Toluene → HCID 66893893, compound

HRID 1810810Notes

Reaction equation

HRID 1810810 reaction equation
[CH3:1][NH:2][C:3]1[N:4]=[C:5]([O:21][C:22](=[O:36])[N:23]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C:6]2[N:7]=[CH:8][N:9]([C:19]=2[N:20]=1)[C@@H:10]1[O:18][C@H:15]([CH2:16][OH:17])[C@@H:13]([OH:14])[C@H:11]1[OH:12].[CH3:37][O:38][C:39]1[CH:60]=[CH:59][C:42]([C:43](Cl)([C:52]2[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=2)[C:44]2[CH:49]=[CH:48][C:47]([O:50][CH3:51])=[CH:46][CH:45]=2)=[CH:41][CH:40]=1.C1(C)C=CC=CC=1>CN(C)C1C=CN=CC=1.N1C=CC=CC=1>[CH3:51][O:50][C:47]1[CH:46]=[CH:45][C:44]([C:43]([O:17][CH2:16][C@H:15]2[O:18][C@@H:10]([N:9]3[C:19]4[N:20]=[C:3]([NH:2][CH3:1])[N:4]=[C:5]([O:21][C:22](=[O:36])[N:23]([C:24]5[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=5)[C:30]5[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=5)[C:6]=4[N:7]=[CH:8]3)[C@H:11]([OH:12])[C@@H:13]2[OH:14])([C:52]2[CH:53]=[CH:54][CH:55]=[CH:56][CH:57]=2)[C:42]2[CH:59]=[CH:60][C:39]([O:38][CH3:37])=[CH:40][CH:41]=2)=[CH:49][CH:48]=1

Participants

6

Reactant 3

HCID 1140TolueneHCID 968311,1'-(Chlorophenylmethylene)bis(4-methoxybenzene)HCID 66894509HCID 66894509, compound2×

Product 1

HCID 66893893HCID 66893893, compoundYield 67.1%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1049PyridineSolvent

Procedure

Compound 5 (0.51 g, 1.05 mmol, 1.0 eq) and 4,4′-dimethoxytritylchloride (0.39 g, 1.14 mmol, 1.09 eq) were azeotroped three times with toluene for ˜15 h. To the dried compound 5, anhydrous pyridine (5 mL) was added. The mixture was stirred at room temperature under Ar atmosphere for 4 h. 4-Dimethylaminopyridine (0.09 g, 0.7 mmol, 0.7 eq) was subsequently added and stirring was continued for 17 h. The reaction was quenched with methanol (1 mL) and evaporated to dryness. The crude residue was dissolved in 50 mL of dichloromethane and washed with 5% sodium bicarbonate followed by saturated sodium chloride. The organic layer was dried over sodium sulfate and filtered. The product was then purified via silica gel chromatography using a solvent mixture of 90% dichloromethane, 9% methanol, 1% triethylamine to give 11 as a light yellow crystalline solid (0.56 g, 67%). TLC (CH2Cl2:MeOH, 9:1 v/v): Rf=0.4; 1H NMR (CD3OD, 400 MHz) 2.71 (br.s, 1H), 2.98-3.03 (q, 1H), 3.21 (d, J=3.2 Hz, 3H), 3.25-3.27 (m, 1H), 3.29-3.32 (m, 1H), 3.60 (d, J=4.8 Hz, 6H), 3.66 (m, 1H), 4.07-4.10 (m, 1H), 4.45 (m, 1H), 4.83 (m, 1H), 5.87 (d, J=4.8 Hz, 1H), 6.64-6.69 (m, 5H), 7.05-7.38 (m, 18H), 8.0 (s, 1H); 13C NMR ((CD3)2SO, 500 MHz) 28.8, 55.6, 72.2, 74.9, 82.3, 85.3, 87.7, 113.8, 114.0, 126.3, 127.8, 128.5, 128.7, 129.1, 129.2, 129.3, 129.9, 130.2, 130.4, 131.2, 141.2, 149.2, 159.9; ESI-MS (ES+) calculated for C45H42N6O8 794.3064, found 795.7 (M+H+), 303.4 ([(MeO)2Tr]+).

Workup

  1. stirringstirring
  2. waitwas continued for 17 h
  3. customThe reaction was quenched with methanol (1 mL)
  4. customevaporated to dryness
  5. dissolutionThe crude residue was dissolved in 50 mL of dichloromethane
  6. washwashed with 5% sodium bicarbonate
  7. dry with materialThe organic layer was dried over sodium sulfate
  8. filtrationfiltered
  9. customThe product was then purified via silica gel chromatography
  10. additiona solvent mixture of 90% dichloromethane, 9% methanol, 1% triethylamine

Sources & evidence

ORD record
ord-e8c676a7f3244ccdab9ccbad8a7b0f38
Source dataset
uspto-grants-2013_01
Patent number
US08362203B2

Reaction notes

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