CN107365239B - A kind of synthetic method of arylalkyne halogen - Google Patents

A kind of synthetic method of arylalkyne halogen Download PDF

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CN107365239B
CN107365239B CN201710481107.6A CN201710481107A CN107365239B CN 107365239 B CN107365239 B CN 107365239B CN 201710481107 A CN201710481107 A CN 201710481107A CN 107365239 B CN107365239 B CN 107365239B
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arylalkyne
halogen
alkynes
added
catalyst
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CN107365239A (en
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石炜
关志朋
陈浩
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Huazhong Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B39/00—Halogenation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C07C17/14—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the side-chain of aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/26—Radicals substituted by halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/12—Radicals substituted by halogen atoms or nitro or nitroso radicals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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

Abstract

The invention discloses heterogeneous catalysis Ag/g-C3N4The purposes in arylalkyne halogen is being catalyzed and synthesized, the synthetic method of arylalkyne halogen is also disclosed.The present invention utilizes the heterogeneous catalysis Ag/g-C synthesized3N4The direct halogenation of (metallic silver is supported in graphite phase carbon nitride) Lai Cuihua terminal aryl group alkynes obtains important organic synthesis intermediate arylalkyne halogen, including alkynes chlorine, alkynes bromine and alkynes iodine.In addition the catalyst can greatly improve the efficiency of this method by simple reduction, centrifugal action with high efficiente callback 5 times or more, while reduce the loss of precious metals ag and to the potential heavy metal pollution of product.

Description

A kind of synthetic method of arylalkyne halogen
Technical field
The invention belongs to the field of chemical synthesis, are related to heterogeneous catalysis Ag/g-C3N4(metallic silver is supported on graphite-phase nitrogen Change on carbon) purposes in arylalkyne halogen is being catalyzed and synthesized, the invention further relates to the synthetic methods of arylalkyne halogen.
Technical background
In recent years, arylalkyne halogen has important value due to its unique property in organic synthesis.Alkynes structure exists It is all widely present in the molecular structures such as natural products, drug, pesticide, new material, is its important composition skeleton；Alkynyl is simultaneously Or many important organic structures, such as the precursor of aldehyde ketone, heterocycle, alkene, and arylalkyne halogen directly can will by coupling reaction Alkine unit is imported into related organic structure, therefore arylalkyne halogen is with a wide range of applications.
Currently, having had some widely used methods for the synthetic method of arylalkyne halogen, such as in synthesis gram quantity grade In the reaction of alkynes bromine, Br is usually utilized2The bromination of end alkynes is carried out as bromine source.But Br2It is volatile, and be more toxic, Smog can consumingly stimulate eyes and respiratory tract, limit its application.Another relatively mild effectively synthetic method is: with silver Salt (such as silver nitrate) is used as catalyst, can synthesize alkynes halogen with N- N-halosuccinimides under relatively mild conditions.But The catalyst that this usual method uses is difficult to be suitable for synthesis alkynes simultaneously all just for the specific alkynes bromine of synthesis or alkynes iodine The reaction of chlorine, alkynes bromine and alkynes iodine.In addition, these catalyst are generally difficult to recycle, it be easy to cause the loss of precious metal and to production The pollution of product limits its application value.
Summary of the invention
The object of the present invention is to provide a kind of arylalkyne halogen, the high efficiency preparation method including alkynes chlorine, alkynes bromine and alkynes iodine, and this Inventive method can high efficiente callback utilize catalyst.
Heterogeneous catalysis Ag/g-C provided by the present invention3N4Preparation method the following steps are included:
1)g-C3N4Preparation:
10g urea is weighed with crucible to be placed in Muffle furnace, is warming up to 550 DEG C with the rate of 5 DEG C/min, keeps the temperature 2h, it is natural It is cooled to room temperature, obtains flaxen solid, sample is finally taken out and grinds up to pure g-C3N4；
2) heterogeneous catalysis Ag/g-C3N4Preparation:
By 0.1g g-C3N4It is dispersed in 50mL ultrapure water, supersonic oscillations 15min, 10ml AgNO is then added3 (0.017g) solution stirs 10h, and 4mL NaBH is finally added dropwise4(0.004g) aqueous solution, three times with milli-Q water, centrifugation, most The dry 12h in 60 DEG C of vacuum ovens afterwards.
The catalyst can be used for catalyzing and synthesizing arylalkyne halogen, synthetic method the following steps are included:
1) catalysis reaction:
0.04-0.1mmol Ag/g-C is sequentially added into Schlenk reaction flask3N4, 1.05-1.5mmol halogenated succinimide acyl Imines, 2mL acetone and 1mmol arylalkyne, must add 0.5mmol potassium carbonate, at 25-50 DEG C when using chlorosuccinimide Under be protected from light 3h, obtain target product；
2) recycling of catalyst:
Reaction system is centrifuged with anhydrous ether, is washed three times, ultrapure water is added and NaBH is added dropwise4Aqueous solution, use are ultrapure Three times, finally dry 12h, recycling obtain catalyst in 60 DEG C of vacuum ovens for water washing, centrifugation.
The beneficial effects of the present invention are: heterogeneous catalysis Ag/g-C3N4Can be used for catalyzing and synthesizing including alkynes chlorine, alkynes bromine and The various arylalkyne halogen of alkynes iodine, compared with existing catalyst, application range is wider, what is catalyzed and synthesized more efficient, product Yield is 90% or more, and catalyst can repeat to recycle 5 times or more, to reduce the loss of precious metal and right The pollution of environment improves the utilization rate of catalyst.
Detailed description of the invention
Fig. 1 is catalyst Ag/g-C3N4Electron micrograph.
Fig. 2 is catalyst Ag/g-C3N4React the XRD curve of front and back.
Specific embodiment
The present invention is described in detail below by embodiment.
The preparation method of arylalkyne halogen provided by the invention the following steps are included:
1)g-C3N4Preparation:
10g urea is weighed with crucible to be placed in Muffle furnace, is warming up to 550 DEG C with the rate of 5 DEG C/min, keeps the temperature 2h, it is natural It is cooled to room temperature, obtains flaxen solid, sample is finally taken out and grinds up to pure g-C3N4。
2)Ag/g-C3N4Synthesis:
0.1g g-C3N4It is dispersed in 50mL ultrapure water, supersonic oscillations 15min, 10ml AgNO is then added3 (0.017g) solution stirs 10h, and 4mL NaBH is finally added dropwise4(0.004g) aqueous solution, three times with milli-Q water, centrifugation, most The dry 12h in 60 DEG C of vacuum ovens afterwards.The electron microscope picture of catalyst is as shown in Figure 1, as can be seen from the figure Ag G-C is attached to diameter about 50nm particle3N4On.
3)Ag/g-C3N4It is catalyzed aryl end alkynes bromination:
0.04mmol Ag/g-C is sequentially added into Schlenk reaction flask3N4(being calculated with the content of Ag), 1.05mmol bromine For succimide (NBS), 2mL acetone and 1mmol aryl end alkynes, 3h is reacted at 25 DEG C, obtains target product.Table 1 is The substrate of synthesizing aryl alkynes bromine is expanded and separation yield.
Table 1. synthesizes alkynes bromine
All yields are isolated yields.a:8mol%catalyst loading.
By taking 2a as an example: under room temperature, 0.04mmol Ag/g-C is sequentially added into Schlenk reaction flask3N4(with the content of Ag Calculate), 1.05mmol bromo-succinimide (NBS), 2mL acetone and 1mmol phenylacetylene, after being protected from light 3h, utilize thin layer Silica gel plate detection phenylacetylene reacts completely.It is extracted twice with saturated salt solution and ethyl acetate, and organic phase twice is merged, With anhydrous Na SO4It dries, filters, after filtrate decompression solvent evaporated, crude product is purified with column chromatography, obtains our target product Phenylacetylene bromine 2a.
4)Ag/g-C3N4It is catalyzed the alkynes iodate of aryl end:
0.04mmol Ag/g-C is sequentially added into Schlenk reaction flask3N4(being calculated with the content of Ag), 1.05mmol iodine For succimide (NIS), 2mL acetone and 1mmol aryl end alkynes, 3h is reacted at 25 DEG C, obtains target product.Table 2 is The structure and its separation yield of the representative arylalkyne iodine in part.
Table 2. synthesizes alkynes iodine
All yields are isolated yields；A:8mol%catalyst loading.
5)Ag/g-C3N4It is catalyzed the alkynes chlorination of aryl end:
0.1mmol Ag/g-C is sequentially added into Schlenk reaction flask3N4(being calculated with the content of Ag), 1.5mmol chloro Succimide (NCS), 2mL acetone and 1mmol aryl end alkynes, react at 50 DEG C, obtain target product.Table 3 is synthesis The substrate of arylalkyne chlorine is expanded.
Table 3. synthesizes alkynes chlorine
All yields are isolated yields；A:8mol%catalyst loading.
By taking 4a as an example: sequentially adding 0.1mmol Ag/g-C into Schlenk reaction flask3N4(being calculated with the content of Ag), 1.5mmol chlorosuccinimide (NCS), 0.5mmol K2CO3, 2mL acetonitrile and 1mmol 4- fluorobenzene acetylene, be warming up to 50 DEG C, It is protected from light, is reacted completely using thin layer silica gel plate detection 4- fluorobenzene acetylene.It is extracted twice with saturated salt solution and ethyl acetate, And organic phase twice is merged, with anhydrous Na SO4It dries, filters.After filtrate decompression solvent evaporated, crude product is mentioned with column chromatography It is pure, obtain our target product 4- fluorobenzene acetylene chlorine 4a.
6) catalyst is recycled and is utilized:
Catalyst treatment: reaction system is centrifuged with anhydrous ether, is washed three times, ultrapure water is added and NaBH is added dropwise4Water Solution, three times with milli-Q water, centrifugation, finally dry 12h, recycling obtain catalyst in 60 DEG C of vacuum ovens.
Recycling catalyst obtains the GC yield of product 2a for being catalyzed reaction: for the first time, 99%；Second, 95%；Third It is secondary, 97%；4th time, 97%；5th time, 99%.
Ag/g-C3N4XRD diagram as catalyst alkynes bromine experiment front and back shows: Ag/g-C3N4It is changed into AgBr/g- C3N4。

Claims (2)

1. a kind of synthetic method of arylalkyne halogen, it is characterised in that the following steps are included:
1) catalysis reaction:
0.04-0.1mmol Ag/g-C is sequentially added into Schlenk reaction flask3N4, 1.05-1.5mmol halogenated succinimide acyl it is sub- Amine, 2mL acetone and 1mmol arylalkyne, the arylalkyne is phenyl, pyridyl group, thienyl end alkynes, when use chloro succinyl 0.5mmol potassium carbonate must be added when imines, be protected from light 3h at 25-50 DEG C, obtained target product；
2) recycling of catalyst:
Reaction system is centrifuged with anhydrous ether, is washed three times, ultrapure water is added and NaBH is added dropwise4Aqueous solution, with ultrapure washing It washs, be centrifuged three times, finally dry 12h, recycling obtain catalyst in 60 DEG C of vacuum ovens.
2. the synthetic method of arylalkyne halogen as described in claim 1, it is characterised in that: the heterogeneous catalysis Ag/g-C3N4's Preparation method the following steps are included:
1)g-C3N4Preparation:
10g urea is weighed with crucible to be placed in Muffle furnace, is warming up to 550 DEG C with the rate of 5 DEG C/min, is kept the temperature 2h, natural cooling To room temperature, flaxen solid is obtained, sample is finally taken out and grinds up to pure g-C3N4；
2) heterogeneous catalysis Ag/g-C3N4Preparation:
By 0.1g g-C3N4It is dispersed in 50mL ultrapure water, supersonic oscillations 15min, 10ml AgNO containing 0.017g is then added3 Solution stirs 10h, and 4mL NaBH containing 0.004g is finally added dropwise4Aqueous solution, three times with milli-Q water, centrifugation, finally at 60 DEG C Dry 12h in vacuum oven.
CN201710481107.6A 2017-06-22 2017-06-22 A kind of synthetic method of arylalkyne halogen Expired - Fee Related CN107365239B (en)

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CN112778076B (en) * 2020-12-29 2022-05-24 华北电力大学 Method for preparing 1-halogenated alkyne under catalysis of heterogeneous Ag catalyst at room temperature

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103586064A (en) * 2013-11-26 2014-02-19 中国科学院福建物质结构研究所 Metal/graphite-like carbon nitride compound catalyst and preparing method thereof
CN103864548A (en) * 2014-04-01 2014-06-18 东北师范大学 Method for rapidly and efficiently preparing 1-haloalkyne
CN106831283A (en) * 2017-03-13 2017-06-13 广东工业大学 A kind of method of the iodo alkynes of high selectivity 1

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103586064A (en) * 2013-11-26 2014-02-19 中国科学院福建物质结构研究所 Metal/graphite-like carbon nitride compound catalyst and preparing method thereof
CN103864548A (en) * 2014-04-01 2014-06-18 东北师范大学 Method for rapidly and efficiently preparing 1-haloalkyne
CN106831283A (en) * 2017-03-13 2017-06-13 广东工业大学 A kind of method of the iodo alkynes of high selectivity 1

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Ag负载g-C3N4及其光催化还原CO2研究;高艳等;《工程热物理学报》;20170228;第411-415页
one pot synthesis of haloacetylenes from trimethylsilylacetylenes;Toshio Nishikawa, et al.;<Synlett>;19940630;485-486页
Silver-Catalyzed Synthesis of 1-Chloroalkynes Directly from Terminal Alkynes;Dunfa Shi, et al.;<ChemCatChem>;20150415;1424-1426页
石墨相氮化碳的化学合成及应用;张金水等;《物理化学学报》;20130617;第1865-1876页

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