STRUCTURAL STUDIES OF 1,8-DISUBSTITUTED NAPHTHALENES AS PROBES FOR NUCLEOPHILE-ELECTROPHILE INTERACTIONS
STRUCTURAL STUDIES OF 1,8-DISUBSTITUTED NAPHTHALENES AS PROBES FOR NUCLEOPHILE-ELECTROPHILE INTERACTIONS
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DOI：
10.1002/hlca.19780610806
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发表时间：
1978-01-01
影响因子：
1.8
通讯作者：
DUNITZ, JD
中科院分区：
文献类型：
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作者：
SCHWEIZER, WB;PROCTER, G;DUNITZ, JD
7种1，8-二取代萘的晶体结构分析结果（2a，8-（N，N-二甲基氨基）-1-萘基甲基酮;2b，8-（N，N-二甲基氨基）萘-1-羧酸;2c，甲基8-（N，N-二甲基氨基）萘-1-甲酸酯;2d，8-甲氧基-1-萘基甲基酮; 2 e，8-甲氧基萘-1-甲酸;2f，N，N-二甲基-8-甲氧基萘1-甲酰胺; 2g，N，N-二甲基-8-羟基萘-1-甲酰胺），其中一个邻位上具有亲核中心（N（CH 3）2，OCH 3，OH），另一个邻位上具有亲电中心（羰基C）。所有七个分子都显示出特征性的畸变模式：亲电中心的环外键向外张开，亲核中心的环外键向内张开;羰基C从其三个键合原子的平面向亲核试剂移位。这种畸变模式与其他1，8-二取代萘中发现的不同，并被解释为对羰基的初期亲核加成的表达。2b的晶体结构包含了等量氨基酸和两性离子分子的有序排列。
Results of crystal structure analyses of seven 1, 8‐disubstituted naphthalenes (2a, 8‐(N,N‐dimethylamino)‐1‐naphthyl methyl ketone;2b, 8‐(N, N‐dimethylamino)naphthalene‐1‐carboxylic acid;2c, methyl 8‐(N, N‐dimethylamino)naphthalene‐1‐carboxylate;2d, 8‐methoxy‐1‐naphthyl methyl ketone;2e, 8‐methoxynaphthalene‐1‐carboxylic acid;2f,N, N‐dimethyl‐8‐methoxynaphthalene 1‐carboxamide;2g,N, N‐dimethyl‐8‐hydroxynaphthalene‐1‐carboxamide) with a nucleophilic centre (N(CH3)2, OCH3, OH) at one of theperipositions and an electrophilic centre (carbonyl C) at the other are described. All seven molecules show a characteristic distortion pattern: the exocyclic bond to the electrophilic centre is splayed outward, and the one to the nucleophilic centre is splayed inward; the carbonyl C is displaced from the plane of its three bonded atoms towards the nucleophile. This distortion pattern differs from that found in other 1,8‐disubstituted naphthalenes and is interpreted as an expression of incipient nucleophilic addition to a carbonyl group. The crystal structure of2bcontains an ordered arrangement of equal numbers of amino acid and zwitterionic molecules.