123-86-4

Basic information

• Product Name: Butyl acetate
• Synonyms: acetatedebutyle(french);Butile;Butile(acetati di);butile(acetatidi);Butyl ester of acetic acid;Butyl ester, acetic acid;Butylacetat;Butylacetaten
• CAS NO: 123-86-4
• Molecular Formula: C₆H₁₂O₂
• Molecular Weight: 116.16
• EINECS: 204-658-1
• Product Categories: Pharmaceutical Intermediates;Organics;Analytical Chemistry;Solvents for HPLC & Spectrophotometry;Solvents for Spectrophotometry;ReagentPlus(R) Solvent Grade ProductsSaturated fatty acids and derivatives;ReagentPlus(R)Semi-Bulk Solvents;ReagentPlus(R)Solvents;Biotech SolventsSolvents;A-B;A-BFlavors and Fragrances;Alphabetical Listings;Certified Natural Products;Flavors and Fragrances;A-BSaturated fatty acids and derivatives;Alcohol AcetatesAlphabetic;Alpha Sort;B;BI - BZAnalytical Standards;Chemical Class;EstersAnalytical Standards;Solvents;Volatiles/ Semivolatiles;A-B, Puriss p.a.Saturated fatty acids and derivatives;Analytical Reagents for General Use;Puriss p.a.;Alcohol AcetatesSolvents;Anhydrous Grade SolventsSolvents;Solvent Bottles;Sure/Seal? Bottles;ACS Grade SolventsSaturated fatty acids and derivatives;ACS GradeSemi-Bulk Solvents;ACS GradeSolvents;Alcohol Acetates;Carbon Steel Cans with NPT Threads;Alcohol AcetatesSolvent Bottles;CHROMASOLV
• Mol File: 123-86-4.mol
• Article Data: 257

Chemical Properties

• Melting Point: −78 °C(lit.)
• Boiling Point: 124-126 °C(lit.)
• Flash Point: 74 °F
• Appearance: ≤10(APHA)/Liquid
• Density: 0.88 g/mL at 25 °C(lit.)
• Vapor Density: 4 (vs air)
• Vapor Pressure: 15 mm Hg ( 25 °C)
• Refractive Index: n20/D 1.394(lit.)
• Storage Temp.: Flammables area
• Solubility: 5.3g/l
• Explosive Limit: 1.4-7.5%(V)
• Water Solubility: 0.7 g/100 mL (20 ºC)
• Stability: Stable. Flammable. Incompatible with strong oxidizing agents, strong acids, strong bases.
• Merck: 14,1535
• BRN: 1741921
• CAS DataBase Reference: Butyl acetate(CAS DataBase Reference)
• NIST Chemistry Reference: Butyl acetate(123-86-4)
• EPA Substance Registry System: Butyl acetate(123-86-4)

Safety Data

• Statements: 10-66-67-R67-R66-R10
• Safety Statements: 25-S25
• RIDADR: UN 1123 3/PG 3
• WGK Germany: 1
• RTECS: AF7350000
• TSCA: Yes
• HazardClass: 3
• PackingGroup: III
• Hazardous Substances Data: 123-86-4(Hazardous Substances Data)

Usage

Description

Butyl acetate?is an organic compound commonly used as a solvent in the production of lacquers and other products. It is also used as a synthetic fruit flavoring in foods such as candy, ice cream, cheeses, and baked goods. Butyl acetate is found in many types of fruit, where along with other chemicals it imparts characteristic flavors. apples, especially of the Red Delicious variety, are fl avored in part by this chemical. It is a colorless flammable liquid with a sweet smell of banana.Butyl acetate is a clear, flammable ester of acetic acid that occurs in n-, sec-, and tert- forms (INCHEM, 2005). Butyl acetate isomers have a fruity, banana-like odor (Furia, 1980). Isomers of butyl acetate are found in apples (Nicholas, 1973) and other fruits (Bisesi, 1994), as a well as in a number of food products, such as cheese, coffee, beer, roasted nuts, vinegar (Maarse and Visscher, 1989). Butyl acetate is manufactured via esterification of the respective alcohol with acetic acid or acetic anhydride (Bisesi, 1994). N-butyl acetate is used as a solvent for nitrocellulose-based lacquers, inks, and adhesives. Other uses include manufacture of artificial leathers, photographic film, safety glass, and plastics (Budavari, 1996). Isomers of butyl acetate are also used as flavoring agents, in manicure products, and as larvicides (Bisesi, 1994). The tert-isomer has been used as a gasoline additive (Budavari, 1996). It may be used as a synthetic fruit flavoring in candy, ice cream, cheeses, and baked goods (Dikshith, 2013).

Chemical Properties

Butyl acetate is a colorless or yellowish liquid with a strong fruity odor. burning and then sweet taste reminiscent of pineapple. It occurs in many fruits and is a constituent of apple aromas. Butyl acetate is incompatible with strong oxidizing agents, strong acids, and strong bases. There are 4 isomers. At 20 °C, the density of the n-butyl isomer is 0.8825 g/ cm3, and the density of the sec-isomer is 0.8758 g/cm3 (Bisesi, 1994). The n-butyl isomer is soluble in most hydrocarbons and acetone, and it is miscible with ethanol, ethyl ether, and chloroform (Haynes, 2010). It dissolves many plastics and resins (NIOSH, 1981).

Physical properties

Clear, colorless liquid with a strong fruity odor resembling bananas. Sweetish taste as low concentrations (<30 μg/L). Experimentally determined detection and recognition odor threshold concentrations were 30 μg/m3 (6.3 ppbv) and 18 μg/m3 (38 ppbv), respectively (Hellman and Small, 1974). Cometto-Mu?iz et al. (2000) reported nasal pungency threshold concentrations ranged from approximately 550 to 3,500 ppm.

Occurrence

Reported present in rum ether, pears, pear brandy, cider, mango, mountain papaya (C. pubescens), soybean, roasted peanuts and honey and other natural products.

Uses

Different sources of media describe the Uses of 123-86-4 differently. You can refer to the following data:
1. n-Butyl acetate is used in the manufactureof lacquers, plastics, photographic films, andartificial leathers.
2. Butyl acetate is one of the more important derivatives of n-butyl alcohol produced commercially, is employed as a solvent in rapid drying paints and coatings. In some instances, butyl acetate, C6H12O2, has replaced ethoxyethyl acetate due to the latter’s reported toxicity and teratogenicity.
3. Butyl Acetate is a flavoring agent which is a clear, colorless liquid possessing a fruity and strong odor. it is sparingly soluble in water and miscible in alcohol, ether, and propylene glycol. it is also termed n-butyl acetate.

Definition

ChEBI: The acetate ester of butanol.

Production Methods

Butyl alcohol is combined with acetic acid in the presence of a catalyst such as sulfuric acid. After esterification is complete, the solution is distilled to yield butyl acetate .

Preparation

By esterification of n-butyl alcohol with acetic acid.

Aroma threshold values

Detection: 10 to 500 ppb

Synthesis Reference(s)

Journal of the American Chemical Society, 73, p. 5265, 1951 DOI: 10.1021/ja01155a075The Journal of Organic Chemistry, 39, p. 3728, 1974 DOI: 10.1021/jo00939a026

General Description

A clear colorless liquid with a fruity odor. Flash point 72 - 88°F. Density 7.4 lb / gal (less than water). Hence floats on water. Vapors heavier than air.

Air & Water Reactions

Highly flammable. Very slightly soluble in water.

Reactivity Profile

Butyl acetate is an ester. Esters react with acids to liberate heat along with alcohols and acids. Strong oxidizing acids may cause a vigorous reaction that is sufficiently exothermic to ignite the reaction products. Heat is also generated by the interaction of esters with caustic solutions. Flammable hydrogen is generated by mixing esters with alkali metals and hydrides. Attacks many plastics. [Handling Chemicals Safely 1980. p. 233].

Hazard

Skin irritant, toxic. Flammable, moderate fire risk. Eye and upper respiratory tract irritant.

Health Hazard

Different sources of media describe the Health Hazard of 123-86-4 differently. You can refer to the following data:
1. Exposures to n-butyl acetate cause harmful effects that include, but are not limited to, coughing and shortness of breath. High concentrations have a narcotic effect, with symp toms such as sore throat, abdominal pain, nausea, vomiting, and diarrhea. High concen trations of n-butyl acetate cause severe poisoning. Prolonged periods of exposure cause adverse effects to the lungs, the nervous system, and the mucous membranes. Repeated skin contact causes skin dryness or cracking, and dermatitis.
2. The narcotic effects of n-butyl acetate isgreater than the lower alkyl esters of aceticacid. Also, the toxicities and irritant actionsare somewhat greater than n-propyl, iso propyl, and ethyl acetates. Exposure to its vapors at about 2000 ppm caused mild irritation of the eyes and salivation in test animals. A 4-hour exposure to 14,000 ppm wasfatal to guinea pigs. In humans, inhalation of 300-400 ppm of n-butyl acetate may produce moderate irritation of the eyes and throat, and headache.

Fire Hazard

HIGHLY FLAMMABLE: Will be easily ignited by heat, sparks or flames. Vapors may form explosive mixtures with air. Vapors may travel to source of ignition and flash back. Most vapors are heavier than air. They will spread along ground and collect in low or confined areas (sewers, basements, tanks). Vapor explosion hazard indoors, outdoors or in sewers. Runoff to sewer may create fire or explosion hazard. Containers may explode when heated. Many liquids are lighter than water.

Flammability and Explosibility

Flammable

Chemical Reactivity

Reactivity with Water No reaction; Reactivity with Common Materials: No reactions; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.

Biochem/physiol Actions

Taste at 30 ppm

Safety Profile

Moderately toxic by intraperitoneal route. Mdly toxic by inhalation and ingestion. An experimental teratogen. A skin and severe eye irritant. Human systemic effects by inhalation: conjunctiva irritation, unspecified nasal and respiratory system effects. A mild allergen. High concentrations are irritating to eyes and respiratory tract and cause narcosis. Evidence of chronic systemic toxicity is inconclusive. Flammable liquid. Moderately explosive when exposed to flame. Ignites on contact with potassium tert-butoxide. To fight fire, use alcohol foam, CO2, dry chemical. When heated to decomposition it emits acrid and irritating fumes. See also ESTERS.

Carcinogenicity

There are no indications of mutagenic or cytogenic effects for n-butyl acetate.

Source

Identified as a volatile constituent released by fresh coffee beans (Coffea canephora variety Robusta) at different stages of ripeness (Mathieu et al., 1998). Also identified among 139 volatile compounds identified in cantaloupe (Cucumis melo var. reticulates cv. Sol Real) using an automated rapid headspace solid phase microextraction method (Beaulieu and Grimm, 2001).

Environmental fate

Biological. Heukelekian and Rand (1955) reported a 5-d BOD value of 0.52 g/g which is 23.5% of the ThOD value of 2.21 g/g. Photolytic. Butyl acetate reacts with OH radicals in the atmosphere at a rate constant of 4.15 x 10-12 cm3/molecule?sec at 296 K (Wallington et al., 1988b). Chemical/Physical. Hydrolyzes in water forming 1-butanol and acetic acid. Estimated hydrolysis half-lives at 20 °C: 11.4 d at pH 9.0, 114 d at pH 8.0, and 3.1 yr at pH 7.0 (Mabey and Mill, 1978). At an influent concentration of 1,000 mg/L, treatment with GAC resulted in an effluent concentration of 154 mg/L. The adsorbability of the carbon was 169 mg/g carbon (Guisti et al., 1974).

storage

n-Butyl acetate should be kept stored in a segregated and approved area. Workers should keep the container in a cool, well-ventilated area, closed tightly, and sealed until ready for use. Workers should avoid all possible sources of ignition/spark at the workplace

Purification Methods

Distil, reflux with successive small portions of KMnO4 until the colour persists, dry with anhydrous CaSO4, filter and redistil. [Beilstein 2 IV 143.]

Waste Disposal

Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed.

Precautions

On exposure to Butyl acetate, immediately wash with plenty of water, also under the eyelids, for at least 15 min. Remove contact lenses. Butyl acetate?is flammable in the pres ence of open flames, sparks, oxidizing materials, acids, and alkalis. It poses explosion risk in the presence of mechanical impact. For health safety, management authorities should provide exhaust ventilation facilities at the workplace to keep the airborne concentrations of vapors of Butyl acetate?below TLV.

InChI:InChI=1/C6H12O2/c1-3-4-5-8-6(2)7/h3-5H2,1-2H3

Synthetic route

acetic acid (64-19-7) + butan-1-ol (71-36-3) → acetic acid butyl ester (123-86-4)

Conditions	Yield
With crosslinked sulphonated polystyrene at 80℃; for 2h; Product distribution; other acids and solvents; var. catalysts, temp. and time;	100%
zirconium(IV) oxide for 2h; Heating;	100%
phosphomolybdic acid hydrate at 65 - 70℃; for 1h; Product distribution; Further Variations:; Catalysts; Reaction partners;	100%

sec-Butyl acetate (105-46-4) + butan-1-ol (71-36-3) → acetic acid butyl ester (123-86-4) + iso-butanol (78-92-2, 15892-23-6)

Conditions	Yield
With water; sodium butanolate at 30℃; for 0.0833333h; carried out in a reaction-distillation unit, industrial preparation;	A n/a B 100%

acetic anhydride (108-24-7) + butan-1-ol (71-36-3) → acetic acid butyl ester (123-86-4)

Conditions	Yield
With N-methylmorpholinium propanesulfonic acid ammonium hydrogensulfate at 25℃; for 0.0333333h; Inert atmosphere; neat (no solvent); chemoselective reaction;	99%
With SBA-15-Ph-Pr-SO3H at 20℃; for 0.05h;	99%
With sulfonic group functionalized polyacrylonitrile preoxidated nanofiber mat at 60℃; for 3h;	99.58%

Reaxys ID: 11464599 → acetic acid butyl ester (123-86-4)

Conditions	Yield
at 105℃;	99.1%
With hydrogen at 95.5℃;	99.1%
at 102℃;	95%
With hydrogen at 95.5℃; under 6750.68 Torr;	94%

ethyl acetate (141-78-6) + butan-1-ol (71-36-3) → acetic acid butyl ester (123-86-4)

Conditions	Yield
With 2C18H22N4*Zn(2+)*2C2F3O2(1-) for 18h;	99%
With K5 for 2h; Heating;	92%
With tin(IV) oxide at 200℃; further conditions: liquid phase, reflux;	82%

vinyl acetate (108-05-4) + butan-1-ol (71-36-3) → acetic acid butyl ester (123-86-4)

Conditions	Yield
With pseudomonas fuorescens lipase immobilized on multiwall carbon nano-tubes at 50℃; for 4.5h; Green chemistry;	99%
With porcine pancreatic lipase In tetrahydrofuran for 48h; Ambient temperature; Yield given;
With steapsin lipase In hexane at 55℃; for 24h; Enzymatic reaction;	99 %Chromat.

acetic acid (64-19-7) + butyloxy(diphenyl)-λ6-sulfanenitrile (143885-04-5) → acetic acid butyl ester (123-86-4) + S,S-diphenylsulphoximine (22731-83-5)

Conditions	Yield
With hydrogenchloride In chloroform-d1 at 20℃; for 0.25h;	A 99% B n/a

Reaxys ID: 11465424 → acetic acid butyl ester (123-86-4)

Conditions	Yield
at 95.5℃;	98.8%

1-bromo-butane (109-65-9) + potassium acetate (127-08-2) → acetic acid butyl ester (123-86-4)

Conditions	Yield
With tetrabutylammomium bromide In neat (no solvent) at 60℃; for 2h;	98%
Aliquat 336 for 20h; Ambient temperature;	93%
PEG-400; silica gel In toluene for 3h; Heating; var. catalysts;	56%
With aluminum oxide 1.) water, 2.) 85 deg C, 20 h;	50%
With 18-crown-6-based covalent organic framework In acetonitrile at 85℃; for 5h;	85 %Chromat.

phosphoric acid tributyl ester (126-73-8) + sodium acetate (127-09-3) → acetic acid butyl ester (123-86-4)

Conditions	Yield
at 200 - 220℃; for 5h;	96%
Heating;

acetyl chloride (75-36-5) + butan-1-ol (71-36-3) → acetic acid butyl ester (123-86-4)

Conditions	Yield
zirconium(IV) oxychloride at 20℃; for 0.0333333h;	95%
With zinc(II) oxide at 20℃; for 0.25h;	95%
bismuth(III) oxychloride at 20℃; for 0.0333333h;	95%

Phenyl acetate (122-79-2) + butan-1-ol (71-36-3) → acetic acid butyl ester (123-86-4)

Conditions	Yield
With 2Zn(2+)*C20H14N4*4C2H3O2(1-)*1.5CH4O In neat (no solvent) at 50℃; for 18h; Temperature; Reagent/catalyst; Solvent;	95%
With acetic acid for 0.166667h; Microwave irradiation; neat (no solvent);
With C21H31N2O12Zn2(1+)*2H2O*C2H3O2(1-) at 50℃; for 20h; Reagent/catalyst; Sealed tube;	68 %Chromat.

Allyl acetate (591-87-7) → acetic acid butyl ester (123-86-4)

Conditions	Yield
at 102℃;	93%

acetic anhydride (108-24-7) + butan-1-ol (71-36-3) → acetic acid butyl ester (123-86-4) + dimethylglyoxal (431-03-8)

Conditions	Yield
With cobalt(II) chloride In acetonitrile at 25℃; for 2h; other primary and secondary alcohols, other temperature;	A 92% B n/a
With cobalt(II) chloride In acetonitrile at 25℃; for 2h;	A 92% B n/a

1-bromo-butane (109-65-9) + acetic acid (64-19-7) → acetic acid butyl ester (123-86-4)

Conditions	Yield
In neat (no solvent) at 20℃; for 0.666667h;	92%
With tetradecyl(trihexyl)phosphonium bistriflamide; potassium carbonate at 70℃; for 6h;	74%
Stage #1: acetic acid With tetradecyl(trihexyl)phosphonium bistriflimide; potassium carbonate at 70℃; for 0.5h; Stage #2: 1-bromo-butane at 70℃; for 6h;	74%
With ISOPROPYLAMIDE; tetra(n-butyl)ammonium hydroxide at 100℃; for 1h; 1) pH 10 - 12;
With tetraethylammonium tosylate In N,N-dimethyl-formamide Ambient temperature; electrolysis;	60 % Chromat.

acetylacetone (123-54-6) + butan-1-ol (71-36-3) → acetic acid butyl ester (123-86-4)

Conditions	Yield
With iron(III) chloride; ammonium persulfate In tetrachloromethane; 1,2-dichloro-ethane at 120℃; for 15h;	92%

1-Acetyl-4(1H)-pyridinon (30074-98-7) + butan-1-ol (71-36-3) → acetic acid butyl ester (123-86-4)

Conditions	Yield
In dichloromethane at 20℃; for 12h;	91%

-butyl vinyl ether (111-34-2) → acetic acid butyl ester (123-86-4)

Conditions	Yield
With oxygen; Pd2060(NO3)360(OAc)360O80; titanium(IV) oxide In N,N-dimethyl acetamide; water at 80℃; for 2h; Wacker oxidation;	91%
With bis-triphenylphosphine-palladium(II) chloride; dihydrogen peroxide; triethylamine In N,N-dimethyl acetamide; water at 60℃; for 1h;	72 %Chromat.
With bis-triphenylphosphine-palladium(II) chloride; dihydrogen peroxide; triethylamine In N,N-dimethyl acetamide; water at 60℃; for 1h; Green chemistry;	72 %Chromat.

1-bromo-butane (109-65-9) + sodium acetate (127-09-3) → acetic acid butyl ester (123-86-4)

Conditions	Yield
With Aliquat 336 at 120℃;	90%
With polyethylene glycol 400 at 65 - 70℃; for 4h;	90%

1-iodo-butane (542-69-8) + sodium acetate (127-09-3) → acetic acid butyl ester (123-86-4)

Conditions	Yield
With polyethylene glycol 400 at 65 - 70℃; for 2h;	90%

allyl n-butyl ether (3739-64-8) + acetyl chloride (75-36-5) → acetic acid butyl ester (123-86-4)

Conditions	Yield
cobalt(II) chloride In acetonitrile for 4h; Ambient temperature;	89%

allyl n-butyl ether (3739-64-8) + acetyl chloride (75-36-5) → acetic acid butyl ester (123-86-4) + dimethylglyoxal (431-03-8)

Conditions	Yield
CoCl2 In acetonitrile Ambient temperature; Yields of byproduct given;	A 89% B n/a

n-Butyl chloride (109-69-3) + sodium acetate (127-09-3) → acetic acid butyl ester (123-86-4)

Conditions	Yield
With polyethylene glycol 400 at 65 - 70℃; for 5h;	89%

-butyl vinyl ether (111-34-2) + acetyl chloride (75-36-5) → n-butyl 1-chloroethyl ether (3450-47-3) + acetic acid butyl ester (123-86-4)

Conditions	Yield
CoCl2 In acetonitrile Ambient temperature;	A 10% B 85%

dibutyl ether (142-96-1) + acetic anhydride (108-24-7) → acetic acid butyl ester (123-86-4)

Conditions	Yield
FeCl3-Montmorillonite K-10 at 70℃; for 24h;	83%
With thallium(III) nitrate Ambient temperature;	57%
With sulfuric acid

benzyl 1-butyl ether (588-67-0) + acetyl chloride (75-36-5) → acetic acid butyl ester (123-86-4) + N-(phenylmethyl)acetamide (588-46-5) + benzyl chloride (100-44-7) + dimethylglyoxal (431-03-8)

Conditions	Yield
CoCl2 In acetonitrile Ambient temperature; Yields of byproduct given;	A 80% B 21% C 15% D n/a

-butyl vinyl ether (111-34-2) + acetyl chloride (75-36-5) → acetic acid butyl ester (123-86-4)

Conditions	Yield
cobalt(II) chloride In acetonitrile at 0℃; for 1h;	79%

Acetanilid (103-84-4) + butan-1-ol (71-36-3) → acetic acid butyl ester (123-86-4)

Conditions	Yield
With hydrogenchloride; iron(III) chloride hexahydrate In hexane; water at 80℃; for 14h;	79%

1-pentyl acetate (628-63-7) + butan-1-ol (71-36-3) → acetic acid butyl ester (123-86-4)

Conditions	Yield
With diethylamine; lithium bromide at 20℃; for 24h; neat (no solvent);	78%
K2CO3 + 5percent Carbowax 6000 at 170℃;	58 % Chromat.

2-butoxytetrahydropyran (1927-68-0) + ethyl acetate (141-78-6) → acetic acid butyl ester (123-86-4)

Conditions	Yield
With indium (III) iodide for 14h; Heating;	78%

acetic acid butyl ester (123-86-4) + 4,4'-bis(carbomethoxy)-2,2'-bipyridine (71071-46-0) → 4,4′-bis(2-carboxyvinyl)-2,2'-bipyridine (773130-04-4)

Conditions	Yield
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; platinum on activated charcoal In tetrahydrofuran at 145℃; under 760.051 Torr; for 36h; Inert atmosphere;	98.5%

acetic acid butyl ester (123-86-4) + benzaldehyde (100-52-7) → (E)-3-(phenyl)acrylic acid butyl ester (52392-64-0)

Conditions	Yield
With titanium tetrachloride; triethylamine In dichloromethane at 0 - 25℃; Inert atmosphere; stereoselective reaction;	98%

acetic acid butyl ester (123-86-4) → ethanol-1,1-d2 (1859-09-2)

Conditions	Yield
With lithium aluminium deuteride In diethyl ether	97%
With carbonylhydrido(tetrahydroborato)[bis(2-diphenylphosphinoethyl)amino]ruthenium(II); deuterium In neat (no solvent) at 70℃; under 37503.8 Torr; for 16h; Inert atmosphere; Glovebox;

acetic acid butyl ester (123-86-4) → tetra(n-butoxy)silane (4766-57-8)

Conditions	Yield
With tetrabutoxytitanium; tetraethoxy orthosilicate Heating;	96%

acetic acid butyl ester (123-86-4) → ethanol (64-17-5)

Conditions	Yield
With (Ppyz)Zr(BH4)2Cl2 In diethyl ether for 4h; Heating;	95%
With sodium tetrahydroborate; [fac-8-(2-diphenylphosphinoethyl)amidotrihydroquinoline]RuH(PPh3)(CO); hydrogen In tetrahydrofuran at 120℃; under 38002.6 Torr; for 18h; Autoclave; Industrial scale;
With sodium tetrahydroborate; [fac-8-(2-diphenylphosphinoethyl)amidotrihydroquinoline]RuH(PPh)3(CO); hydrogen In tetrahydrofuran at 120℃; under 37503.8 Torr; for 18h; Inert atmosphere; Autoclave;

acetic acid butyl ester (123-86-4) → acetyl iodide (507-02-8) + trimethylsilyl acetate (2754-27-0)

Conditions	Yield
With trimethylsilyl iodide; iodine In chloroform-d1 at 50℃; for 2h;	A 6% B 94%

1-amino-3-methylbutane (107-85-7) + acetic acid butyl ester (123-86-4) → N-isopentylacetamide (13434-12-3)

Conditions	Yield
Stage #1: 1-amino-3-methylbutane With diisobutylaluminium hydride In tetrahydrofuran; toluene Stage #2: acetic acid butyl ester In tetrahydrofuran at 20℃; for 2h;	94%

acetic acid butyl ester (123-86-4) + 4-chloro-N-(1,1-dimethylprop-2-ynyl)benzamide (24911-15-7) → 2-(4-chloro-phenyl)-4,4-dimethyl-5-methylene-4,5-dihydrooxazole (247196-65-2)

Conditions	Yield
copper(I) chloride	94%
copper(I) chloride	94%

concentrated sodium hydroxide + acetic acid butyl ester (123-86-4) + (R)-3-methoxy-4-[1-methyl-5-(2-methyl-4,4,4-trifluorobutylcarbamoyl)indol-3-ylmethyl]-N-(2-methylphenylsulphonyl)benzamide (136564-68-6) → 4-(5-carboxy-1-methylindol-3-ylmethyl)-3-methoxy-N-(2-methylphenylsulfonyl)benzamide

Conditions	Yield
With hydrogenchloride In tetrahydrofuran; water	94%

acetic acid butyl ester (123-86-4) + (E)-3-trimethylsilyl-2-propenal (58107-34-9, 64081-45-4, 33755-86-1) → butyl (E)-3-hydroxy-5-(trimethylsilyl)pent-4-enoate (128855-24-3)

Conditions	Yield
Stage #1: acetic acid butyl ester With lithium diisopropyl amide In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #2: (E)-3-trimethylsilyl-2-propenal In tetrahydrofuran; hexane at -78℃; for 0.166667h;	93%
With lithium diisopropyl amide In tetrahydrofuran	77%

acetic acid butyl ester (123-86-4) + N-(α,α-dimethylpropargyl)-1-benzenecarboxamide (33244-86-9) → 4,4-dimethyl-5-methylene-2-phenyl-4,5-dihydrooxazole

Conditions	Yield
With silver nitrate	93%
With silver nitrate	93%

acetic acid butyl ester (123-86-4) + (R,S)-2,2-dimethyl-1,3-dioxolane-4-methanol (100-79-8) → (2,2-dimethyl-1,3-dioxolan-4-yl)methyl acetate (121348-86-5)

Conditions	Yield
With sodium methylate In methanol at 120℃; for 5h;	92.7%

acetic acid butyl ester (123-86-4) + benzylamine (100-46-9) → N-(phenylmethyl)acetamide (588-46-5)

Conditions	Yield
With Candida antarctica lipase B; 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate at 60℃; for 24h; Molecular sieve; Ionic liquid; Enzymatic reaction;	92%
Stage #1: benzylamine With diisobutylaluminium hydride In tetrahydrofuran; toluene Stage #2: acetic acid butyl ester In tetrahydrofuran at 20℃; for 2h;	91%
Stage #1: benzylamine With [m-(1,4-diazabicyclo[2.2.2]octanekN1:kN4)]hexamethyldialuminum In tetrahydrofuran at 40℃; for 1h; Stage #2: acetic acid butyl ester In tetrahydrofuran for 18h; Heating;	70%

1,5-pentanedioic acid (110-94-1) + acetic acid butyl ester (123-86-4) → Pentanedioic acid dibutyl ester (6624-57-3) + Pentanedioic acid monobutyl ester (93504-86-0)

Conditions	Yield
With Dowex 50W-X2 (50-100 mesh) In octane at 70℃; for 7.33333h;	A 5% B 92%
With Dowex 50Wx2 In octane at 70℃; for 7.33333h; Esterification;	A 5% B 92%

acetic acid butyl ester (123-86-4) + 5-bromo-6-methoxy-2-acetylnaphthalene (84167-74-8) → 4-(5-bromo-6-methoxy-2-naphthyl)-4-hydroxybut-3-en-2-one

Conditions	Yield
With hydrogenchloride; sodium methylate In water	92%
With hydrogenchloride; sodium methylate In water	92%

Upstream product

• 98276-11-0 1-butylperoxy-ethanol 
• 591-78-6 n-hexan-2-one 
• 3657-07-6 trichloroacetic acid butyl ester 
• 127-08-2 potassium acetate 
• 108-24-7 acetic anhydride 
• 64-19-7 acetic acid 
• 75-05-8 acetonitrile 
• 71-36-3 butan-1-ol 
• 96-63-9 trifluoroacetic anhydride 
• 76-05-1 trifluoroacetic acid 
• 1767-39-1 butoxydiisobutylaluminum 
• 75-36-5 acetyl chloride 
• 2754-27-0 trimethylsilyl acetate 
• 5593-70-4 titanium (IV) butoxide 

Downstream Products

• 1591-02-2 dimethyldibutoxysilane 
• 109-60-4 1-Propyl acetate 
• 71-36-3 butan-1-ol 
• 37160-77-3 3-hydroxy-octan-2-one 
• 6790-20-1 7-hydroxy-dodecan-6-one 
• 52279-26-2 2-hydroxy-3-octanone 
• 109429-01-8 (S)-2-(benzyloxy)-3-hydroxypropyl acetate 
• 109429-00-7 <(R)-2-(benzyloxy)-3-hydroxypropyl> acetate 
• 87929-19-9 1-ethoxycarbonyl-3-phenyl-5-methyl-pyrazole 
• 778-28-9 butyl para-toluenesulfonate 
• 32343-98-9 n-butyl(phenyl)tellane 
• 106-98-9 1-butylene 
• 590-18-1 (Z)-2-Butene 
• 34557-54-5 methane 

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Relevant articles and documents

Characterization of HNbMoO6, HNbWO6 and HTiNbO 5 as solid acids and their catalytic properties for esterification reaction

HTiNbO5, HNbMoO6·H2O and HNbWO 6·1.5H2O were prepared by proton-exchange of the precursors KTiNbO5, LiNbMoO6 and LiNbWO6, respectively, which were synthesized by a solid-state reaction method. The morphology and the micro-structure were characterized by means of scanning electron microscope (SEM), transmission electron microscope (TEM), powder X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FT-IR). NH 3 temperature-programmed desorption (NH3-TPD) was used to measure the acidic properties of the samples. The Sanderson electronegativity and Kataoka′s bond strength theory were also applied to investigate the acid properties of the as-prepared samples. Finally, their catalytic activities were evaluated through catalyzing the liquid-phase esterification reaction of acetic acid and n-butanol to form n-butyl acetate. It has been revealed that H+ ions existed in different forms and interaction modes with MO bond in the solid acids. The acid strength for these as-prepared samples follows the order HNbMoO6·H2O > HNbWO6·1. 5H2O > HTiNbO5. In this work, HNbMoO 6·H2O presents an excellent catalytic activity for the esterification reaction, while HNbWO6·1.5H2O and HTiNbO5 have little catalytic activity. The result suggested that the catalytic activity of the layered solid acid for the esterification reaction was mainly controlled by gallery height.

PHASE TRANSFER CATALYSTS POLYETHYLENE GLYCOLS IMMOBILIZED ONTO METAL OXIDE SURFACES

Catalysts prepared by reacting polyethylene glycol and polyethylene glycol monomethyl ether with both alumina and silica gel were found to be effective phase transfer agents in displacement and oxidation reactions.

Modulation of starch nanoparticle surface characteristics for the facile construction of recyclable Pickering interfacial enzymatic catalysis

In this work, maize starch (MS) was successively modified via an esterification reaction with acetic anhydride (AA) and phthalic anhydride (PTA). Combined with the gelatinization-precipitation process, the formed starch nanoparticles at an AA/PTA ratio of 2 (MS-AP (2)) and 3 (MS-AP (3)) had similar regular spheres but distinct surface characteristics. In order to enhance the activity of lipase B from Candida antarctica (CALB) in an organic solvent, we designed an oil-in-water (o/w) and a water-in-oil (w/o) Pickering interfacial catalytic system simultaneously by utilizing MS-AP (2) and MS-AP (3) as robust Pickering emulsion stabilizers. Impressively, during the esterification of 1-butanol and vinyl acetate, the specific activity of CALB in the o/w (0.0843 U μL-1) or w/o (0.0724 U μL-1) Pickering interfacial catalytic system was much higher than that of free enzymes in the monophasic (0.0198 U μL-1) and biphasic (0.0282 U μL-1) system. Moreover, after preliminarily elaborating mass transfer discrepancies between the o/w and w/o Pickering interfacial catalytic systems and calculating their mass transfer resistance, we clarified the effects of the location of these two phases on the catalytic capacity of the Pickering emulsion. Impressively, both Pickering interfacial catalytic systems exhibited high effectiveness in product separation. It was found that the w/o Pickering emulsion enabled the organic product to be facilely isolated through a simple decantation, while the o/w Pickering emulsion achieved similar results after adjusting the system temperature. The bio-based nanomaterials and simple protocol, in conjunction with the stability to simultaneously achieve high catalysis efficiency and excellent recyclability, makes us believe that this starch nanoparticle-based Pickering interfacial catalytic system is a promising system for meeting the requirements of green and sustainable chemistry.

Polymers as reagents and catalysts. Part 28. The effect of polymer catalyst structure on the esterification of acids

Crosslinked sulphonated polystyrene (Dowex 20 M) and various salts of crosslinked co-poly[styrene-4-vinylpyridine] with hydrogen halides were used as solid catalysts in investigations of the conversion of acids to esters. The role of the structure of the acid (acetic acid, benzoic acid), solvent (n-octane, toluene, n-butanol) and reaction temperature in the presence of polymer supported catalyst was tested in the reaction with n-butanol. Sulphonated crosslinked polystyrene (3a) was the most active catalys, similar activity was found with crosslinked co-poly[styrene-4-vinyl(pyridinium chloride)], while catalysts bearing a fluoride (3b) and iodide (3e) function were almost unreactive. The important role of co-solvents was also established.

A Convenient Synthesis of Isotopically Labelled Anthraquinones, Chrysophanol, Islandicin, and Emodin. Incorporation of Chrysophanol into Tajixanthone in Aspergillus variecolor

Cycloaddition reactions of labelled 6-methoxy-3-methyl-2-pyrone (1) with naphthoquinones provide the common fungal anthraquinones, chrysophanol (2), islandicin (3), and emodin (4) suitably labelled for biosynthetic studies, as demonstrated by synthesis and incorporation of chrysophanol into the xanthone metabolite, tajixanthone (17) in Aspergillus variecolor.

Magnetic MOF microreactors for recyclable size-selective biocatalysis

In this contribution we report a synthetic strategy for the encapsulation of functional biomolecules within MOF-based microcapsules. We employ an agarose hydrogel droplet Pickering-stabilised by UiO-66 and magnetite nanoparticles as a template around which to deposit a hierarchically structured ZIF-8 shell. The resulting microcapsules are robust, highly microporous and readily attracted to a magnet, where the hydrogel core provides a facile means to encapsulate enzymes for recyclable size-selective biocatalysis.

Zr-La doped sulfated titania with a by far better catalytic activity and stability than pure sulfated titania in the esterification of acetic acid and n-butanol

A novel solid superacid catalyst TiO2-Zr-La/SO4 2- was prepared by doping Zr and La to the bulk of TiO2. The modified TiO2-Zr-La/SO4 2- and the unmodified TiO2/SO4 2- were used to catalyze the esterification of acetic acid and n-butanol, in which these two catalysts were systematically compared in a lost of aspects such as catalytic activity and stability and so on. When a small amount of Zr and La were co-doped into the bulk of TiO2, the modified catalyst obtained a by far better catalytic activity and stability than the unmodified, showing that the modified is more resistive to deactivation than the unmodified. Under the set reaction conditions, the average conversion (of acetic acid) and the 20th-cycle conversion (of acetic acid) are 88.83 and 77.35 % for the modified, 80.83 and 46.15 % for the unmodified, respectively. The two catalysts were characterized by means of FTIR, XRD, BET, SEM, TG, and NH3-TPD methods to find the possible reasons for the superiority of the modified catalyst to the unmodified one. The characteristic results indicated that the incorporation of a small amount of Zr and La into the catalyst was beneficial to the modified catalyst: (1) improving its water-tolerance; (2) increasing its surface sulfate group content; (3) decreasing its crystallinity after calcination by retarding its crystallization from amorphous TiO2 to anatase TiO2; (4) increasing its specific surface area; (5) increasing its acidity including the concentration and acid strength of the surface acidic sites of it. All the above advantageous effects arisen from the two-element-doping are to be responsible for the substantially-improved catalytic performances of the modified catalyst.

Production of aroma esters by immobilized Candida rugosa and porcine pancreatic lipase into calcium alginate gel

Candida rugosa lipase (CRL) and porcine pancreatic lipase (PPL) were immobilized into calcium alginate (Ca-Alg) gel beads by means of entrapment and were used to produce three industrially important flavour esters, namely isoamyl acetate (banana flavour), ethyl valerate (green apple flavour) and butyl acetate (pineapple flavour). Immobilization conditions were optimized in terms of sodium alginate (Na-Alg) and CaCl2 concentrations by determination of the entrapped enzyme amount as well as by esterification of 4-nitrophenol and acetic acid. The best results were obtained at 2.5% Na-Alg and 2.5 M CaCl2 for CRL while at 2.5% Na-Alg and 2.0 M CaCl2 for PPL. On carrying out flavour syntheses in solvent-free medium and also in hexane medium, higher ester yields were obtained in hexane medium for all esters and both types of lipases. Ester esterification efficiency increased in parallel with both enzyme concentrations at immobilization medium and the immobilized lipase amount in esterification medium. Maximum ester production was observed between 40 and 50 °C for CRL and PPL. Besides, the effect of substrate concentrations on ester conversion was remarkable. The best ester yield was obtained for isoamyl acetate when immobilized PPL was used.

Cholinium-based deep eutectic solvents and ionic liquids for lipase-catalyzed synthesis of butyl acetate

The aim of this study was to analyze the advantages and limitations of cholinium-based ionic liquids (ILs) and deep eutectic solvents (DESs) used as green solvents for immobilized Candida antarctica lipase B-catalyzed synthesis. The reaction of acetic anhydride with 1-butanol to give short chain ester butyl acetate was chosen as a model reaction. Results showed that selected ILs (choline glycinate, choline alaninate, choline asparaginate, choline malate) and DESs (choline chloride mixtures with glycerol Gly, ethylene glycol EG, and urea U as hydrogen bond donors in molar ratio 1:2) are poor media for tested reaction if applied as pure solvents (yield 50 >5 mM) for both cell lines. Obtained results suggest that DESs are promising candidates for green biocatalysis.

Molybdena-vanadia supported on alumina: Effective catalysts for the esterification reaction of acetic acid with n-butanol

The paper describes the preparation of alumina-supported molybdena-vanadia catalysts, their structural and textural characterization using XRD, N 2 adsorption, UV-vis and NH3-TPD techniques as well as their catalytic properties in the esterification reaction of acetic acid with n-butanol. The effects of esterification conditions including reaction time, catalyst loading and acid-to-alcohol mole ratio and of reactant pre-adsorption on the conversion were investigated. The catalytic activity correlated well with the number of strong acid sites which increased by increasing the vanadia content. In optimized conditions, conversions higher than 85% with 100% selectivity for n-butyl acetate can be obtained. Reactant pre-adsorption experiments suggested that the reaction follows the Langmuir-Hinshelwood mechanism. A good reusability of the catalysts after three reaction cycles was observed. A local interaction between molybdenum and vanadium on the catalyst surface has been evidenced.

Hydrogenation of ethyl acetate to ethanol over Ni-based catalysts obtained from Ni/Al hydrotalcite-like compounds

A series of Ni-based catalysts were prepared using hydrogen reduction of Ni/Al hydrotalcite-like compounds (Ni/Al HTlcs) synthesized by coprecipitation. The physicochemical properties of Ni/Al hydrotalcite-like compounds and the corresponding Ni-based catalysts were characterized using inductively coupled plasma (ICP), BET surface areas, Xray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) techniques. The results indicated that Ni/Al HTlcs with layered structures could be successfully prepared by the coprecipitation method, and the characteristic HTlcs reflections were also observed in the XRD analysis. The NiO and Ni 0 phases were identified in all Ni-based catalysts, which displayed randomly interconnected pores and no layer structures. In addition, the studies also found the Ni/Al HTlcs and Nibased catalysts had high specific surface areas, low pore volumes and low pore diameters. The catalytic hydrogenation of ethyl acetate to ethanol with Ni-based catalysts was also investigated. Among the studied catalysts, RE1NASH-110-3 showed the highest selectivity and yield of ethyl acetate to ethanol, which were 68.2% and 61.7%, respectively. At thesame time, a major by-product, butyl acetate, was formed due to an ester-exchange reaction. A proposed hydrogenation pathway for ethyl acetate over Ni-based catalysts was suggested.

Kinetic study of transesterification of methyl acetate with n-butanol catalyzed by NKC-9

The transesterification of methyl, acetate and n-butanol catalyzed by cation-exchange resin, NKC-9, was studied in this work to obtain the reaction kinetics. The experiments were carried out in a stirred batch reactor at different temperatures (328.15, 33

Surface, textural and catalytic properties of pyridinium hydrogen sulfate ionic liquid heterogenized on activated carbon carrier

Pyridinium hydrogen sulfate ionic liquid (PHS) heterogenized on activated carbon (AC) is investigated for the first time in the current paper. For that purpose, the xPHS/AC (x = 8, 17, 33 and 66 wt%) samples are analyzed by a number of physicochemical methods such as N2 adsorption–desorption measurements, X-ray diffraction, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. Catalytic activity and reusability of xPHS/AC are evaluated in the reaction of butyl acetate synthesis. Effect of the reaction temperature and catalyst loading on the butyl acetate yield are examined in this work as well. Important thermodynamic parameters such as equilibrium constant, activation energy, Gibbs free energy and activation energy barrier for the reaction of butyl acetate synthesis in the presence of xPHS/AC are determined. Textural characterization revealed the that xPHS/AC are mixed micro-mesoporous materials. The PHS heterogenization on AC affects both ionic liquid and support phases due to a surface PHS–AC interaction. FT-IR and XPS showed that this interaction is: (i) manly expressed as a close contact between the pyridinium cation and the functional groups on the AC surface and (ii) electrostatic in nature. The existence of a PHS–AC interaction is found to be responsible for the formation of surface PHS particles of various size. However, the catalytic activity of xPHS/AC is established to be affected by the surface active phase amount, but not the PHS particle size.

Zinc oxide as a solid acid catalyst for esterification reaction

Zinc oxide and its composites with Hβ zeolite were produced under different synthesis conditions. The synthesized catalysts were evaluated for performance in esterification of n-butanol with acetic acid. BET surface area, XRD, and acidity (using NH3 and pyridine as probe molecules) were measured to correlate the activity with the structural features of the catalysts.

High-temperature synthesis of magnetically active and SO 3H-functionalized ordered mesoporous carbon with good catalytic performance

Magnetically active and SO3H-functionalized ordered mesoporous resin and carbon (MOMR-SO3H, MOMC-SO3H) were successfully prepared by high-temperature hydrothermal synthesis from resol, copolymer surfactant, and iron cations at 180 °C, followed by sulfonation from sulfuric acid fuming. X-ray diffraction patterns show that MOMR-SO3H and MOMC-SO3H have ordered hexagonal mesoporous symmetry. N 2 isotherms indicate that these samples have uniform and opened mesopores, high surface areas (335-591 m2/g), and large pore volumes (0.34-0.35 cm3/g). Transmission electron microscopy shows that iron nanoparticles, which are superparamagnetic in nature, are highly dispersed in MOMC-SO3H sample. Catalytic tests show that MOMC-SO3H is highly active and excellently recyclable in esterification of acetic acid with butanol, esterification of acetic acid with cyclohexanol, and condensation of benzaldehyde with ethylene glycol. More interestingly, MOMC-SO3H catalyst is magnetically active, showing potential applications for separating catalysts by a magnetic field in the future.

Studies on a Synthesis of (RS)-Mevalonic Acid Lactone

Full details of a high yielding synthesis of mevalonic acid lactone (1) which is of particular value in the preparation of 3- and/or 3'-labelled compounds are described.The key step, conversion of 3-hydroxy-3-methylpentane-1,5-dioic acid (3) into 3-hydroxy-3-methylpentane-1,5-dioic anhydride (4) using acetic anhydride, has been fully investigated, and an additional method using acetyl chloride and triethylamine is described.

Calibration-free estimates of batch process yields and detection of process upsets using in situ spectroscopic measurements and nonisothermal kinetic models: 4-(Dimethylamino)pyridine-catalyzed esterification of butanol

The use of an near-IR fiber-optic spectrometer with a high-speed diode array for calibration-free monitoring and modeling of the reaction of acetic anhydride with butanol using the catalyst 4-(dimethylamino)pyridine in a microscale batch reactor was presented. Nonlinear fitting of a first-principles model directly to the reaction spectra gave calibration-free estimates of time-dependent concentration profiles and pure component spectra. Real-time modeling of a batch reaction could be achieved by augmenting prerun batch data with recently acquired spectral data followed by fitting of a multiway kinetic model. In real-time applications, accurate initial guesses of the parameter estimates from prerun data can be used to facilitate rapid convergence of the iterative nonlinear fitting process.

Efficient synthesis of vitamin e intermediate by lipase-catalyzed regioselective transesterification

Trimethylhydroquinone-1-monoacetate (TMHQ-1-MA) is a valuable synthetic intermediate for vitamin E acetate. Immobilized Lipozyme RM IM from Mucor miehei was shown to be the best biocatalyst for the production of TMHQ-1-MA through regioselective transesterification between trimethylhydroquinone diacetate (TMHQ-DA) and alcohol. The effects of lipase-catalyzed reaction conditions including solvent, acyl receptor, substrate mole ratio, reaction temperature and agitation speed were investigated. The optimum conditions for Lipozyme RM IM catalyzed regioselective transesterification were achieved at a substrate mole ratio of 1:1, an agitation of 200 rpm at 50 °C in MTBE/n-hexane (3:7). Under the above conditions, Lipozyme RM IM exhibited high substrate tolerance (substrate concentrations of 1.06 M). Recycling experiments demonstrated that Lipozyme RM IM was quite steady under the reaction conditions. The analysis of kinetic experiment showed that the enzymatic reaction obeys the Ping-Pong bi-bi mechanism with n-butanol inhibition.

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Esterification of acetic acid with butanol over sulfonic acid-functionalized hybrid silicas

Sulfonic acid-functionalized hybrid silicas with different loading of organic moieties were synthesized by grafting and co-condensation followed by oxidation of the precursor thiol groups with hydrogen peroxide or by in situ oxidation methods involving the oxidation by hydrogen peroxide during the condensation reaction. As determined by photoelectron spectroscopy (XPS) complete oxidation of the thiol groups in the differently prepared materials was achieved at room temperature. In the esterification reaction of acetic acid with butanol the samples prepared by the in situ oxidation method exhibited the best catalytic activity. During recycling test with a selected sample, in spite of some sulfur leaching, stable activity was observed.

Alkyl substituted 4-N-oxazadisilinane cations: A new family of Si protic ionic liquids and its application on esterification reactions

A series of oxazadisilinane compounds were prepared and used as Br?nsted bases to form a series of 21 siloxane protic ionic liquids (Si-PILs) with four different acids. This new family of Si-PILs were well characterized and examined to catalyze esterification reactions.

Thermodynamics of phase and chemical equilibrium in a strongly nonideal esterification system

In this study, the reaction equilibrium of the reversible esterification of acetic acid with 1-butanol giving 1-butyl acetate and water was investigated. The entire composition space including the miscibility gap was covered at temperatures relevant for technical processes (353.15 K to 393.15 K). The experiments were carried out in a multiphase batch reactor with online gas chromatography and in a batch reactor with quantitative 1H NMR spectroscopy, respectively. The thermophysical database available in the literature was complemented by measurements of liquid-liquid and vapor-liquid equilibria. On the basis of that comprehensive data, thermodynamically consistent models of the reaction equilibrium were developed which predict the concentration dependence of the mass action law pseudoequilibrium constant, Kx. The following different modeling approaches are compared: the GE models NRTL and UNIQUAC as well as the PC-SAFT equation of state and the COSMO-RS model. All of them can successfully be used, the COSMO-RS model, however, has the highest predictive power.

Transesterification between Ethyl Acetate and n-Butanol in Compressed CO2 in the Critical Region of the Reaction System

The phase behavior (KT) and the equilibrium constant (Kx) of the reaction system for the transesterification between ethyl acetate and n-butanol in compressed CO2 were studied systematically. The Kx was very sensitive to pressure as the reaction mixture approached the critical point (CP), bubble point (BP), and dew point (DP) in the critical region. The Kx increased significantly as the pressure approached the DP and CP, while it decreased as the pressure approached the BP, i.e., pressure had the opposite effect on the Kx in the subcritical region and in the supercritical region. The Peng-Robinson EOS could predict the Kx far from the critical region satisfactorily. However, the difference of the predicted results and the experimental data became larger as the reaction system approached the CP, BP, and DP in the critical region. The reaction could be carried out in the critical region with a suitable amount of CO2, whereas this was impossible without the solvent. Thus, the clean solvent could also be used as a green solvent to adjust the critical point and phase behaviors of the reaction system, so that the reaction could take place in the critical region, and the reaction could be tuned effectively by pressure.

Characterization and catalytic performance of basaltic dust as an efficient catalyst in the liquid-phase esterification of acetic acid with n-butanol

Three natural basaltic samples were collected and used as efficient catalysts for the liquid-phase synthesis of n-butyl acetate. The samples were characterized by X-ray fluorescence analysis (XRF), X-ray diffraction (XRD), thermogravimetry (TG), differential thermal analysis (DTA), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), and N2 sorption. The acidity of the samples was determined using isopropanol dehydration, and the strength of the acid sites was measured using chemisorption of basic probes. The catalytic activity of the samples towards the esterification of acetic acid with n-butanol was extensively examined. The influence of different parameters, such as the reaction refluxing time, molar ratio, catalyst loading, reusability, and calcination temperature, on the esterification reaction was studied in detail. The results revealed that all samples had high catalytic activity with a selectivity of 100% to n-butyl acetate formation. In addition, the sample obtained from the top hill of Volcano had the highest activity with a 80% yield of n-butyl acetate. Moreover, the significant catalytic performances were well correlated with the acidity of the samples and to the reaction rate constants.

Dehydrogenative ester synthesis from enol ethers and water with a ruthenium complex catalyzing two reactions in synergy

We report the dehydrogenative synthesis of esters from enol ethers using water as the formal oxidant, catalyzed by a newly developed ruthenium acridine-based PNP(Ph)-type complex. Mechanistic experiments and density functional theory (DFT) studies suggest that an inner-sphere stepwise coupled reaction pathway is operational instead of a more intuitive outer-sphere tandem hydration-dehydrogenation pathway.

Evaluation of gem-Diacetates as Alternative Reagents for Enzymatic Regio-and Stereoselective Acylation of Alcohols

Geminal diacetates have been used as sustainable acyl donors for enzymatic acylation of chiral and nonchiral alcohols. Especially, it was revealed that geminal diacetates showed higher reactivity than vinyl acetate for hydrolases that are sensitive to acetaldehyde. Under optimized conditions for enzymatic acylation, several synthetically relevant saturated and unsaturated acetates of various primary alcohols were obtained in very high yields up to 98% without E/Z isomerization of the double bond. Subsequently, the acyl donor was recreated from the resulting aldehyde and reused constantly in acylation. Therefore, the developed process is characterized by high atomic efficiency. Moreover, it was shown that acylation using geminal diacetates resulted in remarkable regioselectivity by discriminating among the primary and secondary hydroxyl groups in 1-phenyl-1,3-propanediol providing exclusively 3-acetoxy-1-phenyl-propan-1-ol in good yield. Further, enzymatic kinetic resolution (EKR) and chemoenzymatic dynamic kinetic resolution (DKR) protocols were developed using geminal diacetate as an acylating agent, resulting in chiral acetates in high yields up to 94% with enantiomeric excesses exceeding 99%.