Effect of Crystallization Conditions on Polymorphic Diversity of Malic Acid RS-Racemate  

作　　者：Isakov A I Kotelnikova E N Kryuchkova L Yu Lorenz H 

机构地区：[1]St.Petersburg State University,St.Petersburg 199034,Russia [2]Max Planck Institute for Dynamics of Complex Technical Systems,Magdeburg 39106,Germany

出　　处：《Transactions of Tianjin University》2013年第2期86-91,共6页天津大学学报（英文版）

基　　金：Supported by the Russian Fund for Basic Research (RFBR) under Grant No. 10-05-00891 and 12-05-00876

摘　　要：Enantiomers （R （＋） and S（-））, RS-racemate mixture of enantiomers） of malic acid C4H605 have been （double compound） and （R ＋ S） -conglomerate （mechanical investigated by means of X-ray diffractometry and high tern- perature X-ray diffraction method. The RS-racemate was found to be able to form three polymorphic modifications, which we denominated as M1 （monoclinic, space group P21/c）, M2 （monoclinic, space group Cc）, and Tc （triclinic, space group P-l ）, the latter modification having been unknown before. Modification Tc was also described, and its X- ray diffraction characteristics, including interplanar spacings d, hkl indices, unit cell parameters, were defined. In addi- tion, X-ray diffraction characteristics for both reported earlier M1 and M2 monoclinic polymorphic modifications were measured with higher accuracy. The ability of RS-racemate to form one of the above three modifications （MI, M2, and Tc） or their mixtures containing various proportions and combinations of the components （M1 ＋ M2, M1 ＋ Tc, or M2 ＋ Tc） was found to depend on the type of crystallization medium （a melt, aqueous medium, ethanol or acetone solu- tion）, crystallization rate （from 2--3 minutes to 4 months）, and crystallization temperature. Heating S-enantiomer and M1 RS-racemate up to their respective melting points （100 ℃ and 124 ℃, correspondingly） only made them undergo thermal deformations, while heating （R ＋ S） -conglomerate in the temperature range of 96--110 ℃ resulted in its homogenization to form M2 RS-racemate, which, near the melting point （118 ℃）, namely, in the range of 112-116 ℃, was transformed into MI RS-racemate. Keywords： polvmorDhism; racemic, chiralEnantiomers (R(+) and S(-)),RS-racemate (double compound) and (R+S)-conglomerate (mechanical mixture of enantiomers) of malic acid C 4 H 6 O 5 have been investigated by means of X-ray diffractometry and high temperature X-ray diffraction method.The RS-racemate was found to be able to form three polymorphic modifications,which we denominated as M1 (monoclinic,space group P2 1 /c),M2 (monoclinic,space group Cc),and Tc (triclinic,space group P-1),the latter modification having been unknown before.Modification Tc was also described,and its Xray diffraction characteristics,including interplanar spacings d,hkl indices,unit cell parameters,were defined.In addition,X-ray diffraction characteristics for both reported earlier M1 and M2 monoclinic polymorphic modifications were measured with higher accuracy.The ability of RS-racemate to form one of the above three modifications (M1,M2,and Tc) or their mixtures containing various proportions and combinations of the components (M1+M2,M1+Tc,or M2 +Tc) was found to depend on the type of crystallization medium (a melt,aqueous medium,ethanol or acetone solution),crystallization rate (from 2-3 minutes to 4 months),and crystallization temperature.Heating S-enantiomer and M1 RS-racemate up to their respective melting points (100 ℃ and 124 ℃,correspondingly) only made them undergo thermal deformations,while heating (R+S)-conglomerate in the temperature range of 96-110 ℃ resulted in its homogenization to form M2 RS-racemate,which,near the melting point (118 ℃),namely,in the range of 112-116 ℃,was transformed into M1 RS-racemate.

关 键 词：POLYMORPHISM RACEMIC CHIRAL 

分 类 号：O629[理学—有机化学]