3-Methoxycarbonyl-5-methyl

A series of 2-amino-3-guanidinocarbonylpyrazines has been prepared from the corresponding 2-amino-3-alkoxycaibonylpyrazine when refluxed with guanidine or with a guanidine salt and sodium alkoxide in the alcohol. Some pyrazine esters that have been converted with guanidine to guanidinocarbonyl compounds by the above method are as follows 2-amino-3-methoxycarbonyl (787, 802) 2-amino-3-methoxycarbonyl-5-methyl(ethyl, cyclopropyl, cyclohexyl, phenyl, and... 

Similarly, dimethyl 2,4-dimethyl-4-azaheptanedioate gives A/-methyl-3-methoxycarbonyl-5-methyl-4-oxopiperidine (18).S8... 

Cyclization of 1 -(9-fluorenylmethoxycarbonyl)-2-[(A-methoxycarbonyl-methyl)aminocarbonyl)piperidine and 2-(9-fluorenylmethoxycarbonyl) -3-[(A-methoxycarbonylmethyl)aminocarbonyl]-1,2,3,4-tetrahydroisoquino-lines on the action of piperidine in THF yielded 2-(l,4-dioxoperhydropyr-ido[ 1,2-fl]pyrazin-2-y 1)- and 2-( 1,4-dioxo-1,3,4,6,11,11 a-hexahydro-2//-pyr-azino[l,2-i]isoquinolin-2-yl)acetamides, respectively (99MIP11). 

The first synthesis of a 3//-3-benzazepine, e.g. 65 (R1 = R2 = Me), was achieved by the condensation of phthalaldehyde with a bis[(alkoxycarbonyl)methyl]methylamine.24"25 With sodium methoxide as the base, A%V-bis[(methoxycarbonyl)methyl]pheiiylaniine condenses with the dialdehyde in a similar manner to give dimethyl 3-phenyl-3//-3-benzazepine-2,4-dicar-boxy late (65, Rl — Ph R2 — Me).99 However, replacement of methoxide by potassium tert-butoxide results in formation of 3-phenyl-3//-3-benzazepine-2,4-dicarboxylic acid (65, R1 = Ph R2 = H).25... 

N-(tert-Butoxycarbonyl)-P-4-(methoxycarbonyl)phenyl]alanine methyl ester L-Phenylalanine, N-[(l,l-dimethylethoxy)carbonyl]-4-(methoxycarbonyl)-, methyl ester (160168-19-4)... 

Die Hydrodimerisierung von l,2-Bis-[2-methoxycarbonyl-vinyl]-benzol fiihrt unter Cyclisierung zum 6,12-Bis- [methoxycarbonyl-methyl]-5, t I-dimethoxycarbonyl-4b,5,6,1 Ob, 11,12-hexahydro-chrysen (29% d. Th. F 157-157,5°) neben einem Tetralin- und cincm Hexandisaure-dimelhylester-Derivat (2 0,5 0,5)2 ... 

A method for regioselective introduction of a bis(methoxycarbonyl)-methyl group into the 4-position of the piperidine skeleton was explored, and this method was applied to the preparation of cis- and rra j-2,4-disubstituted piperidines (e.g., 114) starting from 2-piperidinecarboxylic acid <96TL(37)5715>. 

The reaction of 1,2-allenyl sulfoxides with sodium malonate also afforded 2-[bis (methoxycarbonyl)methyl]-2-alkenyl sulfoxides 177, which upon further transformation would provide an efficient access to butenolide derivatives 180 [90, 91]. 

In order to find out whether captodative substitution of a methyl radical can lead to persistency, the rate of disappearance by bimolecular selfreaction was measured for typical sterically unhindered captodative radicals (Korth et al., 1983). The t-butoxy(cyano)methyl radical, t-butylthio(cyano)-methyl radical and methoxy(methoxycarbonyl)methyl radical have rate constants for bimolecular self-reactions between 1.0 x 10 and 1.5 X 10 1 mol s Mn the temperature range —60 to - -60°C. The dilTusion-controlled nature of these dimerizations is supported by the Arrhenius activation parameters. Thus, it has to be concluded that there is no kinetic stabilization for captodative-substituted methyl radicals. On the other hand, if captodative-substituted radicals are encountered which are kinetically stabilized (persistent) or which exist in equilibrium with their dimers, then other influences than the captodative substitution pattern alone must be added to account for this phenomenon. 

Dimethylcarbonate, in presence of K2CO3, has been found to react with benzyl aryl and alkyl aryl sulfones RCH2S02Ar at 180-210 °C to form the corresponding mono-C-methyl derivative selectively and in high yield. The monomethylation has been attributed to a methoxycarbonylation-methylation-demethoxycarbonylation sequence via ArS02C(Me)(C02Me)R. 

An effective reagent for this is RuCyaq. IO(OH)3/CCl -CH3CN, used for oxidation of the lactone (2R,3R,4R)-2-methyl-2-phenylthio-3-methoxycarbonyl-methyl-4-(2 -tert-butyl-diphenylsilyloxy)ethyl-y-butyrolactone to the sulfonyl analogue (Fig. 5.16) other oxidations are listed in Table 5.2 [107]. 

Brom-5-formyl-l-( 4-methoxy-henzyl)-imidazol l-Benzyl-4-brom-5-carboxy-...946 /-Benzyl-4-brom-5-mercapto-...946 4-Brom-5-methoxycarbonyl-]-methyl-...1047 1033 50% 67% 68% 50% ... 

Chlormethyl-(methoxycarbonyl-methyl)-quecksilber reagiert mit Pyrrolidin in Tetrahydrofuran unter N-Substitution zu einem Diamino-methan z. B.2 ... 

Formamido-5-methoxy-2-(methoxycarbonyl) Methyl 2-methyl-3-oxobutanoate HCO,H 72 [6]... 

Benzyloxycarbonyl-5-fluoro-3-(2-methoxycarbonyl-ethyl)-4-(metboxycarbonyl-methvl)-E 10b,. 45 (H -> F) 2-Benzyloxycarbonyl-5-fluoro-4-(2-methoxycarbonyl-ethyl)-3-(methoxycarbonyl-methyl)-ElOb,. 45 (H -> F) 3,5-Bis-[lrifluoromethyl]-2-phcnyl-E6a, 685... 

The diethyl 2-[3-bis(methoxycarbonyl)methyl-4-nitrophenyl]-2-methylmalonate obtained above,(4.13 g, 9.71 mmol) was dissolved in acetic acid (40 ml). To the solution were added water (16 ml) and concentrated sulfuric acid (4 ml), and the resulting mixture was heated for 15 hours under reflux. The acetic acid was distilled off under reduced pressure. The residue was concentrated under reduced pressure after addition of toluene. The precipitated crystals were collected by filtration and washed with water to give 2.06 g of the desired compound as a pale brown crystalline product. The filtrate and washing were combined and subjected to extraction using ethyl acetate. The ethyl acetate portion was washed successively with water and an aqueous saturated sodium chloride solution, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to leave 0.32 g of 2-(3-carboxymethyl-4-nitrophenyl)propionic acid as a yellow crystalline product. The total amount was 2.38 g (yield 96.8%). 

Methoxycarbonyl methyl-1 //-pyrrolo 3,4-r pyridine-l,3(2//)-dione (47) has been reported to undergo ring expansion to afford methyl 4-hydroxy-1-oxo-l,2-dihydro-2,7-naphthyridine-3-carboxylate (48) (MeONa/MeOH, 100°C ... 

With cyclohexene and silyl enol ethers, under these conditions, there was no cyclization the former gave a mixture of 3- and 4-bis(methoxycarbonyl)methyl-cyclohexenes, whereas the latter afforded RC0CH2CH(C02Me)2 (up to 60%) [24], Lactones were formed from PhI=C(C4F9)C02Et with catalysis by cupric triflate [25]. 

Methoxycarbonyl-methyl)- -methyl-5,6-dihydro-(dibenzo[b d] phosphorin)-5- osid 295 Zu 0,21 g (2,5 mmol) Propiolsaure-methylester in 5 ml THF und 0,2 ml Wasser gibt man innerhalb 10 Min. Lropfenweise die Losung von 0,5 g (2,7 mmol) 5-Methyl-dibenzOphosphol in 10m/ THF. AnschlieBend erhitzt man 12 Stdn. zum RiickfluB, dampft ein und kristallisiert den Riickstand aus Ether und Benzol Ausbeute 0,5 g (70°/o) Schmp. 145-148°. 

Methoxycarbonyl-methyl)-5-phenyl-5,6-dihydro- dibenzo b,d]phosphoririy-5-oxid (R = C6H5) 33% 5-Benzyl-6-(methoxycarbonyl-methyl)-5,6-dihydro-(dibenzo[b,d]phosphorin -5-oxid (R — CH2-C6H5) 16% ... 

Phosphinsaure-chloride konnen mit sek. Carbaminsaureestem in Gegenwart molarer Mengen Chlorwasserstoff-Akzeptoren (z.B. Triethylamin) zu N-Acyl-phosphinsaure-amiden reagieren, z.B. Dipentylphosphinsdure-(methoxycarbonyl-methyl-amid)8 9 ... 

Butyl-(methoxy-methoxycarbonyl-methyl)- -ethylester E2, 206 Butyl-methyl- XII/1, 228 tert.-Butyl-methyl- -chlorid-(2,2-dimethyl-hydrazonid) E2, 288 Butyl-methyl- -pentylester XII/1, 261 tert.-Butyl-(4-mcthyl-phcnyl)- -anhydrid E2, 174 terl.-Butyl-(4-melhyl-phenyl)- -chlorid E2, 154 (Butyloxycarbonyl-hydroxy-methyl)-ethyl- -propyl-cstcr E2, 186... 

Chlor-ethyI)-ethyI- -chlorid XII/I, 243 (l-Chlor-ethyl)-(methoxycarbonyl-methyl)- -rae-thylester E2, 221... 

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