Tag: M.W=200-300

Synthetic Route of 51554-93-9, As we all know, there are many different methods for the synthesis of a compound, and people can choose the synthesis method that suits their own laboratory according to the actual situation. 51554-93-9 name is 1-Bromo-4-octylbenzene, This compound is widely used in many fields, so it is necessary to find a new synthetic route. The downstream synthesis method of this compound is introduced below.

Pd(OAc)2 (0.115 mg, 0.514 mumol), and S-Phos (0.211 mg, 0.514 mumol) were added to a suspension of K2CO3 (17.75 mg, 0.128 mmol), 1-bromo-4-octylbenzene (6.12 mul, 0.026 mmol), tert-butyl 4-(6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-yl)piperazine-1-carboxylate (10 mg, 0.026 mmol), in acetonitrile/water (1.5:1). The suspension was degassed for 5 min and then refluxed for 6 h. The reaction mixture was extracted with EtOAc, washed with brine, dried with MgSO4 and filtered. After evaporation of the organic solvent under reduced pressure, the resulting residue was purified by column chromatography over silica gel (100% hexanes to 70/30 hexanes/EtOAc) to provide a yellow oil (93% yield). 1H NMR (500 MHz, CDCl3) delta 7.90 (d, J = 8.3 Hz, 2H), 7.58-7.50 (m, 1H), 7.23 (d, J = 7.6 Hz, 2H), 7.10 (d, J = 7.6 Hz, 1H), 6.57 (d, J = 8.5 Hz, 1H), 3.64-3.55 (m, 8H), 2.67-2.60 (m, 2H), 1.67-1.57 (m, 2H), 1.49 (s, 9H), 1.36-1.24 (m, 8H), 0.87 (t, J = 6.8 Hz, 3H); 13C NMR (126 MHz, CDCl3) delta 158.9, 155.5, 155.0, 143.8, 138.3, 137.3, 128.7, 126.7, 109.9, 105.4, 80.0, 45.2, 35.8, 32.0, 31.5, 29.6, 29.4, 29.3, 28.5, 22.8, 14.2; HRMS (ESI+) m/z calcd for C28H41N3O2 [M+H]+ 452.3199, found 452.3605.The Boc-protected amine was dissolved in 10 mL methanol and HCl (g) was bubbled through the solution for one minute. After evaporation of the methanol, diethyl ether was added and the solid filtered. It was washed with cold diethyl ether to yield the title compound as orange oil (92% yield).

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 1-Bromo-4-octylbenzene, and friends who are interested can also refer to it.

Reference:
Article; Raje, Mithun R.; Knott, Kenneth; Kharel, Yugesh; Bissel, Philippe; Lynch, Kevin R.; Santos, Webster L.; Bioorganic and Medicinal Chemistry; vol. 20; 1; (2012); p. 183 – 194;,
Bromide – Wikipedia,
bromide – Wiktionary

These common heterocyclic compound, 67567-26-4, name is 4-Bromo-2,6-difluoroaniline, 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. Computed Properties of C6H4BrF2N

4-bromo-2,6-difluoroaniline (31.05 g, 0.15 mol)N-isopropylacetamide (30.3 g, 0.30 mmol),Phosphorus oxychloride (20.9 mL, 0.225 mol) was added successively to anhydrous toluene.Triethylamine (31.3 mL, 0.225 mol) was slowly added dropwise to the reaction flask in a constant pressure funnel under ice-Keep the internal temperature less than 60 C.The reaction flask was transferred to an oil bath and heated to solvent reflux.After 2 hours the reaction flask was cooled to room temperature,Slowly poured into a 300 g ice-water mixture,Add 300 ml of ethyl acetate,After mixing well,The aqueous layer was again extracted with 200 ml of ethyl acetate,Combined organic layer,After washing with saturated brine, dried over anhydrous sodium sulfate,Concentrated under reduced pressure to obtain a pale yellow solid,Add 100 ml of petroleum ether beating for 10 minutes,The compound of formula IX-1 (28.0 g) was filtered off under reduced pressure,As an off-white solid (yield 92.3%).

The synthetic route of 4-Bromo-2,6-difluoroaniline has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Chia Tai Tianqing Pharmaceutical Group Co., Ltd.; Zhang, Yinsheng; Liu, Yingshuai; Li, Li; Miao, Lei; Xu, Tongjie; Liu, Haiyan; Ma, Xueqin; Yu, Sen; Xu, Hongjiang; (49 pag.)CN106467517; (2017); A;,
Bromide – Wikipedia,
bromide – Wiktionary

Reference of 627871-16-3,Some common heterocyclic compound, 627871-16-3, name is 5-Bromo-4-fluoro-2-methylaniline, molecular formula is C7H7BrFN, 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.

To a solution of vinylidene chloride (127 ml), tert-butyl nitrite (19 ml) and copper(ll)chloride (18.4 g) in acetonitrile (150 ml) is added a solution of 5-bromo-4-fluoro-2-methyl-phenylamine (Bioorganic & Medicinal Chemistry Letters (2006), 16(2), 457-460) (21.5 g) in acetonitrile (100 ml) dropwise below 200C. The reaction mixture is stirred at room temperature for 48 hours, poured on diluted HCI and extracted with fert-butyl methyl ether (3x). The combined organic layers are washed with brine, dried over sodium sulfate and concentrated. The residue is purified by chromatography on silica gel (ethyl acetate/cyclohexane 1 :4). Yield: 29.20 g of 1-bromo-2-fluoro- 4-methyl-5-(2,2,2-trichloro-ethyl)-benzene as an oil.1H-NMR (CDCI3): 2.42 (s, 3H), 3.93 (s, 2H), 7.00 (d, 3J(H,F)=9.2Hz, 1 H), 7.69 (d, 4J(H,F)=7.0Hz, 1 H).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 5-Bromo-4-fluoro-2-methylaniline, its application will become more common.

Reference:
Patent; SYNGENTA PARTICIPATIONS AG; ZAMBACH, Werner; HUETER, Ottmar Franz; WENGER, Jean; GOEGHOVA, Marcela; PITTERNA, Thomas; MAIENFISCH, Peter; JEANMART, Stephane Andre Marie; MUEHLEBACH, Michel; WO2010/52161; (2010); A2;,
Bromide – Wikipedia,
bromide – Wiktionary

129316-09-2, name is 1,3-Dibromo-5-(tert-butyl)benzene, belongs to bromides-buliding-blocks compound, is considered to be a conventional heterocyclic compound, which is widely used in drug synthesis. The chemical synthesis route is as follows. Product Details of 129316-09-2

(4) (Suzuki) by Suzuki coupling reaction to obtain the final product f: the 9 – benzene anthracene -10 borate 10 mmol, 1, 3 – dibromo – 4, 6 – dihydro -5 – tert butyl 2 mmol, four (triphenylphosphine) palladium 0.4 mmol, toluene 80 ml, ethanol 20 ml, K2CO344 MmoL (for 20 ml distilled water into the solution), is added to the reaction bottle, then the system vacuum, in 110 C under the protection of nitrogen reflux 24 hours. After the completion of the reaction, methanol hot washing and filtering, toluene recrystallization, distillation to obtain the final product f. Yield 66%.

The synthetic route of 129316-09-2 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Shaanxi Normal University; Hu Jianyong; Zhang Jiali; Zhao Zhen; Duan Xuewei; (18 pag.)CN109678645; (2019); A;,
Bromide – Wikipedia,
bromide – Wiktionary

Application of 33070-32-5, A common heterocyclic compound, 33070-32-5, name is 5-Bromo-2,2-difluorobenzodioxole, molecular formula is C7H3BrF2O2, 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.

a) 2,2-Difluoro-5-(3-fluoro-4-nitrophenyl)-1 ,3-benzodioxoleA slurry of 5-bromo-2,2-difluoro-1 ,3-benzodioxole (1.23 g, 5.2 mmol), 4-N- BOC-amino-3-fluorophenylboronic acid (1.58 g, 6.2 mmol), [1,1′- bis(diphenylphosphino)ferrocene]dichloropalladium (II) dichloromethane adduct (0.131 g, 0.16mmol), and 2M aqueous sodium carbonate solution (7.8 mL, 15.6 mmol) in 1 ,4-dioxane (25.0 mL) was heated at reflux for 2.5 hours then cooled to ambient temperature. The reaction was dried over sodium sulfate then filtered and evaporated under reduced pressure to a residue. Purification by column chromatography on silica (0-65% gradient of ethyl acetate in hexanes) gave 1 ,1- dimethylethyl [4-(2,2-difluoro-1 ,3-benzodioxol-5-yl)-2-fluorophenyl]carbamate as a waxy white solid (54%).A solution of 1 ,1-dimethylethyl [4-(2,2-difluoro-1 ,3-benzodioxol-5-yl)-2- fluorophenyl]carbamate (0.992 g, 2.70 mmol) in 1 :1 trifluoroacetic acid and dichloromethane (20 mL) was stirred at ambient temperature for 1.5 hours then EPO evaporated under reduced pressure. The resulting residue was treated with glacial acetic acid (20.0 ml_) and sodium perborate tetrahydrate (2.08 g, 13.5 mmol) then heated at 75 2C for 3 hours. The reaction was cooled to ambient temperature then poured onto ice (120 g). After 1 hour, the slurry was filtered and the collected solids were rinsed with water then suction dried. Purification of the solids by silica chromatography (0 to 50% gradient of ethyl acetate in hexanes) gave the title compound (0.249 g, 31%) as a yellow solid. MS (ES) m/e 298 (M + H)+.

The synthetic route of 33070-32-5 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; SMITHKLINE BEECHAM CORPORATION; WO2006/113432; (2006); A2;,
Bromide – Wikipedia,
bromide – Wiktionary

Electric Literature of 50548-45-3, These common heterocyclic compound, 50548-45-3, name is 1-Bromodibenzo[b,d]furan, 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.

30.0 g (177 mmol, 1.0 eq) of 4-aminobiphenyl are initially charged together with 43.7 g (177 mmol, 1.0 eq) of 1-bromodibenzofuran and 23.4 g (212 mmol, 1.20 eq) of sodium tert-pentoxide [14593-46-5] in 600 ml of absolute toluene and degassed for 30 minutes. Subsequently, 398 mg (1.77 mmol, 0.01 eq) of palladium(II) acetate [3375-31-3] and 1.46 g (3.56 mmol, 0.02 eq) of 2-dicyclohexylphos- phino-2?,6?-dimethoxybiphenyl SPHOS [657408-07-6] are added and the mixture is heated under reflux overnight. After the reaction has ended, the mixture is cooled down to room temperature and extracted with 500 ml of water. Subsequently, the aqueous phase is washed three times with toluene, the combined organic phases are dried over sodium sulphate and the solvent is removed on a rotary evaporator. The brown residue is taken up in about 200 ml of toluene and filtered through silica gel. For further purification, a recrystallization from toluene/heptane is conducted. Yield: 44 g (133 mmol), 76percent of theory.

Statistics shows that 1-Bromodibenzo[b,d]furan is playing an increasingly important role. we look forward to future research findings about 50548-45-3.

Reference:
Patent; Merck Patent GmbH; PARHAM, Amir Hossain; EBERLE, Thomas; JATSCH, Anja; GROSSMANN, Tobias; KROEBER, Jonas Valentin; MONTENEGRO, Elvira; JOOSTEN, Dominik; WERN, Caroline; (238 pag.)US2019/119260; (2019); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

6274-57-3, name is 1-(4-Bromophenyl)-N,N-dimethylmethanamine, belongs to bromides-buliding-blocks compound, is considered to be a conventional heterocyclic compound, which is widely used in drug synthesis. The chemical synthesis route is as follows. SDS of cas: 6274-57-3

General procedure: At room temperature, organic carbonyl acid 3 (R-COOH, 0.5 mmol) was added into a reaction tube equipped with a small magnet. Then a solution of tertiary amine 1 (R1CH2-NR2R3, 0.5 mmol ) in DCM (2.5 mL) was added dropwise in 2 min. After the mixture was stirred at room temperature for a few minutes, 1 equivalents of dimethyl acetylenedicarboxylate (DMAD, 2) was added. The reaction was stirred overnight at room temperature, and then monitored by TLC with silica gel coated plates. After being stirred for 14 h, the solvent was removed and the residue was purified by a flash column chromatography with silica gel with ethyl acetate/hexane (1:25-30) as eluent to give the desired products 4, 5, and 7. Most of compounds are known and confirmed by NMR, ESI-MS, IR.

The synthetic route of 6274-57-3 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Shen, Hao; Lu, Xing; Jiang, Ke-Zhi; Yang, Ke-Fang; Lu, Yixin; Zheng, Zhan-Jiang; Lai, Guo-Qiao; Xu, Li-Wen; Tetrahedron; vol. 68; 43; (2012); p. 8916 – 8923;,
Bromide – Wikipedia,
bromide – Wiktionary

Reference of 314084-61-2, These common heterocyclic compound, 314084-61-2, name is 2-Bromo-1,3-diethyl-5-methylbenzene, 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.

a) Under a nitrogen atmosphere and at normal pressure, 7 g of malonic acid dinitrile dissolved in 3.5 ml of 1-methyl-2-pyrrolidone are added dropwise in the course of 30 minutes, at from 20 to 30C, to a mechanically stirred mixture of 12 g of sodium hydroxide (pellets) in 150 ml of dimethyl sulfoxide. Evacuation to from 10 to 30 mbar is carried out, and 79.1 g of solvent are distilled off at from 80 to 100C. After establishing normal pressure, 24 g (content 94.9%) of 2-bromo-1, 3-diethyl-5-methylbenzene are added, and the reaction mixture is heated to 130C. At that temperature, a mixture of 0.13 g of TRIPHENYLPHOSPHINE, 0.1 g of a commercially available palladium (II) chloride solution in concentrated hydrochloric acid (20% Pd content corresponding to 0.035 g of palladium (li) chloride in 0.071 g of concentrated hydrochloric acid) and 9.6 g of 1-methyl-2-pyrrolidone is added. The reaction mixture is stirred for from 2 to 3 hours at from 125 to 140C. A further 59.5 g of solvent are distilled off at from 20 to 60 mbar. 1.5 g of Hyflo and 75 ml of water are added to the residue which has been cooled to 50C. The reaction mixture is stirred vigorously for 10 minutes and then clarified by filtration over Hyflo. The filter is then washed with 50 ml of water. 23.3 g of 32% hydrochloric acid are added to the filtrate in the course of from 60 to 80 minutes, at from 20 to 25C, during the course of which the product crystallises out and the pH value falls to from 4.0 to 4.5. Suction filtration is carried out, followed by washing with 100 ml of water (divided into 2 portions). The product is dried in a vacuum drying cabinet for 16 hours at from 100 to 250 mbar. 20.6 g (content 97.9% ; yield 95. 1%) of 2- (2, 6-diethyl-4-methylphenyl) malonic acid dinitrile are obtained.

The synthetic route of 314084-61-2 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; SYNGENTA PARTICIPATIONS AG; WO2004/50607; (2004); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

Electric Literature of 67567-26-4,Some common heterocyclic compound, 67567-26-4, name is 4-Bromo-2,6-difluoroaniline, molecular formula is C6H4BrF2N, 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 1; 2-(6-TERT-BUTYLPYRlDIN-3-YL)-N-((1 R)-1-(3.5-DIFLUORO-4-r(METHYLSULFONYL’)AMINOlPHENYL> ETHYL^-METHYLCYCLOPROPANECARBOXAMIDE; 1A^ N-(4-BROMO-2,6-DIFLUOROPHENYLMETHANESULFONAMIDE; To a solution of 4-bromo-2,6-difluoroaniline (3.0 g, 14.4 mmol) in pyridine (20 ml) was added methanesulfonyl chloride (2.23 ml, 28.8 mmol) at room temperature. Then the mixture was stirred at 50 0C for 6 hours. After cooing to room temperature, the mixture was concentrated in vacuo. The resulting residue was dissolved in THF (40 ml). To this solution was added 2M sodium hydroxide aqueous solution (40 ml) and the reaction was stirred at room temperature for 4 hours. The mixture was acidified with 2M HCI aqueous solution and extracted with EtOAc. The organic layer was washed with2M HCI aqueous solution and brine, dried over sodium sulfate and concentrated in vacuo, to give the title compound (4.05 g, 98%) as an orange solid.1H NMR (270 MHz, CDCI3) delta 3.22 (3H, s), 6.08 (1 H, br s), 7.17-7.24 (2H, m).MS (ESI) m/z 286 (M + H)+,284 (M – H)”.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 4-Bromo-2,6-difluoroaniline, its application will become more common.

Reference:
Patent; PFIZER JAPAN INC.; PFIZER INC.; WO2007/129188; (2007); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

Related Products of 49764-63-8, The chemical industry reduces the impact on the environment during synthesis 49764-63-8, name is 4,5-Dibromobenzene-1,2-diamine, I believe this compound will play a more active role in future production and life.

General procedure: Furoin 2 (1.0 mmol, 192 mg) and o-phenylenediamines(1.0 mmol) were dissolved in 3mL H2O. Amberlyst-15 (100 mg)wasadded, the mixture was then heated to reflux for 10 h and cooled toroom temperature. Ethyl acetate (10 mL) was added, the organicphase was washed with water (3 x 10 mL), dried over MgSO4, andconcentrated. The crude products were purified by column chromatography,affording 3a-h and Hit-01.

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, 4,5-Dibromobenzene-1,2-diamine, other downstream synthetic routes, hurry up and to see.

Reference:
Article; Zhang, Ning; Yu, Zhimei; Yang, Xiaohong; Zhou, Yan; Tang, Qing; Hu, Ping; Wang, Jia; Zhang, Shao-Lin; Wang, Ming-Wei; He, Yun; European Journal of Medicinal Chemistry; vol. 157; (2018); p. 37 – 49;,
Bromide – Wikipedia,
bromide – Wiktionary