choice of solvent depends upon the secondary metabolite you want to extract. For polar constituent you can use methanol or ethanol, for lipophilic chloroform, hexane etc. however nowadays industries are more prone towards hydroalcoholic extracts.
Usually start with non-polar solvent such as hexane or petroleum ether to remove the non-polar constituents ( fats and oils). then gradually increase the polarity of the solvent ( more polar solvent): ethyl acetate, ethanol, methanol finally with 80% methanol- water. Take TLC for all fractions, separate single compounds using chrom. techniques.
Extraction is done based on the polarity of the solvents and fractions are obtained in a sequential process using hexane, chloroform, ethyl acetate, and butanol as solvents.
The solvent used for extraction is in a position to dissolve appreciable quantities of substances desired.
Water soluble extractives: This method is applied to drugs contain water soluble active constituents of crude drugs such as tannins, sugars, plant acids, mucilage, glycosides etc.
Alcohol soluble extractives: Alcohol is an ideal solvent for extraction of various chemicals like tannins, resins etc.Therefore this method is frequently employed to determine the approximate resin content of the drug. It is also used as an official method for assay in case of Myrrh and Asafoedtida. Generally 95 % ethyl alcohol is used for determination of alcohol soluble extractives.