37794-15-3

Basic information

• Product Name: p-(methylsulphinyl)benzaldehyde
• Synonyms: p-(methylsulphinyl)benzaldehyde;4-(Methylsulfinyl)benzaldehyde;Methyl 4-formylphenyl sulfoxide;Methyl(4-formylphenyl) sulfoxide
• CAS NO: 37794-15-3
• Molecular Formula: C₈H₈O₂S
• Molecular Weight: 168.21292
• EINECS: 253-669-8
• Mol File: 37794-15-3.mol
• Article Data: 67

Chemical Properties

• Boiling Point: 348.7°Cat760mmHg
• Flash Point: 164.7°C
• Appearance: /
• Density: 1.29g/cm³
• Vapor Pressure: 4.95E-05mmHg at 25°C
• Refractive Index: 1.61
• CAS DataBase Reference: p-(methylsulphinyl)benzaldehyde(CAS DataBase Reference)
• NIST Chemistry Reference: p-(methylsulphinyl)benzaldehyde(37794-15-3)
• EPA Substance Registry System: p-(methylsulphinyl)benzaldehyde(37794-15-3)

Safety Data

• Hazardous Substances Data: 37794-15-3(Hazardous Substances Data)

Usage

Synthesis Reference(s)

Synthetic Communications, 26, p. 1875, 1996 DOI: 10.1080/00397919608003540

InChI:InChI=1/C8H8O2S/c1-11(10)8-4-2-7(6-9)3-5-8/h2-6H,1H3

Synthetic route

4-(Methylthio)benzaldehyde (3446-89-7) → p-methylsulfinylbenzaldehyde (37794-15-3)

Conditions	Yield
With phthaloyl peroxide In dichloromethane at 25℃; for 8h; Schlenk technique; chemoselective reaction;	99%
Stage #1: 4-(Methylthio)benzaldehyde With aluminum (III) chloride In methanol; dichloromethane at 20℃; for 0.0166667h; Stage #2: With [bis(acetoxy)iodo]benzene In methanol; dichloromethane at 20℃; for 12h;	99%
With nitric acid; phosphorus pentoxide; silica gel In water for 0.0833333h;	97%

4-(methylthio)benzyl alcohol (3446-90-0) → p-methylsulfinylbenzaldehyde (37794-15-3)

Conditions	Yield
With iodic acid In N,N-dimethyl-formamide at 60℃; for 2h; Inert atmosphere;	96%
With chromium(VI) oxide; sulfuric acid at 20℃; for 1h;	90%

p-(methanesulfinyl)benzaldehyde dimethylacetal → p-methylsulfinylbenzaldehyde (37794-15-3)

Conditions	Yield
With sulfuric acid In tetrahydrofuran for 1.5h; Ambient temperature;	91%

4-(methylthio)benzyl alcohol (3446-90-0) → p-methylsulfinylbenzaldehyde (37794-15-3) + (4-(methylsulfinyl)phenyl)methanol (93183-64-3, 106732-70-1)

Conditions	Yield
With sodium bromate; ammonium cerium(IV) nitrate; silica gel In dichloromethane at 20℃; for 0.5h;	A 5% B 75%

(E)-4-(methylthio)benzaldehyde oxime (93033-60-4) → 4-(methylsulfinyl)benzaldehyde oxime + p-methylsulfinylbenzaldehyde (37794-15-3) + 4-(methylsulfonyl)benzaldehyde oxime (53147-98-1) + 4-(Methylthio)benzaldehyde (3446-89-7)

Conditions	Yield
With dihydrogen peroxide; bis(acetylacetonato)dioxidomolybdenum(VI) In acetone at 20℃; Product distribution; Further Variations:; Catalysts; Solvents;	A 5% B 3% C 3% D 60%

4-(methylthio)benzyl alcohol (3446-90-0) → p-methylsulfinylbenzaldehyde (37794-15-3) + 4-(Methylthio)benzaldehyde (3446-89-7)

Conditions	Yield
With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical In n-heptane at 80℃; under 760.051 Torr; for 24h;	A 21% B 59%
With polystyrene-supported hypervalent iodine(V) reagent In 1,2-dichloro-ethane at 85℃; for 1h;
With N-(2-iodylphenyl)glutarylamide supported on amonomethylpolystyrene resin In 1,2-dichloro-ethane at 85℃; for 1h;	A 7 %Spectr. B 85 %Spectr.

4-(Methylthio)benzaldehyde (3446-89-7) → para-methanesulfonylbenzaldehyde (5398-77-6) + p-methylsulfinylbenzaldehyde (37794-15-3)

Conditions	Yield
With dihydrogen peroxide at 50℃; for 4h;	A 33% B 53%
With potassium bromide In water; acetonitrile at 20℃; for 24h;
With C68H108N4O4*4H(1+)*Mo8O26(4-); dihydrogen peroxide In water; acetonitrile at 20℃; for 0.666667h; Overall yield = 78 %;
With oxygen; isobutyraldehyde In acetonitrile for 10h; Overall yield = 95.6 percent;

4-(methylthio)benzyl alcohol (3446-90-0) → p-methylsulfinylbenzaldehyde (37794-15-3) + (4-(methylsulfinyl)phenyl)methanol (93183-64-3, 106732-70-1) + 4-(Methylthio)benzaldehyde (3446-89-7)

Conditions	Yield
With 1-iodyl-2-butoxybenzene In acetonitrile for 15h; Heating;	A 16% B 46% C 32%
With 4-(2-iodylphenoxy)butanoylaminomethylated polystyrene In 1,2-dichloro-ethane for 3h; Heating;

4-Methanesulfinyl-thiobenzoic acid S-p-tolyl ester (65935-99-1) → p-methylsulfinylbenzaldehyde (37794-15-3)

Conditions	Yield
In benzene Irradiation;

4-(methylthio)benzoyl chloride (1442-06-4) → p-methylsulfinylbenzaldehyde (37794-15-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: Py 2: aq. H2O2 3: benzene / Irradiation View Scheme

4-Methylsulfanyl-thiobenzoic acid S-p-tolyl ester (65935-84-4) → p-methylsulfinylbenzaldehyde (37794-15-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: aq. H2O2 2: benzene / Irradiation View Scheme

dihydrogen peroxide (7722-84-1) + 4-(Methylthio)benzaldehyde (3446-89-7) → para-methanesulfonylbenzaldehyde (5398-77-6) + p-methylsulfinylbenzaldehyde (37794-15-3)

Conditions	Yield
With sodium dithionite In formic acid; toluene

4-methylthiobenzaldehyde ethylene acetal (180143-69-5) → 2-[4-(methylsulfinyl)phenyl]-1,3-dioxolane + p-methylsulfinylbenzaldehyde (37794-15-3) + 4-(Methylthio)benzaldehyde (3446-89-7) + 2-(4-(methylsulfonyl)phenyl)-1,3-dioxolane (184908-97-2)

Conditions	Yield
With C62H52ClFeN2O2; dihydrogen peroxide In water at 0℃; for 6h; enantioselective reaction;	A 92 %Spectr. B n/a C n/a D 5 %Spectr.

p-methylsulfinylbenzaldehyde (37794-15-3) → 4-(Methylthio)benzaldehyde (3446-89-7)

Conditions	Yield
With indium; tungsten(VI) chloride In tetrahydrofuran at 20℃; for 0.0833333h;	95%
With niobium pentachloride; sodium iodide In acetonitrile at 20℃; for 0.0833333h;	95%
With iododioxobis(triphenylphosphine)rhenium(V); phenylsilane In tetrahydrofuran at 20℃; for 2.25h; chemoselective reaction;	92%

2,3-dimethyl-2,3-butane diol (76-09-5) + p-methylsulfinylbenzaldehyde (37794-15-3) → 4-(4,4,5,5-tetramethyl-1,3-dioxolan-2-yl)phenyl methyl sulfide (1360628-14-3)

Conditions	Yield
With [MoO2Cl2(dmf)2] at 90℃; for 2h; Neat (no solvent); chemoselective reaction;	89%

p-methylsulfinylbenzaldehyde (37794-15-3) + 4-phenyl-1-(p-tolyl)-1H-1,2,3-triazole (634604-04-9) → [4-(methylsulfinyl)phenyl]{2-[1-(p-tolyl)-1H-1,2,3-triazol-4-yl]phenyl}methanone

Conditions	Yield
With tert.-butylhydroperoxide; palladium diacetate; XPhos In 1,2-dichloro-ethane at 120℃; for 24h; Sealed tube;	83%
With tert.-butylhydroperoxide; palladium diacetate; XPhos In water; 1,2-dichloro-ethane at 120℃; for 24h; Sealed tube; regioselective reaction;	66%
With tert.-butylhydroperoxide; triphenylphosphine; palladium dichloride In N,N-dimethyl-formamide at 130℃; for 25h; Catalytic behavior;	65%

1,4-diphenyl-1-butyne (40164-53-2) + p-methylsulfinylbenzaldehyde (37794-15-3) → 4-[(1-phenyl-3,4-dihydronaphthalen-2-yl)thio]benzaldehyde

Conditions	Yield
Stage #1: 1,4-diphenyl-1-butyne; p-methylsulfinylbenzaldehyde With trifluoromethylsulfonic anhydride In dichloromethane at -78 - 20℃; for 1h; Schlenk technique; Inert atmosphere; Stage #2: With triethylamine In dichloromethane at 20℃; for 2h; Schlenk technique; Inert atmosphere;	82%

5-chloro-2-hydroxyacetophenone (1450-74-4) + p-methylsulfinylbenzaldehyde (37794-15-3) → 6-chloro-4'-methylsulfinyl-3-(4''-methylsulfinylbenzyl)-flavone

Conditions	Yield
With pyrrolidine In ethanol at 80℃; for 24h;	76%

p-methylsulfinylbenzaldehyde (37794-15-3) + o-hydroxyacetophenone (118-93-4) → 4'-methylsulfinyl-3-(4''-methylsulfinylbenzyl)-flavone

Conditions	Yield
With pyrrolidine In ethanol at 80℃; for 24h;	76%

p-methylsulfinylbenzaldehyde (37794-15-3) + 1-(hex-1-yn-1-yloxy)-3-methylbenzene (1449549-02-3) → m-tolyl 2-(5-formyl-2-(methylthio)phenyl)hexanoate

Conditions	Yield
With trifluorormethanesulfonic acid In neat (no solvent) at 70℃; for 6h;	75%

2-chloro-4-fluoropyridine (34941-91-8) + p-methylsulfinylbenzaldehyde (37794-15-3) → 4-(((2-chloro-4-oxopyridin-1(4H)-yl)methyl)thio)benzaldehyde

Conditions	Yield
With trifluoromethylsulfonic anhydride In dichloromethane at -43 - 20℃; for 10h; Schlenk technique;	71%

p-methylsulfinylbenzaldehyde (37794-15-3) + ethylene glycol (107-21-1) → 2-(4-(methylsulfinyl)phenyl)-1,3-dioxolane

Conditions	Yield
With toluene-4-sulfonic acid In toluene for 16h; Inert atmosphere; Dean-Stark; Reflux;	66%

p-methylsulfinylbenzaldehyde (37794-15-3) + 2’-hydroxy-5’-(methoxymethoxy)acetophenone (31405-69-3) → 6-methoxymethoxy-4'-methylsulfinyl-3-(4''-methylsulfinylbenzyl)-flavone

Conditions	Yield
With pyrrolidine In ethanol at 80℃; for 24h;	65%

p-methylsulfinylbenzaldehyde (37794-15-3) + triisopropyl(prop-1-ynyl)silane (82192-57-2) → 4-(methylsulfanyl)-3-[3-(triisopropylsilyl)prop-2-yn-1-yl]benzaldehyde

Conditions	Yield
With 2,6-dimethylpyridine; trifluoromethylsulfonic anhydride In dichloromethane at -78 - 65℃; for 16h; Inert atmosphere;	61%

p-methylsulfinylbenzaldehyde (37794-15-3) + 4-(N,N'-dimethylamino)pyridinium-4-toluenesulfonate (78105-28-9) + trifluoroacetic acid (76-05-1) → (E)-1-methyl-4-(4-(methylsulfinyl)styryl)pyridin-1-ium 2,2,2-trifluoroacetate

Conditions	Yield
Stage #1: p-methylsulfinylbenzaldehyde; 4-methyl-N-methylpyridinium p-toluenesulfonate salt With pyrrolidine In methanol for 4h; Knoevenagel Condensation; Reflux; Inert atmosphere; Stage #2: trifluoroacetic acid In acetonitrile	61%

p-methylsulfinylbenzaldehyde (37794-15-3) + 3-hydroxypropyltriphenylphosphonium bromide (51860-45-8) → (E)-4-(4-(methylsulfinyl)phenyl)but-3-en-1-ol

Conditions	Yield
Stage #1: p-methylsulfinylbenzaldehyde; 3-hydroxypropyltriphenylphosphonium bromide With lithium hexamethyldisilazane In tetrahydrofuran at -20℃; for 1h; Inert atmosphere; Stage #2: In tetrahydrofuran at -20 - 20℃; for 14h; Inert atmosphere;	57%

p-methylsulfinylbenzaldehyde (37794-15-3) + bromoacetic acid methyl ester (96-32-2) → methyl 2-((4-formylphenyl)thio)acetate

Conditions	Yield
With 1-(n-butyl)-3-methylimidazolium triflate at 100℃; for 48h;	55%

CYANAMID (420-04-2) + p-methylsulfinylbenzaldehyde (37794-15-3) → N-[(4-formylphenyl)(methyl)(oxo)-λ6-sulfanylidene]cyanamide

Conditions	Yield
Stage #1: CYANAMID; p-methylsulfinylbenzaldehyde With potassium tert-butylate In water for 0.166667h; Sealed tube; Stage #2: With N-chloro-succinimide In water at 20℃; for 2h; Sealed tube;	54%

Tetrahydrothiopyran-4-one (1072-72-6) + p-methylsulfinylbenzaldehyde (37794-15-3) → 3,5-Bis-[1-(4-methanesulfinyl-phenyl)-meth-(Z)-ylidene]-tetrahydro-thiopyran-4-one (62041-00-3)

Conditions	Yield
With piperidine; acetic acid In ethanol Heating;	50%

p-methylsulfinylbenzaldehyde (37794-15-3) + dimethylglyoxal (431-03-8) + 3,5-di-tert-butylaniline (2380-36-1) → 1,4-bis(3,5-di-(tert-butyl)phenyl)-2,5-bis(4-(methylsulfinyl)phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole

Conditions	Yield
Stage #1: p-methylsulfinylbenzaldehyde; 3,5-di-tert-butylaniline In acetic acid; toluene at 50℃; for 1h; Stage #2: dimethylglyoxal With iron(III) perchlorate hydrate In acetic acid; toluene at 50℃;	45%

Tetrahydro-4H-pyran-4-one (29943-42-8) + p-methylsulfinylbenzaldehyde (37794-15-3) → 3,5-Bis-[1-(4-methanesulfinyl-phenyl)-meth-(E)-ylidene]-tetrahydro-pyran-4-one (62513-36-4)

Conditions	Yield
With piperidine; acetic acid In ethanol Heating;	43%

p-methylsulfinylbenzaldehyde (37794-15-3) → (R)-4-(methylsulfinyl)benzaldehyde + 4-(Methylthio)benzaldehyde (3446-89-7)

Conditions	Yield
With DL-dithiothreitol; methionine sulfoxide reductase A from Pseudomonas alcaliphila In aq. phosphate buffer at 30℃; for 1h; pH=8; Resolution of racemate; Enzymatic reaction; enantioselective reaction;	A 43% B n/a
With recombinant methionine sulfoxide reductase A from Pseudomonas monteilii; diothiothreitol In aq. phosphate buffer at 30℃; for 4h; pH=8; Sealed tube; Resolution of racemate; Green chemistry; Enzymatic reaction; enantioselective reaction;	A n/a B n/a

2-fluoropyridine (372-48-5) + p-methylsulfinylbenzaldehyde (37794-15-3) → 1-(((4-formylphenyl)thio)methyl)pyridin-2-one

Conditions	Yield
Stage #1: 2-fluoropyridine; p-methylsulfinylbenzaldehyde With trifluoromethylsulfonic anhydride In dichloromethane at -43 - 20℃; for 10h; Schlenk technique; Stage #2: With water; sodium hydrogencarbonate at 20℃; for 0.166667h;	40%

p-methylsulfinylbenzaldehyde (37794-15-3) + 5-(mesityl)dipyrromethane (159152-14-4) → 10-(4-methylsulfoxyphenyl)-5,15-dimesitylcorrole

Conditions	Yield
Stage #1: p-methylsulfinylbenzaldehyde; 5-(mesityl)dipyrromethane With trifluoroacetic acid In dichloromethane at 20℃; for 5h; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane; toluene at 20℃; for 0.25h; Further stages.;	21%

pyrrole (109-97-7) + p-methylsulfinylbenzaldehyde (37794-15-3) → (5Z,10Z,14Z,19Z)-5,10,15,20-Tetrakis-(4-methanesulfinyl-phenyl)-porphyrin

Conditions	Yield
With propionic acid at 150℃; for 1h;	20%

Upstream product

• 180143-69-5 4-methylthiobenzaldehyde ethylene acetal 
• 3446-90-0 4-(methylthio)benzyl alcohol 
• 7722-84-1 dihydrogen peroxide 
• 3446-89-7 4-(Methylthio)benzaldehyde 
• 65935-84-4 4-Methylsulfanyl-thiobenzoic acid S-p-tolyl ester 
• 1442-06-4 4-(methylthio)benzoyl chloride 
• 93033-60-4 (E)-4-(methylthio)benzaldehyde oxime 
• 65935-99-1 4-Methanesulfinyl-thiobenzoic acid S-p-tolyl ester 

Downstream Products

• 62513-36-4 3,5-Bis-[1-(4-methanesulfinyl-phenyl)-meth-(E)-ylidene]-tetrahydro-pyran-4-one 
• 62041-00-3 3,5-Bis-[1-(4-methanesulfinyl-phenyl)-meth-(Z)-ylidene]-tetrahydro-thiopyran-4-one 
• 1392812-65-5 2-(4-(methylsulfinyl)benzylidene)-1-(6-methyl-2H-[1,3]dioxolo[4,5-g]quinolin-8-yl)hydrazine 
• 22116-70-7 N-(p-Methylmercaptobenzal)-p-anisidin 
• 3446-89-7 4-(Methylthio)benzaldehyde 
• 1360628-14-3 4-(4,4,5,5-tetramethyl-1,3-dioxolan-2-yl)phenyl methyl sulfide 

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