ISOMERIC 5-(SUBSTITUTED)AMINOTHIATRIAZOLE AND 1-SUBSTITUTED-TETRAZOLINETHIONES

1959 ◽  
Vol 37 (1) ◽  
pp. 101-109 ◽  
Author(s):  
Eugene Lieber ◽  
J. Ramachandran
Keyword(s):  
Electrical Properties ◽  
Sodium Azide ◽  
Side Reactions ◽  
Hydrazoic Acid ◽  
Azide Ion ◽  
Rearrangement Mechanism

The reaction of organic isothiocyanates with sodium azide in ethanol and water has been investigated. Water is shown to be the more advantageous solvent for this reaction giving higher yields and initially purer 1-substituted-tetrazoline-5-thiones. A series of these latter compounds was made by this procedure. The yield of product appears to be dependent on the electrical properties of the substituent of the isothiocyanate, the yields decreasing as the electron-donating properties increase. A series of new 4-substituted-thiosemicarbazides has been prepared and converted by diazotization to the corresponding 5-(substituted)aminothiatriazoles. A theory to account for the differences in the mode of reaction of hydrazoic acid and azide ion is presented and discussed. The basic conversion of 5-(substituted)aminothiatriazoles to 1-substituted-tetrazolinethiones may involve a simple dearrangement–rearrangement mechanism complicated by side reactions. A summary of known isomeric 5-(substituted)aminothiatriazoles and 1-substituted-tetrazolinethiones is presented.

Electronic Spectra of the Azide Ion, Hydrazoic Acid, and Azido Molecules

1970 ◽  
Vol 52 (3) ◽  
pp. 1332-1340 ◽  
Author(s):  
J. R. McDonald ◽  
J. W. Rabalais ◽  
S. P. McGlynn
Keyword(s):  
Electronic Spectra ◽  
Hydrazoic Acid ◽  
Azide Ion

ChemInform Abstract: CATALYTIC POLAROGRAPHIC WAVES OF COBALT(II) IN SODIUM AZIDE WITH HYDRAZOIC ACID

1981 ◽  
Vol 12 (44) ◽  
Author(s):  
R. TOKORO ◽  
E. A. NEVES
Keyword(s):  
Sodium Azide ◽  
Hydrazoic Acid

Thermochemistry and reactivity of the azides - I. Thermochemistry of the inorganic azides

1956 ◽  
Vol 235 (1200) ◽  
pp. 106-119 ◽  
Keyword(s):  
Heavy Metal ◽  
Alkali Metal ◽  
Alkaline Earth ◽  
Enthalpies Of Formation ◽  
Hydrazoic Acid ◽  
Explosive Decomposition ◽  
Dissociation Energies ◽  
Azide Ion ◽  
Heavy Metal Azides ◽  
Lattice Energies

The problems of structure and reactivity of the azides are of course closely related to their thermochemistry. Lattice energies, electron affinities and bond energies are especially important. Although numerous investigations have been made both into slow thermal decomposition and explosive decomposition of the azides interpretation has been hampered by lack of reliable thermochemical data. In the literature, only a collection of inconsistent and unreliable data for the heavy-metal azides is available; for the alkali-metal and alkaline-earth azides there are no data at all. This paper deals with the thermochemical relations of the azides and their application to reactivity. In part I the experimental determination of consistent enthalpy data for hydrazoic acid, the aqueous azide ion, the alkali metal, the alkaline-earth and heavy-metal azides is described. The values of the enthalpies of formation (∆ H o f in kcal mole -1 ) are: N - 3 Aq (55∙51 H 2 O), 65∙53; HN 3G , 71∙66; HN 3L , 64∙37; LiN 3 , 2∙58; NaN 3 , 5∙08; KN 3 , 0∙33; RbN 3 , -0∙07; CsN 3 , -2∙37; NH 4 N 3 , 26∙79; CaN 6 , 11∙03; SrN 6 , 1∙72; BaN 6 , -5∙32; CuN 3 , 67∙23; CuN 6 , 140∙4; AgN 3 , 74∙17; Hg 2 N 6 , 141∙5; T1N 3 , 55∙78; PbN 6 , 115∙5. From these and other measurements consistent values for free energies and entropies of the azides are derived. These primary thermodynamic data will be employed in part II of this paper to derive important thermochemical quantities not susceptible to direct measurement such as bond dissociation energies, lattice energies and the electron affinity of the azide ion.

Catalytic polarographic wave of cobalt(II) in sodium azide with hydrazoic acid

1981 ◽  
Vol 125 (1) ◽  
pp. 115-128 ◽  
Author(s):  
Roberto Tokoro ◽  
Eduardo A. Neves
Keyword(s):  
Sodium Azide ◽  
Hydrazoic Acid ◽  
Polarographic Wave

Kinetics of reaction of aquacobalamin with azide ion and hydrazoic acid: pH profile and activation parameters

1991 ◽  
pp. 2941 ◽  
Author(s):  
Helder M. Marques ◽  
Ernst L. J. Breet ◽  
Frans F. Prinsloo
Keyword(s):  
Activation Parameters ◽  
Hydrazoic Acid ◽  
Ph Profile ◽  
Acid Ph ◽  
Azide Ion ◽  
Kinetics Of Reaction ◽  
Kinetics Of

Chiral Sulfur Compounds. XXI. Addition of Azide Ion to β-Aryl-α-phenylsulfinylacrylates

1993 ◽  
Vol 46 (9) ◽  
pp. 1431 ◽  
Author(s):  
Z Dong ◽  
KA Hellmund ◽  
SG Pyne
Keyword(s):  
Acetic Acid ◽  
Hydrochloric Acid ◽  
Michael Addition ◽  
Sodium Azide ◽  
Sulfur Compounds ◽  
Azide Ion

The reaction of methyl β-aryl-α- phenylsulfinylacrylates (1) with sodium azide /acetic acid gives triazoles (6) while the reaction of (1) with sodium azide /hydrochloric acid gives β-azido esters (7a,b). Reaction of (7a) with 1,8-diazabicyclo[5.4.0]undec-7-ene, and (7b) with triethylamine gave the corresponding triazoles (6a) and (6b), respectively. Thus the formation of triazoles from the reaction of acrylates with azide ion most likely involves Michael addition of azide ion followed by cyclization of an incipient β-azido α-anion.

THE REACTION OF NITROUS ACID WITH 4-SUBSTITUTED-THIOSEMICARBAZIDES

1957 ◽  
Vol 35 (8) ◽  
pp. 832-842 ◽  
Author(s):  
Eugene Lieber ◽  
C. N. Pillai ◽  
Ralph D. Hites
Keyword(s):  
Nitrous Acid ◽  
Relative Proportion ◽  
Chemical Degradation ◽  
Hydrazoic Acid ◽  
Melting Points ◽  
Pure Nitrogen ◽  
Competitive Reactions ◽  
Azide Ion ◽  
Lower Melting Point ◽  
Aryl Isothiocyanates

The reaction of nitrous acid with 4-alkyl- or 4-aryl-thiosemicarbazides, as well as the reaction of alkyl- or aryl-isothiocyanates with hydrazoic acid, leads to the identical 5-(substituted)amino-1,2,3,4-thiatriazole. This has been established by infrared absorption and chemical degradation studies. The reaction of the 5-(substituted)amino-1,2,3,4-thiatriazoles with aqueous bases leads to two competitive reactions: (1) degradation to an isothiocyanate and azide ion, and (2) isomerization to a 1-substituted-tetrazole-5-thiol, the extent of path (1) or (2) depending on the nature of the substituent. Path (1) predominates when the substituent is alkyl, whereas when the substituent is aryl both paths (1) and (2) occur, the relative proportion depending on the electrical nature of the aromatic group, path (2) increasing as the electronegativity increases. The 1-aryl-tetrazole-5-thiols were found to be thermally unstable at their melting points, degrading more or less violently to one mole proportion of pure nitrogen with the formation of sulphur and organic products of lower melting point as yet unidentified. Theories to account for these observations are presented and discussed.

Synthesis of the cis and trans isomers of 4-Chloro-L-proline, 4-Bromo-L-proline, and 4-Amino-L-proline

1967 ◽  
Vol 20 (7) ◽  
pp. 1493 ◽  
Author(s):  
RH Andreatta ◽  
V Nair ◽  
AV Robertson ◽  
WRJ Simpson
Keyword(s):  
Methyl Ester ◽  
Sodium Borohydride ◽  
Protecting Groups ◽  
Hydroxyl Group ◽  
Side Reactions ◽  
Trans Isomers ◽  
Azide Ion ◽  
Cis And Trans Isomers ◽  
Proline Derivatives ◽  
Cis And Trans

cis- and trans-4-Chloro- and 4-bromo-L-prolines have been synthesized stereospecifically, the key step being SN2 displacement of a free or substituted 4-hydroxyl group in suitably protected 4-hydroxy-L- prolines. Similar displacements with azide ion followed by reduction provide convenient routes to cis- and trans- 4-amino-L-proline. A less satisfactory pathway to cis-4-aminoproline is reduction of a 4- oximinoproline derivative. In the course of the syntheses, which involve a variety of protecting groups, 45 new L-proline derivatives have been prepared. Unexpected side reactions were the formation of cis-4-hydroxyprolinamide by the action of ammonia on trans-4- bromoproline, and the reduction by sodium borohydride of N- benzyloxycarbonyl-4-oximinoproline methyl ester to N-benzyloxycar- bonyl-4-oximinoprolinol.

scholarly journals Determination of Sodium Azide in Beverages by Ion Chromatography

2000 ◽  
Vol 83 (6) ◽  
pp. 1410-1414 ◽  
Author(s):  
Harumi Oshima ◽  
Eiji Ueno ◽  
Isao Saito ◽  
Hiroshi Matsumoto
Keyword(s):  
Detection Limit ◽  
Sample Preparation ◽  
Sodium Hydroxide ◽  
Ion Chromatography ◽  
Sodium Azide ◽  
Convenient Method ◽  
Sodium Hydroxide Solution ◽  
Hydrazoic Acid ◽  
Suppressed Conductivity Detection

Abstract A convenient method for determination of sodium azide in beverages using ion chromatography is described. This method combines the specificity for azide with a simple sample preparation using a bubble and trap apparatus that removes any interferences. Sodium azide in a sample was acidified, and the azide was converted to the volatile hydrazoic acid, which was trapped in 2.5mM sodium hydroxide solution. Determination was performed by isocratic ion chromatography using suppressed conductivity detection. Calibration curves were linear for 0.5 to 20 μg/mL sodium azide and the detection limit was 0.05 μg/mL. Recoveries of sodium azide from spiked samples (10.0 μg/g) were more than 82.6%. The method was then used to analyze various beverages.

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