Dichloromethane → Purine

HRID 1073105Notes

Reaction equation

HRID 1073105 reaction equation
S(C1C=CC(C)=CC=1)(OC1CCCC=1)(=O)=O.N[C:18]1[N:26]=[C:25]2[C:21]([NH:22][CH:23]=[N:24]2)=[C:20](Cl)[N:19]=1.C([O-])([O-])=O.[K+].[K+].C(Cl)Cl>CS(C)=O>[N:19]1[CH:20]=[C:21]2[C:25]([N:24]=[CH:23][NH:22]2)=[N:26][CH:18]=1

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 53603492-Amino-6-chloropurineHCID 54481545HCID 54481545, compound

Product 1

HCID 1044Purine

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

A mixture of the cyclopentenyl tosylate 2 (0.25 g, 0.58 mmol), 2-amino-6-chloropurine (0.212 g, 1.25 mmol, 2.2 eq), and K2CO3 (~1 g) was suspended in 2 mL of DMSO and stirred at room temperature for 42 h. The suspension was then poured into CH2Cl2 and washed with dilute NaCl. Evaporation of the CH2Cl2 gave an oil which was further dried under high vacuum to remove residual DMSO. Purification by preparative TLC (silica, 3:2 EtOAc:Hexane) gave two major purine containing products of which the faster moving and predominant was the desired N-9 alkylated purine 18 (0.117 g, 47%), mp 137°-140°; 1H-NMR (CDCl3) δ 1.35 (s, 3H, CH3), 1.46 (s, 3H, CH3), 4.27 (s, 2H, H-6'a,b), 4.61 and 4.62 (2H, PhCH2), 4.67 (d, J=5.3 Hz, 1H, H-2'), 5.10 (br s, 2H, NH2, exchangeable), 5.36 (d, J=5.3 Hz, 1H, H-3'), 5.43 (br s, 1H, H-1'), 5.78 (br s, 1H, H-5'), 7.34 (m, 5H, Ph), 7.65 (s, 1H, H-8); 13C-NMR (CDCl3) δ 25.8 (CH3), 27.2 (CH3), 64.3 (C-1'), 66.2 (C-6'), 72.8 (PhCH2), 83.7 (C-2'), 83.9 (C-3'), 112.4 (methylethylidene C), 122.7 (C-5'), 125.2 (d, J=12.6 Hz, C-5), 127.3 (Ph), 127.5 (Ph), 128.1 (Ph), 128.2 (Ph), 137.6 (Ph), 140.1 (dd, J=210 Hz, J'=4.4 Hz, C-8), 149.2 (C-4'), 151.0 (s, C-6), 153.2 (dd, J=4.7 Hz, J'=3.1 Hz, C-4), 159.1 (s, C-2).

Workup

  1. washwashed with dilute NaCl
  2. customEvaporation of the CH2Cl2
  3. customgave an oil which
  4. customwas further dried under high vacuum
  5. customto remove residual DMSO
  6. customPurification by preparative TLC (silica, 3:2 EtOAc:Hexane)

Sources & evidence

ORD record
ord-46c66ede178940f2a1faeceff6f15853
Source dataset
uspto-grants-1990_11
Patent number
US04968690

Reaction notes

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