trimethoxy(3,3,3-trifluoropropyl)silane

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 ml 5-neck round-bottom flask, rendered inert with nitrogen and equipped with paddle stirrer, dropping funnel, thermometer, and water separator with reflux condenser, is charged with 50 g (0.36 mol) of methyl-trimethoxysilane (available commercially from Wacker Chemie AG), 8.8 g (0.04 mol) of 3,3,3-trifluoro-propyltrimethoxysilane (available commercially from Fluka), and 39.7 g of Isopar E (isoparaffinic hydro-carbon mixture having a boiling range of 113-143° C., available commercially from ExxonMobil). The water separator is filled to the brim with Isopar E. Accompanied by stirring at 350 rpm, a solution of 17.2 g of potassium hydroxide (85% strength, available commercially from AppliChem) (0.26 mol of potassium hydroxide) and 15.3 g of demineralized water is metered in over 12 minutes. During this metered addition, the mixture heats up to 67° C. The mixture is heated to boiling temperature (70° C.). The distillate separates out as the bottom phase in the water separator. Up to a boiling temperature of 119° C., 48.5 g of colorless, slightly turbid distillate accumulate. The suspension which remains is subsequently evaporated to dryness with stirring under a full oil-pump vacuum (5 hPa) to 70° C. This gives 45.9 g of fine, white, free-flowable powder with a solids content of 99.7% (determined using the HR73 halogen moisture analyzer from Mettler Toledo at 160° C.). A 50% strength aqueous solution prepared with this powder exhibits no precipitation even after being stored at room temperature for two weeks in the absence of air. A 500 ml 5-neck round-bottom flask, rendered inert with nitrogen equipped with paddle stirrer with reflux condenser is metered in over 12 minutes During this metered addition heats up to 67° C The suspension which remains is subsequently evaporated to dryness with stirring under a full oil-pump vacuum (5 hPa) to 70° C at 160° C. A 50% strength aqueous solution prepared with this powder no precipitation even after being stored at room temperature for two weeks in the absence of air

Conditions: temp:15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3,3,3-Trifluoropropyl(bis(2-ethylhexyl)aminodimethoxysilane--A 500 mL round bottomed flask was charged with tetrahydrofuran (300 mL) and isopropylmagnesium chloride (25 mL of a 2.0 M solution in THF, 50 mmol). The contents were cooled to 15° C. Bis(2-ethylhexyl)amine (50 mmol) was added over fifteen minutes via pressure equalizing addition funnel. The cold bath was removed and the contents stirred for two hours. 3,3,3-Trifluoropropyltrimethoxysilane (45 mmol) was added via pressure equalizing addition funnel. The contents were brought to reflux (65-70° C.) for two hours, and reaction progress was monitored by GC. Isolation was accomplished by removing the THF via rotary evaporation, taking the residue up in ether (250 mL), filtration and ether removal via rotary evaporation. Purification was accomplished by distillation to provide 3,3,3-trifluoropropyl bis(2-ethylhexyl)aminodimethoxysilane (44 mmol; 98% yield). C21H44NO2SiF3 (mw=427.66) bp=200° C. at 1.4 mmHg; 1H NMR: (CDCl3) δ 3.5 (s, 6H), 2.6-2.4 (dd, 4H), 2.2-2.0 (m, 2H), 1.6-1.1 (m, 18H), 1.0-0.7 (m, 14H); 13C NMR: (CDCl3) δ 128 (quartet, J=275 Hz), 50.4, 48.5, 39.4, 36.9, 30.8, 29.1, 28.2 (quartet, J=30 Hz), 23.2, 14.2, 10.3, 3.2; MS: m/z (relative abundance) 328 (100), 230 (25.6), 155 (7.4), 109 (2.9). addition funnel The cold bath was removed addition funnel to reflux (65-70° C.) for two hours reaction progress by removing the THF via rotary evaporation up in ether (250 mL), filtration and ether removal via rotary evaporation Purification was accomplished by distillation

Conditions: temp:15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3,3,3-Tritluoropropyl(1,2,3,4-tetrahydroisoquinolinyl)dimethoxysilane--A 500 mL round bottomed flask was charged with tetrahydrofuran (300 mL) and isopropyl-magnesium chloride (30 mL of a 2.0 M solution in THF, 60 mmol). The contents were cooled to 15° C. 1,2,3,4-Tetrahydroisoquinoline (60 mmol) was added over fifteen minutes via pressure equalizing addition funnel. The cold bath was removed and the contents stirred for two hours. 3,3,3-Trifluoropropyltrimethoxysilane (54.5 mmol) was added via pressure equalizing addition funnel. The contents were brought to reflux (65-70° C.) for two hours and reaction progress was monitored by GC. Isolation was accomplished by removing the THF via rotary evaporation, taking the residue up in ether (250 mL), filtration and ether removal via rotary evaporation. Purification was accomplished by distillation to provide 3,3,3-trifluoropropyl(1,2,3,4-tetrahydroisoquinolinyl)dimethoxysilane (54 mmol; 99% yield). C14H20NO2SiF3 (mw=319.39) bp=98° C. at 0.3 mmHg; 1H NMR: (CDCl3) δ 7.2-6.9 (m, 4H), 4.2-4.0 (d, 2H), 3.6-3.4 (s, 6H), 3.3-3.1 (dt, 2H), 2.8-2.6 (m, 2H), 2.2-1.9 (m, 2H), 0.9-0.8 (m, 2H); 13C NMR: (CDCl3) δ 135.9, 135.1, 129.4, 128 (quartet J=275 Hz), 126.0, 125.9, 125.8, 50.4, 46.5, 42.1, 29.9, 28 (quartet, J=30 Hz), 2.8; MS: m/z (relative abundance) 319 (38.3), 318 (100), 222 (7.9), 132 (21.0), 104 (21.4), 79 (9.8), 59 (13.4). addition funnel The cold bath was removed addition funnel to reflux (65-70° C.) for two hours reaction progress by removing the THF via rotary evaporation up in ether (250 mL), filtration and ether removal via rotary evaporation Purification was accomplished by distillation

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under nitrogen, a 500 ml Schlenk flask was cooled to 0° C. and charged with 150 ml hexane and 3,3,3-trifluoropropyl trimethoxy silane (0.075 mol, 15 ml). A nitrogen purged addition funnel was fitted to the flask and charged with tert-butyllithium (0.075 mol, 34 ml). This was added dropwise to the cooled flask creating a cloudy, white precipitate (LiOCH3). After addition (1 hour), the addition funnel was washed with 20 ml of hexane. The ice bath was removed and the reaction mixture was allowed to warm to room temperature. The flask was fitted with a reflux condenser and the reaction mixture refluxed for two hours. After cooling to room temperature, the reaction mixture was filtered through a medium porosity filter tube, using Celite diatomaceous earth and glass wool as a filtering aid. A white solid was collected, which weighed 11.13 g wet (theoretical=3.0 grams of LiOCH3). The hexane was removed from the filtrate to give 20.33 g of a clear yellow oil. A nitrogen purged addition funnel was fitted to the flask This was added dropwise to the cooled flask After addition (1 hour) the addition funnel was washed with 20 ml of hexane The ice bath was removed to warm to room temperature The flask was fitted with a reflux condenser the reaction mixture refluxed for two hours After cooling to room temperature the reaction mixture was filtered through a medium porosity filter tube A white solid was collected The hexane was removed from the filtrate

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under nitrogen, a 500 ml Schlenk flask was cooled to room temperature, charged with 150 ml of diethyl ether and cyclopentylmagnesium chloride (0.055 mol, 27.7 ml) and warmed slightly to 30° C. A 100 ml Schlenk flask was purged with nitrogen and charged with 75 ml hexane and 3,3,3-trifluoropropyltrimethoxy silane (10 ml, 0.0504 mol). The silane/hexane solution was added dropwise via cannula to the Grignard/diethyl ether mixture producing a white cloudy mixture. After addition (1.25 hrs.), the Grignard containing flask was rinsed once with 25 ml of hexane. The reaction mixture was stirred at room temperature for one hour. warmed slightly to 30° C A 100 ml Schlenk flask was purged with nitrogen producing a white cloudy mixture After addition (1.25 hrs.) the Grignard containing flask was rinsed once with 25 ml of hexane

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under nitrogen, a 500 ml Schlenk flask was cooled to room temperature and charged with 150 ml of diethyl ether and isobutylmagnesium chloride (0.06 mol, 30.24 ml). This was stirred and heated slightly to 30° C. A second Schlenk flask (100 ml) was purged with nitrogen to room temperature and charged with 75 ml hexane and 3,3,3-trifluoropropyltrimethoxy silane (0.0504 mol, 10 ml) and stirred. The silane/hexane solution was added dropwise via cannula to the Grignard/diethyl ether mixture producing a white precipitate midway through the addition. After addition (1.25 hrs.), the reaction mixture was stirred at room temperature for one hour. The flask was fitted with a reflux condenser and the reaction mixture was refluxed for two hours, then allowed to cool to room temperature. The reaction mixture was filtered through a medium porosity frit, using Celite diatomaceous earth and glass wool as a filtering aid. The solids collected weighed 7.55 g (theoretical=4.56 grams of magnesium salts). The slightly cloudy filtrate was kept under nitrogen overnight. heated slightly to 30° C A second Schlenk flask (100 ml) was purged with nitrogen to room temperature stirred producing a white precipitate midway through the addition After addition (1.25 hrs.) the reaction mixture was stirred at room temperature for one hour The flask was fitted with a reflux condenser the reaction mixture was refluxed for two hours to cool to room temperature The reaction mixture was filtered through a medium porosity frit The solids collected

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 ml 5-neck round-bottom flask, rendered inert with nitrogen and equipped with paddle stirrer, dropping funnel, thermometer, and water separator with reflux condenser, is charged with 50 g (0.36 mol) of methyl-trimethoxysilane (available commercially from Wacker Chemie AG), 8.8 g (0.04 mol) of 3,3,3-trifluoro-propyltrimethoxysilane (available commercially from Fluka), and 39.7 g of Isopar E (isoparaffinic hydro-carbon mixture having a boiling range of 113-143° C., available commercially from ExxonMobil). The water separator is filled to the brim with Isopar E. Accompanied by stirring at 350 rpm, a solution of 17.2 g of potassium hydroxide (85% strength, available commercially from AppliChem) (0.26 mol of potassium hydroxide) and 15.3 g of demineralized water is metered in over 12 minutes. During this metered addition, the mixture heats up to 67° C. The mixture is heated to boiling temperature (70° C.). The distillate separates out as the bottom phase in the water separator. Up to a boiling temperature of 119° C., 48.5 g of colorless, slightly turbid distillate accumulate. The suspension which remains is subsequently evaporated to dryness with stirring under a full oil-pump vacuum (5 hPa) to 70° C. This gives 45.9 g of fine, white, free-flowable powder with a solids content of 99.7% (determined using the HR73 halogen moisture analyzer from Mettler Toledo at 160° C.). A 50% strength aqueous solution prepared with this powder exhibits no precipitation even after being stored at room temperature for two weeks in the absence of air. A 500 ml 5-neck round-bottom flask, rendered inert with nitrogen equipped with paddle stirrer with reflux condenser is metered in over 12 minutes During this metered addition heats up to 67° C The suspension which remains is subsequently evaporated to dryness with stirring under a full oil-pump vacuum (5 hPa) to 70° C at 160° C. A 50% strength aqueous solution prepared with this powder no precipitation even after being stored at room temperature for two weeks in the absence of air

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 ml 5-neck round-bottom flask, rendered inert with nitrogen and equipped with paddle stirrer, dropping funnel, thermometer, and water separator with reflux condenser, is charged with 50 g (0.36 mol) of methyl-trimethoxysilane (available commercially from Wacker Chemie AG), 8.8 g (0.04 mol) of 3,3,3-trifluoro-propyltrimethoxysilane (available commercially from Fluka), and 39.7 g of Isopar E (isoparaffinic hydro-carbon mixture having a boiling range of 113-143° C., available commercially from ExxonMobil). The water separator is filled to the brim with Isopar E. Accompanied by stirring at 350 rpm, a solution of 17.2 g of potassium hydroxide (85% strength, available commercially from AppliChem) (0.26 mol of potassium hydroxide) and 15.3 g of demineralized water is metered in over 12 minutes. During this metered addition, the mixture heats up to 67° C. The mixture is heated to boiling temperature (70° C.). The distillate separates out as the bottom phase in the water separator. Up to a boiling temperature of 119° C., 48.5 g of colorless, slightly turbid distillate accumulate. The suspension which remains is subsequently evaporated to dryness with stirring under a full oil-pump vacuum (5 hPa) to 70° C. This gives 45.9 g of fine, white, free-flowable powder with a solids content of 99.7% (determined using the HR73 halogen moisture analyzer from Mettler Toledo at 160° C.). A 50% strength aqueous solution prepared with this powder exhibits no precipitation even after being stored at room temperature for two weeks in the absence of air. A 500 ml 5-neck round-bottom flask, rendered inert with nitrogen equipped with paddle stirrer with reflux condenser is metered in over 12 minutes During this metered addition heats up to 67° C The suspension which remains is subsequently evaporated to dryness with stirring under a full oil-pump vacuum (5 hPa) to 70° C at 160° C. A 50% strength aqueous solution prepared with this powder no precipitation even after being stored at room temperature for two weeks in the absence of air

Conditions: temp:15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3,3,3-Trifluoropropyl(bis(2-ethylhexyl)aminodimethoxysilane--A 500 mL round bottomed flask was charged with tetrahydrofuran (300 mL) and isopropylmagnesium chloride (25 mL of a 2.0 M solution in THF, 50 mmol). The contents were cooled to 15° C. Bis(2-ethylhexyl)amine (50 mmol) was added over fifteen minutes via pressure equalizing addition funnel. The cold bath was removed and the contents stirred for two hours. 3,3,3-Trifluoropropyltrimethoxysilane (45 mmol) was added via pressure equalizing addition funnel. The contents were brought to reflux (65-70° C.) for two hours, and reaction progress was monitored by GC. Isolation was accomplished by removing the THF via rotary evaporation, taking the residue up in ether (250 mL), filtration and ether removal via rotary evaporation. Purification was accomplished by distillation to provide 3,3,3-trifluoropropyl bis(2-ethylhexyl)aminodimethoxysilane (44 mmol; 98% yield). C21H44NO2SiF3 (mw=427.66) bp=200° C. at 1.4 mmHg; 1H NMR: (CDCl3) δ 3.5 (s, 6H), 2.6-2.4 (dd, 4H), 2.2-2.0 (m, 2H), 1.6-1.1 (m, 18H), 1.0-0.7 (m, 14H); 13C NMR: (CDCl3) δ 128 (quartet, J=275 Hz), 50.4, 48.5, 39.4, 36.9, 30.8, 29.1, 28.2 (quartet, J=30 Hz), 23.2, 14.2, 10.3, 3.2; MS: m/z (relative abundance) 328 (100), 230 (25.6), 155 (7.4), 109 (2.9). addition funnel The cold bath was removed addition funnel to reflux (65-70° C.) for two hours reaction progress by removing the THF via rotary evaporation up in ether (250 mL), filtration and ether removal via rotary evaporation Purification was accomplished by distillation

Conditions: temp:15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3,3,3-Tritluoropropyl(1,2,3,4-tetrahydroisoquinolinyl)dimethoxysilane--A 500 mL round bottomed flask was charged with tetrahydrofuran (300 mL) and isopropyl-magnesium chloride (30 mL of a 2.0 M solution in THF, 60 mmol). The contents were cooled to 15° C. 1,2,3,4-Tetrahydroisoquinoline (60 mmol) was added over fifteen minutes via pressure equalizing addition funnel. The cold bath was removed and the contents stirred for two hours. 3,3,3-Trifluoropropyltrimethoxysilane (54.5 mmol) was added via pressure equalizing addition funnel. The contents were brought to reflux (65-70° C.) for two hours and reaction progress was monitored by GC. Isolation was accomplished by removing the THF via rotary evaporation, taking the residue up in ether (250 mL), filtration and ether removal via rotary evaporation. Purification was accomplished by distillation to provide 3,3,3-trifluoropropyl(1,2,3,4-tetrahydroisoquinolinyl)dimethoxysilane (54 mmol; 99% yield). C14H20NO2SiF3 (mw=319.39) bp=98° C. at 0.3 mmHg; 1H NMR: (CDCl3) δ 7.2-6.9 (m, 4H), 4.2-4.0 (d, 2H), 3.6-3.4 (s, 6H), 3.3-3.1 (dt, 2H), 2.8-2.6 (m, 2H), 2.2-1.9 (m, 2H), 0.9-0.8 (m, 2H); 13C NMR: (CDCl3) δ 135.9, 135.1, 129.4, 128 (quartet J=275 Hz), 126.0, 125.9, 125.8, 50.4, 46.5, 42.1, 29.9, 28 (quartet, J=30 Hz), 2.8; MS: m/z (relative abundance) 319 (38.3), 318 (100), 222 (7.9), 132 (21.0), 104 (21.4), 79 (9.8), 59 (13.4). addition funnel The cold bath was removed addition funnel to reflux (65-70° C.) for two hours reaction progress by removing the THF via rotary evaporation up in ether (250 mL), filtration and ether removal via rotary evaporation Purification was accomplished by distillation

Conditions: temp:15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3,3,3-Tritluoropropyl(1,2,3,4-tetrahydroisoquinolinyl)dimethoxysilane--A 500 mL round bottomed flask was charged with tetrahydrofuran (300 mL) and isopropyl-magnesium chloride (30 mL of a 2.0 M solution in THF, 60 mmol). The contents were cooled to 15° C. 1,2,3,4-Tetrahydroisoquinoline (60 mmol) was added over fifteen minutes via pressure equalizing addition funnel. The cold bath was removed and the contents stirred for two hours. 3,3,3-Trifluoropropyltrimethoxysilane (54.5 mmol) was added via pressure equalizing addition funnel. The contents were brought to reflux (65-70° C.) for two hours and reaction progress was monitored by GC. Isolation was accomplished by removing the THF via rotary evaporation, taking the residue up in ether (250 mL), filtration and ether removal via rotary evaporation. Purification was accomplished by distillation to provide 3,3,3-trifluoropropyl(1,2,3,4-tetrahydroisoquinolinyl)dimethoxysilane (54 mmol; 99% yield). C14H20NO2SiF3 (mw=319.39) bp=98° C. at 0.3 mmHg; 1H NMR: (CDCl3) δ 7.2-6.9 (m, 4H), 4.2-4.0 (d, 2H), 3.6-3.4 (s, 6H), 3.3-3.1 (dt, 2H), 2.8-2.6 (m, 2H), 2.2-1.9 (m, 2H), 0.9-0.8 (m, 2H); 13C NMR: (CDCl3) δ 135.9, 135.1, 129.4, 128 (quartet J=275 Hz), 126.0, 125.9, 125.8, 50.4, 46.5, 42.1, 29.9, 28 (quartet, J=30 Hz), 2.8; MS: m/z (relative abundance) 319 (38.3), 318 (100), 222 (7.9), 132 (21.0), 104 (21.4), 79 (9.8), 59 (13.4). addition funnel The cold bath was removed addition funnel to reflux (65-70° C.) for two hours reaction progress by removing the THF via rotary evaporation up in ether (250 mL), filtration and ether removal via rotary evaporation Purification was accomplished by distillation

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following the same general procedure described on Example 1, a flask was charged with one mol (218 gm) of 3,3,3-trifluoropropyltrimethoxysilane was added to one mol of 2-ethylpiperdinylmagnesium chloride, the salt having been prepared in situ by adding 2-ethylpiperidine (120 g, 1.05 mol) to isopropylmagnesium chloride (1 mol) in 500 ml of tetrahydrofuran. The reaction was mildly exothermic and the temperature rose to 45° C. at the end of the addition time of one hour. The reaction mixture was refluxed at the pot temperature of 70° C. for one hour and then cooled to room temperature. The 3,3,3-trifluoropropyl(2-ethylpiperidino)dimethoxysilane was filtered under nitrogen atmosphere from the magnesium methoxychloride. The filter cake was washed with ether (2×200 ml) to obtain the residual product. The solvent was removed by distillation to a pot temperature of 100° C. The residue was distilled under vacuum to yield 263 g of 3,3,3-trifluoropropyl(2-ethylpiperidino)dimethoxysilane as a colorless oil (purity>98%); bp 70° C./0.1 mm. The total yield was 88% of theoretical. the salt having been prepared in situ rose to 45° C. at the end of the addition time of one hour cooled to room temperature The 3,3,3-trifluoropropyl(2-ethylpiperidino)dimethoxysilane was filtered under nitrogen atmosphere from the magnesium methoxychloride The filter cake was washed with ether (2×200 ml) to obtain the residual product The solvent was removed by distillation to a pot temperature of 100° C The residue was distilled under vacuum