Glutaconaldehyde

The stable sodium glutaconaldehyde enolate 48 may be recrystallized from methanol and conserved, but glutaconaldehyde (50) itself is extraordinarily unstable therefore, the enolate (48) is directly... 

The preparation of j8-hydroxyglutaraldehyde (53a) and the bisacetal (53b) have been recently reported. Being more stable than glutaconaldehyde (50), they could perhaps be employed in the preparation of 1. 

The initial exothermic reaction that occurs at this point produces the intermediate glutaconaldehyde iminesulfonate disodium salt shown in the scheme. It separates as a yellow, unstable precipitate that may be isolated by filtering, washing with ice-cold isopropyl alohol, and drying. The yield of the disodium salt is 64 g. (96%). 

Glutaconaldehyde anion serves as an interesting intermediate for the synthesis of heterocyclic compounds. The parent pyrylium perchlorate has been prepared from glutaconaldehyde and 70% perchloric acid in ether at -55°.° The reaction of glutaconaldehyde anion with alkyl and aryl isothiocyanates and... 

Glutaconaldehyde (8) 2-Pentenedial (9) (821-42-1) Glutaconaldehyde, sodium salt, dihydrate Glutaconaldehyde, ion (1 ) sodium (8) 2-Pentenedial, ion (1 ), sodium (9) (24290-36-6) Pyridinium-1-sulfonate Pyridinium, 1-sulfo-, hydroxide, inner salt (8,9) (42824-16-8)... 

FLUORIDE, 58, 75 Pyridinium-l-sulfonate, 59, 79 hydrolysis to glutaconaldehyde sodium salt, 59,79... 

GLUTACONALDEHYDE SODIUM SALT FROM HYDROLYSIS OF PYRIDINIUM-l-SULFONATE... 

The sodium and potassium salts of glutaconaldehyde are soluble only in polar solvents such as water, dimethyl sulfoxide, N,N-dimethylformamide, pyridine, and methanol. However, the stable tetrabutylammonium salt is soluble in relatively nonpolar solvents such as chloroform and ethyl acetate. It may be prepared from the potassium salt in the following manner. In a 1-1. Erlenmeyer flask equipped with a magnetic stirring bar are placed a solution of 13.6g. (0.1 mole) of crude glutaconaldehyde potassium salt in 200 ml. of water and a solution of 33.9 g. (0.1 mole) of tetrabutyl-ammonium hydrogen sulfate in 200 ml. of ice-cold water, the pH of wliich was adjusted to 10 by adding aqueous 2M sodium hydroxide. 

Glutaconaluehyde Enol Benzoates " and 1-Substituted 3-Formyl-2(1H)-Pyridinethiones " Prepared from Glutaconaldehyde Anion and Its... 

This ester was prepared by benzoylation of the corresponding glutaconaldehyde iminesulfonate dianion and subsequent hydrolysis... 

This ester was prepared by halogenation of glutaconaldehyde anion followed by benzoylation. 

The 3-formyl-2(IH)-pyridinethiones were prepared by reaction of glutaconaldehyde anion with the corresponding isothiocyanates (RN—C==S). 

Substituted pyridinium salts of this nature were difficult to obtain by other methods. This sequence is initiated with condensation of the anions of imine 50 with malonaldehyde monoacetals 51 to access glutaconaldehyde monoacetals 52. The monoacetal-aldehyde was then reacted with primary amines ( -BuNH2) to give 3-substituted pyridinium salts 49. When the silylimino derivative (R1=Si(CH3)3) was used, substantially higher yields of intermediate glutaconaldehydes were obtained. 

Treatment of 1-pyridinium sulphonate with sodium or potassium hydroxide generates sodium or potassium salts of 5-hydroxy-2,4-pentadienal (glutaconaldehyde), which are starting materials for a variety of transformations (equation 178)171b 301. For example, the reaction of the potassium salt with a carbon electrophile has been used for the preparation of a dienol aldehyde (equation 179)mb which was an intermediate in the total synthesis of a mutagen, (S)-3-(dodeca-l,3,5,7,9-pentaenyloxy)propane-l,2-diol. 

Preparation of Dianiline Derivative of Glutaconaldehyde. A sample of the niobium(V) chloride-pyridine reaction mixture was hydrolyzed in dilute aqueous ammonia, and the solution was filtered to remove precipitated niobium (V) oxide. 

Finally, the oxidation product was positively identified by preparation of a known derivative of the glutaconaldehyde obtained by basic degradation of the l-(4-pyridyl) pyridinium ion present in a sample of the chloride reaction mixture. 

AE31 C5HSO2 glutaconaldehyde VH2U1VH 0HCCH CHCH2CH0 h2o P0 BR " 5.6 - HMDE SCE —2 C=12... 

The products of the ring opening of pyridinium cations in aqueous base are usually glutaconaldehyde derivatives. Early work in this area has been... 

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