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4544232230
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note
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The formation of products analogous to 8 and 9 has been observed by Zard in his preparation of acyl radical precursors. In his case careful control of the stoichiometry (xanthate salt):(acid chloride) together with the correct order of addition was sufficient to ensure good yields of the radical precursor. See ref. [3].
-
-
-
-
49
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4544325684
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note
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The incorporation of a Cbz group in place of the benzyl group could not be achieved. Keck has reported an example of a carbamoyl xanthate where the nitrogen atom is part of an oxazolidinone ring; see ref. [9h].
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-
-
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50
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4544283811
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(DuPont de Nemours), US 2171420, 1939
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I. Williams (DuPont de Nemours), US 2171420, 1939.
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4544284519
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note
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All dithiocarbamate radical precursors were prepared in > 80% yield from the corresponding secondary amine in a two-step procedure (see Experimental Section), with the exception of 14 which was prepared from the corresponding tertiary dimethylamine.
-
-
-
-
52
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4544236795
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note
-
The coupling constants for the proton on the carbon atom adjacent to the sulfur atom in both 15 and 16 are consistent with an equatorial arrangement of the dithiocarbamate group on the cyclohexane ring. This proton shows a NOE interaction to one of the pyrrolidinone ring hydrogen atoms in the case of 15, whereas no NOE interaction is observed to either of these hydrogen atoms in the case of 16. (diagram presented)
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53
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33751158870
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For a radical-mediated synthesis of tertiary alkyl dithiocarbamates, see: a) G. Bouhadir, N. Legrand, B. Quiclet-Sire, S. Z. Zard, Tetrahedron Lett. 1999, 40, 277;
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