237429-33-3

Usage

Chemical Properties

White to off-white solid

InChI:InChI=1/C6H7BO2S/c8-7(9)5-1-3-6(10)4-2-5/h1-4,8-10H

Synthetic route

4-[(dimethyl-tert-butyl-silyl)thio]-phenylboronic acid (237429-34-4) → 4-mercaptophenylboronic acid (237429-33-3)

Conditions	Yield
With trifluoroacetic acid In dichloromethane desilylation;	88%

trifluoroacetic acid (76-05-1) + 4-[(dimethyl-tert-butyl-silyl)thio]-phenylboronic acid (237429-34-4) → 4-mercaptophenylboronic acid (237429-33-3)

Conditions	Yield
In dichloromethane equimolar amts., stirring overnight; evapn. (reduced pressure), crystn. (water);	88%

para-bromobenzenethiol (106-53-6) → 4-mercaptophenylboronic acid (237429-33-3)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: 92 percent / sodium hydride in oil / tetrahydrofuran / 14 h / 20 °C 2.1: n-butyl lithium / tetrahydrofuran; hexane / 0.25 h / -78 °C 2.2: 77 percent / tri-isopropyl borate / tetrahydrofuran / 4 h / -78 - -20 °C 3.1: 88 percent / trifluoroacetic acid / CH2Cl2 View Scheme

(4-bromophenylsulfanyl)-tert-butyldimethylsilane (153312-70-0) → 4-mercaptophenylboronic acid (237429-33-3)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: n-butyl lithium / tetrahydrofuran; hexane / 0.25 h / -78 °C 1.2: 77 percent / tri-isopropyl borate / tetrahydrofuran / 4 h / -78 - -20 °C 2.1: 88 percent / trifluoroacetic acid / CH2Cl2 View Scheme

C10H13BOS → 4-mercaptophenylboronic acid (237429-33-3)

Conditions	Yield
With sodium hydroxide In water pH=11 - 12; Large scale;	1.93 kg

2,3-dimethyl-2,3-butane diol (76-09-5) + 4-mercaptophenylboronic acid (237429-33-3) → 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzenethiol (1029438-23-0)

Conditions	Yield
With sodium sulfate at 20℃; for 16h; Inert atmosphere;	100%
With magnesium sulfate In diethyl ether at 20℃;	98%
With magnesium sulfate In cyclohexane at 20℃;	98%

ethyl bromoacetate (105-36-2) + 4-mercaptophenylboronic acid (237429-33-3) → {4-[(2-ethoxy-2-oxoethyl)thio]phenyl}boronic acid (1211474-17-7)

Conditions	Yield
With potassium carbonate; sodium iodide In acetonitrile at 20℃; for 18h;	100%

triphenylmethyl alcohol (76-84-6) + 4-mercaptophenylboronic acid (237429-33-3) → 4-(tritylsulfanyl)phenylboronic acid (1310810-82-2)

Conditions	Yield
With trifluoroacetic acid In dichloromethane at 20℃; for 1h;	95%

N'-(cyclohexylmethyl)-N'-((1R,2S,E)-1-hydroxy-1,4-diphenylbut-3-en-2-yl)-4-methoxybenzohydrazide + 4-mercaptophenylboronic acid (237429-33-3) → 4-((7S,8R,Z)-6-(cyclohexylmethyl)-4-(4-methoxyphenyl)-8-phenyl-7-((E)-styryl)-7,8-dihydro-6H-1,3,5,6,2-dioxadiazaborocin-2-yl)benzenethiol

Conditions	Yield
In dichloromethane at 40℃; for 0.5h;	95%

rac-3-sulfanylpropane-1,2-diol (96-27-5) + 4-mercaptophenylboronic acid (237429-33-3) → C9H11BO2S2

Conditions	Yield
In toluene at 20℃; for 24h; Molecular sieve; Glovebox;	94.8%

C14H15BrN2O3S3 (1260364-42-8) + 4-mercaptophenylboronic acid (237429-33-3) → C20H20N2O3S4 (1260364-52-0)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; acetonitrile at 100℃; Suzuki coupling; Microwave irradiation;	88%

1,3-diphenyl-1,3-propanediol (5355-61-3, 5381-86-2, 59825-14-8, 77291-92-0, 108391-15-7, 5471-97-6) + 4-mercaptophenylboronic acid (237429-33-3) → d,l-(4,6-diphenyl-2-(4-mercaptophenyl))-1,3,2-dioxaborinane

Conditions	Yield
In tetrahydrofuran for 0.5h; Esterification;	86%
In tetrahydrofuran equimolar amts., stirring for 30 min; drying (Na2SO4), filtration, evapn., chromy. (SiO2, CH2Cl2);	86%

N-Methyldiethanolamine (105-59-9) + 4-mercaptophenylboronic acid (237429-33-3) → 2-(4-mercaptophenyl)-6-methyl-1,3,6,2-dioxaazaborocane

Conditions	Yield
In tetrahydrofuran for 0.5h; Esterification;	85%

N-Methyldiethanolamine (105-59-9) + 4-mercaptophenylboronic acid (237429-33-3) → 2-(4-mercaptophenyl)-6-methyl-1,3,6,2-dioxaazaborocane (237429-36-6)

Conditions	Yield
In tetrahydrofuran 1.1 equiv. of amine, stirring for 30 min; Et2O addn., washing (water), drying (Na2SO4), evapn.;	85%

3-bromopropanol methyl ether (36865-41-5) + 4-mercaptophenylboronic acid (237429-33-3) → (4-{[3-(methoxy)propyl]thio}phenyl)boronic acid (1032825-16-3)

Conditions	Yield
With potassium carbonate; sodium iodide In acetonitrile at 20℃;	81%

bromoacetic acid tert-butyl ester (5292-43-3) + 4-mercaptophenylboronic acid (237429-33-3) → 4-(((butyloxycarbonyl)methyl)thio)phenylboronic acid (237429-41-3)

Conditions	Yield
With potassium carbonate; sodium iodide In acetonitrile for 20h; Alkylation;	71%
With potassium carbonate; sodium iodide In acetonitrile 1.5 equiv. of K2CO3 and t-BuO2CCH2Br, 0.15 equiv. NaI, stirring for 20 h; evapn. (reduced pressure), water addn., extn. into CH2Cl2, washing (water), drying (Na2SO4), chromy. (SiO2, 2% MeOH in CH2Cl2);	71%

[Pt(2,2':6',2''-terpyridine)(acetonitrile)](nitrate)2 + 4-mercaptophenylboronic acid (237429-33-3) → (2,2':6',2''-terpyridine)(4-mercaptophenylboronic acid(1-))platinum(II) nitrate

Conditions	Yield
In N,N-dimethyl-formamide addn. of DMF soln. of pyridine deriv. to DMF soln. of palladium compd., stirring at room temp. for 1 h; ppn. with diethyl ether, centrifugation, washing with diethyl ether, elem. anal.;	63%

bis(acetonitrile)decacarbonyltriosmium (61817-93-4, 146143-79-5, 871132-66-0) + 4-mercaptophenylboronic acid (237429-33-3) → C16H7BO12Os3S

Conditions	Yield
In tetrahydrofuran at 20℃;	63%

4-mercaptophenylboronic acid (237429-33-3) + methyl iodide (74-88-4) → (4-thiomethoxyphenyl)boronic acid (98546-51-1)

Conditions	Yield
With potassium carbonate In acetonitrile Methylation;	61%
With potassium carbonate In acetonitrile excess of MeI, stirring overnight; water addn., extn. into CH2Cl2, washing (water), drying (Na2SO4), evapn. (reduced pressure), recrystn. (Et2O);	61%

2-bromo-5-(3-methoxyphenyl)thiophene (1078734-14-1) + 4-mercaptophenylboronic acid (237429-33-3) → 4-[5-(3-methoxyphenyl)-2-thienyl]benzenethiol (1193525-23-3)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); caesium carbonate In 1,2-dimethoxyethane; ethanol; water at 150℃; under 11251.1 Torr; for 0.25h; Suzuki coupling; Microwave irradiation;	61%

1-(2-chloroethyl)-N,N-dimethylpiperidin-4-amine + 4-mercaptophenylboronic acid (237429-33-3) → [4-({2-[4-(dimethylamino)piperidin-1-yl]ethyl}thio)phenyl]boronic acid

Conditions	Yield
With caesium carbonate In tetrahydrofuran at 130℃; for 6h; Microwave irradiation;	53%

bromo-acetic acid amide (683-57-8) + 4-mercaptophenylboronic acid (237429-33-3) → {4-[(2-amino-2-oxoethyl)thio]phenyl}boronic acid (1032825-15-2)

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃;	49%

2-chloro-6-(1-oxo-[4-methoxyphenyl]methyl)pyrazine (850221-69-1) + 4-mercaptophenylboronic acid (237429-33-3) → 6-(4-mercaptophenyl)-2-((4-methoxyphenyl)carbonyl)pyrazine (1149759-63-6)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water for 5h; Suzuki-Miyaura cross-coupling; Inert atmosphere; Reflux;	43%

3-cyanopropyl(dimethyl)(vinyl)silane (954114-30-8) + 4-mercaptophenylboronic acid (237429-33-3) → [4-({2-[(3-cyanopropyl)dimethylsilyl]ethyl}thio)phenyl]boronic acid

Conditions	Yield
With di-tert-butyl peroxide at 100℃; for 6h; Inert atmosphere; Sealed tube;	43%

N,N'-thiobisphthalimide (7764-29-6) + 4-mercaptophenylboronic acid (237429-33-3) → C14H10BNO4S2

Conditions	Yield
In 1,2-dichloro-ethane at 80℃;	42%

4-(chloromethyl)-3-(2,6-dichlorophenyl)-5-(propan-2-yl)-1,2-oxazole (700835-81-0) + 4-mercaptophenylboronic acid (237429-33-3) → [4-({[3-(2,6-dichlorophenyl)-5-(1-methylethyl)-4-isoxazolyl]methyl}thio)phenyl]boronic acid (1020577-19-8)

Conditions	Yield
With caesium carbonate In N,N-dimethyl-formamide at 60℃; for 24h;

4-mercaptophenylboronic acid (237429-33-3) → 4-((carboxymethyl)thio)phenylboronic acid

Conditions	Yield
Multi-step reaction with 3 steps 1: 85 percent / tetrahydrofuran / 0.5 h 2: 65 percent / potassium carbonate; sodium iodide / acetonitrile / 20 h 3: 80 percent / trifluoroacetic acid / CH2Cl2 View Scheme
Multi-step reaction with 2 steps 1: 71 percent / potassium carbonate; sodium iodide / acetonitrile / 20 h 2: 80 percent / trifluoroacetic acid / CH2Cl2 View Scheme

4-mercaptophenylboronic acid (237429-33-3) → 2-(4-(t-butyloxycarbonylmethylthiophenyl))-6-methyl-1,3,6,2-dioxaazaborocane

Conditions	Yield
Multi-step reaction with 2 steps 1: 85 percent / tetrahydrofuran / 0.5 h 2: 65 percent / potassium carbonate; sodium iodide / acetonitrile / 20 h View Scheme

4-mercaptophenylboronic acid (237429-33-3) → 2-(4-carboxymethylthiophenyl)-4,6-diphenyl-1,3,2-dioxaborinane

Conditions	Yield
Multi-step reaction with 3 steps 1: 86 percent / tetrahydrofuran / 0.5 h 2: 70 percent / potassium carbonate; sodium iodide / acetonitrile / 20 h 3: 54 percent / trifluoroacetic acid / CH2Cl2 / 2 h View Scheme

4-mercaptophenylboronic acid (237429-33-3) → d,l-2-(4-(t-butyloxycarbonylmethylthiophenyl))-4,6-diphenyl-1,3,2-dioxaborinane

Conditions	Yield
Multi-step reaction with 2 steps 1: 86 percent / tetrahydrofuran / 0.5 h 2: 70 percent / potassium carbonate; sodium iodide / acetonitrile / 20 h View Scheme

4,4'-Dimethoxybenzhydrol (728-87-0) + 4-mercaptophenylboronic acid (237429-33-3) → 4-(4,4'-dimethoxybenzhydryl)thiophenylboronic acid (945244-19-9)

Conditions	Yield
With acetic acid at 60℃; for 1h;
In acetic acid at 60℃; for 1h;
In acetic acid
With acetic acid at 60℃; for 1h;

Upstream product

• 76-05-1 trifluoroacetic acid 
• 237429-34-4 4-[(dimethyl-tert-butyl-silyl)thio]-phenylboronic acid 
• 153312-70-0 (4-bromophenylsulfanyl)-tert-butyldimethylsilane 
• 106-53-6 para-bromobenzenethiol 

Downstream Products

• 237429-41-3 4-(t-butyloxycarbonylmethylthio)-phenyl boronic acid 
• 237429-36-6 2-(4-mercaptophenyl)-6-methyl-1,3,6,2-dioxaazaborocane 
• 1029438-23-0 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzenethiol 
• 1149759-63-6 6-(4-mercaptophenyl)-2-((4-methoxyphenyl)carbonyl)pyrazine 
• 1032825-12-9 (4-{[2-(methoxy)ethyl]thio}phenyl)boronic acid 
• 1032825-15-2 {4-[(2-amino-2-oxoethyl)thio]phenyl}boronic acid 
• 1032825-16-3 (4-{[3-(methoxy)propyl]thio}phenyl)boronic acid 
• 1193525-23-3 4-[5-(3-methoxyphenyl)-2-thienyl]benzenethiol 
• 1260364-52-0 C₂₀H₂₀N₂O₃S₄ 
• 1211474-17-7 {4-[(2-ethoxy-2-oxoethyl)thio]phenyl}boronic acid 
• 1211474-18-8 {[4-(3-Oxo-1-cyclopenten-1-yl)phenyl]thio}acetic acid ethyl ester 
• 1211474-19-9 ({4-[(1R)-3-Oxocyclopentyl]phenyl}thio)acetic acid ethyl ester 
• 1450761-64-4 C₆H₆BO₂S^(1-)*Ag⁽¹⁺⁾ 
• 798548-40-0 diphenyl-{2-[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenylsulfanyl]-ethyl}-phosphane 

Relevant academic research and scientific papers

A process for preparing between neighbour para-substituted hydroxy, thio boric acid

A method of preparing phenylboronic acid ortho- meta- and para-substituted with hydroxy and mercapto is disclosed. The method includes adding a compound of a formula I into an organic solvent, adding 1.2-2.0 eq of acetyl chloride, lowering the temperature of the solution to a temperature between -10 DEG C and 0 DEG C, adding 0.1-0.3 eq of anhydrous aluminium chloride, heating to 20-120 DEG C, stirring for 2-10 h to obtain a compound of a formula II, adding an alkali to adjust pH to be 11-12 after TLC detection proves that the reaction is finished, layering, removing the organic layer, adding hydrochloric acid into the water layer to adjust pH to be 2-3, extracting with ethyl acetate, subjecting the organic layer to rotary drying, and beating the obtained crude product with a mixture of acetone or dichloromethane and n-heptane to obtain a solid product of a formula III, wherein R in the formula I is methyl or tert-butyl, and M in the formula I, M in the formula II and M in the formula III are oxygen simultaneously or sulfur simultaneously. The product produced by the method is high in purity and high in yield.

Boronated thiophenols: A preparation of 4-mercaptophenylboronic acid and derivatives

4-Mercaptophenylboronic acid derivatives were prepared by a metallation/boration sequence from S-protected 4-bromothiophenols; the t-butyldimethylsilylthioether was found suitable to allow subsequent regeneration of the mercapto group after boration. The parent compound, 4-mercaptophenylboronic acid, could thus be obtained and was subsequently S-alkylated; 4-boronophenylthioacetic acid was prepared without the need to protect the boronic acid group.