Diacetylenic diol

Sodium hydrotelluride adds to diacetylene diol 75 to form the corresponding tellurophene 76 in 52% yield (78TL1885). 

Formation of inclusion complexes with a variety of small organic molecules in which O—H- O hydrogen bonds play an important role has been discussed by Toda [43], Toda and Akagi [44] reported that diacetylene diol forms crystalline stoichiometric inclusion complexes with a variety of small molecules. The salient features that assist complex formation are hydrogen-bonding between the poten-... 

Oxidation of the alcoholic group in acetylenic alcohols is discussed in previous sections (equations 218, 219, 250, 254, and 272). Oxidations affecting the rest of the molecule, that is, acetylenic hydrogen, are shown in equation 283. Such oxidations are carried out analogously to those of simple terminal acetylenes and lead to diacetylenic diols [2, 5S]. 

Corey and Wat17 found that the method of forming cycloolefins from allylic dihalides and nickel carbonyl provides an unusually efficient route for the formation of large rings. Because it leads to cyclic 1,5-dienes, it makes available a variety of cyclic structures not obtainable in a practical way via the acyloin synthesis. Diacetylenic diols (10) were converted by selective reduction into the corresponding cis.cis- and owu,/ra -ethylenic diols followed by reaction with PBr3 to form the diallylic dibromides (12), which were then cyclized with nickel carbonyl. 

Reduction-triggered pericyclic reaction has been used for the biomimetic total synthesis of endiandric acids A-G [72]. Endiandric acids are polycychc natural products isolated from the Australian plant Endiandra introrsa and exist naturally as a racemic mixture which is found to have very high antibacterial effect [73]. In 1980, Black and coworkers [74] proposed a hypothesis that these polycyclic systems are formed in nature by a series of electrocycUzation reactions. On the basis of this hypothesis, Nicolaou et al. [72c] in 1982 reported an excellent domino reduction/electrocyclization process for the synthesis of endiandric acid A 127 (Scheme 9.25). Selective hydrogenation using a Lindlar catalyst of diacetylenic diol 123 afforded the bicyclic diol 126. The reaction presumably proceeds via polyene 124, which then undergoes a spontaneous 8 [i-electrocyclization to give 125. It follows a second 6n-electrocyclization to afford bicyclic 126, which is further converted to endiandric acid A 127. 

ABSTRACT. Novel optical resolutions of guest compounds by inclusion complex formation with optically active host compound are reviewed Tertiary acetylenic alcohols, cyanohydrins, and secondary alcohols were resolved by complexation with alkaloids such as brucine or sparteine. Cycloalkanones, 2,3 -epoxycyclohexanones, and some other neutral compounds were resolved by complex formation with optically active diacetylenic diol. Mutual optical resolution of bis-g-naphthol and sulfoxides by complex formation was also reviewed. 

Previously, we have reported a high ability of 1,1,6,6-tetra-phenylhexa-2,4-diyne-l,6-diol ( ) to include various guest compounds. When this diacetylenic diol is optically active, it can be used for an optical resolution of the guest compound. Optically active diacetylenic diol can easily be... 

The resolution method by complexation with optically active diacetylenic diol (i ) was found to be very eff,e ctive for the resolution of 2,3-epoxycyclohexanones when a solution of (-)-J g (5.10 g, 10,... 

This design for hosts was generalized from Toda s initial observations [2] that diacetylenic diols 1 form crystalline stoichiometric host-guest complexes with a variety of small molecules. X-ray structures [2,3] of these complexes showed that they are of the channel type and conform to our proposal. We have extended this design for hosts to structures of the type 2-10 [1]. 

Because of the versatility of the polyurethane system it is possible to introduce comonomers which can affect the physical properties of the derived polymers. For example, photo cross-linkable polyurethanes are formulated using 2,5-dimethoxy-2,4 -diisocyanato stilbene as a monomer (76). Comonomers, having an azoaromatic chromophore, are used in optical bleaching applications (77), or in the formation of photorefractive polymers (78). The latter random poljnners have second-order nonlinear optical (NLO) properties. Linear poljnners are also obtained from HDI/PTMG and diacetylenic diols. These polymers can be cross-linked through the acetylenic linkages producing a network polymer with properties similar to poly(diacetylenes) (79). 

The reaction of diacetylene with propane-1,3-diol gives 2-(prop-2-ynyl)-l,3-dioxane (39), 2-(propa-l,2-dienyl)-l,3-dioxane (40), and 2-(prop-l-ynyl)-l,3-dioxane (41) (74ZOR953). 

The two-step process of epitaxial polymerization has been applied to symmetrically substituted diacetylenes First, the monomers have been crystallized epitaxially on alkali halides substrates from solution and the vapor phase. The oriented monomer crystals are then polymerized under the substrate s influence by gamma-irradiation. The diacetylenes in this study are 2,4-hexadiyn-l,6-diol (HD) and the bis-phenylurethane of 5,7-dodecadiyn-l,12-diol (TCDU). The polydiacetylene crystal structures and morphologies have been examined with the electron microscope. Reactivity and polymorphism are found to be controlled by the substrate. 

The preparation of butadiynyl carbinols needs a prior explanation. Especially those carbinols derived from aldehydes have limited thermostability and bath temperatures higher than 100 C should be avoided. Distillation of amounts larger than 15 g involves the risk of explosive decomposition at the last stage. It is therefore essential that the undistilled product is sufficiently pure. If equivalent amounts of BuLi and diacetylene are used in the preparation of the lithium compound, there is a great chance that diols are formed from LiCeCOCLi ... 

The formation of the diols can be effectively suppressed by using a large excess (- 50%) of diacetylene. 

Numerous diacetylene polymerizations have been characterized. To select a few that have been well studied, 2,4-hexadiyne-l,6-diol(bis-(p-toluene sulfonate)) (16), bis-(phenylurethane) (17) [101], and3,5-octadiyne-l,8-diol (18) [104]... 

We can mention diols but also less abundant ones such as diepoxies [1], diamines [2, 3], diisocyanates [4, 5], dialdehydes [6] and diacetylenic compounds [7]. 

In contrast to conventional methods the polymerization of diacetylenes proceeds within the original monomer crystal which can be grown from solution. In ideal cases, for example TS-6 [bis(p-toluene sulphonate) ester of 2,4hexadiyne-l,6-diol], the polymerization reaction transforms a monomer molecular crystal to a polymer... 

A single crystal of monomer becomes a nearly defect-free single crystal of the polymer . The two most commonly used monomers are the phenylurethane and tosylate derivatives of 2,4-hexadiyne-l,6-diol, 233a and 233b, but the reaction has been accomplished with a variety of symmetrical and unsymmetrical diacetylene derivatives . 

Early work regarding the polymerization of acetylene in zeolites was performed by Tsai et al. They reported that the extent of pol5nnerization on X-zeolites was related to the size of the alkali metal cations present in the cages, and that the cations activate the acetylene molecules. The photopolymerization of diacetylenes (3,5-octadiyne-l,8-diol) on various surfaces, including molecular sieves 5A and 13X, was examined. On polar surfaces, the first molecular layers are absorbed through hydrogen bonds, but due to their relative orientation these molecules do not polymerize. However, additional layers can be photopolymerized to form stable polymer films on the surface. 

A new method useftil for the preparation of small batches of diacetylene as required involves base-catalyzed cleavage of 2,7-dimethyl-3,S-octadiyne-2,7-diol (from oxidative coupling of the carbinol from acetylene and acetone). 

We protect one hydroxyl terminus of the commercially available 1,8-octane diol 1 by reaction with dihydropyran to give the monoalcohol, 8-tetrahydropyranyloxyoctanol 2. The protected alcohol 2 is oxidized to the aldehyde with pyridinium chlorochromate to give 8-tetrahydropyranyl-oxyoctanal 3. 1-Heptyne 4 is coupled with propargyl bromide 5 in a copper catalyzed reaction to produce the diacetylenic 1,4-decadiyne 6. 

Aerial oxidation of acetylene derivatives to diacetylenes in the presence of copper salts is a method that is also often used. As an example, passing air for 6.5 h through an aqueous-alcoholic solution of 3-butyn-2-ol containing copper(i) chloride, ammonium chloride, and hydrogen chloride gives a very good yield of the mixed stereoisomers of 3,5-octadiyne-2,7-diol 296... 

Heterochain polymers of the type -(M-X) - contain polar M-X bonds (for reviews see [1,2,12-15]). Such polymers are often prepared by polycondensation of a bifimctional metal halide (M = B, Si, Ge, Sn, Pb, Sb, Ni, Pd, Pt, Ti, Hf) with a bifunctional Lewis base such as a diol, diamine, dihydrazine, dihydrazide, dioxime, diamideoxime, dithiol, diacetylene (Eq. 7-2). Another possibilitiy is the polyaddition of a bifunctional metal hydride to bifunctional alkenes (Eq. 7-3). Mn and mg containing poly(p-xylylenes) of the composition -(-CH2-C6H4-CH2-M-) - were produced by solid-state UV-photopolymerization of a cocondensated mixture of p-xylylene with Mn or mg at 80 K [16]. Prolonged storage of the polymers at ambient temperature under vacuum led to gradual decomposition. 

The discovery of the photopolymerization of crystalline diacetylenes, such as hexa-3,5-diyne-l,6-diol and other derivatives (see Chart 10.7) [2, 30, 63], initiated scientific and technical developments extending to various fields [31-33, 35, 65, 66]. 

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