Hexanediol and derivs

Dimethylolhexanediol or Bis(hydroxymethyl) hexanediol and Derivatives 2,5 DimethyloUl, 6-hexanediol, [Pg.248]

Dimethylolhexanediol and derivs 5 D1354—D1355 2,5-dinitro-2,5-dimethylol-l, 1-hexanediol tetranitrate 5 D1354—D1355... 

Sila propanediol derivatives (15,16), and butanediol, pentanediol, hexanediol and heptanediol derivatives (17,18, 21, 22) (Table 11.1-17) have also been prepared. 

The strategy involving the use of a C.,4 intermediate has been examined with the four stereoisomeric dienes, namely the 8(E), 11(E) 8(E), 11(Z) 8(Z), 11(E) and 8(Z),11(Z) compounds, and their derivation is shown in the reactions depicted. This work (refe. 154,155,156) is incomplete but considerable progress has been made. Because of the ready availability of the intermediates 1,6-hexanediol and prop-2-yn-1-ol, the Wittig reaction requiring a C7 or Cg component has been less attractive. The synthesis of E and Z hex-2-enol is given in route (a) and their use in obtaining the required C.,4 stereoisomers in route (b). 

Paredes N, Casas M T, Puiggali J, Lotz B (1999), Structural data on the packing of poly(ester amide)s derived from glycine, hexanediol and odd-numbered dicarboxylic acids , J. Pol. Sci. Part B Physics, il (17), 2521-2533. 

Polyester and polyether diols are used with MDI in the manufacture of thermoplastic polyurethane elastomers (TPU). The polyester diols are obtained from adipic acid and diols, such as ethylene glycol, 1,4-butanediol, or 1,6-hexanediol. The preferred molecular weights are 1,000 to 2,000, and low acid numbers are essential to ensure optimal hydrolytic stabihty. Also, caprolactone-derived diols and polycarbonate diols are used. Polyether diols are... 

Devaky and Rajasree have reported the production of a polymer-bound ethylenediamine-borane reagent (63) (Fig. 41) for use as a reducing agent for the reduction of aldehydes.87 The polymeric reagent was derived from a Merrifield resin and a 1,6-hexanediol diacrylate-cross-linked polystyrene resin (HDODA-PS). The borane reagent was incorporated in the polymer support by complexation with sodium borohydride. When this reducing agent was used in the competitive reduction of a 1 1 molar mixture of benzaldehyde and acetophenone, benzaldehyde was found to be selectively reduced to benzyl alcohol. 

Materials. The radical-type photopolymerizable formulation consisted of a mixture of hexanediol diacrylate (HDDA from UCB) and a polyurethane-diacrylate (Actilane 20 from Arkros). A bis-acylphosphine oxide (BAPO from Ciba) was used as photoinitiator at a typical concentration of 1 wt %. The cationic type photopolymerizable resin consisted of a mixture of the divinylether of triethyleneglycol (RapiCure DVE-3 from ISP) and a divinylether derivative of bis-phenol A (DVE-BPA). The cationic photoinitiator (Cyracure UVI-6990 from Union Carbide) had a composition of 50 wt % of mixed triarylsulfonium hexafluorophosphate salts and 50 wt % of propylene carbonate. The BAPO initiator... 

It not tertiary, the product yield is lowered by transfer of the carbinol hydride ion to the aldehyde to produce a new alkoxide and an enolate ion. Thus, propylene oxide, after reductive cleavage with LDBB and trapping with isobutyraldehyde or p-anisaldehyde, provided 5-methyl-2,4-hexanediol in 40-50% yield or 1-p-anisyl-1,3-butanediol in 44% yield, respectively (in both cases about equal mixtures of diastereoisomers were obtained). The cyclohexene oxide-derived dianion, when trapped with isobutyraldehyde, gave 2-(1-hydroxy-2-methylpropyl)cyclohexanol in 71% yield as a mixture of only partially separable isomers in the ratio 15 11 39 35. 

If a diastereomeric mixture of (S,S)-2,5-dimethyl-3.4-hexanediol esters 2 and 3 reacts with methylmagnesium bromide, the result is kinetic resolution, as verified for R1 = Bn. The diastereomeric mixture was prepared from the racemic ethylene glycol a-chloro boronic ester via transesterification with chiral diol. The products isolated were (S,S)-2,5-dimethyl-3,4-hexanediol [(/ )-2-phcnyl-l-methylethyl]boronate, diastereomeric ratio >95 5 as indicated by the rotation of the (/ )- -phenyl-2-propanol derived by deboronation with hydrogen peroxide, and (S,S)-2,5-dimethyl-3.4-hexanediol methylboronate. Phenylacetaldehyde was identified by 1H NMR4. 

A new synthesis of pyrrolizidine, which is based on the reaction of bis-tertiary glycols with co-chloronitriles, was reported by Meyers and Libano.28 The method involves three steps (a) condensation of 2,5-dimethyl-2,5-hexanediol (48) with 4-chlorobutyronitrile in the presence of sulfuric acid to give a derivative of A 1-pyrroline (49), (6) reduction of 49 with sodium borohydride to give the corresponding pyrrolidine (50), and (c) intramolecular cyclization of the pyrrolidine in the presence of alkali to give the pyrrolizidine derivative 51. The three-step synthesis was performed without isolation of the intermediate products. 

Treatment of polymethylene glycols with 50% sulfuric acid gives mixtures of cyclic oxides. Thus, 1,6-hexanediol yields a mixture containing 16% 1,6-, 25% 1,5-, and 65% 1,4-oxidohexane. In other instances, formation of the 1,4-oxido derivatives is also favored. ... 

This transannular addition of a-sulfinyl carbanions to nonactivated double bonds is utilized as the key step in a synthesis of trans-1-thiadecalin (70) in enantiomerically pure form. The required ( )-thiacy-clodec-4-ene 5-oxide (66a,b) was prepared via several steps frtm (/ ,/ )-l,6-dibromo-3,4-hexanediol. Upon treatment with butyllithium, a 4 1 mixture of isomeric sulfoxides (66a and 66b) undergoes smooth cyclizadon to give a mixture of isomeric bicyclic sulfoxides (67a and 67b) in the same 4 1 ratio as the starting material, suggesting that the cyclizadon is essentially stereospecific. The major isomer (67a) is reduced with PCb to a sulfide (68) from which the desired (70) is derived via a thiaoctaline (69 heme 16). 

Derivation (1) By adding hydrochloric or sulfuric acid to a solution of borax and crystallizing. (2) From weak borax brines by extraction with a kerosene solution of a chelating agent such as 2-ethyl-1,3-hexanediol or other polyols. Borates are stripped from the chelate by sulfuric acid. 

Fig. 22 Molecular structures of LC 2-phenylnaphthalene derivative and hexanediol di-acryalte...

Alkaline HjOj oxidation of the 3 2 hydroboration product derived from 1,5-hexadiene and HjB-THF gives 1,6-, 1,5- and 2,5-hexanediols in 73, 19, and 5% yields. 

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