Butyl acetate formate

M-Butyl formate. Ethyl iso-butyrate IsO -butyl acetate Ethyl butyrate -Propyl propionate Iso-amyl formate, -But> l acetate Iso-propyl butyrate Iso-butyl propionate n-Propyl -butyrate -Butyl propionate Iso-butyl isobutyrate Ethyl lactate Iso-butyl butyrate Cycloheicyl formate -Butyl -butyrate Iso-propyl lactate. Cyclohexyl acetate Diethyl oxalate Di-iao-propyl oxalate... 

Successful results have been obtained (Renfrew and Chaney, 1946) with ethyl formate methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl and iso-amyl acetat ethyleneglycol diacetate ethyl monochloro- and trichloro-acetates methyl, n-propyl, n-octyl and n-dodecyl propionates ethyl butyrate n-butyl and n-amyl valerates ethyl laurate ethyl lactate ethyl acetoacetate diethyl carbonate dimethyl and diethyl oxalates diethyl malonate diethyl adipate di-n-butyl tartrate ethyl phenylacetate methyl and ethyl benzoates methyl and ethyl salicylates diethyl and di-n-butyl phthalates. The method fails for vinyl acetate, ieri.-butyl acetate, n-octadecyl propionate, ethyl and >i-butyl stearate, phenyl, benzyl- and guaicol-acetate, methyl and ethyl cinnamate, diethyl sulphate and ethyl p-aminobenzoate. 

Mercaptals, CH2CH(SR)2, are formed in a like manner by the addition of mercaptans. The formation of acetals by noncatalytic vapor-phase reactions of acetaldehyde and various alcohols at 35°C has been reported (67). Butadiene [106-99-0] can be made by the reaction of acetaldehyde and ethyl alcohol at temperatures above 300°C over a tantala—siUca catalyst (68). Aldol and crotonaldehyde are beheved to be intermediates. Butyl acetate [123-86-4] has been prepared by the catalytic reaction of acetaldehyde with 1-butanol [71-36-3] at 300°C (69). 

Esters of medium volatility are capable of removing the water formed by distillation. Examples are propyl, butyl, and amyl formates, ethyl, propyl, butyl, and amyl acetates, and the methyl and ethyl esters of propionic, butyric, and valeric acids. In some cases, ternary azeotropic mixtures of alcohol, ester, and water are formed. This group is capable of further subdivision with ethyl acetate, all of the ester is removed as a vapor mixture with alcohol and part of the water, while the balance of the water accumulates in the system. With butyl acetate, on the other hand, all of the water formed is removed overhead with part of the ester and alcohol, and the balance of the ester accumulates as a high boiler in the system. 

Ethanol can also be obtained by the reaction of methanol with synthesis gas at 185°C and under pressure (6.9—20.7 MPa or 68—204 atm) in the presence of a cobalt octacarbonyl catalyst (177). However, although ethanol was the primary product, methyl formate, methyl, propyl and butyl acetates, propyl and butyl alcohols, and methane were all present in the product. 

X0 to hydroxy compounds. Lower temperatures favor ketone formation and sterically hindered carbonyls, such as 2-thienyl t-butyl ketone, are not reduced. The sensitivity of desulfurization to steric factors is evident by the failure to desulfurize 2,5-di-i-butyl-3-acetylthiophene. The carbonyl groups of both aldehydes and ketones can be protected by acetal formation, as particularly cyclic acetals are stable during desulfurization in methanol at room temperature. " The free aldehydes give primary alcohols on desulfurization. Another method to obtain only keto compounds is to oxidize the mixtures of ketone and secondary alcohol with CrOs after the desulfurization. - Through the desulfurization of 5,5 -diacetyl-2,2, 5, 2"-terthienyl (228), 2,15-hexadecandione (229) has been obtained, which... 

Esters and amides may be sulfinylated. Addition of a mixture of t-butyl acetate and sulfinate ester 19 to a THF-ether solution of magnesium diisopropylamide led to the formation of (R)-(+)-f-butyl p-toluenesulfinylacetate (49) in 90% yield (equation 14)7. t-Butyl propanoate and butanoate also underwent this sulfinylation to give 50 and 51 in yields of 68 and 45%, respectively83. The diastereomeric ratio was 1 1 for 50 and 3 7 for 51. These esters may also be obtained by alkylation of 49. Similarly, treatment of a-lithio-A, A -dimethylacetamide with sulfinate ester 19 gave (R)-( + )-N, Ar-dimethyl-p-toluene-sulfinylacetamide (52) (equation 15)84. 

The Andersen sulphoxide synthesis allows one also to synthesize a variety of a-heteroatom substituted sulphoxides starting from a-heteroatom stabilized carbanions and (—)-(S)-276. The selected examples shown in Scheme 3 are the best illustration of the generality of this approach. The reaction of enolates or enolate like species with (—)-(S)-276 has been used for the synthesis of optically active a-carbalkoxy sulphoxides. For example, treatment of (—)-(S)-276 with the halogenomagnesium enolates of -butyl acetate, t-butyl propionate or t-butyl butyrate resulted in the formation of ( + )-(R)-t-butyl p-toluenesulphinylcarboxylates 298367 (equation 163). 

The Claisen condensation of t-butyl acetate with a methyl ester is a general route for the preparation of complex P-ketoesters.4 The reaction requires an excess of the enolate of t-butyl acetate to rapidly deprotonate the product and prevent tertiary alcohol formation. Some workers have also used excess LDA or t-butoxide for this purpose. 

DMSO or other sulfoxides react with trimethylchlorosilanes (TCS) 14 or trimefhylsilyl bromide 16, via 789, to give the Sila-Pummerer product 1275. Rearrangement of 789 and further reaction with TCS 14 affords, with elimination of HMDSO 7 and via 1276 and 1277, methanesulfenyl chloride 1278, which is also accessible by chlorination of dimethyldisulfide, by treatment of DMSO with Me2SiCl2 48, with formation of silicon oil 56, or by reaction of DMSO with oxalyl chloride, whereupon CO and CO2 is evolved (cf also Section 8.2.2). On heating equimolar amounts of primary or secondary alcohols with DMSO and TCS 14 in benzene, formaldehyde acetals are formed in 76-96% yield [67]. Thus reaction of -butanol with DMSO and TCS 14 gives, via intermediate 1275 and the mixed acetal 1279, formaldehyde di-n-butyl acetal 1280 in 81% yield and methyl mercaptan (Scheme 8.26). Most importantly, use of DMSO-Dg furnishes acetals in which the 0,0 -methylene group is deuter-ated. Benzyl alcohol, however, affords, under these reaction conditions, 93% diben-zyl ether 1817 and no acetal [67]. 

Ethyl acetate, v, 2 butyl acetate, v, 2 propyl formate, v, 4 dimethyl carbonate, 1, 1 ... 

A practical a-heteroarylation of simple esters or amides has been developed via nucleophilic aromatic substitution. Exposure of chlorothiadiazoles 317 and 319 to NaHMDS and tert-butyl acetate or iV-dimethylacetamide leads to the formation of functionalized... 

A typical elution profile the separation of saturated esters by gas-liquid chromatography 1. methyl formate 2. methyl acetate 3. ethyl formate 4. ethyl acetate 5. -propyl formate 6. iso-propyl acetate 7. w-butyl formate 8. sec-butyl acetate 9. iso-butyl acetate 10. n-butyl acetate... 

In the hydroxycyclopropanation of alkenes, esters may be more reactive than N,N-dialkylcarboxamides, as is illustrated by the exclusive formation of the disubstituted cyclopropanol 75 from the succinic acid monoester monoamide 73 (Scheme 11.21) [91]. However, the reactivities of both ester- as well as amide-carbonyl groups can be significantly influenced by the steric bulk around them [81,91]. Thus, in intermolecular competitions for reaction with the titanacydopropane intermediate derived from an alkylmagnesium halide and titanium tetraisopropoxide or methyltitanium triisoprop-oxide, between N,N-dibenzylformamide (48) and tert-butyl acetate (76) as well as between N,N-dibenzylacetamide (78) and tert-butyl acetate (76), the amide won in both cases and only the corresponding cyclopropylamines 77 and 79, respectively, were obtained (Scheme 11.21) [62,119]. 

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... 

AI3-00040, see Cyclohexanol AI3-00041, see Cyclohexanone AI3-00045, see Diacetone alcohol AI3-00046, see Isophorone AI3-00050, see 1,4-Dichlorobenzene AI3-00052, see Trichloroethylene AI3-00053, see 1,2-Dichlorobenzene AI3-00054, see Acrylonitrile AI3-00072, see Hydroquinone AI3-00075, see p-Chloro-rrr-cresol AI3-00078, see 2,4-Dichlorophenol AI3-00085, see 1-Naphthylamine AI3-00100, see Nitroethane AI3-00105, see Anthracene AI3-00109, see 2-Nitropropane AI3-00111, see Nitromethane AI3-00118, see ferf-Butylbenzene AI3-00119, see Butylbenzene AI3-00121, see sec-Butylbenzene AI3-00124, see 4-Aminobiphenyl AI3-00128, see Acenaphthene AI3-00134, see Pentachlorophenol AI3-00137, see 2-Methylphenol AI3-00140, see Benzidine AI3-00142, see 2,4,6-Trichlorophenol AI3-00150, see 4-Methylphenol AI3-00154, see 4,6-Dinitro-o-cresol AI3-00262, see Dimethyl phthalate AI3-00278, see Naphthalene AI3-00283, see Di-rj-butyl phthalate AI3-00327, see Acetonitrile AI3-00329, see Diethyl phthalate AI3-00399, see Tributyl phosphate AI3-00404, see Ethyl acetate AI3-00405, see 1-Butanol AI3-00406, see Butyl acetate AI3-00407, see Ethyl formate AI3-00408, see Methyl formate AI3-00409, see Methanol AI3-00520, see Tri-ocresyl phosphate AI3-00576, see Isoamyl acetate AI3-00633, see Hexachloroethane AI3-00635, see 4-Nitrobiphenyl AI3-00698, see IV-Nitrosodiphenylamine AI3-00710, see p-Phenylenediamine AI3-00749, see Phenyl ether AI3-00790, see Phenanthrene AI3-00808, see Benzene AI3-00867, see Chrysene AI3-00987, see Thiram AI3-01021, see 4-Chlorophenyl phenyl ether AI3-01055, see 1.4-Dioxane AI3-01171, see Furfuryl alcohol AI3-01229, see 4-Methyl-2-pentanone AI3-01230, see 2-Heptanone AI3-01231, see Morpholine AI3-01236, see 2-Ethoxyethanol AI3-01238, see Acetone AI3-01239, see Nitrobenzene AI3-01240, see I idine AI3-01256, see Decahydronaphthalene AI3-01288, see ferf-Butyl alcohol AI3-01445, see Bis(2-chloroethoxy)methane AI3-01501, see 2,4-Toluene diisocyanate AI3-01506, see p,p -DDT AI3-01535, see 2,4-Dinitrophenol AI3-01537, see 2-Chloronaphthalene... 

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]. 

The ultimate levels of esters in fresh and stored apples are determined by the amount of precursors for ester formation, e.g. lipids, which are influenced by cultivar, growing conditions, harvest maturity and storage conditions [47]. In Fuji apples, acetate ester concentrations increase during maturation, 2-methyl-butyl acetate being the major ester component in the volatile compound profile... 

Organic acid esters carbonates (e.g. ethyl carbonate), formates, acetates (e.g. ethyl acetate, butyl acetate, amyl acetate), propionates, etc., oxalates (e.g. ethyl oxalate), maleates, phtha-lates (e.g. butyl phthalate) carbamates and phenylcarbamates (e.g. ethyl phenylcarbamate). 

Fntity Benzyl propionate Butyl acetate Cinnamyl anthranilate. formate Citronellyl acelate. butyrate, isobutyrate. propionate, Delta-decalactone Diethyl malunate Dimethylbenzyl carbinyl acetate Delta-dodecalactone Ethyl p-anlsate. benzoate, butyrate, heptanoate, hexanoate. maltol. nonanoate Isoamyl butyrate, hexanoate. isovalerate, cinnamate Linalyl isobutyrate. propionate Mallol Methyl benzoate, cinnamate 2-Methyl-undecanal, Nerohdol Octanol. Octyl formaie Phencthyl isobuiyrate. isovalerate gamma- Indecalactone. 

A quantitative assessment of the effects of head group bulk on, S k2 and E2 reactions in cationic micelles has been made.148 The kinetics of the acid-catalysed hydrolysis of methyl acetate in the presence of cationic, anionic, and non-ionic surfactants has been reported on.149 The alkaline hydrolysis of -butyl acetate with cetyltrimethylammonium bromide has also been investigated.150 The alkaline hydrolysis of aromatic and aliphatic ethyl esters in anionic and non-ionic surfactants has been studied.151 Specific salting-in effects that lead to striking substrate selectivity were observed for the hydrolysis of /j-nitrophenyl alkanoates (185 n = 2-16) catalysed by the 4-(dialkylamino)pyridine-fimctionalized polymer (186) in aqueous Tris buffer solution at pH 8 and 30 °C. The formation of a reactive catalyst-substrate complex, (185)-(186), seems to be promoted by the presence of tris(hydroxymethyl)methylammonium ion.152... 

---