wherein Q is selected from the group consisting of —S—, —S(═O)—, and —S(═O)2—, Z is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure wherein R1, R2, R3, R4 and R5 are each independently selected from the group consisting of hydrogen, a C1-C4 lower alkyl, a halogen, and an amino group selected from the group consisting of NH2, NHR and NRR′ where R and R′ are each independently selected from the group consisting of a C1-C4 lower alkyl, an aryl, and an alkoxy group, and X is selected from the group consisting of hydrogen, a C1-C4 lower alkyl group, and a fully-deuterated C1-C4 lower alkyl group. The present invention is also directed to a process of preparing labeled compounds, e.g., process of preparing [13C]methacrylic acid by reacting a (CH3CH2O—13C(O)—13CH2)—aryl sulfone precursor with 13CHI to form a (CH3CH2O—13C(O)—13C(13CH3)2)—aryl sulfone intermediate, and, reacting the (CH3CH2O—13C(O)—13C(13CH3)2)—aryl sulfone intermediate with sodium hydroxide, followed by acid to form [13C]methacrylic acid. The present invention is further directed to a process of preparing [2H8]methyl methacrylate by reacting a (HOOC—C(C2H3)2—aryl sulfinyl intermediate with CD3I to form a (2H3COOC—C(C2H3)2)—aryl sulfinyl intermediate, and heating the (2H3COOC—C(C2H3)2)—aryl sulfinyl intermediate at temperatures and for time sufficient to form [2H8]methyl methacrylate."/>
Synthesis of 13C and 2H substituted methacrylic acid, 13c and 2H substituted methyl methacrylate and/ or related compounds
The present invention is directed to labeled compounds of the formulae wherein Q is selected from the group consisting of —S—, —S(═O)—, and —S(═O)2—, Z is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure wherein R1, R2, R3, R4 and R5 are each independently selected from the group consisting of hydrogen, a C1-C4 lower alkyl, a halogen, and an amino group selected from the group consisting of NH2, NHR and NRR′ where R and R′ are each independently selected from the group consisting of a C1-C4 lower alkyl, an aryl, and an alkoxy group, and X is selected from the group consisting of hydrogen, a C1-C4 lower alkyl group, and a fully-deuterated C1-C4 lower alkyl group. The present invention is also directed to a process of preparing labeled compounds, e.g., process of preparing [13C]methacrylic acid by reacting a (CH3CH2O—13C(O)—13CH2)—aryl sulfone precursor with 13CHI to form a (CH3CH2O—13C(O)—13C(13CH3)2)—aryl sulfone intermediate, and, reacting the (CH3CH2O—13C(O)—13C(13CH3)2)—aryl sulfone intermediate with sodium hydroxide, followed by acid to form [13C]methacrylic acid. The present invention is further directed to a process of preparing [2H8]methyl methacrylate by reacting a (HOOC—C(C2H3)2—aryl sulfinyl intermediate with CD3I to form a (2H3COOC—C(C2H3)2)—aryl sulfinyl intermediate, and heating the (2H3COOC—C(C2H3)2)—aryl sulfinyl intermediate at temperatures and for time sufficient to form [2H8]methyl methacrylate.
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