N-(2-Diazo-3-oxoalkanoyl)glycine esters. I. Synthesis of 4- and 5-phenoxyl derivatives and isomerization of N-(2-diazo-3-oxo-3-phenylpropanoyl)glycine ethyl ester

1967 ◽  
Vol 45 (15) ◽  
pp. 1727-1734 ◽  
Author(s):  
James H. Looker ◽  
James W. Carpenter
Keyword(s):  
Ethyl Ester ◽  
Ethyl Esters ◽  
Chromatographic Purification ◽  
Dimroth Rearrangement ◽  
Chromatographic Procedure ◽  
Propionyl Chloride ◽  
Glycine Ethyl Ester ◽  
Crotonyl Chloride ◽  
Weight Data ◽  
Pyrazoline Derivative

A new preparative procedure for N-(diazoacetyl)glycine ethyl ester is described. The interaction of N-(diazoacetyl)glycine ethyl ester with four phenoxyacetyl chlorides gives the 4-phenoxylderivatives of N-(2-diazo-3-oxobutanoyl)glycine ethyl ester, and with β-(o-methoxyphenoxy)-propionyl chloride yields N-[2-diazo-3-oxo-5-(o-methoxyphenoxy)pentanoyl]glycine ethyl ester. A general chromatographic procedure for separating N-(2-diazo-3-oxoalkanoyl)glycine ethyl esters from N-(chloroacetyl)glycine ethyl ester has been developed. Crotonyl chloride reacts with a 1 mole excess of N-(diazoacetyl)glycine ethyl ester to form N-(2-diazo-3-oxo-4-hexenoyl)glycine ethyl ester, and with a 2 mole excess to form N-{2-diazo-3-oxo-3-[4′-methyl-5′(carboethoxymethyl)carbamoyl-Δ2pyrazolin-3′-yl]propanoyl}glycine ethyl ester, presumably by isomerization of an initially formed Δ1-pyrazoline derivative. The interaction of benzoyl and m-bromobenzoyl bromide with N-(diazoacetyl)glycine ethyl ester results initially in yellow oily products which, on the basis of spectral data, are the expected N-(2-diazo-3-oxo-3-rylpropanoyl)glycine ethyl esters. During chromatographic purification and (or) attempted crystallization, there occurs an isomerization to colorless crystalline products. The analytical and molecular weight data, together with the spectral evidence, support the tentative assignment of 1,2,3-triazole structures to the isomerization products. A spontaneous reverse Dimroth rearrangement is postulated.

N-Benzoylthiocarbamoyl Amino Acid Ethyl Esters as Chelate Ligands for Transition Metal Ions

1998 ◽  
Vol 53 (9) ◽  
pp. 981-990 ◽  
Author(s):  
Frank Leßmann ◽  
Lothar Beyer ◽  
Rainer Richter ◽  
Reinhard Meusinger
Keyword(s):  
Amino Acid ◽  
Ethyl Ester ◽  
Optical Rotation ◽  
Transition Metal Ions ◽  
Crystal Structure Analysis ◽  
Ethyl Esters ◽  
Specific Optical Rotation ◽  
X Ray ◽  
Glycine Ethyl Ester ◽  
Benzoyl Isothiocyanate

Abstract The reactions of benzoyl isothiocyanate with amino acid ethyl esters (N-butyl glycine ethyl ester, (S)-(-)-proline ethyl ester) give N-benzoylthiocarbamoyl amino acid ethyl esters. Apart from the expected N-benzoylthiocarbamoyl (S)-(-)-proline ethyl ester the racemic N-benzoyl­ thiocarbamoyl (R)/(S)-proline ethyl ester is formed because of base catalyzed racemization of the educt (S)-(-)-proline ethyl ester during the reaction of (S)-(-)-proline ethyl ester hydrochloride with triethylamine. The structures of both compounds were established by X-ray crystal structure analysis and specific optical rotation measurements. The ligands yield neutral 2:1 chelates with NiII, CuII, PdII and PtII. The carboxylic oxygen atoms are not involved in the chelation. The ligands and the resultant complexes show configurational E/Z isomerism. In the case of the chelates of the racemic N-benzoylthiocarbamoyl (R)/(S)-proline ethyl ester, additional R/S isomerism is observed as shown by NMR spectroscopy.

scholarly journals Synthesis of DHA/EPA Ethyl Esters via Lipase-Catalyzed Acidolysis Using Novozym® 435: A Kinetic Study

Catalysts ◽  
2020 ◽  
Vol 10 (5) ◽  
pp. 565 ◽  
Author(s):  
Chia-Hung Kuo ◽  
Chun-Yung Huang ◽  
Chien-Liang Lee ◽  
Wen-Cheng Kuo ◽  
Shu-Ling Hsieh ◽  
...  
Keyword(s):  
Ethyl Ester ◽  
Ethyl Esters ◽  
Raw Material ◽  
Maximum Reaction Rate ◽  
Mechanism Model ◽  
Maximum Reaction ◽  
Substrate Ratio ◽  
Free Fatty Acid Form ◽  
The Relationship ◽  
Predictive Relationship

DHA/EPA ethyl ester is mainly used in the treatment of arteriosclerosis and hyperlipidemia. In this study, DHA+EPA ethyl ester was synthesized via lipase-catalyzed acidolysis of ethyl acetate (EA) with DHA+EPA concentrate in n-hexane using Novozym® 435. The DHA+EPA concentrate (in free fatty acid form), contained 54.4% DHA and 16.8% EPA, was used as raw material. A central composite design combined with response surface methodology (RSM) was used to evaluate the relationship between substrate concentrations and initial rate of DHA+EPA ethyl ester production. The results indicated that the reaction followed the ordered mechanism and as such, the ordered mechanism model was used to estimate the maximum reaction rate (Vmax) and kinetic constants. The ordered mechanism model was also combined with the batch reaction equation to simulate and predict the conversion of DHA+EPA ethyl ester in lipase-catalyzed acidolysis. The integral equation showed a good predictive relationship between the simulated and experimental results. 88–94% conversion yields were obtained from 100–400 mM DHA+EPA concentrate at a constant enzyme activity of 200 U, substrate ratio of 1:1 (DHA+EPA: EA), and reaction time of 300 min.

scholarly journals Some metabolites of 1-bromobutane in the rabbit and the rat

1968 ◽  
Vol 109 (5) ◽  
pp. 727-736 ◽  
Author(s):  
Sybil P. James ◽  
D. A. Jeffery ◽  
Rosemary H. Waring ◽  
P. B. Wood
Keyword(s):  
Lactic Acid ◽  
Ethyl Ester ◽  
Rat Liver ◽  
Hydroxy Acid ◽  
Rabbit Liver ◽  
Mercapturic Acid ◽  
Acid Form ◽  
Rat Urine ◽  
Glycine Ethyl Ester

1. Rabbits and rats dosed with 1-bromobutane excrete in urine, in addition to butylmercapturic acid, (2-hydroxybutyl)mercapturic acid, (3-hydroxybutyl)mercapturic acid and 3-(butylthio)lactic acid. 2. Although both species excrete both the hydroxybutylmercapturic acids, only traces of the 2-isomer are excreted by the rabbit. The 3-isomer has been isolated from rabbit urine as the dicyclohexylammonium salt. 3. 3-(Butylthio)lactic acid is formed more readily in the rabbit; only traces are excreted by the rat. 4. Traces of the sulphoxide of butylmercapturic acid have been found in rat urine but not in rabbit urine. 5. In the rabbit about 14% and in the rat about 22% of the dose of 1-bromobutane is excreted in the form of the hydroxymercapturic acids. 6. Slices of rat liver incubated with S-butylcysteine or butylmercapturic acid form both (2-hydroxybutyl)mercapturic acid and (3-hydroxybutyl)mercapturic acid, but only the 3-hydroxy acid is formed by slices of rabbit liver. 7. S-Butylglutathione, S-butylcysteinylglycine and S-butylcysteine are excreted in bile by rats dosed with 1-bromobutane. 8. Rabbits and rats dosed with 1,2-epoxybutane excrete (2-hydroxybutyl)mercapturic acid to the extent of about 4% and 11% of the dose respectively. 9. The following have been synthesized: N-acetyl-S-(2-hydroxybutyl)-l-cysteine [(2-hydroxybutyl)mercapturic acid] and N-acetyl-S-(3-hydroxybutyl)-l-cysteine [(3-hydroxybutyl)mercapturic acid] isolated as dicyclohexylammonium salts, N-toluene-p-sulphonyl-S-(2-hydroxybutyl)-l-cysteine, S-butylglutathione and N-acetyl-S-butylcysteinyl-glycine ethyl ester.

Iron-Catalyzed Cyclopropanation with Glycine Ethyl Ester Hydrochloride in Water

2012 ◽  
Vol 14 (8) ◽  
pp. 2162-2163 ◽  
Author(s):  
Bill Morandi ◽  
Amund Dolva ◽  
E. M. Carreira
Keyword(s):  
Ethyl Ester ◽  
Ester Hydrochloride ◽  
Glycine Ethyl Ester

Preparation of eicosapentaenoic acid ethyl ester from fish oil ethyl esters by continuous batch chromatography

2019 ◽  
Vol 42 (24) ◽  
pp. 3697-3702
Author(s):  
Yanmei Li ◽  
Lei Zhao ◽  
Xiaolei Huang ◽  
Liguang Zhang ◽  
Jingjing Li ◽  
...  
Keyword(s):  
Eicosapentaenoic Acid ◽  
Fish Oil ◽  
Ethyl Ester ◽  
Acid Ethyl Ester ◽  
Ethyl Esters ◽  
Eicosapentaenoic Acid Ethyl Ester

Protection of Corn (Zea mays) from Acetanilide Herbicidal Injury with the Antidote R-25788

Weed Science ◽  
1978 ◽  
Vol 26 (6) ◽  
pp. 653-659 ◽  
Author(s):  
J. R. C. Leavitt ◽  
Donald Penner
Keyword(s):  
Zea Mays ◽  
Ethyl Ester ◽  
Isopropyl Ester ◽  
Weed Species ◽  
Greenhouse Study ◽  
Glycine Ethyl Ester

The antidote R-25788 (N,N-diallyl-2,2-dichloroacetamide) protected corn (Zea mays L. ‘DeKalb 315A’) seedlings from injury caused by the acetanilide herbicides, alachlor [2-chloro-2′,6′-diethyl-N-(methoxymethyl)acetanilide], metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide], H-22234 [N-chloroacetyl-N-(2,6-diethylphenyl)glycine ethyl ester], and H-26910 [N-chloroacetyl-N-(2-methyl-6-ethylphenyl)glycine isopropyl ester] in a greenhouse study. R-25788, however, did not protect four weed species tested. R-25788 only partially protected corn from injury caused by acetochlor [2-chloro-N-(ethoxymethyl)-6′-ethyl-o-acetotoluidide]. R-25788 was an effective antidote whether applied preemergence, preplant-incorporated, or as a tank mix. Injury symptoms caused by EPTC (S-ethyl dipropylthiocarbamate) and the acetanilide herbicides were similar; both caused leaf twisting and rolling, and at high rates leaves failed to emerge through the coleoptile.

scholarly journals Synthesis of Potential Haptens with Morphine Skeleton and Determination of Protonation Constants

Molecules ◽  
2020 ◽  
Vol 25 (17) ◽  
pp. 4009
Author(s):  
István Köteles ◽  
Károly Mazák ◽  
Gergő Tóth ◽  
Boglárka Tűz ◽  
Sándor Hosztafi
Keyword(s):  
Ethyl Ester ◽  
Peptide Bond ◽  
Ethyl Acrylate ◽  
Alkaline Media ◽  
Carrier Protein ◽  
Amino Group ◽  
Carboxylic Group ◽  
Promising Alternative ◽  
Glycine Ethyl Ester ◽  
Work Up

Vaccination could be a promising alternative warfare against drug addiction and abuse. For this purpose, so-called haptens can be used. These molecules alone do not induce the activation of the immune system, this occurs only when they are attached to an immunogenic carrier protein. Hence obtaining a free amino or carboxylic group during the structural transformation is an important part of the synthesis. Namely, these groups can be used to form the requisite peptide bond between the hapten and the carrier protein. Focusing on this basic principle, six nor-morphine compounds were treated with ethyl acrylate and ethyl bromoacetate, while the prepared esters were hydrolyzed to obtain the N-carboxymethyl- and N-carboxyethyl-normorphine derivatives which are considered as potential haptens. The next step was the coupling phase with glycine ethyl ester, but the reactions did not work or the work-up process was not accomplishable. As an alternative route, the normorphine-compounds were N-alkylated with N-(chloroacetyl)glycine ethyl ester. These products were hydrolyzed in alkaline media and after the work-up process all of the derivatives contained the free carboxylic group of the glycine side chain. The acid-base properties of these molecules are characterized in detail. In the N-carboxyalkyl derivatives, the basicity of the amino and phenolate site is within an order of magnitude. In the glycine derivatives the basicity of the amino group is significantly decreased compared to the parent compounds (i.e., morphine, oxymorphone) because of the electron withdrawing amide group. The protonation state of the carboxylate group significantly influences the basicity of the amino group. All of the glycine ester and the glycine carboxylic acid derivatives are currently under biological tests.

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