반응식
N([PH3+])=NN.[PH5].N([CH:9]1[C:21]2[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=2[C:15]2[C:10]1=[CH:11][CH:12]=[CH:13][CH:14]=2)=[N+]=[N-].[N+](=C1C2C=CC=CC=2C2C1=CC=CC=2)=[N-].N=NN.C1[CH2:44][O:43]CC1.[OH2:45]>>[CH:17]1[C:16]2[C:44](=[O:43])[C:15]3[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=3)[C:9](=[O:45])[C:21]=2[CH:20]=[CH:19][CH:18]=1참가 물질
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
- customis suppressed sufficiently for this substrate under the reaction conditions
출처 및 근거
- ORD 기록
- ord-4ac8b62f20eb4fa385441a71db4c611b
- 출처 데이터셋
- uspto-grants-2014_10
- 특허 번호
- US08871916B2
연결된 노트
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