Butene-based alcohols

There are also several external plasticisers with almost no proven toxicity, such as, tri-(2-ethylhexyl)trimellitate (TEHTM), di-2-ethylhexyl adipate (DEHA), and acetyl triburyl citrate, (ATBC), which are economically unfeasible for industrial applications, i.e., TEHTM is three times (and for DEHA, four times) as expensive as DEHP. In any case, the use of adipate, mellitate and azoalate type external plasticisers are expected to grow in use at the expense of different phthalate types [19]. Butene based alcohols are also used in the manufacture of flexible PVC [20], whereas polycaprolactone is used as a permanent and safer plasticiser for PVC [21],... 

Butene-based alcohols have been primarily used in the manufacture of flexible PVC [47], whereas polycaprolactone is applied as permanent plasticiser for PVC [48]. 

Base-catalyzed reactions were reviewed in general by Hattori [208,222], and from the reactions described butene isomerization, alcohol conversion, toluene alkylation, acetone condensation/diacetone alcohol decomposition, Knoevenagel condensations, diketone cyclization, ring transformation reactions, and dimerization of aldehydes to the corresponding esters were used to evaluate the acid-base properties in molecular sieves. 

Polygas Olefins. Refinery propylene and butenes are polymerized with a phosphoric acid catalyst at 200°C and 3040—6080 kPa (30—60 atm) to give a mixture of branched olefins up to used primarily in producing plasticizer alcohols (isooctyl, isononyl, and isodecyl alcohol). Since the olefins are branched (75% have two or more CH groups) the alcohols are also branched. Exxon, BASE, Ruhrchemie (now Hoechst), ICl, Nissan, Getty Oil, U.S. Steel Chemicals (now Aristech), and others have all used this olefin source. 

Other Dimer Olefins. Olefins for plasticizer alcohols are also produced by the dimerization of isobutene [115-11-7] 4 8 codimerization of isobutene and / -butene [25167-67-3]. These highly branched octenes lead to a highly branched isononyl alcohol [68526-84-1] product. BASE, Ruhrchemie, ICl, Nippon Oxocol, and others have used this source. 

Acetylene is condensed with carbonyl compounds to give a wide variety of products, some of which are the substrates for the preparation of families of derivatives. The most commercially significant reaction is the condensation of acetylene with formaldehyde. The reaction does not proceed well with base catalysis which works well with other carbonyl compounds and it was discovered by Reppe (33) that acetylene under pressure (304 kPa (3 atm), or above) reacts smoothly with formaldehyde at 100°C in the presence of a copper acetyUde complex catalyst. The reaction can be controlled to give either propargyl alcohol or butynediol (see Acetylene-DERIVED chemicals). 2-Butyne-l,4-diol, its hydroxyethyl ethers, and propargyl alcohol are used as corrosion inhibitors. 2,3-Dibromo-2-butene-l,4-diol is used as a flame retardant in polyurethane and other polymer systems (see Bromine compounds Elame retardants). 

Other Higher Oleiins. Linear a-olefins, such as 1-hexene and 1-octene, are produced by catalytic oligomerization of ethylene with triethyl aluminum (6) or with nickel-based catalysts (7—9) (see Olefins, higher). Olefins with branched alkyl groups are usually produced by catalytic dehydration of corresponding alcohols. For example, 3-methyl-1-butene is produced from isoamyl alcohol using base-treated alumina (15). 

The propylene-based chemicals, n- and isobutanol and 2-ethyl-1-hexanol [104-76-7] (2-EH) dominate the product spectmm. These chemicals represent 71% of the world s total oxo chemical capacity. In much of the developed world, plasticizers (qv), long based on 2-EH, are more often and more frequendy higher molecular weight, less volatile Cg, and C q alcohols such as isononyl alcohol, from dimerized normal butenes isodecanol, from propylene trimer and 2-propyl-1-heptanol, from / -butenes and aldol addition. Because of the competition from the higher molecular weight plasticizer alcohols,... 

The demand for amyl alcohols is expected to remain unchanged until 1993. Competition from other alcohols and limited appHcations limit growth in markets for amyl alcohols. U.S. demand was predicted to grow from 29 x 10 t in 1983 to 32 x Kf t by 1990 (152). In Europe, amyl alcohols account for over 80% of the demand for valeraldehyde (17,000 t in 1984). BASE and Hoechst AG produce both / -valeraldehyde and 2-methylbutyraldehyde from butenes by the oxo process (149). The demand for C-5 in Europe is also predicted not to grow substantially (150). Amyl alcohols are growing at a much lower rate than other oxo alcohols as shown in Table 7. 

Miller et al. [9] hypothesized rules on the regioselectivity of addition from the study of the base-catalyzed addition of alcohols to chlorotnfluoroethylene. Attack occurs at the vinylic carbon with most fluorines. Thus, isomers of dichloro-hexafl uorobutene react with methanol and phenol to give the corresponding saturated and vinylic ethers The nucleophiles exclusively attack position 3 of 1,1-dichloro-l,2,3,4,4,4-hexafluoro-2-butene and position I of 4,4-dichloro-l,l,2,3,3,4-hexafluoro-1-butene [10]. In I, l-dichloro-2,3,3,4,4,4-hexafluoro-l-butene, attack on position 2 is favored [J/] (equation 5) Terminal fluoroolefms are almost invariably attacked at tbe difluoromethylene group, as illustrated by the reaction of sodium methoxide with perfluoro-1-heptene in methanol [/2J (equation 6). 

Butyne-l,4-diol has been hydrogenated to the 2-butene-diol (97), mesityl oxide to methylisobutylketone (98), and epoxides to alcohols (98a). The rhodium complex and a related solvated complex, RhCl(solvent)(dppb), where dppb = l,4-bis(diphenylphosphino)butane, have been used to hydrogenate the ketone group in pyruvates to give lactates (99) [Eq. (15)], and in situ catalysts formed from rhodium(I) precursors with phosphines can also catalyze the hydrogenation of the imine bond in Schiff bases (100) (see also Section III,A,3). 

Very reeently Kureshy et al. [98] further reported non-salen chiral Schiff base derived Ti complexes as eatalysts 70, 71 (Figure 23) in the KR of meso-siiXheae oxide, cyclohexene oxide, cyelooetene oxide and cA-butene oxide with anilines. The study deliberated upon the role of several ehiral and achiral additives with these catalysts to give chiral y9-amino alcohols with high enantioselectivity ee, >99%) in excellent yield (>99%) at 0 °C in lOh. Unlike the monomerie version 72 the chiral catalyst 70 used in this study was recoverable and recyclable several times with retention of its performance (Table 10)... 

In oxidation studies it has usually been assumed that thermal decomposition of alkyl hydroperoxides leads to the formation of alcohols. However, carbonyl-forming eliminations of hydroperoxides, usually under the influence of base, are well known. Of more interest, nucleophlic rearrangements, generally acid-catalyzed, have been shown to produce a mixture of carbonyl and alcohol products by fission of the molecule (6). For l-butene-3-hydroperoxide it might have been expected that a rearrangement (Reaction 1) similar to that which occurs with cumene hydroperoxide could produce two molecules of acetaldehyde. 

This procedure describes the preparation of 3-nitropropanai, 1, employing the rarely encountered 1,4-addition of ambident nitrite ion with its "softer N-atom,2 and further transformations of 1, as reported earlier.3 A similar preparation of 3-nitrobutanal from crotonaldehyde (3-butenal) is known,4 as well as analogous additions to a, 3-enones.2 The reduction of 1 to the alcohol 2, originally carried out with borane-dimethyl sulfide (BMS),3 is now more conveniently and economically done with sodium borohydride. The acetalization of 1 to yield the dimethyl acetal 3 is based on our earlier report.3... 

A further development of this successful technology was achieved to take advantage of the available feedstock base of butene isomers (raffinate II) for the preparation of n-C5 products (n-valeraldehyde, n-isoamyl alcohol, and n-valeric acid). In December 1995 production of n-valeraldehyde was started up in a new plant at Hoechst/Ruhrchemie (138). Generally, there are strong restrictions in the application of the two-phase catalytic processes to higher alkenes (Section IV.B.l), but the adaptation to butenes was possible with little modification of the process developed for propene. 

The two most commonly used types of allyl alcohol linker are 4-hydroxycrotonic acid derivatives (Entry 1, Table 3.7) and (Z)- or ( )-2-butene-l, 4-diol derivatives (Entries 2 and 3, Table 3.7). The former are well suited for solid-phase peptide synthesis using Boc methodology, but give poor results when using the Fmoc technique, probably because of Michael addition of piperidine to the a, 3-unsaturated carbonyl compound [167]. Butene-l,4-diol derivatives, however, are tolerant to acids, bases, and weak nucleophiles, and are therefore suitable linkers for a broad range of solid-phase chemistry. 

Microporous superbasic catalysts based on zeolites suitable for alkene isomerization were developed by Martens et al. [28-30]. They have high activity in the 1-butene isomerization and side-chain alkenylation of xylene [31], and are prepared by impregnating a dehydrated zeolite (NaY) with NaN3 in alcoholic solution. Subsequent decomposition of the azide inside the zeolite pores produces metallic sodium particles Nax°and cationic sodium clusters Na43+. The high catalytic activity was attributed to the ionic sodium clusters as they could be detected using ESR spectroscopy. 

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