Month: December 2022

Sandrock, Paul B. published the artcileIsopropyl 2,4,6-triisopropylphenyl sulfone: an aryl sulfone with unusual atom deviations from the aromatic least-squares plane, Recommanded Product: 2,4,6-Triisopropylbenzenethiol, the publication is Acta Crystallographica, Section E: Structure Reports Online (2004), 60(4), o544-o546, database is CAplus.

Iso-Pr 2,4,6-triisopropylphenyl sulfone, C₁₈H₃₀O₂S, (I), was synthesized for the 1st time. Crystallog. data are given. In spite of the bulky iso-Pr substituents on both ortho positions, crystalline (I) does not exhibit rotational disorder of the iso-Pr group bonded to the sulfonyl. In contrast, the corresponding bromo- and chloroisopropyl groups of crystalline aryl sulfones possessing much smaller di-ortho-Me substituents display striking rotational disorder. While the aryl rings of the latter compounds are essentially planar, considerable atom deviation from the aromatic least-squares plane of (I) was observed None of the intra- or intermol. distances between the Me C atoms of the sulfonylisopropyl group and those of the two ortho-iso-Pr groups of (I) is shorter than the sum of their van der Waals radii, making it unlikely that they would interfere with the rotation of the ¦Á-iso-Pr group prior to crystallization

Acta Crystallographica, Section E: Structure Reports Online published new progress about 22693-41-0. 22693-41-0 belongs to catalysis-chemistry, auxiliary class Other Functionalization Reagent, name is 2,4,6-Triisopropylbenzenethiol, and the molecular formula is C15H24S, Recommanded Product: 2,4,6-Triisopropylbenzenethiol.

Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia

Buchta, Emil published the artcilePolycyclic compounds. IX. 20-Methylcholanthrene and cholanthrene, Related Products of catalysis-chemistry, the publication is Chemische Berichte (1962), 213-21, database is CAplus.

cf. CA 54, 457b. -Methyl-3-(2-bromoethyl)acenaphthene (I) was converted by a modification of the previously described method (loc. cit.) to 20-methylcholanthrene (II). 3-(2-Bromoethyl)acenaphthene (III) was prepared in 8 steps from naphthalene-1,2-dicarboxylic acid anhydride (IV) and converted in an analogous manner to cholanthrene (V). Granulated K (4 g.) in 100 cc. PhMe refluxed 1 hr. with 16 g. CH₂(CO₂Et)₂ in 20 cc. dry PhMe, cooled slightly, treated with stirring dropwise during 0.5 hr. with 16 g. I in 100 cc. PhMe, refluxed 40 hrs., cooled, and poured into H₂O, the aqueous phase extracted with Et₂O, the combined organic phase and Et₂O extract worked up, the resulting viscous brown oil refluxed 3 hrs. with 18 g. KOH in 300 cc. MeOH, concentrated, and filtered, the residue refluxed 2 hrs. with 400 cc. H₂O, filtered, and added dropwise to dilute H₂SO₄, and the product isolated with Et₂O and heated 1 hr. at 180¡ã gave 10.5 g. 4-(8-methyl-3-acenaphthenyl)butyric acid (VI), yellow, m. 116-17¡ã (ligroine). VI (8 g.) and 80 cc. anhydrous HF kept 2 hrs. at room temperature and evaporated with a stream of air, and the residue neutralized with 30% aqueous K₂CO₃ and extracted with C₆H₆ yielded 6 g. 6-methyl-1-oxo-1,2,3,4-tetrahydro-5,10-aceanthrene (VII), m. 118¡ã (sublimed at 180-90¡ã/0.2 mm.). Com. NaOMe (5 g.) in 20 cc. C₆H₆ stirred 15 min., treated dropwise during 15 min. with 5 g. HCO₂Et in 50 cc. dry C₆H₆ with cooling under N, the mixture treated dropwise during 45 min. with cooling and stirring with 5 g. VII in 100 cc. dry C₆H₆, stirred 5 hrs. with cooling, diluted with 50 cc. H₂O, and treated with 100 cc. dilute H₂SO₄, and the C₆H₆ layer worked up gave 5.3 g. 2-hydroxymethylene derivative (VIII) of VII, yellow needles, m. 127-8¡ã (EtOH). VIII (4 g.) in 30 cc. dry C₆H₆, 3 g. AcCH:CH₂, and 10 drops Et₃N kept 5 days and evaporated in vacuo, and the residue chromatographed on Al₂O₃ yielded 2.5 g. 2-formyl-2-(3-oxobutyl) derivative (IX) of VII, yellow, m. 123-4¡ã (EtOH). IX (2 g.) in 25 cc. dioxane refluxed 3 hrs. with 130 cc. 3% aqueous KOH, cooled, poured into H₂O, and extracted with C₆H₆, and the extract filtered through Al₂O₃ and evaporated gave 1.5 g. 20-methyl-2-oxo-2,3,-4,5,6,7-hexahydrocholanthrene (X), light yellow, m. 174-5¡ã (EtOH). X (1 g.) in 100 cc. dry tetrahydrofuran added dropwise with stirring during 0.5 hr. to 1.5 g. powd. LiAlH₄ in 50 cc. tetrahydrofuran, refluxed 2 hrs. with stirring, and worked up, and the viscous, red-brown product heated during 3 hrs. with 0.5 g. 30% Pd-C under N gradually to 300-20¡ã, cooled, diluted with C₆H₆, filtered, and evaporated, and the viscous brown residue sublimed at 180-200¡ã/0.01 mm. yielded 18 mg. II, pale yellow, m. 175-6.5¡ã (PrOH). IV (45 g.) in 400 cc. dry tetrahydrofuran added dropwise during 1 hr. to 15 g. powd. LiAlH₄ in 200 cc. dry tetrahydrofuran, refluxed 1.5 hrs., and worked up yielded 29 g. 1,2-C₁₀H₆(CH₂OH)₂ (XI), m. 122-3¡ã (EtOAc). XI (28 g.) in 250 cc. 1:1 C₆H₆-PhMe stirred about 15 min. at room temperature, treated with stirring with 45 g. PBr₃ in 150 cc. C₆H₆, stirred 2 hrs. at room temperature and 2 hrs. at 50¡ã, cooled, and poured into iced H₂O, and the product isolated with 1:1 PhMe-C₆H₆ yielded 38.5 g. 1,2-C₁₀H₆(CH₂Br)₂ (XII), leaflets, m. 148.5-9.5¡ã (CHCl₃). KCN (15 g.) in 35 cc. H₂O and 125 cc. 96% EtOH treated with stirring during 1 hr. with 28 g. XII in portions, stirred 3 hrs., refluxed 1 hr. with stirring, concentrated in vacuo, added hot to 225 cc. H₂O, cooled, and filtered yielded 14.5 g. 1,2-C₁₀H₆(CH₂CN)₂ (XIII), needles, m. 188¡ã (EtOAc). XIII (18 g.), 200 cc. 40% H₂SO₄, and 20 cc. AcOH refluxed 2 hrs., cooled, diluted with 100 cc. H₂O, and filtered, and the residue reprecipitated from 20% aqueous Na₂CO₃ with dilute H₂SO₄ yielded 14 g. 1,2-C₁₀H₆CH₂CO₂H)₂ (XIV), m. 214¡ã (30% AcOH). XIV (15 g.), 60 g. SOCl₂, 75 cc. Et₂O, and a few drops C₅H₅N kept 0.5 hr. at room temperature, concentrated, diluted with CS₂, evaporated again, dissolved in 300 cc. dry CS₂, treated with stirring during 1 hr. with 30 g. powd. AlCl₃, stirred 3 hrs. with cooling, and worked up gave 7.5 g. acenaphthen-1-one-3-acetic acid (XV), leaflets, m. 168¡ã (hot H₂O). XV (12 g.) and 120 g. amalgamated Zn, 50 cc. H₂O, 75 cc. concentrated HCl, and 40 cc. PhMe refluxed 34 hrs. while adding at 8-hr. intervals four 25-cc. portions concentrated HCl and cooled, the PhMe layer and Zn residues extracted with 20% aqueous Na₂CO₃, and the extract acidified gave 12 g. acenaphthene-3-acetic acid (XVI), leaflets, m. 164¡ã. XVI (10 g.) in 50 cc. dry tetrahydrofuran added dropwise during 0.5 hr. to 2 g. powd. LiAlH₄ in 100 cc. refluxing dry tetrahydrofuran, refluxed 2 hrs. with stirring, and worked up gave 8 g. 3-(2-hydroxyethyl)acenaphthene (XVII), needles, m. 96¡ã (ligroine). XVII (10 g.) in 50 cc. dry CCl₄ treated dropwise during 0.5 hr. at 60¡ã with 10 g. PBr₃ in 10 cc. CCl₄, heated 0.5 hr. at 70¡ã, and worked up gave 7 g. III, leaflets, m. 66¡ã (ligroine). CH₂(CO₂Et)₂ (20 g.) in 50 cc. drytetrahydrofuran added dropwise with stirring to 3 g. powd. Na in 100 cc. dry PhMe, refluxed 1 hr., cooled to about 50¡ã, treated dropwise with stirring during 0.5 hr. with 20 g. III in 50 cc. dry PhMe, refluxed 36 hrs., and worked up gave 19 g. di-Et 2-(3-acenaphthyl)ethylmalonate (XVIII), b_0.03 180¡ã. XVIII (6 g.) and 6 g. KOH in 100 cc. MeOH refluxed 6 hrs. gave 4.8 g. 2-(3-acenaphthenyl)ethylmalonic acid (XIX), leaflets, m. 180¡ã (decomposition). XIX (7 g.) heated 1.5 hrs. at 180-90¡ã yielded 5.2 g. 4-(3-acenaphthenyl)butyric acid (XX), leaflets, m. 154¡ã, b_0.1 212¡ã. XX (5 g.) treated with 50 cc. anhydrous HF during 36 hrs. yielded 3.8 g. 1-oxo-1,2,3,4-tetrahydro-5,10-aceanthrene (XXI), needles, m. 145¡ã (EtOH). XXI (1 g.) in 50 cc. dry tetra hydrofuran added dropwise with stirring to 1.5 g. powd. Li-AlH₄ in 100 cc. dry tetrahydrofuran, the mixture worked up, and the resulting viscous, yellow oil heated with 150 mg. 10% Pd-C at 320-30¡ã and then sublimed at 120¡ã/0.2 mm. yielded 0.48 g. aceanthrene (XXII), pale yellow leaflets, m. 117¡ã. Com. NaOMe (7 g.) in 20 cc. dry C₆H₆ treated during 15 min. with stirring with 7 g. HCO₂Et in 50 cc. dry C₆H₆ and then during 45 min. with 7 g. XXI gave 7.5 g. 2-hydroxymethylene derivative (XXIII) of XXI, yellow needles, m. 120¡ã (EtOH). XXIII (6 g.) in 60 cc. dry C₆H₆ treated with 10 drops Et₃N and 4 g. AcCH:CH₂ and kept 4 days yielded 4 g. 2-formyl-2-(3-oxobutyl) derivative (XXIV) of XXI, needles, m. 146 7¡ã (EtOH). XXIV (4 g.) in 50 cc. dioxane refluxed 2 hrs. with 250 cc. 2% aqueous KOH yielded 3.1 g. 2-oxo-2,3,4,5,6,7-hexahydrocholanthrene (XXV), yellow leaflets, m. 180¡ã (EtOH). XXV (1 g.) in 50 cc. dry tetrahydrofuran reduced in the usual manner with 1.5 g. LiAlH₄ in 50 cc. tetrahydrofuran, and the crude product heated 5 hrs. with 0.5 g. 10% Pd.C at 320-30¡ã gave 80 mg. V, pale yellow leaflets, m. 169-70¡ã (PrOH). MeCH(CO₂Et)₂ (40 g.) added dropwise with stirring to 4 g. powd. Na in 150 cc. dry PhMe, refluxed 1 hr., cooled, treated dropwise with 40 g. PhCH₂CH₂Br, refluxed 7 hrs., and worked up yielded 37.3 g. PhCH₂CH₂CMe(CO₂Et)₂ (XXVI), b₁₀ 176-9¡ã. XXVI (67 g.) and 40 g. KOH in 200 cc. MeOH refluxed 4 hrs. yielded 53 g. PhCH₂-CH₂CMe(CO₂H)₂, m. 166-7¡ã (decomposition); the acid heated 0.5 hr. at 180-90¡ã and then fractionated yielded 34 g. PhCH₂CH₂CHMeCO₂H (XXVII), b₉ 161-4¡ã. XXVII (105 g.) cyclized by the method of Alexander and Mudrak (J. Am. Chem. Soc. 72, 3194(1950)) gave 89 g. 2-methyl-1-tetralone (XXVIII), b₉ 126-7¡ã. MeMgI from 6.25 g. Mg and 35.5 g. MeI in 100 cc. dry Et₂O treated dropwise with stirring with 32.5 g. XXVIII in 50 cc. Et₂O, refluxed 1 hr., and worked up, and the resulting oil refluxed 0.5 hr. with 20 g. AcCl gave 23 g. 1,2-dimethyl-3,4-dihydronaphthalene (XXIX), b₁₂ 123-6¡ã. XXIX (10.6 g.) and 2.1 g. powd. S heated 0.5 hr. at 180¡ã and 15 min. at 220-30¡ã and distilled yielded 9.5 g. 1,2-C₁₀H₆Me₂, b₁₂ 132-3¡ã.

Chemische Berichte published new progress about 1949-41-3. 1949-41-3 belongs to catalysis-chemistry, auxiliary class Carboxylic acid,Benzene, name is 2-Methyl-4-phenylbutanoic acid, and the molecular formula is C11H14O2, Related Products of catalysis-chemistry.

Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia

Saiegh, Tomas J. published the artcileRhodium(III)-Catalyzed Heteroannulations of 3-Sulfolene Derivatives through C(sp²)-H Activation: Access to Pyridine ortho-Quinodimethane Precursors, Application of O-Pivaloylhydroxylamine trifluoromethanesulfonate, the publication is European Journal of Organic Chemistry (2022), 2022(22), e202200509, database is CAplus.

Hydroxamates derived from 3-sulfolene-3-carboxylic acid can be involved in intra- and intermol. rhodium(III)-catalyzed heteroannulations with alkynes proceeding through C(sp²)-H bond activation. These transformations allow for a straightforward access to diversely substituted pyridones, and to pyridines fused to a sulfolene ring after functional group transformations. Subsequent cheletropic elimination of sulfur dioxide can be achieved under microwave irradiation to generate pyridine ortho-quinodimethanes. These results demonstrate that the scope of rhodium(III)-catalyzed C(sp²)-H functionalizations can be extended to sulfolenes, a yet unexplored class of alkenes in these latter transformations, thereby affording access to valuable classes of heterocyclic products.

European Journal of Organic Chemistry published new progress about 1293990-73-4. 1293990-73-4 belongs to catalysis-chemistry, auxiliary class Aliphatic Chain, name is O-Pivaloylhydroxylamine trifluoromethanesulfonate, and the molecular formula is C6H12F3NO5S, Application of O-Pivaloylhydroxylamine trifluoromethanesulfonate.

Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia

Pehlivan, Leyla published the artcileReduction of phosphine oxides to phosphines with the InBr₃/TMDS system, Category: catalysis-chemistry, the publication is Tetrahedron (2012), 68(15), 3151-3155, database is CAplus.

An efficient method for the reduction of phosphine oxide derivatives into their corresponding phosphines is described. The system InBr₃/TMDS allows the reduction of different secondary and tertiary phosphine oxides as well as aliphatic and aromatic phosphine oxides.

Tetrahedron published new progress about 4141-48-4. 4141-48-4 belongs to catalysis-chemistry, auxiliary class Aryl phosphine ligand,Mono-phosphine Ligands, name is Allyldiphenylphosphine oxide, and the molecular formula is C15H15OP, Category: catalysis-chemistry.

Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia

Nageswara Rao, N. published the artcileMicrowave promoted catalyst-free benzylic C-H functionalization of methyl quinoline and Michael addition to beta-nitro styrene, Category: catalysis-chemistry, the publication is Tetrahedron Letters (2013), 54(10), 1315-1317, database is CAplus.

A catalyst-free aqueous mediated C-H activation of Me quinolines and addition to various ¦Â-nitro styrenes were executed under microwave irradiation providing 2-(2-aryl-3-nitropropyl)quinolines, e.g., I. Catalyst-free, additive free, simple workup, clean reaction conditions, easy isolation and environmentally benign medium are the best features of the present protocol.

Tetrahedron Letters published new progress about 4230-93-7. 4230-93-7 belongs to catalysis-chemistry, auxiliary class Alkenyl,Nitro Compound,Benzene,Ether, name is 1,2-Dimethoxy-4-(2-nitrovinyl)benzene, and the molecular formula is C10H11NO4, Category: catalysis-chemistry.

Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia

Hock, Katharina J. published the artcileDifluoro- and trifluoro diazoalkanes – complementary approaches in batch and flow and their application in cycloaddition reactions, Computed Properties of 421-49-8, the publication is Green Chemistry (2017), 19(4), 905-909, database is CAplus.

Herein, the applications of fluorinated diazoalkanes in cycloaddition reactions, with the emphasis on studying subtle differences between diverse fluorinated diazo compounds was reported. These differences led to two major synthetic protocols in batch and flow that allow the safe and scalable synthesis of fluoroalkyl-, sulfone-substituted pyrazolines.

Green Chemistry published new progress about 421-49-8. 421-49-8 belongs to catalysis-chemistry, auxiliary class Trifluoromethyl,Fluoride,Amine,Aliphatic hydrocarbon chain, name is 1,1,1-Trifluoropropan-2-amine, and the molecular formula is C3H6F3N, Computed Properties of 421-49-8.

Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia

Seyhan, Serap published the artcileUse of o-phenylenedioxydiacetic acid impregnated in Amberlite XAD resin for separation and preconcentration of uranium(VI) and thorium(IV), Computed Properties of 5411-14-3, the publication is Journal of Hazardous Materials (2008), 152(1), 79-84, database is CAplus and MEDLINE.

The impregnation of o-phenylene dioxydiacetic acid (OPDA) into a polymeric matrix, Amberlite XAD-2000, is reported and was characterized by IR spectroscopy. The amount of attached OPDA to the polymer resin was found to be 1.77 mmol g^-1 resin. The resin was used for the sorption of U(VI) and Th(IV) from aqueous solution This sorbent was capable of preconcg. U(VI) and Th(IV) from weakly acidic or neutral solution The retained metals were eluted sequentially using 0.25 mol L^-1 HCl for U(VI) and 1 mol L^-1 HCl for Th(IV) and determined spectrophotometrically using arsenazo-(III). The capacity of the resin for U(VI) and Th(IV) was found to be 0.121 and 0.113 mmol g^-1, resp. The impregnated resin exhibits a high chem. stability, reusability, and fast equilibration. The method was used for the determination of U(VI) and Th(IV) in synthetic samples and rock samples.

Journal of Hazardous Materials published new progress about 5411-14-3. 5411-14-3 belongs to catalysis-chemistry, auxiliary class Carboxylic acid,Benzene,Ether, name is 2,2-(1,2-Phenylenebis(oxy))diacetic acid, and the molecular formula is C10H12O5, Computed Properties of 5411-14-3.

Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia

Moons, Sam J. published the artcile¦Á-Selective Glycosylation with ¦Â-Glycosyl Sulfonium Ions Prepared via Intramolecular Alkylation, Recommanded Product: 2,4,6-Trimethoxybenzenethiol, the publication is Journal of Organic Chemistry (2019), 84(7), 4486-4500, database is CAplus and MEDLINE.

Stereoselective glycosylation remains the main challenge in the chem. synthesis of oligosaccharides. Herein we report a simple method to convert thioglycosides into ¦Â-sulfonium ions via an intramol. alkylation reaction leading to highly selective glycosylation for a variety of glycosyl acceptors. The influence of the thioglycoside substituent and the protecting group pattern on the glycosyl donor was investigated and showed a clear correlation with the observed stereoselectivity.

Journal of Organic Chemistry published new progress about 77189-99-2. 77189-99-2 belongs to catalysis-chemistry, auxiliary class Thiophenol,Benzene,Ether, name is 2,4,6-Trimethoxybenzenethiol, and the molecular formula is C9H12O3S, Recommanded Product: 2,4,6-Trimethoxybenzenethiol.

Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia

Qu, Zhe published the artcileProteomic Quantification and Site-Mapping of S-Nitrosylated Proteins Using Isobaric iodoTMT Reagents, Related Products of catalysis-chemistry, the publication is Journal of Proteome Research (2014), 13(7), 3200-3211, database is CAplus and MEDLINE.

S-Nitrosylation is a redox-based protein post-translational modification in response to nitric oxide signaling and is involved in a wide range of biol. processes. Detection and quantification of protein S-nitrosylation have been challenging tasks due to instability and low abundance of the modification. Many studies used mass spectrometry (MS)-based methods with different thiol-reactive reagents to label and identify proteins with S-nitrosylated cysteine (SNO-Cys). The authors developed a novel iodoTMT switch assay (ISA) using an isobaric set of thiol-reactive iodoTMTsixplex reagents to specifically detect and quantify protein S-nitrosylation. Irreversible labeling of SNO-Cys with the iodoTMTsixplex reagents enables immune-affinity detection of S-nitrosylated proteins, enrichment of iodoTMT-labeled peptides by anti-TMT resin, and importantly, unambiguous modification site-mapping and multiplex quantification by liquid chromatog.-tandem MS. Addnl., the authors significantly improved anti-TMT peptide enrichment efficiency by competitive elution. Using ISA, the authors identified a set of SNO-Cys sites responding to lipopolysaccharide (LPS) stimulation in murine BV-2 microglial cells and revealed effects of S-allyl cysteine from garlic on LPS-induced protein S-nitrosylation in antioxidative signaling and mitochondrial metabolic pathways. ISA proved to be an effective proteomic approach for quant. anal. of S-nitrosylation in complex samples and will facilitate the elucidation of mol. mechanisms of nitrosative stress in disease.

Journal of Proteome Research published new progress about 17351-61-0. 17351-61-0 belongs to catalysis-chemistry, auxiliary class Phase Transfer Catalyst, name is Tetraethylammonium hydrogencarbonate, and the molecular formula is C9H21NO3, Related Products of catalysis-chemistry.

Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia

Klingebiel, Uwe published the artcileSilicon-nitrogen-fluorine compounds, VI. Synthesis and cyclization of new aminofluorosilanes, Product Details of C12H10F2Si, the publication is Chemische Berichte (1976), 109(7), 2430-6, database is CAplus.

The reaction of RR1SiX2 with LiNHCMe3 gave 85-90% RR1SiXNHCMe3 (R, R1, X given): F, Ph, F; Me, Ph, F; Ph, Ph, F; Me, Me, Cl. Similarly, RSiF3 and Me3SiNLiCMe3 gave ?87% RSiF2N(CMe3)SiMe3 (R = Me3C, Ph). RR1SiXNHCMe3 cyclodimerized to give 61-92% I (R = F, Me, Ph, R1 = Ph; R = R1 = Me).

Chemische Berichte published new progress about 312-40-3. 312-40-3 belongs to catalysis-chemistry, auxiliary class Organic Silicones, name is Difluorodiphenylsilane, and the molecular formula is C12H10F2Si, Product Details of C12H10F2Si.

Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia