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Method for synthesizing 1- chlorine-2-dihalogenated iodine

A synthesis method and a dihalogenation technology, which are applied in the field of one-pot synthesis of 1-chloro-2-iododihalides, can solve problems such as difficult operation, environmental pollution, and restrictions on large-scale application, and achieve simple reaction operation and high reaction efficiency. Mild conditions and good substrate adaptability

Inactive Publication Date: 2018-07-13
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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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 1- chlorine-2-dihalogenated iodine
  • Method for synthesizing 1- chlorine-2-dihalogenated iodine

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Compound 1

[0031] 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 chloride (353.7 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 (1-chloro-2 -Iodoethyl)benzene (compound 1) 133.9 mg, yield 50.2%.

[0032] Product characterization: white solid, m.p. 47°C. 1 H NMR (500MHz, CDCl 3 )δ 7.51–7.31(m,5H),5.08(dd,J=9.6,5.8Hz,1H),3.91–3.66(m,2H). 13 C NMR (125MHz, CDCl 3 )δ139.15, 129.19, 128.82, 127.24,, 61.72, 9.99.

Embodiment 2

[0034] Compound 2

[0035] 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 chloride (106.1 μL, 1.5 mmol) was added to react for 16 hours. After the reaction was detected by TLC, 1-(1- Chloro-2-iodoethyl)-4-nitrobenzene (compound 2) 56.3 mg, yield 60.2%.

[0036] Product characterization: Pale yellow solid, m.p.57°C. 1 H NMR (500MHz, CDCl 3 )δ 8.38–8.18(m,2H),7.64–7.58(m,2H),5.07(dd,J=8.8,5.7Hz,1H), 3.98(ddd,J=20.2,11.4,7.3Hz,2H). 13 CNMR (125MHz, CDCl 3 )δ 148.15(s), 145.86(s), 128.62(s), 128.43(s), 124.11(d, J=17.9Hz), 59.45(s), 8.41(s).

Embodiment 3

[0038] Compound 3

[0039] Indene (61.1 mg, 0.5 mmol), elemental iodine (63.4 mg, 0.25 mmol), tert-butyl hydroperoxide (128.7 mg, 1 mmol) and N-hydroxybenzotriazole (83.3 mg, 0.6 mmol) were mixed in 2ml of dichloromethane solvent was added into the flask and reacted at 40°C for 4h. After the reaction was detected by TLC, acetyl chloride (176.8 μL, 2.5 mmol) was added to react for 16 hours. After the reaction was detected by TLC, 1-chloro-2-iodo-2 was obtained by column chromatography (eluent: petroleum ether) , 17.1 mg of 3-dihydro-1H-indene (compound 8), yield 12.3%.

[0040] Product characterization: colorless liquid. 1H NMR (500MHz, CDCl3) δ7.46 (d, J = 6.7 Hz, 1H), 7.37–7.27 (m, 3H), 5.35 (d, J = 2.9Hz, 1H), 4.66 (dt, J = 6.3, 3.2Hz,1H),3.45(ddd,J=20.1,16.8,4.7Hz,2H). 13 C NMR(125MHz, CDCl3)δ139.84,129.71,127.94,125.50,125.11,67.62,64.49, 40.75.HRMS(ESI)calcd for C9H8ClI(M+H + ):278.52, found 277.94.

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Abstract

The invention discloses a method for synthesizing 1-chlorine-2-dihalogenated iodine as shown in formula (IV). The method comprises the following steps: mixing an olefin compound as shown in formula (I), an iodine source, tert-butyl hydroperoxide as shown in formula (II) and N-hydroxybenzotriazole as shown in formula (III) into an organic solvent, and reacting completely from the room temperature to a temperature lower than 50 DEG C, thereby obtaining reaction liquor A; adding acetyl chloride into reaction liquor A, completely reacting at the room temperature, and performing post-treatment on reaction liquor B to obtain a 1-chlorine-2-dihalogenated iodine compound. The method is safe and environmentally friendly, does not generate waste gas, and is more beneficial for being applied to pharmaceutical synthesis. And reaction conditions are gentle, substrate adaptation is good, and various substituent groups also can realize corresponding 1-chlorine-2-iodine halogenation.(The formulas is shown in the description.).

Description

(1) Technical field [0001] The invention specifically relates to a method for synthesizing 1-chloro-2-iododihalides in one pot. (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 1-chloro-2-iodine dihalide, with olefin compound, iodine sou...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C17/20C07C22/04C07C201/12C07C205/11C07C23/18C07C41/22C07C43/225C07C67/287C07C69/78C07C253/30C07C255/50
CPCC07C17/02C07C17/202C07C41/22C07C67/287C07C201/12C07C253/30C07C22/04C07C205/11C07C23/18C07C43/225C07C69/78C07C255/50
Inventor 李小青许响生祝欢欢
Owner ZHEJIANG UNIV OF TECH
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