1783-81-9

Usage

Uses

Used in Pharmaceutical Industry:
3-(METHYLTHIO)ANILINE is used as a pharmaceutical intermediate for the synthesis of various drugs and medications. Its unique chemical properties make it a valuable component in the development of new pharmaceutical compounds.
Used in Chemical Synthesis:
3-(METHYLTHIO)ANILINE is used as a key component in the synthesis of phenyl azobenzene sulfonamide derivatives. These derivatives have potential applications in various fields, including the development of dyes, pigments, and other specialty chemicals.

Safety Profile

Moderately toxic by ingestion.When heated to decomposition it emits toxic vapors ofNOx and SOx.

Purification Methods

Purify the aniline by fractional distillation in an inert atmostphere. It has UV max at 226 and 300nm. [Bordwell & Cooper J Am Chem Soc 74 10581952.] The N-acetyl derivative has m 78-78.5o (from aqueous EtOH). The hydrochloride has m 260-261o (aqueous EtOH/HCl) or m 225-227o (EtOH/Et2O). [Beilstein 13 H 533, 13 III 1221, 13 IV 1289.]

InChI:InChI=1/C7H9NS/c1-9-7-4-2-3-6(8)5-7/h2-5H,8H2,1H3

Upstream product

• 17733-22-1 2-chlorothioanisole 
• 2524-76-7 1-(methylsulfanyl)-3-nitrobenzene 
• 7664-41-7 ammonia 
• 19614-16-5 2-bromo-1-(methylsulfanyl)benzene 
• 16278-29-8 3-nitrobenzenediazonium 
• 16671-77-5 3-nitrophenyl thiocyanate 
• 6320-03-2 2-chlorothiphenol 
• 4867-37-2 1-chloro-3-methylsulfanylbenzene 
• 1073-29-6 2-(methylsulfenyl)phenol 
• 39082-89-8 3(R,S)-(methylsulphinyl)aniline 
• 75-18-3 dimethylsulfide 
• 626-01-7 3-Iodoaniline 
• 33733-73-2 3-bromo-1-(methylthio)benzene 
• 537-91-7 bis(3-nitrophenyl) disulfide 

Downstream Products

• 106167-23-1 (3-methylsulfanyl-phenyl)-pyridin-2-yl-amine 
• 18902-93-7 N-(3'-methylthiophenyl)anthranylic acid 
• 33733-73-2 3-bromo-1-(methylthio)benzene 
• 65052-48-4 3-cyanophenyl methyl sulfide 
• 2552-33-2 N,N-dimethyl-3-(methylthio)benzenamine 
• 33890-44-7 3-methylsulfanyl-benzenediazonium; chloride 
• 20926-64-1 2-(3'-Methylthioanilinium)-5-methyl-5-nitro-1,3,2-dioxaphosphorinan 2-oxid 
• 33872-54-7 3'-Methylthio-4-nitrostilben 
• 57330-54-8 1,1-Dimethoxy-2-(3'-methylthioanilino)-propan 
• 50838-35-2 (3-Methylsulfanyl-phenyl)-thiocarbamic acid O-(1,2,3,4-tetrahydro-1,4-methano-naphthalen-6-yl) ester 
• 23745-11-1 Cyclopropan-3-methylthio-carboxanilid 
• 23742-56-5 1-(3-Methylsulfanyl-phenyl)-3-(4-trifluoromethyl-phenyl)-urea 
• 269391-35-7 2-amino-N-(3-(methylthio)phenyl)benzamide 
• 139088-89-4 (3-Methylsulfanyl-phenylamino)-acetic acid tert-butyl ester 

Relevant academic research and scientific papers

Hydroboration reduction reaction of aromatic nitro compounds without transition metal catalysis

The invention relates to a hydroboration reduction reaction of aromatic nitro compounds without transition metal catalysis. According to the method, triethyl boron and potassium tert-butoxide are used as catalysts for the first time, and an aromatic nitro compound and pinacol borane which is low in price and easy to obtain can be conveniently catalyzed to be subjected to a hydroboration reduction reaction under mild conditions to prepare aromatic amine products. Compared with a traditional method, the method generally has the advantages that the catalyst is cheap and easy to obtain, operation is convenient, and reaction is safe. The selective hydroboration reduction reaction of the non-transition metal reagent catalyzed aromatic nitro compound and pinacol borane is realized for the first time, and a practical new reaction strategy is provided for laboratory preparation or industrial production of aromatic amine products.

Modulation of photochemical oxidation of thioethers to sulfoxides or sulfones using an aromatic ketone as the photocatalyst

We have developed an eco-friendly and chemo-selective photocatalytic synthesis of sulfoxides or sulfones via oxidation of sulfides (thioethers) at ambient temperature using air or O2 as the oxidant. An inexpensive thioxanthone was used as the photocatalyst. Our method offers excellent chemical yields and good functional group tolerance. The hydrogen bonding between hexafluoro-2-propanol (HFIP) and sulfoxides may play an important role in minimizing the over-oxidization of sulfoxides.

N-bromosuccinimide/HCl mediated reduction of sulfoxides to sulfides

An efficient reduction of sulfoxides to sulfides mediated by N-bromosuccinimide (NBS)/HCl system has been developed. This protocol shows good functional group compatibility as well as broad substrates scope with operational simplicity.

One-Pot Generation of Benzynes from Phenols: Formation of Primary Anilines by the Deoxyamination of Phenols

Benzynes were selectively generated in situ from phenols and trapped regioselectively with potassium hexamethyldisilazide to form primary anilines following acidic workup. The direct conversion of a phenolic hydroxyl group into a free amino group is a useful method for the preparation of primary aryl amines that are hard to synthesize by using coupling reactions involving phenol derivatives with ammonia. Whereas reactions of ortho- and meta-substituted phenols produced meta-substituted anilines exclusively, those of para-substituted phenols provided ortho-silylanilines.

Identification of MsrA homologues for the preparation of (R)-sulfoxides at high substrate concentrations

Here we report a methionine sulfoxide reductase A (MsrA) homologue with extremely high substrate tolerance and a wide substrate scope for the biocatalytic preparation of enantiopure sulfoxides. This MsrA homologue which was obtained from Pseudomonas alcaliphila (named paMsrA) showed good activity and enantioselectivity towards a series of aryl methyl/ethyl sulfoxides 1a-1k, with electron-withdrawing or electron-donating substituents at the aromatic ring. Chiral sulfoxides in the R configuration were prepared with approximately 50% of yield and up to 99% enantiomeric excess through the asymmetric reductive resolution of racemic sulfoxide catalyzed by the recombinant paMsrA protein. More importantly, kinetic resolution has been successfully accomplished with high enantioselectivity (E > 200) at initial substrate concentrations up to 320 mM (approximately 45 g L-1), which represents a great improvement in the aspect of the substrate concentration for the biocatalytic preparation of chiral sulfoxides.

An examination of the palladium/Mor-DalPhos catalyst system in the context of selective ammonia monoarylation at room temperature

An examination of the [{Pd(cinnamyl)Cl}2]/Mor-DalPhos (Mor-DalPhos=di(1-adamantyl)-2-morpholinophenylphosphine) catalyst system in Buchwald-Hartwig aminations employing ammonia was conducted to better understand the catalyst formation process and to guide the development of precatalysts for otherwise challenging room-temperature ammonia monoarylations. The combination of [{Pd(cinnamyl)Cl}2] and Mor-DalPhos afforded [(κ 2-P,N-Mor-DalPhos)Pd(η1-cinnamyl)Cl] (2), which, in the presence of a base and chlorobenzene, generated [(κ2-P,N- Mor-DalPhos)Pd(Ph)Cl] (1 a). Halide abstraction from 1 a afforded [(κ3-P,N,O-Mor-DalPhos)Pd(Ph)]OTf (5), bringing to light a potential stabilizing interaction that is offered by Mor-DalPhos. An examination of [(κ2-P,N-Mor-DalPhos)Pd(aryl)Cl] (1 b-f) and related precatalysts for the coupling of ammonia and chlorobenzene at room temperature established the suitability of 1 a in such challenging applications. The scope of reactivity for the use of 1 a (5 mol %) encompassed a range of (hetero)aryl (pseudo)halides (X=Cl, Br, I, OTs) with diverse substituents (alkyl, aryl, ether, thioether, ketone, amine, fluoro, trifluoromethyl, and nitrile), including chemoselective arylations. Copyright

NOVEL CATALYSTS

The present invention provides novel compounds and ligands that are useful in transition metal catalyzed cross-coupling reactions. For example, the compounds and ligands of the present invention are useful in palladium or gold catalyzed cross-coupling reactions.

A P,N-Ligand for palladium-catalyzed ammonia arylation: Coupling of deactivated aryl chlorides, chemoselective arylations, and room temperature reactions

(Figure Presented) Amazing ammonia: A new air-stable P,N-ligand (Mor-DalPhos) is reported that enables the palladium-catalyzed crosscoupling of ammonia to a variety of aryl chloride and aryl tosylate substrates with high chemoselectivity and, for the first time, at room temperature (see scheme; Ad = adamantyl, Ts=para-toluenesulfonyl).

A general palladium-catalyzed animation of aryl halides with ammonia

A study was conducted to demonstrate palladium(Pd)-catalyzed amination of aryl halides with ammonia. The active catalyst was formed in situ from Pd(OAc)2, along with air- and moisture stable phosphines as pre-catalysts. It was found that the productivity of the catalyst system was similar to that of competitive Pd and phosphine systems. It was demonstrated that the novel electron-rich sterically demanding phosphine ligand was unable to be displaced from the palladium by ammonia to a significant extent, which prevented the deactivation of the catalyst by the ligand. It was also demonstrated that the Pd-catalyzed animation worked at ambient pressure. It was observed that the optimized system showed an excellent substrate scope including deactivated, electron-neutral, and activated halides, o-, m- p-substituted substrates, aryl chlorides, and heterocycles.

Efficient reduction of nitroarenes over nickel-iron mixed oxide catalyst prepared from a nickel-iron hydrotalcite precursor

Nickel-iron mixed oxide prepared from a nickel-iron hydrotalcite precursor was found to be a highly efficient catalyst for the chemoselective reduction of nitroarenes under mild reaction conditions.