Butyl acetate alcohol, tert

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). 

Ethyl tert-butyl malonate has been prepared by adding tert-butyl acetate and ethyl carbonate to sodium triphenylmethyl,3 and from ethyl malonyl chloride and fer/-butyl alcohol.4 The present procedure is an adaptation of that for the preparation of di-fer(-butyl malonate.2... 

Prior to the actual metathesis event, coupling of 13 and 28 via an ester linkage was required (Scheme 2.3). Two methods were employed in this connection. The first involved the aforementioned two-carbon expansion of aldehyde 28. Thus, condensation of 28 with Rathke anion (lithiated tert-butyl acetate) generated a mixture of dia-stereomeric alcohols the major product was shown to have the requisite 3S configuration. TBS protection of ester 29 and subsequent ester hydrolysis generated the desired add, 31, which could be further esterified with alcohol 13 in 78 % yield. 

METHYL ISOBUTYL KETONE n-PENTYL FORMATE n-BUTYL ACETATE sec-BUTYL ACETATE tert-BUTYL ACETATE ETHYL n-BUTYRATE ETHYL ISOBUTYRATE ISOBUTYL ACETATE n-PROPYL PROPIONATE CYCLOHEXYL PEROXIDE DIACETONE ALCOHOL 2-ETHYL BUTYRIC ACID n-HEXANOIC ACID 2-ETHOXYETHYL ACETATE HYDROXYCAPROIC ACID PARALDEHYDE... 

The next step is to determine the solubility of the substrate (or its salts) in different solvents. This can also be performed by an automated liquid handling system. Depending upon the solubility of the substrate in water-miscible solvent (alcohols, acetone, tetrahydrofuran, etc.) and water-immiscible solvents (ethyl acetate, methyl-tert-butyl ether, heptane, etc.) the process chemist can identify one or many solvent systems from which the substrate (or its salts) could be ciystallized using the antisolvent addition strategy. 

Esterification of linalool requires special reaction conditions since it tends to undergo dehydration and cyclization because it is an unsaturated tertiary alcohol. These reactions can be avoided as follows esterification with ketene in the presence of an acidic esterification catalyst below 30 °C results in formation of linalyl acetate without any byproducts [71]. Esterification can be achieved in good yield, with boiling acetic anhydride, whereby the acetic acid is distilled off as it is formed a large excess of acetic anhydride must be maintained by continuous addition of anhydride to the still vessel [34]. Highly pure linalyl acetate can be obtained by transesterification of tert-butyl acetate with linalool in the presence of sodium methylate and by continuous removal of the tert-butanol formed in the process [72]. 

Butoxy ethanol sec-Butyl acetate t-Butyl acetate n-Butyl acetate sec-Butyl alcohol t-Butyl alcohol n-Butyl alcohol n-Butyl glycidyl ether p-tert-Butyl toluene... 

Sec-Butyl Acetate N-Butyl Acrylate Iso-Butyl Acrylate N-Butyl Acrylate N-butyl Alcohol N-Butyl Alcohol Sec-Butyl Alcohol Tert-butyl Alcohol N -Butyraldehyde N-butyl Methacrylate N-Butylamine N-Butylamine Sec-Butylamine Tert-Butylamine Benzyl N-butyl Phthalate N-Amyl Alcohol N-Amyl Chloride... 

Figure 16 (A) Progression of cITP-NMR spectra displaying acetate chemical shift during passage of interface between focused sample band and TE through RF coil. Each spectrum consists of 8 scans acquired in 10 s. For display purposes, alternating spectra plotted (20-s time resolution). Focused sample band present from 88.83 min to 90.83 min and no longer present at 91.17 min. (B) Acetate and tert-butyl alcohol, full width at half-maximum (FWHM), in Hz and atenolol peak area as a function of run time (min) in cITP-NMR. (Reproduced with permission from Ref. 54. Copyright 2002 American Chemical Society.)...

In the presence of a strong base, the a carbon of a carboxylic ester or other acid derivative can condense with the carbonyl carbon of an aldehyde or ketone to give a p-hydroxy ester, ° amide, and so on., which may or may not be dehydrated to the a,p-unsaturated derivative. This reaction is sometimes called the Claisen reaction an rmfortunate usage since that name is more firmly connected to 16-85. Early reactions used hydroxide or an alkoxide base in water or alcohol solvents, where self-condensation was the major process. Under such conditions, the aldehyde or ketone was usually chosen for its lack of an a-proton. Much better control of the reaction was achieved when amide bases in aprotic solvents, such as ether or THE, were used. The reaction of tert-butyl acetate and in hexane... 

Butane, 1,4-diiodo-, 30, 33 1,4-dinitro-, 34, 37 2-Butanone, 3-acetamido-, 33,1 tert-Butyl acetate, 34, 28 n-BuTYLACETYLENE, 30, 15 tert-Butyl alcohol, 30, 19, 20 32, 20 anhydrous, 34, 54, 55 /erZ-Butylbenzene, 32, 91 terl-Butyl o-benzoylbenzoate, 34, 28 n-Butyl bromide, 30, 16 tert-Butyl bromoacetate, 34, 28 sec-Butyl a-bromopropionate, 35, 15... 

Olefins add anhydrous acetic acid to give esters, usually of secondary or tertiary alcohols propylene [115-07-1] yields isopropyl acetate [108-21 -4] isobutylene [115-11-7] gives tert-butyl acetate [540-88-5]. Minute amounts of water inhibit the reaction. Unsaturated esters can be prepared by a combined oxidative esterification over a platinum group metal catalyst. For example, ethylene-air-acetic acid passed over a palladium—lithium acetate catalyst yields vinyl acetate. 

For the other fuel oxygenates detailed studies on the reaction pathways are not as abundantly available in literature. However, the similarity in chemical structure implies similar reaction by-products. In the case of TAME, tert-amyl formate and tert-amyl alcohol were observed instead of fBF and fBA, and their subsequent degradation products however, acetone and methyl acetate were observed as well [117]. The attack on the methoxy group was observed to be the major pathway, corresponding to the MTBE ehmination. During the elimination of ETBE the same reaction by-products were observed as with MTBE, with the exception of fert-butyl acetate which was formed instead of fBF [30]. 

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