Reaction #1552071

ord-119730a219b044019552533df9a4b658

Reaction equation

O=[N+]([O-])OCC(CO[N+](=O)[O-])(CO[N+](=O)[O-])CO[N+](=O)[O-]
PETN
O=[N+]([O-])N1CN([N+](=O)[O-])CN([N+](=O)[O-])C1
RDX
CCCCCCCCC1(CCCCCCCC)c2ccccc2-c2ccccc21
9,9-dioctylfluorene
COc1ccccc1
anisole
COc1ccccc1OC
1,2-dimethoxybenzene
CCCCCCCCC1(CCCCCCCC)c2ccccc2-c2ccccc21
9,9-dioctylfluorene
CCCCCCCCC1(CCCCCCCC)c2ccccc2-c2ccccc21
9,9-dioctylfluorene
O=[N+]([O-])OCC(CO[N+](=O)[O-])(CO[N+](=O)[O-])CO[N+](=O)[O-]
PETN
O=[N+]([O-])N1CN([N+](=O)[O-])CN([N+](=O)[O-])C1
RDX
→
O=[N+]([O-])N1CN([N+](=O)[O-])CN([N+](=O)[O-])C1
RDX
O=[N+]([O-])OCC(CO[N+](=O)[O-])(CO[N+](=O)[O-])CO[N+](=O)[O-]
PETN
COc1ccccc1
anisole
COc1ccc([N+](=O)[O-])cc1
4-nitroanisole
Yield 1.0%

Reactants

O=[N+]([O-])OCC(CO[N+](=O)[O-])(CO[N+](=O)[O-])CO[N+](=O)[O-]
PETN
O=[N+]([O-])N1CN([N+](=O)[O-])CN([N+](=O)[O-])C1
RDX
CCCCCCCCC1(CCCCCCCC)c2ccccc2-c2ccccc21
9,9-dioctylfluorene
COc1ccccc1
anisole
COc1ccccc1OC
1,2-dimethoxybenzene
CCCCCCCCC1(CCCCCCCC)c2ccccc2-c2ccccc21
9,9-dioctylfluorene
CCCCCCCCC1(CCCCCCCC)c2ccccc2-c2ccccc21
9,9-dioctylfluorene
O=[N+]([O-])OCC(CO[N+](=O)[O-])(CO[N+](=O)[O-])CO[N+](=O)[O-]
PETN
O=[N+]([O-])N1CN([N+](=O)[O-])CN([N+](=O)[O-])C1
RDX

Reagents

None

Solvents

CC#N
acetonitrile
C1CCOC1
THF

Conditions

Detailed conditions
See reaction.notes.procedure_details.

Workup

  1. 1
    Otherthe scope of the photonitration reaction
  2. 2
    Otherwas recovered in ca. 90% yield

Procedure

To probe the scope of the photonitration reaction, the nitration of 9,9-dioctylfluorene, anisole and 1,2-dimethoxybenzene by RDX and PETN was investigated. Extended photolysis (5 h) of a mixture of 9,9-dioctylfluorene and either RDX or PETN in 1:1 acetonitrile:THF at either 254, 313, 334, or 356 nm did not generate any observable products and 9,9-dioctylfluorene was recovered in ca. 90% yield. Photolysis of anisole with RDX or PETN yielded only trace amounts of 4-nitroanisole (<1% GC yield) after 4 hours. Photolysis of 1,2-dimethoxybenzene with either RDX or PETN yielded 1,2-dimethoxy-4-nitrobenzene in only ca. 8% yield after 2 hours; moreover this reaction did not proceed cleanly and numerous polar photoproducts were observed. Based on this set of experiments, anilines were selected as candidates for potential indicators. To create fluorogenic indicators based on the facile nitration reaction between aromatic amines and the photofragmentation products of RDX and PETN, 9,9-disubstituted 9,10-dihydroacridines (DHAs) were targeted as chemosensory.

Source

DOI: 10.6084/m9.figshare.5104873.v1Patent: US08999722B2uspto-grants-2015_04