CELLULOSIC COMPLEX AND APPLICATIONS THEREOF

Abstract

The present invention provides a polysaccharide supported fluorinating agents which can be used in fluorination reactions. The invention particularly describes a new bacterial cellulose supported tetra-n-butyl ammonium fluoride complex [NBu4(Bac-Cell-OH)F] which is stable and non-hygroscopic. The invention further relates to a process for fluorination using the [NBu4(Bac-Cell-OH)F] complex.

Claims

1. A non-hygroscopic, thermally stable complex for aliphatic SN2 fluorination reactions, the complex comprising a polysaccharide support and tetra-n-butyl ammonium fluoride complexed to the polysaccharide support, wherein the w/w ratio of the polysaccharide support to the tetra-n-butyl ammonium fluoride in the complex is from 1:0.3 to 1:6.

2. The non-hygroscopic, thermally stable complex of claim 1, wherein the polysaccharide support is selected from pectin, bacterial cellulose, plant cellulose, or starch.

3. The non-hygroscopic, thermally stable complex of claim 1, wherein the polysaccharide support is a bacterial cellulose obtained from a Komagataeibacter rharticus PG2 strain isolated from a pomegranate host, the bacterial cellulose having a crystallinity index of 80.80 as measured using XRD and a nano-fibrillar width from 30 nm to 80 nm as measured using scanning electron microscopy.

4. The non-hygroscopic, thermally stable complex of claim 3, wherein the w/w ratio of the bacterial cellulose support to the tetra-n-butyl ammonium fluoride is 1:3.

5. A process for the preparation of a non-hygroscopic, thermally stable complex according to claim 1, the process comprising: (a) adding a polysaccharide support and tetra-n-butyl ammonium fluoride hydrate at a w/w ratio of 1:0.3 to 1:6 in hexane to obtain a mixture; (b) refluxing the mixture obtained in (a) under inert atmosphere at 80° C. for 1.5 hours with vigorous stirring to obtain a solution; (c) cooling the solution obtained in (b) to 25-30° C., filtering, washing with hexane followed by drying under high vacuum to obtain the non-hygroscopic, thermally stable complex.

6. A process for fluorination using the non-hygroscopic, thermally stable complex according to claim 1, the process comprising: (i) charging a substrate compound and the complex in a w/w ratio from 1:1 to 2:1 into a solvent to obtain a reaction mixture; (ii) stirring the reaction mixture obtained in (i) at a temperature from 50° C. to 100° C. for 3 hours; (iii) cooling the reaction mixture obtained in (ii) to a temperature from 25° C. to 35° C., filtering, and washing with ethyl acetate solvent; (iv) removing the solvent from the reaction mixture as obtained in (iii) under reduced pressure to obtain a fluorinated compound; (v) purifying the fluorinated compound obtained in (iv) using flash chromatography by using 20% ethyl acetate in hexane eluent to afford pure fluorinated compound.

7. The process of claim 6, wherein the solvent used in (i) of the fluorination reaction is selected from acetonitrile or toluene.

8. The non-hygroscopic, thermally stable complex of claim 1, wherein the polysaccharide support is recyclable up to 4 times as a fluorinating agent.

Description

BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS

[0014] FIG. 1: Energy Dispersive X-ray analysis (EDAX) pattern of NBu.sub.4(Bac-cell-OH)F and scanning electron microscopic (SEM) image (inset) of NBu.sub.4(Bac-cell-OH)F.

[0015] FIG. 2: Transmission electron microscopic (TEM) image of NBu.sub.4(Bac-cell-OH)F

[0016] FIG. 3: Visual demonstration of the hygroscopicity of 1. NBu.sub.4(Pec-OH)F, 2. NBu.sub.4(Bac-OH)F 3. NBu.sub.4 (Pla-cell-OH)F, 4. NBu.sub.4 (Sta-cell-OH)F and 5. NBu.sub.4F.

[0017] FIG. 4: Visual demonstration of the hygroscopicity of 1. NBu.sub.4(Bac-OH)F, 2. NBu.sub.4(tert-Bu-OH)F and 3. NBu.sub.4F

DETAILED DESCRIPTION OF THE INVENTION

[0018] The invention will now be described in detail in connection with certain preferred and optional embodiments, so that various aspects thereof may be more fully understood and appreciated.

[0019] Accordingly, the present invention relates to non-hygroscopic, thermally stable polysaccharide supported TBAF complexes and their applications in aliphatic S.sub.N2 fluorination reaction.

[0020] In an embodiment, the present invention provides non-hygroscopic, thermally stable polysaccharide supported TBAF complexes wherein the w/w ratio of polysaccharide to TBAF is in the range of 1:0.3 to 1:6.

[0021] In another embodiment, the polysaccharide support is selected from the group comprising of pectin, bacterial cellulose, plant cellulose and starch.

[0022] In an embodiment, the bacterial cellulose used as a polysaccharide support which is obtained from Komagataeibacter rharticus PG2 strain isolated from pomegranate host, having a bacterial cellulose has a crystallinity index of 80.80 measured using XRD and a nano-fibrillar width in the range of 30-80 nm measured using scanning electron microscopy.

[0023] In an embodiment the non-hygroscopic, thermally stable polysaccharide supported TBAF complex is synthesized by a process comprising the steps of: [0024] a) adding polysaccharide support and tetra-n-butyl ammonium fluoride hydrate at a w/w ratio of 1:0.3 to 1:6 in hexane to obtain a mixture; [0025] b) refluxing the mixture as obtained in step (a) under inert atmosphere at 80° C. for 1.5 h with vigorous stirring to obtain a solution; [0026] c) cooling the solution as obtained in step (b) to 25-30° C., filtering, washing with hexane followed by drying under high vacuum to obtain the desired non-hygroscopic, thermally stable polysaccharide supported TBAF complex.

[0027] In an embodiment, the polysaccharide supports used in the non-hygroscopic, thermally stable polysaccharide supported TBAF complexes are stable, non-hygroscopic and recyclable.

[0028] In another embodiment, the non-hygroscopic, thermally stable polysaccharide supported TBAF complexes are characterized using EDAX, SEM and TEM (FIGS. 1 and 2). In the SEM image, white dots are observed, confirming the loading of TBAF in the polysaccharides (FIG. 1). The TEM images show TBAF observed with bacterial cellulose (FIG. 2).

[0029] In another embodiment, hygroscopicity of the polysaccharide supported TBAF complexes were evaluated by exposing the samples to air at room temperature. After a time duration in the range of 15 minutes to 2 hours, the polysaccharide supported TBAF complexes were examined visually and the results are shown in FIG. 3 and FIG. 4. The top row indicates visual comparison of samples after exposure for 15 minutes while the bottom row is after two hours of exposure. The reported TBAF(3) and reported complex NBu.sub.4(tert-Bu-OH).sub.4F (2) (Angew. Chem. 2008, 120, 8532-8534) is hygroscopic and became liquid within 15 minutes and 2 h respectively while the bacterial cellulosic-TBAF complexes prepared in present invention remained stable up to more than two hours without getting liquefied. The study was continued and the disclosed non-hygroscopic, thermally stable polysaccharide supported TBAF complexes prepared in present invention were found to be stable for 21 days.

[0030] In another embodiment, the non-hygroscopic, thermally stable polysaccharide supported TBAF complex were used as a fluorinating agent for the fluorination of representative antibiotics, cancer drugs, sugars, steroids, pesticides, herbicides, and fungicide. The disclosed complexes provided 40-99% selectivity. We have preferred to keep the range broad because the agent is versatile and stable towards desired products with minimal side product formation.

[0031] In an embodiment, the fluorination reactions using the non-hygroscopic, thermally stable polysaccharide supported TBAF complex give selectivity towards desired products on recycling the polysaccharide support up to 4 times.

[0032] In an embodiment, the process for fluorination reaction using the non-hygroscopic, thermally stable polysaccharide supported TBAF complex comprises the steps of: [0033] i) charging substrate compound and polysaccharide supported TBAF complex in 1:1-2 w/w ratio into a solvent to get a reaction mixture; [0034] ii) stirring the reaction mixture as obtained in step i) at a temperature in the range of 50-100° C. for 3 hrs; [0035] iii) cooling the reaction mixture as obtained in step ii) to a temperature in the range of 25-35° C., filtering and washing with ethyl acetate solvent; [0036] iv) removing the solvent from the reaction mixture as obtained at step iii) under reduced pressure to obtain the fluorinated compound; [0037] v) purifying the fluorinated compound as obtained in step iv) using flash chromatography by using 20% ethyl acetate in hexane eluent to afford pure fluorinated compounds.

[0038] In one embodiment, the solvent used in step (i) of the fluorination reaction is selected from acetonitrile or toluene The representative process for the fluorination of compound 5 is depicted below in scheme-1; wherein X is a good leaving group to be replaced with fluorine.

##STR00001##

[0039] Table-1 below summarizes the results obtained by using different mole ratios of NBu.sub.4. (Bact-Cell-OH)F complex for different time intervals. 3-(3,4-dimethoxyphenoxy) propyl methane sulphonate (5a) is used as a substrate and compounds 1-(3-fluoropropoxy)-3,5-dimethoxybenzene (6a) and 1-(allyloxy)-3,5-dimethoxy benzene (6b) are the fluorination products.

TABLE-US-00002 TABLE 1 Entry NBu.sub.4(Bac-cell-OH)F Time Yield.sup.c No.sup.a (Mole ratio).sup.b Solvent (h) 6a 6b 1 1 CH.sub.3CN 2 90 — 2 1.5 CH.sub.3CN 2 92 — 3 2 CH.sub.3CN 2 88 trace 4.sup.d 2 CH.sub.3CN 1.5 87 14 5 2 CH.sub.3CN 1 85 13 6 2 CH.sub.3Ph 2 71 19 7.sup.e 2 CH.sub.3CN 2 81 9 .sup.aAll reactions were carried out on a 1.0 mmol scale of substrate in solvent (8.0 mL) at 70° C. .sup.bFluorine complex used equivalent ratio of TBAF (Use 2 eq. of TBAF loaded in 1 eq. bacterial cellulose ie 100% of TBAF). .sup.cIsolated yields. .sup.dReaction carried at 90° C. .sup.eReaction carried in an open atmosphere. — not detected.

[0040] Referring to the scheme-1 and table 1, the fluorination reaction was conducted with bacterial cellulose-TBAF complex using acetonitrile or benzene toluene (entry 6) as a solvent at a temperature in the range of 50-100° C. for a substrate: complex ratio of 1:1 to 1:2 to obtain more that 70% selectivity of desired fluorinated product. The complex used is in the range of 1:1 to 1:2 of TBAF: cellulose. In a preferred embodiment, the cellulose is bacterial cellulose.

[0041] It was found that the polysaccharide can be recycled up to 5 times. After completion of reaction as disclosed in scheme 1, the reaction mass is cooled to 25-35° C. and bacterial cellulose is filtered. It is further washed with ethyl acetate and dried under high-vacuum (2 mbar) to re-use for further loading of TBAF to form complex for further reactions. Only polysaccharide is recyclable So what is recyclable is not the polysaccharide supported TBAF complex but the support as such).

TABLE-US-00003 TABLE 2 Yield of Entry Loading of TBAF fluorinated product 1 Recycling 70% loading of TBAF 94% 2 Recycling 68% loading of TBAF 94% 3 Recycling 68% loading of TBAF 93% 4 Recycling 66% loading of TBAF 94%

[0042] Table 2 summarizes the results obtained by using recycled complex

[0043] The invention will now be described with the help of examples.

EXAMPLES

[0044] Following examples are given by way of illustration and therefore should not be construed to limit the scope of the invention.

Example 1: General Procedure for the Synthesis of Non-Hygroscopic and Thermally Stable Polysaccharide Supported TBAF Complex

[0045] For the reaction pectin, starch and plant cellulose were procured from Sigma Chemicals Co., USA. Bacterial cellulose was synthesized in lab using indigenous bacteria which inventors have isolated as described in RSC Advances, 2018, 8, 29797-29805, DOI: 10.1039/c8ra05295f.

[0046] To a flame-dried round bottom flask equipped with cooling condenser, tetra-n-butyl ammonium fluoride hydrate and polysaccharide support (pectin/starch/plant cellulose/bacterial cellulose) was added in their respective equivalent amount (w/w) in 100 ml of hexane. This mixture was refluxed in nitrogen atmosphere at 80° C. for 1.5 h with vigorous stirring. During the reaction, complex shows the water droplets on sidewall of the condenser, which indicates the completion of the reaction and complex formed. The solution was allowed to cool to 25-30° C., filtered, washed with hexane and dried under high vacuum at 25-35° C. to give the desired non-hygroscopic and thermally stable polysaccharide supported TBAF complex which was used for the aliphatic nucleophilic fluorination reaction.

[0047] In this manner other fluorinating complexes were prepared with polysaccharides including pectin, starch, bacterial cellulose and plant cellulose in the ratios 1:0.1 to 1:6 w/w of polysaccharide:TBAF.

Example 2: Preparation and Characterization of Pectin+TBAF Complex: NBu.SUB.4.(Pec-OH)F

[0048] ##STR00002##

TABLE-US-00004 Loading, weight ratio (%) w/w Sr. No Pectin TBAF Result 1 1 1 Solid 2 1 2 Sticky Solid 3 1 3 Sticky Solid

Example 3: Preparation and Characterization of Bacterial Cellulose+TBAF Complex: NBu.SUB.4.(Bac-Cell-OH)F

[0049] ##STR00003##

TABLE-US-00005 Loading, weight ratio (%)w/w Sr. No Bacterial cellulose TBAF Result 1 1 1 Solid 2 1 2 Solid 3 1 3 Solid 4 1 4 Solid 5 1 5 Slightly Sticky Solid 6 1 6 Sticky Solid

Example 4: Preparation of Characterization of Plant Cellulose+TBAF Complex: NBu.SUB.4 .(Pla-Cell-OH)F

[0050] ##STR00004##

TABLE-US-00006 Loading, weight ratio (%)w/w Sr. No Plant cellulose TBAF Result 1 1 1 Gel 2 1 0.9 Gel 3 1 0.8 Gel 4 1 0.7 Sticky Solid 5 1 0.6 Sticky Solid 6 1 0.5 Sticky Solid 7 1 0.4 Sticky Solid 8 1 0.3 Solid

Example 5: Preparation of Characterization of Starch+TBAF Complex: NBu.SUB.4.(Sta-Cell-OH)F

[0051] ##STR00005##

TABLE-US-00007 Loading, weight ratio (%)w/w Sr. No Starch TBAF Result 1 1 1 Gel 2 1 0.9 Gel 3 1 0.8 Gel 4 1 0.7 Gel 5 1 0.6 Sticky Solid 6 1 0.5 Sticky Solid 7 1 0.4 Sticky Solid 8 1 0.3 Solid

Example 6: A Representative Fluorination Procedure: Synthesis of 4-(3-fluoropropoxy)-1,2-dimethoxybenzene

[0052] In a flame dried round bottom flask, substrate compound (maybe a range should be given 0.290 mg, 1 mmol) and NBu.sub.4(Bac-cell-OH)F.1 (0.3915 mg, 1.5 eq) in dry acetonitrile were taken and the reaction vial was flushed with N.sub.2 and stirred at a temperature in the range of 50-100° C. for a time period in the range of 1-3 h. The reaction mixture was cooled to a temperature in the range of 25-35° C. and the reaction mixture was filtered using sintered funnel. The reaction mixture was washed with ethyl acetate and evaporated under reduced pressure. The crude product was purified by flash column chromatography using (20% EtOAc/hexane) to give corresponding fluorinated compound.

[0053] 4-(3-fluoropropoxy)-1,2-dimethoxybenzene: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 6.10 (s, 3H), 4.71 (t, J=5.8 Hz, 1H), 4.59 (t, J=5.8 Hz, 1H), 4.07 (t, J=6.1 Hz, 2H), 3.78 (s, 6H), 2.25-2.08 (m, 2H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 161.5, 160.6, 93.3, 93.1, 80.4 (d, J=164.15 Hz), 63.5, (d, J=4.62 Hz), 55.3, 30.4 (d, J=20.04 Hz). .sup.19F NMR (400 MHz, CDCl.sub.3) δ 222.14

[0054] A similar procedure was followed for different substrates to obtain following fluorinated products.

##STR00006##

[0055] 2-fluoro-1-(3-methoxyphenyl)ethan-1-one: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.45 (d, J=2.3 Hz, 1H), 7.43-7.38 (m, 2H), 7.19-7.15 (m, 1H), 5.52 (d, J=46.71 Hz, 2H), 3.87 (s, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) δ 193.1, (d, J=15.33 Hz), 160.0, 134.9, 129.9, 120.6, 120.6, (d, J=2.8 Hz), 112.1, (d, J=1.93 Hz), 84.5, (d, J=182.11 Hz), 55.5; .sup.19F NMR (400 MHz, CDCl.sub.3) δ 232.60.

##STR00007##

[0056] 1-(4-chlorophenyl)-2-fluoroethan-1-one; .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.87 (d, J=8.2 Hz, 2H), 7.49 (d, J=8.7 Hz, 2H), 5.49 (d, J=46.71 Hz, 2H); .sup.13C NMR (101 MHz, CDCl.sub.3) δ 192.5 (d, J=15.33 Hz), 140.7, 132.1, 129.4 (d, J=2.88 Hz), 129.3, 84.6 (d, J=184.03 Hz); .sup.19F NMR (400 MHz, CDCl.sub.3) δ 232.60.

##STR00008##

[0057] 1-fluorododecane: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 4.50 (t, J=6.1 Hz, 1H), 4.39 (t, J=6.1 Hz, 1H), 1.75-1.63 (m, 2H), 1.28 (m, 18H), 0.89 (t, J=6.1 Hz, 2H); .sup.13C NMR (101 MHz, CDCl.sub.3) δ 84.2 (d, J 163.68 Hz), 31.9, 30.4 (d, J=19.27 Hz) 29.6, 29.6, 29.5, 29.4, 29.3, 25.2, 25.1, 22.7, 14.1; .sup.19F NMR (400 MHz, CDCl.sub.3) δ 232.60.

##STR00009##

[0058] 1-fluoropentadecane: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 4.50 (t, J=6.1 Hz, 1H), 4.39 (t, J=6.1 Hz, 1H), 1.80-1.61 (m, 2H), 1.44-1.26 (m, 24H), 0.90 (t, J=6.1 Hz, 2H); .sup.13C NMR (101 MHz, CDCl.sub.3) δ 84.2 (d, J=164.15 Hz), 31.9, 30.4 (d, J=19.25 Hz), 29.7, 29.6, 29.5, 29.4, 29.3, 25.2, 25.1, 22.7, 14.1; .sup.19F NMR (400 MHz, CDCl.sub.3) δ 232.60.

##STR00010##

[0059] 9-(2-fluoroethyl)-9H-carbazole: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.16 (d, J=7.9 Hz, 2H), 7.55-7.48 (m, 2H), 7.47-7.42 (m, 2H), 7.35-7.28 (m, 2H), 4.87 (t, J=5.4 Hz, 1H), 4.75 (t, J=4.88 Hz, 1H), 4.64 (t, J=5.4 Hz, 1H), 4.63 (t, J=4.8 Hz, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) δ 140.4, 125.8, 123.0, 120.4, 119.3, 108.5, 81.9 (d, J=172.6 Hz), 43.2, (d, J=22.3 Hz); .sup.19F NMR (400 MHz, CDCl.sub.3) δ 232.60.

##STR00011##

[0060] 2-benzyl-4-chloro-1-(3-fluoropropoxy)benzene: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.33-7.26 (m, 2H), 7.26-7.13 (m, 4H), 7.09 (d, J=2.7 Hz, 1H), 6.79 (d, J=8.7 Hz, 1H), 4.58 (t, J=5.7 Hz, 1H), 4.46 (t, J=6.0 Hz, 1H), 4.06 (t, J=6.0 Hz, 2H), 3.95 (s, 2H), 2.19-2.06 (m, 2H).sup.13C NMR (101 MHz, CDCl.sub.3) δ 155.1, 140.1, 131.5, 130.3, 128.7, 128.4, 127.1, 126.1, 125.4, 112.3, 80.4, (d, J=164.86 Hz), 63.8 (d, J=4.79 Hz), 30.4, (d, J 20.13 Hz); .sup.19F NMR (400 MHz, CDCl.sub.3) δ 232.60.

##STR00012##

[0061] 1-(3-fluoropropoxy)-1H-benzo[d][1,2,3]triazole: .sup.1H NMR, 2N (400 MHz, CDCl.sub.3) δ 7.51 (d, J=2.3 Hz, 1H), 7.33 (dd, J=2.3, 8.7 Hz, 1H), 6.82 (d, J=8.7 Hz, 1H), 4.76 (t, J=5.7 Hz, 1H), 4.64 (t, J=5.7 Hz, 1H), 4.14 (t, J=6.0 Hz, 2H), 2.27-2.17 (m, 2H); .sup.13C NMR (101 MHz, CDCl.sub.3) δ 153.6, 132.7, 130.5, 124.1, 114.6, 112.8, 80.4 (d, J=164.85 Hz), 64.9, (d, J=4.79 Hz), 30.2 (d, J=20.13 Hz); .sup.19F NMR (400 MHz, CDCl.sub.3) δ=232.60.

##STR00013##

[0062] 1-([1,1′-biphenyl]-4-yl)-2-fluoroethan-1-one: .sup.13C NMR (101 MHz, CDCl.sub.3) δ 193.0, (d, J=15.34 Hz 146.8, 139.5, 132.3, 129.0, 128.5, 128.4, 127.5, 127.2, 127.1, .sup.19F NMR (400 MHz, CHLOROFORM-d) δ=232.60.

##STR00014##

[0063] (6S)-4-(2,2-dimethyl-1,3-dioxolan-4-yl)-6-fluoro-2,2-F dimethyltetrahydrofuro[3,4-d][1,3]dioxole: .sup.1H NMR (400 MHz CDCl.sub.3) δ 5.59 (d, J=59.51 Hz 1H), 4.86 (dd, J=3.5, 5.3 Hz, 1H), 4.78 (t, J=6.1 Hz, 1H), 4.44-4.38 (m, 1H), 4.17 (dd, J=3.1, 7.6 Hz, 1H), 4.12 (dd, J=6.10, 8.39 Hz, 1H), 4.09-4.05 (dd, J=4.4, 8.39 Hz, 1H), 1.46 (d, J=2.3 Hz, 6H), 1.39 (s, 3H), 1.35 (s, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) δ 114.7, 113.7 (d, J=69.09 Hz) 109.4, 84.7 (d, J=42.17 Hz) 82.6, 78.6, 72.7, 66.6, 26.9, 25.8, 25.1, 24.5: .sup.19F NMR (400 MHz, CDCl.sub.3) δ 232.60.

##STR00015##

[0064] 3-Fluorostigmasterol:

[0065] .sup.1H NMR (500 MHz, CDCl.sub.3) δ 5.34 (d, J=5.0 Hz, 1H), 5.19-5.14 (m, 1H), 5.02 (dd, J=8.6, 15.1 Hz, 1H), 3.34-3.23 (m, 1H), 2.30 (dd, J=2.9, 13.2 Hz, 1H), 2.27-2.20 (m, 1H), 2.10-1.95 (m, 5H), 1.88-1.82 (m, 2H), 1.74-1.69 (m, 1H), 1.58 (s, 3H), 1.55-1.45 (m, 8H), 1.27 (d, J=7.2 Hz, 2H), 1.20-1.15 (m, 3H), 1.01 (s, 4H), 0.85 (d, J=6.1 Hz, 3H), 0.81 (d, J=7.6 Hz, 7H), 0.70 (s, 3H); .sup.13C NMR (126 MHz, CDCl.sub.3) δ 141.3, 138.3, 129.2, 121.3, 56.5 (d, J=116.34 Hz), 51.2, 50.3, 42.2, 40.5, 40.0, 39.7, 37.4, 36.9, 31.9, 31.9, 29.4, 28.9, 25.4, 24.4, 21.2, 21.1, 19.4, 19.0, 12.2, 12.0; .sup.19F NMR (400 MHz, CDCl.sub.3) δ 232.60.

Example 7: General Process for the Recovery of the Polysaccharide Support from Used Cellulosic Supported TBAF Complex

[0066] After completion of the reaction as disclosed in scheme 1, the reaction mixture was cooled to 25-35° C. Bacterial cellulose was filtered, washed with ethyl acetate and dried under high-vacuum (2 mbar) to re-use for further loading with TBAF.

Advantages of the Invention

[0067] The present invention provides a new thermally stable, non hygroscopic polysaccharide supported TBAF complex as a fluorinating agent. [0068] The polysaccharide component of disclosed complex is recyclable [0069] The complex provides broad substrate scope, good selectivity and excellent yields of fluorinated products