674-82-8

Basic information

• Product Name: Acetyl ketene
• Synonyms: 3-buteno-beta-lactone;3-Butenoic acid, 3-hydroxy-, beta-lactone;3-hydroxy-3-butenoicacibeta-lactone;4-methylene-2-oxetanon;Diketen;diketene,inhibited;Ethenone, dimer;ethenone,dimer
• CAS NO: 674-82-8
• Molecular Formula: C₄H₄O₂
• Molecular Weight: 84.07
• EINECS: 211-617-1
• Product Categories: Pharmaceutical Intermediates;Aromatic amine products
• Mol File: 674-82-8.mol
• Article Data: 7

Chemical Properties

• Melting Point: -7.5°C
• Boiling Point: 69-70 °C100 mm Hg(lit.)
• Flash Point: 95 °F
• Appearance: colorless liquid
• Density: 1.09 g/mL at 25 °C(lit.)
• Vapor Density: 2.9 (vs air)
• Vapor Pressure: 7.9 mm Hg ( 20 °C)
• Refractive Index: n20/D 1.439(lit.)
• Storage Temp.: 2-8°C
• CAS DataBase Reference: Acetyl ketene(CAS DataBase Reference)
• NIST Chemistry Reference: Acetyl ketene(674-82-8)
• EPA Substance Registry System: Acetyl ketene(674-82-8)

Safety Data

• Hazard Codes: Xn
• Statements: 10-20-40-36/37/38
• Safety Statements: 3-36/37-33-24/25-23-16-26
• RIDADR: UN 2929 6.1/PG 2
• WGK Germany: 2
• RTECS: RQ8225000
• F: 19-21-27
• HazardClass: 6.1(a)
• PackingGroup: I
• Hazardous Substances Data: 674-82-8(Hazardous Substances Data)

Usage

Uses

Diketene is used as a reactant in the manufacture of paper and control of its sizing. In addition its used in the preparation of potent and selective inhibitor of histone methyltransferase EZH2 in the treatment of B-Cell lymphomas.

General Description

A colorless liquid with a disagreeable odor. Slightly less dense than water. Flash point 90°F. Irritates skin and eyes. Used to make paints and pharmaceuticals.

Air & Water Reactions

Highly flammable. Slightly soluble in water.

Reactivity Profile

DIKETENE is a very reactive dimer, Acetyl ketene may undergo a spontaneous decomposition followed by explosion or ignition [Vervalin, 1973, p.86]. In the presence of bases, amines, mineral acids or Lewis acids a violent polymerization will occur, accompanied by gas evolution [Zdenek, F. et al., Czech Pat. 156 584, 1975].

Health Hazard

TOXIC; may be fatal if inhaled, ingested or absorbed through skin. Inhalation or contact with some of these materials will irritate or burn skin and eyes. Fire will produce irritating, corrosive and/or toxic gases. Vapors may cause dizziness or suffocation. Runoff from fire control or dilution water may cause pollution.

InChI:InChI=1/C4H4O2/c1-4(6)2-3-5/h2H,1H3

Synthetic route

bis(triphenylphosphine)-3,3-dimethylnickelacyclobutane → 4-methyleneoxetan-2-one (674-82-8) + bis(triphenylphosphine)nickel(0) dicarbonyl (13007-90-4) + isobutene (115-11-7)

Conditions	Yield
With carbon monoxide In toluene High Pressure; 5 atm CO, 50°C, 1 h; pptn. of complex;	A 8% B 83% C n/a

Ketene (463-51-4) → 4-methyleneoxetan-2-one (674-82-8)

Conditions	Yield
With N,N,N,N,-tetramethylethylenediamine In hexane at -15 - -10℃; for 3.5h;	75%

Ketene (463-51-4) + acetic anhydride (108-24-7) → 4-methyleneoxetan-2-one (674-82-8)

Ketene (463-51-4) + ethylmagnesium bromide (925-90-6) → 4-methyleneoxetan-2-one (674-82-8)

N-acetylphthalimide (1971-49-9) → 4-methyleneoxetan-2-one (674-82-8)

Conditions	Yield
at 325℃;

9-acetylcarbazole (574-39-0) → 4-methyleneoxetan-2-one (674-82-8)

Conditions	Yield
at 110℃; under 15 Torr;

Ketene (463-51-4) + buta-1,3-diene (106-99-0) → 4-methyleneoxetan-2-one (674-82-8) + 3-vinylcyclobutanone (66166-61-8)

Conditions	Yield
With nitrogen at 100℃;

triethylamine (121-44-8) + acetyl chloride (75-36-5) → 4-methyleneoxetan-2-one (674-82-8)

Conditions	Yield
With diethyl ether

acetyl chloride (75-36-5) + trimethylamine (75-50-3) → 4-methyleneoxetan-2-one (674-82-8)

Conditions	Yield
With diethyl ether

Ketene (463-51-4) + acetone (67-64-1) → 4-methyleneoxetan-2-one (674-82-8)

dichloromethane (75-09-2) + carbon monoxide (201230-82-2) → 4-methyleneoxetan-2-one (674-82-8)

Conditions	Yield
Pd(PCy3)2(dba) In benzene-d6 at 25℃; under 22501.8 Torr;

3-oxo-N-(p-tolyl)butanamide (2415-85-2) → 4-methyleneoxetan-2-one (674-82-8) + p-toluidine (106-49-0)

Conditions	Yield
In cyclohexane at 25℃; Equilibrium constant;

4'-Chloroacetoacetanilide (101-92-8) → 4-methyleneoxetan-2-one (674-82-8) + 4-chloro-aniline (106-47-8)

Conditions	Yield
In cyclohexane at 25℃; Equilibrium constant;

N-(4-bromophenyl)-3-oxobutyramide (38418-24-5) → 4-methyleneoxetan-2-one (674-82-8) + 4-bromo-aniline (106-40-1)

Conditions	Yield
In cyclohexane at 25℃; Equilibrium constant;

4'-methoxyacetoacetanilide (5437-98-9) → 4-methyleneoxetan-2-one (674-82-8) + 4-methoxy-aniline (104-94-9)

Conditions	Yield
In cyclohexane at 25℃; Equilibrium constant;

3-oxo-N-m-tolylbutanamide (25233-46-9) → 4-methyleneoxetan-2-one (674-82-8) + 1-amino-3-methylbenzene (108-44-1)

Conditions	Yield
In cyclohexane at 25℃; Equilibrium constant;

N-(3'-methoxyphenyl)-3-oxobutanamide (25233-47-0) → 4-methyleneoxetan-2-one (674-82-8) + m-Anisidine (536-90-3)

Conditions	Yield
In cyclohexane at 25℃; Equilibrium constant;

3'-nitroacetoacetanilide (25233-49-2) → 4-methyleneoxetan-2-one (674-82-8) + 3-nitro-aniline (99-09-2)

Conditions	Yield
In cyclohexane at 25℃; Equilibrium constant;

3'-chloroacetoacetanilide (2415-87-4) → 4-methyleneoxetan-2-one (674-82-8) + 3-chloro-aniline (108-42-9)

Conditions	Yield
In cyclohexane at 25℃; Equilibrium constant;

N-(3-bromo-phenyl)-3-oxo-butyramide (61579-06-4) → 4-methyleneoxetan-2-one (674-82-8) + 3-bromoaniline (591-19-5)

Conditions	Yield
In cyclohexane at 25℃; Equilibrium constant;

N-(3-cyanophenyl)-3-oxobutanamide → 4-methyleneoxetan-2-one (674-82-8) + m-cyanoaniline (2237-30-1)

Conditions	Yield
In cyclohexane at 25℃; Equilibrium constant;

N-phenylacetoacetamide (102-01-2) → 4-methyleneoxetan-2-one (674-82-8) + aniline (62-53-3)

Conditions	Yield
In cyclohexane at 25℃; Equilibrium constant;

1,2-propanediene (463-49-0) + p-benzoquinone (106-51-4) → 4-methyleneoxetan-2-one (674-82-8) + Spiro<3.5>nona-5,8-dien-2,7-dion (52727-24-9) + 3-Methylene-1-oxa-spiro[3.5]nona-5,8-dien-7-one (115077-69-5) + C15H12O4 (115077-67-3)

Conditions	Yield
In trichlorofluoromethane at -25℃; under 760 Torr; for 1h; Irradiation; Laser VIS-irradiation, 455-515 nm;	A n/a B n/a C 146 mg D 6.2 mg

Ketene (463-51-4) + acetaldehyde (75-07-0) + H3BO3 → 4-methyleneoxetan-2-one (674-82-8) + 4-methyloxetan-2-one (3068-88-0, 32082-74-9, 36536-46-6, 65058-82-4) + 3-penten-2-one (625-33-2)

Ketene (463-51-4) + acetaldehyde (75-07-0) + ZnCl2 → 4-methyleneoxetan-2-one (674-82-8) + 4-methyloxetan-2-one (3068-88-0, 32082-74-9, 36536-46-6, 65058-82-4) + 3-penten-2-one (625-33-2)

Ketene (463-51-4) + sulfuric acid (7664-93-9) + acetone (67-64-1) → 4-methyleneoxetan-2-one (674-82-8) + Isopropenyl acetate (108-22-5) + acetic anhydride (108-24-7) + 4-oxo-2.2.6-trimethyl-1.3-dioxime

Conditions	Yield
at 55℃;

Ketene (463-51-4) + acetone (67-64-1) + ZnCl2 → 4-methyleneoxetan-2-one (674-82-8) + Isopropenyl acetate (108-22-5) + acetic anhydride (108-24-7) + 4-oxo-2.2.6-trimethyl-1.3-dioxime

Conditions	Yield
at 100℃;

Ketene (463-51-4) + water (7732-18-5) → 4-methyleneoxetan-2-one (674-82-8) + acetone (67-64-1)

n-dodecanoyl chloride (112-16-3) + triethylamine (121-44-8) + acetyl chloride (75-36-5) → 4-methyleneoxetan-2-one (674-82-8) + dimer(ic) decylketene + mixed diketene C14H24O2

4-methyleneoxetan-2-one (674-82-8) + benzylamine (100-46-9) → N-benzyl-3-oxobutanamide (882-36-0)

Conditions	Yield
In dichloromethane at 0 - 20℃;	100%
In dichloromethane at 0 - 20℃;	100%
In dichloromethane at 0 - 20℃;	100%

4-methyleneoxetan-2-one (674-82-8) + 2-(N,N-dimethylamino)ethanol (108-01-0) → acetoacetic acid 2-dimethylamino-ethyl ester (6131-49-3)

Conditions	Yield
With dmap In tetrahydrofuran at 65℃; for 0.5h;	100%
at 70 - 71℃; for 5h;	99%
With triethylamine at 95℃; for 3h;	84%

4-methyleneoxetan-2-one (674-82-8) + cinnamylamine (4360-51-4) → 3-oxo-N-(3-phenyl-2-propen-1-yl) butylamide (26226-10-8)

Conditions	Yield
With triethylamine In toluene at 70℃; for 3h;	100%
In diethyl ether

4-methyleneoxetan-2-one (674-82-8) + diethylamine (109-89-7) → N,N-diethyl-3-oxobutanamide (2235-46-3)

Conditions	Yield
In tetrahydrofuran at 0℃; Inert atmosphere;	100%
In tetrahydrofuran at 0℃; for 0.0833333h; Inert atmosphere;	100%
With triethylamine In methanol; toluene at 0℃; for 2h;	95%

4-methyleneoxetan-2-one (674-82-8) + cyclohexanol (108-93-0) → cyclohexyl 3-oxobutanoate (6947-02-0)

Conditions	Yield
With sodium acetate In tetrahydrofuran for 2h; Reflux;	100%
With triethylamine In chloroform for 10h; Ambient temperature;	96.7%
With triethylamine
With dmap

piperidine (110-89-4) + 4-methyleneoxetan-2-one (674-82-8) → 1-(piperidin-1-yl)-butane-1,3-dione (1128-87-6)

Conditions	Yield
In tetrahydrofuran at 20℃;	100%
for 2h; Yield given;
In toluene at 100℃; for 1h;
In tert-butyl methyl ether at -5 - 0℃; for 1h;	49.55 g

4-methyleneoxetan-2-one (674-82-8) + cycl-isopropylidene malonate (2033-24-1) → 2,2-dimethyl-5-(1-hydroxy-3-oxobutylidene)-1,3-dioxane-4,6-dione (84257-12-5)

Conditions	Yield
With triethylamine In dichloromethane at 0 - 20℃; for 2h;	100%
Stage #1: 4-methyleneoxetan-2-one; cycl-isopropylidene malonate With triethylamine In dichloromethane at 0 - 20℃; for 2h; Stage #2: With hydrogenchloride In dichloromethane; water	100%
With triethylamine In dichloromethane at 20℃;	100%

4-methyleneoxetan-2-one (674-82-8) + methylthiol (74-93-1) → 4-Methylsulfanylmethyl-oxetan-2-one (108615-97-0)

Conditions	Yield
With 2,2'-azobis(isobutyronitrile) In diethyl ether for 2h; Ambient temperature; Irradiation;	100%

4-methyleneoxetan-2-one (674-82-8) + 1-butanethiol (109-79-5) → 4-(n-Butylthiomethyl)oxetan-2-on (72749-29-2)

Conditions	Yield
In diethyl ether at 0℃; for 0.5h;	100%
With sulfuric acid In diethyl ether for 2h; Ambient temperature;	72%
In diethyl ether at 0 - 5℃;

4-methyleneoxetan-2-one (674-82-8) + Octanethiol (111-88-6) → 4-Octylsulfanylmethyl-oxetan-2-one (108615-99-2)

Conditions	Yield
With 2,2'-azobis(isobutyronitrile) In Petroleum ether at 25℃; for 1h;	100%

4-methyleneoxetan-2-one (674-82-8) + Cyclopropylmethanol (2516-33-8) → cyclopropylmethyl 3-oxobutanoate (86780-84-9)

Conditions	Yield
With triethylamine In chloroform for 10h; Ambient temperature;	100%
With sodium hydride at 70 - 80℃; for 2h;	93%
With sodium acetate for 16h; Ambient temperature;

4-methyleneoxetan-2-one (674-82-8) + (-)-menthol (2216-51-5) → (L)-menthyl 3-oxobutyrate (59557-05-0)

Conditions	Yield
With triethylamine In dichloromethane at 20℃; for 3h;	100%
With sodium acetate In acetonitrile for 2h; Heating;	96%
With triethylamine In acetone for 2h; Heating;	92%

4-methyleneoxetan-2-one (674-82-8) + benzyl 2-(2-ethoxy-2-ethoxyethyl)-1-hydrazinecarboxylate (4503-58-6) → benzyl 2-acetoacetyl-2-(ethoxycarbonylmethyl)hydrazine-1-carboxylate (98381-06-7)

Conditions	Yield
With triethylamine In benzene for 16h; Heating;	100%
In benzene Yield given;

4-methyleneoxetan-2-one (674-82-8) + isopropoxyamine hydrochloride (4490-81-7) → N-Isopropoxy-3-oxo-butyramide (133146-80-2)

Conditions	Yield
With triethylamine In methanol; toluene at 0 - 5℃; for 0.5h;	100%

4-methyleneoxetan-2-one (674-82-8) + (-)-8-phenylmenthol (65253-04-5) → (+)-(1R,2S,5R)-8-phenylmenthyl 3-oxobutanoate (90358-31-9)

Conditions	Yield
With triethylamine In dichloromethane at 20℃; for 3h;	100%
With triethylamine In acetone for 3h; Heating;	95%
With sodium acetate In chloroform for 1h; Heating;	85.9%
With sodium acetate In tetrahydrofuran for 2h; Heating;

4-methyleneoxetan-2-one (674-82-8) + 2-<4-(4-benzhydryl-1-piperazinyl)phenyl>ethyl alcohol (116308-40-8) → 2-<4-(4-benzhydryl-1-piperazinyl)phenyl>ethyl acetoacetate (116308-41-9)

Conditions	Yield
With dmap In tetrahydrofuran 1) ice-salt cooling, 30 min, 2) r.t.;	100%

4-methyleneoxetan-2-one (674-82-8) + phenethylamine (64-04-0) → 3-oxo-N-(2-phenylethyl)butanamide (2044-66-8)

Conditions	Yield
In diethyl ether Reflux;	100%
In diethyl ether for 3h; Heating / reflux;	93%
In methanol at 0℃; Inert atmosphere;	46%
In methanol for 3h; Ambient temperature;
In methanol at 0℃; Inert atmosphere;

4-methyleneoxetan-2-one (674-82-8) + methyl 3-<(benzyloxy)amino>-2-propionate (81790-27-4) → 3-[Benzyloxy-(3-oxo-butyryl)-amino]-2-(4-benzyloxy-phenyl)-propionic acid methyl ester (81790-28-5)

Conditions	Yield
With dmap; triethylamine In tetrahydrofuran 1.) -78 deg C, 30 min, 2.) 0 deg C, 30 min;	100%

4-methyleneoxetan-2-one (674-82-8) + (S)-methyl 5,5-dimethyl-1,3-thiazolidine-4-carboxylate (70491-75-7) → methyl (4S)-5,5-dimethyl-3-(3-oxobutanoyl)thiazolidine-4-carboxylate (153823-10-0)

Conditions	Yield
With triethylamine In dichloromethane for 15h; Heating;	100%

4-methyleneoxetan-2-one (674-82-8) + 1-benzyl-3-pyrrolidinol (775-15-5) → 1-benzyl-3-acetoacetyloxypyrrolidine (71863-54-2)

Conditions	Yield
at 70 - 80℃; for 1h;	100%

4-methyleneoxetan-2-one (674-82-8) + 1-benzyl-3-hydroxypiperidine (14813-01-5) → 1-benzylpiperidin-3-yl acetoacetate (85387-34-4)

Conditions	Yield
With triethylamine In chloroform for 10h; Ambient temperature;	100%

4-methyleneoxetan-2-one (674-82-8) + (1R,2R,3R)-3-Benzyloxy-2-(tert-butyl-dimethyl-silanyloxy)-cyclohexanol → 3-Oxo-butyric acid (1R,2S,3R)-3-benzyloxy-2-(tert-butyl-dimethyl-silanyloxy)-cyclohexyl ester

Conditions	Yield
With triethylamine In tetrahydrofuran for 9h; Ambient temperature;	100%

4-methyleneoxetan-2-one (674-82-8) + 3,5-dimethyl-hexa-1,4-dien-3-ol (38552-68-0) → 3-oxo-butyric acid 1,3-dimethyl-1-vinyl-but-2-enyl ester (664343-03-7)

Conditions	Yield
With dmap In diethyl ether at 23℃;	100%

4-methyleneoxetan-2-one (674-82-8) + [13C]methanol (14742-26-8) → [13C]methyl 3-oxobutanoate

Conditions	Yield
With triethylamine In dichloromethane for 2h; Heating;	100%

4-methyleneoxetan-2-one (674-82-8) + N,N-diethylethylenediamine (100-36-7) → N-(2-(diethylamino)ethyl)-3-oxobutanamide (590424-03-6)

Conditions	Yield
In various solvent(s)	100%
In dichloromethane at 0 - 20℃; for 0.5h;	100%
In tert-butyl methyl ether at 0 - 20℃;	93%

4-methyleneoxetan-2-one (674-82-8) + (E)-cinnamylamine (4335-60-8, 4360-51-4, 4226-59-9) → 3-oxo-N-(3-phenyl-2-propen-1-yl)-butylamide

Conditions	Yield
With triethylamine In toluene at 70℃; for 3h;	100%
With triethylamine In toluene

4-methyleneoxetan-2-one (674-82-8) + (E)-3-(thien-2-yl)prop-2-en-1-ol (89639-64-5, 3216-44-2) → (E)-3-thiophen-2-ylprop-2-en-1-yl 3-oxobutanoate

Conditions	Yield
With triethylamine In toluene at 70℃; for 1.5h;	100%
With dmap In tetrahydrofuran at 0℃; for 2h; Inert atmosphere;	80%

4-methyleneoxetan-2-one (674-82-8) → (E)-3-(4-pyridyl)allyl acetoacetate

Conditions	Yield
With triethylamine In toluene at 70℃; for 2h;	100%

4-methyleneoxetan-2-one (674-82-8) + C31H39NOSi (1191252-04-6) → C35H43NO3Si (1191252-05-7)

Conditions	Yield
In tetrahydrofuran at 20℃; for 2.5h; Inert atmosphere;	100%

4-methyleneoxetan-2-one (674-82-8) + (R)-1-phenylethanol (1517-69-7) → (R)-1-phenylethyl acetoacetate (123261-65-4)

Conditions	Yield
With dmap In tetrahydrofuran at 20℃;	100%

Upstream product

• 463-51-4 Ketene 
• 108-24-7 acetic anhydride 
• 925-90-6 ethylmagnesium bromide 
• 1971-49-9 N-acetylphthalimide 
• 121-44-8 triethylamine 
• 75-36-5 acetyl chloride 
• 75-50-3 trimethylamine 
• 463-49-0 1,2-propanediene 
• 106-51-4 p-benzoquinone 
• 75-07-0 acetaldehyde 
• 7732-18-5 water 
• 112-16-3 n-dodecanoyl chloride 
• 67-64-1 acetone 
• 7664-93-9 sulfuric acid 

Downstream Products

• 16695-54-8 1-(morpholin-4-yl)butane-1,3-dione 
• 22511-75-7 1-<2,4-Dimethyl-pyrryl-(5)>-butandion-(1,3) 
• 1657-28-9 3-oxo-N-(pyrid-2-yl)butyramide 
• 16867-45-1 N-(4-methyl-2-pyridinyl)-3-oxobutanamide 
• 35523-67-2 4,7-dihydro-5-methyl-7-oxo[1,2,4]triazolo[1,5-a]pyrimidine 
• 105-45-3 acetoacetic acid methyl ester 
• 1779-60-8 n-propyl acetoacetate 
• 6963-40-2 acetoacetic acid-(2-ethoxyethyl)-ester 
• 623-68-7 trans-crotonic anhydride 
• 128128-28-9 1-allyl-4-methyl-2-quinolone 
• 1555-80-2 phenylacetic anhydride 
• 100718-25-0 acetoacetic acid-(N-allyl-p-anisidide) 
• 719-86-8 3-acetyl-1-phenyl-pyrrolidine-2,4-dione 
• 4692-94-8 N-(1,3-benzothiazol-2-yl)-3-oxobutanamide 

Relevant articles and documents

SYNTHESIS OF HIGH CALORIC FUELS AND CHEMICALS

In one embodiment, the present application discloses methods to selectively synthesize higher alcohols and hydrocarbons useful as fuels and industrial chemicals from syngas and biomass. Ketene and ketonization chemistry along with hydrogenation reactions are used to synthesize fuels and chemicals. In another embodiment, ketene used to form fuels and chemicals may be manufactured from acetic acid which in turn can be synthesized from synthesis gas which is produced from coal, biomass, natural gas, etc.

Aktivierung der C-Cl-Bindung: Katalytische Carbonylierung von Dichlormethan und Chlorbenzol

-

Preparative UV-VIS Laser Photochemistry: Photocycloadditions of Methylenelactones with Benzophenone and p-Benzoquinone. Oxygen Trapping of Paterno-Buechi Triplet 1,4-Diradicals as Model Reactions for Quinghaosu-Type 1,2,4-Trioxanes

The UV-VIS laser irradiation of 4-penten-4-olide (1) with benzophenone (BP) or with p-benzoquinone (BQ) under an argon atmosphere afforded the acetal-type oxetanes 2-BP and 2-BQ, respectively.Only for BP was the oxetane regioisomer 3-BP obtained, actually as major product, while 3-BQ appears to be photolabile under VIS-laser photolysis conditions and thus does not accumulate in sufficient amounts for detection.Under an oxygen atmosphere, besides these oxetane products also the 1,2,4-trioxanes 5-BP and 5-BQ, the oxygen trapping products of the intermediary preoxetanetriplet diradicals 12, were isolated and fully characterized.These results demonstrate that spirolactone-type 1,2,4-trioxanes as quinghaosu analogues are accessible via trapping of Paterno-Buechi triplet 1,4-diradicals by molecular oxygen.In the case of diketene as enol-lactone partner, the Paterno-Buechi reaction with BQ gave a complex product mixture even under an argon atmosphere, leading to the oxetane 6 as major product, and the spirocyclobutanone 7 and spirobioxetane 8 as minor products.Under an oxygen atmosphere also the spiroacetal 9 was obtained, but no trioxanes (oxygen trapping) could be detected in this VIS-laser photolysis.