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Formaldehyde → Benzyl 2-[3-chloro-5-(3-[(dimethylamino)methyl]phenethylamino)-2-methyl-6-oxo-1(6H)-pyrazinyl]acetate

HRID 2228733
ノート
印刷プレビュー

反応式

HRID 2228733 の反応式
[Cl:1][C:2]1[N:7]=[C:6]([NH:8][CH2:9][CH2:10][C:11]2[CH:16]=[CH:15][CH:14]=[C:13]([CH2:17][NH:18][CH3:19])[CH:12]=2)[C:5](=[O:20])[N:4]([CH2:21][C:22]([O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)=[O:23])[C:3]=1[CH3:32].C=O.[C:35](O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>C(Cl)Cl>[Cl:1][C:2]1[N:7]=[C:6]([NH:8][CH2:9][CH2:10][C:11]2[CH:16]=[CH:15][CH:14]=[C:13]([CH2:17][N:18]([CH3:35])[CH3:19])[CH:12]=2)[C:5](=[O:20])[N:4]([CH2:21][C:22]([O:24][CH2:25][C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=2)=[O:23])[C:3]=1[CH3:32]
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 712FormaldehydeHCID 5049666Sodium triacetoxyborohydrideHCID 18470865benzyl 2-[3-chloro-2-methyl-5-(3-[(methylamino)methyl]phenethylamino)-6-oxo-1(6H)-pyrazinyl]acetate

生成物 1

HCID 18470815Benzyl 2-[3-chloro-5-(3-[(dimethylamino)methyl]phenethylamino)-2-methyl-6-oxo-1(6H)-pyrazinyl]acetate収率 77.1%

試薬・触媒・溶媒 1

HCID 6344
Dichloromethane
溶媒
2 回

実験手順

A stirred solution of benzyl 2-[3-chloro-2-methyl-5-(3-[(methylamino)methyl]phenethylamino)-6-oxo-1(6H)-pyrazinyl]acetate (preparation 19) (0.38 g, 0.83 mmol) in CH2Cl2 (10 ml) was treated with formaldehyde (0.31 ml). After stirring at room temperature for 45 mins, the resultant cloudy mixture was treated with sodium triacetoxyborohydride (253 mg, 1.19 mmol) and stirred at room temperature for a further 2 days. The reaction mixture was diluted with CH2Cl2 (200 ml) and washed with sat. aq NaHCO3, sat aq brine and dried over MgSO4. Removal of the drying agent by filtration followed by evaporation of the solvent gave a crude solid which was purified by chromatography (SiO2, gradient elution with 100% CH2Cl2; 95:5 CH2Cl2:MeOH; 90:10 CH2Cl2:MeOH) to give the desired product (0.30 g, 77%). 1H NMR (CDCl3) δ 2.20 (s, 3H), 2.25 (s, 6H), 2.90 (t, 2H), 3.40 (s, 2H), 3.70 (m, 2H), 4.80 (s, 2H), 5.20 (s, 2H), 6.10 (m, br, 1H), 7.10-7.20 (m, 3H), 7.25 (m, 1H), 7.35 (m, 5H). LRMS m/z=469.2, 471.2 (M+1).

後処理

  1. stirringstirred at room temperature for a further 2 days
  2. washwashed with sat. aq NaHCO3
  3. dry with materialdried over MgSO4
  4. customRemoval of the drying agent
  5. filtrationby filtration
  6. customfollowed by evaporation of the solvent
  7. customgave a crude solid which
  8. customwas purified by chromatography (SiO2, gradient elution with 100% CH2Cl2; 95:5 CH2Cl2:MeOH; 90:10 CH2Cl2:MeOH)

出典と根拠

ORDレコード
ord-1ef83a6ceda34780bde35f5481e9daae
出典データセット
uspto-grants-2002_07
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US06417203B1

反応ノート

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