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4-Methylmorpholine → N-(2,2-dimethyl-[1,3]dioxolan-4-ylmethoxy)-3,4-difluoro-2-(2-fluoro-4-iodo-phenylamino)-benzamide

HRID 1062291
ノート
印刷プレビュー

反応式

HRID 1062291 の反応式
[F:1][C:2]1[C:3]([NH:12][C:13]2[CH:18]=[CH:17][C:16]([I:19])=[CH:15][C:14]=2[F:20])=[C:4]([CH:8]=[CH:9][C:10]=1[F:11])[C:5]([OH:7])=O.C1(P(Cl)(C2C=CC=CC=2)=O)C=CC=CC=1.CN1CCOCC1.[CH3:43][C:44]1([CH3:52])[O:48][CH:47]([CH2:49][O:50][NH2:51])[CH2:46][O:45]1>C(OCC)(=O)C.O1CCCC1>[CH3:43][C:44]1([CH3:52])[O:48][CH:47]([CH2:49][O:50][NH:51][C:5](=[O:7])[C:4]2[CH:8]=[CH:9][C:10]([F:11])=[C:2]([F:1])[C:3]=2[NH:12][C:13]2[CH:18]=[CH:17][C:16]([I:19])=[CH:15][C:14]=2[F:20])[CH2:46][O:45]1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

7

反応物 4

HCID 79724-Methylmorpholine2 回HCID 73910Diphenylphosphinic chlorideHCID 10240948O-[(2,2-dimethyl-1,3-dioxolan-4-yl)methyl]hydroxylamineHCID 220256632-(2-Fluoro-4-iodoanilino)-3,4-difluorobenzoic acid

生成物 1

HCID 22061666N-(2,2-dimethyl-[1,3]dioxolan-4-ylmethoxy)-3,4-difluoro-2-(2-fluoro-4-iodo-phenylamino)-benzamide収率 68.6%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
-15 °C

実験手順

To a stirring solution of 3,4-difluoro-2-(2-fluoro-4-iodo-phenylamino)-benzoic acid (4.52 g, 11.5 mmol) in freshly distilled tetrahydrofuran (20 mL) at −15° C. was added diphenylphosphinic chloride (2.85 mL, 14.95 mmol). The resultant reaction mixture was stirred for 30 minutes at −15° C. N-Methylmorpholine (1.26 mL, 11.5 mmol) was added and stirring was continued for 90 minutes at −15° C. The reaction was then charged with O-(2,2-dimethyl-[1,3]dioxolan-4-ylmethyl)-hydroxylamine (2.03 g, 13.8 mmol) and allowed to stir at −15° C. for 30 minutes. N-methylmorpholine (1.9 mL, 17.25 mmol) was added and the reaction was allowed to warm to room temperature. After 17 hours, the mixture was diluted with ethyl acetate and partitioned twice with saturated NaHCO3 solution, then twice with water, and twice with saturated brine solution. Organic layers were collected, dried over sodium sulfate, filtered and concentrated in vacuo. The afforded residue was purified by silica column chromatography in 3:1 hexanes/ethyl acetate. The corresponding fractions were collected, dried in vacuo, and crystallized from ethyl acetate/hexanes affording N-(2,2-dimethyl-[1,3]dioxolan-4-ylmethoxy)-3,4-difluoro-2-(2-fluoro-4-iodo-phenylamino)-benzamide (4.12 g, 68.6%) as light brown solid: m.p.=114-115° C.; 1NMR (400 MHz, DMSO-d6) δ 11.89 (s, 1H), 8.62 (s, 1H), 7.53-7.55 (m, 1H), 7.31-7.37 (m, 2H), 7.17 (dd, 1H, J=16.9, 9.3), 6.60-6.65 (m, 1H), 4.22 (t, 1H, J=6.1), 3.96 (t, 1H, J=8.3), 3.76-3.77 (m, 2H), 3.63 (t, 1H, J=4.9), 1.26 (s, 3H), 1.21 (s, 3H); MS(APCI+)=522.9; Anal.calcd/found for C19H18F3IN2O4: C, 43.70/43.88; H, 3.47/3.43; N, 5.36/5.20; F, 10.91/10.87.

後処理

  1. customThe resultant reaction mixture
  2. stirringstirring
  3. waitwas continued for 90 minutes at −15° C
  4. stirringto stir at −15° C. for 30 minutes
  5. temperatureto warm to room temperature
  6. waitAfter 17 hours
  7. custompartitioned twice with saturated NaHCO3 solution
  8. customOrganic layers were collected
  9. dry with materialdried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customThe afforded residue was purified by silica column chromatography in 3:1 hexanes/ethyl acetate
  13. customThe corresponding fractions were collected
  14. customdried in vacuo
  15. customcrystallized from ethyl acetate/hexanes

出典と根拠

ORDレコード
ord-dc263565e67047ceab0de4094ed2331d
出典データセット
uspto-grants-2005_11
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US06960614B2

反応ノート

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