77785-12-7

Upstream product

• 17889-56-4 macarpine chloride 
• 77784-66-8 [1-(5-Bromo-6-methoxy-benzo[1,3]dioxol-4-yl)-meth-(Z)-ylidene]-(8-methoxy-naphtho[2,3-d][1,3]dioxol-5-yl)-amine 
• 673477-43-5 1-ethynyl-2-methoxy-4,5-methylenedioxybenzene 
• 168098-72-4 4-methoxy-2-(2-methoxy-4,5-methylenedioxyphenyl)-1-(N-methylformamido)-6,7-methylenedioxynaphthalene 
• 10022-35-2 1-bromo-2-methoxy-4,5-methylenedioxybenzene 
• 125032-01-1 oxymacarpine 
• 64-18-6 formic acid 
• 77785-13-8 C₂₁H₁₅NO₆ 
• 77784-67-9 (5-Bromo-6-methoxy-benzo[1,3]dioxol-4-ylmethyl)-(8-methoxy-naphtho[2,3-d][1,3]dioxol-5-yl)-amine 

Relevant academic research and scientific papers

NEW FINDINGS IN BISCHLER-NAPIERALSKI REACTION: FORMATION OF 12-AZONIANAPHTHAZULENES FROM 2-ARYL-1-NAPHTHYLFORMAMIDES AND THEIR UNEXPECTED TRANSFORMATION INTO BENZINDOLES THROUGH HYDRIDE REDUCTION

The Bischler-Napieralski Reaction (BNR) of N--N-methylformamides using POCl3 abnormally gave 12-azonianaphthazulene derivatives, which could be effectively transformed into benzindoles with a 1-alkoxy-8-oxabicyclooct-2-ene skeleton through hydride reduction, as additional cyclized products.In contrast, the BNR of naphthylformamides with methoxy groups in place of a methylenedioxy function at the same position in the phenyl ring led to normal cyclization to give benzophenanthridinium chlorides quantitatively.The speculative mechanism for the abnormal BNR and the indole formation will be discussed.

Nitromethane as a Carbanion Source for Domino Benzoannulation with Ynones: One-Pot Synthesis of Polyfunctional Naphthalenes and a Total Synthesis of Macarpine

A one-pot, transition-metal-free, domino Michael/SNAr protocol of general applicability has been devised for the regioselective synthesis of polyfunctional naphthalenes by employing nitromethane and ortho-haloaryl ynones. Utilization of nitromethane as a one carbon carbanion source that is incorporated into a variety of ynones, ends up as an aromatic nitro substituent. The application of this domino process towards a total synthesis of the polycyclic alkaloid macarpine demonstrate for the efficacy of this methodology. The conceptually simple approach to affect regioselective, multifunctional benzoannulation of ynones displays wide substrate scope and functional-group tolerance and has been implemented with substituted nitromethanes, as well as with alicyclic o-haloynones.

Anomalous substituent effects in the Bischler-Napieralski reaction of 2-aryl aromatic formamides

Treatment of some 1-naphthylformamides (or formanilides) possessing a 2,4,5-trioxygenated phenyl substituent at the 2-position with POCl3 caused an unprecedented carbon insertion reaction into a benzene ring, producing 7-5 ring (azaazulene) systems as valence isomers of isoquinoline skeletons. Precise examination of this abnormal Bischler-Napieralski reaction (BNR) using various substrates led to the following scope and limitations: (i) the 7-5 ring systems were constructed when either 2-alkoxy-4,5-methylenedioxyphenyl- or 4,5-dialkoxy-2-hydroxyphenyl-substituted formamides were used as a starting substrate; (ii) in the former case the formyl carbon was inserted into the C1-C6 bond of the 2-phenyl group, and normal isoquinoline cyclization competed with an abnormal carbon insertion reaction; (iii) the presence of a hydroxy group at the 2′-position as in the latter cases caused exclusive carbon insertion, in which alternative C1-C2 insertion products were quantitatively formed; (iv) 3,6-dimethoxy-2-hydroxyphenyl-substituted formanilide electronically equivalent to 4,5-dialkoxy-2-hydroxy derivatives produced an indole-pyrone as an abnormal BNR product. Theoretical approaches using the PM-3 method indicated that these abnormal BNRs could be triggered by ipso attack at the 1′-position yielding spiro intermediates. Ring cleavege of the six-membered ring in the spiro intermediates to a ketene function followed by recyclization was proposed for the 2′-hydroxy-directed abnormal BNRs leading to the C1-C2 insertion product or the indole-pyrone derivative.

Synthesis of Macarpine and its Cytotoxicity: Toward a Synthetic Route for 12-Alkoxybenzophenanthridine Alkaloids through Aromatic Nitrosation under Basic Condition

Macarpine (1), a 2,3,7,8,10,12-hexaoxygenated benzophenanthridine alkaloid (O6 base), was effectively synthesized from sesamol methyl ether (7) through the newly developed aromatic nitrosation under basic condition.The tests for the cytotoxicity of 1 a

THE STRUCTURE OF THE ALKALOID MACARPINE

The revised structure of the alkaloid macarpine (1c), which was isolated from both the plants and callus of Macleaya cordata, was proposed and unambiguously established by its total synthesis.