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1,3-Dichloro-5,5-dimethylhydantoin → Perfluorophenyl 8-(2-methoxy-4-(trifluoromethyl)phenyl)-1,7-naphthyridine-3-sulfonate

HRID 1473494
ノート
印刷プレビュー

反応式

HRID 1473494 の反応式
C(S[C:9]1[CH:10]=[N:11][C:12]2[C:17]([CH:18]=1)=[CH:16][CH:15]=[N:14][C:13]=2[C:19]1[CH:24]=[CH:23][C:22]([C:25]([F:28])([F:27])[F:26])=[CH:21][C:20]=1[O:29][CH3:30])C1C=CC=CC=1.ClN1C(C)(C)C(=O)N(Cl)C1=O.[S:42](Cl)(Cl)(=[O:44])=[O:43].[F:47][C:48]1[C:53]([F:54])=[C:52]([F:55])[C:51]([F:56])=[C:50]([F:57])[C:49]=1[OH:58].C(N(CC)CC)C>CCOC(C)=O.O.C(O)(=O)C.C(#N)C>[CH3:30][O:29][C:20]1[CH:21]=[C:22]([C:25]([F:27])([F:28])[F:26])[CH:23]=[CH:24][C:19]=1[C:13]1[N:14]=[CH:15][CH:16]=[C:17]2[C:12]=1[N:11]=[CH:10][C:9]([S:42]([O:58][C:49]1[C:48]([F:47])=[C:53]([F:54])[C:52]([F:55])=[C:51]([F:56])[C:50]=1[F:57])(=[O:44])=[O:43])=[CH:18]2
参加物実験手順後処理出典と根拠反応ノート

参加物

10

反応物 5

HCID 83601,3-Dichloro-5,5-dimethylhydantoinHCID 8471TriethylamineHCID 13041PentafluorophenolHCID 24648Sulfuryl chlorideHCID 866875483-(Benzylthio)-8-(2-methoxy-4-(trifluoromethyl)phenyl)-1,7-naphthyridine

生成物 1

HCID 86687549Perfluorophenyl 8-(2-methoxy-4-(trifluoromethyl)phenyl)-1,7-naphthyridine-3-sulfonate
収率 76%

試薬・触媒・溶媒 4

HCID 176Acetic Acid溶媒HCID 962Water溶媒HCID 6342Acetonitrile溶媒HCID 8857Ethyl Acetate溶媒

実験手順

To a vial charged with 3-(benzylthio)-8-(2-methoxy-4-(trifluoromethyl)phenyl)-1,7-naphthyridine (0.295 g, 0.692 mmol) was added acetonitrile (3.26 ml), acetic acid (0.122 ml) and water (0.081 ml). The resulting solution was cooled in an ice water bath prior to the addition of 1,3-dichloro-5,5-dimethylhydantoin (0.068 ml, 0.519 mmol). After 90 min of stirring (ice melt) LC/MS indicated fairly clean conversion to sulfonyl chloride. To the mixture was added 2,3,4,5,6-pentafluorophenol (0.036 ml, 0.346 mmol) followed by the drop wise addition of triethylamine (0.193 ml, 1.384 mmol). After 15 min LC/MS indicated complete conversion to product. The yellow solution was diluted with EtOAc and extracted with water. The aqueous phase was extracted with EtOAc and the combined organics were dried with Na2SO4, filtered, dried under reduced pressure and the crude oil purified with a 40 g silicycle HP column (SiliCycle, Inc. Quebec City, Canada) ramping EtOAc in heptane (0 to 65%, 5% DCM throughout) to afford perfluorophenyl 8-(2-methoxy-4-(trifluoromethyl)phenyl)-1,7-naphthyridine-3-sulfonate (0.145 g, 0.263 mmol, 76% yield) as a white foam. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.30 (s, 1H) 7.45 (dt, J=7.78, 0.81 Hz, 1H) 7.60-7.65 (m, 1H) 7.89 (d, J=5.77 Hz, 1H) 8.90 (d, J=2.35 Hz, 1H) 8.95 (d, J=5.58 Hz, 1H) 9.36 (d, J=2.35 Hz, 1H). m/z (ESI) 551.2 (M+H)+.

後処理

  1. temperatureThe resulting solution was cooled in an ice water bath
  2. waitAfter 15 min LC/MS indicated complete
  3. extractionextracted with water
  4. extractionThe aqueous phase was extracted with EtOAc
  5. dry with materialthe combined organics were dried with Na2SO4
  6. filtrationfiltered
  7. customdried under reduced pressure
  8. customthe crude oil purified with a 40 g silicycle HP column (SiliCycle, Inc. Quebec City, Canada)

出典と根拠

ORDレコード
ord-16dab7c4f87c4c8d9fd55c10e88efbfa
出典データセット
uspto-grants-2015_04
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09012443B2

反応ノート

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