Tag: M.W=100-200

1003-99-2, Each compound has different characteristics, and only by selecting the characteristics of the compound suitable for a specific situation can the compound be applied on a large scale. 1003-99-2, name is 2-Bromo-5-fluoroaniline, This compound has unique chemical properties. The synthetic route is as follows.

To a 2-L reactor equipped with a mechanic agitator, a condenser, a thermocouple, a baffle, and nitrogen inlet were charged 228 g of water, 200 g of 2-bromo-5-fluoroaniline and 80 g of 4-nitrophenol. To this mixture was charged 96percent sulfuric acid in 10-30 min at 20-120¡ã C. The mixture was heated to 135-140¡ã C. and 194 g of glycerol was charged into the reactor over two hours at 135-145¡ã C. The mixture was held at 135-145¡ã C. for 1 hour after the addition. The reaction mixture was cooled to below 20-50¡ã C. and slowly transferred to a 5-L reactor containing 1100 g of water and 1210 g of toluene. The 2-L reactor was washed with 300 g of water and the wash was combined into the 5-L reactor. The pH of the contents in the 5-L reactor was adjusted to pH 8-10 by adding approximately 1233 g (1370 mL) ammonium hydroxide (28-30percent NH3) at 20-40¡ã C. The mixture was stirred at room temperature for 15 min and the solid by-product was filtered off while the filtrate was retained. The filter cake was washed with 400 ml of toluene and the all the filtrate was combined and charged a 3-L reactor. About 500 ml of 8.5percent KOH solution was charged into the 3-L reactor and stirred for 10 min and bottom aqueous layer was spit off. A second portion of 500 ml of 8.5percent KOH solution was added and the mixture was stirred for 15 min and the bottom aqueous layer was split off. Water 500 ml was added and stirred for 15 min before the bottom aqueous layer was split off. The organic layer was heated to distill off about 100-200 ml of toluene to azeotropically remove water. A clear solution will be obtained. Typical yield 178 g real 8-bromo-5-fluoroquinoline, 75percent.Alternatively, 8-bromo-5-fluoroquinoline was prepared by adding a warm mixture containing 2-bromo-5-fluoroaniline (100 g, 1.0 eq), 4-nitrophenol (40 g, 0.54 eq), and glycerol (97 g, 2.0 eq) over 1.5 hours to sulfuric acid (267 ml) and water (114 mL) at 140-150¡ã C. The initial mixture showed 37.8percent 4-nitrophenol by relative HPLC area percent. Samples showed 4.7percent 4-nitrophenol immediately after adding 50percent of mixed starting materials and 5.0percent immediately after adding all of the materials. The yield upon workup was 87.5percent, with total impurities 0.29percent. Addition of less (0.46 eq, 34 g) 4-nitrophenol also successfully produced the intermediate of interest at acceptable yield.

If you are interested in these compounds, you can also browse my other articles.Thank you for taking the time to read this article. I hope you enjoyed it.

Reference:
Patent; Wyeth; US2007/27160; (2007); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

A common heterocyclic compound, 1422-53-3, name is 2-Bromo-4-fluorotoluene, molecular formula is C7H6BrF, 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. 1422-53-3.

a) Preparation of 2-Bromo-1-(Bromomethyl)-4-Fluorobenzene A mixture of 2-Bromo-4-Fluorotoluene (46.6 g, 0.25 mol, Aldrich), N-bromosuccinimide (46.3 g, 0.26 mol, Aldrich) and benzoyl peroxide (0.5 g, 0.002 mol, Aldrich) in carbon tetrachloride (500 ml) was refluxed and illuminated (250 watt, infrared lamp) for 18 h. After cooling to room temperature, the succinimide was filtered and the filtrate was concentrated in vacuo. Chromatography on silica gel with hexanes as eluent gave 41.8 g (62%) of 2-bromo-1-(bromomethyl)-4-fluorobenzene as a white solid: mp 47-49 C.

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

Reference:
Patent; Glaxo Wellcome Inc.; US5708033; (1998); A;,
Bromide – Wikipedia,
bromide – Wiktionary

In the chemical reaction process, reaction time, type of solvent, can easily affect the result of the reaction, thereby determining the yield and properties of the reaction product. An updated downstream synthesis route of 399-94-0 as follows. 399-94-0

Under nitrogen, 2,5-difluorobromobenzene (15.05 g, 78 mmol) was dissolved in dry toluene (50 mL), the ice salt bath was cooled below -10 C,A solution of isopropylmagnesium chloride / lithium chloride tetrahydrofuran (66 mL, 1.3 mol / L) was added dropwise and the mixture was stirred at about -10 C for 1 hour.A solution of 1D (10 g, 39 mmol) in dry tetrahydrofuran (100 mL) was added dropwise to the reaction solution, maintaining the temperature at -10 C, and the reaction was carried out at room temperature for 4 hours.The temperature was lowered to about -10 C, saturated ammonium chloride solution (40 mL) was added dropwise, stirred for 10 minutes, adjusted to pH 5 to 6 with 3 mol / L hydrochloric acid solution,The aqueous phase was extracted with methyl tertiary butyl ether (50 mL x 2). The organic phases were combined, washed with saturated sodium chloride solution (30 mL x 2). The organic phase was dried over anhydrous sodium sulfate, filtered,Column chromatography (petroleum ether / ethyl acetate (v / v) = 50: 1-8: 1) gave a pale yellow solid 1E (10.1 g, yield 83.5%).

According to the analysis of related databases, 399-94-0, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Sichuan Haisco Pharmaceutical Co.,Ltd; FAN, JIANG; CHEN, QINGPING; JIANG, WEI; ZHENG, SUXIN; YE, FEI; (128 pag.)TW2017/8221; (2017); A;,
Bromide – Wikipedia,
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In the chemical reaction process, reaction time, type of solvent, can easily affect the result of the reaction, thereby determining the yield and properties of the reaction product. An updated downstream synthesis route of 5469-19-2 as follows. 5469-19-2

Preparation 1 d: 2-tert-Butyl 5-methyl 6-hromo-2,3-dibydro-1H-isoiiidole-2,5-dicarboxylateStep A: S-Brornobenzene-1,2,4-tricarboxylic acidBromotrimethyl benzene (40.7 g, 205 mmol) was added to a mixture of water (3.25 L), potassium permanganate (232 g, 1.468 mol) and sodium carbonate (28.5 g, 206 mmol). The mixture was stirred at reflux for 60 h. Ethanol (820 mE) was added dropwise, and theresultant mixture was filtered hot through celite, then allowed to cool to ambient temperature. The filtrate was acidified with concentrated aqueous HCI, and the organic solvent was removed in vacuo, The solid product was isolated by filtration.

According to the analysis of related databases, 5469-19-2, the application of this compound in the production field has become more and more popular.

Reference:
Patent; LES LABORATOIRES SERVIER; VERNALIS (R&D) LIMITED; DAVIDSON, James, Edward, Paul; MURRAY, James, Brooke; CHEN, I-Jen; WALMSLEY, Claire; DODSWORTH, Mark; MEISSNER, Johannes, W., G.; BROUGH, Paul; FEJES, Imre; TATAI, Janos; NYERGES, Miklos; KOTSCHY, Andras; SZLAVIK, Zoltan; GENESTE, Olivier; LE TIRAN, Arnaud; LE DIGUARHER, Thierry; HENLIN, Jean-Michel; STARCK, Jerome-Benoit; GUILLOUZIC, Anne-Francoise; DE NANTEUIL, Guillaume; WO2015/11164; (2015); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

Some common heterocyclic compound, 766-46-1, name is 2′-Bromophenylacetylene, molecular formula is C8H5Br, 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. 766-46-1

For the synthesis of 1e, the title compound 1e? wasprepared as follows. A solution of LDA, prepared from iPr2NH(0.93 mL, 6.5 mmol) and nBuLi (2.7M in hexane, 2.4 mL, 6.5 mmol)in THF (6 mL) at 0 C, was added to a solution of 1-bromo-2-ethynylbenzene [766-46-1] (1.1 g, 5.9 mmol) in THF (6 mL)at 78 C for 30 min tert-Butyldimetylsilyl chloride [18162-48-6](1.1 g, 7.1 mmol) was added to the mixture at that temperature.The reaction mixturewas warmed to room temperature and stirredfor 12 h. After adding aqueous NH4Cl, the aqueous mixture wasextracted with hexane three times. The combined organic phasewas dried over Na2SO4 and evaporated. Purification of the residueby silica-gel column chromatography gave 1-bromo-2-[2-[(1,1-dimethylethyl)dimethyl-silyl]ethynyl]benzene in (1.6 g, 5.4 mmol,92%) as a pale yellow liquid. 1H NMR (400 MHz, CDCl3, 7.26 ppm)d 0.21 (s, 6H), 1.02 (s, 9H), 7.15 (ddd, J 7.6, 7.6, 1.6 Hz, 1H), 7.24(ddd, J 7.6, 7.6, 1.2 Hz, 1H), 7.50 (dd, J 7.6, 1.6 Hz, 1H), 7.57 (dd,J 8.0, 1.2 Hz, 1H).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 766-46-1, its application will become more common.

Reference:
Article; Kinoshita, Hidenori; Fukumoto, Hiroki; Ueda, Akihiro; Miura, Katsukiyo; Tetrahedron; vol. 74; 14; (2018); p. 1632 – 1645;,
Bromide – Wikipedia,
bromide – Wiktionary

A common compound: 111721-75-6, name is 2-Bromo-3-fluoroaniline, belongs to bromides-buliding-blocks compound, it can change the direction of chemical reaction, and react with certain compounds to generate new functional products. A new synthetic method of this compound is introduced below. 111721-75-6

To a stirred solution of compound Xlla (155 g, 1.15 mmol) in dichloromethane (2 L) at 0 C under nitrogen atmosphere were added pyridine (750 mL, 5 vol) and 2-bromo-3-fluroaniline (218.0 g, 1.15 mmol). The resulting mixture was continued to stir at room temperature for 16 hours. After that the reaction mixture was quenched with water extracted with dichloromethane (2 x 5 L). The combined organic phase was washed with 1.5N HCl solution (2 x 3 L), brine (1 x 2 L), dried over Na2S04 and concentrated in vacuo. The obtained crude product was purified by column chromatography using silica gel (60-120 mesh) eluting with 20% of ethyl acetate in petroleum ether to get compound Xllb. Yield: 240 g, 64.67% (over a two steps); LC-MS Calc. for CnHnBrFN02, 288.12; Obs: 290.0 [M++2H]; NMR (300 MHz, DMSO-d6): delta 9.26 (s, 1H), 7.61-7.59 (d, 1H, J=8.19 Hz), 7.54-7.49 (m,lH), 7.41-7.34 (m, 1H), 7.17- 7.11 (m, 1H), 5.79-5.75 (d, 1H, J=12.33 Hz), 3.97-3.95 (m, 2H), 1.30-1.25 (m, 3H).

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, 111721-75-6, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; BUGWORKS RESEARCH INDIA PVT LTD; PEER MOHAMED, Shahul Hameed; BHARATHAM, Nagakumar; KATAGIHALLIMATH, Nainesh; SHARMA, Sreevalli; NANDISHAIAH, Radha; RAMACHANDRAN, Vasanthi; VENKATARAMAN, Balasubramanian; (221 pag.)WO2018/225097; (2018); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

Some common heterocyclic compound, 1575-37-7, name is 4-Bromobenzene-1,2-diamine, molecular formula is C6H7BrN2, 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. 1575-37-7

General procedure: A solution of 10 mmol of the appropriate benzene-1,2-diamine in3.5 mL of acetic acid (AcOH) and 1 mL of water was cooled to 0-5 C,followed by the addition of 15 mmol of sodium nitrite in 2 mL ofwater. The mixture was stirred for 2 h at room temperature. Afterthe completion of the reaction, a solventwas evaporated and the residuewasco-evaporatedwith toluene (3 ¡Á 20mL). The crude productwas partitioned between water (20 mL) and ethyl acetate (20 mL),the organic phase was washed with the saturated solution of sodiumhydrogen carbonate and dried overmagnesiumsulfate (MgSO4). Theproducts were purified by crystallization from nitromethane and/orby column chromatography on silica gel using a chloroform – methanol97:3-95:5 v/v mixture as eluent. Reaction products were analyzedby use of mass-spectrometry (Waters Q-TOF Premier MassSpectrometer) and NMR spectroscopy (Varian INOVA 500 Spectrometer,see Supp. Fig. 1). Purity of the products was assessed using internalstandard quantitative NMR method (qNMR) [49]. It shouldbe noted that the formal qNMR-derived purity determined for 4-BrBt, 4-ClBt, 5,6-Cl2Bt and 5,6-Br2Bt increased significantly upon additiona small amount of water to the DMSO solution, which increasedproton exchange rates. This observation indicates that thenuclear relaxation process accompanying protomeric equilibrium(generally N1-H and N3-H forms predominates) significantly contributeto the obtained NMR spectra, the best proof of which is thestrong broadening of the H-7 resonance line in 4-BrBt and 4-ClBt(Supp. Fig. 1A,B).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 1575-37-7, its application will become more common.

Reference:
Article; Szymaniec-Rutkowska, Anna; Bugajska, Ewa; Kasperowicz, S?awomir; Mieczkowska, Kinga; Maciejewska, Agnieszka M.; Pozna?ski, Jaros?aw; Journal of Molecular Liquids; vol. 293; (2019);,
Bromide – Wikipedia,
bromide – Wiktionary

586-61-8, 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. 586-61-8 name is 1-Bromo-4-isopropylbenzene, 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.

General procedure: n-BuLi (1.55 M solution in hexane, 2.32 mL, 3.6 mmol) was added dropwise to a solution of 4-methylphenyl bromide (513 mg, 3.0 mmol) in THF (6.0 mL) at -50 C under Ar atmosphere. After 30 min, DMF (278 muL, 3.6 mmol) was added and the obtained mixture was gradually warmed to r.t. After 1 h at the same temperature, NH2OHxHCl (313 mg, 4.5 mmol) and K2CO3 (622 mg, 4.5 mmol) were added and the obtained mixture was stirred for 2 h at r.t. Then, after removal of the solvent under reduced pressure, toluene (3.0 mL), DPPA (1.61 mL, 7.5 mmol), and DBU (1.57 mL, 10.5 mmol) were added to the obtained residue under Ar atmosphere. After being stirred for 16 h under refluxing conditions, the mixture was cooled to r.t. and then, saturated NaHCO3 aq. (15.0 mL) was added. After being stirred for 5 min, the mixture was diluted with water (5.0 mL). The aqueous layer was then washed with AcOEt (25.0 mL) and acidified with 1.0 M HCl aq. to pH 2. The aqueous layer was extracted with AcOEt (2 x 25.0 mL). Removal of the solvent, followed by purification of the residue by short column chromatography on neutral silica gel (AcOEt: hexane = 1:3-1:1) gave 5-(4?-methylphenyl)tetrazole 3A (336.1 mg, 70%).

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

Reference:
Article; Kobayashi, Eiji; Togo, Hideo; Tetrahedron; vol. 74; 31; (2018); p. 4226 – 4235;,
Bromide – Wikipedia,
bromide – Wiktionary

Adding a certain compound to certain chemical reactions, such as: 38573-88-5, name is 1-Bromo-2,3-difluorobenzene, belongs to bromides-buliding-blocks compound, can increase the reaction rate and produce products with better performance than those obtained under traditional synthetic methods. Here is a downstream synthesis route of the compound 38573-88-5, 38573-88-5

Under a nitrogen atmosphere, 2,2,6,6-tetramethylpiperidine (48.5 mL) and THF (250 mL) were put in a reaction vessel, and the resulting mixture was cooled to 0¡ãC. Then, n-butyllithium (1.60 M; n-hexane solution; 178 mL) was slowly added thereto, and the resulting mixture was stirred for 1 hour. Next, the resulting mixture was cooled to -70¡ãC, and then a THF (500 mL) solution of compound (T-1) (50.0 g) was slowly added thereto, and stirred for 1 hour, and then N,N-dimethylformamide (DMF) (40.1 mL) was slowly added thereto, and stirred for 12 hours while the mixture was returned to room temperature. The resulting reaction mixture was poured into a saturated aqueous solution of ammonium chloride, and the resulting aqueous layer was subjected to extraction with ethyl acetate. Then, organic layers combined were washed with brine, and dried over anhydrous magnesium sulfate. The resulting solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (hexane : ethyl acetate = 5 : 1 in a volume ratio). Then, the resulting product was further purified by recrystallization from a mixed solvent of hexane and ethyl acetate (1 : 1 in a volume ratio) to give compound (T-2) (46.9 g; 82percent).

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, 1-Bromo-2,3-difluorobenzene, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; JNC Corporation; JNC Petrochemical Corporation; TANAKA, Hiroyuki; ENDOU, Hiroshi; EP2957554; (2015); A1;,
Bromide – Wikipedia,
bromide – Wiktionary

38573-88-5,Some common heterocyclic compound, 38573-88-5, name is 1-Bromo-2,3-difluorobenzene, molecular formula is C6H3BrF2, 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.

4-(19): 1-(2,3-Difluorophenyl)-2-(1-(trityloxy)but-3-en-2-yloxy)ethanone Isopropylmagnesiumchloride-LiCl complex (1.30 M in THF, 155.0 mL, 0.0715 mol) under nitrogen was cooled to 0-5¡ã C., and 2,3-difluorobromobenzene (13.8 g, 0.0715 mol, 1.50 equiv.) was added while T<10¡ã C. After 1 h at 0-5¡ã C., a solution of 1-morpholino-2-(1-(trityloxy)but-3-en-2-yloxy)ethanone (21.8 g, 0.048 mol, 1.0 equiv.) in THF (2.0 vols) was added while T<10¡ã C. The reaction mixture was stirred for 2.5 h and monitored for consumption of 1-morpholino-2-(1-(trityloxy)but-3-en-2-yloxy)ethanone (target>97percent). The reaction mixture was quenched by charging into cold sat. aq. NH4Cl (110 mL) and water (33 mL) while T<20¡ã C. 2-Methoxy-2-methylpropane (218 mL) was added and the layers were separated. The organics were washed with sat. aq. NH4Cl (65 mL) and 18percent aq. NaCl (44 mL). The organics were concentrated under vacuum T<25¡ã C. to a light yellow oil (21.6 g). 1H NMR (500 MHz, CDCl3) delta ppm 7.70-7.64 (m, 1H), 7.47-7.42 (m, 6H), 7.37-7.30 (m, 1H), 7.30-7.25 (m, 6H), 7.24-7.19 (m, 3H), 7.19-7.13 (m, 1H), 5.84-5.71 (m, 1H), 5.30 (d, J=17.3 Hz, 1H), 5.25 (d, J=10.4 Hz, 1H), 4.78 (dd, J=17.7, 3.1 Hz, 1H), 4.70 (dd, J=17.7, 3.1 Hz, 1H), 4.03 (dd, J=11.8, 6.5 Hz, 1H), 3.35 (dd, 1=9.8, 6.4 Hz, 1H), 3.18 (dd, J=9.8, 4.6 Hz, 1H); 13C NMR (125 MHz, CDCl3) delta ppm 194.15 (dd, JCF=4.9, 2.4 Hz), 150.77 (dd, JCF=250.3, 14.1 Hz), 150.29 (dd, JCF=256.4, 13.9 Hz), 143.98, 135.34, 128.75, 127.76, 126.95, 125.70 (d, JCF=12.0 Hz), 125.16 (d, JCF=3.5 Hz), 124.55 (dd, JCF=6.4, 4.2 Hz), 121.62 (d, JCF=17.6 Hz), 118.83, 86.78, 81.35, 74.98 (d, JCF=9.5 Hz), 66.71. These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 38573-88-5, its application will become more common. Reference:
Patent; EISAI R&D MANAGEMENT CO., LTD.; Takaishi, Mamoru; Ishida, Tasuku; US2014/179690; (2014); A1;,
Bromide – Wikipedia,
bromide – Wiktionary