Methyl methoxy-cinnamic acid

DMA in 500 ml ether mix rapidly with 270 ml 0.9 M phenyl-Li, boil fifteen hours and extract as for (VI) or as described previously to get 8 g oily 4-methoxy-indoline (or its 1-methyl derivative) (VII). Alternatively, add 36 g naphthalene to 300 ml tetrahydrofuran and add 11 g Na metal cut in small pieces. Reflux and stir three hours and add 18 g (VI) and 8 g DEA in 200 ml tetrahydrofuran rapidly and boil twelve hours. Evaporate in vacuum, dissolve the oily residue in 2N HCI and extract with ether. Proceed as described to get (VII). 4 g (VII) in 200 ml dry pyridine add to 6 g Cu chloride in 400 ml pyridine and reflux 1 xh hours. Pour on water and extract with ether. Wash extract with 4N HCI and then water and dry and evaporate in vacuum the ether to get 2 g of the indole (VIII). Alternatively, dissolve 4 g (VII) and 9.5 g cinnamic acid in 700 ml mesitylene, add 1 g 5% palladium-carbon and reflux five hours. Filter, wash with HCI and NaHC03 and dry and evaporate in vacuum the mesitylene to get the red, oily (VIII) (can chromatograph on alumina and elute with benzene-petroleum ether). 

Scheme 2 shows Rapoport s synthesis [15]. The cinnamic acid derivative 3 prepared from m-methoxy benzaldehyde [20] was ethylated by diethyl sulfate to give ethyl cinnamate derivative 4, followed by Michael addition with ethyl cyanoacetate to afford compound 5. Compound 5 was converted to lactam 6 by the reduction of the cyano group and subsequent cyclization. Selective reduction of the lactam moiety of 6 was achieved by treatment with trimethy-loxonium fluorob orate followed by sodium borohydride reduction. Amine 8 was obtained by the reductive methylation of amine 7. Amine 8 was converted to compound 9 by methylene lactam rearrangement [21], followed by selenium dioxide oxidation to provide compound 10. Allylic rearrangement of compound 10 and subsequent hydrolysis gave compound 12. The construction of the decahydroisoquinoline structure began with compound 12,... 

Cinnamic acids can be created from the methylation of coumarins. Methoxy substituted coumarins produce lower yields than do non-substituted and hydroxy substituted coumarins. 

Activity of the purified en2ymes was assessed on methyl ferulate (methyl 4-hydroxy 3-methoxy cinnamate, MF). Assays were run for 30 min at 50 °C in 50 mM eitrate buffer at pH 4.8 with initial MF concentrations of 50 to 750 pM and an enzyme concentration of 50 nM. The reactions were terminated after 30 min by boiling for 10 min and analyzed for MF and ferulic acid content via C18 high performance liquid chromatography (HPLC) over a 0 to 100% acetonitrile gradient with 0.1% formic acid in all solutions. Preliminary isothermal titration calorimetry (ITC) on both ferulic acid esterase proteins was conducted in SEC buffer on a Microcal VP-ITC system. All reactions were carried out at 37 °C using MF as a substrate. 

Methoxy benzylidene-4-amino-Q -methyl cinnamic acid-n-propylester CH30-QH3-CH=N-QH4-CH=C(CH3)-C00C3H, ... 

Hydroxide ions open the lactone ring of coumarin forming the dianion 6 of (Z)-(2-hydroxy)cinnamic acid (coumarinic acid), which recyclizes to coumarin on addition of acid. On methylation with dimethyl sulfate, the dianion 6 is transformed to the (Z)-methoxy ester 8 however, on prolonged reaction with base it isomerizes to the ( )-dianion 7 ... 

D Auria, M. and Vantaggi, A., Photochemical dimerization of methoxy substituted cinnamic acid methyl esters. Tetrahedron, 48, 2523,1992. 

The conversion of phenylalanine, a C-6—C-3 precursor, to the C-6—C-1 unit of the Amaryllidaceae alkaloids requires the formal loss of two carbon atoms from the side chain of the amino acid as well as the introduction of at least two oxygenated substituents into the aromatic ring. The results shown in the latter part of Table III emphasize the specificity of the C-6—C-1 precursor. Benzaldehyde, -hydroxybenzal-dehyde, isovanillin, and protocatechuic acid are not incorporated to any appreciable extent into the alkaloids, while cinnamic, -hydroxy-cinnamic and caffeic acids, protocatechuic aldehyde, and 3-hydroxy-4-methoxy-i C-A-methyl-i4( ., enzylamine readily become part of the C-6—C-1 unit. 

Depending on the reaction conditions and the nature of the ester side chain in the cinnamates, the resorc[4]arenes can adopt different conformational states, namely, 1,2-altemate, 1,3-altemate, or flattened-cone). In particular, when ( )-2,4-dimethoxycinnamic acid methyl ester 1 was reacted with BF3 Et20 at room temperature, only the 1,2-altemate 2a and flattened-cone 2b stereoisomers were obtained in a 2 3 ratio and 75 % overall yield. In the 1,2-altemate conformation, the assignment of the 12- and 16-OMe signals, by INEPT experiments in conjunction with DIF NOE measurements, allowed to establish the correct stereochemistry at C(14). On the other hand, the presence in the H- and C-NMR spectra of only one signal for both external (H-5) and internal (H-28) aromatic protons and the related carbons, as well as a similar pattern for the methoxy group and the aliphatic... 

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