Benzenethiol, 3,5-difluoro- (9CI)

To a solution of ethyl [(3, 5-difluorophenyl)sulfanyl]methanethioate ( 10 g, 42.68 mmol, 1.00 equiv) in ethanol ( 100 mL) maintained under nitrogen was added a solution of potassium hydrox ide (9.6 g, 171 11 mmol, 4 01 equiv) in water ( 10 mL) dropwise at rt with stirring in 5 min. The resulting solution was heated to reflux for 2.5 h. After cooling to rt, the mixture was concentrated under vacuum The residue was diluted with 200 m L of water and the solution was washed with 3x50 mL of ethyl acetate. The aqueous layer was collected to which zinc powder (0.8 g) was then added, The pH of the solution was adjusted to 5 with concentrated hydrochloric acid at 0- 10 °C. The resulting solution was extracted with 3x 100 mL of ethyl acetate. The combined organic layers was washed with 3x1 00 mL of brine, dried over anhydrous sodium sulfate, and concentrated under vacuum to give 5 0 g (80percent) of 3, 5-difluorobenzene-1-thiol as a brown oil TLC ( 10: 1 petroleum ether/ethyl acetate): RGeneral procedure: All lead thiolates were prepared by modification of previously publishedmethods [32-36]: To a solution of Pb(CH3COO)2 (5.2 mmol) in 100 mL water, thiol (HSRF) (10.0 mmol)dissolved in about 10 mL of ethanol was added under vigorous stirring at room temperature. A white oryellow precipitate was rapidly formed. The solid was filtrated and washed 3x with 50 mL methanol and 3x with 25 mL hexane. Caution: Lead derivatives are extremely toxic and must be handled followingthe proper security procedures. Thiols and thiolates are odorous; consequently, all procedures must becompleted in a fume hood. IR spectra of the lead thiolates are available in the SI.General procedure: Into a dry and clean round bottom flask was weighed 1 g of 1, 3-heptadione (1 mmol). The dione was dissolved in triethyl orthoformateand to it was added 850 mg (1 mmol) of thiophene. Themixturewas heated to 120 C for 1 h under stirring. The completionof the reactionwas monitored by thin layer chromatography in 70%ethyl acetate and hexane. The product was isolated from the reactionmixture by column chromatography using ethyl acetate andhexane (80:20). The product was characterised by 1H NMR, 13CNMR and HRMS techniques.To a solution of 2-chloro-5-nitrobenzonitrile (1 g, 5.49 mmol) and 3, 5- difluorobenzenethiol (960 mg, 6.6 mmol) in DIVIF (20 mL) was added K2C03 (2.3 g, 16 mmol). The reaction was stirred at 80 C overnight. The residue was poured into H20 (20 mL) and the aqueous phase was extracted with EA (30 mL x2). The organic layer was washed with brine (20 mL), dried over Na2SO4 and concentrated. The residue was purified by silica gel column (PE/EA = 10/1) to give 2-((3, 5-difluorophenyl)thio)-5-nitrobenzonitrile (620 mg, yield: 39%) as a yellow solid.

Molecular Weight:146.16
XLogP3:2.3
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:3
Exact Mass:146.00017763
Monoisotopic Mass:146.00017763
Topological Polar Surface Area:1
Heavy Atom Count:9
Complexity:87.1
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes