Possible Piperonal source?

[Dextrose]

SWIM noticed that Piperonal is called Heliotropin in the flavoring industry... Could it be possible that this is the major component of the readily available Oil of Heliotrope ?

SWIM was just wondering, couldn't find any analysis data anywhere...
// Dex

[Organikum]

from MERCK INDEX:

Title: Piperonal.
CAS Registry number: [120-57-0]
CAS name(s): 1,3-Benzodioxole-5-carboxaldehyde Additional name(s): 3,4-(methylenedioxy)benzaldehyde; heliotropin ; piperonyl al dehyde; dioxymethyleneprotocatechuic aldehyde
Molecular formula: C 8 H 6 O 3
Molecular weight: 150.13.
Percent Composition: C 64.00%, H 4.03%, O 31.97%.

Literature references: Prepn: Blair,

Patent US2916499

(1959 to Welsbach Corp.); Holum, J. Org. Chem. 26, 4814 (1961);

Feugeas, Bull. Soc. Chim. France 1964, 1892

(https://www.thevespiary.org/rhodium/Rhodium/pdf/benzodioxole.deriviatives.pdf). Toxicity: Hagan et al., Toxicol. Appl. Pharmacol. 7, 18 (1965).

Properties: Colorless, lustrous crystals, mp 37degrees . Heliotrope odor. bp approximately263degrees ; bp 0.5 88degrees . Sol in 500 parts water; freely sol in alcohol, ether. Keep in cool place protected from light. LD 50 orally in rats: 2700 mg/kg (Hagan).
 
Boiling point: bp approximately 263degrees; bp 0.5 88degrees
Melting Point: 37degrees
USE: In perfumery, in cherry and vanilla flavors, in organic syntheses.
THERAP CAT: Has been used as pediculicide.



50g cost ~11€, it is heavily watched and regulated!
ORGY

for german speaking bees:

more information on chemistry and all (very good) at:

http://www.omikron-online.de/cyberchem/aroinfo/0568-aro.htm

~ Love is the law, love under will. ~

[Rhodium]

U.S. pat. 2,916,499: Ozonization of isosafrole to give piperonal in 93% yield.
J. Org. Chem. 26, 4814 (1961): Oxidation of piperonylalcohol to piperonal in 85% yield using CrO3 in Pyridine.

[jimwig]

2,916,499:

[Rhodium]

Huh?

[terbium]

Oil of heliotrope may or may not contain piperonal. Most Oil of Heliotrope will be compounded rather than being from a single natural source so the composition will depend on the fragrance chemist who determined the formula.

Here is a heliotrope compound formula from Perfumes, Cosmetics & Soaps, Volume 2 by W.A. Poucher.

 

  20  Geraniol, Java
  20  Sweet orange
 250  Heliotropin
  20  Anisic aldehyde
  10  Rose otto
  10  Musk xylene
  20  Peru balsam
 150  Vanillin
 500  Diethyl phthalate
------
1000

[Dextrose]

Would it be worth a try to order a liter and (blindly) try to distill it out?
// Dex

[jimwig]

US2916499
                 
                  Process for producing aromatic carbonyl compounds and peroxide compounds

maybe i misunderstood but

maybe somebody changed something. i dunno.

[Rhodium]

Jimwig: The patent number is correct, the synthesis of piperonal from isosafrole is mentioned in the middle of column three, page two of the patent.