Pyridine → HCID 53827320, compound

HRID 1589638Notes

Reaction equation

HRID 1589638 reaction equation
C1(N=C=NC2CCCCC2)CCCCC1.[CH2:16]([O:23][C@@H:24]1[C@@H:30]([O:31][CH2:32][C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[C@H:29]([O:39][CH2:40][C:41]2[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=2)[C@@H:28]([CH2:47][O:48][CH2:49][C:50]2[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=2)[O:27][CH:25]1[OH:26])[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.[C:56]([O:62][CH2:63][C:64]([Cl:67])([Cl:66])[Cl:65])(=[O:61])[CH2:57][C:58](O)=[O:59].N1C=CC=CC=1>C(Cl)Cl.CCOCC>[C:58]([O:26][CH:25]1[O:27][C@H:28]([CH2:47][O:48][CH2:49][C:50]2[CH:51]=[CH:52][CH:53]=[CH:54][CH:55]=2)[C@@H:29]([O:39][CH2:40][C:41]2[CH:42]=[CH:43][CH:44]=[CH:45][CH:46]=2)[C@H:30]([O:31][CH2:32][C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[C@H:24]1[O:23][CH2:16][C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1)(=[O:59])[CH2:57][C:56]([O:62][CH2:63][C:64]([Cl:66])([Cl:65])[Cl:67])=[O:61]

Participants

7

Reactant 4

HCID 1049PyridineHCID 10868DicyclohexylcarbodiimideHCID 109405022,3,4,6-Tetrakis-O-(phenylmethyl)-D-glucopyranoseHCID 13591229HCID 13591229, compound

Product 1

HCID 53827320HCID 53827320, compoundYield 87.1%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Procedure

Dicyclohexylcarbodiimide (305 mg, 1.47 mmol) was added to a solution of 2,3,4,6-tetra-O-benzyl-D-glucopyranose (810 mg, 1.5 mmol), 2,2,2-trichloroethyl hydrogen malonate (330 mg, 1.4 mmol) and pyridine (196 mg, 2.48 mmol) in dry methylene chloride (6 mL). A white precipitate appeared almost immediately and a slight temperature increase was noticed. The mixture was stirred further for one hour, then diluted with ether (10 mL) and filtered. The solid was washed with ether (2×5 mL) and the filtrates were evaporated under reduced pressure in the presence of silica (2 g). Chromatography over silica gel (60-200 mesh, 40 g, elution with ether-hexanes, 1:1.5) afforded 2,3,4,6-tetra-O-benzyl-D-glucopyranosyl 2,2,2-trichloroethyl malonate 2 (929 mg, 1.22 mmol, 87%) as a viscous colorless syrup; NMR (CDCl3, 90 MHz): δ7.37+7.32 (aromatic protons), 6.43 (d, J=2 Hz, H-1, α-anomer), 5.71 (d, J=7 Hz, H-1, β-anomer), 4.92-4.42 (m, benzylic protons) with a high singlet at 4.78 (OCH2Cl3), 3.87-3.40 (m, sugar skeleton and malonyl protons); aromatic ratio, α:β=1.7 IR (CCl4): 3090, 3075, 3024, 2925, 2875, 1770 (s), 1755 (s), 1100 (s) cm-1.

Workup

  1. temperaturea slight temperature increase
  2. filtrationfiltered
  3. washThe solid was washed with ether (2×5 mL)
  4. customthe filtrates were evaporated under reduced pressure in the presence of silica (2 g)

Sources & evidence

ORD record
ord-4d7bf6731ec04770916026975d7e640a
Source dataset
uspto-grants-1986_02
Patent number
US04572907

Reaction notes

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