Lysergic acid

Lysergic acid
Names
IUPAC name
7-Methyl-4,6,6a,7,8,9-hexahydroindolo[4,3-fg]quinoline-9-carboxylic acid
Other names
6-Methyl-9,10-didehydroergoline-8-carboxylic acid
Identifiers
82-58-6 YesY
3D model (Jmol) Interactive image
ChEBI CHEBI:6604 YesY
ChemSpider 6461 YesY
ECHA InfoCard 100.001.302
139
UNII ITO20DAO7J N
Properties
C16H16N2O2
Molar mass 268.32 g·mol−1
Melting point 238 to 240 °C (460 to 464 °F; 511 to 513 K)
Acidity (pKa) pKa1 = 7.80, pKa2 = 3.30 [1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Lysergic acid, also known as D-lysergic acid and (+)-lysergic acid, is a precursor for a wide range of ergoline alkaloids that are produced by the ergot fungus and found in the seeds of Turbina corymbosa (ololiuhqui), Argyreia nervosa (Hawaiian Baby Woodrose), and Ipomoea tricolor (morning glories, tlitliltzin). Amides of lysergic acid, lysergamides, are widely used as pharmaceuticals and as psychedelic drugs (LSD). Lysergic acid received its name as it was a product of the lysis of various ergot alkaloids.[2]

Total synthesis

Lysergic acid is generally produced by hydrolysis[3] of natural lysergamides, but can also be synthesized in the laboratory by a complex total synthesis for example by Woodward's team in 1956.[4] An enantioselective total synthesis based on a palladium catalyzed domino cyclization reaction has been described in 2011 by Fujii and Ohno.[5] Lysergic acid monohydrate crystallizes in very thin hexagonal leaflets when recrystallized from water. Lysergic acid monohydrate, when dried (140 °C at 2 mmHg or 270 Pa) forms anhydrous lysergic acid. The biosynthetic route is based on the alkylation of the amino acid tryptophan with dimethylallyl diphosphate (isoprene derived from 3R-mevalonic acid) giving 4-dimethylallyl-L-tryptophan which is N-methylated with S-adenosyl-L-methionine. Oxidative ring closure followed by decarboxylation, reduction, cyclization, oxidation, and allylic isomerization yields D-(+)-lysergic acid.[2]

Isomers

Lysergic acid is a chiral compound with two stereocenters. The isomer with inverted configuration at carbon atom 8 close to the carboxy group is called isolysergic acid. Inversion at carbon 5 close to the nitrogen atom leads to L-lysergic acid and L-isolysergic acid, respectively. Lysergic acid is listed as a Table I precursor under the United Nations Convention Against Illicit Traffic in Narcotic Drugs and Psychotropic Substances.[6]

Chemical structures of lysergic acid isomers

See also

References

  1. ↑ Brown, H.C. et al., in Braude, E.A. and F.C. Nachod. Determination of Organic Structures by Physical Methods, Academic Press, New York, 1955.
  2. 1 2 Schiff PL (Oct 15, 2006). "Ergot and its alkaloids". Am J Pharm Educ. 70 (5): 98. doi:10.5688/aj700598. PMC 1637017Freely accessible. PMID 17149427.
  3. ↑ Martínková L, Kren V, Cvak L, Ovesná M, Prepechalová I (Nov 17, 2001). "Hydrolysis of lysergamide to lysergic acid by Rhodococcus equi A4". J Biotechnol. 84 (1): 63–6. doi:10.1016/s0168-1656(00)00332-1.
  4. ↑ Edmund C. Kornfeld; E.J. Fornefeld; G. Bruce Kline; Marjorie J. Mann; Dwight E. Morrison; Reuben G. Jones & R.B. Woodward (1956). "The Total Synthesis of Lysergic Acid". Journal of the American Chemical Society. 78: 3087–3114. doi:10.1021/ja01594a039.
  5. ↑ S. Inuki, A. Iwata, S. Oishi, N. Fujii and H. Ohno, J. Org. Chem. 2011, 76 (7), pp 2072–2083, doi:10.1021/jo102388e.
  6. ↑ List of Precursors and Chemicals Frequently Used in the Illicit Manufacture of Narcotic Drugs and Psychotropic Substances Under International Control, International Narcotics Control Board
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