Alcohols 1,4-butanediol

Poly(ethylene-co-vinyl alcohol) 1,4-butanediol 2007LVR... 

Another possibility for asymmetric reduction is the use of chiral complex hydrides derived from LiAlH. and chiral alcohols, e.g. N-methylephedrine (I. Jacquet, 1974), or 1,4-bis(dimethylamino)butanediol (D. Seebach, 1974). But stereoselectivities are mostly below 50%. At the present time attempts to form chiral alcohols from ketones are less successful than the asymmetric reduction of C = C double bonds via hydroboration or hydrogenation with Wilkinson type catalysts (G. Zweifel, 1963 H.B. Kagan, 1978 see p. 102f.). 

Rea.ctlons, Butynediol undergoes the usual reactions of primary alcohols. Because of its rigid, linear stmcture, many reactions forming cycHc products from butanediol or i j -butenediol give only polymers with butynediol. 

Halogens add to butenediol, giving 2,3-dihalo-l,4-butanediol (90,91). In a reaction typical of aHyhc alcohols, hydrogen haUdes cause substitution of halogen for hydroxyl (103). 

Ma.nufa.cture. Most butanediol is manufactured in Reppe plants via hydrogenation of butynediol. Recendy an alternative route involving acetoxyiation of butadiene has come on stream and, more recendy, a route based upon hydroformylation of allyl alcohol. Woddwide butanediol capacity has climbed steadily for many years. In 1990 it was estimated to be 428,000 metric tons (141), as compared to a Htde more than 70,000 metric tons in 1975... 

In acetic acid solvent, ethylene gives 1,3-propanediol acetates (46) and propylene gives 1,3-butanediol acetates (47). A similar reaction readily occurs with olefinic alcohols and ethers, diolefins, and mercaptans (48). 

Functional Olefin Hydroformylation. There has been widespread academic (18,19) and industrial (20) interest in functional olefin hydroformylation as a route to polyfiinctional molecules, eg, diols. There are two commercially practiced oxo processes employing functionalized olefin feedstocks. Akyl alcohol hydroformylation is carried out by Arco under Hcense from Kuraray (20,21). 1,4-Butanediol [110-63 ] is produced by successive hydroformylation of aHyl alcohol [107-18-6] aqueous extraction of the intermediate 2-hydroxytetrahydrofuran, and subsequent hydrogenation. 

More recendy, however, the technology of introducing a new functional group to the double bond of allyl alcohol has been developed. Adyl alcohol is accordingly used as an intermediate compound for synthesizing raw materials such as epichlorohydrin and 1,4-butanediol, and this development is bringing about expansion of the range of uses of allyl alcohol. 

Hydroformylation. Hydroformylation of aEyl alcohol is a synthetic route for producing 1,4-butanediol [110-63-4] a raw material for poly(butylene terephthalate), an engineering plastic (qv) many studies on the process have been carried out. 

Another butadiene oxidation process to produce butanediol is based on the 1,4-addition of /-butyl hydroperoxide to butadiene (108). Cobalt on siHca catalyzes the first step. This is followed by hydrogenation of the resulting olefinic diperoxide to produce butanediol and /-butyl alcohol. 

Chemicals. Although the amount of butylenes produced ia the United States is roughly equal to the amounts of ethylene and propylene produced, the amount consumed for chemical use is considerably less. Thus, as shown ia Table 10, the utilisation of either ethylene or propylene for each of at least five principal chemical derivatives is about the same or greater than the utilisa tion of butenes for butadiene, their main use. This production is only about one-third of the total the two-thirds is derived directiy from butane. The undedyiag reasons are poorer price—performance compared to derivatives of ethylene and propylene and the lack of appHcations of butylene derivatives. Some of the products are more easily derived from 1-, 2-, and 3-carbon atom species, eg, butanol, 1,4-butanediol, and isobutyl alcohol (see Acetylene-DERIVED chemicals Butyl alcohols). 

Heitz et al. (33) also described the preparation of polyvinyl acetate cross-linked with butanediol divinyl ether. The polymer is the base of the Merckogel series of size exclusion chromatography packings, and its hydrolyzed derivative, polyvinyl alcohol, is marketed as Fractogel and Toyopearls. 

Would you expect the OH stretching frequencies in 2,3-dimethyl-2,3-butanediol to be shifted from the value in tert-butyl alcohol, even in dilute solution. Identify the OH stretching frequencies in the diol and compare them to tert-butyl alcohol. Rationalize your observations by comparing the geometry of the diol with those of tert-butyl alcohol and tert-butyl alcohol dimer. 

Maleic anhydride is also a precursor for 1,4-butanediol through an esterification route followed by hydrogenation. In this process, excess ethyl alcohol esterifies maleic anhydride to monoethyl maleate. In a second step, the monoester catalytically esterifies to the diester. Excess ethanol and water are then removed by distillation. The ethanol-water mixture is distilled to recover ethanol, which is recycled ... 

Finally, reaction of primary, secondary, or tertiary alcohols 11 with Me3SiCl 14 in the presence of equivalent amounts of DMSO leads via 789 and 790 to the chloro compounds 791 [13]. n-Pentanol, benzyl alcohol, yS-phenylefhanol or tert-butanol are readily converted, after 10 min reaction time, into their chloro compounds, in 89-95% yield, yet cyclohexanol affords after reflux for 4 h cyclohexyl chloride 784 in only 6% yield [13] (Scheme 6.5). 1,4-Butanediol is cyclized to tetrahydrofuran (THF) [13a], whereas other primary alcohols are converted in 90-95% yield into formaldehyde acetals on heating with TCS 14 and DMSO in benzene [13b] (cf also the preparation of formaldehyde di(n-butyl)acetal 1280 in Section 8.2.1). 

Alkyl esters often show low reactivity for lipase-catalyzed transesterifications with alcohols. Therefore, it is difficult to obtain high molecular weight polyesters by lipase-catalyzed polycondensation of dialkyl esters with glycols. The molecular weight greatly improved by polymerization under vacuum to remove the formed alcohols, leading to a shift of equilibrium toward the product polymer the polyester with molecular weight of 2 x 10" was obtained by the lipase MM-catalyzed polymerization of sebacic acid and 1,4-butanediol in diphenyl ether or veratrole under reduced pressure. ... 

The enzymatic synthesis of polyesters from activated diesters was achieved under mild reaction conditions. The polymerization of bis(2,2,2-trichloroethyl) glutarate and 1,4-butanediol proceeded in the presence of PPL at room temperature in diethyl ether to produce the polyesters with molecular weight of 8.2 x 10. Vacuum was applied to shift the equilibrium forward by removal of the activated alcohol formed, leading to the production of high molecular weight polyesters. The polycondensation of bis(2,2,2-trifluoroethyl) sebacate and aliphatic diols took place using lipases BC, CR, MM, and PPL as catalyst in diphenyl ether. Under the... 

In addition to the desired polymerization reaction, the dialcohol reactants can participate in deleterious side reactions. Ethylene glycol, used in the manufacture of polyethylene terephthalate, can react with itself to form a dialcohol ether and water as shown in Fig. 24.4a). This dialcohol ether can incorporate into the growing polymer chain because it contains terminal alcohol units. Unfortunately, this incorporation lowers the crystallinity of the polyester on cooling which alters the polymer s physical properties. 1,4 butanediol, the dialcohol used to manufacture polybutylene terephthalate, can form tetrahydrofuran and water as shown in Fig. 24.4b). Both the tetrahydrofuran and water can be easily removed from the melt but this reaction reduces the efficiency of the process since reactants are lost. 

In lipase-catalyzed transesterifications, frequent use of enol esters as acyl agents has been seen [1, 5], since the leaving unsaturated alcohol irreversibly tautomerizes to an aldehyde or a ketone, leading to the desired product in high yields. The polymerization of divinyl adipate and 1,4-butanediol proceeded in the presence of lipase PF at 45 °C [39]. Under similar reaction conditions, adipic acid and diethyl adipate did not afford the polymeric materials, indicating the high polymerizability of bis(enol ester) toward lipase catalyst. 

Allyl alcohol may be a preferred olefin for rhodium hydroformylation routes to 1,4-butanediol. Comparison of allyl acetate and allyl alcohol as... 

Similar results with allyl alcohol were obtained by Kawahito and Ikeda (88). A rhodium tributylphosphine system gave 66% 1,4-butanediol and 22% 2-methyl-1-3-propanediol. 

There are many other commercial alcohols besides methanol. This chapter treats the ones traded in the largest volumes ethyl alcohol, isopropyl alcohol (IPA), normal butyl alcohol (NBA), 2-ethyl hexanol (2-EH) and li4-butanediol (BDO). 

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