Name: 7381-30-8|1,2-Bis(trimethylsiloxy)ethane|98%
Brand: Ambeed
SKU: A994415
Price: 10.0 USD
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1
[ 75-77-4 ]
[ 21062-20-4 ]
[ 1067-55-6 ]
[ 3590-59-8 ]
[ 7381-30-8 ]
[ 7040-23-5 ]

Yield	Reaction Conditions	Operation in experiment
	1.) CHCl₃, 5-7 deg C; 2.) CHCl₃, r.t.; Multistep reaction;

Reference： [1]Roelens, Stefano [Journal of the Chemical Society. Perkin transactions II, 1988, p. 1617 - 1626]

2
[ 930-68-7 ]
[ 7381-30-8 ]
[ 1004-58-6 ]

Yield	Reaction Conditions	Operation in experiment
		(R,R)-3,3-Ethylenedioxycyclohexene oxide (Table 6, entry 6): The olefin was prepared by ketalization of 2-cyclohexenone with 1,2-bis(trimethylsiloxy)ethane. See Tsunoda et al., Tetrahedron Letters 1980, 21, 1357-1358. Colorless oil. IR (KBr): 3031, 2943, 2877, 2836, 1683, 1651, 1439, 1396, 1113, 1028, 935, 732 cm-1. 1H NMR d5.96 (dt, J=10.2, 3.6 Hz, 1H), 5.58 (dt, J=10.2, 2.1 Hz, 1H), 3.96 (m, 4H), 2.03 (m, 2H), 1.79 (m, 4H). 13C NMR d132.7, 127.5, 105.6, 64.39, 33.48, 24.81, 20.71.

Reference： [1]Tetrahedron Letters,1980,vol. 21,p. 1357 - 1358
[2]Tetrahedron,1981,vol. 37,p. 3899 - 3910
[3]Tetrahedron,1999,vol. 55,p. 89 - 118
[4]Patent: US6348608,2002,B1 .Location in patent: Page column 33

3
[ 7381-30-8 ]
[ 14320-37-7 ]
[ 6671-84-7 ]

Yield	Reaction Conditions	Operation in experiment
65%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -70℃; for 5h;Inert atmosphere;	Under nitrogen protection, at -70 CTrimethylsilyl trifluoromethanesulfonate(2.21g,12.2mmol)Add to dichloromethane (100 mL).1,2-bis(trimethylsiloxy)ethane at -70 C(25.1g, 122mmol)And 3-cyclopenten-1-one (66A) (10 g, 122 mmol) was added dropwise to the reaction solution.The reaction was carried out at -70 C for 5 hours. At -70 C,Triethylamine (20 mL) and sodium hydrogencarbonate solution (20 mL) were added dropwise to the reaction mixture.The aqueous phase was extracted with dichloromethane (50 mL×3).Oily liquid 1,4-dioxospiro[4.4]cyclo-7-ene (66B)(10 g, yield: 65%).
	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78℃; for 3h;	Intermediate 44: Benzyl N-[2-(2-methylpropane-2-sulfonamido)-4-oxocyclopentyl]-N-[(1R)-1-phenylethyl]carbamate Step (i): 1,4-Dioxaspiro[4.4]non-7-ene To a solution of trimethylsilyl trifluoromethanesulfonate (CAS number 27607-77-8; 0.22 ml, 1.22 mmol) in DCM (12 ml) at -78 C. was successively added <strong>[7381-30-8]2,2,7,7-tetramethyl-3,6-dioxa-2,7-disilaoctane</strong> (CAS number 7381-30-8; 2.51 g, 12.18 mmol) and cyclopent-3-en-1-one (CAS number 14320-37-7; 1 g, 12.18 mmol). The reaction mixture was stirred at -78 C. for 3 hours, quenched with triethylamine (2 ml, 14.35 mmol), poured into a saturated solution of sodium bicarbonate and extracted with diethyl ether. The organics were dried over sodium sulfate, filtered and concentrated in vacuo to afford the title compound. 1H NMR (300 MHz, CHLOROFORM-d) delta ppm 2.59 (s, 4H), 3.96 (s, 4H), 5.71 (s, 2H)

Reference： [1]Tetrahedron,1981,vol. 37,p. 3899 - 3910
[2]Patent: CN109206417,2019,A .Location in patent: Paragraph 2356; 2359-2364
[3]Patent: US2015/232460,2015,A1 .Location in patent: Paragraph 0755-0757

4
[ 7381-30-8 ]
[ 116-31-4 ]
[ 105539-21-7 ]

Yield	Reaction Conditions	Operation in experiment
74%	With trimethylsilyl trifluoromethanesulfonate In dichloromethane at -78℃; for 4h;

Reference： [1]Hwu, Jih Ru; Leu, Lish-Cheng; Robl, Jeffrey A.; Anderson, Denise A.; Wetzel, John M. [Journal of Organic Chemistry, 1987, vol. 52, # 2, p. 188 - 191]

5
[ 7381-30-8 ]
[ 25112-78-1 ]
[ 84062-01-1 ]

Reference： [1]Journal of Organic Chemistry,1991,vol. 56,p. 4093 - 4094
[2]Tetrahedron,1993,vol. 49,p. 1773 - 1782
[3]Journal of the American Chemical Society,1996,vol. 118,p. 7108 - 7116

6
[ 7381-30-8 ]
[ 150930-65-7 ]
[ 150930-76-0 ]

Reference： [1]Journal of the American Chemical Society,1994,vol. 116,p. 3367 - 3374
[2]Tetrahedron Letters,1993,vol. 34,p. 3523 - 3526

7
[ 7381-30-8 ]
[ 108-94-1 ]
[ 177-10-6 ]

Reference： [1]Tetrahedron Letters,1980,vol. 21,p. 1357 - 1358
[2]Tetrahedron,1981,vol. 37,p. 3899 - 3910
[3]Journal of Organic Chemistry,1984,vol. 49,p. 2808 - 2809

8
[ 7381-30-8 ]
[ 1874-22-2 ]
[ 105562-29-6 ]

Yield	Reaction Conditions	Operation in experiment
93%	With trimethylsilyl trifluoromethanesulfonate In dichloromethane 1.) -78 deg C, 3 h, 2.) RT, 14 h;

Reference： [1]Hwu, Jih Ru; Leu, Lish-Cheng; Robl, Jeffrey A.; Anderson, Denise A.; Wetzel, John M. [Journal of Organic Chemistry, 1987, vol. 52, # 2, p. 188 - 191]

9
[ 7381-30-8 ]
[ 26828-48-8 ]
[ 70833-73-7 ]

Yield	Reaction Conditions	Operation in experiment
95%	at -2 - 0℃; for 10h;

Reference： [1]Mandai; Kaihara; Tsuji [Journal of Organic Chemistry, 1994, vol. 59, # 20, p. 5847 - 5849]

10
[ 7381-30-8 ]
[ 189246-59-1 ]
[ 189246-60-4 ]

Reference： [1]Journal of the American Chemical Society,1998,vol. 120,p. 908 - 919
[2]Tetrahedron,1998,vol. 54,p. 10275 - 10294
[3]Synlett,1997,vol. 1997,p. 301 - 303

11
[ 7381-30-8 ]
[ 225090-33-5 ]
[ 339151-75-6 ]

Reference： [1]Angewandte Chemie - International Edition,1999,vol. 38,p. 683 - 686
[2]Journal of the American Chemical Society,2001,vol. 123,p. 3214 - 3222

12
[ 7381-30-8 ]
[ 100-52-7 ]
[ 936-51-6 ]

Reference： [1]Synthesis,2002,p. 784 - 788
[2]Synthesis,2005,p. 279 - 285
[3]Journal of the American Chemical Society,2007,vol. 129,p. 492 - 493
[4]Australian Journal of Chemistry,1998,vol. 51,p. 1083 - 1096

13
[ 7381-30-8 ]
[ 394738-16-0 ]
[ 394738-17-1 ]

Reference： [1]Angewandte Chemie - International Edition,2001,vol. 40,p. 3658 - 3660
[2]Chemistry - A European Journal,2002,vol. 8,p. 259 - 268

14
[ 7381-30-8 ]
[ 175881-73-9 ]
[ 175881-81-9 ]

Reference： [1]Journal of the American Chemical Society,2001,vol. 123,p. 3214 - 3222

15
[ 816-39-7 ]
[ 7381-30-8 ]
[ 20599-01-3 ]

Reference： [1]Advanced Synthesis and Catalysis,2002,vol. 344,p. 57 - 60

16
[ 2648-71-7 ]
[ 7381-30-8 ]
2-(1-bromo-1-methyl-ethyl)-2-methyl-1,3-dioxolane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
73%	With Nafion-TMS In chloroform for 49h; Heating;

Reference： [1]Carlson, Rolf; Gautun, Hanna; Westerlund, Andreas [Advanced Synthesis and Catalysis, 2002, vol. 344, # 1, p. 57 - 60]

17
[ 7381-30-8 ]
[ 70-11-1 ]
[ 3418-21-1 ]

Reference： [1]Advanced Synthesis and Catalysis,2002,vol. 344,p. 57 - 60

18
[ 7381-30-8 ]
5c-acetyl-1,1-dimethoxy-2b,2c,5,5a,5b,5c-hexahydro-1H,2aH-cyclopenta[a]cyclopropa[cd]pentalen-2-one [ No CAS ]
1,1-dimethoxy-5c-(2-methyl-[1,3]dioxolan-2-yl)-2b,2c,5,5a,5b,5c-hexahydro-1H,2aH-cyclopenta[a]cyclopropa[cd]pentalen-2-one [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2002,vol. 41,p. 4090 - 4093

19
[ 17553-86-5 ]
[ 7381-30-8 ]
[ 260048-45-1 ]

Yield	Reaction Conditions	Operation in experiment
90%	With trimethylsilyl trifluoromethanesulfonate; ethylene glycol In dichloromethane at -78℃;

Reference： [1]Chochrek, Paweł; Kurek-Tyrlik, Alicja; Michalak, Karol; Wicha, Jerzy [Tetrahedron Letters, 2006, vol. 47, # 34, p. 6017 - 6020]

20
[ 7381-30-8 ]
[ 178454-81-4 ]
[3aR,4R(1E),5R,6aS]-5-(benzoyloxy)-4-[4-(3-chlorophenoxy)-3,3-(ethylenedioxy)butenyl]-hexahydro-2H-cyclopenta[b]furan-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	With trimethylsilyl trifluoromethanesulfonate; triethylamine; In dichloromethane; at -78 - 20℃;	A. [3aR,4R(1E),5R,6aS]-5-(Benzoyloxy)-4-[4-(3-chlorophenoxy)-3,3-(ethylenedioxy)butenyl]-hexahydro-2H-cyclopenta[b]furan-2-one (2) To a solution of [3aR,4R(1E),5R,6aS)-5-(benzoyloxy)-4-[4-(3-chlorophenoxy)-3-oxobutenyl]-hexahydro-2H-cyclopenta[b]furan-2-one (1; for preparation see published European Patent Application No. EP 639563 A2, which is incorporated by this reference) (1.32 g, 3.0 mmol), 4A molecular sieves (1.27 g), and 1,2-bis(trimethylsiloxy)ethane (1.27 g, 6.18 mmol) in methylene chloride (23 ML) at -78 C. (bath temperature) was added trimethylsilyl trifluoromethanesulfonate (172 mg, 0.77 mmol).. The reaction was then warmed to -20 C. and maintained at that temperature overnight.. triethylamine (0.8 ML) was added, the solution was warmed to room temperature, saturated sodium bicarbonate (15 ML) was added, the layers were separated, the aqueous phase was extracted with methylene chloride (220 ML), the combined organic layers were dried (magnesium sulfate), filtered, concentrated, and chromatographed on a 19 cm tall26 mm diameter silica gel column eluding with 1:1 ethyl acetate:hexane to afford 2 (1.41 g, 97%) 13C NMR (CDCl3) delta176.17 (C), 165.92 (C), 159.23 (C), 134.71 (C), 133.32 (CH), 131.06 (CH), 130.06 (CH), 129.56 (CH), 129.40 (CH), 128.48 (CH), 121.37 (CH), 115.14 (CH), 113.21 (CH), 106.27 (C), 83.10 (CH), 78.76 (CH), 71.36 (CH2), 65.41 (CH2), 65.23 (CH2), 53.74 (CH), 42.47 (CH), 37.35 (CH2), 34.79 (CH2).

Reference： [1]Patent: US6353014,2002,B1 .Location in patent: Page column 9

21
(3aR,4R,5R,6aS)-5-(benzoyloxy)-4-[4-(3-chlorophenoxy)-3-oxobutyl]-hexahydro-2H-cyclopenta[b]furan-2-one [ No CAS ]
[ 7381-30-8 ]
[3aR,4R,5R,6aS]-5-(benzoyloxy)-4-[4-(3-chlorophenoxy)-3,3-(ethylenedioxy)butyl]-hexahydro-2H-cyclopenta[b]furan-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at 0 - 20℃; for 74h;	To a solution of 8 (1.29 g, 2.91 mmol), 4A molecular sieves (1.7 g) and 1,2-bis(trimethylsiloxy)ethane (1.2 g, 5.8 mmol) in methylene chloride (20 mL) at 0 C. (bath temperature) was added trimethylsilyl trifluoromethanesulfonate (170 mg, 0.76 mmol). After 2 h, the reaction was warmed to room temperature, cooled to 4 C. (bath temperature) and maintained at that temperature over 72 h. Triethylamine (1 mL) and saturated sodium bicarbonate (20 mL) were added sequentially, the solution was extracted with ethyl acetate (3×35 mL), dried (magnesium sulfate), filtered, concentrated, and chromatographed on a 17 cm tall×26 mm diameter silica gel column eluting with 1:1 ethyl acetate:hexane to afford 9 (1.20 g, 84%). 13C NMR (CDCl3) delta176.75 (C), 166.00 (C), 159.22 (C), 134.87 (C), 133.22 (CH), 130.23 (CH), 129.65 (CH), 129.61 (CH), 128.48 (CH), 121.42 (CH), 115.04 (CH), 113.12 (CH), 108.78 (C), 84.41 (CH), 80.26 (CH), 70.15 (CH2), 65.67 (CH2), 65.62 (CH2), 52.70 (CH), 43.40 (CH), 37.61 (CH2), 36.27 (CH2), 33.00 (CH2), 26.60 (CH2).

Reference： [1]Patent: US6353014,2002,B1 .Location in patent: Page column 13

22
[ 7381-30-8 ]
[ 51638-91-6 ]
[ 59618-87-0 ]

Yield	Reaction Conditions	Operation in experiment
82%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78 - -20℃;	To a solution of enone 29 (1.30 g, 3.2 mmol) and 1,2-bis(trimethylsiloxy)ethane (1.34 g, 6.5 mmol) in CH2Cl2 (10 mL) at -78 C. (bath temperature) was added trimethylsilyl trifluoromethanesulfonate (240 mg, 1.1 mmol). After 1 h, the reaction was warmed to -20 C. and kept at that temperature overnight. The reaction was quenched by the addition of NEt3 (360 mg, 3.56 mmol), warmed to room temperature, added to saturated sodium bicarbonate (25 mL), the layers were separated, the aqueous layer was extracted with CH2Cl2 (3×25 mL), ), dried (MgSO4), filtered, concentrated, and chromatographed on a 12 cm tall×41 mm diameter silica gel column to afford 30 (1.19 g, 82%).

Reference： [1]Patent: US6353014,2002,B1 .Location in patent: Page column 20-21

23
[ 927178-26-5 ]
[ 7381-30-8 ]
C₂₇H₄₀O₇ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%		<Example 16>; The compound 26 obtained in Example 10 was ketalized to obtain the compound 32 of the invention. [Show Image] The present reaction was carried out under a nitrogen atmosphere. To a solution of 11 mul (0.0614 mmol) of trimethylsilyl trifluoromethanesulfonate and 0.9 ml (3.69 mmol) of 1,2-bistrimethylsiloxyethane dissolved in 6 ml of dichloromethane was dropwise added a solution of 133 mg (0.307 mmol) of the compound 26 dissolved in 1 ml of dichloromethane under ice cooling. After 50 minutes of stirring, triethylamine was added to the reaction mixture to terminate the reaction. Then, 5 ml of saturated sodium bicarbonate aqueous solution and 5 ml of chloroform were added, followed by partitioning. The organic layer was separated and dried over anhydrous magnesium sulfate and then the solvent was removed by distillation. The obtained residue was purified by silica gel thin-layer chromatography to obtain 114 mg (78%) of a pale yellow, liquid compound having a medium viscosity. The chemical shift values of the product on 1H-NMR spectrum as measured in deuterochloroform were as follows: 1.23-1.64 (17H, m), 1.98-2.06 (4H, m), 2.28 (2H, t), 2.67-2.71 (2H, m), 2.80-2.84 (1H, m), 3.79 (3H, s), 3.91-3.98 (4H, m), 4.12 (2H, q), 5.38 (1H, d), 5.81 (1H, dt), 6.74-6.78 (2H, m), 6.89 (1H, d). The wave numbers (cm-1) with absorption on IR absorption spectrum (KBr pellet method) were as follows: 2924, 1758, 1737, 1608, 1510, 1466, 1420, 1127, 1042. The results of elemental analysis were as follows: carbon 68.04% and hydrogen 8.46%. Based on the above analysis, it was confirmed that the obtained compound was the compound 32.

Reference： [1]Patent: EP1612201,2006,A1 .Location in patent: Page/Page column 37-38

24
[ 7381-30-8 ]
[ 117259-83-3 ]
[ 156910-37-1 ]

Yield	Reaction Conditions	Operation in experiment
91%	p-TsOH; In ethylene glycol; benzene;	EXAMPLE 3 STR15 (a.) [2-(5,6,7,8-Tetrahydro-5,5,8,8-tetramethyl-2-naphthalenyl)-2-(4-carbomethoxyphenyl)]-1,3-dioxolane (8): To a solution of keto-ester 3 (80 mg, 0.228) in 1 mL of benzene was added ethylene glycol (1 mL), <strong>[7381-30-8]1,2-bis(trimethylsilyloxy)ethane</strong> (2 mL) and a catalytic amount of p-TsOH. The reaction mixture was heated at reflux for 4 h and then cooled to room temperature. The solution was poured into saturated aqueous NaHCO3 and extracted with 40% ethyl acetate/hexane. The combined organic layers were dried over anhydrous MgSO4, filtered, and concentrated to afford a solid. Flash chromatography (50% CH2 Cl2 /hexane) yielded the desired ketal 8 as a white solid (0.082 g, 91%): m.p. 145-147 C.; Rf 0.16 (50% CH2 Cl2 /hexane). The structure of the product was also confirmed using IR, 1 H NMR and mass spectroscopy.

Reference： [1]Patent: US5466861,1995,A

25
[ 877319-38-5 ]
[ 7381-30-8 ]
[ 877319-39-6 ]

Yield	Reaction Conditions	Operation in experiment
91%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at 0 - 20℃;	Compound 1017C (200 mg, 0.68 mmol) was stirred in CH2Cl2 (15 mL) at 0C followed by addition of compound 10171 (0.5 mL, 2.04 mmol) and TMS-OTf (13 \|iL, 0.07 mmol). The reaction mixture was stirred at 0 C to 5 C for 6 hr before warmed up to rt and stirred overnight. The solvent was removed and the crude material was purified via PTLC (EtOAc) to give 0.21 g (91%) of compound 1017D.

Reference： [1]Patent: WO2006/19768,2006,A1 .Location in patent: Page/Page column 151

26
[ 7381-30-8 ]
[ 128242-41-1 ]

Yield	Reaction Conditions	Operation in experiment
73%	With trimethylsilyl trifluoromethanesulfonate; In tetrahydrofuran;	Trimethylsilyl trifluoromethanesulfonate (150 muL, 0.78 mmol) was added to a stirred solution of the silyl ether (18 g, 0.0628 mol) and <strong>[7381-30-8]1,2-bis(trimethylsilyloxy)ethane</strong> (16.2 mL, 0.066 mmol) in tetrahydrofuran (36 mL). The solution was stirred for 1 hr at 22 C. and additional trimethylsilyl trifluoromethanesulfonate (150 muL) was then added. The solution was stirred for an additional 0.25 hr and was concentrated to dryness. The residue was flash chromatographed on SiO2 (200 g) with diethyl ether-hexanes (1:1) to afford 2,2-ethylenedioxy-3-isopropoxy-4-methylcyclobut-3-ene-1-one (9 g, 73% yield) as a

Reference： [1]Patent: US5106842,1992,A

27
[ 7381-30-8 ]
[ 13735-13-2 ]

Yield	Reaction Conditions	Operation in experiment
	With trimethylsilyl trifluoromethanesulfonate;	1) 6-Bromo-4-oxothiochroman ethylene ketal Under ice-cooling ethylenedioxybis(trimethylsilane) (13.4 g, 64.78 mmol) and trimethylsilyl triflate (catalytic amount) were added to a solution of 6-bromo-4-oxothiochroman (10.50 g, 43.18 mmol), which was obtained in 8-2), in anhydrous tetrahydrofuran (100 ml).

Reference： [1]Patent: EP1031572,2000,A1

28
[ 192650-25-2 ]
[ 7381-30-8 ]
[ 782475-33-6 ]

Yield	Reaction Conditions	Operation in experiment
72%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -5℃; for 6h;	A clean oven dried flask was charged with the 6-(4-nitro-phenyl)-hexane-2,4-dione (3.7 g, 15.72 mmol), dry CH2Cl2 (20 ml) followed by bisTMS ethylene glycol (38.5 ml, 157.3 ml) were added to the flask and the resulting solution was cooled to -5 C. with stirring under argon. TMSOTf (300 mul) was added to the reaction mixture and the solution was stirred at -5 C. for 6 h. Reaction was quenched with pyridine (10 ml) and poured into sat. NaHCO3. The mixture was extracted with EtOAc and the organic layer was washed with water, brine, dried (Na2SO4) and concentrated to give a yellow solid. The solid was triturated with hexanes to give a free flowing pale yellow solid (3.5 g, 72%) which was dissolved in EtOAc (50 ml) and hydrogenated on a Parr shaker starting with 50 psi of hydrogen pressure. After two hours the reaction was filtered through a pad of celite, the celite was washed thoroughly with CH2Cl2MeOH and combined organics were concentrated to give title compound (1.46 g, 100%) as an oil that solidifies upon standing.
72%		A clean oven dried flask was charged with the 6-(4-nitro-phenyl)-hexane-2,4-dione (3.7 g, 15.72 mmol), dry CH2Cl2 (20 ml) followed by bisTMS ethylene glycol (38.5 ml, 157.3 ml) were added to the flask and the resulting solution was cooled to -5 C. with stirring under argon. TMSOTf (300 mul) was added to the reaction mixture and the solution was stirred at -5 C. for 6 h. Reaction was quenched with pyridine (10 ml) and poured into sat. NaHCO3. The mixture was extracted with EtOAc and the organic layer was washed with water, brine, dried (Na2SO4) and concentrated to give a yellow solid. The solid was triturated with hexanes to give a free flowing pale yellow solid (3.5 g, 72%) which was dissolved in EtOAc (50 ml) and hydrogenated on a Parr shaker starting with 50 psi of hydrogen pressure. After two hours the reaction was filtered through a pad of celite, the celite was washed thoroughly with CH2Cl2/MeOH and combined organics were concentrated to give title compound (1.46 g, 100%) as an oil that solidifies upon standing.

Reference： [1]Patent: US2006/205670,2006,A1 .Location in patent: Page/Page column 103
[2]Patent: US2008/166364,2008,A1 .Location in patent: Page/Page column 105
[3]Tetrahedron Letters,2012,vol. 53,p. 1385 - 1389

29
[ 917984-30-6 ]
[ 7381-30-8 ]
(S)-5-(1,3-dioxolan-2-yl)-1-(4-fluorophenyl)-5,6-dimethyl-4,5-dihydro-1H-indazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at 20℃; for 1h;	Example 169; (S)-5-(l,3-dioxolan-2-yl)-l-(4-fluorophenyl)-5,6-dimethyl-4,5-dihydro-lH- indazole; [00365] To a CH2Cl2 (5 mL) solution of the aldehyde (27.9 mg, 0.103 mmol) from reaction 144i and bis(O-trimethylsilyl)ethylene glycol (350 muL, 14 eq) was added TMSOTf (50 muL, 2.7 eq) at room temperature. The mixture was stirred for 1 h then purified by silica gel chromatography (0-35% EtOAc-hexanes) to give Example 169 (30.9 mg, 95%). MS found: (M+H)+=315.

Reference： [1]Patent: WO2006/138373,2006,A2 .Location in patent: Page/Page column 107

30
[ 7381-30-8 ]
[ 40235-68-5 ]
[ 937262-72-1 ]

Yield	Reaction Conditions	Operation in experiment
	With trimethylsilyl trifluoromethanesulfonate In dichloromethane at -78 - 20℃; for 120h; Cooling with acetone-dry ice;	85 Intermediate 85(2-(Chloromethyl)-l,3-dioxolan-2-yl)methyl acetate. A solution of 1-acetoxy-3-chloroacetone (20.0 g, 133 mmol, TCI America) and 1,2- bis(trimethylsilyloxy)ethane (30.2 g, 146 mmol, Aldrich) in anhydrous CH2Cl2 and under N2 atmosphere was cooled (-78°C, dry ice/acetone) and trimethylsilyl trifluoromethanesulfonate (1.2 mL, 6.6 mmol, Aldrich) was added. The reaction was warmed to room temperature and stirred for 5 days, with monitoring by 1H-NMR. The crude reaction solution was separated by silica gel column, and eluted with CH2Cl2, then 5% Et2O in CH2Cl2. Product fractions were pooled and concentrated in- vacuo giving the title compound (19.05 g) as a yellow oil, contaminated with 1- acetoxy-3-chloroacetone (2.93 g) and CH2Cl2 (1.0 g): 1H NMR (500 MHz, CDCl3) δ ppm 4.17 (2H, s), 4.03 - 4.11 (4H, m), 3.60 (2H, s), 2.09 (3H, s).

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2007/58646, 2007, A1 Location in patent: Page/Page column 84

31
[ 7381-30-8 ]
trans-4-((4-chlorophenyl)thio)-5,8-difluorochroman-3-carbaldehyde [ No CAS ]
trans-4-((4-chlorophenyl)thio)-3-(1,3-dioxolan-2-yl)-5,8-difluorochroman [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78 - 20℃; for 1h;	Step 6To a stirred solution of 9.0 g (26.5 mmol) of compound 15 in 100 ml_ of dichloromethane were added 7.12 g (34.5 mmol) of 1 ,2-bis(trimethylsiloxy)ethane and 0.36 (1.6 mmol) of trimethylsilyl trifluoromethanesulfonate at -78 0C. After 30 min., it was warmed to room temperature and stirred for 30 min. It was diluted with 150 ml_ of dichloromethane and washed with three 200 ml_ portions of saturated sodium bicarbonate. The organic layer was dried over sodium sulfate, concentrated, and the residue was purified by chromatography eluting with a gradient of 2% to 30% of ethyl acetate in hexanes to give 8.8 g of compound 16. 1H NMR (CDCI3 400 MHz) delta 7.42 (d, J = 9.0 Hz, 2 H), 7.31 (d, J = 8.6 Hz, 2 H), 6.95 (m, 1 H), 6.57 (m, 1 H), 4.74 (d, J = 7.4 Hz, 1 H), 4.70 (s, 1 H), 4.59 (s, 2 H), 3.80-3.92 (m, 4 H), 2.10 (m, 1 H). MS: Calcd. for C18H16CIF2O3S(MH+), m/z = 385.1 ; found 385.2. Retention time: 5.28 min.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2013,vol. 23,p. 844 - 849
[2]Patent: WO2009/8980,2009,A2 .Location in patent: Page/Page column 195; 198
[3]ACS Medicinal Chemistry Letters,2012,vol. 3,p. 892 - 896

32
[ 7381-30-8 ]
C₁₅H₁₆O₄ [ No CAS ]
C₁₇H₂₀O₅ [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2009,vol. 131,p. 16905 - 16918

33
[ 947725-04-4 ]
[ 7381-30-8 ]
[ 1207989-40-9 ]

Yield	Reaction Conditions	Operation in experiment
85%	tetrabutyl ammonium fluoride; In dichloromethane; at 20℃; for 2h;Product distribution / selectivity;	Fluoroethyl benzenesulfinate derivates (1-1) ~ (1-7) were prepared by reaction of arylsulfur trifluoride (III) with ethylene glycol, its salts or silyl derivatives in the same manner as described in Example 1. In Example 3, the reaction was carried out in the presence of a base (triethylamine). The results and reaction conditions are shown in Table 1 together with those of Example 1. When a silyl derivative was used as in Examples 5-12, a solution of catalytic amount (0.1 mmol) of tetrabutylammonium fluoride (a silicon atom- activating agent) (1.0 M) in tetrahydrofuran (THF) was added to a solution of a silyl derivative and arylsulfur trifluoride

Reference： [1]Patent: WO2010/22001,2010,A1 .Location in patent: Page/Page column 39; 40; 41
[2]Journal of the American Chemical Society,2010,vol. 132,p. 18199 - 18205

34
[ 7381-30-8 ]
[ 20357-24-8 ]
[ 73428-02-1 ]

Yield	Reaction Conditions	Operation in experiment
99%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78 - 23℃;Inert atmosphere of N2;	5-Methoxy-2-nitro-benzaldehyde (30.00 g, 0.1656 mol) and 1,2-bis- trimethylsilanyloxy-ethane (40.6 mL, 0.166 mol) were placed in a 40 mL vial, followed by Methylene chloride (1000 mL, 20 mol). The reaction mixture was then cooled to -78 C, and trimethylsilyl trifluoromethanesulfonate (1 mL, 0.008 mol) was added dropwise under N2. The reaction mixture was allowed to warm up to at 23 C for 1 day. A solution of saturated K2CO3 (50 mL) was added to quench the reaction, and organic layer was separated. Removal of solvent gave a oily product, which was treated with ether/hexanes to give a pure solid product (37.0g, 99%). 1H NMR (MeOD) delta: 8.01 (d, J = 9.0 Hz, IH), 7.29 (d, J = 2.8 Hz, IH), 7.05 (dd, J = 8.9, 2.9 Hz, IH), 6.49 (s, IH), 4.85 (s, 3H), 3.91 (s, 4H). MS (M+l): 226.10.
99%	With trimethylsilyl trifluoromethanesulfonate; potassium carbonate; In dichloromethane;	Example 53 2-(5-Methoxy-2-nitrophenyl)-1,3-dioxolane 5-Methoxy-2-nitro-benzaldehyde (30.00 g, 0.1656 mol) and 1,2-bis-trimethylsilanyloxy-ethane (40.6 mL, 0.166 mol) were placed in a 40 mL vial, followed by Methylene chloride (1000 mL, 20 mol). The reaction mixture was then cooled to -78 C., and trimethylsilyl trifluoromethanesulfonate (1 mL, 0.008 mol) was added dropwise under N2. The reaction mixture was allowed to warm up to at 23 C. for 1 day. A solution of saturated K2CO3 (50 mL) was added to quench the reaction, and organic layer was separated. Removal of solvent gave a oily product, which was treated with ether/hexanes to give a pure solid product (37.0 g, 99%). 1H NMR (MeOD) delta: 8.01 (d, J=9.0 Hz, 1H), 7.29 (d, J=2.8 Hz, 1H), 7.05 (dd, J=8.9, 2.9 Hz, 1H), 6.49 (s, 1H), 4.85 (s, 3H), 3.91 (s, 4H). MS (M+1): 226.10.

Reference： [1]Patent: WO2010/51031,2010,A1 .Location in patent: Page/Page column 46
[2]Patent: US2014/100195,2014,A1 .Location in patent: Page/Page column

35
[ 7381-30-8 ]
[ 1225229-49-1 ]
[ 1225229-50-4 ]

Yield	Reaction Conditions	Operation in experiment
88%		5-(heptyloxyl)-2-nitrobenzaldehyde (3, 1.00 g, 0.00377 mol) and 1,2-Bis- trimethylsilanyloxy-ethane (0.924 mL, 0.00377 mol) were placed in a 40 mL vial, followed by methylene chloride (50 mL, 0.8 mol). The reaction mixture was then cooled to -78 C, and trimethylsilyl trifluoromethanesulfonate (0.03 mL, 0.0002 mol) was added dropwise under N2. The reaction mixture was allowed to stir for about for 3 hours at -78 0C. The reaction mixture was then warmed up to 23 C, and then cooled down to -78 C again. A solution of NaOH (4N) was added to quench the reaction, and organic layer was separated. The crude mixture was then purified via chromatography (SiO2, 24g, 0-35%ethyl acetate/hexanes) to give the desired product (1030mg, 88%). 1H NMR (CHLOROFORM- d) delta: 8.04 (d, J - 9.0 Hz, IH), 7.29 (d, J = 2.8 Hz, IH), 6.91 (dd, J = 9.0, 2.8 Hz, IH), 6.58 (s, IH), 3.98 - 4.12 (m, 6H), 1.74 - 1.90 (m, 2H), 1.42 - 1.53 (m, 2H), 1.24 - 1.41 (m, 6H), 0.83 - 0.98 (m, 3H). MS (M+ 1): 310.20.

Reference： [1]Patent: WO2010/51031,2010,A1 .Location in patent: Page/Page column 41

36
[ 7381-30-8 ]
[ 37779-49-0 ]
methyl 2-(phenylmethyl)-1,3-dioxolane-2-acetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane;	Treatment of <strong>[37779-49-0]methyl 3-oxo-4-phenylbutyrate</strong> (8.95 g, 46.6 mmol) with ethylenedioxybis(trimethylsilane) (13.5 mL, 58.3 mmol) in the presence of trimethylsilyl triflate (1.72 mL, 9.32 mmol) in CH2Cl2 (110 mL) gave methyl 2-(phenylmethyl)-1,3-dioxolane-2-acetate (10.6 g, 96%).

Reference： [1]Tetrahedron,2016,vol. 72,p. 6640 - 6645
[2]Journal of Organic Chemistry,2010,vol. 75,p. 3113 - 3116

37
[ 7381-30-8 ]
[ 555-16-8 ]
[ 2403-53-4 ]

Reference： [1]Synthesis,2010,p. 2771 - 2775

38
[ 7381-30-8 ]
[ 141419-94-5 ]
[ 1207625-81-7 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 2,2,7,7-tetramethyl-3,6-dioxa-2,7-disilaoctane; ethyl 4-oxotetrahydro-2H-pyran-3-carboxylate With trimethylsilyl trifluoromethanesulfonate In dichloromethane at -15 - 20℃; for 5.5h; Stage #2: With pyridine In dichloromethane Cooling;	106.2 Bis(trimethylsiloxy)ethane (3.68 ml) was added to a solution of the compound obtained in the above Step 1 (860 mg) in dichloromethane (50 ml) at room temperature. The reaction solution was cooled to -15° C. and trimethylsilyl trifluoromethanesulfonate (92 μl) was added. The mixture was stirred for 2 hours while warming to 0° C. and further stirred at room temperature for 3.5 hours. Pyridine (0.2 ml) was added under ice-cooling, and then the mixture was separated by adding dichloromethane and a saturated aqueous sodium bicarbonate solution. The resulting organic layer was washed with brine and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure. The resulting residue was purified by silica gel column chromatography (developed with ethyl acetate-hexane) to give the title compound (956 mg).1H-NMR (CDCl3) δ: 1.28 (3H, t, J=7.3 Hz), 1.65-1.75 (1H, m), 2.00-2.09 (1H, m), 2.75-2.82 (1H, m), 3.75-3.85 (2H, m), 3.90-4.03 (6H, m), 4.18 (2H, q, J=6.9 Hz).

Reference： [1]Current Patent Assignee: DAIICHI SANKYO COMPANY, LIMITED - US2011/82138, 2011, A1 Location in patent: Page/Page column 77

39
[ 7381-30-8 ]
[ 1132652-60-8 ]
(6S,10S)-5-(1,3-dioxolanyl)-10-methoxycarbonyl-6-methylbicyclo[4,4,0]-dec-1-ene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78 - 20℃; for 13h;Inert atmosphere;	To a solution of ketone 15b (700 mg, 2.65 mmol, 1 equiv) in dry dichloromethane was successfully added TMSOTf (24 muL, 0.13 mmol, 0.05 equiv) at -78 C followed by the silyl ether (1.0 g, 5.30 mmol, 2 equiv). The reaction mixture was stirred for 1 h at -78 C and was then allowed to warm slowly to room temperature and was stirred for 12 h. After addition of pyridine, the reaction mixture was quenched with a saturated aqueous NaHCO3 solution. The aqueous phase was extracted with DCM. The combined organic layers were washed with brine, dried over anhydrous MgSO4, filtered, and concentrated under vacuum to quantitatively yield to the protected ester 17b (96% yield). This residue was used in the next reaction without further purification. +57 (c 5.3 CH2Cl2). IR (film, cm-1) nu 2947, 2603, 2497, 1731, 1442, 1375, 1311, 1263, 1201. NMR 1H (300 MHz, CDCl3) delta 5.10 (1H, s, CH), 3.89-4.03 (4H, m, 2× CH2), 3.69 (1H, s, CH3), 3.21-3.25 (1H, m, CH), 2.03-2.29 (2H, m, CH2), 1.46-1.87 (8H, m, 4× CH2), 1.23 (3H, s, CH3). NMR 13C (75 MHz, CDCl3) delta 175.1 (COester), 140.0 (Cquat), 118.8 (Calkene), 112.0 (Cacetal), 65.5 (CH2), 64.9 (CH2), 51.7 (CH3), 47.4 (CH), 43.8 (Cquat), 30.4 (CH2), 30.4 (CH2), 26.9 (CH2), 24.1 (CH2), 21.9 (CH3), 20.8 (CH2). m/z (IC+, NH3): 267.04 (MH+). HRMS (IC+): MH+, found 289.1418 C15H22O4Na requires 289.1416. Chiral GC (oven: 130?170 C, 0.5 C/min, flow: 1.2 mL/min) rt=44.04 min and 45.05 min.

Reference： [1]Tetrahedron,2012,vol. 68,p. 3457 - 3467

40
[ 58010-01-8 ]
[ 7381-30-8 ]
[ 70710-39-3 ]

Yield	Reaction Conditions	Operation in experiment
85%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78℃; for 12.5h;Inert atmosphere;	To a solution of 5d (0.24 g, 1.37 mmol, 1.0 equiv.) and 1,2-bis-trimethylsilyloxyethane (0.28 g, 0.34 mL, 1.37 mmol, 1.0 equiv.) in DCM (10 mL) was added TMSOTf (30.5 mg, 25 muL, 3.76 mmol, 0.1 equiv.) at -78. The mixture was stirred for 12.5 h at -78 C. The reaction was then quenched by the addition of pyridine (1 mL). Then the mixture was concentrated under reduced pressure and the residue was purified by flash column chromatography on silica gel to furnish 4d as faint yellow oil (0.25 g, 85%).

Reference： [1]Tetrahedron Letters,2012,vol. 53,p. 6972 - 6976

41
[ 31752-99-5 ]
[ 7381-30-8 ]
[ 1421320-93-5 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2013,vol. 23,p. 939 - 943

42
[ 7381-30-8 ]
[ 1421940-39-7 ]
[ 1421940-40-0 ]

Yield	Reaction Conditions	Operation in experiment
99%		To a solution of 26 (5.70 g, 21.1 mmol) in dry CH2Cl2 (135 mL) which was pre-cooled to 0 C were successively added (TMSOCH2)2 (19.6 g, 94.9 mmol) and TMSOTf (1.02 mL, 5.28 mmol). After being stirred at 0 C for 2 h, Et3N (34.6 mL) was added, and the resulting mixture was poured into a saturated aqueous NaHCO3 solution (100 mL) and extracted with CH2Cl2 (2 * 250 mL). The combined organic layers were dried over Na2SO4, the solvent was evaporated in vacuo and the residue was chromatographed on silica gel hexane/EtOAc (9:1) to afford 6.56 g (99%) of compound 27 as a colourless oil. 1H NMR (400 MHz, CDCl3): delta 0.86 (3H, t, J = 6.6 Hz, CH3), 1.26-1.30 (16H, m, 8 * CH2), 1.55-1.62 (6H, m, 3 * CH2), 2.03 (3H, s, CH3CO), 3.91 (4H, s, 2 * H-4', 2 * H-5'), 4.03 (2H, t, J = 6.8 Hz, 2 * H-1). 13C NMR (100 MHz, CDCl3): delta 14.1 (C-6"), 21.0 (CH3CO), 22.6 (CH2), 23.7 (CH2), 23.8 (CH2), 25.8 (CH2), 28.5 (CH2), 29.2 (CH2), 29.6 (CH2), 29.8 (CH2), 31.8 (CH2), 37.1 (C-7, C-1"), 64.6 (C-1), 64.8 (H-4', H-5'), 111.8 (C-2'), 171.2 (CH3CO). Anal. Calcd for C18H34O4: C, 68.75; H, 10.90. Found: C, 68.71; H, 10.94.

Reference： [1]Tetrahedron Asymmetry,2013,vol. 24,p. 121 - 133

43
[ 7381-30-8 ]
[ 1431972-65-4 ]
[ 1431972-66-5 ]
[ 1431972-75-6 ]

Yield	Reaction Conditions	Operation in experiment
44%; 39%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at 0 - 20℃; for 42h;	To a solution of 1-(4-hydroxycyclohexyl)-3-(4-(methylsulfonyl)phenyl)-3-o-tolylpropan-1-one (examples 15 and 16, step 2; 1.26 g, 3.14 mmol) and <strong>[7381-30-8]1,2-bis(trimethylsilyloxy)ethane</strong> (810 mg, 3.92 mmol) in dichloromethane (15 mL) was added dropwise a solution of trimethylsilyl trifluoromethanesulfonate (140 mg, 628 mumol) in dichloromethane (2 mL) at 0 C. The yellow solution was allowed to warm to room temperature over 6 h, then kept in the refrigerator for 36 h. After addition of triethylamine (54 mg, 0.64 mmol) the reaction mixture was partitioned between sat. aq. sodium hydrogencarbonate solution and dichloromethane. The organic layer was dried over magnesium sulfate, filtered, and evaporated. Chromatography (SiO2; gradient dichloromethane to dichloromethane/methanol/25% aq. ammonia solution 95:5:0.25) produced the title compound (655 mg, 44%; light yellow foam, MS: 445.2 [M+H]+) and trimethyl(4-(2-(2-(4-(methylsulfonyl)phenyl)-2-o-tolylethyl)-1,3-dioxolan-2-yl)cyclohexyloxy)silane (715 mg, 39%; yellow foam, MS: 517.3 [M+H]+), which could be converted to the title compound by treatment with potassium carbonate in methanol at room temperature.

Reference： [1]Patent: US2013/109718,2013,A1 .Location in patent: Paragraph 0294-0295

44
[ 7381-30-8 ]
[ 1432050-58-2 ]
[ 1432050-59-3 ]

Yield	Reaction Conditions	Operation in experiment
97%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at 20℃;	2-[3-(trifluoromethoxy)phenyl]-5,8-dioxaspiro[3.4]octane-2-carbonitrile [1512] To a solution of Example 235B (11.318 g, 44.4 mmol) and 1,2-bis- (trimethylsilyloxy)ethane (17 mL, 69.2 mmol) in dichloromethane (100 mL) was added trimethylsilyl trifluoromethanesulfonate (1.0 mL, 5.53 mmol). The yellow solution was stirred overnight at ambient temperature. The reaction was quenched with triethylamine (1.2 mL, 8.66 mmol), washed twice with saturated aHC03 solution, dried over Na2S04, filtered, and concentrated. The residue was chromatographed on silica (0-100 % EtOAc in heptane) to give Example 235C (12.851 g, 42.9 mmol, 97 % yield) as a yellow liquid. XH NMR (300 MHz, DMSO-d6) ? 7.65 - 7.52 (m, 2H), 7.48 (s, 1H), 7.44 - 7.36 (m, 1H), 4.00 - 3.92 (m, 2H), 3.90 - 3.81 (m, 2H), 3.23 - 3.13 (m, 2H), 3.03 - 2.92 (m, 2H).

Reference： [1]Patent: WO2013/62964,2013,A2 .Location in patent: Paragraph 1511
[2]Journal of Medicinal Chemistry,2016,vol. 59,p. 4926 - 4947

45
[ 7381-30-8 ]
[ 1379098-58-4 ]
[ 1432050-74-2 ]

Yield	Reaction Conditions	Operation in experiment
99%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at 20℃;	2-[3-(trifluoromethyl)phenyl]-5,8-dioxaspiro[3.4]octane-2-carbonitrile [1533] Example 242B (11.364 g, 47.5 mmol) and l,2-bis(trimethylsilyloxy)ethane (18 mL, 73.2 mmol) were dissolved in dichloromethane (100 mL), followed byt the addition of trimethylsilyl trifluoromethanesulfonate (1.0 mL, 5.53 mmol). The yellow solution was stirred overnight at ambient temperature, quenched with triethylamine (1.2 mL, 8.66 mmol), and washed twice with saturated NaHCC solution. The organic phase was dried over Na2S04, filtered, and concentrated. The mixture was chromatographed on silica (0-100 % EtOAc in heptane) to give Example 242C (13.323 g, 47.0 mmol, 99 % yield) as a yellow liquid. XH NMR (300 MHz, DMSO-d6) ? 7.87 - 7.79 (m, 2H), 7.79 - 7.66 (m, 2H), 4.04 - 3.92 (m, 2H), 3.91 - 3.82 (m, 2H), 3.25 - 3.15 (m, 2H), 3.06 - 2.96 (m, 2H).
99%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at 20℃;	Example 242C 2-[3-(trifluoromethyl)phenyl]-5,8-dioxaspiro[3.4]octane-2-carbonitrile Example 242B (11.364 g, 47.5 mmol) and <strong>[7381-30-8]1,2-bis(trimethylsilyloxy)ethane</strong> (18 mL, 73.2 mmol) were dissolved in dichloromethane (100 mL), followed byt the addition of trimethylsilyl trifluoromethanesulfonate (1.0 mL, 5.53 mmol). The yellow solution was stirred overnight at ambient temperature, quenched with triethylamine (1.2 mL, 8.66 mmol), and washed twice with saturated NaHCO3 solution. The organic phase was dried over Na2SO4, filtered, and concentrated. The mixture was chromatographed on silica (0-100% EtOAc in heptane) to give Example 242C (13.323 g, 47.0 mmol, 99% yield) as a yellow liquid. 1H NMR (300 MHz, DMSO-d6) delta 7.87-7.79 (m, 2H), 7.79-7.66 (m, 2H), 4.04-3.92 (m, 2H), 3.91-3.82 (m, 2H), 3.25-3.15 (m, 2H), 3.06-2.96 (m, 2H).

Reference： [1]Patent: WO2013/62964,2013,A2 .Location in patent: Paragraph 1532; 1533
[2]Patent: US2014/80803,2014,A1 .Location in patent: Paragraph 1225
[3]Journal of Medicinal Chemistry,2016,vol. 59,p. 4926 - 4947

46
[ 7381-30-8 ]
[ 1432051-12-1 ]
[ 1432051-15-4 ]

Yield	Reaction Conditions	Operation in experiment
87%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at 20℃;	2-(3-chloro-4-fluorophenyl)-5,8-dioxaspiro[3.4]octane-2-carbonitrile[1579] Example 255B (12.457 g, 55.7 mmol) and l,2-bis(trimethylsilyloxy)ethane (21 mL, 85 mmol) were dissolved in dichloromethane (120 mL), followed by the addition of trimethylsilyl trifluoromethanesulfonate (1.2 mL, 6.64 mmol). The yellow solution was stirred overnight at ambient temperature. The reaction was quenched with triethylamine (1.5 mL, 10.82 mmol), added dichloromethane (100 mL), and washed twice with saturated aHC03 solution (200 mL). The organic phase was dried over Na2S04, filtered, and concentrated. The residue was chromatographed on silica (0-100 % EtOAc in heptane) to give Example 255C (13.041 g, 48.7 mmol, 87 % yield) as a yellow oil. MS (DCI+): m/z 285 (M+NH4). XH NMR (500 MHz, CD3CN) ? 7.60 (dd, J= 6.9, 2.4 Hz, 1H), 7.44 (ddd, J = 8.5, 4.4, 2.5 Hz, 1H), 7.30 (t, J= 8.9 Hz, 1H), 3.98 (t, J= 6.5 Hz, 2H), 3.88 (t, J= 6.3 Hz, 2H), 3.19 - 3.13 (m, 2H), 2.98 - 2.91 (m, 2H).
87%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at 20℃;	Example 255C 2-(3-chloro-4-fluorophenyl)-5,8-dioxaspiro[3.4]octane-2-carbonitrile Example 255B (12.457 g, 55.7 mmol) and <strong>[7381-30-8]1,2-bis(trimethylsilyloxy)ethane</strong> (21 mL, 85 mmol) were dissolved in dichloromethane (120 mL), followed by the addition of trimethylsilyl trifluoromethanesulfonate (1.2 mL, 6.64 mmol). The yellow solution was stirred overnight at ambient temperature. The reaction was quenched with triethylamine (1.5 mL, 10.82 mmol), added dichloromethane (100 mL), and washed twice with saturated NaHCO3 solution (200 mL). The organic phase was dried over Na2SO4, filtered, and concentrated. The residue was chromatographed on silica (0-100% EtOAc in heptane) to give Example 255C (13.041 g, 48.7 mmol, 87% yield) as a yellow oil. MS (DCI+): m/z 285 (M+NH4). 1H NMR (500 MHz, CD3CN) delta 7.60 (dd, J=6.9, 2.4 Hz, 1H), 7.44 (ddd, J=8.5, 4.4, 2.5 Hz, 1H), 7.30 (t, J=8.9 Hz, 1H), 3.98 (t, J=6.5 Hz, 2H), 3.88 (t, J=6.3 Hz, 2H), 3.19-3.13 (m, 2H), 2.98-2.91 (m, 2H).

Reference： [1]Patent: WO2013/62964,2013,A2 .Location in patent: Paragraph 1578; 1579
[2]Patent: US2014/80803,2014,A1 .Location in patent: Paragraph 1247

47
[ 7381-30-8 ]
3-(4-iodophenyl)-4-(3-methylpent-4-ynyl)cyclohex-2-enone [ No CAS ]
7-(4-iodophenyl)-8-(3-methylpent-4-ynyl)-1,4-dioxaspiro[4.5]dec-6-ene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -70℃; for 40h;Inert atmosphere;	To a solution of iodide 16 (11.2 g, 29.6 mmol) and <strong>[7381-30-8]1,2-bis(trimethylsilyloxy)ethane</strong>(29.0 mL, 118 mmol) in CH2Cl2 (148 mL) was added TMSOTf (1.10 mL, 5.92 mmol)at -70 C under Ar atmosphere, and the mixture was stirred for 40 h at same temperature.The reaction was quenched by addition of pyridine (29.6 mL). After concentration ofthe solvent under reduced pressure, the residue was purified by a silica gel columnchromatography (hexane/AcOEt = 5 : 1) to give acetal 17 which is inseparablediastereomeric mixture (9.40 g, 75% yield) as a colorless oil<BOLD>. </BOLD>IR (neat): 3300, 2110, 1484, 1098 cm-1.1H NMR (300 MHz, CDCl3): = 7.62-7.65 (2H, m), 7.05-7.09 (2H, m), 5.69 (1H, s),3.96-4.05 (4H, m), 2.63 (1H, m), 2.31 (1H, m), 1.76-2.02 (5H, m), 1.24-1.50 (4H, m),1.04-1.10 (3H, m).13C NMR (75 MHz, CDCl3): = 146.7, 146.6, 140.4, 137.4, 137.3, 128.6, 128.5, 126.0,125.8, 106.0, 92.9, 88.8, 88.4, 68.5, 68.2, 64.6, 64.4, 35.5, 35.2, 34.2, 34.1, 30.1, 29.9,29.3, 29.3, 25.6, 25.4, 24.8, 24.5, 20.9, 20.4.MS-FAB: m/z 423 [M + H]+.HRMS-FAB: m/z [M + H]+ calcd for C20H24IO2: 423.0821; found: 423.0828.

Reference： [1]Synlett,2013,vol. 24,p. 1998 - 2002

48
[ 7381-30-8 ]
[ 53068-89-6 ]
[ 123522-75-8 ]

Yield	Reaction Conditions	Operation in experiment
78%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78 - 20℃; for 12.5h;Inert atmosphere;	To a solution of the ketone 9 (302 mg, 1.52 mmol) in CH2Cl2 (5.3 mL) was added TMSO(CH2)2OTMS (1.12 mL, 5.43 mmol) at room temperature. After the resulting mixture was cooled to -78C, to this mixture was added a solution of TMSOTf (55 muL, 0.304 mmol) and the mixture was stirred at same temperature. After 30 min, the mixture was allowed to warm to room temperature and kept at this temperature for 12 h. The reaction was quenched with a saturated aqueous solution of NaHCO3. The aqueous layer was extracted with CH2Cl2 three times. The combined organic layer was dried over Na2SO4, filtrated and concentrated under reduced pressure. Purification by silica gel column chromatography (hexane/EtOAc=9:1) gave 286 mg (78% yield) of the acetal 10 as colorless oil: [alpha]D26 +0.23 (c 0.44, CHCl3); 1H NMR (400 MHz, CDCl3) delta 3.85-3.76 (m, 4H), 3.55 (s, 3H), 2.24-2.11 (m, 2H), 1.75-1.60 (m, 2H), 1.53-1.40 (m, 4H), 1.31 (br s, 4H), 0.81 (s, 3H); 13C NMR (100 MHz, CDCl3) delta 175.1, 112.7, 64.9, 64.6, 51.5, 40.8, 34.7, 30.5, 30.1, 29.2, 23.5, 20.7, 19.3; IR (film, cm-1) 2944, 2878, 1738, 1436, 1174, 1090; HRMS (FAB) calcd for C13H23O4 [(M+H)+] 243.1518, found 243.1552.

Reference： [1]Bioorganic and Medicinal Chemistry,2014,vol. 22,p. 3455 - 3464

49
[ 7381-30-8 ]
1-[10-hydroxy-1-methoxy-4-methyl-10-vinyl-1,3,3a,4,5,7,8,9,9a,9b-decahydro-1,5-methanonaphtho[1,2-c]furan-9-yl]ethanone [ No CAS ]
1-methoxy-4-methyl-9-(2-methyl-1,3-dioxolan-2-yl)-10-vinyl-1,3,3a,4,5,7,8,9,9a,9b-decahydro-1,5-methanonaphtho[1,2-c]furan-10-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78 - -25℃; for 6h;Inert atmosphere;	To a mixture of 14b(243 mg, 0.76 mmol) and bis(trimethylsilyloxy)ethane (0.37 mL, 1.53 mmol) in CH2Cl2 (5 mL) at -78oC was added TMSOTf (0.01 mL, 0.05 mmol) and then stirred at -25 oC for 6 h. The reaction mixturewas neutralized with pyridine (0.06 mL, 0.76 mmol) and concentrated to give the residue. The crudeproduct was purified by silica-gel chromatography (EtOAc/hexanes = 1:6) to give 19b (254 mg, 92%) asa yellowish oil. IR (neat) nu3481, 2954, 2876, 1455, 1377, 1214, 1195, 1150, 1093, 993 cm-1; 1H NMR(400 MHz, CDCl3) delta0.97 (d, J = 7.2 Hz, 3H), 1.27 (s, 3H), 1.48-1.53 (m, 1H), 1.77-1.94 (m, 4H),2.04-2.13 (m, 3H), 2.36-2.39 (m, 1H), 2.98-3.00 (m, 1H), 3.31 (s, 3H), 3.54 (d, J = 8.0 Hz, 1H), 3.86-3.99 (m, 6H), 5.01 (dd, J = 2.8, 10.8 Hz, 1H), 5.39-5.41 (m, 1H), 5.43 (dd, J = 2.8, 16.8 Hz, 1H), 6.01(dd, J = 10.8, 16.8 Hz, 1H); 13C NMR (100 MHz, CDCl3): delta20.0, 20.7, 24.8, 25.8, 32.8, 35.7, 40.1, 42.5,46.6, 50.4, 55.6, 63.5, 64.3, 72.8, 78.5, 108.9, 110.7, 112.1, 124.2, 134.7, 141.0; MS (EI) m/z (% basepeak) 362 (M+, 2), 300 (4), 257 (3), 240 (3), 230 (3), 215 (7), 202 (8), 197 (6), 185 (7), 145 (16), 87(100); HRMS (EI) calcd for C21H30O5 362.2093, found 362.2099

Reference： [1]Tetrahedron Letters,2014,vol. 55,p. 5315 - 5318

50
[ 7381-30-8 ]
4-fluoro-7-((trifluoromethyl)sulfonyl)-2,3-dihydro-1H-inden-1-one [ No CAS ]
4’-fluoro-7’-(trifluoromethylsulfonyl)spiro[ 1,3-dioxolane-2,1‘-indane] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78 - 20℃; for 2h;	Trimethylsily trifluoromethanesulfonate (10.6 g, 47.8 mmol) was added dropwise to a' solution of 4-fluoro-7-(trifluoromethylsulfonyl)indan-l - one (27.0 g, 95.7 mmol) and trimethyl(2-trimethylsiilyloxyethoxy)silane (23.7 g, 1 14.8 mmol) in dichloromethane (500 mL) at -78 C. After addition, the reaction mixture was allowed to warm to ambient temperature. After 2 hours at ambient temperature, the reaction was quenched with triethylamine and the mixture was concentrated under reduced pressure. The residue was dissolved in ethyl acetate ( 500 mL), washed with water (2 x 200 mL), brine (500 mL), dried (sodium sulfate), filtered, and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel eluting with 20% ethyl acetate in hexane to give 4-fluoro-7-((trifluoromethyl)sulfonyl)-2,3-dihydrospiro[indene- l ,2'- [l ,3]dioxolane] (25.0 g, 80%) as a white solid.
80%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78 - 20℃; for 2h;	Trimethylsily trifluoromethanesulfonate (10.6 g, 47.8 mmol) was added dropwise to a solution of 4-fluoro-7-(trifluoromethylsulfonyl)indan- 1-one (27.0 g, 95.7 mmol) and trimethyl(2-trimethylsiilyloxyethoxy)silane (23.7 g, 114.8 mmol) in dichloromethane (500 mL) at -78C. The reaction mixture was allowed to warm to ambient temperature and stirred at ambient temperature for 2 hours. The reaction was then quenched with excess triethyl amine. The volatiles were removed under reduced pressure. The residue was taken up in ethyl acetate (500 mL) and organics were washed with water, brine dried (sodium sulfate), filtered and concentrated under reduced pressure. The residue obtained was purified by flash chromatography on silica gel 4: 1 hexane/ethyl acetate to give 4-fluoro-7-((trifluoromethyl)sulfonyl)-2,3-dihydrospiro[indene-l,2'-[l,3]dioxolane] (25.0 g, 80%) as solid.
55%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78 - 20℃;	Trimethylsily trifluoromethanesulfonate (10.6 g, 47.8 mmol) was added dropwise to a solution of 4-fluoro-7-(trifluoromethylsulfonyl)indan-l-one (27 g, 95.7 mmol) and trimethyl(2-trimethylsilyloxyethoxy)silane (23.7 g, 1 15 mmol) in dichloromethane (500 mL) at -78 C. The reaction mixture was allowed to warm to room temperature. After 2 hours, the reaction was then quenched with triethylamine and evaporated. The residue was taken up in EtOAc (500 mL) and the organic layer was washed with 2 x 200 mL water then 1 x 500 mL saturated brine solution. The organic layer was separated, dried (NaS04), and concentrated to dryness. The crude was purified by flash column chromatography eluting with 20% EtOAc in hexane to give 4-fluoro-7-((trifluoromethyl)sulfonyl)-2,3- dihydrospiro[indene-l,2'-[l,3]dioxolane] (2.1 g, 6.4 mmol, 55% yield) as a white solid.

Reference： [1]Patent: WO2015/35223,2015,A1 .Location in patent: Paragraph 0956
[2]Patent: WO2016/144825,2016,A1 .Location in patent: Paragraph 0746
[3]Patent: WO2016/57242,2016,A1 .Location in patent: Paragraph 0255

51
[ 7381-30-8 ]
4-fluoro-7-(fluoromethylsulfonyl)indan-1-one [ No CAS ]
4’-fluoro-7’-(fluoromethylsulfonyl)spiro[1,3-dioxolane-2,1‘-indane] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78 - 20℃; for 5.5h;	Trimethylsilyl trifluoromethanesulfonate (0.1 mL, 0.570 mmol) was added to a solution of 4-fluoro-7-(fluoromethylsulfonyl)indan-l -one (700 mg, 2.8 mmol) and trimethyl(2-trimethylsilyloxyethoxy)silane (1.4 mL, 5.7 mmol) in dichloromethane (50 mL) cooled to -78 C. The reaction mixture was allowed to warm to ambient temperature. After 5.5 hours, the reaction mixture was quenched with triethylamine (1.58 mL, 1 1.4 mmol) and evaporated. The residue was partitioned between EtOAc and dilute NaCl. The EtOAc was washed with water, brine, dried over MgS04, filtered, and evaporated to afford 4'-fluoro-7'-(fluoromethylsulfonyl)spiro[l ,3-dioxolane-2, -indane] (630 mg, 2.2 mmol, 76% yield).
76%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78 - 20℃;	Trimethylsilyl trifluoromethanesulfonate (0.1 mL, 0.570 mmol) was added to a solution of 4-fluoro-7-(fluoromethylsulfonyl)indan-l-one (700 mg, 2.8 mmol) and trimethyl(2-trimethylsilyloxyethoxy)silane (1.4 mL, 5.7 mmol) in dichloromethane (50 mL) cooled to -78 C. The reaction mixture was allowed to warm to ambient temperature. After 5.5 hours, the reaction mixture was quenched with triethylamine (1.58 mL, 11.4 mmol) and evaporated. The residue was partitioned between EtOAc and dilute NaCl. The EtOAc was washed with water, brine, dried over MgS04, filtered, and evaporated to afford 4'-fluoro-7'-(fluoromethylsulfonyl)spiro[ 1,3 -dioxolane-2, l'-indane] (630 mg, 2.2 mmol, 76% yield).

Reference： [1]Patent: WO2015/35223,2015,A1 .Location in patent: Paragraph 0471
[2]Patent: WO2016/57242,2016,A1 .Location in patent: Paragraph 0171

52
[ 7381-30-8 ]
4-fluoro-7-(methylsulfonyl)-2,3-dihydro-1H-inden-1-one [ No CAS ]
4’-fluoro-7’-methylsulfonyl-spiro[1,3-dioxolane-2,1’-indane] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
64%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78 - 20℃; for 6h;Inert atmosphere;	Trimethylsilyl trifluoromethanesulfonate (4.8 mL, 26.6 mmol) was added dropwise to a solution of 4-fluoro-7-(methylsulfonyl)-2,3-dihydro-lH-inden-l-one (19.1 g, 83.6 mmol) and trimethyl(2-trimethylsilyloxyethoxy)silane (28.5 mL, 1 16 mmol) in dichloromethane (3 0 mL) which was cooled to -78 C under nitrogen. The reaction mixture was allowed to warm to ambient temperature. After 6 hours, the reaction was quenched with triethylamine (46.6 mL, 334 mmol) and evaporated. The residue was partitioned between EtOAc and brine. The organic layer was washed with water and brine, dried over MgS04, filtered, and evaporated. Dichloromethane was added to the residue which caused a solid to form. The precipitated product was collected by filtration, washed with 50% dichloromethane/hexanes and air-dried to afford 4-fluoro-7-(methylsulfonyl)-2,3- dihydrospiro[indene-l ,2'-[l,3]dioxolane] (9.95 g). The filtrate was concentrated and purified by flash chromatography on silica gel (20-60% EtOAc/hexane) to give additional 4-fluoro-7- (methylsulfonyl)-2,3-dihydrospiro[indene-l ,2'-[l ,3]dioxolane] (4.58 g, combined 14.5 g, 64%). LCMS ESI (+) m/z 273 (Mu+Eta).

Reference： [1]Patent: WO2015/35223,2015,A1 .Location in patent: Paragraph 0793

53
[ 7381-30-8 ]
7-(3-cyano-5-fluoro-phenoxy)-3-oxo-indane-4-sulfonamide [ No CAS ]
7’-(3-cyano-5-fluoro-phenoxy)spiro[1,3-dioxolane-2,3‘-indane]-4’-sulfonamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
45%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78 - 20℃; for 3h;	To a stirred solution of 7-(3-cyano-5-fluoro-phenoxy)-3-oxo-indane- 4-sulfonamide (2.80 g, 8.1 mmol) in DCM (54 mL) was added trimethyl(2- trimethylsilyloxyethoxy)silane (2.78 mL,l 1.3 mmol). The reaction mixture was cooled to - 78 C. Trimethylsilyl trifluoromethanesulfonate (0.58 mL, 3.2 mmol) was added dropwise under nitrogen. The reaction mixture was allowed to warm to ambient temperature. After stirring for 2 hours, additional trimethyl(2-trimethylsilyloxyethoxy)silane (1.40 mL, 5.60 mmol) was added, and the reaction was stirred at ambient temperature for additional 1 hour. Triethylamine (3.38 mL, 24.3 mmol) was added dropwise. After stirring for 10 minutes, the reaction was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (20-50% EtOAc/hexane) to give 7'-(3-cyano-5-fluoro- phenoxy)spiro[l ,3-dioxolane-2,3'-indane]-4'-sulfonamide ( 1.41 g, 45%). LCMS ESI (-) m/z 389 (M-H).

Reference： [1]Patent: WO2015/35223,2015,A1 .Location in patent: Paragraph 01416

54
[ 7381-30-8 ]
(R)-3-bromo-5-[(tert-butyldiphenylsilyl)oxy]pentan-2-one [ No CAS ]
(R)-[3-bromo-3-(2-methyl-1,3-dioxolan-2-yl)propoxy](tert-butyl)diphenylsilane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
100%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -20℃; for 18h;	To a solution of33 (492 mg, 1.17 mmol) and (TMSOCH2)2 (2.88 mL, 11.7 mmol) in CH2Cl2 (10 mL) was addedTMSOTf (0.113 mL, 0.587 mmol) at -20 C, and the mixture was stirred for 18 h. Then, saturated aq.NaHCO3 (10 mL) was added, and the mixture was extracted with hexane several times. The combinedorganic layers were washed with brine, dried over anhydrous MgSO4, filtered, and concentrated underreduced pressure. The residue was purified by column chromatography (silica gel, hexane/EtOAc = 50) togive 34 (552 mg, 1.18 mmol, 100%); a colorless oil; [alpha]D25 +22.9 (c 0.910, CHCl3); IR (neat) nu 3071,3049, 2957, 2930, 2883, 2858, 1472, 1463, 1446, 1428, 1380, 1362, 1307, 1274, 1252, 1218, 1188, 1145,1112, 1057, 1038, 1008, 998, 949, 937, 874, 823, 738, 702, 688, 614 cm-1; 1H NMR (300MHz, CDCl3) delta1.05 (9H, s), 1.50 (3H, s), 1.81 (1H, tdd, J = 3.6, 11.3, 14.4 Hz), 2.32 (1H, dddd, J = 2.0, 6.1, 9.6, 14.4Hz), 3.79-3.93 (2H, m), 3.96-4.07 (4H, m), 4.29 (1H, dd, J = 2.0, 11.3 Hz), 7.34-7.47 (6H, m), 7.64-7.72(4H, m); 13C NMR (75 MHz, CDCl3) delta 19.2 (C), 20.8 (CH3), 26.8 (CH3 × 3), 36.7 (CH2), 55.8 (CH), 61.2(CH2), 65.3 (CH2), 65.4 (CH2), 109.7 (C), 127.7 (CH × 4), 129.6 (CH × 2), 133.5 (C), 133.6 (C) 135.5(CH × 2), 135.6 (CH × 2); FD-HRMS (m/z) calcd for C23H32O3Si79Br [M+-H]: 463.1304, found:463.1278.

Reference： [1]Heterocycles,2015,vol. 91,p. 76 - 103

55
[ 7381-30-8 ]
[ 37112-31-5 ]
2,2-(ethylenedioxy)-1,6-anhydro-2,3,4-dideoxy-β-D-glycerohex-3-enopyranose [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78 - 20℃;	A solution of 0.008 mL (0.004 mmol) of trimethylsilyl trifluoro-methanesulfonate in 3 mL of methylene chloride was cooled to -78C, 0.17 g (0.8 mmol) of 1,2-bis(trimeth-ylsiloxy)ethane and 0.05 g (0.4 mmol) of levoglucosenone (3) were added, and the mixture was allowed to warm up to room temperature and stirred until the initial compound disappeared (TLC). The mixture was treated with a few drops of pyridine saturated with aqueous NaHCO 3 and extracted with methylene chloride (3 × 5 mL), the combined extracts were dried over MgSO 4 , the solvent was distilled off, and the residue was purified by silica gel column chromatography. Yield 0.04 g (60%), colorless crystals, mp 110C,[alpha]D20 = -92.0 (c = 0.2, CHCl3), Rf 0.14 (EtOAc-petroleum ether, 3 : 1). 1H NMR spectrum, delta, ppm:3.72 d (1H, 6-HB, 2J = 7.8 Hz), 4.10 m (3H, 6-HA,CH2), 4.75 m (1H, 5-H), 5.2 d (1H, 1-H, J = 2.1 Hz),5.65 m (1H, 3-H), 6.25 m (1H, 4-H). 13C NMR spectrum,deltaC, ppm: 65.26 (CH2), 65.39 (CH2), 67.68 (C6),70.83 (C5), 100.92 (C1), 101.99 (C2), 125.98 (C3),132.48 (C4). Found, %: C 56.39; H 5.89. C8H10O4. Calculated,%: C 56.42; H 5.88

Reference： [1]Russian Journal of Organic Chemistry,2015,vol. 51,p. 569 - 575
Zh. Org. Khim.,2015,vol. 51,p. 587 - 592,6

56
[ 7381-30-8 ]
4-bromo-1-(methylsulfonyl)-5,6-dihydro-7H-cyclopenta[c]pyridin-7-one [ No CAS ]
4-bromo-1-(methylsulfonyl)-5,6-dihydrospiro[cyclopenta[c]pyridine-7,2'-[1,3]dioxolane] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
59%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane;Cooling with ice;	Trimethylsilyl trifluoromethanesulfonate (331 muL, 1.83 mmol) was added to a solution of 4-bromo-1-methylsulfonyl-5,6-dihydrocyclopenta[c]pyridin-7-one (354 mg, 1.22 mmol) and trimethyl(2-trimethylsilyloxyethoxy)silane (1.20 mL, 4.88 mmol) in dichloromethane (14 mL) cooled in an ice bath. The ice bath was removed. After 3 h, an additional portion of trimethyl(2-trimethylsilyloxyethoxy)silane (1.20 mL, 4.88 mmol) was added. The reaction was left to stir overnight. After stirring, for the rest of the day, the reaction was quenched by the addition of triethylamine (1.02 mL, 7.32 mmol). The reaction mixture stirred for 10 min. Volatiles were removed and the residue suspended into 30 mL of saturated aqueous NaHCO3 and extracted with 3*20 mL EtOAc. The combined organics were rinsed with 10 mL of brine, dried with MgSO4, filtered, and concentrated to dryness. Purification was achieved by chromatography on silica using 15-50% EtOAc/hexane to afford 4-bromo-1-(methylsulfonyl)-5,6-dihydrospiro[cyclopenta[c]pyridine-7,2'-[1,3]dioxolane] as a white solid (74.5 mg, 18%). LCMS ESI (+) (M+H) m/z 334/336.
18%		j00559J Step G: Preparation of 4-bromo-1-(methylsulfonyl)-5.6-dihydrospiro[cyclopenta[clpyridine-7.2?-[ 1.3 idioxolanel: Trimethylsilyl trifluoromethanesulfonate (331 tL, 1.83 mmol) was added to a solution of 4-bromo- 1- methyl sulfonyl-5 , 6-dihydrocyclopenta[c]pyridin-7-one (354 mg, 1.22 mmol) and trimethyl(2- trimethylsilyloxyethoxy)silane (1.20 mL, 4.88 mmol) in dichloromethane (14 mL) cooled in an ice bath. The ice bath was removed. After 3 h, an additional portion of trimethyl(2- trimethylsilyloxyethoxy)silane (1.20 mL, 4.88 mmol) was added. The reaction was left to stir overnight. After stirring, for the rest of the day, the reaction was quenched by the addition of triethylamine (1.02 mL, 7.32 mmol). The reaction mixture stirred for 10 mi Volatiles were removed and the residue suspended into 30 mL of saturated aqueous NaHCO3 and extracted with 3 x 20 mL EtOAc. The combined organics were rinsed with 10 mL of brine, dried with Mg504, filtered, and concentrated to dryness. Purification was achieved by chromatography on silica using 15-50% EtOAc/hexane to afford 4-bromo-1- (methylsulfonyl)-5,6-dihydrospiro[cyclopenta[c]pyridine-7,2?-[ 1,3 ]dioxolane] as a white solid (74.5 mg, 18%). LCMS ESI (+) (M+H) m/z 334 / 336. The bulk of the product was isolated as the enol ether (295 mg, 59%).
18%		Trimethylsilyltrifluoromethanesulfonate (331 muL, 1.83 mmol) was added to a solution of 4-bromo-1- methylsulfonyl-5,6-dihydrocyclopenta[c]pyridin-7-one (354 mg, 1.22 mmol) and trimethyl(2- trimethylsilyloxyethoxy)silane (1.20 mL, 4.88 mmol) in dichloromethane (14 mL) cooled in an ice bath. The ice bath was removed. After 3 h, an additional portion of trimethyl(2- trimethylsilyloxyethoxy)silane (1.20 mL, 4.88 mmol) was added. The reaction was left to stir overnight. After stirring, for the rest of the day, the reaction was quenched by the addition of triethylamine (1.02 mL, 7.32 mmol). The reaction mixture stirred for 10 min. Volatiles were removed and the residue suspended into 30 mL of saturated aqueous NaHCO3 and extracted with 3 x 20 mL EtOAc. The combined organics were rinsed with 10 mL of brine, dried with MgS04, filtered, and concentrated to dryness. Purification was achieved by chromatography on silica using 15-50% EtOAc/hexane to afford 4-bromo-l-(methylsulfonyl)-5,6- dihydrospiro[cyclopenta[c]pyridine-7,2'-[l,3]dioxolane] as a white solid (74.5 mg, 18%). LCMS ESI (+) (M+H) m/z 334 / 336. The bulk of the product was isolated as the enol ether (295 mg, 59%).

74.5 mg

With trimethylsilyl trifluoromethanesulfonate; In dichloromethane;Cooling with ice;

Trimethylsilyl trifluoromethanesulfonate (331 mu^, 1.83 mmol) was added to a solution of 4-bromo-l- methylsulfonyl-5,6-dihydrocyclopenta[c]pyridin-7-one (354 mg, 1.22 mmol) and trimethyl(2- trimethylsilyloxyethoxy)silane (1.20 mL, 4.88 mmol) in dichloromethane (14 mL) cooled in an ice bath. The ice bath was removed. After 3 h, an additional portion of trimethyl(2- trimethylsilyloxyethoxy)silane (1.20 mL, 4.88 mmol) was added. The reaction was left to stir overnight. After stirring, for the rest of the day, the reaction was quenched by the addition of triethylamine (1.02 mL, 7.32 mmol). The reaction mixture stirred for 10 min. Volatiles were removed and the residue suspended into 30 mL of saturated aqueous NaHC03 and extracted with 3 x 20 mL EtOAc. The combined organics were rinsed with 10 mL of brine, dried with MgS04, filtered, and concentrated to dryness. Purification was achieved by chromatography on silica using 15-50% EtOAc/hexane to afford 4-bromo-l-(methylsulfonyl)-5,6- dihydrospiro[cyclopenta[c]pyridine-7,2'-[l,3]dioxolane] as a white solid (74.5 mg, 18%). LCMS ESI (+) (M+H) m/z 334 / 336. The bulk of the product was isolated as the enol ether (295 mg, 59%).

Reference： [1]Patent: US2018/140569,2018,A1 .Location in patent: Paragraph 0872
[2]Patent: WO2016/145032,2016,A1 .Location in patent: Paragraph 00559
[3]Patent: WO2016/145045,2016,A1 .Location in patent: Paragraph 00520
[4]Patent: WO2016/144826,2016,A1 .Location in patent: Paragraph 0451

57
[ 7381-30-8 ]
4-bromo-7-((trifluoromethyl)sulfonyl)-2,3-dihydro-1H-inden-1-one [ No CAS ]
4-bromo-7-((trifluoromethyl)sulfonyl)-2,3-dihydrospiro[indene-1,2’-[1,3]dioxolane] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78 - 20℃; for 2h;	j00596J Step H: Preparation of 4-bromo-7-((trifluoromethyl)sulfonyl)-2.3 - dihydrospiro[indene- 1.2?- [1.3 idioxolanel: Trimethylsilyl trifluoromethanesulfonate (177 mg, 0.80 mmol) was added dropwise to a pre-cooled (-78 C) solution of 4-bromo-7- ((trifluoromethyl)sulfonyl)-2,3 -dihydro- 1H-inden- 1-one and trimethyl(2- trimethylsilyloxyethoxy)silane (410 mg, 2.0 mmol) dissolved in dichloromethane (50 mL). The reaction mixture was warmed to ambient temperature and stirred for 2 hours. The reaction was quenched by addition of triethylamine then concentrated in vacuo. The residue was redissolved in ethyl acetate and washed twice with water, and saturated NaC1. The organic layer was separated, dried over Na2504 and concentrated in vacuo. The crude product was purified by chromatography on 5i02 eluting with ethyl acetate / isohexane, (600 mg, 77%).
77%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78 - 20℃; for 2h;	Trimethylsilyl trifluoromethanesulfonate (177 mg, 0.80 mmol) was added dropwise to a pre-cooled (-78 C) solution of 4-bromo-7- ((trifluoromethyl)sulfonyl)-2,3 -dihydro- lH-inden- 1 -one and trimethyl(2- trimethylsilyloxyethoxy)silane (410 mg, 2.0 mmol) dissolved in dichloromethane (50 mL). The reaction mixture was warmed to ambient temperature and stirred for 2 hours. The reaction was quenched by addition of triethylamine then concentrated in vacuo. The residue was redissolved in ethyl acetate and washed twice with water, and saturated NaCl. The organic layer was separated, dried over Na2S04 and concentrated in vacuo. The crude product was purified by chromatography on Si02 eluting with ethyl acetate / isohexane, (600 mg, 77%).
77%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78 - 20℃; for 2h;	Trimethylsilyl trifluoromethanesulfonate (177 mg, 0.80 mmol) was added dropwise to a pre-cooled (-78 C) solution of 4-bromo-7-((trifluoromethyl)sulfonyl)-2,3-dihydro-lH-inden-l-one and trimethyl(2- trimethylsilyloxyethoxy)silane (410 mg, 2.0 mmol) dissolved in dichloromethane (50 mL). The reaction mixture was warmed to ambient temperature and stirred for 2 hours. The reaction was quenched by addition of triethylamine then concentrated in vacuo. The residue was redissolved in ethyl acetate and washed twice with water, and saturated NaCl. The organic layer was separated, dried over Na2SO4 and concentrated in vacuo. The crude product was purified by chromatography on SiO2 eluting with ethyl acetate / isohexane, (600 mg, 77%).

77%	With trimethylsilyl trifluoromethanesulfonate; triethylamine; In dichloromethane; at -78 - 20℃; for 2h;	Trimethylsilyl trifluoromethanesulfonate (177 mg, 0.80 mmol) was added dropwise to a pre-cooled (-78 C.) solution of 4-bromo-7-((trifluoromethyl)sulfonyl)-2,3-dihydro-1H-inden-1-one and trimethyl(2-trimethylsilyloxyethoxy)silane (410 mg, 2.0 mmol) dissolved in dichloromethane (50 mL). The reaction mixture was warmed to ambient temperature and stirred for 2 hours. The reaction was quenched by addition of triethylamine then concentrated in vacuo. The residue was redissolved in ethyl acetate and washed twice with water, and saturated NaCl. The organic layer was separated, dried over Na2SO4 and concentrated in vacuo. The crude product was purified by chromatography on SiO2 eluting with ethyl acetate/isohexane, (600 mg, 77%).
77%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78 - 20℃; for 2h;	Trimethyl silyl trifluoromethanesulfonate (177 mg, 0.80 mmol) was added dropwise to a pre-cooled (-78 C) solution of 4-bromo-7- ((trifluoromethyl)sulfonyl)-2, 3 -dihydro- 1 //-in den- 1 -one and trimethyl(2- trimethylsilyloxyethoxy)silane (410 mg, 2.0 mmol) dissolved in dichloromethane (50 mL). The reaction mixture was warmed to ambient temperature and stirred for 2 hours. The reaction was quenched by addition of triethylamine then concentrated in vacuo. The residue was redissolved in ethyl acetate and washed twice with water, and saturated NaCl. The organic layer was separated, dried over Na2S04 and concentrated in vacuo. The crude product was purified by chromatography on Si02 eluting with ethyl acetate / isohexane, (600 mg, 77%).

Reference： [1]Patent: WO2016/145032,2016,A1 .Location in patent: Paragraph 00596
[2]Patent: WO2016/144825,2016,A1 .Location in patent: Paragraph 0611
[3]Patent: WO2016/145045,2016,A1 .Location in patent: Paragraph 00557
[4]Patent: US2018/140569,2018,A1 .Location in patent: Paragraph 0909
[5]Patent: WO2019/191227,2019,A1 .Location in patent: Paragraph 0281; 0289

58
[ 7381-30-8 ]
4-bromo-1-(trifluoromethyl)-5 , 6-dihydro-7H-cyclopenta[c]pyridin-7-one [ No CAS ]
4-bromo-1-(trifluoromethyl)-5,6-dihydrospiro[cyclopenta[c]pyridine-7,2’-[1,3]dioxolane] [ No CAS ]
4-bromo-1-(trifluoromethyl)-7-(2-((trimethylsilyl)oxy)ethoxy)-5H-cyclopenta[c]pyridine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
58%; 31%		j00539J Step B: Preparation of 4-bromo- 1 -(trifluoromethyl)-5 .6- dihydrospiro[cyclopenta[clpyridine-7.2?-[ 1.3 idioxolanel and 4-bromo- 1 -(trifluoromethyl)-7- (2-((trimethyl silyl)oxy)ethoxy)-5H-cyclopenta[clpyridine: Trimethyl silyl trifluoromethanesulfonate (75.9 tL, 0.42 mmol) was added to a solution of 4-bromo-1- (trifluoromethyl)-5 , 6-dihydrocyclopenta[c]pyridin-7-one (389 mg, 1.39 mmol) and trimethyl(2-trimethylsilyloxyethoxy)silane (1.37 mL, 5.56 mmol) in dichloromethane (13.6 mL) cooled in an ice bath. The mixture was allowed to slowly warm to ambient temperature. After 5 h, an additional 1.3 mL of trimethyl(2-trimethylsilyloxyethoxy)silane and 76 tL of trimethylsilyl trifluoromethanesulfonate were added. After another 16 h, the reaction mixture was treated with triethylamine (770 .iL, 5.56 mmol), stirred for 10mm, and then concentrated. The residue was treated with 20 mL EtOAc and 20 mL of water and the layers separated. The aqueous portion was extracted further with 2 x 20 mL of EtOAc. The combined organic extracts were washed with brine, dried over Mg504, filtered, and evaporated. Purification was achieved by chromatography on silica using 5-20% EtOAc/hexane to afford 4-bromo- 1 -(trifluoromethyl)-5 ,6- dihydrospiro[cyclopenta[c]pyridine-7,2?-[1,3]dioxolane] as a shite solid (262 mg, 58%) and 4-bromo- 1 -(trifluoromethyl)-7-(2-((trimethyl silyl)oxy)ethoxy)-5H-cyclopenta[c]pyridine as a white solid (170 mg, 31%). Data for 4-bromo-1-(trifluoromethyl)-5.6- dihydrospiro[cyclopenta[clpyridine-7.2?-[1.3ldioxolanel: LCMS ESI (+) (M+H) m/z 324 / 326. Data for 4-bromo- 1 -(trifluoromethyl)-7-(2-((trimethyl silyl)oxy)ethoxy)-5H- cyclopenta[clpyridine: ?HNIVIR (400 IVIHz, CDC13): 8.56 (s, 1H), 5.59 (t, 1H), 4.10 (t, 2H), 3.96 (t, 2H), 3.36 (d, 2H), 0.15 (s, 9H).
58%; 31%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at 20℃; for 21h;Cooling with ice;	Trimethylsilyl trifluoromethanesulfonate (75.9 mu^, 0.42 mmol) was added to a solution of 4-bromo- l-(trifluoromethyl)-5, 6- dihydrocyclopenta[c]pyridin-7-one (389 mg, 1.39 mmol) and trimethyl(2- trimethylsilyloxyethoxy)silane (1.37 mL, 5.56 mmol) in dichloromethane (13.6 mL) cooled in an ice bath. The mixture was allowed to slowly warm to ambient temperature. After 5 h, an additional 1.3 mL of trimethyl(2-trimethylsilyloxyethoxy)silane and 76 mu^ of trimethylsilyl trifluoromethanesulfonate were added. After another 16 h, the reaction mixture was treated with triethylamine (770 mu^, 5.56 mmol), stirred for lOmin, and then concentrated. The residue was treated with 20 mL EtOAc and 20 mL of water and the layers separated. The aqueous portion was extracted further with 2 x 20 mL of EtOAc. The combined organic extracts were washed with brine, dried over MgS04, filtered, and evaporated. Purification was achieved by chromatography on silica using 5-20% EtOAc/hexane to afford 4-bromo- 1 -(trifluorom ethyl)- 5,6-dihydrospiro[cyclopenta[c]pyridine-7,2'-[l,3]dioxolane] as a shite solid (262 mg, 58%) and 4-bromo- 1 -(trifluoromethyl)-7-(2-((trimethylsilyl)oxy)ethoxy)-5H-cyclopenta[c]pyridine as a white solid (170 mg, 31%). Data for 4-bromo-l-(trifluoromethyl)-5,6- dihvdrospirolcvclopentalc1pyridine-7.2'-r 1.3 ldioxolanel : LCMS ESI (+) (M+H) m/z 324 / 326. Data for 4-bromo-l-(trifluoromethyl)-7-(2-((trimethylsilyl)oxy)ethoxy)-5H- cvclopentalclpyridine: 1H MR (400 MHz, CDC13): delta 8.56 (s, 1H), 5.59 (t, 1H), 4.10 (t, 2H), 3.96 (t, 2H), 3.36 (d, 2H), 0.15 (s, 9H).
58%; 31%		Trimethyl silyl trifluoromethanesulfonate (75.9 muL, 0.42 mmol) was added to a solution of 4-bromo-1-(trifluoromethyl)-5,6-dihydrocyclopenta[c]pyridin-7-one (389 mg, 1.39 mmol) and trimethyl(2- trimethylsilyloxyethoxy)silane (1.37 mL, 5.56 mmol) in dichloromethane (13.6 mL) cooled in an ice bath. The mixture was allowed to slowly warm to ambient temperature. After 5 h, an additional 1.3 mL of trimethyl(2-trimethylsilyloxyethoxy)silane and 76 tL of trimethylsilyl trifluoromethanesulfonate were added. After another 16 h, the reaction mixture was treated with triethylamine (770 muL, 5.56 mmol), stirred for 10mm, and then concentrated. The residue was treated with 20 mL EtOAc and 20 mL of water and the layers separated. The aqueous portion was extracted further with 2 x 20 mL of EtOAc. The combined organic extracts were washed with brine, dried over MgSO4, filtered, and evaporated. Purification was achieved by chromatography on silica using 5-20% EtOAc/hexane to afford 4-bromo-1-(trifluoromethyl)- 5,6-dihydrospiro[cyclopenta[c]pyridine-7,2?-[1,3]dioxolane] as a shite solid (262 mg, 58%) and4-bromo-1-(trifluoromethyl)-7-(2-((trimethyl silyl)oxy)ethoxy)-5H-cycl openta[c]pyridine as a white solid (170 mg, 31%). Data for 4-bromo-1-(trifluoromethyl)-5.6- dihydrospiro[cyclopenta[clpyridine-7,2?-[1,3ldioxolanel: LCMS ESI (+) (M+H) m/z 324 / 326. Data for 4-bromo- 1 -(trifluoromethyl)-7-(2-((trimethyl silyl)oxy)ethoxy)-5H- cyclopenta[clpyridine: 1H NMR (400 MHz, CDCl3): 8.56 (s, 1H), 5.59 (t, 1H), 4.10 (t, 2H), 3.96 (t, 2H), 3.36 (d, 2H), 0.15 (s, 9H).

58%; 31%		Trimethylsilyl trifluoromethanesulfonate (75.9 muL, 0.42 mmol) was added to a solution of 4-bromo-1-(trifluoromethyl)-5,6-dihydrocyclopenta[c]pyridin-7-one (389 mg, 1.39 mmol) and trimethyl(2-trimethylsilyloxyethoxy)silane (1.37 mL, 5.56 mmol) in dichloromethane (13.6 mL) cooled in an ice bath. The mixture was allowed to slowly warm to ambient temperature. After 5 h, an additional 1.3 mL of trimethyl(2-trimethylsilyloxyethoxy)silane and 76 muL of trimethylsilyl trifluoromethanesulfonate were added. After another 16 h, the reaction mixture was treated with triethylamine (770 muL, 5.56 mmol), stirred for 10 min, and then concentrated. The residue was treated with 20 mL EtOAc and 20 mL of water and the layers separated. The aqueous portion was extracted further with 2*20 mL of EtOAc. The combined organic extracts were washed with brine, dried over MgSO4, filtered, and evaporated. Purification was achieved by chromatography on silica using 5-20% EtOAc/hexane to afford 4-bromo-1-(trifluoromethyl)-5,6-dihydrospiro[cyclopenta[c]pyridine-7,2'-[1,3]dioxolane] as a shite solid (262 mg, 58%) and 4-bromo-1-(trifluoromethyl)-7-(2-((trimethylsilyl)oxy)ethoxy)-5H-cyclopenta[c]pyridine as a white solid (170 mg, 31%). Data for 4-bromo-1-(trifluoromethyl)-5,6-dihydrospiro[cyclopenta[c]pyridine-7,2'-[1,3]dioxolane]: LCMS ESI (+) (M+H) m/z 324/326. Data for 4-bromo-1-(trifluoromethyl)-7-(2-((trimethyl silyl)ox)ethoxy)-5H-cyclopenta[c]pyridine: 1H NMR (400 MHz, CDCl3): delta 8.56 (s, 1H), 5.59 (t, 1H), 4.10 (t, 2H), 3.96 (t, 2H), 3.36 (d, 2H), 0.15 (s, 9H).
58%; 31%		: Trimethylsilyl (0804) trifluoromethanesulfonate (75.9 pL, 0.42 mmol) was added to a solution of 4-bromo-l- (trifluoromethyl)-5,6-dihydrocyclopenta[c]pyridin-7-one (389 mg, 1.39 mmol) (0805) and trimethyl(2-trimethylsilyloxyethoxy)silane (1.37 mL, 5.56 mmol) in dichloromethane (13.6 mL) cooled in an ice bath. The mixture was allowed to slowly warm to ambient temperature. After 5 h, an additional 1.3 mL of trimethyl(2-trimethylsilyloxyethoxy)silane and 76 pL of trimethylsilyl trifluoromethanesulfonate were added. After another 16 h, the reaction mixture was treated with triethylamine (770 pL, 5.56 mmol), stirred for lOmin, and then concentrated. The residue was treated with 20 mL EtOAc and 20 mL of water and the layers separated. The aqueous portion was extracted further with 2 x 20 mL of EtOAc. The combined organic extracts were washed with brine, dried over MgS04, filtered, and evaporated. Purification was achieved by chromatography on silica using 5-20% (0806) EtOAc/hexane to afford 4-bromo-l-(trifluoromethyl)-5,6- dihydrospiro[cyclopenta[c]pyridine-7,2'-[l,3]dioxolane] as a shite solid (262 mg, 58%) and 4-bromo- 1 -(trifluoromethyl)-7-(2-((trimethylsilyl)oxy)ethoxy)-5iT-cyclopenta[c]pyridine as a white solid (170 mg, 31%). Data for 4-bromo- l-(trifluoromethyl)-5, 6- dihydrospiro[cyclopenta[c]pyridine-7,2'-[l,3]dioxolane]: LCMS ESI (+) (M+H) m/z 324 / 326. Data for 4-bromo-l-(trifluoromethyl)-7-(2-((trimethylsilyl)oxy)ethoxy)-5i7- cyclopenta[c]pyridine: 1H NMR (400 MHz, CDCl3): d 8.56 (s, 1H), 5.59 (t, 1H), 4.10 (t, 2H), 3.96 (t, 2H), 3.36 (d, 2H), 0.15 (s, 9H).

Reference： [1]Patent: WO2016/145032,2016,A1 .Location in patent: Paragraph 00539
[2]Patent: WO2016/144826,2016,A1 .Location in patent: Paragraph 0431
[3]Patent: WO2016/145045,2016,A1 .Location in patent: Paragraph 00500
[4]Patent: US2018/140569,2018,A1 .Location in patent: Paragraph 0852
[5]Patent: WO2019/191227,2019,A1 .Location in patent: Paragraph 0266; 0268

59
[ 934388-19-9 ]
[ 7381-30-8 ]
ethyl 4-(2-methyl-[1,3]dioxolan-2-yl)-3-trifluoromethanesulfonyloxybenzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at 20℃; for 18h;Cooling with ice;	(6c) ethyl 4-(2-methyl-[1,3]dioxolan-2-yl)-3-trifluoromethanesulfonyloxybenzoate Ethyl 4-acetyl-3-trifluoromethanesulfonyloxybenzoate (500 mg, 1.47 mmol) produced in Example 6 (6b) was dissolved in methylene chloride (10 mL) and, under ice-cooling, ethylenedioxybis(trimethylsilane) (0.43 mL, 1.8 mmol) and trimethylsilyl trifluoromethanesulfonate (0.05 mL, 0.3 mmol) were added, and the mixture was stirred at room temperature for 18 hr. The reaction mixture was washed with saturated aqueous sodium hydrogen carbonate, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate, 20:1, V/V), and the solvent of the object fraction was evaporated under reduced pressure to give the title object compound as a pale-yellow powder (490 mg, yield 87%). 1H-NMR (CDCl3, 400 MHz) delta: 1.40 (3H, t, J=7.1 Hz), 1.74 (3H, s), 3.78-3.87 (2H, m), 4.05-4.15 (2H, m), 4.40 (2H, q, J=7.1 Hz), 7.74 (1H, d, J=8.1 Hz), 7.89 (1H, d, J=1.4 Hz), 8.01 (1H, dd, J=8.1, 1.4 Hz).

Reference： [1]Patent: US2016/207883,2016,A1 .Location in patent: Paragraph 0363-0365

60
[ 7381-30-8 ]
(1S,4R,4aR,8aR,9S)-9-formyl-1-hydroxy-8a-methyl-3-oxo-2,3,4,7,8,8a-hexahydro-1H-4a,1-ethanonaphthalen-4-yl pivalate [ No CAS ]
(1S,4R,4aR,8aR,9S)-9-(1,3-dioxolan-2-yl)-1-hydroxy-8a-methyl-3-oxo-2,3,4,7,8,8a-hexahydro-1H-4a,1-ethanonaphthalen-4-yl pivalate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%		To a solution of aldehyde 21 (46 mg, 0.14 mmol) in CH2Cl2(2.3 mL) was added 1,2-bis(trimethylsiloxy)ethane (0.17 mg,0.69 mmol) and TMSOTf (0.032 mL, 0.18 mmol) at 78 C. The reactionwas stirred at this temperature for 80 min. The reaction waspoured into ice-cold saturated NaHCO3 (2 mL). The aqueous layerwas separated and extracted with CH2Cl2 (2 mL 3). The combinedorganic layer was washed with brine, dried over MgSO4 and thesolution was concentrated to dryness in vacuo. The crude residuewas dissolved in THF (1 mL) and TBAF (1 M in THF, 0.09 mL,0.09 mmol) was added to the reaction mixture at room temperaturefor 2 h. The mixture was poured into saturated NH4Cl (1 mL).The aqueous layer was separated and extracted with EtOAc(1 mL 3). The combined organic layer was washed with brine,dried over MgSO4 and the solution was concentrated to dryness invacuo. The crude residue was purified by passing through a shortcolumn of silica gel (EtOAc/hexane 1:2) to give 1,3-dioxolane 26(40 mg, 77%) as colorless oil. Rf 0.22 (EtOAc/hexane 1:1); IRnmax(neat, cm1): 1734, 1289, 1152, 1057, 1062, 1044, 944; 1H NMR(400 MHz, CDCl3): d 1.18 (3H, s), 1.23 (9H, s), 1.56e1.62 (1H, m), 1.91(1H, dd, J 16.0,12.0 Hz), 2.11e2.40 (5H, m), 2.52 (1H, d,J 15.0 Hz), 2.94 (1H, dd, J 15.0, 2.8 Hz), 3.70e3.77 (1H, m),3.85e3.94 (3H, m), 4.91 (1H, d, J 7.3 Hz), 5.13 (1H, s), 5.62 (1H, dt,J 10.1, 3.2 Hz), 6.06 (1H, dt, J 10.1, 2.3 Hz); 13C NMR (100 MHz,CDCl3): d 18.0 (CH3), 22.7 (CH2), 24.7 (CH2), 27.1 (CH3 3), 38.9 (C),39.4 (CH2), 41.7 (CH), 47.2 (C), 50.4 (C), 50.4 (CH2), 64.4 (CH2), 64.9(CH2), 79.8 (C), 84.2 (CH), 105.2 (CH), 128.0 (CH), 128.3 (CH), 177.5(C), 200.3 (C); HRMS (ESI): calcd for [C21H30O6H] 379.2115;found 379.2118. [a]D25 18.3 (c 3.2, CHCl3).

Reference： [1]Tetrahedron,2017,vol. 73,p. 2705 - 2714

61
[ 7381-30-8 ]
C₄₃H₄₈N₂O₆Si [ No CAS ]
C₄₅H₅₂N₂O₇Si [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78 - -40℃; for 15.5h;	To a solution of the ketone 35 (1.30 g, 1.81 mmol, 1.00 eq.) in 13.5 mL of CH2Cl2 at -78 C was added <strong>[7381-30-8]1,2-bis(trimethylsilyloxy)ethane</strong> (490 muL, 1.99 mmol, 1.10 eq.) followed by trimethylsilyltrifluoromethanesulfonate (64.0 muL, 0.36 mmol, 0.20 eq.). The reaction mixture was warmed up to -40 Cand stirred for 15.5 h. The mixture was quenched with a solution of saturated aqueous NaHCO3. Theaqueous layer was extracted with CH2Cl2. The combined organic layers were dried over MgSO4, andconcentrated under reduced pressure. The resulting residue was purified by column chromatography onsilica gel (n-hexane:EtOAc = 2:1 to EtOAc:MeOH = 10:1) to afford pure 36 (1.19 g, 86%) as a whiteamorphous solid. [alpha]D26 -50.9 (c 1.00, CHCl3); IR (film) 1676, 1545, 1510, 1427, 1222, 1111 cm-1; 1HNMR (CDCl3) delta 0.14-0.17 (m, 1H), 1.04-1.07 (m, 1H), 1.07(s, 9H), 1.36 (td, J = 13.6, 3.97, 1H), 1.47 (d,J = 10.8, 1H), 1.54-1.67 (m, 3H), 1.83 (td, J = 13.0, 5.10, 1H), 3.15 (dd, J = 10.2, 18.1, 1H), 3.40-3.46(m, 2H), 3.76 (s, 3H), 3.85-3.94 (m, 5H), 4.11 (dd, J = 10.2, 6.80, 1H), 5.01 (d, J = 12.5, 1H), 5.03 (d, J= 12.5, 1H), 6.82 (d, J = 8.50, 2H), 6.95 (br s, 1H), 7.02 (d, J = 8.50, 2H), 7.04 (br s, 1H), 7.29-7.44 (m,11H), 7.64-7.69 (m, 4H); 13C NMR (CDCl3) delta 165.2, 157.2, 153.9, 137.1, 135.6, 135.5, 133.4, 133.2,131.6, 130.6, 129.8, 129.7, 129.6, 128.5, 127.8, 127.7 (2C), 127.4, 120.3, 114.8, 107.3, 69.9, 64.9, 64.4,64.3, 63.8, 57.8, 52.6, 33.5, 32.6 (2C), 31.9, 29.9, 26.9, 19.2; HRMS-ESI: calcd for C45H52N2O7SiNa783.3466 (M+Na)+; found 783.3457.

Reference： [1]Organic Letters,2017,vol. 19,p. 3839 - 3842
[2]Heterocycles,2019,vol. 99,p. 1095 - 1116

62
[ 7381-30-8 ]
[ 3946-26-7 ]
(20S)-20-(ethylenedioxymethyl)-pregna-4,6-dien-3-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
55%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78℃; for 2h;Inert atmosphere;	To a solution of (20S)-20-formyl-pregna-4,6-dien-3-one (3.89 g, 12 mmol) in CH2CI2 (5 vol, 20 mL) under an argon atmosphere was added 1 ,2-bis (trimethylsilyloxy) ethane (2.94 mL, 12 mmol). The reaction mixture was cooled to -78 C and TMSOTf (108 JL, 0.6 mmol) was added. After 2 h the reaction mixture was diluted with CH2CI2 (100 mL) and washed with water (2 x 100 mL) and 5% aq. NaCI (100 mL). The organic phase was dried over Na2S04 and was concentrated under reduced pressure. Purification by column chromatography on silica gel gave the desired product (2.42 g, 55%) as a colourless crystalline solid. deltaEta (700 MHz, CDCb); 6.12 (2H, m), 5.67 (1 H, m), 4.86 (1 H, d, J2.0), 3.94 (2H, m), 3.86 (2H, m,), 2.56 (1 H, m), 2.43 (1 H, m), 2.19 (1 H, t, J 10.6), 2.05-1.95 (3H, m), 1.85 to 1.20 (12H, m), 1.11 (3H, s), 0.95 (3H, d, J = 6.7), 0.77 (3H, s). 5C (176 MHz, CDCb); 199.7, 163.9, 141.4, 127.9, 123.6, 105.6, 65.3, 65.1 , 52.9, 52.2, 50.6, 43.7, 39.3, 39.3, 37.8, 36.1 , 34.0, 33.9, 27.3, 23.9, 20.67, 16.3, 1 1.7, 1 1.6.
55%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78℃; for 2h;Inert atmosphere;	To a solution of (20S)-20-formyl-pregna-4,6-dien-3-one (3.89 g, 12 mmol) in 0H2012 (5 vol, 20 mL) under an argon atmosphere was added 1 ,2-bis (trimethylsilyloxy) ethane (2.94 mL,12 mmol). The reaction mixture was cooled to -78 00 and TMSOTf (108 pL, 0.6 mmol) was added. After 2 h the reaction mixture was diluted with 0H2012 (100 mL) and washed with water (2 >< 100 mL) and 5% aq. NaOl (100 mL). The organic phase was dried over Na2SO4 and was concentrated under reduced pressure. Purification by column chromatography on silica gel gave the desired product (2.42 g, 55%) as a colourlesscrystalline solid. OH (700 MHz, 0D013); 6.12 (2H, m), 5.67 (1H, m), 4.86 (1H, d, J2.0), 3.94(2H, m), 3.86 (2H, m,), 2.56 (1H, m), 2.43 (1H, m), 2.19 (1H, t, J 10.6), 2.05-1.95 (3H, m),1.85 to 1.20 (12H, m), 1.11 (3H, 5), 0.95 (3H, d, J6.7), 0.77 (3H, 5). 00(176 MHz, 0D013);199.7, 163.9, 141.4, 127.9, 123.6, 105.6, 65.3, 65.1, 52.9, 52.2, 50.6, 43.7, 39.3, 39.3,37.8, 36.1, 34.0, 33.9, 27.3, 23.9, 20.67, 16.3, 11.7, 11.6.
55%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78℃; for 2h;Inert atmosphere;	To a solution of (20S)-20-formyl-pregna-4,6-dien-3-one (3.89 g, 12 mmol) in CH2CI2 (5 vol, 20 mL) under an argon atmosphere was added 1 ,2-bis (trimethylsilyloxy) ethane (2.94 mL,12 mmol). The reaction mixture was cooled to -78 00 and TMSOTf (108 pL, 0.6 mmol) was added. After 2 h the reaction mixture was diluted with CH2CI2 (100 mL) and washed with water (2 >< 100 mL) and 5% aq. NaCI (100 mL). The organic phase was dried over Na2SO4 and was concentrated under reduced pressure. Purification by column chromatography on silica gel gave the desired product (2.42 g, 55%) as a colourlesscrystalline solid. OH (700 MHz, CDCI3); 6.12 (2H, m), 5.67 (1H, m), 4.86 (1H, d, J2.0), 3.94(2H, m), 3.86 (2H, m,), 2.56 (1H, m), 2.43 (1H, m), 2.19 (1H, t, J 10.6), 2.05-1.95 (3H, m),1.85 to 1.20 (11H, m), 1.11 (3H, 5), 0.95 (3H, d, J6.7), 0.77 (3H, 5). 00(176 MHz, CDCI3);199.7, 163.9, 141.4, 127.9, 123.6, 105.6, 65.3, 65.1, 52.9, 52.2, 50.6, 43.7, 39.3, 39.3,37.8, 36.1, 34.0, 33.9, 27.3, 23.9, 20.67, 16.3, 11.7, 11.6.

Reference： [1]Patent: WO2017/199033,2017,A1 .Location in patent: Page/Page column 47
[2]Patent: WO2017/199039,2017,A1 .Location in patent: Page/Page column 104
[3]Patent: WO2017/199036,2017,A1 .Location in patent: Page/Page column 91

63
[ 7381-30-8 ]
C₁₄H₁₉NO₃ [ No CAS ]
C₁₆H₂₃NO₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at 30℃; for 168h;	Bts(trimethylsilyl)ethylene glycol (8.26 mL, 33,7 mmol, 7.00 equiv) and triroelhykily itiftoorome&anese fonate (1.74 mL, 9.63 mnaal, 2.00 equiv) were added in sequence to a solutio of the beta-cyam ketone 15 (1.20 g, 4,81 .mmol, 1 equiv) in dichioromethane. (60 ml) at 20 C, The resulting mixture was heated and stirred at 30 C. An additional portion of trimethylsilyl trifiuoromethanesulfonate (1.74 mL, 9.63 mmol, 2.00 equiv) was added every two days thereafter. After stirring at 30 C for 7 days total, the product mixture was cooled to 0 C for 20 min. The cooled product mixture was slowly diluted with saturated aqueous sodium bicarbonate solution (60 mL). The resulting 'mixture was diluted with water (60 mL) and then the organic layer was separated. The aqueous layer was extracted with dichioromethane (2 x 60 mL). The organic layers were combined and the combined organic layers were dried over magnesium sulfate. The dried solution was filtered and the filtrate was concentrated. The residue obtained was purified by flash-column chromatography (elating with 15% ethyl acetate-hexanes initially, linearly grading to 30% ethyl acetate -hexanes) to provide the eyano ketal 16 as a white solid (1 , 18 g, 84%). - 0.36 {20% ethyl acetate-hexanes; PAA stains brown). NMR (500 MHz. CDC ) S 4.03 - 3.96 Cm, IH), 3.94 - 3.85 m 2H), 3.84- 3.77 (m. IH), 3.69 (s, 3H), 3.08 {s, I H), 2.18 - 1.72 (m, 8H), 1.58 - .1.50 (m, IH), 1.32 (s, 3H), 1.13 (d, J- .9 Hz, 3H). NM (126 MHz, CDC) S 175.46, 124.14, 117.50, 64.38, 62.53, 53.35, 51.63, 46.46, 40.28, 36.18, 35.37, 33.79, 31.61, 28.07, 21.37, 6.17. HR S-ES1 (m/z): calculated for [CH N04Na3* 316,1525, found 316 J 530,

Reference： [1]Science,2017,vol. 356,p. 956 - 959
[2]Patent: WO2018/144717,2018,A1 .Location in patent: Page/Page column 52; 53

64
[ 7381-30-8 ]
[ 1277177-84-0 ]
methyl 4-(2-(4-(prop-2-yn-1-yloxy)phenyl)-1,3-dioxolan-2-yl)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With toluene-4-sulfonic acid; In ethylene glycol; toluene; for 4h;Inert atmosphere; Reflux;	A mixtureof ketone 82 (100 mg, 0.34 mmol, 1 equiv), ethylene glycol (1.5 mL), <strong>[7381-30-8]1,2-bis(trimethylsilyloxy)ethane</strong> (2.52 g, 12.2 mmol, 36 equiv), p-toluenesulfonic acidmonohydrate (4.5 mg, 0.024 mmol, 0.1 equiv), and toluene (1.6 mL) was heated underreflux for 4 hours. The mixture was then cooled to room temperature and washed withsaturated aq. NaHCO3 solution. The organic layer was then separated and the aqueouslayer was extracted with hexanes:EtOAc (6:4). The combined organic layers were thendried (MgSO4), filtered, concentrated, and chromatographed (EtOAc:hexanes, 1:9) to give 87 mg of ketal 9 as a colorless oil (75%).

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2018,vol. 28,p. 3431 - 3435

65
[ 7381-30-8 ]
[ 21531-47-5 ]
[ 13149-16-1 ]

Yield	Reaction Conditions	Operation in experiment
	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -78℃; for 3.0h;	(0602) To a solution of trimethylsilyltrifluoromethanesulfonate (0.034 ml) in dry dichloromethane (5 ml) was added 1,2-bis(trimethylsiloxy)ethane (4.55 ml) followed by <strong>[21531-47-5]methyl 3-oxocyclohexanecarboxylate</strong> (2.9 g). The reaction mixture was stirred for 3 hours at -78 C. The reaction mixture was quenched with dry pyridine (0.5 ml), poured into saturated aqueous NaHCO3, and extracted with ether. The ether layer was dried over Na2CO3/Na2SO4. The reaction mixture was concentrated and purified by flash chromatography on silica with 5 to 30% ethyl acetate in hexanes to provide the title compound.

Reference： [1]Patent: US10213433,2019,B2 .Location in patent: Page/Page column 142

66
[ 7381-30-8 ]
1-(5-(2-((4-(trifluoromethyl)phenyl)amino)phenyl)-1,3,4-oxadiazol-2-yl)ethan-1-one [ No CAS ]
2-(5-(2-methyl-1,3-dioxolan-2-yl)-1,3,4-oxadiazol-2-yl)-N-(4-(trifluoromethyl)phenyl)aniline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
29.6%	With trimethylsilyl trifluoromethanesulfonate; In dichloromethane; at -5 - 25℃; for 5h;	To a solution of Compound 85 (50 mg, 0.14 mmol, 1 eq) and compound 79-4a (297.2 mg, 1.44 mmol, 10 eq) in DCM (1 mL) was added TMSOTf (6.4 mg, 28 umol, 5 uL, 0.2 eq) at - 5C. Then the mixture was warmed to 25C and stirred at 25C for 5 hr. The reaction mixture was quenched with TEA (5 drops), concentrated in vacuum. The residue was diluted with EA (20 mL), washed with H20 (5 mL) and brine (5 mL), dried over Na2S04, filtered and concentrated in vacuum. The crude product was purified by prep-TLC. LCMS, HPLC and 1HNMR confirmed that Compound 86 (17.4 mg, 42 umol, 29.6% yield) was obtained. LCMS (ESI): RT = 1.037 min, mass calcd. For C19H13F3N4O, 391.34 m/z found 392.0 [M+H] +. 1H NMR (400 MHz, CDCl3) d 9.62 - 9.37 (m, 1H), 7.90 (d, J= 8.0 Hz, 1H), 7.59 (br d , j= 8.3 Hz, 2H), 7.52 (d, J= 8.5 Hz, 1H), 7.44 - 7.33 (m, 3H), 6.98 (t, J= 7.6 Hz, 1H), 4.30 - 4.18 (m, 1H), 4.24 (br d, J= 5.3 Hz, 3H), 1.96 (s, 3H).

Reference： [1]Patent: WO2019/222431,2019,A1 .Location in patent: Paragraph 00385

67
[ 7381-30-8 ]
methyl 5-bromo-4-fluoro-2-formylbenzoate [ No CAS ]
methyl 5-bromo-2-(1,3-dioxolan-2-yl)-4-fluorobenzoate [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2020

Type	HazMat fee for 500 gram (Estimated)
Excepted Quantity	USD 0.00
Limited Quantity	USD 15-60
Inaccessible (Haz class 6.1), Domestic	USD 80+
Inaccessible (Haz class 6.1), International	USD 150+
Accessible (Haz class 3, 4, 5 or 8), Domestic	USD 100+
Accessible (Haz class 3, 4, 5 or 8), International	USD 200+

Purity	Size	Price	VIP Price	USA Stock *0-1 Day	Global Stock *5-7 Days	Quantity
{[ item.p_purity ]}	{[ item.pr_size ]}	{[ getRatePrice(item.pr_usd, 1,1) ]} {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]}	{[ getRatePrice(item.pr_usd, 1,1) ]}	Inquiry {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]} {[ getRatePrice(item.pr_usd,1,item.mem_rate) ]}	{[ item.pr_usastock ]}	Inquiry -	{[ item.pr_chinastock ]}	Inquiry -

CAS No. :	7381-30-8	MDL No. :	MFCD00009640
Formula :	C₈H₂₂O₂Si₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	JGWFUSVYECJQDT-UHFFFAOYSA-N
M.W :	206.43	Pubchem ID :	81858
Synonyms :

Num. heavy atoms :	12
Num. arom. heavy atoms :	0
Fraction Csp3 :	1.0
Num. rotatable bonds :	5
Num. H-bond acceptors :	2.0
Num. H-bond donors :	0.0
Molar Refractivity :	58.48
TPSA :	18.46 Å²

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-5.59 cm/s

[ CAS No. 7381-30-8 ] {[proInfo.proName]}

Quality Control of [ 7381-30-8 ]

Related Doc. of [ 7381-30-8 ]

Product Details of [ 7381-30-8 ]

Calculated chemistry of [ 7381-30-8 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 7381-30-8 ]

Application In Synthesis of [ 7381-30-8 ]

[ 7381-30-8 ] Synthesis Path-Upstream 1~3

[ 7381-30-8 ] Synthesis Path-Downstream 1~67

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Log Po/w (iLOGP) :	3.64
Log Po/w (XLOGP3) :	2.78
Log Po/w (WLOGP) :	2.69
Log Po/w (MLOGP) :	1.29
Log Po/w (SILICOS-IT) :	-0.85
Consensus Log Po/w :	1.91

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

Log S (ESOL) :	-2.54
Solubility :	0.594 mg/ml ; 0.00288 mol/l
Class :	Soluble
Log S (Ali) :	-2.82
Solubility :	0.31 mg/ml ; 0.0015 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-2.71
Solubility :	0.404 mg/ml ; 0.00196 mol/l
Class :	Soluble

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	4.45

Signal Word:	Danger	Class:	3
Precautionary Statements:	P210-P403+P235	UN#:	1993
Hazard Statements:	H225	Packing Group:	Ⅲ
GHS Pictogram:

Precautionary Statements-General
Code	Phrase
P101	If medical advice is needed,have product container or label at hand.
P102	Keep out of reach of children.
P103	Read label before use
Prevention
Code	Phrase
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P221	Take any precaution to avoid mixing with combustibles
P222	Do not allow contact with air.
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P231	Handle under inert gas.
P232	Protect from moisture.
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P234	Keep only in original container.
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P263	Avoid contact during pregnancy/while nursing.
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P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
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P273	Avoid release to the environment.
P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
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P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
P308	IF exposed or concerned:
P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
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P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
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P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
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P337	If eye irritation persists:
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P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
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P413
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P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling