78502-71-3|Ethyl 2-(bromomethyl)thiazole-4-carboxylate| Ambeed

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Quality Control of [ 78502-71-3 ] Purity: 97% SDS Specification

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Product Details of [ 78502-71-3 ]

CAS No. :	78502-71-3
Formula :	C₇H₈BrNO₂S
M.W :	250.11
SMILES Code :	O=C(C1=CSC(CBr)=N1)OCC
MDL No. :	MFCD09953587
InChI Key :	LHVYKGHESZRJJO-UHFFFAOYSA-N
Pubchem ID :	11043146

Safety of [ 78502-71-3 ]

GHS Pictogram:
Signal Word:	Danger
Hazard Statements:	H302-H314
Precautionary Statements:	P264-P270-P271-P280-P303+P361+P353-P304+P340-P305+P351+P338-P310-P330-P331-P363-P403+P233-P501
Class:	8
UN#:	3261
Packing Group:	Ⅱ

Application In Synthesis of [ 78502-71-3 ]

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

Downstream synthetic route of [ 78502-71-3 ]

[ 78502-71-3 ] Synthesis Path-Downstream 1~35

1
[ 6436-59-5 ]
[ 78502-71-3 ]

Yield	Reaction Conditions	Operation in experiment
38%		Ethyl 2-methyl-l,3-thiazole-4-carboxylate (500 mg, 2.92 mmol) was dissolved in CCU (10 rnL) and NBS (624 mg, 3.50 mmol) was added and the reaction heated at 76 0C for 60 min. AIBN (36 mg, 0.21 mmol) was added and heating continued at 76 0C for 4 h. The reaction mixture was allowed to cool to ambient temperature and filtered through Celite. The filter cake was washed with DCM. The combined organic layers were concentrated in vacuo with silica and purified using FCC, eluting with 50 % EtOAc in heptanes, to afford the title compound. Yield: 274 mg, 38 %.
31%	With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane;Heating / reflux;	2-Bromomethyl-thiazole-4-carboxylic acid ethyl ester was prepared according to N. Kindon et al. (U.S. Pat. No. 6,162,808): A mixture of 2-methyl-thiazole-4-carboxylic acid (available from Maybridge pic, Tintagel, UK; 9.8 g, 57.2 mmol), benzoyl peroxide (40 mg, 0.165 mmol) and NBS (10.6 g, 60.0 mmol) in carbon tetrachloride (250 mL) was heated at reflux over the weekend. The reaction mixture was cooled to room temperature and evaporated under reduced pressure. The crude material was partitioned between ethyl acetate and water. The organic layer was dried (magnesium sulfate), filtered, evaporated, and purified by chromatography on flash silica gel, eluting with 20% ethyl acetate/hexane to give 2-bromomethyl-thiazole-4-carboxylic acid ethyl ester (4.4 g, 31%) as an orange oil. 1HNMR (CDCl3): delta 9.23 (s, 1H), 4.77 (s, 2H), 4.44 (q, J=7.0 Hz, 2H), 1.41 (t, J=7.0 Hz, 3H). MS (APCl+): 252 (100), 250 (90).
31%	With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane;Heating / reflux;	2-Bromomethyl-thiazole-4-carboxylic acid ethyl ester was prepared according to Kindon, N et al. (U.S. Pat. No. 6,162,808): A mixture of 2-methyl-thiazole-4-carboxylic acid (available from Maybridge plc, Tintagel, UK; 9.8 g, 57.2 mmol), benzoyl peroxide (40 mg, 0.165 mmol) and NBS (10.6 g, 60.0 mmol) in carbon tetrachloride (250 mL) was heated at reflux over the weekend. The reaction mixture was cooled to room temperature and evaporated under reduced pressure. The crude material was partitioned between ethyl acetate and water. The organic layer was dried (magnesium sulfate), filtered, evaporated, and purified by chromatography on flash silica gel, eluting with 20% ethyl acetate/hexane to give 2-bromomethyl-thiazole-4-carboxylic acid ethyl ester (4.4 g, 31%) as an orange oil. 1HNMR (CDCl3): delta 9.23 (s, 1H), 4.77 (s, 2H), 4.44 (q, J=7.0 Hz, 2H), 1.41 (t, J=7.0 Hz, 3H). MS (APCI+): 252 (100), 250 (90).

	With N-Bromosuccinimide;dibenzoyl peroxide; In 2-Methylpentane; chloroform;	ii 2-Bromomethyl-4-thiazolecarboxylic acid, ethyl ester 2-Methyl-4-thiazolecarboxylic acid ethyl ester (1 g) (Liebigs Ann. Chem. 1981, 623), N-bromosuccinimide (1.04 g) and a catalytic amount of benzoyl peroxide in chloroform (25 ml) was heated at reflux for 20 hours. After cooling, the reaction mixture was washed with saturated aqueous sodium bicarbonate, dried (MgSO4) and evaporated under reduced pressure. Purification was by chromatography eluding with 40% ethyl acetate in isohexane to give the product as an oil. Yield 0.5 g. MS: GC-MS: 249/251 (M+)
	With N-Bromosuccinimide;2,2'-azobis(isobutyronitrile); In tetrachloromethane; for 3h;Heating / reflux;	Reference Example 80; Ethyl 2-dimethylaminomethylthiazole-4-carboxylate; [Show Image] N-Bromosuccinimide (1.14 g) and a catalytic amount of AIBN were added to a carbon tetrachloride solution (20 ml) of ethyl 2-methylthiazole-4-carboxylate (1.00 g), followed by heating under reflux for 3 hours. After cooling the reaction solution to room temperature, the resulting precipitate was removed by filtration, the filtrate was concentrated, and the thus obtained residue was used in the subsequent reaction without purification.
		Preparation Example 22; The following products were prepared with a partial modification of the method of Liu, et al. (Synthesis, 2001 14, 2078-2080). Ethyl (2-methyl-1,3-thiazol-4-yl)carboxylate (25 g) was added to carbon tetrachloride (500 mL), and subsequently, NBS (53 g), and benzoyl peroxide (4.7 g) (wetted with 75% water) were sequentially added thereto, followed by heating to reflux for 100 minutes under close irradiation with a 300 W lamp. The reaction mixture was left to be cooled, then the insoluble material was collected by filtration, and the obtained filtrate was washed with water, followed by extraction with an appropriate amount of CHCl3. The organic layer was sequentially washed with a 5% (W/W) aqueous sodium thiosulfate solution (600 g) and brine, and dried over MgSO4, and then the solvent was evaporated. To the obtained residue was added THF (300 mL), followed by sequential addition dropwise of diethyl phosphite (18.9 mL) and a Hunig's base (25.4 mL) at about 0 C. under an argon atmosphere. Thereafter, the temperature was slowly elevated, and the mixture was stirred at room temperature for about 2 hours. An appropriate amount of ice water was poured into the reaction mixture, followed by extraction with ethyl acetate several times. The organic layer was sequentially washed with 0.3 M hydrochloric acid (1 L) and brine, and dried over MgSO4, and then the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate=3:1 to 2:1) to prepare ethyl [2-(bromomethyl)-1,3-thiazol-4-yl]carboxylate (26.82 g).

References: [1]Bioorganic and Medicinal Chemistry,2001,vol. 9,p. 1 - 6.
[2]Patent: WO2010/20556,2010,A1 .Location in patent: Page/Page column 156.
[3]Patent: US2006/122256,2006,A1 .Location in patent: Page/Page column 21.
[4]Patent: US2004/266856,2004,A1 .Location in patent: Page/Page column 19.
[5]Patent: US2020/123117,2020,A1 .Location in patent: Paragraph 1108; 1109.
[6]Liebigs Annalen der Chemie,1981,p. 623 - 632.
[7]Bioorganic and medicinal chemistry letters,2002,vol. 12,p. 2443 - 2446.
[8]Patent: US6162808,2000,A .
[9]Patent: EP1612204,2006,A1 .Location in patent: Page/Page column 47.
[10]Patent: US2012/184521,2012,A1 .Location in patent: Page/Page column 23.

2
[ 6436-59-5 ]
[ 78502-71-3 ]
[ 78502-72-4 ]
[ 78502-73-5 ]

References: [1]Liebigs Annalen der Chemie,1981,p. 623 - 632.

3
[ 78502-71-3 ]
[ 603-35-0 ]
[ 78502-85-9 ]

Yield	Reaction Conditions	Operation in experiment
3.7 g	In toluene; at 20 - 100℃; for 3h;	To a solution of ethyl2-(bromomethyl)-1,3-thiazole- 4-carboxylate (19, 2.4 g, 9.7 mmol) in toluene (20 mL) triphenylphosphine (2.7 g,10 mmol) was added at room temperature, and the resulting mixture was stirred at 100 C for 3 h. The reactionmixture was cooled to room temperature, and the precipitate was collected by filtration, washed with hexanes, anddried to afford ((4-(ethoxycarbonyl)-1,3-thiazol-2-yl)methyl)(triphenyl)phosphonium bromide (31, 3.7 g, 74%) as abrown powder, which was used without further purification. To a mixture of compound 30 (2.2 g, 5.5 mmol) andcompound 31 (3.7 g, 7.2 mmol) in N,N-dimethylformamide (20 mL) was added sodium ethoxide (0.75 g, 11 mmol)at room temperature, and the resulting mixture was stirred at room temperature for 3 h. The reaction mixture waspartitioned between ethyl acetate and water. The organic layer was separated, washed with brine, dried over MgSO4,and concentrated in vacuo. The residue was purified by column chromatography (silica gel, eluting with a gradientof 10-50% ethyl acetate in hexanes) to afford the title compound 20a (1.8 g, 60%) as a pale yellow powder.

References: [1]Liebigs Annalen der Chemie,1981,p. 623 - 632.
[2]Bioorganic and Medicinal Chemistry Letters,2017,vol. 27,p. 3565 - 3571.

4
[ 78502-71-3 ]
[ 2244-59-9 ]
[ 149518-61-6 ]

References: [1]Bioorganic and Medicinal Chemistry,2001,vol. 9,p. 1 - 6.

5
[ 54013-91-1 ]
[ 78502-71-3 ]
[ 483987-69-5 ]

References: [1]Bioorganic and medicinal chemistry letters,2002,vol. 12,p. 2443 - 2446.

6
[ 78502-71-3 ]
[ 1002095-82-0 ]

Yield	Reaction Conditions	Operation in experiment
		60% Sodium hydride (1 OOmg, 2.5mmol) was added to a stirred solution of 6-chloro-3- isobutyl-1H-indole (519mg, 2.5mmol; may be prepared as described in D5) in dimethylformamide (8ml) under argon and stirred for 10 minutes when ethyl 2- (bromomethyl)-1 ,3-thiazole-4-carboxylate (625mg, 2.5mmol) were added. The solution was stirred at room temperature for one hour then diluted with ether/water. The organic phase was washed three times with water, dried (magnesium sulphate), evaporated and purified on a Biotage column eluting with (20:80) ethyl acetate/hexane then triturated with hexane to give the title compound as a white solid (388mg). LCMS: Rt= 3.83min, [MH+] 377.19, 379.18.
		60% Sodium hydride (100mg, 2.5mmol) was added to a stirred solution of 6-chloro-3-(2- methylpropyl)-1 H-indole (may be prepared as described in D11 ; 519mg, 2.5mmol) in dimethylformamide (8ml) under argon and stirred for 10 minutes when ethyl 2- (bromomethyl)-1 ,3-thiazole-4-carboxylate (625mg, 2.5mmol) were added. The solution was stirred at room temperature for one hour then diluted with ether/water. The organic phase was washed three times with water, dried (magnesium sulphate), evaporated and purified on a Biotage column eluting with (20:80) ethyl acetate/hexane then triturated with hexane to give the title compound as a white solid (388mg). LCMS: Rt= 3.83min, [MH+] 377.19, 379.18.

References: [1]Patent: WO2008/6793,2008,A1 .Location in patent: Page/Page column 29.
[2]Patent: WO2008/6790,2008,A1 .Location in patent: Page/Page column 31.

7
[ 17496-14-9 ]
[ 78502-71-3 ]
2-(2-methyl-1-oxo-indan-2-ylmethyl)-thiazole-4-carboxylic acid ethyl ester [ No CAS ]

References: [1]Bioorganic and Medicinal Chemistry Letters,2007,vol. 17,p. 6142 - 6146.

8
[ 6436-59-5 ]
[ 78502-71-3 ]
[ 78502-72-4 ]

References: [1]Bioorganic and Medicinal Chemistry Letters,2007,vol. 17,p. 6142 - 6146.

9
[ 78502-71-3 ]
[ 483987-70-8 ]

References: [1]Bioorganic and medicinal chemistry letters,2002,vol. 12,p. 2443 - 2446.

10
[ 78502-71-3 ]
1-(4-chloromethyl-thiazol-2-ylmethyl)-4-(2-isopropoxy-phenyl)-piperazine [ No CAS ]

References: [1]Bioorganic and medicinal chemistry letters,2002,vol. 12,p. 2443 - 2446.

11
[ 78502-71-3 ]
1-{2-[4-(2-isopropoxy-phenyl)-piperazin-1-ylmethyl]-thiazol-4-ylmethyl}-pyrrolidin-2-one [ No CAS ]

References: [1]Bioorganic and medicinal chemistry letters,2002,vol. 12,p. 2443 - 2446.

12
[ 78502-71-3 ]
1-{2-[4-(2-isopropoxy-phenyl)-piperazin-1-ylmethyl]-thiazol-4-ylmethyl}-piperidin-2-one [ No CAS ]

References: [1]Bioorganic and medicinal chemistry letters,2002,vol. 12,p. 2443 - 2446.

13
[ 78502-71-3 ]
2-(8-chloro-11H-dibenzo[b,f][1,4]oxazepin-10-ylmethyl)-thiazole-4-carboxylic acid (pyridin-2-ylmethyl)-amide [ No CAS ]

References: [1]Bioorganic and Medicinal Chemistry,2001,vol. 9,p. 1 - 6.

14
[ 78502-71-3 ]
2-[(8-chlorodibenz[b,f][1,4]oxazepin-10(11H)-yl)methy]-4-thiazolecarboxylic acid, sodium salt [ No CAS ]

References: [1]Bioorganic and Medicinal Chemistry,2001,vol. 9,p. 1 - 6.

15
[ 78502-71-3 ]
[ 78502-91-7 ]

References: [1]Liebigs Annalen der Chemie,1981,p. 623 - 632.

17
[ 40235-65-2 ]
[ 78502-71-3 ]

Yield	Reaction Conditions	Operation in experiment
	With N-Bromosuccinimide;dibenzoyl peroxide; In 1,2-dichloro-ethane; at 70℃; for 85h;	Preparation 23 Ethyl 2-bromomethylthiazole 4-carboxylate [0323] [CHEMMOL-00080] [0324] A mixture of ethyl-2-methylthiazole 4-carboxylate (500 mg, 2.9 mmol), N-bromosuccinimide (877 mg, 4.9 mmol), and benzoyl peroxide (5-10 mg) in 1,2-DCE (3 mL) was heated at 70 C. for 85 h. After cooling to room temperature, DCM (10 ml) was added and washed with water (3 times). The organic layer was dried over Na2SO4 and evaporated in vacuo. The residue was purified by preparative chromatography to yield the above-titled compound (58 mg). 1H NMR (CDCl3): 8.23 (1H, s), 4.77 (2H, s), 4.43 (2H, q), 1.42 (3H, t).

References: [1]Patent: US2004/9998,2004,A1 .Location in patent: Page/Page column 40.

18
[ 506-59-2 ]
[ 78502-71-3 ]
[ 82586-66-1 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; In dichloromethane; at 0 - 20℃;	Reference Example 80 Ethyl 2-dimethylaminomethylthiazole-4-carboxylate N-Bromosuccinimide (1.14 g) and a catalytic amount of AIBN were added to a carbon tetrachloride solution (20 ml) of ethyl 2-methylthiazole-4-carboxylate (1.00 g), followed by heating under reflux for 3 hours. After cooling the reaction solution to room temperature, the resulting precipitate was removed by filtration, the filtrate was concentrated, and the thus obtained residue was used in the subsequent reaction without purification. The above-described residue was dissolved in dichloromethane (30 ml), and triethylamine (16.3 ml) and dimethylamine hydrochloride (714 mg) were added to the mixture at 0C, followed by stirring overnight at room temperature. A saturated aqueous ammonium chloride solution was added to the reacton solution, extracted with dichloromethane and dried over sodium sulfate. The solvent was evaporated, the thus obtained residue was purified by silica gel column chromatography, and the fraction obtained from the elude of dichloromethane:methanol = 100:3 was concentrated under reduced pressure to obtain the title compound (420 mg) as a colorless oil. 1H-NMR (400 MHz, CDCl3) delta: 1.41 (3H, t, J=7.1 Hz), 2.38 (6H, s), 3.83 (2H, s), 4.43 (2H, q, J=7.1 Hz), 8.16 (1H, s).

References: [1]Patent: EP1612204,2006,A1 .Location in patent: Page/Page column 47.

19
[ 6436-59-5 ]
[ 94-36-0 ]
[ 78502-71-3 ]

Yield	Reaction Conditions	Operation in experiment
31%	With N-Bromosuccinimide; In tetrachloromethane;	Preparation of the starting material: A solution of ethyl 2-methyl-4-thiazolecarboxylate [JCS 1946, 87, E. R. H. Jones, F. A. Robinson, M. N. Strachan] (5.0 g, 29.2 mmol) in CCl4 (30 ml) was treated with N-bromosuccinimide (5.2 g, 29.2 mmol) and benzoylperoxide (0.03 g). The reaction was heated to reflux while irradiating with a strong lamp for 21/2 hours. The reaction mixture was allowed to cool to ambient temperature, filtered and evaporated. The residue was purified by chromatography (eluant: CH2 Cl2) to obtain ethyl 2-bromomethyl-4-thiazolecarboxylate (2.27 g, 31%). NMR (250 MH, DMSO-d6): delta8.55 (s, 1H), 5.04 (s, 2H), 4.30 (g, 2H), 1.32 (t, 3H).

References: [1]Patent: US5965741,1999,A .

20
bis(trimethylsilyl)trifluoroacetamide [ No CAS ]
[ 216657-67-9 ]
[ 78502-71-3 ]
[ 216657-68-0 ]

Yield	Reaction Conditions	Operation in experiment
	In 1,2-dichloro-ethane; toluene; acetonitrile;	iv 2-[[5-{5H-Dibenzo[a,d]cyclohepten-5-yl}-3,4-dihydro-2,4-dioxo-1(2H)-pyrimidinyl]methyl]-4-thiazolecarboxylic acid, ethyl ester To a slurry of the product of step (iii) (1.1 g) in dry 1,2-dichloroethane (20 ml) was added bis(trimethylsilyl)trifluoroacetamide (1.9 ml) under nitrogen. The mixture was heated under reflux for 1 hour until the mixture became a homogeneous solution. The solution was allowed to cool to room temperature and a solution of the product of step (ii) (0.83 g) in dry acetonitrile (10 ml) was added. The solution was then heated at reflux for 7 hours. The reaction mixture was allowed to cool and evaporated under reduced pressure. Purification was by chromatography eluding with 30% ethyl acetate in toluene. The resulting oil was triturated with diethyl ether/isohexane to give the product as a cream solid. Yield 1.52 g. MS: FAB(+ve): 472 (M+1, 100%)

References: [1]Patent: US6162808,2000,A .

21
[ 540-38-5 ]
[ 78502-71-3 ]
[ 890051-44-2 ]

Yield	Reaction Conditions	Operation in experiment
65%	With potassium carbonate; In acetone; for 15h;Heating / reflux;	Step 2: 2-(4-Iodo-phenoxymethyl)-thiazole-4-carboxylic acid ethyl ester Ground potassium carbonate (3.4 g, 24.6 mmol) was added to a solution of <strong>[78502-71-3]2-bromomethyl-thiazole-4-carboxylic acid ethyl ester</strong> (12.83 g, 56 mmol; from Step 1 above) and 4-iodophenol (5.5 g, 25 mmol; available from Aldrich Chemical Company, Inc., Milwaukee, Wis.) in acetone (440 mL). The reaction mixture was heated at reflux for 15 h and then it was filtered and water was added to the filtrate until it turned cloudy. The filtrate was left on ice and then the resulting white solid was filtered off, washed with acetone/hexanes (2:1) and dried to give 2-(4-iodo-phenoxymethyl)-thiazole-4-carboxylic acid ethyl ester (5.6 g, 65%) as a white solid. 1H-NMR (CDCl3): delta 1.4 (t, 3H, J=7 Hz), 4.46 (q, 2H, J=7 Hz), 5.4 (s, 2H), 6.7 (d, 2H, J=9 Hz), 7.6 (d, 2H, J=9 Hz), 8.2 (s, 1H).

References: [1]Patent: US2006/122256,2006,A1 .Location in patent: Page/Page column 21.

22
[ 1002095-60-4 ]
[ 78502-71-3 ]
[ 1002095-82-0 ]

References: [1]Bioorganic and Medicinal Chemistry Letters,2008,vol. 18,p. 2684 - 2690.

23
[ 78502-71-3 ]
[ 13097-01-3 ]
[ 1204771-06-1 ]

Yield	Reaction Conditions	Operation in experiment
		Example 7; 2-{(3-phenyl-1H-indazol-1-yl)methyl}thiazole-4-carboxylic acidSodium hydride (added with 40% mineral oil, 9 mg, manufactured by Kanto Chemical Co., Inc.) was added to a solution of 3-phenyl-1H-indazole (40 mg), which had been synthesized according to the literature (T. Edward, C., et al., Tetrahedron, 1991, 47, 9599-9620), in N,N-dimethylformamide (1 mL, manufactured by Kanto Chemical Co., Inc.) under ice cooling, and the mixture was stirred for 5 minutes at the same temperature. Subsequently, ethyl 2-bromomethylthiazole-4-carboxylate (51 mg) synthesized according to the method of the literature (K. Benno, et al., Leibigs. Ann. Chem., 1981, 4, 623-632) was added thereto, and the mixture was stirred overnight at room temperature. Water (1 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (3×2 mL), washed with brine (10 mL), and dried (MgSO4). The solvent was then evaporated. The resulting residue was purified by PTLC (hexane:ethyl acetate=2:1), to give 7.2 mg of the title compound. LC-MS: HPLC retention time 4.08 minutes, m/z 336 (M+H), condition A-1.

References: [1]Patent: US2010/29733,2010,A1 .Location in patent: Page/Page column 42-43.

24
[ 1204773-05-6 ]
[ 78502-71-3 ]
[ 1204771-07-2 ]

Yield	Reaction Conditions	Operation in experiment
14%	With sodium hydride; In N,N-dimethyl-formamide; mineral oil; at 0℃; for 16h;	Ethyl 2-bromomethyl thiazole carboxylate (114 mg, 0.46 mmol, 3.0 eq.) was added to a stirred solution of 25 (40 mg, 0.153 mmol, 1.0 eq.) and NaH (20 mg in 55% mineral oil, 0.47 mmol, 3.0 eq.) in DMF (1 mL) and stirred at 0 C for 16 h. The reaction mixture was quenched with water and extracted with EtOAc, dried over MgSO4 and evaporated in reduced pressure to give the crude product. Purification with Yamazen automated chromatography with Hex:EtOAc = 9:1 as eluent to give 26 (7.2 mg, 14%) as a colourless solid, 1H NMR (300 MHz, CDCl3) delta 8.24 (1H, d, J = 9 Hz), 8.13 (1H, s), 8.01 (2H, d, J = 9 Hz), 7.59-7.48 (5H, m), 6.12 (1H, s), 4.92 (2H, br s), 4.46 (2H, q, J = 7.5 Hz), 1.44 (3H, t, J = 7.5 Hz); MS (ESI) m/z 432 [(M + H)+], RT 1.41 min (Condition A).
		Example 8; Ethyl 2-[{3-phenyl-6-(trifluoromethyl)-1H-indazol-1-yl}methyl]thiazole-4-carboxylateSodium hydride (added with 40% mineral oil, 20 mg, manufacture by Kanto Chemical Co., Inc.) was added to a solution of 3-phenyl-6-(trifluoromethyl)-1H-indazole (40 mg), which had been synthesized in Reference Example 18 according to the methods of Reference Examples 8 and 9, in N,N-dimethylformamide (1 mL, manufactured by Kanto Chemical Co., Inc.) under ice cooling, and the mixture was stirred for 5 minutes at the same temperature. Subsequently, ethyl 2-bromomethylthiazole-4-carboxylate (114 mg) synthesized according to the method of the literature (K. Benno, et al., Liebigs. Ann. Chem., 1981, 4, 623-632) was added thereto, and the mixture was stirred overnight at room temperature. Water (1 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (3×2 mL), washed with brine (10 mL), and dried (MgSO4). The solvent was then evaporated. The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=5:1), to give 7.2 mg of the title compound. LC-MS: HPLC retention time 1.41 minutes, m/z 404 (M+H), condition C-1.

References: [1]Bioorganic and Medicinal Chemistry Letters,2018,vol. 28,p. 2408 - 2412.
[2]Patent: US2010/29733,2010,A1 .Location in patent: Page/Page column 43.

25
[ 17953-46-7 ]
[ 78502-71-3 ]
[ 1204746-22-4 ]

Yield	Reaction Conditions	Operation in experiment
		Example 14 2-{(4-Methyl-3,5-diphenyl-1H-pyrazol-1-yl)methyl}thiazole-4-carboxylic acid To N,N-dimethylformamide (1 mL, manufactured by Kanto Chemical Formula Company) solution of 4-methyl-3,5-diphenyl-1H-pyrazole (40 mg) which had been synthesised according to the method of the literature (C. Francesca et al., J. Chem. Soc. Perkin Trans. 1 1994, 18, 2533-2536.), sodium hydride (added with 40% mineral oil, 7.5 mg, manufactured by Kanto Chemical Formula Company) was added under ice cooling and stirred at the same temperature for 5 minutes. Subsequently, to the reaction solution, ethyl 2-bromomethylthiazole-4-carboxylic acid (43 mg) which had been synthesised according to the method described in the literature (K. Benno et al., Liebigs. Ann. Chem. 1981, 4, 623-632.) was added and stirred at room temperature overnight. Then, water (1 mL) was added to the reaction solution, followed by extraction with ethyl acetate (3*2 mL), washing with brine (10 mL) and drying over MgSO4. The solvent was evaporated. The obtained residue was purified by PTLC (hexane:ethyl acetate=2:1) to give the tile compound (5.5 mg). LC-MS:HPLC retention time 4.62 minutes, m/z 376 (M+H), Condition B-1.

References: [1]Patent: US2010/29690,2010,A1 .Location in patent: Page/Page column 43.

26
[ 1298129-60-8 ]
[ 78502-71-3 ]
[ 1306754-37-9 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate; potassium iodide; In N,N-dimethyl-formamide; at 130℃; for 0.25h;Microwave irradiation;	2-(4',5'-difluoro-2'-methoxy-biphenyl-4-yloxymethyl)-thiazole-4-carboxylic acid A mixture of <strong>[78502-71-3]2-bromomethyl-thiazole-4-carboxylic acid ethyl ester</strong> (prepared according to US 2004/0266856 A1) (3.0 g, 11.99 mmol), 4',5'-difluoro-2'-methoxy-biphenyl-4-ol (3.09 g, 13.08 mmol), potassium carbonate (6.5 g, 47.03 mmol) and potassium iodide (1.1 g, 6.626 mmol) in DMF (25 mL) was heated under microwave conditions at 130 C. for 15 min. The reaction mixture was diluted with water (150 mL) and extracted with ethyl acetate (3×150 mL). The organic layers were combined, washed with 1/1 water/brine (2×100 mL) and brine (100 mL), dried (MgSO4), filtered, concentrated and purified by flash chromatography (silica, 120 g, 20% to 100% ethyl acetate in hexanes) to give 2-(4',5'-difluoro-2'-methoxy-biphenyl-4-yloxymethyl)-thiazole-4-carboxylic acid ethyl ester (4.35 g, 89.5%) as an orange oil. LC-MS (ES) calculated for C20H17F2NO4S, 405.42; found m/z 406 [M+H]+.

References: [1]Patent: US2011/118322,2011,A1 .Location in patent: Page/Page column 10-11.

27
[ 1298129-65-3 ]
[ 78502-71-3 ]
[ 1310037-08-1 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate; potassium iodide; In N,N-dimethyl-formamide; at 130℃; for 0.25h;Microwave irradiation;	2-(2',4',5'-Trifluoro-biphenyl-4-yloxymethyl)-thiazole-4-carboxylic acid ethyl ester; A mixture of 2',4',5'-trifluoro-biphenyl-4-ol (1.04 g, 4.639 mmol), <strong>[78502-71-3]2-bromomethyl-thiazole-4-carboxylic acid ethyl ester</strong> (prepared according to patent US 2004/0266856 A1) (1.2 g, 4.798 mmol), potassium carbonate (2.6 g, 18.81 mmol) and potassium iodide (438 mg, 2.638 mmol) in DMF (12 mL) was heated by microwave at 130 C. for 15 min. The reaction mixture was diluted with water (100 mL) and extracted with ethyl acetate (3×75 mL). The organic layers were combined, washed with brine (50 mL), dried (MgSO4), filtered and concentrated to give crude 2-(2',4',5'-trifluoro-biphenyl-4-yloxymethyl)-thiazole-4-carboxylic acid ethyl ester (1.74 g) as a tan solid which was used as is in the next step. LC-MS (ES) calculated for C19H14F3NO3S, 393.39; found m/z 394 [M+H]+.

References: [1]Patent: US2011/136792,2011,A1 .Location in patent: Page/Page column 19.

28
[ 78502-71-3 ]
[ 1256240-34-2 ]

References: [1]Patent: US2012/95040,2012,A1 .
[2]Patent: US2012/129830,2012,A1 .

29
[ 127-08-2 ]
[ 78502-71-3 ]
[ 1256240-35-3 ]

Yield	Reaction Conditions	Operation in experiment
95%	In acetonitrile; at 20℃; for 14h;	2.7 g (10.80 mmol) of <strong>[78502-71-3]ethyl 2-(bromomethyl)thiazole-4-carboxylate</strong> are dissolved in 108 mL of acetonitrile. 2.225 g (22.67 mmol) of potassium acetate are added and the medium is stirred at room temperature for 14 hours.The resulting mixture is concentrated under reduced pressure. The residue obtained is taken up in aqueous sodium chloride solution and extracted twice with dichloromethane. The combined organic phases are dried over sodium sulfate, filtered and concentrated to dryness. 2.347 g (95%) of expected product are obtained in the form of a wax.1H NMR (CDCl3) delta (ppm) : 8.15 (s, 1H); 5.35 (s, 2H); 4.35 (dq, 2H); 2.10 (s, 3H); 1.35 (t, 3H).
	In acetonitrile; at 20℃; for 14h;	2.7 g (10.80 mmoles) of ethyl 2-(bromomethyl) thiazole-4-carboxylate are dissolved in 108 ml of acetonitrile. 2.225 g (22.67 mmoles) of potassium acetate are added and the mixture is stirred for 14 hrs at ambient temperature.It is concentrated under reduced pressure. The residue obtained is taken up in a saturated aqueous solution of sodium chloride and extracted twice with dichloromethane. The combined organic phases are dried over sodium sulphate, filtered and concentrated to dryness. 2.347 g of the expected product are obtained in the form of a wax.1H NMR (CDCl3) delta (ppm): 8.15 (s, 1H); 5.35 (s, 2H); 4.35 (qd, 2H); 2.10 (s, 3H); 1.35 (t, 3H).

References: [1]Patent: US2012/95040,2012,A1 .Location in patent: Page/Page column 9.
[2]Patent: US2012/129830,2012,A1 .Location in patent: Page/Page column 8.

30
[ 1262881-67-3 ]
[ 78502-71-3 ]
[ 1263298-23-2 ]

Yield	Reaction Conditions	Operation in experiment
		To a solution of 6-fluoro-5-methoxy-2-phenylindole (200 mg) in N,N-dimethylformamide (4.1 mL) was added sodium hydride (dispersed in liquid paraffin, minimum 55%, 54 mg) under cooling with ice, and the mixture was stirred at room temperature for 70 minutes. Then a solution of ethyl 2-bromomethylthiazole-4-carboxylate (249 mg) in N,N-dimethylformamide (0.2 mL) was added, and the mixture was stirred at 80 C. for 25 hours. The reaction mixture was allowed to cool to ambient temperature. A saturated aqueous ammonium chloride solution-water (2/1) were added to the reaction mixture and this resulting mixture was extracted with ethyl acetate. The organic layer was washed successively with water and saturated saline, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluting solvent: ethyl acetate-hexane) to obtain the title compound (125 mg).In addition, structural formula and spectrum data of the title compound are shown in Table 29

References: [1]Patent: US2012/129890,2012,A1 .Location in patent: Page/Page column 47.

31
[ 2038-57-5 ]
[ 78502-71-3 ]
[ 1282549-53-4 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate; In methanol; acetonitrile; at 20℃; for 1h;Cooling with ice;	Preparation Example 26; 3-Phenylpropan-1-amine (11.33 g) and potassium carbonate (11.58 g) were added to acetonitrile (300 mL), and MeOH and a solution of <strong>[78502-71-3]ethyl 2-(bromomethyl)-1,3-thiazole-4-carboxylate</strong> (11.64 g) in acetonitrile (30 mL) in an ice bath were slowly added dropwise thereto, followed by stirring at room temperature for about 1 hour. To the reaction mixture was added an appropriate amount of ice water, followed by extraction with ethyl acetate several times. The organic layer was washed with brine and dried over MgSO4, and then the solvent was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (ethyl acetate:hexane=3:1 to 5:1) to prepare ethyl 2-[(3-phenylpropyl)amino]methyl}-1,3-thiazole-4-carboxylate (13.17 g).

References: [1]Patent: US2012/184521,2012,A1 .Location in patent: Page/Page column 24.

32
[ 78502-71-3 ]
[ 1282549-79-4 ]

References: [1]Patent: US2012/184521,2012,A1 .

33
[ 78502-71-3 ]
[ 1282549-22-7 ]

References: [1]Patent: US2012/184521,2012,A1 .

34
[ 78502-71-3 ]
[ 1282549-96-5 ]

References: [1]Patent: US2012/184521,2012,A1 .

35
[ 78502-71-3 ]
[ 1282544-16-4 ]

References: [1]Patent: US2012/184521,2012,A1 .

Historical Records

Technical Information

• Acyl Group Substitution • Alkyl Halide Occurrence • Bouveault-Blanc Reduction • Catalytic Hydrogenation • Complex Metal Hydride Reductions • Ester Cleavage • General Reactivity • Grignard Reaction • Hiyama Cross-Coupling Reaction • Kinetics of Alkyl Halides • Kumada Cross-Coupling Reaction • Reactions of Alkyl Halides with Reducing Metals • Reactions of Amines • Reactions of Dihalides • Reactions with Organometallic Reagents • Specialized Acylation Reagents-Carbodiimides and Related Reagents • Stille Coupling • Substitution and Elimination Reactions of Alkyl Halides • Suzuki Coupling

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CAS No.: 78502-71-3

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CAS No.: 78502-71-3

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[ 78502-71-3 ] Synthesis Path-Downstream 1~35

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