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Chemical Structure| 1271-19-8
Chemical Structure| 1271-19-8
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Product Details of [ 1271-19-8 ]

CAS No. :1271-19-8 MDL No. :MFCD00003723
Formula : C10H10Cl2Ti Boiling Point : -
Linear Structure Formula :- InChI Key :-
M.W : 248.96 Pubchem ID :-
Synonyms :
Chemical Name :Titanocenedichloride

Safety of [ 1271-19-8 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P201-P261-P280-P305+P351+P338-P405-P501 UN#:N/A
Hazard Statements:H302-H332-H315-H319-H341-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 1271-19-8 ]

* 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.

  • Downstream synthetic route of [ 1271-19-8 ]

[ 1271-19-8 ] Synthesis Path-Downstream   1~90

  • 1
  • [ 1271-19-8 ]
  • [ 676-58-4 ]
  • [ 1271-66-5 ]
YieldReaction ConditionsOperation in experiment
85% In tetrahydrofuran; at -10 - 0℃; for 1.33333h;Schlenk technique; Inert atmosphere; A Schlenk flask was charged with titanocene dichloride (5.0 g, 20.1 mmol)(Aldrich Co)in 50 mL of distilled THF under argon atmosphere. To the red suspension, cooled to -100C, was added dropwise methyl magnesium chloride (3M solution in THF-Aldrich Co)(14.9 mL, 44.8 mmol, 2.23 equiv.). The mixture was stirred for 80 minutes while slowlywarming to 0 0C, affording an orange solution. After cooling to -10 0C, 40 ml of waterwas cautiously added. The organic phase was washed with water (2 x 25 ml) and brine (1x 25 ml) and dried over MgSO4. Removal of the solvent on a rotary evaporator affordedthe crude product as an orange solid (3.9 g, 95%). Recrystallization from 15 ml ofpentane at -30 0C afforded crystalline product (3.5 g, 85%).1H NMR (C6D6): delta 0.05 (s, 6H, CH3), 5.68 (s, 10H, Cp). 13C NMR: delta 45.9, 113.2.
78% In tetrahydrofuran; toluene; at -5 - 5℃; for 2h; [00165] To a solution of titanocene dichloride (Cp2TiCI2, 9.96 g, 40 mmol) in anhydrous toluene (108 ml) was added methylmagnesium chloride (3.0 M in tetrahydrofuran, 32 ml, 96 mmol) dropwise at -5C under nitrogen atmosphere, and then the reaction mixture was stirred at 5C for 2 h. The reaction mixture was cooled to -10C and 6% ammonium chloride solution in water (28 ml) was added, after stirring for a further 1 h at 5C, the mixture was extracted with toluene (100 ml chi 3), and the combined toluene was washed with water and brine, dried over anhydrous Na2S04, concentrated at a bath temperature of no more than 35C to give a solution of dimethyltitanocene (Cp2TiMe2) in toluene as a red liquid (36.7 g, w/w% = 17.7%, 78% yield). [00166] A mixture of compound 93-4 (1.65 g, 7.3 mmol) and dimethyltitanocene in toluene (36.7 g, w/w% = 17.7%, 31.0 mmol) was stirred under nitrogen atmosphere in the dark at 60C overnight. The reaction mixture was cooled to room temperature, diluted with petroleum ether, filtered and the filtrate was concentrated, the residue was purified by flash chromatography on basic aluminum oxide (eluted by petroleum ether) to afford compound 93-5 (816 mg, 50%) as yellow oil. [00167] 1H NMR deltaEta (400 MHz; CDCI3):2.58 (t, J = 6.8 Hz, 2H), 2.86 (t, J = 6.8 Hz, 2H), 4.20 (s, 1 H), 4.59 (s, 1 H), 6.86 (d, J = 8.0 Hz, 1 H), 7.02 (t, J = 8.0 Hz, 1 H), 7.16 (d, J = 8.0 Hz, 1 H)
In toluene; at 0 - 5℃; for 2h; Step-ll: Dimethyl titanocene reagent; Toluene (2.5 Lt) is added to titanocene dichloride (210 gm) under stirring at 25 - 300C, the contents are cooled to O0C and then methyl magnesium chloride (1.25 Lt) is slowly added for 1 hour at 0 - 50C. The resulting mass is stirred for 1 hour at 0 - 50C, quenched the mass into the solution of NH4CI (200 gm) in water (3.25 Lt) at 10 - 150C under N2 atmosphere and stirred for 20 minutes at 10 - 150C. Separated the layers, the organic layer is washed three times with chilled water (each time 3.25 Lt) followed by saturated NaCI solution (3,25 Lt) and then dried over Na2SO4. Distilled off the solvent up to mass weight reaches to 1.6 Kg under vacuum at 400C to give dimethyl titanocene.
In tetrahydrofuran; toluene; at 0 - 8℃; for 2.25h; In a 1 L round-bottom flask titanocene dichloride (60 g, 0.24 mol) was suspended in dry toluene (300 ml) under nitrogen atmosphere and cooled down to 0 C. Methylmagnesium chloride (3 M solution in THF, 180 ml, 0.54 mol) was added dropwise (over 45 min), keeping the internal temperature below 8 C. The resulting mixture was stirred at 0-5 C. for 1.5 h and then transferred (over 30 min) through a siphon in an ice-cooled 6% w/w NH4Cl aqueous solution (180 ml), keeping the internal temperature below 5 C. The mixture was stirred at 0-5 C. for 1 h. Celite (15 g) was added, the mixture stirred at 10 C. for 15 min and then filtered washing with toluene (20 ml). Phases were separated. The organic layer was washed with water (180 ml) and brine (180 ml), dried (Na2SO4), filtered End then distilled down under vacuo to 200 ml. The dimethyltitanocene solution in toluene was charged in a 1 L round-bottom flask under nitrogen atmosphere and 1,1-dimethylethyl (2S)-2-[2-(methyloxy)-2-oxoethyl]-1-piperidinecarboxylate (20 g, 0.078 mol) was ad Led. The resulting mixture was stirred at 90 C. for 3 h. Toluene (500 ml) and iso-octane (50 ml) were added and the mixture filtered through a celite pad to remove inorganic salts. A CU NO filtration (R55S cartridge) was then performed to remove the finest particle size solid. The resulting clear solution was concentrated under vacuo to afford the intermediate 1,1-dimethylethyl (2S)-2-{2-[(methyloxy)methyl]-2-propen-1-yl}-1-piperidinecarboxylate as an orange oil (13.60 g, 0.053 mol, 68% yield). HPLC (walk-up): rt=4.69 min. 1H-NMR (400 MHz, CDCl3) delta (ppm): 4.42-4.58 (m, 1H), 3.94-4.08 (m, 1H), 3.88-3.93 (m, 2H), 3.53 (s, 3H), 2.79 (t, 1H), 2.42 (dd, 1H), 2.27 (dd, 1H), 1.50-1.70 (m, 6H), 1.46 (s, 9H).
In a IL round-bottom flask titanocene dichloride (60 g, 0.24 mol) was suspended in dry toluene (300 ml) under nitrogen atmosphere and cooled down to 0 0C. Methylmagnesium chloride (3 M solution in THF, 180 ml, 0.54 mol) was added dropwise (over 45 min), keeping the internal temperature below 8 0C. The resulting mixture was stirred at 0-5 0C for 1.5 h and then transferred (over 30 min) through a siphon in an ice-cooled 6% w/w NH4Cl aqueous solution (180 ml), keeping the internal temperature below 5 0C. The mixture was stirred at 0-5 0C for 1 h. Celite (15 g) was added, the mixture stirred at 10 0C for 15 min and then filtered washing with toluene (20 ml). Phases were separated. The organic layer was washed with water (180 ml) and brine (180 ml), dried (Na2SO4), filtered and then distilled down under vacuo to 200 ml. The dimethyltitanocene solution in toluene was charged in a 1 L round-bottom flask under nitrogen atmosphere and 1,1-dimethylethyl (2S)-2-[2- (methyloxy)-2-oxoethyl]-l-piperidinecarboxylate (20 g, 0.078 mol) was added. The resulting mixture was stirred at 90 0C for 3 h. Toluene (500 ml) and iso-octane (500 ml) were added and the mixture filtered through a celite pad to remove inorganic salts. A CUNO filtration (R55S cartridge) was then performed to remove the finest particle size solid. The resulting clear solution was concentrated under vacuo to afford the intermediate 1 , 1 -dimethylethyl (2S)-2- {2-[(methyloxy)methyl] -2-propen- 1 -yl} - 1 -piperidinecarboxylate as an orange oil (13.60 g, 0.053 mol, 68% yield). HPLC (walk-up): rt = 4.69 min. 1H-NMR (400 MHz, CDCl3) delta(ppm): 4.42 - 4.58 (m, 1 H), 3.94 - 4.08 (m, 1 H), 3.88-3.93 (m, 2 H), 3.53 (s, 3 H), 2.79 (t, 1 H), 2.42 (dd, IH), 2.27 (dd, 1 H), 1.50 - 1.70 (m, 6 H), 1.46 (s, 9 H). <n="19"/>NBS (8.36 g, 0.047 mol) was added portionwise to a mixture of 1,1-dimethylethyl (2S)-2- {2-[(methyloxy)methyl]-2-propen-l-yl}-l-piperidinecarboxylate (10 g, 0.039 mol) in THF (70 ml) and H2O (15 ml). The mixture was diluted with TBME (100 ml) and water (50 ml). The aqueous phase was back-extracted with TBME (50 ml). The collected organic phases were washed (twice) with a 4% w/w NaHCO3 aqueous solution, dried (Na2SO4), filtered and evaporated under vacuo. The residual oil was purified by filtration through a silica pad (20 g, toluene/EtOAc 90/10). A further filtration through a silica pad (50 g, toluene/TBME 90/10) afforded the title compound D2 (7.80 g, 0.024 mol, 62% yield). 1H-NMR (600 MHz, DMSO-J6) delta(ppm): 4.50 - 4.64 (m, 1 H), 4.35 (s, 2 H), 3.70 - 3. 88 (m, 1 H), 2.86 - 3.01 (m, 1 H), 2.65 - 2.82 (m, 2 H), 1.42 - 1 .60 (m, 5 H), 1.35 (s, 9 H), 1.14 - 1.28 (m, I H).
Toluene (2.5 Lt) is added to titanocene dichloride (210 gm) under stirring at 25-30 C., the contents are cooled to 0 C. and then methyl magnesium chloride (1.25 Lt) is slowly added for 1 hour at 0-5 C. The resulting mass is stirred for 1 hour at 0-5 C., quenched the mass into the solution of NH4Cl (200 gm) in water (3.25 Lt) at 10-15 C. under N2 atmosphere and stirred for 20 minutes at 10-15 C. Separated the layers, the organic layer is washed three times with chilled water (each time 3.25 Lt) followed by saturated NaCl solution (3.25 Lt) and then dried over Na2SO4. Distilled off the solvent up to mass weight reaches to 1.6 Kg under vacuum at 40 C. to give dimethyl titanocene.
In tetrahydrofuran; toluene; at 0 - 0.8℃; for 1h;Inert atmosphere; Schlenk technique; Cp2TiCl2, was taken in an oven dried 2-neck round bottom flask cooled under nitrogen and was dissolved in dry toluene. The mixture was cooled to 0C and 3M solution of methylmagnesium chloride in tetrahydrofuran (THF) was added dropwise via syringe. The orange slurry was stirred at ?8C for 1h. The reaction was quenched by adding 6% aqueous ammonium chloride solution. The mixture was poured into a separating funnel, the organic layer was washed twice with cold water followed by brine and dried over anhydrous sodium sulfate. The organic layer was filtered and concentrated under reduced pressure on a rotary evaporator at a bath temperature below 27C. The orange compound (Cp2TiMe2) obtained was dissolved in toluene or THF and used in the reactions with carbonyl compounds. 1H NMR (CDCl3): delta6.21 (s, 10H), -0.09 (s, 6H).
In tetrahydrofuran; toluene; at -10 - 0℃; for 1h;Inert atmosphere; Petasis reagent was prepared according to the literature procedure19 To a suspension of Cp2TiCl2 (5.00 g, 20.1 mmol) in toluene (54.2 mL) was added 3.0 M MeMgCl in THF (15 mL, 46 mmol) dropwise at -10 C. After stirring for 1 h at 0 C, the resulting orange slurry was diluted with toluene (25 mL), and quenched by transferring into a flask containing 6% aq NH4Cl solution (14 mL) via a cannula under an atmosphere of argon at 0 C. The mixture was poured into a separatory funnel with toluene, and the aqueous phase was separated. The combined organic extracts were sequentially washed with cold water (3 ) and brine (3 ) each, then dried (Na2SO4), and concentrated in vacuo. The resulting orange toluene solution was assayed by 1H NMR to be 42 wt% dimethyltitanocene (3.73 g, 83%). The reagent was diluted with THF (29.9 mL). This Petasis reagent (0.50 M in toluene and THF) was used in the following experiment. To a solution of lactone 11 (100 mg, 0.188 mmol) in toluene (1.9 mL) was added Petasis reagent (0.50 M in toluene and THF, 2.26 mL, 1.13 mmol) at r.t. The mixture was heated at 90 C for 1.5 h. The solution was cooled to r.t., and diluted with hexane (5.0 mL). The resulting slurry was filtered through a Celite pad. Concentration of the filtrate provided crude product, which was purified by PTLC (hexane/EtOAc/ CH2Cl2 3:1:1) to give enol ether 10 (58.6 mg, 56%) and enol ether 31 (20.3 mg, 20%) both as a yellow solid.

  • 2
  • [ 1271-19-8 ]
  • [ 917-54-4 ]
  • [ 1271-66-5 ]
YieldReaction ConditionsOperation in experiment
In diethyl ether; at 0℃; for 0.166667h; Dimethyl titanocene, Cp2Ti(CH3)2 (Petasis' reagent). To a flame-dried flask under argon atmosphere was added titanocene dichloride (14.63 g, 58.8 mmol) and absolute ether (300 mL), which was cooled to 10 C. Methyl lithium (100 mL, 140 mmol, 1.4 M) was carefully added dropwise via an addition funnel in the dark. The cold bath was removed and the red solution was allowed to stir for 10 min. The solution was then cooled to 0 C. and ice water (25 mL) was carefully added to quench the unreacted methyl lithium. The layers were separated and the aqueous layer extracted with ether (2×). The combined organic layers were dried (Na2SO4) under argon for 1 h and concentrated in the dark at 20 C. to give 12.4 g of orange solid. Dry toluene (100 mL) was added and the reagent was stored at 4 C. and used without characterization
In diethyl ether; at 10℃; for 0.166667h;darkness; Preparation of dimethyl titanocene Cp2Ti(CH3)2 (Petasis' reagent). ; To a flame dried flask under argon atmosphere was added titanocene dichloride (14.63 g, 58.8 mmol) and absolute ether (300 ml_), which was cooled to 100C. Methyl lithium (100 ml_, 140 mmol, 1.4 M) was carefully added drop wise via an addition funnel under darkness. The cold bath was removed, and the red solution was allowed to stir for 10 min. The solution was cooled to 00C, and ice water (25 mL) was carefully added to quench the unreacted methyl lithium. The layers were separated, and the aqueous layer was extracted using ether (2x). The combined organic layers were dried over Na2SO4 under argon for 1 hour and concentrated in darkness at 2O0C to produce 12.4 g of orange solid. Dry toluene (100 mL) was added, and the reagent was stored at 4C and used without characterization.
In diethyl ether; toluene; at -10℃; for 1.08333h; Intermediate 131 Dimethyltitanocene To a suspension of dichlorotitanocene (8.3 g, 33.3 mmol) in dry toluene (100 mL) at -10QC a solution of methyllithium in Et20 (1.6M, 47.3 mL, 76 mmol) was slowly added (20 minutes) and the reaction mixture was stirred for 45 minutes at the same temperature. The reaction mixture was added (via cannulation) to a solution of ammonium chloride (1.2g) in water (24ml) cooled to -10QC. Two phases were separated and the organic layer was washed with cool water (3x20ml) and brine (1x20ml), dried over sodium sulphate filtered and concentrated under reduced pressure to 60ml containing 9%w/w ofdimethyltitanocene (5.04 g, 24 mmol) in toluene.XH NM (400MHz, DMSO-d6): delta ppm 6.10 (10H, s), -0.11 (6H, s).
In diethyl ether; toluene; at -10℃; for 1.08333h; Intermediate 131 Dimethyltitanocene [0878] [0879] To a suspension of dichlorotitanocene (8.3 g, 33.3 mmol) in dry toluene (100 mL) at -10 C. a solution of methyllithium in Et2O (1.6M, 47.3 mL, 76 mmol) was slowly added (20 minutes) and the reaction mixture was stirred for 45 minutes at the same temperature. The reaction mixture was added (via cannulation) to a solution of ammonium chloride (1.2 g) in water (24 ml) cooled to -10 C. Two phases were separated and the organic layer was washed with cool water (3×20 ml) and brine (1×20 ml), dried over sodium sulphate filtered and concentrated under reduced pressure to 60 ml containing 9% w/w of dimethyltitanocene (5.04 g, 24 mmol) in toluene. [0880] 1H NMR (400 MHz, DMSO-d6): delta ppm 6.10 (10H, s), -0.11 (6H, s).
In diethyl ether; at 10 - 20℃; for 0.166667h;Inert atmosphere; To an oven-dried, Al foil wrapped flask under Ar was added titanocene dichloride(2.5 g, 10 mmol) and absolute ether (50 mL) and cooled to 10 C . Methyl lithium(1.6M in ether; 15 mL) was added dropwise. The cooling bath was then removedand the solution was stirred at rt for 10 min. The reaction mixture was cooled inan ice bath and ice cold water added. In the dark, the aqueous layer was extracted3 × 50 mL with ether. The combined organic layer was dried (Na2SO4) and spargedwith Ar for 1 h. The product was filtered and concentrated in the dark at rt to givean orange solid which was diluted with toluene (20 mL; 0.5 M) and used withoutfurther purification.

  • 4
  • [ 1271-19-8 ]
  • [ 927-77-5 ]
  • [ 106-99-0 ]
  • [ 53774-20-2 ]
YieldReaction ConditionsOperation in experiment
85% With hydrogenchloride; air; carbon dioxide In diethyl ether Addn. of n-PrMgBr (Et2O) to stirred Et2O suspn. of Cp2TiCl2 and C4H6 (Ar, 0°C) over 5 min, stirring (30 min) at room temp. Bubbling of CO2 through soln. (1 h, room temp.), hydrolysis with aq. HCl, passing of air into react. mixt. for 15 min.; Filtn. gives Cp2TiCl2 in 93% yield recovery. Addn. of aq. NaOH to filtrate, sepn. of org. layer, discarding; extn. of aq. layer with ether, discarding, addn. of concd. HCl, extn. with ether, drying, concn. in vac. Purifn. by trap-to-trap distn.;
  • 5
  • [ 1271-19-8 ]
  • bis(cyclopentadienyl)titanium (III) chloride [ No CAS ]
YieldReaction ConditionsOperation in experiment
With zinc; In tetrahydrofuran; for 1h;Inert atmosphere; Comparative Example 16: Comparison of the effect of the protective groups used in the radical cyclizationGeneral process: Generation of Cp2TiCl: To a solution of titanocene dichloride (0.400 g, 1.61 mmol) in deoxigenated freshly distilled THF (20 mL) under N2 was added activated zinc dust (0.320 g, 4.84 mmol). The resultant dark red solution was stirred for 1 h, during which time the heterogeneous solution turned a deep lime green. Stirring was discontinued and the residual zinc was allowed to settle. The resulting green solution of Cp2TiCl was 0.08 M.Reaction: A 0.08 M solution of Cp2TiCl (17 mL, 1.36 mmol) (vide supra) was added dropwise via syringe pump over 3 h to a stirred solution of the corresponding starting epoxide (see reaction scheme where Ra and Rb are as in Table 2) (0.46 mmol) dissolved in deoxigenated freshly distilled THF (23 mL) at room temperature under an N2 atmosphere. The reaction mixture was stirred for 8 h.Treatment A: A 10% aq. H2SO4 (10 mL) was added and stirred for 5 min. Then, the solution was extracted thoroughly with EtOAc. The bright orange aqueous portion was extracted further with EtOAc. The combined organic phases were washed with saturated aq. NaHCO3 (30 mL) and dried (MgSO4) and concentrated in vacuo. The crude residue was purified by flash chromatography (5% EtOAc/hexane).Treatment B: A saturated solution of NH4Cl (10 mL) was added and the resulting mixture was stirred for 2 h. Then, the solution was extracted thoroughly with EtOAc. The bright orange aqueous portion was extracted further with EtOAc. The combined organic phases were washed with saturated aq. NaHCO3 (15-20 mL) and dried (MgSO4) and concentrated in vacuo The crude residue was purified by flash chromatography.The results obtained are summarized in Table 2.
With zinc; In tetrahydrofuran; at 20℃;Inert atmosphere; General procedure: 4.2.1. Reaction of epoxides with Cp2TiCl. A mixture of Cp2TiCl2 (2.20 mmol) and Zn (6.60 equiv) in strictly deoxygenated THF (10 mL) was stirred at room temperature until the red solution turned green. In a separate flask, the epoxy compound (1 mmol) was dissolved in strictly deoxygenated THF (10 mL). The green Ti(III) solution was slowly added via cannula to the epoxide solution. After 30 min, an excess of saturated NaH2PO4 was added, and the mixture was stirred for 20 min. The mixture was filtered to remove insoluble titanium salts. The product was extracted into ether, and the combined organic layers were washed with saturated NaHCO3 and brine, dried (Na2SO4), and filtered. After removal of the solvent, the crude product was purified by flash chromatography.
With zinc; In tetrahydrofuran; for 1h;Inert atmosphere; Example 1Under nitrogen atmosphere, Cp2TiCl2 (0.182 g, 1.463 mmol) dissolved in THF (20 mL) is introduced to a flask containing activated zinc dust (0.146 g, 4.44 mmol) and the resultant mixture is agitated for 1 hour to provide Cp2TiCl (green solution). In another flask, Compound 25 (0.19 g, 0.635 mmol) is dissolved in THF (16 mL), the temperature is adjusted to 60 C., and then the preliminarily formed Cp2TiCl solution is added thereto for 20 minutes by using a cannula. After carrying out agitation for 20 minutes, I2 (0.105 g, 0.825 mmol) dissolved in THF (4 mL) is added and the reaction solution is agitated for 1 hour. After determining the completion of the reaction by TLC, saturated aqueous NH4Cl solution is added to quench the reaction, followed by extraction with diethyl ether. The extracted organic layer is washed with 10% Na2S2O3 solution and brine solution three times, dried with anhydrous Na2SO4, and filtered through a filter. The filtrate is concentrated and purified by column chromatography (3:1 hexane/EtOAc) to obtain Compound 26 (62 mg, 32.6%) as light red oil. NMR data of Compound 26 is shown below.
With zinc(II) chloride; zinc; In tetrahydrofuran; at 20℃; for 1h;Inert atmosphere; ZnCl2 (2.3 g, 33.60 mmol), Zn (2.2 g, 16.80 mmol) and Cp2TiCl2 (4.2 g, 16.80 mmol) were added sequentially to a flame dried round bottom flask containing THF (100 mL) at room temperature under argon atmosphere and the reaction mixture was stirred for 1 h at the same temperature (the colour changed from deep orange to dark green). The resulting reaction mixture was then cooled to -20 C and to it compound 12 (1.2 g, 5.6 mmol) dissolved in THF (25 mL) was cannulated. The reaction mixture was brought to room temperature in 1 h and stirred for another 14 h. The reaction mixture was then diluted with 1 N aqueous HCl (50 mL) and stirred for additional 2 h. Solvents of the reaction mixture was evaporated in vacuo and extracted with EtOAc (3*100 mL), washed with water (20 mL), brine (20 mL), dried (Na2SO4), filtered and concentrated in vacuo to give the crude product, which was purified by flash chromatography (35% EtOAc/hexane) to give the title compound 11 (647 mg, 68%) as a yellow oil
With hydrogenchloride; zinc; In tetrahydrofuran; for 1h;Inert atmosphere; A solution of titanocene dichloride (1.52 g, 6.1 mmol) in dry deoxygenated THF (10 mL) was stirred with activated zinc dust (904 mg, 13.8 mmol) [activated zinc dust was prepared by washing 20 g of commercially available zinc dust with 60 mL of 4N HCl followed by thorough washing with water until the washings became neutral and finally washing with dry acetone and then drying in vacuo] for 1 h under argon. The resulting green solution was added drop-wise to a stirred solution of methyl-2-formyl benzoate (217 mg, 1.32 mmol) and benzyl bromide (452 mg, 2.64 mmol) in dry deoxygenated THF (5 mL). The reaction mixture was further stirred for an additional 4 h and then decomposed by stirring with 20% H2SO4(2 mL). The solvent was removed under reduced pressure, and the residue was extracted with diethyl ether (3 × 25 mL). The combined ether layer was washed with brine (2 × 10 mL) and dried over anhydrous Na2SO4. It was filtered and after removal of the solvent under reduced pressure the crude residue obtained was purified by column chromatography over silica gel (6.5% ethyl acetate in petroleum ether) to furnish 3-benzylisobenzofuran-1(3H)-one (2a, 191 mg, 88%) as a colourless oil.

  • 7
  • [ 1271-19-8 ]
  • [ 1295-35-8 ]
  • [(η5-C5H5)2TiCl]2 [ No CAS ]
  • [ 71564-36-8 ]
  • 8
  • [ 1271-19-8 ]
  • [ 38402-11-8 ]
  • (C5H5)2Ti(ClClC6H3COO)2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% In benzene a mixt. of (η-C5H5)2TiCl2 and Na salt of the substituted benzoic acid in anhydrous benzene stirred at 30°C for 4 h; orange soln. filtered, concd., crystn. (refrigerator), recrystd. (benzene);
In not given
  • 9
  • [ 1271-19-8 ]
  • [ 4653-11-6 ]
  • (cyclopentadienyl)2Ti(2-thiophenebutyric acid(1-))2 [ No CAS ]
  • 10
  • [ 1271-19-8 ]
  • [ 4653-11-6 ]
  • (cyclopentadienyl)2Ti(2-thiophenebutyric acid(1-))Cl [ No CAS ]
  • 11
  • [ 1271-19-8 ]
  • [ 105-11-3 ]
  • {(C5H5)4Ti2(H2O)2(ONC6H4NO)}(2+)*2NO3(1-)*4H2O={(C5H5)4Ti2(H2O)2(ONC6H4NO)}(NO3)2*4H2O [ No CAS ]
  • 12
  • [ 1271-19-8 ]
  • [ 105-11-3 ]
  • {(C5H5)4Ti2(H2O)2(ONC6H4NO)}(2+)*2Br(1-)*4H2O={(C5H5)4Ti2(H2O)2(ONC6H4NO)}Br2*4H2O [ No CAS ]
  • 13
  • [ 1271-19-8 ]
  • [ 105-11-3 ]
  • {(C5H5)4Ti2(H2O)2(ONC6H4NO)}(2+)*2Cl(1-)*4H2O={(C5H5)4Ti2(H2O)2(ONC6H4NO)}Cl2*4H2O [ No CAS ]
  • 14
  • [ 12087-70-6 ]
  • [ 1271-19-8 ]
  • [ 53774-20-2 ]
YieldReaction ConditionsOperation in experiment
1: 85% 2: 82% With hydrogenchloride; air; carbon dioxide In diethyl ether Passing of gaseous CO2 through Et2O soln. of Ti-compd. (Ar) for 1 h, hydrolysis with aq. HCl and then bubbling of air into react. mixt. for 15 min.; Collecting of pptd. crystals of Cp2TiCl2 by filtn., addn. of aq. NaOH, sepn. of org. layer and discarding. Extn. of aq. layer with ether, discarding, addn. of concd. HCl, extn. with ether, drying, concn. in vac. Purifn. by trap-to-trap distn., (1)H NMR.;
  • 15
  • [ 1271-19-8 ]
  • [ 6921-34-2 ]
  • (π-C5H5)2Ti(CH2C6H5)2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
86% In diethyl ether; at -78 - -20℃; for 2h;Schlenk technique; Inert atmosphere; A Schlenk flask was charged with titanocene dichloride (5 g, 20.05 mmol) wassuspended in dry ether (75 mL) under an argon atmosphere. This mixture was cooled to -78 C. While stirring, benzylmagnesium chloride (2.1 eq., 42.1 mL, 1M) was added over15 minutes. This mixture was allowed to warm to -20 C over 2 hours. The reaction wasthen quenched with water (15 mL). The contents of the flask were transferred to aseparatory funnel, additional water (40 mL) was added and the contents extracted withether (15 x 100 mL). Dichloromethane may be used instead of ether since the product isless soluble in the former solvent, however, a less pure product is obtained. Drying overMgSO4, filtration and evaporation of the solvent left purple needles. Suspension inpetroleum ether (250 mL), cooling to -78C, and filtration afforded small, dry purpleneedles of the product (6.2 g, 86 %) which can be stored in the solid state at -20C.1H NMR (C6D6): delta 1.87 (s, 4H, -CH2), 5.55 (s, 10H, Cp), 6.82-7.22 (m, 10H, Benzyl).13C NMR: delta 73.5, 115.5, 122.1, 126.5, 128.4, 153.8.
  • 16
  • [ 1271-19-8 ]
  • [ 3847-57-2 ]
  • (C5H5)2Ti(OCOC6H4NO2)2 [ No CAS ]
  • 18
  • [ 1271-19-8 ]
  • [ 490-97-1 ]
  • (C5H5)2Ti(FC6H4COO)2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
59% In benzene a mixt. of (η-C5H5)2TiCl2 and Na salt of the substituted benzoic acid in anhydrous benzene stirred at 30°C for 4 h; orange soln. filtered, concd., crystn. (refrigerator), recrystd. (benzene);
36% In benzene mixt. of complex and Na-salt of benzoic acid in dry benzene was stirredfor 3-8 h at 30°C; filtered, filtrate was evapd., recrystd. from boiling benzene; elem. anal.;
In not given
  • 19
  • [ 1271-19-8 ]
  • [ 827-95-2 ]
  • (C5H5)2Ti(OCOC6H4NO2)2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
44% In benzene a mixt. of (η-C5H5)2TiCl2 and Na salt of the substituted benzoic acid in anhydrous benzene stirred at 30°C for 4 h; orange soln. filtered, concd., crystn. (refrigerator), recrystd. (benzene);
  • 20
  • [ 1271-19-8 ]
  • [ 57273-36-6 ]
  • bis(η5-cyclopentadienyl)bis(furan-2-carboxylato-κO)titanium(IV) [ No CAS ]
YieldReaction ConditionsOperation in experiment
65% In benzene; at 40℃; for 4h; A freshly prepared solution of titanocene dichloride (0.25 g, 1.004 mmol) in anhydrousbenzene (15 mL) was added to a stirred suspension of sodium 4-methylbenzoate(0.396 g, 2.504 mmol) in anhydrous benzene (15 mL) and the stirring was continuedat 40 C for 4 h. During reaction, the color of the reaction mixture changed from blood-red to bright-orange. The orange solution was filtered through a frit coveredwith pre-dried neutral silica (1 cm layer, mesh size 100-200) and eluted further withanhydrous benzene (30.5 mL). The clear filtrate was concentrated using a rotaryevaporator to around 5mL and precipitated with excess anhydrous hexane. Theorange solid was collected on a frit, washed with hexane (25 mL), dried, and recrystallizedfrom anhydrous toluene under ambient conditions to afford orange crystals of1 at ambient temperature.
  • 21
  • [ 1271-19-8 ]
  • [ 64394-45-2 ]
  • {(η5-C5H5)2Ti}2C2S4 [ No CAS ]
  • bis(η5-cyclopentadienyl)-(2-oxo-1,3-dithiol-4,5-dithiolato)-titanium(IV) [ No CAS ]
  • 22
  • [ 1271-19-8 ]
  • [ 17264-54-9 ]
  • bis(η5-cyclopentadienyl)bis(4-methylbenzoato-κO)titanium(IV) [ No CAS ]
YieldReaction ConditionsOperation in experiment
55% In benzene; at 40℃; for 4h; A freshly prepared solution of titanocene dichloride (0.25 g, 1.004 mmol) in anhydrousbenzene (15 mL) was added to a stirred suspension of sodium 4-methylbenzoate(0.396 g, 2.504 mmol) in anhydrous benzene (15 mL) and the stirring was continuedat 40 C for 4 h. During reaction, the color of the reaction mixture changed from blood-red to bright-orange. The orange solution was filtered through a frit coveredwith pre-dried neutral silica (1 cm layer, mesh size 100-200) and eluted further withanhydrous benzene (30.5 mL). The clear filtrate was concentrated using a rotaryevaporator to around 5mL and precipitated with excess anhydrous hexane. Theorange solid was collected on a frit, washed with hexane (25 mL), dried, and recrystallizedfrom anhydrous toluene under ambient conditions to afford orange crystals of1 at ambient temperature. Yield: 0.27 g, 55%. m. p.: 176-178 C (dec.) 174-176 C(dec.) [39]. IR absorption (cm2-1) 1625 m(OCO)asym, 1574, 1446, 1335 m(OCO)sym, 1306,1289, 1169, 1135, 1020, 808, 756, 611, 570, 467. 1H NMR (CDCl3): 7.87 (d, J8.6 Hz, 4H,H-2/H-6), 7.18 (d, J8.6 Hz, 4H, H-3/H-5), 6.54 (s, 10H, C5H5), 2.36 (s, 6H, CH3) ppm.13C{1H} NMR (CDCl3): 172.3 (COO), 142.2 (C-1), 130.9 (C-4), 130.0 (C-2/C-6), 128.9 (C-3/C-5), 118.4 (C5H5), 21.6 (CH3) ppm.
  • 24
  • [ 1271-19-8 ]
  • [ 1885-38-7 ]
  • {((C5H5)2Ti(C9H7N))2O}(2+)*2FeCl4(1-)*C9H7N*C6H6={((C5H5)2Ti(C9H7N))2O}{FeCl4}2*C9H7N*C6H6 [ No CAS ]
  • 25
  • [ 1271-19-8 ]
  • [ 2156-56-1 ]
  • [ 123-54-6 ]
  • {(C5H5)2Ti(CH3COCHCOCH3)(Cl2CHCO2)} [ No CAS ]
  • 26
  • [ 1271-19-8 ]
  • [ 17013-01-3 ]
  • ((C5H5)2Ti(OCOC2H2OCO))2*2CHCl3 [ No CAS ]
  • bis(μ-fumarato)bis(di(π-cyclopentadienyl)titanium(IV)) [ No CAS ]
YieldReaction ConditionsOperation in experiment
In chloroform; water equimolar mixt. stirred for 25 min; sepn. of the CHCl3 phase, cooling to 0°C; layering with CCl4 or hexane; crystal obtained upon storing for several hours at 6°C;
  • 27
  • [ 1271-19-8 ]
  • [ 2156-56-1 ]
  • [ 93-91-4 ]
  • {(C5H5)2Ti(CH3COCHCOC6H5)(Cl2HCCO2)} [ No CAS ]
  • 28
  • [ 1271-19-8 ]
  • [ 1118-71-4 ]
  • [ 2156-56-1 ]
  • {(C5H5)2Ti((CH3)3CCOCHCOC(CH3)3)(Cl2HCCO2)} [ No CAS ]
  • 29
  • [ 1271-19-8 ]
  • [ 134-03-2 ]
  • {(C5H5)2Ti(C6H7O6)2} [ No CAS ]
YieldReaction ConditionsOperation in experiment
45% In water (N2); dropwise addn. of a soln. of ascorbate in water to a soln. of the Ti-compd. in water with stirring at 10°C, stirring of the mixt. for 2 h; allowing to warm slowly up to room temp.;; ppt. is collected by filtn., washed with cooled water and redissolved in THF, pptn. by addn. of hexane; elem. anal.;
  • 30
  • [ 1271-19-8 ]
  • [ 120-70-7 ]
  • bis(η5-cyclopentadienyl)titanium(IV)(N,N'-bis(salicylidene)propylenediamine) [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% With triethylamine In tetrahydrofuran byproducts: (C2H5)3NHCl; refluxing under strictly anhydrous conditions for 10-12 h; filtration (Et3NHCl), concn. (vac.), extn. with hexane and drying (vac.) at room temp.; elem. anal.;
  • 31
  • [ 1271-19-8 ]
  • [ 4551-69-3 ]
  • bis(η5-cyclopentadienyl)(4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-onato)titanium chloride [ No CAS ]
YieldReaction ConditionsOperation in experiment
50% With triethylamine In tetrahydrofuran byproducts: (C2H5)3N*HCl; molar ratio of Cp2TiCl2:ligand=1:1, dry THF, (C2H5)3N was added, reflux for 3-4h; (C2H5)3N*HCl filtered off, evapd. under vac., recrystd. from benzene/petroleum ether, elem. anal.;
  • 32
  • [ 1271-19-8 ]
  • [ 4551-69-3 ]
  • (eta1:eta.5-cyclopentadienyl)bis(4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-onato)titanium(IV) [ No CAS ]
YieldReaction ConditionsOperation in experiment
55% With triethylamine In tetrahydrofuran byproducts: (C2H5)3N*HCl, C5H6; reflux for 3-4h in dry THF, molar ratio Cp2TiCl2:ligand:(C2H5)3N=1:2:2; (C2H5)3N*HCl filtered off, evapd. under vac., recrystd. from benzene/petroleum ether, elem. anal.;
  • 33
  • [ 1271-19-8 ]
  • [ 110-20-3 ]
  • (C5H5)2Ti((CH3)2CNNCONH2)Cl [ No CAS ]
  • 34
  • [ 1271-19-8 ]
  • [ 614-65-3 ]
  • [ 97959-92-7 ]
YieldReaction ConditionsOperation in experiment
60% In tetrahydrofuran to stirred soln. of Cp2TiCl2 in THF slowly added soln. of hydrazone in THF, refluxed at 68°C for 10-12 h; filtered, concd. in vac., pptd. ba adding petroleum ether, filtered, washed with petroleum ether, dried in vac., recrystd. from CH2Cl2-petroleum ether; elem. anal.;
60% In tetrahydrofuran at 68℃; Preparation of Complexes General procedure: To a stired solution of bis(cyclopentadienyl)titanium(IV) dichloride, (Cp)2TiCl2 (8 mmol) in 30 ml tetrahydrofuran, a solution containing 8 mmol of appropiate hydrazone or azine in 30 ml tetrahydrofuran was added slowly and the reaction mixture was refluxed for 10-12 h. It was then filtered an the volume of the filtrate was reduced to ca. 20 ml by evaporating the solvent under reduced pressure. The crystals of the product were precipitated by adding 80 ml petroleum ather (60-80 oC) to the concentrated filtrate. These were filtered, washed with petroleum ether and dried under vacuum. Recrystalized from dichloromethane by adding excess of petroleum ether.
  • 35
  • [ 1271-19-8 ]
  • [ 97-23-4 ]
  • (C5H5)2Ti((C6H3(Cl)O)2CH2) [ No CAS ]
YieldReaction ConditionsOperation in experiment
92% With sodium amide In benzene byproducts: NaCl, NH3; refluxing, 2h; cooling to room temp.; filtration; concentrating; pptn.; washing (petroleum ether); drying (room temp., vac.); elem. anal.;
  • 36
  • [ 1271-19-8 ]
  • [ CAS Unavailable ]
  • [ 78966-09-3 ]
YieldReaction ConditionsOperation in experiment
In tetrahydrofuran byproducts: NaCl; refluxing soln. of equimolar amts., 60-70°C, 6-10h; filtration, evapn.; repeated washing (petroleum ether);
  • 37
  • [ 1271-19-8 ]
  • [ 94-91-7 ]
  • dicyclopentadienyl(N,N'-1,2-propylene bis(salicylaldiminato))titanium(IV) [ No CAS ]
  • 39
  • [ 1271-19-8 ]
  • [ 1127-45-3 ]
  • [ 87612-44-0 ]
  • 41
  • [ 1271-19-8 ]
  • [ 6153-56-6 ]
  • [ 78966-09-3 ]
YieldReaction ConditionsOperation in experiment
75% In water Cp2TiCl2 dissolved in boiling water, treated with H2C2O4*2H2O while stirred; crystals dried over P2O5 at 50°C; elem. anal.;
  • 42
  • [ 1271-19-8 ]
  • [ 305-01-1 ]
  • [ 78614-80-9 ]
YieldReaction ConditionsOperation in experiment
80% With triethylamine In tetrahydrofuran byproducts: triethylamine hydrochloride; stirring soln. of Ti complex, coumarin and triethylamine (molar ratio 1:1:2), room temp., 25h; pptn. of triethylamine hydrochloride; filtration; crystn. (n-hexane/THF); elem. anal.;
  • 43
  • [ 1271-19-8 ]
  • [ 1170-02-1 ]
  • [ 774525-44-9 ]
  • 44
  • [ 1271-19-8 ]
  • [ 699-12-7 ]
  • [ 306996-07-6 ]
  • 45
  • [ 1271-19-8 ]
  • [ 85-31-4 ]
  • Ti(C5H5)2(6-thioguanineribose) dichloride complex [ No CAS ]
  • 46
  • [ 1271-19-8 ]
  • [ 122-52-1 ]
  • [ 185991-38-2 ]
YieldReaction ConditionsOperation in experiment
With magnesium; In tetrahydrofuran; at 25℃; for 3h;Molecular sieve; Inert atmosphere; To a flask charged with finely powdered molecular sieves 4A (150 mg),magnesium turnings (40 mg, 1.7 mmol), and Cp2TiCl2 (374 mg, 1.5 mmol) were added THF (2 mL)and P(OEt)3 (0.52 ml, 3.0 mmol) with stirring at 25 C under argon. After 3 h, CPME (3 mL) wasadded and the mixture was further stirred for 5 min. Then 2-(2-methylprop-1-en-1-yl)-1,3-dithiane(3d) (105 mg, 0.6 mmol) and triisopropylsilyl 3-phenylpropanoate (2b) (92 mg, 0.3 mmol) inCPME (3 mL) was added dropwise over 5 min, the reaction mixture was stirred for 14 h at 50 C.After cooling to room temperature, the reaction was quenched by addition of 1M NaOH (15 mL)and the resulting insoluble materials were filtered off through Celite. The filtrate was extracted withether (20 mL x 3) and the combined extract was dried over K2CO3. After removal of solvent, theresidue was purified by preparative TLC (hexane) to give 1d (69 mg, 64%).
With magnesium; In tetrahydrofuran; at 25℃; under 2 - 3 Torr; for 3h;Molecular sieve; Inert atmosphere; General procedure: 4.4.1. Typical procedure for the olefination of ketones 11aec. Finelypowdered molecular sieves 4A (108 mg), magnesium turnings(29 mg, 1.2 mmol), and Cp2TiCl2 (269 mg, 1.1 mmol) were placed ina flask and dried by heating with a heat gun under reduced pressure(2e3 mmHg). After cooling, THF (2 mL) and P(OEt)3 (0.38 mL,2.2 mmol) were added successively with stirring at 25 C underargon. After 3 h, a THF (1 mL) solution of 1,3-bis(phenylthio)-3-(trimethylsilyl)-1-propene (1a) (119 mg, 0.36 mmol) was added tothe mixture at 25 C. After stirring for 10 min, a THF (1 mL) solutionof 1,5-diphenyl-3-pentanone (11a) (72 mg, 0.3 mmol) was addeddropwise over 5 min and the reaction mixture was stirred for 18 h.The reaction was quenched by addition of 1 M NaOH (15 mL), andinsoluble materials were filtered off through Celite and washedwith ether (15 mL). The organic materials were extracted withether (20 mL3) and dried over Na2SO4. After removal of solvent,the residue was purified by PTLC (hexane/AcOEt98:2) to give 3a(61 mg, 61%). In a similar manner, the dienes 3b and 3c wereobtained.
  • 47
  • [ 1271-19-8 ]
  • [ 1170-02-1 ]
  • [(Ti(C6H4OCHCOONHCH2)2H(H2O))2O]*9H2O [ No CAS ]
  • 48
  • [ 1271-19-8 ]
  • [ 1170-02-1 ]
  • Ti(C6H4OCHCOONHCH2)2H2O*5H2O [ No CAS ]
  • 49
  • [ 1271-19-8 ]
  • [ 609-99-4 ]
  • Cp2Ti(3,5-dinitrosalicylato) [ No CAS ]
YieldReaction ConditionsOperation in experiment
In chloroform; water a soln. of Cp2TiCl2 and substituted salicylic acid in CHCl3 added to H2O, stirred for about 1.5-2 h at room temp.; the org. layer sepd., washed (aq. soln. of satd. Na2CO3 and H2O), dried (MgSO4), filtered, evapd. (vac.), recrystd. (CH2Cl2/hexane);
With 5-sulfosalicylic Acid In chloroform; water a soln. of Cp2TiCl2 and substituted salicylic acid in CHCl3 added to 5-sulfosalicylic acid/H2O, stirred for about 5 min at room temp.; the org. layer sepd., washed (aq. soln. of satd. Na2CO3 and H2O), dried (MgSO4), filtered, evapd. (vac.), recrystd. (CH2Cl2/hexane);
With sodium hydroxide In chloroform; water substituted salicylic acid and NaOH dissolved in H2O (pH adjusted to 3.0-5.0 by adding HCl or NaOH), added to Cp2TiCl2/CHCl3, stirred for about 30 min at room temp.; the org. layer sepd., washed (aq. soln. of satd. Na2CO3 and H2O), dried (MgSO4), filtered, evapd. (vac.), recrystd. (CH2Cl2/hexane);
  • 50
  • [ 1271-19-8 ]
  • [ 1071-36-9 ]
  • [ 185038-38-4 ]
  • 51
  • [ 1271-19-8 ]
  • [ 95407-69-5 ]
  • [ 850415-42-8 ]
  • 52
  • [ 1271-19-8 ]
  • [ 1121-24-0 ]
  • [ 5350-41-4 ]
  • (C6H5CH2NMe3)2[Ti(o-mercaptophenolate(2-))3] [ No CAS ]
  • 53
  • [ 1271-19-8 ]
  • [ 441-38-3 ]
  • (C5H5)2Ti(OC6H3(CH3)CHNO) [ No CAS ]
  • 55
  • [ 1271-19-8 ]
  • [ 62968-45-0 ]
  • 2,2,5,5,8,8-hexakis(π-cyclopentadienyl)-1,3,4,6,7,9-hexathia-2,5,8-trititanatrindene [ No CAS ]
YieldReaction ConditionsOperation in experiment
With triethylamine In acetonitrile (inert gas); addn. of NEt3 to the hexathiol in MeCN, addn. of titanocenedichloride, stirring (2 h); solvent removal (vac.), dissoln. (CH2Cl2), filtration, concn., pptn. with MeOH, filtration, washing (MeOH; Et2O), recrystn. (CH2Cl2/MeOH); elem.anal.;
  • 56
  • [ 1271-19-8 ]
  • [ 1079-66-9 ]
  • [ 501-65-5 ]
  • dicyclopentadienyl (1,2-diphenyl-vinyl-diphenylphosphine)titanium chloride [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% (1) Under the protection of highly pure nitrogen gas, 1.2 mmol titanocene dichloride and 5 ml tetrahydrofuran solvent treated by freedom of oxygen and water were added into a 20 ml Schlenk reaction tube and stirred uniformly to form a first mixture; the first mixture was cooled to -78 C. with dry ice-acetone bath or liquid nitrogen-acetone bath; and then 2.4 mmol n-butyl lithium solution was added and kept for 30 min to form a second mixture. (2) N,N-dimethyl-4-methylaminopyridine (DMAP) (2.0 mmol) was added into the second mixture and reacted at room temperature for 1 hour to form a third mixture; diphenylacetylene (1.0 mmol) was added into the third mixture and stirred continuously for 1 hour; and then ClPPh2(1.0 mmol) was add and stirred for 1 hour at this temperature to form a fourth mixture. (3) 2 mL dilute hydrochloric acid (3M) was added into the fourth mixture to form a product; the product was extracted with 30 ml dichloromethane three times to form the filtrates; the filtrates were combined and concentrated by rotary evaporation to obtain the coarse products. (4) The coarse products were column-separated (300 mesh silica gel) with petroleum ether/tetrahydrofuran (10/1) as the eluant to obtain 490 mg white solid 2-cylopentadienyl zirconium chloridate-1,2-diphenyl-vinyl diphenylphosphine with the isolated yield of 85%. The theoretical values (%) and experimental values (%) of the element analysis (C36H30ClPTi) were respectively C, 75.95; H, 5.24, Cl, 6.15, P, 5.37 and C, 75.90; H, 5.16, Cl, 6.02, P, 5.13.
  • 57
  • [ 1271-19-8 ]
  • [ 7732-18-5 ]
  • [ 36603-80-2 ]
  • [Cp2Ti(tricyanomethanide)]2O [ No CAS ]
YieldReaction ConditionsOperation in experiment
66% In water under Ar; sodium salt added to aq. soln. of Cp2TiCl2 at 80°C, mixt. cooled in ice-water bath, stirred for 50 min; precipitate collected, washed with cold water, dried under vac., extd. with CH2Cl2, extract concd. under vac., crystn. at -80°C; elem. anal.;
  • 58
  • [ 1271-19-8 ]
  • [ 16727-43-8 ]
  • [ 1333162-23-4 ]
  • 59
  • [ 1271-19-8 ]
  • [ 1798-09-0 ]
  • [Ti(η5-C5H5)2(OOC-3-mpa)2] [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With triethylamine; In toluene; at 80℃; for 3h;Inert atmosphere; 2.2.1 Synthesis of [Ti(eta5-C5H5)2(OOC-3-mpa)2] (1) NEt3 (0.57 mL, 4.00 mmol) was added dropwise to a suspension of 3-methoxyphenylacetic acid (0.60 g, 4.00 mmol) and [Ti(eta5-C5H5)2Cl2] (0.50 g, 2.00 mmol) in toluene (50 mL) at room temperature. The reaction mixture colour changed immediately from deep red to orange and was then stirred for 3 h at 80 C. The mixture was decanted and filtered to remove the triethylammonium chloride salt. The filtrate was then concentrated and cooled to -30 C to give orange crystals of the complex which were isolated by filtration. Yield: 1.64 g, 81%. 1H NMR (400 MHz, CDCl3, 25 C): delta 3.54 (s, 4H, -CH2-), 3.84 (s, 6H, -OMe), 6.28 (s, 10H, C5H5), 6.81 (d, 2H, Hpara of Ph), 6.89 (br m, 4H, Hortho and Hmeta of Ph) and 7.26 (d, 2H, Hortho of Ph) ppm. 13C{1H} NMR (100 MHz, CDCl3, 25 C): delta 43.3 (-CH2-), 55.3 (-OMe), 112.6 (Cpara of Ph), 115.4, 122.9 (Cortho of Ph), 118.2 (C5H5), 129.5, 159.7 (Cmeta of Ph), 137.5 (-CH2-C) and 188.5 (COO) ppm. FT-IR (KBr) = 1432 (nusym COO-) and 1644 (nuasym COO-) cm-1. FAB-MS: 343.2 (33) [M+ - OOC-CH2-C6H4-m-OMe], 208.0 (10) [MCp2O2-2H], 148.1 (99) [OC-CH2-C6H4-m-OMe] and 121.1 (100) [H3C-C6H4-m-OMe]. Elemental analysis (C28H28O6Ti, 508.14 g/mol) Calculated: C 66.15, H 5.55; Found: C 66.00, H 5.41%.
  • 60
  • [ 104-01-8 ]
  • [ 1271-19-8 ]
  • [Ti(η5-C5H5)2(OOC-4-mpa)2] [ No CAS ]
YieldReaction ConditionsOperation in experiment
71% With triethylamine; In toluene; at 80℃; for 3h;Inert atmosphere; General procedure: NEt3 (0.57 mL, 4.00 mmol) was added dropwise to a suspension of 3-methoxyphenylacetic acid (0.60 g, 4.00 mmol) and [Ti(eta5-C5H5)2Cl2] (0.50 g, 2.00 mmol) in toluene (50 mL) at room temperature. The reaction mixture colour changed immediately from deep red to orange and was then stirred for 3 h at 80 C. The mixture was decanted and filtered to remove the triethylammonium chloride salt. The filtrate was then concentrated and cooled to -30 C to give orange crystals of the complex which were isolated by filtration.
  • 61
  • [ 1271-19-8 ]
  • [ 4442-54-0 ]
  • [Ti(η5-C5H5)2(OOC-bdo)2] [ No CAS ]
YieldReaction ConditionsOperation in experiment
62% With triethylamine; In toluene; at 80℃; for 3h;Inert atmosphere; General procedure: NEt3 (0.57 mL, 4.00 mmol) was added dropwise to a suspension of 3-methoxyphenylacetic acid (0.60 g, 4.00 mmol) and [Ti(eta5-C5H5)2Cl2] (0.50 g, 2.00 mmol) in toluene (50 mL) at room temperature. The reaction mixture colour changed immediately from deep red to orange and was then stirred for 3 h at 80 °C. The mixture was decanted and filtered to remove the triethylammonium chloride salt. The filtrate was then concentrated and cooled to ?30 °C to give orange crystals of the complex which were isolated by filtration.
  • 62
  • [ 1271-19-8 ]
  • [ 636-44-2 ]
  • [Ti(η5-C5H5)2(OOC-dmf)2] [ No CAS ]
YieldReaction ConditionsOperation in experiment
49% With triethylamine; In toluene; at 80℃; for 3h;Inert atmosphere; General procedure: NEt3 (0.57 mL, 4.00 mmol) was added dropwise to a suspension of 3-methoxyphenylacetic acid (0.60 g, 4.00 mmol) and [Ti(eta5-C5H5)2Cl2] (0.50 g, 2.00 mmol) in toluene (50 mL) at room temperature. The reaction mixture colour changed immediately from deep red to orange and was then stirred for 3 h at 80 C. The mixture was decanted and filtered to remove the triethylammonium chloride salt. The filtrate was then concentrated and cooled to -30 C to give orange crystals of the complex which were isolated by filtration.
  • 63
  • [ 1271-19-8 ]
  • [ 7470-38-4 ]
  • [Ti(η5-C5H5)2(OOC-mbz)2] [ No CAS ]
YieldReaction ConditionsOperation in experiment
27% With triethylamine; In toluene; at 80℃; for 3h;Inert atmosphere; General procedure: NEt3 (0.57 mL, 4.00 mmol) was added dropwise to a suspension of 3-methoxyphenylacetic acid (0.60 g, 4.00 mmol) and [Ti(eta5-C5H5)2Cl2] (0.50 g, 2.00 mmol) in toluene (50 mL) at room temperature. The reaction mixture colour changed immediately from deep red to orange and was then stirred for 3 h at 80 C. The mixture was decanted and filtered to remove the triethylammonium chloride salt. The filtrate was then concentrated and cooled to -30 C to give orange crystals of the complex which were isolated by filtration.
  • 64
  • [ 1271-19-8 ]
  • [ 69945-42-2 ]
  • [ 1428772-35-3 ]
YieldReaction ConditionsOperation in experiment
71% With triethylamine; In methanol; for 1h; To a solution of pyridine-2,6-bis(thiocarboxylic) acid (0.200 g, 1.0 mmol) in methanol was added triethyl amine (0.202 g, 2.0 mmol) and stirred for 5 min then bis-cyclopentadienyltitanium dichloride (0.249 g, 1.0 mmol) was added with stirring. Precipitation occurred (yellow) just after addition. The reaction mixture was stirred further for an hour, the residue was then collected by filtration which was washed with methanol (two times) and dried under reduced pressure. The yellow residue was recrystallized from its chloroform solution by slow evaporation of the solvent. Yield: 0.254 g, (71%). Anal. Calc. for C17H13O3NSTi: C, 56.84, H, 3.65, N, 3.90. Found: C, 56.57, H, 3.59, N, 3.93%. IR spectra (KBr, cm-1): 1656 nu(CO), 1402 nu(CS). 1H NMR (CDCl3, ppm) 6.23 (10H of Cp, s), 8.24(1H, m, J(H, H) 7.2 Hz), 8.70(2H, m, J(H, H) 7.5 Hz) (Py). 13C NMR (CDCl3, ppm) 118.62 (Cp) 125.8, 126.3, 129.1, 142.7, 149.7 (Py), 167.0 (CO2), 198.7 (COS).
  • 65
  • [ 1271-19-8 ]
  • [ 64133-31-9 ]
  • (S,R)-[(η5-C5H5)2Ti{κ2NO(phenyl)NH}Cl] [ No CAS ]
YieldReaction ConditionsOperation in experiment
59% With triethylamine; In toluene; at 50℃;Inert atmosphere; General procedure: A toluene (5 mL) solution of [(eta5-C5H5)2TiCl2] (0.25 g, 1.00 mmol), (2S,5R)-{NOH,(Ph)NH} (0.26 g, 1.00 mmol) and NEt3 (0.12 mL, 0.95 mmol) was warmed up to 50 C and stirred overnight. The resulting orange suspension was filtered, to eliminate insoluble NEt3·HCl, and the final orange solution evaporated to dryness to afford a yellow solid which was washed twice with hexane (2 * 5 mL) and dried under vacuum. Yield: 0.28 g, 0.59 mmol, 59%. Solubility in H2O at 24 C (mM): 2.7 +- 0.6. Value of pH ([2.0 mM]) in H2O at 24 C: 4.34. Anal. Calcd for C26H31N2OTiCl: C, 66.32; H, 6.64; N, 5.95; Found: C, 66.62; H, 6.89; N, 5.99. FTIR (KBr): ? 3370 (mr, NH); 1644, 1602 (both m, CN). 1H NMR (plus HSQC, plus HMBC, plus COSY, 400.1 MHz, 293 K, CDCl3): delta 7.15 (m, 2 H, -C6H5), 6.73 (m, 3H, -C6H5), 6.40, 6.41 (both s, each 5H, C5H5), 4.75, 4.72 (both s, each 1H, CH2), 3.53 (br, 1H, NH), 2.83 (m, 1H, - CH26), 2.15 (m, 1H, -CH-C), 2.01 (m, 1H, -CH23), 1.83 (m, 2 H, overlapped -CH24 + 6), 1.73 (m, 1H, - CH23), 1.63 (m, 1H, - CH24), 1.76, 1.56 (both s, each 3H, NC-CH3 + CH3C). 13C NMR (plus APT, plus gHSQC, plus HMBC, 100.6 MHz, 293 K, CDCl3): delta 160.5 (-, CqN), 149.2 (-, Cq-Me), 147.0 (CipsoPh), 129.4, 118.3, 115.8 (+, C6H5), 117.2, 117.1 (+, C5H5), 109.5 (-, CH2), 57.4 (-, Cq-NH), 46.3 (+, -CH5), 44.0 (-, -CH23), 28.0 (-, -CH26), 26.6 (-, -CH24), 23.7, 21.2 (both +, CH3-CNH + CH3-C). 15N NMR (gHMBC, 40.5 MHz, 293 K, CDCl3): delta 400.2 (CN), 86.1 (NHPh).
  • 66
  • [ 1271-19-8 ]
  • [ 64133-30-8 ]
  • (S,R)-[(η5-C5H5)2Ti{κ2NO(benzyl)NH}Cl] [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With triethylamine; at 50℃;Inert atmosphere; General procedure: A toluene (5 mL) solution of 1a·HCl (0.20 g, 0.42 mmol) and NEt3(0.058 mL, 0.42 mmol) was stirred for 30 min at room temperature.The resulting orange suspension was filtered to separate the solution from insoluble NEt3·HCl. The orange solution was evaporated to dryness and the resulting yellow solid washed twice with hexane(2 × 5 mL) and dried under vacuum. Yield: 0.13 g, 0.29 mmol, 69%.CHN analysis data found did not agree with theoretical data calculated for C21H26N2OTiCl2, due toimpurification of the solid with NEt3·HCl. Recrystallization of the solid from toluene at-20 C affords crystals suitablefor X-ray analysis.
88% With triethylamine; An analogous procedure to that described for [(eta5-C5H5)2Ti{(1S,4R)kappaON,(Bn)NH}Cl] [69] was followed, starting from TDC (0.20g, 0.80mmol), (1R,4S)-{NH(Bn),NOH} (0.22g, 0.80mmol) and NEt3 (0.11mL, 0.80mmol). Compound 1a? was obtained as a yellow-orange solid. Yield: 0.32g (88%). [alpha]23D (deg·dm-1·cm3·g-1)-88.9±1.2 (1a? at c=0.7602gdL-1, alphaobs=-0.676 deg),+89.2±1.2 (1a at c=0.7497gdL-1, alphaobs=+0.681 deg). Analytical and spectroscopic data of the compound are identical to those already reported [69]. Solubility in H2O at 24C (mM): 6.6±0.2. Value of pH ([2.0mM]) in H2O at 24C: 5.54. Anal. Calcd for C27H33ClN2OTi: C, 66.88; H, 6.86; N, 5.78; Found: C, 66.80; H, 6.90; N, 5.76. FT IR (KBr, lambdamax/cm-1): 3370 (m, NH), 1646, 1601 (both m, C=N). 1H NMR (plus HSQC, plus HMBC, plus COSY, 400.1MHz, 293K, chloroform-d1): delta 7.32 (m, 5H, -C6H5), 6.39, 6.39 (both s, each 5H, C5H5), 4.76, 4.74 (both s, each 1H,=CH2), 3.76, 3.55 (both m, each 1H, -CH2Ph), 2.92 (m, 1H, -CH23), 2.05 (m, 1H, -CH-C=), 1.90 (m, 1H, -CH26), 1.72 (m, 1H, -CH23), 1.68 (m, 1H, -CH25), 1.59 (m, 1H, -CH26), 1.56 (m, 1H, -CH25), 1.25 (br, 1H, NH), 1.47, 1.25 (both s, each 3H, NC-CH3+CH3C=). 13C NMR (plus APT, plus gHSQC, plus HMBC, 100.6MHz, 293K, chloroform-d1): delta 159.2 (Cq=N), 149.3 (=Cq-Me), 141.6 (CipsoPh), 128.7, 128.7, 127.2 (C6H5), 117.1, 117.1 (C5H5), 109.4 (=CH2), 57.1 (Cq-NH), 47.3 (-CH2Ph), 45.6 (-CH4), 41.2 (-CH26), 27.8 (-CH23), 26.2 (-CH25), 23.9, 21.3 (CH3-CNH+CH3-C=). 15N NMR (gHMBC, 40.5MHz, 293K, chloroform-d1): delta 398.9 (C=N), 60.0 (NHBn).
  • 67
  • [ 1271-19-8 ]
  • [ 691-24-7 ]
  • [ 917-54-4 ]
  • bis-cyclopentadienyl di-tertbutylacetamidinato titanium [ No CAS ]
YieldReaction ConditionsOperation in experiment
60% Stage #1: 1,3-di-tert-butylcarbodiimide; methyllithium In tetrahydrofuran at -78 - 20℃; for 3h; Stage #2: bis(cyclopentadienyl)titanium dichloride In tetrahydrofuran at -78 - 20℃; 5 Example 5 Bis-Cyclopentadienyl Di-Tertbutylacetamidinato Titanium Synthesis (TiCp2(NtBu Me-amd)) To a solution of di-tertbutylcarbodiimide (2.46 g, 16 mmol) in ca. 20 mL of THF at -78° C., was added dropwise MeLi (10 mL, 16 mmol). After stirring 3 h at room temperature, the mixture was added to a solution of Ti(Cp)2(Cl)2 (2.32 g, 7.9 mmol) in ca. 20 mL of THF at -78° C. The mixture was stirred overnight at room temperature. Solvent was then removed under vacuum and the product was extracted with toluene to give a black solid. The material was then purified by sublimation at 90-100° C. 400 mTorr to give 1.64 g (60%) of pure blue solid. (0377) The solid left a 3.0% residual mass during Open-Cup TGA analysis measured at a temperature rising rate of 10° C./min in an atmosphere which flows nitrogen at 200 mL/min (6% during Close-Cup). These results are shown in FIG. 7, which is a TGA graph illustrating the percentage of weight loss upon temperature increase.
  • 68
  • [ 1271-19-8 ]
  • [ 147-93-3 ]
  • Ti(2+)*2C5H5(1-)*C7H6O2S [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With 3-ethyl-1-methyl-1H-imidazol-3-ium bromide; In chloroform; water; at 20℃; for 0.05h; Embodiment 1The 0.249g (1.0mmol) titanocene dichloride 0.201g (1.3mmol) thiosalicylic acid dissolved in 3 ml chloroform, then adding 1mL 0.4mol/L brominated 1-ethyl-3-methyl imidazolium salt aqueous solution, stirring at room temperature 3 minutes, layering, organic reinforced with deionized water after the washing, the water-free magnesium sulfate drying, filtering, 30 C concentrated under reduced pressure to remove chloroform, vacuum drying and a half hours at room temperature, the resulting solid crude product with dichloromethane-hexane recrystallization, to obtain greenish black needle-shaped crystal thiophosphoro salicylic acid titanocene complex, its yield is 82%. After the layering by bromination of 1-ethyl-3-methyl imidazolium salt soluble in the aqueous phase, can be directly reused.
  • 69
  • [ 10544-50-0 ]
  • [ 1271-19-8 ]
  • [ 33120-66-0 ]
  • [Cp2Ti(tBu-1,3-thiazoline-2-thione-4,5-dithiolate)] [ No CAS ]
YieldReaction ConditionsOperation in experiment
68% Under inert atmosphere at 10 C, LDA was prepared by adding BuLi (2.7 mL, 4.3 mmol, 1.6 M in hexanes) to a solution of diisopropylamine (0.4 mL, 4.3 mmol) in 15 mL of anhydrous THF. The LDA solution was then added to a solution of 1,3-thiazoline-2-thione 1 (0.50 g, 2.8 mmol) of 1,3- thiazoline -2-thione 1 dissolved in 40 mLof anhydrous THF. After stirring for 30 min at 10 C, sulfur (S8,0.14 g, 4.3 mmol) was added and the solution was stirred for anadditional 30 min. A solution of 5.7 mmol of LDA was added to the reaction medium and after 3 h of stirring sulfur (0.19 g, 5.7 mmol)was added. After 30 min of stirring Cp2TiCl2 (1.1 g, 4.3 mmol) was added and the reaction mixture was stirred for 15 h. The solventwas evaporated and the residue was extracted with dichloromethane. The organic phase was washed with water and then driedover MgSO4. The resulting solid was purified by column chromatography using dichloromethane as eluent. Cp2Ti(tBu-thiazdt) 2 was isolated as a blue powder (m 0.78 g). in 68% yield,mp 148 C. Rf 0.72, (SiO2, CH2Cl2). 1H NMR (300 MHz) d 1.91 (s,9H, CH3), 5.57 (s, 5H, Cp), 6.09 (s, 5H, Cp); 13C NMR (75 MHz) d 30.5(CeCH3), 68.4 (CeCH3), 107.5 (Cp), 111.6 (Cp), 135.8 (C]C), 147.8(C]C), 193.5 (C]S); HRMS (ASAP) calcd for [MH] C17H20NS4Ti:413.99526 Found: 413.9953. Anal calcd for C17H19NS4Ti: C, 47.38; H,4.63; N, 3.39. Found: C, 47.17; H, 4.47; N, 3.55.
  • 70
  • [ 10544-50-0 ]
  • [ 1271-19-8 ]
  • [ 33120-66-0 ]
  • [ 74-88-4 ]
  • [Cp2Ti(2-MeS-1,3-thiazole-4,5-dithiolate)] [ No CAS ]
YieldReaction ConditionsOperation in experiment
56% General procedure: Under inert atmosphere at 10 C, LDA was prepared by adding BuLi (2.7 mL, 4.3 mmol, 1.6 M in hexanes) to a solution of diisopropylamine (0.4 mL, 4.3 mmol) in 15 mL of anhydrous THF. The LDA solution was then added to a solution of 1,3-thiazoline-2-thione 1 (0.50 g, 2.8 mmol) of 1,3- thiazoline -2-thione 1 dissolved in 40 mLof anhydrous THF. After stirring for 30 min at 10 C, sulfur (S8,0.14 g, 4.3 mmol) was added and the solution was stirred for anadditional 30 min. A solution of 5.7 mmol of LDA was added to the reaction medium and after 3 h of stirring sulfur (0.19 g, 5.7 mmol)was added. After 30 min of stirring Cp2TiCl2 (1.1 g, 4.3 mmol) was added and the reaction mixture was stirred for 15 h. The solvent was evaporated and the residue was extracted with dichloromethane. The organic phase was washed with water and then dried over MgSO4. The resulting solid was purified by column chromatography using dichloromethane as eluent.
  • 71
  • [ 1271-19-8 ]
  • [ 7782-49-2 ]
  • [ 23230-01-5 ]
  • [ 136342-07-9 ]
YieldReaction ConditionsOperation in experiment
46% Starting from 2,3-dihydro-1,4-dithiobenzene, a dark green titanium compound was prepared under anhydrous anaerobic operation, The yield was 46%.
  • 72
  • [ 1271-19-8 ]
  • [ 97-05-2 ]
  • 2C7H5O6S(1-)*4H2O*C10H14O2Ti(2+) [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With benzoic acid; In water; toluene; at 20℃; for 2h; 0.25 g (1.0 mmol) of titanocene dichloride was addedAnd 0.49 g (4.0 mmol) of benzoic acid were dissolved in 30 mL of toluene,0.51 g (2.0 mmol) of 5-sulfosalicylic acid was dissolved in 15 mL of distilled water, and the two solutions were mixed,After stirring at room temperature for 2 hours, The aqueous phase was separated with a separatory funnel, the aqueous phase was concentrated under reduced pressure to 5 mL, crystallized,0.65 g of an orange-colored water-soluble titanocene complex was obtained in a yield of 82%.
  • 73
  • [ 1271-19-8 ]
  • [ 106-38-7 ]
  • bis(η(5)-cyclopentadienyl)titanium di(p-tolyl) [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% A 1-L, three-necked flask equipped with a stirrer, a dropping funnel, and a reflux condenser was charged with 200 mL of anhydrous ether. The apparatus was dried with dry helium, a small piece of lithium wire (17.4 g (2.5 mol)) was cut and dropped into the flask, and a small amount of a solution of 300 mL of ether and 171 g (1 mol) of p-bromotoluene was added dropwise to the flask at room temperature. Then, the whole amount of the solution of p-bromotoluene in ether was gradually added. After the reaction has finished, the reacted solution was filtered under a helium atmosphere to obtain a colorless, transparent p-tolyl lithium solution. A 2-L, three-necked flask purges with dry helium and equipped with a stirrer and a dropping funnel was charged with 99.6 g (0.4 mol) of bis(eta(5)-cyclopentadienyl)titanium dichloride and 500 mL of anhydrous ether. The above-synthesized solution of p-tolyl lithium in ether was added dropwise for about 2 hours at room temperature under stirring. The reaction mixture was filtered in air, and the non-dissolved portion was washed with dichloromethane. Then, the filtrate and the washing solution were combined, and the solvent was removed under a reduced pressure. The resultant residue was dissolved in a small amount of dichloromethane. Then, petroleum ether was added to recrystallize. An operation of filtering the obtained crystals and then again concentrating the filtrate was repeatedly carried out to obtain bis(eta(5)-dichloropentadienyl)titanium di(p-tolyl). The yield was 87%. The obtained crystals were orange-yellow, had a needle shape, exhibited good solubility in toluene and cyclohexane, had a melting point of 145 C., and had elemental analysis values of C, 80.0, H, 6.7, and Ti, 13.3.
  • 74
  • [ 1271-19-8 ]
  • [ 126615-06-3 ]
  • C26H42Si2Ti [ No CAS ]
YieldReaction ConditionsOperation in experiment
33% Dichlorobis(h5-cylopentadienyl)titanium (124 mg, 0.5 mmol)was dissolved in anhydrous THF (2.5 mL) in a Schlenk tube. Thesolution was cooled at 78 C and n-butyllithium (1.54M hexanesolution, 1.0 mmol) was added dropwise. The mixture was stirredat 78 C for 1 h, and 1,4-bis(tert-butyldimethylsilyl)but-1-en-3-yne (2c, 140 mg, 0.5 mmol) was added. The mixture was warmedup to 10 C and stirred for 1 h. The red solution was observed by1H NMR and the formation of 4c was observed. The yield wasdetermined using toluene as internal standard (45%). The mixturewas filtered through Celite, and the volatiles were removed invacuo left the title compound as red solid (33%). Crystals for X-raystudy was obtained by recrystallization from THF solutionat 30 C. 1H NMR (C6D6/THF, Me4Si, 300 MHz): d 5.80 (s, 10H, Cp).
  • 75
  • [ 102-54-5 ]
  • [ 7550-45-0 ]
  • [ 1271-19-8 ]
YieldReaction ConditionsOperation in experiment
91.3% With triethylamine; In N,N-dimethyl-formamide; at 65℃; for 2h;Inert atmosphere; Cooling with ice; The reaction apparatus was taken out from the oven, and the reaction apparatus was set up under heat. Under nitrogen cooling, nitrogen gas was cooled for 10 minutes. Under the protection of nitrogen, 18 mL of DMF was added to the reactor, then 37.94 g of titanium tetrachloride was added, and the mixture was stirred for 20 minutes. The pressure funnel continued to slowly add 150 mL of DMF to the reactor. A yellow precipitate formed upon the start of the addition. The precipitate was slowly dissolved as the solvent was added to obtain a yellow solution. Then, the ice bath was removed and slowly added to the same constant pressure funnel. Diethylamine, the color of the solution changed from yellow to dark green. After the addition was completed, 105.76 g of cyclopentadiene was continuously added, heated to 65 C, refluxed for 2 hours, the reaction was completed, cooled to room temperature, and the solvent was evaporated under reduced pressure. Then, adding ice water and stirring for 15 minutes, a red precipitate was precipitated, filtered under reduced pressure and washed with a small amount of ice water for 5 times to obtain a red precipitate which was a crude dichlorotitanium dichloride; the crude dichlorotitanocene was sufficiently dissolved with DMF, and decompressed. After suction filtration, the filtrate was spin-dried, and the obtained liquid was recovered as a solvent. The obtained solid was weighed with ice-water-dichloromethane-ethanol mixture (ice water, dichloromethane and ethanol in a ratio of 0.2:1.8:1 by volume). Crystal was filtered to give a red needle-like crystals, and dried in vacuo to obtain titanocene dichloride, the resulting solid weighed 45.46g, yield 91.3%.
  • 76
  • [ 1271-19-8 ]
  • sodium 5-[(E)-2-(4-pyridyl)-1-diazenyl]-2-hydroxybenzoate [ No CAS ]
  • C22H17N3O3Ti [ No CAS ]
YieldReaction ConditionsOperation in experiment
77% In benzene; at 40℃; for 4h;Schlenk technique; Inert atmosphere; General procedure: A freshly prepared solution of titanocene dichloride (0.100 g,0.401 mmol) in anhydrous benzene (15 ml) was added to a stirredsuspension of NaHLASA (0.230 g, 0.883 mmol) in anhydrous benzene(15 ml) and the stirring was continued at 40 C for 4 h. The dark-redreaction mixture was evaporated to dryness, washed with hot hexaneand dried in vacuo. The residue was extracted into hot anhydrouschloroform (20 ml) and filtered through a frit covered with pre-driedneutral silica (3 cm layer, mesh size 100-200) and eluted further withanhydrous chloroform (3×1 ml). The clear red filtrate was concentratedusing a rotary evaporator to around 3 ml, which uponstanding overnight afforded orange crystals of 3 at ambient temperature.Crystals were washed with a small amount of benzene and dried invacuo. Yield: 0.15 g, 56%.
  • 77
  • [ 1271-19-8 ]
  • [ 380360-51-0 ]
  • C23H17BrN2O3Ti [ No CAS ]
YieldReaction ConditionsOperation in experiment
55% With triethylamine; In benzene; at 40℃; for 4h;Schlenk technique; Inert atmosphere; General procedure: A freshly prepared solution of titanocene dichloride (0.100 g,0.401 mmol) in anhydrous benzene (20 ml) was added to a clear stirredsolution of H2LMASA (0.102 g, 0.401 mmol) in anhydrous benzene(50 ml). Subsequently, to a clear reaction mixture, a benzene solution(10 ml) of NEt3 (0.080 g, 0.790 mmol) was added drop-wise whereupon the wine-red solution turned dark-red along with precipitation ofEt3NHCl. The reaction mixture was slowly heated to 40 C and stirringwas continued for additional 4 h. The dark-red solution was filteredthrough a frit covered with pre-dried neutral silica (3 cm layer, meshsize 100-200) and eluted with anhydrous benzene (3×1 ml). The clearfiltrate was concentrated using a rotary evaporator to around 15 ml,which upon standing for a week afforded dark-red crystals of 5 atambient temperature. Crystals were washed with small amount of anhydrousbenzene and dried in vacuo. Yield: 0.13 g, 74%.
  • 78
  • [ 1271-19-8 ]
  • 5‐[(E)‐2‐(4‐chlorophenyl)‐1‐diazenyl]‐2‐hydroxybenzoic acid [ No CAS ]
  • C23H17ClN2O3Ti [ No CAS ]
YieldReaction ConditionsOperation in experiment
71% With triethylamine; In benzene; at 40℃; for 4h;Schlenk technique; Inert atmosphere; General procedure: A freshly prepared solution of titanocene dichloride (0.100 g,0.401 mmol) in anhydrous benzene (20 ml) was added to a clear stirredsolution of H2LMASA (0.102 g, 0.401 mmol) in anhydrous benzene(50 ml). Subsequently, to a clear reaction mixture, a benzene solution(10 ml) of NEt3 (0.080 g, 0.790 mmol) was added drop-wise whereupon the wine-red solution turned dark-red along with precipitation ofEt3NHCl. The reaction mixture was slowly heated to 40 C and stirringwas continued for additional 4 h. The dark-red solution was filteredthrough a frit covered with pre-dried neutral silica (3 cm layer, meshsize 100-200) and eluted with anhydrous benzene (3×1 ml). The clearfiltrate was concentrated using a rotary evaporator to around 15 ml,which upon standing for a week afforded dark-red crystals of 5 atambient temperature. Crystals were washed with small amount of anhydrousbenzene and dried in vacuo. Yield: 0.13 g, 74%.
  • 79
  • [ 1271-19-8 ]
  • [ 7355-19-3 ]
  • C40H36N4O8Ti [ No CAS ]
YieldReaction ConditionsOperation in experiment
53% With triethylamine; In benzene; at 40℃; for 4h;Schlenk technique; Inert atmosphere; A freshly prepared solution of titanocene dichloride(0.10 g, 0.40 mmol) in anhydrous benzene (15 ml) was added to astirred solution of H2LOEASA (0.23 g, 0.80 mmol) in anhydrous benzene(15 ml). Subsequently to the clear reaction mixture, a benzene solution(10 ml) of NEt3 (0.080 g, 0.79 mmol) was added drop-wise where uponthe wine-red solution turns dark-red along with precipitation ofEt3NHCl. The reaction mixture was slowly heated to 40 C and stirringwas continued for an additional 4 h. The dark-red solution was filteredthrough a frit covered with pre-dried neutral silica (3 cm layer, meshsize 100-200) and eluted with anhydrous benzene (3×1 ml). The clearfiltrate was concentrated using a rotary evaporator to around 3 ml,which upon standing overnight afforded red-orange crystals of 4 atambient temperature. Crystals were washed with small amount of anhydroushexane and dried in vacuo. Yield: 0.17 g, 53%. M. p.:171-173 C.
  • 80
  • [ 1271-19-8 ]
  • 5-[(E)-2-(4-fluorophenyl)-1-diazenyl]-2-hydroxybenzoic acid [ No CAS ]
  • C23H17FN2O3Ti [ No CAS ]
YieldReaction ConditionsOperation in experiment
68% With triethylamine; In benzene; at 40℃; for 4h;Schlenk technique; Inert atmosphere; General procedure: A freshly prepared solution of titanocene dichloride (0.100 g,0.401 mmol) in anhydrous benzene (20 ml) was added to a clear stirredsolution of H2LMASA (0.102 g, 0.401 mmol) in anhydrous benzene(50 ml). Subsequently, to a clear reaction mixture, a benzene solution(10 ml) of NEt3 (0.080 g, 0.790 mmol) was added drop-wise whereupon the wine-red solution turned dark-red along with precipitation ofEt3NHCl. The reaction mixture was slowly heated to 40 C and stirringwas continued for additional 4 h. The dark-red solution was filteredthrough a frit covered with pre-dried neutral silica (3 cm layer, meshsize 100-200) and eluted with anhydrous benzene (3×1 ml). The clearfiltrate was concentrated using a rotary evaporator to around 15 ml,which upon standing for a week afforded dark-red crystals of 5 atambient temperature. Crystals were washed with small amount of anhydrousbenzene and dried in vacuo. Yield: 0.13 g, 74%.
  • 81
  • [ 1271-19-8 ]
  • [ 380360-50-9 ]
  • C24H20N2O3Ti [ No CAS ]
YieldReaction ConditionsOperation in experiment
74% With triethylamine; In benzene; at 40℃; for 4h;Schlenk technique; Inert atmosphere; A freshly prepared solution of titanocene dichloride (0.100 g,0.401 mmol) in anhydrous benzene (20 ml) was added to a clear stirredsolution of H2LMASA (0.102 g, 0.401 mmol) in anhydrous benzene(50 ml). Subsequently, to a clear reaction mixture, a benzene solution(10 ml) of NEt3 (0.080 g, 0.790 mmol) was added drop-wise whereupon the wine-red solution turned dark-red along with precipitation ofEt3NHCl. The reaction mixture was slowly heated to 40 C and stirringwas continued for additional 4 h. The dark-red solution was filteredthrough a frit covered with pre-dried neutral silica (3 cm layer, meshsize 100-200) and eluted with anhydrous benzene (3×1 ml). The clearfiltrate was concentrated using a rotary evaporator to around 15 ml,which upon standing for a week afforded dark-red crystals of 5 atambient temperature. Crystals were washed with small amount of anhydrousbenzene and dried in vacuo. Yield: 0.13 g, 74%. M. p.:150-152 C. Anal. found: C, 67.10; H, 4.19; N, 7.80. Calcd forC24H20N2O3Ti: C, 66.68; H, 4.66; N, 6.48%. IR absorptions (cm-1):1614 nu(OCO)asym, 1598, 1472, 1414, 1310, 1248, 1175, 1128, 1128,822, 644, 501. 1H NMR (CDCl3) deltaH: 8.45 [d, 1H, H-6], 8.06 [dd, 1H, H-4], 7.74 [XX? portion of AA?XX?, 2H, H-3? & H-5?], 7.25 [AA? portion of AA?XX?, 2H, H-2? & H-6?], 7.05 [d, 1H, H-3], 6.60 [s, 10H, C5H5], 2.37[t, 3H, CH3]. 13C{1H} NMR (CDCl3) deltaC: 173.89 [COO], 165.49 [C-2],151.84 [C-1?], 146.51 [C-5], 142.56 [C-4?], 131.12 [C-3? & C-5?],129.65 [C-4], 128.49 [C-6], 123.95 [C-2? & C-6?], 121.69 [C5H5],119.44 [C-3], 114.45 [C-1], 22.84 [CH3].
  • 82
  • [ 1271-19-8 ]
  • [ 603-11-2 ]
  • C26H18N2O12Ti [ No CAS ]
YieldReaction ConditionsOperation in experiment
67% With 5-sulfosalicylic Acid; In ethanol; water; at 20℃; for 4h; 0.51 g (2.0 mmol) of 5-sulfosalicylic acid was dissolved in 15 mL of distilled water. Then 0.5 g (2.0 mmol) of dichlorotitanium dichloride was added in three portions. Stir until the dichlorotitanocene is completely dissolved; 0.844 g (4.0 mmol) of <strong>[603-11-2]3-nitrophthalic acid</strong> was dissolved in 30 mL of ethanol, and then the two solutions were mixed and stirred at room temperature for 4 hours. Concentrated under reduced pressure, it was dried over anhydrous magnesium sulfate for 15 min and concentrated by rotary evaporation. Recrystallized from ethanol/n-hexane, Obtaining an orange-red titanium alloy complex of 0.801g, Its yield is 67%.
  • 83
  • [ 1271-19-8 ]
  • [ 75-98-9 ]
  • bis(η5-cyclopentadienyl)bis(2,2-dimethylpropanoato-κO)titanium(IV) [ No CAS ]
YieldReaction ConditionsOperation in experiment
45% With triethylamine; In benzene; at 40℃; for 4h; General procedure: A freshly prepared solution of titanocene dichloride (0.25 g, 1.004mmol) in anhydrousbenzene (15mL) was added to a stirred solution of furan-3-carboxylic acid (0.225 g,1.99mmol) in anhydrous benzene (15mL). Subsequently, a benzene solution (10mL) ofNEt3 (0.282mL, 2.008mmol) was added dropwise where upon the blood-red solutionturned bright-orange along with precipitation of Et3NHCl. The reaction mixture wasslowly heated to 40 C and stirring were continued for additional 4 h. The orange solutionwas filtered through a frit covered with pre-dried neutral silica (1 cm layer, mesh size100-200) and eluted with anhydrous benzene (30.5mL). The clear filtrate was concentratedusing a rotary evaporator to around 2mL and precipitated with an excess ofanhydrous hexane. The orange solid was collected on a frit, washed with hexane(25mL), dried, and recrystallized from anhydrous benzene at ambient temperature toafford orange crystals, which were isolated by filtration.
  • 84
  • [ 1271-19-8 ]
  • [ 1070-83-3 ]
  • bis(η5-cyclopentadienyl)bis(3,3-dimethylbutanoato-κO)titanium(IV) [ No CAS ]
YieldReaction ConditionsOperation in experiment
45% With triethylamine; In benzene; at 40℃; for 4h; General procedure: A freshly prepared solution of titanocene dichloride (0.25 g, 1.004mmol) in anhydrousbenzene (15mL) was added to a stirred solution of furan-3-carboxylic acid (0.225 g,1.99mmol) in anhydrous benzene (15mL). Subsequently, a benzene solution (10mL) ofNEt3 (0.282mL, 2.008mmol) was added dropwise where upon the blood-red solutionturned bright-orange along with precipitation of Et3NHCl. The reaction mixture wasslowly heated to 40 C and stirring were continued for additional 4 h. The orange solutionwas filtered through a frit covered with pre-dried neutral silica (1 cm layer, mesh size100-200) and eluted with anhydrous benzene (30.5mL). The clear filtrate was concentratedusing a rotary evaporator to around 2mL and precipitated with an excess ofanhydrous hexane. The orange solid was collected on a frit, washed with hexane(25mL), dried, and recrystallized from anhydrous benzene at ambient temperature toafford orange crystals, which were isolated by filtration.
  • 85
  • [ 488-93-7 ]
  • [ 1271-19-8 ]
  • bis(η5-cyclopentadienyl)bis(furan-3-carboxylato-κO)titanium(IV) [ No CAS ]
YieldReaction ConditionsOperation in experiment
60% With triethylamine; In benzene; at 40℃; for 4h; A freshly prepared solution of titanocene dichloride (0.25 g, 1.004mmol) in anhydrousbenzene (15mL) was added to a stirred solution of furan-3-carboxylic acid (0.225 g,1.99mmol) in anhydrous benzene (15mL). Subsequently, a benzene solution (10mL) ofNEt3 (0.282mL, 2.008mmol) was added dropwise where upon the blood-red solutionturned bright-orange along with precipitation of Et3NHCl. The reaction mixture wasslowly heated to 40 C and stirring were continued for additional 4 h. The orange solutionwas filtered through a frit covered with pre-dried neutral silica (1 cm layer, mesh size100-200) and eluted with anhydrous benzene (30.5mL). The clear filtrate was concentratedusing a rotary evaporator to around 2mL and precipitated with an excess ofanhydrous hexane. The orange solid was collected on a frit, washed with hexane(25mL), dried, and recrystallized from anhydrous benzene at ambient temperature toafford orange crystals, which were isolated by filtration. Yield: 0.35 g, 60%. m. p.:110-112 C (dec.). IR absorption (cm2-1): 1628 m(OCO)asym, 1562, 1504, 1396 m(OCO)sym,1338, 1314, 1194, 1182, 1150, 1006, 837, 779, 766, 559. 1H NMR (CDCl3): 8.05 (s, 2H, H-2),7.39 (urd, 2H, H-5), 6.71 (urd, 2H, H-4), 6.52 (s, 10H, C5H5), ppm. 13C{1H} NMR (CDCl3):168.9 (COO), 149.1 (C-5), 144.0 (C-2), 120.2 (C5H5), 118.7 (C-3), 109.8 (C-4) ppm.
  • 86
  • [ 1271-19-8 ]
  • [ 603-11-2 ]
  • C26H18N2O12Ti [ No CAS ]
  • 87
  • [ 1271-19-8 ]
  • magnesium(II) chloride hexahydrate [ No CAS ]
  • [ 100-21-0 ]
  • [ 170165-84-1 ]
  • 3C8H4O4(2-)*C21H15N3*2Mg(2+)*Ti(4+)*O(2-) [ No CAS ]
YieldReaction ConditionsOperation in experiment
In N,N-dimethyl-formamide at 120℃; for 96h; Sealed tube;
  • 88
  • [ 7550-45-0 ]
  • [ 542-92-7 ]
  • [ 1271-19-8 ]
YieldReaction ConditionsOperation in experiment
55% Step 2: The 30 mL cyclopentadiene monomer prepared in Step 1 is directly mixed with a mixed solution containing titanium tetrachloride, tetrahydrofuran and diethylamine, and the mixed materials are reacted under reflux at 66C for 4 hours; Step 101: In a nitrogen atmosphere, add 10 mL of titanium tetrachloride to a three-necked flask,In an ice bath, 90 mL of tetrahydrofuran was added dropwise to a three-necked flask equipped with titanium tetrachloride. After the addition was completed, the mixture was stirred for 30 min to obtain a yellow suspension;Step 102: Under stirring conditions, add 30 mL of diethylamine to the suspension described in step 101, and continue stirring for 30 min after the completion of the dropwise addition.A dark green mixed solution containing titanium tetrachloride, tetrahydrofuran and diethylamine was obtained;Step 3: Ice bath cooling Step 2: After refluxing, the system was filtered, and the retentate was washed with tetrahydrofuran first.Then washed with petroleum ether to obtain the retentate after washing;Step 4. Add the retentate after washing in Step 3 to 80mL hydrochloric acid solution and stir for 15min.Filtration to obtain the retentate after filtration; the mass concentration of the hydrochloric acid solution is 25%;Step 5: Wash the retentate after filtering in step 4 with ice water first.Then it was washed with absolute ethanol and dried to a constant weight to obtain titanocene dichloride. The product titanocene dichloride has a mass of 12.2 g, a yield of 55%, and a purity of 98.2%.
  • 89
  • [ 1271-19-8 ]
  • [ 2817736-33-5 ]
  • [ CAS Unavailable ]
YieldReaction ConditionsOperation in experiment
68.4% With potassium carbonate In tetrahydrofuran; water at 20℃; for 1h; 2.2. Synthesis of [TiCp2{(OOC)2py-O-myr}] (3) To a solution of [TiCp2Cl2] (1) (0.124 g, 0.5 mmol) in 10 mL of THF,a solution containing myr-O-py(COOH)2 (2) (0.190 g, 0.5 mmol) andK2CO3 (0.070 g, 0.5 mmol) in 1 mL of water was added. The mixture wasstirred for 1 h. After that, the solvent was removed under vacuum andthe residue was solved in CH2Cl2 and washed two times with water. Theorganic phase was dried over MgSO4 anhydrous and the solventsevaporated to yield a yellow complex that was identified as 3. Yield: 190mg (68.4%). 1H NMR (400 MHz, CDCl3): δ: 7.67 (s, 2H, ar), 6.20 (s, 10H, Cp), 4.20(t, 2H, CH2-O), 1.89 (q, 2H, CH2), 1.49 (q, 2H, CH2), 1.28 (m, 20H, CH2),0.89 (t, 3H, CH3).13C{1H} NMR (100 MHz, CDCl3): δ: 171.35 (Cipso-O), 165.57 (C=O),152.11 (Cipso-COO), 118.73 (Cp), 112.28 (Ar), 70.40 (CH2-O), 31.93,29.69, 29.66, 29.57, 29.50, 29.36, 29.19, 28.56, 25.74, 22.70 (CH2),14.14 (CH3).IR (cm 1): 2920 w, 2852 w, 1651 vs, 1617 m, 1361 s, 1119 s, 1049 s,806 s.MS (ESI-QTOF) m/z: Calculated for C31H41NO5Ti: 555.5 [M]+;found: 556.4 [M + H]+, 578.3 [M + Na]+.Anal. Calcd. for C31H41NO5Ti: C, 67.02; H, 7.44; N, 2.52. Found: C,67.11; H, 7.49; N, 2.47
  • 90
  • [ 1271-19-8 ]
  • [ 51751-44-1 ]
  • [ 2758653-00-6 ]
YieldReaction ConditionsOperation in experiment
80% Stage #1: 3,3′-dibromo-2,2′-bithiophene With n-butyllithium In diethyl ether; hexane at -78℃; for 2h; Inert atmosphere; Stage #2: bis(η5-cyclopentadienyl) titanium dichloride In diethyl ether; hexane at -78 - 20℃; 2.3.1. Synthesis of Bis(cyclopentadienyl)dithienotitanacyclopentadiene (2) To a two-necked round bottom 50 mL flask containing 1 (1.0 g, 3.1 mmol) in 30 mL dry Et2O, n-butyllithium in hexane (1.6 M, 4.3 mL, 6.8 mmol) was added dropwise at 78 °C under argon and the resulting mixture was kept stirring at that temperature for 2 h. Bis(cyclopentadienyl)titanium(IV) dichloride (1.0 g, 4.0 mmol) was added slowly to the solution at 78 °C and the reaction mixture was warmed to ambient temperature and kept stirring overnight. After the addition of water (10 mL) to the mixture to quench the reaction, the mixture was extracted with three 20 mL portions of CH2Cl2 and the combined organic fractions were dried over MgSO4. After the removal of the volatile fractions by evaporation, the residue was purified by alumina column chromatography using a mixed solvent of hexane and CH2Cl2 (v/v = 9/ 1) as an eluent to give 2 in 80% yield (0.85 g, 2.5 mmol) as a green powder. 1H NMR (300 MHz, CDCl3, δ ppm): 6.12 (d, J = 7.1 Hz, aromatic, 2H), 6.26 (s, -C5H5, 10H), 6.88 (d, J = 7.1 Hz, aromatic, 2H). 13C{1H} NMR (CDCl3, δ, ppm): 114.76 (-C5H5), 120.01 (aromatic), 125.26 (aromatic), 133.08 (aromatic), 185.97 (aromatic). HRMS (ESI): calcd for C18H14S2Ti, 342.00164; found, 342.001. IR (ATR, cm 1): 3078.1, 3035.2, 1433.4, 1207.8, 1139.3, 1107.9, 1070.8, 1012.7, 916.6, 810.9, 685.3, 599.6, 436.9. mp: 163-165 °C.
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