9-Fluorenylmethanol

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: To (R)-(2,2-dimethyl-5-oxo[1,3]dioxolan-4-yl)acetic acid (5.88 g, 33.8 mmol) was added toluene (100 mL), triethylamine (4.7 mL, 33.8 mmol) and diphenoxyphosphoryl azide (8.0 mL, 37.2 mmol). The reaction mixture was heated to a 100° C and stirred under nitrogen at this temperature for 1.5 hour. 9-Fluorenemethanol (5.1 g, 26 mmol) was added and the reaction mixture was refluxed for 6 hours. After cooling to room temperature the mixture was transferred to a separatory funnel and washed with water (2×50 mL). The solvent was removed in vacuo and co-evaporated with acetonitrile (100 mL). The remaining light brown oil was dissolved in DCM (20 mL) and purified on silica gel column with DCM as eluent. The DCM was removed by evaporation to yield a light yellow oil, which was redissolved in acetonitrile (150 mL) and aqueous hydrochloric acid was added (1 N, 75 mL). The yellow reaction mixture was stirred for 3 hours at room temperature. The solvent was removed in vacuo, toluene (100 mL) was added and the suspension was heated to reflux and allowed to cool to room temperature. (R)-Fmoc-isoserine (3.1 g, 28%) was isolated as a powder by filtration. Mp: 165-166° C. the reaction mixture was refluxed for 6 hours After cooling to room temperature the mixture was transferred to a separatory funnel washed with water (2×50 mL) The solvent was removed in vacuo and co-evaporated with acetonitrile (100 mL) The remaining light brown oil was dissolved in DCM (20 mL) purified on silica gel column with DCM as eluent The DCM was removed by evaporation to yield a light yellow oil, which The yellow reaction mixture was stirred for 3 hours at room temperature The solvent was removed in vacuo, toluene (100 mL) was added the suspension was heated to reflux to cool to room temperature

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

Procedure: To a solution of Boc-sarcosine (30 g, 158 mmole) in 500 mL dichloromethane was added with stirring carbonyl diimidazole (25.7 g, 158 mmole). After 15 minutes, 9-fluorene methanol (29.5 g, 150 mmole) was added and stirring was continued. After 16 hours, the reaction mixture was diluted with 1200 mL ethyl acetate and extracted with 300 mL each of water, 1 M aqueous hydrochloric acid, water, saturated aqueous sodium bicarbonate and brine. The organic phase was dried over anhydrous magnesium sulfate, filtered and the solvent removed in vacuo. The resulting oil was dissolved in 500 mL dichloromethane and treated with 100 mL of a 4.0M solution of hydrochloric acid in dioxane. After 12 hours, the title compound was precipitated by pouring the reaction mixture into ether (1000 mL) with vigorous stirring. The precipitate was filtered and dried in vacuo to provide 35 g (73% yield) of the title compound as an off-white powder. After 16 hours extracted with 300 mL each of water, 1 M aqueous hydrochloric acid, water, saturated aqueous sodium bicarbonate and brine The organic phase was dried over anhydrous magnesium sulfate filtered the solvent removed in vacuo The resulting oil was dissolved in 500 mL dichloromethane treated with 100 mL of a 4.0M solution of hydrochloric acid in dioxane After 12 hours the title compound was precipitated by pouring the reaction mixture into ether (1000 mL) with vigorous stirring The precipitate was filtered dried in vacuo

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

Procedure: DDC (6.00 g, 29 mmol) was added in one portion to a cooled solution (0° C.) of 4-bromobutyric acid (5.00 g, 29.9 mmol), 4-(dimethylamino)pyridine (353 mg, 2.9 mmol) and 9-fluorenemethanol (5.63 g, 25 mmol) in CH2Cl2 (150 mL). The mixture was allowed to stand at 4° C. for 18 h, and then filtered. The filtrate was evaporated to dryness under reduced pressure. The residue was dissolved in EtOAc and the solution washed sequentially with 1N NaHCO3, 1N HCl and H2O. The solution was dried (Na2 -SO4) and evaporated to dryness under reduced pressure. The residue was purified by flash chromatography on silica gel (200 g) using hexane-EtOAc (15:1) as the eluant to give the pure title compound as an oil (7.5 g). filtered The filtrate was evaporated to dryness under reduced pressure The residue was dissolved in EtOAc the solution washed sequentially with 1N NaHCO3, 1N HCl and H2O The solution was dried (Na2 -SO4) evaporated to dryness under reduced pressure The residue was purified by flash chromatography on silica gel (200 g)

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

Procedure: The benzyl alcohols, 2-phenylethanol, 9-fluorenemethanol, 9-anthracenemethanol, 2-chloroethylvinyl ether, cyclohexene oxide and 4-vinylcyclohexene dioxide (VCHDO) were used as purchased from the Aldrich Chemical Co. (Milwaukee, Wis.) unless otherwise noted. PC-1000 was supplied by the Polyset Co. (Mechanicville, N.Y.). Bis(3-ethyl-3-oxetanylmethyl)ether was kindly supplied by Toagosei Chemical Company, LTD (Nagoya, Japan). Limonene dioxide (LDO) was obtained as a gift from the Witco Chemical Co. (Blooming Prairie, Minn.). 3,4-Epoxycyclohexyl methyl 3′,4′-epoxycyclohexancarboxylate (ERL-4221E, ERL) was purchased from the Union Carbide Corp. (Bound Brook, N.J.). Bisphenol-A diglycidyl ether (BPADGE) was obtained from the Dow Chemical Co. (Midland, Mich.). Onium salt cationic photoinitiators, (4-n-decyloxyphenyl) phenyliodonium hexafluoroantimonate (IOC10), (4-n-decyloxyphenyl)diphenylsulfonium hexafluoroantimonate (SOC10) and S-methyl-S-n-dodecylphenacylsulfonium hexafluoroantimonate (DPS-C1C12) were prepared as described in the following references: IOC-10—Crivello, J. V.; Lee, J. L. J. Polym. Sci. Part A: Polym. Chem. Ed. 1989, 27, 3951, SOC10—Akhtar, S. R.; Crivello, J. V.; Lee, J. L. J. Org. Chem. 1990, 55, 4222 and DPS-C1C12—Crivello, J. V.; Kong, S Macromolecules 2000, 33, 833. The structures of the respective monomers and photoinitiators are shown in Table 1. 1H NMR spectra were obtained using a Varian XL 500 MHz spectrometer at room temperature in CDCl3 using tetramethylsilane as an internal standard.

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

Procedure: Methacrloyl chloride (5 ml) was added dropwise to a cooled solution of 9-fluorene methanol (Aldrich Chemical Co. 5.04 g, 0.026 moles) in a mixture of dry tetrahydrofuran (15 ml) and dry triethylamine (10 ml). After 1 hour at 0° C. the reaction was quenched with water and extracted with ether. The resultant oil was flash chromatographed to give 0.70 g, (10% yield) of (9-fluorenyl)-methyl methacrylate (9 FMMA) as a light yellow oil. The original monomer stored at 0° C. polymerized over a period of 3 days. This material was dissolved in toluene and added dropwise to hexane, yielding a precipate of poly(9 FMMA) ([η]=0.28 dl/g). After 1 hour at 0° C. the reaction was quenched with water extracted with ether chromatographed

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

Procedure: To (R)-(2,2-dimethyl-5-oxo[1,3]dioxolan-4-yl)acetic acid (5.88 g, 33.8 mmol) was added toluene (100 mL), triethylamine (4.7 mL, 33.8 mmol) and diphenoxyphosphoryl azide (8.0 mL, 37.2 mmol). The reaction mixture was heated to a 100°0 C. and stirred under nitrogen at this temperature for 1.5 hour, 9-Fluorenemethanol (5.1 g, 26 mmol) was added and the reaction mixture was refluxed for 6 hours. After cooling to room temperature the mixture was transferred to a separatory funnel and washed with water (2×50 mL). The solvent was removed in vacuo and co-evaporated with acetonitrile (100 mL). The remaining light brown oil was dissolved in DCM (20 mL) and purified on silica gel column with DCM as eluent. The DCM was removed by evaporation to yield a light yellow oil, which was redissolved in acetonitrile (150 mL) and aqueous hydrochloric acid was added (1 N, 75 mL). The yellow reaction mixture was stirred for 3 hours at room temperature. The solvent was removed in vacuo, toluene (100 mL) was added and the suspension was heated to reflux and allowed to cool to room temperature. (R)-Fmoc-isoserine (3.1 g, 28%) was isolated as a powder by filtration. Mp: 165-166° C. The reaction mixture was heated to a 100°0 C the reaction mixture was refluxed for 6 hours was transferred to a separatory funnel washed with water (2×50 mL) The solvent was removed in vacuo and co-evaporated with acetonitrile (100 mL) The remaining light brown oil was dissolved in DCM (20 mL) purified on silica gel column with DCM as eluent The DCM was removed by evaporation to yield a light yellow oil, which The yellow reaction mixture was stirred for 3 hours at room temperature The solvent was removed in vacuo, toluene (100 mL) was added the suspension was heated to reflux to cool to room temperature

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

Procedure: To a solution of {2-[(2-tert-butoxy-1,1-dimethyl-2-oxoethyl)thio]-1,3-thiazol-4-yl}acetic acid (160 g) obtained in Example 3 in dichloromethane (500 mL) were added 9H-fluorene-9-ylmethanol (98 g) and 4-dimethylaminopyridine (3.1 g), diisopropylcarbodiimide (78 ml) was added dropwise under ice-cooling, and the mixture was stirred at 0° C. for 1 hr and further stirred at room temperature for 2 hr. The precipitate was removed from the reaction mixture by filtration, and the filtrate was concentrated under reduced pressure and purified by silica gel chromatography (elution solvent; hexane:ethyl acetate=4:1) to give the title compound (260 g) as a yellow oil. was added dropwise under ice- cooling further stirred at room temperature for 2 hr The precipitate was removed from the reaction mixture by filtration the filtrate was concentrated under reduced pressure purified by silica gel chromatography (elution solvent; hexane:ethyl acetate=4:1)

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

Procedure: To a solution of {2-[(2-tert-butoxy-1,1-dimethyl-2-oxoethyl)thio]-1,3-thiazol-4-yl}acetic acid (160 g) obtained in Example 3 in dichloromethane (500 mL) were added 9H-fluorene-9-ylmethanol (98 g) and 4-dimethylaminopyridine (3.1 g), diisopropylcarbodiimide (78 ml) was added dropwise under ice-cooling, and the mixture was stirred at 0° C. for 1 hr and further stirred at room temperature for 2 hr. The precipitate was removed from the reaction mixture by filtration, and the filtrate was concentrated under reduced pressure and purified by silica gel chromatography (elution solvent; hexane:ethyl acetate=4:1) to give the title compound (260 g) as a yellow oil. was added dropwise under ice- cooling further stirred at room temperature for 2 hr The precipitate was removed from the reaction mixture by filtration the filtrate was concentrated under reduced pressure purified by silica gel chromatography (elution solvent; hexane:ethyl acetate=4:1)

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

Procedure: The mixed diesters (E) are readily prepared in two stages from succinic anhydride (r=2) or glutaric anhydride (r=3). In the first stage, the appropriate cyclic anhydride is reacted with 0.5 equivalents of 9-fluorenyl methanol to form the fluorenylmethyl mono-ester of succinic or glutaric acid. In the second stage, reaction of the mono-ester with pentafluorophenol under standard esterification conditions affords the mixed diester.