Dimethylamino acid

RE Bowman, HH Stroud. N-Substituted amino acids. I. A new method of preparation of dimethylamino acids. J Chem Soc 1342, 1950. 

Optically pure 2,3-dihydro-6//-l, 4-oxazin-2-ones were prepared in a two-step reaction from A-protected AAs and a-bromoketones (78JOC135). When heated in boiling toluene and HCl 2,2-dimethylamino acid amides were transformed into the corresponding 3,3-dimethyl-l,4-oxazine-2,5-diones (83TL1921 87HCA329). 

This preparation illustrates the use of dimethyl sulphate to convert a primary amino group into the secondary monomethylamino group, without the methy-lation proceeding to the tertiary dimethylamino stage. The methylation of anthranilic acid is arrested at the monomethylamino stage by using i-i molecular equiN alents of sodium hydroxide and of dimethyl sulphate. The reactions can be considered as ... 

Cool the solution thoroughly in ice-water, and then make it alkaline by the cautious addition (with stirring or shaking) of a solution of 80 g. of sodium hydroxide in ca, 150 ml. of water. Now isolate the free tertiary amine by steam-distillation into hydrochloric acid, etc., precisely as for the primary amine in Stage (D), but preferably using a smaller flask for the final distillation. Collect the 2-dimethylamino- -octane, b.p. 76-78715 mm. Yield, 13-14 g. At atmospheric pressure the amine has b.p. 187-188°. 

Benzoylpropionitrile. To a mixture of 21 4 g. of p dimethylamino propiophenone hydrochloride, 13 0 g. of potassium cyanide in a 500 ml. flask, add 260 ml. of boiling water heat the heterogeneous mixture under reflux for 30 minutes. Part of the dimethylamine, which is eliminated in the reaction, distils collect this in dilute hydrochloric acid. Cool the reaction mixture in ice the oil sohdifies and crystals form from the aqueous layer. Collect the solid (crude p benzoylpropiouitrile, 10-5 g.) by suction filtration and recrystallise it from benzene - light petroleum (b.p. 40-60°) it separates as almost colourless blades, m.p. 76°. 

Asymmetric hydrogenolysis of allylic esters with formic acid with satisfactory ee was observed[387], Geranyl methyl carbonate (594) was reduced to 570 with formic acid using l,8-bis(dimethylamino)naphthalene as a base and MOP-Phen as the best chiral ligand, achieving 85% ee. 

As improvements over P-methylumbeUiferone (55—57), 4-methyl-7-amino-coumarin [26093-31-2] (12a) and 7-dimethylamino-4-methylcoumarin [87-014] (12b) (58—61) were proposed. These compounds are used for brightening wool and nylon either in soap powders or detergents, or as salts under acid dyeing conditions. They are obtained by the Pechmaim synthesis from appropriately substituted phenols and P-ketocarboxyflc acid esters or nitriles in the presence of Lewis acid catalysts (see Coumarin). 

A A Dimethylamino)phenol. 3-Hydroxy-A7,A7-dimethylariiline (14) forms white needles and is soluble in alkaU, mineral acid, ethanol, diethyl ether, acetone, and benzene and practically insoluble in water. 

A A Dimethylamino)phenol. 4-Hydroxy-Ai,A/-dimethylaniline (20) forms large rhombic crystals from diethyl ether—hexane or diethyl ether—ligroin. It forms a salt with sulfuric acid, mp 208—210°C (187). 

Inosine complexed with 4-(acetylamino)ben2oic acid and 1-(dimethylamino)-2-propano1 (1 3 3) nolecular formula = CjgHj2N4O5-SCgH CAS Registry Number = [36703-88-5],... 

Analytical and Test Methods. In addition to the modem spectroscopic methods of detection and identification of pyrroles, there are several chemical tests. The classical Runge test with HCl yields pyrrole red, an amorphous polymer mixture. In addition, all pyrroles with a free a- or P-position or with groups, eg, ester, that can be converted to such pyrroles under acid conditions undergo the Ehrlich reaction with p-(dimethylamino)henzaldehyde to give purple products. 

Levopropoxyphene [2338-37-6] (42), the optical antipode of the dextrorotatory analgetic propoxyphene, is an antitussive without analgetic activity. The 2-naphthalenesulfonate salt has a less unpleasant taste than the hydrochloride salt, and is widely used. Clinical effectiveness has been demonstrated against pathological and artificially induced cough, but the potency is somewhat less than codeine. The compound is reported not to cause addiction. Levopropoxyphene can be prepared (62) by first resolving [ -dimethylamino-CX-methylpropiophenone with dibenzoyl-(+)-tartaric acid. The resolved... 

Dimetilan (dimethylcarbamic acid l-[(dimethylamino)carbonyl]-5-methyl-l//-pyrazol-3-yl ester 724) and isolan (dimethylcarbamic acid 3-methyl-l-isopropyl-l//-pyrazol-5-yl... 

Isoxazole-3-carbaldehyde has been obtained as a minor product from the reaction of acetylene with a mixture of nitric oxide and nitrogen dioxide (61JOC2976). Although 3-aryl-4-formylisoxazoles have been synthesized in good yields from the reaction of benzonitrile Af-oxides with 3-(dimethylamino)-2-propen-l-one (71S433), the parent member of the series, isoxazole-4-carbaldehyde, has never been reported. It may possibly be obtained by the addition of fulminic acid to 3-(dimethylamino)-2-propen-l-one. 

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