3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecane-1-thiol

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

Procedure: 1,1,2,2-Tetrahydroperfluorodecanethiol (12.04 g, 0.025 mole), N-(3-dimethylaminopropyl)methacrylamide (3.88 g, 0.023 mole), and benzyltrimethylammonium hydroxide in methanol (4 drops) were heated overnight at 70° C. The resultant mixture was stripped of volatiles and distilled at 150°/≠0.1 mm Hg to yield 11.7 g of pale-yellow liquid (78.1% theory) which subsequently crystallized to a solid, m.p. 47°-50° C. NMR showed proton resonances at δ1.05, 3 protons, CH CH3 ; δ1.55, 2 protons, NHCH2CH2CH2N(CH3)2 ; δ2.10, 6 protons, 2 × NCH3 ; δ2.00-δ2.80, 10 protons, CF2CH2CH2SCH2 + NHCH2CH2CH2N; δ3.05; 1 proton, CH(CH3)CO; δ7.50, 1 proton, NH. distilled at 150°/≠0.1 mm Hg

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

Procedure: 2-(Perfluorooctyl)ethanethiol (RF =C8F17, 4.80 g, 10.0 mmle) and 1,2-dichloroethane (29.67 g, 300 mmole) and 10 ml of water was stirred by magnet bar under nitrogen at ambient temperature, while sodium hydroxide (0.67 g, 16.7 mmole) in 20 ml of water was added dropwise during a half hour. An exotherm carried the temperature from 24.0° to 25.2°. A thick, white slurry was formed. After 5 hours of stirring at 23.5°, the white slurry had not separated into two liquid layers as in the procedures used above. Stirring was continued for 29 hours and a sample removed for analysis. After 39 hours the thick white paste was made acidic by the addition of 5.0 ml of 6N hydrochloric acid, and the white solid collected on a Buchner funnel, and washed with water. When dry the solid weighed 3.45 g, mp (sinter 82°) 83°-88°, 70% of theory for C8F17CH2CH2SCH2CH2SCH2CH2C8F17. A 1.00-g sample was recrystallized from hot chloroform, that was first filtered while hot, from insoluble salt; 0.54 g, mp (sinter 90°) 92°-94°. The filtrate deposited 0.26 g of less pure solid. The original filtrate containing water and 1,2-dichloroethane (above) was separated into layers, and the organic layer evapd off to give white solid, mp 30°-33°, 1.18 g, 21.7% of theory for C8F17CH2CH2SCH2CH2Cl. was added dropwise during a half hour from 24.0° to 25.2° A thick, white slurry was formed the white slurry had not separated into two liquid layers as in the procedures Stirring was continued for 29 hours a sample removed for analysis After 39 hours the thick white paste was made acidic by the addition of 5.0 ml of 6N hydrochloric acid the white solid collected on a Buchner funnel washed with water When dry the solid 3.45 g, mp (sinter 82°) 83°-88°, 70% of theory A 1.00-g sample was recrystallized from hot chloroform, that was first filtered while hot, from insoluble salt 0.54 g, mp (sinter 90°) 92°-94° The original filtrate containing water and 1,2-dichloroethane (above) was separated into layers

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

Procedure: 2-(Perfluorooctyl)ethanethiol (RF =C8F17, 4.80 g, 10.0 mmle) and 1,2-dichloroethane (29.67 g, 300 mmole) and 10 ml of water was stirred by magnet bar under nitrogen at ambient temperature, while sodium hydroxide (0.67 g, 16.7 mmole) in 20 ml of water was added dropwise during a half hour. An exotherm carried the temperature from 24.0° to 25.2°. A thick, white slurry was formed. After 5 hours of stirring at 23.5°, the white slurry had not separated into two liquid layers as in the procedures used above. Stirring was continued for 29 hours and a sample removed for analysis. After 39 hours the thick white paste was made acidic by the addition of 5.0 ml of 6N hydrochloric acid, and the white solid collected on a Buchner funnel, and washed with water. When dry the solid weighed 3.45 g, mp (sinter 82°) 83°-88°, 70% of theory for C8F17CH2CH2SCH2CH2SCH2CH2C8F17. A 1.00-g sample was recrystallized from hot chloroform, that was first filtered while hot, from insoluble salt; 0.54 g, mp (sinter 90°) 92°-94°. The filtrate deposited 0.26 g of less pure solid. The original filtrate containing water and 1,2-dichloroethane (above) was separated into layers, and the organic layer evapd off to give white solid, mp 30°-33°, 1.18 g, 21.7% of theory for C8F17CH2CH2SCH2CH2Cl. was added dropwise during a half hour from 24.0° to 25.2° A thick, white slurry was formed the white slurry had not separated into two liquid layers as in the procedures Stirring was continued for 29 hours a sample removed for analysis After 39 hours the thick white paste was made acidic by the addition of 5.0 ml of 6N hydrochloric acid the white solid collected on a Buchner funnel washed with water When dry the solid 3.45 g, mp (sinter 82°) 83°-88°, 70% of theory A 1.00-g sample was recrystallized from hot chloroform, that was first filtered while hot, from insoluble salt 0.54 g, mp (sinter 90°) 92°-94° The original filtrate containing water and 1,2-dichloroethane (above) was separated into layers

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

Procedure: A mixture of thiourea (105.7 g, 1.39 moles), 2-(perfluorooctyl)ethyl iodide (531.5 g), 0.926 moles) and anhydrous ethanol (1000 mL) was heated at reflux for 6 hours. Approximately half of the alcohol was removed at reduced pressure and replaced with water. Solid sodium hydroxide (37.0 g) was added and the mixture heated under slow nitrogen purge. The volatile liquid products were collected by steam distillation using a modified Dean-Stark apparatus to yield 414 g (93.1 molar yield) of 2-(perfluorooctyl)ethyl mercaptan. After two consecutive water washes the product was suficiently pure by glc (99.3%) and used without further purification. was heated at reflux for 6 hours Approximately half of the alcohol was removed at reduced pressure Solid sodium hydroxide (37.0 g) was added the mixture heated under slow nitrogen purge The volatile liquid products were collected by steam distillation

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

Procedure: Octadecyl isocyanate (29.5 g, 0.1 mole), C8F17CH2CH2SH (48 g, 0.1 moles) and 2.2.2 diazabicyclooctane (0.1 g) were mixed under nitrogen and heated to 100° C. with stirring for 6 hours. An infrared spectrum showed no --NCO absorption, indicating completion of the reaction. The product is a white wax, melting at 85°-89° C. NMR showed proton resonances at 4.7 ppm (1 proton NH), 3.2 ppm (2 protons CH2CH2NH), 3.1 ppm (2 protons CH2SCO), 2.5 ppm (2 protons C8F17CH2), 1.3 ppm (32 protons CH3 (CH2)16) and 0.8 ppm (3 protons CH3 (CH2)16). -NCO absorption completion of the reaction

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

Procedure: Octadecyl Isocyanate (29.5 g, 0.1 mole), C8F17CH2CH2SH (48 g, 0.1 moles) and 2.2.2 diazabicyclooctane (0.1 g) were mixed under nitrogen and heated to 100° C. with stirring for 6 hours. An infrared spectrum showed no -NCO absorption, indicating completion of the reaction. The product is a white wax, melting at 85°-89° C. NMR showed proton resonances at 4.7 ppm (1 proton NH), 3.2 ppm (2 protons CH2CH2NH), 3.1 ppm (2 protons CH2SCO), 2.5 ppm (2 protons C8F17CH2), 1.3 ppm (32 protons CH3 (CH2)16) and 0.8 ppm (3 protons CH3 (CH2)16). no -NCO absorption completion of the reaction

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

Procedure: 1,1,2,2-Tetrahydroperfluorodecanethiol (12.04 g, 0.025 mole), N-(3-dimethylaminopropyl)methacrylamide (3.88 g, 0.023 mole), and benzyltrimethylammonium hydroxide in methanol (4 drops) were heated overnight at 70° C. The resultant mixture was stripped of volatiles and distilled at 150°/≠0.1 mm Hg to yield 11.7 g of pale-yellow liquid (78.1% theory) which subsequently crystallized to a solid, m.p. 47°-50° C. NMR showed proton resonances at δ1.05, 3 protons, CH CH3 ; δ1.55, 2 protons, NHCH2CH2CH2N(CH3)2 ; δ2.10, 6 protons, 2 × NCH3 ; δ2.00-δ2.80, 10 protons, CF2CH2CH2SCH2 + NHCH2CH2CH2N; δ3.05; 1 proton, CH(CH3)CO; δ7.50, 1 proton, NH. distilled at 150°/≠0.1 mm Hg

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

Procedure: 2-(Perfluorooctyl)ethanethiol (RF =C8F17, 4.80 g, 10.0 mmle) and 1,2-dichloroethane (29.67 g, 300 mmole) and 10 ml of water was stirred by magnet bar under nitrogen at ambient temperature, while sodium hydroxide (0.67 g, 16.7 mmole) in 20 ml of water was added dropwise during a half hour. An exotherm carried the temperature from 24.0° to 25.2°. A thick, white slurry was formed. After 5 hours of stirring at 23.5°, the white slurry had not separated into two liquid layers as in the procedures used above. Stirring was continued for 29 hours and a sample removed for analysis. After 39 hours the thick white paste was made acidic by the addition of 5.0 ml of 6N hydrochloric acid, and the white solid collected on a Buchner funnel, and washed with water. When dry the solid weighed 3.45 g, mp (sinter 82°) 83°-88°, 70% of theory for C8F17CH2CH2SCH2CH2SCH2CH2C8F17. A 1.00-g sample was recrystallized from hot chloroform, that was first filtered while hot, from insoluble salt; 0.54 g, mp (sinter 90°) 92°-94°. The filtrate deposited 0.26 g of less pure solid. The original filtrate containing water and 1,2-dichloroethane (above) was separated into layers, and the organic layer evapd off to give white solid, mp 30°-33°, 1.18 g, 21.7% of theory for C8F17CH2CH2SCH2CH2Cl. was added dropwise during a half hour from 24.0° to 25.2° A thick, white slurry was formed the white slurry had not separated into two liquid layers as in the procedures Stirring was continued for 29 hours a sample removed for analysis After 39 hours the thick white paste was made acidic by the addition of 5.0 ml of 6N hydrochloric acid the white solid collected on a Buchner funnel washed with water When dry the solid 3.45 g, mp (sinter 82°) 83°-88°, 70% of theory A 1.00-g sample was recrystallized from hot chloroform, that was first filtered while hot, from insoluble salt 0.54 g, mp (sinter 90°) 92°-94° The original filtrate containing water and 1,2-dichloroethane (above) was separated into layers