994-05-8

Usage

Uses

Used in Environmental Analysis:
TERT-AMYL METHYL ETHER is used as a reference standard for the identification and quantification of analytes in Catalonian groundwater and soil samples by purge-and-trap gas chromatography/mass spectrometry (P&T-GC/MS) and in aqueous solutions by solid-phase microextraction (SPME) combined with GC-MS. It is also used for the identification of analytes in gasoline-contaminated groundwater by GC combined with various detectors/quantification methods such as photoionization detector (PID), flame ionization detector (FID), or MS.
Used as a Fuel Additive:
TERT-AMYL METHYL ETHER is used as a fuel additive for gasoline, enhancing its performance and reducing emissions.
Used in Chemical Research:
The kinetics of ion exchange resin (Amberlyst 18) catalyzed TERT-AMYL METHYL ETHER reactions have been investigated, contributing to the understanding of its chemical properties and potential applications.

Flammability and Explosibility

Highlyflammable

InChI:InChI=1/C6H14O/c1-5-6(2,3)7-4/h5H2,1-4H3

Synthetic route

tert-Amyl alcohol (75-85-4) + methyl iodide (74-88-4) → tert-Amyl methyl ether (994-05-8)

Conditions	Yield
With sodium hydride; 1-n-butyl-2,3-dimethylimidazolium hexafluorophosphate at 25℃; for 2h; Williamson synthesis;	87%
With potassium hydride 1.)THF, 2 h, reflux, 2.) 0.5 h at 20 deg C, reflux, 1 h; Multistep reaction;

methanol (67-56-1) + tert-Amyl alcohol (75-85-4) → 2-methyl-but-2-ene (513-35-9) + tert-Amyl methyl ether (994-05-8) + 2-Methyl-1-butene (563-46-2)

Conditions	Yield
With Amberlyst-36 In 1,4-dioxane at 80℃; for 4h; Kinetics; Mechanism; Reagent/catalyst; Temperature; Autoclave;	A n/a B 71.37% C n/a
UDCaT-6 at 120℃; Product distribution; Activation energy; Further Variations:; Catalysts; Temperatures; space time;	A n/a B 18% C n/a

2-(benzotriazol-1-yl)-2-methoxypropane (123622-12-8) + EtMgX → tert-Amyl methyl ether (994-05-8)

Conditions	Yield
In diethyl ether Heating;	60%

methanol (67-56-1) + 2,2-dimethyl-1-propyl phenyl selenide (96503-15-0) → tert-Amyl methyl ether (994-05-8) + methyl t-butylmethyl ether (1118-00-9) + diphenyl diselenide (1666-13-3)

Conditions	Yield
With naphthalene-1,4-dicarbonitrile for 8h; Ambient temperature; Irradiation;	A 15% B 35% C 50%

methanol (67-56-1) + tert-Amyl alcohol (75-85-4) → tert-Amyl methyl ether (994-05-8)

Conditions	Yield
With hydrogen; iodine at 100℃; under 60004.8 Torr; for 0.5h;	42%
With Amberlyst 15 at 49.9℃; Product distribution; Rate constant; Kinetics; various reaction conditions;
With sulfuric acid
With Amberlyst 15 at 49.9℃;

diazomethane (186581-53-3, 908094-01-9) + tert-Amyl alcohol (75-85-4) → tert-Amyl methyl ether (994-05-8)

Conditions	Yield
With tetrafluoroboric acid; dichloromethane
With boron trifluoride diethyl etherate
silica gel Ambient temperature;	99 % Chromat.

methanol (67-56-1) + 2-methyl-but-2-ene (513-35-9) → tert-Amyl methyl ether (994-05-8)

Conditions	Yield
With sodium hydroxide; sodium tetrahydroborate; mercury(II) diacetate Product distribution; other alcohols and mercuric salts;
aluminosilicate catalyst at 99.9℃; Equilibrium constant; other temp.;
With Amberlyst 16 at 49.9℃; under 5250.4 Torr; Equilibrium constant; Thermodynamic data; var. temp.; ΔH;

methanol (67-56-1) + 2-Methyl-1-butene (563-46-2) → tert-Amyl methyl ether (994-05-8)

Conditions	Yield
aluminosilicate catalyst at 99.9℃; Equilibrium constant; Thermodynamic data; other temp., ΔH, ΔG, ΔS;
With Amberlyst 16 at 49.9℃; under 5250.4 Torr; Equilibrium constant; Thermodynamic data; var. temp.; ΔH;
(i) Hg(OAc)2, (ii) aq. NaOH, NaBH4; Multistep reaction;

methanol (67-56-1) + 2,2-dimethyl-1-propyl phenyl selenide (96503-15-0) → tert-Amyl methyl ether (994-05-8) + methyl t-butylmethyl ether (1118-00-9)

Conditions	Yield
With naphthalene-1,4-dicarbonitrile Irradiation;

methanol (67-56-1) + C31H30N(1+)*BF4(1-) (90886-05-8) → 2-methyl-but-2-ene (513-35-9) + tert-Amyl methyl ether (994-05-8)

Conditions	Yield
at 150℃; Yield given. Yields of byproduct given;

methanol (67-56-1) + C32H32N(1+)*BF4(1-) (90886-07-0) → 2-methyl-but-2-ene (513-35-9) + tert-Amyl methyl ether (994-05-8)

Conditions	Yield
at 150℃; Rate constant; Thermodynamic data; ΔH(excit.). ΔS(excit.);

deuteromethanol (1455-13-6) + C31H30N(1+)*BF4(1-) (90886-05-8) → 2-methyl-but-2-ene (513-35-9) + tert-Amyl methyl ether (994-05-8)

Conditions	Yield
at 150℃; Yield given. Yields of byproduct given;

methanol (67-56-1) + 2-methyl-but-2-ene (513-35-9) + sulfuric acid (7664-93-9) → tert-Amyl methyl ether (994-05-8)

Conditions	Yield
at 95℃;

methanol (67-56-1) + i-Amyl alcohol (123-51-3) → 2-methyl-but-2-ene (513-35-9) + tert-Amyl methyl ether (994-05-8) + 2-Methyl-1-butene (563-46-2) + 3-Methyl-1-butene (563-45-1)

Conditions	Yield
Stage #1: i-Amyl alcohol at 310 - 330℃; Stage #2: methanol With fibrous sulfonated cation exchanger at 90℃; under 6000.48 Torr; Title compound not separated from byproducts;

methanol (67-56-1) + tert-Amyl alcohol (75-85-4) → 2-methyl-but-2-ene (513-35-9) + tert-Amyl methyl ether (994-05-8) + 2-Methyl-1-butene (563-46-2) + 3-Methyl-1-butene (563-45-1)

Conditions	Yield
Dowex msm 31 at 70℃; under 6000.48 Torr; Product distribution; Further Variations:; Catalysts; Temperatures;

methanol (67-56-1) + 2-methyl-but-2-ene (513-35-9) → tert-Amyl alcohol (75-85-4) + tert-Amyl methyl ether (994-05-8)

Conditions	Yield
With Amberlyst(R) 15; water at 40℃;

3-Methyl-1-butene (563-45-1) → tert-Amyl methyl ether (994-05-8)

methanol (67-56-1) + isopentene → tert-Amyl methyl ether (994-05-8)

Conditions	Yield
With phenolic resin containing sulfonic groups In toluene at 79.84℃; under 2250.23 Torr; Autoclave; Inert atmosphere;

tert-Amyl methyl ether (994-05-8) + cabergoline (81409-90-7) → Form TAME cabergoline

Conditions	Yield
Stage #1: tert-Amyl methyl ether; cabergoline at 41 - 50℃; for 0.25h; Stage #2: cabergoline at 0 - 27℃; for 16.5h;	88.8%

tert-Amyl methyl ether (994-05-8) + 2-allyl-4-methylphenol (6628-06-4) → 2-allyl-6-tert-amyl-4-methylphenol (139573-21-0)

Conditions	Yield
tin(IV) chloride In dichloromethane Ambient temperature;	88%

tert-Amyl methyl ether (994-05-8) + [IrH2(bis(2-(diisopropylphosphino)-4-methylphenyl)amide)] (872682-19-4) → (N(C6H3(CH3)P(iPr)2)2)Ir(tert-amyl methyl ether(-2H))

Conditions	Yield
With norbornene In further solvent(s) byproducts: norbornane, H2; (inert atm.); keeping mixt. of iridium compd. and norbornene in tert-amyl methyl ether at room temp. for 2 h, heating for 20 min; evapn., dissolving in pentane, filtration, drying, NMR and MS;	87%

2-allyl-6-methylphenol (3354-58-3) + tert-Amyl methyl ether (994-05-8) → 2-allyl-4-tert-amyl-6-methylphenol (139553-36-9)

Conditions	Yield
tin(IV) chloride In dichloromethane for 16h; Ambient temperature;	82%

tert-Amyl methyl ether (994-05-8) + 3-n-Pentadecylphenol (501-24-6) → 2-tert-amyl-5-n-pentadecylphenol (139553-41-6)

Conditions	Yield
tin(IV) chloride In dichloromethane for 16h; Ambient temperature;	80%

Estragole (140-67-0) + tert-Amyl methyl ether (994-05-8) → 4-allyl-2-tert-amylanisole (139553-40-5)

Conditions	Yield
tin(IV) chloride In dichloromethane for 16h; Ambient temperature;	73%

tert-Amyl methyl ether (994-05-8) + 2,2,2-trichloroethyl 2-(4-bromophenyl)-2-diazoacetate (1641528-26-8) → 2,2,2-trichloroethyl (R)-2-(4-bromophenyl)-3-(tert-pentyloxy)propanoate

Conditions	Yield
With dirhodium tetrakis[(R)-(1-(biphenyl)-2,2-diphenylcyclopropanecarboxylate)] In dichloromethane at 0℃; enantioselective reaction;	70%

4-allylguaiacol (97-53-0) + tert-Amyl methyl ether (994-05-8) → 4-allyl-2-tert-amyl-6-methoxyphenol (139553-38-1)

Conditions	Yield
tin(IV) chloride In dichloromethane for 16h; Ambient temperature;	65%

tert-Amyl methyl ether (994-05-8) → 2-methyl-but-2-ene (513-35-9) + 2-Methyl-1-butene (563-46-2)

Conditions	Yield
With γ-Al2O3 at 250℃; flow reactor;	A 51% B 49 % Chromat.
With NaX zeolite at 200℃; flow reactor;	A 78 % Chromat. B 22%
With γ-Al2O3 at 300℃; Product distribution; variation of temperatures and reagent;	A 52 % Chromat. B 48 % Chromat.

[N-(trifluoromethylsulfonyl)imino][4-(trifluoromethyl)phenyl]-λ3-bromane (957188-75-9) + tert-Amyl methyl ether (994-05-8) → N-[(1,1-dimethylpropoxy)methyl]trifluoromethanesulfonamide (1378022-09-3)

Conditions	Yield
at 20℃; for 2h; Inert atmosphere; regioselective reaction;	51%

tert-Amyl methyl ether (994-05-8) + 2-Allylphenol (1745-81-9) → 2-allyl-4,6-di-tert-amylphenol (139553-37-0)

Conditions	Yield
tin(IV) chloride In dichloromethane for 16h; Ambient temperature;	35%

tert-Amyl methyl ether (994-05-8) → methanol (67-56-1) + 2-methyl-but-2-ene (513-35-9)

Conditions	Yield
aluminosilicate catalyst at 99.9℃; Equilibrium constant; other temp.;
With acid at 59.85℃; Equilibrium constant;

tert-Amyl methyl ether (994-05-8) → formaldehyd (50-00-0) + 2-methyl-2-butanol nitrate (21823-36-9) + tert-pentyl formate (757-88-0)

Conditions	Yield
With nitrate radical In gas at -16.1 - 89.9℃; under 750.06 Torr; Mechanism; Kinetics;

tert-Amyl methyl ether (994-05-8) → methanol (67-56-1) + 2-Methyl-1-butene (563-46-2)

Conditions	Yield
aluminosilicate catalyst at 99.9℃; Equilibrium constant; Thermodynamic data; other temp., ΔG0m, ΔS0m, ΔH0m;
With acid at 59.85℃; Equilibrium constant;

tert-Amyl methyl ether (994-05-8) → methanol (67-56-1) + 2-methyl-but-2-ene (513-35-9) + 2-Methyl-1-butene (563-46-2) + 3-Methyl-1-butene (563-45-1)

Conditions	Yield
KU-23 sulfonic acid ion exchange resin at 69.9℃; Equilibrium constant; Product distribution; other temperatures;

tert-Amyl methyl ether (994-05-8) → 2-methyl-but-2-ene (513-35-9)

Conditions	Yield
With methanol; Amberlyst 16 at 49.9℃; under 5250.4 Torr; Equilibrium constant; var. temp.;
With Amberlyst 15 In methanol at 24.85℃; Equilibrium constant; Further Variations:; Temperatures; Decomposition;

tert-Amyl methyl ether (994-05-8) → 2-Methyl-1-butene (563-46-2)

Conditions	Yield
With methanol; Amberlyst 16 at 49.9℃; under 5250.4 Torr; Equilibrium constant; var. temp.;
With Amberlyst 15 In methanol at 24.85℃; Equilibrium constant; Further Variations:; Temperatures; Decomposition;

tert-Amyl methyl ether (994-05-8) → methanol (67-56-1) + 2-methyl-but-2-ene (513-35-9) + propene (187737-37-7) + ethene (74-85-1) + 2-Methyl-1-butene (563-46-2) + isobutene (115-11-7)

Conditions	Yield
With oxygen at 300℃; Mechanism; Rate constant; anti-knock effect; oxidative degradation;

Upstream product

• 186581-53-3 diazomethane 
• 75-85-4 tert-Amyl alcohol 
• 67-56-1 methanol 
• 513-35-9 2-methyl-but-2-ene 
• 563-46-2 2-Methyl-1-butene 
• 1455-13-6 deuteromethanol 
• 90886-05-8 C₃₁H₃₀N⁽¹⁺⁾*BF₄^(1-) 
• 96503-15-0 2,2-dimethyl-1-propyl phenyl selenide 
• 7664-93-9 sulfuric acid 
• 123622-12-8 2-(benzotriazol-1-yl)-2-methoxypropane 
• 563-45-1 3-Methyl-1-butene 
• 123-51-3 i-Amyl alcohol 
• 74-88-4 methyl iodide 
• 90886-07-0 C₃₂H₃₂N⁽¹⁺⁾*BF₄^(1-) 

Downstream Products

• 139553-41-6 2-tert-amyl-5-n-pentadecylphenol 
• 139553-37-0 2-allyl-4,6-di-tert-amylphenol 
• 513-35-9 2-methyl-but-2-ene 
• 563-46-2 2-Methyl-1-butene 
• 67-56-1 methanol 
• 187737-37-7 propene 
• 74-85-1 ethene 
• 115-11-7 isobutene 
• 50-00-0 formaldehyd 
• 79-20-9 acetic acid methyl ester 
• 757-88-0 tert-pentyl formate 
• 75-07-0 acetaldehyde 
• 67-64-1 acetone 
• 181134-54-3 3-methoxy-3-methylbutanal 

Relevant academic research and scientific papers

Kinetics of liquid phase synthesis of tert-amyl methyl ether from tert-amyl alcohol and methanol catalyzed by ion exchange resin

Synthesis of tert-amyl methyl ether (TAME) from methanol (MeOH) and tert-amyl alcohol (TAA) in the liquid phase was studied by using an ion exchange resin, Amberlyst l5 (A15) in the H+ form. Experiments were carried out in a stirred batch reactor under atmospheric pressure. The effects of catalyst size, agitation speed, temperatures, feed ratio and water on the reaction rate were investigated. Both of intraparticle and external diffusion effects could be neglected in this system. The dehydration of TAA could be decreased by increasing the ratio of MeOH/TAA and the reaction rates were greatly inhibited by water. A kinetic model which considered the inhibition of water was proposed. The experimental results agreed well with the model.

Tert-amyl methyl ether preparation method and light gasoline modification method

The invention discloses a tert-amyl methyl ether preparation method and a light gasoline modification method. The tert-amyl methyl ether preparation method comprises that methanol and isopentene contact an etherification catalyst under an etherification reaction condition to obtain the reaction product containing tert-amyl methyl ether, wherein the etherification catalyst is a polymer supported ionic liquid catalyst, and has a structure represented by a formula (I) or a formula (II). With the method of the present inventin, the tert-amyl methyl ether preparation reaction can maintain the highreactivity.

Preparation of a novel sulfonated carbon catalyst for the etherification of isopentene with methanol to produce tert-amyl methyl ether

A novel method for the preparation of acid carbon catalyst from glucose and 4-hydroxybenzenesulfonic acid (p-HBSA) was reported. Glucose was first hydrolyzed to hydroxymethylfurfural that reacted with p-HBSA (a phenol compound) to form a phenolic (PF)-like resin containing -SO3H groups. The resin was carbonized and sulfonated further in concentrated sulfuric acid at 443 K to form an amorphous carbon material with a surface area of 22 m2/g. This acidic carbon contained 3.1 mmol/g of strong surface acid sites (-SO3H), and thus exhibited good catalytic activity for the etherification of isopentene with methanol to produce tert-amyl methyl ether.

Multistage catalytic process for olefin etherification

A process for producing ethers by reacting alcohols and olefins in successive catalytic stages is disclosed. The process includes alternating catalytic reaction stages and separation stages.

In situ 13C DEPT-MRI as a tool to spatially resolve chemical conversion and selectivity of a heterogeneous catalytic reaction occurring in a fixed-bed reactor

The distortionless enhancement by polarisation transfer (DEPT) nuclear magnetic resonance (NMR) technique, combined with magnetic resonance imaging (MRI), has been used to provide the first in situ spatially-resolved and quantitative measurement of chemical conversion and selectivity within a fixed-bed reactor using natural abundance 13C NMR. The Royal Society of Chemistry 2005.

Development of a novel mesoporous catalyst UDCaT-6: Kinetics of synthesis of tert-amyl methyl ether (TAME) from tert-amyl alcohol and methanol

UDCaT-6, a novel active mesoporous and stable catalyst, was synthesized by generating in situ nanosized acidic centers of chlorosulfonic acid treated zirconia in the pores of highly ordered hexagonal mesoporous silica (HMS). For the first time, we have used chlorosulfonic acid as a source of sulfating agent to treat zirconia in pores of the HMS. The catalyst is characterized by XRD, FTIR, EDAX, SEM, and BET surface area and pore size analysis, and probe reactions. The structural integrity of HMS is maintained in UDCaT-6. The activity and stability of UDCaT-6 was tested in liquid phase alkylation of toluene with benzyl chloride and vapor phase synthesis of tert-amyl methyl ether (TAME) from ferf-amyl alcohol (TAA) and methanol where corrosive acid HCl and water are generated as biproducts. A complete theoretical and experimental analysis is presented and kinetics are evaluated. The model explains the experimental data very well.

Sorption, acid, and catalytic properties of a sulfonic cation exchanger supported on the carbon fiber

Distribution in strength of the acid centers in sulfonic cation in the form of exchanger granules and fibers was studied by the novel modification of the thermal desorption method.

Synthesis of methyl tert-amyl ether in the presence of a fibrous sulfonated cation exchanger

The influence of exchange capacity of the fibrous sulfonated cation exchanger FIBAN K-1 and the main process parameters of iso-amyl methyl ether production on the yield of the desired product was examined. It was shown that, under the experimental conditions (temperature 60-100°C, the feed weight hour space velocity 2-6 g/(gcath), and CH3OH to iso-C5H10 molar ratio 1: 2), 2-methyl-1-butene can transform into 2-methyl-2-butene, and 3-methyl-1-butene almost does not isomerize and remains uninvolved in the ether synthesis. At a temperature of 80°C and above, the fibrous sulfonated cation exchanger is superior to the beaded resin in activity.

Etherification of tert-amyl alcohol with methanol over ion-exchange resin

tert-Amyl methyl ether (TAME) is a proven high octane additive. The synthesis of tert-amyl methyl ether from tert-amyl alcohol and methanol has been carried out in the presence of a variety of solid acid catalysts. Amberlyst-36 was found to be very effective in comparison with other solid acids. A complete theoretical and experimental analysis is presented for the model studies of tert-amyl alcohol with methanol. The parallel reactions of tert-amyl alcohol adsorbed on the sites were found to control the overall rate of reaction, which led to the formation of TAME, 2-methyl-1-butene (2MB1), and 2-methyl-2-butene (2MB2). The reaction follows pseudo-first-order kinetics at a fixed catalyst loading. The individual rate constants for the formation of TAME, 2MB1, and 2MB2 were also evaluated from the same data.

Tert-amyl methyl ether (TAME). Thermodynamic analysis of reaction equilibria in the liquid phase

Ethers obtained from C5 olefin streams provide a good mix of octane-enhancing and CO-reducing qualities. They are considered as a replacement for the more common isobutylene-derived fuel additives, e.g., MTBE. Data on the thermodynamic reaction equilibria for the synthesis of TAME, which is produced from the etherification reaction of 2-methyl-1-butylene and 2-methyl-2-butylene with methanol, were computed by studying TAME decomposition in a recirculating batch reactor at different temperatures with activity coefficients obtained using the UNIFAC method. A comparison of experimental data and theoretical predictions showed the possibility of erroneous values reported in the literature for the standard Gibbs free energy of TAME formation. Expressions for the thermodynamic equilibrium constants as a function of temperature were developed. A corrected value for the Gibbs free energy of formation for TAME was also provided.