13253-44-6

Basic information

• Product Name: 5-(2-Methylthioethyl)hydantoin
• Synonyms: 5-(2-(methylthio)ethyl)-2,4-imidazolidinedione;5-(2-(methylthio)ethyl)-4-imidazolidinedione;5-(2-(methylthio)ethyl)-hydantoi;5-(beta-(methylthio)ethyl)hydantoin;5-(beta-methylmercaptoethyl)hydantoin;5-[2-(methylthio)ethyl]-4-imidazolidinedione;cp93520;dl-5-(2-(methylthio)ethyl)hydantoin
• CAS NO: 13253-44-6
• Molecular Formula: C₆H₁₀N₂O₂S
• Molecular Weight: 174.22
• EINECS: 236-238-9
• Mol File: 13253-44-6.mol
• Article Data: 16

Chemical Properties

• Melting Point: 108°C
• Boiling Point: °Cat760mmHg
• Flash Point: °C
• Appearance: /
• Density: 1.228g/cm³
• PKA: 8.77±0.10(Predicted)
• CAS DataBase Reference: 5-(2-Methylthioethyl)hydantoin(CAS DataBase Reference)
• NIST Chemistry Reference: 5-(2-Methylthioethyl)hydantoin(13253-44-6)
• EPA Substance Registry System: 5-(2-Methylthioethyl)hydantoin(13253-44-6)

Safety Data

• Safety Statements: 22-24/25
• RTECS: NI9461351
• Hazardous Substances Data: 13253-44-6(Hazardous Substances Data)

Usage

Uses

5-[2-(Methylthio)ethyl]hydantoin is a reagent used in L-amino acid production.

Hazard

Low toxicity by ingestion and skin contact.

Synthetic route

2-hydroxy-4-(methylthio)butyronitrile (17773-41-0) + ammonium bicarbonate → 5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6)

Conditions	Yield
In water at 80℃; for 2h;	99%

sodium cyanide (773837-37-9) + 4-(methylthio)butanal (42919-64-2) + carbon dioxide (124-38-9) → 5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6)

Conditions	Yield
With ammonia under 15001.5 Torr; for 0.266667h; Pressure; Time; Concentration;	94.65%

methylthiol (74-93-1) + 3-cyano-3-hydroxy-1-propene (5809-59-6) → 5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6) + 2-[(aminocarbonyl)amino]-4-(methylthio)butanoamide (55064-40-9)

Conditions	Yield
With ammonium carbonate In methanol at 80℃; for 1.5h;	A 85% B 12%

2-hydroxy-4-(methylthio)butyronitrile (17773-41-0) → hydantoin amide (89033-45-4) + 5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6)

Conditions	Yield
With ammonium carbonate; ammonium bicarbonate In water at 105℃; for 0.583333h; Reagent/catalyst; Autoclave;	A 17.9% B 74.9%

Reaxys ID: 12045731 → 5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6) + DL-methionine (59-51-8) + DL-methionine amide (19298-72-7)

Conditions	Yield
Stage #1: With carbon dioxide In water at 60℃; under 112511 Torr; Stage #2: With ammonia In water at 250℃; Stage #3: titanium(IV) oxide at 180℃;	A n/a B 63% C n/a

DL-methionine (59-51-8) + sodium cyanate → 5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6)

Conditions	Yield
With hydrogenchloride

2-hydroxy-4-(methylthio)butyronitrile (17773-41-0) + ammonium carbonate (506-87-6) → 5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6)

hydrogen cyanide (74-90-8) + 3-(methylsulfenyl)propanal (3268-49-3) + carbon dioxide (124-38-9) → 5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6)

Conditions	Yield
With ammonia; water at 105 - 130℃; Industrial scale;

hydrogen cyanide (74-90-8) + 3-(methylsulfenyl)propanal (3268-49-3) + ammonium carbonate (506-87-6) → 5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6)

Conditions	Yield
In water at 110℃; for 1h;

methylthiol (74-93-1) + hydrogen cyanide (74-90-8) + carbon dioxide (124-38-9) + acrolein (107-02-8) → 5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6)

Conditions	Yield
With ammonia In methanol at 80℃; for 1.5h;

potassium cyanide + 3-(methylsulfenyl)propanal (3268-49-3) + ammonium bicarbonate → 5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6)

Conditions	Yield
at 60 - 140℃; for 0.116667h; Temperature;

2-hydroxy-4-(methylthio)butyronitrile (17773-41-0) + carbon dioxide (124-38-9) → 5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6)

Conditions	Yield
With ammonia; ammonium bicarbonate In water at 80 - 130℃; Temperature; Large scale;

methionine aldehyde → 5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: 20 °C / 760.05 Torr 2: water / 2.5 h / 75 °C / 760.05 Torr View Scheme

ammonium carbonate (506-87-6) + methionine cyanohydrin → 5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6)

Conditions	Yield
In water at 75℃; under 760.051 Torr; for 2.5h;

5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6) → DL-methionine (59-51-8)

Conditions	Yield
Stage #1: 5-[2-(methylthio)ethyl]imidazolidine-2,4-dione With water; potassium carbonate at 120 - 160℃; Sonication; Stage #2: at 80 - 120℃; Reagent/catalyst; Sonication;	99.9%
Stage #1: 5-[2-(methylthio)ethyl]imidazolidine-2,4-dione With water; potassium hydroxide at 173 - 178℃; for 1h; Stage #2: With carbon dioxide; water at 20℃; Crystallization; Presence of polyvinyl alcohol;	97%
With water; potassium hydroxide at 120 - 173℃; pH=10.5;	53.6%

5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6) → L-methionine (63-68-3) + (S)-N-carbamoylmethionine (54896-74-1)

Conditions	Yield
In water at 30℃; for 72h; Mechanism; Pseudomonas sp. strain NS671, air. pH 7.0 - 7.2; different cultivation times, other 5-substituted hydantoins;	A 98% B n/a
With sodium hydroxide; air at 30℃; for 72h; Pseudomonas sp. Strain NS671;	A 93% B n/a
at 40℃; Product distribution; Mechanism; conversion by Pseudomonas sp. strain NS671;

5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6) → (R)-N-carbamoylmethionine (23479-37-0)

Conditions	Yield
With D-hydantoinase 1 In water at 50℃; for 12.7h; pH 8.5;	81%
With Tris-HCl buffer; Pseudomonas sp. AJ-11220 In various solvent(s) at 30℃; for 2h; Mechanism; pH 8.5; enzymatic reaction;
With Tris-HCl buffer; Pseudomonas sp. AJ-11220 In various solvent(s) at 30℃; for 2h;

5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6) + rhodium(III)chloride (10049-07-7) → Rh(3+)*H(1+)*CH3SCH2CH2C3HN2O2(2-)*2Cl(1-)*H2O = Rh(C6H9N2O2S)Cl2(H2O)

Conditions	Yield
With water In not given heating (pH=3); filtration, washing (H2O and EtOH), further product on evapn. of filtrate, addn. of Na2CO3 (pH = 3), drying; elem. anal.;	42%

5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6) + methyl iodide (74-88-4) → [2-(2,5-dioxo-imidazolidin-4-yl)-ethyl]-dimethyl sulfonium ; iodide (7673-71-4)

Conditions	Yield
With water

5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6) → D-methionine (348-67-4)

Conditions	Yield
Mechanism; enzymatic hydrolysis of several hydantoines with Pseudomonas Sp.;
With potassium phosphate buffer; Pseudomonas sp. AJ-11220 In various solvent(s) at 30℃; for 2h; pH 8.0; enzymatic reaction;
at 37℃; Pseudomonas Sp.;
With potassium phosphate buffer; Pseudomonas sp. AJ-11220 In various solvent(s) at 30℃; for 2h;

5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6) → L-methionine (63-68-3)

Conditions	Yield
at 30℃; Product distribution; conversion by E. coli pHPB12;
at 30℃; Arthrobacter globiformis;
Multi-step reaction with 3 steps 1.1: sodium hydroxide; pyrographite / 130 °C 2.1: 5 h / pH 2 - 4 2.2: 65 °C / pH 4 3.1: sodium hydroxide; cobalt(II) chloride / 36 h / 37 °C / pH 6.5 / Large scale; Enzymatic reaction View Scheme

5-[2-(methylthio)ethyl]imidazolidine-2,4-dione (13253-44-6) → D-4-hydroxyphenylglycine (22818-40-2)

Conditions	Yield
In water at 30℃; for 24h; Product distribution; 0.1 M potassium phosphate buffer (pH = 8.0); bacterioal strain H-319; also H-968;

Upstream product

• 17773-41-0 2-hydroxy-4-(methylthio)butyronitrile 
• 506-87-6 ammonium carbonate 
• 74-90-8 hydrogen cyanide 
• 3268-49-3 3-(methylsulfenyl)propanal 
• 124-38-9 carbon dioxide 
• 773837-37-9 sodium cyanide 
• 42919-64-2 4-(methylthio)butanal 
• 74-93-1 methylthiol 
• 107-02-8 acrolein 
• 59-51-8 DL-methionine 
• 121-44-8 triethylamine 
• 40856-81-3 5-[2-(methylthio)ethyl]-2,4-imidazolidinedione 
• 5809-59-6 3-cyano-3-hydroxy-1-propene 
• 151-50-8 potassium cyanide 

Downstream Products

• 348-67-4 D-methionine 
• 63-68-3 L-methionine 
• 54896-74-1 (S)-N-carbamoylmethionine 
• 22818-40-2 D-4-hydroxyphenylglycine 
• 59-51-8 DL-methionine 
• 94087-93-1 2-hydroxy-4-methylmercaptobutyric acid potassium salt 
• 36963-02-7 3,6-bis[2-(methylthio)ethyl]-2,5-piperazinedione 
• 7349-78-2 DD/LL/LD/DL-methionylmethionine 
• 41863-30-3 methionine sodium salt 

Relevant articles and documents

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Single-step synthesis of 5-(β-methylthioethyl)hydantoin from acrolein cyanohydrin and acrolein

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METHOD FOR MANUFACTURING METHIONINE

An object of the present invention is to provide a method for manufacturing methionine capable of achieving an improvement in ammonia removal efficiency. The manufacturing method of the present invention comprises a removal step of supplying a liquid containing a methionine salt, which is obtained by reacting 3-methylmercaptopropionaldehyde and hydrocyanic acid, or a compound obtained by reacting 3-methylmercaptopropionaldehyde and hydrocyanic acid, with carbon dioxide and ammonia to obtain a liquid containing 5-(2-methylmercaptoethyl)hydantoin and then hydrolyzing the 5-(2-methylmercaptoethyl)hydantoin, to a diffusion tower from an upper portion thereof while supplying a stripping gas to the diffusion tower from a lower portion thereof to remove ammonia contained in the liquid through stripping, and the stripping gas contains a process gas generated in a process of manufacturing methionine.

By coarse hydrocyanic acid gas preparation 5 - (2-methylthioamphetamine amido ethyl)-hydantoin method

The invention relates to a method for preparing 5-(2-methylmercapto-ethyl)-hydantoin by utilizing crude hydrocyanic acid gas and relates to the field of chemical industry. The method disclosed by the invention comprises the following steps of: completely reacting hydrocyanic acid mixed gas made by adopting an Ann method with methylmercapto propionaldehyde to obtain a 2-hydroxyl-4-methylmercapto-butyronitrile reaction system under the catalytic action of organic alkali; and sufficiently reacting the 2-hydroxyl-4-methylmercapto-butyronitrile reaction system with ammonium bicarbonate in a water medium to obtain 5-(2-methylmercapto-ethyl)-hydantoin. Due to adoption of raw materials which are not rectified or purified, the method disclosed by the invention is short in production time, high in production efficiency and low in production cost; the prepared 2-hydroxyl-4-methylmercapto-butyronitrile reaction system is steady in property and can be stored for a long time; and 5-(2-methylmercapto-ethyl)-hydantoin with high purity and high yield can be obtained through simple separation and purification operations under the synergistic effect of other substances in reaction liquid.