Nucleophilic aromatic substitution 159Cl
NO 2NO 2N
NO 2NO 2O 2 NO 2 NO 2 NO 2 NR R'
OH
NO 2NO 2NH 2
NO 2NO 2O 2 NOR
NO 2NO 2NH 3 ROH, RO Na874(^53) 7, R = Me
8, R = Et
NaOH (aq)RR'NH
R = H or alkyl
R' = alkyl or aryl
Figure 4.30
the alcohol, yields picryl ethers like 2,4,6-trinitroanisole (7) and 2,4,6-trinitrophenetole (8).^210
The reaction of picryl chloride with the potassium salt of methylnitramine yields the practical
high explosiveN,2,4,6-tetranitro-N-methylaniline (tetryl, Section 5.14).^211
Cl
NO 2
NO 2
87
O 2 N
S
NO 2
88
NO 2
NO 2
NO 2
O 2 N
O 2 N
S O
NO 2
10
NO 2
NO 2
NO 2
O 2 N
O 2 N
Na 2 S 2 O 3 , 90 % fuming HNO 3
Figure 4.31
Many high explosives can be synthesized from the reaction of picryl chloride with var-
ious nucleophiles. 2,2′,4,4′,6,6′-Hexanitrodiphenylsulfide (10) can be prepared from the re-
action of picryl chloride (87) with sodium thiosulfate in ethanol solution in the presence
of magnesium carbonate.^212 Oxidation of (10) with fuming nitric acid forms 2,2′,4,4′,6,6′-
hexanitrodiphenylsulfone (88).^212
NO 2
N
N
NO 2
90
(HNAB)
NO 2
NO 2
NO 2
NH
NH
NO 2
89
O 2 N
O 2 NNOO 2 N 2
O 2 N NO 2
Cl
NO 2
NO 2
87
O 2 N
NH 2 NH 2 [O]
Figure 4.32