2396-68-1

Basic information

• Product Name: 4-TERT-BUTYLTHIOPHENOL
• Synonyms: P-TERT-BUTYLTHIOPHENOL;4-(TERT-BUTYL)BENZENE-1-THIOL;4-TERT-BUTYLBENZENETHIOL;4-TERT-BUTYLTHIOPHENOL;P-t-Butyl ThioPhenol;4-tert-Butylthiophenol, 97+%;P-TERT-BUTYLPHENYLMERCAPTAN;4-tert-Butylbenzolthiol
• CAS NO: 2396-68-1
• Molecular Formula: C₁₀H₁₄S
• Molecular Weight: 166.28
• EINECS: 219-255-6
• Product Categories: Phenol&Thiophenol&Mercaptan;Phenoles and thiophenoles
• Mol File: 2396-68-1.mol
• Article Data: 10

Chemical Properties

• Melting Point: -11 °C
• Boiling Point: 238 °C(lit.)
• Flash Point: >230 °F
• Appearance: clear colorless liquid
• Density: 0.964 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.0992mmHg at 25°C
• Refractive Index: n20/D 1.5480(lit.)
• Storage Temp.: Inert atmosphere,Room Temperature
• PKA: 6.76±0.10(Predicted)
• Water Solubility: Insoluble in water.
• Sensitive: Air Sensitive
• BRN: 606476
• CAS DataBase Reference: 4-TERT-BUTYLTHIOPHENOL(CAS DataBase Reference)
• NIST Chemistry Reference: 4-TERT-BUTYLTHIOPHENOL(2396-68-1)
• EPA Substance Registry System: 4-TERT-BUTYLTHIOPHENOL(2396-68-1)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36
• RIDADR: UN 3334
• WGK Germany: 3
• RTECS: DC1025000
• Hazardous Substances Data: 2396-68-1(Hazardous Substances Data)

Usage

Chemical Properties

clear colorless liquid

Uses

4-tert-butylthiophenol is used as a pharmaceutical intermediate.

Synthesis Reference(s)

The Journal of Organic Chemistry, 31, p. 3980, 1966 DOI: 10.1021/jo01350a023

InChI:InChI=1/C10H14S/c1-10(2,3)8-4-6-9(11)7-5-8/h4-7,11H,1-3H3/p-1

Synthetic route

bis(4-tert-butylphenyl)disulfide (7605-48-3) → 4-t-butylbenzenethiol (2396-68-1)

Conditions	Yield
With hydrogen; rhodium hydrido (PEt3)3 complex In toluene for 0.5h; Heating;	98%

4-tert-butylbenzenesulfonyl chloride (15084-51-2) → 4-t-butylbenzenethiol (2396-68-1)

Conditions	Yield
With hydrogenchloride; chlorosulfonic acid; sodium sulfide; iron; triphenylphosphine In water at 200℃; for 4h; Solvent; Reagent/catalyst; Temperature;	93.7%
With sulfuric acid; zinc for 3.5h; Heating;	85%
With sulfuric acid; water; zinc for 5h; Reflux; Cooling with ice;	85%

thiophenol (108-98-5) + isobutene (115-11-7) → 4-t-butylbenzenethiol (2396-68-1)

Conditions	Yield
In toluene	68%
With boron trifluoride at 80℃; for 6h;

4-tert-butylphenyl tert-butyl thioether (25752-79-8) + thiophenol (108-98-5) → 4-t-butylbenzenethiol (2396-68-1)

Conditions	Yield
In toluene	65%

4-tert-butylbenzenesulfonyl chloride (15084-51-2) → bis(4-tert-butylphenyl)disulfide (7605-48-3) + 4-t-butylbenzenethiol (2396-68-1)

Conditions	Yield
With lithium aluminium tetrahydride; diethyl ether

tert-butyl phenyl sulfide (3019-19-0) + thiophenol (108-98-5) → 4-t-butylbenzenethiol (2396-68-1)

Conditions	Yield
With boron trifluoride

tert-butylbenzene (253185-03-4, 253185-04-5) → 4-t-butylbenzenethiol (2396-68-1)

Conditions	Yield
Multistep reaction;
Multi-step reaction with 2 steps 1: ClSO3H 2: (reduction) View Scheme

4-(tert-butyl)-1-phenyl N,N-dimethylthiocarbamate (13511-96-1) → 4-t-butylbenzenethiol (2396-68-1)

Conditions	Yield
With sodium hydroxide In methanol

1-tert.-butyl-benzene-sulfonic acid-(4)-chloride → 4-t-butylbenzenethiol (2396-68-1)

Conditions	Yield
With hydrogenchloride; tin

tert-butylbenzene (253185-03-4, 253185-04-5) + tetrafluoroboric acid → 4-t-butylbenzenethiol (2396-68-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: 107.5 g / chlorsulfonic acid / CHCl3 / 1 h / -5 - 20 °C 2: 69 percent / Zn, H2SO4 / H2O / 1.) 0 deg C, 1 h, 2.) reflux, 6 h View Scheme

tert-butylbenzene (253185-03-4, 253185-04-5) + silicon dioxide zirconium dioxide aluminium oxide contacts → 4-t-butylbenzenethiol (2396-68-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: chlorosulphuric acid / CHCl3 / 0.33 h / Ambient temperature 2: concd. H2SO4, Zn / 5 h / Heating View Scheme

N,N-Dimethyl-thiocarbamidsaeure-O-<4-tert.-butyl-phenylester> (13522-61-7) → 4-t-butylbenzenethiol (2396-68-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: 270 °C 2: aq. NaOH / methanol View Scheme

sodium 4-tert-butylphenolate (5787-50-8) → 4-t-butylbenzenethiol (2396-68-1)

Conditions	Yield
Multi-step reaction with 3 steps 2: 270 °C 3: aq. NaOH / methanol View Scheme

1-bromo-4-tert-butylbenzene (3972-65-4) → 4-t-butylbenzenethiol (2396-68-1)

Conditions	Yield
With hydrogen sulfide

4-t-butylbenzenethiol (2396-68-1) → bis(4-tert-butylphenyl)disulfide (7605-48-3)

Conditions	Yield
With (S)-tetrahydrotellurophen-3-amine hydrochloride; dihydrogen peroxide In dichloromethane at 25℃; pH=7.5; Flow reactor;	100%
With nickel(II) chloride hexahydrate; cadmium selenide; sodium hydroxide In water at 20℃; for 4h; pH=9; Catalytic behavior; Irradiation; Inert atmosphere;	99%
With N,N,N,N,-tetramethylethylenediamine; oxygen; eosin y In ethanol for 0.333333h; Irradiation;	99%

(R)-6-((R)-4,4-Dimethyl-2-oxo-tetrahydro-furan-3-yloxy)-6H-pyran-3-one (138842-58-7) + 4-t-butylbenzenethiol (2396-68-1) → (5S,6R)-5-(4-tert-Butyl-phenylsulfanyl)-6-((R)-4,4-dimethyl-2-oxo-tetrahydro-furan-3-yloxy)-dihydro-pyran-3-one (138842-63-4)

Conditions	Yield
triethylamine In dichloromethane at 0℃;	100%

4-t-butylbenzenethiol (2396-68-1) + 4-(2-perfluorohexyl)ethylbenzyl crotonate (356055-79-3) → 3-(4-tert-butyl-phenylsulfanyl)-butyric acid 4-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-octyl)-benzyl ester (356055-92-0)

Conditions	Yield
With triethylamine In tetrahydrofuran at 20℃; for 15h; Michael addition;	100%

4-t-butylbenzenethiol (2396-68-1) + 4-(2-perfluorodecyl)ethylbenzyl methacrylate (356055-87-3) → 3-(4-tert-butyl-phenylsulfanyl)-2-methyl-propionic acid 4-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluoro-dodecyl)-benzyl ester (356055-99-7)

Conditions	Yield
With triethylamine In tetrahydrofuran at 20℃; for 15h; Michael addition;	100%

4-t-butylbenzenethiol (2396-68-1) + p-benzoquinone (106-51-4) → C16H18O2S (1408333-63-0)

Conditions	Yield
In methanol	100%

3,5-bis(chloromethyl)-4-methylbenzoic acid (37908-90-0) + 4-t-butylbenzenethiol (2396-68-1) → C30H36O2S2

Conditions	Yield
With potassium carbonate In 1,4-dioxane at 20℃;	100%

acetic acid (64-19-7) + 4-t-butylbenzenethiol (2396-68-1) → S-(4-(tert-butyl)phenyl) ethanethioate

Conditions	Yield
With potassium phosphate; 18-crown-6 ether In tetrahydrofuran Glovebox; Molecular sieve; Schlenk technique; Reflux;	100%
With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; N-ethyl-N,N-diisopropylamine In ethyl acetate at 20℃; for 12h; Green chemistry;	76 %Spectr.

bicyclo[1.1.1]pentane (311-75-1) + 4-t-butylbenzenethiol (2396-68-1) → bicyclo[1.1.1]pentan-1-yl(4-(tert-butyl)phenyl)sulfane

Conditions	Yield
In diethyl ether at 21℃; for 1h; Inert atmosphere;	100%

acrylic acid methyl ester (292638-85-8) + 4-t-butylbenzenethiol (2396-68-1) → methyl 3-((4-(tert-butyl)phenyl)sulfonyl)propanoate

Conditions	Yield
Stage #1: acrylic acid methyl ester; 4-t-butylbenzenethiol With sodium acetate In tetrahydrofuran; water for 18h; Stage #2: With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃;	100%

2,2-difluoroacetic anhydride (401-67-2) + 4-t-butylbenzenethiol (2396-68-1) → C12H14F2OS

Conditions	Yield
With pyridine In dichloromethane at 20℃; for 2h;	100%

1-iodo-butane (542-69-8) + 4-t-butylbenzenethiol (2396-68-1) → butyl-4-(tert-butyl)phenyl sulfane (30506-37-7)

Conditions	Yield
With potassium hydroxide In methanol at 20℃; for 12h;	100%

2,6-dinitrobenzonitrile (35213-00-4) + 4-t-butylbenzenethiol (2396-68-1) → 2-(4-tert-Butyl-phenylsulfanyl)-6-nitro-benzonitrile (168910-31-4)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 0℃; for 0.5h;	99%

4-t-butylbenzenethiol (2396-68-1) + 2-chloro-3-ethoxy-6-nitrobenzonitrile (1026566-04-0) → 3-ethoxy-6-nitro-2-<(4-tert-butylphenyl)thio>benzonitrile (1025967-04-7)

Conditions	Yield
With potassium tert-butylate In dimethyl sulfoxide for 2h;	99%

4-t-butylbenzenethiol (2396-68-1) + ortho-nitrofluorobenzene (1493-27-2) → 1-(4-tert-butyl-phenylsulfanyl)-2-nitro-benzene (3169-88-8)

Conditions	Yield
With potassium fluoride on basic alumina; 18-crown-6 ether In acetonitrile for 3h; Heating;	99%
With potassium fluoride impregnated on clinoptilolite; air In dimethyl sulfoxide at 110 - 115℃; for 0.666667h;	98%

4-tolyl iodide (624-31-7) + 4-t-butylbenzenethiol (2396-68-1) → 1-t-butyl-4-[(4-methylphenyl)thio]benzene

Conditions	Yield
With copper(l) iodide; 5,6,9,10-tetrahydro-4H,8H-pyrido[3,2,1-ij][1,6]naphthyridine; caesium carbonate In toluene at 110℃; for 40h; post-Ullmann reaction;	99%

cyclohexenone (930-68-7) + 4-t-butylbenzenethiol (2396-68-1) → (S)-3-(4-tert-butylphenylthio)-cyclohexanone (113036-75-2)

Conditions	Yield
With 1-(3,5-bis(trifluoromethyl)phenyl)-3-((S)-(6-methoxyquinolin-4-yl)((2S,4S,8R)-8-vinylquinuclidin-2-yl)methyl)urea In toluene at 20℃; for 8h; Michael addition; optical yield given as %ee; enantioselective reaction;	99%

para-iodoanisole (696-62-8) + 4-t-butylbenzenethiol (2396-68-1) → (4-(tert-butyl)phenyl)(4-methoxyphenyl)sulfane

Conditions	Yield
With chloro(1,5-cyclooctadiene)rhodium(I) dimer; triphenylphosphine; sodium t-butanolate In toluene at 100℃; for 24h; Inert atmosphere;	99%
With copper(l) iodide; caesium carbonate; 1-ethyl-3-methylimidazolium tetrafluoroborate at 115℃; for 15h; Ullmann Condensation; Inert atmosphere;	70%

4-t-butylbenzenethiol (2396-68-1) + Diphenylphosphine oxide (4559-70-0) → (S)-(4-(tert-butyl)phenyl) diphenylphosphinothioate

Conditions	Yield
With potassium carbonate In tetrahydrofuran at 20℃; for 6h;	99%
With trifluoromethylsulfonic anhydride In dimethyl sulfoxide; acetonitrile at 20℃; for 12h; Reagent/catalyst; Solvent; Inert atmosphere;	96%
With trifluoromethylsulfonic anhydride; dimethyl sulfoxide In acetonitrile at 20℃; Inert atmosphere;	96%

1-methyl-3-(2-nitrovinyl)benzene (22568-43-0, 62248-93-5) + 4-t-butylbenzenethiol (2396-68-1) → (S)-(4-(tert-butyl)phenyl)(2-nitro-1-(m-tolyl)ethyl)sulfide

Conditions	Yield
With (S)-2-(3-(3,5-bis(trifluoromethyl)phenyl)thioureido)-N-((S)-(6-methoxyquinolin-4-yl)((1S,2S,4S,5R)-5-vinylquinuclidin-2-yl)methyl)-3,3-dimethylbutanamide at -40℃; for 4h; Michael Addition; enantioselective reaction;	99%

4-methyl-β-nitrostyrene (7559-36-6) + 4-t-butylbenzenethiol (2396-68-1) → (S)-(4-(tert-butyl)phenyl)(2-nitro-1-(p-tolyl)ethyl)sulfide

Conditions	Yield
With (S)-2-(3-(3,5-bis(trifluoromethyl)phenyl)thioureido)-N-((S)-(6-methoxyquinolin-4-yl)((1S,2S,4S,5R)-5-vinylquinuclidin-2-yl)methyl)-3,3-dimethylbutanamide at -40℃; for 4h; Michael Addition; enantioselective reaction;	99%

1-fluoro-3-(2-nitrovinyl)benzene (1979-49-3, 705-84-0) + 4-t-butylbenzenethiol (2396-68-1) → (S)-(4-(tert-butyl)phenyl)(1-(3-fluorophenyl)-2-nitroethyl)sulfide

Conditions	Yield
With (S)-2-(3-(3,5-bis(trifluoromethyl)phenyl)thioureido)-N-((S)-(6-methoxyquinolin-4-yl)((1S,2S,4S,5R)-5-vinylquinuclidin-2-yl)methyl)-3,3-dimethylbutanamide at -40℃; for 4h; Michael Addition; enantioselective reaction;	99%

1-chloro-4-(2-nitrovinyl)benzene (706-07-0) + 4-t-butylbenzenethiol (2396-68-1) → (S)-(4-(tert-butyl)phenyl)(1-(4-chlorophenyl)-2-nitroethyl)sulfide

Conditions	Yield
With (S)-2-(3-(3,5-bis(trifluoromethyl)phenyl)thioureido)-N-((S)-(6-methoxyquinolin-4-yl)((1S,2S,4S,5R)-5-vinylquinuclidin-2-yl)methyl)-3,3-dimethylbutanamide at -40℃; for 4h; Michael Addition; enantioselective reaction;	99%

4-bromo-β-nitrostyrene (3156-37-4) + 4-t-butylbenzenethiol (2396-68-1) → (S)-(1-(4-bromophenyl)-2-nitroethyl)(4-(tert-butyl)phenyl)sulfide

Conditions	Yield
With (S)-2-(3-(3,5-bis(trifluoromethyl)phenyl)thioureido)-N-((S)-(6-methoxyquinolin-4-yl)((1S,2S,4S,5R)-5-vinylquinuclidin-2-yl)methyl)-3,3-dimethylbutanamide at -40℃; for 4h; Michael Addition; enantioselective reaction;	99%

2-(2-nitrovinyl)naphthalene (37629-37-1, 21461-46-1) + 4-t-butylbenzenethiol (2396-68-1) → (S)-(4-(tert-butyl)phenyl)(1-(naphthalen-2-yl)-2-nitroethyl)sulfide

Conditions	Yield
With (S)-2-(3-(3,5-bis(trifluoromethyl)phenyl)thioureido)-N-((S)-(6-methoxyquinolin-4-yl)((1S,2S,4S,5R)-5-vinylquinuclidin-2-yl)methyl)-3,3-dimethylbutanamide at -40℃; for 4h; Michael Addition; enantioselective reaction;	99%

indole (120-72-9) + 4-t-butylbenzenethiol (2396-68-1) → 3-((4-(tert-butyl)phenyl)thio)-1H-indole (1605290-39-8)

Conditions	Yield
With manganese(IV) oxide; iodine; oxygen at 80℃; for 16h; Schlenk technique;	99%

4-t-butylbenzenethiol (2396-68-1) → S,S,S-tris(4-(tert-butyl)phenyl) phosphorotrithioate

Conditions	Yield
Stage #1: 4-t-butylbenzenethiol With phosphorus; potassium carbonate In dimethyl sulfoxide; toluene at 20℃; for 4h; Schlenk technique; Stage #2: With dihydrogen peroxide In dimethyl sulfoxide; toluene at 20℃; for 0.5h; Schlenk technique;	99%

cyclohexenone (930-68-7) + 4-t-butylbenzenethiol (2396-68-1) → rac-3-(4-tert-butylphenylthio)-cyclohexanone (64888-90-0, 113036-75-2, 116403-76-0, 36674-55-2)

Conditions	Yield
With potassium fluoride; Quinine In toluene for 20h; Ambient temperature;	98%
With 1,8-diazabicyclo[5.4.0]undec-7-ene In tetrahydrofuran for 24h; Michael addition;	90%
With chiral N-methylmesoporphyrine II derivatives In toluene at -40℃; Rate constant; variation of porphyrine derivatives, enantioselectivity;	75%

4-t-butylbenzenethiol (2396-68-1) + 2-chloro-3-isobutoxy-6-nitrobenzonitrile (1026596-29-1) → 3-isobutoxy-6-nitro-2-<(4-tert-butylphenyl)thio>benzonitrile (1026564-28-2)

Conditions	Yield
With potassium tert-butylate In dimethyl sulfoxide for 2h;	98%

ethyl (Z)-3-iodopropenoate (31930-36-6) + 4-t-butylbenzenethiol (2396-68-1) → (Z)-3-(4-tert-butyl-phenylsulfanyl)-acrylic acid ethyl ester (1227376-30-8)

Conditions	Yield
With potassium phosphate; copper(l) iodide; cis-1,2-cyclohexane In N,N-dimethyl-formamide at 40 - 50℃; for 2h; Inert atmosphere;	98%
With caesium carbonate In N,N-dimethyl-formamide at 20℃; for 2h; Inert atmosphere; stereospecific reaction;	98%
With potassium phosphate; copper(l) iodide; cis-1,2-cyclohexane In N,N-dimethyl-formamide at 30 - 40℃; Inert atmosphere;

Upstream product

• 15084-51-2 4-tert-butylbenzenesulfonyl chloride 
• 3019-19-0 tert-butyl phenyl sulfide 
• 108-98-5 thiophenol 
• 253185-03-4 tert-butylbenzene 
• 7605-48-3 bis(4-tert-butylphenyl)disulfide 
• 25752-79-8 4-tert-butylphenyl tert-butyl thioether 
• 3972-65-4 1-bromo-4-tert-butylbenzene 
• 5787-50-8 sodium 4-tert-butylphenolate 
• 13522-61-7 N,N-Dimethyl-thiocarbamidsaeure-O-<4-tert.-butyl-phenylester> 
• 13511-96-1 4-(tert-butyl)-1-phenyl N,N-dimethylthiocarbamate 
• 115-11-7 isobutene 

Downstream Products

• 52785-77-0 N,N-Bis-[2-(4-tert-butyl-phenylsulfanyl)-ethyl]-propionamide 
• 1158-36-7 Thiokohlensaeure-O-<3-chlorphenylester>-S-<4-tert.-butyl-phenylestser>-imid 
• 5851-38-7 3-((4-(tert-butyl)phenyl)thio)propan-1-ol 
• 115412-34-5 2,4-Bis-(4-tert-butyl-phenylsulfanyl)-butyraldehyde 
• 115412-33-4 [6-tert-Butyl-4-(4-tert-butyl-phenylsulfanyl)-thiochroman-4-yl]-methanol 
• 115412-32-3 (Z)-2,4-Bis-(4-tert-butyl-phenylsulfanyl)-but-2-en-1-ol 
• 115412-32-3 (E)-2,4-Bis-(4-tert-butyl-phenylsulfanyl)-but-2-en-1-ol 
• 115412-30-1 7-tert-Butyl-4,5-bis-(4-tert-butyl-phenylsulfanyl)-2,3,4,5-tetrahydro-benzo[b]thiepine 
• 30506-33-3 1-ethylsulfanyl-4-(1,1-dimethylethyl)benzene 
• 117526-64-4 4-tert-butyl-2-(trimethylsilyl)benzenethiol 
• 76440-47-6 3-((p-tert-butylphenyl)thio)-5,5-dimethylcyclohexanone 
• 102918-96-7 trans-2-(p-t-butylphenylthio)cyclohexanol 
• 161344-81-6 trans-2-(p-tert-butylbenzenethio)cyclohexanol 
• 64888-90-0 rac-3-(4-tert-butylphenylthio)-cyclohexanone 

Relevant articles and documents

Preparation method of alkyl-substituted thiophenol

The invention provides a preparation method of alkyl-substituted thiophenol. Alkyl-substituted benzene sulfonyl chloride is used as a raw material, a mixed solvent and acid are regarded as a reactionsystem, and under synergistic catalysis of metal and organophosphorus and reduction action of reductive salt, the alkyl-substituted thiophenol is obtained. The preparation method of the alkyl-substituted thiophenol has a high industrialized application value, an Iron powder reduction technology can be effectively replaced, the defects that an organic reducing system is high in cost, high in toxicity, difficult in post-treatment and the like are overcome, inorganic salt which is cheap and easy to get is used as a main reducing agent, through the synergistic catalysis action, the reducibility ofthe inorganic salt is significantly improved, the reaction yield stabilizes at 92% or above, and a technology has the characteristics of being simple and convenient to operate, short in production cycle, low in cost, clean, environmentally friendly and suitable for industrialized production.

Preparation of new tert-butyl substituted coumarins, thiocoumarins and dithiocoumarins

6-tert-Butyl-4-methyl- and 6,8-di-tert-butyl-4-methylcoumarin were prepared from tert-butylphenols and diketene via the corresponding aryl acetoacetates. 6-tert-Butyl-4-methyl-thiocoumarin (6) was obtained from 6-tert-butylthiophenol. Thionation with Lawesson's or Davy's reagent led to the related thion- and dithiocoumarins. The structures were proved by NMR spectroscopy and an X-ray structure analysis of 6.

Catalytic kinetic resolution of 5-alkoxy-2(5H)-furanones

The kinetic resolution of racemic 5-alkoxy-2(5H)-furanones, using a chiral aminoalcohol catalyzed 1,4-addition of arylthiols, was examined. Using various butenolides it was shown that a γ-alkoxy substituent appears to be essential to reach high enantioselectivities whereas electron-donating substituents in the arylthiols also increase the selectivity. Cinchona alkaloids are the preferred catalysts for the kinetic resolution, with quinine and quinidine leading to the most efficient and selective thiol additions. A remarkable dilution effect and a strong dependency on the mode of addition of reactants were observed. Optimization studies are presented of the kinetic resolution of 5-methoxy-2(5H)-furanone 2 resulting in (R)-2 or (S)-2 with enantiomeric excesses exceeding 90%. A mechanism for the quinine (quinidine) catalyzed kinetic resolution is given.