652-03-9

Basic information

• Product Name: Tetrafluorophthalic acid
• Synonyms: 1,2-Benzenedicarboxylic acid, 3,4,5,6-tetrafluoro-;RARECHEM AL BO 0016;TETRAFLUOROPHTHALIC ACID;3,4,5,6-TETRAFLUOROBENZENE-1,2-DICARBOXYLIC ACID;3,4,5,6-TETRAFLUOROPHTHALIC ACID;2,3,4,5-TETRAFLUORO-PHTHALIC ACID;TETRAFLUOROPHTHALIC ACID 90%;Tetrafluorophthalicacid,97%
• CAS NO: 652-03-9
• Molecular Formula: C8H2F4O4
• Molecular Weight: 238.09
• EINECS: 211-483-4
• Product Categories: Phthalic Acids, Esters and Derivatives;API intermediates;Carboxylic Acid Monomers;Monomers;Polymer Science
• Mol File: 652-03-9.mol
• Article Data: 22

Chemical Properties

• Melting Point: 152-154 °C(lit.)
• Boiling Point: 345.7 °C at 760 mmHg
• Flash Point: 162.9 °C
• Appearance: White to light yellow crystal powder
• Density: 1.6239 (estimate)
• Vapor Pressure: 2.3E-05mmHg at 25°C
• Storage Temp.: Sealed in dry,Room Temperature
• Solubility: almost transparency in Methanol
• PKA: 1.28±0.10(Predicted)
• BRN: 2057012
• CAS DataBase Reference: Tetrafluorophthalic acid(CAS DataBase Reference)
• NIST Chemistry Reference: Tetrafluorophthalic acid(652-03-9)
• EPA Substance Registry System: Tetrafluorophthalic acid(652-03-9)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38-37/38-36
• Safety Statements: 26-37/39
• WGK Germany: 3
• HazardClass: IRRITANT
• Hazardous Substances Data: 652-03-9(Hazardous Substances Data)

Usage

Chemical Properties

White to light yellow crystal powder

Uses

Tetrafluorophthalic Acid, can be used as a starting material in the synthesis of various chemical compounds such as Perfluoroanthracene (P227605), a perfluorinated graded index polymer optical fiber (PFGI-POF) component.

InChI:InChI=1/C8H2F4O4/c9-3-1(7(13)14)2(8(15)16)4(10)6(12)5(3)11/h(H,13,14)(H,15,16)/p-2

Synthetic route

N-methyl-tetrafluorophthalimide (33795-85-6) → 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
With sulfuric acid; benzyltriethylammonium bromide at 45 - 50℃; for 15h; Temperature;	95.7%

octafluoro-1,3-dihydroisobenzofuran (122180-11-4) → 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
With sulfuric acid for 3h; Heating;	94%

tetrafluoro-N-phenylphthalimide → 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
With sulfuric acid; cetyltrimethylammonim bromide at 110℃; for 8h;	88.6%
With sulfuric acid In water	67%

perfluorobenzocyclobutenedione (59514-37-3) → 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
Stage #1: perfluorobenzocyclobutenedione With bromine at 130℃; for 17.5h; Stage #2: With hydrogenchloride for 120h; Further stages.;	86%
Stage #1: perfluorobenzocyclobutenedione With antimony pentafluoride at 130℃; for 4.5h; Stage #2: With hydrogenchloride Further stages.;	70%

perfluorobenzocyclobutene (52196-63-1) → perfluorobenzocyclobutenedione (59514-37-3) + 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
Stage #1: perfluorobenzocyclobutene With antimony pentafluoride; silica gel at 70℃; for 5h; Stage #2: With hydrogenchloride Further stages.;	A 86% B 7%

perfluorobenzocyclobutene (52196-63-1) → 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
With antimony pentafluoride; trifluoroacetic acid at 95℃; for 28h;	85%

4,5,6,7-tetrafluoroisobenzofuran-1,3-dione (652-12-0) → 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
In water	82%
With hydrogenchloride In water

hexachloro-phthalide (34973-43-8) → 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
With hydrogenchloride; potassium fluoride In tetrahydrofuran; sulfolane	81%

carbon monoxide (201230-82-2) + perfluorobenzocyclobutenone (59514-38-4) → 3,4,5,6-tetrafluorophthalic acid (652-03-9) + perfluoro-1H-isochromen-1-one

Conditions	Yield
Stage #1: carbon monoxide; perfluorobenzocyclobutenone With antimony pentafluoride at 20℃; under 760.051 Torr; for 3h; Stage #2: With hydrogenchloride; water at 0℃;	A 10 %Spectr. B 67%

octafluoronaphthalene (313-72-4) → 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
With dihydrogen peroxide In acetonitrile at 60℃; for 6h;	65%
With nitric acid

Perfluoro(1-ethylindan) (98583-34-7) → perfluoro(3-methyl-1-oxoisochromene-4-carboxylic acid) (1025071-73-1) + 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
Stage #1: perfluoro-1-ethylindane With antimony pentafluoride; silica gel at 90 - 130℃; for 13h; Stage #2: With hydrogenchloride Further stages.;	A 39% B 36%

perfluorobenzocyclobutenone (59514-38-4) → 6-trifluoromethyl-2,3,4,5-tetrafluorobenzoic acid (157337-86-5) + perfluoro-2-acetyl-2'-methylbenzophenone (1105698-74-5) + 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
Stage #1: perfluorobenzocyclobutenone With antimony pentafluoride at 120℃; for 6.5h; Stage #2: With hydrogenchloride Further stages.;	A 18% B 16% C 0.35 g

perfluorobenzocyclobutene (52196-63-1) + trifluoroacetic anhydride (407-25-0) → 3,4,5,6-tetrafluorophthalic acid (652-03-9) + perfluoro-1H-isochromen-1-one

Conditions	Yield
Stage #1: perfluorobenzocyclobutene; trifluoroacetic anhydride With antimony pentafluoride at 20℃; for 75h; Sealed tube; Stage #2: With hydrogenchloride; water at 0℃;	A 14% B n/a

hexafluoro-1,4-naphthoquinone (1024-60-8) → 2-hydroxy-3,5,6,7,8-pentafluoro-1,4-naphthoquinone (20927-18-8) + 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
With dihydrogen peroxide In acetonitrile at 80℃; for 20h; Mechanism;	A 0.25 g B 0.33 g

octafluoronaphthalene (313-72-4) → 2-hydroxy-3,5,6,7,8-pentafluoro-1,4-naphthoquinone (20927-18-8) + 2,3,4,5-tetrafluorobenzoic acid (1201-31-6) + 3,4,5,6-tetrafluorophthalic acid (652-03-9) + 2-(heptafluoronaphthalen-1-yloxy)pentafluoro-1,4-naphthoquinone (34283-00-6) + 2,3,4,5-tetrafluoro-6-(fluoromethyl)phenylglyoxylic acid (69472-72-6) + 1-oxoperfluoro-1,2-dihydronaphthalene (93343-13-6)

Conditions	Yield
With dihydrogen peroxide In acetonitrile at 100℃; for 30h; Product distribution; Mechanism; var. conc.;	A 0.38 g B 0.30 g C 0.65 g D 0.05 g E 0.21 g F 0.30 g

1-perfluoronaphthol (5386-30-1) → hexafluoro-1,4-naphthoquinone (1024-60-8) + 2-hydroxy-3,5,6,7,8-pentafluoro-1,4-naphthoquinone (20927-18-8) + 2,3,4,5-tetrafluorobenzoic acid (1201-31-6) + 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
With dihydrogen peroxide In acetonitrile at 80℃; for 20h; Product distribution; Mechanism; var. conc., var. temp.;	A 0.94 g B 0.21 g C 0.24 g D 1.02 g

1,3,4,5,6,7,8-heptafluoro-2-naphthol (727-49-1) → 2,3,4,5-tetrafluorobenzoic acid (1201-31-6) + 3,4,5,6-tetrafluorophthalic acid (652-03-9) + 2,3,4,5-tetrafluoro-6-(fluoromethyl)phenylglyoxylic acid (69472-72-6)

Conditions	Yield
With dihydrogen peroxide In acetonitrile at 100℃; for 30h; Product distribution; Mechanism; var. conc., var. temp.;	A 0.36 g B 1.32 g C 0.24 g

Tetrafluorophthalonitrile (1835-65-0) → 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
(hydrolysis);
In water
hydrolysis;
hydrolysis;
With sodium hydroxide; zinc

[1S(R),4S(R)]-5,6,7,8-tetrafluoro-1,4-dihydro-1,4-ethenonaphthalene → 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
With potassium permanganate In acetone

1,3-Dihydroxyhexafluornaphthalin (41481-27-0) → 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
With nitric acid Heating;

3,4,5,6,7,8-Hexafluoro-4-nitro-4H-naphthalen-1-one (27041-18-5) → 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
With nitric acid

perfluoroindane (1736-47-6) → 4,5,6,7-tetrafluoro-3-hydroxy-3-trifluoromethyl-2-benzofuran-1-one + 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
With antimony pentafluoride; silica gel at 85 - 180℃; for 9h; Title compound not separated from byproducts;

hexafluoro-1,3-indanedione (58161-60-7) → perfluoro(3-methylphthalide) + 4,5,6,7-tetrafluoro-3-hydroxy-3-trifluoromethyl-2-benzofuran-1-one + 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
With antimony pentafluoride at 130℃; for 2h;

perfluoroindane (1736-47-6) → 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: 34 percent / SiO2; SbF5 / 4.5 h / 70 - 75 °C 2: SbF5 / 2 h / 130 °C View Scheme

4,5,6,7-tetrachloro-1,1,3,3-tetrafluoro-1,3-dihydroisobenzofuran (20687-94-9) → 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: 92 percent / potassium fluoride / tetrahydrothiophene 1,1-dioxide / 1.5 h / 210 - 220 °C 2: 94 percent / sulphuric acid / 3 h / Heating View Scheme

1,3,4,5,6,7,8-heptafluoronaphthalene (784-00-9) → 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: HNO3 / -10 °C 2: HNO3 View Scheme

benzene (71-43-2) + (+-)-pentane-1,4-diol → 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
Multi-step reaction with 2 steps 2: aq. KMnO4 / acetone View Scheme

1,2-dibromo-3,4,5,6-tetrafluorobenzene (827-08-7) → 3,4,5,6-tetrafluorophthalic acid (652-03-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: 160 - 170 °C 2: (hydrolysis) View Scheme

dmap (1122-58-3) + trimethylsilyl trifluoromethanesulfonate (27607-77-8) + 3,4,5,6-tetrafluorophthalic acid (652-03-9) → 2,3,4,5-tetrakis[4-(dimethylamino)-1-pyridinio]benzoic acid tetrakis(trifluoromethanesulfonate)

Conditions	Yield
In chlorobenzene for 24h; Heating;	99%

3,4,5,6-tetrafluorophthalic acid (652-03-9) → 2,3,4,5-tetrafluorobenzoic acid (1201-31-6)

Conditions	Yield
With ammonium hydroxide at 180℃; for 2.5h; Autoclave; Green chemistry;	97.2%
With ammonia at 179.99℃; for 1h; pH=1.94; Temperature;	90%
In tributyl-amine at 130℃; for 4h;	81.6%

3,4,5,6-tetrafluorophthalic acid (652-03-9) → 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione (652-12-0)

Conditions	Yield
With thionyl chloride at 90℃; for 14h;	97%
With thionyl chloride	94%
With acetyl chloride

3,4,5,6-tetrafluorophthalic acid (652-03-9) → 4-amino-3,5,6-trifluorophthalic acid (169542-84-1)

Conditions	Yield
With ammonia at 110℃; for 100h; Autoclave;	95%

pentaphenylphosphorane (2588-88-7) + 3,4,5,6-tetrafluorophthalic acid (652-03-9) → bis(tetraphenylphosphonium) tetrafluorophthalate

Conditions	Yield
With water In benzene at 20 - 80℃;	95%

3,4,5,6-tetrafluorophthalic acid (652-03-9) → 3,4,5,6-tetrafluorophthaloyl dichloride (14900-74-4)

Conditions	Yield
With phosphorus pentachloride at 180℃; for 2h;	94%
With thionyl chloride; N,N-dimethyl-formamide for 18h; Heating;
With thionyl chloride; N,N-dimethyl-formamide for 24h; Inert atmosphere; Schlenk technique; Reflux;
With thionyl chloride for 48h; Schlenk technique; Reflux;

dibutyl ether (142-96-1) + 3,4,5,6-tetrafluorophthalic acid (652-03-9) → 2,3,4,5-tetrafluorobenzoic acid (1201-31-6)

Conditions	Yield
With sulfuric acid; dimethyl sulfoxide; triethylamine In water; toluene	94%

3,4,5,6-tetrafluorophthalic acid (652-03-9) + 1,1,1,3,3,3-hexamethyl-disilazane (999-97-3) → bis(trimethylsilyl) 3,4,5,6-tetrafluorophthalate

Conditions	Yield
In neat (no solvent) at 110 - 120℃; for 2h; Inert atmosphere;	93%

3,4,5,6-tetrafluorophthalic acid (652-03-9) + recorcinol (108-46-3) → 4,5,6,7-tetrafluoro-7a-(6'-hydroxy-3'-oxo-3H-xanthen-9'-yl)benzoic acid

Conditions	Yield
With methanesulfonic acid at 90℃; for 48h;	91%

3,4,5,6-tetrafluorophthalic acid (652-03-9) → 2,4,5-trifluoro-3-hydroxybenzoic acid (116751-24-7)

Conditions	Yield
Stage #1: 3,4,5,6-tetrafluorophthalic acid With sodium hydroxide In water at 90℃; for 9h; Stage #2: With hydrogenchloride; tri-n-propylamine In water at 140℃; under 7500.75 Torr; for 7h; pH=1; Temperature;	90.35%

3,4,5,6-tetrafluorophthalic acid (652-03-9) → 1,2,3,4-tetrafluorobenzene (551-62-2)

Conditions	Yield
With ammonium hydroxide at 250℃; for 0.416667h; Temperature; Time; Autoclave; Green chemistry;	90.1%

3,4,5,6-tetrafluorophthalic acid (652-03-9) → 1,2,3,4-tetrafluorobenzene (551-62-2) + 2,3,4,5-tetrafluorobenzoic acid (1201-31-6)

Conditions	Yield
With ammonium hydroxide at 190℃; for 2h; Temperature; Time; Autoclave; Green chemistry;	A 10.5% B 86.1%
With ammonium hydroxide at 240℃; for 0.666667h; Temperature; Time; Autoclave; Green chemistry;	A 82% B 8.1%

3,4,5,6-tetrafluorophthalic acid (652-03-9) + isopropylamine (75-31-0) → isopropylammonium tetrafluorohydrogenphthalate (1187587-72-9)

Conditions	Yield
In water at 20℃; for 0.166667h;	84%

3,4,5,6-tetrafluorophthalic acid (652-03-9) + N1-methylbenzene-1,2-diamine hydrochloride (81684-80-2) → 2-(2,3,4,5-tetrafluoro-6-(1-methyl-1H-benzo[d]imidazol-2-yl)phenyl)-1-methyl-1H-benzo[d]imidazole

Conditions	Yield
Stage #1: N1-methylbenzene-1,2-diamine hydrochloride With polyphosphoric acid at 80 - 85℃; for 0.25h; Green chemistry; Stage #2: 3,4,5,6-tetrafluorophthalic acid With polyphosphoric acid at 80 - 150℃; Green chemistry;	84%

3,4,5,6-tetrafluorophthalic acid (652-03-9) → 3,4,5,6-Tetrafluoro-cyclohexa-3,5-diene-1,2-dicarboxylic acid

Conditions	Yield
With sulfuric acid In 1,4-dioxane at 25℃; electroreduction (divided cells, lead plates, 0.20 A);	83%

3,4,5,6-tetrafluorophthalic acid (652-03-9) + 3, 5-dinitroaniline (618-87-1) → 2-(3,5-dinitrophenyl)-4,5,6,7-(tetrafluoroisoindoline)-1,3-dione

Conditions	Yield
With acetic acid at 130℃; for 10h; Temperature;	79.1%

3,4,5,6-tetrafluorophthalic acid (652-03-9) + manganese (II) acetate tetrahydrate (6156-78-1) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → Mn(1,2-BDC-F4)(H2O)2(DMF)

Conditions	Yield
In water for 0.005h;	78%

thallium(I) carbonate + 3,4,5,6-tetrafluorophthalic acid (652-03-9) → thallium(I) tetrafluorophthalate

Conditions	Yield
In water Boiling of stoich. amts. of the starting materials in H2O until a clear soln. is obtained.; Filtn., isolation by evapn. under vac., elem. anal.;	76%

[2,2]bipyridinyl (366-18-7) + cobalt(II) nitrate hexahydrate + 3,4,5,6-tetrafluorophthalic acid (652-03-9) → C36H24Co2F8N4O12 (1425942-02-4)

Conditions	Yield
With sodium hydroxide In water at 120℃; Sealed tube;	76%

3,4,5,6-tetrafluorophthalic acid (652-03-9) + silver nitrate + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → 4C8F4O4(2-)*8Ag(1+)*2C3H7NO

Conditions	Yield
In methanol for 0.25h;	75%

Upstream product

• 1024-60-8 hexafluoro-1,4-naphthoquinone 
• 313-72-4 octafluoronaphthalene 
• 122180-11-4 octafluoro-1,3-dihydroisobenzofuran 
• 71-43-2 benzene 
• 52196-63-1 perfluorobenzocyclobutene 
• 407-25-0 trifluoroacetic anhydride 
• 201230-82-2 carbon monoxide 
• 59514-38-4 perfluorobenzocyclobutenone 
• 33795-85-6 N-methyl-tetrafluorophthalimide 
• 1445-69-8 2,3-dihydrophthalazine-1,4-dione 
• 52196-64-2 perfluoro(1-methyl-1,2-dihydrocyclobutabenzene) 
• 1953-99-7 tetrachlorophthalonitrile 
• 116508-58-8 tetrafluoro-N-phenylphthalimide 
• 31039-74-4 4,5,6,7-tetrachloro-2-phenylphthalimide 

Downstream Products

• 652-12-0 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione 
• 185318-75-6 4,5,6,7-tetrafluorofluorescein diacetate 
• 1187587-72-9 isopropylammonium tetrafluorohydrogenphthalate 
• 20833-87-8 Di-K-Tetrafluorphthalat 

Relevant articles and documents

POLYHALOAROMATICS. PART II. SYMTHESIS OF OCTAFLUORO-1,3-DIHYDRO-ISOBENZOFURAN AND ITS CONVERSION TO TETRAFLUOROTEREPHTHALIC ACID

A high yield preparation of the title compound via treament of 4,5,6,7-tetrachloro-1,1,3,3-tetrafluoro-1,3-dihydroisobenzofuran with potassium fluoride in sulpholane is described.Hydrolysis of octafluoro-1,3-dihydroisobenzofuran with concentrated sulphuric acid provides a new and efficient route to tetrafluoroterephthalic acid.

Carbonylation of Polyfluorobenzocyclobutenones in a SbF5 Medium

The carbonylation of perfluoro-2-R-benzocyclobutenones (R = F, CF3, C2F5, C6F5) in a CO-SbF5 system is accompanied by transformations of the four-membered cycle in the substrate to form polyfluorinated 1H-isochromene derivatives. The reaction of perfluoro-2-R-benzocyclobutenes (R = F, CF3, C2F5) with (CF3CO)2O or CF3COOH in a SbF5 medium in a sealed ampule involves formation of polyfluorobenzocyclobutenones and their carbonylation under the reaction conditions.

Synthesis method of 3, 4, 5, 6-tetrafluorophthalic acid

The invention discloses a synthesis method of 3, 4, 5, 6-tetrafluorophthalic acid, comprising the following steps: (1) adding phthalylhydrazine into mixed liquid of fuming sulfuric acid and diluted hydrochloric acid, then adding a catalyst I into the mixed liquid and stirring the mixture, controlling the filling of chlorine, and carrying out a thermal reaction; (2) adding potassium fluoride into a reaction device containing methyl alcohol, methylbenzene and a solvent I, heating up and then stirring the mixture, and carrying out atmospheric distillation on reaction liquid to recover the methyl alcohol and the methylbenzene; after that, under the protection of nitrogen, adding the tetrachloro phthalylhydrazine prepared in the step (1) and a catalyst II into the product, heating up to 120-200 DEG C and carrying out a fluoridation reaction; (3) adding the tetrachloro phthalylhydrazine and sodium peroxide which are prepared in the step (2) into water, carrying out a hydrolysis reaction for 2-8 hours at the temperature of 10-50 DEG C, then adjusting the acidity of the obtained reaction liquid until the pH value of the reaction liquid is equal to 1-4, carrying out suction filtration and drying to obtain the tetrafluorophthalic acid.