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

HRID 1708095Notes

Reaction equation

HRID 1708095 reaction equation
[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

Participants

6

Reactant 4

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

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).

Workup

  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)

Sources & evidence

ORD record
ord-f5c8254c8ef5484983785f0da5ffbe3a
Source dataset
uspto-grants-1994_10
Patent number
US05356886

Reaction notes

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