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Diisopropylethylamine → 4-(5-[(4-Fluorophenyl)methyl]-6-methylpyrimidin-4-yl)-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,3,4,5-tetrahydro-1,4-benzoxazepine

HRID 241170
ノート
印刷プレビュー

反応式

HRID 241170 の反応式
FC(F)(F)C(O)=O.[CH3:8][C:9]1([CH3:27])[C:13]([CH3:15])([CH3:14])[O:12][B:11]([C:16]2[CH:17]=[CH:18][C:19]3[O:25][CH2:24][CH2:23][N:22]=[CH:21][C:20]=3[CH:26]=2)[O:10]1.Cl[C:29]1[C:34]([CH2:35][C:36]2[CH:41]=[CH:40][C:39]([F:42])=[CH:38][CH:37]=2)=[C:33]([CH3:43])[N:32]=[CH:31][N:30]=1.C(N(CC)C(C)C)(C)C>CN1CCCC1=O>[F:42][C:39]1[CH:38]=[CH:37][C:36]([CH2:35][C:34]2[C:29]([N:22]3[CH2:21][C:20]4[CH:26]=[C:16]([B:11]5[O:10][C:9]([CH3:27])([CH3:8])[C:13]([CH3:14])([CH3:15])[O:12]5)[CH:17]=[CH:18][C:19]=4[O:25][CH2:24][CH2:23]3)=[N:30][CH:31]=[N:32][C:33]=2[CH3:43])=[CH:41][CH:40]=1
参加物実験手順後処理出典と根拠反応ノート

参加物

5

反応物 3

HCID 81531DiisopropylethylamineHCID 668206407-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-2,3-dihydro-1,4-benzoxazepine trifluoroacetate saltHCID 866478404-Chloro-5-(4-fluorobenzyl)-6-methylpyrimidine

生成物 1

HCID 668205164-(5-[(4-Fluorophenyl)methyl]-6-methylpyrimidin-4-yl)-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,3,4,5-tetrahydro-1,4-benzoxazepine収率 42%

試薬・触媒・溶媒 1

HCID 13387
N-methyl-2-pyrrolidone
溶媒

実験手順

A mixture of 7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,3-dihydro-1,4-benzoxazepine trifluoroacetate salt (2.9 g, 8.00 mmol, 4-chloro-5-[(4-fluorophenyl)methyl]-6-methylpyrimidine (reagent preparation 5) (1.9 g, 8.00 mmol) and N,N-diisopropylethylamine (7.0 mL, 40.0 mmol) in N-methyl-2-pyrrolidone (10 mL) was reacted in a microwave apparatus (250 W) for 2 h at 150° C. After cooling to room temperature the reaction mixture was partitioned between ethyl acetate (500 mL) and brine (100 mL). The organic layer was separated, washed with brine (100 mL), dried over sodium sulfate then filtered and concentrated. Column chromatography of the residue on silica (gradient 20 to 40% ethyl acetate in hexane) gave 4-{5-[(4-fluorophenyl)methyl]-6-methylpyrimidin-4-yl}-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,3,4,5-tetrahydro-1,4-benzoxazepine (1.6 g, 42% yield). 1H NMR (400 MHz, DMSO-D6): 8.58 (s, 1H), 7.62 (dd, 1H), 7.08 (m, 4H), 7.02 (d, 1H), 6.96 (d, 1H), 4.36 (s, 2H), 4.30 (m, 2H), 3.92 (s, 2H), 3.84 (m, 2H), 2.26 (s, 3H), 1.36 (s, 12H); MS (EI) for C27H31BFN3O3: 476 (MH+).

後処理

  1. customwas reacted in a microwave apparatus (250 W) for 2 h at 150° C
  2. customwas partitioned between ethyl acetate (500 mL) and brine (100 mL)
  3. customThe organic layer was separated
  4. washwashed with brine (100 mL)
  5. dry with materialdried over sodium sulfate
  6. filtrationthen filtered
  7. concentrationconcentrated

出典と根拠

ORDレコード
ord-581438f99b2f4abf81c076b4e4397c62
出典データセット
uspto-grants-2014_02
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08648066B2

反応ノート

読み込み中…

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