1073-29-6

Usage

Uses

Used in Flavor and Fragrance Industry:
2-HYDROXYTHIOANISOLE is used as a flavoring agent for its characteristic aroma, which contributes to the overall sensory experience of coffee and other related products.
Used in Chemical Synthesis:
2-HYDROXYTHIOANISOLE is used as a chemical intermediate for the synthesis of various organic compounds, taking advantage of its reactive functional groups and unique molecular structure.
Used in Research and Development:
2-HYDROXYTHIOANISOLE serves as a valuable compound in the field of research and development, particularly in the study of organic chemistry, synthesis, and the exploration of new applications in various industries.

Preparation

From the diazonium salt of methyl-(2-aminofuryl)-sulfid

InChI:InChI=1/C7H8OS/c1-9-7-5-3-2-4-6(7)8/h2-5,8H,1H3

Upstream product

• 5799-67-7 dimethyl(methylthio)sulfonium tetrafluoroborate 
• 108-95-2 phenol 
• 274-26-0 1,3-benzoxathiole 
• 1073-72-9 4-hydroxythioanisole 
• 1121-24-0 ortho-mercaptophenol 
• 74-88-4 methyl iodide 
• 624-92-0 Dimethyldisulphide 
• 20828-73-3 methylsulfanylium 
• 74-83-9 methyl bromide 
• 5188-07-8 sodium thiomethoxide 
• 1074-02-8 2-(Methylsulfinyl)phenol 
• 10026-11-6 zirconium(IV) chloride 
• 97-93-8 triethylaluminum 
• 6192-52-5 p-toluenesulfonic acid monohydrate 

Downstream Products

• 66264-56-0 1-[4-hydroxy-3-(methylmercapto)phenyl]-ethanone 
• 138538-81-5 1,3-dimethyl-6-[4-(3-[2-methylthiophenoxy]propyl)piperazin-1-yl]-2,4(1H,3H)-pyrimidinedione 
• 75744-85-3 LM 3155 
• 115562-58-8 2'-(methylthio)phenyl 4-toluenesulfonate 
• 2388-73-0 1-methoxy-2-(methylsulfanyl)benzene 
• 210350-55-3 1-(methoxymethoxy)-2-(methylsulfanyl)benzene 
• 115562-59-9 2'-(methylsulfonyl)phenyl 4-toluenesulfonate 
• 65936-17-6 (4-Hydroxy-3-methylsulfanyl-phenyl)-phenyl-methanone 
• 65936-16-5 2-Hydroxy-3-(methylthio)benzophenon 
• 65936-19-8 (2-Hydroxy-3-methanesulfinyl-phenyl)-phenyl-methanone 
• 65936-18-7 (4-Hydroxy-3-methanesulfinyl-phenyl)-phenyl-methanone 
• 65935-95-7 Benzoic acid 2-methanesulfinyl-phenyl ester 
• 1162128-03-1 (2-(hexyloxy)phenyl)(methyl)sulfane 
• 1346671-92-8 C₁₉H₁₇OPS 

Relevant academic research and scientific papers

Oxygenation of Organoboronic Acids by a Nonheme Iron(II) Complex: Mimicking Boronic Acid Monooxygenase Activity

Phenolic compounds are important intermediates in the bacterial biodegradation of aromatic compounds in the soil. An Arthrobacter sp. strain has been shown to exhibit boronic acid monooxygenase activity through the conversion of different substituted phenylboronic acids to the corresponding phenols using dioxygen. While a number of methods have been reported to cleave the C-B bonds of organoboronic acids, there is no report on biomimetic iron complex exhibiting this activity using dioxygen as the oxidant. In that direction, we have investigated the reactivity of a nucleophilic iron-oxygen oxidant, generated upon oxidative decarboxylation of an iron(II)-benzilate complex [(TpPh2)FeII(benzilate)] (TpPh2 = hydrotris(3,5-diphenyl-pyrazol-1-yl)borate), toward organoboronic acids. The oxidant converts different aryl/alkylboronic acids to the corresponding oxygenated products with the incorporation of one oxygen atom from dioxygen. This method represents an efficient protocol for the oxygenation of boronic acids with dioxygen as the terminal oxidant.

Iodine-Mediated Synthesis of Methylthio-Substituted Catechols from Cyclohexanones

A novel and efficient I2-mediated direct synthesis of methylthio-substituted catechols from cyclohexanones was developed. Various cyclohexanones underwent oxygenation, methylthiolation, and dehydrogenative aromatization in one pot to form the desired products in moderate to good yields. DMSO was utilized as the solvent, oxygen source, and methylthiolation agent. A possible reaction mechanism is proposed. (Figure presented.).

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.

Biocatalytic Preparation of Chiral Sulfoxides through Asymmetric Reductive Resolution by Methionine Sulfoxide Reductase A

Here we report an environmentally friendly method for the preparation of chiral sulfoxides under high substrate concentration using recombinant methionine sulfoxide reductase A from Pseudomonas monteilii (pmMsrA) as a biocatalyst. Our results show that this enzyme can effectively accomplish the preparation of (R)-sulfoxides with approximately 50 % yield and 94–99 % enantiomeric excess through asymmetric reductive resolution of racemic sulfoxide. With the establishment of the enzyme regeneration system, the initial substrate concentration could be increased 40–100 times compared to our original report. The (R)-sulfoxides were obtained with high enantioselectivity under the substrate concentration up to 200 mm (approximately 32 g L?1), representing a quite high substrate concentration in biocatalytic preparation of chiral sulfoxides. Moreover, this system showed fairly good activity and enantioselectivity towards a series of ortho- and para-substituted phenyl methyl sulfoxides under high substrate concentration.

A visible-light photocatalytic thiolation of aryl, heteroaryl and vinyl iodides

The general catalytic synthesis of aryl and vinyl thioethers from readily available halides remains a challenge. Herein we report a unified method for the thiolation of aryl and vinyl iodides with dialkyl disulfides using visible light photoredox catalysis. A range of thioether products bearing diverse functional groups can be accessed in high yield and with excellent chemoselectivity. We demonstrate the versatility of this method through the expedient synthesis of a family of thioether-rich natural products. A detailed investigation of the photocatalytic mechanism is presented from both steady-state and time-resolved luminescent quenching as well as transient absorption spectroscopy experiments.

Chemoenzymatic synthesis of enantiopure hydroxy sulfoxides derived from substituted arenes

Enantiopure β-hydroxy sulfoxides and catechol sulfoxides were obtained, by chemoenzymatic synthesis, involving dioxygenase-catalysed benzylic hydroxylation or arene cis-dihydroxylation and cis-diol dehydrogenase-catalysed dehydrogenation. Absolute configurations of chiral hydroxy sulfoxides were determined by X-ray crystallography, ECD spectroscopy and stereochemical correlation. The application of a new range of β-hydroxy sulfoxides as chiral ligands was examined.

Continuous-flow synthesis of functionalized phenols by aerobic oxidation of grignard reagents

Phenols are important compounds in chemical industry. An economical and green approach to phenol preparation by the direct oxidation of aryl Grignard reagents using compressed air in continuous gas-liquid segmented flow systems is described. The process tolerates a broad range of functional groups, including oxidation-sensitive functionalities such as alkenes, amines, and thioethers. By integrating a benzyne-mediated in-line generation of arylmagnesium intermediates with the aerobic oxidation, a facile three-step, one-flow process, capable of preparing 2-functionalized phenols in a modular fashion, is established. Putting on airs: Aerobic oxidation of (hetero)aryl Grignard reagents using compressed air proceeds with a gas-liquid continuous-flow system, thus enabling preparation of fucntionalized phenols. By integrating an in-line generation of ArMgBr intermediates with the aerobic oxidation, ortho-functionalized phenols can be assembled. The method demonstrates good functional-group (FG) compatibility, mild reaction conditions, and short reaction times.

Synthesis and PET evaluation of (R)-[S-methyl-11C] thionisoxetine, a candidate radioligand for imaging brain norepinephrine transporters

Introduction: (R)-3-(2-(methylthio)phenoxy)-N-methyl-3-phenylpropan-1-amine [(R)-thionisoxetine; 1] is a potent inhibitor of the norepinephrine transporter (NET). We aimed to label 1 with carbon-11 (t1/2 = 20.4 min) for evaluation as a radioligand for imaging NET in living brain with positron emission tomography (PET). Methods: Methyl 3-(2-((R)-3-(methylamino)-1- phenylpropoxy)phenylthio)-propanoate (MPPP) and 1 were each prepared from o-hydroxythiophenol in three steps. Treatment of MPPP with potassium t-butoxide and [11C]methyl iodide in tetrahydrofuran gave [5-methyl- 11C]thionisoxetine ([11C]1), which was purified with HPLC. The distribution of radioactivity in brain after intravenous injection of [11C]1 into cynomolgus monkey was followed with PET and the appearance of radiometabolites in plasma monitored with radio-HPLC. Results: [11C]1 was obtained in high yield from [11C]methyl iodide. Of the radioactivity injected into monkey, 2.4% entered brain. Ratios of radioactivity in thalamus, mesencephalon, occipital cortex and caudate to that in cerebellum at 93 min were 1.3, 1.2, 1.2 and 1.1, respectively. The radioactivity in plasma corresponding to unchanged radioligand decreased to 53% at 45 min, with the remainder represented by hydrophilic radiometabolites. Conclusions: MPPP is an effective precursor for 11C-methylation to [11C]1, suggesting that the S-γ-propionic acid methyl ester protecting group may have wider value in the 11C-labeling of aryl methyl sulfides. However, the relatively low ratios of radioactivity to the cerebellum together with an unexpected accumulation of radioactivity in the caudate, makes [11C]1 an unpromising NET radioligand. Copyright

Highly chemoselective methylation and esterification reactions with dimethyl carbonate in the presence of NaY faujasite. The case of mercaptophenols, mercaptobenzoic acids, and carboxylic acids bearing OH substituents

In the presence of NaY faujasite, the reactions of dimethyl carbonate (DMC) with several ambident nucleophiles such as o- and p-mercaptophenols (1a,b), o- and p-mercaptobenzoic acids (2a,b), o- and p-hydroxybenzoic acids (3a,b), mandelic and phenyllactic acids (4, 5), have been explored under batch conditions. Highly chemoselective reactions can be performed: at 150 °C, compounds 1 and 2 undergo only a S-methylation reaction, without affecting OH and CO2H groups; at 165 °C, acids 3-5 form the corresponding methyl esters, while both their aromatic and aliphatic OH substituents are fully preserved from methylation and/or transesterification processes. Typical selectivities are of 90-98% and isolated yields of products (S-methyl derivatives and methyl esters, respectively) are in the range of 85-96%. A comparative study with K2CO3 as a catalyst is also reported. Although the base (K2CO3) turns out to be more active than the zeolite, the chemoselectivity is elusive: compounds 2a,b undergo simultaneous S-methylation and esterification reactions, and acids 3-5 yield complex mixtures of products of O-methylation, O-methoxycarbonylation, and esterification of their OH and CO2H groups, respectively. Overall, the combined use of a nontoxic reagent/solvent (DMC) and a safe promoter (NaY) imparts a genuine ecofriendly nature to the investigated synthesis.

Stereoselective reductase-catalysed deoxygenation of sulfoxides in aerobic and anaerobic bacteria.

Direct and indirect evidence, of unexpected stereoselective reductase-catalysed deoxygenations of sulfoxides, was found. The deoxygenations proceeded simultaneously, with the expected dioxygenase-catalysed asymmetric sulfoxidation of sulfides, during some biotransformations with the aerobic bacterium Pseudomonas putida UV4. Stereoselective reductase-catalysed asymmetric deoxygenation of racemic alkylaryl, dialkyl and phenolic sulfoxides was observed, without evidence of the reverse sulfoxidation reaction, using anaerobic bacterial strains. A purified dimethyl sulfoxide reductase, obtained from the intact cells of the anaerobic bacterium Citrobacter braakii DMSO 11, yielded, from the corresponding racemates, enantiopure alkylaryl sulfoxide and thiosulfinate samples.