Synthesis of N-Benzylated Anilines from the Reaction of Anilines and Benzyl Chloroformate
ACS Citation
Pati, H. N.; Weisbruch, P.; Lemon, A.; Lee, M. Synthesis of N-Benzylated Anilines from the Reaction of Anilines and Benzyl Chloroformate. Synth. Commun. 2004, 34, 933-940.
Version of Record
Abstract
Reactions of benzyl chloroformate with a series of substituted anilines produced N-carbobenzyloxy -œCBZ- products along with the unexpected N-benzylated -œBn- compounds. Reaction of aniline, 1a, gave the CBZ, or 2a, and Bn, or 3a, products in 29% and 14% yield, respectively. For 2-nitro-, 2-bromo-, and 2-bromo-5-nitroanilines, the N-benzylated compounds were produced exclusively. However, 2-methoxy-, 4-bromo, 4-iodo, and 4-ethylanilines gave mainly CBZ products. Other compounds reported in this study gave mixtures of the two products. For 4-chloro-3-nitroaniline, in addition to the Bn and CBZ products (53% and 14% yield, respectively), a N,N-dibenzylated product was isolated in 27% yield. Collectively, the results indicated that electron-withdrawing groups, particularly at the ortho position, directed the formation of Bn compounds, whilst electron-donating groups, especially at the ortho and para positions, favored the synthesis of CBZ products.
Source Name
Synthetic Communications
Publication Date
1-1-2004
Volume
34
Issue
5
Page(s)
4857-4860
Document Type
Citation
Citation Type
Article