16630-52-7

Basic information

• Product Name: 3-(Methylthio)butanal
• Synonyms: 3-(methylthio)-butana;3-(METHYLMERCAPTO)BUTYRALDEHYDE;3-(METHYLTHIO)BUTANAL;3-METHYLTHIO BUTYLALDEHYDE;3-(METHYLTHIO)BUTYRALDEHYDE;FEMA 3374;3-(METHYLTHIO)BUTANAL 96+%;3-(Methylyhio)Butanal
• CAS NO: 16630-52-7
• Molecular Formula: C₅H₁₀OS
• Molecular Weight: 118.2
• EINECS: 240-678-7
• Product Categories: sulfide Flavor;Alphabetical Listings;Flavors and Fragrances;M-N
• Mol File: 16630-52-7.mol
• Article Data: 2

Chemical Properties

• Boiling Point: 62-64 °C10 mm Hg(lit.)
• Flash Point: 144 °F
• Appearance: COA
• Density: 1.001 g/mL at 25 °C(lit.)
• Vapor Density: 4.1 (vs air)
• Vapor Pressure: 60 mm Hg ( 20 °C)
• Refractive Index: n20/D 1.476(lit.)
• Sensitive: Air Sensitive
• CAS DataBase Reference: 3-(Methylthio)butanal(CAS DataBase Reference)
• NIST Chemistry Reference: 3-(Methylthio)butanal(16630-52-7)
• EPA Substance Registry System: 3-(Methylthio)butanal(16630-52-7)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36
• RIDADR: 1989
• WGK Germany: 3
• TSCA: Yes
• Hazardous Substances Data: 16630-52-7(Hazardous Substances Data)

Usage

Description

3-(Methylthio)butanal is an organic compound with a distinct green, musky, and buchu odor, along with a flavor reminiscent of potato chips. It is synthesized by the addition of methanethiol to the corresponding unsaturated aldehyde, which is previously cooled to -20°C, using a catalyst such as piperidine or copper acetate. It can also be produced through a patented oxo process. 3-(Methylthio)butanal is characterized by its taste threshold values and is known to impart vegetative, tomato, fishy, and sulfureous taste characteristics at 0.2 ppm.

Uses

Used in Flavor Industry:
3-(Methylthio)butanal is used as a flavoring agent for its unique potato chip-like flavor. It is particularly useful in the creation of artificial flavors for the food and beverage industry, where it can enhance the taste of various products.
Used in Fragrance Industry:
Due to its green, musky, and buchu odor, 3-(Methylthio)butanal can be employed as a component in the development of fragrances and perfumes. It can contribute to the overall scent profile and provide a distinct character to the final product.
Used in Chemical Research:
3-(Methylthio)butanal can be utilized in chemical research and development, particularly in the study of organic compounds and their properties. It may also be used as a starting material for the synthesis of more complex molecules with potential applications in various industries.
Used in Analytical Chemistry:
3-(Methylthio)butanal can be employed in analytical chemistry for the detection and identification of specific substances, as well as in the development of new analytical methods and techniques.
Used in the Food Industry:
3-(Methylthio)butanal is used as an additive in the food industry to impart a potato chip-like flavor to various products, such as snacks, chips, and other processed foods. It can enhance the taste and overall sensory experience of these products, making them more appealing to consumers.

Preparation

By addition of methanethiol to the corresponding unsaturated aldehyde (previously cooled to -20°C), using piperidine or copper acetate as catalyst; by a patented oxo process

InChI:InChI=1/C5H10OS/c1-5(7-2)3-4-6/h4-5H,3H2,1-2H3/t5-/m1/s1

Synthetic route

crotonaldehyde (123-73-9) + sodium thiomethoxide (5188-07-8) → 3-(methylthio)butyraldehyde (16630-52-7)

Conditions	Yield
With propionic acid In water; toluene at 2 - 70℃; Product distribution / selectivity; Inert atmosphere;	95%
With acetic acid In water; toluene at 2 - 22℃; under 39.754 Torr; Product distribution / selectivity; Inert atmosphere;

trans-Crotonaldehyde (123-73-9) + methylthiol (74-93-1) → 3-(methylthio)butyraldehyde (16630-52-7) + 1,3-bis-methylsulfanyl-but-1-ene (99116-25-3)

Conditions	Yield
With hydrogenchloride; tetrachloromethane

methylthiol (74-93-1) + crotonaldehyde (123-73-9) → 3-(methylthio)butyraldehyde (16630-52-7)

Conditions	Yield
With ascaridole
With piperidine
With hydrogenchloride In tetrachloromethane

pyrrolidine (123-75-1) + 3-(methylthio)butyraldehyde (16630-52-7) → 3-(methylthio)-1-(pyrrolidin-1-yl)-1-butene (1045854-57-6)

Conditions	Yield
With potassium carbonate at -5℃; for 0.166667h;	96%
With potassium carbonate at 4 - 20℃; Inert atmosphere;
In toluene at 3 - 26℃; under 18.0018 Torr; Product distribution / selectivity;

methyl 4-{1-[(tert-butoxycarbonyl)amino]prop-2-yn-1-yl}benzoate + 3-(methylthio)butyraldehyde (16630-52-7) → tert-butyl 2-[4-(methoxycarbonyl)phenyl]-5-[2-(methylthio)propyl]-1H-pyrrole-1-carboxylate

Conditions	Yield
Stage #1: methyl 4-{1-[(tert-butoxycarbonyl)amino]prop-2-yn-1-yl}benzoate; 3-(methylthio)butyraldehyde With bis(norbornadiene)rhodium(l)tetrafluoroborate; 1,1-dicyclohexyl-N-(dicyclohexylphosphino)-N-methylphosphinamine In acetone at 20℃; for 4h; Inert atmosphere; Stage #2: With toluene-4-sulfonic acid In acetone; acetonitrile at 20℃; for 4h; Inert atmosphere;	75%

3-(methylthio)butyraldehyde (16630-52-7) → (4,4-dibromobutan-2-yl)(methyl)sulfane

Conditions	Yield
With triphenyl phosphite; bromine; triethylamine In dichloromethane at -78 - 20℃; Schlenk technique; Inert atmosphere;	41%

methyl (2E)-3-methoxy-2-propenoate (5788-17-0) + 3-(methylthio)butyraldehyde (16630-52-7) → 4-methoxy-5-(2-methyl-sulfanyl-propyl)-5H-furan-2-one (852530-60-0)

Conditions	Yield
Stage #1: methyl (2E)-3-methoxy-2-propenoate With lithium diisopropyl amide In tetrahydrofuran at -100 - -95℃; for 0.1h; Stage #2: 3-(methylthio)butyraldehyde In tetrahydrofuran at -100 - -78℃; for 1.53333h;	30%

formaldehyd (50-00-0) + 3-(methylthio)butyraldehyde (16630-52-7) → 2-(hydroxymethyl)-2-(1-(methylthio)ethyl)propane-1,3-diol

Conditions	Yield
Stage #1: formaldehyd With sodium hydroxide In acetonitrile at 60℃; for 0.333333h; Cannizzaro Reaction; Stage #2: 3-(methylthio)butyraldehyde In acetonitrile for 1h; Reflux;	28%

3-(methylthio)butyraldehyde (16630-52-7) + sodium cyanide (143-33-9) → 5-(2-methylsulfanyl-propyl)-imidazolidine-2,4-dione (858206-51-6)

Conditions	Yield
With ammonium carbonate

pyrrolidine (123-75-1) + 3-(methylthio)butyraldehyde (16630-52-7) → 1-((E)-3-methylthiobut-1-enyl)pyrrolidine

Conditions	Yield
With potassium carbonate at 10 - 20℃;
With potassium carbonate at 4 - 20℃;
With potassium carbonate at 4 - 20℃;

3-(methylthio)butyraldehyde (16630-52-7) + dimethyl amine (124-40-3) → N,N-dimethyl-(3-methylthiobut-1-enyl)amine

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 1.5h;

3-(methylthio)butyraldehyde (16630-52-7) → 4-methyl-D,L-methionine (16820-66-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: 4>2CO3 2: Hydrolysis View Scheme

3-(methylthio)butyraldehyde (16630-52-7) → 2-amino-4-methanesulfinyl-valeric acid

Conditions	Yield
Multi-step reaction with 3 steps 1: 4>2CO3 2: Hydrolysis 3: H2O2 View Scheme

3-(methylthio)butyraldehyde (16630-52-7) → 2-amino-4-(imino-methyl-oxo-λ6-sulfanyl)-valeric acid (70056-02-9)

Conditions	Yield
Multi-step reaction with 4 steps 1: 4>2CO3 2: Hydrolysis 3: H2O2 4: HN3 View Scheme

3-(methylthio)butyraldehyde (16630-52-7) → 2-amino-4-methanesulfonyl-valeric acid

Conditions	Yield
Multi-step reaction with 4 steps 1: 4>2CO3 2: Hydrolysis 3: H2O2 4: H2O2 View Scheme

3-(methylthio)butyraldehyde (16630-52-7) + 1-Phenyl-2-propyn-1-ol (4187-87-5) → C14H16OS (1360610-97-4)

Conditions	Yield
Multi-step reaction with 2 steps 1: bis(norbornadiene)rhodium(l)tetrafluoroborate; 1,2-bis-(diphenylphosphino)ethane / 1,2-dichloro-ethane / 1 h / 65 °C / Inert atmosphere 2: toluene-4-sulfonic acid / 1,2-dichloro-ethane / 2 h / 20 °C / Inert atmosphere View Scheme

3-(methylthio)butyraldehyde (16630-52-7) + 1-Phenyl-2-propyn-1-ol (4187-87-5) → C14H18O2S

Conditions	Yield
With bis(norbornadiene)rhodium(l)tetrafluoroborate; 1,2-bis-(diphenylphosphino)ethane In 1,2-dichloro-ethane at 65℃; for 1h; Inert atmosphere;

3-(methylthio)butyraldehyde (16630-52-7) + 1-triphenylphosphoranylidene-2-propanone (1439-36-7) → (E)-6-methylsulfanylhept-3-en-2-one (1615212-09-3)

Conditions	Yield
In dichloromethane for 7h; Reflux;	5.409 g
In dichloromethane for 7h; Reflux;	5.409 g

3-(methylthio)butyraldehyde (16630-52-7) → ethyl 2-(2-methylsulfanylpropyl)-4,6-dioxocyclohexanecarboxylate (1615212-10-6)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: dichloromethane / 7 h / Reflux 2.1: sodium / ethanol / 1.33 h / 20 °C / Inert atmosphere; Cooling with ice 2.2: 20 °C / Inert atmosphere; Cooling with ice View Scheme
Multi-step reaction with 2 steps 1.1: dichloromethane / 7 h / Reflux 2.1: sodium; ethanol / 1.33 h / 20 °C / Cooling with ice; Inert atmosphere 2.2: 4 h / 20 °C / Cooling with ice View Scheme

3-(methylthio)butyraldehyde (16630-52-7) → 5-(2-methylsulfanylpropyl)cyclohexane-1,3-dione (108463-70-3)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: dichloromethane / 7 h / Reflux 2.1: sodium / ethanol / 1.33 h / 20 °C / Inert atmosphere; Cooling with ice 2.2: 20 °C / Inert atmosphere; Cooling with ice 3.1: hydrogenchloride / water / 6 h / Heating View Scheme
Multi-step reaction with 3 steps 1.1: dichloromethane / 7 h / Reflux 2.1: sodium; ethanol / 1.33 h / 20 °C / Cooling with ice; Inert atmosphere 2.2: 4 h / 20 °C / Cooling with ice 3.1: hydrogenchloride / water / 6 h / Heating View Scheme

3-(methylthio)butyraldehyde (16630-52-7) → sulfoxaflor (946578-00-3)

Conditions	Yield
Multi-step reaction with 5 steps 1: potassium carbonate / toluene / 5 h / 10 - 20 °C / Inert atmosphere 2: acetonitrile / 15 - 20 °C / Inert atmosphere 3: ammonium acetate / acetonitrile / 0.5 h / 80 °C / Inert atmosphere 4: [bis(acetoxy)iodo]benzene / acetonitrile / 2.17 h / 10 - 30 °C 5: sodium permanganate / water; dichloromethane / 1.92 h / 13 - 20 °C View Scheme

3-(methylthio)butyraldehyde (16630-52-7) → 1,1,1-trifluoro-6-(methylthio)-5-(pyrrolidine-1-ylmethylene)hept-3-en-2-one (1380070-36-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: potassium carbonate / toluene / 5 h / 10 - 20 °C / Inert atmosphere 2: acetonitrile / 15 - 20 °C / Inert atmosphere View Scheme

3-(methylthio)butyraldehyde (16630-52-7) → (1-{6-[trifluoromethyl]pyridin-3-yl}ethyl)-(methyl)-λ4-sulfanylidenecyanamide (1049684-75-4, 1049684-74-3, 1046119-63-4)

Conditions	Yield
Multi-step reaction with 4 steps 1: potassium carbonate / toluene / 5 h / 10 - 20 °C / Inert atmosphere 2: acetonitrile / 15 - 20 °C / Inert atmosphere 3: ammonium acetate / acetonitrile / 0.5 h / 80 °C / Inert atmosphere 4: [bis(acetoxy)iodo]benzene / acetonitrile / 2.17 h / 10 - 30 °C View Scheme

3-(methylthio)butyraldehyde (16630-52-7) → (±)5-(1-(methylthio)ethyl)-2-trifluoromethyl pyridine

Conditions	Yield
Multi-step reaction with 3 steps 1: potassium carbonate / toluene / 5 h / 10 - 20 °C / Inert atmosphere 2: acetonitrile / 15 - 20 °C / Inert atmosphere 3: ammonium acetate / acetonitrile / 0.5 h / 80 °C / Inert atmosphere View Scheme

3-(methylthio)butyraldehyde (16630-52-7) → C20H29NO5S

Conditions	Yield
Multi-step reaction with 2 steps 1: formic acid / water; methanol / 20 h / 20 °C / Inert atmosphere 2: C46H34I4O6; potassium fluoride / o-xylene / 24 h / 25 °C / Inert atmosphere View Scheme

3-(methylthio)butyraldehyde (16630-52-7) → C20H29NO5S

Conditions	Yield
Multi-step reaction with 2 steps 1: formic acid / water; methanol / 20 h / 20 °C / Inert atmosphere 2: Tetraethylene glycol; potassium fluoride / o-xylene / 24 h / 25 °C / Inert atmosphere View Scheme

3-(methylthio)butyraldehyde (16630-52-7) + tert-Butyl N-hydroxycarbamate (36016-38-3) + sodium benzenesulfonate (873-55-2) → C16H25NO5S2

Conditions	Yield
With formic acid In methanol; water at 20℃; for 20h; Inert atmosphere;

3-(methylthio)butyraldehyde (16630-52-7) + C20H21F4N3O → 1-benzyl-3-(3-fluoro-5-(trifluoromethyl)phenyl)-1-(1-(3-(methylthio)butyl)piperidin-4-yl)urea

Conditions	Yield
With phenylsilane; dibutyltin chloride In tetrahydrofuran at 20℃; for 16h;

3-(methylthio)butyraldehyde (16630-52-7) → (3-(methylthio)butane-1,1-diyl)bis(dimethyl(phenyl)silane)

Conditions	Yield
Multi-step reaction with 2 steps 1: triphenyl phosphite; bromine; triethylamine / dichloromethane / -78 - 20 °C / Schlenk technique; Inert atmosphere 2: copper(I) bromide dimethylsulfide complex; 4,4'-di-tert-butyl-2,2'-bipyridine; lithium tert-butoxide / tetrahydrofuran; dimethyl sulfoxide / 0 - 20 °C / Schlenk technique; Inert atmosphere View Scheme

Upstream product

• 123-73-9 trans-Crotonaldehyde 
• 74-93-1 methylthiol 
• 123-73-9 crotonaldehyde 
• 5188-07-8 sodium thiomethoxide 

Downstream Products

• 1049684-75-4 (1-{6-[trifluoromethyl]pyridin-3-yl}ethyl)-(methyl)-λ⁴-sulfanylidenecyanamide 
• 946578-00-3 sulfoxaflor 
• 108463-70-3 5-(2-methylsulfanylpropyl)cyclohexane-1,3-dione 
• 1615212-10-6 ethyl 2-(2-methylsulfanylpropyl)-4,6-dioxocyclohexanecarboxylate 
• 1360610-97-4 C₁₄H₁₆OS 

Relevant articles and documents

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PROCESS FOR THE ADDITION OF THIOLATES TO ?,?-UNSATURATED CARBONYL OR SULFONYL COMPOUNDS

Alkylthio substituted aldehydes, ketones, esters and sulfones are prepared by reacting α,β-unsaturated carbonyl and sulfonyl compounds with a sodium or potassium thiolate in the presence of a alkane carboxylic acid and water.