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, harsh reaction conditions, complex experimental operations, etc., and achieve the effects of environmental friendliness, simple operation, and simple post-processing

Active Publication Date: 2018-10-16
ZUNYI MEDICAL UNIVERSITY
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  • 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

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  • Preparation method of 1-bromoalkyne and 1-iodoalkyne
  • Preparation method of 1-bromoalkyne and 1-iodoalkyne
  • 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 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 react at room temperature , reacted for 2 hours, after the reaction was over, filtered, and the organic solvent was removed under reduced pressure; eluting with petroleum ether / ethyl acetate, separated by silica gel column, 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.

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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

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Application Information

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Patent Type & Authority Applications(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
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