540-63-6

Basic information

• Product Name: 1,2-Ethanedithiol
• Synonyms: 1,2- B twoMercaptan;1,2-Ethanedithiol >=98.0% (GC);1,2-Ethanedithiol technical grade, >=90%;1,2-Ethanedithiol, 95%, SpcSeal;EDT(L);EDT)1,2-Ethane;a-ethylenedimercaptan;alpha-Ethylene dimercaptan
• CAS NO: 540-63-6
• Molecular Formula: C₂H₆S₂
• Molecular Weight: 94.2
• EINECS: 208-752-3
• Product Categories: Phenoles and thiophenoles;Other Reagents;thiol Flavor;Chemistry;Building Blocks;Chemical Synthesis;Contact Printing;Dithiols;Materials Science;Micro/NanoElectronics;Organic Building Blocks;Self Assembly &Self-Assembly Materials;Sulfur Compounds;Thiols;Thiols/Mercaptans
• Mol File: 540-63-6.mol

Chemical Properties

• Melting Point: −41 °C(lit.)
• Boiling Point: 144-146 °C(lit.)
• Flash Point: 122 °F
• Appearance: Clear slightly colored/Liquid
• Density: 1.123 g/mL at 25 °C(lit.)
• Vapor Density: >1 (vs air)
• Vapor Pressure: 4.8 mm Hg ( 20 °C)
• Refractive Index: n20/D 1.558(lit.)
• Storage Temp.: Store at 0-5°C
• PKA: pK1:8.96;pK2:10.54 (25°C)
• Water Solubility: insoluble
• Sensitive: Air Sensitive
• Stability: Stable. Flammable. Incompatible with oxidizing agents, bases, reducing agents, alkali metals.
• Merck: 14,3725
• BRN: 505946
• CAS DataBase Reference: 1,2-Ethanedithiol(CAS DataBase Reference)
• NIST Chemistry Reference: 1,2-Ethanedithiol(540-63-6)
• EPA Substance Registry System: 1,2-Ethanedithiol(540-63-6)

Safety Data

• Hazard Codes: T,Xn,F
• Statements: 10-23/24/25-23/25-21-36-23-21/22-36/37/38-20/21/22
• Safety Statements: 36/37/39-45-26-16-36/37-36-7/9
• RIDADR: UN 3071 6.1/PG 2
• WGK Germany: 3
• RTECS: KI3325000
• F: 10-13-23
• TSCA: Yes
• HazardClass: 3
• PackingGroup: III
• Hazardous Substances Data: 540-63-6(Hazardous Substances Data)

Usage

Uses

1. Used in Organic Synthesis:
1,2-Ethanedithiol is used as a reagent in organic synthesis for converting carbonyl compounds to thioacetals (1,3-dithiolanes). It serves as a safer alternative to the toxic reagent arsenic trichloride, which is traditionally involved in the synthesis of membrane-permeant fluorogenic biarsenicals from precursor dyes such as fluorescein and resorufin.
2. Used as a Metal-Complexing Agent:
In the field of chemistry, 1,2-Ethanedithiol acts as a bidendate ligand, enabling it to form complexes with metal ions like Pt(PPh3)4, Pd(PPh3)4, and Ni(PPh3)4. This property makes it a valuable component in various chemical reactions and processes.
3. Used in Biological Research:
1,2-Ethanedithiol has been found to reverse the inhibition by α-keto aldehydes on mitosis in E. coli, making it an essential tool in biological research and understanding cellular processes.
4. Used in Flavoring Agent:
EDT is also applied as a flavoring agent, contributing to the distinct taste of various animal foods, particularly in cooked beef and chicken.
Occurrence:
1,2-Ethanedithiol has been reported to be found in cooked beef and chicken, which may be attributed to its use as a flavoring agent in the food industry.

Chemical and Physical properties

1, 2-ethanedithiol (C2H6S2) has a molecular weight of 94.19 g/mol, a monoisotopic mass of 93.991 g/mol and an exact mass of 93.991 g/mol. It has a heavy atom count of 4, a topographical surface area of 2 A^2, and a complexity of 6. EDT has a hydrogen bond donor and acceptor count of 2 and 2 respectively. EDT gas a boiling point of 146 deg C at 760 mm Hg and a melting point of -41.2 °C. It dissolves in benzene, acetone, ether, ethanol and oxygenated solvents, while it is sparingly soluble in alkali. EDT dissolves in water at 1.12X10+4 mg/L at 25 deg C (est). 1,2-ethanedithiol has an extrapolated vapor pressure of 5.61 mm Hg at 25 deg C. When heated, EDT decomposes to emit toxic fumes comprising of sulfur oxides. Its odor is mild at 31 ppb and it gets more noticeable at 5.6 ppm.

Preparation

1,2-ethanedithiol can be synthesized by reacting an alkali metal hydrosulfide with an alkylene halide. However, this method does not yield a good amount of EDT due to the formation of by-products such as polymeric materials. The formation of these by-products could be reduced by conducting the reaction in an autoclave where the pressure is regulated to H 8. EDT can also be prepared through the decomposition of thiourea and the isothiuronium salt of ethylene bromide. This method yields slightly higher dithiol yields as indicated in the general formula where n is equal to or more than 3, for instance, 1,4-butanedithiol and 1,3-propanedithiol. However, this method also imposes significant constraints in the preparation of lower members of the dithiol series, such as 1,2-ethanedithiol. An additional method for the preparation of the compound entails the reaction between ethylene sulfide and H 8 in methanol, which yields approximately 49% of 1,2-ethanedithiol. However, this method also yields products with a relatively high molecular weight, which account for about 20% of the total products. There is a wide range of other methods that have been suggested for the synthesis of 1,2-ethanedithiol but they have been disqualified based on certain justifications. The process highlighted below entails three major steps: 1) the generation of ethylene sulfide, 2) reaction of ethylene sulfide with hydrosulfide and 3) the liberation of 1,2-ethanedithiol through acid treatment. Z-mercaptoethy-lcarbonate is added to an alkaline solution in the portions highlighted above over a 30-minute period, the pH of the alkaline solution should be above 6.8, where the base is indicated with the general formula MOH, where M indicates an alkali-metal hydroxides such as potassium, lithium or sodium. The contents should also include 1-2 moles of the reacting ammonium hydrosulfide per mole of the alkyl 2-mercaptoethylcarbonate. Stir the reaction contents while maintaining the temperature at -100 C while adding the alkyl portions. The solution can be saturated with hydrogen sulfide by passing the gas through the reaction contents for about 2 hours. The contents should be stirred for a period of 10-20 hours or more while maintaining the temperature at 15300 C. The solution is cooled and reacted with an acid such as phosphoric, sulfuric or hydrochloric acids, and 1,2-ethanedithiol is separated from the mixture through conventional means such as extraction using a volatile solvent such as benzene or chloroform, or by distillation. This step is followed by the evaporation of the contents to remove the solvent. A combination of both processes could be more effective, where the dried product is taken through fractional distillation. This method involving ammonium hydrosulfide and ethyl Z-mercaptoethyl carbonate is highly preferred for the preparation of 1,2-ethanedithiol.

Preparation

Prepared by reacting ethanol, thiourea and ethylene dibromide and subsequent alkaline hydrolysis of the ethylenediisothiuronium bromide

Precautions

One should wash their hands thoroughly after contact with 1,2-ethanedithiol. It is not recommended to smoke, eat or drink while handling EDT. If ingested, one should contact a doctor immediately or the poison center. In the event of a fire, one should use appropriate apparatus to extinguish the fire. If the chemical comes into contact with one’s clothes or skin, they should take off the clothes and rinse their skin with plenty of water.

Hazard Statements

1,2-ethanedithiol is a flammable liquid. EDT is toxic when ingested and it may result in acute toxicity. It may cause acute dermal toxicity upon contact with the skin. EDT may result in serious eye irritation/damage and it may also cause acute toxicity upon inhalation. Inhalation of EDT vapours may cause severe nausea or headaches.

Hazard

Vapors cause severe headache and nausea.

Safety Profile

Poison by ingestion, intraperitoneal, and intravenous routes. When heated to decomposition it emits very toxic fumes of SOx. See also MERCAPTANS .

InChI:InChI=1/C2H4S2/c1-2(3)4/h3-4H,1H2

Synthetic route

Benzeneselenol (645-96-5) + poly(ethylene disulfide) → diphenyl diselenide (1666-13-3) + ethane-1,2-dithiol (540-63-6)

Conditions	Yield
at 50 - 55℃; for 0.5h; Reduction; oxidation;	A 94% B 96.4%

2-methyl-2-phenyl[1,3]dithiolane (5769-02-8) → ethane-1,2-dithiol (540-63-6) + acetophenone (98-86-2)

Conditions	Yield
With magnesium(II) perchlorate; water; methylene green In acetonitrile Irradiation;	A n/a B 91%

(2-Methyl-1,3-dithiolan-2-yl)essigsaeure-ethylester (66278-17-9) → ethyl acetoacetate (141-97-9) + ethane-1,2-dithiol (540-63-6)

Conditions	Yield
With magnesium(II) perchlorate; water; methylene green In acetonitrile Irradiation;	A 90% B n/a

1,3-dithiolane-2-thione (822-38-8) → ethane-1,2-dithiol (540-63-6)

Conditions	Yield
With lithium aluminium tetrahydride In tetrahydrofuran	86%

polymer, product of thiylation with 0.19 g/mol of sulfur, where content of sulfur moieties 2.0 in repeating units; monomer(s): 1,2-dichloroethane, charged content 0.095 g/mol → ethane-1,2-dithiol (540-63-6)

Conditions	Yield
With potassium hydroxide; hydrazine hydrate at 80℃; for 2.5h;	56.8%

polymer: monomers(s): 1,2-dichloroethane; sulfur → 3-thiapentan-1,5-dithiol (3570-55-6) + ethane-1,2-dithiol (540-63-6)

Conditions	Yield
With sodium hydroxide; hydrazine hydrate Heating;	A 37% B 37%

polymer: monomers(s): 1,2-dibromoethane; sulfur → ethane-1,2-dithiol (540-63-6)

Conditions	Yield
With sodium hydroxide; hydrazine hydrate Heating;	33%

thirane (420-12-2) → ethane-1,2-dithiol (540-63-6)

Conditions	Yield
With methanol; hydrogen sulfide at 60℃; unter Druck;
With 2,2'-thiobis-ethanol; hydrogen sulfide at 45℃;

1,2-bis-sulfosulfanyl-ethane → ethane-1,2-dithiol (540-63-6)

Conditions	Yield
With hydrogenchloride

ethene (74-85-1) → ethane-1,2-dithiol (540-63-6)

Conditions	Yield
With sulfur; benzene at 175℃; under 77228.3 - 88260.9 Torr; und Hydrieren des Reaktionsprodukts unter Druck an Co2S3 bei 150grad oder an Nickel-Kieselgur bei 160grad;

bis (2-chloroethyl) sulphide (505-60-2) → ethane-1,2-dithiol (540-63-6)

Conditions	Yield
With ethanol; zinc

S,S'-ethane-1,2-diyl diethanethioate (10017-60-4) → ethane-1,2-dithiol (540-63-6)

Conditions	Yield
With methanol; barium methoxide at -10℃;
With sodium hydroxide In acetone Ambient temperature;

1,2-diphenylisothiocarbamidoethane (201943-51-3) → ethane-1,2-dithiol (540-63-6)

Conditions	Yield
beim Schmelzen;

ethylene glycol (107-21-1) → ethane-1,2-dithiol (540-63-6)

Conditions	Yield
With diphosphorus pentasulfide at 110 - 140℃; und Folgenden Destillieren mit Wasser;

1,2-dichloro-ethane (107-06-2) → ethane-1,2-dithiol (540-63-6)

Conditions	Yield
With sodium hydrogensulfide; water at 80 - 100℃;
With sodium hydrogensulfide; ethanol at 80 - 100℃;
With magnesium hydroxide; sodium disulfide; water und Behandeln des entstandenen Polysulfid mit Natriumamalgam;
With ethanol; potassium hydrosulfide

1,2-dichloro-ethane (107-06-2) → 3,6-dithiaoctan-1,8-dithiol (25423-55-6) + ethane-1,2-dithiol (540-63-6)

Conditions	Yield
With sodium hydrogensulfide; water unter Druck;

ethylene dibromide (106-93-4) + thiourea (17356-08-0) → ethane-1,2-dithiol (540-63-6)

Conditions	Yield
With ethanol und Hydrolyse des entstandenen S.S'-Aethylen-diisothioharnstoff-dihydrobromids mit Kalilauge;

ethylene dibromide (106-93-4) → ethane-1,2-dithiol (540-63-6)

Conditions	Yield
With potassium hydrosulfide Darstellung;
With sodium hydrogensulfide; ethanol
With ethanol; potassium hydrosulfide

[1,2,5,6]tetrathiocane (1940-01-8) → ethane-1,2-dithiol (540-63-6)

Conditions	Yield
With 2-hydroxyethanethiol In d(4)-methanol; water-d2 at 25℃; Equilibrium constant; phosphate buffer(0.5 mM, pH7.0);

2,2-diphenyl-1,3-dithiolane (6317-10-8) → benzophenone (119-61-9) + ethane-1,2-dithiol (540-63-6)

Conditions	Yield
With oxonium In 1,4-dioxane; water at 25℃; Rate constant; Mechanism; ionic strength: 0.053-0.95M; thallium ion concentration: 0-0.004M; hydrogen ion concentration: 0.05-0.95M; 25percent (v/v) dioxane-water.;

1-(2-Mercapto-ethyl)-2-methylsulfanyl-4,6-diphenyl-pyridinium; iodide (83318-96-1) → ethane-1,2-dithiol (540-63-6)

Conditions	Yield
With sodium hydroxide; thiourea 1.) 130 deg C, 0.5 h; 2.) reflux, 3 h; Yield given. Multistep reaction;

C6H14O2S6(75)Se2 → ethane-1,2-dithiol (540-63-6)

Conditions	Yield
With hydrogenchloride; 75Se-sodium selenite; sodium acetate at 5℃; for 0.833333h; Equilibrium constant; pH= 1.8; apparent equilibrium constant;
With hydrogenchloride; 75Se-sodium selenite; sodium acetate at 5℃; for 0.833333h; Equilibrium constant; pH= 2.5; apparent equilibrium constant;
With hydrogenchloride; 75Se-sodium selenite; sodium acetate at 5℃; for 0.833333h; Equilibrium constant; pH= 3.7; apparent equilibrium constant;

1,3-dithiolane-2-thione (822-38-8) + alcoholic potash → ethane-1,2-dithiol (540-63-6)

1,3-dithiol-2-thione (930-35-8) + diethyl ether (60-29-7) + lithium alanate → ethane-1,2-dithiol (540-63-6)

1,3-dithiol-2-thione (930-35-8) + ethanol (64-17-5) + sodium → methylthiol (74-93-1) + ethane-1,2-dithiol (540-63-6)

1,3-dithiolane-2-thione (822-38-8) + ammonia (7664-41-7) → ammonium thiocyanate (1147550-11-5) + ethane-1,2-dithiol (540-63-6)

Conditions	Yield
at 150℃; im Rohr;

2-imino-1,3-dithiolane (4472-81-5) + hydrogenchloride (7647-01-0) → [1,2,5,6]tetrathiocane (1940-01-8) + ethane-1,2-dithiol (540-63-6) + methylammonium carbonate (15719-64-9, 15719-76-3, 97762-63-5)

Conditions	Yield
at 120℃;

2-(1,3-dithiolan-2-yl)-1-phenylethan-1-one (5653-29-2) + furan-2,3,5(4H)-trione pyridine (1:1) + zinc dust → ethane-1,2-dithiol (540-63-6) + 1-phenyl-propan-1-one (93-55-0)

Conditions	Yield
unter Durchleiten von Wasserdampf;

2-[1,3]dithiolan-2-ylidene-1-phenyl-ethanone (5653-30-5) + furan-2,3,5(4H)-trione pyridine (1:1) + zinc → ethane-1,2-dithiol (540-63-6) + 1-phenyl-propan-1-one (93-55-0)

Conditions	Yield
im Wasserdampf-Strom;

1,3-dithiolan-2-one (2080-58-2) + ammonia (7664-41-7) → ethane-1,2-dithiol (540-63-6) + urea (57-13-6)

Conditions	Yield
at 100℃;

cyclohexanone (108-94-1) + ethane-1,2-dithiol (540-63-6) → 1,4-dithiaspiro[4.5]decane (177-16-2)

Conditions	Yield
With thionyl chloride; silica gel In toluene for 24h; Heating;	100%
With bentonite In toluene for 3h; Heating;	99%
With silica gel; iron(III) chloride In dichloromethane Ambient temperature;	99%

4-methyl-benzaldehyde (104-87-0) + ethane-1,2-dithiol (540-63-6) → 2-(4-methylphenyl)-1,3-dithiolane (23229-29-0)

Conditions	Yield
With silica gel; toluene-4-sulfonic acid In dichloromethane for 1.5h; Heating;	100%
With Cu(OTf)2-SiO2 for 0.5h; Ambient temperature;	99%
With PPA; silica gel In 1,2-dichloro-ethane at 20℃; for 0.5h;	99%

benzaldehyde (100-52-7) + ethane-1,2-dithiol (540-63-6) → 2-phenyl-1,3-dithiane (5616-55-7)

Conditions	Yield
With thionyl chloride; silica gel In benzene at 20℃; for 5h;	100%
With silica gel; toluene-4-sulfonic acid In dichloromethane for 3h; Heating;	100%
With acetophenone In dichloromethane at 20℃; for 0.5h; chemoselective reaction;	100%

benzophenone (119-61-9) + ethane-1,2-dithiol (540-63-6) → 2,2-diphenyl-1,3-dithiolane (6317-10-8)

Conditions	Yield
Nafion-H In benzene Heating;	100%
With cobalt(II) bromide In dichloromethane for 4h; Ambient temperature;	99%
With amberlyst-15 In acetonitrile for 1h;	99.91%

dihydrocholesterone (566-88-1) + ethane-1,2-dithiol (540-63-6) → 5α-cholestan-3-one ethanediyl S,S-acetal (2791-43-7)

Conditions	Yield
With zeolite HSZ-360 In dichloromethane for 15h; Ambient temperature;	100%
tellurium tetrachloride In 1,2-dichloro-ethane for 3h; Ambient temperature;	94%
With cadmium(II) iodide for 0.0222222h; Irradiation;	78%

ethane-1,2-dithiol (540-63-6) + acetophenone (98-86-2) → 2-methyl-2-phenyl[1,3]dithiolane (5769-02-8)

Conditions	Yield
With perchloric acid; silica gel at 25 - 30℃; for 5h;	100%
With toluene-4-sulfonic acid In benzene Heating;	99%
With cobalt(II) bromide In dichloromethane for 1.25h; Ambient temperature;	99%

ethane-1,2-dithiol (540-63-6) → 1,2-bis(chlorosulfanyl)ethane (24127-98-8)

Conditions	Yield
With chlorine In tetrachloromethane at -20℃;	100%
With sulfuryl dichloride
With chlorine at -15 - -5℃; for 2h;

ethane-1,2-dithiol (540-63-6) → 2-Chloro-1,3,2-dithiaphospholane (4669-51-6)

Conditions	Yield
With phosphorus trichloride at 20℃; for 3h;	100%
With phosphorus trichloride at 20℃; for 3h;	95%
With phosphorus trichloride at 20℃; for 3h; Inert atmosphere;	95%

2-chloro-benzaldehyde (89-98-5) + ethane-1,2-dithiol (540-63-6) → 2-(2-chlorophenyl)-1,3-dithiolane (83521-68-0)

Conditions	Yield
With Iron(III) nitrate nonahydrate; sodium iodide In dichloromethane at 20℃; for 16h;	100%
With phosphoric acid functionalized ethanolamine grafted polyacrylonitrile fiber In methanol at 65℃; for 4h; Solvent; Temperature; Green chemistry;	98%
tungsten(VI) chloride In dichloromethane at 0 - 5℃; for 0.0833333h;	96%

4-nitrobenzaldehdye (555-16-8) + ethane-1,2-dithiol (540-63-6) → 2-(4-nitrophenyl)-1,3-dithiolane (41159-02-8)

Conditions	Yield
With PPA; silica gel In 1,2-dichloro-ethane at 20℃; for 0.5h;	100%
With boron trifluoride diethyl etherate In dichloromethane for 6h; Ambient temperature;	99%
With iron(III) In dichloromethane for 10h; Ambient temperature;	98%

3,4-dimethoxy-benzaldehyde (120-14-9) + ethane-1,2-dithiol (540-63-6) → 2-(3,4-dimethoxyphenyl)-1,3-dithiolane (69922-36-7)

Conditions	Yield
amberlyst-15 In chloroform for 48h; Ambient temperature;	100%
With N-Bromosuccinimide for 0.05h;	98%
With silica-supported sulfuric acid at 20℃; for 0.133333h; Neat (no solvent); chemoselective reaction;	98%

10-Undecenal (112-45-8) + ethane-1,2-dithiol (540-63-6) → 2-(9-decenyl)-1,3-dithiolane (101033-01-6)

Conditions	Yield
With thionyl chloride; silica gel In benzene at 20℃; for 5h;	100%
With PPA; silica gel In 1,2-dichloro-ethane at 20℃; for 0.5h;	100%

methyl levulinate (13984-50-4) + ethane-1,2-dithiol (540-63-6) → methyl 5,5-ethylenedithiohexanoate (146405-06-3)

Conditions	Yield
With boron trifluoride diethyl etherate In chloroform	100%

2-Phenylpropanal (34713-70-7) + ethane-1,2-dithiol (540-63-6) → 2-(1-Phenyl-ethyl)-[1,3]dithiolane (83521-78-2)

Conditions	Yield
With thionyl chloride; silica gel In benzene at 20℃; for 5h;	100%
With trichloroisocyanuric acid In chloroform at 20℃; for 1.5h;	92%
	76%

19-nortestosterone (434-22-0) + ethane-1,2-dithiol (540-63-6) → 3,3-Ethandiyldimercapto-oestro-4-en-17β-ol (74531-93-4)

Conditions	Yield
With boron trifluoride diethyl etherate In methanol; dichloromethane	100%

kryptogenin diacetate (7554-95-2) + ethane-1,2-dithiol (540-63-6) → (25R)-22-oxocholest-5-ene-3β,26-diol 16,16-(cycloethylene dithioketal) 3,26-diacetate (96455-87-7)

Conditions	Yield
With boron trifluoride diethyl etherate In acetic acid for 1.5h; Ambient temperature;	100%

1,5-Bis<(9'-oxofluoren-2'-yl)oxy>-3-oxapentane (120342-79-2) + ethane-1,2-dithiol (540-63-6) → 1,5-Bis<<9',9'-(ethylenedithio)fluoren-2'-yl>oxy>-3-oxapentane (120342-82-7)

Conditions	Yield
With boron trifluoride diethyl etherate In acetic acid for 6h; Heating;	100%
With boron trifluoride diethyl etherate In acetic acid for 6h; Heating; Yield given;

1,11-Bis<(9'-oxofluoren-2'-yl)oxy>-3,6,9-trioxaundecane (120342-80-5) + ethane-1,2-dithiol (540-63-6) → 1,11-Bis<<9',9'-(ethylenedithio)fluoren-2'-yl>oxy>-3,6,9-trioxaundecane (120342-84-9)

Conditions	Yield
With boron trifluoride diethyl etherate In acetic acid for 6h; Heating;	100%
With boron trifluoride diethyl etherate In acetic acid for 6h; Heating; Yield given;

C17H23NO4 (149310-98-5) + ethane-1,2-dithiol (540-63-6) → C19H27NO3S2 (130760-83-7)

Conditions	Yield
With thionyl chloride; silica gel In dichloromethane for 12h; Ambient temperature;	100%
With thionyl chloride; silica gel

(-)-(1R,2R,6R,7R)-6,7-dimethyl-3-oxo-2,8-dioxabicyclo[3.3.0]octane (104486-84-2) + ethane-1,2-dithiol (540-63-6) → (-)-(3R,4R,5R)-4,5-dimethyl-3-(1,3-dithiolan-2-yl)pentanolide (104431-97-2)

Conditions	Yield
With boron trifluoride diethyl etherate In dichloromethane at 0℃; for 0.5h; Cyclization;	100%
With boron trifluoride diethyl etherate In dichloromethane Ambient temperature;	81%

ethane-1,2-dithiol (540-63-6) + 1-benzyl-3-formyl-9-methoxy-1H-benzindole (151646-90-1) → 1-benzyl-3-<2-(1,3-dithiolanyl)>-9-methoxy-1H-benzindole (151646-91-2)

Conditions	Yield
With boron trifluoride diethyl etherate In acetic acid for 0.75h; Ambient temperature;	100%

ethane-1,2-dithiol (540-63-6) + <4R-<3(4R*,5S*),4α,5α>>-3,3'-(1,4,7-Trioxo-1,7-heptanediyl)bis<4-methyl-5-phenyl-2-oxazolidinone> → <4R-<3(4R*,5S*),4α,5α>>-3,3'-<1,3-Dithiolan-2-ylidenebis(1-oxo-3,1-propanediyl)>bis<4-methyl-5-phenyl-2-oxazolidinone>

Conditions	Yield
With boron trifluoride diethyl etherate at 0℃; for 0.5h;	100%

ethane-1,2-dithiol (540-63-6) + 12-chloro-5-hydroxy-9-oxo-6a,7,8,9,10,10a-hexahydronaphthacene-6,11-dione → 12-chloro-9,9-ethylenedithio-5-hydroxy-6a,7,8,9,10,10a-hexahydronaphthacene-6,11-dione (89564-59-0)

Conditions	Yield
With boron trifluoride diethyl etherate In dichloromethane for 2h; Ambient temperature;	100%

ethane-1,2-dithiol (540-63-6) + cyclohexanecarbaldehyde (2043-61-0) → Cyclohexancarboxaldehyde dithioethyleneacetal (70777-60-5)

Conditions	Yield
With zeolite HSZ-360 In dichloromethane for 15h; Ambient temperature;	100%
With cobalt(II) bromide In dichloromethane for 0.05h; Ambient temperature;	99%
With PPA; silica gel In 1,2-dichloro-ethane at 20℃; for 0.5h;	96%

ethane-1,2-dithiol (540-63-6) + crotonaldehyde (123-73-9) → 2-prop-1-enyl-1,3-dithiolane (61685-38-9)

Conditions	Yield
With thionyl chloride; silica gel In benzene at 20℃; for 5h;	100%
With N-Bromosuccinimide In chloroform at 20℃; for 0.0833333h;	94%
With H-Rho zeolite In hexane for 2.5h; Heating;	89%
With iron(III) In dichloromethane for 4h; Ambient temperature;	75%
With natural kaolinitic clay In benzene for 2h; Heating;	70%

ethane-1,2-dithiol (540-63-6) + cycloheptanone (502-42-1) → 1,4-dithia-spiro[4.6]undecane (184-32-7)

Conditions	Yield
Nafion-H In benzene Heating;	100%
With perchloric acid; silica gel at 25 - 30℃; for 0.05h;	97%
With P-benzyltriphenylphosphonium tribromide at 20℃; for 1.5h;	96%

ethane-1,2-dithiol (540-63-6) + 1,3-Diphenylpropanone (102-04-5) → 2,2-bis(benzyl)-1,3-dithiolane (76312-47-5)

Conditions	Yield
Nafion-H In benzene Heating;	100%
With silica gel; zirconium(IV) chloride In dichloromethane for 0.5h; Ambient temperature;	99%
With silica gel; iron(III) chloride In dichloromethane Ambient temperature;	98%

ethane-1,2-dithiol (540-63-6) + cis-bicyclo<5.3.1>undecan-3-one → spiro(cis-bicyclo<5.3.1>undecane-3,2':1'3'-dithiolane)

Conditions	Yield
With boron trifluoride diethyl etherate for 0.0833333h;	100%

ethane-1,2-dithiol (540-63-6) + 13α-acetyl-8β(H)-podocarpane (163397-73-7) → 13α-acetyl-8β(H)-podocarpane ethylenedithioketal

Conditions	Yield
With boron trifluoride diethyl etherate In dichloromethane Ambient temperature;	100%

5,7-dimethoxy-4-oxo-1,2,3,4-tetrahydro-2-naphthoic acid methyl ester (61571-90-2) + ethane-1,2-dithiol (540-63-6) → methyl 3',4'-dihydro-6',8'-dimethoxyspiro[1,3-dithiolane-2,1'(2H)-naphthalene-3-carboxylate] (61571-94-6)

Conditions	Yield
With boron trifluoride diethyl etherate In dichloromethane at 25℃; for 18h; Cyclization;	100%

Upstream product

• 420-12-2 thirane 
• 74-85-1 ethene 
• 505-60-2 bis (2-chloroethyl) sulphide 
• 10017-60-4 S,S'-ethane-1,2-diyl diethanethioate 
• 201943-51-3 1,2-diphenylisothiocarbamidoethane 
• 107-21-1 ethylene glycol 
• 107-06-2 1,2-dichloro-ethane 
• 106-93-4 ethylene dibromide 
• 17356-08-0 thiourea 
• 1940-01-8 [1,2,5,6]tetrathiocane 
• 822-38-8 1,3-dithiolane-2-thione 
• 5769-02-8 2-methyl-2-phenyl[1,3]dithiolane 
• 66278-17-9 (2-Methyl-1,3-dithiolan-2-yl)essigsaeure-ethylester 
• 6317-10-8 2,2-diphenyl-1,3-dithiolane 

Downstream Products

• 98026-19-8 2-(2-mercapto-ethylsulfanyl)-ethanol 
• 5244-34-8 2,2'-ethane-1,2-diylbissulfanyl-bis-ethanol 
• 176-41-0 1,4,7-trithia-spiro[4.4]nonane 
• 85102-57-4 2-methyl-2-(thiophen-2-yl)-1,3-dithiolane 
• 21057-05-6 1,2-bis(2-aminoethylthio)ethane 
• 55100-40-8 2-methyl-2-azabicyclo<2.2.2>octane 
• 38168-18-2 spiro[[1,3]dithiolane-2,3'-indolin]-2'-one 
• 177-16-2 1,4-dithiaspiro[4.5]decane 
• 23229-29-0 2-(4-methylphenyl)-1,3-dithiolane 
• 23229-32-5 2-(4-chlorophenyl)-1,3-dithiolane 
• 565-31-1 2-(4-fluorophenyl)-2-methyl-1,3-dithiolane 
• 6302-91-6 2-(4-chlorophenyl)-2-methyl-1,3-dithiolane 
• 83521-87-3 2-phenyl-2-[2]thienyl-[1,3]dithiolane 
• 42938-52-3 1,2-bis-(2,4-dinitro-phenyldisulfanyl)-ethane 

Relevant articles and documents

Thiylation of polyelectrophiles with sulfur in hydrazine hydrate-amine systems

Thiylation of polyhaloalkanes and Paraform with elemental sulfur activated in hydrazine hydrate-organic amine systems is performed. Monoethanolamine, triethanolamine, and triethylamine were used as amines. The reactions gave thiocols of various structures. The products were characterized by elemental analysis and IR spectroscopy. Reductive cleavage of the synthesized thiocols was performed to obtain di- and polythiols. 2005 Pleiades Publishing, Inc.

Reactions of bielectrophiles (ClCH2CH2)2Y with sulfur in basic reducing systems

A simple procedure was developed for preparing bis(β-mercaptoethyl) ether and bis(β-mecraptoethyl) sulfide from commercially available chemicals: elemental sulfur, alkali, and bis(β-chloroethyl) ether or sulfide, based on thiylation with elemental sulfur of these substrates in the aqueous system hydrazine hydrate-alkali, with initial formation of the corresponding polysulfide polymers (thiokols). Their reduction with the system hydrazine hydrate-alkali, followed by acidification of dithiolate anions, yields the corresponding dithiols. Thiokols based on bis(β-chloroethyl) ether are soluble in organic solvents; they were studied by 1H NMR.

Reduction of thiokols in the system hydrazine hydrate-base as a new route to alkanedithiols

A new procedure for preparative synthesis of alkanedithiols from simple commercially available products is based on reduction of the S-S bond in appropriate polyalkylene disulfides (thiokols) in the system hydrazine hydrate-base. Thiokols were prepared by reaction of dihaloalkanes with Na2S2 or K2S2 generated from elemental sulfur and alkali in aqueous hydrazine hydrate. Reaction of 1,2-dibromocyclohexane with sodium or potassium disulfide yields bis(2-bromocyclohexyl) sulfide as the only product.

Reduction of thiocols to alkanepolythiols with benzeneselenol

Heating of benzeneselenol with polymethylene disulfides to 40-120°C results in formation of the corresponding alkanedithiols or alkanetrithiols and diphenyl diselenide. Poly(tetramethylene disulfide) reacts with benzeneselenol to give 1,2-dithiane and diphenyl diselenide. A radical mechanism of this reaction is discussed.

A general and mild synthesis of thioesters and thiols from halides

The conversion of a wide variety of halides to thioesters by reaction with potassium thiocetate under mild conditions is described, and the generality of the method is demonstrated.

Photosensitized cleavage of the dithio protecting group by visible light

Dithio derivatives of aldehydes and ketones have been deprotected under neutral conditions using visible light provided by a 120 Watt spotlight and methylene green as a sensitizer. The key step in the deprotection is apparently an electron transfer from the dithio derivative to the electronically excited visible dye. The resulting dithio radical cation undergoes fragmentation, and the corresponding aldehydes and ketones are isolated in excellent yields.

CONVERSION OF CYCLIC TRITHIOCARBONATES TO THIOACETALS, INCLUDING 1,3-DITHIANE, BY REDUCTION WITH DIISOBUTYLALUMINIUM HYDRIDE (DIBAL)

Cyclic trithiocarbonates can be desulfurized with diisobutylaluminium hydride (DIBAL) to form the corresponding thioacetals.This new synthetic pathway was exploited for the preparation of several Umpolung reagents, including 1,3-dithiane.An efficient isolation of sodium trithocarbonate is described.

STUDIES ON THE REACTIONS OF SELENITE ION WITH 1,2-DIMERCAPTOETHANE OR THIOACETIC ACID

The reactions are reported between selenite and 1,2-dimercaptoethane (DME) or thioacetic acid (TAA) to form moderately stable derivatives having an enhanced absorptions in the 230-360 nm region in combining molar ratios 3:2 and 4:1, respectively.Both reactions invariably yield one product corresponding to the selenium-containing derivative of DME or TAA.The formation of products is a pH dependent process.The equilibrium constants of reactions between selenite and DME or TAA were measured.

A Kinetic Study of the Soft Metal Ion-promoted Hydrolyses of Some S-Acetals

The S-acetals (III)-(VII) hydrolyse readily in aqueous ethanol or in aqueous dioxan solutions containing an excess of Tl3+ or Ag+ ions to give benzophenone and the appropriate sulphide.The hydrogen-ion catalysed hydrolyses are very slow by comparison and the supposedly soft ions Cd2+ and Cu2+ have even less effect than H3O+.Kinetic and spectroscopic studies of the hydrolyses, mainly at 25 deg C, show that the Tl3+-promoted reactions occur via the rapid formation of a 1 Tl3+ : 1-S-acetal adduct.This adduct is formed stoicheiometrically with (IV), (V), and(VII), but in small amounts with (III) and (VI).The tripositive adduct probably reacts with water in the slow step of the overall hydrolysis.This adduct can also lose charge by proton dissociation from hydroxy groups in the bound S-acetal, or from thallium-bound water.The resulting dipositive adducts, however formed, hydrolyse much less rapidly than the tripositive adducts.The (chelated) dipositive adduct from (V) is sufficiently stable for contributions to hydrolysis from a 4+ adduct to be detected.The Ag+-promoted hydrolyses proceed principally via small amounts of rapidly formed dipositive 2 Ag+ : 1-S-acetal adducts.For (V), where loss of a carboxy proton can occur, the formation constant of the monopositive + adduct is very large (K ca. 107 l mol-1) but that of the dipositive adduct is small, as for the other S-acetals.With (V) and (VI) the 1 Ag+ : 1-S-acetal adduct is formed stoicheiometrically and with (IV) its formation constant is large (K ca, 900 l mol-1).For (III), (IV), (VI), and (VII) these 1:1 adducts contribute significantly to the hydrolysis at low silver ion concentrations.For both the Tl3+-and the Ag+-promoted reactions the effects of ionic strength are consistent: where more charged adduct can form an increase in ionic strength increases the reaction rate; where adduct formation is complete, changes in ionic strength have little effect on the rate.The S-acetals display wide (up to 105-fold) differences in reactivity towards hydrolysis and their sequence of reactivity alters markedly with the promoting ion.With both ions (VI) hydrolyses relatively slowly.For all the substrates Tl3+ is a better promoter than Ag+.Exact comparisons of reactivity are impossible owing to the differences in mechanistic detail and in solvent.In view of its soft acid character Tl3+ is surprisingly more acidic towards the O-containing acetals than towards those having just two S atoms.For (IV) and Ag+ the establishment of the pre-equilibrium giving the 1 Ag+ : 1-S-acetal adduct is slow enough at 25 deg C to be followed by stopped-flow spectroscopy.