Triphenylphosphine → (E)-2-amino-6-chloro-9-[4-(diisopropoxyphosphoryl)but-3-enyl]purine

HRID 1708095ノート

反応式

HRID 1708095 の反応式
[NH2:1][C:2]1[N:10]=[C:9]2[C:5]([NH:6][CH:7]=[N:8]2)=[C:4]([Cl:11])[N:3]=1.O[CH2:13][CH2:14]/[CH:15]=[CH:16]/[P:17](=[O:26])([O:22][CH:23]([CH3:25])[CH3:24])[O:18][CH:19]([CH3:21])[CH3:20].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>CN(C)C=O>[NH2:1][C:2]1[N:10]=[C:9]2[C:5]([N:6]=[CH:7][N:8]2[CH2:13][CH2:14]/[CH:15]=[CH:16]/[P:17]([O:22][CH:23]([CH3:24])[CH3:25])([O:18][CH:19]([CH3:20])[CH3:21])=[O:26])=[C:4]([Cl:11])[N:3]=1

参加物

6

反応物 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 53603492-Amino-6-chloropurineHCID 10399205diisopropyl (E)-4-hydroxybut-1-enylphosphonate

生成物 1

HCID 10340194(E)-2-amino-6-chloro-9-[4-(diisopropoxyphosphoryl)but-3-enyl]purine収率 35.2%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
0 °C

実験手順

To a mixture of 2-amino-6-chloropurine (0.6 g, 3.81 mmol) , diisopropyl (E)-4-hydroxybut-1-enylphosphonate (0.90 g, 3.81 mmol) and triphenyl phosphine (2.00 g, 7.62 mmol) in dry N,N-dimethylformamide (30 ml) stirred at 0° C. under dry nitrogen was added diethyl azodicarboxylate (1.33 g, 7.62 mmol). The mixture was allowed to warm to room temperature and stirred for 1.3 hr. The solvent was removed and the residue was purified by column chromatography on silica gel eluting with dichloromethane-methanol (9:1) to afford (E)-2-amino-6-chloro-9-[4-(diisopropoxyphosphoryl)but-3-enyl]purine as a light brown gum (0.52 g, 35%), m.p. 150° C.; λmax (EtOH) 311 (6,760), 249 (5,420) and 224 (24,320)nm; υmax (KBr) 3385, 3320, 3208, 1635, 1615, 1560, 1520, 1410 and 1240 cm-1 ; δH [(CD3) 2 SO] 1.08 (6H, d, J 6 Hz, CH(CH3)2), 1.16 (6H, d, J 6 Hz, CH(CH3)2), 2.77 (2H, m, CH2), 4.27 (4H, m, CH2N and CH(CH3)2), 5.69 (1H, dd, J 17 Hz and 21Hz, PCH=CH), 6.52 (1H, ddt, J 6 Hz, 17 Hz and 22 Hz PCH=CH), 6.89 (2H, br.s, D2O exchangeable, NH2), 8.11 (1H, s, H-8) (Found: MH+ 388.1288. C15H23ClN5O3P requires MH+ 388.1305).

後処理

  1. temperatureto warm to room temperature
  2. stirringstirred for 1.3 hr
  3. customThe solvent was removed
  4. customthe residue was purified by column chromatography on silica gel eluting with dichloromethane-methanol (9:1)

出典と根拠

ORDレコード
ord-f5c8254c8ef5484983785f0da5ffbe3a
出典データセット
uspto-grants-1994_10
特許番号
US05356886

反応ノート

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