Methyl inner salt

Chemical Name Pyrrolidinium, l-(((6R,7R)-7-(((2Z)-(2-amino-4-thiazolyl) (methoxyimino)acetyl)amino)-2-carboxy-8-oxo-5-thia-l-azabicyclo(4.2.0) oct-2-en-3-yl)methyl)-l-methyl-, inner salt... 

The papaver alkaloid Narcotoline (265) can be converted into the yellow colored Cotarnoline (267) on hydrolysis which adopts a zwitterionic ground state (56MI1, 57MI1) (Scheme 87). The corresponding dihydro derivative was also identified in nature. The UV spectrum of the zwitterionic Tarkonine (268), which forms red crystals from acetone, is shifted bathochromically in comparison to the chloride. Tarkonine is a very weak base (pA b = 9.58), which is well in accord with the formation of an inner salt, and Cotarnoline (267) is a stronger base than Tarkonine (268) (pA b = 9.15). The pK values are larger than 13 (66MI3). The methylated derivative of Narcotoline is Narcotine (266). 

Theoretical calculations (B3LYP/6-31G ) were reported for geometries (bond lengths and bond angles) and chemical shifts of 3-methyl- and 3-phenyl-4-hydroxy-2-oxo-2/7-pyrido[2,l-f>][l, 3]oxazinium inner salts (00JCS(P2)2096). 

Methyl- and 3-phenyl-4-hydroxy-2-oxo-2//-pyrido[2,1 -Z)]oxazinium inner salts were prepared in the reaction of 2-pyridone and 2-substituted malonyl chloride, prepared in situ from 2-substituted malonic acid with PCI5 in CH2CI2 (00JCS(P2)2096). 

Chemical Name (6R-trans)-1-[ [2-Carboxy-8-oxo-7-[(2-thienylacetyl)amino] -5-thia-1-azabi-cyclo[4.2.0]oct-2-en-3-yl] methyl] pyridinium hydroxide inner salt... 

Chemical Name Endo( )-3-(3-hydroxy-1-oxo-2-phenYlpropOXY)-8-methyl-8-(3-sulfopropYl)-8-azoniabicyclo[3.2.11 octane hydroxide, inner salt... 

CONVERSION OF PRIMARY ALCOHOLS TO URETHANES via THE INNER SALT OF METHYL (CARBOXYSULFAMOYL)TRIETHYLAMMONIUM HYDROXIDE METHYL n-HEXYLCARBAMATE... 

The above procedure describes the only known preparation of the inner salt of methyl (carboxysulfamoyl)triethylammonium hydroxide and illustrates the use of this reagent to convert a primary alcohol to the corresponding urethane.2 Hydrolysis of the urethane would then provide the primary amine. The method is limited to primary alcohols secondary and tertiary alcohols are dehydrated to olefins under these conditions, often in synthetically useful yields.2... 

A. Carbobenzoxy-L-asparaginyl-L-lewine Methyl Ester. A mixture of 2.024 g. (0.0080 mole) of A -ethyl 5 phenylisoxazolium-3 -sulfonate [Isoxazolium, 2-ethyl-5-(3-sulfophenyl)-, hydroxide, inner salt] (Note 1) and 20 ml. of nitromethane (Note 2) is prepared in a 50-ml., glass-stoppered Erlenmeyer flask at room temperature and stirred vigorously... 

RN 13422-55-4 MF Cf,3H CoN,.,Oi4P MW 1344.41 EINECS 236-535-3 CN cobinamide Co-methyl deriv. hydroxide dihydrogen phosphate (ester) inner salt 3 -ester with 5,6-dimethyl-l-a-D-ribofur mosyl-l//-benzimidazole... 

Methyl- and 3-phcnyl+-hydroxy-2-oxo-2//-pyrido[2,1 +]oxazinium inner salts were prepared in the reaction of... 

Both the inner salts 6 of anhydro 177-[l,2,4]triazolo[4,3-6][l,2,4]triazolium hydroxides and their methylation products 7, when heated above the melting points, suffer loss of sulfur or of methyl iodide and sulfur, respectively, and concomitant ring opening into 1-methyl-3-methylthio-5 (arylcyanamino)[l,2,4]triazoles 8 takes place (Equation 1) <1984TL5427,1986T2121>. 

When thioxo (or thiol) derivatives (as part of a thiourea function incorporated into the heterocyclic system) are present, effective. Y-alkylation is observed. Thus, the 3-heteroaryl-substituted [l,2,4]triazolo[3,4-/)][l,3,4]thiadiazole-6(5//)-thiones 37 dissolved in sodium hydroxide solution react with alkyl halides to afford the corresponding 6-alkylthio derivatives 38 (Equation 4) <1992IJB167>. The mesoionic compounds 39, inner salts of anhydro-7-aryl-l-methyl-3-methylthio-6-sulfonyl-[l,2,4]triazolo[4,3-A [l,2,4]triazolium hydroxides, are methylated with methyl iodide to give the corresponding quaternary salts 40 (Equation 5) <1984TL5427, 1986T2121>. 

Methyl (carboxysulfamoyl)triethylammonium hydroxide, inner salt (Burgess reagent). 

Ring-opened products were obtained from pyrido[l,2-6]cinnolin-6-ium hydroxide inner salt (17, R = H) by oxidation with 3-chloroperoxybenzoic acid, or by reduction with Zn in acetic acid, and from the 5-methyl derivative 43 by reduction with Zn in acetic acid (74JHC125). 

Alkylation of ll-mercaptopyrido[l,2-h]cinnolin-6-ium hydroxide inner salts (e.g., 41) with ethyl bromoacetate gave ll-(ethoxycarbonylmethyl(thio derivatives 64 (R = H), which could be hydrolyzed to the ll-(carboxy-methyl)thio derivative or back to the starting compound 41 (74JHC125). Hydrolysis of the ll-bis(methoxycarbonyl)methylene 66 (R = H), and 2-cyano derivatives of 17 (R = H) in boiling HCl afforded 11-methyl and 2-carboxylic acid derivatives, respectively (74JHC125). The 2-nitro derivative of 17 (R = H) was reduced to the 2-amino derivative over Pd/C with NaBH4 in aqueous methanol, and the 2-amino group was acylated with acetic anhydride at 100°C. 

Dye oxidation (e.g., tetrazolium reductase activity with 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl tetrazolium bromide, MTT 2-[4-iodophenyl]-3-[4-nitrophenyl]-5-[2,4-disulfophenyl]-2H tetrazolium monosodium salt, WST-1 3- (4,5 -carboxymethoxyphenyl) -2-(4-sulfophenyl)-2 H-tetra-zolium, MTS 2,3-bis(2-methoxy-4-nitro-5-sulfophenyl)-2H-tetrazolium-5-carboxanilide inner salt, XTT 2,2 -di-p-nitrophenyl-5,5 -diphenyl-3,3 -(3,3 -dimethoxy-4,4 -diphe-nylenej-ditetrazolium chloride, NET), Alamar blue assays, ATP concentration (e.g., luciferase assay), oxygen consumption (e.g., oxygen electrodes, phosphorescent oxygen-sensitive dyes), mitochondrial protein and nucleic acid synthesis mitochondrial mass (e.g., mitotracker dyes) mitochondrial membrane potential (e.g., tetramethylrho-damine methyl ester, TMRM tetramethylrhodamine ethyl ester, TMRE)... 

Dimethylspiro[3.3]hept-1-en-1-yl) Phenyl Sulfide (4 Table 15, Entry 6) Method G Under N2, a mixture of 2,2-dimethyl-l-(l-phenylsulfanylcyclopropyl)cyclobutan-l-ol (1.0 g, 4.0 mmol) and (carboxysulfa-moyl)tricthylammonium hydroxide inner salt methyl ester (1.19 g, 5.0 mmol) in anhyd benzene (10 mL) was refluxed for 2 h. After cooling, H20 (2 mL) was added and the product isolated as above yield 850 me (92%). 

On treatment with (carboxysulfamoyl)triethylammonium hydroxide inner salt methyl ester (Burgess reagent), the adducts of ketones yielded 1-vinylcyclopropyl selenides, but the adducts of aldehydes, e.g. 4, rearranged to cyclobut-1-enyl selenides.176... 

Ottinger el al.2S6 have applied their comparative taste dilution analysis (cTDA) to examine the extractable products from heated aqueous D-glucose and L-alanine that were not solvent-extractable. One HPLC fraction proved to be a strong sweetness enhancer. It was isolated and submitted to LC-MS and NMR, both ID and 2D the results, together with its synthesis from HMF and alanine, unequivocally identified it as the inner salt of /V-( I -carboxycthyl)-6-(hydroxy-methyl)pyridinium-3-ol (alapyridaine, Structure 45). It has no taste on its own, which in many applications would be an advantage. Depending on the pH, it lowers the detection threshold of sweet sugars, amino acids, and aspartame, the... 

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