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Method for synthesizing 2-bromo-1-iododihalide by one-pot process

A synthesis method and a dihalogenation technology are applied in the field of synthesizing 2-bromo-1-iodine dihalide, can solve problems such as difficult operation, environmental pollution, limitation of large-scale application, etc., and achieve simple reaction operation, mild reaction conditions, Good substrate adaptability

Inactive Publication Date: 2018-09-07
ZHEJIANG UNIV OF TECH
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  • Abstract
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Problems solved by technology

But so far, there are few reports about the synthetic methods of these compounds.
The most common method is to directly halogenate the carbon-carbon double bond with a simple halogen. Although this method is simple, it is not easy to operate and easily causes environmental pollution, which greatly limits the large-scale application of this method.

Method used

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  • Method for synthesizing 2-bromo-1-iododihalide by one-pot process
  • Method for synthesizing 2-bromo-1-iododihalide by one-pot process
  • Method for synthesizing 2-bromo-1-iododihalide by one-pot process

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Experimental program
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Effect test

Embodiment 1

[0029] Styrene (114.9 μL, 1 mmol), elemental iodine (26.9 mg, 0.5 mmol), 70% tert-butyl hydroperoxide (257.5 mg, 2 mmol) and N-hydroxybenzotriazole (166.6 mg, 1.2 mmol) were mixed Add 3ml of dichloromethane solvent into the flask and react at 40°C for 4h. After the reaction was detected by TLC, it was lowered to room temperature, and acetyl bromide (202.2 μL, 5 mmol) was added to react for 16 hours. After the reaction was detected by TLC, it was separated by column chromatography (eluent: petroleum ether) to obtain (2-bromo-1 -Iodoethyl)benzene (compound 1) 117.7 mg, yield 56.2%.

[0030] Product characterization: white solid, m.p. 60°C. 1 H NMR (500MHz, CDCl 3 )δ7.39 (tdd, J=8.6, 5.6, 3.2Hz, 5H), 5.15 (dd, J=10.7, 5.4Hz, 1H), 4.12–4.00 (m, 2H). 13 C NMR (125MHz, CDCl 3 )δ138.63, 129.20, 128.88, 127.67, 50.89, 35.03. HRMS (ESI) calcd for C 8 h 8 BrI(M+H + ):310.96, found 309.89.

Embodiment 2

[0032]

[0033] P-nitrostyrene (44.7mg, 0.3mmol), elemental iodine (38.1mg, 0.15mmol), 70% tert-butyl hydroperoxide (77.25mg, 0.6mmol) and N-hydroxybenzotriazole (49.1 mg, 0.36mmol) were mixed with 1ml of dichloromethane solvent into the flask and reacted at 40°C for 6h. After the reaction was detected by TLC, it was lowered to room temperature, and acetyl bromide (121.33 μL, 1.5 mmol) was added to react for 16 hours. After the reaction was detected by TLC, 1-(2- Bromo-1-iodoethyl)-4-nitrobenzene (compound 2) 68.6 mg, yield 64.2%.

[0034] Product characterization: Pale yellow solid, m.p.79°C. 1 H NMR (500MHz, CDCl 3 )δ 8.30–8.22(m,2H),7.62–7.56(m,2H),5.17(dd,J=11.3,4.9Hz,1H), 4.13–3.94(m,2H). 13 C NMR (125MHz, CDCl 3 )δ148.06, 145.50, 128.83, 124.12, 47.78, 33.88. HRMS (ESI) calcd for C 8 h 7 BRINO 2 (M+H + ):355.96, found 354.87.

Embodiment 3

[0036]

[0037]3-chlorostyrene (43.3mg, 0.3mmol), elemental iodine (38.1mg, 0.15mmol), 70% tert-butyl hydroperoxide (77.25mg, 0.6mmol) and N-hydroxybenzotriazole (49.1 mg, 0.36mmol) was mixed with 1ml of dichloromethane solvent into the flask and reacted at 40°C for 4h. After the reaction was detected by TLC, it was lowered to room temperature, and acetyl bromide (121.3 μL, 1.5 mmol) was added to react for 16 hours. After the reaction was detected by TLC, 1-chloro-3 was separated by column chromatography (eluent: petroleum ether). -(1-bromo-2-iodoethyl)benzene (compound 3) 68.1 mg, yield 65.7%.

[0038] Product characterization: white solid, m.p.95°C. 1 H NMR (500MHz, CDCl 3 )δ7.40 (d, J = 0.9Hz, 1H), 7.33 (dd, J = 3.8, 1.7Hz, 2H), 7.29 (ddd, J = 7.4, 4.5, 1.3Hz, 1H), 5.07 (dd, J =11.0,5.1Hz,1H),4.08–3.94(m,2H). 13 C NMR (126MHz, CDCl 3 )δ140.56, 134.68, 130.10, 129.36, 127.91, 125.91, 49.30, 34.56. HRMS (ESI) calcd for C 8 h 7 BrClI (M+H + ):345.40, found343.85.

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Abstract

The invention discloses a method for synthesizing 2-bromo-1-iododihalide represented by the formula (IV). The method comprises the following steps: mixing an olefin compound represented by formula (I)with an iodine source, tert-butyl hydroperoxide represented by formula (II) and N-hydroxybenzotriazole represented by formula (III) in an organic solvent, and completely reacting the obtained solution at a temperature from room temperature to 50 DEG C to obtain a reaction solution A; and adding acetyl bromide to the reaction solution A, completely reacting the obtained solution at room temperature to obtain a reaction solution B, and post-treating the reaction solution B to obtain the 2-bromo-1-iododihalide. The method has the advantages of safety, environmental protection, no generation of waste gas, facilitation of application in pharmaceutical synthesis, mild reaction conditions, good substrate adaptability, and realization of corresponding 2-bromo-1-iododihalides from various substituent groups.

Description

(1) Technical field [0001] In particular, the present invention relates to a method for the one-pot synthesis of 2-bromo-1-iododihalides. (2) Background technology [0002] Dihalides are often key intermediates in the artificial synthesis of some natural products and drug molecules, and some halides are also very useful synthons in organic synthesis, so the development of novel dihalogenation reactions is important for both scientific research and practice. production is important. But so far, there are few reports on the synthetic methods of these compounds. The most common method is to directly halogenate carbon-carbon double bonds with simple halogens. Although this method is simple, it is not easy to operate and easily causes environmental pollution, which greatly limits the large-scale application of this method. (3) Contents of the invention [0003] The object of the present invention is to provide a new method of dihalides, using olefinic compound, iodine source,...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B39/00C07C17/00C07C19/075C07C22/04C07C25/02C07C25/13C07C23/34C07C67/287C07C69/78C07C201/12C07C205/11C07C253/30C07C255/50
CPCC07B39/00C07C17/00C07C67/287C07C201/12C07C253/30C07C2602/08C07C19/075C07C22/04C07C25/02C07C25/13C07C23/34C07C69/78C07C205/11C07C255/50
Inventor 李小青许响生祝欢欢
Owner ZHEJIANG UNIV OF TECH
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