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United States Patent (19) 11 Patent Number: 5,198,429 König Et Al

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United States Patent (19) 11 Patent Number: 5,198,429 König Et Al USOO5198429A United States Patent (19) 11 Patent Number: 5,198,429 König et al. (45) Date of Patent: Mar. 30, 1993 54 SUBSTITUTED CYCLODEXTRINS AND cally Modified Cyclodextrins", pp. 1417, 1427-1433, PROCESS FOR CHROMATOGRAPHC 1472, see page 1431. SEPARATION OF CHRAL ORGANIC Starch/Starke, vol. 39, No. 10, Oct. 1987, VCH Ver COMPOUNDS lagsgesellschaft mbH (Weinheim, DE), J. Szejtli: "Ap plication of Cyclodextrins in the Chromatography', pp. 75) Inventors: Wilfried König, Pinneberg; Gerhard 357-362, see page 358. Wenz, Mainz; Sabine Lutz, Hamburg; Chemical Abstracts, vol. 109, No. 15, Oct. 10, 1988 Eva von der Bey, Mainz, all of Fed. (Columbus, Ohio, US), W. A. Koenig et al.: "Modified Rep. of Germany cyclodextrin a New Highly Enantioselective Stationary 73) Assignee: Macherey-Nagel & Co., Phase for Gas Chromatography', p. 331, Abstract No. Duren-Rolsdorf, Fed. Rep. of 125206x of Angew. Chem. 1988, 100(7), 989-90. Germany Primary Examiner-Ronald W. Griffin 21) Appl. No.: 585,117 57 ABSTRACT (22) PCT Filed: Mar. 25, 1989 Substituted cyclodextrins of the general formula (86 PCT No.: PCT/EP89/00332 S 371 Date: Dec. 3, 1990 S 102(e) Date: Dec. 3, 1990 87 PCT Pub. No.: WO89/09235 PCT Pub. Date: Oct. 5, 1989 30 Foreign Application Priority Data Mar. 30, 1988 DE Fed. Rep. of Germany ....... 38,0737 51 Int. Cl. ....................... C08B 37/16; CO7B 63/00 in which 52 U.S. C. ...................................... 514/58; 536/103; R2 and R6 mean straight-chain or branched alkyl or 435/280,562/401; 210/632; 210/634; 210/635; alkenyl groups with 1 to 8 carbon atoms or cycloal 210/636 kyl groups with 5 to 8 carbon atoms which can be 58) Field of Search .......................... 536/103; 514/58; the same or different, and 435/280; 562/401; 210/632, 634, 635, 636 R3 represents a straight-chain or branched alkyl or (56) References Cited alkenyl group, which can be the same or different to the residues R2 and R6, with 1 to 8 carbon atoms U.S. PATENT DOCUMENTS or a cycloalkyl group with 5 to 8 carbon atoms, or 4,582,900 4/1986 Brandt et al. ....................... 536/103 an acyl group with an optionally substituted, satu 4,590,167 5/1986 Gunther et al. .................... 436/162 rated or olefinically unsaturated aliphatic or cyclo 5,078,886 l/1992 Hsu ...................................... 562/401 aliphatic or with an aromatic hydrocarbon residue with 1 to 8 carbon atoms, and FOREIGN PATENT DOCUMENTS n=6 or 7, 0.146841 7/1985 European Pat. Off. a process for their production, and a process for the separation of chiral organic compounds by chro OTHER PUBLICATIONS matographic separation processes in which the Chemical Abstracts, vol. 109, Oct. 10, 1988 Abstract substituted cyclodextrins are used as stationary 109: 125206X. phase. Tetrahedron, vol.39, No. 9, 1983 Pergamon Press Ltd. (Oxford, GB), A. P. Croft et al.: "Synthesis of Chemi 15 Clains, 6 Drawing Sheets U.S. Patent Mar. 30, 1993 Sheet 1 of 6 5,198,429 - - - 1,2-BUTANEDIOL ,2-PENTANEDIOL 1,2-HEXANEDIOL 1,2-TR.CYCLOHEXANEDIOL g 1,2-HEPTANEDIOL 1,2-TRCYCLOHEPTANEDIOL ,2-OCTANEDIOL S. PHENYGLYCOL 1,2-NONANEDIOL - U.S. Patent Mar. 30, 1993 Sheet 2 of 6 5,198,429 22 XC-3 CH-O CH3 CH2-O-COCF3 RS IO - 5MIN O FG.2 COOCH3 H-C-O-COCF3 F3 Co C-O-CH COOCH3 -l 5MIN s- O U.S. Patent Mar. 30, 1993 Sheet 3 of 6 5,198,429 IO -- 5 MIN O FG4 ( )-CH-CH2Cd co CF3 (C-GH-CH2BrO Rs co CFs U.S. Patent Mar. 30, 1993 Sheet 5 of 6 . 5,198,429 HC-CH-CH2COOCH3 NH CH3 bo Ha-GH-COOCH3 efs HN as to H-CH2CH W. fe O -- - 5 MN O FIG.8 fisco-O-CH2CH-CH C-CH2CH-CH O -CH3 NH -: s O CH3 CO ' '. U.S. Patent Mar. 30, 1993 Sheet 6 of 6 5,198,429 5, 198,429 1 2 R2 and R6 mean straight-chain or branched alkyl or SUBSTITUTED CYCLODEXTRENS AND PROCESS alkenyl groups with 1 to 8 carbon atoms or cyclo FOR CHROMATOGRAPHIC SEPARATION OF alkyl groups with 5 to 8 carbon atoms which can be CHRAL, ORGANIC COMPOUNDS the same or different, and 5 R3 represents a straight-chain or branched alkyl or The present invention relates to substituted cyclodex alkenyl group, which can be the same or different trins, to a process for their production, and to a process to the residues R2 and R6, with 1 to 8 carbon atoms for the separation of chiral organic compounds by chro or a cycloalkyl group with 5 to 8 carbon atoms, or matographic separation processes, particularly gas an acyl group with an optionally substituted, satu chromatography, using the substituted cyclodextrins as 10 rated or olefinically unsaturated aliphatic or cyclo stationary phase. aliphatic or with an aromatic hydrocarbon residue Substituted cyclodextrins are known, for example, with 1 to 8 carbon atoms, and from DE-OS 37 10569, which is no prior publication, n=6 or 7, which describes the production of ultrathin films from whereby compounds with these cyclodextrin compounds or an inclusion com 15 R2 = R3 =R6= methyl, n=6 or 7 pound on the basis of the cyclodextrin compounds. R2 = R3 =R6=ethyl, n=7 These ultrathin films can be used, for example, as pro R2 =R6=allyl, R3 = methyl, n = 7 tective film for compounds which are sensitive to light R2s=R6=prop-1-enyl, R3=methyl, n=7 and oxygen, or as carrier in chromatography. R2=R6= methyl, R3 =n-butyl, n = 7 Triethyl-g-cyclodextrin is described in Journal of R2 =R6=methyl, R3=benzoyl, n=7 and Pharmaceutical Sciences (1987, 660). An alkyl-acyl R2 = R3 = alkyl or acyl, R6=C>4-alkyl compound (R2=R6= methyl, R3 =benzoyl, n=7, of the are excluded. following general formula) is described in J. Chem. Soc. A further solution. of the problem underlying the Perkin Trans. (1987), 1323. present invention is the provision of a process for the Single cyclodextrin derivatives were also mentioned 25 chromatographic separation of chiral compounds, par as possible stationary phases, however, realization of ticularly of enantiomers. this possibility was limited due to the properties of the In this connection, compounds with known substances, this is described, for example, in R2 = R3 =R6=methyl, n=6 or 7 ACS Symposium Series, 1987, vol. 342, pages 200 to R2=R6=allyl, R3 = methyl, n = 7 217, and in Starch/Stärke, 1987, pages 357 to 358. 30 R2=R6=prop-1-enyl, R3 = methyl, n = 7 Up to now, the separation of enantiomeric, low R2=R6= methyl, R3 =n-butyl, n=7 molecular chiral compounds by gas-chromatography are excluded. has been conducted by using chiral low-molecular or The substituted cyclodextrins according to the pres polymeric separation phases with amide or diamide: ent invention permit a separation of enantiomers which Structure. 35 is mainly caused by inclusion effects at the macrocyclic Such a separation is almost exclusively limited to chiral cyclodextrins, and which-due to the separation enantioners with amide, carbamate, oxime, or hydroxyl mechanism which, compared to the separation phases groups. In this connection, intermolecular hydrogen according to the prior art, is completely different-can bridge bonds are built so that diastereomeric associates be employed even for those enantiomers not being able between chiral separation phase and chiral substrates to form hydrogen bridges and therefore could not be are formed. separated on the chiral separating phases used until In order to improve the separation results, the enan OW. tiomers to be separated were mostly converted into For the use as separation phases in gas-chromatogra derivatives with amide or carbamoyl functions. phy the compounds according to the present invention Due to the fact that the formed derivatives are diffi 45 on the one hand have the advantage of having a very cultly volatile, high operating temperatures of the chro high temperature stability of more than 200 C., on the matographic columns are required and thus leads to other hand, the separation mechanism which-com uneven courses of the base-lines of the chromatrograms pared to the separation phases known until now-is and to reduced separation efficiency due to cross diffu different in most cases permits the conversion into very SO. readily volatile derivatives, such as trifluoroacetylated It was the object of the present invention to provide compounds, which in case of correspondingly low tem improved stationary phases for the separation of chiral peratures are eluted from the column. compounds, particularly of enantiomers, and a process Those compounds in which the residues R2, R and for the separation of chiral compounds. R6 are alkyl or alkenyl groups with 3 to 6 carbon atoms 55 and/or R3 means the acetyl group are particularly pre Surprisingly,it was found that this object is achieved ferred from the series of compounds according to the by substituted cyclodextrins of the general formula: present invention of the O-peralkylated a- and 3 cyclodextrin derivatives and those in which the hy droxyl groups of the cyclodextrin are alkylated in the 2 OR6 and 6-position of the glucose units and the hydroxyl group is acylated in 3-position. O Particularly preferred are the substituted cyclodex OR3 trins consisting of 6 or 7 glucose rings and having as substituents R2, R3 and R6 the n-pentyl-group or as 65 substituent R3 the acetyl group and as R2 and Rn-pen OR2 tyl groups. The products according to the present invention are in which: produced in that at first a- or g-cyclodextrin is dis 5, 198,429 3 4.
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