1699-51-0

Basic information

• Product Name: DL-LAUDANOSINE
• Synonyms: (+-)-1,2,3,4-tetrahydro-6,7-dimethoxy-2-methyl-1-veratrylisoquinoline;(+-)-laudanosine;2,3,4-tetrahydro-6,7-dimethoxy-2-methyl-1-veratryl-(+-)-isoquinolin;N-METHYLTETRAHYDROPAPAVERINE;DL-LAUDANOSIDE;DL-LAUDANOSINE;(+/-)-LAUDANOSIDE;LAUDANOSINE, DL-
• CAS NO: 1699-51-0
• Molecular Formula: C₂₁H₂₇NO₄
• Molecular Weight: 357.44
• EINECS: 216-923-9
• Mol File: 1699-51-0.mol
• Article Data: 24

Chemical Properties

• Melting Point: 115°C
• Boiling Point: 490.07°C (rough estimate)
• Flash Point: 131.2°C
• Appearance: /
• Density: 1.1729 (rough estimate)
• Vapor Pressure: 6.19E-09mmHg at 25°C
• Refractive Index: 1.5614 (estimate)
• PKA: 7.80±0.40(Predicted)
• CAS DataBase Reference: DL-LAUDANOSINE(CAS DataBase Reference)
• NIST Chemistry Reference: DL-LAUDANOSINE(1699-51-0)
• EPA Substance Registry System: DL-LAUDANOSINE(1699-51-0)

Safety Data

• Statements: 26/28-40
• Safety Statements: 22-24/25
• RIDADR: 2810
• HazardClass: 6.1(b)
• PackingGroup: III
• Hazardous Substances Data: 1699-51-0(Hazardous Substances Data)

Usage

Description

This opium alkaloid occurs in the liquor following precipitation of Thebaine (q.v.) and is purified by extraction with small quantities of Et20, followed by precipitation with potassium iodide. The base crystallizes from hot C6H6 in small, colourless needles and has [α]15D+ 103.23° (EtOH). It is freely soluble in CHCI3, EtOH, Et20 or hot C6H6 but insoluble in H20 or alkalies. No colour is produced with FeCl 3 but with Fe203 and H2S04, a brown colour is formed, changing to green when warmed to ISOoC. With concentrated H2S04 alone, the alkaloid gives a rose-red colour, changing to deep violet at ISO°C. The solution of the alkaloid in EtOH is alkaline to litmus and both it, and its salts, are bitter to the taste. The crystalline methiodide has m.p. 218-221°C; [α]D + 120°. The oxidation products with Mn02 and H2S04 are veratraldehyde, 2:3:6:7- tetramethoxy-9: I O-dihydroanthracene and laudaline (4: S-dimethoxy-2: - methylaminoethylbenzaldehyde, m.p. 123-4°C. On exhaustive methylation it yields trimethylamine and laudanosene (tetramethoxy-o-vinylstilbene). Laudanosine is one of the most convulsant of the opium alkaloids but possesses only a slight analgesic action.

Chemical Properties

light yellow fine crystalline powder

Purification Methods

Crystallise these from EtOH. The (±)-picrate crystallises from EtOH with m 177-178o. The (-)-isomer has m 83-85o and

References

Pictet, Athanasescu., Ber., 33, 2347 (1900) Pictet, Finkelstein., ibid, 42, 1979 (1909) Pyman, Reynolds.,J. Chern. Soc., 97, 1324 (1910) Kondo, Mori.,J. Ph arm. Soc., Japan, 51,615 (1931) Craig, Tarbell., J. Amer. Chern. Soc., 70,2783 (1948) Synthesis: Pictet, Finkelstein., Compt. rend., 148,925 (1909) Elliot.,J. Heterocycl. Chern., 7, 1229 (1970) Pharmacology: Zunz., Elements de Pharmacodynamie speciale, Tome I, 178, Masson & Co., Paris (1932) Krueger, Eddy, Sumwalt., U.S. Public Health Reports, Suppl. 165, 1007 (1943)

InChI:InChI=1/C21H27NO4/c1-22-9-8-15-12-20(25-4)21(26-5)13-16(15)17(22)10-14-6-7-18(23-2)19(11-14)24-3/h6-7,11-13,17H,8-10H2,1-5H3/p+1/t17-/m1/s1

Upstream product

• 24948-17-2 N-methyl-laudanosinium iodide 
• 2246-26-6 1,2-dihydro-2-methylpapaverine 
• 21852-32-4 4-bromomethyl-1,2-dimethoxybenzene 
• 30045-07-9 2-methyl-6,7-dimethoxy-3,4-dihydroisoquinolinium iodide 
• 58-74-2 Papaverine 
• 51714-24-0 6,7-dimethoxy-2-methyl-1,2,3,4-tetrahydroisoquinoline-1-carbonitrile 
• 93-03-8 (3,4-dimethoxyphenyl)methanol 
• 7306-46-9 4-chloromethyl-1,2-dimethoxy-benzene 
• 140367-63-1 3,4-dihydro-6,7-dimethoxy-1-(3,4-dimethoxyphenyl)methyl-2(1H)-isoquinolinecarboxylic acid 1,1-dimethylethyl ester 
• 127119-08-8 3,4-dihydro-6,7-dimethoxy-2(1H)-isoquinolinecarboxylic acid 1,1-dimethylethyl ester 
• 1745-07-9 6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline 
• 148679-66-7 (2-Benzenesulfinyl-ethyl)-[1,2-bis-(3,4-dimethoxy-phenyl)-ethyl]-carbamic acid methyl ester 
• 210696-90-5 N-[1,2-Bis-(3,4-dimethoxy-phenyl)-ethyl]-N-(2-phenylsulfanyl-ethyl)-formamide 
• 846601-41-0 [2-(2-iodo-4,5-dimethoxyphenyl)ethyl]methylamine 

Downstream Products

• 2688-77-9 (S)-laudanosine 
• 120-14-9 3,4-dimethoxy-benzaldehyde 
• 100710-88-1 2-(3,4-dimethoxybenzyl)pyridine 
• 21965-92-4 1-(3',4'-dimethoxybenzyl)isoquinoline 

Relevant articles and documents

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Berberis alkaloids XXXIX. New alkaloids from B. densiflora

The alkaloid composition of the leaves of Berberis densiflora has been studied. Berberine, β-allocryptopine, oxyacanthine, glautine, thalicmidine, isocorydine, O-methylcorypalline and the new bases densinine and densiberine have been isolated. The structures of the new alkaloids have been established by a study of spectral characteristics and chemical transformations. This is the first time that any of the known alkaloids, apart from berberine, have been isolated from a plant of this species and it is the first time that β-allocryptopine and O-methylcorypalline have been isolated from the Berberis genus.

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Total Synthesis of (-)-Oxycodone via Anodic Aryl-Aryl Coupling

A fully regio- and diastereoselective electrochemical 4a-2′-coupling of a 3′,4′,5′-trioxygenated laudanosine derivative enables the synthesis of the corresponding morphinandienone. This key intermediate is further transformed into (-)-oxycodone through conjugate nucleophilic substitution for E-ring closure and [4 + 2] cycloaddition with photogenerated singlet oxygen to accomplish diastereoselective hydroxylation at C-14. The anodic transformation provides high yields and can be performed under constant current conditions both in a simple undivided cell or in continuous flow.

Total Synthesis of Tetrahydroisoquinoline-Based Bioactive Natural Products Laudanosine, Romneine, Glaucine, Dicentrine, and Their Unnatural Analogues Isolaudanosine and Isoromneine

Starting from suitably substituted homophthalic acids, total synthesis of titled alkaloids have been demonstrated in very good yields. The obtained natural products laudanosine and romneine were utilized to accomplish synthesis of two isoquinoline-based alkaloids glaucine and dicentrine. Base-induced selective generation of two different types of benzylic carbanions, their coupling reactions with 3,4-dimethoxybenzyl mesylate, and the regioselective iodination followed by intramolecular aryl-aryl coupling reactions to form the fused biaryl systems were the strategic steps.

Synthesis of alkaloids by stevens rearrangement of nitrile-stabilized ammonium ylides: (±)-laudanosine, (±)-laudanidine, (±)-armepavine, (±)-7-methoxycryptopleurine, and (±)-xylopinine

The Stevens rearrangement of nitrile-stabilized ammonium ylides in conjunction with the reductive removal of the nitrile function permits the facile construction of α-branched amines from α-aminonitriles. We employed this reaction sequence for the preparation of (±)-laudanosine, (±)-laudanidine and (±)-armepavine, (±)-7- methoxycryptopleurine, and (±)-xylopinine from two closely related and readily accessible bicyclic α-aminonitriles. The final products were obtained in high to almost quantitative yields (71-98%) from the quaternary ammonium salts obtained by N-alkylation of these starting materials.