Glycine hydrochloride

Glycine hydrochloride [6000-43-7] M 111.5, m 176-178". Crystd from absolute EtOH. 

S g of ethyl glycinate hydrochloride were dissolved in 400 cc of ethanol and 33.5 g of salicylic aldehyde were added. It is refluxed for half an hour and cooled. 38 cc of triethylamlne and 25 g of Raney nickel are then added whereafter hydrogenation is carried out at room temperature and under atmospheric pressure. After hydrogen adsorption was complete, the mixture was filtered and the alcohol evaporated off. The residue was taken up with acidified water, extracted with ether to eliminate part of the by-products, consisting mainly of o-cresol, then made alkaline with ammonia and extracted with ethyl acetate. The solvent was removed in vacuo and the residue crystallized from ether/petroleum ether. 36.7 g of o-hydroxybenzyl-aminoacetlc acid ethyl ester melting at 47°C are obtained. 

The value of using the preformed HHT with diphenyl phosphite in this procedure was readily apparent from the nearly quantitative conversion to glyphosate observed from 25. A much lower yield (38%) of glyphosate was obtained after hydrolysis when the same components (ethyl glycinate hydrochloride and formaldehyde) were mixed and heated with neat triphenyl phosphite to give triester 30 (43). 

The same reagents can be used to form amides from carboxylic acids and amines, a method which is applicable to peptide synthesis. Condensation of A-benzyloxycarbonyl-L-phenylalanine and ethyl glycinate hydrochloride gave an 85% yield of purified dipeptide. 

The study of these fluorine-containing salts was then extended, and we prepared other new compounds in this series, e.g. 2-fluoroethyl glycine hydrochloride and 2-fluoroethyl betaine hydrochloride (that is, carbofluoroethoxy-methyl trimethyl ammonium chloride). The first of these was readily prepared by the Fischer-Speier esterification of glycine with fluoro-ethyl alcohol ... 

The 2-fluoroethyl glycine hydrochloride was found to have s l.d. 50 of about 10 mg. /kg. by subcutaneous injection into mice. The corresponding figure for 2-fluoroethyl betaine hydrochloride was 45 mg./kg. 

Diazepam From a chemical point of view, diazepam, 7-chloro-l,3-dihydro-l-methyl-5-phenyl-2H-l,4-benzodiazepin-2-one (5.1.2), is the most simple of all of the examined derivatives of l,4-benzodiazepin-2-ones. Various ways for the synthesis of diazepam from 2-amino-5-chlorobenzophenone have been proposed. The first two ways consist of the direct cyclocondensation of 2-amino-5-chlorobenzophenone or 2-methylamino-5-chlorobenzophenone with the ethyl ester of glycine hydrochloride. The amide nitrogen atom of the obtained 7-chloro-l,3-dihydro-5-phenyl-2H-l,4-benzodiazepin-2-one (5.1.1), is methylated by dimethylsulfate, which leads to the formation of diazepam (5.1.2). 

The second way differs from the first in that the methylation of nitrogen is accomphshed before the cyclocondensation reaction. In order to do this, the initial 2-amino-5-chlorobenzo-phenone is first tosylated by p-toluenesulfonylchloride and the obtained tosylate (5.1.3) transformed into the N-sodium salt, which is then alkylated by dimethylsulfate. The resulting 2-A -tosyl-A -methyl-5-chlorobenzophenone (5.1.4) is hydrolyzed in an acidic medium, giving 2-methylamino-5-chlorobenzophenone (5.1.5), which undergoes cyclocondensation by reaction with ethyl ester of glycine hydrochloride, forming the desired diazepam (5.1.2) [1-5]. 

A. Methyl a-[(methoxyethylidene)amino]acetate (1). A flame-dried, 500-mL, twonecked, round-bottomed flask is equipped with a stir bar, rubber septum, eind an argon inlet. The flask is charged with methyl acetimidate hydrochloride (10.0 g, 91 mmol) (Note 1) and dry dichloromethane (140 mL) (Note 2). The stirred suspension is cooled to 0°C and solid methyl glycinate hydrochloride (11.5 g, 91 mmol, Note 1) is added in one portion with a powder funnel under a stream of Ar. After the mixture is stirred for 45 min at 0°C, a solution of dry triethylamine (12.7 mL, 91 mmol) (Note 2) in dry dichloromethane (11 mL) is added via syringe pump during 2.5 hr. Stirring is continued for 5 hr while the mixture is... 

Methyl acetimidate hydrochloride, methyl glycinate hydrochloride, potassium tert-butoxide, and methyl formate were purchased from Aldrich Chemical Company, Inc., and were used without further purification. The checkers purchased methyl glycinate hydrochloride from Tokyo Chemical Industry Co. and potassium tert-butoxide and methyl formate from Kanto Chemical Co. Step A is very sensitive to moisture. Ethyl acetimidate hydrochloride is very hygroscopic. It must be dried before use in a desiccator over phosphorus pentoxide (P2O5) under reduced pressure and handled under argon. 

Methyl glycinate hydrochloride ALDRICH Glycine methyl ester hydrochloride Glycine, methyl ester, hydrochloride (8,9) (5680-79-5)... 

R H5C6 N COOH H R - CH2-Cl 1. 6NHa Ruckfl. 18hB 2. Eindampfen (-+ HCI-Salz) 3. H20 RuckH. 12 h 2-(4-Hydroxy-methyl-phenyl) -dl -glycin-Hydrochlorid 82 171-173 (Zers.) 1... 

Ethyiglycinate Hydrochloride Ethyl glycine Hydrochloride,Ethylglycocoll Hydrochloride or Glycine Ethylester Hydrochloride,... 

Ethylglycocoll Hydrochloride. See Ethyl-glycinate hydrochloride in this vol... 

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]. 

Testosterone (TS) used for treating TS deficiency is limited by its low aqueous solubility. With a water-soluble prodrug, TS 17P-lV,lV-dimethyl-glycinate hydrochloride, the aqueous solubility was increased to more than 100 mg/mL, compared with 0.01 mg/mL for TS. The bioavailabilities of both the prodrug and TS after nasal administration of the prodrug were similar to that after equivalent intravenous (IV) doses.66... 

CN [/ -(/ , / )]-2,2-dichloro-Al-l2-hydroxy-l-(hydroxymethyl)-2-[4-(methylsulfonyl)phenyl]ethyl]acetamide glycinate hydrochloride... 

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