Formation of racemic compound crystals by mixing of two enantiomeric crystals in the solid state. Liquid transport of molecules from crystal to crystal
Formation of racemic compound crystals by mixing of two enantiomeric crystals in the solid state. Liquid transport of molecules from crystal to crystal
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通过固态混合两种对映体晶体形成外消旋化合物晶体。
DOI：
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发表时间：
1997
期刊：
影响因子：
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通讯作者：
K. Hirotsu
中科院分区：
文献类型：
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作者：
F. Toda;Koichi Tanaka;H. Miyamoto;H. Koshima;I. Miyahara;K. Hirotsu
粉状(-)-和(+)-对映体的混合
固态的晶体形成外消旋化合物的晶体。这
在外消旋晶体形成之后，用红外光谱测量了一个
1：1的(-)和(+)对映体混合物
作为Nujol毛拉的水晶。随着外消旋晶体的形成，
对映体的羟基吸收逐渐消失，产生新的羟基
由于外消旋化合物而产生的吸收出现了。外消旋的形成
从对映体晶体中提取的晶体已被用于各种不同类型的
手性化合物：2，2‘-二羟基-1，1’-联萘(1)及其
10，10‘-二羟基-9，9’-联苯基衍生物(4)，
2，2‘-二羟基-4，4’，6，6‘-四甲基联苯(5)和
它的衍生产品，
4，4′-dihydroxy-2，2′，3，3′，6，6′-hexamethylbiphenyl
(8)，1，6-di(o-chlorophenyl)-1，6-diphenylhexa-2，4-diyne-1，6-diol
(11)及其衍生产品，
Trans-4，5-bis[hydroxy(diphenyl)methyl]-2，2-dimethyl-1，3-
二氧杂环戊烷(17)及其衍生物酒石酸(20)二甲基二甲基
酒石酸(21)、苹果酸(22)、扁桃酸(23)和去甲麻黄碱
(24)。这些分子运动和混合迅速发生在
存在液体如液体石蜡(Nujol)、种子油如
橄榄油、椰子油、菜籽油和大豆油、人造油等
硅油和水，尽管同样的运动也发生在
液体的缺失。例如，将粉末状混合物
室温下的(-)-1(1a)和(+)-1(1b)
48h得到外消旋晶体(1c)。然而，分子聚集
有时发生在溶液中，而不是在固体中。例如,
(-)-16(16a)和(+)-16的再结晶
(16b)从溶剂中得到16c的外消旋晶体，尽管混合
这两种成分作为粉末在液体中不能给出
16C。为了确定分子运动的机制
研究了旋光活性和X射线晶体结构。
外消旋化合物及其光学活性的分子运动
从晶体到外消旋晶体的研究。
Mixing of powdered (-)- and (+)-enantiomer
crystals in the solid state gives crystals of the racemic compound. This
racemic crystal formation was followed by IR spectral measurement of a
1∶1 mixture of (-)- and (+)-enantiomer
crystals as a Nujol mull. As the formation of racemic crystals proceeds,
the OH absorptions of the enantiomer disappear gradually and new OH
absorptions due to the racemic compound appear. The formation of racemic
crystals from enantiomer crystals has been studied for various kinds of
chiral compounds: 2,2′-dihydroxy-1,1′-binaphthyl (1) and its
derivatives, 10,10′-dihydroxy-9,9′-biphenanthryl (4),
2,2′-dihydroxy-4,4′,6,6′-tetramethylbiphenyl (5) and
its derivatives,
4,4′-dihydroxy-2,2′,3,3′,6,6′-hexamethylbiphenyl
(8), 1,6-di(o-chlorophenyl)-1,6-diphenylhexa-2,4-diyne-1,6-diol
(11) and its derivatives,
trans-4,5-bis[hydroxy(diphenyl)methyl]-2,2-dimethyl-1,3-
dioxacyclopentane (17) and its derivatives, tartaric acid (20) dimethyl
tartrate (21), malic acid (22), mandelic acid (23), and norephedrine
(24). These molecular movements and blending occur rapidly in the
presence of liquids such as liquid paraffin (Nujol), seed oils such as
olive, coconut, rapeseed and soybean oil, artificial oil such as
silicone oil and water, although the same movement also occurs in the
absence of the liquid. For example, keeping a mixture of powdered
(-)-1 (1a) and (+)-1 (1b) at room temperature
for 48 h gives racemic crystals (1c). However, molecular aggregation
sometimes occurs in solution but not in the solid state. For example,
recrystallization of (-)-16 (16a) and (+)-16
(16b) from solvent gives racemic crystals of 16c, although mixing of
these two components as powders in the presence of liquid does not give
16c. In order to determine the mechanism of the molecular movement in
the solid state, X-ray crystal structures of optically active and
racemic compounds and also the molecular movements from optically active
crystal to racemic crystal have been studied.