Phosphine → 2-Diazofluorene

HRID 1803034

반응식

HRID 1803034 반응식
[N:1]([CH:4]1[C:16]2[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=2[C:10]2[C:5]1=[CH:6][CH:7]=[CH:8][CH:9]=2)=[N+:2]=[N-].P>C1(C)C=CC=CC=1>[N+:1](=[C:4]1[C:16]2[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=2[C:10]2[C:5]1=[CH:6][CH:7]=[CH:8][CH:9]=2)=[N-:2]

참가 물질

4

반응물 2

HCID 24404PhosphineHCID 43300859-azido-9H-fluorene

생성물 1

HCID 700282-Diazofluorene수율 85%

시약·촉매·용매 1

HCID 1140Toluene용매

실험 절차

To probe the scope of the reaction even further, we investigated the synthesis of semi-stabilized diazo-compounds. Treatment of 9-azido-fluorene 2j with phosphine 1e under anhydrous conditions at low temperature (toluene, 0° C.), followed by loading the red solution directly on basic alumina (Grade 5) and eluting with 10% CH2Cl2/hexanes, 9-diazo-fluorene 5j was isolated in 85% yield and excellent purity (96%). Apparently, thermal fragmentation of the putative triazenophosphonium salt, which more than likely exists in its neutral λ5-phosphorane form[16] is suppressed sufficiently for this substrate under the reaction conditions. The low temperature and low polarity of the solvent probably contribute to that greater stability. Under the standard conditions (THF/H2O), incomplete conversion of the azide 2j and contamination of the diazo-compound 5j with substantial amounts of other products, probably arising from alternative triazene decomposition and dimerization of the diazo-compound, were apparent. Finally, a vinylogous diazo-carbonyl compound 5k (96% purity) was prepared in good yield from anthraquinone-based azide 2k using the standard conditions.

후처리

  1. customthe scope of the reaction even further
  2. customthe synthesis of semi-stabilized diazo-compounds
  3. washeluting with 10% CH2Cl2/hexanes

출처 및 근거

ORD 기록
ord-f7d6f5af2f2b46f5b552941ce946307e
출처 데이터셋
uspto-grants-2013_01
특허 번호
US08350014B2

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