Spektroskopische Untersuchungen an Naphtho[1,2-d]thiazolen. II. Bandenanalyse der Absorptions- und Fluoreszenzspektren von 2-Aryl-naphtho[1,2-d]thiazolen

Spectroscopic Investigations on Naphtho[1.2-d]thiazoles. II. Deconvolution of Absorption and Fluorescence Spectra of 2-Aryl-naphtho[1.2-d]thiazoles Fluorescence measurements were carried out of organic fluorescent compounds of the type of 2-aryl-naphtho[1.2-d]thiazoles ( 1a–k ) substituted in the aryl group by different electronic donor and acceptor substituents. 2-Phenyl-naphtho[1.2-d]thiazole was used in the series of these compounds as the reference system for optical properties. A scheme of vibronic terms in ground and excited states resulting from the spectra of emission, ultraviolet absorption and excitation is given.     

Versuche an einer neuen Caprolactamsynthese. II [1]. Umlagerung von 3,3-Pentamethylen-oxaziridin in Caprolactam

Efforts into a Novel Caprolactame Synthesis. II. Rearrangement of 3,3-Pentamethylene Oxaziridine to Caprolactame 3,3-Pentamethylene-oxaziridine 1 is converted to caprolactame 2 by flash pyrolysis at 300 °C. In the presence of catalytic amounts of vanadium compounds the rearrangement proceeds in boiling benzene or toluene with yields up to 95 percent. A homolytic mechanism is discussed and made plausible by radical alkylation of acetyl acetonates.     

Zur Bindungsisomerisierung von Acetylen- und Allen-Kohlenwasserstoffen. II [1]. Kinetische Untersuchungen über die Isomerisierung von Propin und Allen an einem sauren Molekularsiebkatalysator in der Gasphase

About the Bond Isomerization of Acetylenic and Allenic Hydrocarbons. II. Kinetic Studies on the Isomerization of Propine and Allene with an Acidic Molecular Sieve Catalyst in the Gas Phase The gas phase isomerization of propine and allene (propadiene) was studied on a molecular sieve 13X, modified with Ni and Ca, in the temperature range of 108–173 °C with the aid of a close circulation apparatus. The bond isomerization may be considered as an example of a monomolecular, reversible, heterogeneous catalyzed reaction of the type A ⇌ B. For the studied isomerizations the rate equations of the Langmuir-Hinshelwood-type were derived by kinetic analysis of the experimentally obtained dependence of the mole fractions from the residence time. The rate and adsorption constants of the Langmuir-Hinshelwood equations were determined, their physical interpretation was possible.     

Folgeprodukte halogenierter Aldehyde. VI [1]. Die Addition von Phosphorpentachlorid an Chloral

Derivatives of Halogenated Aldehydes. VI. The Addition of Phosphorus Pentachloride to Chloral 1,2,2,2-Tetrachloroethoxy-phosphorus-tetrachloride 1 is obtained by reaction of chloral with an excess of phosphorus pentachloride in carbon tetrachloride at 35–40°C. Hydrolysis of 1 with water yields 1,2,2,2-tetrachloroethyl-phosphorodichloridate 2 . Compound 1 is reduced with white phosphorus to give 1,2,2,2-tetrachloroethyl-phosphorodichloridite 3 . The structures of 1, 2 , and 3 are determined by i. r. and n.m.r. analysis.     

Aluminiumalkyle mit Heteroatomen. II [1]. Darstellung von Tris(3-trimethylsilyl-propyl)aluminium

Aluminium Alkyls with Heteroatoms. II. Preparation of Tris[(3-trimethylsilyl)-propyl]aluminium Tris[(3-trimethylsilyl)-propyl]aluminium is prepared by disproportionation and by an olefine displacement reaction in a circulation process. The reaction way is investigated with the aid of ¹H-n.m.r.- and i.r.-spectroscopy.     

Folgeprodukte halogenierter Aldehyde. XVI [1]. Untersuchungen über Chloralammoniak

Derivatives of Halogenated Aldehydes. XVI. Investigations of Chloralammonia N-(1,2,2,2-Tetrachloroethyl)trichloroacetaldimine 8 is formed by heating of chloral-ammonia 2 with thionyl chloride. The reaction of 2 with phosphorus pentachloride in ether leads to a mixture of aldimine 8 , 1,2,2,2-tetrachloroethyl-phosphorodichloridate 5 , N-(1,2,2,2-tetrachloroethyl)-phosphorimidic acid trichloride 6 and N-(1,2,2,2-tetrachloroethyl)-phosphoramidic acid dichloride 7 . From compound 7 , the phosphoramidic acid ester 9 , the substituted phosphoric acid triamide 10 and the N-dichlorophosphoryl trichloroacetaldimine 11 are obtained on treatment with methanol, isopropyl amine or triethyl amine, respectively. Compound 9 is also formed from 6 by reaction with methanol. The data of i. r. spectra are concordant with the assigned structures of the compounds 6–11 .     

Photochemie diarylsubstituierter 2H-Tetrazole. XI [1] Sydnone V [2]. Blitzlichtphotolytische Untersuchungen an 2,5-Diaryl-2H-tetrazolen und 3,4-Diarylsydnonen Absolute Cycloadditionsgeschwindigkeitskonstanten von Diarylnitriliminen an Dipolarophile

Photochemistry of Diarylsubstituted 2H-Tetrazoles, XI and Sydnones. V. Flashphotolytic Investigations with 2,5-Diaryl-2H-tetrazoles and 3,4-Diarylsydnones. Absolute Rate Constants of Cycloadditionreactions of Diarylnitrile Imines to Dipolarophils The flash photolysis of 2,5-Diaryl-2H-tetrazoles 1 and 3,4-Diarylsydnones 2 was investigated. The nitrile imines were detected spectroscopically as short living intermediates. Rate constants of the cycloaddition reaction of nitrile imines and dipolarophiles were determined and the influence of substituents in the dipolarophile as well as in the nitrile imine is discussed. The results agree quite well with SUSTMANN 'S theroetical classification of 1,3-dipolar cycloaddition reactions.     

1,2,3-Triazabutadiene. VIII [1]. Untersuchungen zum Mechanismus der sensibilisierten Fotoisomerisierung von 1-Aryl-3-[3-methyl-benzthiazolinyliden-(2)]-triazenen

1,2,3-Triazabutadienes. VIII. Investigations of the Mechanism of the Sensitized Photoisomerization of 1-Aryl-3-[3-methyl-benzthiazolinyliden-(2)]-triazenes. It is possible to sensitize the photochemical cis-trans-isomerization of triazabutadienes by sensitizers with tripletenergies ranging from 40 to 80 kcal/mol. It was proved by flash photolysis that triazabutadienes quench the triplet states of sensitizers. The dependence of the photostationary state on the triplet energy of the sensitizer as well as the dependence of the quantum yields of the sensitized photoisomerization on the concentration of triazabutadiene were investigated, and the desactivation ratios of the sensitized photoisomerization were determinated. The found correspondence of desactivation ratios of the direct and sensitized photoisomerization make a triplet mechanism in both cases probable.     

Untersuchungen über Poly(arylenvinylen)e. XVIII [1]. Synthese von Poly(1,4-phenylen- 1 -phenylvinylen) durch Dehydrochlorierung

Investigations on Poly(arylenevinylene)s. XVIII. Synthesis of Poly(1,4-phenylene-1-phenylvinylene) by Dehydrochlorination Reaction Dehydrochlorination reaction has been applied successfully to the polycondensation of 4-chloromethylbenzhydryl chloride 2 with potassium tert-butoxide in hexamethylphosphoric triamide, whereby soluble poly(1,4-phenylene-1-phenylvinylene) 1 was obtained. Some properties of 1 are described.     

Zur Einwirkung starker Basen auf quartäre Methallyl-ammoniumverbindungen. II[1]. Die baseninitiierte Umlagerung von Dimethyl-alkyl-methallyl-ammoniumsalzen

The Reaction of Strong Bases with Quaternary Methallylammonium Compounds. II. The Base Promoted Rearrangement of Dimethyl-alkyl-methallyl-ammonium Salts The STEVENS rearrangement of quaternary salts of methallylamines was studied using sodium amide, methylsulfinyl carbanion, and butyllithium, respectively. The direction of the rearrangement depends on the structure of the salts. The methoiodides of methyl-ethyl-, methyl-propyl-, and methyl-butyl-methallylamine mainly yield products of [3,2]-rearrangement, especially with sodium amide. This is in contrast to the rearrangement of the quaternary salt of methyl-ethyl-allylamine. With dimethyl-isopropyl-, and dimethyl-cyclohexyl-methallyl-ammonium iodides, a [1,2]-rearrangement of the most bulky alkyl group is observed. The methobromide of methyl-tert.-butyl-methallylamine does not form any product of rearrangement.     

Cyansäureester. 25 [1]. Umsetzung von Mercapto-N-heterocyclen mit Arylcyanaten

Cyanic Acid Esters. 25 The Reaction of Mercapto-N-heterocycles with Aryl Cyanates Unsaturated N-heterocycles containing a cyclic thio urea structure and aryl cyanates (molar ratio 1:2), react to form azolo(1,2-d) (1,2,4)thiadiazoles. This reaction has a wide scope concerning starting materials and gives good yields. Under the same conditions 2-thione-benzthiazolin is transformed to the corresponding disulfide. 4,5-Bis-mercaptomethylene-o-xylene and aryl cyanates give 2,3-dithia-6, 7-dimethyl-tetraline.