Formamide hydrochloride

Formamide Hydrochloride, CH NO+HCl niw 81.51 ndls, insol in eth stable when cold but explodes at 15° yielding NH Cl CO (Refs 1 2)- For this reason its use is limited as there ate few reactions that can be handled with so unstable a compd Refs 1) Beil 2, l59f 2) P-L. Magill, lEC 2.63 613 (1934)... 

Busch 67 used ethyl formamidate hydrochloride (CCXXIX) for the preparation of 5-unsubstituted-2-thio-1,3,4-thiadiazolines (method C, Table 39). 

A combination of the preceding type of synthesis and of cyclization of 4-amino-5-arylazopyrimidine can be seen in the novel procedure of Richter and Taylor. Proceeding from phenylazomalonamide-amidine hydrochloride (180), they actually close both rings in this synthesis. The pyrimidine ring (183) is closed by formamide, the triazole (181) one by oxidative cyclization in the presence of cupric sulfate. Both possible sequences of cyclization were used. The synthetic possibilities of this procedure follow from the combination of the two parts. The synthesis was used for 7-substituted 2-phenyl-l,2,3-triazolo[4,5-d]-pyrimidines (184, 185). An analogous procedure was employed to prepare the 7-amino derivatives (188) from phenylazomalondiamidine (186). 

In a departure from the prototype molecule, the benzylpiperi-done is first converted to the corresponding aminonitrile (a derivative closely akin to a cyanohydrin) by treatment with aniline hydrochloride and potassium cyanide (126). Acid hydrolysis of the nitrile affords the corresponding amide (127). Treatment with formamide followed by reduction affords the spiro oxazinone... 

To the mixture of 85.5 g ethyl a-(3chloro-4.aminophenyl)-propionate hydrochloride, 142 g sodium carbonate and 600 ml dimethyl formamide, 107 g 1,4room temperature. The mixture is filtered, the filtrate evaporated in vacuo, the residue is triturated with hexane, the mixture filtered, the residue washed with petroleum ether and the filtrate evaporated. The residue is combined with 280 ml 25% aqueous sodium hydroxide and the mixture refluxed for 8 hours. After cooling, it is diluted with water, washed with diethyl ether, the pH adjusted to 5 to 5.2 with hydrochloric acid and extracted with diethyl ether. The extract is dried, filtered, evaporated and the residue crystallized from benzene-hexane, to yield the a-(3-chloro-4-pyrrolinophenyl)-propionic acid melting at 94°C to 96°C. 

It is obvious that N,0-bis(trimethylsilylated)acetamides or N,0-bis(trimethyl-silylated)formamides 22 or N,0-bis(trimethylsilyl)benzamide 296 should react likewise with the hydrochlorides or hydriodides of primary or secondary amines or with the free amines in the presence of equivalent amounts of e.g., NH4CI or NH4I to give the corresponding amidinium salts. 

The hydrochloride salt of 4-amino-1-benzylimidazole (83 R = H) was acetylated readily by acetic anhydride to give the acetamide derivative (83 R = COCHj) (55%) (74JMC1168). Treatment with acetic-formic anhydride gave the corresponding formamide (83 R = CHO). 

Compound 123 affords on treatment with P20j/N,/V-dimethyl-cyclohexylamine hydrochloride the pyrazolo[3,4-(i]pyrimidines 129. It is also possible to isolate 130 when using o-toluidene hydrochloride. Reaction of 123 with formamide affords the oxopyrazolo[3,4-d]pyrimidine 131 (76JIC426 77JAP7753854 83JHC1447). 

EXTENSIONS AND COMMENTARY N-Methyltryptamine (monomethyltryptamine, NMT) is an alkaloid that has been found in the bark, shoots and leaves of several species of Virola, Acacia and Mimosa. However, the major snuffs associated with these plant have been shown to also contain 5-MeO-DMT and are discussed there. NMT has been synthesized in a number of ways. One can react 3-(2-bromoethyl)indole with methylamine. NMT can be isolated as the benzoyl derivative from the methylation of tryptamine with methyl iodide followed by reaction with benzoyl chloride, with the hydrolysis of this amide with alcoholic KOH. It can also be synthesized from indole with oxalyl chloride, with the resulting glyoxyl chloride reacting with methylamine in ether to give indol-3-yl N-methylglyoxalylamide (mp 223-224 °C from IPA) which is obtained in a 68% yield, which is reduced to NMT to give the amine hydrochloride (mp 175-177 °C from ) in a 75% yield. The most simple and direct synthesis is the formamide reduction given above. 

Dimethylamino)propyl-3-ethylcarbodiimide hydrochloride Carbodiimide, [3-(dimethylamino)propyl]ethyl-, monohydrochloride (8) 1,3-Propanediamine, N -(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochloride (9) (25952-53-8) N.N-Dimethylformamide cancer suspect agent Formamide, N,N-dimethyl- (8,9) (68-12-2)... 

This method is a modification of the procedure described by Taylor and Ehrhart.2 Formamidine has previously been prepared (as its hydrochloride) from hydrogen cyanide via the formimino ether, which is then treated with ammonia,3 or by desulfurization of thiourea in the presence of ammonium chloride.4 The methosulfate salt of formamidine has been reported to be formed by reaction of formamide with dimethyl sulfate.8... 

Further hydrolysis of the compound 55 with 7% HCl-MeOH followed by treatment with MsCl-pyridine and then with LiCl in dimethyl-formamide (DMF) (90-100°, 18 hr) afforded a monomesylate [56, mp 253-254° (as hydrochloride)] via deacetyldeoxyyuzurimine (57) and dimesylate (58). In the NMR spectrum of 56, a broad singlet resulting from two olefinic protons was observed at 5.93. Finally, catalytic hydrogenation of this compound over Pt02 gave yuzurimine-B mesylate (54) which was directly obtained from yuzurimine-B on mesylation with MsCl-pyridine. 

To a stirred mixture of the above amine hydrochloride (55.0 g, 0.22 mole) and [[(2,4-dioxo-l-imidazolidinyl)imino]methyl]formyl chloride (42.0 g, 0.22 mole) was added a solution of 440 ml of dimethylformamide and 44 ml of pyridine. The mixture was stirred for 20 h and poured into 2 L of water. The solid was collected by filtration and washed with ethanol and ether to give 36.0 g (28%) of N-[2-(4-bromophenyl)-2-oxoethyl]-[[(2,4-dioxo-l-imidazolidinyl)-imino]methyl]formamide, melting point 267°-269°C (recrystallization from 2200 ml acetic acid). 

In an initial step, 2-chloroacetic acid ethyl ester is reacted with formamide to give 5-methylimidazole-4-carboxylic acid ethyl ester. Then sodium in ammonia is used to convert that to 4-hydroxymethyl-5-methylimidazole-hydrochloride. Cysteamine HCI (HSCH2CH2NH2-HCI) is then reacted to give 4-(2-aminomethyl)-thiomethyl-5-methyl-imidazole dihydrochloride. Then N-cyanamido-5,5-dimethyl-dithio-carbonate (from cyanamid, KOH, CS2 and ((CH3)2S04) is reacted to give a further intermediate which is finally reacted with methylamine to give cimetidine. 

To the mixture of 85.5 g ethyl a-(3-chloro-4-aminophenyl)-propionate hydrochloride, 142 g sodium carbonate and 600 ml dimethyl formamide, 107... 

To 35 g of ethyl a-alaninate hydrochloride is added 10 g of formamide and the resulting mixture is heated slowly to 105°C over a period of 30 to 45 min. After heating at 105°C for 10 min, about 75 ml of toluene is added. After standing for about 1 h, the mixture is then refluxed for about 6 h. After cooling the ammonium chloride formed is removed and the resulting solution is evaporated to remove the solvent. The ethyl N-formyl-a-alaninate is obtained by distillation at 100°C. 

Superdex, Superose, Sephacryl and Sepharose CL are chemically relatively inert they can be used between pH 3 and 11, and will survive more extreme conditions (pH 2-12) for short periods. They are also resistant to a range of other conditions such as 1 % (w/v) SDS, chaotropic denaturing agents (6 M guanidinium hydrochloride or 8 M urea) as well as some organic solvents (e.g formamide, DMSO, methanol, ethanol and acetone). 

---