Month: December 2022

Brintzinger, Herbert published the artcileOrganic sulfur chlorides. VII. Syntheses with α-chloroethylsulfur chloride, Product Details of C4H8Cl2S2, the publication is Chemische Berichte (1954), 300-14, database is CAplus.

cf. C.A. 47, 7433a. Adding 68 g. SO₂Cl₂ dropwise at -20° to 61.5 g. (EtS)₂ in 150 cc. CCl₄, adding another 123 g. SO₂Cl₂ at -15°, warming the mixture to 20°, keeping it overnight, and distilling it give 90% MeCHClSCl (I), b₂₇ 38°. Passing CHCH into 13.1 g. I in 50 cc. CCl₄ 3 h. and distilling the mixture give CHCl:CHSCHClMe, b₁₄ 75°, which decompose on standing. Adding dropwise 10.5 g. cyclohexene in 40 cc. CCl₄ to 13.5 g. I at 20° gives α-chloroethyl 2-chlorocyclohexyl sulfide (II) which decompose on distillation at 2 mm. Heating II at 150° until HCl is no longer split off and distilling off the volatile part leave a thermoplastic dark brown resin. Adding 6.6 g. cyclopentadiene in 35 cc. CCl₄ to 13.1 g. I at below 30° and fractionating the mixture give 4-chlorocyclopenten-2-yl vinyl sulfide, b₇ 65°, which polymerizes readily when the solvent is distilled off at atm. pressure; on heating it 4 h. at 120° a dark thermoplastic resin is formed. Adding dropwise 10.4 g. styrene in 30 cc. CCl₄ to 13.1 g. I at below 25° and distilling the mixture give β-chlorophenethyl vinyl sulfide (III), b₈ 135°. Heating III 50 h. at 80° gives a thermoplastic styrene soft resin, soluble in chlorinated hydrocarbons. Heating III at 160° until HCl is no longer evolved (50 h.) gives a hard black resin containing 3% Cl. Adding dropwise 26.2 g. I in 10 cc. THF (THF) to 10.4 g. cycloöctatetraene in 20 cc. THF at 20° and distilling off the THF in vacuo give what may be 2,7-dichloro-5,8-bis(α-chloroethylmercapto)bicyclo[0.2.4]oct-3-ene (IV) as a viscous yellow-red oil. Heating IV 18 h. at 100° gives a hard nonthermoplastic polymer, (C₁₂H₁₄Cl₂S₂)_x. When IV is heated 10 h. at 160° a Cl-free nonthermoplastic resin of the composition (C₁₂H₁₂S₂)_x is obtained. Adding 13.1 g. I slowly at 35° to 6.6 g. CH₂(CN)₂ in 10 cc. THF causes the evolution of HCl; distilling off the THF in vacuo leaves a red oil which soon polymerizes with the evolution of heat and HCl, giving a soft resin which, on heating 24 h. at 100°, gives a dark brown thermoplastic polymer, (C₅H₅N₂ClS)_x. Refluxing 13.1 g. I and 7.4 g. THF 28 h. and distilling the mixture give δ-chlorobutyl α-chloroethanesulfenate, CH₂Cl(CH₂)₃OSCHClMe, b₁₂ 88°, decomposing to a red oil after a few days. Adding slowly CH₂N₂ [from 10 g. MeN(NO)CONH₂] to 8.5 g. I and distilling off the ether in vacuo give ClCH₂SCHClMe, b₁ 40°, mobile oil, decomposing on standing at 20°. Shaking 26 g. I 3 h. with 25 g. Hg and warming the decanted solution with fresh Hg 0.5 h. at 50° give (CH₂ClCH₂S)₂, yellow oil, b₉ 84°. Adding 15 g. I dropwise at 5° to 40 g. dry Me₂CO, warming the mixture 0.5 h. at 35°, and fractionating it give hexakis(α-chloroethylmercapto)acetone, b₂ 70°, which, heated 10 h. at 80°, polymerizes to a hard Cl-free resin. When equal parts of I and Me₂CO are mixed, heat and HCl are evolved; the mixture, heated 5 h. at 80° and fractionated, gives hexakis(ethylmercapto)acetone, light yellow oil, b₁₅ 53°. Mixing 12 g. PhAc and 13.1 g. I and distilling off the volatile parts in vacuo give a compound, MeCHClSCHBzSCHMeCHBzSCHClMe, which splits off HCl at 20°, completely after heating at 100°, giving a hard resin of the composition (C₂₂H₂₂O₂S₃)_x. Adding 13.1 g. I to 20 g. CH₂Ac₂ at below 30° and distilling the mixture give 3-(α-chloroethylmercapto)pentane-2,4-dione (V), b₁ 82°. Shaking 8 g. V with a small excess of 10% KOH 10 min. and adding 150 cc. H₂O give (3-vinylmercapto)pentane-2,4-dione, mobile oil, b_0.5 70°. Adding 39.3 g. I in 3 portions to 10 g. CH₂Ac₂, keeping the mixture several hrs., and distilling it give tris(α-chloroethylmercapto)pentane-2,4-dione, b₁₂ 104-7°. Similarly, equimolar amounts of I and AcCH₂CO₂Et give (as primary reaction product) Et α-(α’-chloroethylmercapto)acetoacetate (VI), which, heated 15 h. at 65°, gives Et α-(vinylmercapto)acetoacetate, yellow mobile oil, b₁₈ 115°. Adding 39.3 g. I slowly to 7.2 g. MeCOEt at 30° causes a strong evolution of HCl; the mixture is heated several hrs. at 100°, giving a Cl-free polymer, (C₂₀H₂₄OS₈)_x, as a nonthermoplastic black resin. Similarly, 39.3 g. I and 7 g. MeCOCH: CH₂ give MeCOCHClMe, b₂₈ 40°, and a resin which, heated 4 h. at 100°, gives a nonthermoplastic insoluble resin of the composition (C₁₄H₁₆OS₅)_x. Adding 6.5 g. I to 8 g. carbazole in 125 cc. warm xylene, heating the mixture 1.5 h. at 60°, and concentrating the filtered black solution in vacuo give (α-N-carbazolylethyl) (N-carbazolyl) sulfide, yellow crystals, m. 212° (decomposition), and a polymer which is obtained as the main product when 8 g. carbazole and 6.5 g. I are refluxed in 125 cc. xylene 2.5 h., the cooled solution is filtered, concentrated, filtered again, and evaporated, the residue extracted with CCl₄, and the residue of the CCl₄ extract heated 1 h. at 80°/12 mm. Adding dropwise 6.5 g. I in 15 cc. AcOH to 12.1 g. PhNMe₂ in 15 cc. AcOH, stirring the mixture 1 h. at 35°, adding 22.5 g. KOH in 200 cc. H₂O, extracting with ether, distilling off the PhNMe₂ from the residue of the dried ether extract, and recrystallizing the residue 3 times from EtOH give [α-(4-dimethylaminophenyl)ethyl] 4-dimethylaminophenyl sulfide, yellow needles, m. 125°. Adding in small portions with cooling 30 g. AlCl₃ to 13.1 g. I in 100 cc. C₆H₆, keeping the mixture overnight, distilling off about 50 cc. C₆H₆, pouring the residue into iced HCl, extracting with ether, and distilling the washed (NaOH) and dried organic solution at 30°/10 mm. leave Ph α-phenethyl sulfide, yellow crystals, m. 161°. Treating 11.4 g. CO(NHPh)₂ in 250 cc. CHCl₃ several hrs. with 13.1 g. I and distilling off the CHCl₃ give N,N’-diphenyl-N,N’-bis(α-chloroethylmercapto)thiourea-2HCl, m. 132°. Adding 13.1 g. I to 22.8 g. CO(NHPh)₂ in 120 cc. THF and distilling off the THF leave a viscous yellow soft resin which is heated 1 h. at 60°/12 mm. and has the composition (C₁₅H₁₆N₂Cl₂S₂)_x, soluble in CCl₄ and ether, and giving a clear solid film. Adding dropwise 13.1 g. I to 21.1 g. diphenylguanidine in 200 cc. CHCl₃ and distilling off the CHCl₃ give a polymer, (C₁₅H₁₇N₃Cl₂S)_x, as a tough thermoplastic film-forming red resin. Adding 13.1 g. I to 9.8 g. cyclohexanone in 50 cc. CCl₄ at below 40°, keeping the mixture 48 h. at 20°, and fractionating the solution give a colorless Cl-containing oil, b₈ 45°, which readily decompose, giving a Cl-containing dark red soft resin. When I and cyclohexanone are mixed without cooling, the mixture is heated 20 h. on a water bath, and the volatile portion is distilled off a red thermoplastic hard resin of the composition (C₈H₁₂OS)_x is obtained. Treating 9.4 g. PhOH in 50 cc. CHCl₃ with 13.1 g. I, distilling off the CHCl₃, and heating the residue 5 h. at 60° give a soft resin, containing 12.4% Cl, which after heating another 5 h. at 100° gives a Cl-free hard resin of the composition (C₈H₉OS)_x.

Chemische Berichte 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 C4H8Cl2S2, Product Details of C4H8Cl2S2.

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

Mahvidi, S. published the artcileInfluence of protonation on the photochromic behavior, phase transfer and thermal stability of phenylamine-substituted diarylethenes, Category: chlorides-buliding-blocks, the publication is Progress in Color, Colorants and Coatings (2020), 13(2), 105-119, database is CAplus.

This paper examines the role of protonation on the photochromic reactions of multi-responsive Ph amine diarylethene derivatives (PA-DAEs). Reversible protonation and deprotonation provide a secondary stimulus for controlling the properties of light-responsive PA-DAEs, including solubility and thermal stability. For this reason, the phenylamine substituted DAEs were synthesized using a novel and efficient microwave-assisted synthetic route. Steady-state spectroscopy results indicated that the photocyclization and photocycloreversion reactions were reversible at different pH values. Even though, the acidic condition caused red-shift of the visible light absorption bands and generated a new absorption band at near-IR to IR region in the closed-ring structure but made blue-shift in the absorption spectra of the open-ring isomers. Also, it was showed that the excess amount of proton locked back the photochromic reaction. Results also indicated that the protonated closed-ring isomers of PA-DAEs are hydrophilic, whereas the deprotonated forms and protonated open-ring forms are hydrophobic. In addition to photoswitching and solubility of PA-DAEs under irradiation at different light wavelengths, the thermal stability of P-type PA-DAEs was also monitored in the presence of trifluoroacetic acid at different temperatures as external stimuli.

Progress in Color, Colorants and Coatings published new progress about 219537-97-0. 219537-97-0 belongs to chlorides-buliding-blocks, auxiliary class Fused/Partially Saturated Cycles,Cyclopentenes, name is 5-Chloro-3-[2-(5-chloro-2-methylthien-3-yl)cyclopent-1-en-1-yl]-2-methylthiophene, and the molecular formula is C15H14Cl2S2, Category: chlorides-buliding-blocks.

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

Donzel, Maxime published the artcileBioinspired Photoredox Benzylation of Quinones, SDS of cas: 939-99-1, the publication is Journal of Organic Chemistry (2021), 86(15), 10055-10066, database is CAplus and MEDLINE.

3-Benzylmenadiones were obtained in good yield by using a blue-light-induced photoredox process in the presence of Fe(III), oxygen, and γ-terpinene acting as a hydrogen-atom transfer agent. This methodol. is compatible with a wide variety of diversely substituted 1,4-naphthoquinones as well as various cheap, readily available benzyl bromides with excellent functional group tolerance. The benzylation mechanism was investigated and supports a three-step radical cascade with the key involvement of the photogenerated superoxide anion radical.

Journal of Organic Chemistry published new progress about 939-99-1. 939-99-1 belongs to chlorides-buliding-blocks, auxiliary class Fluoride,Chloride,Benzyl chloride,Benzene, name is 1-(Chloromethyl)-4-(trifluoromethyl)benzene, and the molecular formula is C8H6ClF3, SDS of cas: 939-99-1.

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

Nafie, Mohamed S. published the artcileControl of ER-positive breast cancer by ERα expression inhibition, apoptosis induction, cell cycle arrest using semisynthetic isoeugenol derivatives, Product Details of C7H6Cl2, the publication is Chemico-Biological Interactions (2022), 109753, database is CAplus and MEDLINE.

New semi-synthetic effective and safe anticancer agents isoeugenol derivatives were synthesized, characterized, and screened for their cytotoxic activity against MCF-7. Moreover, their selective cytotoxicity was assessed against MCF-10A. Three derivatives, 2, 8 and 10 were significantly more active than the reference drug 5-FU with IC50 values of 6.59, 8.07 and 9.63 and 30.93 μM, resp. Also interestingly, these derivatives demonstrated some degree of selectivity to cancer cells over normal cells. Furthermore, derivative 2 was subjected to other in vitro experiments against MCF-7 where it inhibited colony formation by 87.5% and lowered ERα concentration to 395.7 pg/mL compared to 1129 pg/mL in untreated control cells. In continuation of the investigation, the apoptotic activity of compound 2, was assessed where it significantly enhanced total apoptotic cell death by 9.16-fold (18.70% compared to 1.64% for the untreated MCF-7 control cells) and arrested the cell cycle at the G2/M phase. Furthermore, the mol. mechanism of apoptotic activity was investigated at both the gene (RT-PCR) and protein (western plotting) levels where upregulation of pro-apoptotic and down regulation of anti-apoptotic genes was detected. Addnl., compound 2 treatment enhanced the antioxidant (GSH, CAT, SOD) activities. Finally, in vivo experiments verified the effective anticancer activity of compound 2 through inhibition of tumor proliferation by 47.6% compared to 22.9% for 5-FU and amelioration of the hematol., biochem., and histopathol. examinations near normal. In effect, compound 2 can be viewed as a promising semi-synthetic derivative of isoeugenol with some degree of selectivity for management of breast cancer through apoptotic induction and ERα downregulation.

Chemico-Biological Interactions published new progress about 620-20-2. 620-20-2 belongs to chlorides-buliding-blocks, auxiliary class Chloride,Benzyl chloride,Benzene, name is 3-Chlorobenzylchloride, and the molecular formula is C7H6Cl2, Product Details of C7H6Cl2.

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

Subiros-Funosas, Ramon published the artcileUse of Oxyma as pH modulatory agent to be used in the prevention of base-driven side reactions and its effect on 2-chlorotrityl chloride resin, Category: chlorides-buliding-blocks, the publication is Biopolymers (2012), 98(2), 89-97, database is CAplus and MEDLINE.

The presence of low pKa N-hydroxylamines is beneficial in peptide chem. as they reduce some base-mediated side reactions. Here we evaluated the applicability and buffering capacity of Et 2-cyano-2-(hydroxyimino)acetate (Oxyma) in the prevention of aspartimide/piperidide formation and Pro-based overcoupling and compared it with the performance of HOBt and HOAt. In addition, the compatibility of these additives with the highly acid-labile 2-chlorotrityl chloride resin is examined © 2011 Wiley Periodicals, Inc. Biopolymers, 2011.

Biopolymers 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 C4H6N2, Category: chlorides-buliding-blocks.

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

Al Musaimi, Othman published the artcileBypassing osmotic shock dilemma in a polystyrene resin using the green solvent cyclopentyl methyl ether (CPME): a morphological perspective, Quality Control of 42074-68-0, the publication is Polymers (Basel, Switzerland) (2019), 11(5), 874, database is CAplus and MEDLINE.

The “osmotic shock” phenomenon is the main thing that is responsible for morphol. structure alteration, which can jeopardize the use of a polymer in a chem. process. This is extremely important in solid-phase peptide synthesis (SPPS), which is the method of choice for the preparation of these important biol. active compounds Herein, we have used Hildebrand solubility parameters (d) to investigate the influence of different ethers that are used in the precipitation step of the SPPS using a polystyrene resin. The green cyclopentyl Me ether (CPME) has shown to be slightly superior to 2-methyltetrahydrofurane, which is also a green ether and clearly better than the hazardous di-Et ether and tert-Bu Me ether. These results have been corroborated by scanning electron microscope (SEM) anal. and computational studies. All together, these confirm the adequacy of CPME for being the ether of choice to be used in SPPS.

Polymers (Basel, Switzerland) 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, Quality Control of 42074-68-0.

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

Yuan, Yunyun published the artcileStructure selectivity relationship studies of 17-cyclopropylmethyl-3,14β-dihydroxy-4,5α-epoxy-6β-[(4′-pyridyl)carboxamido]morphinan derivatives toward the development of the mu opioid receptor antagonists, Name: 2-Chloroisonicotinic acid, the publication is Bioorganic & Medicinal Chemistry Letters (2011), 21(18), 5625-5629, database is CAplus and MEDLINE.

Mu opioid receptor antagonists have been applied to target a variety of diseases clin. The current study is designed to explore the structure selectivity relationship (SSR) of 17-cyclopropylmethyl-3,14β-dihydroxy-4,5α-epoxy-6β-[(4′-pyridyl)carboxamido]morphinan (NAP), a lead compound identified as a selective mu opioid receptor antagonist based on the previous study. Among a series of NAP derivatives synthesized, compounds 6 (NMP) and 9 (NGP) maintained comparable binding affinity, selectivity and efficacy to the lead compound Particularly, the mu opioid receptor selectivity over kappa opioid receptor of NGP was considerably enhanced compared to that of NAP. Overall, the preliminary SSR supported our original hypothesis that an alternate address’ domain may exist in the mu opioid receptor, which favors the ligands carrying a hydrogen bond acceptor and an aromatic system to selectively recognize the mu opioid receptor.

Bioorganic & Medicinal Chemistry Letters published new progress about 6313-54-8. 6313-54-8 belongs to chlorides-buliding-blocks, auxiliary class Pyridine,Chloride,Carboxylic acid, name is 2-Chloroisonicotinic acid, and the molecular formula is C22H18O2, Name: 2-Chloroisonicotinic acid.

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

Yuan, Yunyun published the artcileDesign, Synthesis, and Biological Evaluation of 17-Cyclopropylmethyl-3,14β-dihydroxy-4,5α-epoxy-6β-[(4′-pyridyl)carboxamido]morphinan Derivatives as Peripheral Selective μ Opioid Receptor Agents, Computed Properties of 6313-54-8, the publication is Journal of Medicinal Chemistry (2012), 55(22), 10118-10129, database is CAplus and MEDLINE.

Peripheral selective μ opioid receptor (MOR) antagonists could alleviate the symptoms of opioid-induced constipation (OIC) without compromising the analgesic effect of opioids. However, a variety of adverse effects were associated with them, partially due to their relatively low MOR selectivity. A 6β-N-4′-pyridyl substituted naltrexamine derivative, NAP, I (R = 4-pyridyl) was identified previously as a potent and highly selective MOR antagonist mainly acting within the peripheral nervous system. The noticeable diarrhea associated with it prompted the design and synthesis of its analogs in order to study its structure-activity relationship. Among them, compound I (R = 2-methyl-4-pyridyl) showed improved pharmacol. profiles compared to the original lead, acting mainly at peripheral while increasing the intestinal motility in morphine-pelleted mice (ED₅₀ = 0.03 mg/kg). The slight decrease of the ED₅₀ compared to the original lead was well compensated by the unobserved adverse effect. Hence, this compound seems to be a more promising lead to develop novel therapeutic agents toward OIC.

Journal of Medicinal Chemistry published new progress about 6313-54-8. 6313-54-8 belongs to chlorides-buliding-blocks, auxiliary class Pyridine,Chloride,Carboxylic acid, name is 2-Chloroisonicotinic acid, and the molecular formula is C12H12N2O, Computed Properties of 6313-54-8.

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

Ismail, I. Imam published the artcileReactions with coumarin. VI, Application In Synthesis of 10543-42-7, the publication is Afinidad (2002), 59(498), 151-154, database is CAplus.

The present investigation is designed to study the reaction of some active methylene compounds with coumarin-6-sulfonyl hydrazones, I (X = O, S). The following active methylene compounds were used: malononitrile, Et cyanoacetate, di-Et malonate and 2,4-pentanedione. It was found that, the active methylene compound is added to the double bond of the hydrazone to give an adduct, which cyclized directly to pyrazole or pyrazoline-5-one derivatives, e.g. II.

Afinidad published new progress about 10543-42-7. 10543-42-7 belongs to chlorides-buliding-blocks, auxiliary class Other Aromatic Heterocyclic,Chloride,Sulfonyl chlorides,Ester, name is Coumarin-6-sulfonyl chloride, and the molecular formula is C9H5ClO4S, Application In Synthesis of 10543-42-7.

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

El-Aleem, A. H. Abd published the artcileReactions with coumarin, Related Products of chlorides-buliding-blocks, the publication is Modelling, Measurement & Control, C: Energetics, Chemistry, Earth, Environmental & Biomedical Problems (1994), 46(3), 17-23, database is CAplus.

Some reactions of coumarin-6-sulfonyl chloride (I) with hydrazines or acid hydrazides were investigated. E.g., reaction of I with hydrazine hydrate gave the hydrazino derivative, which reacted with aldehydes or ketones to yield hydrazones.

Modelling, Measurement & Control, C: Energetics, Chemistry, Earth, Environmental & Biomedical Problems published new progress about 10543-42-7. 10543-42-7 belongs to chlorides-buliding-blocks, auxiliary class Other Aromatic Heterocyclic,Chloride,Sulfonyl chlorides,Ester, name is Coumarin-6-sulfonyl chloride, and the molecular formula is C9H5ClO4S, Related Products of chlorides-buliding-blocks.

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