Method for producing fluoroamine

A kind of amine-substituted and fluorinated technology, which is applied in the preparation of sulfonic acid amides, organic chemistry methods, chemical instruments and methods, etc., can solve the problems such as inability to apply secondary amines

Inactive Publication Date: 2013-09-25
CENT GLASS CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In Patent Documents 1 and 2, phthaloyl and benzylidene groups are disclosed as protecting groups for amino groups, but these protecting groups can only be applied to primary amines, not to secondary amines

Method used

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  • Method for producing fluoroamine
  • Method for producing fluoroamine
  • Method for producing fluoroamine

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0137] Add the following formula to 30.0mL (0.752L / mol) of dichloromethane:

[0138]

[0139] 3.00g (39.9mmol, 1.00eq) of the indicated amino alcohols and 29.0g (287mmol, 7.19eq) of triethylamine were dissolved, and 8.89g (40.1mmol, 1.01eq) of o-nitrobenzenesulfonyl chloride was added at 0°C , and stirred at room temperature for one hour. Add 40.0 mL of water to the reaction-finished solution, extract with 80.0 mL of ethyl acetate, re-extract the recovered aqueous layer with 80.0 mL of ethyl acetate, combine the recovered organic layers, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and dry in vacuo , Purified by column chromatography (silica gel / ethyl acetate:n-hexane=2:1) ​​to obtain the following formula:

[0140]

[0141] The amino alcohol protected body (purified product) shown is 7.93g. The yield is 76%. Gas chromatographic purity was 95.8%. 1 H-NMR is shown below.

[0142] 1 H-NMR (reference substance: Me 4 Si; deuterated solvent: C...

Embodiment 2

[0154] Add the following formula to 2.20L (1.03L / mol) of acetonitrile:

[0155]

[0156] 180g (2.40mol, 1.13eq) of the indicated amino alcohols and 241g (2.38mol, 1.12eq) of triethylamine were dissolved, and 473g (2.13mol, 1.00eq) of o-nitrobenzenesulfonyl chloride was added at 0°C, at room temperature Stir overnight. After completion of the reaction, the precipitated triethylamine hydrochloride was removed by filtration, and the salt was washed with 1.00 L of ethyl acetate. Combine the filtrate and washing liquid, concentrate under reduced pressure to reduce the volume to about 1 / 3, add 1.00L of water, and extract with 1.50L of ethyl acetate. The aqueous layer was re-extracted twice with 500 mL of ethyl acetate, and the combined organic layers were concentrated under reduced pressure. After concentration, add 200mL toluene and then concentrate under reduced pressure to obtain the following formula:

[0157]

[0158] The amino alcohol protected body shown is 533g. Th...

Embodiment 3

[0166] Add the following formula to 53.0 mL (0.987 L / mol) of acetonitrile:

[0167]

[0168] 5.12g (57.4mmol, 1.07eq) of the indicated amino alcohols and 5.66g (55.9mmol, 1.04eq) of triethylamine were dissolved, and 11.9g (53.7mmol, 1.00eq) of o-nitrobenzenesulfonyl chloride was added at 0°C ), and stirred overnight at room temperature. After the reaction was completed, 100 mL of ethyl acetate and 30.0 mL of water were added for double-layer separation, and the aqueous layer was re-extracted twice with 30.0 mL of ethyl acetate. After merging the organic layers, the organic layer was concentrated under reduced pressure after passing through a small amount of silica gel column to obtain the following formula:

[0169]

[0170] 13.2 g of the amino alcohol protected body shown. The yield is 90%. Gas chromatographic purity was 99.0%. 1 H-NMR is described below.

[0171] 1 H-NMR (reference substance: Me 4 Si, deuterated solvent: CDCl 3 ), δppm: 1.82 (m, 2H), 2.65 (br, ...

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Abstract

A fluoroamine can be produced by: protecting an amino group of an amino alcohol with a nitrobenzenesulfonyl group, thereby converting into a protected amino alcohol (amino group protection step); causing the protected amino alcohol to react with sulfuryl fluoride (SO2F2) in the presence of an organic base, thereby converting into a protected fluoroamine (dehydroxyfluorination step); and eliminating the protective group of the amino group of the protected fluoroamine (deprotection step). Since a nitrobenzenesulfonyl group highly satisfies the conditions required for the protective group of an amino group of the present invention, an aimed fluoroamine can be obtained with high purity and high yield.

Description

technical field [0001] The present invention relates to a method for producing fluoroamines. Background technique [0002] The patent applicant discloses the use of sulfuryl fluoride (SO 2 f 2 ) and an organic base (performed in the presence of a "salt or complex formed of an organic base and hydrogen fluoride" if necessary) for dehydroxyfluorination of alcohols (Patent Document 1). In addition, a method for producing optically active fluoroamines using this method is also disclosed (Patent Document 2). [0003] In the dehydroxyfluorination reaction of amino alcohols using a combination of sulfuryl fluoride and an organic base, the choice of the protecting group for the amino group is important. When the amino group protected by the protecting group remains nucleophilic, it will cause the rearrangement of the 1 and 2 positions caused by the participation of adjacent groups (Japanese Patent Laid-Open No. 2009-286779), the intermolecular affinity for the intermediate fluoro...

Claims

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Application Information

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IPC IPC(8): C07C303/40C07C209/62C07C211/15C07C311/16C07B61/00
CPCC07C303/38C07C209/62C07C303/40Y02P20/55C07C311/17C07C311/16C07C211/15
Inventor 石井章央鹤田英之名仓裕力浊川泰子
Owner CENT GLASS CO LTD
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