Category: 594-81-0

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

Bladon, P. published the artcileLattice defects in plastic organic solids. 9. Nuclear magnetic resonance studies of translational molecular motion in solids of intermediate entropies of fusion, Application of 2,3-Dibromo-2,3-dimethylbutane, the publication is Molecular Crystals and Liquid Crystals (1973), 19(3-4), 315-26, database is CAplus.

Studies were made of the effects of temperature and sample purity on the continuous wave, NMR line narrowing behavior at high temperatures for the following rotator phase organic solids of intermediate entropies of fusion: perfluorocyclohexane, triethylenediamine, 2-bromo-2,3,3-trimethylbutane, 2-chloro-2,3,3-trimethylbutane, 2,3-dibromo-2,3-dimethylbutane and tetra(fluoromethyl)methane. The evaluated correlation times and activation energies for the solids of high entropy of fusion are equivalent to those for self-diffusion as measured by the radiotracer (or plastic deformation) technique. Proceeding to lower entropies of fusion there is a gradually increasing divergence between the 2 sets of data. It is proposed that this variation is a consequence of the way in which the different techniques reflect translational motion in systems with increasing defect disorder.

Molecular Crystals and Liquid Crystals 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 of 2,3-Dibromo-2,3-dimethylbutane.

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

Kharasch, M. S. published the artcileVapor-phase photochemical bromination of 2,3-dimethylbutane and 2,2,4,4-tetramethylpentane, Category: bromides-buliding-blocks, the publication is Journal of Organic Chemistry (1955), 680-8, database is CAplus.

cf. C.A. 50, 173e. The vapor-phase, photochem. bromination of 700 g. (CHMe₂)₂ (I) with 360 g. Br is carried out in the apparatus described earlier (cf. Zimmt, Dissertation, Univ. of Chicago, 1951). After 10 h. the bromination products are stripped of HBr with N and the residue is fractionally distilled, giving 35% 2-bromo-2,3-dimethylbutane, b_27.5 41-1.5°, n_D²⁰ 1.4541. Cooling the distillation residue gives 4% (CBrMe₂)₂, subliming 170-5° without melting. High-vacuum distillation of the high-boiling residue gives 3 fractions: (a) 46 g., b_0.2 44-6°; (b) 5.4 g., b_0.2 67-70°; (c) 10.1 g., b_0.4 96-100°. Redistillation of a gives 25% of a mixture of cis- and trans-(:CMeCH₂Br)₂, b_0.1 40°, needles, m. 57-7.5°; b is a mixture of tri- and tetrabromides and is not investigated further; recrystallization of c gives 5% tetrabromide, needles, m. 149-52°, of unknown structure. Treating 2 g. of a in 25 cc. CCl₄ with 1.5 g. Br 40 min. at 20° with moderate illumination gives 1.8 g. (CBrMeCH₂Br)₂, faintly yellow needles, m. 137-8°. Because little or no bromination of 2,2,4,4-tetramethylpentane (II) occurs in the vapor phase photochem. bromination at 100° and because of the limited amount of II available a special apparatus, similar to that for I, is used. The bromination of 27 g. II with 14 g. Br is carried out over a period of 7.5 h. at 200°. The reaction product is freed of Br and HBr with N and fractionally distilled in vacuo giving 3 fractions: (d) 0.7 g., b₅ 51°, n_D²⁰ 1.4690; (e) 1.1 g., b₅ 51-2°, n_D²⁰ 1.4695; (f) 11.2 g., b₅ 52°, n_D²⁰ 1.4719; and 0.6 g. residue, apparently a dibromide. The total yield of d-f is 72.2% and is shown to be 2-bromo-2,3,4,4-tetramethylpentane (III). Treating f 0.5 h. with AgNO₃ gives 92.5% AgBr. Shaking 2.1 g. f with 2 g. AgOAc in 30 cc. AcOH and 0.3 cc. Ac₂O 1 h. and distilling off the solvent in vacuo leave 0.5 g. residue which gives a pos. hydroxamic acid test for esters. Neutralizing the distillate with Na₂CO₃, extracting with Et₂O, and evaporating the extract leave 0.6 g. unsaturated material which, on ozonization, gives HCHO. Shaking 2.07 g. f in 45 cc. anhydrous Et₂O with 7.3 g. 3,4-(O₂N)₂C₆H₃CO₂Ag 36 h. gives 2,3,4,4-tetramethylpent-1-ene, b₇₅₄ 125-6°, n_D²⁰ 1.4261, which (0.1 g.), ozonized in 100 cc. EtOAc 2.5 min. at -40°, gives 3,4,4-trimethylpentan-2-one identified via its 2,4-dinitrophenylhydrazone, orange needles, m. 109-10°. III is formed by rearrangement of a Me group. Mechanisms which account for the formation of mono- and dibromides with free radicals as intermediates are proposed.

Journal of Organic Chemistry 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, Category: bromides-buliding-blocks.

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

Liu, Lilian Kao published the artcileReaction of aromatic and unsaturated compounds with the potassium permanganate/HCl (HBr) acetonitrile reagent, Computed Properties of 594-81-0, the publication is Journal of the Chinese Chemical Society (Taipei) (1996), 43(1), 61-6, database is CAplus.

Addition of hydrochloric or hydrobromic acid to a solution of potassium permanganate in acetonitrile produced a homogeneous mixture, which is suitable for laboratory chlorination or bromination, resp. Aromatic compounds more reactive than alkylbenzenes can be chlorinated or brominated without addnl. catalyst. Alkenes and alkynes give the corresponding vicinal dihaloalkanes and vinyl halides. All reactions complete within two hours under mild condition (25-60°) with excellent to moderate yields.

Journal of the Chinese Chemical Society (Taipei) 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

Ding, Rui published the artcileA Highly Efficient Method for the Bromination of Alkenes, Alkynes and Ketones Using Dimethyl Sulfoxide and Oxalyl Bromide, Application In Synthesis of 594-81-0, the publication is Synthesis (2018), 50(21), 4325-4335, database is CAplus.

The pairing of DMSO and oxalyl bromide is reported as a highly efficient brominating reagent for various alkenes, alkynes and ketones. This bromination approach demonstrates remarkable advantages, such as mild conditions, low cost, short reaction times, provides excellent yields in most cases and represents a very attractive alternative for the preparation of dibromides and α-bromoketones.

Synthesis 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

Jenkins, T. E. published the artcileThe Raman spectrum of 2,3-dibromo-2,3-dimethylbutane between 15 K and room temperature, Recommanded Product: 2,3-Dibromo-2,3-dimethylbutane, the publication is Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy (1980), 36A(5), 491-4, database is CAplus.

The Raman spectrum of (BrCMe₂)₂ was determined at 15-300 K. A gauche conformer is present at room temperature A phase transition was observed at 185 K. Another orientational phase transition at ∼77 K was discussed.

Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy 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, Recommanded Product: 2,3-Dibromo-2,3-dimethylbutane.

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

Raphael Karikachery, Alice published the artcileHigh Quantum Yield Molecular Bromine Photoelimination from Mononuclear Platinum(IV) Complexes, Recommanded Product: 2,3-Dibromo-2,3-dimethylbutane, the publication is Inorganic Chemistry (2013), 52(7), 4113-4119, database is CAplus and MEDLINE.

Pt(IV) complexes trans-Pt(PEt₃)₂(R)(Br)₃ (R = Br, aryl and polycyclic aromatic fragments) photoeliminate mol. bromine with quantum yields as high as 82%. Photoelimination occurs both in the solid state and in solution Calorimetry measurements and DFT calculations (PMe₃ analogs) indicate endothermic and endergonic photoeliminations with free energies from 2 to 22 kcal/mol of Br₂. Solution trapping experiments with high concentrations of 2,3-dimethyl-2-butene suggest a radical-like excited state precursor to bromine elimination.

Inorganic Chemistry 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, Recommanded Product: 2,3-Dibromo-2,3-dimethylbutane.

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

Carrera, Elisa I. published the artcileA Mechanistic Study of Halogen Addition and Photoelimination from π-Conjugated Tellurophenes, Application In Synthesis of 594-81-0, the publication is Journal of the American Chemical Society (2016), 138(8), 2678-2689, database is CAplus and MEDLINE.

The ability to drive reactivity using visible light is of importance for many disciplines of chem. and has significant implications for sustainable chem. Identifying photochem. active compounds and understanding photochem. mechanisms is important for the development of useful materials for synthesis and catalysis. Here we report a series of photoactive diphenyltellurophene compounds bearing electron-withdrawing and electron-donating substituents synthesized by alkyne coupling/ring closing or palladium-catalyzed ipso-arylation chem. The redox chem. of these compounds was studied with respect to oxidative addition and photoelimination of bromine, which is of importance for energy storage reactions involving X₂. The oxidative addition reaction mechanism was studied using d. functional theory, the results of which support a three-step mechanism involving the formation of an initial η¹ association complex, a monobrominated intermediate, and finally the dibrominated product. All of the tellurophene derivatives undergo photoreduction using 430, 447, or 617 nm light depending on the absorption properties of the compound Compounds bearing electron-withdrawing substituents have the highest photochem. quantum efficiencies in the presence of an alkene trap, with efficiencies of up to 42.4% for a pentafluorophenyl-functionalized tellurophene. The photoelimination reaction was studied in detail through bromine trapping experiments and laser flash photolysis, and a mechanism is proposed. The photoreaction, which occurs by release of bromine radicals, is competitive with intersystem crossing to the triplet state of the brominated species, as evidenced by the formation of singlet oxygen. These findings should be useful for the design of new photochem. active compounds supported by main-group elements.

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, Application In Synthesis of 594-81-0.

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

Cleveland, Forrest F. published the artcileSubstituted ethanes. II. Raman and infrared spectra of 2,3-dibromo-2,3-dimethylbutane, 2,2,3,3-tetramethylbutane, Product Details of C6H12Br2, the publication is Journal of Chemical Physics (1950), 1320-4, database is CAplus.

cf. C.A. 39, 2254.3. Raman displacements and infrared absorption wave numbers for 2,3-dibromo-2,3-dimethylbutane and 2,2,3,3-tetramethylbutane (hexamethylethane) are reported, together with depolarization factors for the Raman lines and relative intensities for both the Raman lines and the infrared absorption bands. The spectra were obtained in both benzene and CCl₄ solutions and the infrared measurements covered the region 400-5000 cm^-1. The results indicate that both mols. possess a center of symmetry and that the structure is the same in the two solvents. The dipole moment of 1.01 D. obtained by Mizushima, Morino, and Miyagawa (private communication) for 2,3-dibromo-2,3-dimethylbutane in CCl₄ solution can be explained by oscillations of 48° amplitude about the equilibrium trans position. Cf. C.A. 38, 3908.7.

Journal of Chemical Physics 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, Product Details of C6H12Br2.

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

Kuznetsova, Lidia I. published the artcileOxidative Bromination of Alkenes Mediated with Nitrite in Ionic Liquids, Recommanded Product: 2,3-Dibromo-2,3-dimethylbutane, the publication is Catalysis Letters (2014), 144(9), 1499-1506, database is CAplus.

An oxidative bromination of C₂-C₈ alkenes with HBr-NaNO₂-O₂ in solutions of BMImBr, HMImBr or BMImBF₄ containing 16-28 wt% H₂O was studied using a volumetric method, GC-MS anal., ¹⁴N NMR and UV-VIS spectroscopy. The optimal conditions to conduct the reaction at high selectivity for 1,2-dibromoalkanes in BMImBr were determined The composition of ionic liquid affects the catalytic performance. Although in BMImBF₄ the reaction runs with equal rate as in bromide ionic liquid, the fraction of bromohydrin in the reaction products increases to 20%. Generated from NaNO₂, NO_x operated as a catalyst in the oxidation of bromide ion (Br^–) and was oxidized to catalytically inert nitrate (NO₃^–) anions when complete conversion of HBr was attained. The synthesis of the target compounds was achieved using 1-butyl-3-methylimidazolium bromide as ionic liquid Alkenes included 1-propene, 1-butene (α-alkenes), 2-methyl-1-propene, cyclohexene, 1-octene, 2,3-dimethyl-2-butene. The title compounds thus formed included 1,2-dibromopropane, 1,2-dibromobutane, 1,2-dibromo-2-methylpropane and similar substances. Alcs., such as 1-bromo-2-propanol, 1-bromo-2-butanol, 1-bromo-2-methyl-2-propanol, 2-bromocyclohexanol, 1-bromo-2-octanol, 2-bromoethanol were also observed Formation of 2,3-dimethyl-2,3-dinitrobutane and 2,2,3,3-tetramethyloxirane was reported.

Catalysis Letters 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, Recommanded Product: 2,3-Dibromo-2,3-dimethylbutane.

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