Triethylamine → 1,1-Dimethylethyl {[4-methyl-2-oxo-6-(phenylmethyl)-1,2-dihydro-3-pyridinyl]methyl}carbamate

HRID 85542

反応式

HRID 85542 の反応式
[C:1]([O-:4])(=[O:3])C.[Na+].CC1NC(=O)[C:10](C#N)=[C:9]([CH2:16]C2C=CC=CC=2)[CH:8]=1.[CH3:23][C:24]1[CH:29]=[C:28]([CH2:30][C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[NH:27][C:26](=[O:37])[C:25]=1[C:38]#[N:39].NCC1C(=O)NC(C)=CC=1CC1C=CC=CC=1.NCC1C(=O)NC(CC2C=CC=CC=2)=CC=1C.C(N(CC)CC)C>C(O)(=O)C.C1COCC1.CN(C=O)C.[Pd].[Pt]=O>[CH3:23][C:24]1[CH:29]=[C:28]([CH2:30][C:31]2[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=2)[NH:27][C:26](=[O:37])[C:25]=1[CH2:38][NH:39][C:1](=[O:3])[O:4][C:9]([CH3:16])([CH3:10])[CH3:8]

参加物

12

反応物 6

HCID 8471TriethylamineHCID 517045Sodium AcetateHCID 674636783-(aminomethyl)-6-methyl-4-(phenylmethyl)-2(1H)-pyridinoneHCID 674668016-Methyl-2-oxo-4-(phenylmethyl)-1,2-dihydro-3-pyridinecarbonitrileHCID 674670424-Methyl-2-oxo-6-(phenylmethyl)-1,2-dihydro-3-pyridinecarbonitrileHCID 674681903-(aminomethyl)-6-benzyl-4-methylpyridin-2(1H)-one

生成物 1

HCID 679517321,1-Dimethylethyl {[4-methyl-2-oxo-6-(phenylmethyl)-1,2-dihydro-3-pyridinyl]methyl}carbamate

試薬・触媒・溶媒 5

HCID 23938Palladium触媒HCID 82844Platinum oxide (PtO)触媒HCID 176Acetic Acid溶媒2 回HCID 6228Dimethylformamide溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

Sodium acetate (6.14 g, 74.8 mmol), Pd/C (0.65 g, 1 mmol), and platinum (II) oxide (45 mg, 1 mmol) were placed in a dried Parr bottle equipped with nitrogen inlet. A small amount of acetic acid was added to wet the catalysts. A solution of 6-methyl-2-oxo-4-(phenylmethyl)-1,2-dihydro-3-pyridinecarbonitrile and 4-methyl-2-oxo-6-(phenylmethyl)-1,2-dihydro-3-pyridinecarbonitrile (6 g, 26.7 mmol) in acetic acid (300 mL) was added to the vessel. The contents were sealed and hydrogenated on Parr shaker at 45 psi for 12 h. The reaction mixture was filtered and washed with acetic acid. The filtrate was removed under reduced pressure. The residue was washed with methanol and filtered to afford a crude mixture of 3-(aminomethyl)-6-methyl-4-(phenylmethyl)-2(1H)-pyridinone and 3-(aminomethyl)-4-methyl-6-(phenylmethyl)-2(1H)-pyridinone. The reaction was run in duplicate to afford a total crude recovery of 14.5 g. To a solution of the above crude product mixture (4.0 g, 17.5 mmol) in THF (10 mL) and DMF (10 mL) was added di-tert-butoxycarbonyl anhydride (5.0 g, 23.4 mmoL) and triethylamine (5.2 g, 52.5 mmol) at 0° C. The reaction mixture was stirred with warming to room temperature and then stirred for an additional 4 h. The contents were diluted with ice water and then filtered. The collected solid was dried and the products separated by HPLC to furnish 1.2 g of 1,1-dimethylethyl {[4-methyl-2-oxo-6-(phenylmethyl)-1,2-dihydro-3-pyridinyl]methyl}carbamate (1H NMR (400 MHz, DMSO-d6) δ 11.55-1.60 (br s, 1H), 7.20-7.29 (m, 5H), 5.85 (s, 1H), 3.92 (s, 2H), 3.90 (s, 2H), 2.10 (s, 3H), 1.32 (s, 9H) and 1.0 g of 1,1-dimethylethyl {[6-methyl-2-oxo-4-(phenylmethyl)-1,2-dihydro-3-pyridinyl]methyl}carbamate (1H NMR (400 MHz, DMSO-d6) δ 11.50-11.55 (br s, 1H), 7.18-7.25 (m, 5H), 5.75 (s, 1H), 4.02 (s, 2H), 3.85 (s, 2H), 2.05 (s, 3H), 1.32 (s, 9H).

後処理

  1. customequipped with nitrogen inlet
  2. customThe contents were sealed
  3. filtrationThe reaction mixture was filtered
  4. washwashed with acetic acid
  5. customThe filtrate was removed under reduced pressure
  6. washThe residue was washed with methanol
  7. filtrationfiltered
  8. customto afford a crude
  9. customto afford a total crude recovery of 14.5 g
  10. stirringstirred for an additional 4 h
  11. filtrationfiltered
  12. customThe collected solid was dried
  13. customthe products separated by HPLC

出典と根拠

ORDレコード
ord-006cc5a916534f2f817ab29709d8fa54
出典データセット
uspto-grants-2014_09
特許番号
US08846935B2

関連ノート

読み込み中…