Sodium nitrite, glycine reaction

A solution of 140 g. (1 mole) of glycine ethyl ester hydrochloride 1 and 3 g. of sodium acetate in 150 ml. of water is added to the flask and cooled to 2° by means of an ice-salt bath. A cold solution of 80 g. (1.15 moles) of sodium nitrite in 100 ml. of water is added, and the mixture is stirred until the temperature has fallen to 0°. The temperature is maintained below 2°, and stirring is continued throughout all the following operations. To the cold mixture are added 80 ml. of cold, alcohol-free ethyl ether (Note 1) and 3 ml. of cold 10% sulfuric acid. After 5 minutes, the reaction mixture is blown over into the 1-1. separatory funnel by application of air pressure. The lower aqueous layer is quickly sucked back into the reaction flask. The ether layer is removed and immediately washed with 50 ml. of cold 10% sodium carbonate solution. This ether solution should be neutral to moist lilmus paper if not, the washing with sodium carbonate is repeated. The ether solution is finally dried over 10 g. of anhydrous sodium sulfate. 

The best known example of the treatment of a primary aliphatic amine with nitrous acid involves the reaction of esters of glycine hydrochloride with sodium nitrite to form esters of diazoacetic acid. This reaction is carried out at low temperatures and under such reaction conditions that any IV-nitroso primary amine which might have been formed is immediately converted to the diazoacetate [15, 16]. Treatment of 1-methyl-2,2,2-trifluoroethylamine hydrochloride, another primary amine, with sodium nitrite in an aqueous system also evidently leads to the corresponding diazoalkane [17]. 

A dichloromethane extract of the reaction product of glucose and glycine in the presence of sodium nitrite, after purification, had low cytotoxicity and no genotoxi-city, but did act as a tumour promoter in a two-stage oncogenesis with C3H10T1/2 cells initiated with benzo[a]pyrene.294... 

Place 2 ml of glycine solution and 2 ml of 10 per cent sodium nitrite solution in a test tube. In another tube place 2 ml of the nitrite solution and 2 ml of water. Hold both together in the left hand, and to each tube add 5 drops of dilute acetic acid, shake, and observe any reaction. What is the name of the product formed Write the equation for the reaction. 

Question on stability of the pyrazoline intermediates formed in 1,3-dipolar cycloadditions of alkyl diazoacetates with fullerenes was addressed in subsequent publication [15]. The reaction of glycine ethyl ester hydrochloride (or glycine octyl ester hydrochloride) with sodium nitrite was utilized to prepare ethyl diazoacetate in situ under the HSVM conditions. After 30min of vigorous milling at room temperature, 2-pyrazolines 32a and 32b were formed in 48% and 49% yield, respectively (Scheme 7.8). These pyrazolines were formed via isomerizations of 1-pyrazolines 31a,b which are obtained directly by 1,3-dipolar cycloadditions. 

A mixture of Z-menthyl glycine [39] (19.7 g, 92 mmol), isoamyl nitrite (12.0 g, 100 mmol), and acetic acid (1.6 g, 27 mmol) in chloroform (400 mL) was heated under reflux for 25 min [40]. The reaction mixture was washed with IM sulfuric acid, with a saturated aqueous solution of sodium bicarbonate, and finally with water. After removal of the solvent, the residue was purified by column chromatography on silica gel (160 g, methylene chloride) to give yellow waxy crystals (15.0 g, 73%), [a]p-86.8 ° (c 1.0, chloroform), IR t) 2125 cm (film) and H-NMR 8 5.29 ppm (chloroform-d, TMS). 

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