Photoreaktionen von 5-Phenyl-pyrazolinen. Vorläufige Mitteilung

On irradiation in benzene 1-methyl-5-phenyl-Δ²-pyrazoline ( 1 ) is partly converted into trans- and cis-1-methylazo-2-phenyl-cyclopropanes ( 2 and 3 ) in the ratio of 23:77. Both 2 and 3 on thermal treatment are reconverted to 1 . A concurrent thermal equilibration of 2 and 3 is also observed. 1, 3-Dimethyl-5-phenyl-Δ²-pyrazoline ( 5 ) on irradiation in benzene yields the corresponding trans- and cis-1-methylazo-1-methyl-2-phenyl-cyclopropanes ( 6 and 7 ). In contrast similar treatment of 5-phenyl-Δ²-pyrazoline gives benz- and cinnamaldazine ( 9 and 11 ) along with the corresponding mixed aldazine ( 10 ).     

Photoinduzierte 1, 3-dipolare Cycloaddition von 3-Phenyl-2H-azirinen an Azodicarbonsäure-diäthylester. 32. Mitteilung über Photoreaktionen

Irradiation of 2, 2-dimethyl-3-phenyl- ( 1a ), 2, 3-diphenyl-2H-azirine ( 1b ) or the azirine-precursors 1-azido-1-phenyl-propene ( 2a ) and 1-azido-1-phenyl-ethylene ( 2b ), respectively, in benzene in the presence of azodicarboxylic acid diethylester, yields the corresponding 1, 2-carbethoxy-3-phenyl-Δ³-1, 2, 4-triazolines 4a–d (Scheme 1). Refluxing 4 ( a, c or d ) in 0, 2–0, 4M aqueous ethanolic potassium hydroxide leads to the formation of the 1-carbethoxy-3-phenyl-Δ²-1, 2, 4-triazolines 6 ( a, c or d ). Under the same conditions 4b is converted to 3, 5-diphenyl-1, 2, 4-triazole ( 7b , Scheme 2). In 10M aqueous potassium hydroxide solution heating of either 4 ( c or d ) or 6 ( c or d ) yields the 3-phenyl-1, 2, 4-triazoles 7 ( c or d ). Photolysis of 1-carbethoxy-5, 5-dimethyl-3-phenyl-Δ²-1, 2, 4-triazoline ( 6a ) in benzene in the presence of oxygen and trifluoroacetic acid methylester gives the 5-methoxy-2, 2-dimethyl-4-phenyl-5-trifluoromethyl-3-oxazoline ( 13 , Scheme 5). 5, 5-Dimethyl-3-phenyl-1, 2, 4-triazole seems to be the intermediate, which on losing nitrogen gives the benzonitrile-isopropylide ( 3a ).     

Synthesis of 1,2,4,5-Tetrakis(1,2,4-Triazolyl) Benzene and 1,2,4,5-Tetrakis(1,3,4-Oxadiazolyl) Benzene Derivatives

Abstract

A series of 1,2,4,5-tetrakis(1,2,4-triazolyl)benzenes and 1,2,4,5-tetrakis(1,3,4-oxadiazolyl)benzenes was synthesized by nucleophilic addition of sodium salts of 4-phenyl-2,4-dihydro-3H-1,2,4-triazole-3-thiones and 1,3,4-oxadiazole-2(3H)-thiones to 1,2,4,5-tetrakis(bromomethyl)benzene. The structure of the newly synthesized compounds was confirmed by elemental analysis, IR and ¹H and ¹³C NMR spectra.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: 1H and 13C NMR spectra of products (Figures S1-S24).     

Structural modifications in imide-aryl ether phenylquinoxaline random copolymers

A rigid rod polyimide derived from biphenyldianhydride (BPDA) and p-phenylenediamine (PDA) was modified by the incorporation of diamines containing performed phenylquinoxaline and aryl ether linkages, and the morphology and mechanical properties of the resulting imide-aryl ether phenylquinoxaline copolymers were investigated. These phenylquinoxaline containing diamines, 1, 4-bis[6-(3-aminophenoxy)-3-phenyl-2-quinoxalinyl] benzene and 1, 4-bis[6-(4-aminophenoxy)-3-phenyl-2-quinoxalinyl] benzene, were prepared by a novel nucleophilic aromatic substitution reaction of 1,4-(6-fluoro-3-phenyl-2-quinoxalinyl) benzene with either 1, 3- or 1, 4-aminophenol in the presence of K₂CO₃, respectively. The diamines were utilized as co-monomers with BPDA and PDA to synthesize poly(amicacids.) Films were cast and cured (350°C) to effect imidization, affording films which showed high elongations and moduli. The copolymers with high phenylquinoxaline compositions displayed T_g's in the 300°C range, and the thermal stability of the copolymers was comparable to that of the parent polyimide. The copolymers also showed improved auto- or self-adhesion, particularly those which showed a T_g, allowing sufficient molecular motion for interdiffusion.     

Photochemische Cycloadditionen von 3-Phenyl-2H-azirinen mit kumulierten Doppelbindungen. Vorläufige Mitteilung

Irradiation of 2-methyl- ( 1c ) and 2,2-dimethyl-3-phenyl-2H-azirine ( 1d ) in benzene solution in the presence of carbon dioxide yields 2-methyl-4-phenyl- ( 3c ) and 2,2-dimethyl-4-phenyl-3-oxazolin-5-one ( 3d ), respectively. Similar cycloadducts are observed (see table) when 2,3-diphenyl-2H-azirine ( 1b ) and 1d are irradiated in the presence of phenylisocyanate, o-tolylisocyanate, phenylisothiocyanate or di-o-tolyl-carbodiimide.     

Photoinduced reactions of aryl-2H-azirines with carbonyl compounds. Preliminary communication

Irradiation of 3-phenyl-( 4 ), 2-methyl-3-phenyl-( 8 ), and 2,3-diphenyl-2H-azirine ( 10 ), in benzene solution in the presence of aldehydes, yields the corresponding aryl-3-oxazolines. Photochemical reaction of 4 and 10 with carbon dioxide leads to the formation of 4-phenyl- ( 15 ) and 2,4-diphenyl-3-oxazolin-5-one ( 16 ), respectively.     

X-Ray Investigation of (E)-2-phenyl-1-chlorocyclopropane-1-carboxylic Acid — A Convenient Synthon for Transamine Synthesis

A method for the synthesis of (E,Z)-2-phenyl-1-chlorocyclopropane-1-carboxylic acid by the addition of ethyl trichloroacetate to styrene in the presence of copper(I) ammine complexes is suggested. The major isomer was isolated as the corresponding acid. The results of X-ray diffraction (XRD) analysis unequivocally prove that the benzene ring and the carboxylic group are in the cis-position and that the molecules form centrosymmetric dimers. (E)-2-phenyl-1-chlorocyclopropane-1-carboxylic acid can serve as a convenient synthon for transamine synthesis.     

Partial Dehydrogenation of Saturated 4-Phenyl-1(2H)-phthalazinone Derivatives by Thionyl Chloride

cis-4a, 5,6,7,8,8a-Hexahydro-4-phenyl-1(2H)-phthalazinones (2) react with thionyl chloride in benzene to give tetrahydro derivatives (3); the corresponding reaction of methylene bridged derivatives (5) is also described.     

Stickstoffhaltige Dieisen-hexacarbonyl-Komplexe aus 3-Phenyl-2H-azirinen

Nitrogen-containing diiron-hexacarbonyl complexes from 3-phenyl-2H-azirines Reaction of 2,2-dimethyl-3-phenyl-2H-azirine ( 1 ) with diiron-enneacarbonyl yields as an insertion product, and in addition to other products, the diiron-hexacarbonyl complex 2 (Scheme 1), whose structure was derived from spectral data, in particular ¹³C-NMR.-data (Table 1). With trimethylamine oxide in benzene, 2 is converted into the urea derivative 3 , and yields with cerium (IV) ammonium nitrate the nitrate 4 (Scheme 1). The analogous complexes 6 and 9 have been obtained by irradiation of 1-phenyl-vinyl azide ( 5 ) and ironpentacarbonyl (Scheme 1) and from vinyl isocyanate ( 8 ) and diiron-enneacarbonyl at 40° (Scheme 2), respectively. The azirine 1 , an acetylenic compound and diiron-enneacarbonyl in benzene react to give complexes of type 10 as the main product (Scheme 3). The structure of complex 10 has been established by X-ray single crystals analysis. On the ¹³C-NMR. time scale the carbonyl groups of compound 10 show a fluxional behaviour: below ?50° the CO-groups of one of the two Fe(CO)₃-groups undergo intranuclear exchange, above ?50° the CO-groups of both Fe(CO)₃-groups undergo intranuclear exchange. Tentative reaction mechanisms for the formation of the complexes of type 2 and 10 are formulated in Schemes 5, 6 and 7.     

Zur Photodimerisierung von 3-Phenyl-2H-azirinen. Vorläufige Mitteilung

Irradiation of 3-phenyl-2H-azirine ( 2 ) in benzene solution with a high-pressure mercury lamp yields 4,5-diphenyl-1,3-diazabicyclo[3,1,0]hex-3-ene ( 4 ) and not 3-phenylimino-4-phenyl-1-azabicyclo[2,1,0]pentane ( 1 ), as had been reported previously by others [2]. 2-Methyl-3-phenyl-2H-azirine ( 3 ) yields on irradiation a 2:1 mixture of 2-exo, 6-exo- and 2-exdo, 6-exo-dimethyl-4,5-diphenyl-1,3-diazabicyclo[3,1,0]hex-3-ene (2-exo,6-exo- and 2-endo, 6-exo- 5 ). Irradiation of 2,3-diphenyl-2H-azirine ( 8 ) leads to the formation of 2,4,5-triphenyl-imidazole ( 9 ) and tetra-phenylpyrazine ( 10 ). The suggested reaction path for the generation of 9 and 10 is shown in Scheme 2.     

Oxidative azacyclization of 1-monosubstituted thioureas in reaction with [bis(acyloxy)iodo]arenes to form 1,2,4-thiadiazole derivatives

For the first time, derivatives of 1,2,4-thiadiazoles have been obtained by the reaction of [bis(acyloxy)iodo]arenes with 1-monosubstituted thioureas. 1-Acetylthiourea is subject to intermolecular azacyclization to form 3,5-bis-(acetylamino)-1,2,4-thiadiazole in reaction with [bis(acyloxy)iodo]benzene. 1-Phenylthiourea forms 3,5-bis-(phenylamino)-1,2,4-thiadiazole in a single-stage reaction with (diacetoxyiodo)benzene. The reaction of 1-phenylthiourea with [bis(trifluoroacetoxy)iodo]benzene leads to the formation of 5-imino-4-phenyl-3-phenylamino-4H-1,2,4-thiadiazoline.     

SYNTHESIS OF SPIRO [1,3-BENZODIOXOLE-2,4′-(3′H) QUINAZOLINES]

Abstract

In the present investigation, the authors could obtain a new series of spiranes (1) through the reaction of the high potential quinone tetrachloro-o-benzoquinone with 2-aryl-3-phenyl-3H-quinazoline-4-thiones. Thus, 2,3-diphenyl- (2a), 2-p-tolyl-3-phenyl- (2b) and 2-p-anisyl-3-phenyl- (2c)-3H-quinazoline-4-thiones react readily with tetrachloro-o-benzoquinone, in boiling toluene, to give the corresponding spiro-1,3-benzodioxole-2,4′-(3′H)-quinazolines (1a-c), respectively.     

Heterocyclic compounds from 3,3-dimercapto-1 -aryl-2-propen-1-ones. Note 2. Condensation with o-aminothophenol and o-aminophenol

The condensation of 3,3-dimercapto-1-phenyl-2-propen-1-one with o-aminothiophenol and o-aminophenol in hot xylene gave 2-phenacylbenzothiazole ( 3 ) and 2-phenacylbenzoxazole ( 5 ). When the reaction with o-aminophenol was carried out in hot benzene, 2-beuzoylthioacctamidophenol ( 4 ) was obtained, which, heated in hot xylene gave 5. Ethyl benzoylacetale by reaction with o-aminothiophenol gave 3 , whereas by reaction with o-aminophenol gave no heterocyclic compound. However, we were able to isolate 2-benzoylacetamidophenol ( 6 ), ethyl β-phenyl-β-(o-hydroxy)phenyliminopropionate ( 7 ), and 2-[β-(o-hydroxy)anilino] cinnamoylamidophenol ( 8 ). Ir and nmr spectra of synthesized compounds point out the existence of tautomers.     

Photochemische Cycloadditionen von 3-Phenyl-2H-azirinen an Carbonsäurechloride. 35. Mitteilung über Photoreaktionen

Irradiation of 2, 3-diphenyl-2H-azirine ( 1a ) and 1-azido-1-phenyl-propene, the precursor of 2-methyl-3-phenyl-2H-azirine ( 1b ), in benzene, with a high pressure mercury lamp (pyrex filter) in the presence of acid chlorides yields the oxazoles 5a–d (Scheme 2). Photolysis of 2, 2-dimethyl-3-phenyl-2H-azirine ( 1c ) under the same conditions gives after methanolysis the 5-methoxy-2, 2-dimethyl-4-phenyl-3-oxazolines 7a, b, d , while hydrolysis of the reaction mixture leads to the formation of the 1, 2-diketones 8a, c, d (Scheme 4). The suggested reaction path for all these reactions is a 1, 3-dipolar cycloaddition of the photochemically generated benzonitrilemethylides 2 to the carbonyl double bond of the acid chlorides to give the intermediates 4 , followed by either elimination of hydrogen chloride or solvolysis (Schemes 2 and 4). Irradiation of 1c in the presence of acetic acid anhydride leads via the intermediate 9 to the 5-hydroxy-3-oxazoline 10 and the 5-methylidene-3-oxazoline 11 (Scheme 5).     

1,4,5-trigermabicyclo[2.1.0]pent-2-en-5-ylium: the isolable bishomocyclopropenylium ion containing a heavier group 14 element

The isolable bishomoaromatic cation containing a heavier Group 14 element, (2,3,5-deloc)-2-phenyl-1,4,5-tris(tri-tert-butylsilyl)-1,4,5-trigermabicyclo[2.1.0]pent-2-en-5-ylium TPFPB- (2+.TPFPB-; TPFPB- = tetrakis(pentafluorophenyl)borate) was synthesized by the reaction of 5-bromo-2-phenyl-1,4,5-tris(tri-tert-butylsilyl)-1,4,5-trigermabicyclo[2.1.0]pent-2-ene (1) with [Et3Si(benzene)]+.TPFPB- in benzene at room temperature. The characteristic bishomoaromatic structure was unambiguously determined by X-ray crystallographic analysis. NMR measurements on 2+.TPFPB- confirmed the nonclassical germyl cation structure in solution and showed strong shielding of homoconjugative carbon atoms. The bishomoaromaticity in 2+ was also investigated by theoretical calculations.     

Research on the synthesis of 5, 6-benzoquinoline derivatives. Infrared spectra of 2-phenyl-5, 6-benzoquinoline derivatives

The infrared spectra of a number of 2-phenyl-5, 6-benzoquinoline derivatives are measured. It is found that in the 690–900 cm^–1 range, correlations found for benzene homologs and applicable to pyridine and quinoline derivatives also apply to these 2-phenyl-5, 6-benzoquinoline derivatives.     

A convenient synthesis of 3-alkyl-2,3-dihydro-2,4-dioxo-6-phenyl-, 3-alkyl-2,3-dihydro-4-oxo-6-phenyl-2-thioxo-, and 3-alkyl-2-arylimino-2,3-dihydro-4-oxo-6-phenyl-4H-1,3-thiazines

The reactions of 1-alkylamino-1-alkylthio-3-phenylpropene-3-thiones 3 with thiophosgene and phosgene in toluene, followed by treatment of the reaction mixture with triethylamine gave 3-alkyl-2,3-dihydro-4-oxo-6-phenyl-2-thioxo- 4 , 3-alkyl-2,3-dihydro-2,4-dioxo-6-phenyl-4H-1,3-thiazines 5 , respectively in good to excellent yields. Similarly treatment of compounds 3 with N-arylimidoyl dichloride in benzene at room temperature gave 3-alkyl-2-arylimino-2,3-dihydro-4-oxo-6-phenyl-4H-1,3-thiazines 6 in excellent yields. The reactions of compounds 3 with oxalyl chloride in toluene gave also 5 in good yields.     

酸催化甘油与苯甲醛缩合制备六员环缩醛

比较了对甲苯磺酸（PTSA）、磷钨酸（PWA）、KHSO₄和FeCl₃催化对甘油与苯甲醛的缩合反应收率,及对产物中六元环缩醛5-羟基-2-苯基-1,3-二氧六环(1)与五元环缩醛4-羟甲基-2-苯基-1,3-二氧五环(2)比例的影响。 当以环己烷为带水剂及苯甲醛与甘油的摩尔比为2∶3的情况下,KHSO4为催化剂的缩合产物（1+2）收率较高,为96.8%;PTSA催化的缩合产物中,化合物1的比例最高(m(1)∶m(2)=48.6∶51.4)。 室温下PTSA、PWA、KHSO₄和FeCl₃均可催化化合物2向化合物1的转化。 在-20 ℃下,只有PTSA能催化化合物2向化合物1的转化。 在-20 ℃,PTSA催化化合物[STHZ]2转化成化合物1a,并以晶体形式从苯（40%）-石油醚（60%）中析出。 母液循环转化3次后,化合物1a的累计收率可达91.1%。     

(5R,6R)-6-苯基-5-(苯磺酰基乙酰基)二环[2.2.1]-2-庚烯的合成及结构表征

报道了一种制备4-苯基-1-苯磺酰基-3-丁烯-2-酮的新合成方法. 4-苯基-3-丁烯-2-酮与溴化试剂Ph₃P^＋CH₂CH₂- COOHBr 作用, 得到1-溴-4-苯基-3-丁烯-2-酮, 不经分离直接与苯亚磺酸钠发生亲核取代反应, 得到4-苯基-1-苯磺酰基-3-丁烯-2-酮. 将此反应产物作为亲双烯体与环戊二烯在手性钛金属催化剂催化下进行不对称Diels-Alder反应, 得到了＞99% ee 的环加成产物(5R,6R)-6-苯基-5-(苯磺酰基乙酰基)二环[2.2.1]-2-庚烯. 用X衍射法对产物的晶体结构进行了测定, 讨论了反应机理, 通过元素分析, NMR, MS对产物的结构进行了表征.     

Zum rotameren Verhalten des Phenyl- und Phenyltricarbonylchrom-liganden in 2-substituierten 1,3-Dioxanen: Ein Vergleich

Dipole moment measurements, NMR-spectroscopical methods and dipole-dipole interaction calculations applied to 2-benchrotrenyl-1,3-dioxanes and a comparison with o-substituted 2-phenyl derivatives furnish evidence, that in both cases the rotameric state is mainly determined by the steric demand of the substituent being attached to phenyl: the declination angle () of the Cr(CO)₃-group from the bisectional cisoid relation (with respect to H on C-2) is identical with that for the ortho substituent and amounts to about 60 degs. The influence of the Cr(CO)₃-fragment on the conformational behaviour of the benzene moiety in geminal 2,2-disubstituted derivatives is consistent with these results: the assumption of an axial and gonal conformation for the phenyl ring, which had recently been established for 2-alkyl-2-phenyl-1,3-dioxanes, is no longer valid for the 2-alkyl-2-phenyltricarbonylchromium compounds.

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Mit 4 Abbildungen

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40. Mitt. über Stereochemie von Metallocenen; 39. Mitt. siehe Lit.

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Herrn Prof. Dr.H. Nowotny mit besten Wünschen zum Geburtstag gewidmet.