Methyl isonicotinate

A mixture of 274 g of methyl isonicotinate, 367 g of ethyl bromoacetate and 125 cc of ethyl alcohol was stirred without heating for 4 hours in a flask equipped with a reflux condenser. (The reaction was exothermic and precautions were taken to keep the temperature below 70°C.) The reaction mixture was then left for 15 hours at room temperature. 

Likewise, pyridines such as methyl isonicotinate 1999 or quinolines are readily oxidized by BTSP 1949 in the presence of HOReOs in CH2CI2 to give, after 6 h at 24°C, 98% yield of, e.g., methyl isonicotinate N-oxide 2000 [174] (Scheme 12.49). The oxidation of diphenylsulfide with BTSP 1949 and triphenylphosphine dichloride in acetonitrile results, after 60 h at room temperature, in only 12% diphenyl sulfoxide 2001 and 88% recovered diphenyl sulfide [175] (Scheme 12.49), whereas thianthrene 5-oxide 2002 is oxidized by the peroxy-Mo complex 2003 to give 58% of a mixture of 2004 to 2007 in which the trans 5,10-thioxide 2005 predominates [176] (Scheme 12.50). 

A mixture of methyl isonicotinate 1999 (2.74 g, 20 mmol) and perrhenic add (HOReOs 25 mg, 0.1 mmol) in 3 mL CH2CI2 is treated with 1949 (6 mL, 30 mmol). The mixture is stirred for 6 h at 24°C in a water bath then diluted with 6 mL hexane, cooled to 0°C, and filtered. The resulting solid is washed with cold hexane (2x4mL) and dried in vacuo to give 3.00 g (98%) of the N-oxide 2000 [174] (Scheme 12.76). 

Methyl isobutenyl ketone, m370 Methyl isobutyl ketone, m3 67 Methyl isonicotinate, m413 ), bl76 Methyl isopentyl ketone, m271... 

Although many antibiotics are effective to some extent in arresting the progress of tuberculosis, none is uniformly successful. One of the most effective is isonicotinic hydrazide (73), available from methyl isonicotinate by reaction with hydrazine (B-75MI20903). Extensive clinical use of this agent showed the drug to possess an additional antidepressant effect and led to the development of iproniazid (74), an established antidepressant (53JOC994). 

Hydrogen ionophore IV ETH 1778 (octadecyl isonicotinate) [ 103225-02-1 ] M 375.6, m 57.5". Dissolve in Et2O and wash 3 times with H2O. Dry, evaporate, and recrystallise the residue from EtOAc/hexane (4 1). The pKa of the short chain homologue methyl isonicotinate is 3.6. [AC 58 2285 1986. ... 

Methyl isonicotinate, m402 Methylmercaptoanilines, m422, m423 5-Methyl-2-(l -methylethyl)cyclohexanone, ml3 ... 

Ikegami and Watanabe dia vered that l-benzyl-4-carbomethoxypyridinyl was unstable to light. In a matrix, photolysis of the radical led to methyl isonicotinate and benzyl radical (Eq. 21). 

Kosower and Teuerstein showed that o-xylylene bis-pyridinyl and 1,8-biphenyl-ene bis-pyridinyl diradicals could be photolyzed in low quantum yields at 400 nm to yield the corresponding pyridine (methyl isonicotinate) and either a carbomethoxy-azaanthracene or 1,8-dimethylbiphenylene (Eqs. 22). 

Palladacycle complexes of this type readily undergo ring closure (Eq. 13), particularly in the presence of bulky ort/io substituents such as t-Bu [7,17,23]. Ring enlargement of the same complex can also be effected by reaction with internal acetylenes such as dimethyl acetylenedicarboxylate (R=C02Me, L= methyl isonicotinate) (Eq. 14) [24]. 

Reductive alkylation of methyl isonicotinate with benzyl chloride yields 4-pyridyl benzyl ketone (X-182). ... 

Synthesis of Pyridine-V-Oxides. Methyl isonicotinate was oxidized by (TMSO)2 in the presence of CHsReOs, or other inorganic rhenium derivatives such as ReOs, Re20v and HOReOs, to the V-oxide in high yield (95-98% isolated yields). With ReCls or NaOReOs as catalyst, only trace amounts of oxidation products were obtained (eq 10). The importance of a trace amount of water in this oxidation process was confirmed when the reaction was retarded by the presence of molecular sieves. The optimal water content was found to be between a trace and 15 mol %, with higher proportions leading to lower conversion. A commercial 65-70% solution of perrhenic acid in water was found to be a convenient source of both Re and water. 

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