4124-31-6

Basic information

• Product Name: TRICHLOROACETIC ANHYDRIDE
• Synonyms: PERCHLOROACETIC ANHYDRIDE;TCAA;trichloro-aceticacianhydride;TRICHLOROACETIC ACID ANHYDRIDE;TRICHLOROACETIC ANHYDRIDE;Trichloroacetic acid anhydride (TCAA);TRICHLOROACETIC ANHYDRIDE, TECH., 95%;TrichloroaceticAnhydride97%
• CAS NO: 4124-31-6
• Molecular Formula: C₄Cl₆O₃
• Molecular Weight: 308.76
• EINECS: 223-925-3
• Product Categories: Carbonyl Compounds;Carboxylic Acid Anhydrides;Organic Building Blocks;Building Blocks;Carbonyl Compounds;Carboxylic Acid Anhydrides;Chemical Synthesis;Organic Building Blocks
• Mol File: 4124-31-6.mol
• Article Data: 5

Chemical Properties

• Boiling Point: 139-141 °C60 mm Hg(lit.)
• Flash Point: 98-100°C/11mm
• Appearance: colourless liquid
• Density: 1.69 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.106mmHg at 25°C
• Refractive Index: n20/D 1.484(lit.)
• Solubility: Miscible with ether and acetic acid.
• Sensitive: Moisture Sensitive
• Stability: Stable. Moisture sensitive - store under dry atmosphere. Incompatible with strong bases, strong oxidizing agents.
• BRN: 980355
• CAS DataBase Reference: TRICHLOROACETIC ANHYDRIDE(CAS DataBase Reference)
• NIST Chemistry Reference: TRICHLOROACETIC ANHYDRIDE(4124-31-6)
• EPA Substance Registry System: TRICHLOROACETIC ANHYDRIDE(4124-31-6)

Safety Data

• Hazard Codes: C
• Statements: 22-35
• Safety Statements: 26-36/37/39-45
• RIDADR: UN 3265 8/PG 2
• WGK Germany: 3
• F: 10-21
• TSCA: Yes
• HazardClass: 8
• PackingGroup: II
• Hazardous Substances Data: 4124-31-6(Hazardous Substances Data)

Usage

Chemical Properties

colourless liquid

Uses

Trichloroacetic Anhydride is used in organometallic reactions as well as oxadiazole containing 5-lipoxygenase activating protein inhibitors.

General Description

Trichloroacetic anhydride is reported to be an efficient derivatization reagent, since it produces stable derivatives having both a higher mass fragmentation pattern and lesser volatility than derivatives of trifluoroacetic anhydride (TFAA) or heptafluorobutyric anhydride (HFBA). The interaction of thymidine 5′-phosphate with trichloroacetic anhydride in dimethylformamide and acetonitrile in the presence of tertiary amines hs been studied.

InChI:InChI=1/C4Cl6O3/c5-3(6,7)1(11)13-2(12)4(8,9)10

Synthetic route

trichloroacetic acid (76-03-9) → trichloroacetic acid anhydride (4124-31-6)

Conditions	Yield
With thionyl chloride In N,N-dimethyl-formamide at 120℃; for 5h;	60%
With phosphorus pentoxide at 210℃;
With 1-ethoxyacetylene

O-acetyl S,S-dipropyl phosphorodithioite (84103-77-5) → mixed anhydride of acetic and trichloroacetic acids (32676-68-9) + dipropyl phosphorochloridodithioite (4104-04-5) + acetic anhydride (108-24-7) + trichloroacetic acid anhydride (4124-31-6)

Conditions	Yield
With trifluoroacetyl chloride for 1h; Ambient temperature;	A n/a B 50% C n/a D n/a

Trichloroacetyl chloride (76-02-8) + trichloroacetic acid (76-03-9) → trichloroacetic acid anhydride (4124-31-6)

Conditions	Yield
zeitlicher Verlauf bei Siedetemperatur;
With potassium chloride

dichloromethane (75-09-2) + ethynyl methyl ether (6443-91-0) + trichloroacetic acid (76-03-9) → trichloroacetic acid anhydride (4124-31-6)

1-Ethoxyvinyl trichloroacetate (90724-35-9) + trichloroacetic acid (76-03-9) → trichloroacetic acid anhydride (4124-31-6)

Conditions	Yield
With diethyl ether

trichloroacetic acid (76-03-9) → Trichloroacetyl chloride (76-02-8) + trichloroacetic acid anhydride (4124-31-6)

Conditions	Yield
With phosphorus trichloride

Trichloroacetyl chloride (76-02-8) + trichloroacetic acid (76-03-9) + potassium chloride → trichloroacetic acid anhydride (4124-31-6)

Conditions	Yield
zeitlicher Verlauf bei Siedetemperatur;

diethyl ether (60-29-7) + 1-ethoxyacetylene (927-80-0) + trichloroacetic acid (76-03-9) → 1-Ethoxyvinyl trichloroacetate (90724-35-9) + ethyl acetate (141-78-6) + trichloroacetic acid anhydride (4124-31-6) + 4-ethoxy-1,1,1-trichloro-4ξ-trichloroacetoxy-but-3-en-2-one

sodium trichloroacetate → trichloroacetic acid anhydride (4124-31-6)

Conditions	Yield
With phosgene; acetic acid ester
With phosgene; oxalic acid ester
With sulfuryl dichloride; acetic acid ester
With sulfuryl dichloride; oxalic acid ester

Dimethylsulfonium-trifluoracetyl-methylid (104917-77-3) + trichloroacetic acid anhydride (4124-31-6) → 1-Trichloracetyl-2-oxo-3-trifluor-1-dimethylsulfonium-1-yl-propanid

Conditions	Yield
In tetrahydrofuran at 24℃; for 4h;	100%

2,3,4,6-tetra-O-benzyl-D-galactopyranose (6386-24-9) + trichloroacetic acid anhydride (4124-31-6) → 2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl trichloroacetate (155500-50-8)

Conditions	Yield
With sodium trichloroacetate In dichloromethane for 2h; Heating;	100%

N-hydroxyisobutyramidine (849833-56-3, 35613-84-4, 1202858-97-6) + trichloroacetic acid anhydride (4124-31-6) → 3-isopropyl-5-(trichloromethyl)-1,2,4-oxadiazole (1199-49-1)

Conditions	Yield
In toluene for 1h; Reflux;	100%
In toluene for 1h; Reflux;
In toluene for 1h; Reflux;

di-p-tolyldi(2-pyrrolyl)methane (1343487-95-5) + trichloroacetic acid anhydride (4124-31-6) → C27H20Cl6N2O2

Conditions	Yield
With dmap In dichloromethane at 0 - 20℃; for 2h; Inert atmosphere;	100%

benzyl crotyl amine (107733-62-0) + trichloroacetic acid anhydride (4124-31-6) → N-benzyl-N-(but-2-enyl)carbamoyl chloride

Conditions	Yield
With pyridine In benzene for 96h;	99.5%

N-benzyl-N-<1-(2'-benzyloxyethyl)-3-methylbut-2-enyl>amine (132872-29-8) + trichloroacetic acid anhydride (4124-31-6) → N-benzyl-N-<1-(2'-benzyloxyethyl)-3-methylbut-2-enyl>carbamoyl chloride (132872-30-1)

Conditions	Yield
With pyridine In benzene for 96h;	99.5%

methyl 2,3-di-O-benzyl-6-O-acetyl-α-D-glucopyranoside (20771-21-5, 51842-23-0, 51842-24-1, 117561-20-3, 125884-32-4, 51842-22-9) + trichloroacetic acid anhydride (4124-31-6) → Methyl-6-O-acetyl-2,3-di-O-benzyl-4-O-trichloracetyl-α-D-glucopyranosid (79705-88-7)

Conditions	Yield
In pyridine at -20℃; for 0.416667h;	99%

1,6-anhydro-2-azido-4-O-benzyl-2-deoxy-β-D-galactopyranose (59464-21-0) + trichloroacetic acid anhydride (4124-31-6) → 1,6-Anhydro-2-azido-4-O-benzyl-2-desoxy-3-O-trichloracetyl-β-D-galactopyranose

Conditions	Yield
In pyridine at -20℃; for 0.5h;	99%

Acetic acid (3R,4S,5R,6R)-3-acetoxy-6-acetoxymethyl-2-hydroxy-5-[(2S,3R,4S,5S,6R)-3,4,5-triacetoxy-6-(2-oxo-propyl)-tetrahydro-pyran-2-yloxy]-tetrahydro-pyran-4-yl ester + trichloroacetic acid anhydride (4124-31-6) → 2,3,4-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-α/β-D-glucopyranosyl trichloroacetate

Conditions	Yield
With sodium trichloroacetate In dichloromethane for 6h; Heating;	99%

2,3,4,6-tetra-O-benzyl-D-galactopyranose (6386-24-9) + trichloroacetic acid anhydride (4124-31-6) → 2,3,4,6-tetra-O-benzyl-D-galactopyranosyl trichloroacetate (383905-63-3)

Conditions	Yield
With sodium trichloroacetate In dichloromethane for 1.5h; Heating;	99%

2-cyclopentylidene-1,1-diphenylhydrazine (39672-00-9) + trichloroacetic acid anhydride (4124-31-6) → trichloroacetic acid 1-(1-cyclopenten-1-yl)-2,2-diphenylhydrazide

Conditions	Yield
With 2,4,6-trimethyl-pyridine In dichloromethane at 0℃;	99%

N-(2,2-dimethylpent-4-enyl)-N-propylamine (155693-23-5) + trichloroacetic acid anhydride (4124-31-6) → N-(2,2-dimethylpent-4-enyl)-N-propylcarbamoyl chloride (155693-24-6)

Conditions	Yield
With pyridine In benzene for 72h;	98%

6--4-chloro-2-(methylthio)pyrimidine (155670-17-0) + trichloroacetic acid anhydride (4124-31-6) → C16H11Cl4N3O2S

Conditions	Yield
With triethylamine In dichloromethane	98%

7-isopropyl-1,4-dimethyl-azulene (489-84-9) + trichloroacetic acid anhydride (4124-31-6) → 3-trichloroacetylguaiazulene (846-33-3)

Conditions	Yield
In dichloromethane	98%
In dichloromethane	76%
In dichloromethane
In dichloromethane at 20℃; for 2h;

O-(2,3,4,6-Tetra-O-acetyl-β-D-galactopyranosyl)-(1->4)-3,6-di-O-acetyl-2-desoxy-2-phthalimido-D-glucopyranose (81243-75-6, 81243-76-7, 91852-38-9) + trichloroacetic acid anhydride (4124-31-6) → 3,6-di-O-acetyl-2-deoxy-2-phthalimido-4-O-(2,3,4-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranosyl trichloroacetate

Conditions	Yield
With sodium trichloroacetic In dichloromethane Heating;	98%
With sodium trichloroacetate In dichloromethane Heating;	98%

Acetic acid (3S,4S,5R,6R)-6-acetoxymethyl-4,5-bis-benzyloxy-2-hydroxy-tetrahydro-pyran-3-yl ester + trichloroacetic acid anhydride (4124-31-6) → 2,6-di-O-acetyl-3,4-di-O-benzyl-α-D-mannopyranosyl trichloroacetate (183885-17-8)

Conditions	Yield
With sodium trichloroacetate In dichloromethane for 1h; Heating;	98%
With sodium trichloroacetate In dichloromethane for 1h; Heating; Yield given;

(Z)-(oxiran-2-yl)methyl octadec-9-enoate (5431-33-4) + trichloroacetic acid anhydride (4124-31-6) → 2-O-oleoyl-1,3-bis-O-(trichloroacetyl)glycerol

Conditions	Yield
In dichloromethane at -20 - 20℃;	98%

6,7-dimethylinden-1-ol + trichloroacetic acid anhydride (4124-31-6) → 1-(3',3',3'-trichloroacetoxy-6,7-dimethyl)indene (1263309-94-9)

Conditions	Yield
With pyridine In tetrahydrofuran for 0.25h; Inert atmosphere;	98%

benzylamine (100-46-9) + trichloroacetic acid anhydride (4124-31-6) → benzyl 2,2,2-trichloroacetamide (4257-83-4)

Conditions	Yield
	98%

N-(3-butenyl)n-butylamine (18903-55-4) + trichloroacetic acid anhydride (4124-31-6) → N-but-3-enyl-N-butylcarbamoyl chloride (155693-21-3)

Conditions	Yield
With pyridine In benzene for 96h;	97%

N-benzyl-N-(1,3-dimethylbut-2-enyl)amine (60519-98-4) + trichloroacetic acid anhydride (4124-31-6) → N-benzyl-N-(1,3-dimethylbut-2-enyl)carbamoyl chloride (156627-40-6)

Conditions	Yield
With pyridine In benzene for 72h;	97%

6-fluoro-3-methylisoquinolin-5-amine (608515-64-6) + trichloroacetic acid anhydride (4124-31-6) → 2,2,2-trichloro-N-(6-fluoro-3-methylisoquinolin-5-yl)acetamide (1221445-04-0)

Conditions	Yield
With pyridine In acetonitrile at -10℃; for 0.166667h;	97%
With pyridine In acetonitrile at -10 - -5℃; for 0.25h;	87%
With pyridine at -10 - -5℃;	86%
With pyridine at -10 - -5℃;	86%

4-methoxyphenyl 2-amino-4-O-benzoyl-3-O-tert-butyldimethylsilyl-2,6-dideoxy-β-D-glucopyranoside + trichloroacetic acid anhydride (4124-31-6) → 4-methoxyphenyl 4-O-benzoyl-3-O-tert-butyldimethylsilyl-2,6-dideoxy-2-trichloroacetamido-β-D-glucopyranoside

Conditions	Yield
In pyridine at 0℃;	97%

morphine (57-27-2, 143-70-4, 6912-73-8, 16206-77-2, 27067-73-8, 65165-99-3, 70982-47-7) + trichloroacetic acid anhydride (4124-31-6) → C19H18Cl3NO4

Conditions	Yield
With pyridine In tetrahydrofuran; water at 0 - 10℃; for 1.5h; Reagent/catalyst; Solvent; Temperature; Industrial scale;	97%

1,3,4,6-tetra-O-acetyl-D-glucosamine hydrochloride (5432-46-2, 10034-19-2, 10034-20-5, 34948-62-4, 110253-00-4) + trichloroacetic acid anhydride (4124-31-6) → 1,3,4,6-tetra-O-acetyl-2-deoxy-2-(2,2,2-trichloroacetamido)-β-D-glucopyranose (56644-75-8, 10353-00-1)

Conditions	Yield
With pyridine In dichloromethane at 0℃;	97%

N-allyl-N-butylamine (4538-09-4) + trichloroacetic acid anhydride (4124-31-6) → N-allyl-N-butylcarbamoyl chloride (125012-90-0)

Conditions	Yield
With pyridine In benzene for 96h;	96%

(Z)-4-amino-N'-hydroxy-1,2,5-oxadiazole-3-carbimidoyl chloride (13490-32-9) + trichloroacetic acid anhydride (4124-31-6) → 2,2,2-trichloro-N-[4-(5-trichloromethyl-[1,2,4]oxadiazol-3-yl)-furazan-3-yl]-acetamide

Conditions	Yield
at 120℃; for 5h;	96%

6-chloro-3-methylisoquinolin-5-amine (919994-53-9) + trichloroacetic acid anhydride (4124-31-6) → 2,2,2-trichloro-N-(6-chloro-3-methylisoquinolin-5-yl)acetamide

Conditions	Yield
With pyridine In acetonitrile at -10 - -5℃; for 0.333333h;	96%

3,3,3-trifluoro-N'-hydroxypropanimidamide (1016726-53-6) + trichloroacetic acid anhydride (4124-31-6) → 5-(trichloromethyl)-3-(2,2,2-trifluoroethyl)-1,2,4-oxadiazole

Conditions	Yield
With trichloroacetic acid at 110℃; for 1h; Inert atmosphere;	96%

ethyl trimethylsilyl ether (1825-62-3) + trichloroacetic acid anhydride (4124-31-6) → trimethylsilyl trichloroacetate (25436-07-1)

Conditions	Yield
With iron perchlorate hexahydrate at 25℃; for 0.5h;	96%

Upstream product

• 76-02-8 trifluoroacetyl chloride 
• 76-03-9 trichloroacetic acid 
• 60-29-7 diethyl ether 
• 927-80-0 1-ethoxyacetylene 
• 84103-77-5 O-acetyl S,S-dipropyl phosphorodithioite 
• 90724-35-9 1-Ethoxyvinyl trichloroacetate 
• 75-09-2 dichloromethane 
• 6443-91-0 ethynyl methyl ether 

Downstream Products

• 15166-50-4 N-(Trichloroacetyl)glycine 
• 30362-65-3 bis-(4-chloro-phenyl)-trichloromethyl-[1,3,5]triazine 
• 67467-20-3 2-trichloroacetylcyclohexanone 
• 27389-43-1 2-(4-chloro-phenyl)-5-trichloromethyl-[1,3,4]oxadiazole 
• 30030-90-1 2,2,2-trichloro-1-(1H-indol-3-yl)ethan-1-one 
• 79705-88-7 Methyl-6-O-acetyl-2,3-di-O-benzyl-4-O-trichloracetyl-α-D-glucopyranosid 
• 624-92-0 Dimethyldisulphide 
• 73682-73-2 (Methylsulfinyl)-trichloracetat 
• 103224-64-2 1-acetyl-2-(nitromethyl)-3,4,5,6-tetramethylbenzene 
• 78740-44-0 2-(nitrooxymethyl)-3,4,5,6-tetramethylacetophenone 
• 75565-44-5 3-(N-methyl-N-phenylamino)-5-trichlormethyl-1,2,4-oxadiazole 
• 156627-40-6 N-benzyl-N-(1,3-dimethylbut-2-enyl)carbamoyl chloride 
• 1474-28-8 <α-Carbaethoxy-α-trichloracetyl-methylen>-triphenylphosphoran 
• 132872-30-1 N-benzyl-N-<1-(2'-benzyloxyethyl)-3-methylbut-2-enyl>carbamoyl chloride 

Relevant articles and documents

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The Interaction of Trihalogenoacetic Anhydrides and Trihalogenoacetyl Chlorides with Thymidine 5′-Phosphate as an Approach to New Activating Agents in the Phosphorylation Reactions for Nucleotides

The interaction of thymidine 5′-phosphate with trichloroacetic anhydride, trichloroacetyl chloride, and tribromoacetyl bromide was studied in dimethylformamide and acetonitrile in the presence of tertiary amines. The first two reactions gave the mixed anhydride of trichloroacetic and thymidylic acids (acyl phosphate) as the major product and P1,P 2-dithymidine 5′-pyrophosphate as the byproduct. The third reaction proceeded by a more complicated mechanism and mainly led to substituted polyphosphates. The subsequent treatment of the reaction mixtures with morpholine resulted in thymidine 5′-phosphoromorpholidate in a high yield. The phosphorylating activities of the trichloroacetyl and tribromoacetyl phosphates were 77 and 89%, respectively.

Hydroxy protection groups

The present invention concerns a method for preparing unprotected hydroxy compounds or acylated derivatives thereof by conversion of silyl alkyl-protected hydroxy compounds. The invention also relates to novel intermediates useful in the method and for other purposes.