5873-93-8

Basic information

• Product Name: Diphenyldithioperoxyanhydride
• Synonyms: Bis(thiobenzoyl) disulfide;Bis(thiobenzoyl) disulfide >90% (HPLC);Di(thiobenzoyl) disulfide;Disulfide,bis(phenylthioxomethyl)
• CAS NO: 5873-93-8
• Molecular Formula: C₁₄H₁₀S₄
• Molecular Weight: 306.497
• Mol File: 5873-93-8.mol
• Article Data: 31

Chemical Properties

• Melting Point: 94-96°C
• Boiling Point: 446.8 °C at 760 mmHg
• Flash Point: 224 °C
• Appearance: /
• Density: 1.367 g/cm³
• Storage Temp.: ?20°C
• CAS DataBase Reference: Diphenyldithioperoxyanhydride(CAS DataBase Reference)
• NIST Chemistry Reference: Diphenyldithioperoxyanhydride(5873-93-8)
• EPA Substance Registry System: Diphenyldithioperoxyanhydride(5873-93-8)

Safety Data

• Hazard Codes: N
• Statements: 50/53
• Safety Statements: 60-61
• RIDADR: UN 3077 9 / PGIII
• WGK Germany: 2
• Hazardous Substances Data: 5873-93-8(Hazardous Substances Data)

Usage

Uses

Different sources of media describe the Uses of 5873-93-8 differently. You can refer to the following data:
1. Diphenyldithioperoxyanhydride RAFT agent; used in manufacturing of polymer using disulfide compd. with radical initiator in solvent or no solvent
2. Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization

General Description

Need help choosing the correct RAFT Agent? Please consult the RAFT Agent to Monomer compatibility table.

Synthetic route

carbon disulfide (75-15-0) + bromobenzene (108-86-1) → bis(thiobenzoyl) disulfide (5873-93-8)

Conditions	Yield
Stage #1: bromobenzene With iodine; magnesium In tetrahydrofuran at 30 - 75℃; for 3h; Inert atmosphere; Stage #2: carbon disulfide In tetrahydrofuran at 0 - 20℃; for 3h; Inert atmosphere;	90%
Stage #1: bromobenzene With magnesium; iodine In tetrahydrofuran Stage #2: carbon disulfide In tetrahydrofuran Grignard reaction; Stage #3: With dimethyl sulfoxide; iodine In ethanol at 20℃; for 1h; Further stages.;	82%
Stage #1: bromobenzene With iodine; magnesium In tetrahydrofuran Stage #2: carbon disulfide In tetrahydrofuran at 20℃; for 1h; Stage #3: With p-toluenesulfonyl chloride In tetrahydrofuran at 0 - 20℃; for 1.5h;	55%
Stage #1: bromobenzene With iodine; magnesium In tetrahydrofuran for 3h; Stage #2: carbon disulfide In tetrahydrofuran for 3h; Stage #3: With iodine In water
Stage #1: carbon disulfide; bromobenzene With magnesium In tetrahydrofuran at 0℃; Inert atmosphere; Stage #2: With water; potassium hexacyanoferrate(III) for 1.5h;	4.88 g

diethyl meso-2,3-dibromosuccinate (1114-31-4) + dithiobenzoic acid triethylammonium salt (42967-74-8) → bis(thiobenzoyl) disulfide (5873-93-8) + diethyl Fumarate (623-91-6)

Conditions	Yield
In ethanol	A 54% B 50%

dithiobenzoic acid sodium salt (3682-36-8) → bis(thiobenzoyl) disulfide (5873-93-8)

Conditions	Yield
With iodine In water at 20℃; for 0.25h;	50%
With potassium hexacyanoferrate(III) In water at 20℃; for 1h;
With potassium hexacyanoferrate(III)

carbon disulfide (75-15-0) + phenylmagnesium bromide (100-58-3) → bis(thiobenzoyl) disulfide (5873-93-8)

Conditions	Yield
at 0 - 20℃; for 0.5h;	35%
In tetrahydrofuran; 2-methyltetrahydrofuran at 0℃; for 0.75h; Inert atmosphere;	31%
Stage #1: carbon disulfide; phenylmagnesium bromide In tetrahydrofuran Stage #2: With iodine; potassium carbonate In water

N-chloro-succinimide (128-09-6) + thiobenzoyl diphenylphosphino sulfide (97270-46-7) → bis(thiobenzoyl) disulfide (5873-93-8) + N-(thiobenzoylthio)succinimide (80031-12-5) + Tetraphenyldiphosphin (1101-41-3)

Conditions	Yield
In tetrahydrofuran	A n/a B 16% C n/a

sodium molybdate dihydrate (7631-95-0) + diethylammonium dithiobenzoate (50929-87-8) → Mo(4+)*O(2-)*2S2CC6H5(1-)=MoO(S2CC6H5)2 + (η3-dithiobenzoato-SCS')oxo(trithioperoxybenzoato-S,S'S'')molybdenum(IV) (81844-27-1, 71900-01-1) + (C6H5CS2)4Mo + bis(thiobenzoyl) disulfide (5873-93-8)

Conditions	Yield
With NaCH3COO; hydrochloric acid In water to aq. soln. of Na2MoO4*2H2O, (NEt2H2)(S2CPh), and MeCO2Na added HCl (1.0 M) dropwise with stirring at room temp.; ppt. filtered off, washed with water and methanol, dried in vac., chromd. (SiO2, CS2), orange fraction evapd. in vac., recrystd. from CH2Cl2-light petroleum; elem. anal.;	A n/a B 6% C n/a D n/a

tetraethylammonium dithiobenzoate (19911-87-6) → methyl thiobenzoate (5873-86-9) + benzaldehyde dimethyl acetal (1125-88-8) + bis(thiobenzoyl) disulfide (5873-93-8) + Bis(thiobenzoylthio-benzyl)disulfid

Conditions	Yield
With tetraethylammonium perchlorate In methanol at 80℃; for 3h; electrochemical reaction, 14 mA*cm-2, 2.5 F; Further byproducts given;	A n/a B n/a C n/a D 5%

diethyl ether (60-29-7) + S-ethyl dithiobenzoate (936-63-0) + phenylmagnesium bromide → bis(thiobenzoyl) disulfide (5873-93-8) + S-trityl benzothioate (1727-16-8)

Conditions	Yield
nachf. Behandeln mit Benzoylchlorid;

S-ethyl dithiobenzoate (936-63-0) + phenylmagnesium bromide → bis(thiobenzoyl) disulfide (5873-93-8)

diethylammonium dithiobenzoate (50929-87-8) → bis(thiobenzoyl) disulfide (5873-93-8)

Conditions	Yield
With iodine In ethanol at -5℃; for 0.166667h;

dithiobenzoic acid (121-68-6) + sulfuric acid (7664-93-9) → bis(thiobenzoyl) disulfide (5873-93-8)

dithiobenzoate sodium → bis(thiobenzoyl) disulfide (5873-93-8)

Conditions	Yield
With iodine
With iodine

dithiobenzoic acid (121-68-6) → bis(thiobenzoyl) disulfide (5873-93-8)

Conditions	Yield
With sodium hydroxide; potassium hexacyanoperferrate for 0.5h;
With iodine; dimethyl sulfoxide In ethanol at 20℃; for 2h;	11.04 g
With potassium hexacyanoferrate (III) In water for 1h;

benzyl chloride (100-44-7) + N,N-diethyl-glycine-<4-hydroxy-anilide> → bis(thiobenzoyl) disulfide (5873-93-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: sulfur; MeONa / methanol / 10 h / 70 °C 2: potassium ferricyanide / H2O / 1 h / 20 °C View Scheme

4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) + dithiobenzoic acid sodium salt (3682-36-8) → bis(thiobenzoyl) disulfide (5873-93-8)

Conditions	Yield
Stage #1: dithiobenzoic acid sodium salt With iodine In water for 1h; Stage #2: 4,4'-dicyano-4,4'-azo-di-valeric acid In ethyl acetate for 18h;

bromobenzene (108-86-1) → bis(thiobenzoyl) disulfide (5873-93-8)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: iodine; magnesium / tetrahydrofuran / 1 h 1.2: 2 h / 0 °C 2.1: iodine; dimethyl sulfoxide / ethanol / 2 h / 20 °C View Scheme
Multi-step reaction with 2 steps 1: tetrahydrofuran / 1.5 h / Inert atmosphere; Reflux 2: 0.5 h / 0 - 20 °C View Scheme
Multi-step reaction with 2 steps 1: magnesium / tetrahydrofuran / 4 h / 40 °C 2: iodine / ethyl acetate; dimethyl sulfoxide / Darkness View Scheme

benzyl chloride (100-44-7) → bis(thiobenzoyl) disulfide (5873-93-8)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: sodium methylate; sulfur / methanol / 10 h / Inert atmosphere; Reflux 2.1: sodium hydroxide / water 2.2: 1 h View Scheme
Multi-step reaction with 3 steps 1: sulfur; sodium methylate / methanol / 10 h / 67 °C / Inert atmosphere 2: sodium hydroxide / water 3: potassium hexacyanoferrate(III) / water / 1 h View Scheme
Stage #1: benzyl chloride With sodium methylate; sulfur In methanol for 10h; Inert atmosphere; Reflux; Stage #2: With potassium hexacyanoferrate(III) for 1h;
Stage #1: benzyl chloride With sodium methylate; sulfur In methanol at 20 - 67℃; for 12h; Inert atmosphere; Stage #2: With potassium hexacyanoferrate(III) In water for 1h;
Multi-step reaction with 2 steps 1: sulfur; sodium methylate / methanol / 10 h / Reflux; Inert atmosphere 2: potassium hexacyanoferrate (III) / 1 h View Scheme

phenyldithiocarboxylic acid magnesium bromide → bis(thiobenzoyl) disulfide (5873-93-8)

Conditions	Yield
With iodine-potassium iodide

2,2'-azobis-(2,4-dimethylvaleronitrile) (4419-11-8) + bis(thiobenzoyl) disulfide (5873-93-8) → 2-cyano-4-methylpent-2-yl dithiobenzoate (851729-55-0)

Conditions	Yield
In ethyl acetate Heating;	95%

tetraethylammonium tetrathioperrhenate + bis(thiobenzoyl) disulfide (5873-93-8) → Re(S2CC6H5)(S3CC6H5)2

Conditions	Yield
In acetonitrile Ar-atmosphere; stirring at room temp. for 2 d; elem. anal.;	93%

2,2'-azobis(isobutyronitrile) (78-67-1) + bis(thiobenzoyl) disulfide (5873-93-8) → 2-cyanoprop-2-yl dithiobenzoate (201611-85-0)

Conditions	Yield
In ethyl acetate for 18h; Reflux;	84%
In ethyl acetate for 18h; Heating;	69%
In cyclohexane for 4h; Heating;	56%

azobis(2-cyanobutane) (13472-08-7) + bis(thiobenzoyl) disulfide (5873-93-8) → 1-cyano-1-methylpropyl dithiobenzoate (220182-83-2)

Conditions	Yield
In ethyl acetate at 70℃; for 24h;	82%

bis(pentamethylcyclopentadienyl)iron(II) (12126-50-0) + bis(thiobenzoyl) disulfide (5873-93-8) + bis(pentafluorophenyl)zinc toluene monosolvate → [Cp*2Fe][(PhC(S)S)Zn(C6F5)2]

Conditions	Yield
In chlorobenzene at 20℃; for 0.0833333h; Inert atmosphere;	82%

bis(thiobenzoyl) disulfide (5873-93-8) + 4,4'-dicyano-4,4'-azo-di-valeric acid (2638-94-0) → 4-cyano-4-(thiobenzoylthio)pentanoic acid (201611-92-9)

Conditions	Yield
In ethyl acetate at 85℃; for 12h; Inert atmosphere;	75%
In ethyl acetate for 18h; Heating;	68%
In ethyl acetate Reflux;	65%

tetrabutyl thiotungstate + bis(thiobenzoyl) disulfide (5873-93-8) → WS(4+)*S2(2-)*2S2CC6H5(1-)=WS(S2)(S2CC6H5)2 + (CH3(CH2)3)4N(1+)*WO(S2)2(S2CC6H5)(1-)=[(CH3(CH2)3)4N][WO(S2)2(S2CC6H5)]

Conditions	Yield
With air In dichloromethane stirring under inert atmosphere at room temp. for 1 h, filtration in air; concn., chromy. (SiO2, hexane/CHCl3=1:1); elem. anal.;	A 73% B n/a

bis(tetra-n-butylammonium) tetrathiomolybdate + bis(thiobenzoyl) disulfide (5873-93-8) → Mo(4+)*4S2CC6H5(1-)=Mo(S2CC6H5)4

Conditions	Yield
In dichloromethane inert atmosphere; stirring at room temp. overnight; filtration, vol. reduction, collection (filtration), washing (MeCN, ether);	69%

dimethyl 2,2'-azobis(isobutyrate) (2589-57-3) + bis(thiobenzoyl) disulfide (5873-93-8) → methyl 2-methyl-2-((phenylcarbonothioyl)thio)propanoate

Conditions	Yield
In chlorobenzene for 4h; Heating;	65%

bis(pentafluorophenyl)azobis(4-cyanovalerate) + bis(thiobenzoyl) disulfide (5873-93-8) → pentafluorophenyl 4-cyano-4-((phenylcarbonothioyl)thio)pentanoate (1160527-68-3)

Conditions	Yield
In ethyl acetate for 16h; Inert atmosphere; Reflux;	63%

tetraethylammonium tetrathioperrhenate + bis(thiobenzoyl) disulfide (5873-93-8) → bis(perthiobenzoato)(dithiobenzoato)rhenium(III)

Conditions	Yield
In acetonitrile for 48h; Inert atmosphere; Schlenk technique;	60.4%

bis(thiobenzoyl) disulfide (5873-93-8) + 2-[1-cyano-1-methyl-4-oxo-4-(2-thioxo-thiazolidin-3-yl)-butylazo]-2-methyl-5-oxo-5-(2-thioxothiazolidin-3-yl)-pentanenitrile (870779-03-6) → dithiobenzoic Acid 1-cyano-1-methyl-4-oxo-4-(2-thioxothiazolidin-3-yl)butyl ester (887764-14-9)

Conditions	Yield
In ethyl acetate at 80℃; for 6h;	56%
In ethyl acetate at 80℃; for 20h;	54.7%

bis(thiobenzoyl) disulfide (5873-93-8) + 2-hydroxyethyl-α-bromopropionate (208446-93-9) → 2-hydroxyethyl 2-(phenylcarbonothioylthio)propionate

Conditions	Yield
With N,N,N',N'',N'''-pentamethyldiethylenetriamine; copper; copper(I) bromide In toluene at 80℃; for 3h; Inert atmosphere;	49%

bis(thiobenzoyl) disulfide (5873-93-8) + 4,4′-azobis(4-cyano-1-pentanol) (4693-47-4) → 4-cyano-1-hydroxypent-4-yl dithiobenzoate (211818-45-0)

Conditions	Yield
In ethyl acetate at 70℃; for 24h;	46%
In ethyl acetate at 70℃; for 24h;	46%

bis(thiobenzoyl) disulfide (5873-93-8) + azobis(cyanovaleric acid) (91263-49-9) → C14H15NO2S2 (1060725-15-6)

Conditions	Yield
In ethyl acetate at 90℃; for 12h; Inert atmosphere;	42.3%

bis(thiobenzoyl) disulfide (5873-93-8) + C48H54N10O6 (1268268-75-2) → 4-cyano-4-(thiobenzoylthio)pentanoic acid (201611-92-9)

Conditions	Yield
In ethyl acetate at 80℃; for 20h; Inert atmosphere;	34%

bis(thiobenzoyl) disulfide (5873-93-8) + 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] → 2-[N-(2-hydroxyethyl)carbamoyl]prop-2-yl dithiobenzoate

Conditions	Yield
In ethanol; ethyl acetate for 24h; Heating;	18%

bis(thiobenzoyl) disulfide (5873-93-8) → dithiobenzoic acid (121-68-6)

Conditions	Yield
With potassium hydroxide

ethanol (64-17-5) + bis(thiobenzoyl) disulfide (5873-93-8) + aniline (62-53-3) → hydrogen sulfide (7783-06-4) + N-Phenylbenzothioamide (636-04-4) + sulfur

Upstream product

• 60-29-7 diethyl ether 
• 936-63-0 S-ethyl dithiobenzoate 
• 19911-87-6 tetraethylammonium dithiobenzoate 
• 121-68-6 dithiobenzoic acid 
• 7664-93-9 sulfuric acid 
• 3682-36-8 dithiobenzoic acid sodium salt 
• 7631-95-0 sodium molybdate dihydrate 
• 50929-87-8 diethylammonium dithiobenzoate 
• 100-44-7 benzyl chloride 
• 108-86-1 bromobenzene 
• 2638-94-0 4,4'-dicyano-4,4'-azo-di-valeric acid 
• 75-15-0 carbon disulfide 
• 100-58-3 phenylmagnesium bromide 
• 1114-31-4 diethyl meso-2,3-dibromosuccinate 

Downstream Products

• 121-68-6 dithiobenzoic acid 
• 201611-85-0 2-cyanoprop-2-yl dithiobenzoate 
• 7783-06-4 hydrogen sulfide 
• 65-85-0 benzoic acid 
• 851729-55-0 2-cyano-4-methylpent-2-yl dithiobenzoate 
• 201611-92-9 4-cyano-4-(thiobenzoylthio)pentanoic acid 
• 887764-14-9 dithiobenzoic Acid 1-cyano-1-methyl-4-oxo-4-(2-thioxothiazolidin-3-yl)butyl ester 
• 1060725-15-6 C₁₄H₁₅NO₂S₂ 
• 1160527-68-3 pentafluorophenyl 4-cyano-4-((phenylcarbonothioyl)thio)pentanoate 
• 220182-83-2 1-cyano-1-methylpropyl dithiobenzoate 
• 220182-89-8 1-cyano-1-cyclohexyl dithiobenzoate 
• 81844-27-1 (η3-dithiobenzoato-SCS')oxo(trithioperoxybenzoato-S,S'S'')molybdenum(IV) 
• 636-04-4 N-Phenylbenzothioamide 

Relevant articles and documents

Controlled free radical polymerization in water-borne dispersion using reversible addition-fragmentation chain transfer

A novel approach to conducting controlled free radical polymerization in water-borne organic dispersions using reversible addition-fragmentation chain transfer (RAFT) has been studied. The novel approach in this study focused on eliminating monomer and oligomer transport and comprised two fundamental steps: the synthesis of dithiobenzoate-end-capped styrene oligomers in bulk followed by emulsification of these oligomers to yield a polymerizable water-borne dispersion. Dithioesters that act as chain transfer agents in the RAFT process were synthesized in situ. The free radical polymerization of the dithiobenzoate-end-capped styrene oligomers in the water-borne organic dispersion proceeded in a controlled manner: molar mass increased in a linear fashion with increasing conversion, while polydispersities remained low. The familiar red layer formation associated with RAFT polymerization in conventional emulsions was not observed under these conditions. The effects of changing the costabilizer (hydrophobe) and the degree of polymerization of the emulsified oligomers were investigated. Better control was achieved with a less hydrophilic costabilizer and for the shorter of the oligomers tested.

Ubiquitous Nature of Rate Retardation in Reversible Addition-Fragmentation Chain Transfer Polymerization

Reversible addition-fragmentation chain transfer (RAFT) polymerization is one of the most powerful reversible deactivation radical polymerization (RDRP) processes. Rate retardation is prevalent in RAFT and occurs when polymerization rates deviate from ideal conventional radical polymerization kinetics. Herein, we explore beyond what was initially thought to be the culprit of rate retardation: dithiobenzoate chain transfer agents (CTA) with more active monomers (MAMs). Remarkably, polymerizations showed that rate retardation occurs in systems encompassing the use of trithiocarbonates and xanthates CTAs with varying monomeric activities. Both the simple slow fragmentation and intermediate radical termination models show that retardation of all these systems can be described by using a single relationship for a variety of monomer reactivity and CTAs, suggesting rate retardation is a universal phenomenon of varying severity, independent of CTA composition and monomeric activity level.

Tert-amyl methyl ether preparation method and light gasoline modification method

The invention discloses a tert-amyl methyl ether preparation method and a light gasoline modification method. The tert-amyl methyl ether preparation method comprises that methanol and isopentene contact an etherification catalyst under an etherification reaction condition to obtain the reaction product containing tert-amyl methyl ether, wherein the etherification catalyst is a polymer supported ionic liquid catalyst, and has a structure represented by a formula (I) or a formula (II). With the method of the present inventin, the tert-amyl methyl ether preparation reaction can maintain the highreactivity.