Water-soluble polythiophene polymers (2023)

The use of these polymers for such applications has been hampered by some of the properties of these polymers, most importantly their lack of water solubility.

Conventional meth...

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[0038] The at least two stable leaving groups can either be anionic or neutral leaving groups. Examples of anionic or neutral leaving groups include a halide, tosylate, triflate, phenolate, brosylate, trialkyl amine, triaryl amine, mixed tri(alkyl/aryl)amine trialkyl phosphine, triaryl phosphine, mixed tri(alkyl/aryl)phosphine, trialkyl stannane, triaryl stannane, mixed tri(alkyl/aryl)stannane, thiophene (—SC6H5), phenolate (—OC6H5), and the like. By “mixed tri(alkyl/aryl)” amine, phosphine, stannane, it is meant that the nitrogen, phosphorus, and tin can be substituted with both alkyl and aryl groups. For example, a neutral leaving group can be P(CH3)2(C6H5). In one embodiment, an anionic leaving group is a halide or triflate. In another embodiment, an ionic leaving group is a halide. That is, the organozinc reagents include organozinc halides, i.e...

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[0053]1H NMR (CDCl3) spectra were recorded on a 200-MHz or a 360-MHz NMR spectrometer. Analytical gas chromatography analysis was carried out using stainless steel columns or a “megabore” glass capillary column. Stainless steel columns (⅛″ diameter) were typically packed with Silicon OV-17 (3%) on Chromosorb W-AW (100/120 mesh) with column lengths varying from 10 to 15 feet.

[0054] Reactions were carried out on a dual manifold vacuum/argon system. The Linde™ prepurified grade argon was further purified by passing it through a 150° C. catalyst column (BASF R3-11) and then through a column of phosphorous pentoxide, followed by a column of granular potassium hydroxide. The handling of air-sensitive materials was often performed under argon in a Vacuum Atmospheres Company drybox. Chemical reagents were primarily purchased from Aldrich Chemical Co., Inc. (Milwaukee, Wis.), and were used as received unless indicated otherwise. THF and DME were freshly distilled before use from sodium/potassium alloy under a purified argon atmosphere.

Example #1

Synthesis of 4-thiophen-3-yl-butyric acid ethyl ester

[0055] Scheme 1 below illustrates the production of 4-Thiophen-3-yl-butyric acid ethyl ester.

[0056] A 250 mL two-necked round bottom flask, stir bar, and condenser were taken from the oven. The joints of the round bottom flask were greased and the flask was equipped with a septum and an air inlet valve. The flask was charged with argon and a vacuum was drawn for about 15 minutes. This was repeated three times. Next, approximately 4.9 grams of Rieke Zinc (Rieke Metals, Inc., Lincoln, Nebr.) was transferred to the flask via a teflon cannula. 11.3 grams of ethyl 4-bromo butyrate was weighed into a disposable 10 mL plastic syringe. The ethyl 4-bromo butyrate was added to the round bottom flask in increments of about 1 mL every about 5 minutes. After all of the ethyl 4-bromo butyrate had been added (about 40 minutes) the flask was stirred for about 30 minutes and returned to room temperature. A G.C. quench was then taken and added to about 3 mL HCl/ether and shot at 80° C. on a packed column. The G.C. quench showed that all of the halide had been converted to the organozinc reagent. The organozinc reagent was drawn off, centrifuged down, and diluted to 100 mL in tetrahydrofuran (THF).

[0057] 3.0 grams of Nickel(II) 1,2-bis(diphneylphosphino)ethane (NiDPPE) was placed into a 100 mL round bottom flask. A septa was placed on the flask and 90 mL of tetrahydrohran (THF) was added. The NiDPPE/THF solution was added as a slurry to a 1 L two-necked round bottom flask under an argon atmosphere. The organozinc reagent prepared above, was added quickly via cannula. 34 g of 3-bromothiophene was added via an addition funnel over 5 minutes. The solution was heated to about 50° to 60° C. for about 5 minutes. The heat was turned off, and the mixture sat overnight. Then, 0.66 g NiDPPE was added and the solution was heated for 5 minutes. Based on gas chromatography, almost all of the 3-bromothiophene was consumed from the reaction mixture.

[0058] The reaction mixture was then poured into a 2 L beaker containing ice. 3 M HCl was added to keep the layers separated. The mixture was then placed into a separatory funnel, and 500 mL ether was added. The solution was extracted and washed with 2×250 mL water, 1×250 mL bicarbonate solution, and 1×250 mL brine. The extracts were then dried and concentrated.

[0059] The concentrated product was dissolved in 300 mL of heptane (Fisher, Fairlawn N.J.) and run through 2 inches of silica gel. The silica gel was washed with 750 mL heptane. 7 g of 50% pure product was recovered. The silica gel was washed with 1 L of heptane, and 5 more grams of product was recovered. The silica gel was washed with a 30/70 mixture of ethyl acetate (Fisher)/heptane and 19 g of product was obtained. The product was an orange oil.

[0060] A 10 cm wide column was packed with 800 g of silica gel in heptane. The product was loaded onto the column and the column was eluted with a 10/90 ethyl acetate/heptane solution. 100 mL fractions were collected as soon as the product started eluting. Fractions A-L were collected. Fractions B-H included 11.63 g of a yellow oil that was 81% pure product. Fractions I-L included 4 g of yellow oil that were 57% pure.

[0061] Gas chromatography mass spectrometry (GCMS) was run on the product and it was determined that the product had a molecular ion (MI) of 198, indicating that 4-Thiophen-3-yl-butyric acid ethyl ester had been formed.

Synthesis of 4-(2,5-dibromo-thiophen-3-yl)-butyric acid ethyl ester

[0062] Scheme 2 below shows the synthesis of 4-(2,5-Dibromo-thiophen-3-yl)-butyric acid ethyl ester starting from the product of Example 1.

[0063] 11.6 g of 4-thiophen-3-yl-butyric acid ethyl ester and 30 mL of CH2Cl2 were placed into a 100 mL 2-neck round bottom flask fitted with an addition funnel. The flask was connected to a potassium hydroxide/oil bubbler. 7 mL of CH2Cl2 were placed into the addition funnel, followed by 5 mL of Br2. The CH2Cl2/Br2 mixture was swirled and the mixture was added to the round bottom flask over 20 minutes. The mixture was stirred for 5 minutes after the CH2Cl2/Br2 mixture was done being added. Another 0.23 g of Br2 was added and the solution was stirred for 5 minutes. 25 mL of sodium thiosulfate was added and the solution was stirred for 15 minutes.

[0064] 100 mL of ether was added to the separatory funnel. The product was extracted and washed with 3×50 mL sodium thiosulfate, 1×50 mL bicarbonate solution, and 1×50 mL brine. The extract was then dried and concentrated to result in 19.54 g of a dark black oil.

[0065] The product was diluted to 200 mL with heptane and the mixture was filtered through 3 inches of silica gel. 500 mL of heptane was ran through the silica gel in order to remove some of the impurities. Next, 1 L of 10/90 ethyl acetate/heptane was run through the silica gel. The 1 L of 10/90 ethyl acetate/heptane containing the product was then rotovapped after drying and filtering.

[0066] The dried extract was then distilled giving four fractions.

Fraction Temperature A 61-71° C. B 95-118° C. C 118-125° C. 99% pure 4.33 g; light yellow oil D 125-128° C. 99% pure 1.77 g; light yellow oil

GC-MS of fractions C and D showed a molecular ion of 356.