Fumaronitrile

Fumaramide. A mixture of 516 g. (3.0 moles) of diethyl fumarate (Notes 1 and 2), 600 ml. of concentrated ammonium hydroxide (28%, sp. gr. 0.90, 9.0 moles), and 60 g. of ammonium chloride is placed in a 2-1. flask equipped with a stirrer and a thermometer. The reaction mixture is stirred at 25-30° with slight cooling for 7 hours (Note 3). The thick slurry of fumaramide is then filtered with suction, reslurried with 1 1. of water, filtered, and washed with about 50 ml. of ethanol. The white crystalline product is then dried in air or in an oven below 75° (Note 4). The yield is 270-300 g. (80-88%). 

Diethyl fumarate liquid and vapors often cause reddening and itching of the skin, which usually disappear after a few hours. 

Dimethyl fumarate gives equally good results but is less convenient to handle because it is a solid. 

Additional ammonium hydroxide may be added if the slurry becomes too thick. 

Temperatures higher than 75° often cause yellowing of the amide and excessive foaming during the dehydration with phosphorus pentoxide. 

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Electron-deficient alkenes add stereospecifically to 4-hydroxy-THISs with formation of endo-cycloadducts. Only with methylvinyl-ketone considerable amounts of the exo isomer are produced (Scheme 8) (16). The adducts (6) may extrude hydrogen sulfide on heating with methoxide producing 2-pyridones. The base is unnecessary with fumaronitrile adducts. The alternative elimination of isocyanate Or sulfur may be controlled using 7 as the dipolarenOphile. The cycloaddition produces two products, 8a (R = H, R = COOMe) and 8b (R = COOMe, R =H) (Scheme 9) (17). Pyrolysis of 8b leads to extrusion of furan and isocyanate to give a thiophene. The alternative S-elimi-nation can be effected by oxidation of the adduct and subsequent pyrolysis. 

Polymerization Solvent. Sulfolane can be used alone or in combination with a cosolvent as a polymerization solvent for polyureas, polysulfones, polysUoxanes, polyether polyols, polybenzimidazoles, polyphenylene ethers, poly(l,4-benzamide) (poly(imino-l,4-phenylenecarbonyl)), sUylated poly(amides), poly(arylene ether ketones), polythioamides, and poly(vinylnaphthalene/fumaronitrile) initiated by laser (134—144). Advantages of using sulfolane as a polymerization solvent include increased polymerization rate, ease of polymer purification, better solubilizing characteristics, and improved thermal stabUity. The increased polymerization rate has been attributed not only to an increase in the reaction temperature because of the higher boiling point of sulfolane, but also to a decrease in the activation energy of polymerization as a result of the contribution from the sulfonic group of the solvent. 

Phthalocyanines with side groups which can undergo Diels-Alder reactions can be synthesized as precursors for ladder polymers (see pp772, 773).344-345 For these kinds of compounds an intrinsic conductivity is predicted.346 Both dienophilic and enophilic phthalocyanines have been prepared. The possibility to undergo a Diels-Alder reaction was tested with fumaronitrile and 2,3-dimethylbutadiene.345 Via a Diels-Alder reaction, a connection between a phthalocyanine and [60]fullercne was also achieved.336... 

Several other complexes, M(CNBu )jL (L = an activated olefin), have also been reported recently (110). This group of complexes, with the ligands (L) including maleic anhydride, fumaronitrile, and tetracyano-ethylene, arises from isocyanide ligand substitution by the olefin. Less active olefins such as ethylene and diphenylacetylene, and azobenzene did not react. 

A number of other ligand groups are found to add to [Ni(CNBu )2] t, including azobenzene, tetracyanoethylene, fumaronitrile, and maleonitrile, diphenylacetylene and dimethyl acetylenedicarboxylate 109,110) [Eq. (29)]. 

Other substituted olefins such as acrylonitrile, fumaronitrile, crotono-nitrile, cinnamonitrile, and diethylfumarate also formed adducts with Co (DMG)2 complexes containing py, H2O, or PBuj and, in one case, with [Co (DMG-BF2)2py]. Second-order rate constants were reported for the formation of several Tr-olefin-Co(I) complexes from organocobalt(III) complexes containing, for example, NCCH2CH2- with DMG, DPG, DMG-BF, py, H2O, and PBuj. 

In another publication, Holsboer et al. [280] have investigated bond properties in the five-coordinated Ir(I) complexes (PPh3)3lr(CO)H, (PPh3)3lr (CO)CN, and the tetracyanoethylene, fumaronitrile, and acrylonitrile adducts of (PPh3)2lr(CO)Cl by X-ray photoelectron and fr Mossbauer spectroscopy. 

Figure 111 Mo2Pd2(pyphos)4(L)2 [L = acrylonitrile, fumaronitrile, tetracyanoethylene].

Similarly, fumaronitrile yields cyclobutane (115) when irradiated in the solid state<120> ... 

Forster, Th 211, 278, 282, 285 Forster resonance energy transfer, 282 Forster singlet energy transfer, 378 Franck-Condon factors, 23 Franck-Condon principle, 5 Franck-Condon transition, 5 French, C. S., 555 Friedman, G., 353 Fritzsche, J., 37 Frosch, R. P 252, 267, 269 Fumaronitrile, photodimerization in solid state, 478... 

Thermolysis of 12 with frans-cinnamaldehyde afforded the insertion compound 19, formed through the di-insertion of two carbonyl ligands into the C—Si bond of 12. The reaction of 12 with fumaronitrile yielded the cyclization product 20. X-ray study revealed 20 to be a cyclization product which contains two types of disilyl moieties, imino and N,N-bis(silyl)amino, which are connected by a five-membered ring. 

A nitrilase from the hyperthermophile Pyrococcus abyssi, which exhibits optimal growth at 100 °C, was cloned and overexpressed. Characterization of this nitrilase revealed that it is operational as a dimer (rather than the more common multimeric structure for nitrilases), with optimal pH at 7.4 and optimal apparent activity at 80 °C with Tm (DSC) at 112.7 °C. The substrate specificity of the nitrilase is narrow and it does not accept aromatic nitriles. The nitrilase converts the dinitriles fumaronitrile and malononitrile to their corresponding mononitriles [58],... 

Petrillo reported that the bis-acetoxymethylpyrrole 83 undergoes a sequential Diels-Alder reaction of the in situ generated 2,3-dimethylpyrrole with carbodienophiles (such as maleic anhydride, maleimide, ethyl maleate, fumaronitrile, and ethyl acrylate) to afford the octahydrocarbazoles 84 which can be oxidized with DDQ to the corresponding carbazole derivatives . 

Recently, dipolarophile 1)13 (fumaronitrile) (777) has been used in the synthesis of indolizine lactone (677). Both, intermolecular and intramolecular cycloadditions were studied. Intermolecular 1,3-cycloaddition of nitrone (671) to D13 led to the formation of isoxazolidine (672). Subsequent deprotection and esterification of the obtained alcohol (673) with (674) gave isoxazolidine (675) in 65% yield. Ester (675), when refluxed in xylene for 10 min, after elimination of fumaronitrile by cyclo-reversion, underwent spontaneously intramolecular cycloaddition to give the tricyclic cycloadduct (676) in 84% yield (Scheme 2.291). 

In the presence of a more reactive dienophile, a retro Diels-Alder reaction can be carried out at or below room temperature when catalyzed by a Lewis acid.78 In fact, this process can be regarded as a trans-Diels-Alder reaction in which the C C bond is replaced by another more reactive functionality. Thus, when treated with fumaronitrile in the presence of EtAlCl2 at ambient temperature for 2 hours, compound 159 can easily be converted to compound 160 with the removal of cyclopentadiene (Scheme 5-48). 

Irradiation of the sodium salt 517 in a solution of maleonitrile in THF gave a 30% yield of the as-spiro[2.6]nonatrienedicarbonitrile 524 (Scheme 6.106). Analogously, fumaronitrile led to the trans-diastereomer 525 exclusively in 29% yield [193b], which was also obtained from (trimethylsilyl)tropylium tetrafluoroborate (519) as precursor of 5 [208]. The interception of 5 by dimethyl fumarate succeeded by generating 5 from 517 by either photolysis [193] or thermolysis [193, 194] and from 519 [208] and afforded the dimethyl trans-dicarboxylate 526 in yields of 50, 40 and 42%, respectively. Liberation of 5 in the presence of dimethyl maleate led also to 526 [194, 214], In this reaction, the isomerization of dimethyl maleate to fumarate could have interfered and hence pretended the loss of the stereochemical information, since... 

A type iii-d reaction leads to the formation of (69). Trifluoromethyl radicals generated electrochemically from triflu-oroacetate can attack electron-deficient olefins leading to trifluoromethylated carbon radicals whose chemical and electrochemical follow-up reactions can be controlled by current density, reaction temperature, and substituents of the olefins. With fumaronitrile (86) at 50 °C the monotri-fluoromethylated compound (87) was obtained in 65% yield (Scheme 31) [110]. 

The reactions of anhydro 2-aryl-3-hydroxythiazolo[2,3-a]phthalizinium hydroxides (171) with methyl propiolate (87EUP226196 88EUP294599), dimethyl acetylenedicarboxylate (85JOC1677), or fumaronitrile (85JOC1677) gave 4//-pyrido[2,l-a]phthalazin-4-ones (173) via cycloadducts 171. When methyl vinyl ketone was reacted with 171 (R = H), in addition to 9% of 4//-pyrido[2,l-a]phthalazin-4-one (173, R = H, R = COMe), a cycloadduct was also isolated (85JOC1677). 

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