Method for hydrogenolysis of halides

A compound, halogen technology, applied in the field of halide hydrogenolysis

Pending Publication Date: 2020-12-29
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0009] The technical problem to be solved by the present invention is to provide a method for hydrogenoly...

Method used

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  • Method for hydrogenolysis of halides
  • Method for hydrogenolysis of halides
  • Method for hydrogenolysis of halides

Examples

Experimental program
Comparison scheme
Effect test

preparation example 1

[0108]

[0109] Under argon protection, 4-bromopiperidine hydrogen bromide (2.45g, 10mmol) was added successively to the reaction flask equipped with a stirring bar, pyridine (30mL) was fully dissolved, and p-toluenesulfonyl chloride (2.86 g, 15mmol), react at room temperature for 24h. Add deionized water to the system to quench the reaction, spin off a large amount of pyridine, extract the organic phase with 1M hydrochloric acid / dichloromethane, dry over anhydrous sodium sulfate, concentrate, and perform silica gel column chromatography. The eluent is petroleum ether: ethyl acetate: Dichloromethane=10:1:1 to 10:1:2, the product is 3.10 g of white solid, yield 97%, 1 H NMR purity greater than 98%. 1 H NMR (400MHz, CDCl 3 )δ7.65(d, J=8.0Hz, 2H), 7.34(d, J=8Hz, 2H), 4.25-4.24(m, 1H), 3.21-3.17(m, 2H), 3.10-3.09(m, 2H),2.45(s,3H),2.23-2.16(m,2H),2.09-2.01(m,2H); 13 C NMR (100MHz, CDCl 3 )δ143.69, 133.02, 129.72, 127.52, 47.79, 43.74, 34.61, 21.51.

preparation example 2

[0111]

[0112] Under argon protection, 2-indanol (1.34g, 10mmol), carbon tetrabromide (3.61g, 10.9mmol), and dichloromethane (50mL) were successively added to the reaction flask equipped with a stirring bar. After fully dissolving, the Under an ice bath, triphenylphosphine (dissolved in 10 mL of dichloromethane) (2.89 g, 11 mmol) was slowly added to the system. After the addition was complete, the reaction was returned to room temperature for 8 h, and the reaction was complete by TLC. Quenched with saturated sodium bicarbonate solution, extracted the organic phase with dichloromethane, dried over anhydrous sodium sulfate, and spin-dried, followed by silica gel column chromatography with petroleum ether as the eluent. The product was 1.51 g of a colorless liquid with a yield of 77%. 1H NMR (400MHz, CDCl 3 )δ7.26-7.19 (m, 4H), 4.78-4.73 (m, 1H), 3.50 (dd, J = 16.8Hz, 6.4Hz, 2H), 3.33 (dd, J = 16.8Hz, 4Hz, 2H); 13 C NMR (100MHz, CDCl 3 )δ140.48,126.94,124.50,49.57,44.59.IR(...

preparation example 3

[0114]

[0115] Under the air, add 5-methoxy-2-tetralone (3.52g, 20mmol) and methanol (100mL) successively to the egg-shaped bottle equipped with a stirrer. After fully dissolving, add boron to the system in four batches. Sodium hydride (907.9mg, 24mmol) was added within 15 minutes, reacted at room temperature for 2h, and the reaction was complete as detected by TLC. Saturated ammonium chloride solution was quenched, the organic phase was extracted with dichloromethane, dried over anhydrous sodium sulfate, concentrated, filtered through a short silica gel column, washed with dichloromethane, spin-dried, and directly used in the next reaction.

[0116] Under the protection of argon, add the above-mentioned crude product, carbon tetrabromide (7.23g, 21.8mmol), dichloromethane (100mL) to the reaction flask equipped with a stirring bar in sequence, after fully dissolving, add to the system under ice bath Slowly added triphenylphosphine (dissolved in 20 mL of dichloromethane) (5...

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Abstract

The invention discloses a method for hydrogenolysis of halides. The invention discloses a preparation method of a compound represented by a formula I. The preparation method comprises the following step: in a polar aprotic solvent, zinc, H2O and a compound represented by a formula II are subjected to a reaction as shown in the specification, wherein X is halogen; Y is -CHR<1>R<2> or R<3>; hydrogenin H2O exists in the form of natural abundance or non-natural abundance. According to the preparation method, halide hydrogenolysis can be simply, conveniently and efficiently achieved through a simple and mild reaction system, and good functional group compatibility and substrate universality are achieved.

Description

technical field [0001] The present invention relates to a method for hydrogenolysis of halides. Background technique [0002] Deuterium, as a stable isotope of hydrogen, has received extensive attention from scientists. compared to 13 C and 14 C, deuterium is cheaper and easier to obtain, and it is easier to be introduced into the compound. The introduction of deuterium into the solvent can be used for nuclear magnetic resonance spectrum analysis to realize the analysis and confirmation of the structure of various compounds, and can even be used for real-time monitoring of reactions. It is an indispensable and important part of organic chemistry; the introduction of deuterium into Among the substrates of the reaction, the determination of deuterium in the product also plays an important role in the study of the reaction mechanism; the introduction of deuterium into the drug molecule can study the drug in vivo without affecting its drug activity. The process of absorption...

Claims

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Application Information

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IPC IPC(8): C07B39/00C07B59/00C07C1/26C07C13/465C07C13/273C07C13/615C07C17/16C07C23/34C07C23/02C07C22/04C07C19/075C07C41/22C07C43/225C07C41/24C07C43/20C07C43/205C07C41/26C07C43/174C07C45/65C07C49/794C07C49/792C07C49/825C07C49/67C07C49/76C07C51/377C07C53/126C07C67/317C07C69/24C07C253/30C07C255/33C07C273/18C07C275/50C07C303/40C07C311/21C07D209/48C07D211/96C07D295/26C07D307/33C07J1/00C07J9/00
CPCC07B59/001C07B59/002C07B59/007C07B39/00C07D211/96C07C17/16C07C41/22C07J1/0011C07J9/00C07C67/08C07C303/40C07C41/26C07D295/26C07C1/26C07C41/24C07C45/65C07D307/33C07C67/317C07C51/377C07D209/48C07C253/30C07C273/1863C07B2200/05C07C2602/08C07C2602/10C07C2601/18C07C2603/74C07C2602/42C07C2601/02C07C23/34C07C43/225C07C23/02C07C43/174C07C22/04C07C69/63C07C311/21C07C43/1742C07C19/075C07C13/465C07C43/20C07C13/273C07C13/615C07C43/164C07C43/205C07C15/12C07C49/627C07C49/67C07C69/24C07C53/126C07C49/76C07C255/33C07C49/825C07C43/2055C07C49/792C07C49/794C07C275/50
Inventor 刘元红夏爱游解鑫胡晓苹徐炜
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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