Structure of 1293-65-8
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CAS No. : | 1293-65-8 |
Formula : | C10Br2Fe |
M.W : | 335.76 |
SMILES Code : | Br[C-]12[Fe+2]3456789([C-]%10(Br)C6=C7C8=C9%10)C1=C3C4=C25 |
MDL No. : | MFCD01075755 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-P264-P271-P280-P302+P352-P304+P340+P312-P305+P351+P338-P332+P313-P337+P313-P403+P233-P405-P501 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In tetrahydrofuran; hexane; at -30℃; for 0.5 - 1.5h;Product distribution / selectivity; | Preparation of i-phenylchlorophosphine-i '-bromoferrocene (X1 )14.5 ml (23.2 mmol) of n-BuLi (1.6 M in hexane) are added dropwise to a solution of 8 g (23.2 mmol) of 1 ,1 '-<strong>[1293-65-8]dibromoferrocene</strong> in 30 ml of THF at a temperature of < -30 C. The mixture is stirred for a further 30 minutes at this temperature. It is then cooled to -78C and 3.15 ml (23.2 mmol) of phenyldichlorophosphine are added dropwise at such a rate that the temperature does not exceed -60C. After stirring the mixture at -78C for a further 10 minutes, the temperature is allowed to rise to room temperature and the mixture is stirred for another one hour. This gives a suspension of the monochlorophosphine X1.; Preparation of i-dicyclohexylphosphino-i '-bromoferrocene of the formula (A2)120 ml (0.3 mol) of n-BuLi (2.5 M in hexane) are added dropwise to a solution of 103 g (0.3 mol) of 1 ,1 '-<strong>[1293-65-8]dibromoferrocene</strong> in 300 ml of THF at a temperature of < -30C. The mixture is stirred at this temperature for a further 1.5 hours. It is then cooled to -50C and 66.2 ml (0.3 mol) of dicyclohexylphosphine chloride are added dropwise at such a rate that the temperature does not exceed -45C. After stirring the mixture for a further 10 minutes, the temperature is allowed to rise to room temperature and the mixture is stirred for another one hour. After addition of 150 ml of water, the reaction mixture is shaken with hexane. The organic phases are dried over sodium sulphate and the solvent is distilled off under reduced pressure on a rotary evaporator. The residue is crystallized in ethanol. The product A2 is obtained in a yield of 84% (yellow solid). 1H NMR (300 MHz, C6D6): delta 1.20-2.11 (m, 22H), 3.97 (m, 2H), 4.23 (m, 2H), 4.26 (m, 2H), 4.41 (m, 2H). 31P NMR (121.5 MHz, C6D6): delta -8.3 (s).; Example B17: Preparation of the compound (Rc,SFc,SP)-1-[2-(1-dimethylaminoethyl)ferrocen- i-yllcyclohexylphosphino-i '-bis-beta.S-d^trifluoromethylJphenyllphosphinoferrocene (B17):4 ml (10 mmol) of n-BuLi (2.5 M in hexane) are added dropwise to a solution of 3.44 g (10 mmol) of 1 ,1 '-<strong>[1293-65-8]dibromoferrocene</strong> in 10 ml of tetrahydrofuran (THF) at a temperature of < -30C. The mixture is stirred at this temperature for a further 1.5 hours to give a suspension of 1-bromo-1 '-lithioferrocene X5.In a second reaction vessel, 7.7 ml (10 mmol) of S-BuLi (1.3 M in cyclohexane) are added dropwise to a solution of 2.57 g (10 mmol) of (R)-1-dimethylamino-1-ferrocenylethane in 15 ml of TBME at <-10C. After stirring the mixture at the same temperature for 10 minutes, the temperature is allowed to rise to 0 and the mixture is stirred for another 1.5 hours. The reaction mixture is then cooled to -78C and 1.51 ml (10 mmol) of dichlorocyclohexyl- phosphine are added. Further stirring at -78C for 30 minutes and, after removal of cooling, at room temperature for another one hour gives a suspension of the chlorophosphine X4 which is subsequently added at a temperature of <-10C to the suspension of 1-bromo-1 '-lithio- ferrocene X5. The cooling is then removed and the mixture is stirred at room temperature for a further 1.5 hours. After renewed cooling to <-50C, 4 ml (10 mmol) of n-BuLi (2.5 M in hexane) are added dropwise. After the addition, the temperature is allowed to rise to 0C and the mixture is stirred for a further 30 minutes. It is then cooled to -20C and 4.63 g (10 mmol) of bis[3,5-di(trifluoromethyl)phenyl]chlorophosphine are added. The cooling is subsequently removed and the mixture is stirred at room temperature for another 1.5 hours. The reaction mixture is admixed with 1 N NaOH and extracted. The organic phase is dried over sodium sulphate and the solvent is distilled off under reduced pressure on a rotary evaporator. The residue is subsequently heated at 150C for one hour. Chromatographic purification (silica gel 60; eluent = hexane/ethyl acetate 8:1 ) gives the compound B17 as a yellow solid (yield: 66%). <n="39"/>1H NMR (300 MHz, C6D6): delta 1.25 (d, 3H, J = 6.7 Hz), 1.00-2.29 (m, 1 1 H), 2.20 (s, 6H), 3.78 (m, 1 H), 4.02 (m, 1 H), 4.04 (s, 5H), 4.09 (m, 1 H), 4.14 (m, 1 H), 4.17 (m, 1 H), 4.21 (m, 1 H), 4.40 (m, 2H), 4.60 (m, 1 H), 7.80 (d, 2H, J = 6.8 Hz), 8.00 (d, 4H, J = 6.0 Hz). 31P NMR (121.5 MHz, C6D6): delta -27.1 (s); -14.1 (s).; Example B18: Reaction schemeX24 ml (10 mmol) of n-BuLi (2.5 M in hexane) are added dropwise to a solution of 3.44 g (10 mmol) of 1 ,1 '-<strong>[1293-65-8]dibromoferrocene</strong> in 10 ml of tetrahydrofuran (THF) at a temperature of < -30C. The mixture is stirred at this temperature for a further 1.5 hours. 2.21 ml (10 mmol) of dicyclohexylphosphine chloride are then added dropwise at such a rate that the temperature does not exceed -20C. After stirring the mixture for a further 10 minutes, the temperature is allowed to rise to room temperature and the mixture is stirred for another one hour. It is cooled back down to 30C and 4.4 ml (11 mmol) of n-BuLi (2.5 M in hexane) are added dropwise. The mixture is subsequently stirred at -10C for 30 minutes. The reaction mixture is the... | |
In tetrahydrofuran; hexane; at -30℃; | A) Preparation of Intermediates; EXAMPLE A1; Preparation of (Rc,SFc,SP)-1-[2-(1-dimethylaminoethyl)ferrocen-1-yl]phenylphosphino-1'-bromoferrocene of the formula (A1) [Ph=phenyl; Me=methyl]; a) Preparation of 1-phenylchlorophosphino-1'-bromoferrocene (X1); 14.5 ml (23.2 mmol) of n-BuLi (1.6 M in hexane) are added dropwise to a solution of 8 g (23.2 mmol) of <strong>[1293-65-8]1,1'-<strong>[1293-65-8]dibromoferrocene</strong></strong> in 30 ml of THF at a temperature of <-30 C. The mixture is stirred for another 30 minutes at this temperature. It is then cooled to -78 C. and 3.15 ml (23.2 mmol) of phenyldichlorophosphine are added dropwise at such a rate that the temperature does not exceed -60 C. After stirring at -78 C. for a further 10 minutes, the temperature is allowed to rise to room temperature and the mixture is stirred for another one hour. This gives a suspension of the monochlorophosphine X1.; b) Preparation of 1-bromo-1'-lithioferrocene X5; 4 ml (10 mmol) of n-BuLi (2.5 M in hexane) are added dropwise to a solution of 3.43 g (10 mmol) of <strong>[1293-65-8]1,1'-<strong>[1293-65-8]dibromoferrocene</strong></strong> in 10 ml of tetrahydrofuran (THF) at a temperature of <-30 C. The mixture is stirred at this temperature for another 1.5 hours and subsequently cooled to -78 C. This gives a suspension of 1-bromo-1'-lithioferrocene X5.; Reaction mixture b): In a second reaction flask, 4.0 ml (10 mmol) of n-BuLi (2.5 M in hexane) are added dropwise to a solution of 3.43 g (10 mmol) of 1,1'-dibromo-ferrocene in 10 ml of THF which has cooled to -30 C. at such a rate that the temperature does not exceed -30 C. The mixture is subsequently stirred at -30 C. for a further 1.5 hours and the mixture containing the 1-bromo-1'-lithioferrocene is finally cooled to -78 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In diethyl ether; pentane; at -78℃; | Example 1; L11,1' bis-[(Sp,Rc,SFe)(1-N,N- Dimethylamino)ethylferrocenyl)phenylphosphino] ferrocene L1To a solution of (R)-N, N-dimethyl-1-ferrocenylethylamine [(R)-Ugi's amine] (3.09 g, 12 mmol) in Et2O (20 ml) was added 1.5 M t-BuLi solution in pentane(8.0 ml, 12.0 mmol) at -78 0C. After addition was completed, the mixture was warmed to room temperature, and stirred for 1.5 h at room temperature. The mixture was then cooled to -78 0C again, and dichlorophenylphosphine (1.63 ml, 12.0 mmol) was added in one portion. After stirring for 20 min at -78 0C, the mixture was slowly warmed to room temperature, and stirred for 1.5 h at room temperature. The mixture was then cooled to -78 0C again, and a suspension of 1 ,1' dilithioferrocene [prepared from 1 ,1' <strong>[1293-65-8]dibromoferrocene</strong>(1.72 g, 5.0 mmol) and 1.5 M t-BuLi solution in pentane (14.0 ml, 21.0 mmol) in Et2O (20 ml) at -78 0C] was added slowly via a cannula. The mixture was warmed to room temperature and allowed to stir for 12 h. The reaction was quenched by the addition of saturated NaHCO3 solution (20 ml). The organic EPO <DP n="18"/>layer was separated and dried over MgSO4 and the solvent removed under reduced pressure. The filtrate was concentrated. The residue was purified by chromatography (SiO2, hexane-EtOAc-Et3N = 85:10:5) to afford an orange solid (3.88 g, 85%) as a mixture of 95% his-(Sp,Rc,SFe) title compound L1 and 5% (Rp, Rc, S Fe-S p, Rc, S Fe) meso compound. The meso compound can be removed by further careful purification using chromatography (SiO2, hexane- EtOAc-Et3N = 85:10:5). Orange/yellow crystalline solid m.p. 190-192 0C. [alpha]D = -427 (c=0.005 (g/ml), toluene); 1H NMR (CDCI3, 400.13 MHz): delta 1.14 (d,6H,J = 6.7 Hz), 1.50 (s, 12H); 3.43 (m; 2H); 3.83 (m, 2H); 3.87 (m, 2H); 4.01 (s, 10H), 4.09 (t, 2H, J = 2.4 Hz); 4.11 (m, 2H); 4.20 (m, 2H); 4.28 (m, 2H); 4.61 (m, 2H); 4.42 (d, 2H1 J = 5.3 Hz); 7.18 (m, 6H); 7.42(m, 4H) ppm. 13C NMR (CDCI3, 100.61 MHz): delta 38.28, 57.40 (d, J = 5.6 Hz); 67.02, 69.04 (d, J = 4.0 Hz); 69.16 (d, J = 51.6 Hz); 69.66, 71.60 (d, J = 4.8 Hz), 71.91 (d, J = 7.2 Hz), 72.18 (d, J = 5.6 Hz), 75.96 (d, J = 35.7 Hz), 79.96 (d, J = 6.4 Hz), 95.73 (d, J = 19.1 Hz), 127.32 (d, J = 7.9 Hz), 127.62, 133.12 (d, J = 21.4 Hz), 139.73 (d, J = 4.0 Hz). 31P NMR (CDCI3, 162 MHz): delta -34.88 (s). Found: C, 65.53; H, 5.92; N 3.01 Calculated for C50H54Fe3N2P2; C, 65.81 ; H, 5.97; N, 3.07. HRMS (1OeV, ES+): Calcd for C50H55Fe3N2P2 [M+H]+: 913.1889; Found: 913.1952. The label SP refers to S configuration at phosphorus, Rc refers to R configuration at carbon (or other auxiliary) and Spe refers to S configuration at the planar chiral element. |