Structure of 33976-43-1
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CAS No. : | 33976-43-1 |
Formula : | C9H15NO3Si |
M.W : | 213.31 |
SMILES Code : | CO[Si](OC)(C1=CC=C(N)C=C1)OC |
MDL No. : | MFCD00054700 |
InChI Key : | CNODSORTHKVDEM-UHFFFAOYSA-N |
Pubchem ID : | 118583 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* 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 |
---|---|---|
The aminosilicon compounds can be concretely exemplified as follows: ... 2-aminoethyltriethoxysilane, 2-aminoethylmethyldimethoxysilane, 2-aminoethylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminophenyltrimethoxysilane, 4-aminophenyltriethoxysilane, 4-aminophenylmethyldimethoxysilane, 4-aminophenylmethyldiethoxysilane, ... | ||
Specific examples of such amino-containing silane compounds include ... N-(beta-dimethylaminoethyl)-gamma-aminopropyltrimethoxysilane, N-(beta-aminoethylaminoethyl)-gamma-aminopropyltrimethoxysilane, N-(gamma-aminopropyl)-gamma-aminoisobutylmethyldiethoxysilane, N-(beta-aminoethyl)-gamma-aminopropyltriethoxy-silane, 1,4-aminophenyltrimethoxysilane, beta-amino(polyethyleneimine) propyltrimethoxy-silane, | ||
Specific examples of such amino-containing silane compounds include ... N-(beta-dimethylaminoethyl)-gamma-aminopropyltrimethoxysilane, N-(beta-aminoethylaminoethyl)-gamma-aminopropyltrimethoxysilane, N-(gamma-aminopropyl)-gamma-aminoisobutylmethyldiethoxysilane, N-(beta-aminoethyl)-gamma-aminopropyltriethoxysilane, 1,4-aminophenyltrimethoxysilane, |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium methylate; In methanol; | A 300-milliliter four-neck flask equipped with a thermometer, stirrer, and a refluxing cooler was loaded with 5.35 g (0.22 mole) of magnesium and 54 g of tetrahydrofuran, and then the content was activated by adding 1.85 g (0.02 mole) of t-butyl chloride, while the components were stirred in a nitrogen flow.[0054]An appropriate Grignard reagent was prepared by adding a solution of 54.0 g (0.2 mole) of the compound of the aforementioned formula obtained in Practical Example 1 in 54 g of tetrahydrofuran. The solution was added dropwise at 55C. The obtained Grignard reagent solution was added dropwise to a solution of 21.7 g (0.2 mole) of chlorotrimethylsilane in 30 g of tetrahydrofuran. The salt formed in the reaction was removed by filtering, and a deprotection reaction was carried out by adding 50 g of methanol. Sodium methoxide was added until the liquid became neutral, the solvent was removed by distillation, and the product was again distilled in vacuum to produce a p-aminophenyltrimethoxysilane with a yield of 62%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With dibutyltin dilaurate; In tetrahydrofuran; at 20℃; for 8h;Dry environment; | Example 6; Compound F; 52.2 g of TDI trimer was dissolved in 400 mL of anhydrous tetrahydrofuran (THF), and the solution was added to a mixture of 21.3 g of p-aminophenyl- trimethoxysilane and 0.08 g of dibutyltin dilaurate (DBTDL). The resultant solution was stirred for 8 hs at room temperature under a dry environment. Subsequently, THF was removed with reduced pressure distillation and 63.0 g of compound F was obtained, with a yield of 86%. The compound F has a formula of [Show Image] Elemental analysis of C36H33N7O8Si: measured value (calculated value)%: C 69.88(70.1), H 4.44(4.59), N 13.53(13.63), O 17.69(17.8), Si 3.76(3.89); 1HNMR(delta/ppm): 0.66(m, 3H), 2.35(s,1H), 5(s, 3H, 3.5), 6.0(s, 1H), 6.9(q, 1H), 7.0(q,1H), 7.26(q,1H), 7.5(s, 1H), 7.6(m, 1H), 7.9(m,1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With N-ethyl-N,N-diisopropylamine; In tetrahydrofuran; at 70℃; for 3.5h;Schlenk technique; Inert atmosphere; | In a Schlenk tube under nitrogen atmosphere, triphosgene (59 mg,0.20 mmol, 3.2 equiv) was dissolved in anhydrous THF (0.8 mL) andthe solution was cooled to 0 C. In another tube, trimethoxysilylani-line (85 mg, 0.40 mg, 2.1 equiv) and anhydrous DIPEA (160 muL, 0.88mmol, 4.6 equiv) were dissolved in anhydrous THF (0.9 mL) and theresulting mixture was added dropwise under vigorous stirring to thetriphosgene solution; a white precipitate was immediately observed.The suspension was then warmed to 70 C. After 3.5 h, no more tri-methoxysilylaniline was detected by TLC, so the mixture was cooledto r.t. and dye MB25 (125 mg, 0.19 mmol, 1.0 equiv), more anhydrousDIPEA (67 muL, 0.38 mmol, 2.0 equiv) and anhydrous THF (0.5 mL) wereadded. The suspension was warmed to 50 C and stirred overnight.The mixture was diluted with EtOAc (100 mL), and was washed withH 2 O (2 × 100 mL) and brine (130 mL). The organic phase was driedover Na 2 SO 4 and the solvent was removed under reduced pressure.The crude product was then washed with pentane (4 × 10 mL) andMeOH (4 × 10 mL) to obtain purified siloxane MB56.Yield: 75 mg (0.088 mmol, 46%); dark-red amorphous solid.IR (KBr): 2924, 2196, 1583, 1497, 1276 cm -1 .1 H NMR (CDCl 3 , 300 MHz): delta = 8.57 (s, 1 H), 7.88 (s, 1 H), 7.67-7.65(m, 2 H), 7.40-7.25 (m, 6 H), 7.15-6.90 (m, 12 H), 4.07 (s, 2 H), 3.98 (s,2 H), 3.63 (s, 2 H), 1.39-1.26 (m, 16 H), 0.92-0.89 (m, 6 H).13 C NMR (CDCl 3 , 75 MHz): delta = 159.9, 156.3, 148.6, 147.3, 145.8, 141.4,139.8, 136.0, 135.8, 133.0, 131.7, 129.9, 129.5, 128.2, 125.2, 123.7,122.7, 119.5, 118.5, 115.5, 113.4, 94.1, 78.3, 78.1, 51.0, 43.8, 32.7,32.2, 29.8, 22.7, 14.2.ESI-MS: m/z = 856.41 [M + H] + .HRMS: m/z [M + H] + calcd for C 50 H 57 O 6 N 3 SSi: 856.3816; found:856.3807. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | at 115℃; for 3h;Inert atmosphere; | To a dry round bottom flask were added 2.15 g <strong>[33976-43-1]4-aminophenyltrimethoxysilane</strong> (1.00 × 10-2 mol) and 1.52 g triethanolamine (1.02 × 10-2 mol). A reflux condenser was attached and the mixture was heated to 115 C while stirring under a nitrogen atmosphere. After 3 h, the reaction was cooled and the methanol was removed under reduced pressure to yield a crude solid. This was recrystallized twice from chloroform and filtered to yield a white solid (1.68 g, 62%). 1H NMR (400 MHz, CDCl3, delta): 7.53 (d, J = 8.6 Hz, 2H, Ar-H), 6.63 (d, J = 8.6 Hz, 2H, Ar-H), 3.87 (t, J = 5.9 Hz, 6H, O-CH2), 3.53 (br s, 2H, NH2), 2.88 (t, J = 5.9 Hz, 6H, N-CH2). 13C (100 MHz, CDCl3, delta): 146.1, 135.3, 130.3, 114.6, 57.9, 51.2. HRMS (API, QTOF) m/z calcd for C12H19N2O3Si [M+H]+, 267.1159; Found, 267.1166. |
62% | With sodium hydroxide; In toluene; at 100℃; for 2h;Inert atmosphere; | To a dry round bottom flask were added 2.15g <strong>[33976-43-1]4-aminophenyltrimethoxysilane</strong> (1.00×10-2mol) and 1.52g triethanolamine (1.02×10-2mol). A reflux condenser was attached and the mixture was heated to 115C while stirring under a nitrogen atmosphere. After 3h, the reaction was cooled and the methanol was removed under reduced pressure to yield a crude solid. This was recrystallized twice from chloroform and filtered to yield a white solid (1.68g, 62%). 1H NMR (400 MHz, CDCl3, delta): 7.53 (d, J=8.6Hz, 2H, Ar-H), 6.63 (d, J=8.6Hz, 2H, Ar-H), 3.87 (t, J=5.9Hz, 6H, O-CH2), 3.53 (br s, 2H, NH2), 2.88 (t, J=5.9Hz, 6H, N-CH2). 13C (100MHz, CDCl3, delta): 146.1, 135.3, 130.3, 114.6, 57.9, 51.2. HRMS (API, QTOF) m/z calcd for C12H19N2O3Si [M+H]+, 267.1159; Found, 267.1166. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
38% | Compound No.A-1(0.05mmol, 30), the inputdimethylformamide(0.1), chloroform (2) to the flask, and by the additionof oxalyl chloride (0.06mmol, 8) was stirred for one hour. Then, at 0 C 4trimethoxysilylaniline (0.05mmol, 10), by theaddition of diisopropyl ethyl amine (0.09mmol, 12) it was stirred for one hour. To the reaction mixture was added to water(10) and chloroform (10) was carried out oil-water separation. The resulting organic layer was purified by silica gel columnchromatography and by refining (mobile phase chloroform) to give an orange solid 30 (yield 38%). The resulting solid wasconfirmed using the compound No.A-11in that the UVVIS(lambdamax), 1HNMR,IR. Represents the data in Table 1 ~ Table 3 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With triethylamine; In N,N-dimethyl-formamide; toluene; for 6h;Reflux; Inert atmosphere; Schlenk technique; | An appropriate organotrialkoxysilane (1.0 mmol) and triethanolamine (0.15 g, 1.0 mmol) were dissolved in toluene-DMF(8:1 v/v, 10 ml) mixture in a 50-ml Schlenk flask underargon atmosphere. The solution was heated at reflux on anoil bath until the reaction was complete (approx. 6-12 h).The reaction was monitored by TLC (hexane-CH2Cl2, 1:1).Toluene (and partly DMF) was removed under vacuum andthe residue was purified by recrystallization from MeCN toafford crystalline material. (4-Aminophenyl)silatrane (1). From (p-aminophenyl)-trimethoxysilane (0.21 g, 1.0 mmol). After the synthesis(reaction time 6 h), the concentrated residue was purifiedby flash chromatography (MeCN-CH2Cl2, 2:1) on SiO2,and the brownish solid crude product was recrystallizedfrom MeCN. Yield 0.2 g (76%), light-yellow crystals.1H NMR spectrum, delta, ppm (J, Hz): 7.51 (2H, d, J = 8.4,H-3,5 Ar); 6.62 (2H, d, J = 8.4, H-2,6 Ar); 3.88 (6H, t,J = 5.8, 3OCH2); 3.58 (2H, s, NH2); 2.88 (6H, t, J = 5.8,3NCH2). 13C NMR spectrum, delta, ppm: 154.8; 135.3; 126.0;114.6; 57.9; 51.2. Found, %: C 54.07; H 6.84; N 10.53;O 18.08; Si 10.51. C12H18N2O3Si. Calculated, %: C 54.11;H 6.81; N 10.52; O 18.02; Si 10.54. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
13.6 g | To a 2000 mL round bottom flask under nitrogen was added THF (700 mL) and magnesium particles (11.8 g, 485 mmol) was added to the mixture, and 1,2-dibromoethane (2 drop)And stirred at 45 & lt; 0 & gt; C for 20 minutes.The compound 74-3 (70 g, 220 mmol) obtained previously was added to the reaction solution at the same temperature (45 DEG C) is slowly added and stirred at reflux for 3 hours.The reaction was cooled to room temperature (25 deg C) (compound 74-2)A solution of tetramethylorthosilicate (32.6 mL, 220 mmol / 60 mL of THF) is slowly added dropwise.After stirring at room temperature (25 deg C) for 30 min (Compound 98-6)The saturated NH4Cl aqueous solution is added in excess and stirred overnight.The reaction mixture was stirred with EA, and the organic layer was separated,It is dried over MgSO4 and concentrated under reduced pressure.The obtained concentrate was purified by column chromatography (EA: hexane = 1: 12) using silica gel,The product 98-5 (13.6 g, total of 29 wt% in three steps) was obtained by purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
41 g | A 2000 mL round bottom flask was charged with nitrogen, THF (100 mL)(25 g, 117 mmol) was added thereto, followed by stirring.The reaction is cooled to -78 C and methyllithium (MeLi) (1.6 M concentration in diethyl ether, 412.5 mL, 258 mmol) is slowly added dropwise.After completion of dropwise addition, stirring is carried out for 2 hours while raising the temperature naturally.The reaction was cooled again to -78 deg C and then chlorotrimethylsilane (32.5 mL, 258 mmol)Slowly.After completion of dropwise addition, the reaction mixture is stirred for 1 hour while raising the temperature naturally.The reaction is concentrated under reduced pressure. Hexane (100 mL) was added to the concentrate and stirredThe resulting salt was removed by filtration and the filtrate was concentrated under reduced pressure to give the product 98-4 (41 g, 98 wt%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With 5%-palladium/activated carbon; hydrogen; In tetrahydrofuran; at 20℃; | N, N-dibenzyl-4-trimethoxysilylaniline (11.1 g, 28.4 mmol) was dissolved in tetrahydrofuran (100 mL), and palladium carbon (0.56 g, Pd 5%, about 55% wet with water) was added. The reaction was carried out by stirring at room temperature under a hydrogen gas atmosphere. After replacing the hydrogen gas in the reaction vessel with nitrogen gas, palladium carbon was filtered off from the reaction solution, and the filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by distillation under reduced pressure to obtain 5.8 g of the objective colorless and transparent product of 4-trimethoxysilylaniline in a yield of 5.8 g and a yield of 96%. |