C O M M U N I C A T I O N S
Table 1. Polyfunctional Amines of Type 1 Obtained by the
Reaction of Arylmagnesium Halides with Nitroarenes
also thank Chemetall GmbH (Frankfurt a.M.) and BASF AG
(Ludwigshafen) for generous gifts of chemicals.
Supporting Information Available: Detailed experimental pro-
cedures and characterization data of each compound (PDF). This
References
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(7) Berti, C. Synthesis 1983, 793-794.
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M.; Boymond, L.; Berillon, L.; Lepreˆtre, A.; Varchi, G.; Avolio, S.;
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(12) There is good evidence for this mechanism, since no products of type
Ar1-NH-Ar1 are detected. Such products should appear if C-N-bond
formation takes place via a type of 1,2-addition to the nitroarene 1. Yost,
Y.; Gutmann, H. R.; Muscoplat, C. C. J. Chem. Soc. C 1971, 2119-
2122.
(13) The reaction of nitrosobenzene with 4-carbethoxyphenylmagnesium
chloride (2a) (1.2 equiv) furnished under standard conditions ethyl
4-anilinobenzoate in 70% yield. See also: Bartoli, G.; Rosini, G.; Synthesis
1976, 270-271.
(14) Typical Experimental Procedure. In a dry and argon-flushed 25-mL
flask, equipped with a magnetic stirrer and a septum, the iodobenzene
derivative (3.5 mmol) was dissolved in dry THF (8 mL) and cooled to
-20 °C, and i-PrMgCl (3.6 mmol, 0.85 M in THF) was added dropwise.
The I/Mg exchange was complete after 30 min, and functionalized
nitrobenzene (1.5 mmol) was added. After 2 h of stirring at -20 °C, the
reaction was quenched with ethanol (1 mL), and FeCl2 (3 mmol) and
NaBH4 (1.5 mmol) were added. After 2 h stirring at room temperature,
the reaction mixture was poured into water (25 mL). The aqueous phase
was extracted with diethyl ether (3 × 40 mL). The organic fractions were
washed with brine (30 mL), dried (Na2SO4), and concentrated in vacuo.
Chromatographical purification on silica gel furnished the product.
a The dotted line indicates the new C-N bond formed during the reaction.
b Yield of analytically pure compound.
Acknowledgment. Dedicated to Professor Theodor Severin. We
thank the Deutsche Forschungsgemeinschaft (Leibniz program) and
I.S. thanks Aventis Pharma (Frankfurt a. M.) for a fellowship. We
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