Month: November 2022

Hine, Jack published the artcileEffect of halogen atoms on the reactivity of other halogen atoms in the same molecule. IV. The mechanism of the transformation of vicinal dihalides to olefins by reaction with iodide ion, Computed Properties of 594-81-0, the publication is Journal of the American Chemical Society (1955), 361-4, database is CAplus.

cf. C.A. 48, 10531g. It is shown that the dehalogenation of (CH₂Br)₂, MeCHBrCH₂Br, and EtCHBrCH₂Br by iodide ions is largely initiated by an S_N2 attack to form a bromoiodide which is directly dehalogenated. The dehalogenation of the 2,3-dibromobutanes is believed to be largely direct, as previously suggested. In evidence is the fact that (CH₂Br)₂ is the most reactive of the dibromides mentioned. Furthermore it is shown that the rate constant for the reaction of (CH₂Br)₂ is in excellent agreement with that which would be predicted for the S_N2 reaction of the compound with iodide ion under the conditions employed. It is improbable that a very large fraction of the reaction follows a path involving the formation of a vicinal diiodide. It is proposed that the dehalogenation reaction proper involves the formation of an intermediate in which 1 of the halogen atoms is bound equally to 2 C atoms. F(CH₂)₂Br (about 0.01 mole) was weighed into about 48 cc. MeOH, the solution equilibrated at 40°, mixed with 50 cc. 0.1M KI in MeOH (40°), the mixture diluted to 100 cc., and the iodide ion concentration determined within a few min., by withdrawing a 5-cc. sample and titrating with KIO₃ in cold concentrated HCl; the rate constant was in 2 similar runs 5.49 ± 0.30 and 5.74 ± 0.06 × 10^-6 sec.^-1 mole^-1; no observable amount of iodine was formed in either run.

Journal of the American Chemical Society published new progress about 594-81-0. 594-81-0 belongs to bromides-buliding-blocks, auxiliary class Bromide,Aliphatic hydrocarbon chain, name is 2,3-Dibromo-2,3-dimethylbutane, and the molecular formula is C6H12Br2, Computed Properties of 594-81-0.

Referemce:
https://en.wikipedia.org/wiki/Bromide,
bromide – Wiktionary

Greedy, Benjamin M. published the artcileOrvinols with Mixed Kappa/Mu Opioid Receptor Agonist Activity, Computed Properties of 18928-94-4, the publication is Journal of Medicinal Chemistry (2013), 56(8), 3207-3216, database is CAplus and MEDLINE.

Dual-acting kappa opioid receptor (KOR) agonist and mu opioid receptor (MOR) partial agonist ligands have been put forward as potential treatment agents for cocaine and other psychostimulant abuse. Members of the orvinol series of ligands are known for their high binding affinity to both KOR and MOR, but efficacy at the individual receptors has not been thoroughly evaluated. In this study, it is shown that a predictive model for efficacy at KOR can be derived, with efficacy being controlled by the length of the group attached to C20 and by the introduction of branching into the side chain. In vivo evaluation of two ligands with the desired in vitro profile confirms both display KOR, and to a lesser extent MOR, activity in an analgesic assay suggesting that, in this series, in vitro measures of efficacy using the [³⁵S]GTPγS assay are predictive of the in vivo profile.

Journal of Medicinal Chemistry published new progress about 18928-94-4. 18928-94-4 belongs to bromides-buliding-blocks, auxiliary class Bromide,Aliphatic cyclic hydrocarbon, name is (2-Bromoethyl)cyclopentane, and the molecular formula is C7H13Br, Computed Properties of 18928-94-4.

Referemce:
https://en.wikipedia.org/wiki/Bromide,
bromide – Wiktionary

Ford, E. J. H. published the artcileCellular damage and changes in biliary excretion in a liver lesion of cattle, HPLC of Formula: 518-67-2, the publication is Journal of Pathology and Bacteriology (1962), 39-48, database is CAplus and MEDLINE.

Liver lesions, produced in adult cattle only, by parenteral administration of dimidium bromide can be used to assess a number of tests of hepatic dysfunction. Symptoms of early histol. changes, as detected by liver biopsies, first appeared 30-40 days after injection, and were reflected by marked increases in the serum levels of glutamic-oxalacetic transaminase, lactic dehydrogenase, isocitric dehydrogenase, and glutamic dehydrogenase. The level of glutamic-pyruvic transaminase was unchanged. Significant changes in serum enzyme levels occur even when histol. demonstrable damage is slight. These serum enzyme levels are sensitive indicators of early and mild hepatocellular damage. The later stages of hepatic lesion (40-50 days after injection) are accompanied by a fall in the rate of Bromsulphalein excretion. The phylloerythrin retention which was observed is likely to have been the underlying cause of the photosensitization observed in the original dimidium intoxication in Africa.

Journal of Pathology and Bacteriology published new progress about 518-67-2. 518-67-2 belongs to bromides-buliding-blocks, auxiliary class Other Aromatic Heterocyclic,Salt,Amine,Benzene, name is Dimidium bromide, and the molecular formula is C20H18BrN3, HPLC of Formula: 518-67-2.

Referemce:
https://en.wikipedia.org/wiki/Bromide,
bromide – Wiktionary

Balme, Genevieve published the artcileTotal synthesis of the triquinane marine sesquiterpene (±)-Δ⁹⁽¹²⁾-capnellene using a palladium-catalyzed bis-cyclization step, SDS of cas: 69361-41-7, the publication is Tetrahedron (1994), 50(2), 403-14, database is CAplus.

Details of a novel palladium catalyzed cyclization approach to linear condensed cyclopentanoids are reported. The mechanism of this reaction which involves a δ-ethylenic (or δ-acetylenic) carbon nucleophile and an unsaturated halide is a “Wacker type process” i.e., an attack by the nucleophile onto the unsaturation electrophilically activated by an organopalladium(II) species. In this paper, the authors will show the intramol. version of this reaction which then leads to the tricyclic framework of the sesquiterpene (±)-Δ⁹⁽¹²⁾-capnellene (I; R = Me), the total synthesis of which is described. Thus, cyclopentene II was prepared and underwent palladium-catalyzed cyclization to give triquinane I (R = CO₂Me) which gave I (R = Me) in 2 steps.

Tetrahedron published new progress about 69361-41-7. 69361-41-7 belongs to bromides-buliding-blocks, auxiliary class PROTAC Linker,Aliphatic Linker, name is (4-Bromobut-1-yn-1-yl)trimethylsilane, and the molecular formula is C7H13BrSi, SDS of cas: 69361-41-7.

Referemce:
https://en.wikipedia.org/wiki/Bromide,
bromide – Wiktionary

Olah, George A. published the artcileStable carbonium ions. XLVIII. Halonium ion formation via neighboring halogen participation. Tetramethylethylene halonium ions, Formula: C6H12Br2, the publication is Journal of the American Chemical Society (1967), 89(18), 4744-52, database is CAplus.

cf. preceding abstracts Bridged halonium ions (e.g. I) formed on ionization of 2,3-dihalo-2,3-dimethylbutanes in SbF5-SO2 solution at -60°, when the participating halogen atom is Cl, Br, or iodine. 2,3-Difluoro-2,3-dimethylbutane, on the other hand, gave α-fluoroisopropyl-dimethylcarbonium ion in which the F atom is rapidly exchanging intramolecularly between the two equivalent sites. 2-Halo-3-acetoxy-2,3-dimethylbutanes and 2-halo-3-methoxy-2,3-dimethylbutanes also ionize in SbF5-SO2 to similar ions. Bridged acetoxonium ion formation but not bridged methoxonium ion formation accompany these ionizations. 27 references.

Journal of the American Chemical Society published new progress about 594-81-0. 594-81-0 belongs to bromides-buliding-blocks, auxiliary class Bromide,Aliphatic hydrocarbon chain, name is 2,3-Dibromo-2,3-dimethylbutane, and the molecular formula is C6H12Br2, Formula: C6H12Br2.

Referemce:
https://en.wikipedia.org/wiki/Bromide,
bromide – Wiktionary

Ardon-Munoz, Luis G. published the artcileOxidative Cyclization of 4-(2-Mercaptophenyl)-Substituted 4H-1,2,4-Triazolium Species to Tricyclic Benzothiazolium Salts, Application In Synthesis of 111-83-1, the publication is European Journal of Organic Chemistry (2022), 2022(20), e202200121, database is CAplus.

Herein authors report a generally applicable method for the preparation of N-substituted benzo[4,5]thiazolo[2,3-c][1,2,4]triazol-1-ium salts from air stable precursors. This transformation features selective deprotection of a para-methoxybenzyl protected thiol followed by C-H functionalization of the linked 1,2,4-triazolium salts under oxidative conditions. Using this procedure, authors synthesized a variety of tricyclic thiazolium salts which contain both electron-withdrawing and electron-donating aromatic substituents as well as aliphatic substituents. Authors approach also tolerates many functional groups including alkynes, alcs., diols, amides, and polyethers.

European Journal of Organic Chemistry published new progress about 111-83-1. 111-83-1 belongs to bromides-buliding-blocks, auxiliary class Bromide,Aliphatic hydrocarbon chain, name is 1-Bromooctane, and the molecular formula is C8H17Br, Application In Synthesis of 111-83-1.

Referemce:
https://en.wikipedia.org/wiki/Bromide,
bromide – Wiktionary

Arbuzov, B. A. published the artcileReaction of some chloro and bromo derivatives with sodium diethyl phosphite, Formula: C6H12Br2, the publication is Sbornik Statei po Obshchei Khimii (1953), 1144-8, database is CAplus.

(EtO)₂PONa from 0.9 g. Na and 5.35 g. (EtO)₂POH in Et₂O was treated with 10 g. Ph₂CHBr in Et₂O-C₆H₆; after 2 hrs. on the steam bath the filtered solution gave on evaporation 61.33% (CHPh₂)₂ and 5.3 g. yellow oil. No reaction took place when (EtO)₂PONa, prepared as above, was treated with Ph₂CHCl; the reaction also failed in hot (iso-Am)₂O. The reaction did proceed in refluxing MePh (2 hrs.), yielding (EtO)₂POH, Ph₂CHOH, (Ph₂CH)₂O, and a low yield of Ph₂CHP(O)(OEt)₂, b₄ 184-8°, d₀²⁰ 1.12775, n_D²⁰ 1.5450, m. 38-40°; hydrolyzed with 10% HCl 8 hrs. at 170-5° in a sealed tube, it gave the free acid, m. 223-5° (from H₂O). Addition of 8 g. (EtO)₃P in Et₂O to 12 g. Ph₂CHBr in Et₂O, followed by refluxing 1 hr. gave 43.6% yield of the same product, b₂ 180-1°, d₀²⁰ 1.1287, n_D²⁰ 1.5445, which slowly solidified and m. 39-40°; hydrolysis with 10% HCl at 150-80° gave the free acid, m. 227-8°. Addition of 13.8 g. PhCH₂Cl to (EtO)₂ONa from 15.6 g. ester in Et₂O, followed by 0.5 hr. reflux gave 49.35% PhCH₂P(O)(OEt)₂, b₁₁ 153-4°, d₀⁰ 1.1200, n_D²⁰ 1.4965; hydrolysis gave the free acid, m. 169-70° (from EtOH). Similar reaction with PhCH₂Br gave 44% yield of the same ester, b₁₂ 153-5°, d₀⁰ 1.1189, n_D²⁰ 1.4892, while PhCH₂I gave 21.1% yield of the same ester. To (EtO)₂PONa (from 15.85 g. ester) in Et₂O was added 14 g. (Me₂CBr)₂ resulting in a rapid reaction (7 min.); after filtration the mixture yielded 50% Me₂C:CMe₂.

Sbornik Statei po Obshchei Khimii published new progress about 594-81-0. 594-81-0 belongs to bromides-buliding-blocks, auxiliary class Bromide,Aliphatic hydrocarbon chain, name is 2,3-Dibromo-2,3-dimethylbutane, and the molecular formula is C6H12Br2, Formula: C6H12Br2.

Referemce:
https://en.wikipedia.org/wiki/Bromide,
bromide – Wiktionary

Negishi, Eiichi published the artcileMetal promoted cyclization. 18. Novel cycloalkylation reactions of (ω-halo-1-alkenyl)metal derivatives. Synthetic scope and mechanism, SDS of cas: 69361-41-7, the publication is Journal of the American Chemical Society (1988), 110(16), 5383-96, database is CAplus.

(ω-Haloalkenyl)metals undergo both σ- and π-type cyclization reactions. The σ-cycloalkylation reaction, which has so far been observed only with alkenyllithiums, provides 3- through 7-membered rings in high yields. It requires the cis relationship between Li and the ω-haloalkyl group in the cyclization step. The presence of a trialkylsilyl group on the Li-bearing C atom facilitates configurational isomerization. However, it is not necessary for cyclization. The reaction proceeds with retention of regiochem. The cycloalkylation reactions of (ω-halo-1-silyl-1-alkenyl)metals containing Al, Zn, Zr, or Si, on the other hand, proceed via π-type cyclization processes. Thus, cyclization of X(CH₂)₂CMe:C(SiMe₃)(AlMe₂), prepared by the reaction of X(CH₂)₂CCSiMe₃ (X = Cl, Br, iodo, 4-MeC₆H₄SO₂) with Me₃Al in presence of (η⁵-C₅H₅)₂ZrCl₂ in CH₂Cl₂, gave 2-methyl-1-(trimethylsilyl)cyclobutene. The relative ease of ring formation with respect to ring size is 3 and 4 ≫ 5 < 6. Formation of cyclobutenylsilanes is nonregiospecific. The stereochem. of alkenylmetal intermediates is unimportant, but the presence of a silyl group as the second metal group is necessary. The reaction can be inhibited by some polar solvents, such as THF. All of these facts can be accommodated by π-cyclization mechanisms and Baldwin’s cyclization rules.

Journal of the American Chemical Society published new progress about 69361-41-7. 69361-41-7 belongs to bromides-buliding-blocks, auxiliary class PROTAC Linker,Aliphatic Linker, name is (4-Bromobut-1-yn-1-yl)trimethylsilane, and the molecular formula is C7H13BrSi, SDS of cas: 69361-41-7.

Referemce:
https://en.wikipedia.org/wiki/Bromide,
bromide – Wiktionary

Negishi, Eiichi published the artcileNovel silicon-promoted cycloalkylation of alkenylmetal derivatives, Category: bromides-buliding-blocks, the publication is Journal of the American Chemical Society (1983), 105(20), 6344-6, database is CAplus.

Two novel cycloalkylation reactions of alkenylmetals, in which Si plays subtle but critical roles, are described. Such cycloalkylation reactions appear to be unprecedented. Significantly, neither appears to be affected by the stereochem. integrity of alkenylmetal intermediates. Together, they provide novel and convenient routes to cycloalkenylsilanes. X(CH₂)₂CCSiMe₃ (I, X = C, Br, I) are either hydroaluminated with diisobutylaluminum hydride or carboaluminated with Me₃Al-Cl₂ZrCp₂ in nonpolar solvents, such as hexane, benzene or (CH₂Cl)₂, and were converted into 1-trimethylsilyl-1-cyclobutene and its derivatives in 80-100% yields. The available data suggest that the reaction involves a π-type process via cyclopropylcarbinyl cationic series. A similar reaction occurs with 1-trimethylsilylpropargyl bromide. Its reaction with Me₃Al-Cl₂ZrCp₂ gives II instead of III. Application of the method to the preparation of five- and six-membered alkenylsilanes have not been successful. Fortunately, an alternate procedure was developed which presumably involves a σ-type process. Thus, treatment of appropriate ω-bromo-1-trimethylsilyl-1-iodo-1-alkenes with 2 equivalent of Me₃CLi in ether at -78° followed by gradual warming has produced 1-trimethyl-1-cycloalkenes containing four-, five-, and six-membered rings in 64-81% yields. The synthetic utility of these cyclization reactions may be indicated by a 4-step conversion of I to grandisol (IV) as a 2:1 mixture of the Z and E isomers in overall 40% yield.

Journal of the American Chemical Society published new progress about 69361-41-7. 69361-41-7 belongs to bromides-buliding-blocks, auxiliary class PROTAC Linker,Aliphatic Linker, name is (4-Bromobut-1-yn-1-yl)trimethylsilane, and the molecular formula is C7H13BrSi, Category: bromides-buliding-blocks.

Referemce:
https://en.wikipedia.org/wiki/Bromide,
bromide – Wiktionary

Nikiforov, Petar O. published the artcileFragment-Sized EthR Inhibitors Exhibit Exceptionally Strong Ethionamide Boosting Effect in Whole-Cell Mycobacterium tuberculosis Assays, Name: (2-Bromoethyl)cyclopentane, the publication is ACS Chemical Biology (2017), 12(5), 1390-1396, database is CAplus and MEDLINE.

Small-mol. inhibitors of the mycobacterial transcriptional repressor EthR have previously been shown to act as boosters of the second-line antituberculosis drug ethionamide. Fragment-based drug discovery approaches have been used in the past to make highly potent EthR inhibitors with ethionamide boosting activity both in vitro and ex vivo. Herein, we report the development of fragment-sized EthR ligands with nanomolar min. effective concentration values for boosting the ethionamide activity in Mycobacterium tuberculosis whole-cell assays.

ACS Chemical Biology published new progress about 18928-94-4. 18928-94-4 belongs to bromides-buliding-blocks, auxiliary class Bromide,Aliphatic cyclic hydrocarbon, name is (2-Bromoethyl)cyclopentane, and the molecular formula is C7H13Br, Name: (2-Bromoethyl)cyclopentane.

Referemce:
https://en.wikipedia.org/wiki/Bromide,
bromide – Wiktionary