[ CAS No. 1535-67-7 ]

Name: 1535-67-7|Difluoromethyl Phenyl Sulfide|98% GC
Brand: Ambeed
SKU: A862472
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Quality Control of [ 1535-67-7 ]

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Product Details of [ 1535-67-7 ]

CAS No. :	1535-67-7	MDL No. :	MFCD16301013
Formula :	C₇H₆F₂S	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	KDNBCPHMQJEQLV-UHFFFAOYSA-N
M.W :	160.18 g/mol	Pubchem ID :	73752
Synonyms :

Calculated chemistry of [ 1535-67-7 ]

Physicochemical Properties

Num. heavy atoms :	10
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.14
Num. rotatable bonds :	2
Num. H-bond acceptors :	2.0
Num. H-bond donors :	0.0
Molar Refractivity :	38.27
TPSA :	25.3 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-4.66 cm/s

Lipophilicity

Log Po/w (iLOGP) :	1.97
Log Po/w (XLOGP3) :	3.69
Log Po/w (WLOGP) :	3.84
Log Po/w (MLOGP) :	3.21
Log Po/w (SILICOS-IT) :	2.79
Consensus Log Po/w :	3.1

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	2.0
Bioavailability Score :	0.55

Water Solubility

Log S (ESOL) :	-3.47
Solubility :	0.0543 mg/ml ; 0.000339 mol/l
Class :	Soluble
Log S (Ali) :	-3.91
Solubility :	0.0196 mg/ml ; 0.000123 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-3.1
Solubility :	0.126 mg/ml ; 0.000789 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	2.0
Synthetic accessibility :	1.56

Safety of [ 1535-67-7 ]

Signal Word:	Danger	Class:	3
Precautionary Statements:	P501-P240-P210-P233-P243-P241-P242-P264-P280-P370+P378-P337+P313-P305+P351+P338-P303+P361+P353-P332+P313-P362-P403+P235	UN#:	1993
Hazard Statements:	H315-H319-H225	Packing Group:	Ⅲ
GHS Pictogram:

Application In Synthesis of [ 1535-67-7 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

Upstream synthesis route of [ 1535-67-7 ]
Downstream synthetic route of [ 1535-67-7 ]

[ 1535-67-7 ] Synthesis Path-Upstream 1~4

1
[ 1535-67-7 ]
[ 91-66-7 ]
[ 120-21-8 ]

Yield	Reaction Conditions	Operation in experiment
42%	Stage #1: With tin(IV) chloride In dichloromethane at 20℃; for 2 h; Inert atmosphere Stage #2: With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In water; dimethyl sulfoxide at 20℃; for 2 h;	General procedure: In a round-bottomed flask equipped with a stirring bar and rubber septum was placed a 1 M solution of SnCl4 in anhydrous CH2Cl2 (1 mL, 1 mmol). To this solution was added PhSCF2H (1; 240.2 mg, 1.5 mmol) in anhydrous CH2Cl2 (1.5 mL), followed by a solution of an aromatic compound (0.5 mmol) in anhydrous CH2Cl2 (1 mL). The reaction was allowed to proceed for 2 h before it was quenched with a solution of IBX (140 mg, 0.5 mmol) in DMSO/H2O (4 mL; 3:1 v:v). After 2 h of stirring at rt, the reaction mixture was quenched by addition of a saturated aqueous solution of sodium thiosulfate (10 mL), then basified with a saturated aqueous solution of sodium hydrogen carbonate (10 mL), followed by stirring and extraction with CH2Cl2 (3 × 10 mL). The combined organic layers were washed with water (3 × 10 mL) and brine (10 mL), dried (anhydrous MgSO4), filtered and concentrated (aspirator). The residue was purified by PTLC, radial chromatography or column chromatography to furnish analytically pure product.

Reference： [1] Synthesis (Germany), 2018, vol. 50, # 10, p. 2033 - 2040

2
[ 634-36-6 ]
[ 1535-67-7 ]
[ 2103-57-3 ]

Yield	Reaction Conditions	Operation in experiment
72%	Stage #1: With tin(IV) chloride In dichloromethane at 20℃; for 2 h; Inert atmosphere Stage #2: With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In water; dimethyl sulfoxide at 20℃; for 2 h;	General procedure: In a round-bottomed flask equipped with a stirring bar and rubber septum was placed a 1 M solution of SnCl4 in anhydrous CH2Cl2 (1 mL, 1 mmol). To this solution was added PhSCF2H (1; 240.2 mg, 1.5 mmol) in anhydrous CH2Cl2 (1.5 mL), followed by a solution of an aromatic compound (0.5 mmol) in anhydrous CH2Cl2 (1 mL). The reaction was allowed to proceed for 2 h before it was quenched with a solution of IBX (140 mg, 0.5 mmol) in DMSO/H2O (4 mL; 3:1 v:v). After 2 h of stirring at rt, the reaction mixture was quenched by addition of a saturated aqueous solution of sodium thiosulfate (10 mL), then basified with a saturated aqueous solution of sodium hydrogen carbonate (10 mL), followed by stirring and extraction with CH2Cl2 (3 × 10 mL). The combined organic layers were washed with water (3 × 10 mL) and brine (10 mL), dried (anhydrous MgSO4), filtered and concentrated (aspirator). The residue was purified by PTLC, radial chromatography or column chromatography to furnish analytically pure product.

Reference： [1] Synthesis (Germany), 2018, vol. 50, # 10, p. 2033 - 2040

3
[ 621-23-8 ]
[ 1535-67-7 ]
[ 830-79-5 ]

Yield	Reaction Conditions	Operation in experiment
99%	Stage #1: With tin(IV) chloride In dichloromethane at 20℃; for 2 h; Inert atmosphere Stage #2: With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In water; dimethyl sulfoxide at 20℃; for 2 h;	General procedure: In a round-bottomed flask equipped with a stirring bar and rubber septum was placed a 1 M solution of SnCl4 in anhydrous CH2Cl2 (1 mL, 1 mmol). To this solution was added PhSCF2H (1; 240.2 mg, 1.5 mmol) in anhydrous CH2Cl2 (1.5 mL), followed by a solution of an aromatic compound (0.5 mmol) in anhydrous CH2Cl2 (1 mL). The reaction was allowed to proceed for 2 h before it was quenched with a solution of IBX (140 mg, 0.5 mmol) in DMSO/H2O (4 mL; 3:1 v:v). After 2 h of stirring at rt, the reaction mixture was quenched by addition of a saturated aqueous solution of sodium thiosulfate (10 mL), then basified with a saturated aqueous solution of sodium hydrogen carbonate (10 mL), followed by stirring and extraction with CH2Cl2 (3 × 10 mL). The combined organic layers were washed with water (3 × 10 mL) and brine (10 mL), dried (anhydrous MgSO4), filtered and concentrated (aspirator). The residue was purified by PTLC, radial chromatography or column chromatography to furnish analytically pure product. 2,4,6-Trimethoxybenzaldehyde (4b) White solid (97.12 mg, 99 percent) from EtOAc/hexanes; mp 118–120 °C; Rf = 0.23 (hexanes/EtOAc, 5:1). IR (KBr): 2976, 2949, 2880, 1664 (C=O), 1600, 1475, 1333, 1161, 1127, 1025 cm–1. 1H NMR (300 MHz, CDCl3): δ = 10.36 (s, 1 H), 6.09 (s, 2 H), 3.89 (s, 9H). 13C NMR (75 MHz, CDCl3): δ = 187.6 (CO), 166.2 (C), 164.1 (2 × C), 108.9 (C), 90.3 (2 × CH), 56.0 (2 × CH3), 55.5 (CH3). HRMS (ESI-TOF): m/z [M + Na]+ calcd for C10H12O4Na: 219.0633; found: 219.0627.

Reference： [1] Synthesis (Germany), 2018, vol. 50, # 10, p. 2033 - 2040

4
[ 1535-67-7 ]
[ 1535-65-5 ]

Yield	Reaction Conditions	Operation in experiment
88%	With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0 - 20℃; for 24 h;	To a solution of difluoromethyl phenyl sulfide 2 (3.98 g, 25 mmol) in dry CH2Cl2 (69 mL) at 0°C, a solid m-CPBA (15.9 g, 92.0 mmol) was added portionwise. The reaction was then warmed to room temperature and left for overnight stirring. CH2Cl2 (50 mL) was then added and the mixture was washed with 10percent aqueous Na2SO3 (2 100 mL), 5percent aqueous NaHCO3 (4 50 mL) and brine(2 100 mL), respectively. Organic layer was dried (Na2SO4) and concentrated under reduced pressure. The residue was purified by silica gel column chromatography using CH2Cl2 and hexane as eluents (3:1). Rf = 0.40 (CH2Cl2/hexane, 3:1).Yield: 4.24 g, 22.1 mmol, 88percent. 1H NMR (300 MHz, CDCl3): d 8.01 (dt, J = 8.7; 1.7 Hz, 2H, HAr),7.85–7.78 (m, 1H, HAr), 7.72–7.62 (m, 2H, HAr), 6.20 (t, J = 53.4 Hz,1H, CF2H); 13C NMR (101 MHz, CDCl3): d 136.0 (s, CAr), 131.9 (s,CAr), 130.8 (s, CAr), 129.7 (s, CAr), 114.8 (t, J = 285.9 Hz, CF2H); 19FNMR (282 MHz, CDCl3): d 122.1 (d, J = 53.4 Hz, 2F, CF2H). TheNMR data were in a good agreement with those already reported.
83%	With 3-chloro-benzenecarboperoxoic acid In dichloromethane	EXAMPLE 2 Difluoromethyl Phenyl Sulfone A solution of 2.0 g (12 mmol) of difluoromethyl phenyl sulfide in 20 mL of dichloromethane was cooled to 0°-5° C. and treated portionwise with 5.4 g (27 mmol) of 85percent meta-chloroperbenzoic acid. The mixture was allowed to warm to room temperature, stirred for 4 hours, treated with an additional 1.1 g (5.4 mmol) of 85percent meta-chloroperbenzoic acid, and stirred overnight. Filtration and washing of the filter cake with 30 mL of dichloromethane gave a solution which was washed with three 25 mL portions of saturated NaHCO₃ and one 25 mL portion of water, dried (MgSO₄), and concentrated in vacuo. The residue was purified by flash chromatography on 50 g of silica gel (eluted with 25percent dichloromethane, 75percent petroleum ether) to give 1.92 g (83percent yield) of difluoromethyl phenyl sulfone as a colorless liquid: IR (neat) 3069, 1771, 1447, 1348, 1301, 1162, 1113, 1077, 760, 725, 685, 621, 606, 557, 545, 515, cm^-1; ¹ H NMR (CDCl₃) δ6.29 (t, 1H, J_HF =54Hz), 7.50-8.10 (m, 5H); mass spectrum (70 eV) m/e (relative intensity) 192 (22, M⁺), 141 (45), 77 (100), 51 (54).

Reference： [1] Angewandte Chemie - International Edition, 2014, vol. 53, # 7, p. 1827 - 1831[2] Angew. Chem., 2014, vol. 126, # 7, p. 1858 - 1862,5
[3] Journal of Fluorine Chemistry, 2015, vol. 179, p. 175 - 178
[4] Patent: US4837327, 1989, A,
[5] Journal of the American Chemical Society, 1960, vol. 82, p. 6178 - 6181
[6] Journal of Fluorine Chemistry, 1989, vol. 43, p. 53 - 66
[7] Journal of Fluorine Chemistry, 2007, vol. 128, # 10, p. 1098 - 1103
[8] Organic Letters, 2016, vol. 18, # 22, p. 5912 - 5915

[ 1535-67-7 ] Synthesis Path-Downstream 1~26

1
[ 1535-67-7 ]
[ 1535-65-5 ]

Yield	Reaction Conditions	Operation in experiment
88%	With 3-chloro-benzenecarboperoxoic acid; In dichloromethane; at 0 - 20℃; for 24h;	To a solution of <strong>[1535-67-7]difluoromethyl phenyl sulfide</strong> 2 (3.98 g, 25 mmol) in dry CH2Cl2 (69 mL) at 0C, a solid m-CPBA (15.9 g, 92.0 mmol) was added portionwise. The reaction was then warmed to room temperature and left for overnight stirring. CH2Cl2 (50 mL) was then added and the mixture was washed with 10% aqueous Na2SO3 (2 100 mL), 5% aqueous NaHCO3 (4 50 mL) and brine(2 100 mL), respectively. Organic layer was dried (Na2SO4) and concentrated under reduced pressure. The residue was purified by silica gel column chromatography using CH2Cl2 and hexane as eluents (3:1). Rf = 0.40 (CH2Cl2/hexane, 3:1).Yield: 4.24 g, 22.1 mmol, 88%. 1H NMR (300 MHz, CDCl3): d 8.01 (dt, J = 8.7; 1.7 Hz, 2H, HAr),7.85-7.78 (m, 1H, HAr), 7.72-7.62 (m, 2H, HAr), 6.20 (t, J = 53.4 Hz,1H, CF2H); 13C NMR (101 MHz, CDCl3): d 136.0 (s, CAr), 131.9 (s,CAr), 130.8 (s, CAr), 129.7 (s, CAr), 114.8 (t, J = 285.9 Hz, CF2H); 19FNMR (282 MHz, CDCl3): d 122.1 (d, J = 53.4 Hz, 2F, CF2H). TheNMR data were in a good agreement with those already reported.
83%	With 3-chloro-benzenecarboperoxoic acid; In dichloromethane;	EXAMPLE 2 Difluoromethyl Phenyl Sulfone A solution of 2.0 g (12 mmol) of <strong>[1535-67-7]difluoromethyl phenyl sulfide</strong> in 20 mL of dichloromethane was cooled to 0-5 C. and treated portionwise with 5.4 g (27 mmol) of 85% meta-chloroperbenzoic acid. The mixture was allowed to warm to room temperature, stirred for 4 hours, treated with an additional 1.1 g (5.4 mmol) of 85% meta-chloroperbenzoic acid, and stirred overnight. Filtration and washing of the filter cake with 30 mL of dichloromethane gave a solution which was washed with three 25 mL portions of saturated NaHCO3 and one 25 mL portion of water, dried (MgSO4), and concentrated in vacuo. The residue was purified by flash chromatography on 50 g of silica gel (eluted with 25% dichloromethane, 75% petroleum ether) to give 1.92 g (83% yield) of difluoromethyl phenyl sulfone as a colorless liquid: IR (neat) 3069, 1771, 1447, 1348, 1301, 1162, 1113, 1077, 760, 725, 685, 621, 606, 557, 545, 515, cm-1; 1 H NMR (CDCl3) δ6.29 (t, 1H, JHF =54Hz), 7.50-8.10 (m, 5H); mass spectrum (70 eV) m/e (relative intensity) 192 (22, M+), 141 (45), 77 (100), 51 (54).

Reference： [1]Angewandte Chemie - International Edition,2014,vol. 53,p. 1827 - 1831
Angew. Chem.,2014,vol. 126,p. 1858 - 1862,5
[2]Journal of Fluorine Chemistry,2015,vol. 179,p. 175 - 178
[3]Patent: US4837327,1989,A
[4]Journal of the American Chemical Society,1960,vol. 82,p. 6178 - 6181
[5]Journal of Fluorine Chemistry,1989,vol. 43,p. 53 - 66
[6]Journal of Fluorine Chemistry,2007,vol. 128,p. 1098 - 1103
[7]Organic Letters,2016,vol. 18,p. 5912 - 5915
[8]Chemical Communications,2021,vol. 57,p. 12337 - 12340

2
[ 75-45-6 ]
[ 108-98-5 ]
[ 1535-67-7 ]

Yield	Reaction Conditions	Operation in experiment
78%		To a solution of MeONa in MeOH, prepared by reaction of sodium metal Na (4.88 g, 212 mmol) and dry methanol (35 mL),was added dropwise thiophenol 1 (4.41 g, 4.11 mL, 40 mmol). The resulting mixture was stirred at room temperature for 2 h, and then placed in cooling bath,- 78C. To the cooled reaction mixture CF2ClH (6.92 g, 80 mmol) was added. After 3 h the reaction was quenched with water (200 mL) and extracted with CH2Cl2(3x200 mL). The combined organic layers were dried (Na2SO4) and concentrated under reduced pressure. The residue was purified by silica gel column chromatography using pentane as eluent. Rf = 0.40 (pentane).Yield: 5.00 g, 31.2 mmol, 78%.1H NMR (300 MHz, CDCl3): d 7.62-7.54 (m, 2H, HAr), 7.44-7.33(m, 3H, HAr), 6.81 (t, J = 57.0 Hz, 1H, CF2H); 13C NMR (75 MHz,CDCl3): d 135.5 (s, CAr), 129.8 (d, J = 12.7 Hz, CAr), 129.8-129.3 (m,CAr), 126.3 (t, J = 3.0 Hz, CAr), 121.2 (t, J = 275.1 Hz, CF2H); 19F NMR(282 MHz, CDCl3): d 91.9 (d, J = 57.0 Hz, 2F, CF2). The NMR data were in a good agreement with those already reported.

Reference： [1]Journal of Fluorine Chemistry,1988,vol. 41,p. 247 - 262
[2]Organic Letters,2007,vol. 9,p. 1863 - 1866
[3]Journal of Fluorine Chemistry,2015,vol. 179,p. 175 - 178
[4]Angewandte Chemie - International Edition,2014,vol. 53,p. 1827 - 1831
Angew. Chem.,2014,vol. 126,p. 1858 - 1862,5
[5]Journal of Fluorine Chemistry,1989,vol. 43,p. 53 - 66
[6]Journal of Fluorine Chemistry,2007,vol. 128,p. 1241 - 1247
[7]Journal of Fluorine Chemistry,2007,vol. 128,p. 1098 - 1103
[8]Organic Letters,2016,vol. 18,p. 5912 - 5915

3
[ 1535-67-7 ]
[ 24933-64-0 ]

Yield	Reaction Conditions	Operation in experiment
70%	With dihydrogen peroxide; trifluoroacetic acid; In water; at 25 - 28℃; for 4h;	General procedure: To the solution of sulfide 1, 3, or 5 (10 mmol) in CF3COOH (15-20 mL) 15 mass% aqueous solution of H2O2 (containing 10 mmol of H2O2) was added dropwise very slowly (during 40-90 min)at room temperature. Reaction is strongly exothermic; H2O2 was added at such a rate that the temperature was kept in the range 25-28 C inside the flask (20 C for compounds 1k, 3f,g, and 0 C for compounds 5e,f). Reaction mixture was stirred overnight at r.t. (for compound 3d -96h,for 7-7 days), poured into water, neutralized with solid NaHCO3 to pH=6-7, then extracted with ether or ethyl acetate (4x30 mL). Compounds 2k, 4f,g, and 6e,f were extracted with dichloromethane before neutralizing the TFA with NaHCO3. The organic phase was washed with water (4 20 mL),dried with MgSO4 or Na2SO4. Solvent was removed at atmospheric pressure for low-boiling liquids or on a rotary evaporator for solids or high-boiling liquids. Crude product was analyzed by NMR and purified if necessary.

Reference： [1]Journal of Fluorine Chemistry,2007,vol. 128,p. 1241 - 1247
[2]Chemistry - A European Journal,2016,vol. 22,p. 1262 - 1265
[3]Organic Letters,2007,vol. 9,p. 1863 - 1866
[4]Chemical Communications,2017,vol. 53,p. 5706 - 5709
[5]Molecules,2019,vol. 24
[6]European Journal of Organic Chemistry,2021,vol. 2021,p. 5019 - 5026
[7]Journal of general chemistry of the USSR,1969,vol. 39,p. 2011 - 2016
Zhurnal Obshchei Khimii,1969,vol. 39,p. 2057 - 2062
[8]Organic Letters,2018,vol. 20,p. 6925 - 6929

4
[ 611-94-9 ]
[ 1535-67-7 ]
[ 1363319-75-8 ]

Yield	Reaction Conditions	Operation in experiment
89%	With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at -50℃; for 2h; Inert atmosphere;	4.2. General procedure for reaction of 1 (PhXCF2H, X = S, Se, Te) with 2 and 6 Under a nitrogen atmosphere, to a stirred solution of PhSeCF2H (1b) (414 mg, 2.0 mmol) and benzaldehyde (2a) (318 mg, 3.0 mmol) with 3 mL DMF in a Schlenk tube, t-BuOK (448 mg, 4.0 mmol) (dissolved in 2 mL DMF) was added dropwise at -50 °C. The mixture was stirred at this temperature for 2 h. Then quenched with saturated aqueous ammonium chloride or brine, the reaction mixture was extracted with Et2O (3 × 10 mL). The combined organic layer was washed with H2O (2 × 10 mL), followed by brine (10 mL), dried over MgSO4 and concentrated under vacuum. The residue was purified by flash chromatography with ethyl acetate/petroleum ether (1:10) as eluent to give 520 mg 4a as a colorless oil. Yield 86%.

Reference： [1]Location in patent: experimental part Hu, Mingyou; Wang, Fei; Zhao, Yanchuan; He, Zhengbiao; Zhang, Wei; Hu, Jinbo [Journal of Fluorine Chemistry, 2012, vol. 135, p. 45 - 58]

5
[ 119-61-9 ]
[ 1535-67-7 ]
[ 878808-68-5 ]

Yield	Reaction Conditions	Operation in experiment
96%	With potassium tert-butylate; In N,N-dimethyl-formamide; at -50℃; for 2h;Inert atmosphere;	Under a nitrogen atmosphere, to a stirred solution of PhSeCF2H (1b) (414 mg, 2.0 mmol) and benzaldehyde (2a) (318 mg, 3.0 mmol) with 3 mL DMF in a Schlenk tube, t-BuOK (448 mg, 4.0 mmol) (dissolved in 2 mL DMF) was added dropwise at -50 C. The mixture was stirred at this temperature for 2 h. Then quenched with saturated aqueous ammonium chloride or brine, the reaction mixture was extracted with Et2O (3 × 10 mL). The combined organic layer was washed with H2O (2 × 10 mL), followed by brine (10 mL), dried over MgSO4 and concentrated under vacuum. The residue was purified by flash chromatography with ethyl acetate/petroleum ether (1:10) as eluent to give 520 mg 4a as a colorless oil. Yield 86%.

Reference： [1]Journal of Fluorine Chemistry,2012,vol. 135,p. 45 - 58
[2]European Journal of Organic Chemistry,2014,vol. 2014,p. 4162 - 4169

6
[ 486-25-9 ]
[ 1535-67-7 ]
[ 1363319-52-1 ]

Yield	Reaction Conditions	Operation in experiment
96%	With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at -50℃; for 2h; Inert atmosphere;	4.2. General procedure for reaction of 1 (PhXCF2H, X = S, Se, Te) with 2 and 6 Under a nitrogen atmosphere, to a stirred solution of PhSeCF2H (1b) (414 mg, 2.0 mmol) and benzaldehyde (2a) (318 mg, 3.0 mmol) with 3 mL DMF in a Schlenk tube, t-BuOK (448 mg, 4.0 mmol) (dissolved in 2 mL DMF) was added dropwise at -50 °C. The mixture was stirred at this temperature for 2 h. Then quenched with saturated aqueous ammonium chloride or brine, the reaction mixture was extracted with Et2O (3 × 10 mL). The combined organic layer was washed with H2O (2 × 10 mL), followed by brine (10 mL), dried over MgSO4 and concentrated under vacuum. The residue was purified by flash chromatography with ethyl acetate/petroleum ether (1:10) as eluent to give 520 mg 4a as a colorless oil. Yield 86%.

Reference： [1]Location in patent: experimental part Hu, Mingyou; Wang, Fei; Zhao, Yanchuan; He, Zhengbiao; Zhang, Wei; Hu, Jinbo [Journal of Fluorine Chemistry, 2012, vol. 135, p. 45 - 58]

7
[ 2128-93-0 ]
[ 1535-67-7 ]
[ 1363319-80-5 ]

Yield	Reaction Conditions	Operation in experiment
82%	With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at -50℃; for 2h; Inert atmosphere;	4.2. General procedure for reaction of 1 (PhXCF2H, X = S, Se, Te) with 2 and 6 Under a nitrogen atmosphere, to a stirred solution of PhSeCF2H (1b) (414 mg, 2.0 mmol) and benzaldehyde (2a) (318 mg, 3.0 mmol) with 3 mL DMF in a Schlenk tube, t-BuOK (448 mg, 4.0 mmol) (dissolved in 2 mL DMF) was added dropwise at -50 °C. The mixture was stirred at this temperature for 2 h. Then quenched with saturated aqueous ammonium chloride or brine, the reaction mixture was extracted with Et2O (3 × 10 mL). The combined organic layer was washed with H2O (2 × 10 mL), followed by brine (10 mL), dried over MgSO4 and concentrated under vacuum. The residue was purified by flash chromatography with ethyl acetate/petroleum ether (1:10) as eluent to give 520 mg 4a as a colorless oil. Yield 86%.

Reference： [1]Location in patent: experimental part Hu, Mingyou; Wang, Fei; Zhao, Yanchuan; He, Zhengbiao; Zhang, Wei; Hu, Jinbo [Journal of Fluorine Chemistry, 2012, vol. 135, p. 45 - 58]

8
[ 90-90-4 ]
[ 1535-67-7 ]
[ 1363319-64-5 ]

Yield	Reaction Conditions	Operation in experiment
92%	With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at -50℃; for 2h; Inert atmosphere;	4.2. General procedure for reaction of 1 (PhXCF2H, X = S, Se, Te) with 2 and 6 Under a nitrogen atmosphere, to a stirred solution of PhSeCF2H (1b) (414 mg, 2.0 mmol) and benzaldehyde (2a) (318 mg, 3.0 mmol) with 3 mL DMF in a Schlenk tube, t-BuOK (448 mg, 4.0 mmol) (dissolved in 2 mL DMF) was added dropwise at -50 °C. The mixture was stirred at this temperature for 2 h. Then quenched with saturated aqueous ammonium chloride or brine, the reaction mixture was extracted with Et2O (3 × 10 mL). The combined organic layer was washed with H2O (2 × 10 mL), followed by brine (10 mL), dried over MgSO4 and concentrated under vacuum. The residue was purified by flash chromatography with ethyl acetate/petroleum ether (1:10) as eluent to give 520 mg 4a as a colorless oil. Yield 86%.

Reference： [1]Location in patent: experimental part Hu, Mingyou; Wang, Fei; Zhao, Yanchuan; He, Zhengbiao; Zhang, Wei; Hu, Jinbo [Journal of Fluorine Chemistry, 2012, vol. 135, p. 45 - 58]

9
[ 1535-67-7 ]
[ 100-52-7 ]
[ 351195-17-0 ]

Yield	Reaction Conditions	Operation in experiment
94%	With potassium tert-butylate; In N,N-dimethyl-formamide; at -50℃; for 2h;Inert atmosphere;	Under a nitrogen atmosphere, to a stirred solution of PhSeCF2H (1b) (414 mg, 2.0 mmol) and benzaldehyde (2a) (318 mg, 3.0 mmol) with 3 mL DMF in a Schlenk tube, t-BuOK (448 mg, 4.0 mmol) (dissolved in 2 mL DMF) was added dropwise at -50 C. The mixture was stirred at this temperature for 2 h. Then quenched with saturated aqueous ammonium chloride or brine, the reaction mixture was extracted with Et2O (3 × 10 mL). The combined organic layer was washed with H2O (2 × 10 mL), followed by brine (10 mL), dried over MgSO4 and concentrated under vacuum. The residue was purified by flash chromatography with ethyl acetate/petroleum ether (1:10) as eluent to give 520 mg 4a as a colorless oil. Yield 86%.

Reference： [1]Journal of Fluorine Chemistry,2012,vol. 135,p. 45 - 58
[2]European Journal of Organic Chemistry,2014,vol. 2014,p. 4162 - 4169

10
[ 1535-67-7 ]
[ 630-19-3 ]
[ 1363319-44-1 ]

Yield	Reaction Conditions	Operation in experiment
94%	With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at -50℃; for 2h; Inert atmosphere;	4.2. General procedure for reaction of 1 (PhXCF2H, X = S, Se, Te) with 2 and 6 Under a nitrogen atmosphere, to a stirred solution of PhSeCF2H (1b) (414 mg, 2.0 mmol) and benzaldehyde (2a) (318 mg, 3.0 mmol) with 3 mL DMF in a Schlenk tube, t-BuOK (448 mg, 4.0 mmol) (dissolved in 2 mL DMF) was added dropwise at -50 °C. The mixture was stirred at this temperature for 2 h. Then quenched with saturated aqueous ammonium chloride or brine, the reaction mixture was extracted with Et2O (3 × 10 mL). The combined organic layer was washed with H2O (2 × 10 mL), followed by brine (10 mL), dried over MgSO4 and concentrated under vacuum. The residue was purified by flash chromatography with ethyl acetate/petroleum ether (1:10) as eluent to give 520 mg 4a as a colorless oil. Yield 86%.

Reference： [1]Location in patent: experimental part Hu, Mingyou; Wang, Fei; Zhao, Yanchuan; He, Zhengbiao; Zhang, Wei; Hu, Jinbo [Journal of Fluorine Chemistry, 2012, vol. 135, p. 45 - 58]

11
[ 1535-67-7 ]
[ 66-99-9 ]
[ 878808-64-1 ]

Yield	Reaction Conditions	Operation in experiment
91%	With potassium tert-butylate; In N,N-dimethyl-formamide; at -50℃; for 2h;Inert atmosphere;	Under a nitrogen atmosphere, to a stirred solution of PhSeCF2H (1b) (414 mg, 2.0 mmol) and benzaldehyde (2a) (318 mg, 3.0 mmol) with 3 mL DMF in a Schlenk tube, t-BuOK (448 mg, 4.0 mmol) (dissolved in 2 mL DMF) was added dropwise at -50 C. The mixture was stirred at this temperature for 2 h. Then quenched with saturated aqueous ammonium chloride or brine, the reaction mixture was extracted with Et2O (3 × 10 mL). The combined organic layer was washed with H2O (2 × 10 mL), followed by brine (10 mL), dried over MgSO4 and concentrated under vacuum. The residue was purified by flash chromatography with ethyl acetate/petroleum ether (1:10) as eluent to give 520 mg 4a as a colorless oil. Yield 86%.

Reference： [1]European Journal of Organic Chemistry,2014,vol. 2014,p. 4162 - 4169
[2]Journal of Fluorine Chemistry,2012,vol. 135,p. 45 - 58

12
[ 1535-67-7 ]
[ 134-85-0 ]
[ 1363319-58-7 ]

Yield	Reaction Conditions	Operation in experiment
79%	With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at -50℃; for 2h; Inert atmosphere;	4.2. General procedure for reaction of 1 (PhXCF2H, X = S, Se, Te) with 2 and 6 Under a nitrogen atmosphere, to a stirred solution of PhSeCF2H (1b) (414 mg, 2.0 mmol) and benzaldehyde (2a) (318 mg, 3.0 mmol) with 3 mL DMF in a Schlenk tube, t-BuOK (448 mg, 4.0 mmol) (dissolved in 2 mL DMF) was added dropwise at -50 °C. The mixture was stirred at this temperature for 2 h. Then quenched with saturated aqueous ammonium chloride or brine, the reaction mixture was extracted with Et2O (3 × 10 mL). The combined organic layer was washed with H2O (2 × 10 mL), followed by brine (10 mL), dried over MgSO4 and concentrated under vacuum. The residue was purified by flash chromatography with ethyl acetate/petroleum ether (1:10) as eluent to give 520 mg 4a as a colorless oil. Yield 86%.

Reference： [1]Location in patent: experimental part Hu, Mingyou; Wang, Fei; Zhao, Yanchuan; He, Zhengbiao; Zhang, Wei; Hu, Jinbo [Journal of Fluorine Chemistry, 2012, vol. 135, p. 45 - 58]

13
[ 1535-67-7 ]
[ 100-10-7 ]
[ 1363319-11-2 ]

Yield	Reaction Conditions	Operation in experiment
91%	With potassium tert-butylate; In N,N-dimethyl-formamide; at -50℃; for 2h;Inert atmosphere;	Under a nitrogen atmosphere, to a stirred solution of PhSeCF2H (1b) (414 mg, 2.0 mmol) and benzaldehyde (2a) (318 mg, 3.0 mmol) with 3 mL DMF in a Schlenk tube, t-BuOK (448 mg, 4.0 mmol) (dissolved in 2 mL DMF) was added dropwise at -50 C. The mixture was stirred at this temperature for 2 h. Then quenched with saturated aqueous ammonium chloride or brine, the reaction mixture was extracted with Et2O (3 × 10 mL). The combined organic layer was washed with H2O (2 × 10 mL), followed by brine (10 mL), dried over MgSO4 and concentrated under vacuum. The residue was purified by flash chromatography with ethyl acetate/petroleum ether (1:10) as eluent to give 520 mg 4a as a colorless oil. Yield 86%.

Reference： [1]Journal of Fluorine Chemistry,2012,vol. 135,p. 45 - 58
[2]European Journal of Organic Chemistry,2014,vol. 2014,p. 4162 - 4169

14
[ 634-36-6 ]
[ 1535-67-7 ]
[ 2103-57-3 ]

Yield	Reaction Conditions	Operation in experiment
72%	Stage #1: 1,2,3-trimethoxybenzene; difluoromethyl phenyl sulfide With tin(IV) chloride In dichloromethane at 20℃; for 2h; Inert atmosphere; Stage #2: With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In water; dimethyl sulfoxide at 20℃; for 2h;	Aldehydes 4 and 8; General Procedure General procedure: In a round-bottomed flask equipped with a stirring bar and rubber septum was placed a 1 M solution of SnCl4 in anhydrous CH2Cl2 (1 mL, 1 mmol). To this solution was added PhSCF2H (1; 240.2 mg, 1.5 mmol) in anhydrous CH2Cl2 (1.5 mL), followed by a solution of an aromatic compound (0.5 mmol) in anhydrous CH2Cl2 (1 mL). The reaction was allowed to proceed for 2 h before it was quenched with a solution of IBX (140 mg, 0.5 mmol) in DMSO/H2O (4 mL; 3:1 v:v). After 2 h of stirring at rt, the reaction mixture was quenched by addition of a saturated aqueous solution of sodium thiosulfate (10 mL), then basified with a saturated aqueous solution of sodium hydrogen carbonate (10 mL), followed by stirring and extraction with CH2Cl2 (3 × 10 mL). The combined organic layers were washed with water (3 × 10 mL) and brine (10 mL), dried (anhydrous MgSO4), filtered and concentrated (aspirator). The residue was purified by PTLC, radial chromatography or column chromatography to furnish analytically pure product.

Reference： [1]Betterley, Nolan M.; Kongsriprapan, Sopanat; Chaturonrutsamee, Suppisak; Deelertpaiboon, Pramchai; Surawatanawong, Panida; Pohmakotr, Manat; Soorukram, Darunee; Reutrakul, Vichai; Kuhakarn, Chutima [Synthesis, 2018, vol. 50, # 10, p. 2033 - 2040]

15
[ 1535-67-7 ]
[ 151-10-0 ]
[ 613-45-6 ]

Yield	Reaction Conditions	Operation in experiment
78%	Stage #1: difluoromethyl phenyl sulfide; 1,3-Dimethoxybenzene With tin(IV) chloride In dichloromethane at 20℃; for 2h; Inert atmosphere; Stage #2: With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In water; dimethyl sulfoxide at 20℃; for 2h;	Aldehydes 4 and 8; General Procedure General procedure: In a round-bottomed flask equipped with a stirring bar and rubber septum was placed a 1 M solution of SnCl4 in anhydrous CH2Cl2 (1 mL, 1 mmol). To this solution was added PhSCF2H (1; 240.2 mg, 1.5 mmol) in anhydrous CH2Cl2 (1.5 mL), followed by a solution of an aromatic compound (0.5 mmol) in anhydrous CH2Cl2 (1 mL). The reaction was allowed to proceed for 2 h before it was quenched with a solution of IBX (140 mg, 0.5 mmol) in DMSO/H2O (4 mL; 3:1 v:v). After 2 h of stirring at rt, the reaction mixture was quenched by addition of a saturated aqueous solution of sodium thiosulfate (10 mL), then basified with a saturated aqueous solution of sodium hydrogen carbonate (10 mL), followed by stirring and extraction with CH2Cl2 (3 × 10 mL). The combined organic layers were washed with water (3 × 10 mL) and brine (10 mL), dried (anhydrous MgSO4), filtered and concentrated (aspirator). The residue was purified by PTLC, radial chromatography or column chromatography to furnish analytically pure product.

16
[ 93-04-9 ]
[ 1535-67-7 ]
[ 5392-12-1 ]