118-45-6

Basic information

• Product Name: 4-Chlorophthalic anhydride
• Synonyms: 4-CHLOROPHTHALIC ACID ANHYDRIDE;4-CHLOROPHTHALIC ANHYDRIDE;CHLOROPHTHALIC ANHYDRIDE;Chlorophtalicanhydre,95%;ChlorophthalicAnhydride,4-;4-Chlorophthalic;5-Chloroisobenzofuran-1,3-dione;4-CHLOROPHTHALIC ANHYDRIDE 95+%
• CAS NO: 118-45-6
• Molecular Formula: C₈H₃ClO₃
• Molecular Weight: 182.56
• EINECS: 204-251-9
• Product Categories: Acids and Derivatives;Phthalic Acids, Esters and Derivatives;Anhydride;API Intermediate
• Mol File: 118-45-6.mol
• Article Data: 26

Chemical Properties

• Melting Point: 96°C
• Boiling Point: 290 °C
• Flash Point: 142.4 °C
• Appearance: white crystal powder
• Density: 1.594 g/cm³
• Vapor Pressure: 0.00116mmHg at 25°C
• Refractive Index: 1.626
• Storage Temp.: under inert gas (nitrogen or Argon) at 2-8°C
• Solubility: soluble in Toluene
• CAS DataBase Reference: 4-Chlorophthalic anhydride(CAS DataBase Reference)
• NIST Chemistry Reference: 4-Chlorophthalic anhydride(118-45-6)
• EPA Substance Registry System: 4-Chlorophthalic anhydride(118-45-6)

Safety Data

• Statements: 36/37/38
• Safety Statements: 26-36/37/39
• Hazardous Substances Data: 118-45-6(Hazardous Substances Data)

Usage

Uses

4-chlorophthalic anhydride is an important monomer synthesis of polyimide and polyimide is considered to be the highest tolerance has been industrialized in the polymer and the shape and chemical stability of other materials can not like the outburst strength, wear resistance and extreme temperatures, excellent, has been widely used in aviation, aerospace, microelectronics and atom to the field of high technology. 4- of 4-chlorophthalic anhydride is mainly used in the synthesis of diphenyl ether dianhydride anhydride, two single and two double ether, thioether dianhydride anhydride two, two, and two amine polymerization ring was a series of polyimide engineering plastic with excellent performance. 4- of 4-chlorophthalic anhydride is not only the ideal raw material for the synthesis of various intermediates of polyimide, and can be used as a drug or pesticide.

Synthesis Reference(s)

Tetrahedron Letters, 23, p. 371, 1982 DOI: 10.1016/S0040-4039(00)86833-1

InChI:InChI=1/C8H3ClO3/c9-4-1-2-5-6(3-4)8(11)12-7(5)10/h1-3H

Synthetic route

trimellitic anhydride acid chloride (1204-28-0) → phthalic anhydride (85-44-9) + 4-chlorophthalic anhydride (118-45-6)

Conditions	Yield
palladium dichloride In melt at 290℃; for 2h; Product distribution; other temperatures and other catalysts (Pd/C, Pd(PPh3)4);	A 1% B 99%
tetrakis(triphenylphosphine) palladium(0) In melt at 265℃; for 16h;	A 10% B 79%

4-chlorophthalic acid (89-20-3) → 4-chlorophthalic anhydride (118-45-6)

Conditions	Yield
With acetic anhydride for 3h; Heating;	98%
With acetic anhydride for 1h; Heating;	90%
With acetic anhydride for 2h; Reflux;	88%

trimellitic anhydride acid chloride (1204-28-0) → 4-chlorophthalic anhydride (118-45-6)

Conditions	Yield
With bis(tri-ortho-tolylphosphine)palladium(0); dicyclohexyl-(2′,4′,6′-triisopropyl-3,6-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine In toluene at 130℃; for 20h; Inert atmosphere; Glovebox;	84%

monosodique de l'acide chloro-4 phtalique (56047-23-5) → 4-chlorophthalic anhydride (118-45-6)

Conditions	Yield
With thionyl chloride for 2h; Heating;	70%
With sulfuric acid In acetic anhydride for 3h; Heating;
With thionyl chloride for 2h; Reflux;

phthalic anhydride (85-44-9) → 4-chlorophthalic anhydride (118-45-6)

Conditions	Yield
With sulfuric acid; chlorine at 50℃; in Gegenwart von Jod;
With chlorine In water at 70℃; for 12h;

tetrachloromethane (56-23-5) + 4-nitrophthalic anhydride (5466-84-2) → 4-chlorophthalic anhydride (118-45-6)

Conditions	Yield
at 280℃;

4-nitrophthalic anhydride (5466-84-2) → 4-chlorophthalic anhydride (118-45-6)

Conditions	Yield
With chlorine at 230 - 250℃;

4-chlorophthalic acid (89-20-3) + acetyl chloride (75-36-5) → 4-chlorophthalic anhydride (118-45-6)

phthalic anhydride (85-44-9) → 4-chlorophthalic anhydride (118-45-6) + 3-chlorophthalic anhydride (117-21-5) + 4,5-dichlorophthalic anhydride (942-06-3) + 4,6-dichloroisobenzofuran-1,3-diketone (51971-64-3)

Conditions	Yield
With chlorine at 390℃; Product distribution; var. temp, var. conc. of Cl2;
With chlorine at 420℃; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
With chlorine at 390℃; Yield given. Yields of byproduct given. Title compound not separated from byproducts;

2-chloronaphthalene (91-58-7) + air + titanium yl vanadate + titanium oxide + pumice stone → phthalic anhydride (85-44-9) + 4-chlorophthalic anhydride (118-45-6)

Conditions	Yield
at 340℃;

2,6-dichloronaphthalene (2065-70-5) → 4-chlorophthalic anhydride (118-45-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: nitric acid / 190 - 200 °C / im geschlossenen Rohr 2: durch Sublimation View Scheme

6-chloronaphthalen-2-ol (40604-49-7) → 4-chlorophthalic anhydride (118-45-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: bei der Oxydation 2: durch Sublimation View Scheme

benzene-1,2-dicarboxylic acid (88-99-3) → 4-chlorophthalic anhydride (118-45-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: diluted NaOH-solution; chlorine View Scheme

2C6H15N*C8H9ClO4 + 2C6H15N*C8H5ClO4 → 4-chlorophthalic anhydride (118-45-6) + 4-chloro-1,2,3,6-tetrahydrophthalic anhydride (14737-08-7)

Conditions	Yield
In water

4-chlorophthalic acid (89-20-3) + 3-chlorobenzene-1,2-dicarboxylic acid (27563-65-1) → 4-chlorophthalic anhydride (118-45-6) + 3-chlorophthalic anhydride (117-21-5)

Conditions	Yield
With acetic anhydride at 122 - 136℃; for 2h; Product distribution / selectivity;
at 175℃; under 60.006 Torr; for 3h; Product distribution / selectivity;

2-chloromaleic anhydride (96-02-6) + dichloromaleic acid anhydride (1122-17-4) + 10H-phenothiazine (92-84-2) + chloroprene (126-99-8) → 4-chlorophthalic anhydride (118-45-6)

4-chlorotetrahydrophthalic anhydride + pyrographite (7440-44-0) → 4-chlorophthalic anhydride (118-45-6)

4-chlorotetrahydrophthalic anhydride + 1,2,4-Trichlorobenzene (120-82-1) → 4-chlorophthalic anhydride (118-45-6)

4-chloro-1,2-dimethylbenzene (615-60-1) → 4-chlorophthalic anhydride (118-45-6) + 4-chlorophthalic acid (89-20-3)

Conditions	Yield
With hydrogenchloride; potassium permanganate In water; acetic anhydride
With hydrogenchloride; potassium permanganate In water; acetic anhydride

monosodium salt of 4-chlorophthalic acid → 4-chlorophthalic anhydride (118-45-6)

Conditions	Yield
With thionyl chloride for 2h; Reflux;

4-chlorophthalic anhydride (118-45-6) + m-phenylenediamine (108-45-2) → 1,3-bis[N-(4-chlorophthalimidio)]benzene (148935-94-8)

Conditions	Yield
Sodium phenylphosphinate In methoxybenzene at 200℃; under 760.051 - 1824.12 Torr; for 2 - 7h; Conversion of starting material;	99.44%
In glycerol at 150℃; for 15h;	55.3%
In 1,2-dichloro-benzene at 20 - 180℃; for 32h;

4-chlorophthalic anhydride (118-45-6) → 3,3′,4,4′-diphenylsulfidetetracarboxylic dianhydride (25884-43-9)

Conditions	Yield
With carbon disulfide; sulfur; sodium t-butanolate In dimethyl sulfoxide at 150℃; Temperature; Reagent/catalyst; Solvent;	99.08%
With sodium sulfide; 18-crown-6 ether at 200℃; for 24h;	70%

4-chlorophthalic anhydride (118-45-6) → 4-chlorophthalimide (7147-90-2)

Conditions	Yield
With choline chloride; urea at 140℃; for 1h; Green chemistry;	99%
With urea for 0.666667h; Heating;	98%
With formamide for 0.0333333h; microwave irradiation;	93%

4-chlorophthalic anhydride (118-45-6) + C8H3O4(1-)*Na(1+) → 4,4'-oxydiphthalic dianhydride (1823-59-2)

Conditions	Yield
In N,N-dimethyl-formamide; toluene at 110℃; for 6h;	98.1%

4-chlorophthalic anhydride (118-45-6) + (2R*,3R*)-3-Amino-2-(2,4-difluoropropyl)-1-(1H-1,2,4-triazol-1-yl)-2-butanol (126916-57-2, 127000-91-3, 132563-71-4) → (2R*,3R*)-3-(4-Chlorophthalimido)-2-(2,4-difluorophenyl)-1-(1H-1,2,4-triazol-1-yl)-2-butanol (126917-83-7)

Conditions	Yield
With triethylamine In toluene for 4h; Heating;	98%

4-chlorophthalic anhydride (118-45-6) → 6-chloro-2,3-dihydrophthalazine-1,4-dione (3682-29-9)

Conditions	Yield
Stage #1: 4-chlorophthalic anhydride With hydrazine hydrate Inert atmosphere; Stage #2: With hydrogenchloride In water for 24h; Reflux; Inert atmosphere;	97%
With hydrazine In acetic acid for 2h; Heating / reflux;	95%
With hydrazine hydrate In acetic acid for 0.5h; Heating;
With hydrazine hydrate In ethanol for 5h; Ambient temperature;
With hydrogenchloride; hydrazine hydrate In quinoline for 24h; Reflux;

4-chlorophthalic anhydride (118-45-6) + 1-(3-aminophenyl)-1,1-bis(4-hydroxyphenyl)ethane (579472-20-1) → N-{3-[1,1-bis(4-hydroxyphenyl)]ethylphenyl}-4-chlorophthalimide (579472-24-5)

Conditions	Yield
Stage #1: 4-chlorophthalic anhydride; 1-(3-aminophenyl)-1,1-bis(4-hydroxyphenyl)ethane In N,N-dimethyl acetamide at 20℃; Stage #2: In N,N-dimethyl acetamide; xylene Heating;	97%

4-chlorophthalic anhydride (118-45-6) + 4-amino-4',4''-dihydroxytriphenylmethane (579472-19-8) → N-[4-bis(4-hydroxyphenyl)toluoyl]-4-chlorophthalimide (579472-21-2)

Conditions	Yield
Stage #1: 4-chlorophthalic anhydride; 4-amino-4',4''-dihydroxytriphenylmethane In N,N-dimethyl acetamide at 20℃; for 24h; Stage #2: In N,N-dimethyl acetamide; xylene for 10h; Heating;	95%

4-chlorophthalic anhydride (118-45-6) + benzylamine (100-46-9) → 2-benzyl-5-chloroisoindolin-1,3-dione (136860-33-8)

Conditions	Yield
In xylene Heating;	93%

4-chlorophthalic anhydride (118-45-6) + ethylenediamine (107-15-3) → C18H10Cl2N2O4

Conditions	Yield
at 150℃; for 16h;	92.4%

4-chlorophthalic anhydride (118-45-6) + 1,4-phenylenediamine (106-50-3) → C22H10Cl2N2O4

Conditions	Yield
In paraffin oil at 170℃; for 10h;	92.1%

4-chlorophthalic anhydride (118-45-6) + 2,2'-bis(trifluoromethyl)benzidine (341-58-2) → C30H12Cl2F6N2O4

Conditions	Yield
With 4-hydroxymethyl-1,3-dioxolan-2-one at 180℃; for 14h;	91.8%

4-chlorophthalic anhydride (118-45-6) + dapsone (80-08-0) → C28H14Cl2N2O6S

Conditions	Yield
at 180℃; for 12h;	91.5%

4-chlorophthalic anhydride (118-45-6) + 4,4'-oxydiphenylene diamine (101-80-4) → 4,4'-bis(4-chlorophthalimido)diphenyl ether

Conditions	Yield
With ethylene glycol carbonate at 190℃; for 10h;	91.4%
With acetic acid for 24h; Heating;	88%

1,2-dimethylindole (875-79-6) + 4-chlorophthalic anhydride (118-45-6) → C18H14ClNO3

Conditions	Yield
at 110℃;	90.6%

4-chlorophthalic anhydride (118-45-6) + 3-amino-4',4''-dihydroxytriphenylmethane (109811-59-8) → N-[3-bis(4-hydroxyphenyl)toluoyl]-4-chlorophthalimide (579472-23-4)

Conditions	Yield
Stage #1: 4-chlorophthalic anhydride; 3-amino-4',4''-dihydroxytriphenylmethane In N,N-dimethyl acetamide at 20℃; Stage #2: In N,N-dimethyl acetamide; xylene Heating;	90%

4-chlorophthalic anhydride (118-45-6) + 1-(4-aminophenyl)-1,1-bis(4-hydroxyphenyl)ethane (266001-57-4) → N-{4-[1,1-bis(4-hydroxyphenyl)]ethylphenyl}-4-chlorophthalimide (579472-22-3)

Conditions	Yield
Stage #1: 4-chlorophthalic anhydride; 1-(4-aminophenyl)-1,1-bis(4-hydroxyphenyl)ethane In N,N-dimethyl acetamide at 20℃; Stage #2: In N,N-dimethyl acetamide; xylene Heating;	90%

4-chlorophthalic anhydride (118-45-6) + o-toluidine (95-53-4) → N-(2-methylphenyl)-4-chlorophthalimide

Conditions	Yield
	90%

4-chlorophthalic anhydride (118-45-6) + 3-chlorophthalic anhydride (117-21-5) → 2,3',3,4'-biphenyltetracarboxylic acid dianhydride (36978-41-3)

Conditions	Yield
With N-phenylpicolinamide; sodium bromide; nickel dichloride; zinc at 30℃; for 8h; Catalytic behavior; Reagent/catalyst; Temperature; Time; Inert atmosphere;	87.7%

4-chlorophthalic anhydride (118-45-6) + C28H6F36O2 → C44H10F36O8

Conditions	Yield
With sodium carbonate In N,N-dimethyl-formamide; toluene for 15h; Reflux;	87.7%

4-chlorophthalic anhydride (118-45-6) → C8H3ClO2S

Conditions	Yield
With sodium sulfide In tetrahydrofuran at 20℃; for 4h;	87.6%

4-chlorophthalic anhydride (118-45-6) + 4-amino-n-butyric acid (56-12-2) → C12H10ClNO4

Conditions	Yield
With acetic acid at 100℃; for 3h;	86.4%

4-chlorophthalic anhydride (118-45-6) + 1,1'-bis(3-methyl-4-aminophenyl)cyclohexane (6442-08-6) → 4,4'-bis(4-chlorophthalimido)-3,3'-dimethyldiphenyl-1,1'-cyclohexane (582303-39-7)

Conditions	Yield
With acetic acid for 24h; Heating;	85%

4-chlorophthalic anhydride (118-45-6) → 4,4'-oxydiphthalic dianhydride (1823-59-2)

Conditions	Yield
With potassium carbonate; hexaethylguanidinium chloride In water; 1,2-dichloro-benzene for 3.5h; Heating / reflux;	85%
With potassium carbonate; sodium nitrite In N,N-dimethyl acetamide; toluene at 162 - 170℃; for 5h;	85%
Stage #1: 4-chlorophthalic anhydride With monopotassium carbonate; tetraphenylphosphonium bromide; potassium hydrogencarbonate In 2,4-dichlorotoluene for 7.5h; Heating / reflux; Nitrogen atmosphere; Stage #2: Conversion of starting material; Heating / reflux;	82%

4-chlorophthalic anhydride (118-45-6) + urea (57-13-6) + copper(l) chloride → C32H12Cl4CuN8, β (16040-69-0)

Conditions	Yield
In further solvent(s) stirring of a mixt. of CuCl, urea and C8H3ClO3 in trichlorobenzene at ambient temp. for 30 minutes; heating at 175-180°C for 4 h; evapn.; heating with 5% HCl; heating with 2% aq. Na2CO3;; washing with H2O and ethanol; drying at 95-100°C;;	85%

BPA (80-05-7) + 4-chlorophthalic anhydride (118-45-6) → 4,4'-bis(4,4'-isopropylidene diphenoxy)-bis(phthalic anhydride) (38103-06-9)

Conditions	Yield
Stage #1: BPA With N-benzyl-N,N,N-triethylammonium chloride; sodium hydroxide In water at 85 - 172℃; for 15h; Stage #2: 4-chlorophthalic anhydride In water; 1,3,5-trimethyl-benzene at 130 - 145℃; for 5h; Time;	85%

4-chlorophthalic anhydride (118-45-6) + diphenyl acetylene (501-65-5) → 3-chloro-5,6,7,8-tetraphenyl-1-naphthoic acid

Conditions	Yield
With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; tetrabutylammomium bromide In N,N-dimethyl-formamide at 100℃; for 12h; Sealed tube;	85%
With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; tetrabutylammomium bromide; 5-methyl-dihydro-furan-2-one In N,N-dimethyl-formamide at 100℃; for 12h;	83%

Upstream product

• 85-44-9 phthalic anhydride 
• 56-23-5 tetrachloromethane 
• 5466-84-2 4-nitrophthalic anhydride 
• 89-20-3 4-chlorophthalic acid 
• 75-36-5 acetyl chloride 
• 56047-23-5 monosodique de l'acide chloro-4 phtalique 
• 1204-28-0 trimellitic anhydride acid chloride 
• 91-58-7 2-chloronaphthalene 
• 2065-70-5 2,6-dichloronaphthalene 
• 40604-49-7 6-chloronaphthalen-2-ol 
• 88-99-3 benzene-1,2-dicarboxylic acid 
• 27563-65-1 3-chlorobenzene-1,2-dicarboxylic acid 
• 96-02-6 2-chloromaleic anhydride 
• 1122-17-4 dichloromaleic acid anhydride 

Downstream Products

• 856806-80-9 5-chloro-2-(methoxycarbonyl)benzoic acid 
• 1470-36-6 5-chloro-2-phenylindan-1,3-dione 
• 583838-21-5 2-(4-bromo-benzoyl)-4-chloro-benzoic acid 
• 860696-87-3 4-chloro-2-(4-chloro-3-methyl-benzoyl)-benzoic acid 
• 40116-27-6 4-chloro-2-(thiophene-2-carbonyl)-benzoic acid 
• 40116-41-4 5-chloro-2-(thiophene-2-carbonyl)-benzoic acid 
• 53103-13-2 4-chloro-2-(4-chloro-benzoyl)-benzoic acid 
• 1220-95-7 6-chloroquinizarin 
• 7147-90-2 4-chlorophthalimide 
• 319-03-9 4-fluorophthalic anhydride 
• 19722-72-6 (4-Chlor-2-methoxycarbonyl-phenyl)-diazomethyl-keton 
• 89-20-3 4-chlorophthalic acid 
• 58138-38-8 dimethyl 4-chlorophthalate 
• 33184-56-4 2-benzoyl-4-chlorobenzoic acid 

Relevant articles and documents

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Preparation method, preparation device and intermediate of 4 -chlorophthalic anhydride

The invention discloses a preparation method of 4 -chlorophthalic anhydride, a preparation device and an intermediate. The preparation method comprises the following steps: 2, 3 - dichloro maleic anhydride and 2 - chlorine -1, 3 - butadiene takes place cyclization reaction to obtain 1, 2 and 4 - trichloroacetic anhydride. Reaction of the 1, 2 and 4 - trichloroalternative dihydrophthalic anhydride in the removal HCl results in 4 -chlorophthalic anhydride. The chlorination reaction of maleic anhydride and thionyl chloride under the conditions of pyridine catalysts gives the 2, 3 -dichloromaleic anhydride. By adopting 2, 3 -dichloromaleic anhydride and 2 - chlorine -1, 3 - butadiene takes place D-A cyclization reaction, HCl-chlorophthalic anhydride is synthesized with high selectivity, and the 4 - 4 -chlorophthalic anhydride process disclosed by the invention realizes continuous production.

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