Pentanediols

Trimethylene dibromide (Section 111,35) is easily prepared from commercial trimethj lene glycol, whilst hexamethylene dibromide (1 O dibromohexane) is obtained by the red P - Br reaction upon the glycol 1 6-hexanediol is prepared by the reduction of diethyl adipate (sodium and alcohol lithium aluminium hydride or copper-chromium oxide and hydrogen under pressure). Penta-methylene dibromide (1 5-dibromopentane) is readily produced by the red P-Brj method from the commercially available 1 5 pentanediol or tetra-hydropyran (Section 111,37). Pentamethylene dibromide is also formed by the action of phosphorus pentabromide upon benzoyl piperidine (I) (from benzoyl chloride and piperidine) ... 

Compare 2 3 pentanediol and 2 4 pentanediol with respect to the number of stereoisomers possible for each constitution Which stereoisomers are chiraL Which are achiraL... 

Write equations showing how 3 methyl 1 5 pentanediol could be prepared from a dicarboxylic acid or a diester I... 

On the basis of the mechanism for the acid catalyzed formation of diethyl ether from ethanol in Figure 15 3 write a stepwise mechanism for the formation of oxane from 1 5 pentanediol (see the equation on page 637)... 

Vinyl ethers and a,P unsaturated carbonyl compounds cyclize in a hetero-Diels-Alder reaction when heated together in an autoclave with small amounts of hydroquinone added to inhibit polymerisation. Acrolein gives 3,4-dihydro-2-methoxy-2JT-pyran (234,235), which can easily be hydrolysed to glutaraldehyde (236) or hydrogenated to 1,5-pentanediol (237). With 2-meth5lene-l,3-dicarbonyl compounds the reaction is nearly quantitative (238). 

In addition to its ptincipal use in biocide formulations (94), glutaialdehyde has been used in the film development and leather tanning industries (95). It may be converted to 1,5-pentanediol [111 -29-5J or glutaric acid [110-94-1]. 

Trimethyl-l,3-pentanediol (7) is a white, crystalline soHd. It is used in surface coating and unsaturated polyester resins. It also appears promising as an intermediate for synthetic lubricants and polyurethane elastomers and foams. 

Manufacture and Processing. 2,2,4-Trimethyl-l,3-pentanediol can be produced by hydrogenation of the aldehyde trimer resulting from the aldol condensation of isobutyraldehyde [78-84-2]. 

Esters. The monoisobutyrate ester of 2,2,4-trimethyl-1,3-pentanediol is prepared from isobutyraldehyde ia a Tishchenko reaction (58,59). Diesters, such as trimethylpentane dipelargonate (2,2,4-trimethylpentane 1,3-dinonanoate), are prepared by the reaction of 2 mol of the monocarboxyhc acid with 1 mol of the glycol at 150—200°C (60,61). The lower aUphatic carboxyHc acid diesters of trimethylpentanediol undergo pyrolysis to the corresponding ester of 2,2,4-trimethyl-3-penten-l-ol (62). These unsaturated esters reportedly can be epoxidized by peroxyacetic acid (63). 

Fig. 9. SEM photographs of cellulose acetate membranes cast from a solution of acetone (volatile solvent) and 2-meth5l-2,4-pentanediol (nonvolatile solvent). The evaporation time before the stmcture is fixed by immersion ia water is shown (24).

Kuraray has commercialized a process for producing 3-meth5l-l,5-pentanediol [4457-71-0] from 3-methyl-3-butenol (20). 

The by-products of these reactions are sulfides. The sulfide formed in the synthesis of 2-mercaptoethanol, 3-thia-l,5-pentanediol (thiodiglycol), has a variety of uses ranging from lubricant additive intermediates to textile finishing. 

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