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Process for Preparing Dithiine-tetracarboxy-diimides

The present invention relates to a new process for preparing dithiine-tetracarboxy-diimides.

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Benzopyrazinoisoindigo or Its Reduced Form? Synthesis, Clarification, and Application in Field-Effect Transistors

Benzopyrazinoisoindigo, a pigment reported 40 years ago, should be a good candidate for n-type semiconductors if the reported structure is correct. Reinvestigation of this molecule revealed that it is actually (4H,4?H)-benzopyrazinoisoindigo, which could be considered as the reduced form of benzopyrazinoisoindigo, and hence, it is a good candidate for p-type semiconductors. The route toward the synthesis of this molecule was optimized, and a mechanism was accordingly proposed. A field-effect transistor based on this material showed a hole mobility up to 2.5 ¡Á 10-2 cm2 V-1 s-1. An expedient route for the synthesis of unexpectedly alkylated (4H,4?H)-benzopyrazinoisoindigo is developed, which also clarifies the previously reported structure. A mechanism is accordingly proposed. A field-effect transistor based on this material shows a hole mobility up to 2.5 ¡Á 10-2 cm2 V-1 s-1.

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Intramolecular photocycloaddition of N-alkenyl substituted maleimides: A potential tool for the rapid construction of perhydroazaazulene alkaloids

UV irradiation of a number of N-alkenyl-substituted maleimide derivatives leads to the formation of complex perhydroazaazulenes in excellent yields. The overall process can be considered as a formal intramolecular [5+2] cycloaddition. Substrates were prepared by Mitsunobu coupling of the appropriate alkenols with various maleimides. Methyl substitution of the alkenyl side chain gave the cycloadducts 13a-g in good yields, with moderate to high stereoselectivity being observed for 13e and 13g, respectively. Use of cyclic alkene side chains led to the formation of tri- and tetracyclic products with high degrees of stereoselectivity in most cases. Some of the polycyclic ring systems that were prepared constitute the core skeleton of a number of complex alkaloids. The substrate 29 underwent an unexpected [2+2] photocyclo-addition to yield the unusual cyclobutane 31.

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One-step synthesis of heteroaromatic-fused pyrrolidines via cyclopropane ring-opening reaction: Application to the PKCbeta inhibitor JTT-010

A ring-opening reaction of cyclopropanes with five-membered heteroaromatics having a leaving group at C(2) was found to provide heteroaromatic-fused pyrrolidines in one step. This reaction was successfully applied to the synthesis of the protein kinase C-beta inhibitor JTT-010, which possesses a dihydropyrrolo[1,2-a]indole core.

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A rapid stereocontrolled entry to the ABCD tetracyclic core of neotuberostemonine

Four out of the five rings of the alkaloid neotuberostemonine (1) are present in the advanced precursor 2. The tetracyclic compound 2 has now been prepared in a short, linear route via lactone acid 3. A key step in the synthesis was the cuprate-mediated SN2? ring-opening desymmetrization of the C2-symmetric bislactone 4.

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Structures of hydro-, chloro-, and bromo-substituted maleimides and 2,6-diaminopyridines, and of some of their 1:1 heterodimers

The crystal structures of a series of 3,4-diX-substituted maleimides and 3,5-diY-substituted-2,6-diaminopyridines (X, Y = H, Cl, Br) have been determined. Some of their hydrogen-bonded 1:1 heterodimers have also been synthesized and their crystal structures studied to investigate the influence of halogens on the crystal packing and to determine a possible role for halogen bonding. Single-crystal X-ray analysis of the crystals of the heterodimers revealed that the expected triple H-bonded structures were formed. This crystal engineering exercise has been partially successful, giving six mixed hydrogen- and (when possible) halogen-bonded compounds whose structures were found to be dependent on the nature and the position of the halogen substituents. The Royal Society of Chemistry 2011.

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6H-PYRROLO[3,2-B:4,5-B’]BIS[1,4]BENZOTHIAZINE-6-CARBOXYLIC ACID ESTERS AS ORGANIC SEMICONDUCTOR MATERIALS FOR USE IN ELECTRONIC DEVICES

The present invention provides compounds of formula (I) wherein X is O, S or NR10,wherein R10 is H, C1-30-alkyl, substituted C1-30-alkyl, C2-30-alkenyl, substituted C2-30-alkenyl, C2-30-alkynyl, substituted C2-30-alkynyl or C(0)-OR11, R1 and R11 are independently from each other selected from the group consisting of C1-30-alkyl, substituted C1-30-alkyl, C2-30-alkenyl, substituted C2-30-alkenyl, C2-30-alkynyl, substituted C2-30-alkynyl, C5-8-cycloalkyl, substituted C5-8-cycloalkyl, C5-8-cycloalkenyl, and substituted C5-8-cycloalkenyl, and an electronic device comprising the compounds as semiconducting material.

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Synthesis, Properties, and Light Fastness of Diaminomaleimide and Some of its Derivatives

Reaction of ammonia with dichloromaleimide (3) yields the aminomaleimides 1 and 4, 2,3-dichloromaleamide (6), and 2,3-diaminofumaramide (2) depending on solvent, temperature, and pressure.The reactivity of the eneamino groups in 1 and 4 are remarkably different, 1 reacts like an amine while 4 resembles an amide.Interpretation of the ultraviolett and fluorescence spectra shows that 1, 4, and the acyl derivatives 13 – 15 can be classified as meropolar dyes.Light fastness values and fluorescence yields show a reverse correlation by change of solvent.Photochemical decomposition and fluorescence show a reactivity-selectivity correlation by variation of substituents at the double bond.

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On the Difficulty of Classifying Diels-Alder-Reactions into “Normal” and “Inverse”

The reactivity of the investigated cyclic dienophiles with 9,10-dimethylanthracene (7) decreases in the order maleic anhydride (1), maleic thioanhydride (2), and maleic imide (3).An analogous behaviour is equally found for the derivatives 4-6 which are dichlorinated at the double bond.In both series this can be understood with the model of the frontier orbitals only if besides the energies of these orbitals, the differing frontier orbital densities of the dienophiles and the electrophilicity of the diene are also taken into account.

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Batch versus flow photochemistry: A revealing comparison of yield and productivity

The use of flow photochemistry and its apparent superiority over batch has been reported by a number of groups in recent years. To rigorously determine whether flow does indeed have an advantage over batch, a broad range of synthetic photochemical transformations were optimized in both reactor modes and their yields and productivities compared. Surprisingly, yields were essentially identical in all comparative cases. Even more revealing was the observation that the productivity of flow reactors varied very little to that of their batch counterparts when the key reaction parameters were matched. Those with a single layer of fluorinated ethylene propylene (FEP) had an average productivity 20% lower than that of batch, whereas three-layer reactors were 20% more productive. Finally, the utility of flow chemistry was demonstrated in the scale-up of the ringopening reaction of a potentially explosive [1.1.1] propellane with butane-2,3-dione.

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