Imido Ester Formation in Aromatic Nitriles

Bayliss, N. S.; Heppolette, R. L.; Little, L. H.; Miller, Joseph M.

doi:10.1021/ja01590a060

Cited by 20 publications

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“…Useful yields of about 60% could be obtained in a reasonable amount of time when sodium methoxide was used as the catalyst. Base-catalyzed imidate formation from nitriles is known to be reversible and commonly does not go to completion, especially when the nitrile is unsubstituted or substituted with a weak electrophile (Bayliss et al, 1956;Schaefer and Peters, 1961). Since the extent of this reaction at a given temperature is not affected by changing the concentration of nitrile or base or their ratio, it seems likely that an equilibrium is established between nitrile and imidate, slightly favoring the imidate.…”

Section: Discussionmentioning

confidence: 99%

“…-Amylase (Aspergillus oryzae) was prepared as previously described (McKelvy and Lee, 1969). Chicken egg white lysozyme and bovine serum albumin were from Sigma Chemical Co. Enzymatic activities of -amylase were measured by the starch-iodine method (McKelvy and Lee, 1969) or by the 3,5-dinitrosalicylic acid method (Bernfeld, 1951). Lysozyme activity was measured by the turbidometric method, using a suspension of Micrococcus lysodeikticus cells (Shugar, 1952) Protein concentrations were calculated from the measurement of absorbance at 280 nm (£'2801% = 16.7 for -amylase, 26.0 for lysozyme, and 6.6 for bovine serum albumin), or by a microbiuret method (Zamenof, 1957).…”

Section: Methodsmentioning

confidence: 99%

“…(A) By Hydrolysis. Imidates can be quantitatively hydrolyzed to esters and ammonia in the presence of strong acid (Bayliss et al, 1956). The imidate content of the sample hydrolyzed can be determined by measuring the ammonia produced using the TNBS method described above.…”

Section: Methodsmentioning

confidence: 99%

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2-Imino-2-methoxyethyl 1-thioglycosides: new reagents for attaching sugars to proteins

Lee¹,

Stowell²,

Krantz³

1976

Biochemistry

332

147

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Cyanomethyl 1-thioglycosides ofD-galactose, D-glucose, 2-acetamido-2-deoxy-D-glucose, and D-mannose were prepared from the respective pseudothiourea derivatives and chloroacetonitrile. The nitrile group in these cyanomethyl thioglycosides can be converted to a methyl imidate group by treatment with sodium methoxide or HC1 in dry methanol to yield 2-imino-2-methoxyethyl 1-thioglycosides (IME-thioglycosides). The factors influencing the yield of IME-thioglycosides were investigated. The most convenient method of preparing IME-thioglycosides was treating 0.1 M cyanomethyl thioglycoside peracetate in dry methanol with 0.01 M sodium methoxide at room temperature for 24-48 h (50-60% yield). These IME-thioglycosides reacted readily with simple amines, amino acids, and proteins in mildly alkaline buffer solutions. Alpha-amylase and lysozyme modified with these reagents under appropriate conditions retained full activities. Thus the IME-thioglycosides constitute a new group of reagents for attaching sugars to proteins.

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Section: Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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2-Imino-2-methoxyethyl 1-thioglycosides: new reagents for attaching sugars to proteins

Lee¹,

Stowell²,

Krantz³

1976

Biochemistry

332

147

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“…There are many different types of compounds which contain the imidoyl function and in total the body of work on this subject is quite substantial 1 . We have, for a long time, maintained interest in compounds containing >C=N-X functions and have included some comparisons of >C=O; >C=N and >C=N-X functions [2][3][4][5][6][7][8] . Later, we reported studies on NMR spectroscopy 9 and biological activity of some >C=N-X compounds 10,11 .…”

Section: Introductionmentioning

confidence: 99%

NMR Spectroscopy, Hammett Correlations and Biological Activity of Some Schiff Bases Derived from Piperonal

Echevarrı́a

Nascimento

Gerônimo

et al. 1999

J. Braz. Chem. Soc.

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Uma série de Bases de Schiff foi sintetizada através da reação de condensação do piperonal (3,4-metilenodioxibenzaldeido) com as correspondentes aminas primárias aromáticas. Seus espectros de RMN de 1 H e 13 C foram obtidos e estudou-se as correlações de Hammett envolvendo os deslocamentos químicos e as constantes dos substituíntes (σp, σR e σI). Observou-se correlações lineares e bilineares significativas para o carbono imínico (C-α) e C-1', indicando maior contribuição do efeito de ressonância do substituinte sobre os deslocamentos químicos. Os assinalamentos dos C-4' apresentaram-se bem alterados pelos efeitos dos substituíntes, especialmente pelos halogênios, na direção esperada. A série de Bases de Schiff foi ensaiada contra microorganismos, sendo que apresentou atividade significativa frente a fungos filamentosos, especialmente o Epidermophyton floccosum. Não foram observadas correlações significativas entre a atividade biológica e os efeitos eletrônicos.A series of eleven Schiff Bases have been synthesized. They were obtained by condensation of piperonal (3,4-methylenedioxybenzaldehyde) with the corresponding aromatic primary amines. Their 1 H and 13 C-NMR spectra have been obtained and the Hammett correlations including chemical shifts and the subsitutent constants (σp, σR e σI) were studied. Linear and bilinear significant correlations were observed for iminic carbon (C-α) and C-1', showing a more significant ressonance effect on chemical shifts. The chemical shifts for C-4' were highly affected by substituent effects, especially for halogens in the expected direction. Their biological activity against microorganisms has also been measured and significant activity was showed against Epidermophyton floccosum.The biological activity did not give a reasonable relationship with electronic effects.

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“…Imido esters were determined by two methods previously described in detail (Lee et al, 1976) with a few modifications. Method A (by hydrolysis): Imido esters can be quantitatively hydrolyzed to esters and ammonia by acid (Bayliss et al, 1956), and the ammonia can be determined by the trinitrobenzenesulfonic acid assay. Method B (by reaction with amines): A sample containing 1-10 gmol of IME-thioglycoside (in 0.01 M sodium methoxide in methanol) was 1 Abbreviations used: IME, 2-imino-2-methoxyethyl; CNM, cyanomethyl; BSA, bovine serum albumin; TLC, thin-layer chromatography; Glyc"-AI-BSA, a preparation of BSA to which n moles of thioglycosides had been attached by amidination with IME-thioglycoside.…”

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Preparation of some new neoglycoproteins by amidination of bovine serum albumin using 2-imino-2-methoxyethyl 1-thioglycosides

Stowell¹,

Lee²

1980

Biochemistry

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The cyanomethyl 1-thioglycosides of beta-D-galactose, 6-O-methyl-beta-D-galactose, alpha-L-arabinose, beta-D-fucose, beta-L-fucose, beta-D-glucose, beta-D-xylose, beta-D-allose, alpha-D-mannose, 2-acetamido-2-deoxy-beta-D-glucose, 2-acetamido-2-deoxy-beta-D-galactose, 2-deoxy-beta-D-glucose, and 3-O-methyl-beta-D-glucose were prepared from the respective pseudothiourea derivatives and chloroacetonitrile. The nitrile function in the aglycon of the cyanomethyl 1-thioglycosides was converted to a methyl imido ester by treatment with sodium methoxide in methanolic solutions, thereby affording the 2-imino-2-methoxyethyl 1-thioglycosides [Lee, Y.C., Stowell, C.P., & Krantz, M.J. (1976) Biochemistry 15, 3956-3963]. The stability of these reagents was investigated. The 2-imino-2-methoxyethyl 1-thioglycosides were then used to attach carbohydrates to bovine serum albumin. Amidination could be accomplished within a few hours in a pH range of 7-10. The extent of amidination could be controlled by varying the ratio of imido ester to protein amino group. These new neoglycoproteins were used to determine stereospecificity of the rabbit hepatic carbohydrate-binding system [Stowell, C.P., Lee, R.T., & Lee, Y.C. (1980) Biochemistry (following paper in this issue)].

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Imido Ester Formation in Aromatic Nitriles

Cited by 20 publications

References 0 publications

2-Imino-2-methoxyethyl 1-thioglycosides: new reagents for attaching sugars to proteins

2-Imino-2-methoxyethyl 1-thioglycosides: new reagents for attaching sugars to proteins

NMR Spectroscopy, Hammett Correlations and Biological Activity of Some Schiff Bases Derived from Piperonal

Preparation of some new neoglycoproteins by amidination of bovine serum albumin using 2-imino-2-methoxyethyl 1-thioglycosides

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