62968-45-0

Basic information

• Product Name: Benzenehexathiol
• Synonyms: Benzenehexathiol
• CAS NO: 62968-45-0
• Molecular Formula: C₆H₆S₆
• Molecular Weight: 270.50184
• Mol File: 62968-45-0.mol
• Article Data: 4

Chemical Properties

• Boiling Point: 519.9±50.0 °C(Predicted)
• Appearance: /
• Density: 1.638±0.06 g/cm3(Predicted)
• PKA: 3.77±0.50(Predicted)
• CAS DataBase Reference: Benzenehexathiol(CAS DataBase Reference)
• NIST Chemistry Reference: Benzenehexathiol(62968-45-0)
• EPA Substance Registry System: Benzenehexathiol(62968-45-0)

Safety Data

• Hazardous Substances Data: 62968-45-0(Hazardous Substances Data)

Usage

General Description

Benzenehexathiol, also known as 1,2,3,4,5,6-Hexathiahenzene, is a chemical compound consisting of a benzene ring with six attached thiol (sulfhydryl) groups. It is a highly aromatic and volatile compound with a strong odor and is commonly used as a reagent in organic synthesis and as a corrosion inhibitor. Benzenehexathiol is also known for its ability to form self-assembled monolayers on gold surfaces, making it useful in the development of sensor and electronic devices. Due to its toxic and flammable nature, proper handling and storage are essential when working with benzenehexathiol.

Synthetic route

Hexa-natrium-benzen-hexathiolat (110431-65-7) → hexamercaptobenzene (62968-45-0)

Conditions	Yield
With hydrogenchloride	96%
With hydrogenchloride In water	93%

hexakis(benzylthio)benzene (127022-77-9) → hexamercaptobenzene (62968-45-0)

Conditions	Yield
With ammonia; sodium

hexakis(isopropylthio)benzene (74542-72-6) → hexamercaptobenzene (62968-45-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: Na, liq. NH3 / -78 °C 2: 96 percent / 5percent aq. HCl View Scheme
Stage #1: hexakis(isopropylthio)benzene With sodium at 100℃; Stage #2: With hydrogenchloride In methanol; water

Hexafluorobenzene (392-56-3) → hexamercaptobenzene (62968-45-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1,3-dimethyl-2-imidazolidinone / 0 °C / Inert atmosphere 2: sodium / 100 °C View Scheme
Multi-step reaction with 2 steps 1: 1,3-dimethyl-2-imidazolidinone / 0 °C / Inert atmosphere 2: sodium / 100 °C View Scheme
Multi-step reaction with 2 steps 1: 1,3-dimethyl-2-imidazolidinone / 0 °C / Inert atmosphere 2: sodium / 100 °C View Scheme

hexabromobenzene (87-82-1) → hexamercaptobenzene (62968-45-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1,3-dimethyl-2-imidazolidinone / 100 °C / Inert atmosphere 2: sodium / 100 °C View Scheme
Multi-step reaction with 2 steps 1: 1,3-dimethyl-2-imidazolidinone / 100 °C / Inert atmosphere 2: sodium / 100 °C View Scheme
Multi-step reaction with 2 steps 1: 1,3-dimethyl-2-imidazolidinone / 100 °C / Inert atmosphere 2: sodium / 100 °C View Scheme

hexakis(methylthio) benzene (58468-22-7) → hexamercaptobenzene (62968-45-0)

Conditions	Yield
Stage #1: hexakis(methylthio) benzene With sodium at 100℃; Stage #2: With hydrogenchloride In methanol; water

hexakis(ethylthio)benzene (70648-34-9) → hexamercaptobenzene (62968-45-0)

Conditions	Yield
Stage #1: hexakis(ethylthio)benzene With sodium at 100℃; Stage #2: With hydrogenchloride In methanol; water

pyridine (110-86-1) + carbon disulfide (75-15-0) + hexamercaptobenzene (62968-45-0) → 7-mercapto-2,5-dithioxobenzo<1,2-d:3,4-d'>bis<1,3>dithiole-8-thiolate (134172-93-3)

Conditions	Yield
for 0.25h; Ambient temperature;	97%

hexamercaptobenzene (62968-45-0) + silver nitrate → C6S6(6-)*4Ag(1+)*Ag(2+)

Conditions	Yield
In water; toluene at 60℃; for 49h;	95%

tetrakis(acetonitrile)copper(I)tetrafluoroborate + hexamercaptobenzene (62968-45-0) → Cu5.5C6S6

Conditions	Yield
Stage #1: tetrakis(acetonitrile)copper(I)tetrafluoroborate In 1,2-dimethoxyethane at 45℃; for 1h; Inert atmosphere; Stage #2: hexamercaptobenzene In 1,2-dimethoxyethane at 45℃; for 168h; Inert atmosphere;	93.6%

tetrakis(acetonitrile)copper(I)tetrafluoroborate + hexamercaptobenzene (62968-45-0) → Cu4C6S6

Conditions	Yield
Stage #1: tetrakis(acetonitrile)copper(I)tetrafluoroborate In methanol at 45℃; for 1h; Inert atmosphere; Stage #2: hexamercaptobenzene In methanol at 45℃; for 168h; Inert atmosphere;	91%

bis[dichloro(pentamethylcyclopentadienyl)iridium(III)] (12354-84-6, 12354-85-7) + hexamercaptobenzene (62968-45-0) → Ir3(η5-C5Me5)3(S6C6) (1147522-92-6)

Conditions	Yield
With triethylamine In dichloromethane (under N2, Schlenk); triethylamine added to soln. of C6(SH)6 in CH2Cl2, CH2Cl2 soln. of Ir-complex added, stirred for 2 h at room temp.; filtered, solvent evapd. under vac., alumina column chromy. with CH2Cl2-hexane (1:1), recrystd. from CH2Cl2-hexane; elem. anal.;	90%

dibutyltin chloride (683-18-1) + hexamercaptobenzene (62968-45-0) → C30H54S6Sn3

Conditions	Yield
Stage #1: hexamercaptobenzene With triethylamine In tetrahydrofuran Schlenk technique; Inert atmosphere; Stage #2: dibutyltin chloride for 4h; Inert atmosphere; Schlenk technique;	85%

lead acetate (301-04-2) + hexamercaptobenzene (62968-45-0) → [Pb3(benzenehexathiolato)](n)

Conditions	Yield
In ethylenediamine for 16 h at 60°C;	83%

hexamercaptobenzene (62968-45-0) + copper(II) nitrate → copper(II) benzenehexathiolate

Conditions	Yield
In chloroform; water for 24h; Inert atmosphere;	82%

[(divinyl)(phenyl)phosphine] gold(I) chloride (286384-11-0) + hexamercaptobenzene (62968-45-0) → ([(C2H3)2(C6H5)P]Au)6(C6S6)*3(CH3CH2)3NH(1+)*3Cl(1-) = ([(C2H3)2(C6H5)P]Au)6(C6S6)*3(CH3CH2)3NHCl

Conditions	Yield
With triethylamine In dichloromethane byproducts: Et3NHCl; stirred at room temp., 2 h; soln. filtered; solvent removed under reduced pressure; residue recrystd. at room temp. (CH2Cl2/hexane); elem. anal.;	80%

[(P(C6H5)3)2PtCl2]*(CH3CH2)3NH(1+)*Cl(1-)*3CH2Cl2 = [(P(C6H5)3)2PtCl2]*(CH3CH2)3NHCl*3CH2Cl2 + hexamercaptobenzene (62968-45-0) → [(P(C6H5)3)2Pt]3(C6S6)*(CH3CH2)3NH(1+)*Cl(1-)*3CH2Cl2 = [(P(C6H5)3)2Pt]3(C6S6)*(CH3CH2)3NHCl*3CH2Cl2

Conditions	Yield
With sodium carbonate; triethylamine In methanol; dichloromethane stirred, room temp., 2 h; solvent removed under reduced pressure; residue dissolved (CH2Cl2); ppt. (hexane), room temp.; elem. anal.;	80%

dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer + hexamercaptobenzene (62968-45-0) → Rh3(η5-C5Me5)3(S6C6) (1147522-90-4)

Conditions	Yield
With triethylamine In dichloromethane (under N2, Schlenk); triethylamine added to soln. of C6(SH)6 in CH2Cl2, CH2Cl2 soln. of Rh-complex added, stirred for 2 h at room temp.; filtered, solvent evapd. under vac., alumina column chromy. with CH2Cl2-hexane (1:1), recrystd. from CH2Cl2-hexane; elem. anal.;	77%

hexamercaptobenzene (62968-45-0) → benzo<1,2-d><3,4-d'><5,6-d''>-tris-1,2,3-trithiole (167564-25-2) + benzo<3,4-d><5,6-d'>-bis-1,2,3-trithiolo-<1,2-d''>pentathiepin

Conditions	Yield
With sulfur dichloride; methyllithium 1.) THF, 30 min; 2.) THF, 1 h, r.t.;	A 74% B 20%

[(cis-bis(diphenylphosphino)ethylene)dichloroplatinum(II)] * triethylammonium chloride * 3 methylene chloride + hexamercaptobenzene (62968-45-0) → [(cis-bis(diphenylphosphino)ethylene)platinum(II)]3(C6S6) * triethylammonium chloride * 3 methylene chloride

Conditions	Yield
With sodium carbonate; triethylamine In methanol; dichloromethane stirred, room temp., 2 h; solvent removed under reduced pressure; residue dissolved (CH2Cl2); ppt. (hexane), room temp.; elem. anal.;	70%

[(1,2-bis(dimethylphosphino)ethane)dichloroplatinum(II)]* 7 water + hexamercaptobenzene (62968-45-0) → [(1,2-bis(dimethylphosphino)ethane)platinum(II)]3(C6S6) * 7 water

Conditions	Yield
With sodium carbonate; triethylamine In methanol; dichloromethane stirred, room temp., 2 h; solvent removed under reduced pressure; residue dissolved (CH2Cl2); ppt. (hexane), room temp.; elem. anal.;	70%

[(bis(diphenylphosphino)methane)dichloroplatinum(II)] * triethylammonium chloride * 3 methylene chloride + hexamercaptobenzene (62968-45-0) → [(bis(diphenylphosphino)methane)platinum(II)]3(C6S6) * triethylammonium chloride * 3 methylene chloride

Conditions	Yield
With sodium carbonate; triethylamine In methanol; dichloromethane stirred, room temp., 2 h; solvent removed under reduced pressure; residue dissolved (CH2Cl2); ppt. (hexane), room temp.;	69%

carbonyl(pentamethylcyclopentadienyl)cobalt diiodide + hexamercaptobenzene (62968-45-0) → Co3(η5-C5Me5)3(S6C6)*H2O

Conditions	Yield
With triethylamine In acetone (under N2, Schlenk); triethylamine added to soln. of C6(SH)6 in acetone,acetone soln. of Co-complex added, stirred for 2 h at room temp.; filtered, solvent evapd. under vac., alumina column chromy. with CH2Cl2-hexane (1:1), recrystd. from CH2Cl2-hexane;	59%
With triethylamine In dichloromethane (under N2, Schlenk); triethylamine added to soln. of C6(SH)6 in CH2Cl2, CH2Cl2 soln. of Co-complex added, stirred for 2 h at room temp.; filtered, solvent evapd. under vac., alumina column chromy. with CH2Cl2-hexane (1:1), recrystd. from CH2Cl2-hexane; elem. anal.;	53%
With triethylamine In tetrahydrofuran (under N2, Schlenk); triethylamine added to soln. of C6(SH)6 in THF, THFsoln. of Co-complex added, stirred for 2 h at room temp.; filtered, solvent evapd. under vac., alumina column chromy. with CH2Cl2-hexane (1:1), recrystd. from CH2Cl2-hexane;	38%
With NaOCH3 In methanol; dichloromethane (under N2, Schlenk); NaOCH3 added to soln. of C6(SH)6 in CH2Cl2-MeOH, CH2Cl2-MeOH soln. of Co-complex added, stirred for 2 h at room temp.; filtered, solvent evapd. under vac., alumina column chromy. with CH2Cl2-hexane (1:1), recrystd. from CH2Cl2-hexane;	32%
With Na2CO3 In methanol; dichloromethane (under N2, Schlenk); Na2CO3 added to soln. of C6(SH)6 in CH2Cl2-MeOH, CH2Cl2-MeOH soln. of Co-complex added, stirred for 2 h at room temp.; filtered, solvent evapd. under vac., alumina column chromy. with CH2Cl2-hexane (1:1), recrystd. from CH2Cl2-hexane;	11%

carbonyl(η-5-cyclopentadienyl)diiodocobalt(III) + hexamercaptobenzene (62968-45-0) → Co3(η5-C5H5)3(S6C6) (168281-33-2)

Conditions	Yield
With triethylamine In dichloromethane (under N2, Schlenk); triethylamine added to soln. of C6(SH)6 in CH2Cl2, CH2Cl2 soln. of Co-complex added, stirred for 2 h at room temp.; filtered, solvent evapd. under vac., alumina column chromy. with CH2Cl2-hexane (1:1), recrystd. from CH2Cl2-hexane; elem. anal.;	58%

(triphenylphosphine)gold(I) chloride (14243-64-2) + hexamercaptobenzene (62968-45-0) → [CSAu(P(C6H5)3)]6 + [CSAu(P(C6H5)3)]6*2N(C2H5)3H(1+)*2Cl(1-)*4CHCl3=[CSAu(P(C6H5)3)]6*2[N(C2H5)3H]Cl*4CHCl3

Conditions	Yield
With NEt3 In dichloromethane molar ratio Au-complex:thiol:NEt3=6:1:6; stirring (room temp., 2 h); filtration, solvent removal (vac.), recrystn. (CH2Cl2/hexane=1:1);	A 30% B n/a

hexamercaptobenzene (62968-45-0) + triiron dodecacarbonyl (100447-70-9) → C24Fe6O18S6

Conditions	Yield
In toluene at 130℃; for 2h;	17%

hexamercaptobenzene (62968-45-0) + acetonitrile (75-05-8) → [((Ph2PCH2CH2PPh2)Ni)3(hexathiolatobenzene)]*8CH3CN

Conditions	Yield
In not given reaction of nickel compd. with hexamercaptobenzene in presence of base; chromy. (alumina), NMR and MS;	14%

cyclohexane (110-82-7) + hexamercaptobenzene (62968-45-0) → [((pentamethylcyclopentadienyl)Ru)3(hexathiolatobenzene)]*C6H12

Conditions	Yield
In not given reaction of ruthenium compd. with hexamercaptobenzene in presence of base; chromy. (alumina), NMR annd MS;	5%

hexamercaptobenzene (62968-45-0) → [((4,4'-di-tert-butyl-2,2'-pyridine)Pt)3(hexathiolatobenzene)] (1313753-76-2)

Conditions	Yield
In not given reaction of platinum compd. with hexamercaptobenzene in presence of base; chromy. (alumina), NMR and MS;	1%

carbon disulfide (75-15-0) + diiodomethane (75-11-6) + hexamercaptobenzene (62968-45-0) → 1,3,4,6,7,9-Hexathia-trindene-2,5-dithione (134172-99-9)

Conditions	Yield
With pyridine 1) RT, 15 min, 2) 10 min; Yield given. Multistep reaction;

carbon disulfide (75-15-0) + amyl iodide (628-17-1) + hexamercaptobenzene (62968-45-0) → 4,5-Bis-pentylsulfanyl-benzo[1,2-d;3,4-d']bis[1,3]dithiole-2,7-dithione (134172-98-8)

Conditions	Yield
With pyridine 1) RT, 15 min, 2) 10 min; Yield given. Multistep reaction;

carbon disulfide (75-15-0) + hexamercaptobenzene (62968-45-0) + ethyl iodide (75-03-6) → 4,5-Bis-ethylsulfanyl-benzo[1,2-d;3,4-d']bis[1,3]dithiole-2,7-dithione (134172-97-7)

Conditions	Yield
With pyridine 1) RT, 15 min, 2) 10 min; Yield given. Multistep reaction;

carbon disulfide (75-15-0) + hexamercaptobenzene (62968-45-0) + methyl iodide (74-88-4) → 4,5-Bis-methylsulfanyl-benzo[1,2-d;3,4-d']bis[1,3]dithiole-2,7-dithione (134172-94-4)

Conditions	Yield
With pyridine 1) RT, 15 min, 2) 10 min; Yield given. Multistep reaction;

4-methyl-benzaldehyde (104-87-0) + hexamercaptobenzene (62968-45-0) → 2,5,8-tri-p-tolyl-1,3,4,6,7,9-hexathia-trindene + 2,5,8-tri-p-tolyl-1,3,4,6,7,9-hexathia-trindene

Conditions	Yield
With zinc trifluoromethanesulfonate In chloroform Heating;

Upstream product

• 70648-34-9 hexakis(ethylthio)benzene 
• 58468-22-7 hexakis(methylthio) benzene 
• 87-82-1 hexabromobenzene 
• 392-56-3 Hexafluorobenzene 
• 74542-72-6 hexakis(isopropylthio)benzene 
• 127022-77-9 hexakis(benzylthio)benzene 
• 110431-65-7 Hexa-natrium-benzen-hexathiolat 

Relevant articles and documents

Highly Conductive 2D Metal-Organic Framework Thin Film Fabricated by Liquid-Liquid Interfacial Reaction Using One-Pot-Synthesized Benzenehexathiol

Metal-organic frameworks (MOF) are studied extensively in applications like catalysts, gas storage, and sensors due to their various functional groups and structures. Two-dimensional (2D) MOFs such as triphenylene-based materials show excellent charge transport properties, but thin-film fabrication and organic ligand synthesis are difficult. In this work, we synthesize thiol-based organic ligand, benzenehexathiol (BHT), by a simple one-pot reaction. This facile method is safer and faster than conventional synthesis procedure that requires using liquid ammonia as solvent. Two novel 2D MOF materials, Ag3BHT2 and Au3BHT2, are fabricated by coordinating BHT with either silver (Ag) or gold (Au) ions through liquid-liquid interfacial reaction. The Ag3BHT2 thin film reaches a high electrical conductivity of 363 S cm-1, which has potential applications in electronic devices and sensors.

Benzenehexathiol as a Template Rim for a Golden Wheel: Synthesis and Structure of 6>

The reaction of benzenehexathiol, C6(SH)6, with in the presence of triethylamine gave the hexanuclear gold(I) compound 6> whose structure has been determined; the hexagon of the central benzene carbon atoms is surrounded by a hexagon of sulfur atoms, followed by a hexagon of gold atoms and the wheel-like structure is completed by six peripheral phosphine ligands with interlocked aryl groups.