Pyridine, 2-chloromethyl

Chloromethyl)pyridine hydrochloride [1822-51-1] M 164.0, m 170-175°, 172-173°, pK , -5.6. Purified by recrystn from EtOH or EtOH-dry Et20. It melts between 171° and 175° and the clear melt resolidifies on further heating at 190° and turns red to black at 280° but does not melt again. The picrate-hydrochloride (prepared in EtOH) has m 146-147°. The free base is an oil, [Mosher and Tessieri J Am Chem Soc 73 4925 1951.]... 

A solution of 82 parts by weight of 7-chloromethyl-pyridine-hydrochloride in 60 parts of water is added dropwise, at 0 to 5°C, to 250 parts by weight of a 50% aqueous ethyl amine solution. The mixture is stirred for 1 hour at 60°C, whereupon it is cooled down and separated in the cold with solid potassium hydroxide. The oil formed is separated off, dried over potassium hydroxide and distilled. The ethyl-(7-picolyl)-amine formed boils over at 103° to 104°C under a pressure of 13 mm Hg. Its dihydrochloride melts at 198° to 200°C. 

Hoomaert has studied Diels-Alder reactions of pyridine oquinodimethane analogs generated from functionalized o-bis(chloromethyl)pyridines <96T(52)11889>. The photochemical cycloaddition of 2-alkoxy-3-cyano-4,6-dimethylpyridine with methacrylonitrile gives a bicyclic azetine, 6-alkoxy-3,5-dicyano-2,5,8-trimethyl-7-azabicyclo[4.2.0]octa-2,7-diene, in moderate yield <96CC1349>. Regiospecific hydroxylation of 3-(methylaminomethyl)pyridine to 5-(methylaminomethyl)-2-(17/)-pyridone by Arthrobacter ureafaciens has been reported <96MI173>. 

Iodide 48), As(OCH2)3CMe, S(t-Bu)2 (79), and pyridines 80) do not react with CpMo(CO)3Me in THE or MeCN. However, interaction between Na[CpMo(CO)3] and 2-(chloromethyl)pyridine has afforded (XIX) 144),... 

Methoxyphenylene diamine 12 was treated with potassium ethylxanthate to afford benzimidazole-thiol 13. The coupling of thiol 13 and chloromethyl-pyridine 11 was then... 

Omeprazole was prepared [19] by reaction of 4-methoxy-o-phenyl-enediamine 1 with potassium ethyl xanthogenate 2 to give 5-methoxy-2-mercapto-lH-benzimidazole 3. Treatment of compound 3 with 3,5-dimethyl-4-methoxy-2-chloromethyl pyridine 4 in sodium hydroxide... 

Acetyltropic acid chloride y-Chloromethyl pyridine hydrochloride Hydrogen chloride... 

Kauffmann et al.4) reported the synthesis of 2 (1 %) by the lithiation of 2,6-7>/j-(chloromethyl)pyridine and subsequent coupling in the presence of copper(II) chloride. The utilization of high dilution techniques did not affect the yields. 

Hexaza 18-crown-6 151 (7.8%) and 152 (8.0%) have also been synthesized by treatment of 2,6-fc(chloromethyl)pyridine with jym-dimethylethylenediamine or piperazine in dimethylformamide, utilizing potassium carbonate as the base. The cobalt(II) and copper(II) complexes 153 of 151 have been made and the single crystal X-ray structure determination of each shows that in both cases the metal ion is octahedrally coordinated by the six nitrogen atoms of the ligand. In the case of... 

Ligands 179 and 180 were synthesized by the nucleophilic substitution of the sodium glycolate of TV-methyldiethanol amine on either 2,6-dichloropyridine or 2,6-6 (chloromethyl)pyridine. However, 183 and 184 were synthesized by the qua-temization of 181 or 182 with l,2-6is(P-ethoxy)ethane in acetonitrile. In both instances the resulting diquatemary ammonium salts were demethylated by L-Selec-tride in refluxing tetrahydrofuran to afford the desired pyridino coronand. Com-piexation studies have not been performed on any of these coronands and the physical properties of these compounds do not indicate any unusual characteristics m). 

The 4-picolyl esters are prepared from N-protected annino acids by treatment with 4-(chloromethyl)pyridine/TEA (or tetramethylguanidine) in DMF (90-100 °C, 2 h) or by using DCC and pyridine-4-methanol. 

The reaction of tetra- -butylammonium salt of the zinc complex 418 with electrophilic reagents such as methyl iodide, 3-bromopropionitrile, or benzyl chloride in the presence of pyridine hydrochloride as well as 3-chloromethyl-pyridine hydrochloride and 4-chloromethylpyridine hydrochloride led to formation of the difficultly accessible thiones 419 and 420 (Scheme 58) <20010L1941>. 

Three of the five fragments have now been assembled, and only the two amine alkylations remain. The first alkylation makes use of the epoxide to introduce the required 1,2-amino-alcohol functionality. The protected enantiomerically pure piperazine reacted with the epoxide, and the product was treated with acid to deprotect both the second piperazine nitrogen and the acetonide group left over from the earlier chiral auxiliary step. The newly liberated secondary amine was alkylated with the reactive electrophile 3-chloromethyl pyridine, and the final product was crystallized as its sulfate salt... 

The PflN ligands 10a,b as well as the corresponding palladium complexes were synthesized as depicted in Fig. 2.14. Treatment of 2-(chloromethyl)pyridine with one equivalent of bis(2-methylphenyl)phosphane in the presence of potassium tert-butylate yielded ligand 10 a which was directly converted into the palladium diiodide complex 11b. Purification of 11b was achieved by column chromatography on sihca. 

---