(E)-hex-3-ene

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

Procedure: Chlorosulfonylisocyanate (5.17 ml, 59.4 mmol) in DCM (12 ml) was stirred at 25° C. and treated dropwise with (E)-hex-3-ene (7.39 ml, 59.4 mmol) in DCM (6 ml). The mixture was stirred at RT for 72 hrs. The reaction mixture was heated over 6 hrs at 40° C., before being poured onto ice. The mixture was extracted with DCM (3×100 ml) and the combined organics were washed with water (×1), dried MgSO4 and evaporated to dryness to afford the title compound; The reaction mixture was heated over 6 hrs at 40° C. before being poured onto ice The mixture was extracted with DCM (3×100 ml) the combined organics were washed with water (×1), dried MgSO4 evaporated to dryness

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

Procedure: The 3-hexene feedstock was assumed to have a composition of 33 wt % cis-3-hexene and 67 wt % trans-3-hexene. The normal boiling points for 1-, 2-, and 3-hexene are listed in Example 2. The normal boiling for DMF, the extraction solvent in this example, is 152° C. (305° F.). The isomerization reaction was assumed to occur at the bottom of the column. The column was assumed to have 150 theoretical stages, a kettle reboiler, and a total condenser. The operating conditions for the column consisted of a pressure of 7 atm, condenser temperature of 140° C. (283° F.), and reboiler temperature of 232° C. (450° F.). In addition, 100 lb/hr of DMF was added to the 10th theoretical stage of the column (near the top). This resulted in a column with a diameter of 11.8 ft and a reflux ratio of 518. For this case, the 1000 lb/hr 3-hexene feed resulted in 980 lb/hr of 99 wt % 1-hexene product. The column bottoms contained 91 wt % DMF, which can be recycled back to the column. A detailed material balance is shown in the following table. RXFEED is the distillation column feed stream, SOLVENT is the DMF extractive distillation solvent stream, BOTTOMS is the distillation column bottoms stream, and 1-HEXENE is the product stream, which is obtained from the top of the column. is 152° C. (305° F.) The isomerization reaction consisted of a pressure of 7 atm, condenser temperature of 140° C. (283° F.), and reboiler temperature of 232° C. (450° F.) This resulted in a column with a diameter of 11.8 ft

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

Procedure: The 3-hexene feedstock was assumed to have a composition of 33 wt % cis-3-hexene and 67 wt % trans-3-hexene. The normal boiling points for 1-, 2-, and 3-hexene are listed in Example 2. The normal boiling for NMP, the extraction solvent in this example, is 204° C. (400° F.). The isomerization reaction was assumed to occur at the bottom of the column. The column was assumed to have 150 theoretical stages, a kettle reboiler, and a total condenser. The operating conditions for the column consisted of a pressure of 5 atm, condenser temperature of 124° C. (255° F.), and reboiler temperature of 279° C. (533° F.). In addition, 500 lb/hr of NMP was added to the 10th theoretical stage of the column (near the top). This resulted in a column with a diameter of 11.4 ft and a reflux ratio of 455. For this case, the 1000 lb/hr 3-hexene feed resulted in 980 lb/hr of 99 wt % 1-hexene product. The column bottoms contained 98 wt % NMP, which can be recycled back to the column. A detailed material balance is shown in the following table. RXFEED is the distillation column feed stream, SOLVENT is the NMP extractive distillation solvent stream, BOTTOMS is the distillation column bottoms stream, and 1-HEXENE is the product stream, which is obtained from the top of the column. is 204° C. (400° F.) The isomerization reaction consisted of a pressure of 5 atm, condenser temperature of 124° C. (255° F.), and reboiler temperature of 279° C. (533° F.) This resulted in a column with a diameter of 11.4 ft

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

Procedure: The 3-hexene feedstock was assumed to have a composition of 33 wt % cis-3-hexene and 67 wt % trans-3-hexene. The normal boiling points for 1-, 2-, and 3-hexene are listed in Example 2. The normal boiling for NMP, the extraction solvent in this example, is 204° C. (400° F.). The isomerization reaction was assumed to occur at the bottom of the column. The column was assumed to have 150 theoretical stages, a kettle reboiler, and a total condenser. The operating conditions for the column consisted of a pressure of 5 atm, condenser temperature of 124° C. (255° F.), and reboiler temperature of 279° C. (533° F.). In addition, 500 lb/hr of NMP was added to the 10th theoretical stage of the column (near the top). This resulted in a column with a diameter of 11.4 ft and a reflux ratio of 455. For this case, the 1000 lb/hr 3-hexene feed resulted in 980 lb/hr of 99 wt % 1-hexene product. The column bottoms contained 98 wt % NMP, which can be recycled back to the column. A detailed material balance is shown in the following table. RXFEED is the distillation column feed stream, SOLVENT is the NMP extractive distillation solvent stream, BOTTOMS is the distillation column bottoms stream, and 1-HEXENE is the product stream, which is obtained from the top of the column. is 204° C. (400° F.) The isomerization reaction consisted of a pressure of 5 atm, condenser temperature of 124° C. (255° F.), and reboiler temperature of 279° C. (533° F.) This resulted in a column with a diameter of 11.4 ft

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

Procedure: General procedure (described for trans-3-hexene) as illustrated in FIG. 2, entry 1: To a mixture of trans-3-hexene (252 mg, 3 mmol; see above discussion for employable olefins (FIG. 1); 1.0 equivalents used) and anhydrous N-sodio-N-chloro sulfonamide (chloramine T/751 mg, 3.3 mmol; see above discussion for employable salts or chloramine trihydrates (chloramine T trihydrate can be effectively used in the same concentration); effective range: 1.0-2.0 equivalents; optimal concentration 1.1 equivalents) in CH3CN (15 ml, 0.2 Molar; see above discussion for employable solvents; effective range: 0.01 Molar to 1.0 Molar) was added PTAB (113 mg, 0.3 mmol; effective range: 0.05 to 0.50 equivalents; optimal concentration: 0.10 equivalents) at 25° C. (effective range 25° C. to 60° C.). After vigorous stirring for 12 h (time can vary from 1 h- to 24 h depending on scale and substrate). The reaction mixture was worked up using standard workup conditions. A typical procedure may be carried out as follows: The reaction mixture was concentrated (about up to 1/10 volume) and filtered through a short column of silica gel (4×4 cm, 10% EtOAc in hexane). After evaporation of the solvent, the resultant solid was purified by recrystallization in hexane to give 710 mg (93%) of trans-2,3-diethyl-1-[(4-methylphenyl)sulfonyl]aziridine as colorless crystals; 1H NMR (CDCl3400 MHz)δ7.81 (d, J=8.2 Hz, 2H), 7.28 (d, J=8.2 Hz, 2H), 2.56-2.61 (m, 2H), 2.40 (s, 3H), 1.63-1.79 (m, 4H), 0.90 (t, J=7.5 Hz, 6H); 13C NMR (CDCl3, 100 MHz) d 143.7, 137.9, 129.4, 127.4, 50.9, 23.2, 21.5, 11.7; MS (FAB, NBA/NaI): 254 (M+H)+; HRMS (FAB, NBA/NaI): calculated for C13H19NO2S (MNa)+276.1034, found 276.1029; m.p. 69-70° C. (hexane). can be effectively used in the same concentration) The reaction mixture was concentrated (about up to 1/10 volume) filtered through a short column of silica gel (4×4 cm, 10% EtOAc in hexane) After evaporation of the solvent the resultant solid was purified by recrystallization in hexane

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

Procedure: General procedure (described for trans-3-hexene) as illustrated in FIG. 2, entry 1: To a mixture of trans-3-hexene (252 mg, 3 mmol; see above discussion for employable olefins (FIG. 1); 1.0 equivalents used) and anhydrous N-sodio-N-chloro sulfonamide (chloramine T/751 mg, 3.3 mmol; see above discussion for employable salts or chloramine trihydrates (chloramine T trihydrate can be effectively used in the same concentration); effective range: 1.0-2.0 equivalents; optimal concentration 1.1 equivalents) in CH3CN (15 ml, 0.2 Molar; see above discussion for employable solvents; effective range: 0.01 Molar to 1.0 Molar) was added PTAB (113 mg, 0.3 mmol; effective range: 0.05 to 0.50 equivalents; optimal concentration: 0.10 equivalents) at 25° C. (effective range 25° C. to 60° C.). After vigorous stirring for 12 h (time can vary from 1 h- to 24 h depending on scale and substrate). The reaction mixture was worked up using standard workup conditions. A typical procedure may be carried out as follows: The reaction mixture was concentrated (about up to 1/10 volume) and filtered through a short column of silica gel (4×4 cm, 10% EtOAc in hexane). After evaporation of the solvent, the resultant solid was purified by recrystallization in hexane to give 710 mg (93%) of trans-2,3-diethyl-1-[(4-methylphenyl)sulfonyl]aziridine as colorless crystals; 1H NMR (CDCl3400 MHz)δ7.81 (d, J=8.2 Hz, 2H), 7.28 (d, J=8.2 Hz, 2H), 2.56-2.61 (m, 2H), 2.40 (s, 3H), 1.63-1.79 (m, 4H), 0.90 (t, J=7.5 Hz, 6H); 13C NMR (CDCl3, 100 MHz) d 143.7, 137.9, 129.4, 127.4, 50.9, 23.2, 21.5, 11.7; MS (FAB, NBA/NaI): 254 (M+H)+; HRMS (FAB, NBA/NaI): calculated for C13H19NO2S (MNa)+276.1034, found 276.1029; m.p. 69-70° C. (hexane). can be effectively used in the same concentration) The reaction mixture was concentrated (about up to 1/10 volume) filtered through a short column of silica gel (4×4 cm, 10% EtOAc in hexane) After evaporation of the solvent the resultant solid was purified by recrystallization in hexane

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

Procedure: Chlorosulfonylisocyanate (5.17 ml, 59.4 mmol) in DCM (12 ml) was stirred at 25° C. and treated dropwise with (E)-hex-3-ene (7.39 ml, 59.4 mmol) in DCM (6 ml). The mixture was stirred at RT for 72 hrs. The reaction mixture was heated over 6 hrs at 40° C., before being poured onto ice. The mixture was extracted with DCM (3×100 ml) and the combined organics were washed with water (×1), dried MgSO4 and evaporated to dryness to afford the title compound; The reaction mixture was heated over 6 hrs at 40° C. before being poured onto ice The mixture was extracted with DCM (3×100 ml) the combined organics were washed with water (×1), dried MgSO4 evaporated to dryness

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

Procedure: The 3-hexene feedstock was assumed to have a composition of 33 wt % cis-3-hexene and 67 wt % trans-3-hexene. The normal boiling points for 1-, 2-, and 3-hexene are listed in Example 2. The normal boiling for DMF, the extraction solvent in this example, is 152° C. (305° F.). The isomerization reaction was assumed to occur at the bottom of the column. The column was assumed to have 150 theoretical stages, a kettle reboiler, and a total condenser. The operating conditions for the column consisted of a pressure of 7 atm, condenser temperature of 140° C. (283° F.), and reboiler temperature of 232° C. (450° F.). In addition, 100 lb/hr of DMF was added to the 10th theoretical stage of the column (near the top). This resulted in a column with a diameter of 11.8 ft and a reflux ratio of 518. For this case, the 1000 lb/hr 3-hexene feed resulted in 980 lb/hr of 99 wt % 1-hexene product. The column bottoms contained 91 wt % DMF, which can be recycled back to the column. A detailed material balance is shown in the following table. RXFEED is the distillation column feed stream, SOLVENT is the DMF extractive distillation solvent stream, BOTTOMS is the distillation column bottoms stream, and 1-HEXENE is the product stream, which is obtained from the top of the column. is 152° C. (305° F.) The isomerization reaction consisted of a pressure of 7 atm, condenser temperature of 140° C. (283° F.), and reboiler temperature of 232° C. (450° F.) This resulted in a column with a diameter of 11.8 ft

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

Procedure: The 3-hexene feedstock was assumed to have a composition of 33 wt % cis-3-hexene and 67 wt % trans-3-hexene. The normal boiling points for 1-, 2-, and 3-hexene are listed in Example 2. The normal boiling for NMP, the extraction solvent in this example, is 204° C. (400° F.). The isomerization reaction was assumed to occur at the bottom of the column. The column was assumed to have 150 theoretical stages, a kettle reboiler, and a total condenser. The operating conditions for the column consisted of a pressure of 5 atm, condenser temperature of 124° C. (255° F.), and reboiler temperature of 279° C. (533° F.). In addition, 500 lb/hr of NMP was added to the 10th theoretical stage of the column (near the top). This resulted in a column with a diameter of 11.4 ft and a reflux ratio of 455. For this case, the 1000 lb/hr 3-hexene feed resulted in 980 lb/hr of 99 wt % 1-hexene product. The column bottoms contained 98 wt % NMP, which can be recycled back to the column. A detailed material balance is shown in the following table. RXFEED is the distillation column feed stream, SOLVENT is the NMP extractive distillation solvent stream, BOTTOMS is the distillation column bottoms stream, and 1-HEXENE is the product stream, which is obtained from the top of the column. is 204° C. (400° F.) The isomerization reaction consisted of a pressure of 5 atm, condenser temperature of 124° C. (255° F.), and reboiler temperature of 279° C. (533° F.) This resulted in a column with a diameter of 11.4 ft

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

Procedure: General procedure (described for trans-3-hexene) as illustrated in FIG. 2, entry 1: To a mixture of trans-3-hexene (252 mg, 3 mmol; see above discussion for employable olefins (FIG. 1); 1.0 equivalents used) and anhydrous N-sodio-N-chloro sulfonamide (chloramine T/751 mg, 3.3 mmol; see above discussion for employable salts or chloramine trihydrates (chloramine T trihydrate can be effectively used in the same concentration); effective range: 1.0-2.0 equivalents; optimal concentration 1.1 equivalents) in CH3CN (15 ml, 0.2 Molar; see above discussion for employable solvents; effective range: 0.01 Molar to 1.0 Molar) was added PTAB (113 mg, 0.3 mmol; effective range: 0.05 to 0.50 equivalents; optimal concentration: 0.10 equivalents) at 25° C. (effective range 25° C. to 60° C.). After vigorous stirring for 12 h (time can vary from 1 h- to 24 h depending on scale and substrate). The reaction mixture was worked up using standard workup conditions. A typical procedure may be carried out as follows: The reaction mixture was concentrated (about up to 1/10 volume) and filtered through a short column of silica gel (4×4 cm, 10% EtOAc in hexane). After evaporation of the solvent, the resultant solid was purified by recrystallization in hexane to give 710 mg (93%) of trans-2,3-diethyl-1-[(4-methylphenyl)sulfonyl]aziridine as colorless crystals; 1H NMR (CDCl3400 MHz)δ7.81 (d, J=8.2 Hz, 2H), 7.28 (d, J=8.2 Hz, 2H), 2.56-2.61 (m, 2H), 2.40 (s, 3H), 1.63-1.79 (m, 4H), 0.90 (t, J=7.5 Hz, 6H); 13C NMR (CDCl3, 100 MHz) d 143.7, 137.9, 129.4, 127.4, 50.9, 23.2, 21.5, 11.7; MS (FAB, NBA/NaI): 254 (M+H)+; HRMS (FAB, NBA/NaI): calculated for C13H19NO2S (MNa)+276.1034, found 276.1029; m.p. 69-70° C. (hexane). can be effectively used in the same concentration) The reaction mixture was concentrated (about up to 1/10 volume) filtered through a short column of silica gel (4×4 cm, 10% EtOAc in hexane) After evaporation of the solvent the resultant solid was purified by recrystallization in hexane

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

Procedure: Chlorosulfonylisocyanate (5.17 ml, 59.4 mmol) in DCM (12 ml) was stirred at 25° C. and treated dropwise with (E)-hex-3-ene (7.39 ml, 59.4 mmol) in DCM (6 ml). The mixture was stirred at RT for 72 hrs. The reaction mixture was heated over 6 hrs at 40° C., before being poured onto ice. The mixture was extracted with DCM (3×100 ml) and the combined organics were washed with water (×1), dried MgSO4 and evaporated to dryness to afford the title compound; The reaction mixture was heated over 6 hrs at 40° C. before being poured onto ice The mixture was extracted with DCM (3×100 ml) the combined organics were washed with water (×1), dried MgSO4 evaporated to dryness