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A Cheap and Efficient Synthesis Method of Halohydrin and Its Derivatives

A synthetic method and technology of haloalcohols, which are applied in organic chemical methods, chemical instruments and methods, and the preparation of organic compounds, and can solve problems such as high cost, low atomic economic rate, and difficult reaction operations

Active Publication Date: 2017-05-17
PEKING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But so far, the conditions of this type of oxidative hydroxyhalogenation reaction are all relatively complicated. Usually, it is necessary to add halides, reagents for providing oxygen sources, oxidizing agents, additives, solvents, etc. in the reaction system, and sometimes it is necessary to add catalysts (Pandit, P.; Gayen, K.S.; Khamarui, S.; Chatterjee, N.; Maiti, D.K. Chem. Commun. 2011, 47, 6933 and Dewkar, G.K.; Narina, S.V.; Sudalai, A. Org. Lett. 2003, 5, 4501), These reactions lead to difficult operation, low atom economy rate and high cost

Method used

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  • A Cheap and Efficient Synthesis Method of Halohydrin and Its Derivatives
  • A Cheap and Efficient Synthesis Method of Halohydrin and Its Derivatives
  • A Cheap and Efficient Synthesis Method of Halohydrin and Its Derivatives

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Example 1 Synthesis of 2-bromo-1-(2-naphthyl)-ethanol

[0028]

[0029] a): Take a 25mL Schlenk reaction tube, add 77mg of naphthalene ethylene, 101mg of 48% hydrobromic acid aqueous solution, 2mL of dimethyl sulfoxide, and stir at 60°C for 12 hours. Add 15 mL of ethyl acetate after the reaction to quench the reaction, add 5 mL of brine to wash, separate the organic phase, extract the aqueous phase with ethyl acetate for 3 times, combine the organic phases, and separate by column chromatography to obtain 2-bromo-1-(2- Naphthyl)-ethanol 105 mg, yield 84%.

[0030] b): Take a 25mL Schlenk reaction tube, add 77mg of naphthalene ethylene, 101mg of 48% hydrobromic acid aqueous solution, 2mL of dimethyl sulfoxide, and stir at 70°C for 12 hours. Add 15 mL of ethyl acetate after the reaction to quench the reaction, add 5 mL of brine to wash, separate the organic phase, extract the aqueous phase with ethyl acetate for 3 times, combine the organic phases, and separate by colu...

Embodiment 2

[0036] Example 2 Synthesis of 2-bromo-1-phenyl-ethanol

[0037]

[0038] Take a 25mL Schlenk reaction tube, add 52mg of styrene, 101mg of 48% hydrobromic acid aqueous solution, and 2mL of dimethyl sulfoxide, and stir at 60°C for 12 hours. After the reaction was completed, 15 mL of ethyl acetate was added to quench the reaction, and 5 mL of brine was added for washing. The organic phase was separated, and the aqueous phase was extracted three times with ethyl acetate. The organic phases were combined and separated by column chromatography to obtain 2-bromo-1-phenyl- Ethanol 72 mg, yield 71%.

[0039] 1 H NMR (400MHz, CDCl 3 )δ7.38–7.31(m,5H),4.92(dt,J=8.9,3.1Hz,1H),3.63(dd,J=10.5,3.3Hz,1H),3.56–3.51(m,1H),2.68 (d,J=3.2Hz,1H); 13 C NMR (100MHz, CDCl 3 ) δ 140.2, 128.7, 128.4, 125.9, 73.8, 40.2.

Embodiment 3

[0040] Example 3 Synthesis of 2-bromo-1-(4-methyl-phenyl)-ethanol

[0041]

[0042] Take a 25mL Schlenk reaction tube, add p-methylstyrene 59mg, 48% hydrobromic acid aqueous solution 101mg, dimethyl sulfoxide 2mL, and stir at 60°C for 12 hours. After the reaction was completed, 15 mL of ethyl acetate was added to quench the reaction, and 5 mL of brine was added for washing. The organic phase was separated, and the aqueous phase was extracted 3 times with ethyl acetate. The organic phases were combined and separated by column chromatography to obtain 2-bromo-1-(4- Methyl-phenyl)-ethanol 97 mg, yield 90%.

[0043] 1 H NMR (400MHz, CDCl 3 )δ7.25(d,J=8.3Hz,2H),7.18(d,J=7.9Hz,2H),4.88–4.86(m,1H),3.60(dd,J=10.4,3.4Hz,1H), 3.52(dd,J=10.4,3.4Hz,1H),2.64(d,J=3.0Hz,1H),2.35(s,3H); 13 C NMR (100MHz, CDCl 3 ) δ 138.2, 137.3, 129.3, 125.9, 73.6, 40.2, 21.1.

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Abstract

The invention discloses a cheap and efficient synthesis method of halogenated alcohols. Olefin compounds expressed by a formula I as shown in the specification are mixed with halides, sulfoxide and additives in an organic solvent, and the halogenated alcohols expressed by a formula II as shown in the specification can be prepared highly selectively by virtue of the hydroxyhalogenation of the olefins, wherein R1, R2, R3, R4, R5 and R6 are selected from hydrogen, halogens, alkyl, hydroxyalkyl, alkoxy, ester group, acyl, acylamino, dialkylamino, aryl, substituted aryl, heterocyclic aryl and substituted heterocyclic aryl, respectively; R1, R2, R3, R4, R5 and R6 can be the same or different when existing independently; or R1 and R2, R1 and R3, R2 and R4, R3 and R4, and R5 and R6 are bonded to form a cycloalkyl or a substituted cycloalkyl, a benzocycloalkyl or a substituted benzocycloalkyl, and a heteroaromatic ring or a substituted heteroaromatic ring; M is selected from hydrogen, lithium, sodium, potassium, cesium, beryllium, magnesium, calcium, strontium, barium, zinc, copper, iron, ammonio or tetra-allkylammonio; X is selected from chlorine, bromine or iodine.

Description

technical field [0001] The invention relates to a method for synthesizing a compound, in particular to a method for synthesizing a halogenated alcohol, and belongs to the field of chemical synthesis. Background technique [0002] Halohydrins are important organic synthons in drug synthesis. Many intermediates widely used in drug synthesis, such as amino alcohols, hydroxy acids, epoxy compounds, and aziridines, can be conveniently synthesized through halohydrins. Therefore, the development of efficient halohydrin synthesis methods is currently an important topic in academia and industry. (Dagani, M.J.; Barda, H.J.; Benya, T.J.; Sanders, D.C. Eds. Ulmann's Encyclopedia of Industrial Chemistry: Bromine Compounds, Wiley-VCH, Weinheim, 2002). Among the many methods for synthesizing halohydrins, the synthesis of halohydrins through the hydroxyhalogenation reaction of alkenes has aroused great interest of researchers due to the convenience and easy availability of alkenes. In the...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07B41/02C07B39/00C07B43/00C07C31/36C07C35/48C07C29/64C07C33/46C07C35/52C07C41/26C07C43/23C07C247/10C07D209/48C07D307/80C07D333/56C07D311/22C07D311/58C07D301/26C07D303/04C07J1/00
Inventor 焦宁宋颂
Owner PEKING UNIV
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