turn 2cl 2extract product, extract 3 times, organic layer anhydrous sodium sulfate drying, concentrates to obtain primary products, through ethanol and methylene dichloride (V:V=2:1) recrystallization, obtains sterling 0.52g (73%, isotropic substance yield 63%). 1H?NMR(CDCl 3,300MHz)δ：7.56-7.45(m,4H)，7.33-7.25(m,4H)，5.02(m,1H)；HRMS(EI,positive,m/z)：calcd?mass?for 12C 2 13C 12H 9 35Cl 4 37Cl，[M] +：365.9520。Found:365.9513。
Embodiment 6
2,2-pair (4-chloro-phenyl-- 13c 6)-1,1-ethylene dichloride ( 13c 12-DDD)
In 50mL two-mouth bottle, add 0.23g (1.94mmol) 13c 6-chlorobenzene, 0.13g (0.97mmol) dichloro acetaldehyde hydrate and 2.3mL phosphoric acid in then adding 4.6 grams of shrends reaction of going out, are used 5mL CH at every turn 2cl 2extract product, extract 3 times, organic layer anhydrous sodium sulfate drying, concentrates to obtain primary products, through ethanol and methylene dichloride (V:V=2:1) recrystallization, obtains sterling 0.23g (70%, isotropic substance yield 60%). 1H?NMR(CDCl 3,300MHz)δ：7.46-7.19(m,8H)，6.29(d,J=7.9Hz,1H)，4.56-4.53(m,1H)；HRMS(EI,positive,m/z)：calcd?mass?for 12C 2 13C 12H 10 35Cl 3 37Cl，[M] +：331.9910。Found:331.9914。
Embodiment 7
2,2-pair (4-chloro-phenyl-- 13c 6)-vinylidene chloride ( 13c 12-DDE)
In 50mL two-mouth bottle, add 0.13g (0.34mmol) 13c 12-DDT and 1.5mg polyoxyethylene glycol-600, slowly dripped 1g aqueous sodium hydroxide solution, in 130 ℃ of stirring reactions 10 hours, be cooled to room temperature, hot wash, is dried to obtain head product, through ethanol and methylene dichloride (V:V=5:1) recrystallization, obtain sterling 0.11g (96%, isotropic substance yield 60%). 1H?NMR(CDCl 3,300MHz)δ：7.47-7.12(m,8H)；HRMS(EI,positive,m/z)：calcd?mass?for 12C 2 13C 12H 8 35Cl 3 37Cl，[M] +：329.9753。Found:329.9757。

Claims (9)

1.一种碳13标记的DDT、DDD和DDE的合成方法，其特征在于，包括步骤如下：1. a synthetic method of carbon-13 labeled DDT, DDD and DDE, is characterized in that, comprises steps as follows: （1）以13C6-苯为原料，通过氧氯化反应得到12C6-氯苯，再分别与三氯乙醛水合物或二氯乙醛水合物在催化剂作用下进行缩合反应制得13C12-DDT或13C12-DDD；(1) With 13 C 6 -benzene as raw material, 12 C 6 -chlorobenzene is obtained through oxychlorination reaction, and then condensed with chloral hydrate or dichloro aldehyde hydrate under the action of a catalyst. 13 C 12 -DDT or 13 C 12 -DDD; （2）13C12-DDT在相转移催化剂作用下通过脱氯化氢法制得13C12-DDE。(2) 13 C 12 -DDT is prepared by dehydrochlorination under the action of phase transfer catalyst to prepare 13 C 12 -DDE. 2.根据权利要求1所述的合成方法，其特征在于，步骤（1）中所述氧氯化反应的条件为：氯化剂为氯气、盐酸或氯化硫酰，氧化剂为五氯化磷、氯化亚砜、双氧水中的一种以上，催化剂为溴化十六烷基三丁基鏻、甲基三辛基氯化铵、四丁基溴化铵、聚乙二醇或聚乙二醇醚。2. The synthetic method according to claim 1, characterized in that, the conditions of the oxychlorination reaction described in step (1) are: the chlorination agent is chlorine, hydrochloric acid or sulfuryl chloride, and the oxidizing agent is phosphorus pentachloride , thionyl chloride, and hydrogen peroxide, and the catalyst is cetyltributylphosphonium bromide, methyltrioctylammonium chloride, tetrabutylammonium bromide, polyethylene glycol or polyethylene glycol alcohol ether. 3.根据权利要求2所述的合成方法，其特征在于，所述氧氯化反应中13C6-苯、氯化剂、氧化剂、催化剂的摩尔比为1～10：2～8：0.1～2.0：0.1～1；反应温度为1～180℃，反应时间为5～140分钟。3. The synthesis method according to claim 2, characterized in that the molar ratio of 13 C 6 -benzene, chlorinating agent, oxidant, and catalyst in the oxychlorination reaction is 1 to 10:2 to 8:0.1 to 2.0: 0.1 to 1; the reaction temperature is 1 to 180°C, and the reaction time is 5 to 140 minutes. 4.根据权利要求1所述的合成方法，其特征在于，步骤（1）中所述催化剂为磷酸、硫酸、盐酸、甲酸或醋酸。4. The synthesis method according to claim 1, characterized in that the catalyst in step (1) is phosphoric acid, sulfuric acid, hydrochloric acid, formic acid or acetic acid. 5.根据权利要求1所述的合成方法，其特征在于，步骤（1）中所述缩合反应的温度为0～50℃，反应时间为0.5～4小时；三氯乙醛水合物或二氯乙醛水合物与12C6-氯苯的摩尔比为1～1.5：2。5. The synthesis method according to claim 1, characterized in that the temperature of the condensation reaction in step (1) is 0-50°C, and the reaction time is 0.5-4 hours; chloral hydrate or dichloro The molar ratio of acetaldehyde hydrate to 12 C 6 -chlorobenzene is 1-1.5:2. 6.根据权利要求1所述的合成方法，其特征在于，步骤（1）中合成产物13C12-DDT和13C12-DDD的纯化方法为：用CH2Cl2萃取出产物，萃取3次，有机层用无水硫酸钠干燥，浓缩得初级产品，经体积比为2：1的乙醇和二氯甲烷混合溶剂重结晶得纯品。6. The synthesis method according to claim 1, characterized in that the purification method of the synthetic products 13 C 12 -DDT and 13 C 12 -DDD in step (1) is: extract the product with CH 2 Cl 2 , extract 3 Next, the organic layer was dried with anhydrous sodium sulfate, concentrated to obtain the primary product, and recrystallized from a mixed solvent of ethanol and dichloromethane at a volume ratio of 2:1 to obtain the pure product. 7.根据权利要求1所述的合成方法，其特征在于，步骤（2）中所述相转移催化剂为十六烷基三甲基溴化铵、苄基三乙基溴化铵或聚乙二醇600，催化剂用量占13C12-DDT总量的1～10%。7. The synthetic method according to claim 1, characterized in that, the phase transfer catalyst described in step (2) is hexadecyltrimethylammonium bromide, benzyltriethylammonium bromide or polyethylene glycol Alcohol 600, the amount of catalyst accounts for 1-10% of the total amount of 13 C 12 -DDT. 8.根据权利要求1所述的合成方法，其特征在于，步骤（2）中所述的脱氯化氢反应条件为，缚酸剂为氢氧化钠、氢氧化钾、三乙胺、二乙胺或氨水，缚酸剂与13C12-DDT的摩尔比1～2:1，反应温度为0～210℃，反应时间1～15h。8. The synthesis method according to claim 1, wherein the dehydrochlorination reaction condition described in step (2) is that the acid-binding agent is sodium hydroxide, potassium hydroxide, triethylamine, diethylamine or The molar ratio of ammonia water, acid-binding agent and 13 C 12 -DDT is 1-2:1, the reaction temperature is 0-210°C, and the reaction time is 1-15h. 9.根据权利要求1所述的合成方法，其特征在于，步骤（2）中所述产物13C12-DDE的纯化方法：40～60℃热水洗涤，干燥得初产物，经体积比为5：1的乙醇：二氯甲烷混合溶剂重结晶得纯品。9. The synthesis method according to claim 1, characterized in that the purification method of the product 13 C 12 -DDE in step (2): washing with hot water at 40-60°C and drying to obtain the initial product, the volume ratio is 5:1 ethanol: dichloromethane mixed solvent recrystallization to obtain pure product.
CN201310612782.XA 2013-11-27 2013-11-27 Synthesis method of C13-labelled DDT (Dichlorodiphenyl Trichloroethane), DDD (Dichlorodiphenyl Dichloroethane) and DDE (Dichlorodiphenyl Dichloroethene) Expired - Fee Related CN103601610B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310612782.XA CN103601610B (en) 2013-11-27 2013-11-27 Synthesis method of C13-labelled DDT (Dichlorodiphenyl Trichloroethane), DDD (Dichlorodiphenyl Dichloroethane) and DDE (Dichlorodiphenyl Dichloroethene)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310612782.XA CN103601610B (en) 2013-11-27 2013-11-27 Synthesis method of C13-labelled DDT (Dichlorodiphenyl Trichloroethane), DDD (Dichlorodiphenyl Dichloroethane) and DDE (Dichlorodiphenyl Dichloroethene)

Publications (2)

Publication Number Publication Date
CN103601610A true CN103601610A (en) 2014-02-26
CN103601610B CN103601610B (en) 2015-04-01

Family

ID=50119894

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310612782.XA Expired - Fee Related CN103601610B (en) 2013-11-27 2013-11-27 Synthesis method of C13-labelled DDT (Dichlorodiphenyl Trichloroethane), DDD (Dichlorodiphenyl Dichloroethane) and DDE (Dichlorodiphenyl Dichloroethene)

Country Status (1)

Country Link
CN (1) CN103601610B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104557449A (en) * 2015-02-06 2015-04-29 上海化工研究院 Synthetic method of stable isotope deuterium-labeled DDT
CN104610012A (en) * 2015-01-27 2015-05-13 上海化工研究院 Synthetic method for stable isotope labeled halobenzene
CN117105816A (en) * 2023-08-17 2023-11-24 湖北迅宏材料科技有限公司 Method for preparing dichloroacetonitrile

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090214734A1 (en) * 2005-03-04 2009-08-27 Nippon Meat Packers, Inc. Method of Extracting Residual Pesticides and Extraction Kit
CN101880215A (en) * 2009-05-07 2010-11-10 北京化工大学 Synthesis and Purification of Carbon-13 Labeled DDT
CN102260127A (en) * 2011-06-16 2011-11-30 华东师范大学 Method for preparing halogenated aryl compounds through oxidation and halogenation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090214734A1 (en) * 2005-03-04 2009-08-27 Nippon Meat Packers, Inc. Method of Extracting Residual Pesticides and Extraction Kit
CN101880215A (en) * 2009-05-07 2010-11-10 北京化工大学 Synthesis and Purification of Carbon-13 Labeled DDT
CN102260127A (en) * 2011-06-16 2011-11-30 华东师范大学 Method for preparing halogenated aryl compounds through oxidation and halogenation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
折冬梅等: "高纯度o,p-DDT的合成", 《核农学报》 *
高明: "典型农田土壤对BHC和DDT的吸附特征研究", 《中国优秀硕士学位论文全文数据库(电子期刊)工程科技Ⅰ辑》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104610012A (en) * 2015-01-27 2015-05-13 上海化工研究院 Synthetic method for stable isotope labeled halobenzene
CN104557449A (en) * 2015-02-06 2015-04-29 上海化工研究院 Synthetic method of stable isotope deuterium-labeled DDT
CN117105816A (en) * 2023-08-17 2023-11-24 湖北迅宏材料科技有限公司 Method for preparing dichloroacetonitrile

Also Published As

Publication number Publication date
CN103601610B (en) 2015-04-01

Similar Documents

Publication Publication Date Title
Chun et al. Single‐Step Radiosynthesis of “18F‐Labeled Click Synthons” from Azide‐Functionalized Diaryliodonium Salts
Zhou et al. Copper-mediated nucleophilic radiobromination of aryl boron precursors: Convenient preparation of a radiobrominated PARP-1 inhibitor
CN103601610A (en) Synthesis method of C13-labelled DDT (Dichlorodiphenyl Trichloroethane), DDD (Dichlorodiphenyl Dichloroethane) and DDE (Dichlorodiphenyl Dichloroethene)
Cardinale et al. Carrier‐effect on palladium‐catalyzed, nucleophilic 18F‐fluorination of aryl triflates
Wüst et al. Synthesis of 18 F-labelled cyclooxygenase-2 (COX-2) inhibitors via Stille reaction with 4-[18 F] fluoroiodobenzene as radiotracers for positron emission tomography (PET)
CN113149801A (en) Deuterated polyhalogen aromatic compound, preparation method thereof and organic intermediate
CN104016901A (en) Aryl halide derivatives and synthesis method thereof
Eriksson et al. Synthesis of [11C]/[13C] acrylamides by palladium‐mediated carbonylation
CN110305052A (en) Radioactive isotope carbon-14 labeled vanillyl thiopyr, its preparation method and application
Basuli et al. Syntheses of meta‐[18F] fluorobenzaldehyde and meta‐[18F] fluorobenzylbromide from phenyl (3‐Formylphenyl) iodonium salt precursors
Dahl et al. Improved yields for the palladium‐mediated 11C‐carbonylation reaction using microwave technology
CN105348194B (en) Fluorine-containing phenanthridine derivatives and preparation method thereof
CN107556261A (en) Containing CF22 oxazoline ketone compounds and preparation method thereof
CN103588647B (en) Synthetic method for stable isotope labeled N,N-dimethylaminochloropropane hydrochloride
Xu et al. Nickel-mediated C (sp2)-H amidation in synthesis of secondary sulfonamides via sulfonyl azides as amino source
CN106316900A (en) 1, 2, 3-tri-substituted benzene and method for synthesizing same
Zhu et al. Copper-mediated fluoroalkylation reactions with [(phenylsulfonyl)-difluoromethyl] trimethylsilane: synthesis of PhSO2CF2-containing allenes and alkynes
CN107118215B (en) A kind of preparation method for treating breast cancer medicines Rui Boxini intermediate
Cardinale et al. Convenient preparation of (4-iodophenyl) aryliodonium salts
CN115583871B (en) All C 13 Preparation method of isotope labeled decabromodiphenyl ether
JP2012522051A (en) Radiolabeling method
Charbonnière et al. Synthesis of mono-, bis-and tris-tridentate ligands based on 5′-substituted-2, 2′-bipyridine-6-carboxylic acid
Hiller et al. Investigations to the synthesis of nca [18F] FClO3 as electrophilic fluorinating agent
Li et al. A mild, phosphine-free method for the conversion of alcohols into halides (Cl, Br, I) via the corresponding O-alkyl isoureas
Sharma et al. Butadiene sulfone-catalyzed monobromination of arenes with nbs as the bromination source: a simple, mild, efficient, and chemoselective protocol

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20150401