1587-20-8

Basic information

• Product Name: TRIMETHYL CITRATE
• Synonyms: 2,3-propanetricarboxylicacid,2-hydroxy-trimethylester;3-Hydroxy-3-methoxycarbonylpentanedioic acid, dimethyl ester;Trimethyl 2-hydroxy-1,2,3-propanetricarboxylate;METHYL CITRATE;CITRIC ACID TRIMETHYL ESTER;TRIMETHYL CITRATE;1,2,3-Propanetricarboxylic acid, 2-hydroxy-, trimethyl ester;2-Hydroxy-1,2,3-propanetricarboxylic acid trimethyl ester
• CAS NO: 1587-20-8
• Molecular Formula: C₉H₁₄O₇
• Molecular Weight: 234.2
• EINECS: 216-449-2
• Product Categories: Functional Materials;Hydroxycarboxylic Acid Esters (Plasticizer);Plasticizer;C8 to C9;Carbonyl Compounds;Esters;Miscellaneous
• Mol File: 1587-20-8.mol
• Article Data: 22

Chemical Properties

• Melting Point: 75-78 °C
• Boiling Point: 176 16mm
• Flash Point: 79.2 °C
• Appearance: /
• Density: 1.3363 (rough estimate)
• Vapor Pressure: 0.00732mmHg at 25°C
• Refractive Index: 1.4455 (estimate)
• Storage Temp.: Sealed in dry,Room Temperature
• Solubility: Chloroform (Sparingly), Methanol (Slightly)
• PKA: 10.43±0.29(Predicted)
• Water Solubility: 53.2g/L at 20℃
• BRN: 1796169
• CAS DataBase Reference: TRIMETHYL CITRATE(CAS DataBase Reference)
• NIST Chemistry Reference: TRIMETHYL CITRATE(1587-20-8)
• EPA Substance Registry System: TRIMETHYL CITRATE(1587-20-8)

Safety Data

• Safety Statements: 22-24/25
• WGK Germany: 3
• Hazardous Substances Data: 1587-20-8(Hazardous Substances Data)

Usage

Description

Trimethyl citrate is an ester of citric acid. It is a kind of non-toxic plasticizer1. Trimethyl citrate is one of the constituents of Dioscorea opposita2. The IC50 value for monoamine oxidase-B of trimethyl citrate was studied. It has various applications3: it can do the main flame retardant candle flame color, its melting point and can fully meet the flammability requirements of candle products. It can be used for the synthesis of pharmaceutical and pesticide. It can act as the main raw material for the production of citric acid hydrochloride, citric acid hydrochloride as well as the synthetic hot melt adhesive. It can also be used as the methyl methacrylate polymer a blowing agent, a stabilizer acrylamide, polyamide adhesive initiators, PVC plasticizers. It can also be used as solvent for household and II cleaner, film-former4.

Reference

Huang, Li, L. I. Chun-Lian, and H. U. Qing-Guo. "Study on Catalytic Synthesis of Trimethyl Citrate by Solid Acid." Liaoning Chemical Industry (2012). https://www.sigmaaldrich.com/catalog/product/aldrich/27502?lang=en®ion=US www.zhonglanindustry.com/product/trimethyl-citrate https://www.lookchem.com/Trimethyl-citrate/

Uses

Trimethyl Citrate is a reagent used in the preparation of citrate-ciprofloxacin conjugates which has antibacterial activity.

General Description

Trimethyl citrate is one of the constituents of Dioscorea opposita. The IC50 value for monoamine oxidase-B of trimethyl citrate was studied.

Flammability and Explosibility

Notclassified

InChI:InChI=1/C9H14O7/c1-14-6(10)4-9(13,8(12)16-3)5-7(11)15-2/h13H,4-5H2,1-3H3

Synthetic route

methanol (67-56-1) + citric acid (77-92-9) → trimethyl citrate (1587-20-8)

Conditions	Yield
With zirconium(IV) oxychloride In toluene at 120℃; for 1h;	99%
With thionyl chloride at 0 - 20℃;	98%
With thionyl chloride In methanol at 0 - 20℃; Inert atmosphere;	98%

methanol (67-56-1) + malonic acid (141-82-2) → trimethyl citrate (1587-20-8)

Conditions	Yield
With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione at 70℃; for 20h;	94%

diazomethane (186581-53-3, 908094-01-9) + citric acid (77-92-9) → trimethyl citrate (1587-20-8)

Conditions	Yield
In methanol; diethyl ether at 0℃;	90%
In methanol; diethyl ether

methanol (67-56-1) + sym-dimethyl citrate * H2O → trimethyl citrate (1587-20-8)

Conditions	Yield
With sulfuric acid; 2,2-dimethoxy-propane for 7h; Heating;	88%

methanol (67-56-1) + citric acid (77-92-9) → 3-oxopentanedioic acid dimethyl ester (1830-54-2) + dimethyl 2-methoxypropene-1,3-dicarboxylate (100009-70-9) + trimethyl aconitate (20820-77-3) + trimethyl citrate (1587-20-8) + acetoacetic acid methyl ester (105-45-3)

Conditions	Yield
Stage #1: citric acid With chlorosulfonic acid In dichloromethane at 10 - 15℃; for 5 - 6h; Stage #2: methanol In dichloromethane at 3 - 35℃; for 2h; Conversion of starting material;	A 87.3% B n/a C n/a D n/a E n/a

diazomethane (186581-53-3, 908094-01-9) + 2-Hydroxy-1,2,3-propanetricarboxylic Acid 2-Methyl Ester (26163-65-5) → trimethyl citrate (1587-20-8)

Conditions	Yield
In methanol; diethyl ether at 0℃;	85%

acetic acid tert-butyl ester (540-88-5) + 1,5-dimethyl citrate (53798-96-2) → trimethyl citrate (1587-20-8) + 2-tert-butyl 1,3-dimethyl 2-hydroxypropane-1,2,3-tricarboxylate (114340-51-1)

Conditions	Yield
With perchloric acid for 72h; Ambient temperature;	A n/a B 78%

1,5-dimethyl citrate (53798-96-2) + 2,2-dimethoxy-propane (77-76-9) → trimethyl citrate (1587-20-8)

Conditions	Yield
With sulfuric acid for 7h; Reflux;	62%

citric acid (77-92-9) → trimethyl citrate (1587-20-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 29 percent / 98percent H2SO4 / 1 h / Heating 2: 60percent HClO4 / 72 h / Ambient temperature View Scheme

methanol (67-56-1) + citric acid triethyl ester (77-93-0) → trimethyl citrate (1587-20-8) + 1,6-dimethyl 5-ethyl citrate (1242516-57-9) + 1,2-diethyl-3-methyl-2-hydroxypropane-1,2,3-tricarboxylate (1242516-58-0)

Conditions	Yield
With SEC-BUTYLAMINE at 20℃; Product distribution / selectivity;

methanol (67-56-1) + triethyl O-acetylcitrate (77-89-4) + tert-butylamine (75-64-9) → trimethyl citrate (1587-20-8) + citric acid triethyl ester (77-93-0) + dimethyl 3-(tertbutylcarbamoyl)-3-acetoxy-pentanedioate (1242516-65-9) + 3-(tertbutylcarbamoyl)-3-acetoxy-pentanedioic acid (1242516-64-8)

Conditions	Yield
at 20℃;

methanol (67-56-1) + citric acid (77-92-9) → dimethyl methylsuccinate (21307-96-0, 22644-27-5, 63163-08-6, 1604-11-1) + trimethyl citrate (1587-20-8)

Conditions	Yield
With hydrogen In water at 200℃; under 3000.3 Torr; for 6h;	A 7 %Spectr. B n/a

trimethyl citrate (1587-20-8) → 3-hydroxy-5-methoxy-3-(methoxycarbonyl)-5-oxopentanoic acid (53798-97-3)

Conditions	Yield
With sodium hydroxide; water In methanol at 20℃; for 2h;	99%
With sodium hydroxide In methanol; water for 2h; Ambient temperature;	57%
With sodium hydroxide In methanol; water at 20℃; for 2h; regioselective reaction;	39%

trimethyl citrate (1587-20-8) + N,N-dimethylethylenediamine (108-00-9) → C18H38N6O4

Conditions	Yield
at 106℃; for 3h;	99%

4-hydroxy-2,2,6,6-tetramethylpiperidine (2403-88-5) + trimethyl citrate (1587-20-8) → C33H59N3O7

Conditions	Yield
With titanium(IV) isopropylate at 130℃; for 16h;	91%

1,2,2,6,6-pentamethyl-piperidin-4-ol (2403-89-6) + trimethyl citrate (1587-20-8) → C36H65N3O7

Conditions	Yield
With titanium(IV) isopropylate at 130℃; for 16h; Reagent/catalyst;	90.24%

1-cyclohexyloxy-4-hydroxy-2,2,6,6-tetramethylpiperidine (87018-00-6) + trimethyl citrate (1587-20-8) → C51H89N3O10

Conditions	Yield
With titanium(IV) isopropylate at 130℃; for 24h;	86.77%

trimethyl citrate (1587-20-8) → 2-hydroxypropane-1,2,3-tricarbohydrazide (18960-42-4)

Conditions	Yield
With hydrazine hydrate In ethanol; water Heating;	85%
With hydrazine In ethanol; water Heating / reflux;	85%

1-ethoxy-4-hydroxy-2,2,6,6-tetramethylpiperidine + trimethyl citrate (1587-20-8) → C39H71N3O10

Conditions	Yield
With titanium(IV) isopropylate at 130℃; for 22h;	83.2%

1-methoxy-2,2,6,6-tetramethylpiperidin-4-ol (122586-72-5) + trimethyl citrate (1587-20-8) → C36H65N3O10

Conditions	Yield
With titanium(IV) isopropylate at 130℃; for 18h; Reagent/catalyst;	82.33%

trimethyl citrate (1587-20-8) + nonyl alcohol (143-08-8) → trinonyl citrate (16544-71-1)

Conditions	Yield
With tetramethylammonium methyl carbonate In tetrahydrofuran for 15h; Solvent; Molecular sieve; Reflux; Green chemistry;	79%

trimethyl citrate (1587-20-8) → 2-Hydroxy-1,2,3-propanetricarboxylic Acid 2-Methyl Ester (26163-65-5)

Conditions	Yield
With sodium hydroxide In methanol; water for 2h;	73%

1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine (131807-04-0) + trimethyl citrate (1587-20-8) → C57H107N3O10

Conditions	Yield
With titanium(IV) isopropylate at 130℃; for 28h;	65.56%

trimethyl citrate (1587-20-8) + 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine (52185-71-4) → C54H77N3O7

Conditions	Yield
With titanium(IV) isopropylate at 130℃; for 32h;	60.96%

trimethyl citrate (1587-20-8) + methyl iodide (74-88-4) → trimethyl 2-methoxypropane-1,2,3-tricarboxylate

Conditions	Yield
With silver(l) oxide at 100℃; for 40h; Autoclave;	10%
With silver(l) oxide

trimethyl citrate (1587-20-8) → citric acid α,α'-diamide (725679-43-6) + citric acid α-amide (130839-31-5)

Conditions	Yield
With ammonia; water Nebenprod.2:Citronensaeure-triamid;

trimethyl citrate (1587-20-8) → citric acid triamide (597-59-1)

Conditions	Yield
With ammonia; water

trimethyl citrate (1587-20-8) → trimethyl trans-aconitate (4271-99-2)

Conditions	Yield
bei der Destillation;
Multi-step reaction with 2 steps 1: phosphorus pentachloride 2: bei der Destillation View Scheme

trimethyl citrate (1587-20-8) → 2-chloro-propane-1,2,3-tricarboxylic acid trimethyl ester

Conditions	Yield
With phosphorus pentachloride

trimethyl citrate (1587-20-8) → citric acid α,β-dimethyl ester-α'-propyl ester

trimethyl citrate (1587-20-8) → citric acid α,β-dimethyl ester-α'-pentyl ester

trimethyl citrate (1587-20-8) → citrazinic acid (99-11-6)

Conditions	Yield
With ammonia im Rohr;
With ammonium hydroxide Erhitzen des Reaktionsprodukts mit wss. H2SO4 auf 130grad;

trimethyl citrate (1587-20-8) + chloral (75-87-6) → (5-oxo-2-trichloromethyl-[1,3]dioxolane-4,4-diyl)-bis-acetic acid dimethyl ester

Conditions	Yield
With sulfuric acid

trimethyl citrate (1587-20-8) + acetyl chloride (75-36-5) → 2-acetoxy-propane-1,2,3-tricarboxylic acid trimethyl ester (146340-22-9)

Upstream product

• 67-56-1 methanol 
• 77-92-9 citric acid 
• 141-82-2 malonic acid 
• 77-89-4 triethyl O-acetylcitrate 
• 75-64-9 tert-butylamine 
• 77-93-0 citric acid triethyl ester 
• 53798-96-2 1,5-dimethyl citrate 
• 77-76-9 2,2-dimethoxy-propane 
• 540-88-5 acetic acid tert-butyl ester 
• 186581-53-3 diazomethane 
• 26163-65-5 2-Hydroxy-1,2,3-propanetricarboxylic Acid 2-Methyl Ester 

Downstream Products

• 725679-43-6 citric acid α,α'-diamide 
• 130839-31-5 citric acid α-amide 
• 597-59-1 citric acid triamide 
• 53798-97-3 3-hydroxy-5-methoxy-3-(methoxycarbonyl)-5-oxopentanoic acid 
• 38116-04-0 citric acid tris-benzylamide 
• 99-11-6 citrazinic acid 
• 4271-99-2 trimethyl trans-aconitate 

Relevant articles and documents

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A FACILE PREPARATION OF ASYM-MONOMETHYL, SYM-MONOMETHYL AND ASYM-DIMETHYL CITRATE

Asym-monomethyl citrate was prepared by hydrolysis of sym-dimethyl citrate.Sym-monomethyl and sym-dimethyl citrate were prepared by a selective hydrolysis of trimethyl citrate.

A Br?nsted acidic, ionic liquid containing, heteropolyacid functionalized polysiloxane network as a highly selective catalyst for the esterification of dicarboxylic acids

A Br?nsted acidic, ionic liquid containing, heteropolyanion functionalized polysiloxane network was formed by self-condensation of dodecatungstophosphoric acid and a zwitterionic organosilane precursor containing both imidazolinium and sulfonate groups. The resulting hybrid material POS-HPA-IL was investigated as a catalyst for the selective esterification of dicarboxylic acids.

METHOD FOR THE PRODUCTION OF METHYLSUCCINIC ACID AND THE ANHYDRIDE THEREOF FROM CITRIC ACID

A process for the preparation of methylsuccinic acid in any form, including its salts, its mono- and diester derivatives and the anhydride thereof, which comprises reacting citric acid or a derivative thereof in decarboxylation conditions, said process comprising (i) reacting citric acid or mono- and diester derivatives thereof in a non- aqueous solvent, specifically excluding alcohols, on a metallic catalyst at a temperature between 50 to 400°C and under a partial hydrogen pressure from 0.1 to 50 bar or (ii) reacting citric acid or any salt thereof or mono-, di- and triester derivatives thereof on a metallic catalyst in solvents comprising at least 5% water, at a temperature of from 50 to 400°C under a hydrogen partial pressure from 0.1 to 400 bar