Diacetylenes, preparation

Microcrystals of some diacetylenes, prepared by the reprecipitation method, have been studied as dispersions in liquid media. Interesting behavior has been observed in the solid-state polymerization of diacetylene monomers and with the optical properties of polydiacetylene (PDA) microcrystals. First, the polymerization perfectly proceeded from one end to the other end of the diacetylene microcrystals. Next, the excitonic absorption peak position was found to shift to higher energy side with decreasing size of the PDA microcrystals. The size effect was observed even for crystals as large as 100 nm or more in contrast to conventional quantum effect of inorganic semiconductors where size effect is observed only for microciystals of less than about 10 nm size. In addition, since the microcrystal dispersions in water have low optical loss, the c tical Kerr shutter response of PDA microciystals could be measured, and the non-resonant value was estimated to be on the order of 10 to 10" esu in very low concentrations (ca. 10 M). 

Figure C2.4.8 Diacetylene stmcture employed to prepare polymeric LB films (a) and principle in diacetylene polymerization (b).

A solution of the monosodium salt of diacetylene in 300 ml of liquid ammonia is prepared from 13.8 g (0.6 g-atoms) sodium and 24.6 g (0.2 moles) l,4-dichlorobut-2-yne. To this mixture is added a suspension of 5 g (17.6 mmoles) 3-methoxyestra-l,3,5(10)-trien-17-one in anhydrous tetrahydrofuran at —40° and the reaction mixture is stirred and maintained at this temperature for 2 hr. Ammonium chloride is then added and the ammonia is allowed to evaporate overnight. The residual solids are extracted with methylene dichloride and the extracts washed with water, dried over magnesium sulfate, and evaporated at 70°. The resultant dark gum is... 

The synthesis can be conducted both in solution and without solvents. The reaction in solvent (e.g., methanol, ethanol, dioxane, dimethylformamide) is recommended for volatile 1,3-diynes and amines in this case the pyrroles are purer and the yield is higher. With disubstituted diacetylenes, ammonia and primary alkyl- and arylamines produce 1,2,3-trisubstituted pyrroles under the same conditions (65CB98 71MI1). Since disubstituted diacetylenes are readily obtained by oxidative coupling of acetylenes (98MI2), this reaction provides a preparative route to a wide range of pyrroles. 

A process for the preparation of functionalized pyridines from diacetylene and the ethyl ester of /3-aminocrotonic acid and acetylacetonimine (72ZOR1328 75DIS) has been described. Owing to the lower nucleophilicity of nitrogen in the initial enamine esters and enamine ketone, the reaction with diacetylene occurs in the presence of sodium metal (80°C, dioxane, 3 h, yield of up to 20%). 

A general process for the preparation of pyrimidines from diacetylene and carbamide derivatives RC(X)NH2 (X = NH, O, S R = Ph, OH, NH2) with fixation and subsequent cyclization of primary products has been patented (94GEP4308073). 

As mentioned in the introduction, l-heterobut-l-en-3-ynes, RXCH=CHC=CH (X = RN, O, S R = organic radical), are the nearest and most important diacetylene derivatives readily formed by nucleophilic addition of amines, alcohols, and thiols to diacetylene. In many heterocyclization reactions (especially those leading to fundamental heterocycles) l-heterobut-l-en-3-ynes behave as diacetylene synthetic equivalents, but unlike diacetylene, they are nonhazardous. Therefore, the syntheses of heterocycles therefrom are often more attractive in preparative aspect. 

I. A. Maretina and B. A. Trofimov (Irkutsk, Russia) have contributed a chapter covering applications of diacetylenes in the preparation of heterocycles. This is another field that has grown immensely in the past decade and one which has been significantly enriched by work from these authors laboratories. 

By using a cocatalyst of Pd-Cu, aryl-alkenyl halides couple efficiently widi alkynes to generate die disubstituted alkynes (Scheme 9.6).8 This coupling reaction has been applied to die synthesis of polyphenyleneethynylenes by Yamamoto et al. in 1984 (Scheme 9.7).9a Due to the ready availability of diacetylenes and the mild coupling condition, this strategy has been widely used for die preparation of many poly(aryleneethynylene)s.9... 

Cyclodimer 3 proved to be somewhat difficult to manipulate, thus contributing to the complexity of its characterization. The bowed diacetylenic linkages revealed in the X-ray data impart surprising physical characteristics to the molecule. The energy-rich hydrocarbon was sufficiently strained that it decomposed explosively upon grinding (i. e. preparing a Nujol mull) or when heated above 80°C. At room temperature, crystals blackened within a few days and apparently auto-polymerized, even when stored under vacuum in the dark. Only dilute solutions of 3 in benzene or pyridine were fairly stable over time, especially when stored cold under an inert atmosphere. 

Immobilization of the bilayer membranes as thin solid films is required when the bilayer membranes are used as novel functional materials. Casting method is a simple way to immobilize the bilayer membrane on a solid support from an aqueous solution by drying. Polymer film is easily prepared when the cast film of polymerizable bilayer membrane is polymerized. A free standing polymer film prepared by photo polymerization of the cast film of diacetylene amphiphiles was reported by O Brien and co-workers [34]. Composition with macromolecular materials is another way of polymer film preparation. Bilayer membranes are immobilized as polymer composites by the following physical methods ... 

The coupling reaction of acetylenic carbinols was also extended to the thiophene series (80). The diacetylenic glycols were of particular interest, since they provide convenient synthetic routes to bifunctional compounds difficult to prepare by other means. The coupling reaction, which took place, could be represented as follows ... 

In this paper methods are described for preparing the 1,3,5-triethynylbenzene monomer and oligomers. Evidence is then presented to support the theory that these diacetylene oligomers tend to thermally cure by an aromatization reaction. 

Diacetylenes like [30o] after being laboriously prepared, are not polymerized either by heat or ultraviolet irradiation (Iwamura, 1990). Control of molecular packing in crystals is now needed. Introduction of the technology of liquid crystals or Langmuir-Blodgett membranes (Hupfer et al., 1981 Koch and Ringsdorf, 1981) may be of help. 

Diacetylenes having an internal and a terminal triple bond can be reduced selectively at the internal triple bond if they are first converted to sodium acetylides at the terminal bond by sodamide prepared in situ from sodium in... 

Polymers containing pyrrole units have been prepared by the in situ condensation of bis-l,3-oxazol-5-ones with diacetylenes. ... 

Glycolipid incorporated liposomes have found extensive use as sensors for the detection of Escherichia coli bacteria. Liposomes prepared using a diacetylene and a glucosyl lipid underwent a chromatic transition upon the addition of E. coli (Ma et al. 1998). The chromatic transition is sensitive to the diyne and glycolipid stmc-ture (Ma et al. 2000). An optimized vesicle assembly, consisting of a maltotriosyl lipid, phospholipid, and diyne, detected E. coli at a concentration of 2x10 cells/mL... 

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