hexanoyl hexanoate

Conditions: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a dry 2 L round-bottomed flask equipped with a magnetic stirrer was added (+)-pseudoephedrine (40.0 g, 242.06 mmol, 1.0 equiv) and tetrahydrofuran (500 mL), and the mixture was stirred in a 23° C. water bath. Hexanoic anhydride (55.51 g, 259 mmol, 1.07 equiv) was added via cannula over a 10 minute interval, and transfer was quantitated with an additional portion of tetrahydrofuran (10 mL). After 25 minutes, the reaction was quenched with saturated sodium bicarbonate (300 mL). Volatile components were removed under reduced pressure, and the residue was extracted from water (500 mL) with ethyl acetate (3×250 mL). The organic extracts were dried over sodium sulfate, and after removal of the solvent under reduced pressure, a white solid was obtained, which was recrystallized from 1:1 ether/hexanes (200 mL) to afford the hexanamide as white crystals (58.2 g, 91% yield): mp 62°-63° C.; 1H NMR (300 MHz, C 6D6) δ7.0-7.4 (m, 5H), 4.9 (br, 1H), 4.52 (d, 1H, J=6.9 Hz), 4.14 (m, 1H), 3.77 (m, 1H), 2.79 (s, 3H), 2.42 (m, 2H), 2.13 (s, 3H), 1.83 (m, 2H), 1.59 (qn, 2H, J=7.6 Hz), 1.1-1.4 (m, 4H), 0.99 (d, 3H, J=7.0 Hz), 0.86 (t, 3H, J=7.0 Hz), 0.59 (d, 3H, J=6.8 Hz); 13C NMR (75.5 MHz, CDCl3) δ175.2, 174.2, 142.3, 141.6, 128.3, 128.0, 127.8, 127.3, 126.7, 126.2, 76.1, 75.1, 58.2, 57.0, 34.1, 33.4, 32.4, 31.5, 31.3, 26.6, 24.9, 24.5, 22.31, 22.29, 15.2, 14.2, 13.82, 13.79; FTIR (neat film) cm-1 3378 (br, m), 2956 (m), 2931 (m), 2871 (m), 1618 (s), 1453 (m), 1406 (m), 1051 (m), 701 (m); HRMS (FAB) Calcd for C16H26N02 (MH+): 264.1965. Found: 264.1966. In a dry 2 L round-bottomed flask equipped with a magnetic stirrer the reaction was quenched with saturated sodium bicarbonate (300 mL) Volatile components were removed under reduced pressure the residue was extracted from water (500 mL) with ethyl acetate (3×250 mL) The organic extracts were dried over sodium sulfate after removal of the solvent under reduced pressure a white solid was obtained which was recrystallized from 1:1 ether/hexanes (200 mL)

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a reaction vessel, resorcinol is placed with an equimolar amount of hexanoic acid anhydride (from Aldrich Chemicals). Concentrated sulfuric acid (98%) is added to the solution and heated at 100° C. for 3 hours. A crude reaction product was obtained from this acid catalysis containing the 1,3 dihexanoyloxybenzene (resorcinol dihexanoate) and hexanoic acid. A crude reaction product was obtained from this acid catalysis

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a reaction vessel, resorcinol is placed with an equimolar amount of hexanoic acid anhydride (from Aldrich Chemicals). Concentrated sulfuric acid (98%) is added to the solution and heated at 100° C. for 3 hours. A crude reaction product was obtained from this acid catalysis containing the 1,3 dihexanoyloxybenzene (resorcinol dihexanoate) and hexanoic acid. A crude reaction product was obtained from this acid catalysis

Conditions: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a dry 2 L round-bottomed flask equipped with a magnetic stirrer was added (+)-pseudoephedrine (40.0 g, 242.06 mmol, 1.0 equiv) and tetrahydrofuran (500 mL), and the mixture was stirred in a 23° C. water bath. Hexanoic anhydride (55.51 g, 259 mmol, 1.07 equiv) was added via cannula over a 10 minute interval, and transfer was quantitated with an additional portion of tetrahydrofuran (10 mL). After 25 minutes, the reaction was quenched with saturated sodium bicarbonate (300 mL). Volatile components were removed under reduced pressure, and the residue was extracted from water (500 mL) with ethyl acetate (3×250 mL). The organic extracts were dried over sodium sulfate, and after removal of the solvent under reduced pressure, a white solid was obtained, which was recrystallized from 1:1 ether/hexanes (200 mL) to afford the hexanamide as white crystals (58.2 g, 91% yield): mp 62°-63° C.; 1H NMR (300 MHz, C 6D6) δ7.0-7.4 (m, 5H), 4.9 (br, 1H), 4.52 (d, 1H, J=6.9 Hz), 4.14 (m, 1H), 3.77 (m, 1H), 2.79 (s, 3H), 2.42 (m, 2H), 2.13 (s, 3H), 1.83 (m, 2H), 1.59 (qn, 2H, J=7.6 Hz), 1.1-1.4 (m, 4H), 0.99 (d, 3H, J=7.0 Hz), 0.86 (t, 3H, J=7.0 Hz), 0.59 (d, 3H, J=6.8 Hz); 13C NMR (75.5 MHz, CDCl3) δ175.2, 174.2, 142.3, 141.6, 128.3, 128.0, 127.8, 127.3, 126.7, 126.2, 76.1, 75.1, 58.2, 57.0, 34.1, 33.4, 32.4, 31.5, 31.3, 26.6, 24.9, 24.5, 22.31, 22.29, 15.2, 14.2, 13.82, 13.79; FTIR (neat film) cm-1 3378 (br, m), 2956 (m), 2931 (m), 2871 (m), 1618 (s), 1453 (m), 1406 (m), 1051 (m), 701 (m); HRMS (FAB) Calcd for C16H26N02 (MH+): 264.1965. Found: 264.1966. In a dry 2 L round-bottomed flask equipped with a magnetic stirrer the reaction was quenched with saturated sodium bicarbonate (300 mL) Volatile components were removed under reduced pressure the residue was extracted from water (500 mL) with ethyl acetate (3×250 mL) The organic extracts were dried over sodium sulfate after removal of the solvent under reduced pressure a white solid was obtained which was recrystallized from 1:1 ether/hexanes (200 mL)

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

Procedure: By following in principle the appropriate procedures of Example 4, Parts A and B or Example 5, but substituting other acyl anhydrides for acetic anhydride and caproic anhydride, such as propionic anhydride, butyric anhydride or valeric anhydride, the following compounds are obtained:

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

Procedure: By following in principle the appropriate procedures of Example 4, Parts A and B or Example 5, but substituting other acyl anhydrides for acetic anhydride and caproic anhydride, such as propionic anhydride, butyric anhydride or valeric anhydride, the following compounds are obtained:

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Preparation of 5,5′″-Bis(4-n-hexyl)-2,2′:5′,2″:5″,2′″-quaterthiophene (6TTTT6) is now discussed. A mixture of 6.2 g of bithiophene, 8.0 g of hexanoic anhydride, and 0.4 g boron trifluoride etherate is heated to about 100° C. and allowed to cool. The resulting mixture is dissolved in toluene, washed with aqueous sodium bicarbonate (allowing for venting of carbon dioxide gas), dried with magnesium sulfate, filtered, concentrated on a rotary evaporator, and chromatographed on 160 grams of silica gel eluting with hexane/methylene chloride mixtures. The product 5′-hexanoylbithiophene is isolated. The 5′-hexanoylbithiophene (3.9 g sample) is added to a stirred mixture of 3.0 g of aluminum chloride and 3.4 g of lithium aluminum hydride suspended in 300 mL of ethyl ether. After 1 hour, 50 mL ethyl acetate and 15 mL of concentrated hydrochloric acid are cautiously added, and the mixture is filtered, concentrated, and eluted through 30 g of silica gel with hexane. The product 5′-hexylbithiophene is isolated. A measured 2.4 g of this compound is dissolved in 150 mL of tetrahydrofuran. A measured 9.6 mmol of butyllithium as a hexane solution is added with stirring and cooling to −78° C. After 20 minutes, 2.6 g of cupric chloride is added. The mixture is allowed to warm to room temperature. After one day, dilute hydrochloric acid is added to dissolve the copper salts, and the mixture is dissolved in toluene, washed with concentrated hydrochloric acid and dilute aqueous ammonia, dried with magnesium sulfate, filtered, concentrated, and triturated with hexane, methanol, and petroleum ether. to cool washed with aqueous sodium bicarbonate (allowing for venting of carbon dioxide gas) dried with magnesium sulfate filtered concentrated on a rotary evaporator chromatographed on 160 grams of silica gel eluting with hexane/methylene chloride mixtures

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

Procedure: By reacting each of the resulting products with acetic anhydride, propionic anhydride, n-butyric anhydride, valeric anhydride or caproic anhydride as discussed in Parts A and C of Preparation I, the corresponding 17 alpha-acetate, -propionate, -n-butyrate, valerate and caproate are preprepared. as discussed in Parts A and C of Preparation I

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

Procedure: The anhydride may be, but not limited to, acetic acid anhydride, propionic anhydride, butyric anhydride, pentanoic anhydride or hexanoic anhydride. Preferably, the anhydride is acetic acid anhydride. According to an embodiment, the esterification of 1,4-bunediol is performed with acetic acid anhydride to form CH3C(O)O—(CH2)4—OH.

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

Procedure: Benzaldehyde (26.3 g, 0.25 mol) and hexanoic acid anhydride (53.3 g, 0.25 mol) were dissolved in carbontetrachloride (200 ml) under N2 -atrnosphere. Catalytic amounts of sulfuric acid was added and the reaction mixture stirred at room temperature for 1 hr. The reaction mixture was evaporated over night, the residue dissolved in hexane and the solution filtered through a bed of silica. The filtrate was purified on a silica column, eluting with hexane. The evaporated eluate was a colourless oil and the yield was 14.0 g, 18% of the theoretical. 1H- and 13C NMR (CDCl3) d (ppm) rel. to TMS: 7.72 (s, 1H, CH(OC5H11)2), 7.58-7.39 (m, 5H, Ar-H), 2.37 (double t, 4 H, COCH2), 1.64 (m, 4H, COCH2CH2), 1.30 (m, 4H,CH2CH2CH3) and 0.88 (t, 6H, CH3); 171.524 (C=O), 135.688, 129.523, 128.466 and 126.547 (Ar), 89.398 (CH(OC5H11)2), 33.965, 31.030, 24.235 and 22.179 (CH2) and 13.777 (CH3). The reaction mixture was evaporated over night the residue dissolved in hexane the solution filtered through a bed of silica The filtrate was purified on a silica column eluting with hexane

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

Procedure: In a manner similar to Example 12, a mixture of 8-chloro-1-(hydroxymethyl)-6-phenyl-4H-s-triazolo[4,3-a][1,4]benzodiazepine and hexanoic anhydride was heated on the water bath to give 8-chloro-1-(hydroxymethyl)-6-phenyl-4H-s-triazolo[4,3-a][1,4]benzodiazepine hexanoate (ester).

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a reaction vessel, resorcinol is placed with an equimolar amount of hexanoic acid anhydride (from Aldrich Chemicals). Concentrated sulfuric acid (98%) is added to the solution and heated at 100° C. for 3 hours. A crude reaction product was obtained from this acid catalysis containing the 1,3 dihexanoyloxybenzene (resorcinol dihexanoate) and hexanoic acid. A crude reaction product was obtained from this acid catalysis