99-14-9

Basic information

• Product Name: TRICARBALLYLIC ACID
• Synonyms: beta-Carboxyglutaric acid;Carballylic acid;Tricarballylate;1,2,3-PROPANETRICARBOXYLIC ACID;3-CARBOXY-PENTANEDIOIC ACID;AKOS 223-48;PROPANE-1,2,3-TRICARBOXYLIC ACID;TRICARBALLYLIC ACID
• CAS NO: 99-14-9
• Molecular Formula: C₆H₈O₆
• Molecular Weight: 176.12
• EINECS: 202-733-3
• Mol File: 99-14-9.mol
• Article Data: 11

Chemical Properties

• Melting Point: 156-161 °C(lit.)
• Boiling Point: 227.71°C (rough estimate)
• Flash Point: 129.2 °C
• Appearance: Off-white to light brown/Fine Crystalline Powder
• Density: 1.3744 (rough estimate)
• Vapor Pressure: 0.00249mmHg at 25°C
• Refractive Index: 1.5860 (estimate)
• Storage Temp.: Store below +30°C.
• Solubility: H2O: 50 mg/mL, clear
• PKA: pK1 (30°): 3.49; pK2: 4.58; pK3: 5.83
• Water Solubility: Soluble in water (500 mg/ml at 18°C), methanol, and ether (slightly).
• Merck: 14,9622
• BRN: 1783567
• CAS DataBase Reference: TRICARBALLYLIC ACID(CAS DataBase Reference)
• NIST Chemistry Reference: TRICARBALLYLIC ACID(99-14-9)
• EPA Substance Registry System: TRICARBALLYLIC ACID(99-14-9)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36
• WGK Germany: 3
• TSCA: Yes
• Hazardous Substances Data: 99-14-9(Hazardous Substances Data)

Usage

Uses

It is used as an alternative to DMDHEU (formaldehyde releasing cross- linking agent).

Definition

ChEBI: A tricarboxylic acid that is glutaric acid in which one of the beta-hydrogens is substituted by a carboxy group.

Purification Methods

Crystallise the acid from diethyl ether. [Beilstein 2 IV 2366.]

InChI:InChI=1/C6H8O6/c7-4(8)1-3(6(11)12)2-5(9)10/h3H,1-2H2,(H,7,8)(H,9,10)(H,11,12)

Synthetic route

vinyl glycolic acid (600-17-9) + carbon monoxide (201230-82-2) → tricarallylic acid (99-14-9)

Conditions	Yield
With HeMaRaphos; water; toluene-4-sulfonic acid; palladium dichloride In tetrahydrofuran at 125℃; under 30003 Torr; for 24h; Autoclave; Green chemistry; regioselective reaction;	86%

Dimethyl 2-dimethoxycarbonylmethyl-3-nitro-1,1-cyclopropanedicarboxylate (59210-90-1) → tricarallylic acid (99-14-9)

Conditions	Yield
With hydrogenchloride for 10h; Heating;	70%
With hydrogenchloride for 10h; Product distribution; Mechanism; Heating;	70%

(-)-3-dehydroshikimic acid (2922-42-1) → 3,4-Dihydroxybenzoic acid (99-50-3) + tricarallylic acid (99-14-9) + 3,4,5-trihydroxybenzoic acid (149-91-7) + dihydrogallic acid (184105-29-1) + 2-hydroxyresorcinol (87-66-1)

Conditions	Yield
With air; Na1.5H1.5PO4 at 40℃; for 50h; Rate constant; Mechanism; other oxidant, var. time;	A 12 % Spectr. B 14 % Spectr. C 13% D n/a E 3 % Spectr.

methanol (67-56-1) + citraconic acid dimethyl ester (617-54-9) + potassium cyanide (151-50-8) → dimethyl 2-(methoxymethyl)succinate (25306-99-4) + tricarallylic acid (99-14-9)

Conditions	Yield
at 25℃; und Behandeln des Reaktionsprodukts mit HCl oder NaOH bei 25grad;

methanol (67-56-1) + citraconic acid dimethyl ester (617-54-9) + potassium cyanide (151-50-8) → tricarallylic acid (99-14-9)

Conditions	Yield
at 25℃; beim Kochen des Reaktionsprodukts mit HCl oder NaOH;

2,3-Dichloroprop-1-ene (78-88-6) + ethanol (64-17-5) + potassium cyanide (151-50-8) → tricarallylic acid (99-14-9)

Conditions	Yield
zerlegt das Prokukt mit alkoholischem Kali;

2,3-Dichloroprop-1-ene (78-88-6) + potassium cyanide (151-50-8) → tricarallylic acid (99-14-9)

Conditions	Yield
With ethanol Zerlegen des Reaktionsproduktes mit alkohol.Kalilauge;

2-allyl-4-pentenoic acid (99-67-2) → tricarallylic acid (99-14-9)

Conditions	Yield
With nitric acid

3-chlorocrotonic acid ethyl ester (6127-93-1) + potassium cyanide (151-50-8) → tricarallylic acid (99-14-9)

Conditions	Yield
With ethanol Zerlegen des Reaktionsproduktes mit Kaliumhydroxyd;

1 propene 1,2,3 tricarboxylic acid (499-12-7) → succinic acid (110-15-6) + tricarallylic acid (99-14-9)

Conditions	Yield
With bacterium succinicum n.sp; phosphate-buffer

1 propene 1,2,3 tricarboxylic acid (499-12-7) → tricarallylic acid (99-14-9)

Conditions	Yield
durch Natriumamalgam;
Durch elektolitische Reduktion von halb mit Natron neutralisierter Aconitsaeure in der Kaelte unter Verwendung einer Quecksilberkathode;
With sodium amalgam bei der Reduktion der Aconitsaeure mit Natriumamalgam entstehende Loesung des Natriumsalzes nach starker Verduennung mit Bleizucker und zerlegt den Niederschlag durch Schwefelwasserstoff;

cis-aconitic acid (585-84-2) → tricarallylic acid (99-14-9)

Conditions	Yield
With water; platinum Hydrogenation;

trans-acotinic acid (4023-65-8) → tricarallylic acid (99-14-9)

Conditions	Yield
Hydrogenation;
With water; platinum Hydrogenation;

1,3-Dichloro-2-propanol (96-23-1) + potassium cyanide (151-50-8) → tricarallylic acid (99-14-9)

Conditions	Yield
bei nachfolgenden Verseifung;

propane-1,2,2,3-tetracarboxylic acid (52163-78-7) → tricarallylic acid (99-14-9) + methylammonium carbonate (15719-64-9, 15719-76-3, 97762-63-5)

Conditions	Yield
at 151℃;

1,1,1-Tricyan-propan (5247-13-2) → tricarallylic acid (99-14-9)

Conditions	Yield
With potassium hydroxide; ethanol

3,4,5-trihydroxybenzoic acid (149-91-7) → tricarallylic acid (99-14-9)

Conditions	Yield
With hydrogenchloride; potassium chlorate at 90℃; extrahiert mit Aether,trennt aus dem Aetherabdampfungsrueckstand die auskrystallisierende Trichlorbrenztraubensaeure ab und kocht die verduennte Mutterlauge mit Zinn und Salzsaeure;

cyclohex-4-ene-1,3-dicarboxylic acid (4717-55-9) → tricarallylic acid (99-14-9)

Conditions	Yield
beim Ozonisieren und folgenden Behandeln mit Kaliumpermanganat-Loesung bei 0grad.;

3,4-dioxo-cyclopentanecarboxylic acid (98198-38-0) → tricarallylic acid (99-14-9)

Conditions	Yield
With potassium hydroxide; dihydrogen peroxide

4-carboxy-2,6-dihydroxypyridine (84660-84-4) → tricarallylic acid (99-14-9)

Conditions	Yield
With hydrogenchloride; tin

sodium diethylmalonate (996-82-7, 34727-00-9, 73177-21-6) + diethyl Fumarate (623-91-6) → tricarallylic acid (99-14-9)

Conditions	Yield
dann Kochen den erhaltenen Propan-α.α.β.γ-tetracarbonsaeure-tetraaethylester mit maessig verduennter Salzsaeure;
dann Kochen den erhaltenen Propan-α.α.β.γ-tetracarbonsaeure-tetraaethylester mit konz.Kalilauge;

potassium cyanide (151-50-8) + E-Ethyl β-chlorocrotonate (6127-92-0) → 2-methylenesuccinic acid (97-65-4) + tricarallylic acid (99-14-9)

Conditions	Yield
und nachfolgender Verseifung mit Kali;

potassium cyanide (151-50-8) + E-Ethyl β-chlorocrotonate (6127-92-0) → tricarallylic acid (99-14-9)

Conditions	Yield
With ethanol Zerlegen des Reaktionsproduktes mit Kaliumhydroxyd;

2-<2,2,2-Trinitro-ethyl>-bernsteinsaeure (14314-67-1) → tricarallylic acid (99-14-9)

Conditions	Yield
(hydrolysis);

3,3-Bis--2-aethoxycarbonyl-glutarsaeure-diaethylester → tricarallylic acid (99-14-9)

Conditions	Yield
With hydrogenchloride at 110 - 120℃; Heating;

3-cyclopentene-1-carboxylic acid (7686-77-3) → tricarallylic acid (99-14-9)

Conditions	Yield
With sodium hydroxide; potassium permanganate

(2,5-dioxo-pyrrolidin-3-yl)-acetic acid (6324-87-4) + sulfuric acid (7664-93-9) → tricarallylic acid (99-14-9)

(3-cyano-5-imino-2-oxo-pyrrolidin-3-yl)-acetonitrile (872264-22-7) + sulfuric acid (7664-93-9) → tricarallylic acid (99-14-9)

sulfuric acid (7664-93-9) + 3-carbamoylmethyl-2-imino-5-oxo-pyrrolidine-3-carboxylic acid ethyl ester → tricarallylic acid (99-14-9)

sulfuric acid (7664-93-9) + 3-carbamoylmethyl-2,5-dioxo-pyrrolidine-3-carboxylic acid ethyl ester → tricarallylic acid (99-14-9)

cadmium(II) perchlorate hexahydrate + tricarallylic acid (99-14-9) + 4-((2-(pyridine-4-yl)propyl)pyridine) (116117-86-3) + water (7732-18-5) → [Cd(hydro(tricarballylate))(1,2-di(4-pyridyl)propane)(H2O)]n

Conditions	Yield
at 80℃; for 72h; High pressure; Sealed tube;	91%

tricarallylic acid (99-14-9) + (bromomethyl)pentafluorobenzene (1765-40-8) → tris(2,3,4,5,6-pentafluorobenzyl)(1,2,3-propanetricarboxylate)

Conditions	Yield
Stage #1: tricarallylic acid With caesium carbonate In N,N-dimethyl-formamide for 0.5h; Schlenk technique; Inert atmosphere; Stage #2: (bromomethyl)pentafluorobenzene In N,N-dimethyl-formamide at 20℃; for 16h; Schlenk technique; Inert atmosphere;	90%

tricarallylic acid (99-14-9) → propane-1,2,3-tricarboxylic acid (1,2-anhydride) (4756-10-9)

Conditions	Yield
With acetic anhydride 1.) 45 deg C, 1h 2.) glacial CH3COOH, 65 deg C, 1h;	87%
With acetic anhydride at 20℃;	77.8%
beim Destillieren unter vermindertem Druck;

tricarallylic acid (99-14-9) + 2-fluorobenzoic anhydride (64508-63-0) → 6a-(2-fluorophenyl)dihydrofuro[2,3-b]furan-2,5(3H,6aH)-dione

Conditions	Yield
With pyridine In m-xylene at 140℃;	85%

trans-2-methyl-cyclohexylamine + tricarallylic acid (99-14-9) → 1,2,3-propanetricarboxylic acid tris(trans-2-methylcyclohexylamide)

Conditions	Yield
With pyridine; triphenyl phosphite In 1-methyl-pyrrolidin-2-one at 100℃; for 4h;	80%

europium(III) nitrate pentahydrate + tricarallylic acid (99-14-9) → Eu(HOOCCH(CH2COO)2)(H2O)2*10H2O

Conditions	Yield
In H2O Eu-compd. and carboxy-compd. in H2O refluxed for 8 h; concentrated, EtOH added, washed with EtOH, dried in vac. at 80°Cfor 2 h, elem. anal.;	80%

tricarallylic acid (99-14-9) + benzoic acid anhydride (93-97-0) → 6a-phenyldihydrofuro[2,3-b]furan-2,5(3H,6aH)-dione (100953-23-9)

Conditions	Yield
With pyridine In m-xylene at 140℃;	78%
at 150 - 160℃;

1,2-bis(4'-pyridyl)ethane (4916-57-8) + cadmium(II) sulfate octahydrate + tricarallylic acid (99-14-9) → [Cd2(hydro(tricarballylate))2(1,2-di(4-pyridyl)ethane)2]n

Conditions	Yield
In water at 80℃; for 72h; High pressure; Sealed tube;	78%

Ni(2+)*CO3(2-)*Ni(OH)2*H2O = NiCO3*Ni(OH)2*H2O + tricarallylic acid (99-14-9) + water (7732-18-5) → Ni(HOOCCH(CH2COO)2)(H2O)2*10H2O

Conditions	Yield
In H2O Ni-compd. and carboxy-compd. in H2O refluxed for 8 h; concentrated, EtOH added, washed with EtOH, dried in vac. at 80°Cfor 2 h, elem. anal.;	75%

tricarallylic acid (99-14-9) + β-alanine hydrochloride (6057-90-5) → C15H23N3O9 (1401230-29-2)

Conditions	Yield
With 4-methyl-morpholine; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide In dichloromethane at 20℃;	75%
With 4-methyl-morpholine; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane at 20℃;	75%

1,3-diazido 2-propanol (57011-48-0) + tricarallylic acid (99-14-9) → tris(1,3-diazidopropan-2-yl) propane-1,2,3-tricarboxylate

Conditions	Yield
With dmap; dicyclohexyl-carbodiimide In dichloromethane at 20℃; Green chemistry;	73%

tricarallylic acid (99-14-9) + dibutylamine (111-92-2) → N,N,N',N',N",N"-hexabutyl-propane-1,2,3-tricarboxamide

Conditions	Yield
Stage #1: tricarallylic acid With thionyl chloride In N,N-dimethyl-formamide at 90℃; for 2h; Stage #2: dibutylamine With triethylamine In dichloromethane; N,N-dimethyl-formamide for 120h;	72%
Stage #1: tricarallylic acid With thionyl chloride; N,N-dimethyl-formamide at 90℃; for 2h; Stage #2: dibutylamine With triethylamine In dichloromethane for 120h;	72%

tricarallylic acid (99-14-9) + 2-chlorobenzoic anhydride (49619-43-4) → 6a-(2-chlorophenyl)dihydrofuro[2,3-b]furan-2,5(3H,6aH)-dione

Conditions	Yield
With pyridine In m-xylene at 140℃;	70%

tricarallylic acid (99-14-9) + cyclohexanol (108-93-0) → 3-Cyclohexyloxycarbonyl-pentanedioic acid dicyclohexyl ester

Conditions	Yield
With sulfuric acid In toluene at 190℃; for 24h;	68%

1,2-bis(4'-pyridyl)ethane (4916-57-8) + zinc hydroxide hydrate + tricarallylic acid (99-14-9) + water (7732-18-5) → [Zn(tricarballylic acid-2H)(1,2-bis(4-pyridine)ethane)](n)*4nH2O

Conditions	Yield
In ethanol; water wet Zn(OH)2 was suspn. in water, 0.5 M soln. of tricarballylic acid was added, a soln. of pyridine-compound in abs. ethanol was added dropwise, left overnight; elem. anal.;	68%

tricarallylic acid (99-14-9) + 3-fluorobenzoic acid anhydride (56666-54-7) → 6a-(3-fluorophenyl)dihydrofuro[2,3-b]furan-2,5(3H,6aH)-dione

Conditions	Yield
With pyridine In m-xylene at 140℃;	68%

tricarallylic acid (99-14-9) + cyclohexylamine (108-91-8) → 1,2,3-propanetricarboxylic acid tris(cyclohexylamide)

Conditions	Yield
tricresole borate In xylene for 3h; Product distribution / selectivity; Heating / reflux;	67.2%

4,4'-bipyridine (553-26-4) + zinc hydroxide hydrate + tricarallylic acid (99-14-9) + water (7732-18-5) → [Zn(tricarballylic acid-2H)(4,4'-bipyridine)](n)*3nH2O

Conditions	Yield
In ethanol; water wet Zn(OH)2 was suspn. in water, 0.5 M soln. of tricarballylic acid was added, a soln. of bipyridine in abs. ethanol was added dropwise, left overnight; elem. anal.;	67%

chromium chloride hexahydrate + tricarallylic acid (99-14-9) + water (7732-18-5) + sodium hydroxide (1310-73-2) → Cr(HOOCCH(CH2COO)2)(H2O)2*14H2O

Conditions	Yield
In H2O Cr-compd. dissolved in H2O, 1 M NaOH added, centrifuged, washed with H2O, dispersed in H2O with carboxy-compd. under continuosly stirring, refluxed for 8 h; cooled, filtered, concentrated, EtOH added, dried at 80°C for 2 h, dried in vac., elem. anal.;	65%

tricarallylic acid (99-14-9) + 2-METHYLCYCLOHEXYLAMINE (7003-32-9) → 1,2,3-propanetricarboxylic acid tris(2-methylcyclohexylamide)

Conditions	Yield
tricresole borate In xylene for 3h; Product distribution / selectivity; Heating / reflux;	63%
Stage #1: tricarallylic acid With pyridine; diisopropyl-carbodiimide at 50℃; for 3h; Stage #2: 2-METHYLCYCLOHEXYLAMINE for 8h;	61%
Stage #1: tricarallylic acid With pyridine; diisopropyl-carbodiimide at 50℃; for 3h; Stage #2: 2-METHYLCYCLOHEXYLAMINE for 8h;	61%

1,10-Phenanthroline (66-71-7) + zinc hydroxide hydrate + tricarallylic acid (99-14-9) + water (7732-18-5) → [Zn(tricarballylic acid-2H)(1,10-phenanthroline)(H2O)]2*4H2O

Conditions	Yield
In ethanol; water wet Zn(OH)2 was suspn. in water, 0.5 M soln. of tricarballylic acid was added, a soln. of phenanthroline in abs. ethanol was added dropwise, left overnight; elem. anal.;	61%

tricarallylic acid (99-14-9) + 4-chlorobenzoic anhydride (790-41-0) → 6a-(4-chlorophenyl)dihydrofuro[2,3-b]furan-2,5(3H,6aH)-dione

Conditions	Yield
With pyridine In m-xylene at 140℃;	61%

Gd(3+)*H(1+)*H2CCO2CHCO2CH2CO2(3-)=Gd(H2CCO2CHCO2CH2CO2H)(1+) + tricarallylic acid (99-14-9) → Gd(3+)*2H(1+)*2H2CCO2CHCO2CH2CO2(3-)=Gd(H2CCO2CHCO2CH2CO2H)2(1-)

Conditions	Yield
In water byproducts: H(1+); reaction of Gd(tricarballylateH)(1+) with tricarballylic acid at pH 3.00; nuclear magnetic relaxation;	60%

manganese(II) chloride monohydrate + tricarallylic acid (99-14-9) → [Mn3(tricarballylic acid-3H)2(H2O)4]n

Conditions	Yield
With NaOH In water High Pressure; by a react. of Mn-contg. compd. (0.5 mmol), tricarballylic acid (0.25 mmol), NaOH (1 mmol) in aq. soln. in Teflon-lined autoclave; heating at 160°C for 120 h; cooling over a period of 12 h at a rate of 10°C/h; crystals were collected by filtration, washed with water, and dried at ambient temp.; elem. anal.;	59%

tricarallylic acid (99-14-9) + 4-(trifluoromethyl)benzoic anhydride (25753-16-6) → 6a-(4-(trifluoromethyl)phenyl)dihydrofuro[2,3-b]furan-2,5(3H,6aH)-dione

Conditions	Yield
With pyridine In m-xylene at 140℃;	59%

tricarallylic acid (99-14-9) + 6-chlorohexanoic anhydride → C11H15ClO4

Conditions	Yield
With calcium chloride at 150℃; for 8h;	57%

tricarallylic acid (99-14-9) + Chloroacetic anhydride (541-88-8) → 1-chloromethyl-2,8-dioxabicyclo[3.3.0]octane-3,7-dione (1361185-57-0)

Conditions	Yield
With dmap at 180℃; under 200 Torr; for 3h;	56%

tricarallylic acid (99-14-9) + 3-methylbenzoic acid anhydride (21436-44-2) → 6a-(m-tolyl)dihydrofuro[2,3-b]furan-2,5(3H,6aH)-dione

Conditions	Yield
With pyridine In m-xylene at 140℃;	56%

Upstream product

• 99-67-2 2-allyl-4-pentenoic acid 
• 96-23-1 1,3-Dichloro-2-propanol 
• 151-50-8 potassium cyanide 
• 7647-01-0 hydrogenchloride 
• 95800-58-1 2-ethoxycarbonylmethyl-4,5-dioxo-tetrahydro-furan-2,3-dicarboxylic acid diethyl ester 
• 28781-91-1 propane-1,1,2,2,3,3-hexacarboxylic acid hexamethyl ester 
• 5672-10-6 hex-2-enyl-succinic acid 
• 10028-15-6 ozone 
• 141-78-6 ethyl acetate 
• 68-04-2 sodium citrate 
• 5435-96-1 propane-1,1,2,2,3,3-hexacarboxylic acid hexaethyl ester 
• 4023-65-8 trans-acotinic acid 
• 320-77-4 1-hydroxy-propane-1,2,3-tricarboxylic acid 
• 922-84-9 ethane-1,1,2-tricarboxylic acid 

Downstream Products

• 6138-26-7 1,2,3-propanetricarboxylic acid trimethyl ester 
• 100953-23-9 6a-phenyldihydrofuro[2,3-b]furan-2,5(3H,6aH)-dione 
• 77461-97-3 Tricarballylic α,β-Anhydride Acid Chloride 
• 498-21-5 2-methylbutanedioic acid 
• 188290-36-0 thiophene 

Relevant articles and documents

Selective defunctionalization of citric acid to tricarballylic acid as a precursor for the production of high-value plasticizers

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