2,3-Dihydroxybenzoic Acid → HCID 21660233、化合物

HRID 75069

反応式

HRID 75069 の反応式
[OH:1][C:2]1[C:10]([OH:11])=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].[H-].[Na+].[CH3:14][O:15][C:16]1[CH:23]=[CH:22][C:19]([CH2:20]Br)=[CH:18][CH:17]=1.[OH-].[Na+].CN([CH:29]=[O:30])C>O1CCOCC1>[CH3:14][O:15][C:16]1[CH:23]=[CH:22][C:19]([CH2:20][O:1][C:2]2[C:10]([O:11][CH2:4][C:3]3[CH:7]=[CH:8][C:9]([O:30][CH3:29])=[CH:10][CH:2]=3)=[CH:9][CH:8]=[CH:7][C:3]=2[C:4]([OH:6])=[O:5])=[CH:18][CH:17]=1

参加物

7

反応物 5

HCID 192,3-Dihydroxybenzoic AcidHCID 6228DimethylformamideHCID 14798Sodium HydroxideHCID 24758Sodium hydrideHCID 1650214-Methoxybenzyl bromide

生成物 1

HCID 21660233HCID 21660233、化合物

試薬・触媒・溶媒 1

HCID 312751,4-Dioxane溶媒

実験手順

A catechol protecting group other than methyl, that is, one that could be removed concurrently with the BOC functionality while leaving the disulfide intact, was required. Thus, 2,3-dihydroxybenzoic acid (18) was converted to its trianion with NaH in DMF and treated with excess 4-methoxybenzyl bromide to make ester 19 in 62% yield. Hydrolysis of 19 with NaOH (aqueous) in dioxane produced 2,3-bis(4-methoxybenzyloxy)benzoic acid (20) in 90% recrystallized yield (Scheme 1: Synthesis of 20a. aReagents: (a) 60% NaH, 4-methoxybenzyl bromide (3.5 equivalents), DMF, 62%; (b) 2N NaOH, dioxane, 90%). Activation of an equivalent of carboxylic acid 20 with CDI and stirring with N12-(phthaloyl)thermospermine (12) in CH2Cl2 and NEt3 afforded diamine 21 in 57% yield (FIG. 6).

出典と根拠

ORDレコード
ord-2abcd06651724ea1ab6cd1f708996577
出典データセット
uspto-grants-2014_09
特許番号
US08834890B2

関連ノート

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