Formylation amines

Corey et al have also synthesized 3 from 1. Their route involves reduction of 1 with a rhodium oxide-platinum oxide catalyst (this volume) to the corresponding amine, formylation, and dehydration to give 3. 

Amin Formyl-(formyloxy-methyl)-methyl- IV/lb, 1025 Bemsteinsanre -amid VIII, 656 Butan 2-Nitro-3-oxo- X/l, 167 Bntanal 4-Nitro- X/l, 202f. Bntansaure -Salpetersaure-Anhydrid Elbe, 18 (R-COOAg + NOCl) 19 (R-COOH + NaN02)... 

Formyl derivatives. Formic acid condenses with primary and secondary amines to yield formyl derivatives ... 

Amine B.P. M.P. Aceta- mide Benz- amlde Benzene- SUlphOD- amlde p-Tolu- enesul- phoD- amlde Benzal Derivative Picrate 3-Nitro- phthal- imide 2 4-Dinitro-phenyl Derivative Formyl Derivative Phenyl thio- urea... 

Other carbonyl compounds are within the scope of the reaction ketones give amides, and aldehydes yield nitriles and formyl derivatives of amines ... 

Isomer separation beyond physical fractional crystallization has been accompHshed by derivatization using methyl formate to make /V-formyl derivatives and acetic anhydride to prepare the corresponding acetamides (1). Alkaline hydrolysis regenerates the analytically pure amine configurational isomers. 

The yield of the more active RRR-a-tocopherol can be improved by selective methylation of the other tocopherol isomers or by hydrogenation of a-tocotrienol (25,26). Methylation can be accompHshed by several processes, such as simultaneous halo alkylation and reduction with an aldehyde and a hydrogen haUde in the presence of staimous chloride (27), amino alkylation with ammonia or amines and an aldehyde such as paraformaldehyde followed by catalytic reduction (28), or via formylation with formaldehyde followed by catalytic reduction (29). 

Amines react with CO in the presence of metal carbonyls forming /V-formyl derivatives or substituted ureas (152,153). 

Dimethylisoxazol-5-amine is easily acylated to its formyl derivative (697) which, on catalytic hydrogenation, undergoes ring cleavage and recyclization to yield 5,6-dimethyl-pyrimidin-4(3H)-one (698) other acyl derivatives give analogous 2-substituted pyrimidines... 

The reaction ot tormamides with sulfur tetrafluoride in the presence of potassium fluoride leads to replacement of both carbonyl oxygen and hydrogen with fluorine. The formyl group is directly converted into the trifluoromethyl group A-(trifluoromethyl)amines are formed in near quantitative yields [233] (equation 121)... 

The idea that dichlorocarbene is an intermediate in the basic hydrolysis of chloroform is now one hundred years old. It was first suggested by Geuther in 1862 to explain the formation of carbon monoxide, in addition to formate ions, in the reaction of chloroform (and similarly, bromoform) with alkali. At the end of the last century Nef interpreted several well-known reactions involving chloroform and a base in terms of the intermediate formation of dichlorocarbene. These reactions included the ring expansion of pyrroles to pyridines and of indoles to quinolines, as well as the Hofmann carbylamine test for primary amines and the Reimer-Tiemann formylation of phenols. 

Reaction of 3-formyl-2-[A-(2-alkenyl)-A-benzylamino]-4//-pyrido[l, 2-n]-pyrimidin-4-ones 252 and primary amines in the presence of MS (4 A) afforded pyrido[l, 2 l,2]pyrimido[4,5-Z)]azepin-6-ones 253 (96T13081). 

Reaction of 2-[A -(rra -crotyl)-A -benzylamino]-3-formyl-4/f-pyrido[l,2-n]pyrimidin-4-one (269) with chiral primary amines 270 and 271 gave mixtures of diastereoisomers of tetracyclic compounds 273 and tricyclic 275 (96T131]]). The chiral centers in 272 and 274 did not provide any stereocontrol for the formation of diastereomers 273 and 275, respectively. 

The well-known reaction of a-alkyl-/3-ketoaldehydes and hydroxyl-amine has been applied to the elucidation of the structure of formyl-ation products of ketones the conclusions are, however, open to question. Some workers attempted to overcome the ambiguity of the reaction of j8-ketoaldehydes and hydroxylamine, which results in a mixture of 3- and 5-monosubstituted isoxazoles and thus considerably lowers the preparative value of the method, by using various derivatives of yS-ketoaldehydes, especially those of their enolic forms (jS-substituted vinylketones) investigated by Kochetkov et al. The use of readily available /3-chlorovinylketones (12) in the reaction with hydroxylamine represents a rather useful preparative method to synthesize monoalkylisoxazoles but again gives rise to a mixture of 3- (13) and 5-alkylisoxazoles (14). This is due to the attack... 

With respect to aromatic substrates, the Vilsmeier formylation reaction works well with electron-rich derivatives like phenols, aromatic amines and aromatic heterocycles like furans, pyrroles and indoles. However various alkenes are also formylated under Vilsmeier conditions. For example the substituted hexatriene 6 is converted to the terminal hexatrienyl aldehyde 7 in 70% yield ... 

A solution in dry benzene of 82 grams of bis(/3-chloroethyl)amine freshly liberated from its hydrochloride is added gradually to a solution of 36 grams of carbonyl chloride (phosgene) in benzene at a temperature below 10°C. The mixture is mechanically stirred for 3 hours, the precipitate of bis()3-chloroethyl)amine hydrochloride is removed by filtration and the benzene is distilled off on a water bath. The residue is distilled in vacuo and the N-ch oro-formyl-bis((3-chloroethy )amine is obtained as a pale yellow oil with a 8P of 114° to 116°C at 1 mm Hg. 

For example, 5 mols of dimethyl amine and 5 mols of formic acid and water are distilled to 135°C distilling off most of the water. To the remaining liquid, consisting for the most part of the formyl derivative of dimethyl amine, 1 mol of furfural mixed with 1 mol of formic acid is slowly added with heating, the temperature being maintained at 150°C to 170°C, until the reaction is complete. The mixture is then distilled into a receiver. The course of this reaction may be illustrated as follows ... 

The formyl derivative is then hydrolyzed by refluxing with 50% sulfuric acid for about 4 hours, after which the hydrolysate is extracted with ether to remove the acid-insoluble material and the aqueous solution made strongly alkaline with any suitable alkalizing agent, for example, sodium hydroxide, to liberate the amine. 

The reaction proceeds via die hydrolysis of nitrile groups to an amide. The amides may also be A-formyl amines, which react with acid groups whereby volatile formic acid is shipped10 ... 

Formaldehyde-to-phenol ratios, 404 V-Formyl amines, 158 Fourier transform infrared (FTIR) spectrometry, 116, 300, 387, 407-408 Fradet, Alain, 17 Free-radical copolymerization, 59 Friedel-Crafts acrylation polymerization, 332-334... 

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