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Synthetic Route of 51376-06-8, The chemical industry reduces the impact on the environment during synthesis 51376-06-8, name is 5-Bromobenzo[c][1,2,5]oxadiazole, I believe this compound will play a more active role in future production and life.

A solution of 5-bromobenzo[c][1,2,5]oxadiazole (3 g , 15.0 mmol, Combiblocks ) in toluene (10 mL) was degassed for 30 min. 1 -Ethoxy vinyl tributyltin (6.01 mL, 16.5 mole, Frontier Scientific) and bis(triphenylphosphine)palladium(ll) dichloride (1.16 g, 1 .65 mmol) were added at rt and the resulting mixture was stirred at 90 C overnight. It was cooled to rt and filtered through celite. HCl aqueous solution (20 mL, 6N) was added and the mixture was stirred for 1 hour at rt. It was concentrated and neutralized with sat. NaHCO3 solution (25 mL). The product was extracted with DCM (100 mL), dried over Na2SO4 and concentrated. The crude product was purified by flash column chromatography to afford the title compound. Yield: 60% (1 .5 g, pale yellow solid). 1 H NMR (400 MHz, DMSO-d6): delta 8.90 (s, 1H), 8.14 (d, J = 9.6 Hz, 1H), 7.98-7.39 (m, 1H), 2.72 (s, 3H). LCMS: (Method B) 162.0 (M+H), Rt. 4.6 min, 98.01 % (Max).

In the field of chemistry, the synthetic routes of compounds are constantly being developed and updated. I will also mention this compound in other articles, 5-Bromobenzo[c][1,2,5]oxadiazole, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; ASCENEURON SA; QUATTROPANI, Anna; KULKARNI, Santosh S.; GIRI, Awadut Gajendra; (243 pag.)WO2016/30443; (2016); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

Reference of 960203-41-2, A common heterocyclic compound, 960203-41-2, name is (2-Bromophenyl)(2,4-dimethylphenyl)sulfane, molecular formula is C14H13BrS, its traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.

Example 19; A solution of 10 gram l-(2-Bromo-phenylsulfanyl)-2,4-dimethyl-benzene (34 mmol) in 50 ml dry toluene was added 7 gram boc-piperazine (38 mmol), degassed with nitrogen for 5 minutes, added 312 mg Pd2dba3 (2 mol-%) and 637 mg ralphac-BINAP (3 mol-%), degassed for another 5 minutes before adding 3.9 gram Bu1ONa (41 mmol) and heated to 80 0C for 15 hours. The reaction mixture was cooled to RT and extracted twice with 20 ml 15 % brine, dried over Na2SO4, added charcoal, re fluxed for 15 minutes, filtered though celite and evaporated to 14.2 gram of brownish oil (4- [2-(2,4-Dimethyl-phenylsulfanyl)-phenyl]-BOC-piperazine) having a purity of 95 % determined by NMR. The crude oil was dissolved in 200 ml MeOH and 20 ml 6M HCl (aq.) and refluxed for 1 hour after which HPLC showed full deprotection. After cooling to RT the methanol was removed by vacuum on a rotary-evaporator, 20 ml cone. NaOH (pH was measured to 13-14) was added after which the mixture was stirred 15 minutes with 100 ml EtOAc. The organic phase was collected and extracted twice with 30 ml 15 % brine, dried over Na2SO4 and added 5.2 g fumaric acid (44 mmol) in 30 ml MeOH. During heating to reflux a homogenous solution forms from which a rapid precipitation takes place either during further heating or upon cooling. The precipitate was collected, washed with 20 ml EtOAc and 20 ml acetone, dried in vacuum giving 9.3 gram of l-[2-(2,4-Dimethyl-phenylsulfanyl)-phenyl]-piperazine fumarate (22 mmol) as a white powder in 66 % overall yield having a purity of 99.5 % by LC-MS.; Example 22; 500 ml toluene was placed in a IL three-necked round bottle with a mechanical stirrer and added 809 mg Pd2dba3 (0.88 mmol; 0.5 mol-%) and 952 mg DPEPhos (1.77 mmol; 0.5 mol-%). The dark-red solution was purged with nitrogen for 5 minutes before addition of 100 g 2-bromoiodobenzene (353 mmol) and 48.9 g 2,4- dimethylthiophenol (353 mmol) took place. Addition of 43.6 g KOBu’ (389 mmol) caused an exothermic reaction increasing the temperature from 20 0C to 42 0C simultaneously with the formation of a heterogeneous mixture and the colour changed from dark-red into orange/brownish. The suspension was heated to 100 0C under nitrogen. After only 20 minutes a HPLC showed full conversion into l-(2-Bromo- phenylsulfanyl)-2,4-dimethyl-benzene. The mixture was cooled to 40 0C, added 600 ml 15-wt% NaCl and stirred for 5 minutes. The organic phase was separated and the aqueous phase was washed with 2 x 100 ml toluene. The combined organic phases were washed with 100 ml 2M HCl (aq.), 100 ml 15-wt% NaCl, dried over Na2SO4, refiuxed for 15 minutes with activated charcoal (10 g), filtered twice and evaporated to 107.3 g orange-red oil (103 %) that was found to be 98 % pure by HPLC.A solution of 90 gram of the orange-red oil (307 mmol) in 500 ml dry toluene was added 57 gram boc-piperazine (307 mmol), degassed with nitrogen for 5 minutes, added 1.4 g Pd2dba3 (1.53 mmol; 0.5 mol-%) and 2.9 g ralphac-BINAP (4.6 mmol; 1.5 mol-%), degassed for another 2 minutes before adding 35.4 gram Bu1ONa (368 mmol) and heated to 80 0C for 18 hours. HPLC showed full conversion and the reaction mixture was cooled to RT, filtered and the filter cake was washed with 2 x 100 ml toluene. The combined filtrates was extracted twice with 2 x 150 ml 15-wt% NaCl, dried over Na2SO4, added charcoal, refiuxed for 30 minutes, filtered twice and evaporated to 140.7 gram of brownish oil (4-[2-(2,4-Dimethyl-phenylsulfanyl)- phenyl]-BOC-piperazine). The crude oil was dissolved in 300 ml MeOH and 200 ml 6M HCl (aq.) and refiuxed for 1 hour after which HPLC showed full deprotection. After cooling to RT the methanol was removed by vacuum on a rotary-evaporator, 200 ml cone. NaOH (pH was measured to 13-14) was added after which the mixture was stirred 15 minutes with 1000 ml EtOAc. The organic phase was collected and extracted with 300 ml 15-wt% brine, dried over Na2SO4 and added to a solution of 46.3 g fumaric acid (399 mmol) in 300 ml MeOH. The mixture was heated to reflux, cooled to room temperature and then left in the freezer overnight (-18 0C). The precipitate was collected, washed with 100 ml EtOAc and 100 ml acetone, dried in vacuum (50 0C) producing 103.2 g of l-[2-(2,4-Dimethyl-phenylsulfanyl)-phenyl]- piperazine fumarate (249 mmol) as a white powder in 81 % overall yield having a purity of 99 % by LC-MS. The fumarate was transfer into the free base (l-[2-(2,4- Dimethyl-phenylsulfanyl)-phenyl]-piperazine) using EtOAc/H2O/conc. NaOH, the organic phase was washed with brine, dried using Na2SO4, filtered and to the filtrate was added 34 ml 48-wt% HBr (aq.) causing a precipitation of a white solid. The solid was collected, treated with 1000 ml boiling H2O, which upon cooling to room temperature formed a slurry. The final product (l-[2-(2,4-Dimethyl-phenylsulfanyl)- phenylj-piperazine hydrobromide) was collected by filtration and dried in vacuum (50 0C) producing 83 g of white powder (71 % …

The synthetic route of 960203-41-2 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; H. LUNDBECK A/S; WO2007/144005; (2007); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

Application of 2635-13-4,Some common heterocyclic compound, 2635-13-4, name is 5-Bromobenzo[d][1,3]dioxole, molecular formula is C7H5BrO2, traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.

EXAMPLE 3 Alternative syntheses of (S)-alpha-methyl-1,3 benzodioxole-5-ethanol 3.47 grams of 4-bromo-1,2(methylenedioxy)benzene were dissolved in 100 ml of tetrahydrofuran at -78 C., 13.9 ml of 1.3M sec-butyllithium in cyclohexane was then added to consume the aryl halide in less than 30 minutes. 1.00 grams of (S)-(-)-propylene oxide in 2 ml THF was added by syringe and the solution stirred for 45 minutes. The solution was then warmed to 23 C. for 16 hours. The reaction mixture was poured into 3M ammonium chloride solution and the product isolated by extraction with ethyl acetate. The combined extracts were dried over magnesium sulfate filtered through florisil and concentrated by rotary evaporation. The residual oil was purified by silica gel chromatography and eluted with a 50:50 mixture of hexane and diethyl ether to yield 1.40 g (45%) of the subtitled intermediate. Pchem: [alpha]365 +117.2 (c 1.0, CHCl3) TLC Rf =0.26 (50:50 hexane:ether); IR (CHCl3) 3598, 3012, 2973, 2887, 1490, 1249, 1041 cm-1; 13 C NMR (CDCl3) d 147.75, 146.19, 132.26, 122.27, 109.68, 108.30; mass spectrum, m/z (FD, M+) 180; Anal. Calcd. for C10 H12 O3: C, 66.65; H, 6.71. Found: C, 66.42; H, 6.66.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 5-Bromobenzo[d][1,3]dioxole, its application will become more common.

Reference:
Patent; Eli Lilly and Company; US5795886; (1998); A;,
Bromide – Wikipedia,
bromide – Wiktionary

Some common heterocyclic compound, 3972-65-4, name is 1-Bromo-4-(tert-butyl)benzene, molecular formula is C10H13Br, traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route. Product Details of 3972-65-4

Under nitrogen protection conditions,Dissolve 0.015 mmol of the nitrogen heterocyclic carbene precursor in 2 mL of anhydrous toluene.Add 0.01 mmol of palladium acetate and stir for 15 minutes.Add 0.6 mmol of sodium bis(trimethylsilyl)amide and stir for 20 minutes.0.4 mmol of compound A-1, 0.2 mmol of 4-tert-butylbromobenzene was added to the reaction solution.The reaction was carried out at 60 C for 12 hours. After the reaction is completed, Add 5 drops of water to extract the reaction, and take a suction filter funnel into the diatomaceous earth.After suction filtration, the mixture was washed three times with ethyl acetate.Column chromatography (petroleum ether: ethyl acetate = 3:1) gave product A-2.Yield: 95%;

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 3972-65-4, its application will become more common.

Reference:
Patent; Zhejiang University City College; Li Jie; Yang Fan; Zhou Bihui; He Weiping; (24 pag.)CN108456172; (2018); A;,
Bromide – Wikipedia,
bromide – Wiktionary