Dicarboximide derivatives

More recently a whole series of derivatives with excellent fungicidal action has been discovered, in which the heterocyclic part is mostly pyrrolidine dione, oxazolidine dione or imidazolidine dione, while the analogous functional group is N-(3,5-dichlorophenyl) dicarboximide. 

Procymidone, N-(3,5-dichlorophenyl)-1,2-dimethyl-cyclopropane-1,2-dicarbox-imide (27), is a fungicide with moderate systemic action (Fujinami et a/., 1969). The active substance is a white crystalline material stable to the action of light, heat and humidity. It is slightly soluble in water. It is moderately toxic to mammals, the acute oral LDjo for rats being 6800 mg/kg. It is not toxic to fish or bees. 

Iprodione, 3-(3,5-dichlorophenyl)-N-isopropyl-imidazolidine-2,4-dione-l-carboxamide (30), is actually a hidantoin derivative (Sauli, 1970). 

Glycine ester (31) is reacted with 3,5-dichlorophenylisocyanate (32) to yield the ethyl ester of 5-(3,5-dichlorophenyl)hidantoic acid (33). By the cyclisation of this product 3-(3,5-dichlorophenyl)imidazolidine-2,4-dione (34) is formed, which with isopropylisocyanate, yields the end product. 

It is not phytotoxic. It does not affect the alcoholic fermentation of must (Lacroix et al, 1974). It is efficient against storage rot of apples (Bompeix et al., 1979). Combined with carbendazime it is very effective for the seed dressing of cereals. It gives excellent protection against Helminthosporium gramineum, H. avenae, H. sativum, Tilletia caries, Fusarium roseum and Septoria nodorum (Chalandon et al., 1979). 

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Along the same lines, it is exdting to monitor chemical transformations of single molecules. The perylene dicarboximide derivative 55 has a high pradical potential as a thermotropic dye for writ-... 

Photoinduced electron transfer occurs through excitation of the 400-nm absorption bands of the donor chromophores based on the aminonapthalene-dicarboximide derivatives. The tails of the dopants absorption bands extend to at least 500 nm, which allows for the use of an Ar+ laser. Figure 8 illustrates the ground-state absorption spectra of the donor and acceptor for both the intramolecular and intermolecular charge transfer dopants in toluene. The spectra are similar for all of the dopants, with the exception of 2, which has a 50-nm red-shifted absorption band. The inset illustrates the broadened spectra in the liquid crystalline environment. The extinction coefficient at 457 nm varies from approximately 1000 M-1 cm-1 for 4, 2000 M-1 cm-1 for 1, 5000 M-1 cm-1 for 3, and 10,000 M-1 cm-1 for 2. 

Considerable interest is given nowadays to the possibility of using natural products as parasiticides in agriculture to replace or enhance phytochemical products, because of the serious environmental problems caused by the often indiscriminate use of pesticides. Massive use of synthetic fungicides against parasites has led to the appearance of strains which are resistant to both the dicarboximide derivatives (iprodione, procymidone, vinclozolin [64-65] and the benzimidazoles (benomyl, carbendazim, thio-phanates, etc.) [66-67] making it much more difficult to control the pathogens. 

Very recently, BASF AG applied for patents on UV absorbers based on 4-cyano-naphthalene-dicarboximide derivatives, such as 4-cyano-N(2,6-diisopropylphenyl)naphthalene-l,8-dicarboximide [139], and pyridindione derivatives such as 1,4-dimethyl-5-dimethylaminomethylene-2,6-dioxo-3-cy ano-1,2,5,6-tetrahydropyridine [140]. It remains to be seen how the patenting process will proceed, and whether a commercial product will result. 

MiiUer, G.R.J., Meiners, C., Enkelmann, V., Geerts, Y., Mullen, K. Liquid crystalline perylene-3,4-dicarboximide derivatives with high thermal and photochemical stabdity. J. Mater. Chem. 8, 61-64 (1998)... 

Synthesis of block copolymers of norbornene derivatives, with different side groups, has been reported via ROMP [101]. Initially, exo-N-bulyl-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide was polymerized in acetone at room temperature with a ruthenium initiator (Scheme 40). The conversion of the reaction was quantitative. Subsequent addition of norbornene derivative carrying a ruthenium complex led to the formation of block copolymers in 85% yield. Due to the presence of ruthenium SEC experiments could not be performed. Therefore, it was not possible to determine the molecular weight... 

Photocycloadditions of naphthalene derivatives to alkcnes have been recently reviewed.60 Examples of such reactions are the photocycloaddition of naphthalene to 2,3-dihy-drofuran,61 of 4-methoxy-l-naphthonitrile to acrylonitrile62 and of 2-trimethylsiloxynaph-thalene to methyl acrylate.63 2-Naphthols undergo cycloaddition with ethene in the presence of aluminum trihalides only.64 Other bicyclic aromatic compounds, e.g. A-acylindoles65-67 and /V-methylphenanthrene-9,10-dicarboximide,68 have also been studied in detail. Irradiation of 5/f-dibenzo[u,i7]cyclohepten-5-one (21) and dimethyl 2-methylfumarate (22) in dioxane gives the cyclobutane adduct 23 in 73% yield.69... 

Various dihydro-1,4-oxathiins and dihydro-1,4-dithiins are reported to be useful in areas other than agriculture. Thus, 2,3-dihydro-l,4-dithiin-5,6-dicarboximides display a wide spectrum of biological activity (77SST(4)332) while derivatives of the basic structure (243) have been patented as tranquilizers, anticonvulsants and hypnotics (76GEP2550163). Sedative, myorelaxant and cataleptic properties are associated with certain 2,1-benzoxathiane 2,2-dioxides (75BRP1383459). 

Turquoise shades are obtained from derivatives of 1,4-diaminoanthraquinone-2,3-dicarboximide [128-81-4] (47). 

Toda, F., Miyamoto, H., and Ohta, H. (1994) Efficient Optical Resolution of c7.s -4-Methylcyclohex-4-enc-l, 2-dicarboxylic Anhydride, c/.v-4-Methylcyclohex-4-ene-1,2-dicarboximide, and Their Derivatives by Complexaion with Optically Active Host Compounds Derived from Tartaric Acid, J. Chem. Soc., Perkin Trans 1. 1601-1604. 

When stericaUy demanding peptide fragments are coupled in the presence of HOSu, a side reaction that leads to a P-alanine derivative becomes donninant (Scheme In this side reaction, HOSu is activated by DCC and attacked by a second equivalent of HOSu. The nitrene is probably not a real intermediate as it is rearranged conconoitantly to its formation to an isocyanate moiety, which is trapped by a third equivalent of HOSu.t By replacing the HOSu additive with A-hydroxy-5-norbornene-2,3-dicarboximide (18)t or other dinucleo-phUes, this side reaction is efficiently bypassed. 

Block copolymers produced from the sequential polymerization of exo-N-bulyl-7-oxabicyclo 2.2.1 hcpl-5-ene-2,3-dicarboximide and another nor-bornene derivative carrying an adenine group were employed using a ruthe-niirm catalyst, as shown in Scheme 38 [99]. The first monomer was polymerized in CH2CI2 at room temperature followed by the addition of the second monomer and succinimide. In the presence of succinimide the conversion of the adenine-containing monomer was almost quantitative, probably due to the formation of hydrogen bonds with the adenine moiety, which prevents any undesired interaction with the catalyst. Monomodal peaks were obtained by SEC analysis with polydispersity indices ranging from 1.20 up to 1.60. 

Biagini and Parry [73] showed that the block copolymerization of di- and tripeptide-based NBE dicarboximide with PEG-functionalized NBE derivative using a first-generation Grubbs ruthenium initiator yielded water-compatible copolymers. The copolymers formed aggregates upon dispersion in water, and the type of aggregates (folded worms, interpenetrating networks) was directed by the specific peptide sequence rather than by the hydrophobic/hydrophilic balance [74]. 

More recently, by using a similar approach and derivatives of norbornene-exo-2,3-dicarboximide, cobaltocenium-containing copolymers were obtained [5]. Two classes of copolymers were studied (i) a cobaltocenium-containing block... 

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