The mode of scission of cis- and trans-3-methoxycyclohexene oxides by hydrogen chloride, hydrogen bromide, ammonia, acetic acid, and methanol (under both acidic and alkaline conditions) has been examined using vapor-phase chromatography to detect and isolate minor isomers. Approximately 10% of the product from opening of the trans oxide is formed by attack at position-2 with each of these nucleophiles, whereas opening of the cis oxide proceeds exclusively by attack at position-1. The results are interpreted as reflecting very similar transition states for all of these reactions, with differences in product distributions for the two oxides being governed by the inductive effect of the methoxyl group and by steric factors in the corresponding transition states.

1-Guanyl-3,5-diniethylpyrazolc nitrate is superior to S-methylisothiourorlium sulphate as a reagent for preparation of simple salts of mono-and N,N-di-allcylg~~anitlines from cyclohesylaniine, tra~zs-2-anii11ocyclo1~~~a11o1, pyrrolidine, and piperidir~e. S-h'Icthylisothiouro~~iurn sulphate, however, gave a higher conversion in the case of tlimctIi>.lan~ine. Cyanamide is not as useful a guanylatilig agent as those n i c~~t i o~i e d above. The paper cliromatography of the nio~io-and N,N-di-alkylguanidines and the parent arni~rcs \\,as studied using four solvent systems. l NTRODUCTIONOf the ilumerous methods reported in the literature for preparation of mono-and N,N-di-alliylguanidines, those \vhich have been used most frecluently are the Erlenmeyer synthesis ( I ) , from amine salts and cyanamide (2, 3 , 1 , 5 , G ) , and the Rath1.e synthesis ( 7 ) , from amines and an all;ylisothiouronium or alkylisouronium salt (8, 9,10,11,12). Both methods, however, frequently lead to poor jrields of all

111 paper strip electrophoretograms on Whatman 3MM paper, clam poison migrated toward the cathode when forrnic acid (1 IV and 0

A semimicro (10–25 mg) paper chromatographic method for purification of clam poison has been developed. This procedure when applied to a partially purified (toxicity 4150 MU/mg) sample of the toxin gave a 74% recovery of clam poison dihydrochloride of purity identical with that of the best material obtained by Schantz etal. (2) via the alumina chromatographic method. The upper limit of purity of toxin resulting from paper chromatography is estimated to be 98% because of traces of impurity introduced by the paper. The paper chromatographic procedure has been found capable of enriching low-grade toxic residues (35%) from the alumina process to a purity of 75% with an over-all recovery of 70%.

A simple method for isolating pure compounds on a gram scale by means of paper chromatography is described. The mixture of compounds to be isolated is applied as a streak to a sheet of heavy paper which is suspended in a chromatographic cabinet. A solvent develops the chromatograms. The resulting resolved bands are located on a print which is made by sandwiching the wet heavy-paper chromatogram, with a sheet of dry Whatman No. 1 paper, between two sheets of glass. The bands are then cut from the heavy paper and isolated by chromatographic extraction.