872-36-6

Basic information

• Product Name: Vinylene carbonate
• Synonyms: 1,3-DIOXOL-2-ONE;1,3-Dioxo-2-one;VINYLENE CARBONATE;Carbonic acid, cyclic vinylene ester;carbonicacid,cyclicvinyleneester;Vinylene carbonate (stabilized with HQ);Vinylenecarbonate,97%;VINYLENE CARBONATE, STAB.
• CAS NO: 872-36-6
• Molecular Formula: C₃H₂O₃
• Molecular Weight: 86.05
• EINECS: 212-825-5
• Product Categories: fine chemicals;Fine Chemical
• Mol File: 872-36-6.mol
• Article Data: 23

Chemical Properties

• Melting Point: 19-22 °C(lit.)
• Boiling Point: 162 °C(lit.)
• Flash Point: 163 °F
• Appearance: Colorless to pale yellow/Liquid
• Density: 1.360 g/mL at 20 °C
• Vapor Pressure: 89.9mmHg at 25°C
• Refractive Index: n20/D 1.421(lit.)
• Storage Temp.: 2-8°C
• Solubility: 11.5 g/100 mL
• Water Solubility: 11.5 g/100 mL
• Sensitive: Moisture Sensitive
• BRN: 105683
• CAS DataBase Reference: Vinylene carbonate(CAS DataBase Reference)
• NIST Chemistry Reference: Vinylene carbonate(872-36-6)
• EPA Substance Registry System: Vinylene carbonate(872-36-6)

Safety Data

• Hazard Codes: Xi,N,T
• Statements: 43-36-51/53-48/22-41-38-24-22
• Safety Statements: 37/39-26-24-61-45-36/37/39
• RIDADR: UN2810 - class 6.1 - PG 3 - EHS - Toxic, liquids, organic, n.o.s
• WGK Germany: 3
• RTECS: FG3325000
• TSCA: Yes
• Hazardous Substances Data: 872-36-6(Hazardous Substances Data)

Usage

Chemical Properties

clear colorless to light yellow liquid

Uses

Vinylene carbonate is used as an additive to electrolyte solutions for anode side Lithiumion batteries. It also acts as a sealant to seal at least a portion of the silicon-polyvinyl acid interface. It is further used for great improvement of high temperature performance of the battery.

Application

Vinylene carbonate (VC) can be used as an electrolytic additive for ionic liquid electrolyte for the formation of lithium-ion batteries. It can also be used in the formation of hybrid solid electrolyte interphase (SEI) for the fabrication of lithium-based batteries.

Preparation

Vinylene carbonate is produced by the known method by eliminating hydrogen chloride from chloroethylene glycol carbonate by means of tertiary amines, in particular triethylamine. Chloroethylene glycol carbonate is obtained by free radical chlorination of ethylene glycol carbonate by means of chlorine or sulphuryl chloride. This synthesis was published for the first time in 1953 by Newman and Addor (JACS, 1953, page 1263; JACS 1955, page 3789).

General Description

This product has been enhanced for energy efficiency. Carbonate building block offered as a solution in ethyl acetate for more convenient handling. Vinylene carbonate may also be used as a dienophile in Diels-Alder reactions.

Flammability and Explosibility

Nonflammable

Purification Methods

Purify it by zone melting, or distillation, and stabilize it with 0.5% of 2,6-di-tert-butyl-p-cresol. [Beilstein 19 III/IV 1597, 19/4 V 72.]

InChI:InChI=1/C3H2O3/c4-3-5-1-2-6-3/h1-2H

Synthetic route

4-chloro-1,3-dioxolan-2-one (3967-54-2) → vinylene carbonate (872-36-6)

Conditions	Yield
With 4-tert-Butylcatechol; triethylamine In ethyl acetate at 25 - 30℃; for 1.66667h; Solvent; Reagent/catalyst; Temperature; Flow reactor; Large scale;	96.5%
With 3-amino-2-propanol In ethyl acetate at 4℃; for 3h; Temperature; Reagent/catalyst;	95%
With ethanolamine; p-benzoquinone at 55℃; for 5h; Reagent/catalyst; Temperature; Concentration;	85%

Vinyl chloroformate (5130-24-5) → vinylene carbonate (872-36-6)

Conditions	Yield
With triethylamine at 34 - 49℃; for 0.0555556h; Temperature; Flow reactor; Sonication; Inert atmosphere;	95.6%

α-(2-oxo-1,3-dioxolan-4-yl)cobalamin → vinylene carbonate (872-36-6) + {Co(C20H6N4(CH3)8(CH2CH2CONH2)3(CH2CONH2)3(CH2CH2CONHCH2CH(CH3)OPO2OC4H8O3C9H9N2))(H2O)}(1+) (27085-12-7)

Conditions	Yield
In water Irradiation (UV/VIS); in pH 7 phosphate buffer, aerobic irrdn. with a 275-W sunlamp, not stirred;	A 70% B n/a

4-chloro-1,3-dioxolan-2-one (3967-54-2) → vinylene carbonate (872-36-6) + 2-chloroethanal (107-20-0) + acetic acid (64-19-7)

Conditions	Yield
catalyst from examples 1 and 2 (ZnCl2 on silica, calcined) at 200 - 400℃; for 6.5 - 332h; Product distribution / selectivity;	A 69% B n/a C n/a

[1,3]-dioxolan-2-one (96-49-1) → vinylene carbonate (872-36-6)

Conditions	Yield
With sulfuryl dichloride In tetrachloromethane at 80℃; for 3h; Irradiation;	50%

4-chloro-1,3-dioxolan-2-one (3967-54-2) + diethyl ether (60-29-7) + triethylamine (121-44-8) → vinylene carbonate (872-36-6)

trans-4,5-dichloro-<1,3>dioxolan-2-one → vinylene carbonate (872-36-6)

Conditions	Yield
With 1,2-dimethoxyethane; zinc; benzene

1,2-dimethoxyethane (110-71-4) + (+/-)-trans-4,5-dichloro-[1,3]dioxolan-2-one (3967-55-3, 36368-37-3, 127213-77-8, 127213-84-7) + benzene (71-43-2) + zinc-powder → vinylene carbonate (872-36-6)

2,2'-Dithiobis(1,3-dioxolium)-bis(trifluormethansulfonat) (88734-22-9) → vinylene carbonate (872-36-6) + Vinylene thioxocarbonate (37635-87-3) + S

Conditions	Yield
With sodium hydroxide In acetonitrile Product distribution; Mechanism;	A 1.15 mmol B 1.29 mmol C n/a

4-chloro-1,3-dioxolan-2-one (3967-54-2) → vinylene carbonate (872-36-6) + triethylamine hydrochloride (554-68-7)

Conditions	Yield
With triethylamine In diethyl ether for 20h; Heating / reflux;
With triethylamine In Dibutyl carbonate at 50℃; for 20h;

cis+trans-dibromoethylene (540-49-8) + sodium carbonate (497-19-8) → vinylene carbonate (872-36-6)

Conditions	Yield
With potassium iodide In water at 40 - 92℃; for 12h; Reagent/catalyst; Temperature; Inert atmosphere;	320 g

cis+trans-dibromoethylene (540-49-8) + potassium carbonate (584-08-7) → vinylene carbonate (872-36-6)

Conditions	Yield
With N-benzyl-N,N,N-triethylammonium chloride; potassium iodide In water at 40 - 92℃; for 12h; Reagent/catalyst; Inert atmosphere;

vinylene carbonate (872-36-6) + p-Chlorothiophenol (106-54-7) → 4-(p-chlorophenylthio)-1,3-dioxolan-2-one (304881-41-2)

Conditions	Yield
With triethylamine In tetrahydrofuran for 4h; Heating;	100%

vinylene carbonate (872-36-6) + 2-bromoanthracene (7321-27-9) → 2-bromo-9,10-dihydro-9,10-ethanoanthracene-11,12-diol cyclic carbonate

Conditions	Yield
for 18h; Reflux;	99%

vinylene carbonate (872-36-6) → 4,-dichloro-1,3-dioxolane-2-one (3967-55-3)

Conditions	Yield
With chlorine at 30℃; Temperature; Inert atmosphere;	97.8%

vinylene carbonate (872-36-6) → dibromoethylene carbonate

Conditions	Yield
With bromine at 25℃; Temperature; Inert atmosphere;	97.45%

vinylene carbonate (872-36-6) + anthracene (120-12-7) → cis-9,10-dihydro-9,10-ethanoanthracene-11,12-diol cyclic carbonate (5675-70-7)

Conditions	Yield
for 8h; Heating;	95%
In various solvent(s) for 36h; Heating;	94%
In 1,2-dichloro-benzene for 36h; Heating / reflux;	94%

vinylene carbonate (872-36-6) + Tetracen (92-24-0) → 5,12-dihydro-5,12-ethanonaphthacene-cis-13,14-diyl carbonate (71440-73-8, 79982-79-9, 80009-62-7)

Conditions	Yield
In 5,5-dimethyl-1,3-cyclohexadiene at 180℃; for 72h; Diels-Alder Cycloaddition; Autoclave;	95%
for 8h; Heating;	11%

vinylene carbonate (872-36-6) + endo-3,4,5,6-tetrachlorobicyclo[6.2.2.02,7]dodeca-3,4,9-triene (185097-99-8) → 1,8,14,15-Tetrachlor-10,12-dioxapentacyclo[6.5.2.23,6.02,7.09,13]heptadeca-4,14-dien-11-on (185098-07-1)

Conditions	Yield
With 4-tert-Butylcatechol In tetrahydrofuran at 100℃; under 5850470 Torr; for 72h;	95%

vinylene carbonate (872-36-6) + N-methyl-2-phenylacrylamide (1256971-44-4) → 1-methyl-3-phenylpyridin-2(1H)-one (13180-21-7)

Conditions	Yield
With silver hexafluoroantimonate; carbonyl(pentamethylcyclopentadienyl)cobalt diiodide; zinc diacetate In 2,2,2-trifluoroethanol at 100℃; for 24h; Inert atmosphere; Schlenk technique; Sealed tube;	95%

vinylene carbonate (872-36-6) + 1-naphthalenecarboxylic acid (86-55-5) → 1H-benzo[h]isochromen-1-one (4708-19-4)

Conditions	Yield
With silver hexafluoroantimonate; dichloro[1,3-di(ethoxycarbonyl)-2,4,5-trimethylcyclopentadienyl]rhodium(III) dimer In 1,2-dichloro-ethane at 120℃; for 15h; Schlenk technique; Inert atmosphere;	95%

vinylene carbonate (872-36-6) + 1,4-dimethylanthracene (781-92-0) → C19H16O3 (71489-48-0)

Conditions	Yield
for 8h; Heating;	94%

vinylene carbonate (872-36-6) + 5,5-dimethoxy-1,2,3,4-tetrachlorocyclopentadiene (2207-27-4) → 1,7,8,9-tetrachloro-10,10-dimethoxy-3,5-dioxa-tricyclo[5.2.1.02,6]dec-8-en-4-one

Conditions	Yield
at 60 - 90℃; for 67h;	94%

vinylene carbonate (872-36-6) + naphthalene-2-carboxylate (93-09-4) → 1H-benzo[g]isochromen-1-one

Conditions	Yield
With silver hexafluoroantimonate; dichloro[1,3-di(ethoxycarbonyl)-2,4,5-trimethylcyclopentadienyl]rhodium(III) dimer In 1,2-dichloro-ethane at 120℃; for 15h; Schlenk technique; Inert atmosphere;	94%

vinylene carbonate (872-36-6) + 6-hydroxy-2-phenyl-3(2H)-pyridazinone (1698-54-0) → C12H8N2O2

Conditions	Yield
With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; sodium acetate; silver(I) triflimide In 1,2-dichloro-ethane for 12h; Inert atmosphere; Heating;	94%

vinylene carbonate (872-36-6) + C10H10FNO → 3-(4-fluorophenyl)-1-methylpyridin-2(1H)-one

Conditions	Yield
With silver hexafluoroantimonate; carbonyl(pentamethylcyclopentadienyl)cobalt diiodide; zinc diacetate In 2,2,2-trifluoroethanol at 100℃; for 24h; Inert atmosphere; Schlenk technique; Sealed tube;	93%

vinylene carbonate (872-36-6) + 5,12-di([1,1'-biphenyl]-4-yl)-naphthacene (272459-50-4) → 5,12-di([1,1'-biphenyl]-4-yl)-6,11-dihydro-6,11-ethanonaphthacene-cis-13,14-diyl carbonate (1426414-30-3)

Conditions	Yield
In 5,5-dimethyl-1,3-cyclohexadiene at 180℃; for 72h; Diels-Alder Cycloaddition; Autoclave;	92%

vinylene carbonate (872-36-6) + 2,6-bis(diphenylamino)anthracene → C41H30N2O3

Conditions	Yield
In 5,5-dimethyl-1,3-cyclohexadiene at 180℃; for 24h; Diels-Alder Cycloaddition; Sealed tube; Inert atmosphere;	92%

vinylene carbonate (872-36-6) + N-benzylbenzamide (1485-70-7) → 2-benzyl-1-(2H)-isoquinoline ketone (59168-21-7)

Conditions	Yield
With silver hexafluoroantimonate; carbonyl(pentamethylcyclopentadienyl)cobalt diiodide; zinc diacetate In 2,2,2-trifluoroethanol at 100℃; for 24h; Inert atmosphere; Schlenk technique; Sealed tube;	92%

vinylene carbonate (872-36-6) + 2-phenyl-4(3H)-quinazolinone (1022-45-3) → 8H-isoquinolino[1,2-b]-quinazolin-8-one (892-36-4)

Conditions	Yield
With silver tetrafluoroborate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer In acetonitrile at 60℃; for 24h; Schlenk technique; Sealed tube;	92%

vinylene carbonate (872-36-6) + 7-fluoro-2-phenylquinazolin-4(3Η)-one (1315337-24-6) → 11-fluoro-6-hydroxy-5,6-dihydro-8H-isoquinolino[1,2-b]quinazolin-8-one

Conditions	Yield
With silver hexafluoroantimonate; [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; sodium acetate In 1,2-dichloro-ethane at 80℃; for 12h; Inert atmosphere;	92%

vinylene carbonate (872-36-6) + Chlorotrifluoroethylene (79-38-9) → polymer, Mn = 2300 g/mol, PDI = 2.3; monomer(s): chlorotrifluoroethylene; vinylene carbonate

Conditions	Yield
With tert-butyl peroxypivalate In ethyl acetate at 80℃; for 4h;	91.6%

vinylene carbonate (872-36-6) + Chlorotrifluoroethylene (79-38-9) → polymer, Mn = 4250 g/mol, PDI = 2.3; monomer(s): chlorotrifluoroethylene; vinylene carbonate

Conditions	Yield
With tert-butyl peroxypivalate In acetic acid methyl ester at 80℃; for 4h;	91.6%

vinylene carbonate (872-36-6) + cyclopenta-1,3-diene (542-92-7) → (3ar,7ac)-3a,4,7,7a-tetrahydro-4c,7c-methano-benzo[1,3]dioxol-2-one (36444-42-5)

Conditions	Yield
With hydroquinone In toluene at 180℃; for 20h; Diels-Alder Cycloaddition; Schlenk technique;	91%
Diels-Alder reaction;

vinylene carbonate (872-36-6) + 9,10-diethyl-2,3,6,7-tetramethoxy-anthracene (140648-13-1) → 2,3,6,7-tetramethoxy-9,10-dihydro-9,10-ethanoanthracene-11,12-diol

Conditions	Yield
Stage #1: vinylene carbonate; 9,10-diethyl-2,3,6,7-tetramethoxy-anthracene In xylene at 180℃; for 72h; Stage #2: With sodium hydroxide for 2h; Heating; Further stages.;	91%

vinylene carbonate (872-36-6) + C46H48N4 → C49H50N4O3

Conditions	Yield
In toluene at 140℃; for 72h; Diels-Alder reaction; Autoclave; Inert atmosphere;	91%

vinylene carbonate (872-36-6) + 2,6-bis(3,6-dioctyl-9H-carbazol-9-yl)anthracene → 2,6-bis(3,6-dioctyl-9H-carbazol-9-yl)-9,10-[4,5]epidioxoloanthracen-13-one

Conditions	Yield
With hydroquinone In 5,5-dimethyl-1,3-cyclohexadiene at 180℃; Diels-Alder Cycloaddition; Inert atmosphere;	91%

vinylene carbonate (872-36-6) + ortho-methylbenzoic acid (118-90-1) → 8-methyl-1H-isochromen-1-one

Conditions	Yield
With silver hexafluoroantimonate; dichloro[1,3-di(ethoxycarbonyl)-2,4,5-trimethylcyclopentadienyl]rhodium(III) dimer In 1,2-dichloro-ethane at 120℃; for 15h; Schlenk technique; Inert atmosphere;	91%

vinylene carbonate (872-36-6) + 5-(α-tetrahydrofuryl)pentachlorocyclopentadiene (85832-93-5) → cyclic carbonate of 1,4,5,6,7-pentachloro-7-(α-tetrahydrofuryl)bicyclo<2.2.1>hept-5-ene-2,3-diol (85833-04-1)

Conditions	Yield
at 160 - 165℃; for 4h;	90.1%

vinylene carbonate (872-36-6) + 1-chloroanthracene (4985-70-0) → C17H11ClO3 (71440-52-3, 81873-80-5)

Conditions	Yield
for 8h; Heating;	90%

Upstream product

• 110-71-4 1,2-dimethoxyethane 
• 3967-55-3 (+/-)-trans-4,5-dichloro-[1,3]dioxolan-2-one 
• 71-43-2 benzene 
• 540-49-8 cis+trans-dibromoethylene 
• 584-08-7 potassium carbonate 
• 497-19-8 sodium carbonate 
• 5130-24-5 Vinyl chloroformate 
• 3967-54-2 4-chloro-1,3-dioxolan-2-one 
• 88734-22-9 2,2'-Dithiobis(1,3-dioxolium)-bis(trifluormethansulfonat) 
• 96-49-1 [1,3]-dioxolan-2-one 
• 60-29-7 diethyl ether 
• 121-44-8 triethylamine 

Downstream Products

• 32384-16-0 exo-/endo-3,5,10-Trioxatricyclo<5.2.1.0^2.6>dec-8-en-4-on 
• 5675-70-7 cis-9,10-dihydro-9,10-ethanoanthracene-11,12-diol cyclic carbonate 
• 36444-42-5 (3ar,7ac)-3a,4,7,7a-tetrahydro-4c,7c-methano-benzo[1,3]dioxol-2-one 
• 4717-64-0 (3aRS,7aSR)-5,6-dimethyl-3a,4,7,7a-tetrahydrobenzo[d][1,3]dioxol-2-one 
• 3967-55-3 (+/-)-trans-4,5-dichloro-[1,3]dioxolan-2-one 
• 91237-27-3 (3S,3aS,6aR)-2-Benzyl-3-((4S,5S)-2,2,5-trimethyl-[1,3]dioxolan-4-yl)-tetrahydro-[1,3]dioxolo[4,5-d]isoxazol-5-one 
• 91190-37-3 (3R,3aR,6aS)-2-Benzyl-3-((4S,5S)-2,2,5-trimethyl-[1,3]dioxolan-4-yl)-tetrahydro-[1,3]dioxolo[4,5-d]isoxazol-5-one 
• 183854-52-6 (3R,3aR,6aS)-2-((R)-1-Phenyl-ethyl)-3-((4S,5S)-2,2,5-trimethyl-[1,3]dioxolan-4-yl)-tetrahydro-[1,3]dioxolo[4,5-d]isoxazol-5-one 
• 1426414-32-5 5,12-di([1,1':3',1''-terphenyl]-5'-yl)-6,11-dihydro-6,11-ethanonaphthacene-cis-13,14-diyl carbonate 
• 1426414-30-3 5,12-di([1,1'-biphenyl]-4-yl)-6,11-dihydro-6,11-ethanonaphthacene-cis-13,14-diyl carbonate 
• 1211578-89-0 2-(3-bromo-4-methyl-phenyl)-oxazole 
• 1398048-21-9 C₁₂H₁₁FN₂O₃ 
• 62882-05-7 2-(3-methylphenyl)oxazole 
• 66553-02-4 1,2-bis-(4-methoxycarbonylphenyl)-ethane-1,2-dione 

Relevant articles and documents

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Method for producing a vinylene carbonate

[Problem] to a dehydrochlorination reaction of tertiary amine [monokuroroechirenkaboneto[monokuroroechirenkaboneto], high yield production of coloring of the vinylene carbonate is suppressed. [Solution] using the tertiary amine [monokuroroechirenkaboneto[monokuroroechirenkaboneto] dehydrochlorination reaction, performed in the first reaction solution obtained in the first step of the first solvent, the second solvent can be added to the first reaction to a second reaction in the second step, the reaction solvent was removed from the first second third reaction in the second step, the fourth step may be removed from the reaction solution-third fourth reaction, a fourth method for producing a vinylene carbonate from the reaction liquid, the third liquid and fourth liquid reaction mixture obtained was washed with a solvent for the solid mixture liquid from the fourth method for producing a vinylene, a fourth step of solvent washing liquid obtained from the first solid-liquid mixed solvent was removed from the reaction solution with a fourth manufacturing method for obtaining a fourth bottom vinylene, further, a fourth step of solvent washing liquid obtained by washing the solid second reaction liquid mix of the fifth manufacturing method is solved by a vinylene carbonate. [Drawing] no

Synthesis method of vinylene carbonate

The invention discloses a synthesis method of vinylene carbonate, which comprises the following steps: by using chlorine and ethylene carbonate as reaction raw materials and carbon tetrachloride as amedium, synthesizing monochloroethylene carbonate at 70 DEG C under the illumination of an LED blue light lamp; after the reaction is finished, evaporating out the carbon tetrachloride, and carrying out reduced pressure distillation to obtain the monochloroethylene carbonate; mixing the monochloroethylene carbonate obtained with methyl tert-butyl ether according to a certain ratio; dropwise addingtriethylamine at 55-58 DEG C under the condition of taking 2,2,6,6-tetramethyl-4-hydroxypiperidine nitroxide free radicals as a polymerization inhibitor; reacting the mixture at 60-62 DEG C after addition is finished; and after the reaction is finished, carrying out suction filtration, washing, and evaporation to obtain the triethylamine and the methyl tert-butyl ether; and carrying out reduced pressure distillation to obtain the vinylene carbonate. According to the improvement of the synthesis method, the raw materials are simple and easy to obtain, the process is simple, less waste is generated, and the total yield can reach 58% or above; the method is suitable for large-scale industrial production.

The tubular reactor for the continuous production of vinylene carbonate

The invention provides a method for continuously preparing vinylene carbonate by a tubular reactor. The method includes using chlorosulfuric acid and ethylene carbonate as raw materials to be synthesized into chloroethylene carbonate in the tubular reactor under the action of initiator, rectifying the chloroethylene carbonate and subjecting the rectified chloroethylene carbonate to elimination reaction with trimethylamine in the tubular reactor with existence of organic solvent and generating the vinylene carbonate. By the method for continuously preparing vinylene carbonate by the tubular reactor, existing intermittent production methods are changed, reaction speed is greatly increased, reaction period is reduced, yield is increased and productivity can be effectively improved.