Piperine

Abstract

This article presents a comprehensive overview of Piperine, including its general information, physico-chemical properties, chemical reactions, obtaining of piperoylpiperidide, conclusion and bibliography.

Information of Piperine

Other synonyms names are: 1-Piperoylpiperidine; Piperin; Bioperine; piperoylpiperidide; Piperoylpiperidine; (2E,4E)-5-(benzo[d][1,3]dioxol-5-yl)-1-(piperidin-1-yl)penta-2,4-dien-1-one; N-(E,E)-piperoyl-piperidine; 1-Piperoyl-piperidine; 1,3-Benzodioxol-5-yl-1-oxo-2,4-pentadienyl-piperine

• IUPAC Names: (2E,4E)-5-(1,3-benzodioxol-5-yl)-1-piperidin-1-ylpenta-2,4-dien-1-one
• CAS number: 94-62-2

Physico-Chemical Properties of Piperine

• Molecular Formula C₁₇H₁₉NO₃

• Molar Weight 285.34 g/mol

• Melting Point 128-135 ℃

• Solubility: Very slightly soluble in water; Soluble in ether, oils, ethanol.

• Solubility in chloroform 1 g in1.7 ml

• Color/Form: Light yellow to yellow solid with a pungent odor. Aroma reminiscent of pepper

Piperoylpiperidine, along with its isomer chavicine, is a notable compound found in black pepper and other species within the Piper genus. Chavicine, a potentially pungent substance, is one of the four geometric isomers. The structural formulas of both isomers and chavicine are presented.

Structure of Piperine and Its Isomer Chavicine

Crystalline solid and Powder possible of the Piperoylpiperidine can be seen in the pictures.

Crystalline Solid of Piperine

Powder of Piperine

General Information and Reactions

(2E,4E)-5-(1,3-benzodioxol-5-yl)-1-piperidin-1-ylpenta-2,4-dien-1-one, first isolated in 1819 by Hans Christian Ørsted, was extracted from the fruits of Piper nigrum, the plant responsible for black and white pepper. Additionally, piperine is found in Piper longum and Piper officinarum, commonly known as “long pepper.” These species have been traditionally used for their pungency and medicinal properties.

Piperic acid, a derivative of (2E,4E)-5-(1,3-benzodioxol-5-yl)-1-piperidin-1-ylpenta-2,4-dien-1-one, can be synthesized from the commercially available alkaloid. Piperoylpiperidine, a cyclic amide with a piperidine group, undergoes base hydrolysis when treated with a hydroxide, such as potassium hydroxide. This reaction forms a piperate salt, which is subsequently acidified using hydrochloric acid or another acid to yield piperic acid.

Piperoylpiperidine is a precursor for Piperonal.

During the hydrolysis process, the toxic compound piperidine is released. Piperoylpiperidine, a volatile amine, can pose health risks due to its toxicity and strong odor.

Hydrolysis of Piperine

Piperine reacts to form salts only with strong acids. Its platinichloride, represented as B₄•H₂PtCl₆ (where “B” denotes one mole of the alkaloid base), crystallizes as orange-red needles. When iodine in potassium iodide is added to an alcoholic solution of the base, along with a small amount of hydrochloric acid, a distinctive periodide, B₂•HI•I₂, forms. This compound crystallizes into steel-blue needles with a melting point of 145°C.

Under exposure to light, particularly ultraviolet light, the substance undergoes isomerization. This process converts it into its isomers: chavicine, isochavicine, and isopiperine. Unlike piperoylpiperidine, these isomers are tasteless, which significantly alters the sensory properties of the compound.

Piperine Isomerization

Producing of Piperine

Because piperoylpiperidine has limited solubility in water, its extraction from black pepper is commonly carried out using organic solvents such as dichloromethane. Its content differs significantly among pepper types, ranging from 1–2% in long pepper to 5–10% in commercially available black and white peppers.

Piperine Extraction Video

Piperine Purification Video 

Piperoylpiperidine can also be obtained by processing the solvent-free residue of a concentrated alcoholic extract of black pepper. This is achieved by treating the residue with a potassium hydroxide solution to remove resin, which is reported to contain chavicine, an isomer of piperine.

Black and white peppers contain varying levels of piperine and other compounds that contribute to their distinct characteristics.

Black and White Peppers With Piperine

The solution is separated from the insoluble residue and allowed to rest in alcohol overnight. Over time, the alkaloid gradually crystallizes out of the solution.

(2E,4E)-5-(1,3-benzodioxol-5-yl)-1-piperidin-1-ylpenta-2,4-dien-1-one can also be synthesized through the reaction of piperonoyl chloride with piperidine.

Conclusion

(2E,4E)-5-(1,3-benzodioxol-5-yl)-1-piperidin-1-ylpenta-2,4-dien-1-one, a key alkaloid in black and white pepper, is notable for its chemical and biological significance. With limited water solubility, it is typically extracted using organic solvents like dichloromethane, and its content varies from 1–2% in long pepper to 5–10% in commercial varieties. Piperoylpiperidine forms salts with strong acids, crystallizes into distinct forms, and can be synthesized via piperonoyl chloride and piperidine.

Under ultraviolet light, piperine isomerizes into tasteless forms like chavicine, altering its sensory properties. Additionally, piperic acid, a derivative, is obtained through hydrolysis, though this process releases toxic piperidine. Piperine’s versatility and unique properties make it a subject of ongoing scientific interest with potential for broader applications.

Bibliography

1. https://en.wikipedia.org/wiki/

2. https://en.wikipedia.org/wiki/Chavicine

3. https://pubchem.ncbi.nlm.nih.gov/compound/638024

4. https://pubchem.ncbi.nlm.nih.gov/compound/1548912

5. https://www.chemspider.com/Chemical-Structure.1265935.html

6. https://www.chemspider.com/Chemical-Structure.553590.html

7. https://en.wikipedia.org/wiki/Piperic_acid

8. https://bbgate.com/threads/extraction-of-piperine-from-black-pepper-by-direct-method-without-using-soxhlet-extractor.15621/

9. Thomas Anderson Henry The Plant Alkaloids. Fourth edition. Philadelphia, Toronto, 1949, p. 1 https://www.google.com/url?sa=i&url=https%3A%2F%2Flibrary.sciencemadness.org%2Flibrary%2Fbooks%2Fthe_plant_alkaloids.pdf&psig=AOvVaw1M9936Ifh1TjQhKIHuvuy2&ust=1736945578589000&source=images&cd=vfe&opi=89978449&ved=0CAcQr5oMahcKEwiAvaaBpPWKAxUAAAAAHQAAAAAQBA

10. https://bbgate.com/threads/purification-of-piperine-by-recrystallization.14340/