[ CAS No. 2923-18-4 ] {[proInfo.proName]}

Name: 2923-18-4|Sodium 2,2,2-trifluoroacetate|98%
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Quality Control of [ 2923-18-4 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

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Product Details of [ 2923-18-4 ]

CAS No. :	2923-18-4	MDL No. :	MFCD00013217
Formula :	C₂F₃NaO₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	UYCAUPASBSROMS-UHFFFAOYSA-M
M.W :	136.01	Pubchem ID :	517019
Synonyms :

Calculated chemistry of [ 2923-18-4 ]

Physicochemical Properties

Num. heavy atoms :	8
Num. arom. heavy atoms :	0
Fraction Csp3 :	0.5
Num. rotatable bonds :	1
Num. H-bond acceptors :	5.0
Num. H-bond donors :	0.0
Molar Refractivity :	11.75
TPSA :	40.13 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	Yes
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-6.48 cm/s

Lipophilicity

Log Po/w (iLOGP) :	-7.91
Log Po/w (XLOGP3) :	0.91
Log Po/w (WLOGP) :	0.56
Log Po/w (MLOGP) :	0.27
Log Po/w (SILICOS-IT) :	0.93
Consensus Log Po/w :	-1.05

Druglikeness

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

Water Solubility

Log S (ESOL) :	-1.19
Solubility :	8.77 mg/ml ; 0.0645 mol/l
Class :	Very soluble
Log S (Ali) :	-1.34
Solubility :	6.24 mg/ml ; 0.0459 mol/l
Class :	Very soluble
Log S (SILICOS-IT) :	-0.08
Solubility :	112.0 mg/ml ; 0.826 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.0

Safety of [ 2923-18-4 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 2923-18-4 ]

* 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 [ 2923-18-4 ]
Downstream synthetic route of [ 2923-18-4 ]

[ 2923-18-4 ] Synthesis Path-Upstream 1~8

1
[ 109-04-6 ]
[ 2923-18-4 ]
[ 368-48-9 ]

Reference： [1] Chemistry Letters, 1981, p. 1719 - 1720

2
[ 2923-18-4 ]
[ 4595-60-2 ]
[ 116470-67-8 ]

Reference： [1] Journal of Organic Chemistry, 2015, vol. 80, # 5, p. 2676 - 2699
[2] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1988, p. 921 - 926

3
[ 2923-18-4 ]
[ 104-87-0 ]
[ 446-65-1 ]

Reference： [1] Journal of Fluorine Chemistry, 2005, vol. 126, # 6, p. 937 - 940
[2] Tetrahedron Letters, 2005, vol. 46, # 18, p. 3161 - 3164

4
[ 7745-93-9 ]
[ 2923-18-4 ]
[ 89976-12-5 ]

Reference： [1] Patent: EP1840122, 2007, A1, . Location in patent: Page/Page column 12-13

5
[ 2923-18-4 ]
[ 2966-50-9 ]

Yield	Reaction Conditions	Operation in experiment
1.5 g	at 20℃;	3.4 g of sodium trifluoroacetate was dissolved in 6 g of water to prepare an aqueous solution. An aqueous solution prepared by dissolving 3.39 g of silver nitrate in 3 g of water was added thereto at room temperature. The resulting aqueous solution was extracted 10 times with 5 ml of diethyl ether and the combined extracts were dried over anhydrous magnesium sulfate. The magnesium sulfate was filtered off and the ether solution was concentrated on a rotary evaporator to precipitate a white solid. Further, the mixture was dried by heating on a rotary evaporator under reduced pressure at 50 ° C. for 2 hours to obtain 1.5 g of a white powder of silver trifluoroacetate.

Reference： [1] Patent: JP2018/52831, 2018, A, . Location in patent: Paragraph 0060

6
[ 138490-95-6 ]
[ 2923-18-4 ]
[ 138490-96-7 ]

Reference： [1] Journal of Medicinal Chemistry, 1992, vol. 35, # 3, p. 466 - 479
[2] Tetrahedron Letters, 2004, vol. 45, # 13, p. 2731 - 2733
[3] Patent: US2004/15015, 2004, A1, . Location in patent: Page 9-10

7
[ 112220-68-5 ]
[ 2923-18-4 ]
[ 75-05-8 ]
[ 72287-26-4 ]
[ 494829-03-7 ]
[ 494828-93-2 ]

Reference： [1] Journal of Organometallic Chemistry, 2002, vol. 658, # 1-2, p. 159 - 168

8
[ 51934-41-9 ]
[ 2923-18-4 ]
[ 898787-14-9 ]

Reference： [1] Organic and Biomolecular Chemistry, 2018, vol. 16, # 6, p. 913 - 918

[ 2923-18-4 ] Synthesis Path-Downstream 1~88

1
[ 507-52-8 ]
[ 2923-18-4 ]
[ 407-25-0 ]
[ 2266-38-8 ]

Reference： [1]Journal of the Chemical Society,1958,p. 3268,3278

2
[ 109-04-6 ]
[ 2923-18-4 ]
[ 368-48-9 ]

Reference： [1]Chemistry Letters,1981,p. 1719 - 1720

3
[ 400-53-3 ]
[ 2923-18-4 ]

Yield	Reaction Conditions	Operation in experiment
98%	With sodium trimethylsilanolate In tetrahydrofuran at 25℃; for 16h;

Reference： [1]Langanis, E. D.; Chenard, B. L. [Tetrahedron Letters, 1984, vol. 25, # 51, p. 5831 - 5834]

4
[ 18306-29-1 ]
[ 2923-18-4 ]
[ 400-53-3 ]

Yield	Reaction Conditions	Operation in experiment
80%	at 170 - 200℃;

Reference： [1]Voronkov, M. G.; Roman, V. K.; Maletina, E. A. [Synthesis, 1982, # 4, p. 277 - 280]

6
[ 624-38-4 ]
[ 2923-18-4 ]
[ 433-19-2 ]

Reference： [1]Journal of the Chemical Society. Perkin transactions I,1988,p. 921 - 926

7
[ 624-38-4 ]
[ 2923-18-4 ]
[ 433-19-2 ]
[ 455-13-0 ]

Reference： [1]Journal of the Chemical Society. Perkin transactions I,1988,p. 921 - 926

8
[ 696-62-8 ]
[ 2923-18-4 ]
[ 402-52-8 ]

Reference： [1]Chemistry Letters,1981,p. 1719 - 1720

9
[ 455-13-0 ]
[ 2923-18-4 ]
[ 433-19-2 ]

Reference： [1]Journal of the Chemical Society. Perkin transactions I,1988,p. 921 - 926

10
[ 138490-95-6 ]
[ 2923-18-4 ]
[ 138490-96-7 ]

Yield	Reaction Conditions	Operation in experiment
	With copper(l) iodide; In 1-methyl-pyrrolidin-2-one; at 165 - 175℃; for 4.0h;	3,4-dimethoxy-2-(trifluoromethyl)benzaldehyde (8) was prepared according to methods known in the art. See Miller et al. (1992), Matsui et al. (1981) Chem. Lett. 1710-1720, which is herein incorporated by reference. Specifically, CUI (24.11 g, 126.6 mmol) and sodium trifluoroacetate (34.43 g, 253.2 mmol) was added to a solution of 2-iodo-3,4-dimethoxybenzaldehyde (7) (18.48 g, 63.31 mmol) in N-methyl-2-pyrrolidinone (360 ml, bp=81 C./10 mm) under anhydrous conditions. A 1000 ml single neck flask equipped with a stir bar and flowing Ar via an adapter was used. At 165 C. CO2 was liberated. Then the solution was heated to 175 C. for 4 hours followed by cooling to room temperature. The contents of the flask were added to 700 ml water with stirring. Then the mixture was stirred for 0.5 hour and then centrifuge at 25 C. at 3700 rpm for 15 minutes. The supernatant was decanted into a separatory funnel and extracted 3 times with 500 ml diethyl ether. The ether layers were combined and then washed with 500 ml brine. Flash chromatograph twice using CH2Cl2 (100%) followed by EtOAc/hexane (20/80) yielded 3,4-dimethoxy-2-(trifluoromethyl)benzaldehyde (8) as a yellow oil; MS m/z=234. 1H NMR (400 MHz) delta 10.28 (s, 1H), 7.81 (d, 1H, J=9.2 Hz), 7.16 (d, 1H, J=8.8 Hz), 3.98 (s, 3H), 3.91 (s, 3H). 13C NMR in CDCl3 (100.5 MHz) 189.0, 158.0, 148.0, 128.1, 126.0, 124.6 (q, J=30 Hz), 124.1 (q, J=275 Hz), 114.5, 61.8, 56.3. 19F (376.2 Mz) -51.9.

Reference： [1]Journal of Medicinal Chemistry,1992,vol. 35,p. 466 - 479
[2]Tetrahedron Letters,2004,vol. 45,p. 2731 - 2733
[3]Patent: US2004/15015,2004,A1 .Location in patent: Page 9-10

11
[ 402-43-7 ]
[ 2923-18-4 ]
[ 433-19-2 ]

Reference： [1]Journal of the Chemical Society. Perkin transactions I,1988,p. 921 - 926

12
[ 2923-18-4 ]
[ 4595-60-2 ]
[ 116470-67-8 ]

Reference： [1]Journal of Organic Chemistry,2015,vol. 80,p. 2676 - 2699
[2]Journal of the Chemical Society. Perkin transactions I,1988,p. 921 - 926

13
[ 2923-18-4 ]
[ 75833-63-5 ]
1-methyl-2-(trifluoromethyl)-1H-indole [ No CAS ]

Reference： [1]Heterocycles,1996,vol. 43,p. 1471 - 1475

14
[ 2923-18-4 ]
[ 62-53-3 ]
[ 404-24-0 ]

Reference： [1]Synthetic Communications,2000,vol. 30,p. 3189 - 3194

15
[ 74316-55-5 ]
[ 2923-18-4 ]
8-methyl-5-(trifluoromethyl)quninoline [ No CAS ]

Reference： [1]Tetrahedron,2005,vol. 61,p. 9696 - 9704

16
[ 2923-18-4 ]
[ 100-52-7 ]
[ 340-05-6 ]

Yield	Reaction Conditions	Operation in experiment
99.2%	Stage #1: sodium 2,2,2-trifluoroacetate; benzaldehyde With copper(l) iodide In N,N-dimethyl-formamide at 170℃; for 2h; Stage #2: With hydrogenchloride In N,N-dimethyl-formamide at 170℃; for 4h;
99.2 % Chromat.	Stage #1: sodium 2,2,2-trifluoroacetate; benzaldehyde In N,N-dimethyl-formamide at 170℃; for 2h; Stage #2: With hydrogenchloride In water; N,N-dimethyl-formamide at 170℃; for 4h;

Reference： [1]Chang, Ying; Cai, Chun [Journal of Fluorine Chemistry, 2005, vol. 126, # 6, p. 937 - 940]
[2]Chang, Ying; Cai, Chun [Tetrahedron Letters, 2005, vol. 46, # 18, p. 3161 - 3164]

17
[ 2923-18-4 ]
[ 98-88-4 ]
[ 340-05-6 ]
[ 718-64-9 ]

Yield	Reaction Conditions	Operation in experiment
1: 56.5% 2: 43.5%	Stage #1: sodium 2,2,2-trifluoroacetate; benzoyl chloride With copper(l) iodide In N,N-dimethyl-formamide Stage #2: With hydrogenchloride
1: 56.5 % Chromat. 2: 43.5 % Chromat.	Stage #1: sodium 2,2,2-trifluoroacetate; benzoyl chloride In N,N-dimethyl-formamide at 170℃; for 2h; Stage #2: With hydrogenchloride In water; N,N-dimethyl-formamide at 170℃;

Reference： [1]Chang, Ying; Cai, Chun [Journal of Fluorine Chemistry, 2005, vol. 126, # 6, p. 937 - 940]
[2]Chang, Ying; Cai, Chun [Tetrahedron Letters, 2005, vol. 46, # 18, p. 3161 - 3164]

18
[ 2923-18-4 ]
[ 67-64-1 ]
[ 507-52-8 ]

Reference： [1]Journal of Fluorine Chemistry,2005,vol. 126,p. 937 - 940

19
[ 7745-93-9 ]
[ 2923-18-4 ]
[ 89976-12-5 ]

Yield	Reaction Conditions	Operation in experiment
	With copper(l) iodide; In 1-methyl-pyrrolidin-2-one; at 160℃; for 4.0h;	Preparation of the intermediate 4-(4-methy(piperazin-1-yl)-3-(trifluoromethyl)aniline: To a solution of 2-bromo-4-nitrotoluene (23.2 mmol) in NMP (200 mL) was added sodium trifluoroacetate (8.5 g, 62.5 mmol) and CuI (8.75 g, 46 mmol) and the reaction mixture was stirred at 160C for 4 hours. The solution was cooled and water (300 mL) was added. The solution was filtrated and the solid was washed with ethyl ether (250 mL × 3). The organic phase was washed with water and brine, dried, filtered, concentrated and purified through column chromatography to give 2-(trifluoromethyl)- 4-nitrotoluene (3.12 g). To a mixture of the intermediate of the previous step (0.5 g, 2.44 mmol) and acetic acid (1.9 mL) was added NBS (0.651 g, 3.66 mmol) and benzoyl peroxide (6 mg, 0.024 mmol) and the reaction mixture was refluxed overnight. After the solution was cooled, the solvent was removed under reduced pressure. Ethyl acetate and saturated sodium bicarbonate solution were added and the organic phase was dried, filtered, concentrated to give a intermediate: 1-(bromomethyl)-4-nitro-2-(trifluoromethyl)benzene. To a mixture of the intermediate of the previous step (400 g) and CH2Cl2 (2800 mL) was added triethylamine (197 mL) and N-methylpiperazine (157 mL, 1.41 mmol) and the mixture was stirred at room temperature for 2 hours. Then saturated sodium bicarbonate solution was added and the organic phase was separated, dried, filtered, concentrated and purified through column chromatography to give a intermediate: 1-[4-nitro-2-(trifluoromethyl)benzyl]-4-methylpiperazine. To a flask was added the intermediate of the previous step (3.0 g), activated nickel (0.3 g) and methanol (100 mL), and then hydrogen was added to the mixture at atmospheric pressure till the starting material disappeared. Filtered, concentrated and purified through column chromatography to give 4-(4-methylpiperazin-1-yl)-3-(trifluoromethyl)aniline.

Reference： [1]Patent: EP1840122,2007,A1 .Location in patent: Page/Page column 12-13

20
[ 32024-15-0 ]
[ 2923-18-4 ]
3,4-dimethoxy-5-(trifluoromethyl)benzaldehyde [ No CAS ]

Reference： [1]Patent: US2004/15015,2004,A1 .Location in patent: Page 12

21
[ 6876-00-2 ]
[ 2923-18-4 ]
1-(m-phenoxy-phenyl)-2,2,2-trifluoro-ethanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With magnesium; In tetrahydrofuran; dichloromethane;	STEP A 1-(m-phenoxy-phenyl)-2,2,2-trifluoro-ethanone A few drops of m-phenoxy-bromobenzene were added to a mixture of 16.6 g of magnesium (50% turnings) in 53 ml of tetrahydrofuran and the mixture was heated to 40-45 C. Crystallization began and the rest of 62.2 g of m-phenoxy-bromobenzene was added dropwise at reflux over 45 minutes. 183 ml of tetrahydrofuran were added and the mixture was refluxed for one hour and was cooled to 0 C. to obtain a solution of a magnesium compound. The said solution was then added at 0 C. over 40 minutes to a mixture of 40.8 g of sodium trifluoroacetate in 240 ml of tetrahydrofuran and the mixture was stirred for two hours and was poured into aqueous 0.1N hydrochloric acid solution. The mixture was extracted with ether and the ether phase was washed with water, with aqueous N sodium hydroxide and with water. The ether phase was added to two liters of methylene chloride and the mixture was evaporated to dryness under reduced pressure to obtain 56.2 g of raw 1-(m-phenoxy-phenyl)-2,2,2-trifluoro-ethanone which was used as is for the next step.

Reference： [1]Patent: US4833163,1989,A

22
sodium hypobromide [ No CAS ]
[ 354-38-1 ]
[ 75-63-8 ]
[ 2923-18-4 ]

Reference： [1]Journal of the Chemical Society,
Journal of the Chemical Society,1957,p. 30 - 39
[2]Gmelin Handbuch der Anorganischen Chemie,Gmelin Handbook: F: PerFHalOrg.7, 1, page 1 - 84

23
[ 112220-68-5 ]
[ 2923-18-4 ]
[ 75-05-8 ]
[ 72287-26-4 ]
[ 494829-03-7 ]
[ 494828-93-2 ]

Reference： [1]Journal of Organometallic Chemistry,2002,vol. 658,p. 159 - 168

24
[ 123-03-5 ]
[ 2923-18-4 ]
[ 76-05-1 ]
[ 282109-43-7 ]

Yield	Reaction Conditions	Operation in experiment
	In methanol; ethanol; for 0.5h;	To a solution of sodium trifluoroacetate in methanol was added tnfluoroacetic acid The resulting methanolic solution of TFA-Na was then added dropwisely to the solution of <strong>[123-03-5]cetylpyridinium chloride</strong> in ethanol with stirring After 30 mm, precipitated NaCI was filtered off and evaporated with rotary evaporator (< 4O0C). The residue was dissolved in dichloromethane and insoluble components were filtered off. After evaporation, tert- buta?ol was added and lyophilized to obtain as a white crystal

Reference： [1]Patent: WO2008/92257,2008,A1 .Location in patent: Page/Page column 11

25
[ 913000-15-4 ]
[ 2923-18-4 ]
[ 913000-16-5 ]

Yield	Reaction Conditions	Operation in experiment
29%	With copper(l) iodide In N,N-dimethyl-formamide at 150℃; for 23h;	20.20B A mixture of (2,4-bis-benzyloxy-5-bromo-phenyl)-(1 ,3-dihydro-isoindol-2-yl)-methanone (491 mg, 0.95 mmol), sodium trifluoroacetate (649 mg, 4.8 mmol) and copper (I) iodide (364 mg, 1.91 mmol) were dried under vacuum (0.04 mbar) for 6 hours. The flask was flushed with nitrogen, DMF (5 rtiL) was added and the mixture heated at 150 0C for 17 hours. After cooling to r.t., the mixture was diluted with DCM (100 mL) and filtered through Celite, rinsing with DCM. The filtrate was concentrated to dryness and the residue was partially purified by flash chromatography on silica (ethyl acetate/petrol gradient, 0 - 20%). The purest fraction was recrystallised from methanol to afford the title compound as a white solid (140 mg, 29%). 1H NMR (methanol-d4) 7.60 (1 H, s), 7.48- 7.44 (2H, m), 7.40 (2H, t), 7.37-7.21 (m, 9H), 7.17 (1H1 d), 7.02 (1 H, s), 5.29 (2H, s), 5.24 (2H, S)1 4.88 (2H, s), 4.62 (2H, s). MS: [M+H]+ 504.
29%	With copper(l) iodide In N,N-dimethyl-formamide at 150℃; for 17h;	20.B A mixture of (2,4-bis-benzyloxy-5-bromo-phenyl)-(1,3-dihydro-isoindol-2-yl)-methanone (491 mg, 0.95 mmol), sodium trifluoroacetate (649 mg, 4.8 mmol) and copper (I) iodide (364 mg, 1.91 mmol) were dried under vacuum (0.04 mbar) for 6 hours. The flask was flushed with nitrogen, DMF (5 mL) was added and the mixture heated at 150 0C for 17 hours. After cooling to r.t., the mixture was diluted with DCM (100 mL) and filtered through Celite, rinsing with DCM. The filtrate was concentrated to dryness and the residue was partially purified by flash chromatography on silica (ethyl acetate/petrol gradient, 0 - 20%). The purest fraction was recrystallised from methanol to afford the title compound as a white solid (140 mg, 29%). 1H NMR (methanol-d4) 7.60 (1 H, s), 7.48- 7.44 (2H1 m), 7.40 (2H, t), 7.37-7.21 (m, 9H), 7.17 (1H, d), 7.02 (1 H, s), 5.29 (2H, s), 5.24 (2H, s), 4.88 (2H, s), 4.62 (2H, s). MS: [M+H]+ 504.
29%	With copper(l) iodide In N,N-dimethyl-formamide at 150℃; for 17h;	20.B A mixture of (2,4-bis-benzyloxy-5-bromo-phenyl)-(1 ,3-dihydro-isoindol-2-yl)-methanone (491 mg, 0.95 mmol), sodium trifluoroacetate (649 mg, 4.8 mmol) and copper (I) iodide (364 mg, 1.91 mmol) were dried under vacuum (0.04 mbar) for 6 hours. The flask was flushed with nitrogen, DMF (5 mL) was added and the mixture heated at 150 0C for 17 hours. After cooling to r.t., the mixture was diluted with DCM (100 mL) and filtered through Celite, rinsing with DCM. The filtrate was concentrated to dryness and the residue was partially purified by flash chromatography on silica (ethyl acetate/petrol gradient, 0 - 20%). The purest fraction was recrystallised from methanol to afford the title compound as a white solid (140 mg, 29%). 1H NMR (methanol-d4) 7.60 (1 H1 s), 7.48- 7.44 (2H, m), 7.40 (2H1 1), 7.37-7.21 (m, 9H), 7.17 (1 H, d), 7.02 (1 H1 s), 5.29 (2H1 s), 5.24 (2H, s), 4.88 (2H, S)1 4.62 (2H1 s). MS: [M+H]+ 504.

29%	With copper(l) iodide In N,N-dimethyl-formamide at 150℃; for 17h;	20.20B A mixture of (2,4-bis-benzyloxy-5-bromo-phenyl)-(1 ,3-dihydro-isoindol-2-yl)-methanone (491 mg, 0.95 mmol), sodium trifluoroacetate (649 mg, 4.8 mmol) and copper (I) iodide (364 mg, 1.91 mmol) were dried under vacuum (0.04 mbar) for 6 hours. The flask was flushed with nitrogen, DMF (5 mL) was added and the mixture heated at 150 0C for 17 hours. After cooling to r.t, the mixture was diluted with DCM (100 mL) and filtered through Celite, rinsing with DCM. The filtrate was concentrated to dryness and the residue was partially purified by flash chromatography on silica (ethyl acetate/petrol gradient, 0 - 20%). The purest fraction was recrystallised from methanol to afford the title compound as a white solid (140 mg, 29%). 1H NMR (methanol-d4) 7.60 (1 H, s), 7.48- 7.44 (2H, m), 7.40 (2H, t), 7.37-7.21 (m, 9H), 7.17 (1H, d), 7.02 (1 H, s), 5.29 (2H, s), 5.24 (2H, s), 4.88 (2H, s), 4.62 (2H, s). MS: [M+H]+ 504
29%	With copper(l) iodide In N,N-dimethyl-formamide at 150℃; for 17h;	20.B 20B. A mixture of (2,4-bis-benzyloxy-5-bromo-phenyl)-(1,3-dihydro-isoindol-2-yl)-methanone (491 mg, 0.95 mmol), sodium trifluoroacetate (649 mg, 4.8 mmol) and copper (I) iodide (364 mg, 1.91 mmol) were dried under vacuum (0.04 mbar) for 6 hours. The flask was flushed with nitrogen, DMF (5 mL) was added and the mixture heated at 150° C. for 17 hours. After cooling to r.t., the mixture was diluted with DCM (100 mL) and filtered through Celite, rinsing with DCM. The filtrate was concentrated to dryness and the residue was partially purified by flash chromatography on silica (ethyl acetate/petrol gradient, 0-20%). The purest fraction was recrystallised from methanol to afford the title compound as a white solid (140 mg, 29%). 1H NMR (methanol-d4) 7.60 (1H, s), 7.48-7.44 (2H, m), 7.40 (2H, t), 7.37-7.21 (m, 9H), 7.17 (1H, d), 7.02 (1H, s), 5.29 (2H, s), 5.24 (2H, s), 4.88 (2H, s), 4.62 (2H, s). MS: [M+H]+ 504.

Reference： [1]Current Patent Assignee: OTSUKA HOLDINGS CO LTD - WO2008/44029, 2008, A1 Location in patent: Page/Page column 223-224
[2]Current Patent Assignee: OTSUKA HOLDINGS CO LTD - WO2008/44041, 2008, A1 Location in patent: Page/Page column 245-246
[3]Current Patent Assignee: OTSUKA HOLDINGS CO LTD - WO2008/44045, 2008, A1 Location in patent: Page/Page column 298
[4]Current Patent Assignee: OTSUKA HOLDINGS CO LTD - WO2008/44054, 2008, A2 Location in patent: Page/Page column 142
[5]Current Patent Assignee: OTSUKA HOLDINGS CO LTD - US2010/152184, 2010, A1 Location in patent: Page/Page column 87

26
[ 2923-18-4 ]
[ 100858-33-1 ]
[ 960508-13-8 ]

Yield	Reaction Conditions	Operation in experiment
92 - 94%		Sodium trifluoroacetate (1.34 g) was suspended in toluene (8.9 g), DFI (1.34 g) was added dropwise thereto at room temperature, and the mixture was stirred at room temperature for 1 hour. Subsequently, <strong>[100858-33-1](R)-N-benzyloxycarbonyl-3-hydroxypyrrolidine</strong> (hereinafter abbreviated as R-CHP) (1.81 g) was added thereto. The reaction solution was stirred at room temperature for 1 hour, and then at 50 C for 2 hours. To the reaction solution was added toluene (20 g), and the mixture was added dropwise to an ice-cooled, 5 wt% aqueous sodium hydrogen carbonate solution (25.2 g). The toluene layer was separated, and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was separated by filtration, and then the filtrate was concentrated under reduced pressure to obtain a target compound. Amount 2.92 g Yield 92% 1H-NMR (toluene-d8, 400 MHz) delta 7.20-6.98 (m, 5H), 5.08 (d, 1H, J=11.6 Hz), 4.93 (dd,1H, J=5.2,11.6 Hz), 4.65 (bs, 1H), 3.42-3.02 (m, 4H), 1.40-1.28 (m, 1H), 1.28-1.15 (m, 1H) The stereoselectivity in the reaction was determined by dissolving the obtained compound in toluene (10 ml), and stirring it in a 1 N-aqueous NaOH solution (20 ml) at room temperature for 30 min to derive a corresponding (S)-N-benzyloxycarbonyl-3-hydroxypyrrolidine (hereinafter abbreviated as S-CHP), and using the peak area ratio of S-CHP and R-CHP under an HPLC analysis condition 6. S-CTFAP:R-CTFAP=97:3 HPLC analysis condition 6 Chiral column used DAICEL CHIRALPACK AD-H Eluent hexane/2-propanol=95/5 Flow rate 1 ml/min Detection wavelength UV 210 nm Column temperature 35C; [Example 28] Preparation of S-CTFAP [Show Image] Sodium trifluoroacetate (1.34 g) was suspended in toluene (8. 9 g), and DFI (1.34 g) was added dropwise thereto at 0C. The mixture was stirred at 0C for 1 hour, and then R-CHP (1.81 g) was added thereto. The reaction solution was stirred at 0C for 1 hour, and then at 50C for 2 hours. To the reaction solution was added toluene (20 g), and the mixture was added dropwise to an ice-cooled, 5 wt% aqueous sodium hydrogen carbonate solution (25.2 g). The toluene layer was separated, and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was separated by filtration, and then the filtrate was concentrated under reduced pressure to obtain a target compound. Amount 2.98 g Yield 94% 1H-NMR (toluene-d8, 400 MHz) was consistent with that in Example 27. The stereoselectivity in the reaction was determined in the same method as in Example 27. S-CTFAP:R-CTFAP=99.8:0.2
84%		Sodium trifluoroacetate (2.04 g) was suspended in toluene (10 g), and PPDA (3.35 g) was added dropwise thereto at 0C. The mixture was stirred at 0C for 1 hour, and then R-CHP (1.11 g) was added thereto. The reaction solution was stirred at 0C for 1 hour, and then at 50 C for 2 hours. To the reaction solution was added toluene (20 g), and the mixture was added dropwise to an ice-cooled, 5 wt% aqueous sodium hydrogen carbonate solution (38 g). The toluene layer was separated, and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was separated by filtration, and then the filtrate was concentrated under reduced pressure to obtain a target compound. Amount 1.63 g Yield 84% 1H-NMR (toluene-d8, 400 MHz) was consistent with that in Example 27. The stereoselectivity in the reaction was determined in the same method as in Example 27. S-CTFAP:R-CTFAP=96:4
80%		Sodium trifluoroacetate (2.04 g) was suspended in toluene (10 g), and BDDF (2.07 g) was added dropwise thereto at 0C. The mixture was stirred at 0C for 1 hour, and then R-CHP (1.11 g) was added thereto. The reaction solution was stirred at 0C for 1 hour, and then at 50 C for 2 hours. To the reaction solution was added toluene (20 g), and the mixture was added dropwise to an ice-cooled, 5 wt% aqueous sodium hydrogen carbonate solution (38 g). The toluene layer was separated, and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was separated by filtration, and then the filtrate was concentrated under reduced pressure to obtain a target compound. Amount 1.55 g Yield 80% 1H-NMR (toluene-d8, 400 MHz) was consistent with that in Example 27. The stereoselectivity in the reaction was determined in the same method as in Example 27. S-CTFAP:R-CTFAP=94:6

Reference： [1]Patent: EP2039680,2009,A1 .Location in patent: Page/Page column 41-43
[2]Patent: EP2039680,2009,A1 .Location in patent: Page/Page column 43-44
[3]Patent: EP2039680,2009,A1 .Location in patent: Page/Page column 45

27
[ 106-38-7 ]
[ 2923-18-4 ]
[ 6140-17-6 ]

Reference： [1]Journal of Fluorine Chemistry,2010,vol. 131,p. 1108 - 1112

28
[ 2923-18-4 ]
[ 171058-17-6 ]
[ 367522-97-2 ]

Reference： [1]Chemical Communications,2011,vol. 47,p. 3222 - 3224

29
[ 1006-47-9 ]
[ 2923-18-4 ]
[ 317-57-7 ]

Reference： [1]Synlett,2011,p. 1713 - 1716

30
[ 51934-41-9 ]
[ 2923-18-4 ]
[ 583-02-8 ]

Reference： [1]Synlett,2011,p. 1713 - 1716

31
[ 2974-94-9 ]
[ 2923-18-4 ]
[ 2367-02-4 ]

Reference： [1]Synlett,2011,p. 1713 - 1716

32
[ 5182-67-2 ]
[ 2923-18-4 ]
[ 2341-35-7 ]

Yield	Reaction Conditions	Operation in experiment
72%	With copper(l) iodide In 1-methyl-pyrrolidin-2-one at 20 - 165℃; for 22h; Inert atmosphere;	1 With reference to Compound 3 of FIG. 4, an exemplary synthesis and characterization of ] ,2-bis(trifluoromethyl)-4,5-dimethylbenzene (hereinafter "Compound 3") is depicted. In particular, dry sodium trifluoroacetate (about 21 .8 g, 0.16 mol) and copper iodide (about 30.5 g, 0.16 mol) is mixed in about 150 mL dry NMP. To this suspension, a solution of Compound 2 (about 7.2 g, 0.02 mol) in about 50 mL dry NMP is added under stirring at approximately room temperature. The reaction mixture is then heated under nitrogen and kept at about 165 °C for about 22 h. Evolution of C02 may be monitored with an oil bubbler. After cooling, the mixture is poured into about 500 mL of hexanes, stirred intensively for about 30 min and allowed to settle. The upper hexane phase is filtered over silica gel, washed with water (about 3 χ 150 mL) and then dried over MgSC¼, filtered off and evaporated under reduced pressure until about 150 mL remain. This solution is further separated by flash chromatography with hexanes over silica gel. The product is collected as the top fraction. Careful removal of the solvent under a nitrogen stream followed by standing in the freezer for approximately 30 min allowed for separation of Compound 3 as colorless crystals in about 72% yield (about 3.5 g).[0068] Specifically, the exemplary properties of Compound 3 are as follows: Mp: 38-39 °C (taught by prior literature as ranging from 38- 40 °C (see, e.g., Pawlowski, G. et al., Synthetic Communications, 1 1, 351 (1981 ) and Chambers, R. D. et al., Tetrahedron, 54, 4949, (1998))); fH NMR (300 MHz, CDC ): δ 2.37 (6H, s, C¾), 7.58 (2H, s, Ph-H); 19F NMR (282 MHz, CDC13): δ -59.58 (6F, s, CF3).

Reference： [1]Current Patent Assignee: GOVERNMENT OF THE UNITED STATES - WO2012/61344, 2012, A1 Location in patent: Page/Page column 10

33
(1'S,3'S,6'R)-methyl 3'-acetyloxy-7-iodo-2',2',6'-trimethyl-3H-spiro[1-benzofuran-2,1'-cyclohexane]-5-carboxylate [ No CAS ]
[ 2923-18-4 ]
(1'S,3'S,6'R)-methyl 3'-acetyloxy-7-trifluoromethyl-2',2',6'-trimethyl-3H-spiro[1-benzofuran-2,1'-cyclohexane]-5-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With copper(l) iodide In 1-methyl-pyrrolidin-2-one at 180℃; for 1.5h; Inert atmosphere;	10 5.1.10 5.1.10(1'S,3'S,6'R)-Methyl 3'-acetyloxy-7-trifluoromethyl-2',2',6'-trimethyl-3H-spiro[1-benzofuran-2,1'-cyclohexane]-5-carboxylate (19) CuI (71.9 mg, 0.657 mmol) and NaCF3CO2 (102 mg, 0.75 mmol) were added to a solution of iodide 16 (48 mg, 0.102 mmol) in anhydrous NMP (0.6 mL). The slurry was purged with dry argon and placed in an oil bath pre-heated at 180 °C during 1.5 h. The product was chromatographed yielding 19 (45.4 mg, 85%) as an oil. = +8.7 (c 1.1, CHCl3). 1H NMR (CDCl3): δ 0.78 (d, 3H, J = 6.6), 0.88 (s, 3H), 1.24 (s, 3H), 1.37-1.71 (m, 3H), 1.87-1.99 (m, 1H), 2.11 (s, 3H), 2.36-2.44 (m, 1H), 3.11 (d, 1H, J = 17.7), 3.53 (d, 1H, J = 17.7), 3.89 (s, 3H), 4.86 (t, 1H, J = 2.8), 7.97 (s, 1H) and 8.05 (s, 1H). 13C NMR (CDCl3): δ 14.8, 20.3, 21.2, 22.0, 25.9, 26.3, 28.9, 30.2, 35.6, 42.0, 52.1, 78.9, 98.8, 111.1 (q, J = 33.7, ArCF3), 121.9, 127.5 (q, J = 4.6, ArCF3), 129.1, 131.0, 160.9, 166.1 and 169.9. HRMS (ESI) found: 437.1532 [M + Na]+; C21H25F3NaO5 requires 437.1546.

Reference： [1]Larghi, Enrique L.; Kaufman, Teodoro S.; Operto, Maria A.; Torres, Rene [European Journal of Medicinal Chemistry, 2012, vol. 55, p. 74 - 84,11]

34
[ 2923-18-4 ]
[ 123324-71-0 ]
[ 80783-57-9 ]

Yield	Reaction Conditions	Operation in experiment
52%	With potassium phosphate; 1,10-Phenanthroline; copper(I) thiocyanate; sulfur; silver carbonate In N,N-dimethyl-formamide at 130℃; for 24h; Inert atmosphere; Sealed tube; Glovebox;	4.2. General procedure for synthesis of aryl trifluoromethylthioethers General procedure: In a glovebox, to a test tube equipped with a magnetic stir bar, aryl boronic acid 1 (0.2 mmol), CuSCN (24.1 mg, 0.2 mmol, 1 equiv), 1,10-phenanthroline (36.0 mg, 0.2 mmol, 1 equiv), S8 (19.2 mg, 0.6 mmol, 3.0 equiv), CF3CO2Na (136 mg, 1.0 mmol, 5 equiv), Ag2CO3 (110 mg, 0.4 mmol, 2.0 equiv), K3PO4 (127 mg, 0.6 mmol, 3.0 equiv), and DMF(4 mL) were added. The vessel was sealed with a septum and taken out from the glovebox. The mixture was stirred vigorously at 130 °C for 24 h. Phenyl trifluoromethyl sulfide (35.6 mg, 0.2 mmol) was added as an internal standard, and the yield of the crude reaction was measured by 19F NMR before workup. The reaction solution was filtered through Celite on silica and the filter cake was washed with diethyl ether. The filtrate was then washed with brine and concentrated. The residue was purified by silica gel column chromatography with petroleum ether to provide pure aryl trifluoromethyl thioether.

Reference： [1]Zhai, Lijuan; Li, Yaming; Yin, Jun; Jin, Kun; Zhang, Rong; Fu, Xinmei; Duan, Chunying [Tetrahedron, 2013, vol. 69, # 48, p. 10262 - 10266]

35
[ 5122-94-1 ]
[ 2923-18-4 ]
[ 177551-63-2 ]

Yield	Reaction Conditions	Operation in experiment
68%	With potassium phosphate; 1,10-Phenanthroline; copper(I) thiocyanate; sulfur; silver carbonate In N,N-dimethyl-formamide at 130℃; for 24h; Inert atmosphere; Sealed tube; Glovebox;	4.2. General procedure for synthesis of aryl trifluoromethylthioethers General procedure: In a glovebox, to a test tube equipped with a magnetic stir bar, aryl boronic acid 1 (0.2 mmol), CuSCN (24.1 mg, 0.2 mmol, 1 equiv), 1,10-phenanthroline (36.0 mg, 0.2 mmol, 1 equiv), S8 (19.2 mg, 0.6 mmol, 3.0 equiv), CF3CO2Na (136 mg, 1.0 mmol, 5 equiv), Ag2CO3 (110 mg, 0.4 mmol, 2.0 equiv), K3PO4 (127 mg, 0.6 mmol, 3.0 equiv), and DMF(4 mL) were added. The vessel was sealed with a septum and taken out from the glovebox. The mixture was stirred vigorously at 130 °C for 24 h. Phenyl trifluoromethyl sulfide (35.6 mg, 0.2 mmol) was added as an internal standard, and the yield of the crude reaction was measured by 19F NMR before workup. The reaction solution was filtered through Celite on silica and the filter cake was washed with diethyl ether. The filtrate was then washed with brine and concentrated. The residue was purified by silica gel column chromatography with petroleum ether to provide pure aryl trifluoromethyl thioether.

Reference： [1]Zhai, Lijuan; Li, Yaming; Yin, Jun; Jin, Kun; Zhang, Rong; Fu, Xinmei; Duan, Chunying [Tetrahedron, 2013, vol. 69, # 48, p. 10262 - 10266]

36
[ 5720-05-8 ]
[ 2923-18-4 ]
[ 352-68-1 ]

Yield	Reaction Conditions	Operation in experiment
50%	With potassium phosphate; 1,10-Phenanthroline; copper(I) thiocyanate; sulfur; silver carbonate In N,N-dimethyl-formamide at 130℃; for 24h; Inert atmosphere; Sealed tube; Glovebox;	4.2. General procedure for synthesis of aryl trifluoromethylthioethers General procedure: In a glovebox, to a test tube equipped with a magnetic stir bar, aryl boronic acid 1 (0.2 mmol), CuSCN (24.1 mg, 0.2 mmol, 1 equiv), 1,10-phenanthroline (36.0 mg, 0.2 mmol, 1 equiv), S8 (19.2 mg, 0.6 mmol, 3.0 equiv), CF3CO2Na (136 mg, 1.0 mmol, 5 equiv), Ag2CO3 (110 mg, 0.4 mmol, 2.0 equiv), K3PO4 (127 mg, 0.6 mmol, 3.0 equiv), and DMF(4 mL) were added. The vessel was sealed with a septum and taken out from the glovebox. The mixture was stirred vigorously at 130 °C for 24 h. Phenyl trifluoromethyl sulfide (35.6 mg, 0.2 mmol) was added as an internal standard, and the yield of the crude reaction was measured by 19F NMR before workup. The reaction solution was filtered through Celite on silica and the filter cake was washed with diethyl ether. The filtrate was then washed with brine and concentrated. The residue was purified by silica gel column chromatography with petroleum ether to provide pure aryl trifluoromethyl thioether.

Reference： [1]Zhai, Lijuan; Li, Yaming; Yin, Jun; Jin, Kun; Zhang, Rong; Fu, Xinmei; Duan, Chunying [Tetrahedron, 2013, vol. 69, # 48, p. 10262 - 10266]

37
4-(3-{2-[(tert-butoxycarbonyl)amino]ethyl}ureido)-1-methyl-5-triphenylmethylaminopyrazole [ No CAS ]
(6R,7R)-4-methoxybenzyl 3-(chloromethyl)-7-((Z)-(2-hydroxybenzylidene)amino)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate [ No CAS ]
[ 2923-18-4 ]
C₅₄H₅₇N₈O₈S⁽¹⁺⁾*C₂F₃O₂^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86.5%	Stage #1: 4-(3-{2-[(tert-butoxycarbonyl)amino]ethyl}ureido)-1-methyl-5-triphenylmethylaminopyrazole; (6R,7R)-4-methoxybenzyl 3-(chloromethyl)-7-((Z)-(2-hydroxybenzylidene)amino)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate With N,O-bis-(trimethylsilyl)-acetamide; potassium iodide In 1-methyl-pyrrolidin-2-one at 15 - 25℃; Stage #2: sodium 2,2,2-trifluoroacetate In 1-methyl-pyrrolidin-2-one at 20℃; for 3h;	1.2 (2) Synthesis of Compound (III-1) (2) Synthesis of Compound (III-1) 5-amino-4-(3-(2-((tert-butoxycarbonyl)amino)ethyl)ureido)-2-(((6R,7R)-7-((Z)-(2-hydroxybenzylidene)amino)-2-(((4-methoxybenzyl)oxy)carbonyl)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-en-3-yl)methyl)-1-methyl-1H-pyrazol-2-ium trifluoroacetate Compound (III-1) was prepared by coupling the compound (6R,7R)-4-methoxybenzyl 3-(chloromethyl)-7-((Z)-(2-hydroxybenzylidene)amino)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate (purchased from Nippon Chemicals, Japan) with the compound tert-butyl (2-(3-(1-methyl-5-(tritylamino)-1H-pyrazol-4-yl)ureido)ethyl)carbamate (UBT, prepared according to the method disclosed in U.S. Pat. No. 7,129,232). In a reactor, UBT (274 g) was dissolved in 1 L of N-methylpyrrolidone (NMP) at 35-45° C. The solution was cooled to 15-20° C. SCLE (200 g) was added to the solution and stirred until it was completely dissolved. Then added 104 mL of N,O-Bis(trimethylsilyl)acetamide (BSA) dropwise in 30 minutes, followed by addition of 98.2 g potassium iodide (KI) in 6-8 portions, and maintained the temperature between 20-25° C. The resulting mixture was stirred at 15-25° C. for about 45-50 hours. The forgoing solution was then slowly added to 5% sodium trifluoro acetate (4 L) at room temperature in 3 hours and precipitates were formed. The slurry was filtered and washed with 2 L deionized water for 4 times, and 4 L of heptanes for 3 times. The wet cake was dried under nitrogen with vacuum until it reached a constant weight. The resulting compound (III-1) was isolated as a light yellow solid (569 g, 86.5%). Exact Mass (-TFA):977.40. HRMS:977.4025 (M+).

Reference： [1]Current Patent Assignee: MERCK & CO INC - US2014/274958, 2014, A1 Location in patent: Paragraph 0126-0128

38
1-butyl-3-(4-phenoxybutyl)-1H-imidazol-3-ium bromide [ No CAS ]
[ 2923-18-4 ]
1-butyl-3-(4-phenoxybutyl)-1H-imidazol-3-ium trifluroacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	In acetonitrile at 70℃; for 0.75h; Sonication; Green chemistry;	General procedure for the ultrasound-assisted methathesis reaction of (8-11) leading to compounds(13-36) General procedure: Imidazolium-halides salts (1 eq) and NaBF4, KPF6, CF3COONa, NaN(CN)2, NaNCS or NaNO3 (1 eq) were placed in a closed vessel and exposed to irradiation for 45 min at 70 °C using a sonication bath. The product was then collected as described in the conventional procedure outlined earlier.

Reference： [1]Messali, Mouslim; Aouad, Mohamed R.; El-Sayed, Wael S.; Ali, Adeeb Al-Sheikh; Hadda, Taibi Ben; Hammouti, Belkheir [Molecules, 2014, vol. 19, # 8, p. 11741 - 11759]

39
1-pentyl-3-(4-phenoxybutyl)-1H-imidazol-3-ium bromide [ No CAS ]
[ 2923-18-4 ]
1-pentyl-3-(4-phenoxybutyl)-1H-imidazol-3-ium trifluroacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	In acetonitrile at 70℃; for 0.75h; Sonication; Green chemistry;	General procedure for the ultrasound-assisted methathesis reaction of (8-11) leading to compounds(13-36) General procedure: Imidazolium-halides salts (1 eq) and NaBF4, KPF6, CF3COONa, NaN(CN)2, NaNCS or NaNO3 (1 eq) were placed in a closed vessel and exposed to irradiation for 45 min at 70 °C using a sonication bath. The product was then collected as described in the conventional procedure outlined earlier.

Reference： [1]Messali, Mouslim; Aouad, Mohamed R.; El-Sayed, Wael S.; Ali, Adeeb Al-Sheikh; Hadda, Taibi Ben; Hammouti, Belkheir [Molecules, 2014, vol. 19, # 8, p. 11741 - 11759]

40
1-hexyl-3-(4-phenoxybutyl)-1H-imidazol-3-ium bromide [ No CAS ]
[ 2923-18-4 ]
1-hexyl-3-(4-phenoxybutyl)-1H-imidazol-3-ium trifluroacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	In acetonitrile at 70℃; for 0.75h; Sonication; Green chemistry;	General procedure for the ultrasound-assisted methathesis reaction of (8-11) leading to compounds(13-36) General procedure: Imidazolium-halides salts (1 eq) and NaBF4, KPF6, CF3COONa, NaN(CN)2, NaNCS or NaNO3 (1 eq) were placed in a closed vessel and exposed to irradiation for 45 min at 70 °C using a sonication bath. The product was then collected as described in the conventional procedure outlined earlier.

Reference： [1]Messali, Mouslim; Aouad, Mohamed R.; El-Sayed, Wael S.; Ali, Adeeb Al-Sheikh; Hadda, Taibi Ben; Hammouti, Belkheir [Molecules, 2014, vol. 19, # 8, p. 11741 - 11759]

41
1-propyl-3-(4-phenoxybutyl)-1H-imidazol-3-ium bromide [ No CAS ]
[ 2923-18-4 ]
1-propyl-3-(4-phenoxybutyl)-1H-imidazol-3-ium trifluroacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
98%	In acetonitrile at 70℃; for 0.75h; Sonication; Green chemistry;	General procedure for the ultrasound-assisted methathesis reaction of (8-11) leading to compounds(13-36) General procedure: Imidazolium-halides salts (1 eq) and NaBF4, KPF6, CF3COONa, NaN(CN)2, NaNCS or NaNO3 (1 eq) were placed in a closed vessel and exposed to irradiation for 45 min at 70 °C using a sonication bath. The product was then collected as described in the conventional procedure outlined earlier.

Reference： [1]Messali, Mouslim; Aouad, Mohamed R.; El-Sayed, Wael S.; Ali, Adeeb Al-Sheikh; Hadda, Taibi Ben; Hammouti, Belkheir [Molecules, 2014, vol. 19, # 8, p. 11741 - 11759]

42
[ 2923-18-4 ]
4-(dimethylamino)-1-(2-hydroxyethyl)pyridinium bromide [ No CAS ]
4-(dimethylamino)-1-(2-hydroxyethyl)pyridinium trifluoroacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	In dichloromethane at 70℃; for 0.75h; Sonication; Green chemistry;	General procedure for the methathesis reaction of (1-6) leading to compounds (7-24) under ultrasound irradiation General procedure: The quaternary salt (0.3 g, 1 eq) was dissolved in in 10 mL of dichloromethane to obtain a clear solution. To this was added (1 eq) of sodium tetrafluoroborate, potassium hexafluorophosphate or sodium trifluoroacetate. The mixture were placed in a closed vessel and exposed to irradiation for 45 min at 70 °C using a sonication bath. The cooled reaction mixture was filtered through Celite to remove the solid metal halide. Evaporation of the dichloromethane quantitatively afforded the desired ionic liquids.

Reference： [1]Messali, Mouslim [Molecules, 2015, vol. 20, # 8, p. 14936 - 14949]

43
4-(dimethylamino)-1-(3-hydroxypropyl)pyridinium bromide [ No CAS ]
[ 2923-18-4 ]
4-(dimethylamino)-1-(3-hydroxypropyl)pyridinium trifluoroacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	In dichloromethane at 70℃; for 0.75h; Sonication; Green chemistry;	General procedure for the methathesis reaction of (1-6) leading to compounds (7-24) under ultrasound irradiation General procedure: The quaternary salt (0.3 g, 1 eq) was dissolved in in 10 mL of dichloromethane to obtain a clear solution. To this was added (1 eq) of sodium tetrafluoroborate, potassium hexafluorophosphate or sodium trifluoroacetate. The mixture were placed in a closed vessel and exposed to irradiation for 45 min at 70 °C using a sonication bath. The cooled reaction mixture was filtered through Celite to remove the solid metal halide. Evaporation of the dichloromethane quantitatively afforded the desired ionic liquids.

Reference： [1]Messali, Mouslim [Molecules, 2015, vol. 20, # 8, p. 14936 - 14949]

44
4-(dimethylamino)-1-(2-methoxyethyl)pyridinium bromide [ No CAS ]
[ 2923-18-4 ]
4-(dimethylamino)-1-(2-methoxyethyl)pyridinium trifluoroacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	In dichloromethane at 70℃; for 0.75h; Sonication; Green chemistry;	General procedure for the methathesis reaction of (1-6) leading to compounds (7-24) under ultrasound irradiation General procedure: The quaternary salt (0.3 g, 1 eq) was dissolved in in 10 mL of dichloromethane to obtain a clear solution. To this was added (1 eq) of sodium tetrafluoroborate, potassium hexafluorophosphate or sodium trifluoroacetate. The mixture were placed in a closed vessel and exposed to irradiation for 45 min at 70 °C using a sonication bath. The cooled reaction mixture was filtered through Celite to remove the solid metal halide. Evaporation of the dichloromethane quantitatively afforded the desired ionic liquids.

Reference： [1]Messali, Mouslim [Molecules, 2015, vol. 20, # 8, p. 14936 - 14949]

45
4-(dimethylamino)-1-(4-phenoxybutyl)pyridinium bromide [ No CAS ]
[ 2923-18-4 ]
4-(dimethylamino)-1-(4-phenoxybutyl)pyridinium trifluoroacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	In dichloromethane at 70℃; for 0.75h; Sonication; Green chemistry;	General procedure for the methathesis reaction of (1-6) leading to compounds (7-24) under ultrasound irradiation General procedure: The quaternary salt (0.3 g, 1 eq) was dissolved in in 10 mL of dichloromethane to obtain a clear solution. To this was added (1 eq) of sodium tetrafluoroborate, potassium hexafluorophosphate or sodium trifluoroacetate. The mixture were placed in a closed vessel and exposed to irradiation for 45 min at 70 °C using a sonication bath. The cooled reaction mixture was filtered through Celite to remove the solid metal halide. Evaporation of the dichloromethane quantitatively afforded the desired ionic liquids.

Reference： [1]Messali, Mouslim [Molecules, 2015, vol. 20, # 8, p. 14936 - 14949]

46
1-(3-cyanopropyl)-4-(dimethylamino)pyridinium chloride [ No CAS ]
[ 2923-18-4 ]
1-(3-cyanopropyl)-4-(dimethylamino)pyridinium trifluoroacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	In dichloromethane at 70℃; for 0.75h; Sonication; Green chemistry;	General procedure for the methathesis reaction of (1-6) leading to compounds (7-24) under ultrasound irradiation General procedure: The quaternary salt (0.3 g, 1 eq) was dissolved in in 10 mL of dichloromethane to obtain a clear solution. To this was added (1 eq) of sodium tetrafluoroborate, potassium hexafluorophosphate or sodium trifluoroacetate. The mixture were placed in a closed vessel and exposed to irradiation for 45 min at 70 °C using a sonication bath. The cooled reaction mixture was filtered through Celite to remove the solid metal halide. Evaporation of the dichloromethane quantitatively afforded the desired ionic liquids.

Reference： [1]Messali, Mouslim [Molecules, 2015, vol. 20, # 8, p. 14936 - 14949]

47
4-(dimethylamino)-1-(2-ethoxyethyl)pyridinium chloride [ No CAS ]
[ 2923-18-4 ]
4-(dimethylamino)-1-(2-ethoxyethyl)pyridinium trifluoroacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	In dichloromethane at 70℃; for 0.75h; Sonication; Green chemistry;	General procedure for the methathesis reaction of (1-6) leading to compounds (7-24) under ultrasound irradiation General procedure: The quaternary salt (0.3 g, 1 eq) was dissolved in in 10 mL of dichloromethane to obtain a clear solution. To this was added (1 eq) of sodium tetrafluoroborate, potassium hexafluorophosphate or sodium trifluoroacetate. The mixture were placed in a closed vessel and exposed to irradiation for 45 min at 70 °C using a sonication bath. The cooled reaction mixture was filtered through Celite to remove the solid metal halide. Evaporation of the dichloromethane quantitatively afforded the desired ionic liquids.

Reference： [1]Messali, Mouslim [Molecules, 2015, vol. 20, # 8, p. 14936 - 14949]

48
[ 2923-18-4 ]
[ 214360-58-4 ]
[ 658-75-3 ]

Yield	Reaction Conditions	Operation in experiment
2 %Spectr.	With potassium fluoride; copper(II) bis(trifluoromethanesulfonate) In acetonitrile at 25℃; for 16h; Sealed tube;	General Procedure for Cu-Mediated Nucleophile Scope of Potassium (4-Fluorophenyl) (1) Trifluoroborate or Potassium (4-Biphenyl)Trifluoroborate withTetraalkylammonium and Alkali Salts Potassium (4-fluorophenyl)trifluoroborate (1) (101 mg, 0.5 mmol, 1 equiv) or potassium(4-biphenyl)trifluoroborate (130 mg, 0.5 mmol, 1 equiv), Cu(OTf)2 (722 mg, 2 mmol, 4equiv) and tetraalkylammonium or alkali salt (2 mmol, 4 equiv) were weighed into a 20mL vial equipped with a magnetic stir bar. CH3CN (6 mL) was added, and the vial wassealed with a Teflon-lined cap. The reaction mixture was allowed to stir at roomtemperature for 16 h. For products that were isolated, the reactions were diluted withdiethyl ether or pentane (10 mL), and this solution was washed with water (3 x 10 mL).The organic layer was dried over MgSO4, filtered, and concentrated under vacuum. Theproducts were purified by column chromatography on silica gel. For product yieldsdetermined by 19F NMR spectroscopy, the crude reaction mixture was diluted withCH3CN, 1,3,5-trifluorobenzene was added as an internal standard, and the reaction wasanalyzed by 19F NMR spectroscopy.

Reference： [1]Schimler, Sydonie D.; Sanford, Melanie S. [Synlett, 2016, vol. 27, # 15, p. 2279 - 2284]

49
1-butyl-1-(2-cyano-ethyl)-azepanium bromide [ No CAS ]
[ 2923-18-4 ]
1-butyl-1-(2-cyano-ethyl)azepanium trifluoroacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	In dichloromethane at 20℃; for 24h;	3 2.3. 1-Butyl-1-(2-cyano-ethyl)azepanium trifluoroacetate [C4CNAzp][TFA] To a solution of [C4CNAzp][Br] (5 g, 17.27 mmol) in dichloromethane (25 mL), sodium trifluoroacetate (2.58 g, 19.0 mmol) was added and stirred at room temperature for 24 h. The precipitate formed was filtered off and the organic phase was washed several times with ice cold water. The dichloromethane was removed using rotary evaporator and the product obtained was further dried in vacuum oven at 50 °C for 24 h. The [C4CNAzp][TFA] obtained as a pale yellow solid. Yield = 5 g (89%). 1H NMR (DMSO, d6): δ = 0.90 (t, 3H), 1.35 (m, 2H), 1.78 (m, 6H), 1.22 (m, 4H), , 3.10 (m, 6H), 3.28 (m, 2H), 3.58 (m, 2H). 13C NMR (DMSO, d6): 12.4, 19.6, 21.9, 23.2, 26.4, 28. 1, 56.0, 60. 1, 62.3, 117.7. 128.3(q), 178.6. CHN elemental analysis: Calculated: C; 55.89, H; 7.82, N; 8.69. Experimental: C; 55.84, H; 7.89, N; 8.78.

Reference： [1]Lethesh, Kallidanthiyil Chellappan; Shah, Syed Nasir; Ayodele, Olumide Bolarinwa; Mutalib, M.I. Abdul; Uemura, Yoshimitsu [Journal of Molecular Liquids, 2016, vol. 221, p. 1140 - 1144]

50
[ 621-23-8 ]
[ 41252-97-5 ]
[ 2923-18-4 ]
4-methyl-3-nitrophenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2016,vol. 55,p. 15812 - 15815
Angew. Chem.,2016,vol. 128,p. 16044 - 16047,4

51
[ 621-23-8 ]
[ 41252-96-4 ]
[ 2923-18-4 ]
2-chloro-4-nitrophenyl (2,4,6-trimethoxyphenyl)iodonium trifluoroacetate [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2016,vol. 55,p. 15812 - 15815
Angew. Chem.,2016,vol. 128,p. 16044 - 16047,4

52
[ 7209-11-2 ]
[ 2923-18-4 ]
1-[4-(trifluoromethyl)thiophen-2-yl]ethanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
4.1 g	With copper(l) iodide; In 1-methyl-pyrrolidin-2-one; at 200℃; for 2.5h;	Preparation Example 31 To a mixture of <strong>[7209-11-2]1-(4-bromothiophen-2-yl)ethanone</strong> (20 g) and N-methylpyrrolidone (400 mL) were added sodium trifluoroacetate (140 g) and copper iodide (I) (100 g), followed by stirring at 200C for 2.5 hours. The reaction mixture was cooled to room temperature, water and ethyl acetate were added thereto, and the insoluble materials were separated by filtration over Celite. The organic layer of the filtrate was separated, washed with water and saturated brine, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane-ethyl acetate) and purified by basic silica gel column chromatography (hexane-ethyl acetate) to obtain 1-[4-(trifluoromethyl)thiophen-2-yl]ethanone (4.1 g) as an oil.

Reference： [1]Patent: EP3153511,2017,A1 .Location in patent: Paragraph 0171

53
8-iodonaphtho[2,3-b]thiophene-4,9-dione [ No CAS ]
[ 2923-18-4 ]
8-trifluoromethylnaphtho[2,3-b]thiophene-4,9-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
63%	With copper(l) iodide In N,N-dimethyl acetamide at 150℃; for 4h; Inert atmosphere;	5.1.1.4. 8-Trifluoromethylnaphtho[2,3-b]thiophene-4,9-dione (10) A solution of 9 (1.00 g, 2.94 mmol), sodium trifluoroacetate (11.80 mmol) and CuI (5.88 mmol) in N,N-dimethylacetamide (40 mL) was stirred under N2 at 150 °C for 4 h. Purification by chromatography afforded bright yellow crystals; 63% yield; mp 206 °C; 1H NMR (CDCl3) δ 8.57 (dd, J = 7.9, 1.3 Hz, 1H), 8.15 (dd, J = 7.9,1.3 Hz, 1H), 7.89 (t, J = 7.9 Hz, 1H), 7.76 (d, J = 5.1 Hz, 1H), 7.69 (d, J = 5.1 Hz, 1H); 19F NMR (CDCl3, 600 MHz) δ -59.53; FTIR 1670 cm-1; HRMS-ESI m/z [M + Na]+ calcd for C13H5F3O2S, 304.9855, found 304.9775; purity (HPLC) 99.73%. Anal. C13H5F3O2S (C, H).

Reference： [1]Lindenschmidt, Cathrin; Krane, Dirk; Vortherms, Silke; Hilbig, Lars; Prinz, Helge; Müller, Klaus [European Journal of Medicinal Chemistry, 2016, vol. 110, p. 280 - 290]

54
[ 2923-18-4 ]
[ 211434-29-6 ]
2,2'-bis(trifluoromethyl)-4,4',5,5'-tetramethylbiphenyl [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With copper(l) iodide In N,N-dimethyl-formamide; toluene at 150 - 170℃;	1b B. To the reaction flask was added 300 mL of N, N'-dimethylformamide, 80 mL of toluene, 50 g of 2,2'-dibromo-4,4 ', 5,5'-tetramethylbiphenyl, Copper 36g and sodium trifluoroacetate 73g, atmospheric distillation of most of the toluene, the temperature to 150 ~ 170 reaction to complete. Distillation recovery solvent, the material cooled to room temperature, slowly dripping into the water, stirring crystallization, filtration, washing. Ethanol was recrystallized to give 37.6 g of 2,2'-bis (trifluoromethyl) -4,4 ', 5,5'-tetramethylbiphenyl as a pale yellow solid in a yield of 80.0% and a purity of 98.0% HPLC), mp 113 ~ 115 ° C.

Reference： [1]Current Patent Assignee: JIANGSU SUNLIGHT PHARMACEUTICAL CHEMICAL MAT - CN106699709, 2017, A Location in patent: Paragraph 0022-0023

55
[ 3998-04-7 ]
[ 1212-08-4 ]
[ 2923-18-4 ]
9-(4,4,4-trifluoro-2-(phenylthio)butyl)-9H-carbazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
61%	With [4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridine-N1,N1′]bis{3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-κN]phenyl-κC}iridium(III) hexafluorophosphate In acetonitrile at 20℃; for 18h; Schlenk technique; Inert atmosphere; Irradiation;

Reference： [1]Kong, Weiguang; An, Hejun; Song, Qiuling [Chemical Communications, 2017, vol. 53, # 64, p. 8968 - 8971]

56
methyl (phenyl 3,5-dideoxy-2-thio-4-O-chloroacetyl-9-O-benzyl-5-trifluoroacetamido-D-glycero-β-D-galactononulopyranosid)onate [ No CAS ]
[ 2923-18-4 ]
methyl (phenyl 3,5-dideoxy-2-thio-4-O-chloroacetyl-7,8-di-O-trifluoroacetyl-9-O-benzyl-5-trifluoroacetamido-D-glycero-β-D-galactononulopyranosid)onate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
100%	With trifluoroacetic anhydride In dichloromethane at 20℃;	4.15. General procedure for trifluoroacetylation of compoundscontaining one or two OH groups General procedure: The starting material was dried in vacuo (0.1 Torr, 1 h), dissolved in anhydrous CH2Cl2 (1.5 mL per 0.1 mmol), then TFA2O (1.5 mL per0.1 mmol) was added followed by sodium trifluoroacetate (15.0 mgper 0.1 mmol, freshly dried in vacuo (0.1 Torr, 1 h) at 80 °C) was added. The mixture was stirred at room temperature (~20 °C) until complete consumption of the starting material (TLC monitoring).The reaction mixture was further processed as described above insection 4.14 to give trifluoroacetylated product (94% for 23, quantitative for 24). The obtained trifluoroacetylated thiosialosides were used in the sialylation reactions without further purification.

Reference： [1]Podvalnyy, Nikita M.; Malysheva, Nelly N.; Panova, Maria V.; Zinin, Alexander I.; Chizhov, Alexander O.; Orlova, Anna V.; Kononov, Leonid O. [Carbohydrate Research, 2017, vol. 451, p. 12 - 28]

57
methyl (phenyl 3,5-dideoxy-2-thio-4,8,9-tri-O-benzoyl-5-trifluoroacetamido-D-glycero-β-D-galactononulopyranosid)onate [ No CAS ]
[ 2923-18-4 ]
methyl (phenyl 3,5-dideoxy-2-thio-4,8,9-O-tri-O-benzoyl-7-O-trifluoroacetyl-5-trifluoroacetamido-D-glycero-β-D-galactononulopyranosid)onate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With trifluoroacetic anhydride In dichloromethane at 20℃;	4.15. General procedure for trifluoroacetylation of compoundscontaining one or two OH groups General procedure: The starting material was dried in vacuo (0.1 Torr, 1 h), dissolved in anhydrous CH2Cl2 (1.5 mL per 0.1 mmol), then TFA2O (1.5 mL per0.1 mmol) was added followed by sodium trifluoroacetate (15.0 mgper 0.1 mmol, freshly dried in vacuo (0.1 Torr, 1 h) at 80 °C) was added. The mixture was stirred at room temperature (~20 °C) until complete consumption of the starting material (TLC monitoring).The reaction mixture was further processed as described above insection 4.14 to give trifluoroacetylated product (94% for 23, quantitative for 24). The obtained trifluoroacetylated thiosialosides were used in the sialylation reactions without further purification.4.15.1. Data for methyl (phenyl 3,5-dideoxy-2-thio-4,8,9-O-tri-Obenzoyl-7-O-trifloroacetyl-5-trifluoroacetamido-D-glycero-β-Dgalacto-nonulopyranosid)onate (23)Rf 0.77 (benzene-EtOAc 8:1). [a]D23 96.1 (c 1.97, CHCl3). HR ESIMS: found m/z 900.1519 [M Na]. Calcd for C41H33F6NNaO12S:900.1520. 1H NMR (300 MHz, CDCl3, d, ppm, J, Hz): 2.43 (dd, 1H, H-3a, J3a,3e 13.9, J3a,4 11.7), 3.01 (dd, 1H, H-3e, J3e,3a 13.9, J3e,4 4.8), 3.67(s, 3H, OMe), 4.37 (dd, 1H, H-9a, J9a,9b 12.5, J9a,8 8.8), 4.40 (ddd, 1H,H-5, J5,6 10.6, J5,4 10.3, J5,NH 9.5), 4.82 (dd, 1H, H-9b, J9b,9a 12.5, J9b,82.4), 5.09 (dd, 1H, H-6, J6,5 10.6, J6,7 2.2), 5.42 (ddd, 1H, H-8, J8,9a 8.8,J8,7 1.8, J8,9b 2.4), 5.81 (dd, 1H, H-7, J7,8 1.8, J7,6 2.2), 6.02 (ddd, 1H, H-4, J4,3a 11.7, J4,5 10.3, J4,3e 4.8), 7.04e7.09 (m, 1H, Ph), 7.15e7.20 (m,2H, Ph), 7.34 (d, 1H, NH, JNH,5 9.5), 7.37e7.65 (m, 11H, Ph), 7.87e7.90(m, 2H, Ph), 7.98e8.05 (m, 4H, Ph). 13C NMR (75 MHz, CDCl3, d, ppm,J, Hz): 37.6 (C-3), 50.4 (C-5), 52.9 (OMe), 62.5 (C-9), 69.2 (C-4), 72.1(C-6), 73.0 (C-8), 73.8 (C-7), 88.8 (C-2),114.4 (q, CF3, JC,F 285.8),115.2(q, CF3, JC,F 288.0), 127.9, 128.3, 128.6, 128.8, 129.0, 129.3, 129.5,129.7, 129.8, 129.9, 130.1, 133.1, 133.7, 134.1, 136.1 (Ph), 156.7 (q,OCOCF3, JC,F 43.7), 158.0 (q, NHCOCF3, JC,F 38.7), 165.6, 166.3, 167.3,167.9 (COPh, COOMe). 19F NMR (282 MHz, CDCl3, d,ppm): 77.04, 75.14.

58
[ 51934-41-9 ]
[ 2923-18-4 ]
[ 898787-14-9 ]
ethyl 4-(2,2,2-trifluoro-1,1-dihydroxyethyl)benzoate [ No CAS ]

Reference： [1]Organic and Biomolecular Chemistry,2018,vol. 16,p. 913 - 918

59
[ 76-05-1 ]
[ 2923-18-4 ]

Yield	Reaction Conditions	Operation in experiment
66%	With sodium carbonate In water at 20℃; for 0.5h;	4.8 Alkali metal trifluoroacetates preparation General procedure: Anhydrous trifluoroacetic acid (1.7ml, 22mmol, 10% excess) was added to water solution (50ml) of alkali metal carbonate (10mmol of Li2CO3, Na2CO3, K2CO3, or Cs2CO3) at room temperature and stirred for 30min. Then the solvent was removed using rotary evaporator at 60° at 40mbar. Obtained solid samples were further freeze-dried at room temperature and 0.2mbar (Christ Alpha 1-2 LD plus freeze dryer) for 12h. White-colored products were obtained with quantitative yields and identified as respective alkaline-metal trifluoroacetates using IR data in good accordance with earlier reported data [28-30].
	With sodium hydrogencarbonate Cooling;	Preparation of sodium trifluoroacetate The conversion of trifluoroacetic acid into corresponding acetate salt is usually achieved by stirring the acid with sodium bicarbonate under cold condition. 50 ml of trifluoroacetic acid was taken in a 100 ml round bottom flask and neutralized with 54.6 g of sodium bicarbonate with constant stirring under cold condition. After completion of this reaction (pH 7), the solution was evaporated to dryness using vacuum evaporator. Finally, the salts of sodium trifluoroactetate were obtained.
	With sodium hydroxide In water

Reference： [1]Bogdanov, Viktor P.; Dmitrieva, Veronika A.; Ioutsi, Vitaliy A.; Belov, Nikita M.; Goryunkov, Alexey A. [Journal of Fluorine Chemistry, 2019, vol. 226]
[2]Raja Beryl; Joseph Raj [Oriental Journal of Chemistry, 2018, vol. 34, # 4, p. 2098 - 2105]
[3]Brennessel, William W.; Knowles, Kathryn E.; Sanchez-Lievanos, Karla R.; Tariq, Mehrin [Dalton Transactions, 2020, vol. 49, # 45, p. 16348 - 16358]

60
[ 75487-82-0 ]
[ 2923-18-4 ]
6-fluoro-3-((trifluoromethyl)thio)-2H-chromen-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With iron(III) chloride; sulfur In ethanol at 60℃; for 3h; Sealed tube;	3 Example 3 6 mmol of 6-fluorocoumarin was added to the reaction vessel,Sodium trifluoroacetate 1 mmol,Elemental sulfur 1mmol,0.01 mmol of ferric chloride and 2 ml of ethanol,Sealing reaction at 60 ° C for 3 hours,The reaction column is subjected to column chromatography,After identification,Performing a nuclear magnetic spectrum analysis on the above white solid powder,The spectral data corresponds to the structural formula,It was proved that the synthesis was 3-trifluoromethylthio-6-fluorocoumarin.The yield was 95%.

Reference： [1]Current Patent Assignee: QINGDAO AGRICULTURAL UNIVERSITY - CN109053660, 2018, A Location in patent: Paragraph 0054-0057; 0060

61
[ 2725-81-7 ]
[ 2923-18-4 ]
6-nitro-3-((trifluoromethyl)thio)-2H-chromen-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With iron(III) chloride; sulfur In ethanol at 60℃; for 3h; Sealed tube;	4 Example 4 6mmol of 6-nitrocoumarin was added to the reaction vessel,Sodium trifluoroacetate 1 mmol,Elemental sulfur 1mmol,0.005mmol of ferric chloride and 2ml of ethanol,Sealing reaction at 60 ° C for 3 hours,The reaction column is subjected to column chromatography,Performing a nuclear magnetic spectrum analysis on the above white solid powder,After identification,The spectral data corresponds to the structural formula,Proven synthesis of 3-trifluoromethylthio-6-nitrocoumarinPrime,The yield was 95%.

Reference： [1]Current Patent Assignee: QINGDAO AGRICULTURAL UNIVERSITY - CN109053660, 2018, A Location in patent: Paragraph 0061-0064; 0067

62
[ 1807-36-9 ]
[ 2923-18-4 ]
8-methyl-3-((trifluoromethyl)thio)-2H-chromen-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With iron(III) chloride; sulfur In ethanol at 60℃; for 2h; Sealed tube;	5 Example 5 Add 1 mmol of 8-methylcoumarin to the reaction vessel.Sodium trifluoroacetate 1 mmol,Elemental sulfur 1mmol,0.005mmol of ferric chloride and 2ml of ethanol,Sealing reaction at 60 ° C for 2 hours,The reaction column is subjected to column chromatography,The above-mentioned yellow solid powder is subjected to nuclear magnetic spectroscopy analysis, and after identification, the spectral data corresponds to the structural formula,Proven synthesis of 3-trifluoromethylthio-8-methylcoumarinPrime,The yield was 95%.

Reference： [1]Current Patent Assignee: QINGDAO AGRICULTURAL UNIVERSITY - CN109053660, 2018, A Location in patent: Paragraph 0068-0071; 0074

63
[ 19063-54-8 ]
[ 2923-18-4 ]
7-chloro-3-((trifluoromethyl)thio)-2H-chromen-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With iron(III) chloride; sulfur In ethanol at 60℃; for 2h; Sealed tube;	6 Example 6 7 mmol of 7-chlorocoumarin was added to the reaction vessel,Sodium trifluoroacetate 1 mmol,Elemental sulfur 1mmol,0.005mmol of ferric chloride and 2ml of ethanol,Sealing reaction at 60 ° C for 2 hours,The reaction column is subjected to column chromatography,Performing a nuclear magnetic resonance spectrum analysis on the above yellow solid powder,After identification,The spectral data corresponds to the structural formula,It was proved that the synthesis was 3-trifluoromethylthio-7-chlorocoumarin.The yield was 94%.

Reference： [1]Current Patent Assignee: QINGDAO AGRICULTURAL UNIVERSITY - CN109053660, 2018, A Location in patent: Paragraph 0075-0078; 0081

64
6-bromo-8-methoxy-chromen-2-one [ No CAS ]
[ 2923-18-4 ]
6-bromo-8-methoxy-3-((trifluoromethyl)thio)-2H-chromen-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With iron(III) chloride; sulfur In ethanol at 40℃; for 3h; Sealed tube;	7 Example 7 Add 1 mmol of 8-methoxy-6-bromocoumarin to the reaction vessel.Sodium trifluoroacetate 1 mmol,Elemental sulfur 1mmol,0.005mmol of ferric chloride and 2ml of ethanol,The reaction was sealed at 40 ° C for 3 hours.The reaction column is subjected to column chromatography,Performing a nuclear magnetic spectrum analysis on the above white solid powder,Data are as follows:After identification,The spectral data corresponds to the structural formula,It was proved that the synthesis was 3-trifluoromethylthio-6-bromo-8-methoxycoumarin.The yield was 95%.

Reference： [1]Current Patent Assignee: QINGDAO AGRICULTURAL UNIVERSITY - CN109053660, 2018, A Location in patent: Paragraph 0082-0085; 0088

65
[ 15185-05-4 ]
[ 2923-18-4 ]
4-phenyl-3-((trifluoromethyl)thio)-2H-chromen-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With iron(III) chloride; sulfur In ethanol at 60℃; for 3h; Sealed tube;	8 Example 8 4 mmol of 4-phenylcoumarin was added to the reaction vessel,Sodium trifluoroacetate 1 mmol,Elemental sulfur 1mmol,0.005mmol of ferric chloride and 2ml of ethanol,Sealing reaction at 60 ° C for 3 hours,The reaction column is subjected to column chromatography,Performing a nuclear magnetic spectrum analysis on the above white solid powder,After identification,The spectral data corresponds to the structural formula,It was proved that the synthesis was 3-trifluoromethylthio-4-phenylcoumarin,The yield was 95%.

Reference： [1]Current Patent Assignee: QINGDAO AGRICULTURAL UNIVERSITY - CN109053660, 2018, A Location in patent: Paragraph 0089-0092; 0095

66
[ 607-71-6 ]
[ 2923-18-4 ]
4-methyl-3-((trifluoromethyl)thio)-2H-chromen-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	With iron(III) chloride; sulfur In ethanol at 60℃; for 2h; Sealed tube;	9 Example 9 4 mmol of 4-methylcoumarin was added to the reaction vessel,Sodium trifluoroacetate 1 mmol,Elemental sulfur 1mmol,0.005mmol of ferric chloride and 2ml of ethanol,Sealing reaction at 60 ° C for 2 hours,The reaction column is subjected to column chromatography,Performing a nuclear magnetic spectrum analysis on the above white solid powder,After identification,The spectral data corresponds to the structural formula,It was proved that the synthesis was 3-trifluoromethylthio-4-methylcoumarin.The yield was 97%.

Reference： [1]Current Patent Assignee: QINGDAO AGRICULTURAL UNIVERSITY - CN109053660, 2018, A Location in patent: Paragraph 0096-0099; 0102

67
[ 2923-18-4 ]
[ 91-64-5 ]
3-((trifluoromethyl)thio)-2H-chromen-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	With iron(III) chloride; sulfur In ethanol at 60℃; for 2h; Sealed tube;	1 Example 1 Add 1 mmol of coumarin to the reaction vessel.Sodium trifluoroacetate 1 mmol,Elemental sulfur 1mmol,0.01 mmol of ferric chloride and 2 ml of ethanol,Sealing reaction at 60 ° C for 2 hours,After the reaction is completed, column chromatography is performed.The following target compounds were obtained:Performing a nuclear magnetic spectrum analysis on the above white solid powder, After identification,The spectral data corresponds to the structural formula,It was proved that the synthesis was 3-trifluoromethylthio-coumarin,The yield was 97%.

Reference： [1]Current Patent Assignee: QINGDAO AGRICULTURAL UNIVERSITY - CN109053660, 2018, A Location in patent: Paragraph 0040-0043; 0046

68
[ 19063-55-9 ]
[ 2923-18-4 ]
6-bromo-3-((trifluoromethyl)thio)-2H-chromen-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With iron(III) chloride; sulfur; In ethanol; at 50℃; for 3h;Sealed tube;	6 mmol of <strong>[19063-55-9]6-bromocoumarin</strong> was added to the reaction vessel,Sodium trifluoroacetate 1 mmol,Elemental sulfur 1mmol,0.01 mmol of ferric chloride and 2 ml of ethanol,Sealing reaction at 50 C for 3 hours,The reaction column is subjected to column chromatography,The following target compounds were obtained:After identification,Performing a nuclear magnetic spectrum analysis on the above white solid powder,It was proved that the synthesis was 3-trifluoromethylthio-<strong>[19063-55-9]6-bromocoumarin</strong>.The yield was 99%.

Reference： [1]Patent: CN109053660,2018,A .Location in patent: Paragraph 0047-0050; 0053

69
[ 2923-18-4 ]
[ 1864-94-4 ]
[ 920-66-1 ]