Thionyl Chloride → 4-(Chloromethyl)-N-methyl-2-nitroaniline
Reaction equation
[BH4-].[Na+].[CH3:3][NH:4][C:5]1[CH:10]=[CH:9][C:8]([CH2:11]O)=[CH:7][C:6]=1[N+:13]([O-:15])=[O:14].O=S(Cl)[Cl:18]>>[CH3:3][NH:4][C:5]1[CH:10]=[CH:9][C:8]([CH2:11][Cl:18])=[CH:7][C:6]=1[N+:13]([O-:15])=[O:14]Participants
Procedure
4-Chloro-3-nitro-benzaldehyde is reacted with methylamine to yield 4-(methylamino)-3-nitrobenzaldehyde (8) which is then reduced by NaBH4 to N-methyl-4-hydroxymethyl-2-nitroaniline (9). Reaction of SOCl2 with 8 will give N-methyl-4-chloromethyl-2-nitroaniline (10). Structures of 8, 9 and 10 may be characterized by 1H NMR and elemental analysis. 10 is used as an electrophile to react with sodium CD alkoxide (11) to yield 2-O-(4-methylamino-3-nitro) benzyl-β-CD (12). The addition of 10 to 11 is a novel method for mono-functionalizing the 2-position of CD's (Rong, P., and D'Souza, V. T., Tetrahedron Lett., 31:4275 (1990)). 12 is hydrogenated by agents such as H2 /Pd, H2 /Pt, H2 /Ni, Sn/HCl, Fe/HCl and Zn/HCl, and then condensed with alloxan monohydrate to yield 2-flavo-CD (13). Compounds 11 and 12 can be characterized by 1H and 13C NRM. 2-Flavo-α-CD, β-CD and γ-CD may be synthesized by the same method. ##STR12##
Sources & evidence
- ORD record
- ord-96052feccabb47dfae9fa378f34b1adc
- Source dataset
- uspto-grants-1993_11
- Patent number
- US05258370
Reaction notes
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