Picolines amino

Chapter V. Quinaldine (V,2) 2-methyl-, 2 5-dimethyl- and 2-acetyl-thiophene (V,8-V,10) 2 5-dimethyl and 2 4-dimethyl-dicarbethoxy-p3nrole (V,12-V,13) 2-amino- and 2 4 dimethyl-thiazole (V,15-V,16) 3 5-dimethyl-pyrazole (V,17) 4-ethylp3rridine (from pyridine) (V,19) n-amyl-pyridines from picolines) (V,28) picolinic, nicotinic and isonicotinic acid (V,21-V,22) (ethyl nicotinate and p-cyanop3n idine (V,23-V,24) uramil (V,25) 4-methyl-(coumarin (V,28) 2-hyi-oxylepidine (V,29). 

The picolinamide is prepared in 95% yield from picolinic acid/DCC and an amino acid, and is hydrolyzed in 75% yield by aqueous Cu(OAc)2. ... 

Similarly, 1-alkylpyrroles, indoles, furans, thiophenes [60], a-picoline [61], enols, malonates [76], and organometallic compounds [56, 62] react with acyl imines of trifluoropyruvates to give derivatives of a-trifluoromethyl a-amino acids... 

Attempts to get more information on this interesting meta-rearrangement by choosing derivatives of 2-bromopyridine containing various substituents in the 6-position for the starting material led to a remarkable result. Whereas 2-bromo-6-picoline gave a mixture of 2-and 4-amino-6-picoline (in a ratio of 60 1) in 25% total yield together with a resinous mass, 2,6-dibromopyridine (79) was converted into a pyrimidine, i.e. 4-amino-2-methylpyrimidine (80), in 20% yield. The same pyrimidine was obtained from 2,6-dichloropyridine and, in small amount, also from 2,4-dibromopyridine (81). The course of the... 

The electrochemical oxidation of diethyl 7V,jV-bis(2,4,6-trimethoxy-phenyl)aminomethylmalonate in acetonitrile in the presence of lithium perchlorate and 4-picoline gave A[,A/-bis(2,4,6-trimethoxyphenyl)amino-methylenemalonate in 76% yield (81MI4). 

Taranenko, N.I. Tang, K. Alhnan, S.L. Ch ang, L.Y. Chen, C.H. 3-Amino-picolinic Acid As a Matrix for Laser De-sorption-MS of Biopolymers. Rapid Commun. Mass Spectrom. 1994, 8, 1001-1006. 

Photodecomposition products included acidic compounds and five methylated derivatives (Plimmer, 1970). When picloram in an aqueous solution (25 °C) was exposed by a high intensity monochromatic UV lamp, dechlorination occurred yielding 4-amino-3,5-dichloro-6-hydroxy-picolinic acid which underwent decarboxylation to give 4-amino-3,5-dichloropyridin-2-ol. In addition, decarboxylation of picloram yielded 2,3,5-trichloro-4-pyridylamine which may undergo dechlorination yielding 4-amino-3,5-dichloro-6-hydroxypicolinic acid (Burkhard and Guth, 1979). 

Mixed donor ligands. The complex [FeL3]Cl3 (L = acetylhydrazine) contains the ligand in its bidentate form, bonded via the carbonyl and primary amino-groups.Pyridine-2-carboxaldehyde and l,l,l-tris(aminoethyl)ethane react with Fe" via a template reaction to form [Fejlpyljltame) ], in which three molecules of carboxaldehyde have condensed with one molecule of triamine to produce (pyljltame). MeC(CH2N=CH-oc-py)3 the complex cation is octahedral. The complexes [FeL ] (L = l,10-phenanthroline-2-carboxamide, n = 1 or 2) have been isolated they are both six-co-ordinate. Very weak d-d bands have been identified in the spectra of complexes of ot-picolinic acid and quinaldic acid with Fe". ... 

The total consumption of 2-methylpyridine (a-picoline) in 1980 has been estimated at 12,000 tons [81CI(L)23]. Half is produced for the U.S. market, whereas the demand in both Western Europe and Japan lies between 2000 and 2500 tons per annum. A significant outlet for 2-methylpyridine is in the production of 2-chloro-6-(trichloromethyl)pyri-dine, which is used as a nitrification inhibitor in agricultural chemistry and in the manufacture of the defoliant 4-amino-2,5,6-trichloropicolinic acid. The major commercial outlet for 2-methylpyridine is, however, its use as a starting material for the production of 2-vinylpyridine [Eq.(7)]. 

Optimized reaction conditions call for the use of Wilkinson s catalyst in conjunction with the organocatalyst 2-amino-3-picoline (60) and a Br0nsted add. Jun and coworkers have demonstrated the effectiveness of this catalyst mixture for a number of reactions induding hydroacylation and C—H bond fundionalization [25]. Whereas, in most cases, the Lewis basic pyridyl nitrogen of the cocatalyst ads to dired the insertion of rhodium into a bond of interest, in this case the opposite is true - the pyridyl nitrogen direds the attack of cocatalyst onto an organorhodium spedes (Scheme 9.11). Hydroamination of the vinylidene complex 61 by 3-amino-2-picoline gives the chelated amino-carbene complex 62, which is in equilibrium with a-bound hydrido-rhodium tautomers 63 and 64. 

Nitraminopicolinic Acid, Oa N-HN(CSNH3)-COOH, mw 183.12, N 22.95%. Crysts, mp 178—80° with decompn. Was prepd by cautiously adding nitric acid(d 1.4) to 3-amino-picolinic acid in coned sulfuric acid at a temp not above 5°, allowing to stand for... 

Analogous to the tautomerism of the hydroxy- and amino-pyridines (Sections 3.2.3.7.1 and 3.2.3.5.5), there are alternative tautomeric alkylidene forms of the 2- and 4-alkylpyridines e.g. 609 for 2-picoline). Although the proportion of alkylidene form at equilibrium is very small (as is discussed in Section 2.2.5.1.2), it can be important as a reactive intermediate (see above). 

The reaction of isothiocyanate 2 and 30 with 2-amino-4-picoline has also been reported.55 Dorn and coworkers56"59 reported the synthesis of a number of substituted thioureido derivatives by treatment of isothiocyanates 2 and 5 with 2-phenylethylamine, bis(2-chloroethyl)amine, and 2-(4-ethoxyphenyl)-1 -phenylethylamine. 

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