Piperidine

Source: Wikipedia, the free encyclopedia.
Piperidine[1]
Names
IUPAC name
Piperidine
Preferred IUPAC name
Piperidine[2]
Other names
Hexahydropyridine
Azacyclohexane
Pentamethyleneamine
Azinane
Identifiers
3D model (
JSmol
)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard
 100.003.467 Edit this at Wikidata
EC Number
  • 203-813-0
IUPHAR/BPS
KEGG
RTECS number
  • TM3500000
UNII
UN number 2401
  • InChI=1S/C5H11N/c1-2-4-6-5-3-1/h6H,1-5H2 checkY
    Key: NQRYJNQNLNOLGT-UHFFFAOYSA-N checkY
  • InChI=1/C5H11N/c1-2-4-6-5-3-1/h6H,1-5H2
  • InChI=1/C5H11N/c1-2-4-6-5-3-1/h6H,1-5H2
    Key: NQRYJNQNLNOLGT-UHFFFAOYAY
  • C1CCNCC1
Properties
C5H11N
Molar mass 85.150 g·mol−1
Appearance Colorless liquid
Odor Semen-like,[3] fishy-ammoniacal, pungent
Density 0.862 g/mL
Melting point −7 °C (19 °F; 266 K)
Boiling point 106 °C (223 °F; 379 K)
Miscible
Acidity (pKa) 11.22 (protonated)[4]
-64.2·10−6 cm3/mol
Viscosity 1.573 cP at 25 °C
Hazards
GHS labelling:
GHS02: FlammableGHS05: CorrosiveGHS06: Toxic
Danger
H225, H311, H314, H331
P210, P233, P240, P241, P242, P243, P260, P261, P264, P271, P280, P301+P330+P331, P302+P352, P303+P361+P353, P304+P340, P305+P351+P338, P310, P311, P312, P321, P322, P361, P363, P370+P378, P403+P233, P403+P235, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 3: Liquids and solids that can be ignited under almost all ambient temperature conditions. Flash point between 23 and 38 °C (73 and 100 °F). E.g. gasolineInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
3
3
0
Safety data sheet (SDS) MSDS1
Legal status
Related compounds
Related compounds
 Pyridine
Pyrrolidine
Piperazine
Phosphorinane
Arsinane
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)

Piperidine is an

Piper, which is the Latin word for pepper.[7] Although piperidine is a common organic compound, it is best known as a representative structure element within many pharmaceuticals and alkaloids, such as natural-occurring solenopsins.[8]

Production

Piperidine was first reported in 1850 by the Scottish chemist Thomas Anderson and again, independently, in 1852 by the French chemist Auguste Cahours, who named it.[9][10][11] Both of them obtained piperidine by reacting piperine with nitric acid.

Industrially, piperidine is produced by the hydrogenation of pyridine, usually over a molybdenum disulfide catalyst:[12]

C5H5N + 3 H2 → C5H10NH

Pyridine can also be reduced to piperidine via a modified Birch reduction using sodium in ethanol.[13]

Natural occurrence of piperidine and derivatives

Piperidine itself has been obtained from black pepper,[14][15] from Psilocaulon absimile (Aizoaceae),[16] and in Petrosimonia monandra.[17]

The piperidine structural motif is present in numerous natural

poison hemlock, which was used to put Socrates to death.[19]

Conformation

Piperidine prefers a

ring inversion.[22] In the case of N-methylpiperidine, the equatorial conformation is preferred by 3.16 kcal/mol,[20] which is much larger than the preference in methylcyclohexane
, 1.74 kcal/mol.

axial conformation equatorial conformation

Reactions

Piperidine is widely used to convert ketones to enamines.[23] Enamines derived from piperidine are substrates in the Stork enamine alkylation reaction.[24]

Upon treatment with

chloramine with the formula C5H10NCl. The resulting chloramine undergoes dehydrohalogenation to afford the cyclic imine.[25]

NMR chemical control

Uses

Piperidine is used as a

organic solvents
.

A significant industrial application of piperidine is for the production of dipiperidinyl dithiuram tetrasulfide, which is used as an accelerator of the sulfur vulcanization of rubber.[12]

List of piperidine medications

Minoxidil is a piperidine derivative widely used to prevent hair loss.

Piperidine and its derivatives are ubiquitous building blocks in pharmaceuticals[26] and fine chemicals. The piperidine structure is found in, for example:

Piperidine is also commonly used in chemical degradation reactions, such as the sequencing of

Fmoc-amino acids used in solid-phase peptide synthesis
.

Piperidine is listed as a Table II precursor under the United Nations Convention Against Illicit Traffic in Narcotic Drugs and Psychotropic Substances due to its use (peaking in the 1970s) in the clandestine manufacture of phencyclidine.[27]

References

  1. ^ "International Chemical Safety Card 0317".
  2. ISBN 978-0-85404-182-4
    .
  3. S2CID 19318345
    .
  4. doi:10.1021/ja01577a030
    .
  5. ^ Anvisa (2023-03-31). "RDC Nº 784 - Listas de Substâncias Entorpecentes, Psicotrópicas, Precursoras e Outras sob Controle Especial" [Collegiate Board Resolution No. 784 - Lists of Narcotic, Psychotropic, Precursor, and Other Substances under Special Control] (in Brazilian Portuguese). Diário Oficial da União (published 2023-04-04). Archived from the original on 2023-08-03. Retrieved 2023-08-15.
  6. ^ Frank Johnson Welcher (1947). Organic Analytical Reagents. D. Van Nostrand. p. 149.
  7. ISBN 978-0-444-52239-9
    .
  8. doi:10.1016/j.tetasy.2012.05.005
    .
  9. ^ Warnhoff, Edgar W. (1998). "When piperidine was a structural problem" (PDF). Bulletin for the History of Chemistry. 22: 29–34. Open access icon
  10. doi:10.1002/jlac.18500750110. Open access icon
  11. ^ Cahours, Auguste (1852). "Recherches sur un nouvel alcali dérivé de la pipérine" [Investigations of a new alkali derived from piperine]. Comptes Rendus. 34: 481–484. L'alcali nouveau dérivé de la pipérine, que je désignerai sous le nom de 'pipéridine',… (The new alkali derived from piperine, which I will designate by the name of 'piperidine',… Open access icon
  12. ^
    ISBN 978-3527306732
    .
  13. doi:10.15227/orgsyn.009.0016
    .
  14. doi:10.1002/cber.19350681211
    .
  15. doi:10.1002/hlca.19270100175
    .
  16. hdl:10520/AJA00382353_6425
    .
  17. ^ Juraschewski; Stepanov (1939). J. Gen. Chem. USSR. 9: 1687. {{cite journal}}: Missing or empty |title= (help)
  18. PMID 16990598
    .
  19. ^ Thomas Anderson Henry (1949). The Plant Alkaloids (4th ed.). The Blakiston Company.
  20. ^
    S2CID 98028598
    .
  21. doi:10.1021/ar50093a003
    .
  22. doi:10.1021/ja00450a064
    .
  23. ^ Kane, Vinayak V.; Jones, Maitland Jr. (1990). "Spiro[5.7]trideca-1,4-dien-3-one". Organic Syntheses; Collected Volumes, vol. 7, p. 473.
  24. ISBN 978-0-471-58589-3
    .
  25. doi:10.15227/orgsyn.056.0118
    .
  26. PMID 25255204
    .
  27. ^ "List of Precursors and Chemicals Frequently Used in the Illicit Manufacture of Narcotic Drugs and Psychotropic Substances Under International Control" (PDF). International Narcotics Control Board. Archived from the original (PDF) on 2008-02-27.

External links

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