37830-90-3

Basic information

• Product Name: 4,5-Dimethyl-1,3-dioxol-2-one
• Synonyms: 4,5-DIMETHYL-1,3-DIOXOL-2-ONE;1,3-DIOXOL-2-ONE, 4,5-DIMETHYL-;DIMETHYLDIOXOLONE;4,5-DIMETHYL-1,3-DIOXOLENE-2-ONE (DMDO);5-Dimethyl-1,3-dioxol-2-one;4,5-Dimethyl-1,3-dioxolen-3-one;4,5-Dimethyl-1,3-dioxolen-2-one;4,5-dimethyl-2-oxo-1,3-dioxolene
• CAS NO: 37830-90-3
• Molecular Formula: C₅H₆O₃
• Molecular Weight: 114.1
• EINECS: 1592732-453-0
• Product Categories: Oxygen cyclic compounds;Fluorobenzene;Agricultural chemicals(bactericide);Pharmaceutical Intermediates
• Mol File: 37830-90-3.mol

Chemical Properties

• Melting Point: 78°C
• Boiling Point: 130 °C / 6mmHg
• Flash Point: 55.8 °C
• Appearance: white powder
• Density: 1.181 g/cm³
• Vapor Pressure: 17.8mmHg at 25°C
• Refractive Index: 1.454
• Storage Temp.: Keep in dark place,Sealed in dry,Room Temperature
• Solubility: Chloroform, Methanol
• CAS DataBase Reference: 4,5-Dimethyl-1,3-dioxol-2-one(CAS DataBase Reference)
• NIST Chemistry Reference: 4,5-Dimethyl-1,3-dioxol-2-one(37830-90-3)
• EPA Substance Registry System: 4,5-Dimethyl-1,3-dioxol-2-one(37830-90-3)

Safety Data

• Statements: 36/37/38-37-36
• Safety Statements: 26-36/37/39-36
• Hazardous Substances Data: 37830-90-3(Hazardous Substances Data)

Usage

Uses

Used in Pharmaceutical Industry:
4,5-Dimethyl-1,3-dioxol-2-one is used as an intermediate in the synthesis of chemotherapeutic antibiotics for the treatment of various bacterial infections. Its role in the production of antibiotics like Prulifloxacin (P838885) highlights its importance in the development of new and effective treatments for bacterial diseases.
Used in Antibiotic Production:
4,5-Dimethyl-1,3-dioxol-2-one is used as a key component in the preparation of synthetic antibiotics. Its chemical properties make it a valuable building block for the creation of new and improved antibiotics, which are essential in combating drug-resistant bacteria and ensuring the effectiveness of treatments for bacterial infections.

InChI:InChI=1/C5H6O3/c1-3-4(2)8-5(6)7-3/h1-2H3

Synthetic route

trans-4,5-dichloro-4,5-dimethyl-1,3-dioxolan-2-one → 4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3)

Conditions	Yield
With acetic anhydride; zinc In toluene at 30 - 80℃; for 6h; Catalytic behavior; Reagent/catalyst; Temperature; Solvent;	83%

carbon dioxide (124-38-9) + 3-hydroxy-2-butanon (513-86-0, 52217-02-4) → 4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3)

Conditions	Yield
Stage #1: carbon dioxide; 3-hydroxy-2-butanon With sodium carbonate; potassium hydrogencarbonate at 28 - 32℃; for 5h; Autoclave; Large scale; Green chemistry; Stage #2: With potassium methanolate; sodium ethanolate at 38 - 42℃; under 26252.6 Torr; Temperature; Reagent/catalyst; Pressure; Large scale; Green chemistry;	80.7%

phosgene (75-44-5) + 3-hydroxy-2-butanon (513-86-0, 52217-02-4) → 4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3)

Conditions	Yield
In dichloromethane; N,N-dimethyl-aniline; toluene	55%
In dichloromethane; N,N-dimethyl-aniline	3.53 g (25%)

bis(trichloromethyl) carbonate (32315-10-9) + 3-hydroxy-2-butanon (513-86-0, 52217-02-4) → 4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3)

Conditions	Yield
Stage #1: bis(trichloromethyl) carbonate; 3-hydroxy-2-butanon With N,N-dimethyl-aniline In dichloromethane at 20℃; for 2h; Stage #2: at 160℃; for 4h;	42%

C5H7ClO3 → 4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3)

Conditions	Yield
at 160℃; for 4h;

3-hydroxy-2-butanon (513-86-0, 52217-02-4) + methyl chloroformate (79-22-1) → 4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3)

Conditions	Yield
In N,N-dimethyl-aniline at 15℃; for 5.5h; Temperature;	450 g

3-hydroxy-2-butanon (513-86-0, 52217-02-4) + chloroformic acid ethyl ester (541-41-3) → 4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3)

Conditions	Yield
In dichloromethane; N,N-dimethyl-aniline at 12℃; for 6h; Temperature; Solvent;	850 g

3-hydroxy-2-butanon (513-86-0, 52217-02-4) + propoxycarbonyl chloride (109-61-5) → 4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3)

Conditions	Yield
In dichloromethane; N,N-dimethyl-aniline at 20℃; for 0.5h; Temperature; Solvent;	190 g

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) → 4-bromomethyl-1,3-dioxa-5-methylcyclopentene-2-one (80715-22-6)

Conditions	Yield
With N-Bromosuccinimide In chloroform Reflux; Large scale;	93.8%
With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethane at 77℃; for 6h;	92%
With bromine; pyridine hydrochloride-aluminum trichloride In acetone for 1.66667h; Reagent/catalyst; Wavelength; Solvent; Microwave irradiation;	92%

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) + a,a-azobisisobutyronitrile (AIBN) → 4-bromomethyl-1,3-dioxa-5-methylcyclopentene-2-one (80715-22-6)

Conditions	Yield
With N-Bromosuccinimide In tetrachloromethane	90%

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) → 4-chloromethyl-5-methyl-1,3-dioxol-2-one (80841-78-7)

Conditions	Yield
With chlorine In 1,2-dichloro-ethane for 0.5h; Solvent; Reagent/catalyst; Reflux; Molecular sieve;	89.3%
With N-chloro-succinimide In tetrachloromethane for 80h; Ambient temperature; Irradiation;	9.2%
With chlorine; copper 1.) dichloromethane, 90 min, reflux, 2.) dichloromethane, 2 h, reflux; Yield given. Multistep reaction;
With sulfuryl dichloride In dichloromethane
With N-chloro-succinimide; dibenzoyl peroxide at 90℃; for 5.5h; Temperature; Solvent; Large scale;	326 g

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) + C19H11ClN2S → C23H15ClN2S

Conditions	Yield
With tris(acetonitrile)pentamethylcyclopentadienylrhodium(III) hexafluoroantimonate In 1,2-dichloro-ethane at 80℃; for 20h; Inert atmosphere;	89.3%

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) → 4-chloro-4-methyl-5-methylene-1,3-dioxolane-2-one (95579-71-8)

Conditions	Yield
With sulfuryl dichloride In dichloromethane for 0.5h; Heating;	75%
With sulfuryl dichloride In dichloromethane
With thionyl chloride In dichloromethane for 4.5h; Solvent; Reflux;
With sulfuryl dichloride In dichloromethane at 40℃; for 2h;

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) → 4,5-di(bromomethyl)-2-oxo-1,3-dioxole (62458-19-9)

Conditions	Yield
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In benzene at 110℃; for 2h; Inert atmosphere;	66%
With N-Bromosuccinimide; azobisisobutyronitrile In tetrachloromethane
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In benzene for 1h; Reflux;

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) + azobisisobutyronitrile (34241-39-9) → 4-bromomethyl-1,3-dioxa-5-methylcyclopentene-2-one (80715-22-6)

Conditions	Yield
With N-Bromosuccinimide In tetrachloromethane	48%
With N-Bromosuccinimide In tetrachloromethane

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) → 4-chloromethyl-5-methyl-1,3-dioxol-2-one (80841-78-7) + 4-chloro-4-methyl-5-methylene-1,3-dioxolane-2-one (95579-71-8) + 4,5-dimethyl-4,5-dichloro-1,3-dioxolan-2-one (129482-56-0)

Conditions	Yield
With chlorine In dichloromethane at 43 - 45℃; Product distribution; further solvents;	A 1.4 % Chromat. B 87.5 % Chromat. C n/a

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) → (5-methyl-2-oxo-1,3-dioxolen-4-yl)methyl trans-4-<<(tert-butoxycarbonyl)amino>methyl>cyclohexanecarboxylate (100165-57-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: N-bromosuccinimide, α,α-azobis(isobutyronitrile) / CCl4 2: 41 percent / K2CO3, (C4H9)4NBr (QBr) / trichloroethene / 20 h / 60 °C View Scheme

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) → (5-methyl-2-oxo-1,3-dioxolen-4-yl)methyl trans-4-(aminomethyl)cyclohexanecarboxylate hydrochloride (100165-54-6)

Conditions	Yield
Multi-step reaction with 3 steps 1: N-bromosuccinimide, α,α-azobis(isobutyronitrile) / CCl4 2: 41 percent / K2CO3, (C4H9)4NBr (QBr) / trichloroethene / 20 h / 60 °C 3: 70 percent / HCl(g) / ethyl acetate / 2.5 h / 0 - 20 °C View Scheme

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) → C21H32N2O7*2ClH (100165-55-7)

Conditions	Yield
Multi-step reaction with 3 steps 1: N-bromosuccinimide, α,α-azobis(isobutyronitrile) / CCl4 2: K2CO3, (C4H9)4NBr (QBr) / trichloroethene / 20 h / 60 °C 3: HCl(g) / ethyl acetate / 2.5 h / 0 - 20 °C View Scheme

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) → C31H48N2O11

Conditions	Yield
Multi-step reaction with 2 steps 1: N-bromosuccinimide, α,α-azobis(isobutyronitrile) / CCl4 2: K2CO3, (C4H9)4NBr (QBr) / trichloroethene / 20 h / 60 °C View Scheme

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) → (5-methyl-2-oxo-1,3-dioxol-4-yl)methyl iodide (80841-79-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 80.8 percent / sodium bicarbonate, α,α'-azobisisobutyronitrile, Br2 / CCl4 / 1.08 h / 70 °C 2: 92 percent / potassium iodide / acetone / Ambient temperature View Scheme

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) → (2S,5R,6R)-3,3-Dimethyl-7-oxo-6-(2-phenyl-2-{[1-phenyl-meth-(E)-ylidene]-amino}-acetylamino)-4-thia-1-aza-bicyclo[3.2.0]heptane-2-carboxylic acid 5-methyl-2-oxo-[1,3]dioxol-4-ylmethyl ester

Conditions	Yield
Multi-step reaction with 2 steps 1: 80.8 percent / sodium bicarbonate, α,α'-azobisisobutyronitrile, Br2 / CCl4 / 1.08 h / 70 °C 2: 1.) potassium bicarbonate / 1.) DMF, 0 deg C, 3 h; 2.) 0 deg C, 3 h View Scheme

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) → ampicillin (5-methyl-2-oxo-1,3-dioxolen-4-yl)methyl ester hydrochloride (80734-02-7)

Conditions	Yield
Multi-step reaction with 3 steps 1: 80.8 percent / sodium bicarbonate, α,α'-azobisisobutyronitrile, Br2 / CCl4 / 1.08 h / 70 °C 2: 1.) potassium bicarbonate / 1.) DMF, 0 deg C, 3 h; 2.) 0 deg C, 3 h 3: 60 percent / 1N HCl / acetonitrile / 0.5 h / 0 - 5 °C / pH=2.0 View Scheme

N-Bromosuccinimide (128-08-5) + 4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) → 4-bromomethyl-1,3-dioxa-5-methylcyclopentene-2-one (80715-22-6)

Conditions	Yield
2,2'-azobis(isobutyronitrile) In benzene at 20℃; for 0.5h; Heating / reflux;

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) → 4-hydroxymethyl-5-methyl-[1,3]dioxol-2-one (91526-18-0)

Conditions	Yield
With selenium(IV) oxide In 1,4-dioxane
With selenium(IV) oxide In 1,4-dioxane
With selenium(IV) oxide In 1,4-dioxane for 1h; Heating / reflux;

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) → (5-methyl-2-oxo-1,3-dioxol-4-yl)methyl 4-{[(4,5-dichloro-2-thienyl)sulfonyl]amino}-2-hydroxybenzoate

Conditions	Yield
Multi-step reaction with 2 steps 1: N-Bromosuccinimide; dibenzoyl peroxide / tetrachloromethane / 2 h / Reflux 2: sodium hydrogencarbonate / N,N-dimethyl-formamide / 20 °C View Scheme

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) → prulifloxacin (123447-62-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: N-Bromosuccinimide / chloroform / Reflux; Large scale 2: potassium hydrogencarbonate / N,N-dimethyl-formamide / 5 h / 0 °C / Large scale View Scheme

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) → (5-methyl-2-oxo-1,3-dioxol-4-yl)methyl (1S,2R,4aS,6aS,6bR,8aR,10S,12aR,12bR,14bS)-10-hydroxy-1,2,6a,6b,9,9,12a-heptamethyl-1,3,4,5,6,6a,6b,7,8,8a,9,10,11,12,12a,12b,13,14b-octadecahydropicene-4a(2H)-carboxylate

Conditions	Yield
Multi-step reaction with 2 steps 1: N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) / tetrachloromethane / 2 h / 80 °C 2: potassium carbonate / acetone / 24 h / 55 °C View Scheme

4,5-Dimethyl-1,3-dioxole-2-one (37830-90-3) → (S)-3-(tert-butoxycarbonylamino-methyl)-5-methyl-hexanoic acid 5-methyl-2-oxo-[1,3]dioxol-4-ylmethyl ester (1026789-40-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: N-Bromosuccinimide / 2,2'-azobis(isobutyronitrile) / tetrachloromethane 2: caesium carbonate / methanol / 2 h / 20 °C View Scheme

Upstream product

• 32315-10-9 bis(trichloromethyl) carbonate 
• 513-86-0 3-hydroxy-2-butanon 
• 75-44-5 phosgene 
• 124-38-9 carbon dioxide 
• 79-22-1 methyl chloroformate 
• 541-41-3 chloroformic acid ethyl ester 
• 109-61-5 propoxycarbonyl chloride 
• 116857-05-7 trans-4,5-dichloro-4,5-dimethyl-1,3-dioxolan-2-one 
• 102-09-0 bis(phenyl) carbonate 
• 513-85-9 2.3-butanediol 

Downstream Products

• 80715-22-6 4-bromomethyl-1,3-dioxa-5-methylcyclopentene-2-one 
• 80841-78-7 4-chloromethyl-5-methyl-1,3-dioxol-2-one 
• 95579-71-8 4-chloro-4-methyl-5-methylene-1,3-dioxolane-2-one 
• 129482-56-0 4,5-dimethyl-4,5-dichloro-1,3-dioxolan-2-one 
• 100165-57-9 (5-methyl-2-oxo-1,3-dioxolen-4-yl)methyl trans-4-<<(tert-butoxycarbonyl)amino>methyl>cyclohexanecarboxylate 
• 100165-54-6 (5-methyl-2-oxo-1,3-dioxolen-4-yl)methyl trans-4-(aminomethyl)cyclohexanecarboxylate hydrochloride 
• 100165-55-7 C₂₁H₃₂N₂O₇*2ClH 
• 80734-02-7 ampicillin (5-methyl-2-oxo-1,3-dioxolen-4-yl)methyl ester hydrochloride 
• 91526-18-0 4-hydroxymethyl-5-methyl-[1,3]dioxol-2-one 
• 123447-62-1 prulifloxacin 
• 91526-17-9 4-formyloxymethyl-5-methyl-1,3-dioxolen-2-one 

Relevant articles and documents

Preparation method of olmesartan medoxomil key intermediate

The invention discloses a preparation method of an olmesartan medoxomil key intermediate, and belongs to the technical field of medicine synthesis. The key points of the technical scheme are as follows: triphosgene with relatively low toxicity is adopted to replace gaseous phosgene, so that the problems of storage and transportation are solved; and a molecular distillation technology is utilized to treat the crude product, so that the occurrence of a polymer at high temperature is avoided, and a high-yield product is obtained.

MONOETHYLENICALLY UNSATURATED MONOMERS AND USES THEREOF

The invention relates to a monoethylenically unsaturated monomer of formula (I), and to the use thereof for producing a polymer. The invention also relates to the polymer obtained by polymerising said monomer, and to the use thereof in a composition for producing coatings.

Organocatalytic Synthesis of Substituted Vinylene Carbonates

The organocatalytic synthesis of substituted vinylene carbonates from benzoins and acyloins was studied using diphenyl carbonate as a carbonyl source. A range of N-Heterocyclic Carbene (NHC) precursors were screened and it was found that imidazolium salts were the most active for this transformation. The reaction occurs at 90 °C under solvent-free conditions. A wide range of substituted vinylene carbonates (symmetrical and unsymmetrical, aromatic or aliphatic), including some derived from natural products, were prepared with 20–99% isolated yields (24 examples). The reaction was also developed using thermomorphic polyethylene-supported organocatalysts as recoverable and recyclable species. The use of such species facilitates the workup and allows the synthesis of vinylene carbonates on the preparative scale (>30 g after 5 runs). (Figure presented.).

Method for preparing 4,5-dimethyl-1,3-dioxol-2-one

The invention provides a method for preparing 4,5-dimethyl-1,3-dioxol-2-one by using diphenyl carbonate as a high-activity green carbonyl source, which comprises the following steps: adding 2,3-butanediol and diphenyl carbonate as raw materials into an organic solvent, and carrying out heat preservation and stirring reaction under the action of a catalyst; and carrying out reduced pressure distillation on an obtained reaction solution to remove a solvent, further conducting recrystallizing to obtain high-purity 4,5-dimethyl-1,3-dioxol-2-one, washing the recrystallized mother solution by using alkali liquor, conducting separating to obtain a water phase, and then adjusting the pH value of the water phase to 5-7 to recover phenol. Through the process technology, the method has the advantages of simplified production process, mild reaction conditions, high product purity, safety, environmental protection and low production cost, and diphenyl carbonate can be regenerated through a byproduct phenol.

Method for synthesizing 4, 5-dimethyl-1, 3-dioxole-2-one

The invention discloses a method for synthesizing 4, 5-dimethyl-1, 3-dioxole-2-one, which comprises the following steps: step 1, cyclizing 2, 3-butanedione and triphosgene to obtain 4, 5-dichloro-4, 5-dimethyl-1, 3-dioxole-2-one, and carrying out dechlorination on the 4, 5-dichloro-4, 5-dimethyl-1, 3-dioxole-2-one under the action of a reduction reagent to prepare 4, 5-dimethyl-1, 3-dioxole-2-one.The method is mild in condition, simple and efficient.

Preparation method for 4-chloromethyl-5-methyl-1,3-dioxol-2-one

The invention specifically relates to a preparation method for 4-chloromethyl-5-methyl-1,3-dioxol-2-one, belonging to the technical field of chemical synthesis. According to the invention, acetoin isused as a raw material and reacts with chloroformate in a solvent under the action of a catalyst so as to produce DMDO; the prepared DMDO is further reacts with a chlorinating reagent and a free radical initiator in a solvent to obtain a crude DMDO-Cl product; and then rectification is carried out so as to obtain a fine DMDO-Cl product. The fine DMDO-Cl product has a purity of 99% or above.

By using the carbon dioxide preparation 4, 5 - dimethyl - 1, 3 - dioxo heterocyclic pentene - 2 - one method

The invention discloses a method for preparing 4,5-dimethyl-1,3-dioxole-2-ketone by using carbon dioxide. The method comprises the steps as follows: 3-hydroxy-2-butanone is isomerized into an enol structure; under the condition of alkaline esterification catalysis, the enol structure and the non-toxic, non-corrosive and low-cost carbon dioxide are synthesized with a one-step method, so that an annular carbonic ester compound is formed; a 4,5-dimethyl-1,3-dioxole-2-ketone crude product is prepared through the steps of washing, crystallization, and filtering or centrifugation; and the crude product is recrystallized for purification further, so that a 4,5-dimethyl-1,3-dioxole-2-ketone product is obtained. The method accords with an atom economy reaction, greatly reduces generation and discharge of three wastes of by-products such as hydrochloric acid and the like, and is an environment-friendly and safe production process.

A convenient and safe synthesis of 4,5-disubstituted-2-oxo-1,3-dioxolenes

Employing bis(trichloromethyl)carbonate (BTC), a safe and crystalline substitute of phosgene, 4,5-disubstituted-2-oxo-1,3-dioxolenes 3 have been synthesized by cyclocarbonylation of α-hydroxyketones 1 in 47-67% yield.

Biphenyl-substituted quinoline derivatives

Compounds of the formula wherein X, R1, R2, R3, R4, R5, R6, A, B, D and E are as defined herein. These compounds inhibit the action of angiotensin II and are useful, therefore, for example, as antihypertensive agents.

Bis-esters of 4,5-di(hydroxymethyl)-2-oxo-1,3-dioxole as antibacterial agents

Derivatives of 4,5-di(hydroxymethyl)-2-oxo-1,3-dioxole in which one hydroxy group has been esterified through the carboxy group of ampicillin or amoxicillin, and the other hydroxy group has been esterified through the carboxy group of sulbactam (penicillanic acid 1,1-dioxide), are useful as antibacterial agents. Certain novel compounds, which are useful as intermediates to the aforesaid antibacterial agents, are also disclosed.