Category: 100524-09-2

Dornow, Alfred; Siebrecht, Manfred published an article in 1960, the title of the article was Syntheses of nitrogen-containing heterocycles. XXII. The synthesis of some pyrazolo[3,4-b]pyridines.Product Details of 100524-09-2 And the article contains the following content:

5-Amino-3-pyrazolone (I) with β-dicarbonyl compounds gave good yields of pyrazolopyridines. AcMeCHCHO (II) condensed with I gave as the main product the corresponding pyrazolopyrimidine. NCCH2CONHNH2 (99 g.) and 89 g. NaOEt in 400 cc. EtOH heated 1 hr. at 100°-cooled, and filtered gave 116 g. Na salt (III) of I; the concentrated aqueous solution of III acidified with glacial AcOH gave I, m. 204°. III (12.1 g.) in 45 cc. H2O treated with stirring and warming with 13.0 g. AcCH2CO2Et to solution, cooled, filtered, and the residue dissolved in H2O and acidified with AcOH gave 16.2 g. 3,6-dihydroxy-4-methyl-1-pyrazolo [3,4-b]pyridine (IV), m. 335° (decomposition) (MeOH). CH2(CO2Et)2 (8 g.) and 4.95 g. I added to 10.5 g. NaOEt in 100 cc. EtOH, heated 4 hrs. on the water bath and filtered, and the residue dissolved in H2O and acidified with AcOH gave 7.1 g. 4-OH analog of IV, m. 370° (decomposition) (glacial AcOH). III (12.1 g.) in 30 cc. H2O, 11.1 g. AcCH: CHONa in 15 cc. H2O, and 2.5 g. piperidine acetate refluxed 2 hrs., cooled, neutralized with AcOH, and filtered gave 9.9 g. 3-hydroxy-6-methyl-1-pyrazolo[3,4-b]pyridine (V), m. 282° (EtOH). III (6 g.) in 30 cc. H2O treated with 8.5 g. BzCH:CHONa in 20 cc. H2O, heated 2 hrs. with 2 g. piperidine acetate on the water bath, cooled, and acidified with glacial AcOH yielded 6.7 g. 6-Ph analog of V, m. 288° (MeOH). III (6 g.) in 20 cc. H2O treated with 6 g. Na salt of II in 10 cc. H2O, refluxed 2 hrs. with 2 g. piperidine acetate, and worked up gave 5.1 g. orange precipitate; the precipitate extracted with hot EtOH and the extract cooled gave 3.4 g. 2-hydroxy-6,7-dimethylpyrazolo[2,3-a]pyrimidine (VI), m. 239° with sintering from 226° (EtOH); the residue from the extraction gave 1.7 g. 5-Me derivative (VII) of V, m. 343°. I (3 g.) and 3.7 g. Na salt of 1-formyl-2-cyclohexanone in 40 cc. absolute EtOH refluxed 2 hrs., filtered after 2 hrs., and the residue dissolved in H2O and neutralized with glacial AcOH yielded 3.4 g. 3-hydroxy-5,6,7,8-tetrahydro-1-pyrazolo[3,4-b]quinoline (VIII), yellow, m. 297° (EtOH). IV (1 g.) and 10 g. Raney Ni in 230 cc. EtOH refluxed 2 hrs., filtered hot, evaporated, and the residue washed with Et2O gave 0.65 g. 6-hydroxy-2-amino-4-methylnicotinic acid amide (IX), m. 250° (PhMe). V (0.5 g.) and 8 g. Raney Ni in 200 cc. EtOH gave similarly 0.45 g. 2-amino-6-methylnicotinic acid amide (X), m. 219° (PhMe). VII (0.5 g.) and 8 g. Raney Ni refluxed 3 hrs. in 200 cc. EtOH yielded 0.5 g. 5-Me derivative of X, m. 230° (PhMe). VIII (2 g.) and 12 g. Raney Ni in 300 cc. EtOH heated 3 hrs. gave 1.2 g. amide (XI) of 2-amino-5,6,7,8-tetrahydroquinoline-2-carboxylic acid (XII), m. 223° (PhMe). XI (0.7 g.) in 5 cc. concentrated HCl refluxed 3 hrs. and neutralized with aqueous NaOH-NaOAc gave 0.6 g. XII. XII (3 g.) distilled at 250° gave with CO2 evolution 2.1 g. 2,4,5-trimethylpyrimidine, b12 107°; picrate m. 198° (EtOH). The experimental process involved the reaction of 2-Amino-6-methylnicotinamide(cas: 100524-09-2).Product Details of 100524-09-2

2-Amino-6-methylnicotinamide(cas:100524-09-2) belongs to amides. Amides are pervasive in nature and technology. Proteins and important plastics like Nylons, Aramid, Twaron, and Kevlar are polymers whose units are connected by amide groups (polyamides); these linkages are easily formed, confer structural rigidity, and resist hydrolysis. Product Details of 100524-09-2

Referemce:
Amide – Wikipedia,
Amide – an overview | ScienceDirect Topics

Dornow, Alfred; Neuse, Eberhard published an article in 1951, the title of the article was The reaction of amidines with β-dicarbonyl compounds.Application In Synthesis of 2-Amino-6-methylnicotinamide And the article contains the following content:

cf. C.A. 34, 6629.3.-β-Dicarbonyl compounds react with RO2CCH2C(:NH)OR (Ia) via an amidine derivative, RCOCH2CR’:C(CO2R)C(:NH)N:C(OR)CH2CO2R, to form pyridine derivatives This reaction is studied further. MeCOCHNaCHO (23 g.) and 30 g. H2NCOCH2C(:NH)NH2.HCl (I) are refluxed in 80 cc. absolute EtOH 12 h. and the hot filtered solution is cooled, giving 56% 2-amino-6-methylnicotinamide (II), long needles, m. 220° [picrate, yellow leaflets, m. 253-4° (decomposition)]. Refluxing 1 g. II with concentrated HCl 10 h. and neutralizing the mixture with NH4OH give 100% free acid, m. 296°. Treating 0.35 g. II in 20 cc. dilute H2SO4 with 0.45 g. NaNO2 and warming the mixture on a water bath give 2-hydroxy-6-methylnicotinic acid, m. 227° (decomposition), which, decarboxylated, gives 6-methyl-2-pyridone, m. 157°. Refluxing 17.5 g. PhCOCHNaCHO and 13.5 g. I in 50 cc. absolute EtOH and 30 g. anhydrous KOAc 2 h., distilling off the solvent, extracting the residue with H2O, and refluxing the residue several hrs. with concentrated HCl give 11.6 g. 2-amino-6-phenylnicotinic acid-HCl, sintering at 219-20°, m. 240° (decomposition); free acid (III), m. 243° [picrate, m. 189-90° (decomposition)]. Only in 1 experiment was the amide, thick yellowish crystals, m. 220-1°, obtained; it shows strong blue fluorescence in alc. solution [picrate, yellow needles, m. 229-30° (decomposition)]. Diazotization of 0.22 g. III in 20 cc. dilute H2SO4 with 0.3 g. NaNO2 and boiling the mixture give 2-hydroxy-6-phenylnicotinic acid, m. 304° (decomposition), which, heated above its m.p., gives 6-phenyl-2-pyridone, m. 197°. Condensation of 20 g. EtCOCHNaCHO (IV) with 22 g. I in 100 cc. 50% MeOH gives 66% 2-amino-5,6-dimethylnicotinamide (V), fine yellowish crystals, m. 230-1° [picrate, m. 269-70° (decomposition)]. Diazotization of 2.5 g. V with 1.7 g. NaNO2 and boiling the mixture give 59% 2-hydroxy-5,6-dimethylnicotinic acid (VI) needles, m. 306° (decomposition) (cf. Barat, C.A. 26, 2979), also obtained on saponification of the cyanopyridone obtained on condensation of NCCH2CONH2 with IV. Heating VI above its m.p. gives 5,6-dimethyl-2-pyridone, m. 205-6°. Keeping 6.95 g. I in 50 cc. N NaOH with 5.1 cc. Ac2CH2 overnight at 20° gives 60% 2-amino-4,6-dimethylnicotinamide, m. 156.5°; from the aqueous mother liquor a compound, m. 295-300°, is isolated. 2-Hydroxy-4,6-dimethylnicotinic acid, prepared in 60% yield like VI, m. 254°. Refluxing 15 g. I 24 h. in 100 cc. EtOH containing 2.3 g. Na with 16 g. BzCH2COMe gives 21% 2-amino-4-methyl-6-phenylnicotinamide, yellowish crystals, m. 227°; from the mother liquor some CH2(CONH2)2, m. 166°, is isolated. Adding 11 g. EtO2CCH2C(:NH)OEt.HCl to 40 cc. satd Na2CO3 overlayered with ether and heating the residue of the dried ether solution with 5 g. BzCH2COMe 16 h. on a water bath give 52% Et 2-amino-4-methyl-6-phenylnicotinate (VII), cubelike crystals, m. 129°; its alc. solution fluoresces strongly blue [HCl salt, m. 205° (decomposition)]. Refluxing 1.1 g. VII 8 h. with 10 cc. concentrated HCl gives 90% HCl salt (VIII) of the free acid, needles, m. 171-2° (decomposition), from which, with NH4OH and AcOH, the free acid, m. 267° (decomposition), is obtained. Treating 0.9 g. VIII in dilute H2SO4, with 0.5 g. NaNO2 with warming gives 90% 2-hydroxy-4-methyl-6-phenylnicotinic acid (IX), crystals from AcOH, m. 278°, which is also obtained in 92% yield from the acid amide, m. 227°. Treating 0.9 g. VII in 15 cc. warm AcOH with 0.3 g. NaNO2 and boiling the mixture give 78% Et ester (X) of IX, broad leaflets, m. 163°; its aqueous solution shows weak bluish fluorescence. Heating 0.4 g. IX 10 min. at 300-5° gives 62% 4-methyl-6-phenyl-2-pyridone, m. 180°, which is also formed on heating IX or X with 80% H2SO4 or concentrated HCl. Refluxing 27.3 g. I and 29.5 g. 2-hydroxymethylenecyclohexanone (XI) 2 h. in 100 cc. absolute MeOH and keeping the mixture 12 h. in the cold give 51% 2-amino-5,6,7,8-tetrahydro-3-quinolinecarboxamide (XII), needles, m. 224-5°, soluble in concentrated H2SO4 with strong blue-violet fluorescence [picrate, yellow needles, m. 259-60° (decomposition)]. Refluxing Ia (R = Et) from 200 g. HCl salt 30 h. with 52 g. XI on a water bath gives 20 g. Et 2-amino-5,6,7,8-tetrahydro-3-quinolinecarboxylate (XIII), m. 127°. Distillation of the residue of the mother liquor gives addnl. XIII, b12 185°, bringing the total yield to 36%. XIII dissolves in concentrated H2SO4 or EtOH with strong blue-violet fluorescence [picrate, yellow needles, m. 212-13° (decomposition)]. Refluxing 5 g. XIII 10 h. with 30 cc. concentrated HCl gives 70% HCl salt of the acid, m. 232-4° (decomposition); free acid (XIV), needles from AcOH, m. 291-2° (decomposition), also obtained on refluxing 0.9 g. XII 10 h. with 20 cc. concentrated HCl. 2-OH analog (XV) of XIV, m. 268-9° (decomposition). Heating 0.15 g. XV 15 min. above its m.p. gives 5,6,7,8-tetrahydro-2-quinolone, needles, m. 201°. Treating 18 g. BzCH2C(:NH)OEt. HCl (XVI) in ether with 10 g. Na2CO3 in 100 cc. H2O, adding 3.1 g. Ac2CH2 to the dried ether solution, evaporating the ether, heating the residue 15 h. at 140-150°, and acidifying the mixture with concentrated HCl give 50% 4,6-dimethyl-2-phenacylpyrimidine-HCl (XVII), crystals from 6 N HCl, m. 201° (free base, yellow leaflets, m. 74°; picrate, yellow needles, m. 203°). Treating 1 g. XVII in 30 cc. 3 N HCl at 40-5° with 0.5 g. NaNO2 in 10 cc. H2O gives 80% 2-(α-isonitrosophenacyl) derivative (XVIII), leaflets, m. 212°. Hydrogenation of 0.8 g. XVIII in 200 cc. absolute EtOH with 0.15 g. PtO2 gives 4,6-dimethyl-2-(β-hydroxy-α-aminophenethyl)pyrimidine, which is converted into its picrate, m. 175-80° (decomposition). Refluxing 2 g. CHCCHO with BzCH2C(:NH)OEt from 25 g. XVI gives 54% 2-phenacylpyrimidine, m. 150°. The experimental process involved the reaction of 2-Amino-6-methylnicotinamide(cas: 100524-09-2).Application In Synthesis of 2-Amino-6-methylnicotinamide

2-Amino-6-methylnicotinamide(cas:100524-09-2) belongs to amides. Amides are pervasive in nature and technology. Proteins and important plastics like Nylons, Aramid, Twaron, and Kevlar are polymers whose units are connected by amide groups (polyamides); these linkages are easily formed, confer structural rigidity, and resist hydrolysis. Application In Synthesis of 2-Amino-6-methylnicotinamide

Referemce:
Amide – Wikipedia,
Amide – an overview | ScienceDirect Topics

On December 30, 2015, Aizawa, Ryo; Araki, Koichi published a patent.SDS of cas: 100524-09-2 The title of the patent was Method for producing 2-amino-6-methylnicotinic acid. And the patent contained the following:

Disclosed is a preparation method of 2-amino-6-methylnicotinic acid, characterized by (1) reaction of 2-chloro-3-cyano-6-methylpyridine with ammonia aqueous solution to obtain reaction mixture containing 2-amino-6-methylnicotinamide (2) removal of ammonia from the resulting reaction mixture followed by treatment with a base. Thus, to 2-chloro-3-cyano-6-methylpyridine (6.10 g) was added 28% aqueous ammonia (70 mL), the resulting mixture was reacted at 170° for 7 h and cooled to room temperature After removal of ammonia under reduced pressure, the residue was treated with KOH (9.00 g) [100°, 3 h], precipitated using 4 N HCl at room temperature (pH 4-5), filtered, washed with water, and dried to give 2-amino-6-methylnicotinic acid (82.9% yield, 97.06% purity). The experimental process involved the reaction of 2-Amino-6-methylnicotinamide(cas: 100524-09-2).SDS of cas: 100524-09-2

The Article related to aminomethylnicotinic acid preparation, amination amidation hydrolysis, Heterocyclic Compounds (One Hetero Atom): Pyridines and other aspects.SDS of cas: 100524-09-2

Referemce:
Amide – Wikipedia,
Amide – an overview | ScienceDirect Topics

On December 30, 2015, Aizawa, Ryo; Araki, Koichi published a patent.SDS of cas: 100524-09-2 The title of the patent was Method for producing 2-amino-6-methylnicotinic acid. And the patent contained the following:

Disclosed is a preparation method of 2-amino-6-methylnicotinic acid, characterized by (1) reaction of 2-chloro-3-cyano-6-methylpyridine with ammonia aqueous solution to obtain reaction mixture containing 2-amino-6-methylnicotinamide (2) removal of ammonia from the resulting reaction mixture followed by treatment with a base. Thus, to 2-chloro-3-cyano-6-methylpyridine (6.10 g) was added 28% aqueous ammonia (70 mL), the resulting mixture was reacted at 170° for 7 h and cooled to room temperature After removal of ammonia under reduced pressure, the residue was treated with KOH (9.00 g) [100°, 3 h], precipitated using 4 N HCl at room temperature (pH 4-5), filtered, washed with water, and dried to give 2-amino-6-methylnicotinic acid (82.9% yield, 97.06% purity). The experimental process involved the reaction of 2-Amino-6-methylnicotinamide(cas: 100524-09-2).SDS of cas: 100524-09-2

The Article related to aminomethylnicotinic acid preparation, amination amidation hydrolysis, Heterocyclic Compounds (One Hetero Atom): Pyridines and other aspects.SDS of cas: 100524-09-2

Referemce:
Amide – Wikipedia,
Amide – an overview | ScienceDirect Topics

On February 28, 2007, Galenko, A. V.; Lobanov, P. S.; Potekhin, A. A. published an article.Name: 2-Amino-6-methylnicotinamide The title of the article was Reactions of α-tosyl- and α-cyanoacetamidoximes with 1,3-dicarbonyl compounds. And the article contained the following:

Cyclocondensation of α-tosylacetamidoxime and α-cyanoacetamidoxime with 1,3-dicarbonyl compounds affords the corresponding pyrimidine N-oxides. The 2-(cyanomethyl)pyrimidine-3-oxides isolated readily undergo cyclization to isoxazolopyrimidinium salts via intramol. addition of N-oxide to the nitrile group under acidic conditions. The experimental process involved the reaction of 2-Amino-6-methylnicotinamide(cas: 100524-09-2).Name: 2-Amino-6-methylnicotinamide

The Article related to isoxazolopyrimidinium preparation ring opening, pyrimidine oxide cyano preparation intramol cycloaddition, acetamidoxime cyclocondensation dicarbonyl compound, Heterocyclic Compounds (More Than One Hetero Atom): Pyrimidines and Quinazolines and other aspects.Name: 2-Amino-6-methylnicotinamide

Referemce:
Amide – Wikipedia,
Amide – an overview | ScienceDirect Topics