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| - Deamination of trans-2-Methyl- andtrans-2-Phenylcyclopropylamines
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| - The deaminations of trans-2-methyl- and 2-phenylcyclopropylamine hydrochlorides in acetic acidsolution have been examined. A major product in each case was an allylic chloride, and the amountof chlorides increased when the chloride ion concentration was increased. With the methyl-substituted amine, increasing the chloride ion concentration changed the major chloride productfrom crotyl chloride to methallyl chloride. The addition of lithium perchlorate led to a reduction inthe amount of chlorides formed. These results indicate that an ion pair is involved in the reaction.The deamination of the related open chain amines gave only small amounts of chlorides. B3LYP/6-31G* calculations found cyclopropyldiazonium chloride to prefer to have the chloride ion overthe cyclopropyl ring. The transition state was located, and when followed down to products, allylchloride was found. Similar calculations for the methyl-substituted series led to crotyl chloridefrom the ion pair with one chloride ion and to methallyl chloride from the ion-triplet with twochloride ions. The deaminations of the corresponding nitrosoureas in basic methanol also werestudied. The products were the expected ethers. The addition of azide ion led to azides that werelargely formed by initial reaction with the diazonium ion to give a pentazene that lost nitrogen togive the azide. However, some of the azide was formed by an SN2 displacement.
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