piperonal from pepper

cleavage of piperic acid

2002, by 3base

via KMnO4

via Br2 and NaOH

nitrosation of piperine

via KMnO4

piperic acid --> piperonal
KMnO4, alkali, 3°C
byproducts: piperonylic acid, racem. 2,3-dihydroxy-succinic acid, oxalic acid
[18], [03], [24]

via Br2 and NaOH

... piperic acid ... reacts quickly with Br2 in CCl4 without forming of HBr
to a compound with the molecular formula C12H10Br4O4 ... [07, page 877]

... piperic acid ... addition occured when bromine was added ...
tetrabromopiperic acid (C12H10Br4O4, mp 160-165°C) resulted when
bromine in carbon disulfide was the reagent. ...
hot sodium hydroxide converted the tetrabromo acid to piperonal ... [04]

nitrosation of piperine

... we have nitrosated piperine using HN02, NOCl and N2O4. the
compounds identified from the nitrosation of piperine are piperonal ... [05]

references

[03]
analen der chemie und pharmacie 1874 172: 134-167
"untersuchungen ueber die constitution des piperins und seiner
spaltproducte piperinsaeure und piperidin - vierte abhandlung"
rud fittig, w h mielck

[04]
leo marion, II. the pepper alkaloides, 1. piperine, p.168,
the alkaloids, chemistry and physiology, volume I,
academic press inc, publishers, new york, 1950

[05]
j agric food chem 1992 40(11): 2211-2215
"nitrosation of piperine using different nitrosating agents:
characterization and mutagenicity of the products"
narmada r shenoy, ahmed s u choughuley, tulsi k shetty, rathin k bhattacharya
abstract: piperine, an N,N-disubstituted amide possessing a methylenedioxy moiety,
is the main pungent principle of pepper, a spice consumed by people throughout the
world. on nitrosation the reaction mixture exhibits mutagenic activity toward salmonella
typhimurium strains. in the present work we have nitrosated piperine using nitrous acid
(HN02), nitrosyl chloride (NOCl), and dinitrogen tetraoxide (N2O4). the compounds
identified from the nitrosation of piperine are piperonal (PA), 6-nitropiperonal (NPA),
3,4-(methylenedioxy)cinnamaldehyde (MDCA),
1- [5-(1,3-benzodioxol-6-nitro-5-yl)-l-oxo-2(E) ,4(E)-pentadienyllpiperidine (MNAP),
1- [5-(1,3-benzodioxol-5-yl)-l-oxo-2-nitro-2(E),4(E)-pentadienyl] - piperidine (MNOP),
1- [5-(1,3-benzodioxol-6-nitro-5-yl)-l-oxo-2-nitro-2(E),4(E)-pentadienyllpiperidine (DNP),
and N-nitrosopiperidine (NPIP). the mutagenicity of the unfractionated nitrosated reaction
mixture (UPNM) and compounds NPA, MNAP, MNOP and DNP toward S. typhimurium
TA 98 and TA 100 strains was studied. compounds NPA and DNP and the unfractionated
reaction mixture were found to be mutagenic toward both the strains.

[07]
"lehrbuch der organischen chemie", 2.berichtigte auflage 1983
robert t morrison, robert n boyd; verlag chemie, weinheim; ISBN 3-527-25761-6

[18]
analen der chemie und pharmacie 1869 152: 25-58
"untersuchungen ueber die constitution des piperins und seiner
spaltproducte piperinsaeure und piperidin - erste abhandlung"
rud fittig, w h mielck

[24]
berichte der deutschen chemischen gesellschaft 1890 23: 2372-2377
"ueber die bildung von traubensaeure durch oxydation ungesaettigter saeuren"
o doebner