Category: 350-19-6

Kashiwabara, Taigo published the artcileDecarbonylative Coupling of Fluorobenzoyl Chlorides with Hexamethyldisilane in the Presence of a Palladium Complex Catalyst: Extremely Facile Decarbonylation of Pentafluorobenzoyl-Pd Complex Relevant to C₆F₅SiMe₃ Formation, Formula: C9H8F2O2, the publication is Organometallics (2006), 25(19), 4648-4652, database is CAplus.

Pd-phosphite complexes (PdCl₂(PhCN)₂ + P(OEt₃)₃ or P(OPr)₃ most effective) catalyze the reaction of pentafluorobenzoyl chloride with hexamethyldisilane to selectively form pentafluorophenyltrimethylsilane as virtually the sole product. The reaction of 3,5-difluoro- or 4-fluorobenzoyl chloride was less selective, giving a mixture of corresponding benzoyl- and phenylsilanes. Oxidative addition of pentafluorobenzoyl chloride with Pd(PPh₃)₄ or with Pd[P(OEt)₃]₂ generated in situ proceeds readily, but decarbonylation occurs, giving trans-C₆F₅PdClL₂ (L = PPh₃, P(OEt)₃), selectively. The crystal and mol. structures of trans-C₆F₅PdCl(PPh₃)₂ were determined by x-ray crystallog.

Organometallics published new progress about 350-19-6. 350-19-6 belongs to esters-buliding-blocks, auxiliary class Fluoride,Benzene,Ester, name is Ethyl 3,5-difluorobenzoate, and the molecular formula is C9H8F2O2, Formula: C9H8F2O2.

Referemce:
https://en.wikipedia.org/wiki/Ester,
Ester – an overview | ScienceDirect Topics

Wu, Tianxiao published the artcileRational drug design to explore the structure-activity relationship (SAR) of TRK inhibitors with 2,4-diaminopyrimidine scaffold, Quality Control of 350-19-6, the publication is European Journal of Medicinal Chemistry (2022), 114096, database is CAplus and MEDLINE.

Tropomyosin receptor kinase (TRK) is an ideal target for treating cancers caused by the NTRK gene fusion. In this study, more than 60 2,4-diaminopyrimidine derivatives were prepared to understand the structure-activity relationship and confirm the rationality of the pharmacophore model reported previously. Among them, compound I was found to be a potent pan-TRK inhibitor that inhibits the proliferation of Km-12 cell lines. Addnl., compound I induced the apoptosis of Km-12 cells in a concentration-dependent manner. Western blot anal. revealed that compound I inhibited the phosphorylation of TRK to block downstream pathways. Compound I also possessed outstanding plasma stability and liver microsomal stability in vitro, with half-lives greater than 289.1 min and 145 min, resp. Pharmacokinetic studies indicated that the oral bioavailability of compound I is 17.4%. These results demonstrate that compound I could serve as a novel lead compound for overcoming NTRK-fusion cancers.

European Journal of Medicinal Chemistry published new progress about 350-19-6. 350-19-6 belongs to esters-buliding-blocks, auxiliary class Fluoride,Benzene,Ester, name is Ethyl 3,5-difluorobenzoate, and the molecular formula is C19H14Cl2, Quality Control of 350-19-6.

Referemce:
https://en.wikipedia.org/wiki/Ester,
Ester – an overview | ScienceDirect Topics

Maekawa, Hirofumi published the artcileReductive carboxylation of aromatic esters by electron transfer from magnesium metal, Recommanded Product: Ethyl 3,5-difluorobenzoate, the publication is Tetrahedron Letters (2017), 58(3), 206-209, database is CAplus.

Magnesium-promoted reductive carboxylation of Et benzoates in the presence of chlorotrimethylsilane in N,N-dimethylformamide brought about a new carbon-carbon bond formation between the carbonyl carbon atom and carbon dioxide to give the corresponding benzoylformic acids in good yield. It is noteworthy that only Et benzoates with substituents at the meta-position were converted into benzoylformic acid derivatives Moreover, no mandelic acid was detected even under the reductive conditions. This result indicates that benzoylformic acid was obtained after hydrolysis of a carboxylated intermediate, which would exist as a stabilized structure in the reaction media.

Tetrahedron Letters published new progress about 350-19-6. 350-19-6 belongs to esters-buliding-blocks, auxiliary class Fluoride,Benzene,Ester, name is Ethyl 3,5-difluorobenzoate, and the molecular formula is C9H8F2O2, Recommanded Product: Ethyl 3,5-difluorobenzoate.

Referemce:
https://en.wikipedia.org/wiki/Ester,
Ester – an overview | ScienceDirect Topics

Roe, Arthur published the artcileThe preparation of some fluoro- and trifluoromethylphenothiazines, and some observations regarding determination of their structure by infrared spectroscopy, Application of Ethyl 3,5-difluorobenzoate, the publication is Journal of Organic Chemistry (1955), 1577-90, database is CAplus.

A number of fluorophenothiazines which may be of interest as antioxidants in lubricating oils are prepared Adding slowly with stirring 16 g. Br in 25 cc. AcOH to 12.9 g. 2,4-F₂C₆H₃NH₂ in 75 cc. AcOH at 25°, removing after 0.5 hr. any excess Br with Na₂S₂O₃, then adding 11.2 g. NaOAc in 100 cc. H₂O, and cooling the mixture in an ice bath give 81% 2,4,6-F₂BrC₆H₂NH₂ (I), m. 41-2°. I has a high vapor pressure [N-Ac derivative (II), 90%, prepared with Ac₂O, m. 156-7°]. 2,4-F₂C₆H₃NHAc cannot be brominated in AcOH. Deamination of I with H₃PO₂ gives 74% 3,5-F₂C₆H₃Br (III), b. 140°, d₂₃ 1.676, n_D²³ 1.4989. Adding a Grignard reagent of 14.5 g. III and 1.9 g. Mg in 50 cc. Et₂O to Dry Ice in Et₂O gives 64% 3,5-F₂C₆H₃CO₂H, m. 121-2°, also obtained when 18 g. 3,5-(H₂N)₂C₆H₃CO₂Et in 480 g. 45% HBF₄ is treated at -10° with 15 g. NaNO₂, the bis(diazonium fluoborate) (40 g., decomposing about 175°) is decomposed at 30 mm., and the Et ester, b₄₆ 103-5°, b₇₆₀ 200°, n_D²⁵ 1.4670, d₂₅ 1.201, saponified with KOH. Stirring 23 g. 2,6-ClFC₆H₃CO₂H in 100 cc. concentrated H₂SO₂4 1 hr. at 60°, adding (1.5 hrs.) 10 g. NaN₃ in small portions at 65°, keeping the mixture overnight, making it basic with NH₄OH, and steam distilling it give 70% 2,6-ClFC₆H₃NH₂ (IV), b₃₀ 91°, n_D²³ 1.5511, d₂₃ 1.316 (Ac derivative, prepared in 71% yield by refluxing 6 g. IV 1.5 hrs. in 25 cc. AcOH and 4.2 g. Ac₂O, platelets, m. 134-5°). Adding 9.1 g. NaNO₂ in small portions to 24 g. 2,3-O₂N(H₂N)C₆H₃CF₃ in 300 cc. 50% H₂SO₄ at 0°, stirring the mixture 15 min., pouring it into 160 cc. 10% CuCl at 20°, keeping it 1 hr. at 20°, diluting it with 100 cc. H₂0, and steam distilling it give 52% 3-Cl analog, b₂₇ 125-6°, n_D²⁴ 1.4782, d₂₄ 1.531. 3,4-Cl(O₂N)C₆H₃CF₃, prepared in the same way in 53% yield, b₂₈ 116°, n_D²⁴ 1.4864, d₂₄ 1.527. Refluxing 17 hrs. 0.1 mole of the appropriate acetanilide, 0.2 mole PhBr, 0.1 mole anhydrous K₂CO₃, 20 cc. PhNO₂, 6 g. catalyst mixture (consisting of equal parts by weight of CuI, KI, and Cu powder), and a crystal of iodine, steam distilling the mixture, extracting the distillation residue with Et₂O, refluxing the Et₂O residue 3.5 hrs. in 100 cc. 20% alc. KOH, pouring the solution into 800 cc. saturated NaCl solution, and extracting with Et₂O give the fluorodiphenylamine of which the following are prepared: 2-F (V), 80%, yellow oil, b₃ 111.5°, d₂₃ 1.165, n_D²³ 1.6171 (N-Bz derivative, m. 129-30°); 3-F (VI), 56%, yellow oil, b₁₀ 149-50°, d₂₃ 1.176, n_D²³ 1.6203; 2,5-di-F (VII), 68%, b₉ 138°, m. 45-5.5°; 2,4-di-F (VIIa), 63%, b₃ 110-13°, m. 42-2.5°; 3,5-di-F (VIII), 51%, b₄ 121-4°, m. 45-5.5°; 2,3′,5-tri-F, 63%, b_2.5 105-6°, m. 31.5-2°; 2,4′,5-tri-F, 71%, b_2.5 104-5°, m. 39.2-40°; 3,3′,5-tri-F (VIIIa), 49%, b_3.5 121°, m. 27.5-8.5°; 3,4′,5-tri-F (IX), 65%, b₄ 127-8°, m. 60-1°; 3,3′,5,5′-tetra-F (X), 43%, m. 117-18°; 2,6-ClF (XI), 34%, b₄ 138-40°, m. 69-9.3°. Adding 4 g. NaOH in 30 cc. H₂O to 12.5 g. o-H₂NC₆H₄SH in 300 cc. absolute EtOH, then adding 0.1 mole of the appropriate halonitrobenzene in 100 cc. absolute EtOH, refluxing the mixture 0.5 hr. (3.5 hrs. in the preparation of XIII below), adding 100 cc. H₂O to the boiling filtered solution, and cooling it slowly give the substituted o-H₂NC₆H₄SC₆H₃RNO₂-x,2 (XII) of which the following are prepared: R = 3-CF₃(XIII), 67%, m. 72-3°; 4-CF₃ (XIV), 89%, yellow, m. 108-9°; 5-CF₃, 80%, yellow, m. 110-11°; 4-F, 70%, red, m. 73-4°; 5-F, 54%, yellow, m. 115-16.5°. Refluxing XII with 10 times its weight of 90% HCO₂H 9-10 hrs. gives the substituted N-formyl derivative, o-OHCNHC₆H₄SC₆H₃RNO₂-x,2, of which the following are prepared: x-R = 3-CF₃ (XV), 92%,m. 137-8°; 4-CF₃(XVI), 88%, yellow, m. 132-3°; 5-CF₃ (XVII), 83%, yellow, m. 95-6°; 4-F (XVIII), 74%, yellow, m. 128-9°; 5-F (XIX), 74%, yellow, m. 116-17°. Refluxing 6.3 g. XIV 1 hr. with 2.8 g. BzCl in 25 cc. C₅H₅N gives 89% 2-[4,2-CF₃(O₂N)C₆H₃S]C₆H₄NHBz (XX), m. 127.5-8°. Heating 15 g. V, 5 g. S, and a few crystals of iodine 3 hrs. at 200-10° under reflux, boiling the tar obtained with 20% Na₂S (to remove the excess S), extracting it with Et₂O, treating the Et₂O solution with Norit and Zn dust, and distilling the residue of the filtered Et₂O solution give 2.2 g. unchanged V and 3 g. of a yellow solid, b_2.5 140°, from which 9.3% 1-fluorophenothiazine (XXI), m. 81.5-2°, and 1.4% phenothiazine (XXII), m. 180-2°, are isolated. XXI gives a blood-red color with concentrated HNO₃. When 1.9 g. V, 0.6 g. S, and a crystal of iodine are heated 1.5 hrs. in a sealed tube at 310-40° a few mg. XXI and 0.175 g. XXII are obtained. When 2.2 g. XI, 0.6 g. S, and a crystal of iodine are heated 1.5 hrs. at 300°, no crystalline product can be isolated. Heating 5 g. VI, 1.7 g. S, and a few crystals of iodine 1 hr. at 180° ± 5° gives 52% 2-fluorophenothiazine (XXIII), light yellow powder, m. 199° (decomposition); it gives a blood-red color with HNO₃. In an attempted synthesis of 1,4-difluorophenothiazine (XXIV), XXIII is obtained. Several other attempts to prepare XXIV from VII, from VIIa, or 1,3-difluorophenothiazine also failed. Heating a carefully purified VIII with S and a crystal of iodine 35 min. at 175° gives 43% 2,4-difluorophenothiazine, subliming 130°/2.5 mm., m. 129-30°. Attempts to prepare 1,4,7- and 1,4,8-trifluorophenothiazines by ring closure of the appropriate trifluorodiphenylamines failed. Ring closure of IX with S and iodine 1 hr. at 190° gives 20% 2,4,7-trifluorophenothiazine, m. 147-8° (decomposition); 6.1 g. VIIIa, 1.75 g. S, and a crystal of iodine 2.5 hrs. at 170° give 44% 2,4,8-trifluorophenothiazine, m. 142-3°; 1.2 g. X, 0.31 g. S, and a crystal of iodine 1 min. at 230° and 20 min. at 210° (or 1.5 hrs. at 210-40°) give 13% (or 20%) 2,4,6,8-tetrafluorophenothiazine, needles, m. 193-3.5°. Refluxing 15 g. XVI in 150 cc. Me₂CO 0.5 hr. with 44 cc. N NaOH, evaporating the solution to dryness, and extracting the residue with boiling CCl₄ give 52% 3-trifluoromethylphenothiazine, m. 217-18°, also obtained in much lower yield from XX. In a similar way, XVII gives 59% 2-trifluoromethylphenothiazine, m. 189-90°, and XVIII gives 43% 3-fluorophenothiazine, m. 178-9°. Attempts to prepare 4-trifluoromethylphenothiazine by treating 4.6 g. XV in 46 cc. Me₂CO with NaOH, or 2-fluorophenothiazine by refluxing 4.4 g. XIX in Me₂CO with NaOH were unsuccessful. The infrared absorption spectra of these compounds are determined and an attempt is made to see if a reliable method of structure determination of fluorophenothiazines can be made with these spectra. It is found that this kind of structural determination should be approached with discretion.

Journal of Organic Chemistry published new progress about 350-19-6. 350-19-6 belongs to esters-buliding-blocks, auxiliary class Fluoride,Benzene,Ester, name is Ethyl 3,5-difluorobenzoate, and the molecular formula is C9H8F2O2, Application of Ethyl 3,5-difluorobenzoate.

Referemce:
https://en.wikipedia.org/wiki/Ester,
Ester – an overview | ScienceDirect Topics

Zhu, Dunming published the artcileHow carbonyl reductases control stereoselectivity: approaching the goal of rational design, Related Products of esters-buliding-blocks, the publication is Pure and Applied Chemistry (2010), 82(1), 117-128, database is CAplus.

Although Prelog’s rule and two hydrophobic binding pockets model have been used to predict and explain the stereoselectivity of enzymic ketone reduction, the mol. basis of stereo-recognition by carbonyl reductases has not been well understood. The stereo-selectivity is not only determined by the structures of enzymes and substrates, but also affected by the reaction conditions such as temperature and reaction medium. Structural anal. coupled with site-directed mutagenesis of stereo-complementary carbonyl reductases readily reveals the key elements of controlling stereo-selectivity in these enzymes. Enzyme-substrate docking and mol. modeling have been engaged to understand the enantio-selectivity diversity of the carbonyl reductase from Sporobolomyces salmonicolor (SSCR), and to guide site-saturation mutagenesis for altering the enantioselectivity of this enzyme. These studies provide valuable information for understanding of how the residues involved in substrate binding affect the orientation of bound substrate, and thus control the reaction stereo-selectivity. The in silico docking-guided semi-rational approach should be a useful methodol. for discovery of new carbonyl reductases.

Pure and Applied Chemistry published new progress about 350-19-6. 350-19-6 belongs to esters-buliding-blocks, auxiliary class Fluoride,Benzene,Ester, name is Ethyl 3,5-difluorobenzoate, and the molecular formula is C42H63O3P, Related Products of esters-buliding-blocks.

Referemce:
https://en.wikipedia.org/wiki/Ester,
Ester – an overview | ScienceDirect Topics

Belfield, Andrew J. published the artcileSynthesis of Meta-substituted aniline derivatives by nucleophilic substitution, Quality Control of 350-19-6, the publication is Tetrahedron (1999), 55(46), 13285-13300, database is CAplus.

Substitution by amines of fluorobenzenes containing a meta-substituted electron withdrawing group (EWG), in DMSO at 100°C over 60 h gave meta-substituted aniline derivatives in isolated yields of up to 98%. The scope of the reaction is explored in terms of reaction conditions and substrates. It is postulated that facile meta-substitutions are facilitated through field stabilization of the intermediate anion by EWG substituents.

Tetrahedron published new progress about 350-19-6. 350-19-6 belongs to esters-buliding-blocks, auxiliary class Fluoride,Benzene,Ester, name is Ethyl 3,5-difluorobenzoate, and the molecular formula is C9H8F2O2, Quality Control of 350-19-6.

Referemce:
https://en.wikipedia.org/wiki/Ester,
Ester – an overview | ScienceDirect Topics

Hoque, Emdadul Md published the artcileNoncovalent interactions in Ir-catalyzed C-H activation: L-shaped ligand for para-selective borylation of aromatic esters, Category: esters-buliding-blocks, the publication is Journal of the American Chemical Society (2017), 139(23), 7745-7748, database is CAplus and MEDLINE.

An efficient strategy for the para-selective C-H-borylation of aromatic esters is described, utilizing iridium(I) precatalyst [Ir(cod)(OMe)]₂ and an L-shaped ligand I (L1), which enables coordination of the iridium center through its bipyridine moiety and substrate coordination through 2-quinolinol hydrogen bond. For achieving high para-selectivity, a new catalytic system has been developed modifying the core structure of the bipyridine. It has been proposed that the L-shaped ligand is essential to recognize the functionality of the oxygen atom of the ester carbonyl group via noncovalent interaction, which provides an unprecedented controlling factor for para-selective C-H activation/borylation.

Journal of the American Chemical Society published new progress about 350-19-6. 350-19-6 belongs to esters-buliding-blocks, auxiliary class Fluoride,Benzene,Ester, name is Ethyl 3,5-difluorobenzoate, and the molecular formula is C9H8F2O2, Category: esters-buliding-blocks.

Referemce:
https://en.wikipedia.org/wiki/Ester,
Ester – an overview | ScienceDirect Topics

Salamanca, Vanesa published the artcileDeuterium Exchange between Arenes and Deuterated Solvents in the Absence of a Transition Metal: Synthesis of D-Labeled Fluoroarenes, HPLC of Formula: 350-19-6, the publication is European Journal of Organic Chemistry (2020), 2020(22), 3206-3212, database is CAplus.

Fluoroarenes can be selectively deuterated by H/D exchange with common deuterated solvents in the presence of a catalytic amount of an alkali metal carbonate or, for the less acidic arenes, stoichiometric quantities of potassium phosphate. This is a sustainable method that does not need transition metal catalysis or the multistep synthesis of a main-group organometallics. This exchange needs to be taken into account when using H/D scrambling as a mechanistic probe in reactions involving fluoroarenes.

European Journal of Organic Chemistry published new progress about 350-19-6. 350-19-6 belongs to esters-buliding-blocks, auxiliary class Fluoride,Benzene,Ester, name is Ethyl 3,5-difluorobenzoate, and the molecular formula is C9H8F2O2, HPLC of Formula: 350-19-6.

Referemce:
https://en.wikipedia.org/wiki/Ester,
Ester – an overview | ScienceDirect Topics