Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

A kind of preparation method of 1-bromoalkyne and 1-iodoalkyne

A technology for substituting alkynes and alkynes, applied in the field of organic synthetic chemistry, can solve the problems of toxic and harmful halogenated reagents, complex experimental operations, harsh reaction conditions, etc., and achieve the effects of environmental friendliness, simple post-processing, and simple operation

Active Publication Date: 2020-03-27
ZUNYI MEDICAL UNIVERSITY
View PDF1 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, these methods have some disadvantages such as the use of expensive metal catalysts, toxic and harmful halogenation reagents, harsh reaction conditions and complicated experimental operations, thus limiting the practical application of these methods

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • A kind of preparation method of 1-bromoalkyne and 1-iodoalkyne
  • A kind of preparation method of 1-bromoalkyne and 1-iodoalkyne
  • A kind of preparation method of 1-bromoalkyne and 1-iodoalkyne

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Example 1: Synthesis of 1-chloro-2-(iodoethynyl)benzene (1a)

[0031]

[0032] Add 1-chloro-2-ethynylbenzene (68mg, 0.5mmol), acetonitrile (3mL), chloramine B (160mg, 0.75mmol) and potassium iodide (99mg, 0.6mmol) into a 25mL Schlenk bottle successively, and then next reaction,

[0033] React for 2 hours. After the reaction, filter and remove the organic solvent under reduced pressure; elute with petroleum ether / ethyl acetate and separate on a silica gel column. The yield of 1-chloro-2-(iodoethynyl)benzene is 95%. 1 H NMR (400MHz, Chloroform-d) δ7.45 (ddd, J=7.1, 2.1, 0.9Hz, 1H), 7.37 (dt, J=7.8, 1.1Hz, 1H), 7.27–7.14 (m, 2H). 13 C NMR (101MHz, cdcl 3 )δ136.65, 134.13, 129.73, 129.18, 126.33, 123.17, 90.83, 12.28. HRMS-ESI (m / z): calcd for C 8 h 5 ClI[M+H] + :262.9119, found 262.9120.

Embodiment 2

[0034] Example 2: Synthesis of 1-(iodoethynyl)-3-toluene (1b)

[0035]

[0036] Add 1-acetylene-3-toluene (58mg, 0.5mmol), acetonitrile (3mL), chloramine B (160mg, 0.75mmol) and potassium iodide (99mg, 0.6mmol) into a 25mL Schlenk bottle successively, and then react at room temperature , reacted for 2 hours, after the reaction was finished, filtered, and the organic solvent was removed under reduced pressure; eluted with petroleum ether / ethyl acetate, separated on a silica gel column, and the yield of 1-(iodoethynyl)-3-toluene was 98%. 1 H NMR (400MHz, Chloroform-d) δ7.27–7.22 (m, 2H), 7.19 (td, J=7.5, 1.3Hz, 1H), 7.16–7.11 (m, 1H), 2.31 (s, 3H). 13 C NMR (101MHz, cdcl 3 )δ137.94, 132.89, 129.72, 129.38, 128.13, 123.17, 94.34, 21.22, 5.69.HRMS-ESI(m / z): calcd for C 9 h 8 I[M+H] + :242.9665, found 242.9662.

Embodiment 3

[0037] Example 3: Synthesis of 3-(iodoethynyl)thiophene (1c)

[0038]

[0039]3-Ethynylthiophene (54mg, 0.5mmol), acetonitrile (3mL), chloramine B (160mg, 0.75mmol) and potassium iodide (99mg, 0.6mmol) were successively added to a 25mL Schlenk bottle, and then reacted at room temperature. After 2 hours, after the reaction was completed, filter and remove the organic solvent under reduced pressure; elute with petroleum ether / ethyl acetate, separate on a silica gel column, and the yield of 3-(iodoethynyl)thiophene is 95%. 1 H NMR (400MHz, Chloroform-d) δ7.46 (dd, J = 2.9, 1.4Hz, 1H), 7.24 (dd, J = 5.2, 1.4Hz, 1H), 7.10 (dt, J = 5.1, 1.3Hz, 1H). 13 C NMR (101MHz, cdcl 3 )δ130.30, 129.98, 125.16, 122.49, 89.15, 5.81. HRMS-ESI (m / z): calcd for C 6 h 4 IS[M+H] + :234.9073,found234.9073.

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention discloses a preparation method of 1-bromoalkyne and 1-iodoalkyne. The preparation method comprises the following steps that terminal alkyne is adopted as a raw material, a chloramine salt and an iodine salt or a bromine salt is adopted as a halogenation system, and reaction is carried out in a solvent to synthesize a series of 1-bromoalkyne and 1-iodoalkyne type compounds. In the formula shown in the description, R in terminal alkyne is selected from chain-like alkyne, ring-shaped alkyne, olefin, ester group, cyanogroup, substituted phenyl group and heterocyclic arene; the chloramine salt is selected from one of chloramine B, chloramine T or o-chloramine T; the iodine salt is selected from one of sodium iodide, potassium iodide, ammonium iodide, lithium iodide or tetrabutylammonium iodide; the bromine salt is selected from one of sodium bromide, potassium bromide, lithium bromide, magnesium bromide, ammonium bromide or tetrabutylammonium bromide; the solvent is selected from one or is mixed by two of water, benzene, methylbenzene, 1, 4-dioxane, ethyl acetate, dimethyl sulfoxide, methanol, tetrahydrofuran, alcohol, isopropyl alcohol, N, N-dimethyl formamide, n-pentane,dichloromethane, petroleum ether, methyl tert-butyl ether, chloroform, n-hexane, carbon tetrachloride, n-butyl alcohol, 1,2-dichloroethane or acetonitrile. The preparation method disclosed by the invention has the beneficial effect that the application is wide.

Description

technical field [0001] The invention relates to a preparation method of 1-bromoalkyne and 1-iodoalkyne, belonging to the field of organic synthesis chemistry. Background technique [0002] Halogen-containing compounds widely exist in organic synthesis intermediates, active natural products, drugs, pesticides and material molecules. Among them, 1-bromoalkynes and 1-iodoalkynes have attracted the attention of chemists, because they are not only used as synthetic building blocks in organic chemistry, but also as important synthetic precursors in materials and polymer chemistry. Wide range of uses. For the synthesis of 1-bromoalkynes and 1-iodoalkynes, the most common strategy is the direct C–H oxidative halogenation of terminal alkynes. The synthesis reports of 1-iodoalkyne include: strong base / iodine simple substance, ionic liquid, metal reagent, electrode oxidation method, N-iodo-morphonine, KI or Me 3 SI / PhI(OAc) 2 , Hypervalent iodonium salt and iodosuccinimide system. ...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Patents(China)
IPC IPC(8): C07C17/14C07C25/24C07C22/04C07D333/12C07D213/26C07C41/22C07C43/225
CPCC07C17/14C07C41/22C07D213/26C07D333/12C07C25/24C07C22/04C07C43/225
Inventor 刘小卒刘培均
Owner ZUNYI MEDICAL UNIVERSITY
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com