Triphenylphosphine → Triphenyl(3,3,3-trifluoropropyl)phosphanium iodide

HRID 1454078

反応式

HRID 1454078 の反応式
ClC1C=CC(S(N[C@H](CO)C(CC(F)(F)F)CC(F)(F)F)(=O)=O)=CC=1.[F:26][C:27]([F:32])([F:31])[CH2:28][CH2:29][I:30].[C:33]1([P:39]([C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=2)[C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1>>[I-:30].[F:26][C:27]([F:32])([F:31])[CH2:28][CH2:29][P+:39]([C:40]1[CH:41]=[CH:42][CH:43]=[CH:44][CH:45]=1)([C:46]1[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1)[C:33]1[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=1

参加物

4

反応物 3

HCID 11776TriphenylphosphineHCID 1561651,1,1-Trifluoro-3-iodopropaneHCID 575292724-chloro-N-[(1S)-4,4,4-trifluoro-1-hydroxymethyl-2-(2,2,2-trifluoroethyl)-butyl]benzenesulfonamide

生成物 1

HCID 19694095Triphenyl(3,3,3-trifluoropropyl)phosphanium iodide

実験手順

In another embodiment, a method for preparing 4-chloro-N-[(1S)-4,4,4-trifluoro-1-hydroxymethyl-2-(2,2,2-trifluoroethyl)-butyl]benzenesulfonamide is provided and includes (a) reacting 1,1,1-trifluoro-3-iodopropane with triphenylphosphine to form (3,3,3-trifluoropropyl)-triphenylphosphonium iodide; (b) reacting (3,3,3-trifluoropropyl)-triphenylphosphonium iodide and a base at a temperature of −70° C. to 25° C.; (c) reacting the product of step (b) with ethylchloroformate at a temperature below about −20° C. to form 4,4,4-trifluoro-2-(triphenyl-λ5-phosphanylidene)-butyric acid ester; (d) isolating 4,4,4-trifluoro-2-(triphenyl-λ5-phosphanylidene)-butyric acid ester by hydrocarbon trituration; (e) reacting dehydrated trifluoroacetaldehyde, which is free of acidic impurities, and 4,4,4-trifluoro-2-(triphenyl-λ5-phosphanylidene)-butyric acid ester to form 4,4,4-trifluoro-2-(2,2,2-trifluoroethyl)-but-2-enoic acid ester; (f) hydrogenating 4,4,4-trifluoro-2-(2,2,2-trifluoroethyl)-but-2-enoic acid ester to form 4,4,4-trifluoro-2-(2,2,2-trifluoroethyl)-butyric acid ester; (g) reacting 4,4,4-trifluoro-2-(2,2,2-trifluoroethyl)-butyric acid ester with N,O-dimethylhydroxylamine hydrochloride to form 4,4,4-trifluoro-N-methoxy-N-methyl-2-(2,2,2-trifluoroethyl)-butyramide; (h) reacting 4,4,4-trifluoro-N-methoxy-N-methyl-2-(2,2,2-trifluoroethyl)-butyramide with a first reducing agent to form 4,4,4-trifluoro-2-(2,2,2-trifluoroethyl)-butyraldehyde; (i) reacting 4,4,4-trifluoro-2-(2,2,2-trifluoroethyl)-butyraldehyde, a titanium alkoxide, and (S)-(+)-p-toluenesulfinamide to form N-methyl-N-[(1S)-4,4,4-trifluoro-2-(2,2,2-trifluoroethyl)-butylidene]benzenesulfinamide; (j) cyanating N-methyl-N-[(1S)-4,4,4-trifluoro-2-(2,2,2-trifluoroethyl)-butylidene]benzenesulfinamide to form N-methyl-benzenesulfinic acid [(1S)-1-cyano-4,4,4-trifluoro-2-(2,2,2-trifluoroethyl)-butyl]amide; (k) reacting N-methyl-benzenesulfinic acid [(1S)-1-cyano-4,4,4-trifluoro-2-(2,2,2-trifluoroethyl)-butyl]amide with an aqueous acid; (l) reacting the product of step (k) with an alcohol in the presence of an acid to form (2S)-2-amino-5,5,5-trifluoro-3-(2,2,2-trifluoroethyl)-pentanoic acid methyl ester; (m) reacting (2S)-2-amino-5,5,5-trifluoro-3-(2,2,2-trifluoroethyl)-pentanoic acid methyl ester with 4-chlorobenzenesulfonyl chloride to form (2S)-2-(4-chloro-benzenesulfonylamino)-5,5,5-trifluoro-3-(2,2,2-trifluoroethyl)-pentanoic acid methyl ester; (n) combining (2S)-2-(4-chloro-benzenesulfonylamino)-5,5,5-trifluoro-3-(2,2,2-trifluoroethyl)-pentanoic acid methyl ester and a second reducing agent to form 4-chloro-N-[(1S)-4,4,4-trifluoro-1-hydroxymethyl-2-(2,2,2-trifluoroethyl)-butyl]benzenesulfonamide; (o) quenching the product of step (n); and (p) isolating the 4-chloro N-[(1S)-4,4,4-trifluoro-1-hydroxymethyl-2-(2,2,2-trifluoroethyl)-butyl]benzenesulfonamide.

後処理

  1. customis provided

出典と根拠

ORDレコード
ord-638b383ebae847cf86a08ddbd02dec11
出典データセット
uspto-grants-2009_01
特許番号
US07476762B2

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