10599-69-6

Basic information

• Product Name: 2-METHYL-5-PROPIONYL-FURAN
• Synonyms: 1-(5-Methyl-2-furyl)-1-propanone;1-Propanone, 1-(5-methyl-2-furanyl)-;1-Propanone, 1-(5-methyl-2-furyl)-;5-Methyl-2-propionylfuran;5-Methyl-5-propionylfuran;Furan, 2-methyl-5-propionyl;2-METHYL-5-PROPIONYL-FURAN;1-(5-methyl-2-furyl)propan-1-one
• CAS NO: 10599-69-6
• Molecular Formula: C₈H₁₀O₂
• Molecular Weight: 138.16
• EINECS: 234-215-8
• Product Categories: Pharmaceutical intermediates
• Mol File: 10599-69-6.mol

Chemical Properties

• Boiling Point: 72°C/5mmHg(lit.)
• Flash Point: 90.1 °C
• Appearance: Clear yellow/Liquid
• Density: 1.0742 (rough estimate)
• Vapor Pressure: 0.191mmHg at 25°C
• Refractive Index: 1.5037-1.5057
• Storage Temp.: Refrigerator, under inert atmosphere
• Solubility: Acetonitrile (Slightly), Chloroform (Slightly)
• CAS DataBase Reference: 2-METHYL-5-PROPIONYL-FURAN(CAS DataBase Reference)
• NIST Chemistry Reference: 2-METHYL-5-PROPIONYL-FURAN(10599-69-6)
• EPA Substance Registry System: 2-METHYL-5-PROPIONYL-FURAN(10599-69-6)

Safety Data

• Safety Statements: 24/25
• Hazardous Substances Data: 10599-69-6(Hazardous Substances Data)

Usage

Chemical Properties

Clear yellow liquid

InChI:InChI=1/C8H10O2/c1-3-7(9)8-5-4-6(2)10-8/h4-5H,3H2,1-2H3

Synthetic route

2-methylfuran (534-22-5) + propionic acid anhydride (123-62-6) → 5-methyl-2-propionylfuran (10599-69-6)

Conditions	Yield
With phosphoric acid In dichloromethane; water at 120℃; for 1h; Temperature;	95.3%
With tin(IV) chloride at 100℃; for 3h;	66%
phosphoric acid for 3h; Heating;	40%

Diazoethan (1117-96-0) + 5-Methylfurfural (620-02-0) → 5-methyl-2-propionylfuran (10599-69-6)

Conditions	Yield
With diethyl ether

2-methyl-3-ethyl-4-hydroxypyrylium cation (62968-77-8) → 5-methyl-2-propionylfuran (10599-69-6) + 6-methyl-5-ethyl-2-pyrone (72185-13-8) + 4-methyl-3-ethyl-2-pyrone (62968-84-7) + 5-methyl-6-ethyl-2-pyrone (62968-85-8)

Conditions	Yield
In various solvent(s) Mechanism; Ambient temperature; Irradiation; irradiation of the cation in conc. H2SO4, then neutralization with aq. sodium bicarbonate;

furfural (98-01-1) → 5-methyl-2-propionylfuran (10599-69-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: hydrazine hydrate; ethylene glycol; aqueous NaOH-solution / bei aufeinanderfolgendem Erhitzen 2: tin (IV)-chloride View Scheme

2-methylfuran (534-22-5) + propionyl chloride (79-03-8) → 5-methyl-2-propionylfuran (10599-69-6)

Conditions	Yield
Stage #1: propionyl chloride With aluminum (III) chloride In 1,2-dichloro-ethane at 0℃; for 0.166667h; Stage #2: 2-methylfuran In 1,2-dichloro-ethane at 0 - 50℃;

5-methyl-2-propionylfuran (10599-69-6) + isopropyl chloride (75-29-6) → 1-(4-isopropyl-5-methyl-2-furyl)propan-1-one (1000993-74-7)

Conditions	Yield
Stage #1: 5-methyl-2-propionylfuran With aluminum (III) chloride at 0 - 30℃; for 0.5h; Neat (no solvent); Stage #2: isopropyl chloride at 0 - 10℃; Product distribution / selectivity; Neat (no solvent);	100%
Stage #1: 5-methyl-2-propionylfuran With aluminum (III) chloride In dichloromethane at 0 - 35℃; for 0.5h; Stage #2: isopropyl chloride In dichloromethane at 0 - 10℃; for 1h; Industry scale; Stage #3: With sodium hydroxide; water at 0℃; pH=1; Product distribution / selectivity;	100%
Stage #1: 5-methyl-2-propionylfuran With aluminum (III) chloride at 0 - 30℃; for 0.5h; Stage #2: isopropyl chloride at 0 - 10℃; Stage #3: With water at 0℃;

5-methyl-2-propionylfuran (10599-69-6) → emoxypine (2364-75-2)

Conditions	Yield
With ammonia; toluene-4-sulfonic acid at 170℃; under 10501.1 Torr; for 5h; Temperature; Pressure; Autoclave;	96.2%
With ethanol; ammonia at 170℃;
Multi-step reaction with 3 steps 1: NH2OH*HCl, NaOH / ethanol; H2O / 0.33 h / Heating 2: Raney Ni alloy, 2 N aq. NaOH / ethanol / 1 h / Ambient temperature 3: 1.) oxygen, tetraphenylporphine, 2.) triphenylphosphine / 1.) CH2Cl2, -70 deg C, irradiation, 2 h, 2.) -70 deg C, 10 min View Scheme

ortho-methylbenzoic acid (118-90-1) + 5-methyl-2-propionylfuran (10599-69-6) → C16H14O4

Conditions	Yield
With pyridine; bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; copper diacetate; silver carbonate; silver(I) triflimide In toluene at 120℃; for 22h; Inert atmosphere;	80%

5-methyl-2-propionylfuran (10599-69-6) + bis(pinacol)diborane (73183-34-3) → 1-[5-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)furan-2-yl]propan-1-one

Conditions	Yield
Stage #1: bis(pinacol)diborane With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; 4,4'-di-tert-butyl-2,2'-bipyridine In octane at 20℃; for 0.25h; Inert atmosphere; Stage #2: 5-methyl-2-propionylfuran In octane at 20℃; for 16h; Reagent/catalyst; Solvent; Temperature; regioselective reaction;	76%

5-methyl-2-propionylfuran (10599-69-6) + 3-cyanobromobenzene (6952-59-6) → 3-(2-methyl-5-propionylfuran-3-yl)benzonitrile (1160844-01-8)

Conditions	Yield
With bis(η3-allyl-μ-chloropalladium(II)); potassium acetate In N,N-dimethyl acetamide at 120℃; for 12h; Inert atmosphere; regioselective reaction;	67%

5-methyl-2-propionylfuran (10599-69-6) + 4-methoxycarbonylphenyl bromide (619-42-1) → methyl 4-(2-methyl-5-propionylfuran-3-yl)benzoate (1160843-97-9)

Conditions	Yield
With bis(η3-allyl-μ-chloropalladium(II)); potassium acetate In N,N-dimethyl acetamide at 120℃; for 12h; Inert atmosphere; regioselective reaction;	65%

5-methyl-2-propionylfuran (10599-69-6) → (S)-2-hydroxy-1-(5-methylfuran-2-yl)propan-1-one

Conditions	Yield
With iodine; dimethyl sulfoxide at 60℃; for 24h;	65%
With iodine; dimethyl sulfoxide at 60℃; for 24h; Schlenk technique;	65%

methanol (67-56-1) + 5-methyl-2-propionylfuran (10599-69-6) → 2-methyl-1-(5-methylfuran-2-yl)propan-1-one (90673-64-6)

Conditions	Yield
With C50H32F12N4O4Pd2; lithium tert-butoxide; tricyclohexylphosphine at 120℃; for 48h; Inert atmosphere; Schlenk technique;	65%

5-methyl-2-propionylfuran (10599-69-6) + 4-bromobenzenecarbonitrile (623-00-7) → 4-(2-methyl-5-propionylfuran-3-yl)benzonitrile (1160843-95-7)

Conditions	Yield
With bis(η3-allyl-μ-chloropalladium(II)); potassium acetate In N,N-dimethyl acetamide at 120℃; for 12h; Inert atmosphere; regioselective reaction;	63%

5-methyl-2-propionylfuran (10599-69-6) + 3,6-bis(trifluoromethyl)bromobenzene (328-70-1) → 1-(4-(3,5-bis(trifluoromethyl)phenyl)-5-methylfuran-2-yl)propan-1-one (1160844-02-9)

Conditions	Yield
With bis(η3-allyl-μ-chloropalladium(II)); potassium acetate In N,N-dimethyl acetamide at 120℃; for 12h; Inert atmosphere; regioselective reaction;	61%

5-methyl-2-propionylfuran (10599-69-6) + N,N-dimethyl acetamide (127-19-5) → C10H12O4

Conditions	Yield
With (trifluoromethyl)trimethylsilane; copper(ll) bromide for 24h;	60%

5-methyl-2-propionylfuran (10599-69-6) + p-trifluoromethylphenyl bromide (402-43-7) → 1-(5-methyl-4-(4-(trifluoromethyl)phenyl)furan-2-yl)propan-1-one (1160843-98-0)

Conditions	Yield
With bis(η3-allyl-μ-chloropalladium(II)); potassium acetate In N,N-dimethyl acetamide at 120℃; for 12h; Inert atmosphere; regioselective reaction;	58%

5-methyl-2-propionylfuran (10599-69-6) + 4-bromo-benzaldehyde (1122-91-4) → 4-(2-methyl-5-propionylfuran-3-yl)benzaldehyde (1160843-99-1)

Conditions	Yield
With bis(η3-allyl-μ-chloropalladium(II)); potassium acetate In N,N-dimethyl acetamide at 120℃; for 12h; Inert atmosphere; regioselective reaction;	58%

5-methyl-2-propionylfuran (10599-69-6) + N-(2-methylbenzoyl)-8-aminoquinoline (1182669-71-1) → 7-methyl-3-(2-(5-methylfuran-2-yl)-2-oxoethyl)-2-(quinolin-8-yl)isoindolin-1-one

Conditions	Yield
With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; copper diacetate; cobalt(II) acetate; triphenylphosphine; silver carbonate In 1,2-dichloro-benzene at 110℃; for 21h; Schlenk technique; Inert atmosphere; Sealed tube;	51%

5-methyl-2-propionylfuran (10599-69-6) + ethylenediamine (107-15-3) → 1-ethyl-6-methyl-3,4-dihydropyrrolo[1,2-a]pyrazine (138350-45-5)

Conditions	Yield
In water for 3h; Heating;	50%

5-methyl-2-propionylfuran (10599-69-6) + para-bromoacetophenone (99-90-1) → 1-(4-(4-acetylphenyl)-5-methylfuran-2-yl)propan-1-one (1160843-96-8)

Conditions	Yield
With bis(η3-allyl-μ-chloropalladium(II)); potassium acetate In N,N-dimethyl acetamide at 120℃; for 12h; Inert atmosphere; regioselective reaction;	48%

5-methyl-2-propionylfuran (10599-69-6) + 1-hydroxy-pyrrolidine-2,5-dione (6066-82-6) → 1-((1-(5-methylfuran-2-yl)-1-oxopropan-2-yl)oxy)pyrrolidine-2,5-dione

Conditions	Yield
With tert.-butylhydroperoxide; tetra-(n-butyl)ammonium iodide In N,N-dimethyl acetamide; water at 80℃; for 2h; Green chemistry; chemoselective reaction;	44%

4-methyleneoxetan-2-one (674-82-8) + 5-methyl-2-propionylfuran (10599-69-6) → C12H14O4

Conditions	Yield
Stage #1: 5-methyl-2-propionylfuran With 2,2,6,6-tetramethyl-piperidine; n-butyllithium In diethyl ether; hexane at -78 - 0℃; for 1h; Inert atmosphere; Stage #2: 4-methyleneoxetan-2-one In diethyl ether; hexane at -40℃; for 1h; Inert atmosphere; diastereoselective reaction;	44%

5-methyl-2-propionylfuran (10599-69-6) + bis(pinacol)diborane (73183-34-3) → 1-[5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)furan-2-yl]propan-1-one

Conditions	Yield
Stage #1: bis(pinacol)diborane With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; triphenyl-arsane In octane at 20℃; for 0.25h; Inert atmosphere; Stage #2: 5-methyl-2-propionylfuran In octane at 120℃; for 16h; Reagent/catalyst; Solvent; regioselective reaction;	43%

5-methyl-2-propionylfuran (10599-69-6) + ethyl trifluoroacetate, (383-63-1) → 4,4,4-trifluoro-2-methyl-1-(5-methyl-[2]furyl)-butane-1,3-dione (579-40-8)

Conditions	Yield
With diethyl ether; sodium methylate

5-methyl-2-propionylfuran (10599-69-6) + hydrazine carboxamide (4426-72-6, 51433-48-8) → 1-(5-methyl-[2]furyl)-propan-1-one semicarbazone (90648-53-6)

5-methyl-2-propionylfuran (10599-69-6) + acrylonitrile (107-13-1) → 4-methyl-4-(5-methyl-furan-2-carbonyl)-heptanedinitrile

Conditions	Yield
With N-benzyl-trimethylammonium hydroxide; tert-butyl alcohol

5-methyl-2-propionylfuran (10599-69-6) + (2,4-dinitro-phenyl)-hydrazine (119-26-6) → 1-(5-methyl-[2]furyl)-propan-1-one-(2,4-dinitro-phenylhydrazone) (100885-35-6)

5-methyl-2-propionylfuran (10599-69-6) → 2-methyl-5-propylfuran (1456-16-2)

Conditions	Yield
With sodium hydroxide; hydrazine hydrate; diethylene glycol

5-methyl-2-propionylfuran (10599-69-6) → 5-methylfuran-2-carboxylic acid (1917-15-3)

Conditions	Yield
With alkaline aqueous alkali hypochlorite solution

5-methyl-2-propionylfuran (10599-69-6) → 1-(5-methyl-[2]furyl)-propan-1-one oxime (133712-93-3)

Conditions	Yield
With hydroxylamine
With sodium hydroxide; hydroxylamine hydrochloride In ethanol; water for 0.333333h; Heating; Yield given;

5-methyl-2-propionylfuran (10599-69-6) + 1,2-diaminopropan (78-90-0, 10424-38-1) → 1-Ethyl-3,6-dimethyl-3,4-dihydro-pyrrolo[1,2-a]pyrazine

Conditions	Yield
In water for 3h; Heating;

Upstream product

• 1117-96-0 Diazoethan 
• 620-02-0 5-Methylfurfural 
• 62968-77-8 2-methyl-3-ethyl-4-hydroxypyrylium cation 
• 534-22-5 2-methylfuran 
• 79-03-8 propionyl chloride 
• 98-01-1 furfural 
• 123-62-6 propionic acid anhydride 

Downstream Products

• 1160843-99-1 4-(2-methyl-5-propionylfuran-3-yl)benzaldehyde 
• 1160843-96-8 1-(4-(4-acetylphenyl)-5-methylfuran-2-yl)propan-1-one 
• 1160844-02-9 1-(4-(3,5-bis(trifluoromethyl)phenyl)-5-methylfuran-2-yl)propan-1-one 
• 1160843-98-0 1-(5-methyl-4-(4-(trifluoromethyl)phenyl)furan-2-yl)propan-1-one 
• 1160843-97-9 methyl 4-(2-methyl-5-propionylfuran-3-yl)benzoate 
• 1160843-95-7 4-(2-methyl-5-propionylfuran-3-yl)benzonitrile 
• 1160844-01-8 3-(2-methyl-5-propionylfuran-3-yl)benzonitrile 
• 64271-00-7 1-(5-methyl-2-furyl)propylamine 
• 2364-75-2 emoxypine 
• 100885-35-6 1-(5-methyl-[2]furyl)-propan-1-one-(2,4-dinitro-phenylhydrazone) 
• 579-40-8 4,4,4-trifluoro-2-methyl-1-(5-methyl-[2]furyl)-butane-1,3-dione 

Relevant articles and documents

Improved synthesis method of 6-methyl-2-ethyl-3-hydroxypyridine

The invention discloses an improved synthesis method of 6-methyl-2-ethyl-3-hydroxypyridine, and belongs to the technical field of synthesis of medical intermediates. The method comprises the following steps: 1) reacting propionic anhydride with 2-methyl furan in the presence of a catalyst, washing with water after the reaction is finished, and performing reduced pressure distillation to obtain 5-methyl2-propionyl furan; and 2) mixing the 5-methyl-2-propionyl furan, ammonia water and p-toluenesulfonic acid, carrying out heating reaction, acidifying to be neutral, filtering to obtain a 6-methyl-2-ethyl-3-hydroxypyridine crude product, and recrystallizing to obtain a 6-methyl-2-ethyl-3-hydroxypyridine refined product. The raw materials are easy to obtain, common Lewis acid is added in the step (1), the reaction time is greatly shortened, the good yield is obtained, the acid aqueous solution obtained through washing in the step 1) is used for the acid adjusting process in the step 2), and the three-waste emission problem is basically solved; and 2) the reaction process is simple, a closed heating and pressurizing method is adopted, the raw materials react thoroughly, the yield is high, and the method is suitable for industrial production.

A chemoselective α-aminoxylation of aryl ketones: a cross dehydrogenative coupling reaction catalysed by Bu4NI

Tetrabutyl ammonium iodide (TBAI) catalyzed α-aminoxylation of ketones using aq. TBHP as an oxidant has been accomplished. We have shown that the CDC (cross dehydrogenative coupling) reactions of ketones with N-hydroxyimidates such as N-hydroxysuccinimide (NHSI), N-hydroxyphthalimide (NHPI), N-hydroxybenzotriazole (HOBt) and 1-hydroxy-7-azabenzotriazole (HOAt) lead to the corresponding oxygenated products in good to moderate yields. The application of this method has been demonstrated by transforming a few coupled products into synthetically useful intermediates and products.

Process for producing 2-aceylfuran derivatives

2-Acylfuran derivatives STR1 (R: alkyl, phenyl, etc.; R1 : H, alkyl) are prepared in high yield by reaction, in the presence of a boron trifluoride complex catalyst, of a furan compound STR2 (X: H, Cl, Br; Y: Cl, Br) or with RCOOH in the presence of (XYCHCO)2 O.

Friedel-Crafts Reaction of 2-Methylfuran with Saturated and α,β-Unsaturated Acid Anhydrides

2-Methylfuran (5) reacts with the saturated acid anhydrides 16 - 26 in the presence of SnCl4 to give the 2-acyl-5-methylfurans 37 - 47 selectively.The unsaturated anhydrides 27 - 32, however, yield mixtures which only in the case of senecioic acid anhydride (29) contain the respective primary product 48.Subsequent reactions lead to the addition products 55 (from 27) and 56 (from 29), and to (E,Z)-mixtures of their enol esters 57 - 62 which could partially be separated and assigned. - The olfactory properties of 2, 37 - 48, 50, 52, and 53 were investigated.

Photoisomerization of 4-Hydroxypyrylium Cations in Concentrated Sulfuric Acid

Irradiation of di-, tri-, and tetraalkyl-4-hydroxypyrylium cations in concentrated sulfuric acid leads to the formation of 2-hydroxypyrylium cations as phototransposition products and, in certain cases, to furyl cations by a photo-ring-contraction reaction.Product analysis by spectroscopic techniques, deuterium labeling, and unambiguous synthesis reveals that 2-hydroxypyrylium cations are formed by two distinct transposition patterns and accordingly, by two distinct mechanistic pathways.The bond-forming and -breaking requirements of the major transposition pattern, which constitutes approximately 95percent of the reaction, are consistent with a mechanism initiated by 2,6-bridging in the first excited state of the 4-hydroxypyrylium cation.Similarly, the bond-formation and -breaking requirements of the minor pattern are consistent with a mechanism involving 2,5-bridging in the first excited state of the starting cation.