反応式
[CH:1]1[C:18]2=[C:19]3[C:8]([C:9]4[C:20]5[C:13](=[CH:14][CH:15]=[CH:16][C:17]2=5)[CH:12]=[CH:11][CH:10]=4)=[CH:7][CH:6]=[CH:5][C:4]3=[CH:3][CH:2]=1.[CH:21](=[O:28])C1C=CC=CC=1.C(C1C2=C3C(C4C5C(=CC=CC2=5)C=CC=4)=CC=CC3=CC=1)#C.BrC1C=C(C=C(Br)C=1)C=O>[Cu]I>[C:16]1([CH:21]=[O:28])[C:17]2=[C:20]3[C:9]([C:8]4[C:19]5[C:4](=[CH:3][CH:2]=[CH:1][C:18]2=5)[CH:5]=[CH:6][CH:7]=4)=[CH:10][CH:11]=[CH:12][C:13]3=[CH:14][CH:15]=1参加物
実験手順
The first route employs bromoperylene PMI-12 and 3,5-diethynylbenzaldehyde (16) as the starting materials. The reaction under copper-free conditions, similar to those employed for the Sonogashira coupling of two porphyrins (Wagner, R. W. et al., Chem. Mater. 1999, 11, 2974-2983) afforded only a small amount (8.9%) of perylene-aldehyde 18 (entry 1, Table 1). The same reaction in the presence of CuI failed to produce perylene-aldehyde 18 (entry 2). We next examined the reaction with the reverse ethyne/bromo substitution pattern on the perylene and benzaldehyde. The reaction of ethynylperylene PMI-12′ and 3,5-dibromobenzaldehyde (14) (2:1 ratio) with CuI cocatalysis afforded 18 in 31% yield (entry 3). A further increase in the amount of perylene PMI-12′ (2.4:1 ratio) gave 18 in 66% yield (entry 4). Repetition of this reaction furnished 18 in 83% yield. While of limited scope, the survey of the Sonogashira reaction of perylene PMI-12 or PMI-12′ with aldehyde 14 or 16 revealed important reactivity differences between a bromoperylene and an ethynylperylene. Unlike perylene-aldehyde 15, compound 18 proved to be very soluble, thereby enabling subsequent porphyrin-forming reactions.
出典と根拠
- ORDレコード
- ord-4a1d6b126265482db2938c418aa76f83
- 出典データセット
- uspto-grants-2005_07
- 特許番号
- US06916982B2
関連ノート
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