55021-77-7

Basic information

• Product Name: 4-(METHYLTHIO)-1-BUTYLAMINE
• Synonyms: 4-(METHYLTHIO)-1-BUTYLAMINE;4-Methylsulfanyl-butylamine;4-(Methylthio)-1-butanamine
• CAS NO: 55021-77-7
• Molecular Formula: C₅H₁₃NS
• Molecular Weight: 119.22842
• EINECS: 604-604-1
• Product Categories: Chemical Amines;Aliphatics;Amine;Intermediates;Sulfur & Selenium Compounds
• Mol File: 55021-77-7.mol
• Article Data: 12

Chemical Properties

• Boiling Point: 188-190°C
• Flash Point: 64.2 °C
• Appearance: /
• Density: 0.926 g/cm³
• Vapor Pressure: 0.809mmHg at 25°C
• Refractive Index: 1.482
• CAS DataBase Reference: 4-(METHYLTHIO)-1-BUTYLAMINE(CAS DataBase Reference)
• NIST Chemistry Reference: 4-(METHYLTHIO)-1-BUTYLAMINE(55021-77-7)
• EPA Substance Registry System: 4-(METHYLTHIO)-1-BUTYLAMINE(55021-77-7)

Safety Data

• Hazardous Substances Data: 55021-77-7(Hazardous Substances Data)

Usage

Chemical Properties

Pale Yellow Oil

Uses

4-(Methylthio)-1-butylamine is used in the synthesis of sulforaphane and related isothiocyanates.

InChI:InChI=1/C5H13NS/c1-7-5-3-2-4-6/h2-6H2,1H3

Synthetic route

4-(methylthio)butyronitrile (59121-24-3) → 4-(methylthio)-1-butylamine (55021-77-7)

Conditions	Yield
With lithium aluminium tetrahydride In diethyl ether for 0.5h; Reflux;	93%
With borane In tetrahydrofuran at 20℃;	63%
With ethanol; sodium

2-<2-(Methylthio)butyl>-1H-isoindole-1,3(2H)-dione (52096-68-1) → 4-(methylthio)-1-butylamine (55021-77-7)

Conditions	Yield
With hydrazine hydrate In ethanol for 5h; Reflux;	83.2%
With hydrazine In ethanol for 3h; Heating / reflux;	80%
With hydrazine hydrate In ethanol for 3h; Reflux;	80%

1-azido-(4-methylsulfenyl)butane (57775-01-6) → 4-(methylthio)-1-butylamine (55021-77-7)

Conditions	Yield
With lithium aluminium tetrahydride	54%

ethanol (64-17-5) + 4-(methylthio)butyronitrile (59121-24-3) + sodium → 4-(methylthio)-1-butylamine (55021-77-7)

ω-chloro-1-methylsulfanylbutane (27160-24-3) → 4-(methylthio)-1-butylamine (55021-77-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: tetrabutylammomium bromide / toluene / 18 h / 0 - 20 °C 2: hydrazine hydrate / ethanol / 5 h / Reflux View Scheme

4-(methylthio)-1-butylamine (55021-77-7) → (+/-)-1-amino-4-(methylsulfinyl)butane (84104-30-3)

Conditions	Yield
With dihydrogen peroxide In 2,2,2-trifluoroethanol at 0 - 20℃; for 1.33333h; Inert atmosphere;	90%
With sulfuric acid; dihydrogen peroxide; isopropyl alcohol In methanol at 20℃; for 2h;	64%
With sulfuric acid; dihydrogen peroxide In methanol; water; isopropyl alcohol at 20℃; for 3h;	63%
With dihydrogen peroxide; acetone

4-(methylthio)-1-butylamine (55021-77-7) + erucin (4430-36-8) → 1,3-bis(4-(methylthio)-butyl)thiourea

Conditions	Yield
In dichloromethane for 2h; Reflux;	89%

thiophosgene (463-71-8) + 4-(methylthio)-1-butylamine (55021-77-7) → erucin (4430-36-8)

Conditions	Yield
With sodium hydroxide In dichloromethane at 0 - 20℃; for 3h;	86.5%
With sodium hydroxide In dichloromethane at 0 - 20℃; for 3.5h;	84%
With sodium hydroxide In dichloromethane at 0 - 20℃; for 3.5h; Inert atmosphere;	84%

4-(methylthio)-1-butylamine (55021-77-7) → 4-methanesulfonyl-butylamine (552838-69-4)

Conditions	Yield
With potassium permanganate

4-(methylthio)-1-butylamine (55021-77-7) + phenyl isothiocyanate (103-72-0) → 1-benzyl-3-(4-(methylthio)butyl)thiourea (100317-76-8)

carbon disulfide (75-15-0) + 4-(methylthio)-1-butylamine (55021-77-7) → erucin (4430-36-8)

Conditions	Yield
Yield given. Multistep reaction;
Stage #1: carbon disulfide; 4-(methylthio)-1-butylamine With triethylamine In tetrahydrofuran at 0 - 20℃; Stage #2: With methanesulfonyl chloride In tetrahydrofuran at 0 - 20℃; for 0.5h;

4-(methylthio)-1-butylamine (55021-77-7) + CS2 → erucin (4430-36-8)

Conditions	Yield
With ethanol Oxydation des Reaktionsprodukts mit 0.5 Mol Jod in Aethanol, Einwirkung von Natriumaethylat-Loesung und erneute Oxydation mit 0.5 Mol Jod in Aethanol bei 0grad;

4-(methylthio)-1-butylamine (55021-77-7) + CS2 → 1,3-bis(4-(methylthio)-butyl)thiourea

4-(methylthio)-1-butylamine (55021-77-7) → D,L-sulforaphane (4478-93-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: 12.5 mmol / sodium hydroxide / CHCl3 2: 100 percent / m-chloroperbenzoic acid / CH2Cl2 / 0.5 h View Scheme
Multi-step reaction with 2 steps 1: 64 percent / aq. H2O2; H2SO4; i-PrOH / methanol / 2 h / 20 °C 2: 57 percent / aq. NaOH / CHCl3 / 0.58 h View Scheme
Multi-step reaction with 2 steps 1: sulfuric acid; dihydrogen peroxide / methanol; water; isopropyl alcohol / 3 h / 20 °C 2: sodium hydroxide / chloroform / 1 h / 20 °C View Scheme

4-(methylthio)-1-butylamine (55021-77-7) → N-acetyl-S-{N-[4-(methylthio)butyl]thiocarbamoyl}-L-cysteine

Conditions	Yield
Multi-step reaction with 2 steps 1: 12.5 mmol / sodium hydroxide / CHCl3 2: 7.1 mmol / sodium hydrogen carbonate / ethanol; H2O View Scheme

4-(methylthio)-1-butylamine (55021-77-7) → N-acetyl-S-{N-[4-(methylsulfinyl)butyl]thiocarbamoyl}-L-cysteine

Conditions	Yield
Multi-step reaction with 3 steps 1: 12.5 mmol / sodium hydroxide / CHCl3 2: 100 percent / m-chloroperbenzoic acid / CH2Cl2 / 0.5 h 3: 69.5 percent / sodium hydrogen carbonate / ethanol; H2O View Scheme

4-(methylthio)-1-butylamine (55021-77-7) → R-sulforaphane (142825-10-3)

Conditions	Yield
Multi-step reaction with 2 steps 2: aq. ethanol / 48 h / 27 °C / Helminthosporium species NRRL 4671 View Scheme

4-(methylthio)-1-butylamine (55021-77-7) → (S)-Sulforaphane (155320-20-0)

Conditions	Yield
Multi-step reaction with 2 steps 2: aq. ethanol / 48 h / 27 °C / Helminthosporium species NRRL 4671 View Scheme

4-(methylthio)-1-butylamine (55021-77-7) → (4-methylsulfanyl-butyl)-thiourea (7431-78-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: ethanol / Oxydation des Reaktionsprodukts mit 0.5 Mol Jod in Aethanol, Einwirkung von Natriumaethylat-Loesung und erneute Oxydation mit 0.5 Mol Jod in Aethanol bei 0grad 2: ethanol; NH3 View Scheme

4-(methylthio)-1-butylamine (55021-77-7) → N,N'-bis-(4-methylsulfanyl-butyl)-urea

Conditions	Yield
Multi-step reaction with 2 steps 1: ethanol / Oxydation des Reaktionsprodukts mit 0.5 Mol Jod in Aethanol, Einwirkung von Natriumaethylat-Loesung und erneute Oxydation mit 0.5 Mol Jod in Aethanol bei 0grad 2: Ag2O; aqueous dioxane / 70 °C View Scheme

4-(methylthio)-1-butylamine (55021-77-7) → erysolin (504-84-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: KMnO4 2: alcohol / laesst auf das Reaktionsprodukt Jod einwirken, versetzt mit Natriumaethylatloesung und behandelt mit Jod View Scheme
Multi-step reaction with 3 steps 1.1: dihydrogen peroxide / 2,2,2-trifluoroethanol / 1.33 h / 0 - 20 °C / Inert atmosphere 2.1: triethylamine / ethanol / 0.5 h / 20 °C / Inert atmosphere 2.2: 2.25 h / 0 - 20 °C 3.1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 3 h / -20 - 20 °C / Inert atmosphere View Scheme
Multi-step reaction with 2 steps 1: sodium hydroxide / dichloromethane / 3.5 h / 0 - 20 °C / Inert atmosphere 2: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 2 h / Inert atmosphere View Scheme

4-(methylthio)-1-butylamine (55021-77-7) → N,N'-bis-(4-methanesulfonyl-butyl)-thiourea

Conditions	Yield
Multi-step reaction with 2 steps 1: KMnO4 View Scheme

4-(methylthio)-1-butylamine (55021-77-7) → (4-methanesulfonyl-butyl)-trimethyl-ammonium; iodide

Conditions	Yield
Multi-step reaction with 2 steps 1: KMnO4 2: sodium methylate View Scheme

4-(methylthio)-1-butylamine (55021-77-7) → N-benzyl-N'-(4-methylsulfanyl-butyl)-thiourea (100801-39-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: chloroform; aqueous NaOH-solution View Scheme

4-(methylthio)-1-butylamine (55021-77-7) → N-(4-(methylsulfonyl)butyl)morpholine-4-carbothioamide (1356472-68-8)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: dihydrogen peroxide / 2,2,2-trifluoroethanol / 1.33 h / 0 - 20 °C / Inert atmosphere 2.1: triethylamine / ethanol / 0.5 h / 20 °C / Inert atmosphere 2.2: 2.25 h / 0 - 20 °C 3.1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 3 h / -20 - 20 °C / Inert atmosphere 4.1: dichloromethane / 1 h / Reflux View Scheme

4-(methylthio)-1-butylamine (55021-77-7) → O-ethyl 4-(methylsulfinyl)butylcarbamothioate (1356472-67-7)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: dihydrogen peroxide / 2,2,2-trifluoroethanol / 1.33 h / 0 - 20 °C / Inert atmosphere 2.1: triethylamine / ethanol / 0.5 h / 20 °C / Inert atmosphere 2.2: 2.25 h / 0 - 20 °C 3.1: Reflux; Inert atmosphere View Scheme

4-(methylthio)-1-butylamine (55021-77-7) → 1-(4-(methylsulfinyl)butyl)-3-(5-oxohexyl)thiourea (1356346-97-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: dihydrogen peroxide / 2,2,2-trifluoroethanol / 1.33 h / 0 - 20 °C / Inert atmosphere 2: dichloromethane / 3 h / Reflux View Scheme

4-(methylthio)-1-butylamine (55021-77-7) → N,N’-di-(4-methylsulfinylbutyl)thiourea

Conditions	Yield
Multi-step reaction with 2 steps 1: dihydrogen peroxide / 2,2,2-trifluoroethanol / 1.33 h / 0 - 20 °C / Inert atmosphere 2: dichloromethane / 1 h / Reflux View Scheme
Multi-step reaction with 3 steps 1.1: dihydrogen peroxide / 2,2,2-trifluoroethanol / 1.33 h / 0 - 20 °C / Inert atmosphere 2.1: triethylamine / ethanol / 0.5 h / 20 °C / Inert atmosphere 2.2: 2.25 h / 0 - 20 °C 3.1: dichloromethane / 1 h / Reflux View Scheme

4-(methylthio)-1-butylamine (55021-77-7) → N-(4-(methylsulfinyl)butyl)piperidine-1-carbothioamide (1350914-98-5)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: dihydrogen peroxide / 2,2,2-trifluoroethanol / 1.33 h / 0 - 20 °C / Inert atmosphere 2.1: triethylamine / ethanol / 0.5 h / 20 °C / Inert atmosphere 2.2: 2.25 h / 0 - 20 °C 3.1: dichloromethane / 1 h / Reflux View Scheme

4-(methylthio)-1-butylamine (55021-77-7) → 4-methyl-N-(4-(methylsulfinyl)-butyl)piperazine-1-carbothioamide (1356472-66-6)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: dihydrogen peroxide / 2,2,2-trifluoroethanol / 1.33 h / 0 - 20 °C / Inert atmosphere 2.1: triethylamine / ethanol / 0.5 h / 20 °C / Inert atmosphere 2.2: 2.25 h / 0 - 20 °C 3.1: dichloromethane / 1 h / Reflux View Scheme

4-(methylthio)-1-butylamine (55021-77-7) → N-(4-(methylsulfinyl)butyl)-morpholine-4-carbothioamide (1356346-82-1)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: dihydrogen peroxide / 2,2,2-trifluoroethanol / 1.33 h / 0 - 20 °C / Inert atmosphere 2.1: triethylamine / ethanol / 0.5 h / 20 °C / Inert atmosphere 2.2: 2.25 h / 0 - 20 °C 3.1: dichloromethane / 1 h / Reflux View Scheme

Upstream product

• 59121-24-3 4-(methylthio)butyronitrile 
• 52096-68-1 2-<2-(Methylthio)butyl>-1H-isoindole-1,3(2H)-dione 
• 57775-01-6 1-azido-(4-methylsulfenyl)butane 
• 64-17-5 ethanol 
• 27160-24-3 ω-chloro-1-methylsulfanylbutane 

Downstream Products

• 100317-76-8 1-benzyl-3-(4-(methylthio)butyl)thiourea 
• 504-84-7 erysolin 
• 1356346-85-4 1-(1-benzyl-piperidin-4-yl)-3-4-(methylsulfinyl)butyl thiourea 
• 100801-39-6 N-benzyl-N'-(4-methylsulfanyl-butyl)-thiourea 
• 142825-10-3 R-sulforaphane 
• 84104-30-3 (+/-)-1-amino-4-(methylsulfinyl)butane 
• 334829-66-2 sulforaphane-N-acetyl-cysteine 
• 4478-93-7 D,L-sulforaphane 

Relevant articles and documents

Antioxidant activity of two edible isothiocyanates: Sulforaphane and erucin is due to their thermal decomposition to sulfenic acids and methylsulfinyl radicals

Sulforaphane (SFN) and erucin (ERN) are isothiocyanates (ITCs) bearing, respectively, methylsulfinyl and methylsulfanyl groups. Their chemopreventive and anticancer activity is attributed to ability to modulate cellular redox status due to induction of Phase 2 cytoprotective enzymes (indirect antioxidant action) but many attempts to connect the bioactivity of ITCs with their radical trapping activity failed. Both ITCs are evolved from their glucosinolates during food processing of Cruciferous vegetables, therefore, we studied antioxidant behaviour of SFN/ERN at elevated temperature in two lipid systems. Neither ERN nor SFN inhibit the oxidation of bulk linolenic acid (below 100 °C) but both ITCs increase oxidative stability of soy lecithin (above 150 °C). On the basis of GC-MS analysis we verified our preliminary hypothesis (Antioxidants 2020, 9, 1090) about participation of sulfenic acids and methylsulfinyl radicals as radical trapping agents responsible for the antioxidant effect of edible ITCs during thermal oxidation of lipids at elevated temperatures (above 140 °C).

ISOTHIOCYNATES AND GLUCOSINOLATE COMPOUNDS AND ANTI-TUMOR COMPOSITIONS CONTAINING SAME

The present invention provides glucosinolate and isothiocyanate compounds and related methods for synthesizing these compounds and analogs. In certain embodiments, these glucosinolate and isothiocyanate compounds are useful and chemopreventive and or chemotherapeutic agents.

PROCESS FOR THE SYNTHESIS OF ISOTHIOCYANATES AND DERIVATIVES THEREOF AND USES OF SAME

A method for synthesizing an isothiocyanate of general formula (I) [in-line-formulae]SCN—R1—R4—R2??(I)[/in-line-formulae] wherein R1 and R2 represent independently of each other an alkyl-aryl or aryl group, R4 represents a carbonyl, sulfinyl, sulfonyl group or a sulfide group and of its derivatives comprising a step for reacting an alkylalkylamine having the general formula (II) [in-line-formulae]NH2—R1—R4—R2??(II)[/in-line-formulae] wherein R1 and R2 represent independently of each other an alkyl, aryl or alkylaryl group, R4 represents a carbonyl, sulfinyl, sulfonyl or sulfide group, in the presence of carbon sulfide and of di-tert-butyl dicarbonate with formation of the corresponding aforesaid isothiocyanate, compounds obtained by this method as well as their uses.