Showing papers on "Triazene published in 1988"
44 citations
TL;DR: In this article, the structure of the p-toluidine adduct, [Ru(ArNNNAr)(CO)2(NH2Ar)]2 has been determined by X-ray diffraction methods.
13 citations
TL;DR: In this paper, arylazothiazolidines were shown to have rotational isomerism of the exocyclic N2-N3 bond in the triazene moiety, and were used as prodrugs for the active metabolite of the antitumour dimethyltriazenes.
Abstract: Reaction of 3-acetoxymethyl-1-aryl-3-methyltriazenes with sodium thiophenolate or thiocresolate in anhydrous dimethylformamide affords a new series of 3-arylthiomethyltriazenes (2), Ar-S-CH2-NMe-N=N-Ar′. These triazenes are remarkably labile in aqueous buffer and may be good pro-drugs for the active metabolite of the antitumour dimethyltriazenes. The reaction of arenediazonium fluoroborates with 1,3-thiazolidine in aqueous acetone affords a new series of N-arylazo-1,3-thiazolidines (4); the arylazothiazolidines represent a new class of triazene in which the N3 nitrogen is incorporated into a heterocyclic unit, in this case a 1,3-thiazolidine. Nuclear magnetic resonance spectra of the arylazothiazolidines show evidence for rotational isomerism of the exocyclic N2—N3 bond in the triazene moiety.
10 citations
TL;DR: In this article, the authors investigated the resistance of triaziridine derivatives to ring opening by thermolysis in the N3-homocycle by using CDCl3 and showed that the triazizimine derivatives 1, 16, and 18 underwent thermal ring opening between N(1) and N(2), while the derivatives 5, 14, 24, 27, 31, and 32 were ruptured between n(2) and n(3); no conclusion was possible on the ring opening of the derivatives 26 and 30.
Abstract: Triaziridines. Ring Openings of Triaziridines
Eleven triaziridine derivatives were heated at 60° in CDCl3 to obtain information on the tendency towards, resp. the resistance to, ring opening of the N3-homocycle by thermolysis. Among these triaziridines, there are three which contain, as one of the substituents, a methoxycarbonyl group (ester derivatives 1, 5 and 16), three a methyl group (methyl derivatives 18, 24, and 26), three an H-atom (14, 27, and 30), and two a negative charge (31 and 32). The other two substituents in each of these four classes of triaziridines are trans-located i-Pr groups (1, 18, 27, and 31), cis-located i-Pr groups (5, 24, 14, and 32), and a 1,3-cis-cyclopentylidene group (16, 26, and 30). As major products these mild thermolyses, we isolated : from the trans-ester 1 and from the annellated ester derivative 16, the 1-acyl-azimines 2 and 17, respectively, from the cis-ester 5, the 3-acyl-triazene 4, from the trans-methyl derivative 18, the (E)-diazene 19, and hexamine 21, from the cis-methyl derivative 24 the 2-methylazimine 25, both from the trans- and cis-H-derivatives 27, and 14, respectively, the H- triazene 13 and, finally, both from the trans-and cis-anion 31 and 32, respectively – after protonation the H-triazene 13 and – after methylation – the methyl-triazene 33. The same thermolysis of the annellated methyl and H-derivatives 26 and 30, respestively, resulted only in decomposition.
These results can be uniformly interpreted with a primary opening of the triaziridine ring by rupture of one of the two types of NN bonds lending to azimines or triazenide anions. Some of the azimines were isolable, namely 2, 17, and 25, and one was spectroscopically observable as an intermediate, namely 11 on the way to the triazene 4. The other azimines are plausible intermediates to the isolated products, namely 15 on the way to 13, and 22 on the way to 19 and 21. The triazenide anion 28 is the evident intermediate on the way to 13 or to 33. The annellated azimines are assumed not be formed from 26 and 30, or then to be be decomposed under the conditions of their formation. We conclude that the triaziridine derivatives 1, 16, and 18 underwent thermal ring opening between N(1) and N(2), while the derivatives 5, 14, 24, 27, 31, and 32 were ruptured between N(2) and N(3); no conclusion was possible on the ring opening of the derivatives 26 and 30.
The predominant formation of the (Z)-azimine 2 from the trans-triaziridine 1, and of the (E)-isomer 3 – among the two azimines – from the cis-triaziridine 5 suggests a stereospecificity in the triaziridine ring openings. This would, however, not be expected to be observable in the products from the other triaziridines, since both NN bonds of the azimine 25 and of the anion 28 probably rotate rapidly and since the secondary trans formations of the other primary products are not able to retain configurational information.
8 citations
TL;DR: In this article, the authors describe the triazene as centrosymmetric dimers held together by weak hydrogen bonds, and the CNNNC part of the molecule is planar and forms an angle of 160 ° with the plane of the phenyl ring.
Abstract: tert-Butyl N-trifluoromethylcarbamate, C6HIoF3NO 2, Mr= 185.146, Pbca, a = 11.801 (2), b=17.030(4), c=9.262(1)A, V=1861.3(6)A 3, Z = 8, D x = 1.321 Mg m -3, 2(Mo Ktx) = 0.71073/~, g = 0.13 mm -I, F(000) = 768, 296 K, R = 0.059, 878 observed reflections. The carbamate possesses an unusually short N-CF 3 bond, 1.361 (6)/~, and a somewhat lengthened N-C(O 2) bond, 1.369 (5) A. The CNC(=O)OC section of the molecule is planar with the CC 3 and CF 3 groups staggered with respect to the C-O bond. Hydrogen bonding links the molecules into infinite chains. 3-Phenyl- 1-trifluoromethyltriazene, CTH6F3N3, Mr= 189.143, P2Jn, a=9.792(2), b =5.240(1), c=16.328(5)/~, fl=95.44(2) °, V= 834.0 (6) A 3, Z = 4, D x = 1.506 Mg m -3, 2(Mo K~t) = 0.71073 ,/~, g --- 0.13 mm -I, F(000) = 384, 295 K, R = 0.052, 1172 observed reflections. A short N--CF 3 bond, 1.409 (3) A, is found in the triazene, which exists as centrosymmetric dimers held together by weak hydrogen bonds. The CNNNC part of the molecule is planar and forms an angle of 160 ° with the plane of the phenyl ring. The C F 3 group is disordered.
1 citations
TL;DR: The Ca-ATPase of the sarcoplasmic reticulum of rabbit hind limb muscles was selected as the model biological object for studying the activity of the substances and the enzyme preparation obtained contained a protein complex of Ca- ATPase in an amount of 80-90% of the total protein content of the membrane.
Abstract: The Ca-ATPase of the sarcoplasmic reticulum (SR) of rabbit hind limb muscles was selected as the model biological object for studying the activity of the substances. The enzyme preparation was isolated by the method of successive centrifugation in a sucrose density gradient on a VAC-601 centrifuge according to the procedure described in [6]. The SR preparations obtained contained a protein complex of Ca-ATPase in an amount of 80-90% of the total protein content of the membrane and did not contain the proteolytic fragments and membrane proteins. The specific activity of the SR preparations obtained was 15,000 nmoles of inorganic phosphate per mg protein per min.
Patent•
09 May 1988
TL;DR: In this article, a triazene compd. is used as the coupler and three kinds of compds are used to form the material for indicating the exposed heat energy quantity, and the color density after a specified time when the reaction is accelerated by heat is measured.
Abstract: PURPOSE:To inexpensively and surely indicate heat energy quantity by using an acidic color developer, coupler and specific triazene compd. to form a material for indicating the exposed heat energy quantity. CONSTITUTION:A zinc salicylate color developer, etc., are used as the acidic color developer. The compd. expressed by the formula is used as the triazene compd. In the formula, Ar denotes an aryl group, heterocyclic group; R , R denote H, alkyl, cycloalkyl, aralkyl, alkenyl, aryl, heterocyclic group, etc. A compd. which forms color by bonding to the triazene compd. is used as the coupler. The acidic color developer and the triazene compd. are isolated by a microcapsule and three kinds of the compds. are coated on a sheet to form the material for indicating the exposed heat energy quantity. The microcapsule is broken to bring the acidic color developer and the triazene compd. into contact with each other to initiate reaction at the time of using such material. The color density after the specified time when the reaction is accelerated by heat is measured. The exposed heat energy quantity is, therefore, indicated with high accuracy.