Toluene → HCID 66906291, compound

HRID 659840Notes

Reaction equation

HRID 659840 reaction equation
[OH:1][C@:2]12[C@@H:9]([CH2:10][OH:11])[O:8][C@@H:7]([N:12]3[CH:20]=[C:18]([CH3:19])[C:16](=[O:17])[NH:15][C:13]3=[O:14])[C@@:6]1([O:21][CH3:22])[O:5][CH2:4][CH2:3]2.[CH3:23][O:24][C:25]1[CH:46]=[CH:45][C:28]([C:29](Cl)([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C:30]2[CH:35]=[CH:34][C:33]([O:36][CH3:37])=[CH:32][CH:31]=2)=[CH:27][CH:26]=1.C1(C)C=CC=CC=1.C(=O)([O-])O.[Na+]>N1C=CC=CC=1.ClCCl>[CH3:37][O:36][C:33]1[CH:32]=[CH:31][C:30]([C:29]([O:11][CH2:10][C@H:9]2[O:8][C@@H:7]([N:12]3[CH:20]=[C:18]([CH3:19])[C:16](=[O:17])[NH:15][C:13]3=[O:14])[C@:6]3([O:21][CH3:22])[C@@:2]2([OH:1])[CH2:3][CH2:4][O:5]3)([C:38]2[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=2)[C:28]2[CH:45]=[CH:46][C:25]([O:24][CH3:23])=[CH:26][CH:27]=2)=[CH:35][CH:34]=1

Participants

7

Reactant 4

HCID 1140TolueneHCID 968311,1'-(Chlorophenylmethylene)bis(4-methoxybenzene)HCID 516892Sodium BicarbonateHCID 10663046HCID 10663046, compound

Product 1

HCID 66906291HCID 66906291, compoundYield 92.8%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 6344DichloromethaneSolvent

Procedure

A mixture of compound 17 (0.95 g, 3.03 mmol) and 4,4′-dimethoxytrityl chloride (1.54 g, 4.77 mmol) was dissolved in anhydrous pyridine (20 cm3) and stirred for 4 h at room temperature. The reaction mixture was evaporated to give an oily residue which was co-evaporated with toluene (2×20 cm3). Dichloromethane (50 cm3) and a saturated aqueous solution of sodium hydrogencarbonate (50 cm3) were added, the organic phase was separated and evaporated, and the residue purified by silica gel HPLC (the residue was dissolved in the minimum amount of dichloromethane containing 0.5% triethylamine (v/v) and applied to the column equilibrated by the same solvent. The column was washed (ethylacetate:petroleum ether:triethylamine; 15:84.5:0.5 (v/v/v, 1000 cm3) and the product was eluted in a gradient of methanol (C-2%) in dichloromethane containing 0.5% of triethylamine (v/v/v) to give compound 18 (1.71 g, 92.8%) as white solid material. δH (CDCl3) 7.51-7.17 (10H, m, DMT, 6-H), 6.79-6.85 (4H, m, DMT), 6.04 (1H, s, 1′-H), 4.12-3.98 (3H, m, 5-Ha, 5′-Hb, 4′-H), 3.77 (6H, s, CH3-DMT), 3.49 (3H, s, CH3—O), 3.45-3.32 (2H, m, 2″-Ha, 2″-Hb), 2.11-2.01 (1H, m, 1″-Ha), 1.94-1.87 (1H, m, 1″-Hb), 1.93 (3H, s, CH3). δC (CDCl3) 164.2 (C-4), 158.6, 144.7, 135.7, 130.1, 128.2, 127.9, 126.8, 113.2 (DMT), 150.7 (C-2), 137.7 (C-6), 109.8, 109.7 (C-5, C-2′), 86.5, 85.3, 85.0, 81.4 (DMT, C-1′, C-3′, C-4′), 69.2, 62.4 (C-5′, C-2″), 55.2 (CH3-DMT), 51.7 (CH3—O), 35.5 (C-1″), 12.7 (CH3). FAB-MS m/z 617.26 [M+H]+, 639.23 [M+Na]+ (Found: C, 66.4; H, 6.1; N, 4.2; C34H36O9N2 requires C, 66.2; H, 5.9; N, 4.5%).

Workup

  1. customThe reaction mixture was evaporated
  2. customto give an oily residue which
  3. customthe organic phase was separated
  4. customevaporated
  5. customthe residue purified by silica gel HPLC (the residue
  6. dissolutionwas dissolved in the minimum amount of dichloromethane containing 0.5% triethylamine (v/v)
  7. washThe column was washed (ethylacetate
  8. wash15:84.5:0.5 (v/v/v, 1000 cm3) and the product was eluted in a gradient of methanol (C-2%) in dichloromethane containing 0.5% of triethylamine (v/v/v)

Sources & evidence

ORD record
ord-32b17991b46e448492fb695bfc7a6d88
Source dataset
uspto-grants-2011_12
Patent number
US08080644B2

Reaction notes

Loading…