A series of phenylated polydihydrophthalimides has been synthesized by the Diels-Alder reactions of 3,3′-(oxydi-p-phenylene)bis(2,4,5-triphenylcyclopentadienone) and 3,3′-(p-phenylene)bis(2,4,5-triphenylcyclopentadienone) with N,N′-o-, -m-, and -p-phenylenedimaleimide. The polydihydrophthalimides were soluble in dimethylformamide (DMF) and had intrinsic viscosities that ranged from 0.33 to 1.01, the polymers were dehydrogenated thermally and chemically to afford the corresponding phenylated polyphthalimides. The totally aromatic polyimides were also soluble in DMF but had intrinsic viscosities only as high as 0.41. The thermogravimetric analyses of the polyphthalimides showed breaks near 530°C in air and in nitrogen atmospheres. 相似文献
Zusammenfassung Durch gemeinsame Einwirkung von primären aliphat. Aminen und Schwefel auf Methylarylketone in Methanol bei Raumtemp. erhält man in meist guten Ausbeuten 8-Alkylamino-8-aryl-1,2,3,4,5,6-hexathiocan-7-thione (1a-h). Die Umsetzung von 1,4-Diacetylbenzol mit n-Propyl-bzw. n-Butylamin und Schwefel liefert Phenylen-1,4-di-hexathiocanderivate (3 a, b).Bei der Reaktion von Acetophenon mit 3-N,N-Diäthylaminopropylamin und Schwefel entstehen neben dem 8-(3-N,N-Diäthylaminopropylamino)-8-phenyl-1,2,3,4,5,6-hexathiocan-7-thion (1e) 51% einer Verbindung der Summenformel C15H22N2S2 (2), der die Struktur der (3-N,N-Diäthylaminopropylimino)-phenyldithioglyoxylsäure zugeordnet wird.1 e läßt sich durch Behandlung mit wäßr. Natriumsulfit-Lösung zu2 abbauen,2 durch Reaktion mit Schwefel wieder in1 e überführen.
Synthesis of 8-alkylamino-8-aryl-1,2,3,4,5,6-hexathiocan-7-thiones (Joint action of elemental sulfur and gaseous ammonia upon ketones, LXXVIII: Action of sulfur and amines on acetophenone, IX)
8-Alkylamino-8-aryl-1,2,3,4,5,6-hexathiocan-7-thiones (1a toh) are obtained mostly in good yields by the concomitant action of primary aliphatic amines and sulfur upon methyl aryl ketones in methanol at room temperature. Reaction of 1,4-diacetyl benzene and sulfur with n-propylamine or n-butylamine respectively leads to phenylene-1,4-dihexathiocane derivatives (3 a, b).Besides 8-(3-N,N-diethylaminopropylamino)-8-phenyl-1,2,3,4,5,6-hexathiocan-7-thione (1 e), which is obtained by reaction of acetophenone with 3-N,N-diethylaminopropylamine and sulfur, a product with the formula C15H22N2S2 (2) is isolated in 51% yield, to which the structure (3-N,N-diethylaminopropylimino)phenyl dithioglyoxylic acid is assigned. By treatment of1 e with aqueous sodium sulfite solution2 is obtained, which can be transformed back into1 e by reaction with sulfur.
77. Mitt.:F. Asinger, A. Saus, H. Offermanns undP. Scherberich, Ann. Chem.753, 151 (1971).8. Mitt.:F. Asinger, A. Saus, H. Offermanns undF. Abo Dagga, Ann. Chem.723, 119 (1969).Teil der DiplomarbeitJ. Hartig, Techn. Hochschule Aachen, 1969. 相似文献
The irradiations of 1, 1-dimethyl- (8), 1, 1-di-(tri-deuteriomethyl)- (d6– 8 ), 1, 1, 2, 2-tetramethyl- ( 9 ) and cis- and trans-1, 2-dimethyl-1, 2-dihydronaphthalenes (cis- and trans- 10 ) were investigated in 2, 2-dimethylbutane/pentane at ?100° using a mercury high-pressure lamp, and with mercury high- and low-pressure lamps at room temperature. The results were compared with one another, and those of the individual compounds are collected in schemes 2 and 4–7. The most important results are the following: 1. The 1, 2-dihydronaphthalenes undergo a conrotatory ring opening to the o-quinodimethanes on irradiation with high- or low-pressure lamps at room temperature or at ?100°. Thermal reactions ([1, 7a]H-shifts, electrocyclisations) are suppressed at ?100°. The o-quinodimethanes formed from 8 (scheme 2), 9 (scheme 5) or cis- 10 (scheme 6) undergo on irradiation with the high-pressure lamp, [1, 5]H-shifts or photochemical Diels-Alder reactions after renewed photochemical excitation, to yield the benzobicyclo[3.1.0]hex-2-ene derivatives. These Diels-Alder reactions do not proceed stereospecifically, and therefore are not orbital symmetry controlled reactions. 2. If the 1, 2-dihydronaphthalenes are irradiated at room temperature with either a high- or a low-pressure lamp, then the initially formed o-quinodimethanes undergo thermal [1, 7a]H-shifts, in preference to all other reactions, as long as this is sterically possible; the resulting products can undergo secondary photochemical transformations. Such o-quinodimethanes are formed on irradiation of 8, 9 and cis- 10 . From trans- 10 , an o-quinodimethane mixture is formed, of which one component (cis, cis- 22 ) undergoes thermal [1, 7a] H-shifts, while the other (trans, trans- 22 ) suffers a thermal disrotatory electrocyclisation to give cis- 10 . If a high-pressure lamp is used in the last experiment, then the competing photochemical Diels-Alder cyclisation to bicyclic compounds of the type 23 (scheme 7) can result in the trans, trans- 22 . As was shown by Salisbury [3], and confirmed by ourselves in other cases [2], photochemical Diels-Alder reactions or [1, 5]H-shifts in the o-quinodimethanes require light of wavelength ? 400 nm (high-pressure lamp). The present photochemical investigations amplify and confirm our earlier conclusions concerning the photochemistry of the 1, 2-dihydronaphthalenes [2]. 相似文献
Glyoxaldiimines (I) RN=CHCH=NR show in the NMR a downfield shift of glyoxalic protons (Hgly) when complexed to (II: M = Mo, W), but increasing high field shifts when going to (III) and complexes (IV). In the tungsten complexes II HglyW coupling satellites are resolved (J(WH) ≈4–6 Hz); in the phosphine compounds III, IV long range PHgly coupling is clearly visible. Mechanisms of spinspin interaction are briefly discussed in connection with the EPR results on monoanionic radicals of II–IV. 相似文献
Mechanics of Composite Materials - In this research, the maximum stress, Hashin, Puck, LaRC03, and Northwestern University (NU) criteria are analyzed based literature data, analytical results... 相似文献
Zusammenfassung Frühere Strukturvorschläge für dastrans-Chalcon-oxim, semicarbazon und thiosemicarbazon1 werden mit Hilfe von NMR-Spektren richtiggestellt: Die sauer katalysierte Reaktion führt zwar zum Oxim, Semicarbazon und Thiosemicarbazon destrans-Chalcons; basische Katalysatoren bewirken dagegen eine interne Cyclisierung zu 3,5-Diphenyl-2-isoxazolin bzw. zu 1-substituierten 3,5-Diphenyl-2-pyrazolinen. Die Zuordnungen in den NMR-Spektren wurden durch Vergleich mittrans-Dypnon und seinem Semicarbazon getroffen.
NMR spectra of trans-chalcone oxime, semicarbazone and thiosemicarbazone and their cyclic isomers (3,5-diphenyl-2-isoxazoline and 1-substituted 3,5-diphenyl-2-pyrazolines)
Earlier tentatively assigned structures fortrans-chalcone oxime, semicarbazone and thiosemicarbazone, resp., have been corrected by means of NMR spectra: open-chain structures have been found for the title compounds formed in the acid catalyzed reaction, whereas basic catalysts lead to intramolecular cyclization with formation of 3,5-diphenyl-2-isoxazoline and 1-substituted 3,5-diphenyl-2-pyrazolines resp. Assignments in the NMR spectra were made by comparison with those from authentic samples oftrans-dypnone and its semicarbazone.
Summary Large, perfect crystals of urea nitrate were obtained by the addition of concentrated nitric acid to an aqueous solution of the salt, followed by spontaneous evaporation. The crystal angles have been measured.
Zusammenfassung Große, gut ausgebildete Kristalle von Harnstoffnitrat erhält man bei Zugabe konz. Salpetersäure zu einer wäßrigen Lösung des Salzes und nachheriger Spontanverdampfung. Die Kristallwinkel wurden gemessen.
