14458-05-0

Basic information

• Product Name: TETRAMETHYLTEREPHTHALIC ACID
• Synonyms: 2,3,5,6-tetramethylterephthalic acid;1,4-Benzenedicarboxylic acid, 2,3,5,6-tetramethyl-
• CAS NO: 14458-05-0
• Molecular Formula: C₁₂H₁₄O₄
• Molecular Weight: 222.23716
• Mol File: 14458-05-0.mol
• Article Data: 7

Chemical Properties

• Boiling Point: 402.6°Cat760mmHg
• Flash Point: 211.4°C
• Appearance: /
• Density: 1.237g/cm³
• Vapor Pressure: 3.33E-07mmHg at 25°C
• Refractive Index: 1.575
• PKA: 2.89±0.38(Predicted)
• CAS DataBase Reference: TETRAMETHYLTEREPHTHALIC ACID(CAS DataBase Reference)
• NIST Chemistry Reference: TETRAMETHYLTEREPHTHALIC ACID(14458-05-0)
• EPA Substance Registry System: TETRAMETHYLTEREPHTHALIC ACID(14458-05-0)

Safety Data

• Hazardous Substances Data: 14458-05-0(Hazardous Substances Data)

Usage

General Description

Tetramethylterephthalic acid is a chemical compound with the molecular formula C12H14O4. It is a derivative of terephthalic acid and is a white crystalline solid at room temperature. TETRAMETHYLTEREPHTHALIC ACID is used primarily as a monomer in the production of high-performance polymers and plastics, such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). Tetramethylterephthalic acid is also used as an intermediate in the synthesis of organic compounds and as a precursor to various dyes and pigments. Its unique molecular structure and properties make it a versatile and valuable chemical in the manufacturing and chemical industries.

InChI:InChI=1/C12H14O4/c1-5-6(2)10(12(15)16)8(4)7(3)9(5)11(13)14/h1-4H3,(H,13,14)(H,15,16)

Synthetic route

2,3,5,6-tetramethyl-p-xylene-α,α'-diol (7522-62-5) → 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0)

Conditions	Yield
With chromium(VI) oxide; sulfuric acid In water; acetone at 0 - 20℃;	84%
With chromium(VI) oxide; sulfuric acid In water; acetone at 0 - 20℃;	16%
With chromium(VI) oxide; sulfuric acid
With chromium(VI) oxide; hydrogenchloride; sulfuric acid In water

carbon dioxide (124-38-9) + Potassium benzoate (582-25-2) → terephthalic acid (100-21-0) + 2-methylterephthalic acid (5156-01-4) + 2,5-dimethylterephthalic acid (6051-66-7) + 2,3,5-trimethyl-1,4-dicarboxybenzene (18087-49-5) + 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0)

Conditions	Yield
With potassium acetate; potassium phthalate; zinc(II) oxide at 450℃; under 25858.1 Torr; Henkel Reaction;	A 50% B n/a C n/a D n/a E n/a

2,3,5,6-tetramethyl-1,4-benzenedicarboxaldehyde (7072-01-7) → 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0)

Conditions	Yield
With potassium permanganate

2,2-dimethylvaleroyl chloride (15721-22-9) + 2,3,5,6-tetramethyl-p-xylene-α,α'-diol (7522-62-5) → 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0)

Conditions	Yield
With sulfuric acid In water; acetone

carbon dioxide (124-38-9) + 1,4-dibromodurene (1646-54-4) → 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0)

Conditions	Yield
Stage #1: 1,4-dibromodurene With tert.-butyl lithium In diethyl ether at -78 - 20℃; Inert atmosphere; Stage #2: carbon dioxide In diethyl ether at -78℃; for 0.5h; Stage #3: With hydrogenchloride In diethyl ether; water

1,2,4,5-tetramethylbenzene (95-93-2) → 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: sodium chloride; hydrogenchloride / water / 5 h / 120 °C 1.2: 24 h / Reflux 2.1: acetic acid; potassium acetate / 24 h / 120 °C 3.1: potassium hydroxide / ethanol / 24 h / 90 °C 4.1: chromium(VI) oxide; sulfuric acid / water; acetone / 0 - 20 °C View Scheme
Multi-step reaction with 4 steps 1: sodium chloride; zinc(II) chloride; hydrogenchloride / water / 120 °C 2: potassium acetate / 120 °C 3: ethanol; potassium hydroxide / 90 °C 4: chromium(VI) oxide; sulfuric acid; hydrogenchloride / water View Scheme
Multi-step reaction with 4 steps 1: sodium chloride; hydrogenchloride / water / 31 h / 120 °C 2: acetic acid / 24 h / 120 °C 3: potassium hydroxide; water / tetrahydrofuran; ethanol / 24 h / 90 °C 4: chromium(VI) oxide; sulfuric acid / water; acetone / 0 - 20 °C View Scheme

1,4-bis(chloromethyl)-2,3,5,6-tetramethylbenzene (3022-16-0) → 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: acetic acid; potassium acetate / 24 h / 120 °C 2: potassium hydroxide / ethanol / 24 h / 90 °C 3: chromium(VI) oxide; sulfuric acid / water; acetone / 0 - 20 °C View Scheme
Multi-step reaction with 3 steps 1: potassium acetate / 120 °C 2: ethanol; potassium hydroxide / 90 °C 3: chromium(VI) oxide; sulfuric acid; hydrogenchloride / water View Scheme
Multi-step reaction with 3 steps 1: acetic acid / 24 h / 120 °C 2: potassium hydroxide; water / tetrahydrofuran; ethanol / 24 h / 90 °C 3: chromium(VI) oxide; sulfuric acid / water; acetone / 0 - 20 °C View Scheme

(2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene) diacetate (1447-10-5) → 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: ethanol; potassium hydroxide / 90 °C 2: chromium(VI) oxide; sulfuric acid; hydrogenchloride / water View Scheme

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + nickel(II) nitrate hexahydrate + terephthalic acid (100-21-0) + 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) → Ni(BDC)0.8(TMBDC)0.2(1,4-diazabicyclo[2.2.2]octane)0.5

Conditions	Yield
In N,N-dimethyl-formamide at 120℃; for 48h;	86%

2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) + cesium chloride + K(2 - x)(NMe4)x[I2Mo10O10S10(OH)10(H2O)5]·20H2O → Cs1.9(NMe4)0.1[Mo12O12S12(OH)12(H2O)2TMT]·21H2O

Conditions	Yield
Stage #1: 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid; K(2 - x)(NMe4)x[I2Mo10O10S10(OH)10(H2O)5]·20H2O With potassium hydroxide In water at 50℃; for 0.5h; pH=4.5; Stage #2: cesium chloride In water at 20℃;	83%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + nickel(II) nitrate hexahydrate + terephthalic acid (100-21-0) + 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) → Ni(BDC)0.55(TMBDC)0.45(1,4-diazabicyclo[2.2.2]octane)0.5

Conditions	Yield
In N,N-dimethyl-formamide at 120℃; for 48h;	80%

potassium permanganate (7722-64-7) + 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) + manganese (II) acetate tetrahydrate (6156-78-1) → O(2-)*3H2O*3C12H12O4(2-)*2Mn(3+)*Mn(2+)

Conditions	Yield
With acetic acid In N,N-dimethyl-formamide at 45℃;	80%

cobalt(II) chloride hexahydrate + tris(4-(pyridin-4-yl) phenyl) amine (1366291-62-4) + 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) → [Co(tris(4-(pyridin-4-yl)phenyl)amine)(2,3,5,6-tetramethyl-1,4-benzenedicarboxylate)]n

Conditions	Yield
In methanol; N,N-dimethyl-formamide at 60℃; for 48h;	77%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + nickel(II) nitrate hexahydrate + terephthalic acid (100-21-0) + 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) → Ni(BDC)0.29(TMBDC)0.71(DABCO)0.5

Conditions	Yield
In N,N-dimethyl-formamide at 120℃; for 48h;	73%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + nickel(II) nitrate hexahydrate + 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) → Ni(TMBDC)(1,4-diazabicyclo[2.2.2]octane)0.5

Conditions	Yield
In N,N-dimethyl-formamide at 120℃; for 48h;	68%

K(2-x)(NMe4)(x)[I2Mo10O10S10(OH)10(H2O)5*20H2O + 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) + tetramethlyammonium chloride (75-57-0) + potassium hydroxide → (NMe4)2[Mo12O12S12(OH)12(tetramethylterephthalate)(H2O)2]*17H2O

Conditions

Yield

With HCl In water aq. soln. of KOH (0.34 mmol) was added to a suspn. of H2TMT (0.17 mmol) in H2O; the soln. was added to a suspn. of Mo-contg. compd. (0.21 mmol) in H2O; pH=4.5 (HCl or KOH addn.); the mixt. was heated to 50°C for 15 min; NMe4Cl (0.45 mmol) addn.; the mixt. was slowly evapd. in air and clarified by centrifugation; after 1 d crystals were obtained, isolated by filtration, washed by water and dried in air; elem. anal.;

57%

zinc(II) nitrate hexahydrate + 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → Zn(2,3,5,6-tetramethyl-1,4-benzenedicarboxylate)*H2O*(N,N-dimethylformamide)

Conditions	Yield
In ethanol; N,N-dimethyl-formamide Zn-contg. compd. (0.07 mmol) and a ligand (0.045 mmol) were suspended ina mixed solvent of DMF and EtOH and heated in an unsealed glass bottle at 75°C for 2 d; crystals were collected, washed with EtOH and dried in the air;	56%

zinc(II) nitrate hexahydrate + 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) → Zn(2,3,5,6-tetramethyl-1,4-benzenedicarboxylate)

Conditions	Yield
In ethanol; water High Pressure; Zn-contg. compd. (0.07 mmol) and a ligand (0.045 mmol) were suspended ina mixed solvent of H2O and EtOH and heated in a teflon-lined steel bomb at 140°C for 3 d; crystals were collected, washed with water and dried in the air; elem. anal.;	54%

manganese(II) nitrate + 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → [Mn(tetramethylterephthalic acid(-2H))(dimethylformamide)]n (1444309-45-8)

Conditions	Yield
In ethanol; water at 90℃; for 66.6667h; Heating;	48%

2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) → 1,4,5,6,7,8-hexahydro-naphthalene-2,3-dicarboxylic acid (100118-02-3)

Conditions	Yield
With potassium hydroxide

2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) + Z-L-phenylalanyl-L-alanyl bromomethyl ketone (115186-22-6) → N-(benzyloxycarbonyl)-L-phenylalanyl-L-alanyl<(2,3,5,6-tetramethyl-4-carboxybenzoyl)oxy>methyl ketone + 2,3,5,6-Tetramethyl-terephthalic acid bis-[(S)-3-((S)-2-benzyloxycarbonylamino-3-phenyl-propionylamino)-2-oxo-butyl] ester

Conditions	Yield
With potassium fluoride 1.) DMF, RT, 3 min, 2.) DMF, RT, 3 h; Yield given. Multistep reaction. Yields of byproduct given;

2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) + chromium (7440-47-3) → Cr(3+)*OH(1-)*O2CC6(CH3)4CO2(2-)*99H2O = Cr(OH)[O2CC6(CH3)4CO2]*99H2O

Conditions	Yield
With HF; H2O In water High Pressure; Cr:2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid:HF:H2O = 1:1:1:280, stirred, autoclaved at 493 K for 4 d;

zinc(II) nitrate hexahydrate + 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → Zn(2,3,5,6-tetramethyl-1,4-benzenedicarboxylate)(H2O)1.5(N,N'-dimethylformamide)0.5(N,N'-dimethylformamide)(H2O)

Conditions	Yield
With trimethylamine In N,N-dimethyl-formamide; chlorobenzene slow diffusion of chlorobenzene-trimethylamine mixt. (700:1 v/v) into soln. of Zn(NO3)2*6H2O and 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (1 equiv.) in DMF-chlorobenzene; room temp.; 4-7 d; elem. anal.;

zinc(II) nitrate hexahydrate + 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) → Zn4O(TMBDC)3

Conditions	Yield
In N,N-dimethyl-formamide dissolving of 2,3,5,6-tetramethylbenzene-1,4-dicarboxylic acid and Zn(NO3)2*6H2O in DMF; heating at 70°C for 48 h;

Tm(3+)*3NO3(1-)*3H2O=Tm(NO3)3*3H2O + 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → Tm2(2,3,5,6-tetramethyl-1,4-benzenedicarboxylate)3(dimethylformamide)2(H2O)2*4H2O

Conditions	Yield
In ethanol; water; N,N-dimethyl-formamide High Pressure; solvothermal reaction of 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid and Tm(NO3)2*3H2O in DMF/EtOH/H2O;

1,10-Phenanthroline (66-71-7) + erbium(III) chloride hexahydrate + 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → Er2(2,3,5,6-tetramethyl-1,4-benzenedicarboxylate)3(1,10-phenanthroline)2*4(dimethylformamide)*2H2O

Conditions	Yield
In ethanol; water; N,N-dimethyl-formamide High Pressure; solvothermal reaction of 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid, 1,10-phenanthroline, and ErCl3*6H2O in DMF/EtOH/H2O;

iron(III) chloride hexahydrate + 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) → MIL-88B-4CH3(Fe) (X=OH)

Conditions	Yield
With sodium hydroxide In water; N,N-dimethyl-formamide at 100℃; for 12h;

2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) → 2,3,5,6-tetramethylterephthaloyl dichloride

Conditions	Yield
With thionyl chloride Inert atmosphere; Reflux;	3.5 g

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + zinc(II) nitrate hexahydrate + terephthalic acid (100-21-0) + 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) → 0.5C8H4O4(2-)*Zn(2+)*0.5C6H12N2*0.5C12H12O4(2-)

Conditions	Yield
In N,N-dimethyl-formamide at 120℃;

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + zinc(II) nitrate hexahydrate + 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) → Zn(1,4-diazabicyclo[2.2.2]octane)0.5(2,3,5,6-tetramethyl-1,4-benzenedicarboxylate)

Conditions	Yield
In N,N-dimethyl-formamide at 120℃;
In ethanol; N,N-dimethyl-formamide at 20 - 120℃; for 50 - 51h; High pressure;

4,4'-bipyridine (553-26-4) + zinc(II) nitrate hexahydrate + 2,3,5,6-tetramethyl-1,4-benzenedicarboxylic acid (14458-05-0) → Zn(1,4-diazabicyclo[2.2.2]octane)0.5(2,3,5,6-tetramethyl-1,4-benzenedicarboxylate)

Conditions	Yield
In N,N-dimethyl-formamide at 20 - 120℃; for 51h;

Upstream product

• 7072-01-7 2,3,5,6-tetramethyl-1,4-benzenedicarboxaldehyde 
• 1447-10-5 (2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene) diacetate 
• 3022-16-0 1,4-bis(chloromethyl)-2,3,5,6-tetramethylbenzene 
• 95-93-2 1,2,4,5-tetramethylbenzene 
• 124-38-9 carbon dioxide 
• 1646-54-4 1,4-dibromodurene 
• 15721-22-9 2,2-dimethylvaleroyl chloride 
• 7522-62-5 2,3,5,6-tetramethyl-p-xylene-α,α'-diol 
• 582-25-2 Potassium benzoate 

Downstream Products

• 1444309-45-8 [Mn(tetramethylterephthalic acid(-2H))(dimethylformamide)]_n 

Relevant articles and documents

Tuning the electrocatalytic hydrogen evolution reaction promoted by [Mo2O2S2]-based molybdenum cycles in aqueous medium

We report the syntheses and characterizations, in the solid state and in solution, of three new cyclic polyoxothiomolybdates self-assembled around 2,5-dimethylterephthalate (DMT) and 2,5-bis(trifluoromethyl)terephthalate (DFMT) ligands, namely [Mo12DMT]2-, [Mo12DFMT] 2- and [Mo16DFMT]2-. A series of these two Mo12-compounds completed by the two Mo12-compounds obtained with 2,3,5,6-tetramethylterephthalate and trimesate ligands offer the opportunity to compare their electro-catalytic properties for reduction of protons into hydrogen. The ability of these compounds to promote the reduction of protons into hydrogen in aqueous medium is evidenced and the influence of the embedded ligand is highlighted, thus allowing proposal of a mechanism for the hydrogen evolution reaction catalyzed by these clusters.

Pore environment engineering in metal-organic frameworks for efficient ethane/ethylene separation

Selective adsorption of trace amounts of C2H6 from bulk C2H4 is a significantly important and extremely challenging task in industry, which requires an adsorbent with specific pore properties. Herein, we describe a strategy for adjusting the pore environment of metal-organic frameworks (MOFs) by introducing different amounts of methyl groups in the channel to enhance the guest-host interaction between C2H6 and the framework. To prove this concept, 2,3,5,6-tetramethylterephthalic acid (TMBDC) was deliberately added to a microporous MOF, Ni(BDC)(DABCO)0.5, affording a series of mixed-ligand materials, Ni(BDC)1-x(TMBDC)x(DABCO)0.5 (x = 0, 0.2, 0.45, 0.71, 1), having different pore environments. Significantly, these mixed-ligand materials demonstrated improved performance in terms of the adsorption capacity of C2H6 and C2H4 with an unprecedented C2H6 uptake of 2.21 mmol g-1 for Ni(TMBDC)(DABCO)0.5 at 0.0625 bar and 298 K. With the best theoretical C2H6/C2H4 selectivity predicted by IAST, Ni(TMBDC)(DABCO)0.5 exhibited effective separation of C2H6/C2H4 (1/15, v/v) and great recyclability in five consecutive adsorption/desorption cycles throughout the breakthrough experiment.

ALKYL CARBOXYLATE SALTS AS SOLVENTS FOR HENKEL-RELATED PROCESSES

Disclosed is the use of one or more molten salts or a mixture thereof for use as a reaction medium in a process for the preparation of an aromatic diacid which comprises heating an alkali metal salt of an aromatic monocarboxylic acid or asymmetrical aromatic dicarboxylic acid under pressure with carbon dioxide gas in the presence of a catalyst at suitable reaction conditions. The molten salt reaction medium provides advantages in a disproportionation reaction to produce, for example, purified terephthalic acid. In another aspect of the invention, novel methylated diacids are produced.