Month: December 2022

Williams, A. H. published the artcileNew organic sulfur vesicants. II. Analogues of 2,2′-dichlorodiethyl sulfide and 2,2′-di(2-chloroethylthio)diethyl ether, Related Products of chlorides-buliding-blocks, the publication is Journal of the Chemical Society (1948), 38-42, database is CAplus and MEDLINE.

MeCH.CH₂.O (680 g.), introduced at the rate of 0.7 cc./min., and H₂S (throughput 45 l./h.) at 60° give 948 g. of product which yields 488 g. 2-hydroxy-1-propanethiol, b₈ 44.5-5°, n¹⁸_D 1.4850, and 390 g. 2,2′-dihydroxydipropyl sulfide (I), b₄ 125°. ClCH₂CHMeOH (b. 126-8°) and Na₂S in EtOH, refluxed 10 min., give I. I (50 g.) in 200 cc. CHCl₃, treated dropwise with 62 cc. SOCl₂ and refluxed 30 min., gives bis(2-chloropropyl) sulfide, b₁₀ 105°, m. -40°. EtCHO (58 g.) in 300 cc. AcOEt at -5°, treated dropwise (3 h.) with 45 g. Br in 100 cc. AcOEt, and the mixture poured into 500 cc. absolute EtOH and kept 18 h. at room temperature, give CHMeBrCH(OEt)₂, b₁₃ 67°; reaction with HSC₂H₄OH in EtONa-EtOH (refluxing 25 h.) gives α-(2-hydroxyethylmercapto)propionaldehyde di-Et acetal, b_0.5 87°; hydrolysis of 40 g. with 200 cc. 3% HCl (24 h.) gives α-(2-hydroxyethylmercapto)propionaldehyde, an oil, reduction of which with (iso-PrO)₃Al gives 2-hydroxyethyl 2-hydroxyisopropyl sulfide, b₅ 136-7°; SOCl₂ yields 2-chloroethyl 2-chloroisopropyl sulfide, b₇ 88°, b₁₂ 105°, m. -24.5° (sulfilimine, m. 132°). S(CH₂CH₂SCH₂CH₂OH)₂ (II) (C.A. 16, 409) and SOCl₂ in CHCl₃ (refluxed 30 min.) give 2,2′-bis(2-chloroethylmercapto)diethyl sulfide (III), m. 73-5° (chloroplatinate, mustard color, m. 136°; piperidide picrate, m. 180° (decomposition)). The Cl atom of III is removed by AgNO₃ in boiling EtOH in 5 min. and by boiling H₂O in 45 min. The following ethers were prepared from III and the appropriate phenol in EtOH-EtONa: diphenoxy, m. 59°; di-2-naphthoxy, m. 122°; bis(sym-tribromophenoxy), m. 107°; dieugenoxy, m. 86°; bis(phenylmercapto), m. 92-4°. III and NaI in MeOH, refluxed 10 min., give the bis(2-iodoethyl) analog, m. 102-3°; bis(2-thiocyanatoethyl) analog, m. 52°; the bis(2-cyanoethyl) analog could not be prepared, the reaction yielding (NCCH₂CH₂)₂S and dithiane. II and PBr₃ in CHCl₃, refluxed 2 h., give the bis(2-bromoethyl) analog, b_3.5 158-63.5° [bis(1-naphthylurethane), m. 150-2°]. (ClCH₂CH₂)₂S₂ b₅ 132-4° [bis(sym-tribromophenoxy) analog, m. 76°; dieugenoxy analog, m. 97°]. III in AcOH, treated with 6 mols. 30% H₂O₂ (1 h.) gives 2,2′-bis(2-chloroethylsulfonyl)diethyl sulfone, m. 174.5°; 2,2′-bis(2-hydroxyethylmercapto)diethyl sulfoxide, m. 57°; the sulfone m. 85-6°; the disulfide m. 79-81°; 2,2′-bis(2-chloroethylmercapto)diethyl sulfoxide, m. 63°; the sulfone m. 107-9°; 2,2′-bis(2-hydroxypropylmercapto)diethyl sulfide, m. 59°; di-2-Cl analog, m. 43.5°; 2,3-bis(2-hydroxyethylmercapto)-1,4-dioxane, oily [bis(1-naphthylurethane), m. 152°]; 2,3-bis(2-chloroethylmercapto)-1,4,-dioxane, b₁₅ 138-41°. 2-Hydroxyethyl 2-hydroxypropyl sulfide, b₈ 154°; 2-chloroethyl 2-chloropropyl sulfide, b₄ 88°, m. -23°. 2,2′-Bis(2-hydroxypropylmercapto)diethyl ether, b₅ 217-18°; di-2-Cl analog, b_0.02 95-8°. 2,2′-Bis(2-hydroxyethymercapto)dipropyl sulfide, b_1.5 240°; di-2-Cl analog. 2,2′-Bis(2-hydroxypropylmercapto)dipropyl sulfide, b_0.5 210°; di-2-Cl analog, b_0.02 108-9° (slight decomposition). If mustard gas is assigned an empirical vesicant power of 100, these compounds show values of 10 to 50.

Journal of the Chemical Society published new progress about 1002-41-1. 1002-41-1 belongs to chlorides-buliding-blocks, auxiliary class Aliphatic Chain, name is 1,2-Bis(2-chloroethyl)disulfane, and the molecular formula is C5H2ClF3N2, Related Products of chlorides-buliding-blocks.

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

Bubert, Christian published the artcileSynthesis of aromatase inhibitors and dual aromatase steroid sulfatase inhibitors by linking an arylsulfamate motif to 4-(4H-1,2,4-triazol-4-ylamino)benzonitrile: SAR, crystal structures, in vitro and in vivo activities, Computed Properties of 33697-81-3, the publication is ChemMedChem (2008), 3(11), 1708-1730, database is CAplus and MEDLINE.

4-(((4-Cyanophenyl)(4H-1,2,4-triazol-4-yl)amino)methyl)phenyl sulfamate (I) was the first dual aromatase-sulfatase inhibitor (DASI) reported. Several series of its derivatives with various linker systems between the steroid sulfatase (STS) and the aromatase inhibitory pharmacophores were synthesized and evaluated in JEG-3 cells. The X-ray crystal structures of the aromatase inhibitors, DASI precursors II (n = 2, R¹ = R² = H) and III, and DASI II (n = 5, R¹ = H, R² = SO₂NH₂) were determined Nearly all derivatives show improved in vitro aromatase inhibition over I but decreased STS inhibition. The best aromatase inhibitor is II (n = 2, R¹ = Cl, R² = H) (IC₅₀ = 0.26 nM) and the best DASI is II (n = 2, R¹ = Cl, R² = SO₂NH₂) (IC_50aromatase = 0.45 nM, IC_50STS = 1200 nM). SAR for aromatase inhibition shows that compounds containing an alkylene- and thioether-based linker system are more potent than those that are ether-, sulfone-, or sulfonamide-based, and that the length of the linker has a limited effect on aromatase inhibition beyond two methylene units. Compounds II (R² = SO₂NH₂: n = 2, R¹ = H; n = 2, R¹ = Cl; n = 3, R¹ = H, n = 4, R¹ = H) were studied in vivo (10 mg kg^-1, single, p.o.). The most potent DASI is II (n = 2, R¹ = H, R² = SO₂NH₂), which inhibited PMSG-induced plasma estradiol levels by 92% and liver STS activity by 98% 3h after dosing. These results further strengthen the concept of designing and developing DASIs for potential treatment of hormone-related cancers.

ChemMedChem published new progress about 33697-81-3. 33697-81-3 belongs to chlorides-buliding-blocks, auxiliary class Chloride,Carboxylic acid,Benzene,Phenol, name is 3-Chloro-4-hydroxyphenylacetic acid, and the molecular formula is C8H7ClO3, Computed Properties of 33697-81-3.

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

Linghu, Xin published the artcileDevelopment of a Practical Synthesis of ERK Inhibitor GDC-0994, SDS of cas: 1263414-46-5, the publication is Organic Process Research & Development (2017), 21(3), 387-398, database is CAplus.

The process development of a synthetic route to manufacture ERK inhibitor GDC-0994, I, on multikilogram scale is reported herein. The API was prepared as the corresponding benzenesulfonate salt in 7 steps and 41% overall yield. The synthetic route features a biocatalytic asym. ketone reduction, a regioselective pyridone S_N2 reaction, and a safe and scalable tungstate-catalyzed sulfide oxidation The end-game process involves a telescoped S_NAr/desilylation/benzenesulfonate salt formation sequence. Finally, the development of the API crystallization allowed purging of process-related impurities, obtaining >99.5A% HPLC and >99% ee of the target mol.

Organic Process Research & Development published new progress about 1263414-46-5. 1263414-46-5 belongs to chlorides-buliding-blocks, auxiliary class Fluoride,Chloride,Alkenyl,Benzene, name is 4-Chloro-3-fluorostyrene, and the molecular formula is C8H6ClF, SDS of cas: 1263414-46-5.

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

Vega, Beatriz published the artcileCharge-Directed Fiber Surface Modification by Molecular Assemblies of Functional Polysaccharides, Quality Control of 6249-56-5, the publication is Langmuir (2013), 29(44), 13388-13395, database is CAplus and MEDLINE.

Mol. assemblies, namely, polyelectrolyte complexes (PECs) composed of neg. charged xylan-based derivatives and a novel pos. charged cellulose derivative (CN⁺), were used for interfacial modification of wood fibers by charge directed self-assembly. The adsorption process was studied using polyelectrolyte titration and elemental anal. X-ray spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used as advanced techniques for the characterization of the modified fiber surfaces. The measurements revealed an intense interaction between the pulp fibers and PECs, and provided essential information for a better understanding of the adsorption process. The information gathered on this paper might contribute to the basis for the development of new value added products by the use of underutilized biomass.

Langmuir published new progress about 6249-56-5. 6249-56-5 belongs to chlorides-buliding-blocks, auxiliary class Phase Transfer Catalyst,Inhibitor,Natural product, name is 3-Carboxy-N,N,N-trimethylpropan-1-aminium chloride, and the molecular formula is C10H9IO4, Quality Control of 6249-56-5.

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

Vega, Beatriz published the artcilePreparation of reactive fiber interfaces using multifunctional cellulose derivatives, Computed Properties of 6249-56-5, the publication is Carbohydrate Polymers (2015), 261-273, database is CAplus and MEDLINE.

Cellulose fibers have poor reactivity and limited potential for surface engineering with advanced chem. functionalization in water. In this work, cellulose fibers were decorated with azide functions by charge-directed self-assembly of a novel water-soluble multifunctional cellulose derivative yielding reactive fibers. Propargylamine and 1-ethynylpyrene were utilized as a proof of concept that alkyne mols. may react with the azide functions of the reactive fibers via copper(I)-catalyzed azide-alkyne Huisgen cycloaddition (CuAAc) reaction in mild conditions. Chem. characterization of the fibers was carried out using classical techniques such as Raman-, fluorescence-, and UV-vis spectroscopy. Among other techniques, time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray spectroscopy (XPS), two-photon microscopy (TPM), and inductively coupled plasma mass spectrometry (ICP-MS) were useful tools for addnl. characterization of the fibers decorated with amino- or photoactive groups. The information gathered in this work might contribute to the basis for the preparation of reactive cellulose-based interfaces with potential application in CuAAc reactions.

Carbohydrate Polymers published new progress about 6249-56-5. 6249-56-5 belongs to chlorides-buliding-blocks, auxiliary class Phase Transfer Catalyst,Inhibitor,Natural product, name is 3-Carboxy-N,N,N-trimethylpropan-1-aminium chloride, and the molecular formula is C44H58NO5PPdS, Computed Properties of 6249-56-5.

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

Grigoray, Olga published the artcileFluorescent Multifunctional Polysaccharides for Sustainable Supramolecular Functionalization of Fibers in Water, Computed Properties of 6249-56-5, the publication is ACS Sustainable Chemistry & Engineering (2017), 5(2), 1794-1803, database is CAplus.

The paper describes the synthesis of multifunctional cellulose derivatives (MCD) containing a fluorescent- and a cationic moiety and their application in the functionalization of pulp fibers. The cellulose derivatives, namely N-(3-propanoic acid)- and N-(4-butanoic acid)-1,8-naphthalimide esters of cellulose, differed in the degree of substitution (DS) and by the aliphatic chain connecting naphtalimide photoactive groups to the polymer backbone. The derivatives were decorated with a cationic moiety, namely (3-carboxypropyl)trimethylammonium chloride. The fluorescent pulp fibers were prepared by direct self-assembly of the water-soluble fluorescent MCDs on the fibers in water at room temperature The results indicated that the adsorption was mainly driven by ion exchange mechanism. UV-vis- and fluorescence spectroscopic studies showed that the adsorption yield of the fluorescent MCDs depended on the length of the aliphatic chain of the photoactive groups. Because of the adsorption, the modified pulp fibers gained fluorescence in the visible part of the spectrum. Under the black light illumination, the modified fibers fluoresced, which made them visually distinguishable from the reference fibers. Thus, the fluorescent pulp fibers prepared in a simple way can be potentially used in fiber-based photoactive materials and authenticity indicators in papers and packaging.

ACS Sustainable Chemistry & Engineering published new progress about 6249-56-5. 6249-56-5 belongs to chlorides-buliding-blocks, auxiliary class Phase Transfer Catalyst,Inhibitor,Natural product, name is 3-Carboxy-N,N,N-trimethylpropan-1-aminium chloride, and the molecular formula is C7H16ClNO2, Computed Properties of 6249-56-5.

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

Kim, Yeong Bum published the artcileNi-Catalyzed Intermolecular C(sp³)-H Amidation Tuned by Bidentate Directing Groups, Safety of ((1S,4R)-7,7-Dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methanesulfonyl chloride, the publication is ACS Catalysis (2021), 11(5), 3067-3072, database is CAplus.

Herein a directing group-assisted nickel-catalyzed intermol. C(sp³)-H amidation using organic azides as nitrene precursors is disclosed. With the installation of an electronically tailored directing group, enhanced amidation efficiency has been achieved. A series of exptl. and computational studies suggested that a putative nickel(III)-nitrenoid species is a key intermediate in the C-N bond-forming process.

ACS Catalysis published new progress about 21286-54-4. 21286-54-4 belongs to chlorides-buliding-blocks, auxiliary class Chiral,Chloride,Sulfonyl chlorides,Aliphatic cyclic hydrocarbon,Ketone, name is ((1S,4R)-7,7-Dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methanesulfonyl chloride, and the molecular formula is C10H15ClO3S, Safety of ((1S,4R)-7,7-Dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methanesulfonyl chloride.

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

Yearick, Kimberly published the artcileCatalytic enantioselective addition of diethylzinc to trifluoromethyl ketones. [Erratum to document cited in CA149:307341], Quality Control of 5860-95-7, the publication is Organic Letters (2008), 10(19), 4391, database is CAplus.

On page 3915, we overlooked previous work by Sasaki et. al. which discusses the enantioselective synthesis of tertiary alcs. via addition of diethylzinc to trifluoromethyl ketones in the presence of nitrogen-containing polydentate ligands. The following reference citation should be included: “Higashiyama, K.; Sasaki, S.; Kubo, H.; Yamauchi, T.; Ishii, A.; Kanai, M. Japanese Patent 200609692, Apr. 13, 2006.”.

Organic Letters published new progress about 5860-95-7. 5860-95-7 belongs to chlorides-buliding-blocks, auxiliary class Trifluoromethyl,Fluoride,Chloride,Benzene,Ketone, name is 1-(2-Chlorophenyl)-2,2,2-trifluoroethanone, and the molecular formula is C5H9IO2, Quality Control of 5860-95-7.

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

Yearick, Kimberly published the artcileCatalytic Enantioselective Addition of Diethylzinc to Trifluoromethyl Ketones, Synthetic Route of 5860-95-7, the publication is Organic Letters (2008), 10(17), 3915-3918, database is CAplus and MEDLINE.

A procedure for nucleophilic addition of diethylzinc to trifluoromethyl ketones was developed. The TMEDA-catalyzed method converts aromatic substrates to the corresponding 2-aryl-1,1,1-trifluorobutan-2-ols in up to 99% yield, and it is also applicable to less reactive aliphatic ketones if stoichiometric ligand amounts are employed. The first asym. variant producing tertiary alcs. with up to 61% ee when TBOX is used as catalyst is described.

Organic Letters published new progress about 5860-95-7. 5860-95-7 belongs to chlorides-buliding-blocks, auxiliary class Trifluoromethyl,Fluoride,Chloride,Benzene,Ketone, name is 1-(2-Chlorophenyl)-2,2,2-trifluoroethanone, and the molecular formula is C9H12O, Synthetic Route of 5860-95-7.

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

Androvic, Ladislav published the artcileCyclotriphosphazene-Based Star Copolymers as Structurally Tunable Nanocarriers with Programmable Biodegradability, COA of Formula: C19H14Cl2, the publication is Macromolecules (Washington, DC, United States) (2021), 54(7), 3139-3157, database is CAplus.

Myriad nanocarriers have been developed to improve the therapeutic index of low-mol.-weight drugs for cancer treatment, but many have suboptimal size and/or are too stable for optimal penetration into tumors and their subsequent excretion from the body. To address this challenge, we developed a series of novel nanocarriers based on star polymers consisting of hydrophilic poly[N-(2-hydroxypropyl)methacrylamide] (PHPMA) or poly(ethylene glycol) (PEG) polymer arms attached to hexavalent cyclotriphosphazene (CTP)-derived cores through either stable or stimuli-responsive linkers. The star polymers were assembled using either “grafting from” or “grafting onto” approaches and characterized by quant. arm substitution at the core. The resulting star polymers were precisely defined water-soluble nanomaterials with a suitable hydrodynamic size (~10-25 nm) for tumor uptake; those with stimuli-responsive linkers exhibited programmable pH- or cathepsin-mediated degradability. Finally, low-mol.-weight drugs-an anthracycline-based cancerostatic and an imidazoquinoline-based immunostimulant-were linked to exemplary CTP-based star polymers to demonstrate their suitability for drug delivery.

Macromolecules (Washington, DC, United States) published new progress about 42074-68-0. 42074-68-0 belongs to chlorides-buliding-blocks, auxiliary class Chloride,Benzyl chloride,Benzene, name is 2-Chlorotrityl chloride, and the molecular formula is C19H14Cl2, COA of Formula: C19H14Cl2.

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