481-81-2

Usage

Chemical Properties

Light Yellow Solid

Uses

An impurity of Heroin (H281180).

InChI:InChI=1/C16H14O3/c1-18-12-7-5-10-3-4-11-6-8-14(19-2)16(17)15(11)13(10)9-12/h3-9,17H,1-2H3

Upstream product

• 64-17-5 ethanol 
• 19826-49-4 4,5-epoxy-3,6-dimethoxy-17,17-dimethyl-morphina-6,8-dienium; iodide 
• 930-69-8 sodium thiophenolate 
• 88840-40-8 C₂₂H₂₈NO₃⁽¹⁺⁾*I^(1-) 
• 115-37-7 thebaine 
• 108-24-7 acetic anhydride 

Downstream Products

• 4504-38-5 4-benzoyloxy-3,6-dimethoxy-phenanthrene 
• 85-01-8 phenanthrene 

Relevant academic research and scientific papers

Conveniant Method for Replacement of Tertiary N-Methyl by Other Alkyl Groups: Application to Morphine Alkaloids

The replacement of N-methyl of N-methylpiperidine (1), 4-methylmorpholine (4), 2-methyl-1,2,3,4-tetrahydroisoquinoline (7) and tropine (10) by n-propyl, n-butyl and isopropyl groups (3a-3c, 6c, 9a-9c and 12a-12c) has been achieved in high yields by quaternization of the respective tertiary amine with appropriate alkyl halide and demethylation of the resulting quaternary salt with thiophenoxide.It has been established that demethylation is strongly favoured over the removal of n-propyl and n-butyl groups, whereas deisopropylation occurs to some extent.Surprisingly, in the case of 11c, deisopropylation predominates.This method has been applied to morphine (13b), codeine (13d) and thebaine (14b) for similar replacements.The rapid quaternization of thebaine (14b) has been assigned to the absence of H-14 in this alkaloid.The fact that quaternary salts of thebaine, which are susceptible to aromatization of the nucleus by extrusion of the ethanamine chain, are smoothly demethylated to N-alkylnorthebaines (18a-18c) in good yields indicates that demethylation, a bimolecular nucleophilic displacement, competes very successfully with elimination reaction.

Thebaine Rearrangements: Nonclassical D Ring Migrations

3,6-Dimethoxy-4-acetoxy-5-phenanthrene (3) and its isomer 3,6-dimethoxy-4-acetoxy-8-phenanthrene (4) have been detected as manufacturing byproducts at trace levels in illicit heroin.These compounds are novel rearrangement products obtained by the action of acetic anhydride (Ac2O) on thebaine (1).The syntheses of 3 and 4 from 1 proceed via the intermediate Δ5,7,9(14)-N-acetyldesthebaine (2).Structural characterization and optimization of synthetic conditions for 3 and 4 are described.A brief discussion is also giving concerning other neutral products of 1 obtained under Ac2O conditions.