Chiral separation media
This is a division of application Ser. No. 07/564,628 filed Aug. 8, 1990, now U.S. Pat. No. 5,064,944, which, in turn, is a continuation-in-part of application Ser. No. 406,141 filed Sept. 12, 1989 and now U.S. Pat. No. 4,948,395 issued Aug. 14, 1990. 
    
    
     This invention relates to a composition used for separation of optical isomers or chiral compounds, as well as other isomeric and non-isomeric compounds, by means of gas chromatography and, more particularly, to the separation of enantiomers by capillary gas chromatography. The composition used is a media of an ether derivative of a cyclodextrin such as a permethylated hydroxy or a dialkyl trifluoroacetyl ether of cyclodextrin. 
     The configuration of a chiral molecule is generally what determines its biological and pharmaceutical activity and effectiveness. One of the enantiomers of the chiral molecule may be active and the other may be inactive or even toxic. It is therefore essential to be able to separate the different enantiomers from each other to obtain an isolated enantiomer in pure form. The isolated enantiomers are used in the pharmaceutical, pesticide and/or herbicide industries, among others. 
     A conventional way to separate enantiomers is by gas chromatography using a chiral stationary phase. Chiral stationary phases can rapidly and reversibly form diastereomeric association complexes with chiral analytes. Successful chiral stationary phases for wall-coated capillary tubes should have some characteristic properties. They need to be highly viscous even at elevated temperatures and have the proper surface tension to wet the capillary wall completely. They should be able to form rapid and reversible diastereomeric associate complexes with the chiral analytes via various interactions such as hydrogen bonding, dispersion, dipole-dipole and steric interactions to give reasonable chiral selectivity. Other desirable properties include high temperature stability, no racemization at elevated temperatures and low levels of bleeding. 
     Most of the early work on chiral stationary phases for gas chromatography used amino acids, peptides, and various derivatives thereof. Some efforts have been made to use other naturally occurring chiral molecules as chiral stationary phases such as tartaric acid, malic acid, mandelic acid and chrysanthemic acid. Despite a large amount of work in this area, the only resulting widely available and commercially viable chiral stationary phase for gas chromatography has been Chirasil-Val from Macherey-Nagel of the Federal Republic of Germany which consists of a siloxane copolymer to which L-valine-tert-butylamide was coupled. 
     There are a number of limitations to these early amino acid based gas chromatography chiral stationary phases. First, they do not seem to be widely applicable. Most of the reported separations were of racemic amino acid derivatives. Just as significant was the fact that, using these early chiral separation phases, the high column temperature needed for gas chromatography often results in racemization, decomposition and bleeding of the chiral stationary phase. Even the moderately successful Chirasil-Val is not recommended to be used at temperatures much above 200° C. Also, the enantioselectivity of the chiral stationary phase decreases significantly at the higher temperatures needed for gas chromatography. 
     Previously there have been a number of efforts to use alpha- and beta-cyclodextrin as gas chromatography stationary phases. It was apparent from the early gas chromatography and more recent liquid chromatography work that cyclodextrins had potential as gas chromatographic stationary phases. Unfortunately, the cyclodextrin gas chromatography stationary phases were not as successful as the liquid chromatography bonded stationary phases. Although interesting selectivities, mainly for achiral solutes, were obtained, the efficiency and reproducibility were less than desirable. Cyclodextrins are crystalline solids and had to be dissolved or suspended in another solvent prior to coating the separation column. The fact that native cyclodextrins and their simple derivatives (dimethyl, acetyl, etc.) are crystalline solids with high melting or decomposition points, makes them difficult to use directly as gas chromatography stationary phase coatings. Recently, there have been reports on derivatized cyclodextrins that are liquids or lower melting point amorphous solids and therefore can be used directly as stationary phase coatings. All of these previous compounds are lipophilic derivatives of cyclodextrin (such as perpentyl-beta-cyclodextrin). 
     Cyclodextrins (also called &#34;Schardinger dextrins&#34;) are known to be cyclic oligosaccharides composed of glucose residues bonded together by alpha 1,4 bonds. The six, seven and eight membered rings are called alpha-, beta-, and gamma-cyclodextrin, respectively. The cyclodextrins have different chemical and physical properties from the linear oligosaccharides derived from starch in that they are non-reducing dextrins and the ring structure is widely used as a host for the inclusion of various compounds, usually organic compounds for the food, pharmaceutical, and chemical fields. 
     As is also well-known, cyclodextrins are produced from starch of any selected plant variety such as corn, potato, waxy maize and the like which may be modified, or unmodified starch derived from cereal or tuber origin and the amylose or amylopectin fractions thereof. The selected starch in aqueous slurry at selected concentrations up to about 35% by weight solids is usually liquefied as by gelatinization or treatment with a liquefying enzyme such as bacterial alpha-amylase enzyme and then subjected to treatment with a transglycosylase (CGT) enzyme to form the cyclodextrins. 
     The amount of the individual alpha-, beta- and gamma-cyclodextrins produced by treating the starch with the CGT enzyme will vary depending on the selected starch, selected CGT enzyme and processing conditions. The parameters to select for the CGT enzyme conversion for the desired result in the amount of each individual cyclodextrin to be produced is conventional and well-described in the literature. 
     Conventionally, the DE of the liquefied starch is maintained below about 20 DE, the starch solids concentration is below about 35% by weight, the pH for conversion may be about 4.5 to 8.5 at a selected temperature from ambient up to about 75° C. for a selected period of time, typically from about 10 hours up to seven days and more. The amount of CGT enzyme used for conversion is conventional and well-known in the art. 
     It has now been discovered that ether derivatives of cyclodextrin such as permethylated hydroxy ethers of cyclodextrin and dialkyl trifluoroacetyl ethers of cyclodextrin can be used to separate a wide variety of optical isomers. The optical isomers resolved include chiral alcohols, diols, polyols, amines, amino alcohols, halohydrocarbons, ketones, lactones, alpha-halocarboxylic acid esters, carbohydrates, epoxides, glycidyl analogues, haloephihydrins, nicotine compounds, pyrans, furans, bicyclic and heterocyclic compounds and other miscellaneous compounds. 
     The permethylated hydroxy ether of cyclodextrin is hydrophilic and relatively polar compared to previous cyclodextrin derivatives used as chiral stationary phases. The dialkyl trifluoroacetyl derivative is of intermediate polarity. Both of these ether derivatives of cyclodextrin have better coating properties on fused silica capillaries than the hydrophobic cyclodextrin derivatives. The more hydrophilic permethylated hydroxy ether of cyclodextrin and the dialkyl trifluoroacetyl derivatives have different selectivities for the enantiomers as compared to the hydrophobic cyclodextrin derivatives. Also, they can be used at higher temperatures than Chirasil-Val without racemization. 
     With respect to the ether derivative of cyclodextrin which is a permethylated hydroxy cyclodextrin, the degree of substitution (DS) of the hydroxy ether groups for the hydroxyl groups on the underivatized cyclodextrin molecule is from about 10% to about 75% of the available hydroxyl groups on the cyclodextrin. For example, for alpha-cyclodextrin the DS for the hydroxy ether groups is about 2 to about 12; for beta-cyclodextrin, about 2 to about 14; and for gamma-cyclodextrin, about 2 to about 16. More preferably, the DS is about 25% to about 60% of the available sites and more preferred is about 40%. It is important that the degree of substitution of the cyclodextrin hydroxy groups by the ether side chains be random and non-uniform. 
     The DS of the methyl groups for the remaining hydroxyl groups on the cyclodextrin and the hydroxyl groups on the ether side chains of the cyclodextrin is greater than about 90% and more preferably above about 95%. Ideally, all of the available hydroxyl sites on the hydroxy ether of cyclodextrin are methylated; although this is sometimes difficult to achieve. 
     The permethylated hydroxy ether of cyclodextrin is made in a conventional manner starting from either individual cyclodextrin or mixtures of the alpha-, beta- and/or gamma-cyclodextrins. However, it is preferred to use only a single cyclodextrin, i.e. either alpha-, beta-, or gamma-cyclodextrin. The separation and/or purification of the alpha-, beta-, and gamma-cyclodextrin may be done before, after, or at any stage of the derivatization process. The procedure for making the hydroxy ether of cyclodextrin and the subsequent step of methylating are accomplished in a conventional manner. The order of reaction for forming the permethylated hydroxy ether cyclodextrin derivative is first to make the hydroxy ether and then to methylate it. 
     In order to etherify the underivatized cyclodextrin, the cyclodextrin is suitably reacted with an epoxide. Suitable epoxides include ethylene oxide, propylene oxide, butylene oxide, amylene oxide, glycidol (hydroxypropylene oxide), butadiene oxide, glycidyl methyl ether, glycidyl isopropyl ether, alkyl glycidyl ether, styrene oxide, and t-butyl glycidyl ether. Preferably, the epoxide is selected from the group consisting of propylene oxide, glycidyl methyl ether, glycidyl isopropyl ether, alkyl glycidyl ether, t-butyl glycidyl ether and styrene oxide. Good results have been obtained with an epoxide selected from the group consisting of propylene oxide, glycidyl methyl ether and glycidyl isopropyl ether. 
     As is known, the reaction of cyclodextrin with the above noted epoxides produces an ether of cyclodextrin with two hydroxy groups on adjacent carbon atoms on the side chains. Such hydroxy ethers of cyclodextrin are sometimes referred to as dihydroxyalkyl ethers of cyclodextrin. 
     The preferred permethylated ether derivatives of cyclodextrin for use in the present invention include hydroxy propylated cyclodextrin, hydroxy propylated methyl ether cyclodextrin, hydroxy propylated isopropyl ether cyclodextrin, hydroxy propylated vinyl ether cyclodextrin, hydroxy propylated t-butyl ether cyclodextrin, and hydroxy ethylated phenyl cyclodextrin. Good results have been obtained with hydroxy propylated cyclodextrin, hydroxy propylated methyl ether cyclodextrin and hydroxy propylated isopropyl ether cyclodextrin. 
     With respect to the ether derivative of cyclodextrin which is a dialkyl trifluoroacetyl cyclodextrin, the degree of substitution (DS) of the alkyl groups for the hydrogens of the hydroxyl groups on the underivatized cyclodextrin molecule to form the etherified derivative is from about 20% to about 80% of the available hydrogens on the cyclodextrin. For example, for alpha-cyclodextrin the DS for the alkyl groups is about 1 to about 15; for beta-cyclodextrin, about 1 to about 16; and for gamma-cyclodextrin, about 1 to about 18. More preferably, the DS is about 40% to about 70% of the available sites and more preferred is about 65%. Generally, the alkyl groups will substitute for the hydrogens on the 2 and 6 carbons. It is important that the degree of substitution of the cyclodextrin hydroxy groups by the ether side chains be random and non-uniform. 
     The DS of the trifluoroacetyl group for the hydrogen of the remaining available hydroxyl group on the cyclodextrin is greater than about 90% and more preferably above about 95%. 
     The dialkyl trifluoroacetyl ether of cyclodextrin is made in a conventional manner starting from either individual cyclodextrin or mixtures of the alpha-, beta- and/or gamma-cyclodextrins. However, it is preferred to use only a single cyclodextrin, i.e. either alpha-, beta-, or gamma-cyclodextrin. The separation and/or purification of the alpha-, beta-, and gamma-cyclodextrin may be done before, after, or at any stage of the derivatization process. The procedure for making the ether of cyclodextrin and the subsequent step of esterifying are accomplished in a conventional manner. The order of reaction for forming the cyclodextrin derivative is first to make the ether derivative and then to esterify it. 
     In order to form the dialkylated ether derivative of cyclodextrin, the cyclodextrin is first suitably reacted with an alkyl halide to form an ether derivative. Suitable alkyl halides include chlorinated, brominated, iodiated or fluorinated alkanes such as methane, ethane, propane, butane, pentane or hexane. The alkanes may be straight-chained or branched. Preferably, the alkyl halide is selected from the group consisting of n-propyl bromide, n-propyl chloride, n-butyl chloride, n-butyl bromide, n-pentyl bromide and n-pentyl chloride. Best results have been obtained with n-pentyl bromide. 
     Suitably, in order to esterify the ether derivative of cyclodextrin, fluorinated anhydrides are used. It is more preferred to use fluorinated anhydrides such as trifluoroacetic anhydride, trifluorobutanoic anhydride, or trifluoropropanoic anhydride. It is most preferred to use trifluoroacetic anhydride. 
     The preferred dialkyl trifluoroacetic ether derivatives of cyclodextrin for use in the present invention include dipentyl trifluoroacetic ether cyclodextrin, dipentyl trifluoroacetic ether cyclodextrin, dipentyl trifluorobutanoic ether cyclodextrin and dipentyl trifluoropropanoic ether cyclodextrin. 
     The gas chromatography is performed in a conventional manner. 
     It is preferred to use fused silica capillaries when performing the gas chromatography operation. Fused silica capillaries are much more flexible, practical and easier to handle than conventional glass capillaries. 
     The ether derivatives of cyclodextrin of the present invention are liquids at room temperature and can be used to coat undeactivated fused silica capillaries. They are nonvolatile and are thermally stable at temperatures up to about 300° C. in the absence of oxygen. 
     The gas chromatography can also be performed by administering the ether derivative of cyclodextrin of the present invention to a packed column by means of a carrier such as polysiloxane or polyethylene glycol. The admixture of the ether derivative of cyclodextrin of the present invention with the carrier and the administration of this admixture to the column is performed in a conventional manner. 
     The solid support in the packed column may be any suitable support such as diatomaceous earth, Teflon powder, or fine glass beads. The selection of the type, size and shape of the solid support depends on the molecules being isolated and the flow rate desired. The determination of which solid support to use is conventional and well-known to those of skill in the art. 
     Although it is less common, enantioselective reversals also can occur among like-derivatized alpha-, beta-, and gamma-cyclodextrins. Reversals in elution order have been observed between alpha- and beta-cyclodextrin and between beta- and gamma-cyclodextrin. 
     Further details and advantages of the present invention may be more fully understood by reference to the following examples. 
    
    
     EXAMPLE 1 
     This example illustrates making a permethylated hydroxypropylated ether derivative of cyclodextrin of the present invention. 
     The permethyl hydroxypropyl ether derivative of cyclodextrin was made in two steps. First, propylene oxide, sodium hydride and the desired cyclodextrin (either alpha-, beta-, or gamma-) were dissolved in dimethyl sulfoxide (DMSO) at 60° C. and allowed to react for one hour with stirring. After cooling to room temperature for 15 hours, the mixture was further cooled in an ice bath. Excess methyl iodide was added dropwise. After 24 hours the reaction was complete. 
     EXAMPLE 2 
     This example illustrates the making of the dialkyl trifluoroacetyl ether derivative of cyclodextrin of the present invention. The alkane used herein is pentane. 
     3.0 g of dried cyclodextrin and excess 1-bromopentane were added to 30 ml dimethyl sulfoxide (DMSO). The reaction was carried out at 60° C. for 6 hours. Water was then added to the reaction mixture and a waxy precipitate was obtained. The raw product was dissolved in chloroform (CHCl 3 ) and the solution was washed with water. CHCl 3  was removed under vacuum and the product was used for the next reaction without further purification. 
     The above material and an excess of trifluoroacetic anhydride were added to 30 ml tetrahydrofuran (THF). The mixture was boiled for 2 hours, then poured over ice to precipitate the product. The precipitate was washed with cold water and dissolved in CHCl 3 . The CHCl 3  solution was extracted three times with 5% aqueous sodium bicarbonate (NaHCO 3 ) and three times with water. The CHCl 3  layer was collected and dried with anhydrous sodium sulfate (Na 2  SO 4 ). CHCl 3  was allowed to evaporate in a vacuum desiccator and the final viscous liquid was dried in a vacuum overnight to form the final product of dipentyl trifluoroacetyl ether cyclodextrin derivative. 
     EXAMPLE 3 
     This example illustrates separating optical isomers using the medium made in Example 1 above. The optical isomers were derivatized in order to decrease their volatility for better resolution in the gas chromatograph process. 
     Fused silica capillary tubes (0.25 mm ID) were obtained from Alltech or Supelco. The capillaries were coated with the cyclodextrin derivatives of the present invention via the static method. 
     Untreated 10 m capillary columns were placed in a water bath at 36° C. A 0.2% w/v ether solution of the cyclodextrin derivative of the present invention filled the capillary. One end of the capillary was sealed and the other connected to a vacuum line. It took about 4 hours to coat a 10 m column. The column efficiency was tested at 100° C. by using n-hydrocarbons (C11 and C12) as test solutes. Only columns that produced ≧3600 plates per column meter were used. 
     Racemic mixtures of amines and alcohols to be resolved were derivatized with trifluoroacetic anhydride, acetic anhydride or chloroacetic anhydride. Other compounds containing hydroxyl and/or amine functionalities were also derivitized. All chemicals were obtained from Aldrich Chemical Co., Sigma Chemical Co., or Fluka Chemical Co. In each case, approximately 1.0 mg of the racemic analyte was dissolved in 0.5 ml of methylene chloride and 200 μl of the desired anhydride added. After reacting for about 5-30 minutes, dry nitrogen was bubbled through the solution to remove excess reagent. The solution residue was dissolved in 0.5 ml of ether or methanol for chromatographic analysis. Racemic mixtures of sugars to be resolved were trifluoroacetylated by the above procedure except that tetrahydrofuran was used as the solvent. Also, because this reaction was somewhat slower and the trifluoroacetic anhydride was volatile, three additional aliquots of trifluoroacetic anhydride were added at seven minute intervals. 
     Both Hewlett Packard (5710A) and Varian (3700) gas chromatographs were used for all separations. Split injection and flame ionization detection were utilized. The injection and detector port temperatures were 200° C. and nitrogen was used as the carrier gas. Gas velocity was about 10-15 cm/sec. A split ratio of 100/1 was used for all the columns and at all of the column temperatures. The injection volume was 0.5 μl. 
     Referring to the following tables, the separation factor, α, is a measure of the separation between the eluted peaks. The greater the separation between the peaks, the greater is α. Mathematically, α is defined as the ratio of the corrected retention times of the two peaks being compared i.e., ##EQU1## where t&#39;=corrected retention time, t=uncorrected time and t 0  =retention time of an unretained compound. Traditionally, the longest retained peak time, t 2 , is put in the numerator so that α will be greater than 1. An α-value of 1 means that there is no separation (the peaks co-elute). 
     Tables IA, IB and IC illustrate the separation results using permethylated hydroxypropyl ether cyclodextrin (PHCD) as the ether derivative of cyclodextrin. Tables IA, IB and IC show the results using alpha-, beta-, and gamma-cyclodextrin, respectively. The permethylated hydroxypropyl ether cyclodextrin was made in accordance with Example 1 above. 
     
                                           TABLE Ia                                
__________________________________________________________________________
Alpha-Cyclodextrin                                                        
(DS by hydroxypropyl = average about 7, ranged between 2-12)              
                         Column               Elution                     
                         Length                                           
                              Temperature     Order                       
Structure    Compound    (m)  (°C.)                                
                                     R     α                        
                                              (if known)                  
__________________________________________________________________________
Sugars*                                                                   
 ##STR1##    allose      9    100                                         
                                      ##STR2##                            
                                           1.10                           
                                              --                          
 ##STR3##    ribose      9    100                                         
                                      ##STR4##                            
                                           1.02                           
                                              --                          
Alcohols                                                                  
 ##STR5##    isopinocamphenol                                             
                         9     90                                         
                                      ##STR6##                            
                                           1.01                           
                                              --                          
 ##STR7##    trans-1,2-dithiane- 4,5-diol                                 
                         9    100                                         
                                      ##STR8##                            
                                           1.12                           
                                              --                          
 ##STR9##    1,2,3,4-tetrahydro- 1-naphthol                               
                         9    100                                         
                                      ##STR10##                           
                                           1.03                           
                                              S, R                        
Amines                                                                    
 ##STR11##   3-aminoheptane                                               
                         9     90                                         
                                      ##STR12##                           
                                           1.04                           
                                              --                          
 ##STR13##   2-aminoheptane                                               
                         9     90                                         
                                      ##STR14##                           
                                           1.05                           
                                              --                          
 ##STR15##   1,5-dimethylhexyl- amine                                     
                         9     90                                         
                                      ##STR16##                           
                                           1.04                           
                                              --                          
 ##STR17##   1-phenyl ethyl amine                                         
                         9     90                                         
                                      ##STR18##                           
                                           1.02                           
                                              --                          
 ##STR19##   1,2,3,4-tetrahydro-1- naphthylamine                          
                         9    130                                         
                                      ##STR20##                           
                                           1.03                           
                                              --                          
 ##STR21##   1-(1-naphthyl)- ethylamine                                   
                         9    150                                         
                                      ##STR22##                           
                                           1.03                           
                                              S, R                        
Amino Alcohols                                                            
 ##STR23##   2-amino-1-methoxy- propane                                   
                         9    100                                         
                                      ##STR24##                           
                                           1.03                           
                                              --                          
 ##STR25##   2-amino-1-propanol                                           
                         9    120                                         
                                      ##STR26##                           
                                           1.02                           
                                              --                          
 ##STR27##   1-amino-2-propanol                                           
                         9    120                                         
                                      ##STR28##                           
                                           1.01                           
                                              --                          
 ##STR29##   2-amino-1-butanol                                            
                         9    120                                         
                                      ##STR30##                           
                                           1.02                           
                                              --                          
Bicyclic Compounds                                                        
 ##STR31##   exo-2-amino- norbornane                                      
                         9    100                                         
                                      ##STR32##                           
                                           1.01                           
                                              --                          
 ##STR33##   endo-2-amino- norbornane                                     
                         9     90                                         
                                      ##STR34##                           
                                           1.02                           
                                              --                          
__________________________________________________________________________
 *only Dform is shown                                                     
 
    
     
                                           TABLE Ib                                
__________________________________________________________________________
Beta-Cyclodextrin                                                         
(DS by hydroxypropyl = average 8, range 2-14)                             
                          Column               Elution                    
                          Length                                          
                               Temperature     Order                      
Structure     Compound    (m)  (°C.)                               
                                      R     α                       
                                               (if known)                 
__________________________________________________________________________
Alcohols                                                                  
 ##STR35##    trans-1,2-dithiane- 4,5-diol                                
                          10   100                                        
                                       ##STR36##                          
                                            1.06                          
                                               --                         
 ##STR37##    isopinocamphenol                                            
                          10    90                                        
                                       ##STR38##                          
                                            1.10                          
                                               --                         
 ##STR39##    1,2,3,4-tetrahydro- 1-naphthol                              
                          20   120                                        
                                       ##STR40##                          
                                            1.07                          
                                               R, S                       
 ##STR41##    1-indanol   20   110                                        
                                       ##STR42##                          
                                            1.05                          
                                               --                         
 ##STR43##    trans-cyclohexane 1,2 diol                                  
                          30                                              
                                       ##STR44##                          
                                            1.05                          
                                               --                         
Amino Alcohols                                                            
 ##STR45##    2-amino-1-methoxy propane                                   
                          20   110                                        
                                       ##STR46##                          
                                            1.06                          
                                               --                         
 ##STR47##    2-amino-1-propanol                                          
                          20   120                                        
                                       ##STR48##                          
                                            1.04                          
                                               --                         
 ##STR49##    1-amino-2-propanol                                          
                          20   120                                        
                                       ##STR50##                          
                                            1.06                          
                                               --                         
 ##STR51##    2-amino-1-propanol                                          
                          30   120                                        
                                       ##STR52##                          
                                            1.04                          
                                               --                         
 ##STR53##    2-amino-1-methoxy propane                                   
                          30   120                                        
                                       ##STR54##                          
                                            1.07                          
                                               --                         
 ##STR55##    2-amino-1-butanol                                           
                          20   120                                        
                                       ##STR56##                          
                                            1.05                          
                                               --                         
 ##STR57##     2-amino-3-methyl- butanol                                  
                          10   120                                        
                                       ##STR58##                          
                                            1.03                          
                                               --                         
Amines                                                                    
 ##STR59##    2-aminopentane                                              
                           9    70                                        
                                       ##STR60##                          
                                            1.05                          
                                               --                         
 ##STR61##    1,3-dimethylbutyl- amine                                    
                           9    70                                        
                                       ##STR62##                          
                                            1.04                          
                                               --                         
 ##STR63##    3-aminoheptane                                              
                           9    80                                        
                                       ##STR64##                          
                                            1.08                          
                                               --                         
 ##STR65##    2-aminoheptane                                              
                           9    80                                        
                                       ##STR66##                          
                                            1.12                          
                                               --                         
 ##STR67##    1,5-dimethylhexyl amine                                     
                           9    80                                        
                                       ##STR68##                          
                                            1.15                          
                                               --                         
 ##STR69##    1-cyclohexyl- ethylamine                                    
                           9   100                                        
                                       ##STR70##                          
                                            1.05                          
                                               --                         
 ##STR71##    1-phenyl-ethyl-amine                                        
                           9   100                                        
                                       ##STR72##                          
                                            1.04                          
                                               --                         
 ##STR73##    1-aminoindan                                                
                          20   150                                        
                                       ##STR74##                          
                                            1.01                          
                                               --                         
 ##STR75##    1-cyclohexylethyl- amine                                    
                           30                                             
                                       ##STR76##                          
                                            1.05                          
                                               --                         
 ##STR77##    1-alpha-naphthyl)- ethylamine                               
                           30                                             
                                       ##STR78##                          
                                            1.02                          
                                               --                         
 ##STR79##    1,2,3,4-tetrahydro- 1-naphthylamine                         
                          20   150                                        
                                       ##STR80##                          
                                            1.04                          
                                               --                         
Nicotine Compounds                                                        
 ##STR81##    3-(1-trifluoromethyl carbonyl-2-pyrrolidinyl) pyridine      
                          20   140-180                                    
                                       ##STR82##                          
                                            1.01 1.00                     
                                               --                         
Lactones                                                                  
 ##STR83##    β, β-dimethyl-γ- (hydroxymethyl)- γ-bu
              tyrolactone  9   100                                        
                                       ##STR84##                          
                                            1.02                          
                                               --                         
 ##STR85##    α-amino-γ-butyrl lactone                        
                          30   100                                        
                                       ##STR86##                          
                                            1.03                          
                                               --                         
Sugars                                                                    
 ##STR87##    mannose      9    90                                        
                                       ##STR88##                          
                                            1.02                          
                                               --                         
 ##STR89##    galactose    9   100                                        
                                       ##STR90##                          
                                            1.05                          
                                               --                         
 ##STR91##    ribose       9   100                                        
                                       ##STR92##                          
                                            1.08                          
                                               D, L                       
 ##STR93##    arabinose    9    90                                        
                                       ##STR94##                          
                                            1.04                          
                                               D, L                       
 ##STR95##    xylose       9    80                                        
                                       ##STR96##                          
                                            1.03                          
                                               L, D                       
 ##STR97##    lyxose       9    80                                        
                                       ##STR98##                          
                                            1.04                          
                                               D, L                       
 ##STR99##    erythrose   20    80                                        
                                       ##STR100##                         
                                            1.03                          
                                               L, D                       
 ##STR101##   sorbose      9    90                                        
                                       ##STR102##                         
                                            1.12                          
                                               L, D                       
 ##STR103##   1-O-methyl-β-D,L- arabinopyranoside                    
                          20    90                                        
                                       ##STR104##                         
                                            1.09                          
                                               D, L                       
 ##STR105##   glyceraldehyde                                              
                          30   130                                        
                                       ##STR106##                         
                                            1.04                          
                                               --                         
Bicyclic Compounds                                                        
 ##STR107##   5-norbornen-2-ol                                            
                           9    60                                        
                                       ##STR108##                         
                                            1.00 1.10                     
                                               --                         
 ##STR109##   exo-norbornenol                                             
                           9   70                                         
                                       ##STR110##                         
                                            1.04                          
                                               --                         
Miscellaneous                                                             
 ##STR111##   butyl lactate                                               
                           9    60                                        
                                       ##STR112##                         
                                            1.04                          
                                               --                         
__________________________________________________________________________
 
    
     
                                           TABLE Ic                                
__________________________________________________________________________
Gamma-Cyclodextrin                                                        
(DS by hydroxypropyl = average about 9, range between 2-16)               
                         Column               Elution                     
                         Length                                           
                              Temperature     Order                       
Structure    Compound    (m)  (°C.)                                
                                     R     α                        
                                              (if known)                  
__________________________________________________________________________
 ##STR113##  2-amino-1-propanol                                           
                         9    120                                         
                                      ##STR114##                          
                                           1.02                           
                                              --                          
 ##STR115##  1-phenyl-ethylamine                                          
                         9    100                                         
                                      ##STR116##                          
                                           1.04                           
                                              --                          
 ##STR117##  2-aminoheptane                                               
                         9     90                                         
                                      ##STR118##                          
                                           1.02                           
                                              --                          
 ##STR119##  1,5-dimethylhexylamine                                       
                         9     90                                         
                                      ##STR120##                          
                                           1.03                           
                                              --                          
 ##STR121##  trans-1,2-dithiane 4,5-diol                                  
                         9    100                                         
                                      ##STR122##                          
                                           1.03                           
                                              --                          
 ##STR123##  solketal    9     70                                         
                                      ##STR124##                          
                                           1.02                           
                                              --                          
__________________________________________________________________________
 
    
     EXAMPLE 4 
     This example illustrates separating non-derivatized optical isomers using the medium of permethylated hydroxypropyl ether derivative of cyclodextrin as made in Example 1 above. 
     The capillary tubes, the gas chromatographs and the determination of α were as set forth in Example 3 above. 
     Tables IIa, IIb and IIc illustrate the results using alpha-, beta-, and gamma-cyclodextrin, respectively. 
     
                                           TABLE IIa                               
__________________________________________________________________________
Alpha-Cyclodextrin                                                        
(DS by hydroxypropyl = average about 7, range between 2-12)               
                                 Column         Elution                   
                                 Length                                   
                                      Temperature                         
                                                Order                     
Structure        Compound        (m)  (°C.)                        
                                             α                      
                                                (if known)                
__________________________________________________________________________
 ##STR125##      limonene oxide  9    90     1.06 1.20                    
                                                --                        
 ##STR126##      limonene        9    70     1.03                         
                                                --                        
 ##STR127##      carvon          9    100    1.02                         
                                                --                        
 ##STR128##      4-phenyl-1,3-dioxane                                     
                                 9    100    1.03                         
                                                --                        
 ##STR129##      mandelic acid methyl ester                               
                                 9    120    1.04                         
                                                --                        
 ##STR130##      mandelic acid ethyl ester                                
                                 9    120    1.03                         
                                                R, S                      
Lactones                                                                  
 ##STR131##      γ-phenyl-γ-butyro lactone                    
                                 9    130    1.02                         
                                                --                        
Bicyclic Compounds                                                        
 ##STR132##      exo-2-bromonorbornane                                    
                                 9    90     1.01                         
                                                --                        
Furan and Pyran Derivatives                                               
 ##STR133##      2-ethoxy-tetra hydrofuran                                
                                 9    60     1.22                         
                                                --                        
 ##STR134##      3,4-dihydro-2-methoxy-2H-pyran                           
                                 9    60     1.06                         
                                                --                        
 ##STR135##      3,4-dihydro-2-ethoxy-2H-pyran                            
                                 9    60     1.16                         
                                                --                        
 ##STR136##      2,5-dimethoxy-3-tetrahydrofuran carboxaldehyde           
                                 9    90     1.03 1.02 1.05 1.08          
                                                --                        
__________________________________________________________________________
 
    
     
                                           TABLE IIb                               
__________________________________________________________________________
Beta-Cyclodextrin                                                         
(DS by hydropropyl = average about 8, ranged between 2-14)                
                                Column         Elution                    
                                Length                                    
                                     Temperature                          
                                               Order                      
Structure       Compound        (m)  (°C.)                         
                                            α                       
                                               (if known)                 
__________________________________________________________________________
Alcohols                                                                  
                2-amino-4-methyl 1-butanol                                
                                30          1.11                          
                                               --                         
 ##STR137##     trans-1,2-cyclohexanediol                                 
                                20   120    1.04                          
                                               --                         
 ##STR138##     trans-1,2-cycloheptanediol                                
                                20   120    1.03                          
                                               --                         
Nicotine Compounds                                                        
 ##STR139##     3-(1-trifluoromethyl carbonyl-2- pyrrolidinyl)pyridine    
                                20   120˜180                        
                                            1.01                          
                                               --                         
 ##STR140##     3-(1-difluoromethyl-2- pyrrolidinyl)pyridine              
                                20   140-180                              
                                            1.01                          
                                               --                         
Lactones                                                                  
 ##STR141##     pantoyl lactone 20   120    1.04                          
                                               --                         
 ##STR142##     N-acetyl-homocystein thiolactone                          
                                20   150    1.02                          
                                               --                         
 ##STR143##     β-butyrolactone                                      
                                 9   70     1.03                          
                                               --                         
 ##STR144##     α-methyl-γ-butyro lactone                     
                                 9   70     1.02                          
                                               --                         
 ##STR145##     α-acetyl-α-methyl- γ-butyrolactone      
                                 9   90     1.06                          
                                               --                         
Furan and Pyran Derivatives                                               
 ##STR146##     2-ethoxy-tetrahydrofuran                                  
                                 9   50     1.11                          
                                               --                         
 ##STR147##     3,4-dihydro-2-methoxy-2H-pyran                            
                                 9   50     1.03                          
                                               --                         
 ##STR148##     3,4-dihydro-2-ethoxy-2-H-pyran                            
                                 9   50     1.05                          
                                               --                         
 ##STR149##     tetrahydro-2-(2-propynyloxy)- 2H-pyran                    
                                 9   60     1.05                          
                                               --                         
 ##STR150##     2,5-dimethoxy-3-tetrahydrofuran carboxaldehyde            
                                 9   100    1.05 1.10 1.09 1.02           
                                               --                         
Epoxides and                                                              
Glycidyl Analogues                                                        
 ##STR151##     1,2-epoxy-hexane                                          
                                20   50     1.02                          
                                               --                         
 ##STR152##     1,2-epoxyoctane 20   50     1.01                          
                                               --                         
 ##STR153##     1,2-epoxy-7-octene                                        
                                20   50     1.02                          
                                               --                         
 ##STR154##     styrene oxide    9   80     1.06                          
                                               --                         
 ##STR155##     limonene oxide  20   100    1.02 1.03                     
                                               --                         
 ##STR156##     glycidyl methyl ether                                     
                                20   45     1.04                          
                                               --                         
 ##STR157##     glycidyl isopropyl ether                                  
                                20   45     1.03                          
                                               --                         
 ##STR158##     allyl glycidyl ether                                      
                                20   45     1.05                          
                                               --                         
 ##STR159##     t-butyl glycidyl ether                                    
                                20   45     1.06                          
                                               --                         
 ##STR160##     glycidyl methacrylate                                     
                                20   70     1.01                          
                                               --                         
Bicyclic Compounds                                                        
 ##STR161##     2-acetyl-5-nornbornene                                    
                                 9   90     1.00 1.07                     
                                               --                         
 ##STR162##     3-chloro-2-norbornanone                                   
                                 9   90     1.00 1.05                     
                                               --                         
 ##STR163##     exo-2-bromonorbornanone                                   
                                 9   90     1.06                          
                                               --                         
Miscellaneous                                                             
 ##STR164##     limonene        20   100    1.03                          
                                               --                         
 ##STR165##     butyl lactate    9   60     1.02                          
                                               --                         
 ##STR166##     solketal         9   80     1.04                          
                                               --                         
 ##STR167##     α-(trichloromethyl)benzyl acetate                   
                                20   140    1.03                          
                                               --                         
__________________________________________________________________________
 
    
     
                                           TABLE IIc                               
__________________________________________________________________________
Gamma Cyclodextrin                                                        
(DS by hydroxypropyl = average about 9, range between 2-16)               
                            Column         Elution                        
                            Length                                        
                                 Temperature                              
                                           Order                          
Structure   Compound        (m)  (°C.)                             
                                        α                           
                                           (if known)                     
__________________________________________________________________________
 ##STR168## 2-(bromomethyl)-tetrahydrofuran                               
                            9    70     1.02                              
                                           --                             
 ##STR169## limonene oxide  9    70     1.03 1.03                         
                                           --                             
 ##STR170## 3,4-dihydro 2-ethoxy 2H-pyran                                 
                            9    50     1.04                              
                                           --                             
__________________________________________________________________________
 
    
     EXAMPLE 5 
     This Example illustrates separating enantiomers using the medium of dipentyl trifluoroacetyl ether derivative of cyclodextrin as made in Example 2 above. 
     Table III illustrates the separation results using the dipentyl trifluoroacetyl ether cyclodextrin (DP-TFA-CD) as the ether derivative of cyclodextrin. 
     The capacity factor of the first eluted enantiomer, k, is determined as follows: ##EQU2## where k&#39;=retention time of the eluted solute; and k&#34;=retention time of an unretained compound. 
     The column in the Table for &#34;Stationary Phase&#34; indicates which cyclodextrin was used for the ether derivative. &#34;A&#34; indicates that the ether derivative was dipentyl trifluoroacetyl alpha cyclodextrin; &#34;B&#34; that it was dipentyl trifluoroacetyl beta cyclodextrin; and &#34;G&#34; that it was dipentyl trifluoroacetyl ether gamma cyclodextrin. 
     The capillary tubes, the gas chromatographs and the determination of α were as set forth in Example 3 above. 
     
                                           TABLE III                               
__________________________________________________________________________
Dipentyl Trifluoroacetyl Ether Cyclodextrin                               
(DP-TFA-CD)                                                               
                                                         Stationary       
Structure           Compound                 (°C.)                 
                                                 k   α              
                                                         Phase            
__________________________________________________________________________
Alcohols, Diols and Polyols                                               
 ##STR171##         2-butanol                40 40                        
                                                 0.69 0.82                
                                                     1.22 1.16            
                                                         B G              
 ##STR172##         3-butyn-2-ol             70 40                        
                                                 0.57 0.77                
                                                     1.08 1.09            
                                                         B G              
 ##STR173##         2-pentanol               40 40                        
                                                 1.31 1.61                
                                                     1.26 1.27            
                                                         B G              
 ##STR174##         2-hexanol                40  3.75                     
                                                     1.31                 
                                                         G                
 ##STR175##         4-methyl-2-pentanol      40 40                        
                                                 1.58 2.18                
                                                     1.19 1.17            
                                                         B G              
 ##STR176##         2-heptanol               40 40                        
                                                 7.85 8.39                
                                                     1.25 1.26            
                                                         B G              
 ##STR177##         3-heptanol               40  4.14                     
                                                     1.08                 
                                                         G                
 ##STR178##         2-octanol                70 40                        
                                                 2.80 20.7                
                                                     1.06 1.15            
                                                         B G              
 ##STR179##         2-decanol                70 40                        
                                                 13.4 67.1                
                                                     1.18 1.22            
                                                         B G              
 ##STR180##         1,2-propanediol          70 70                        
                                                 2.06 1.67                
                                                     1.08 1.18            
                                                         A  B             
 ##STR181##         1,3-butanediol           70 70 70                     
                                                 4.92 4.86 4.79           
                                                     1.06 1.14 1.21       
                                                         A B G            
 ##STR182##         (2R, 3R)- and (2S, 3S)-butanediol                     
                                             70  1.43                     
                                                     1.58                 
                                                         G                
 ##STR183##         1,2-pentanediol          70 70                        
                                                 7.77 3.54                
                                                     1.09 1.03            
                                                         A B              
 ##STR184##         1,4-pentanediol          90 70                        
                                                 5.23 13.6                
                                                     1.06  1.05           
                                                         B G              
 ##STR185##         1,2-hexanediol           70  22.5                     
                                                     1.08                 
                                                         A                
 ##STR186##         1,2-octanediol           90  10.6                     
                                                     1.05                 
                                                         B                
 ##STR187##         trans-1,2-cyclohexanediol                             
                                             70  12.0                     
                                                     1.58                 
                                                         G                
 ##STR188##         trans-1,2-cycloheptanediol                            
                                             70  19.6                     
                                                     1.15                 
                                                         G                
 ##STR189##         trans-1,2-cycloocanediol 70  36.0                     
                                                     1.12                 
                                                         G                
 ##STR190##         1,2,4-butanetriol        110 8.10                     
                                                     1.02                 
                                                         B                
 ##STR191##         1,2,6-hexanetriol        110 23.3                     
                                                     1.07                 
                                                         B                
 ##STR192##         arabitol                 100 20.6                     
                                                     1.06                 
                                                         B                
Amino Alcohols                                                            
 ##STR193##         2-amino-1-propanol       100 110 100                  
                                                 5.88 3.81 6.53           
                                                     1.07 1.16 1.99       
                                                         A B G            
 ##STR194##         1-amino-2-propanol       100 110 100                  
                                                 6.25 4.76 5.71           
                                                     1.14 1.03 1.20       
                                                         A B G            
 ##STR195##         2-amino-1-butanol        110 110 100                  
                                                 7.31 3.42 7.04           
                                                     1.08 1.06 1.17       
                                                         A B G            
 ##STR196##         2-amino-1-pentanol       110 100                      
                                                 4.33 8.93                
                                                     1.14 1.14            
                                                         B G              
 ##STR197##         2-amino-3-methyl-1-butanol                            
                                             110 100                      
                                                 2.95 6.43                
                                                     1.07 1.19            
                                                         B G              
 ##STR198##         2-amino-1-hexanol        110 110 100                  
                                                 15.0 7.57 10.4           
                                                     1.04 1.11 1.1        
                                                         A B G            
 ##STR199##         leucinol                 120 110                      
                                                 3.81 4.33                
                                                     1.06 1.14            
                                                         A B              
 ##STR200##         3-amino-1,2-propanediol  140 6.14                     
                                                     1.12                 
                                                         B                
Amines                                                                    
 ##STR201##         2-aminobutane            80  4.29                     
                                                     1.04                 
                                                         G                
 ##STR202##         2-aminopentane           80  3.75                     
                                                     1.03                 
                                                         A                
 ##STR203##         1,3-dimethylbutylamine   80  4.88                     
                                                     1.06                 
                                                         A                
 ##STR204##         2-aminoheptane           90 80                        
                                                 10.3 19.6                
                                                     1.07 1.02            
                                                         A G              
 ##STR205##         3-aminoheptane           90 80                        
                                                 7.19 13.4                
                                                     1.06 1.03            
                                                         A G              
 ##STR206##         1,5-dimethylhexylamine   90 80                        
                                                 10.1 28.4                
                                                     1.01 1.01            
                                                         A G              
 ##STR207##         1-cyclohexylethylamine   100 11.2                     
                                                     1.08                 
                                                         B                
 ##STR208##         1-phenylethylamine       100 12.9                     
                                                     1.05                 
                                                         B                
 ##STR209##         1-aminoindan             140 4.06                     
                                                     1.06                 
                                                         A                
 ##STR210##         1,2,3,4-tetrahydro-1-naphthylamine                    
                                             140 140                      
                                                 6.12 8.21                
                                                     1.04 1.03            
                                                         A G              
Carboxylic Acid Esters                                                    
 ##STR211##         lactic acid methyl ester 50  6.79                     
                                                     1.47                 
                                                         G                
 ##STR212##         lactic acid butyl ester  60  15.0                     
                                                     1.05                 
                                                         G                
 ##STR213##         mandelic acid methyl ester                            
                                             110 4.00                     
                                                     1.04                 
                                                         B                
 ##STR214##         mandelic acid ethyl ester                             
                                             110 120                      
                                                 3.57 4.11                
                                                     1.03 1.09            
                                                         B G              
 ##STR215##         D,L-tartaric acid dimethyl ester                      
                                             90  2.79                     
                                                     1.04                 
                                                         B                
 ##STR216##         D,L-tartaric acid diisopropyl ester                   
                                             90  8.57                     
                                                     1.07                 
                                                         B                
 ##STR217##         2-chloropropionic acid methyl ester                   
                                             60 60                        
                                                 6.25 5.00                
                                                     2.69 2.14            
                                                         B G              
 ##STR218##         2-bromobutyric acid sec-butyl ester.sup.+             
                                             80  10.0 10.6                
                                                     1.22 1.07            
                                                         G                
 ##STR219##         2-bromopropionic acid methyl ester                    
                                             80 80                        
                                                 9.38 2.44                
                                                     1.12 1.47            
                                                         B G              
 ##STR220##         2-bromopropionic acid ethyl ester                     
                                             80 80                        
                                                 3.85 3.50                
                                                     1.14 1.16            
                                                         B G              
 ##STR221##         2-bromopropionic acid btuyl ester                     
                                             80  8.00                     
                                                     1.05                 
                                                         G                
 ##STR222##         2-bromopropionic acid pentyl ester                    
                                             80  15.6                     
                                                     1.04                 
                                                         G                
 ##STR223##         2-bromopropionic acid hexyl ester                     
                                             80  30.9                     
                                                     1.04                 
                                                         G                
 ##STR224##         2-bromopropionic acid sec-butyl ester.sup.+           
                                             60 80                        
                                                 12.0 12.5 4.89 5.39      
                                                     1.25 1.05 1.29       
                                                         B G2             
 ##STR225##         2-bromopropionic acid sec-pentyl ester.sup.+          
                                             60 80                        
                                                 21.5 22.9 8.00 8.37      
                                                     1.28 1.12 1.24       
                                                         B G5             
 ##STR226##         2-bromopropionic acid sec-hexyl ester.sup.+           
                                             60 80                        
                                                 45.6 49.5 14.7 15.1      
                                                     1.26 1.10 1.25       
                                                         B G7             
 ##STR227##         2-bromopropionic acid sec-heptyl ester.sup.+          
                                             90  15.1 15.4                
                                                     1.16 1.04            
                                                         G                
 ##STR228##         2-bromopropionic acid sec-octyl ester.sup.+           
                                             90  29.3 29.6                
                                                     1.16 1.03            
                                                         G                
Halohydrocarbons                                                          
 ##STR229##         2-bromo-1-chloropropane  40 40 30                     
                                                 4.31 4.00 7.64           
                                                     1.06 1.12 1.05       
                                                         A B G            
 ##STR230##         2-chlorobutane           30 30                        
                                                 0.73 0.91                
                                                     1.10 1.12            
                                                         A G              
 ##STR231##         3-chloro-1-butene        30 30                        
                                                 0.72 0.82                
                                                     1.06 1.13            
                                                         A G              
 ##STR232##         2-bromobutane            30 35 30                     
                                                 1.65 1.74 2.44           
                                                     1.38 1.04 1.09       
                                                         A B G            
 ##STR233##         2-iodobutane             40 60 30                     
                                                 2.92 1.31 6.36           
                                                     1.04 1.24 1.06       
                                                         A B G            
 ##STR234##         1,2-dichlorobutane       60 60                        
                                                 2.45 0.89                
                                                     1.09 1.04            
                                                         B G              
 ##STR235##         (2R, 3R) and (2S, 3S) 2,3-dichlorobutane              
                                             60 60                        
                                                 2.15 2.05                
                                                     1.59 1.60            
                                                         B G              
 ##STR236##         1,2-dibromobutane        90 70 60                     
                                                 4.13 4.54 8.57           
                                                     1.03 1.03 1.13       
                                                         A B G            
 ##STR237##         1,3-dibromobutane        90 70 60                     
                                                 6.38 7.38 13.6           
                                                     1.02 1.05 1.79       
                                                         A B G            
 ##STR238##         2-bromopentane           35 30                        
                                                 3.44 8.27                
                                                     1.03 1.32            
                                                         B G              
 ##STR239##         2-bromoheptane           70 50                        
                                                 4.15 8.57                
                                                     1.07 1.18            
                                                         B G              
 ##STR240##         2-bromo-1-phenylpropane  100 6.39                     
                                                     1.06                 
                                                         G                
Epoxides, Glycidyl Analogoues                                             
and Haloepihydrine                                                        
 ##STR241##         1,2-epoxyhexane          50 40                        
                                                 3.31 5.36                
                                                     1.02 1.10            
                                                         A G              
 ##STR242##         1,2-epoxyoctane          50  22.3                     
                                                     1.04                 
                                                         A                
 ##STR243##         1,2-epoxydecane          90  9.88                     
                                                     1.02                 
                                                         A                
 ##STR244##         1,2-epoxydodecane        90  108 1.02                 
                                                         A                
 ##STR245##         1,2-epoxytetradecane     100 125 1.02                 
                                                         A                
 ##STR246##         styrene oxide            80 80                        
                                                 5.57 10.7                
                                                     1.01 1.57            
                                                         B G              
 ##STR247##         limonene oxide.sup.+     80  8.57 8.57                
                                                     1.06 1.10            
                                                         G                
 ##STR248##         trans-stilbene oxide     140 20.0                     
                                                     1.02                 
                                                         G                
 ##STR249##         ±-1,3-butadiene diepoxide                          
                                             80  3.93                     
                                                     1.11                 
                                                         G                
 ##STR250##         glycidol                 60  4.29                     
                                                     1.06                 
                                                         G                
 ##STR251##         glycidyl methyl ether    40 45                        
                                                 3.33 5.89                
                                                     1.04 1.16            
                                                         B G              
 ##STR252##         glycidyl isopropyl ether 40 45                        
                                                 6.00 10.5                
                                                     1.04 1.04            
                                                         B G              
 ##STR253##         allyl glycidyl ether     50 45                        
                                                 3.23 21.6                
                                                     1.02 1.42            
                                                         A G              
 ##STR254##         n-butyl glycidyl ether   50 45                        
                                                 11.8 23.2                
                                                     1.02 1.04            
                                                         B G              
 ##STR255##         t-butyl glycidyl ether   45  14.5                     
                                                     1.06                 
                                                         G                
 ##STR256##         glycidyl acrylate        80  10.1                     
                                                     1.14                 
                                                         G                
 ##STR257##         glycidyl methacrylate    80  10.4                     
                                                     1.04                 
                                                         G                
 ##STR258##         (2S, 3S) and (2R, 3R)-2-methyl-3-phenyl-glycidol      
                                             100 13.6                     
                                                     1.06                 
                                                         G                
 ##STR259##         epifluorohydrin          30  2.50                     
                                                     1.02                 
                                                         G                
 ##STR260##         epichlorohydrin          60  4.82                     
                                                     1.20                 
                                                         G                
 ##STR261##         epibromohydrin           60  4.82                     
                                                     1.20                 
                                                         G                
Lactones                                                                  
 ##STR262##         β-butyrolactone     110 2.73 13.7 7.14           
                                                     1.14 1.62 1.20       
                                                         A B G            
 ##STR263##         3-hydroxy-4,4,4-trichlorobutyric-β-lactone       
                                             120 100                      
                                                 3.50 15.6                
                                                     1.11 1.19            
                                                         B G              
 ##STR264##         α-methyl-γ-butyrolactone                  
                                             110 110                      
                                                 3.03 11.5                
                                                     1.29 1.07            
                                                         A B              
 ##STR265##         α-acetyl-α-methyl-γ-butyrolactone   
                                             120 6.28                     
                                                     1.59                 
                                                         B                
 ##STR266##         pantoyl lactone          120 120                      
                                                 4.25 1.57                
                                                     1.04 1.05            
                                                         A B              
 ##STR267##         β,β&#39;-dimethyl-γ-(hydroxymethyl)-.gamma
                    .-butyrolactone          120 12.3                     
                                                     1.10                 
                                                         B                
 ##STR268##         γ-nonanoiclactone  160 4.07                     
                                                     1.06                 
                                                         B                
 ##STR269##         α-bromo-γ-valerolactone.sup.+             
                                             150 4.64 5.36                
                                                     1.09 1.09            
                                                         G                
 ##STR270##         γ-decanolactone    140 9.24                     
                                                     1.05                 
                                                         G                
 ##STR271##         δ-decanolactone    140 11.8                     
                                                     1.02                 
                                                         G                
Furan and Pyran Derivatives                                               
 ##STR272##         2-ethoxy-tetrahydrofuran 40 40 45                     
                                                 3.63 3.08 3.04           
                                                     1.03 1.05 1.20       
                                                         A B G            
 ##STR273##         3,4-dihydro-2-methoxy-2H-pyran                        
                                             40 40 45                     
                                                 3.38 4.33 4.29           
                                                     1.07 1.22 1.13       
                                                         A B G            
 ##STR274##         3,4-dihydro-2-ethoxy-2H-pyran                         
                                             40  40 45                    
                                                 5.85 5.92 6.07           
                                                     1.04 1.06 1.09       
                                                         A B G            
 ##STR275##         tetrahydro-2-(2-propynyloxy)-2H-pyran                 
                                             80 70                        
                                                 3.71 8.14                
                                                     1.01 1.08            
                                                         B G              
 ##STR276##         2-(chloromethyl)tetrahydropyran                       
                                             80 70                        
                                                 3.24 8.04                
                                                     1.28 1.03            
                                                         B G              
 ##STR277##         2-(bromomethyl)tetrahydropyran                        
                                             80  6.07                     
                                                     1.25                 
                                                         B                
 ##STR278##         3-hydroxy-tetrahydropyran                             
                                             50  7.14                     
                                                     1.18                 
                                                         G                
 ##STR279##         trans-2,5-dimethyltetrahydrofuran                     
                                             45  8.57                     
                                                     1.06                 
                                                         G                
 ##STR280##         trans-2,5-dimethoxytetrahydrofuran                    
                                             60  1.46                     
                                                     1.92                 
                                                         G                
Nicotine Compounds                                                        
 ##STR281##         nicotine                 160 2.14                     
                                                     1.13                 
                                                         B                
 ##STR282##         1-methyl-2-phenyl-pyrrolidine                         
                                             160 1.43                     
                                                     1.20                 
                                                         B                
 ##STR283##         2-benzylpyrrolidine      140 10.2                     
                                                     1.06                 
                                                         B                
Bicyclic Compounds                                                        
 ##STR284##         endo- and exo-2-acetyl-5-norbornene.sup.+             
                                             110 100                      
                                                 1.73 2.45 4.39 6.32      
                                                     1.03 1.00 1.11       
                                                         B G9             
 ##STR285##         endo- and exo-2-aminonorbornane.sup.+                 
                                             110 4.71 6.21                
                                                     1.18 1.10            
                                                         B                
 ##STR286##         endo- and exo-2-benzoyl-5-norbornene.sup.+            
                                             120 34.6 41.8                
                                                     1.00 1.04            
                                                         G                
 ##STR287##         exo-2-bromonorbornane    70  11.3                     
                                                     1.02                 
                                                         G                
 ##STR288##         exo-2-chloronorbornane   70  5.79                     
                                                     1.01                 
                                                         G                
 ##STR289##         endo- and exo-3-chloro-2-norbornanone.sup.+           
                                             120  6.57 10.2               
                                                     1.06 1.04            
                                                         G                
 ##STR290##         DL-isoborneol            70  8.68                     
                                                     1.05                 
                                                         G                
Ketones                                                                   
 ##STR291##         2-methyl-cyclohexanone   80  5.29                     
                                                     1.08                 
                                                         G                
 ##STR292##         carvone                  90 110 100                   
                                                 13.6 7.05 11.4           
                                                     1.04 1.09 1.01       
                                                         A B G            
Miscellaneous                                                             
 ##STR293##         3-chloro-2-butanone      50 60                        
                                                 3.46 2.43                
                                                     1.62 1.59            
                                                         B G              
 ##STR294##         solketal                 90 60                        
                                                 1.57 7.86                
                                                      1.04 1.07           
                                                         B G              
 ##STR295##         3-chloro-1,2-propanediol 90  3.52                     
                                                     1.09                 
                                                         B                
 ##STR296##         2-chloropropionitrile    80 70                        
                                                 1.93 1.65                
                                                     1.07 1.06            
                                                         B G              
 ##STR297##         2-bromopropionitrile     80 70                        
                                                 4.07 4.13                
                                                     1.14 1.06            
                                                         B G              
 ##STR298##         1-chloro-2-propanol      70  5.21                     
                                                     1.02                 
                                                         G                
 ##STR299##         4-phenyl-1,3-dioxane     120 7.36                     
                                                     1.04                 
                                                         G                
 ##STR300##         2-chlorocyclopentanone   90 110                       
                                                 12.6 2.47                
                                                     2.51 1.33            
                                                         B G              
 ##STR301##         2-amino-1-methoxy-propane                             
                                             90 100                       
                                                 1.90 1.71                
                                                     1.25 1.08            
                                                         B G              
 ##STR302##         2-chlorocyclohexanone    90 110                       
                                                 21.2 4.26                
                                                     1.06 1.10            
                                                         B G              
 ##STR303##         2-methyl-piperidin       100 5.54                     
                                                     1.13                 
                                                         G                
 ##STR304##         3-methyl-piperidin       100 5.00                     
                                                     1.14                 
                                                         G                
 ##STR305##         mandelonitrile           100 5.21                     
                                                     1.10                 
                                                         G                
 ##STR306##         ethyl-3-phenyl-glycidate.sup.+                        
                                             120 16.6 23.8                
                                                     1.05 1.04            
                                                         G                
__________________________________________________________________________
 .sup.+ compound containing more than one chiral center.                  
 
    
     EXAMPLE 6 
     This Example illustrates retention and selectivity results of homologous racemic amines, diols, and α-halocarboxylic acid esters using the medium of dipentyl trifluoroacetyl ether cyclodextrin as made in Example 2 above. These results are set forth in the following Table IV. 
     The capillary tubes, the gas chromatographs and the determination of α were as set forth in Example 3 above. 
     The capacity factor and the indication of the base cyclodextrin used were as set forth in Example 4 above. 
     
                                           TABLE IV                                
__________________________________________________________________________
                                            Stationary                    
Structure          Compound        (°C.)                           
                                      k  α                          
                                            Phase                         
__________________________________________________________________________
 ##STR307##        2-aminobutane   90 1.55                                
                                         1.14                             
                                            B                             
 ##STR308##        2-amino-3,3-dimethylbutane                             
                                   90 2.10                                
                                         1.22                             
                                            B                             
 ##STR309##        2-aminopentane  90 2.40                                
                                         1.22                             
                                            B                             
 ##STR310##        1,3-dimethylbutylamine                                 
                                   90 2.80                                
                                         1.22                             
                                            B                             
 ##STR311##        2-aminoheptane  90 8.15                                
                                         1.22                             
                                            B                             
 ##STR312##        1,5-dimethylhexylamine                                 
                                   90 12.5                                
                                         1.22                             
                                            B                             
 ##STR313##        1,2-propanediol 70 1.61                                
                                         1.49                             
                                            G                             
 ##STR314##        1,2-pentanediol 70 3.50                                
                                         1.23                             
                                            G                             
 ##STR315##        1,2-hexanediol  70 6.64                                
                                         1.23                             
                                            G                             
 ##STR316##        1,2-octanediol  70 29.3                                
                                         1.23                             
                                            G                             
 ##STR317##        2-bromobutyric acid methyl ester                       
                                   80 80                                  
                                      5.07 6.71                           
                                         1.56 1.57                        
                                            B G                           
 ##STR318##        2-bromobutyric acid ethyl ester                        
                                   80 80                                  
                                      5.25 9.93                           
                                         1.29 1.16                        
                                            B G                           
 ##STR319##        2-bromobutyric isopropyl ester                         
                                   80 6.57                                
                                         1.08                             
                                            G                             
 ##STR320##        2-bromobutyric acid butyl ester                        
                                   80 80                                  
                                      15.5 20.5                           
                                         1.16 1.09                        
                                            B G                           
 ##STR321##        2-bromobutyric acid pentyl ester                       
                                   80 80                                  
                                      32.3 39.5                           
                                         1.16 1.08                        
                                            B G                           
 ##STR322##        2-bromobutyric acid hexyl ester                        
                                    80 80                                 
                                      66.4 80.0                           
                                         1.16 1.09                        
                                            B G                           
__________________________________________________________________________
 
    
     EXAMPLE 7 
     A test was made to determine if the stereochemistry of the ether side chain has any effect on separation. 
     Three different media were prepared, permethyl-(S)-hydroxypropyl-beta-cyclodextrin; permethyl-(R)-hydroxypropyl-beta cyclodextrin; and permethyl-(racemic)-hydroxypropyl-beta-cyclodextrin. 
     Three identical columns were coated with these materials and a series of tests were run. Each of the three columns produced essentially identical separations. 
     It will be understood that it is intended to cover all changes and modifications of the preferred embodiments herein chosen for the purpose of illustration which do not constitute a departure from the spirit and scope of the invention.