2,4-D methylester

Oxo 4-pheny1 2-[4-d)1or-pliei l]-1.4.5.6 tels hydro pyridm-carb(MaB iire ( 5) methylester 88 II 25d. 

Bei der Reduktion von Phenylessigsaure-methylester in Tetrahydrofuran wird neben 74% d.Th. 2-Phenyl-athanol auch wenig 2,4-Diphenyl-butandiol-(l,3) erhalten (s.a.S. 148)1. 

Dagegen reagiert 5-Phenyl-pentadien-(2,4)-saure-methylesterin einer 1,6-Addition zu 5-Phenyl-6-oxo-hep-ten-(2)-sdure-methylester (15% d.Th.)3 und unter 1,4-Addition zum 5-Phenyl-3,3-diacetyl-penten-(4)-sdure-methylester (30% d.Th.). 

Die Umsetzung von 2-Amino-2-deoxy-D-(- -)-glucose oder alternativ 1-Amino-1-deoxy-D-fruc-tose mit 2-Ethoxy-acrylsaure-imid-methylester (in situ erzeugt aus 2-Ethoxy-acrylnitril mit Natriummethanolat) liefert 2-Acetyl-4(5 )-[l (R), 2( S),3( R), 4-tetrahydroxy-bulyl]-imidazol... 

Dtainino.azobenzol-oarbona ure-(2)-methylester 18, 386. 2.2 -Diinethyl-diphenyl-bis-diazoniam> hydroxyd-(4.4 ) 16 II286. 3.3 -D)methyl.diphenyl-biS djazonium> hydroxyd-(4.4 ) 16, 518. 2-Nitramlno.acetophenon-phenyUiydiazon 16 1401. 

CggHggNOg 4.4-D thoxy-2.6-diphenyl-l-cyan-cydohezan-carbonsaure-fl )-methylester 10 n 627. 

Analog erhalt man aus 3-Acetoxy-phthalsaure-2-methylester mit 0,13 Mol Lithiumala-nat 4-Hydroxy-phthalid (68% d.Th. F 252—254°). 

Carbonsaureester konnen ebenfalls kathodisch unter Reduktion der Alkohol-Kompo-nente gespalten werden. So entsteht z. B. aus 4-Acetoxymethyl-benzoesaure-athylcster der 4-Methyl-benzoesdure-methylester (Methanol/Natriumacetat 93% d.Th.)4. Die op-tisch aktive 2-Benzoyloxy-2-phenyl-propansaure sowie deren Methylester werden unter nahezu totalcr Racemisierung reduziert5 ... 

Introduction of nitrogen into the anulene ring (e.g. of 95) leads to a methano-azaanulene 107 121) with Q-symmetry which is therefore chiral (like its mono- or disubstituted derivatives)118). The low basicity of 107 (pKa 3.20) prevented its optical resolution by conventional methods (e.g. through salts with optically active acids). Excellent results were obtained, however, (as also in the case of the two isomeric carbocyclic methylesters 97 and 101 and of several derivatives of azaanulene) by chromatography on microcrystalline triacetyl cellulose in ethanol at 7 bar 1221 (see also Section 2.7.1). In many cases base line separations were accomplished to give both (optically pure) enantiomers. Enantiomeric relations were confirmed in all cases by recording the CD-spectra of both fractions. Some results of these separations are shown in Fig. 4 together with the optical rotations ([a]D in ethanol) of the enantiomers. 

Fig. 9. Proton NMR spectra at 220 Me of solutions in d5-pyridine of the Zn(II)-complexes with porphin, and the dimethylesters of mesoporphyrin IX, deuteropor-phyrin IX, and protoporphyrin IX. The resonance assignments were based on the relative resonance intensities and the observed fine-structure from spin-spin coupling they agree with previously published data by Caughey and Koski (17 a = ring methyls (for porphin protons at positions 1 to 8), b = mesoprotons, c and d = methylene protons of the propionates, e = methylesters, / and g = resonances of the substituents at positions 2 and 4. Three strong resonances between —7 and —9 ppm come from d5-pyridine, the line at ca. —4.9 ppm from HDO. T = 25 °C...

Methan-dithiophosphonsdure-O-methylester-S-(4-oxo-3,4-dihydro-(benzo d]-l, 2,3-triazin)-3-ylmethylester) 72% Schmp. 103-104°... 

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