Month: December 2022

Wang, Dengjin published the artcileOne-Carbon Chain Extension of Esters to α-Chloroketones: A Safer Route without Diazomethane, Name: trimethyloxosulphonium chloride, the publication is Journal of Organic Chemistry (2004), 69(5), 1629-1633, database is CAplus and MEDLINE.

The reaction of a variety of Me esters with dimethylsulfoxonium methylide at 0-25 °C affords the chain-extended β-keto dimethylsulfoxonium ylides. Subsequent treatment with hydrogen chloride in THF proceeds with loss of DMSO to afford the corresponding α-chloro ketones. This sequence has been utilized to convert the Me esters of CBZ-protected alanine and valine to the anti N-protected α-amino epoxides, which are important pharmaceutical intermediates. When the same protocol is applied to BOC-protected phenylalanine Me ester, epimerization occurs so that the use of a more reactive aryl ester is required. This chem. provides a practical route to α-chloroketones that avoids the use of toxic and explosive diazomethane.

Journal of Organic Chemistry published new progress about 5034-06-0. 5034-06-0 belongs to chlorides-buliding-blocks, auxiliary class Salt,Aliphatic hydrocarbon chain, name is trimethyloxosulphonium chloride, and the molecular formula is C11H14O2, Name: trimethyloxosulphonium chloride.

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

Spinnato, Davide published the artcileA Photochemical Organocatalytic Strategy for the α-Alkylation of Ketones by using Radicals, Formula: C8H6ClF3, the publication is Angewandte Chemie, International Edition (2020), 59(24), 9485-9490, database is CAplus and MEDLINE.

Reported herein is a visible-light-mediated radical approach to the α-alkylation of ketones. This method exploits the ability of a nucleophilic organocatalyst to generate radicals upon S_N2-based activation of alkyl halides and blue light irradiation The resulting open-shell intermediates are then intercepted by weakly nucleophilic silyl enol ethers, which would be unable to directly attack the alkyl halides through a traditional two-electron path. The mild reaction conditions allowed functionalization of the α position of ketones with functional groups that are not compatible with classical anionic strategies. In addition, the redox-neutral nature of this process makes it compatible with a cinchona-based primary amine catalyst, which was used to develop a rare example of enantioselective organocatalytic radical α-alkylation of ketones. Thus, e.g., treatment of acetophenone O-TBS silyl enol ether with chloroacetonitrile afforded I (91%) in presence of dithiocarbonyl catalyst II using blue LED irradiation and TFA or TBAF workup.

Angewandte Chemie, International Edition 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 C9H10O3S, Formula: C8H6ClF3.

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

Bourquin, J. P. published the artcileSyntheses in the phenothiazine family. II. N-Substituted phenothiazinethiol derivatives, Formula: C5H13Cl2N, the publication is Helvetica Chimica Acta (1958), 1072-108, database is CAplus.

cf. C.A. 52, 18423d. 2-(N-Methyl-2-pyrrolidyl)ethanol (31.0 g.) in 200 ml. CHCl₃ treated with HCl 10 min. at 10°, 59.0 g. SOCl₂ added, after 2 hrs. at 70° the mixture concentrated, treated with 160 ml. 3N NaOH, extracted with Et₂O, and the dried extracts distilled gave 90% 2-(N-methyl-2-pyrrolidyl)-1-chloroethane (I), b₁₁ 65-6°; picrate, m. 133-5° (EtOH). BuNHMe (60.9 g.) and 54.6 g. Br(CH₂)₃Cl in boiling Et₂O 24 hrs. gave 68% BuMeN(CH₂)₃Cl, b₁₃ 71-2°; picrate, m. 94-6° (EtOH). BrCH₂CHMeCH₂Cl (68.6 g.), 36.0 g. Me₂NH, and 20 ml. C₆H₆ heated in an autoclave at 110° 7 hrs., 100 ml. H₂O and 320 ml. 10% HCl added, and the mixture extracted with 250 ml. Et₂O and 140 ml. 30% NaOH gave 68% Me₂NCH₂CHMeCH₂Cl, b₁₁ 35-6°. To 50.0 g. N-methylpiperazine in 150 ml. MeOH was added 37.7 g. propylene oxide, the mixture boiled 3 hrs., and distilled giving 70% N-methyl-N’-(2-hydroxypropyl)piperazine (II), b₁₁ 91-3°. II (50.7 g.) in 250 ml. C₆H₆ saturated with HCl, 78.2 g. SOCl₂ added, the mixture refluxed 5 hrs. then concentrated, 100 ml. H₂O and 120 ml. 30% NaOH added, the mixture extracted with 600 ml. C₆H₆, and the extract distilled gave 60% N-methyl-N’-(2-chloropropyl)piperazine, b₁₁ 87-9°; di-HCl salt, m. 233-5° (EtOH). N-Methylpiperazine (46.8 g.) and 40 g. BrCH₂CHMeCH₂Cl in 120 ml. refluxing Et₂O 24 hrs. gave 30% N-methyl-N’-(3-chloro-2-methylpropyl)piperazine, b₁₁ 99-100°; di-HCl salt, m. 234-6° (MeOH). Similarly, 233 g. N-benzylpiperazine and 104 g. Br(CH₂)₃Cl in 370 ml. Et₂O 48 hrs. gave 75% N-benzyl-N’-(3-chloropropyl)piperazine, b_0.01 132-6°; di-HCl salt, m. 249-51° (absolute EtOH). 2-(Methylthio)phenothiazine (III) (16.65 g.), 3.18 g. NaNH₂, and 100 ml. absolute xylene refluxed 3 hrs., 10.0 g. I in 10 ml. absolute xylene added during 1.5 hrs., after refluxing 3 hrs. and cooling 5 g. NH₄Cl and 150 ml. H₂O added, the xylene layer extracted with 115 ml. 15% tartaric acid, 35 ml. concentrated NaOH added, and the freed base extracted with 100 ml. C₆H₆ gave 85% 10-[2-(N-methyl-2-pyrrolidyl)ethyl]-2-(methylthio)phenothiazine, b_0.008 209°; tartrate, sintered 70°, m. 115°. Similarly prepared were the following 10-[2-(N-methyl-2-pyrrolidyl)ethyl]-2-(alkylthio)phenothiazines (alkyl groups given): Et, b_0.01 213° (tartrate-0.5-H₂O, sintered 65°, m. 90°); iso-Pr, b_0.008 217° (tartrate-0.5H₂O, sintered 70°, m. 90°); Bu, b_0.01 225° (tartrate-0.5H₂O, sintered 60°, m. 75°). 10-[2-(N-Methyl-2-piperidyl)ethyl]-2-(alkylthio)phenothiazines (alkyl groups given): Et (IV) [80% from 18.89 g. 2-(ethylthio)phenothiazine (V) and 14.7 g. 2-(N-methyl-2-piperidyl)-1-chloroethane], b_0.008, m. 57-9° (iso-PrOH) (tartrate, sintered 70°, decompose 135°); Pr, b_0.01 247° (tartrate, sintered 70°, decompose 120°); iso-Pr, b_0.05 223°, m. 73-5° (tartrate, sintered 70°, decompose 120°); Bu, b_0.005 227°; iso-Bu, b_0.003 215°; sec-Bu, b_0.007 215°; n-hexyl, b_0.015 235°; PhCH₂ (VI), b_0.01 246° (tartrate-0.5-H₂O, sintered 75°, m. 105°). 10-(N-Methyl-3-piperidylmethyl)-2-alkylphenothiazines (alkyl groups given): Me [60% from 50.0 g. III and 33.8 g. N-methyl-3-(chloromethyl)piperidine], b_0.01 207° [HCl salt, sintered 110°, decompose 124-6° (Me₂CO); tartrate-0.5H₂O, sintered 75°, decompose 140° (EtOAc); oxalate, decompose 182-4° (absolute EtOH)]; Et, b_0.01 222° (tartrate, sintered 75°, m. 140°); Pr, b_0.01 225°, sintered 85°, m. 145°; iso-Pr, b_0.01 216° (tartrate-0.5H₂O, sintered 75°, decompose 140°); Bu, b_0.01 223° (tartrate, sintered 80°, decompose 100°); iso-Bu, b_0.005 207° (tartrate-0.5H₂O, sintered 85°, m. 120°); sec-Bu, b_0.005 206°, tartrate-0.5H₂O, sintered 80°, m. 110°); PhCH₂, b_0.007 236° (tartrate-H₂O, sintered 90°, m. 120°). 10-(3-Dimethylaminopropyl)-2-(alkylthio)phenothiazines (alkyl group given): Et (80-5% from 20.0 g. V and 11.3 g. Me₂N(CH₂)₃Cl), b_0.008 200° [tartrate, sintered 110°, m. 117-9° (absolute EtOH)]; Pr, b_0.02 227° (tartrate-0.5H₂O, sintered 55°, decompose 90°); iso-Pr, b_0.01 198° (tartrate-0.5H₂O, sintered 60°, decompose 90°; oxalate, decompose 206-8°); Bu, b_0.005 202°; iso-Bu, b_0.004 195°; sec-Bu, b_0.006 189°; PhCH₂, b_0.01 224° (tartrate, sintered 65°, m. 85°). 10-Dialkylaminoalkyl-2-(methylthio)phenothiazines (dialkylaminoalkyl groups given): Me₂NCH₂CH₂ (85% from 50.0 g. III and 22.0 g. Me₂NCH₂CH₂Cl), b_0.01 195-6°, m. 72-4° (iso-PrOH) [HCl salt, m. 175-7° (absolute EtOH)]; Et₂NCH₂CH₂, b_0.01 198° (HCl salt, m. 160-2°); Et₂NCHMeCH₂, b_0.01 182° (HCl salt, sintered 194°, m. 202-4°); 2-(N-pyrrolidyl)ethyl, b_0.01 219-21°, m. 73-5° (HCl salt, m. 170-2°); 2-(N-methyl-N’-piperazyl)ethyl, b_0.02 228-30°, m. 85-7° (di-HCl salt, decompose 243-5°); 3-(N-piperidyl)propyl, b_0.05 235-7° (tartrate, sintered 65°, decompose 100°; methobromide, sintered 165°, m. 178-80°); 3-(N-benzyl-N’-piperazyl)propyl, m. 82-4° (di-HCl salt, sintered 225°, decompose 236-8°); 3-(N-morpholyl)propyl, b_0.03 240-2°, m. 100-2° (HCl salt, sintered 146°, m. 152-4°); 2-(N-pyrrolidyl)propyl, b_0.015 204° (HCl salt, m. 177-9°); 2-(N-methyl-N’-piperazyl)propyl, b_0.01 211° (di-HCl salt-0.5H₂O, sintered 210°, m. 224-6°). 10-Dialkylaminoalkyl-2-(isopropylthio)phenothiazines: Me₂NCH₂CH₂, b_0.015 189° (HCl salt, m. 182-4°); Et₂NCH₂CH₂, b_0.01 187° (HCl salt, m. 162-4°);

Helvetica Chimica Acta published new progress about 4584-49-0. 4584-49-0 belongs to chlorides-buliding-blocks, auxiliary class Chloride,Salt,Amine,Aliphatic hydrocarbon chain, name is 2-Chloro-N,N-dimethylpropan-1-amine hydrochloride, and the molecular formula is C5H13Cl2N, Formula: C5H13Cl2N.

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

Rehder, Dieter published the artcileWater and bromide in the active center of vanadate-dependent haloperoxidases, HPLC of Formula: 19652-33-6, the publication is Journal of Inorganic Biochemistry (2000), 80(1-2), 115-121, database is CAplus and MEDLINE.

Two aqua-oxovanadium complexes, viz. [A-VO(H₂O)(sal-L-Leu)] (I) and [VO(H₂O)₂(5-Br-sal-Gly)]·H₂O(II·H₂O ), containing the water ligands in cis- and trans-positions to the oxo group at V-OH₂ distances ranging from 2.008 to 2.228 Å, have been structurally characterized in order to model the apical electron d. feature found in the structures of fungal and algal vanadate-dependent peroxidases. Br K-edge XAS of bromide-treated bromoperoxidase from Ascophyllum nodosum and model compounds (including II·H₂O) has been used to show that the substrate bromide does not bind to active site vanadium but to a light atom, possibly carbon, in its vicinity.

Journal of Inorganic Biochemistry published new progress about 19652-33-6. 19652-33-6 belongs to chlorides-buliding-blocks, auxiliary class Chloride,Bromide,Benzene,Phenol,Aldehyde, name is 5-Bromo-3-chloro-2-hydroxybenzaldehyde, and the molecular formula is C7H4BrClO2, HPLC of Formula: 19652-33-6.

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

Bazzi, Sakna published the artcileElectrogenerated Sm(II)-Catalyzed CO₂ Activation for Carboxylation of Benzyl Halides, Quality Control of 939-99-1, the publication is Organic Letters (2019), 21(24), 10033-10037, database is CAplus and MEDLINE.

Sm(II)-catalyzed carboxylation of benzyl halides is reported through the electrochem. reduction of CO₂. The transformation proceeds under mild reaction conditions to afford the corresponding phenylacetic acids in good to excellent yields. This user-friendly and operationally simple protocol represents an alternative to traditional strategies, which usually proceeds through the C(sp³)-halide activation pathway.

Organic Letters 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, Quality Control of 939-99-1.

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

Markushyna, Yevheniia published the artcileChromoselective Synthesis of Sulfonyl Chlorides and Sulfonamides with Potassium Poly(heptazine imide) Photocatalyst, Quality Control of 939-99-1, the publication is Angewandte Chemie, International Edition (2021), 60(37), 20543-20550, database is CAplus and MEDLINE.

Among external stimuli used to promote a chem. reaction, photocatalysis possesses a unique one-light. Photons are traceless reagents that provide an exclusive opportunity to alter chemoselectivity of the photocatalytic reaction varying the color of incident light. This strategy may be implemented by using a sensitizer capable to activate a specific reaction pathway depending on the excitation light. Herein, we use potassium poly(heptazine imide) (K-PHI), a type of carbon nitride, to generate selectively three different products from S-arylthioacetates simply varying the excitation light and otherwise identical conditions. Namely, arylchlorides are produced under UV/purple, sulfonyl chlorides with blue/white, and diaryl disulfides at green to red light (e.g., S-Ph thioacetate → benzenesulfonyl chloride (93%) under blue light irradiation using HCl in water/MeCN and O₂ as electron acceptor). A combination of the neg. charged polyanion, highly pos. potential of the valence band, presence of intraband states, ability to sensitize singlet oxygen, and multi-electron transfer is shown to enable this chromoselective conversion of thioacetates.

Angewandte Chemie, International Edition 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, Quality Control of 939-99-1.

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

Jones, Richard T. published the artcileChromatography of human hemoglobin. Factors influencing chromatography and differentiation of similar hemoglobins, Related Products of chlorides-buliding-blocks, the publication is Journal of Chromatography (1963), 421-31, database is CAplus and MEDLINE.

The method of Allen, et al. (CA 52, 10344d) and its modifications for hemoglobin (I) determination are reviewed. The methods are affected by temperature, pH, and ionic concentration of developers, state of equilibrium of the Amberlite IRC-50, amount of I, and oxidation state of the heme in the I applied. By the use of a radioactive tracer technique, differences in the chromatographic behavior of I S and I D and of the ferrihemoglobin cyanide and oxyhemoglobin forms of I F were demonstrated.

Journal of Chromatography 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, Related Products of chlorides-buliding-blocks.

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

Kamenova-Nacheva, Mariana published the artcileSynthesis of ferrocenylmethylidene and arylidene substituted camphane based compounds as potential anticancer agents, HPLC of Formula: 21286-54-4, the publication is New Journal of Chemistry (2017), 41(17), 9103-9112, database is CAplus.

Herein is described the synthesis of (+)-camphor derivatives containing sulfonamide groups, ferrocenylmethylidene or arylidene moieties. The obtained derivatives were tested against seven human cancer cells lines, namely BV-173, K-256a, NB-4, A549, H1299, MCF-7, and MDA-MB231, and two normal human cell lines, HEK293 and HUVEC, to determine their activity against malignant cells. Some of them exhibit IC₅₀ values below 10 μM in at least one of the cancer cell lines. Ferrocenylmethylidene ketone 16 (1-((1S,4S)-3-((E)-ferrocenylmethylidene)-7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)-N-(tert-butyl)methanesulfonamide) can be outlined as the most potent and selective in the current study (IC₅₀ for cancer cells – up to 4.0 μM; IC₅₀ for HEK293 and HUVEC – 68 and 69 μM, resp.). There is a clear trend showing that the presence of a conjugated ferrocenylmethylidene group is essential for the cytotoxicity, however different sulfonamide substituents and derivatization of the carbonyl group can modify the activity. Thus, this class of compounds could have good prospects for further structural optimization.

New Journal of Chemistry 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, HPLC of Formula: 21286-54-4.

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

Wodtke, Robert published the artcileSynthesis and kinetic characterization of water-soluble fluorogenic acyl donors for transglutaminase 2, Application of 2-Chlorotrityl chloride, the publication is ChemBioChem (2016), 17(13), 1263-1281, database is CAplus and MEDLINE.

Small Glu-containing peptides bearing coumarin derivatives as fluorescent leaving groups attached to the γ-carboxylic acid group of the Glu residue were synthesized and investigated with regard to their potential to act as substrates for transglutaminase 2 (TGase 2). Their synthesis was accomplished by an efficient solid-phase approach. The excellent water solubility of the compounds enabled their extensive kinetic characterization in the context of TGase 2-catalyzed hydrolysis and aminolysis. The influence of the coumarin skeleton’s substitution pattern on the kinetic properties was studied. Derivatives containing 7-hydroxy-4-methylcoumarin (HMC) revealed properties superior to those of their 7-hydroxycoumarin counterparts; analogous amides were not accepted as substrates. Z-Glu(HMC)-Gly-OH, which exhibited the best substrate properties out of the investigated derivatives, was selected for representative kinetic characterization of acyl acceptor substrates and irreversible inhibitors.

ChemBioChem 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 C7H13BrSi, Application of 2-Chlorotrityl chloride.

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

Selmani, Aymane published the artcileTransition-Metal-Free, Formal C-H Germylation of Arenes and Styrenes via Dibenzothiophenium Salts, Application In Synthesis of 637-07-0, the publication is Organic Letters (2021), 23(12), 4779-4784, database is CAplus and MEDLINE.

We report an operationally simple, selective, and transition-metal-free germylation of arenes and styrenes at room temperature, using a robust and bench-stable Ge source (R₃Ge-SiR₃) and dibenzothiophenium salts as enabling intermediates. The first direct engagement in cross-coupling of the newly made E-alkenyl germanes is also presented, allowing the chemoselective arylation under air-tolerant nanoparticle catalysis.

Organic Letters published new progress about 637-07-0. 637-07-0 belongs to chlorides-buliding-blocks, auxiliary class Inhibitor,Cell Cycle,PPAR, name is Ethyl 2-(4-chlorophenoxy)-2-methylpropanoate, and the molecular formula is C16H12O, Application In Synthesis of 637-07-0.

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