Category: bromides-buliding-blocks

Wollweber, H. published the artcile1-Phenethyl-2-iminoimidazolidines, a new class of compounds with ganglion-regulating activity, SDS of cas: 1997-80-4, the publication is Med. Chem., Abhandl. Med. Chem. Forschungsstaetten Farbwerke Hoechst A.G. (1963), 248-61, database is CAplus.

To a solution of the Grignard reagent from 225 g. 3-Br-C₆H₄CF₃, 26 g. Mg, and 500 ml. Et₂O was added dropwise a solution of 44 g. ethylene oxide in 200 ml. Et₂O to give after hydrolysis with aqueous NH₄Cl 74.9 g. 3-F₃CC₆H₄CH₂CH₂OH (I), b₁₂ 102-6°. I (38 g.) was saturated at 100° with dry HBr to give 45 g. 3-F₃CC₆H₄CH₂CH₂Br (II), b₁₂ 92-4°. A mixture of 45 g. II and 50 g. (CH₂NH₂)₂ was refluxed overnight, distilled in vacuo, the residue basified, and the oil separated to give 19.4 g. 3-F₃CC₆H₄CH₂CH₂-NHC₂H₄NH₂, b_0.15 96-8°. A mixture of 80 g. PhCH₂CH₂Cl and 160 g. H₂NCH₂CH₂NHCO₂Et was refluxed 8 hrs. to give 62 g. PhCH₂CH₂NHCH₂CH₂NHCO₂Et (III), b_0.05 140°. III (53 g.) in 500 ml. Et₂O was reduced with LiAlH₄ to give 16.1 g. PhCH₂CH₂NHCH₂CH₂NHMe, b₁₂ 84-6°. A mixture of 55 g. PhCH₂CH₂NHCH₂CH₂NH₂ (IV), 47 g. S-methylisothiuronium sulfate, 200 ml. EtOH. and 40 ml. water was refluxed 2 hrs. to give 80 g. 2PhCH₂CH₂NHCH₂CH₂NHC(:NH)NH₂.H₂SO₄ (V), m. 188° (decomposition) (EtOH-AcOEt). V (60 g.) was heated 1.5 hrs. at 150-60, 200 ml. amyl alc. added, and the mixture refluxed 6 hrs. to give 28 g. VI (R¹ = R² = R³ = R⁴ = R⁵ = R⁶ = R⁷ = H, m = n = 1, X = NH) (VII).0.5 H₂SO₄, m. 206.5-7.5°. A solution of 10.6 g. BrCN in 50 ml. benzene was added dropwise at 20-30° to a solution of 18 g. IV in 100 ml. benzene and the mixture stirred 1 hr. to give VII HBr salt, m. 144-6° (AcOEt). PhCH₂CH₂NHCH₂CH₂OH with concentrated HBr at 170° gave PhCH₂CH₂NHCH₂CH₂Br HBr salt, m. 173-5°; this (15.5 g.) in 45 ml. water treated with a solution of 4.05 g. KOCN in 10 ml. water gave an oil which slowly dissolved upon vigorous shaking. After 0.5 hr. the solution was treated with K₂CO₃ and the oil extracted with CH₂Cl₂ to give 8.5 g. X = O analog of VII, b_0.25 122-5°; HCl salt m. 178-9°. Similarly prepared were VI (R¹, R¹, R¹, R¹, R¹, R², R², n, m, m, m.p. HBr salt, and b.p./mm. of diamine corresponding to IV given): H, H, OMe, H, H, H, H, 1, 1, NH, 166-7°, 140°/0.1; H, OMe, H, H, H, H, H, 1, 1, NH, 139°, 124°/0.1; H, (R²R³ =) CH₂O₂, H, H, H, H, 1, 1, NH, 217°, 130°/0.2; H, H, Me, H, H, H, H, 1, 1, NH, 193-5°, 100°/0.2; H, Me, H, H, H, H, H, 1, 1, NH, 148-9°, 116°/0.5; Me, H, H, H, H, H, H, 1, 1, NH, 173-5°, 118°/0.2; H, H, Cl, H, H, H, H, 1, 1, NH, 187°, 112°/0.1; H, Cl, H, H, H, H, H, 1, 1, NH, 138°, 110°/0.05; H, H, H, H, H, H, H, 1, 1, NMe, 180°, 85°/12; H, H, H, H, H, H, Me, 1, 1, NH, 186-7°, 90°/0.1; H, H, H, H, H, Me, H, 1, 1, NH, 111-13°, 80°/0.1; H, OMe, H, H, Me, Me, H, 1, 1, NH, 156°, 125°/0.05; H, H, H, OH, H, H, H, 1, 1, NH, 173°, 164°/0.05; H, H, H, H, H, H, H, 1, 0, NH, 202-3°, 84°/0.2; Cl, H, H, H, H, H, H, 1, 0, NH, 270-3° (decomposition) (1/2H₂SO₄ salt), 102°/0.1. Also prepared were VIII (R¹, R², m.p. HBr salt, and b.p./mm. diamine given): H, H, 153°, 100°/0.1; H, Me, 140°, 125°/12; Me, H, 115-17°, 126°/12. Similarly prepared from α-phenyl-ethylenediamine, b_0.3 84°, was 4-phenyl-2-iminoimidazolidine HBr salt, m. 177°. Toxicity and pharmacol. data are given for all compounds

Med. Chem., Abhandl. Med. Chem. Forschungsstaetten Farbwerke Hoechst A.G. published new progress about 1997-80-4. 1997-80-4 belongs to bromides-buliding-blocks, auxiliary class Trifluoromethyl,Fluoride,Bromide,Benzene, name is 1-(2-Bromoethyl)-3-(trifluoromethyl)benzene, and the molecular formula is C12H9N3O4, SDS of cas: 1997-80-4.

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

Song, Bingrui published the artcilePalladium/Copper-Catalyzed Di-α-arylation of Acetic Acid Esters, Name: Bromo(1,10-phenanthroline)(triphenylphosphine)copper(I), the publication is Advanced Synthesis & Catalysis (2011), 353(10), 1688-1694, database is CAplus.

A bimetallic palladium/copper catalyst system was found to effectively promote the diarylation of alkyl acetates with aryl halides under unprecedentedly mild conditions. The phenanthroline-copper-phosphine catalyst stabilizes the enolate intermediate to the extent that the deprotonation of esters can be achieved even with the mild base potassium phosphate. The palladium tri-tert-butylphosphine co-catalyst mediates the coupling of the resulting copper enolate with a wide variety of aryl halides with selective formation of the corresponding diarylacetic acid esters.

Advanced Synthesis & Catalysis published new progress about 25753-84-8. 25753-84-8 belongs to bromides-buliding-blocks, auxiliary class Copper, name is Bromo(1,10-phenanthroline)(triphenylphosphine)copper(I), and the molecular formula is C10H14O, Name: Bromo(1,10-phenanthroline)(triphenylphosphine)copper(I).

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

Mukai, Chisato published the artcileRh(I)-catalyzed allenic Pauson-Khand reaction: first construction of the bicyclo[6.3.0]undecadienone ring system, Category: bromides-buliding-blocks, the publication is Tetrahedron (2005), 61(46), 10983-10994, database is CAplus.

The Rh(I)-catalyzed Pauson-Khand reaction of allenynes afforded the bicyclo[6.3.0]undecadienones as well as their benzo and furo derivatives E.g., [RhCl(CO)₂]₂ catalyzed the Pauson-Khand reaction of CH₂:C:C(SO₂Ph)CH₂C(CO₂Me)₂(CH₂)₃CCPh to give 43% bicyclo[6.3.0] compound I. In addition, a novel [RhCl(CO)₂]₂-catalyzed [2,3]-sigmatropic rearrangement of the sulfinic ester species of propargyl alcs. was developed. E.g., [RhCl(CO)₂]₂ catalyzed the [2,3]-sigmatropic rearrangement of PhCCCH₂OSOPh to give 63% PhSO₂CPh:C:CH₂.

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, Category: bromides-buliding-blocks.

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

Wang, Bing Hui published the artcileInhibition of eukaryote protein kinases by isoquinoline and oxazine alkaloids, SDS of cas: 518-67-2, the publication is Planta Medica (1997), 63(6), 494-498, database is CAplus and MEDLINE.

The aporphine isoquinoline alkaloid apomorphine is a potent inhibitor of the catalytic subunit (cAK) of rat liver cAMP-dependent protein kinase (PKA), myosin light chain kinase (MLCK), and Ca²⁺– and phospholipid-dependent protein kinase C (PKC) (IC₅₀ values 1, 11, and 8 μM, resp.). However, a number of O-methylated analogs of apomorphine are inactive or poor inhibitors of cAK. The benzophenanthridine isoquinoline alkaloid sanguinarine is a potent inhibitor of cAK but is a relatively poor inhibitor of PKC (IC₅₀ values 6 and 217 μM, resp.). However a number of methylated analogs of sanguinarine are inactive as cAK inhibitors. The aporphine isoquinoline alkaloids (+)-boldine and bulbocapnine are noncompetitive inhibitors of MLCK with respect to both peptide substrate and ATP. The inhibition of cAK, MLCK, and PKC by apomorphine and sanguinarine is competitive with respect to ATP as substrate. The oxazine alkaloids darrow red, nile blue A, and oxazine 170 are variously effective as inhibitors of cAK, MLCK, PKC, and CDPK (IC₅₀ values 4-65 μM). Ca²⁺ binds to apomorphine and (+)-boldine which, together with nile blue A and oxazine 170, are potent inhibitors of calmodulin (CaM)-dependent MLCK (IC₅₀ values 11, 12, 4, and 7 μM, resp.), and interact with dansyl-CaM.

Planta Medica 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 C3H5BN2O2, SDS of cas: 518-67-2.

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

Wang, Pingyuan published the artcileSynthesis and Biochemical Evaluation of Noncyclic Nucleotide Exchange Proteins Directly Activated by cAMP 1 (EPAC1) Regulators, Application In Synthesis of 401-55-8, the publication is Journal of Medicinal Chemistry (2020), 63(10), 5159-5184, database is CAplus and MEDLINE.

EPAC plays a central role in various biol. functions, and activation of the EPAC1 protein has shown potential benefits for the treatment of various human diseases. Herein, the synthesis and biochem. evaluation of a series of non-cyclic nucleotide EPAC1 activators is reported. Several potent EPAC1 binders were identified, e.g., I, which promote EPAC1 GEF activity in vitro. These agonists can also activate EPAC1 protein in cells, where they exhibit excellent selectivity towards EPAC over PKA and GPCRs. Moreover, four compounds exhibited improved selectivity towards activation of EPAC1 over EPAC2 in cells. Of these, I was found to robustly inhibit IL-6-activated STAT3 and subsequent induction of the pro-inflammatory VCAM1 cell adhesion protein. These novel EPAC1 activators may therefore act as useful pharmacol. tools for elucidation of EPAC function as well as promising drug leads for the treatment of relevant human diseases.

Journal of Medicinal Chemistry published new progress about 401-55-8. 401-55-8 belongs to bromides-buliding-blocks, auxiliary class Fluoride,Bromide,Aliphatic hydrocarbon chain,Ester, name is Ethylbromofluoroacetate, and the molecular formula is C19H15NO3, Application In Synthesis of 401-55-8.

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

Kulhanek, Jiri published the artcile3,4-Dinitrothiophene as a central unit of quadrupolar push-pull-push systems, Related Products of bromides-buliding-blocks, the publication is Chemistry of Heterocyclic Compounds (New York, NY, United States) (2017), 53(1), 46-53, database is CAplus.

A series of quadrupolar D-π-A-π-D mols. bearing methoxythiophene terminal donor and systematically enlarged/varied π-linkers, e.g., I was synthesized by employing cross-coupling and Knoevenagel reactions. 3,4-Dinitrothiophene was utilized as a central acceptor unit in quadrupolar D-π-A-π-D push-pull-push chromophores. Optical properties were studied by electronic absorption spectra. Fundamental optoelectronic properties were investigated by semiempirical PM7 calculations It was shown that by varying the p-conjugated system the longest wavelength absorption maxima could be shifted from 341 to 489 nm. The calculated HOMO-LUMO gaps were found within the range of 6.69-7.29 eV, while the second-order mol. polarizabilities could be tuned from 0.038 to 1.578 × 10-27 esu.

Chemistry of Heterocyclic Compounds (New York, NY, United States) published new progress about 52431-30-8. 52431-30-8 belongs to bromides-buliding-blocks, auxiliary class Liquid Crystal &OLED Materials, name is 2,5-Dibromo-3,4-dinitrothiophene, and the molecular formula is C4Br2N2O4S, Related Products of bromides-buliding-blocks.

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

Freese, Tyll published the artcileAnionic N-heterocyclic carbenes derived from sydnone imines such as molsidomine. Trapping reactions with selenium, palladium, and gold, SDS of cas: 52431-30-8, the publication is Tetrahedron (2017), 73(36), 5350-5357, database is CAplus.

The sydnone imines Molsidomine and 5-(benzoylimino)-3-(2-methoxyphenyl)-1,2,3-oxadiazolium-2-ide gave anionic N-heterocyclic carbenes on deprotonation at C4 which were trapped as methylated selenium adducts, gold complexes (x-ray anal.) as well as palladium complexes (x-ray anal.). The ¹³C NMR resonance frequencies of the carbene carbon atom are extremely shifted upfield and appear at δ = 142.1 ppm (Molsidomine carbene) and δ = 159.8 ppm (sydnone imine carbene). The Pd complexes were applied as catalysts in Suzuki-Miyaura and Sonogashira-Hagihara cross-coupling reactions.

Tetrahedron published new progress about 52431-30-8. 52431-30-8 belongs to bromides-buliding-blocks, auxiliary class Liquid Crystal &OLED Materials, name is 2,5-Dibromo-3,4-dinitrothiophene, and the molecular formula is C4Br2N2O4S, SDS of cas: 52431-30-8.

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

Pruschinski, Lucas published the artcileSuzuki-Miyaura Cross-Couplings under Acidic Conditions, Application of 2,5-Dibromo-3,4-dinitrothiophene, the publication is Synthesis (2020), 52(6), 882-892, database is CAplus.

Suzuki-Miyaura reactions with Pd(PPh₃)₄ had carried out using lithium N-phenylsydnone-4-carboxylate as additive, which gave best yields at pH 5.7 in a mixture of acetic acid, water, and sodium carbonate. Reaction parameters such as the Pd source, the solvent, reaction time and temperature, acid, base and carboxylate have been varied and some representative examples of the Suzuki-Miyaura reaction have been examined

Synthesis published new progress about 52431-30-8. 52431-30-8 belongs to bromides-buliding-blocks, auxiliary class Liquid Crystal &OLED Materials, name is 2,5-Dibromo-3,4-dinitrothiophene, and the molecular formula is C4Br2N2O4S, Application of 2,5-Dibromo-3,4-dinitrothiophene.

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

Arbuzov, B. A. published the artcileAction of triethyl phosphite and diethyl sodium phosphite on some dihalo derivatives, Application In Synthesis of 594-81-0, the publication is Zhurnal Obshchei Khimii (1951), 99-107, database is CAplus.

To (EtO)₂PONa (from 44.2 g. ester and 7.2 g. Na) in 450 ml. dry Et₂O was added 28.5 g. ClCH₂CH₂CN, b₁₀ 63-5°, n²⁰_D 1.4370, d²⁰₂₀ 1.1461, over 0.5 hr.; after refluxing 1 hr., the filtrate yielded 42.7 g. (70.2%) (EtO)₂P(O)CH₂CH₂CN, b₇ 150-2°, b₂ 127-8°, n²⁰_D 1.4380, d²⁰₂₀ 1.1127; this (9.9 g.) heated 8 hrs. to 115-30° in a sealed tube with 30 ml. 2:1 HCl and evaporated gave 6.2 g. (78.5%) (HO)₂P(O)CH₂CH₂CO₂H, m. 166° (by Soxhlet extraction with dry C₆H₆, then with dry Me₂CO). Addition of 40.6 g. BrCH₂CHBrCN, b₁₀ 89-90°, n²⁰_D 1.5390, d²⁰₂₀ 2.0955, to (EtO)₂PONa (from 53.3 g. ester and 8.7 g. Na) in 500 ml. Et₂O and treatment as above gave after repeated fractionation 7 g. (11.9%) (EtO)₂POH, b₇ 60-5°, n²⁰_D 1.4080, d²⁰₂₀ 1.0667, and 9.5 g. (26.4%) (EtO)₂P(O)C(CN):CH₂ or (EtO)₂P(O)CH:CHCN, b₁ 124-7°, n²⁰_D 1.4360, d²⁰₂₀ 1.1277, soluble in H₂O and reacting rapidly with Br water or KMnO₄; hydrolysis with 1:1 HCl 10 hrs. at 150-65° gave on evaporation a mixture of products, which, on removal of NH₄Cl by addition of dry EtOH and evaporation of the extract, gave 4 g. oil; this with BaCO₃ gave a mixture of Ba salts, from which was isolated a H₂O-insoluble Ba salt, possibly C₆H₄P₂O₁₁Ba₃, BaHPO₄, or Ba phosphonoacrylate; a considerable amount of H₂O-soluble C₆H₈O₁₀P₂Ba was also isolated. The products were not identified further. Addition of 32.8 g. (EtO)₃P to 20.2 g. BrCH₂CHBrCN over 0.5 hr. led to a temperature rise to 87°, where it was kept for removal of the EtBr; after 15 min. at 150°, the mixture yielded a total of 19 g. EtBr, but distillation of the residue failed to yield definite products. Addition of 16.1 g. PhCH:CHBr, b₁₀ 88-90°, n²⁰_D 1.6018, d²⁰₂₀ 1.4094, to (EtO)₂PONa (from 13.1 g. ester and 2 g. Na) in 100 ml. MePh (in Et₂O the reaction does not occur) gave no immediate NaBr, but after a 4-hr. reflux 6.6 g. NaBr precipitated and fractionation of the solution gave 7.1 g. (44%) original bromide and 1.9 g. (12%) PhCH(PO₃Et₂)CH₂P(O)(OEt)₂, b₁ 181°, n²⁰_D 1.4920, d²⁰₂₀ 1.1524, which on hydrolysis 7 hrs. at 120-30° with 1:1 HCl gave the free diphosphonic acid, m. 212-14° (from H₂O). Possibly, both phosphono groups are attached to the terminal C atom, but no further characterization was attempted. PhCH:CHBr (14.9 g.) added to 14.5 g. (EtO)₃P at 200-10° did not react and practically all the (EtO)₃P was recovered; heating the components 8 hrs. to 180-200° in a sealed tube gave only traces of high-boiling products. Addition of 34.6 g. PhCHBrCH₂Br in Et₂O over 35 min. to (EtO)₂PONa (from 37.5 g. ester and 6 g. Na) in 500 ml. Et₂O, gave a precipitate of NaBr and, after refluxing 2 hrs., 6.3 g. (53.7%) styrene, about 12 g. (EtO)₂POH, 4.8 g. unreacted dibromide, and about 14 g. of a fraction b₁₁ 90-132°, which on redistillation gave a liquid, b₃ 105-130°; this with 2-C₁₀H₇NH₂ gave 1.2 g. (EtO)₂P(O)NHC₁₀H₇-2, m. 69°, which indicated that the high-boiling liquid was probably (EtO)₂POP(O)(OEt)₂ (cf. Arbuzov and Arbuzov, C.A. 25, 3618). Addition of 22 g. (EtO)₃P over 1 hr. to 16 g. PhCHBrCH₂Br preheated to 155-60° and heating 1 hr. to 165-70° gave 8.6 g. EtBr, 4.7 g. (50.2%) styrene, 3.8 g. crude (EtO)₂POH, b₁₁ 69-72°, 1.7 g. unreacted dibromide, and 10.3 g. crude liquid, b₂ 103-57°, which on redistillation gave a product, b₂ 117-31°, forming with 2-C₁₀H₇NH₂, 0.8 g. (EtO)₂P(O)NHC₁₀H₇, corresponding to a 4.8% yield of tetra-Et subphosphate. When PhCHBrCH₂Br is heated alone to 155-70°, much HBr forms, thus explaining the formation of (EtO)₂POH above. Heating 9.2 g. dibromide to 195-205°, gradual addition of 10.2 g. (EtO)₂POH, and heating 1 hr. to 210-15° gave 4.1 g. EtBr and about 1.5 g. styrene (crude). Addition of 21.4 g. PhCMe:CHBr, b₁₁ 103-5°, n²⁰_D 1.5880, d²⁰₂₀ 1.3790, to (EtO)₂PONa (from 16 g. ester and 2.5 g. Na) in 200 ml. Et₂O and refluxing 1 hr. gave 2.1 g. unreacted bromide and 4 g. (16%) PhCMe:CHP(O)(OEt)₂, b₁ 146-9°, n²⁰_D 1.5210, d²⁰₂₀ 1.1094, which immediately reacts with Br; hydrolysis by 1:1 HCl 6 hrs. at 135-45° in a sealed tube and evaporation gave some crude PhCMe:CH₂ and H₃PO₄, isolated as the PhNHNH₂ salt, m. 155° (from EtOH). Addition over 40 min. of 12.5 g. (EtO)₃P to 13.6 g. PhCMe:CHBr preheated to 150-60° and heating 1 hr. to 165-70° gave 2.3 g. EtBr, 2.1 g. unreacted bromide, 3.1 g. (EtO)₂POH, and 5 g. (33.5%) PhCMe:CHP(O)(OEt)₂, b_1.5 149-50°, n²⁰_D 1.5190, d²⁰₂₀ 1.1009, which on hydrolysis with 1:1 HCl at 120-30° cleaves into H₃PO₄ and PhCMe:CH₂. PhCMeBrCH₂Br (30.6 g.) with (EtO)₂PONa (from 33 g. ester and 5.3 g. Na) in 400 ml. Et₂O, refluxed 2 hrs., gave 5.9 g. (45.4%) PhCMe:CH₂ and apparently about 6 g. (EtO)₂POH; no individual substances of higher b.p. were identified. (EtO)₂PONa with (Me₂CBr)₂ yields apparently tetra-Et subphosphate and Me₂C:CMe₂.

Zhurnal 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, Application In Synthesis of 594-81-0.

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

Lepeltier, Marc published the artcileNew azaborine-thiophene heteroacenes, Quality Control of 52431-30-8, the publication is Chemical Communications (Cambridge, United Kingdom) (2010), 46(37), 7007-7009, database is CAplus and MEDLINE.

A new class of heteroacenes containing B, N and S elements in the 22-electron aromatic nucleus was synthesized by reaction of diaminoterthiophenes with dichlorophenylborane. Their structure was studied by x-ray crystallog. and DFT calculations UV-visible absorption /emission spectroscopy shows high rigidity and deep-blue fluorescence of these compounds

Chemical Communications (Cambridge, United Kingdom) published new progress about 52431-30-8. 52431-30-8 belongs to bromides-buliding-blocks, auxiliary class Liquid Crystal &OLED Materials, name is 2,5-Dibromo-3,4-dinitrothiophene, and the molecular formula is C4Br2N2O4S, Quality Control of 52431-30-8.

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