Fumaramide

Poly(l,3,4-oxadia2ole-2,5-diyl-vinylene) and poly(l,3,4-oxadia2ole-2,5-diyl-ethynylene) were synthesi2ed by polycondensation of fumaramide or acetylene-dicarboxamide with hydra2ine sulfate in PPA to study the effect of the two repeating units on polymer electronic and thermal properties (55). 

A. 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 fumar-amide 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%). 

Dehydration, of chloroacetamide, 22 of fumaramide, 46 of frons-methylstyrylcarbinol, 76 a-phenylglutaric acid to a-phenylglu-taric anhydride, 82... 

On somewhat smaller runs it may he more convenient to effect heating by the use of a wax or Wood s metal bath or an electric mantle. A hath or mantle temperature of 200° is sufficient for optimum 3neld. The reaction may froth vigorously if heated too rapidly or if the fumaramide is impure. 

Fig. 10. Bis(Feu-EDTA-distamycin) fumaramide (BEDF-Fe11) (from Ref. U5>, modified)...

Among the different types of compounds whose complexation properties have been studied are various amides linear oxoamide 9 [22], fumaramide 10 [23,24] and methanetricarboxamide 11 [25], biphenyl derivatives 12 [26], and derivatives of tartaric acid 13-16, that can also be prepared in an optically active form [27], The above-mentioned chiral hosts have been found to form inclusion complexes with chiral guests 17 and 18. Molecular recognition between chiral hosts and... 

The chemical structures of [2]catenane 19 and the related [3]catenane 20 (Fig. 8) were conceived as an extension of their work on molecular shuttles. The larger macrocycle in 19 comprises two fumaramide stations with differing macro cycle binding affinities. In station B (red) the methyl groups on the fumaramide motif cause it to have lower affinity than the standard fumaramide station. The non-methylated fumaramide station (station A, green) is located next to a benzophenone unit. This allows selective, photosensitized isomerization of station A by irradiation at 350 nm. Station B (red) can be photoisomerized by direct irradiation at 254 nm. The third station, a succinic amide ester (station C, orange), is not photoactive and is intermediate in macrocycle binding affinity between the two fu-... 

Similar acryloyl imidazolidinones have been used in the asymmetric 1,4-addition of organomagnesium compounds in the presence of a Lewis acid. The diastereoselectivity is variable and was found to be highly depending on the nature of all the reaction participants.227 A symmetric fumaramide, obtained from the camphor-derived Oppolzer sultam, adds Grignard reagents, yielding after hydrolysis monosubstituted succinic acids with up to 90% ee (Scheme 73).228... 

Fumarate- and fumaramide-containing hydrogels have been prepared with silicone as a co-component that are highly oxygen permeable. These agents are biocompatible and useful as biomedical devices, particularly as contact lenses. 

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