2. 'Halo'benzene to PhMgX

Query Query

Results

Date

17 reactions in Reaxys

2016-05-12 15h:18m:11s (EST)

X X

Mg

1. Query

Search as: As drawn, No salts, No mixtures

1/10

2016-05-12 15:20:55

Mg

Br

Br Mg

Rx-ID: 28138297 View in Reaxys 1/17 Yield

Conditions & References 4.3 :A 100 mL 3 -neck flask, was placed under N2 and equipped with a condenser and an addition funnel. Magnesium (2.9 g, 120 mmol) were added. Bromobenzene (15.7 g, 100 mmol) was taken up in dry THF (120 mL), and transferred to the addition funnel. The Grignard reaction was initiated with approximately 5 mL of the bromobenzene solution and iodine. The remained bromobenzene solution was added and the reaction was heated under reflux for 1 hour. The resulting solution was used for next step directly. With iodine in tetrahydrofuran, Time= 1h, Heating / reflux, Grignard Reaction Patent; VITAE PHARMACEUTICALS, INC.; WO2008/156817; (2008); (A2) English View in Reaxys in tetrahydrofuran Umeda, Rui; Namba, Teruaki; Yoshimura, Tomohiro; Nakatsukasa, Masamichi; Nishiyama, Yutaka; Tetrahedron; vol. 69; nb. 5; (2013); p. 1526 - 1531 View in Reaxys in tetrahydrofuran, Time= 1.5h, Inert atmosphere, Reflux Yu, Lihong; Lo, Kin Cheung; Xi, Jingyu; Phillips, David Lee; Chan, Wai Kin; New Journal of Chemistry; vol. 37; nb. 6; (2013); p. 1833 - 1842 View in Reaxys With iodine in tetrahydrofuran, Time= 2h, Inert atmosphere, Reflux Yu, Fabiao; Li, Peng; Wang, Bingshuai; Han, Keli; Journal of the American Chemical Society; vol. 135; nb. 20; (2013); p. 7674 - 7680 View in Reaxys

Br

Mg

Br

Rx-ID: 1711246 View in Reaxys 2/17 Yield

Conditions & References With magnesium in tetrahydrofuran Chan, L. K. M.; Gray, G. W.; Lacey, D.; Toyne, K. J.; Molecular Crystals and Liquid Crystals (1969-1991); vol. 158; (1988); p. 209 - 240 View in Reaxys With magnesium in diethyl ether, T= 19.9 °C , various concentrations of aryl halide, Rate constant Maslennikov; Spirina; Russian Journal of General Chemistry; vol. 68; nb. 2; (1998); p. 274 - 276 View in Reaxys With magnesium in diethyl ether, benzene, T= 19.85 °C , magnesium oxidation with hydrocarbon halides; character of adsorption; diffusion of reagent to metal surface; rate of oxidation; energy of activation; kinetics; formation of Grignard reagents, Rate constant, Product distribution, Thermodynamic data Maslennikov; Spirina; Russian Journal of General Chemistry; vol. 68; nb. 12; (1998); p. 1876 - 1877 View in Reaxys With 18-crown-6 ether, magnesium in tetrahydrofuran, T= 20 °C , Product distribution, Further Variations: Reagents, Solvents Hazimeh, Hassan; Mattalia, Jean-Marc; Marchi-Delapierre, Caroline; Barone, Rene; Nudelman, Norma S.; Chanon, Michel; Journal of Physical Organic Chemistry; vol. 18; nb. 12; (2005); p. 1145 - 1160 View in Reaxys

2/10

2016-05-12 15:20:55

With magnesium in diethyl ether, T= 35 °C , Kinetics, Further Variations: Solvents Simuste, Hannes; Panov, Dmitri; Tuulmets, Ants; Nguyen, Binh T.; Journal of Organometallic Chemistry; vol. 690; nb. 12; (2005); p. 3061 - 3066 View in Reaxys 35.c; 58.b :c) [2- (4-Isopropyl-phenyl)-7-methoxy-1- (2-methoxy-ethyl)-1 H-benzoimidazol-5-yl]-phenyl- methanol; A solution of 150mg (0. 426mol) 2-(4-isopropyl-phenyl)-7-methoxy-1-(2-methoxy-ethyl)-1 H- benzoimidazole-5-carbaldehyde in 2ml THF is treated with excess phenylmagnesiumbromide (prepared from 112jJ bromobenzene and 26mg magnesium in 5ml diethyl ether). The resulting mixture is stirred at room temperature for 1 h. The reaction mixture is poured on water and extracted (3x) with ethyl acetate. The combined organic layers are washed with water (2x) and brine, dried over MgS04, filtered and concentrated in vacuo. The residue is purified by flash-chromatography on silica gel (hexane: EtOAc = 1: 2) to afford 136mg of the title compound as a white solid. With magnesium in diethyl ether Patent; NOVARTIS AG; NOVARTIS PHARMA GMBH; WO2005/68433; (2005); (A1) English View in Reaxys 3 :A solution of compound 3716 (0.88 g, 3.8 mmol) in dry THF (10 mL) was dropwise added to a solution of PhMgBr in ethyl ether [obtained from 1.23 g of PhBr, 0.185 g of Mg turnings and 8 mL of Et2O]. The mixture was refluxed for 30 min, then cooled to rt and quenched by the addition of NH4Cl saturated solution. Chloroform extraction and evaporation gave a residue which was purified by column chromatography to give the title compound 26 (0.7 g, 59percent yield) along with some other unidentified by-products. The title compound was obtained as colorless crystals by crystallization: mp 137-141 C. (ethanol); IR (KBr) 3210 broad, 1620 cm-1; 1H NMR (CDCl3) δ 8.02 (m, 1H), 7.85 (m, 1H), 7.60-7.10 (m, 7H), 3.87 (m, 1H), 3.55 (m, 2H), 3.08 (br s, 1H), 1.95 (m, 4H). Anal. (C18H17NO2S)C, H, N. With magnesium in diethyl ether Patent; The United States of America as represented by the Department of Health and Human Services; US7015212; (2006); (B1) English View in Reaxys 10.A :Example 10: General procedure for the preparation of benzoyl-imidazo[1 ,5- a]pyrimidines of general formula (I) following Scheme 1 EPO <DP n="20"/>N-[3-(8-benzoyl-imidazo[1 ,5-a]pyrimidin-4-yl)-phenyl]-N-methyl- methanesulfonamidePart A A solution of phenylmagnesium bromide was prepared from 1.0 g ( 42 mmol) of magnesium and 6.6 g (42 mmol) of bromobenzene in 40 ml of dry tetrahydrofuran.To the solution of the Grignard reagent, cooled by an ice-salt bath, a mixture of 1 g (9.3 mmol)of δ-amino-I H-imidazole^-carbonitrile and 20 ml of dry tetrahydrofuran was slowly added with stirring. After standing at room temperature for 2 hours, the mixture was cooled and decomposed by adding, with stirring, 40 ml of 3M hydrochloric acid. When the decomposition was completed (1 hour at a temperature between 90-950C), the reaction mixture was basified to ph 10 with 25percent ammonium hydroxide and was extracted with methylene chloride. The solution was dried with anhydrous sodium sulfate and the methylene chloride was distilled under diminished pressure to yield an oil which was chromatographied (silica gel) using ethyl acetate/methanol as eluent to produce 0.89 g (yield 52percent) of (5-amino-1 H-imidazol-4-yl)-phenyl- methanone. 1H NMR (400 MHz, CD OD): δ 7.27 (1 H, b), 7.44-7.51 (5H, m), 7.82 (3H, b). MS (ES) m/z = 188 (MH+) HPLC = 3 97percent With magnesium in tetrahydrofuran Patent; FERRER INTERNACIONAL, S. A.; WO2006/84835; (2006); (A1) English View in Reaxys 72.b : b A tetrahydrofuran solution of phenylmagnesium bromide which was prepared from 0.65 ml of bromobenzene, 200 mg of magnesium and 5 ml of tetrahydrofuran was added dropwise into the mixture, followed by stirring at room temperature overnight as it was. The reaction solution was extracted with an aqueous saturated ammonium chloride and ethyl acetate, and the organic phase was washed with water and brine, dried over anhydrous magnesium sulfate and then concentrated. With magnesium in tetrahydrofuran Patent; Eisai Co., Ltd.; US6599917; (2003); (B1) English View in Reaxys

3/10

2016-05-12 15:20:55

5.B : 1,2,3,3a,4,5,9,13b-octahydro-2-methyl-2-benzazepino[4,3,2-ij]-pyrazino[1,2-a]-5-hydroxy-5-phenylquinoline (Compound 9) STR31 EXAMPLE 5B 1,2,3,3a,4,5,9,13b-octahydro-2-methyl-2-benzazepino[4,3,2-ij]-pyrazino[1,2-a]-5-hydroxy-5-phenylquinoline (Compound 9) STR31 Phenylmagnesium bromide was prepared from bromobenzene (0.78 g, 0.005 mol) and magnesium (0.12 g, 0.005 mol) using dry THF as solvent. To this mixture was added the ketone (0.5 g, 0.0016 mol) in dry THF. The reaction mixture was stirred at room temperature for 2 hours before ammonium chloride was added and the product extracted into ethyl acetate. With ammonium chloride, magnesium in tetrahydrofuran Patent; Beecham Group Limited; US4442098; (1984); (A1) English View in Reaxys With magnesium in tetrahydrofuran Bonfanti, Jean-Francois; Meyer, Christophe; Doublet, Frederic; Fortin, Jerome; Mueller, Philippe; Queguiner, Laurence; Gevers, Tom; Janssens, Peggy; Szel, Heidi; Willebrords, Rudy; Timmerman, Philip; Wuyts, Koen; Van Remoortere, Pieter; Janssens, Frans; Wigerinck, Piet; Andries, Koen; Journal of Medicinal Chemistry; vol. 51; nb. 4; (2008); p. 875 - 896 View in Reaxys With iodine, magnesium in tetrahydrofuran, Time= 1h, T= 40 °C , Heating / reflux Patent; Takasago International Corporation; EP1167372; (2002); (A1) english View in Reaxys B7.2 : B7.2. [2-METHYL-6-PHENETHYL-ISONICOTINIC] acid. A solution of [PHENETHYLMAGNESIUMBROMIDE] (freshly prepared from phenethylbromide (0.66 g, 3.6 [MMOL)] and magnesium (0.083 g, 3.4 [MMOL))] in ether (10 mL) is added to a cooled [(-40°C)] and mechanically stirred solution of 2- chloro-6-methyl-isonicotinic acid tert-butyl ester (Example B7.1, 0.76 g, 3.34 [MMOL),] Fe (acac) 3 (21.2 mg, 0.06 mmol) and NMP (0.6 mL) in THF (60 mL). The mixture is warmed to r. t. during 0.5 h, diluted with ether (150 mL) and quenched with aq. KHS04 [(1M,] 40 mL). The phases are separated and the aq. phase is extracted with ether (2 x 50 mL). The combined organic extracts are dried [(MGS04),] filtered and evaporated. The residue is purified by MPLC [(C18,] [MEOH-] H20) and the 2-methyl-6-phenethyl-isonicotinic acid tert-butyl ester dissolved in [CH2CI2] (10 mL). TFA (10 mL) is added and the mixture stirred at r. t. for 0.5 h. The mixture is evaporated and the residue dried in HV to provide the title compound. With magnesium in diethyl ether Patent; ACTELION PHARMACEUTICALS LTD; WO2004/26836; (2004); (A2) English View in Reaxys With iodine, magnesium in tetrahydrofuran, Time= 0.5h, T= 25 °C , Inert atmosphere Chaudhuri, Rupsha; Liao, Hsin-Yi; Liu, Rai-Shung; Chemistry - A European Journal; vol. 15; nb. 35; (2009); p. 8895 - 8901 View in Reaxys With magnesium in diethyl ether Ito, Yosuke; Jogo, Shunsuke; Fukuda, Noriko; Okumura, Ryo; Nishino, Hiroshi; Synthesis; nb. 9; (2011); p. 1365 - 1374; Art.No: F16411SS View in Reaxys 2 :Example 2 Syntheses of Compounds 2a-4a A mixture of bromobenzene (5.5 ml, 52.2 mmol), magnesium turnings (3.81 g, 157 mmol), and a few iodine crystals was stirred to give Grignard reagent and was added to norcamphor (5.75 g, 52.2 mmol) to give a crude alcohol as a red oil (2a, 9.2 g, 93percent yield). Treatment of this alcohol (9.0 g, 47.8 mmol) with TFA (32 ml, 430 mmol) in the presence of sodium azide (9.3 g, 143 mmol) resulted in the tertiary azide as a red oil (3a, 9.3 g, 91percent yield), This azide (9.3 g, 40 mmol) was reduced

4/10

2016-05-12 15:20:55

to the corresponding amine with LiAlH4 (2.5 g, 67 mmol) to give (+)-2-phenylbicyclo[2.2.1]heptan-2-amine (4a) as a clear oil (7.8 g, 90percent yield). This oil (0.2 g) was purified by preparative TLC developed using a mixture of chloroform and diethyl ether (9:1, v/v) as mobile phase. A pale yellow oil was obtained, which solidified at 0° C. 1H NMR (CDCl3): δ ppm 7.3-7.4 (m, 5H), 1.0-2.6 (b, 10 H, 4CH2 and 2CH). 13C

NMR (CDCl3): δ 148.3, 128.6, 127.0, 126.4, 64.1, 48.5, 45.2, 37.1, 36.9, 28.8, 24.8; MS (ESI+) m/z: 188 (10per-

cent), [M+H], 171 (100percent), [M-16]. With magnesium, iodine in tetrahydrofuran Patent; Adeboye Adejare; US2012/190710; (2012); (A1) English View in Reaxys With magnesium in tetrahydrofuran Yadav, Jhillu Singh; Rao, Gokada Maheswara; Thirupathaiah, Bodakuntala; Helvetica Chimica Acta; vol. 96; nb. 12; (2013); p. 2233 - 2239 View in Reaxys With magnesium in tetrahydrofuran, Inert atmosphere Huang, Meng-Ting; Wu, Hsin-Yi; Chein, Rong-Jie; Chemical Communications; vol. 50; nb. 9; (2014); p. 1101 1103 View in Reaxys With magnesium in tetrahydrofuran, Time= 1h, Inert atmosphere, Reflux He, Tian; Gao, Wen-Chao; Wang, Wei-Kun; Zhang, Chi; Advanced Synthesis and Catalysis; vol. 356; nb. 5; (2014); p. 1113 - 1118 View in Reaxys With magnesium in tetrahydrofuran, Inert atmosphere Kolay, Siddhartha; Kumar, Mukesh; Wadawale, Amey; Das, Dasarathi; Jain, Vimal K.; Dalton Transactions; vol. 43; nb. 42; (2014); p. 16056 - 16065 View in Reaxys With magnesium in tetrahydrofuran, T= 83 °C Goldbach, Michel; Danieli, Ernesto; Perlo, Juan; Kaptein, Bernard; Litvinov, Victor M.; Blümich, Bernhard; Casanova, Federico; Duchateau, Alexander L.L.; Tetrahedron Letters; vol. 57; nb. 1; (2016); p. 122 - 125 View in Reaxys

O

Br

F

O

F

Mg

Br

F F

Rx-ID: 24883354 View in Reaxys 3/17 Yield 24%

Conditions & References 9 : EXAMPLE 9 EXAMPLE 9 In repeating the process of Example 8, the phenyllithium solution was replaced by a solution of phenylmagnesium bromide, which was prepared from 0.24 g (10 mmol) of magnesium and 1.25 g (8 mmol) of bromobenzene, in tetrahydrofuran, and the reaction was carried out at 50° C. for 24 hr. By column treatment, 1-phenyltetrafluoro-2-propenylacetate (E:Z=87:13) was obtained at 48percent yield and pentafluoro-2-propenylacetate at 24percent yield. 19 F-NMR: E-form; -12.3 (CF , d), 43.3 (F, q), JCF -F=15.0 Hz; Z-form; -13.7 (CF , d), 15.3 (F, q), JCF -F=7.5 Hz. 1 3 3 3 3 H-NMR: E-form; 2.20 (CH3, s, 3H), 7.0-7.7 (Ar, 5H); Z-form; 2.13 (CH3, s, 3H), 7.5-7.6 (Ar, 5H). With magnesium in tetrahydrofuran

5/10

2016-05-12 15:20:55

Patent; Central Glass Company, Limited; US4910348; (1990); (A1) English View in Reaxys

Mg

Br

N-Z-(S)-serine methyl ester

Rx-ID: 24650427 View in Reaxys 4/17 Yield

Conditions & References 16 : (S)-2-N-(Benzyloxycarbonyl)-2,2-diphenyl-1,3-propanediol EXAMPLE 16 (S)-2-N-(Benzyloxycarbonyl)-2,2-diphenyl-1,3-propanediol Phenyl magnesium bromide was prepared by addition of bromobenzene (209 ml, 1.98 mol) in Et2 O (300 ml) at 0° C. to Mg metal (48 g, 1.98 g atom) in Et2 O (500 ml). To this red solution was added N-Z-(S)-serine methyl ester 800 in ether (114 g, 0.45 mol) via an addition funnel at 0° C. The reaction was stirred for an additional 12 hr and quenched with 250 ml of conc. HCl in ice (~1 kg). The entire mass was extracted with EtOAc (3*100 ml). The combined organic phase was washed with water followed by brine. With hydrogenchloride in diethyl ether Patent; NDSU-Research Foundation; US5623087; (1997); (A1) English View in Reaxys

Br

O

N

F

N

Mg Cl

Br

3-fluorodiazepam

Cl

Rx-ID: 25401947 View in Reaxys 5/17 Yield

Conditions & References 130 : EXAMPLE 130 EXAMPLE 130 A solution of phenylmagnesium bromide is prepared from 7.85 g. of bromobenzene and 1.25 g. of Mg in 100 ml. of THF and a solution of 2.61 g. of 1-methyl-3-fluoro-5,7-dichloro-2,3-dihydro-1H-1,4-benzodiazepin-2-one, obtainable by addition of HF to 1-methyl-2,5-dihydro-1H-1,4-benzodiazepin-2,5-dione to give the 3-fluoro derivative and reaction with PCl5, in 150 ml. of THF is added dropwise at about 20° to the stirred mixture. After 2 hours heating under reflux and stirring, the mixture is cooled, diluted with 100 ml. of ether and decomposed by ammonium chloride solution. Working up in the customary manner gives 3-fluorodiazepam, m.p. 152°-154°. With HF in tetrahydrofuran Patent; Merck Patent Gesellschaft mit beschraenkter Haftung; US4232016; (1980); (A1) English View in Reaxys

Br

O

dimethyl-2,3-O-cyclohexylidene-L-tartrate

O

Mg

Br

O O

Rx-ID: 25460238 View in Reaxys 6/17 Yield

Conditions & References

17 g (34%) 33 : Example 33

6/10

2016-05-12 15:20:55

A diethyl ether solution (300 mL) of phenylmagnesium bromide obtained from the reaction of 50 mL of bromobenzene and 11.6 g of magnesium was added dropwise with stirring to a diethyl ether solution (130 mL) of the 28.6 g of dimethyl-2,3-O-cyclohexylidene-L-tartrate obtained above at 3-5° C. over 4.5 h. The resulting mixture was heated at reflux for 2 h, allowed to cool to room temperature, and poured onto ice-water (approx. -5° C.) containing NH4 Cl. The resulting organic layer was washed with 10percent HCl (10 mL) and water, and then dried over MgSO4. Evaporation of the solvent provided allowed the product to crystallize to afford 17 g (34percent) of the above-titled compound: mp.=200-202° C. (lit. 195-196° C.; Helv. Chim. Acta, 1987, 70, 954); 1 H NMR (CDCl3) δ1.2-1.6 (m, 5H), 4.65 (c, 2CH), 4.77 (c, 2OH), 7.3-7.6 (m, 20 CH aromatic). With magnesium in diethyl ether Patent; Zeeland Chemicals, Inc.; US6090950; (2000); (A1) English View in Reaxys

F

Mg

F

Rx-ID: 1710162 View in Reaxys 7/17 Yield

Conditions & References

100 %

With magnesium, T= -196.1 °C Sergeev, G. B.; Smirnov, V. V.; Badaev, F. Z.; Journal of Organometallic Chemistry; vol. 224; nb. 3; (1982); p. C29 - C30 View in Reaxys

Cl

Mg

Cl

Rx-ID: 5011086 View in Reaxys 8/17 Yield

Conditions & References With magnesium in diethyl ether, T= 19.9 °C , various concentrations of aryl halide, Rate constant Maslennikov; Spirina; Russian Journal of General Chemistry; vol. 68; nb. 2; (1998); p. 274 - 276 View in Reaxys With magnesium in toluene, T= 90 - 110 °C , Kinetics, Activation energy Simuste, Hannes; Panov, Dmitri; Tuulmets, Ants; Nguyen, Binh T.; Journal of Organometallic Chemistry; vol. 690; nb. 12; (2005); p. 3061 - 3066 View in Reaxys 1 :a Grignard reagent which had been prepared from 14.6 g (0.6 mole) of metallic magnesium, 67.5 g (0.6 mole) of chlorobenzene and 168 g of tetrahydrofuran (THF) With magnesium in tetrahydrofuran Patent; Shin-Etsu Chemical Co., Ltd.; EP1780198; (2007); (A1) English View in Reaxys 1 :Diphenyl sulfoxide, 40 g (0.2 mole), was dissolved in 400 g of dichloromethane, which was stirred under ice cooling. At a temperature below 20°C, 65 g (0.6 mole) of trimethylsilyl chloride was added dropwise to the solution, which was aged for 30 minutes at the temperature. Then, a Grignard reagent which had been prepared from 14.6 g (0.6 mole) of metallic magnesium, 67.5 g (0.6 mole) of chlorobenzene and 168 g of tetrahydrofuran (THF) was added dropwise at a temperature below 20°C. The reaction solution was aged for one hour, after which 50 g of water at a temperature below 20°C was added to quench the reaction. To this solution, 150 g of water, 10 g of 12N hydrochloric acid, and 200 g of diethyl ether were further added. The water layer was separated and washed with 100 g of diethyl ether, yielding an aqueous solution of triphenylsulfonium chloride. The compound in aqueous solution form was used in the subsequent reaction without further isolation. With magnesium in tetrahydrofuran

7/10

2016-05-12 15:20:55

Patent; Shin-Etsu Chemical Co., Ltd.; EP1780199; (2007); (A1) English View in Reaxys

Mg

Br

(S)-Carbomethoxy oxazolidinone

Rx-ID: 24650429 View in Reaxys 9/17 Yield

Conditions & References 8 : (S)-4-(hydroxyethyldiphenyl-2-oxazolidinone EXAMPLE 8 (S)-4-(hydroxyethyldiphenyl-2-oxazolidinone Phenyl magnesium bromide was prepared by slow addition of bromobenzene (14.53 ml, 137.93 ml) in THF (50 ml) to Mg (3.31 g, 137.93 g atom). The reaction mixture was stirred for one hour or until most of the Mg had been consumed. (S)-Carbomethoxy oxazolidinone (5 g, 34.48 mmol; prepared according to Example 7), dissolved in THF (25 ml), was added dropwise over 15 min period and allowed to stir an additional hour. in tetrahydrofuran Patent; NDSU-Research Foundation; US5623087; (1997); (A1) English View in Reaxys

Mg

Br

O N

O

Rx-ID: 25330588 View in Reaxys 10/17 Yield

Conditions & References 47 : EXAMPLE 47 EXAMPLE 47 Preparation of Ethyl β-Amino-m-Trifluoromethylcinnamate. Phenylmagnesium bromide was prepared from 70 g (0.445 mol) of bromobenzene and 11.1 g (0.458 mol) of magnesium in 300 ml of ether. Then, 50.3 g (0.445 mol) of ethyl cyanoacetate was added dropwise with stirring at -55° to -35° (vigorous exothermic reaction after about 20-30percent of the ethyl cyanoacetate added, even with Dry ice-acetone bath cooling). With magnesium Patent; Monsanto Company; US4187099; (1980); (A1) English View in Reaxys Patent; Monsanto Company; US4144047; (1979); (A1) English View in Reaxys

I

Mg

I

Rx-ID: 4070182 View in Reaxys 11/17 Yield

Conditions & References With magnesium in diethyl ether, T= 19.9 °C , also phenyl bromide; var. solvents, Mechanism Kondin, A. V.; Smirnova, M. Yu.; Maslennikov, V. P.; Russian Journal of General Chemistry; vol. 64; nb. 1.1; (1994); p. 32 - 34; Zhurnal Obshchei Khimii; vol. 64; nb. 1; (1994); p. 35 - 37 View in Reaxys With magnesium in diethyl ether, T= 4.9 °C , various concentrations of aryl halide, Rate constant Maslennikov; Spirina; Russian Journal of General Chemistry; vol. 68; nb. 2; (1998); p. 274 - 276 View in Reaxys

8/10

2016-05-12 15:20:55

3 : Example 3 Production of platinum complex (1'-3) 20 ml of a tetrahydrofuran solution of 1.1 g of iodobenzene was added dropwise to 0.13 g of magnesium to produce phenylmagnesium iodide. To the reaction solution, 0.44 g of the dihydrate of the platinum complex (1'-1) obtained in the first half of Example 1 was added. The resulting mixture was stirred under reflux for 3 hours. After cooling to room temperature, the reaction solution was extracted with methylene chloride. Then, a neutral silica gel column chromatography (methylene chloride / methanol = 1/0 to 20/1) was carried out, resulting in 0.10 g of a target compound (1'-3) in the form of a yellow solid. Elementary analysis: calculated values (C,34.73; H, 2.00; N, 5.06percent). measured values (C, 34.70; H, 2.25; N, 4.96 percent). With magnesium in tetrahydrofuran Patent; Takasago International Corporation; EP1577300; (2005); (A1) English View in Reaxys

Mg

Cl

Cl Mg

Rx-ID: 28257757 View in Reaxys 12/17 Yield

Conditions & References 1-1 :Synthesis Example 1-1; Synthesis of triphenylsulfonium chloride; Diphenyl sulfoxide, 40 g (0.2 mole), was dissolved in 400 g of dichloromethane, which was stirred under ice cooling. At a temperature below 20°C, 65 g (0.6 mole) of trimethylsilyl chloride was added dropwise to the solution, which was aged for 30 minutes at the temperature. Then, a Grignard reagent which had been prepared from 14.6 g (0.6 mole) of metallic magnesium, 67.5 g (0.6 mole) of chlorobenzene and 168 g of tetrahydrofuran (THF) was added dropwise at a temperature below 20°C. The reaction solution was aged for one hour, after which 50 g of water at a temperature below 20°C was added to quench the reaction. To this solution, 150 g of water, 10 g of 12N hydrochloric acid, and 200 g of diethyl ether were further added. The water layer was separated and washed with 100 g of diethyl ether, yielding an aqueous solution of triphenylsulfonium chloride. The compound in aqueous solution form was used in the subsequent reaction without further isolation. in tetrahydrofuran Patent; Shin-Etsu Chemical Co., Ltd.; EP2033966; (2009); (A2) English View in Reaxys 2H

2H

Br

2H

Br Mg

Mg

2H

Rx-ID: 28545235 View in Reaxys 13/17 Yield

Conditions & References 3.1 :d5-Phenylmagnesium bromide: The procedure of Step 1 is carried out using the methods described by Dejaegher et al, Synlett 2002, 113-115. A solution of d5-bromobenzene (available commercially from Sigma Aldrich, St. Lousis Mo.) in diethyl ether is added to magnesium shavings and heated at reflux to give the title product. in diethyl ether, Heating / reflux Patent; AUSPEX PHARMACEUTICALS, INC.; US2009/176792; (2009); (A1) English View in Reaxys 2

H

2H 2H

Br

2H

2H 2H

2

H

Mg

2H

Br

2H 2

H

Rx-ID: 1988871 View in Reaxys 14/17 Yield

Conditions & References With magnesium in tetrahydrofuran, Time= 0.5h, Heating

9/10

2016-05-12 15:20:55

Currie, Graeme J.; Bowie, John H.; Massy-Westropp, Ralph A.; Adams, Gregory W.; Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999); (1988); p. 403 - 408 View in Reaxys With magnesium in tetrahydrofuran, T= 45 °C , Inert atmosphere Li, Lu; Wang, Xiuli; Li, Qingling; Liu, Pengyuan; Xu, Kehua; Chen, Hao; Tang, Bo; Chemical Communications; vol. 51; nb. 56; (2015); p. 11317 - 11320 View in Reaxys

I

Mg

Cl

Rx-ID: 36603994 View in Reaxys 15/17 Yield

Conditions & References With isopropylmagnesium chloride in tetrahydrofuran, Time= 0.916667h, T= 0 - 10 °C , Inert atmosphere Reeves, Jonathan T.; Sarvestani, Max; Song, Jinhua J.; Tan, Zhulin; Nummy, Laurence J.; Lee, Heewon; Yee, Nathan K.; Senanayake, Chris H.; Organic Process Research and Development; vol. 10; nb. 6; (2006); p. 1258 1262 View in Reaxys 2H

2H 2H

2H

Br

Mg

Br

magnesium turnings 2H

2H

2H 2H

Rx-ID: 8414654 View in Reaxys 16/17 Yield

Conditions & References in diethyl ether Ozasa, Shigeru; Fujioka, Yasuhiro; Kikutake, Jun-ichiro; Ibuki, Eiichi; Chemical and Pharmaceutical Bulletin; vol. 31; nb. 5; (1983); p. 1572 - 1581 View in Reaxys

I

Mg

I

magnesium powder Rx-ID: 6680886 View in Reaxys 17/17 Yield

Conditions & References Spencer; Chemische Berichte; vol. 41; (1908); p. 2303 View in Reaxys Spencer; Stokes; Journal of the Chemical Society; vol. 93; (1908); p. 71 View in Reaxys

10/10

2016-05-12 15:20:55

Turn static files into dynamic content formats.

Create a flipbook