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Synthesis of Tropinone & 2-CMT

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Rhodium:
Die Synthese von Naturstoffen, insbesondere von Alkaloiden, unter physiologischen Bedingungen und ihre Bedeutung für die Frage der Entstehung einiger pflanzlicher Naturstoffe in der Zelle
IV. Die Synthese der Tropaalkaloide and des Pseudopelletierins unter physiologischen Bedingungen.
Prof. Dr. Clemens Schöpf
Angewandte Chemie, Vol 50, No. 40, pp. 779-790 (1937) (https://www.thevespiary.org/rhodium/Rhodium/pdf/tropinone.angew.chem.1937.pdf)

Summary
A section about the Robinson synthesis of tropinone from a review article on alkaloids, prepared under physiological reaction conditions (no exotic catalysts, near neutral pH, etc.). It shows very nice graphs of the relationship between the solution pH and the yield of tropinone isolated from a mixture of acetonedicarboxylic acid, succindialdehyde and methylamine allowed to stand at room temp for 72h. The graph peaks at 80% at pH=5, but the yield stays at 60%+ all the way between pH 3-11.
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One-pot synthesis of tropinone by tandem (domino) ene-type reactions of acetone silyl enol ethers
Koichi Mikami and Hirofumi Ohmura
Chem. Commun. (22), 2626-2627 (2002) (https://www.thevespiary.org/rhodium/Rhodium/pdf/tropinone-acetone.silyl.enol.ether.pdf)
DOI:10.1039/b208066d



Abstract
A synthetic approach for tropane alkaloids on the basis of tandem (domino) ene-type reactions of acetone silyl enol ethers with iminium ions is shown to be triggered by intermolecular ene-type reactions followed by 6-(2,5)silatropic ene-type cyclizations.
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Concerning 2-Carbomethoxytropinone
Steven P. Findlay
J. Org. Chem. 22, 1389-1394 (1957) (https://www.thevespiary.org/rhodium/Rhodium/pdf/2-carbomethoxytropinone.pdf)

Abstract
Racemic 2-carbomethoxytropinone is obtainable by the partial saponification of 2,4-dicarbomethoxytropinone and, more conveniently, by the condensation of monomethyl beta-ketoglutarate, got from beta-ketoglutaric anhydride, with succindialdehyde and methylamine. 2-Carbomethoxytropinone can conceivably exist in three racemic and six optically active forms. Of these only one has been obtained heretofore. The configurational relation of d-(2-carbomethoxytropinone) and its l antipode to l-cocaine is established by the Kiliani chromic acid oxidation of pseudoecgonine methyl ester to the former. Previous methods of preparing racemic 2-carbomethoxytropinone, the properties of 2,4-dicarbomethoxytropinone, and incidental experimental data are discussed.
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Stereoselective reduction of Tropinone and 2-Carbomethoxytropinone

Post 458047 (Rhodium: "Stereochemistry of the Reduction of Tropinone", Serious Chemistry)
Post 458140 (roger2003: "2-Carbomethoxytropinone to Methyl Ecgonine", Serious Chemistry)

Rhodium:
The Effects of Microwave Irradiation on Occluded Solvents in Illicitly Produced Cocaine Hydrochloride
David R. Morello, John F. Casale, Margaret L. Stevenson, and Robert F. X. Klein
J Forensic Sci, Vol. 45, No. 5, pp. 1126-1132 (2000) (https://www.thevespiary.org/rhodium/Rhodium/pdf/cocaine.microwave.drying.pdf)

Abstract
The current clandestine methodology for the manufacture of illicit cocaine hydrochloride utilizes microwave heating in order to dry the finished product. This study addresses the effects this step has on the occluded solvents present in newly prepared cocaine hydrochloride. Nine 1-kilogram-sized batches of cocaine hydrochloride were prepared from cocaine base using a variety of solvents or solvent mixtures commonly utilized in clandestine laboratories, pressed into bricks, and submitted to microwave heating. Residual solvents were qualitatively and quantitatively monitored before, during, and following the microwaving step by static headspace-gas chromatography-mass spectrometry. All solvents used in the conversion process were easily detected in the bricks even after extensive irradiation, confirming that occluded solvents are extremely resistant to removal by microwave heating. Qualitative and quantitative data corresponding to the residual solvents in the prepared cocaine hydrochloride bricks are presented.
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Comparative Determination of 2-Carbomethoxy-3-Alkyloxy- and Heteroaroyloxy-Substituted Tropanes in Illicit South American Cocaine Using Capillary Gas Chromatography-Single Ion Monitoring
John F. Casale, James M. Moore, and Norman G. Odeneal
J Forensic Sci, Vol. 43, No. 1, pp. 125-132 (1998) (https://www.thevespiary.org/rhodium/Rhodium/pdf/cocaine.trace.methylecgonines.pdf)
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Detection of Cocaine on Various Denominations of United States Currency
Adam Negrusz, Jennifer L. Perry, Christine M. Moore
J Forensic Sci, Vol. 43, No. 3, pp. 626-629 (1998) (https://www.thevespiary.org/rhodium/Rhodium/pdf/cocaine.currency.pdf)
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Identification of cis- and trans-Cinnamoylcocaine in Illicit Cocaine Seizures
James M. Moore
J. Ass. Off. Anal. Chem. 56(5), 1199-1205 (1973) (https://www.thevespiary.org/rhodium/Rhodium/pdf/cinnamoylcocaine.pdf)

Abstract
During the in-depth analysis of illicit cocaine samples small amounts of other coca alkaloids and cocaine degradation products have been detected. One of these alkaloids, cinnamoylcocaine, has been found in more than half of the samples examined, usually in concentrations of 1% or less of the amount of cocaine present. The presence of cinnamoylcocaine, as its cis and trans isomers, was established by column partition chromatographic isolation of the isomers, followed by ultraviolet, infrared, nuclear magnetic resonance, and mass spectrometric identification.

Rhodium:
Ueberführung von Tropinon in r-Cocaïn
R. Willstätter & A. Bode
Chem. Ber. 34, 1457-1461 (1901) (https://www.thevespiary.org/rhodium/Rhodium/pdf/cocaine.willstatter-1901a.pdf)
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Bildung von Tropin aus Tropidin und die Synthese des Atropins
A. Ladenburg
Chem. Ber. 35, 1159-1162 (1902) (https://www.thevespiary.org/rhodium/Rhodium/pdf/tropine-tropidine.pdf)
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Ueber Pseudotropin
Richard Willstätter
Chem. Ber. 29, 936-947 (1896) (https://www.thevespiary.org/rhodium/Rhodium/pdf/pseudotropine.pdf)
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Ein Neuer Synthetischer weg in der Tropan-Reihe
C. Grundmann & G. Ottmann
Ann. Chem. 605, 24-32 (1957) (https://www.thevespiary.org/rhodium/Rhodium/pdf/anhydroecgonine.cycloheptatriene.pdf)

Summary:
Racemic anhydroecgonine is prepared by addition of methylamine to cycloheptatriene-carboxylic acid, which itself is prepared by the addition of ethyl diazoacetate to benzene [Ann. Chem. 582, 163 (1953)].

Rhodium:
A Synthesis of Tropinone
Robert Robinson
J. Chem. Soc. 762-768 (1917) (https://www.thevespiary.org/rhodium/Rhodium/pdf/tropinone.robinson-1917.pdf)
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Ueber das Tropinon
Richard Willstätter
Chem. Ber. 393-403 (1896) (https://www.thevespiary.org/rhodium/Rhodium/pdf/tropinone.willstatter-1896.pdf)
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Ueber das dritte racemische Cocain
Karl Zeile & Werner Schulz
Chem. Ber. 678-679 (1956) (https://www.thevespiary.org/rhodium/Rhodium/pdf/dritte.racemische.cocain.pdf)

roger2003:
2-carbomethoxytropinone from succindialdehyde, methylamin and Ethyl acetoacetate

Patent DE345759

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