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Synthesis method of beta-iodo-N-alkoxyamine compounds

A synthesis method and alkoxyamine technology are applied in the field of synthesizing beta-iodo-N-alkoxyamine compounds, and the effects of avoiding metal residues, simple reaction operation and good substrate adaptability are achieved.

Active Publication Date: 2017-11-24
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, so far, the synthesis methods of such compounds are rarely reported.

Method used

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  • Synthesis method of beta-iodo-N-alkoxyamine compounds
  • Synthesis method of beta-iodo-N-alkoxyamine compounds
  • Synthesis method of beta-iodo-N-alkoxyamine compounds

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033]

[0034] N-hydroxyphthalimide (48.9mg, 0.3mmol), styrene (156mg, 1.5mmol), elemental iodine (38.1mg, 0.15mmol) and tert-butyl hydroperoxide (77.2mg, 0.6mmol , 70% aqueous solution) into the flask, add 2ml of solvent 1,2-dichloroethane, and react at 80°C for 10 hours. After the reaction was detected by TLC, compound 1 (84.6 mg) was isolated by column chromatography (eluent: petroleum ether / ethyl acetate volume ratio 6:1), with a yield of 72%.

[0035] Product characterization: white solid; mp 134-135°C; 1 H NMR (500MHz, CDCl 3 ) δ7.77(td, J=5.2,2.0Hz,2H),7.73(td,J=5.2,2.0Hz,2H),7.52(dd,J=5.2,3.4Hz,2H),7.31-7.27(m ,2H),7.22-7.18 (m,1H),5.51(dd,J=9.8,5.7Hz,1H),4.94-4.89(m,1H),4.69 (dd,J=10.8,5.7Hz,1H). 13 C NMR (125MHz, CDCl 3 )δ163.1, 139.7, 134.6, 128.8, 128.6, 128.5, 127.8, 123.5, 81.3, 25.13. HRMS (ESI) calcd for C 16 h 16 IN 2 o 3 (M+NH 4 + )411.0206, found 411.0195.

Embodiment 2

[0037]

[0038]N-hydroxyphthalimide (48.9mg, 0.3mmol), styrene (156mg, 1.5mmol), elemental iodine (38.1mg, 0.15mmol) and tert-butyl peroxybenzoate (116.4mg, 0.6 mmol) into the flask, add 2ml of solvent 1,2-dichloroethane, and react at 80°C for 10 hours. After the reaction was detected by TLC, compound 1 (80.2 mg) was isolated by column chromatography (eluent: petroleum ether / ethyl acetate volume ratio 6:1), with a yield of 68%.

[0039] Product characterization: white solid; mp 134-135°C; 1 H NMR (500MHz, CDCl 3 ) δ7.77(td, J=5.2,2.0Hz,2H),7.73(td,J=5.2,2.0Hz,2H),7.52(dd,J=5.2,3.4Hz,2H),7.31-7.27(m ,2H),7.22-7.18 (m,1H),5.51(dd,J=9.8,5.7Hz,1H),4.94-4.89(m,1H),4.69 (dd,J=10.8,5.7Hz,1H). 13 C NMR (125MHz, CDCl 3 )δ163.1, 139.7, 134.6, 128.8, 128.6, 128.5, 127.8, 123.5, 81.3, 25.13. HRMS (ESI) calcd for C 16 h 16 IN 2 o 3 (M+NH 4 + )411.0206, found 411.0195.

Embodiment 3

[0041]

[0042] N-hydroxyphthalimide (48.9mg, 0.3mmol), styrene (156mg, 1.5mmol), elemental iodine (38.1mg, 0.15mmol) and di-tert-butyl peroxide (87.6mg, 0.6 mmol) into the flask, add 2ml of solvent 1,2-dichloroethane, and react at 80°C for 10 hours. After the reaction was detected by TLC, compound 1 (76.6 mg) was isolated by column chromatography (eluent: petroleum ether / ethyl acetate volume ratio 6:1), with a yield of 65%.

[0043] Product characterization: white solid; mp 134-135°C; 1 H NMR (500MHz, CDCl 3 ) δ7.77(td, J=5.2,2.0Hz,2H),7.73(td,J=5.2,2.0Hz,2H),7.52(dd,J=5.2,3.4Hz,2H),7.31-7.27(m ,2H),7.22-7.18 (m,1H),5.51(dd,J=9.8,5.7Hz,1H),4.94-4.89(m,1H),4.69 (dd,J=10.8,5.7Hz,1H). 13 C NMR (125MHz, CDCl 3 )δ163.1, 139.7, 134.6, 128.8, 128.6, 128.5, 127.8, 123.5, 81.3, 25.13. HRMS (ESI) calcd for C 16 h 16 IN 2 o 3 (M+NH 4 + )411.0206, found 411.0195.

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Abstract

The invention provides a synthesis method of beta-iodo-N-alkoxyamine compounds shown as a formula (III). Substituted hydroxylamine shown as a formula (I), olefin compounds shown as a formula (II), an iodine source and an oxidizing agent are mixed into a polar solvent to completely react to obtain reaction liquid; after the reaction for 2 to 12 hours at 20 to 120 DEG C, the reaction liquid is subjected to post treatment to obtain the beta-iodo-N-alkoxyamine compounds. The addition mole ratio of the substituted hydroxylamine shown as the formula (I) to the olefin compounds shown as the formula (II) to the iodine source to the oxidizing agent is 1:(5 to 15):(0.5 to 1):(1 to 5). The reaction conditions are mild; safety and environment protection are realized; the substrate applicability is high; no metal catalyst participates; the operation is simple; the application to medicine synthesis is facilitated. The formulas (I), (II) and (III) are shown in the specification.

Description

(1) Technical field [0001] The invention relates to a method for synthesizing β-iodo-N-alkoxyamine compounds. Using substituted hydroxylamine as a raw material, the substituted olefin compound is converted into the corresponding β-iodo- The N-alkoxyamine compound realizes obtaining a series of β-iodo-N-alkoxyamine derivatives under mild conditions. (2) Background technology [0002] β-iodo-N-alkoxyamine is an important building block that can be transformed into a variety of other important organic compounds. [0003] For example, the halogen iodine atom contained in its molecule can undergo cross-coupling reaction with aryl boronic acid, aryl alkyne, etc. under palladium catalysis. The N-alkoxyamine structure contained in its molecule can also be converted into corresponding alkoxyamine hydrochloride, hydroxyl and other groups in the presence of acid, alkali or oxidizing agent, so as to further transform. However, so far, the synthesis methods of such compounds are rarely...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D209/48C07D471/04
CPCC07D209/48C07D249/04C07D249/18C07D471/04
Inventor 李小青陈昆许响生唐裕才
Owner ZHEJIANG UNIV OF TECH
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