Relation between chemical constitution and pepper taste. I was written by Staudinger, H.;Schneider, Hermann. And the article was included in Berichte der Deutschen Chemischen Gesellschaft [Abteilung] B: Abhandlungen in 1923.Safety of Benzo[d][1,3]dioxol-5-yl(piperidin-1-yl)methanone This article mentions the following:
Crystallized piperine (I) has only a very slightly sharp taste while an alc. solution, even when very dilute, is so sharp that the characteristic pleasant taste of pepper does not appear. Again, if I is ground with 20 parts flour only a short time (6 hrs.) the product has only a faint pepper taste, while after 10 days’ grinding it has the same sharpness as pepper. There seems to be no doubt, therefore, that I is the chief active principle of pepper and that the characteristic pepper taste is produced by a reaction with colloidal substances on the tongue and is therefore dependent on a suitable degree of dispersion of the I. A systematic study has shown that the I mol. can be varied considerably without destroying the pepper taste. An essential factor is the amide-like union of piperidine (II) with an aliphatic-aromatic acid and the taste is most pronounced in derivatives of δ-phenylvaleric acid, so that the grouping seems to be of importance for the production of the pepper taste. The II salt of piperic acid (III) is not sharp, showing that the amide union in I is essential for the pepper taste. On the other hand β-cinnamenylacrylic piperidide (IV) has an even sharper taste than I, a 2.5% mixture of IV having about the same sharpness as ground pepper, which contains 5-10% of I. The same is true of the allo-isomer (V) of IV. The methylenedioxy group in I is therefore not essential for its taste. The 3 dihydro and the tetrahydro derivatives of IV have an equally strong pepper taste, which consequently does not depend on the double bonds. Tetrahydropiperine (VI) likewise has a pepper taste. The piperidides of sorbic and many other purely aliphatic or purely aromatic acids either have an unpleasant burning taste or are tasteless. Cinnamylidenemalonic acid (VII) is obtained in 88.6% yield from 189 g. PhCH:CHCHO and 1.5 mols. CH2(CO2)2Ca in 400 g. AcOH heated at 60-70° until the mass solidifies (0.5-1.0 hr.), then 2 days at 80° and 1 day at 100°; with PCl5 in C6H6 it gives the golden yellow chloride, m. 83°; the piperidide, prepared by the Schotten-Baumann method, has no pronounced pepper taste. β-Cinnamenylacrylic acid (VIII), m. 165°, was prepared by Döbner’s method (condensation of PhCH:CHCHO with CH2(CO2H)2 in the presence of C5H5N; with quinoline as the condensing agent, the alloisomer (IX) of VIII, m. 138°, is obtained). The acid pyridine salt of VII m. 114-5° with evolution of CO2 and formation of a mixture of about 60% VIII and a low melting acid, and the acid quinoline salt m. 114-5° and decomposes about 130° with formation chiefly of IX and only very little VIII. Chloride of VIII, from the acid refluxed 4 hrs. in petroleum ether with SOCl2, m. 47° (that of IX has thus far not been obtained in crystalline form). IV m. 91-2° (Riedel, C. A. 2, 2238, gives 203°, and his product was evidently not IV). V could not be obtained crystalline and could not be distilled even in a high vacuum without decomposition The β,γ-dihydro derivative of VII decomposes in boiling H2O with formation of 90-5% of phenyl-β,γ-pentenic acid (X), whereas with 4 parts of boiling 5% C5H5N it gives 90% of a mixture containing about 30% X and 70% of its α,β-isomer (XI). Chloride of XI, prepared with excess of SOCl2, b15 149-50° (yield, 68%); Et(?) ester, b13 156-9°; piperidide, obtained in 77% yield from the acid heated 24 hrs. with II at 195-200°, also made by the Schotten-Baumann method, b0.2 164-9°. Chloride of X, b12, 139-40°, b0.2 98-100°; Et ester, b11 154-6°; piperidide (17-8 g. from 17 6 g. of the acid heated 7 hrs. at 80-90° with 8.5 g. II), b0.2 163-5°. Chloride of the γ,δ-isomer of X, b0.15 100-5°; piperidide, faintly yellow, b0.2 165-7°. α-Phenylcinnamenylacrylic chloride, from the acid heated a long time with SOCl2 in C6H6, m. 87-9°; piperidide, m. 135°, has no sharp taste when ground with flour. Sorbic chloride, obtained in 50% yield from the acid and SOCl2 in boiling C6H6, b12 69-71°; piperidide, m. 83-4°. The following piperidides have an unpleasant, generally not very sharp taste or are tasteless: valeric, b12 122-5°; caproic, b12 140°; heptylic, b12 158-62°; acetic, b30 125°; crotonic, b30 160°; palmilic, m. 35-6°; mono-Me malonic, b0.5 130-5°; benzoic, m. 48°, b15 180°; p-methoxybenzoic, m. 35°, b16 210°; methyleneprotocatechuic, m. 45°; α-naphthoic, m. 85-7°; ε-naphthoic, m. 88-90°; toluene-p-sulfonic, m. 98-9°; cinnamic, m. 122°; p-methoxycinnamic, b0 200-10°; methylenecaffeic, m. 80-2°. In the experiment, the researchers used many compounds, for example, Benzo[d][1,3]dioxol-5-yl(piperidin-1-yl)methanone (cas: 34023-62-6Safety of Benzo[d][1,3]dioxol-5-yl(piperidin-1-yl)methanone).
Benzo[d][1,3]dioxol-5-yl(piperidin-1-yl)methanone (cas: 34023-62-6) belongs to dioxole derivatives. Dioxoles, particularly fluorinated dioxoles, are used as co-monomers to make polymers that find use in forming protective coatings for chemical resistance. Dioxole functionalized metal-organic frameworks have also been recently reported.Safety of Benzo[d][1,3]dioxol-5-yl(piperidin-1-yl)methanone
Referemce:
1,3-Benzodioxole – Wikipedia,
Dioxole | C3H4O2 – PubChem