Separable diastereomeric cis-1-menthyl 2-phenyl-3-aziridinecarboxylates (4 and 5) were prepared by the Gabriel reaction. N-Acylation with p-nitrobenzoyl chloride or p-anisoyl chloride of 4 and 5 gives 7 and 8, and 23 and 24, respectively. Sodium iodide-catalyzed rearrangement of the N-acylated aziridines is rcgiospecific with exclusive attack at C-2 and from 8 is obtained the chiral 2-oxazolines cis-9 and trans-10 in a ratio of 30:70 together with the unsaturated amide 11. The structure of the latter was proven by independent synthesis. The intermediate I-menthyl N-p-nitrobenzoyl-3-iodophenyl-alaninate (18) was isolated at lower temperatures and shown to form the equilibrium mixture of 9 and 10 with triethylamine owing to partial racemization by a Finkelstein identity reaction. Use of an N-p-anisoyl substituent in the aziridine improves the yield of chiral 2-oxazolines by preventing the formation of 11, and allows the separation of pure cis-and trans-oxazolines for characterization. The aziridines bearing N-p-anisoyl substituents display a greater sensitivity to attack by weaker nucleophiles than thep-N-nitrobenzoyl analogs.Acid hydrolysis of 9 and 10 gives D-allo-a-phenylserine in an optical yield of about 17% from which 5 and 8 are tentatively assigned the 2R,3R configuration. Similar acid hydrolysis of the 2-p-anisyl-2-oxazoline (266) allowed the isolation of the interrnediatc I-menthyl 0-anisoyl-allo-p-phenylserinate (30a), hydrolysis of which gave D-allo-p-phenylserine in about 18% optical yield. The isolation of alloa-phenylserine only from cis-and trans-2-oxazolines is attributed to acid-catalyzed inversion at the benzylic center to the conformationally more stable allo form.

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The cyclic allylic "in‐o compounds (I) react with sodium benzenesulfinate (II) in the presence of Pd(pphj)′ to give the kinetically controlled products (III) and only small amounts of (heil‐ n. gio‐isomers (IV).

A New Synthesis of 1-Phenylthio-and 1-Alkylamino-4-nitrobuta-1,3dienes.-A simple method for the synthesis of 1-phenylthiobutadiene (VII) from acrolein and its conversion into 1-alkylaminobutadienes (IX) is described. Moreover, preliminary results of the nonlinear optical activity of these new push-pull dienes are reported. -(ONO, N.; MATSUMOTO, K.; OGAWA, T.; TANI, H.; UNO, H.; J.

A New Synthesis of [2,3]Naphthoporphyrins.-A new synthesis of title compounds (VII), (IX) and (XIII) using compounds (V) and (VIII) as synthons of benzisoindole is described. The soluble precursors of [2,3]naphthoporphyrins are converted into insoluble [2,3]naphthoporphyrins by simple heating to 290 • C. -(ITO, SATOSHI; OCHI, NAOYUKI; UNO,