98-80-6

Basic information

• Product Name: Phenylboronic acid
• Synonyms: phenyboronic;phenyl-boronicaci;phenyldihydroxyborane;t-500;usafbo-2;BIO-FARMA BF001405;BORONIC ACID, PHENYL-;BENZENEBORONIC ACID
• CAS NO: 98-80-6
• Molecular Formula: C₆H₇BO₂
• Molecular Weight: 121.93
• EINECS: 202-701-9
• Product Categories: Boron compounds;blocks;BoronicAcids;Boronic Acid series;PHARMACEUTICAL INTERMEDIATES;Substituted Boronic Acids;Organometallics;Boronic Acid;Aryl;Organoborons;Analytical Chemistry;B (Classes of Boron Compounds);Boronic Acid, etc. (GC Derivatizing Reagents);Boronic Acids;GC Derivatizing Reagents;organic or inorganic borate;Aryl Boronic Acids;Boronic Acids and Derivatives;Chemical Synthesis;Organometallic Reagents;Unsubstituted Aryl Boronic Acids;OLED materials,pharm chemical,electronic;Boronate Ester;Potassium Trifluoroborate
• Mol File: 98-80-6.mol
• Article Data: 115

Chemical Properties

• Melting Point: 216-219 °C(lit.)
• Boiling Point: 265.856 °C at 760 mmHg
• Flash Point: 114.586 °C
• Appearance: White to off-white/Crystalline Powder
• Density: 1.139 g/cm³
• Vapor Pressure: 0.00446mmHg at 25°C
• Refractive Index: 1.534
• Storage Temp.: 0-6°C
• Solubility: Chloroform (Slightly), DMSO (Slightly), Methanol (Slightly)
• PKA: 8.83(at 25℃)
• Water Solubility: 10 g/L (20 ºC)
• Sensitive: Hygroscopic
• Stability: Hygroscopic
• Merck: 14,1068
• BRN: 970972
• CAS DataBase Reference: Phenylboronic acid(CAS DataBase Reference)
• NIST Chemistry Reference: Phenylboronic acid(98-80-6)
• EPA Substance Registry System: Phenylboronic acid(98-80-6)

Safety Data

• Hazard Codes: Xn,Xi,N
• Statements: 22-36/37/38-20/21/22
• Safety Statements: 22-24/25-36/37/39-26-36
• WGK Germany: 3
• RTECS: CY8575000
• TSCA: Yes
• HazardClass: IRRITANT, MOISTURE SENSITIVE
• Hazardous Substances Data: 98-80-6(Hazardous Substances Data)

Usage

Chemical Description

Different sources of media describe the Chemical Description of 98-80-6 differently. You can refer to the following data:
1. Phenylboronic acid is an organic compound containing a boronic acid functional group attached to a phenyl group.
2. Phenylboronic acid is an organic compound with the chemical formula C6H5B(OH)2.

Chemical Properties

white to light yellow crystal powder

Uses

Different sources of media describe the Uses of 98-80-6 differently. You can refer to the following data:
1. Reagent used for? ;Rhodium-catalyzed intramolecular amination1 ? ;Pd-catalyzed direct arylation2 ? ;Mizoroki-Heck and Suzuki-Miyaura coupling reactions catalyzed by palladium nanoparticles3 ? ;Palladium-catalyzed stereoselective Heck-type reaction4 ? ;Highly effective Palladium-catalyzed arylation Suzuki-Miyaura cross-coupling in water5 Reagent used in Preparation of? ;Ni(II) pincer complex and Pd(II) pyridoxal hydrazone metallacycles as catalysts for the Suzuki-Miyaura cross-coupling reactions6,7? ;N-type polymers for all-polymer solar cells8 ?
2. suzuki reaction
3. Phenylboronic Acid is a compound used in organic synthesis of various pharmaceutical goods. Phenylboronic acid (PBA) and its derivatives can bind sugars and other diol compounds to form cyclic boronate esters. These esters bear negative charges. Due to this reaction, sugars can be detected by means of electrochemical and optical techniques. PBA modified electrodes have been constructed as reagentless electrochemical sensors. There, PBA is absorbed on the electrode surface either as a self- assembled monolayer film ore a polymer thin film. Basically, for optical detection techniques for the detection of sugars, PBA is modified with a chromophore that should change its properties on reaction with a sugar. Reaction of Phenylboronic acid with a sugar
4. Phenylboronic acid and its derivatives form complexes with polyol compounds such as saccharides and poly(vinyl alcohol) (PVA). Glucose-sensitive hydrogels can be prepared by using phenylhoronic acid as a ligand for target glucose. For example. a copolymer with phenylboronic acid moieties was synthesized by copolymerization of 4V-vinyl-2-pyrrolidone (NVP) and 3-(acryl- amide)phcnylhoronic acid (PBA). The complexes between the NVP-PBA copolymer and PVA enable us to construct glucose-sensitive insulin release systems because the complexes dissociated in response to the glucose concentration. This phenylboronic acid is soluble in water and the coupling reaction can even be carried out in water. It is compatible with many organic substituents such as esters, ketones, alcohols, etc. which would prohibit the use of Grignard reagents in coupling reactions.

Synthesis Reference(s)

Organic Syntheses, Coll. Vol. 4, p. 68, 1963The Journal of Organic Chemistry, 49, p. 5237, 1984 DOI: 10.1021/jo00200a045

General Description

Phenylboronic acid (PBA) is an organoboronic acid. It behaves as a molecular receptor that can attach to compounds containing cis-diol group. Microwave-assisted Suzuki coupling of aryl chlorides with phenylboronic acid in the presence of Pd/C (catalyst) and water (solvent) has been described. Palladium-catalyzed cross-coupling reaction of phenylboronicacid with haloarenes to afford biaryls has been reported.

Safety Profile

Poison by intravenous andintraperitoneal routes. Moderately toxic by ingestion.Mildly toxic by skin contact. When heated to decomposition it emitsacrid smoke and irritating fumes.

InChI:InChI=1/C6H7BO2/c8-7(9)6-4-2-1-3-5-6/h1-5,8-9H

Synthetic route

2-phenyl-4,4,5,5-tetramethyl-1,3,2-dioxoborole (24388-23-6) → phenylboronic acid (98-80-6)

Conditions	Yield
Stage #1: 2-phenyl-4,4,5,5-tetramethyl-1,3,2-dioxoborole With potassium hydrogen difluoride In methanol at 20℃; for 0.25h; Stage #2: With lithium hydroxide In acetonitrile at 20℃; for 20h;	100%
With hydrogenchloride In water at 20℃; for 15h;	100%
With polystyrene boronic acid; trifluoroacetic acid In acetonitrile for 18h; Heating;	98%
Multi-step reaction with 2 steps 1: diethyl ether / 0.5 h / 20 °C 2: hydrogenchloride / water / 0.33 h View Scheme
With dimyristoylphosphatidylcholine; water In dimethyl sulfoxide at 20℃; for 168h;

1-chloro-3,5-dimethylbenzene (556-97-8) → 3,5-dimethylbiphenyl (17057-88-4) + phenylboronic acid (98-80-6)

Conditions	Yield
With cesium fluoride; Pd(dba)2 In toluene	A n/a B 99%

tetrahydroxydiboron (13675-18-8) + phenyltrimethylammonium iodide (98-04-4) → phenylboronic acid (98-80-6)

Conditions	Yield
In methanol at 15℃; for 3h; Microwave irradiation;	98%

water (7732-18-5) + potassium phenyltrifluoborate → phenylboronic acid (98-80-6)

Conditions	Yield
With montmorillonite K10 at 25℃; for 0.5h; Catalytic behavior; Reagent/catalyst; Temperature;	97%
With 1H-imidazole; iron(III) chloride at 20℃; for 0.25h; Catalytic behavior; Solvent; Reagent/catalyst; Time; Inert atmosphere;	87%
With glass or Cs2CO3 In tetrahydrofuran; water Kinetics; hydrolysis at 55°C in THF/H2O in the presence of glass powder or Cs2CO3; not isolated;

dihydroxy-methyl-borane (13061-96-6) + 2-phenyl-4,4,5,5-tetramethyl-1,3,2-dioxoborole (24388-23-6) → phenylboronic acid (98-80-6)

Conditions	Yield
With trifluoroacetic acid In dichloromethane at 20℃; Reagent/catalyst; Solvent;	97%

tributylphenylstannane (960-16-7) → phenylboronic acid (98-80-6)

Conditions	Yield
With borane; water In tetrahydrofuran for 1h; Heating;	96%

diisopropopylaminoborane (22092-92-8) + phenylmagnesium bromide (100-58-3) → phenylboronic acid (98-80-6)

Conditions	Yield
at -78 - -45℃;	95%

diisopropopylaminoborane (22092-92-8) + water (7732-18-5) + phenylmagnesium bromide (100-58-3) → phenylboronic acid (98-80-6)

Conditions	Yield
Stage #1: diisopropopylaminoborane; phenylmagnesium bromide In tetrahydrofuran at 0℃; for 1h; Inert atmosphere; Stage #2: water With hydrogenchloride In tetrahydrofuran at 0℃; for 0.583333h; Inert atmosphere;	95%

diisopropylamine borane (55124-35-1) + water (7732-18-5) + phenylmagnesium bromide (100-58-3) → phenylboronic acid (98-80-6)

Conditions	Yield
Stage #1: diisopropylamine borane; phenylmagnesium bromide In tetrahydrofuran at 20℃; Stage #2: water In tetrahydrofuran; methanol	95%

Sb2O4B2(C6H5)8 (244109-23-7) + acetic acid (64-19-7) → diacetoxotriphenylantimony + phenylboronic acid (98-80-6)

Conditions	Yield
excess acid addn. to soln. of Sb-compd., refluxing (3 h), volatile products collecting in cooled trap; products sepn. by ether;	A 94% B 92%

Trimethyl borate (121-43-7) + phenylmagnesium bromide (100-58-3) → phenylboronic acid (98-80-6)

Conditions	Yield
In tetrahydrofuran at 20℃; Temperature; Concentration; Flow reactor;	93.9%

bromobenzene (108-86-1) + tetrahydroxydiboron (13675-18-8) → phenylboronic acid (98-80-6)

Conditions	Yield
In methanol at 15℃; for 3h; Microwave irradiation;	92%
With [{Pd(μ-Cl){κ2-P,C-P(iPr)2(OC6H3-2-Ph)}}2]; sodium acetate In dichloromethane; water at 40℃; for 6h; Inert atmosphere;
With 1,3-bis[(diphenylphosphino)propane]dichloronickel(II); N-ethyl-N,N-diisopropylamine; triphenylphosphine In ethanol at 80℃; for 4h; Miyaura Borylation Reaction; Schlenk technique; Inert atmosphere; Sealed tube;

dicyclohexylamine borane complex (131765-96-3) + water (7732-18-5) + phenylmagnesium bromide (100-58-3) → phenylboronic acid (98-80-6)

Conditions	Yield
Stage #1: dicyclohexylamine borane complex; phenylmagnesium bromide In tetrahydrofuran at 20℃; Stage #2: With methanol In tetrahydrofuran Stage #3: water In tetrahydrofuran	92%

benzene (71-43-2) → phenylboronic acid (98-80-6)

Conditions	Yield
With bis(pinacol)diborane; Ir(o-O-C6H4-CH=N=CH2Ph)(cod) at 80℃; for 21h; Product distribution; Further Variations:; Solvents;	91%
Stage #1: benzene With Pinacolborane; bis(pinacol)diborane; 4,4'-di-tert-butyl-2,2'-bipyridine; (1,5-cyclooctadiene)(methoxy)iridium(l) dimer at 80℃; for 24h; Stage #2: With sodium periodate In tetrahydrofuran; water for 0.5h; Stage #3: With hydrogenchloride In tetrahydrofuran; water at 20℃; for 17h;
Multi-step reaction with 2 steps 1: Pd 2: H2O View Scheme

bis(pinacol)diborane (73183-34-3) + benzene (71-43-2) → phenylboronic acid (98-80-6)

Conditions	Yield
With tetra-2-pyridinylpyrazine; [Ir(I)(salicylidenebenzyliminato)(1,5-cyclooctadiene)] In dichloromethane; benzene under Ar; mixt. was heated at 80°C for 21 h in mixt. of 3 ml benzene and 2 ml each CH2Cl2 and ionic liquid TBPD (tributyltetradecylphosphonium dodecylbenzenesulfonate) as solvent; solvent was removed under reduced pressure, Et2O was added, after 10% aq. HCl was added, mixt. stirred for 4 h, organic layer dried with MgSO4, solvent was removed under reduced pressure, residue was chromd. (flash chromy, SiO2); NMR;	91%
With tetra-2-pyridinylpyrazine; [Ir(I)(salicylidenebenzyliminato)(1,5-cyclooctadiene)] In benzene under Ar; soln. of Ir complex and pyridinylpyrazine was prepared, pinacolato soln. was added, mixt. was then heated at 80°C for 21 h; solvent was removed under reduced pressure, Et2O was added, after 10% aq. HCl was added, mixt. stirred for 4 h, organic layer dried with MgSO4, solvent was removed under reduced pressure, residue was chromd. (flash chromy, SiO2); NMR;	70%
With tetra-2-pyridinylpyrazine; [Ir(I)(salicylidenebenzyliminato)(1,5-cyclooctadiene)] In benzene High Pressure; under Ar; soln. of Ir complex and pyridinylpyrazine was prepared in glove box, pinacolato soln. and prepared catalyst and ligand soln. were placed in autoclave, mixt. was then heated at 100°C for 40 h; solvent was removed under reduced pressure, Et2O was added, after 10% aq. HCl was added, mixt. stirred for 4 h, organic layer dried with MgSO4, solvent was removed under reduced pressure, residue was chromd. (flash chromy, SiO2); NMR;	67%

4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane (25015-63-8) + benzene (71-43-2) → phenylboronic acid (98-80-6)

Conditions	Yield
With hydrogenchloride In dichloromethane; benzene other Radiation; under Ar atm. mixt. HBpin, nano-Ir(0) cat. prepd by reduction (Ph3P)2Ir(H)(7,8-nido-C2B9H11), tetra-2-pyridinylpyrazine, benzene, CH2Cl2 and trihexyltetradecylphosphonium methylsulfonate was heated at 130°C for 1 h in microwave, hydrolysis aq.HCl; flash chromy.;	91%
With hydrogenchloride In dichloromethane; benzene Sonication; under Ar atm. mixt. HBpin, nano-Ir(0) cat. prepd by reduction (Ph3P)2Ir(H)(7,8-nido-C2B9H11), tetra-2-pyridinylpyrazine, benzene, CH2Cl2 and trihexyltetradecylphosphonium methylsulfonate was heated at 80°C for4 h in ultrasonic, hydrolysis aq.HCl; flash chromy.;	61%
With hydrogenchloride In dichloromethane; benzene High Pressure; under Ar atm. mixt. HBpin, nano-Ir(0) cat. prepd by reduction (Ph3P)2Ir(H)(7,8-nido-C2B9H11), tetra-2-pyridinylpyrazine, benzene, CH2Cl2 and trihexyltetradecylphosphonium methylsulfonate was heated at 180°C for 12 h, hydrolysis with aq.HCl; flash chromy.;	50%

C22H27BN4O3 + boric acid (11113-50-1) → phenylboronic acid (98-80-6)

Conditions	Yield
With acetic acid In water	90%

methanol (67-56-1) + bromobenzene (108-86-1) + diisopropylamine borane (55124-35-1) → phenylboronic acid (98-80-6)

Conditions	Yield
Stage #1: diisopropylamine borane With magnesium; phenylmagnesium bromide In tetrahydrofuran at 20℃; for 0.166667h; Stage #2: bromobenzene In tetrahydrofuran at 70℃; Stage #3: methanol Further stages;	88%

potassium phenyltrifluoborate → phenylboronic acid (98-80-6)

Conditions	Yield
With iron(III) chloride; water In tetrahydrofuran at 20℃; for 0.5h;	86%
With water; silica gel at 20℃; for 4h; Inert atmosphere;	65%
In phosphate buffer pH=6.9 - 7.0; Kinetics;
With water In tetrahydrofuran at 55℃; Kinetics; Reagent/catalyst;

bromobenzene (108-86-1) + triethyl borate (150-46-9) → phenylboronic acid (98-80-6)

Conditions	Yield
With n-butyllithium In tetrahydrofuran at -78℃; Inert atmosphere;	82.7%
With n-butyllithium In tetrahydrofuran

bromobenzene (108-86-1) → phenylboronic acid (98-80-6)

Conditions	Yield
Stage #1: bromobenzene With triethylamine; bis-triphenylphosphine-palladium(II) chloride In tetrahydrofuran at 65℃; Stage #2: With sodium hydroxide In tetrahydrofuran Further stages.;	82%
Stage #1: bromobenzene With Trimethyl borate In tetrahydrofuran at -20 - 0℃; Inert atmosphere; Stage #2: With sulfuric acid In tetrahydrofuran at 0 - 10℃; for 10h; Inert atmosphere;	82.4%
Stage #1: bromobenzene With magnesium In tetrahydrofuran Stage #2: With Trimethyl borate In tetrahydrofuran at -70℃;	82.4%

(S,S)-2-(phenyl)-4,5-dicyclohexyl-1,3,2-dioxaborolane + water (7732-18-5) → phenylboronic acid (98-80-6)

Conditions	Yield
With 1H-imidazole; thionyl chloride In acetonitrile the B complex was obtained by a treatment of the boronic ester with SOCl2 and imidazole in the presence of borosilicate glass (the catalyst); this complex was hydrolized in aq. CH3CN;	82%

5-(4-methoxyphenyl)-4,4-dimethyl-2-phenyl-[1,3,2]dioxaborolane → phenylboronic acid (98-80-6)

Conditions	Yield
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane; water at 20℃; for 8h;	81%

Trimethyl borate (121-43-7) + phenylmagnesium bromide (100-58-3) → phenol (108-95-2) + phenylboronic acid (98-80-6)

Conditions	Yield
In tetrahydrofuran at -12℃; Temperature; Concentration; Flow reactor;	A 7.9% B 80.7%

iodobenzene (591-50-4) → phenylboronic acid (98-80-6)

Conditions	Yield
Stage #1: iodobenzene With diisopropopylaminoborane; triethylamine; triphenylphosphine; palladium dichloride In tetrahydrofuran at 65℃; for 12h; Alcaraz-Vaultier borylation; Inert atmosphere; Stage #2: With methanol In tetrahydrofuran at 0℃; Inert atmosphere; Further stages;	80%
Multi-step reaction with 2 steps 2: H2O View Scheme

Trimethyl borate (121-43-7) + phenylmagnesium bromide (100-58-3) → chlorobenzene (108-90-7) + phenol (108-95-2) + phenylboronic acid (98-80-6)

Conditions	Yield
In tetrahydrofuran at 22℃; Temperature; Concentration; Flow reactor;	A 8.9% B 5.7% C 79.6%

bromobenzene (108-86-1) + chloro-bis(dimethylamino)borane (6562-41-0) → phenylboronic acid (98-80-6)

Conditions	Yield
With lithium In tetrahydrofuran at -10℃; Inert atmosphere;	76%

borane (13283-31-3) → phenylboronic acid (98-80-6)

Conditions	Yield
With water; phenylmagnesium bromide In tetrahydrofuran slow addn. of 10 mmol of the Grignard reagent to a stirred soln. of borane in THF (40 mmol); the mixt. was poured into ice-water and acidified with 10% HCl;; extn. into ether three-times; the combined extracts were dried over NaSO4; removal of solvent under reduced pressure; trituration with petroleum ether; recrystn. from H2O;;	75%
With bromobenzene; water; magnesium In tetrahydrofuran a 2.0 M soln. of borane (40 mmol) in THF was added to flame dried Mg turnings (12 mmol) at 0°C; slow addn. of the aryl bromide (10 mmol)in THF; stirring at room temp. for 12-16 h; the mixt. was poured into ice-water and acidified with 10% HCl;; extn. into ether three-times; the combined extracts were dried over NaSO4; removal of solvent under reduced pressure; trituration with petroleum ether; recrystn. from H2O;;

Phenyl triflate (17763-67-6) → phenylboronic acid (98-80-6)

Conditions	Yield
Stage #1: Phenyl triflate With tris(dibenzylideneacetone)dipalladium(0) chloroform complex; diisopropopylaminoborane; triethylamine; triphenylphosphine In tetrahydrofuran at 65℃; for 12h; Alcaraz-Vaultier borylation; Inert atmosphere; Stage #2: With methanol In tetrahydrofuran at 0℃; Inert atmosphere; Further stages;	74%

benzene-1,2-diol (120-80-9) + phenylboronic acid (98-80-6) → 2-phenyl-1,3,2-benzodioxaborole (5747-23-9)

Conditions	Yield
at 80℃; for 1h;	100%
for 0.166667h; Schlenk technique;	96%
In dichloromethane; ethyl acetate at 20℃;	81%

1,2-diamino-benzene (95-54-5) + phenylboronic acid (98-80-6) → 2-phenyl-2,3-dihydro-1H-benzo[1,3,2]diazaborole (2479-64-3)

Conditions	Yield
at 40℃; for 1h;	100%
In toluene for 2h; Reflux;	92%
In toluene stirring mixt. of diamine deriv. and phenylboric acid in toluene for 2 hat reflux; filtration, washing with petroleum ether, NMR;	92%

2-hydroxyresorcinol (87-66-1) + phenylboronic acid (98-80-6) → 2-phenyl-1,3,2-benzodioxaborole-4-ol (108880-02-0)

Conditions	Yield
at 40℃; for 2h;	100%

mannitol (69-65-8) + phenylboronic acid (98-80-6) → (2R,3R,4R,5R)-1:2,3:4,5:6-O1:O2,O3:O4,O5:O6-tris(phenylboranato)-D-mannitol (6638-75-1, 62560-54-7)

Conditions	Yield
at 20℃; for 1h;	100%

phenylboronic acid (98-80-6) → triphenylboroxine (3262-89-3)

Conditions	Yield
at 110℃; for 6h;	100%
at 110℃; for 6h; Inert atmosphere; Neat (no solvent);	100%
Stage #1: phenylboronic acid With barium(II) hydroxide In water at 80℃; for 0.0833333h; Stage #2: With Au38(SCH2CH2Ph)24 In toluene at 80℃; for 12h; Reagent/catalyst;	100%

anthranilic acid (118-92-3) + phenylboronic acid (98-80-6) → 2-phenyl-1,2-dihydro-benzo[a][1,3,2]-oxazaborinin-4-one (42409-65-4)

Conditions	Yield
at 20℃; for 1h;	100%
In toluene for 16h; Inert atmosphere; Dean-Stark; Reflux;	93%
In toluene
In tetrahydrofuran for 24h; Reflux;	72 %Spectr.

2,2-Dimethyl-1,3-propanediol (126-30-7) + phenylboronic acid (98-80-6) → 5,5-dimethyl-2-phenyl-1,3,2-dioxaborinane (5123-13-7)

Conditions	Yield
With magnesium sulfate In diethyl ether at 25℃; for 20h; Inert atmosphere;	100%
In tetrahydrofuran for 0.666667h; Inert atmosphere; Dean-Stark; Reflux;	100%
With magnesium sulfate In diethyl ether at 20℃; for 20h;	100%

N1,N1'-diphenyloxaldiamidrazone (3449-06-7) + phenylboronic acid (98-80-6) → 2,3,2',3'-tetraphenyl-3,4,3',4'-tetrahydro-2H,2'H-[5,5']bi[1,2,4,3]triazaborolyl

Conditions	Yield
	100%
In di-isopropyl ether

naphthalene-1,8-diamine (479-27-6) + phenylboronic acid (98-80-6) → 2-phenyl-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (24341-81-9)

Conditions	Yield
at 0℃; for 1h;	100%
With 1H-imidazole; iron(III) chloride In water; acetonitrile at 20℃; for 2h; Catalytic behavior; Temperature; Time; Inert atmosphere;	93%
at 150℃; for 0.25h; Microwave irradiation; Sealed tube;	90%

oxalodihydrazonic acid dianilide (29180-72-1) + phenylboronic acid (98-80-6) → 3,4,3',4'-tetraphenyl-3,4,3',4'-tetrahydro-2H,2'H-[5,5']bi[1,2,4,3]triazaborolyl

Conditions	Yield
	100%
In di-isopropyl ether

3-Chloropyridine (626-60-8) + phenylboronic acid (98-80-6) → 3-phenylpyridine (1008-88-4)

Conditions	Yield
With potassium phosphate; bis(tricyclohexylphosphine)nickel(II) dichloride In tert-Amyl alcohol for 12h; Solvent; Suzuki-Miyaura Coupling; Heating;	100%
With cesiumhydroxide monohydrate; 2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl; palladium diacetate In water; butan-1-ol at 25℃; for 0.25h; Solvent; Reagent/catalyst; Suzuki-Miyaura Coupling; Inert atmosphere;	100%
With potassium phosphate; catacxium A; palladium diacetate In toluene at 100℃; for 20h; Suzuki reaction;	99%

2-bromo-pyridine (109-04-6) + phenylboronic acid (98-80-6) → 2-phenylpyridine (1008-89-5)

Conditions	Yield
With [Pd(N-(naphthyl)-salicylaldimine(-2H))(triphenylphosphine)]; sodium hydroxide at 120℃; for 24h; Reagent/catalyst; Suzuki Coupling;	100%
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene for 18h; Inert atmosphere; Reflux;	100%
With potassium phosphate; (PdCl2)(2-pyridyl)-6-isopropyl cis piperidine complex In water; N,N-dimethyl-formamide at 110℃; for 2h;	99%

2-chloropyrazin (14508-49-7) + phenylboronic acid (98-80-6) → 2-phenylpyrazine (29460-97-7)

Conditions	Yield
With tetrabutyl ammonium fluoride; tricyclohexylphosphine; dichloro bis(acetonitrile) palladium(II) at 85 - 90℃; for 5h; Suzuki-Miyaura reaction;	100%
With potassium phosphate; C46H52Cl3N3O2Pd In tetrahydrofuran; water at 60℃; for 4h; Suzuki-Miyaura Coupling;	99%
With 2-((3-sulfonatomesityl)-5-sulfonatoindenyl)dicyclohexylphosphinehydrate sodium salt; palladium diacetate; potassium carbonate In water at 100℃; for 24h; Suzuki-Miyaura Coupling;	95%

5-bromopyrimidine (4595-59-9) + phenylboronic acid (98-80-6) → 5-phenylpyrimidine (34771-45-4)

Conditions	Yield
With caesium carbonate; palladium diacetate In N,N-dimethyl-formamide at 80℃; for 6h; Suzuki-Miyaura cross-coupling reaction;	100%
With potassium carbonate In ethanol; water at 30℃; for 1h; Suzuki-Miyaura Coupling;	100%
With N,N,N′,N′-tetra(diphenylphosphinomethyl)-1,2-ethylenediamine; potassium carbonate; palladium dichloride In 1,4-dioxane; N,N-dimethyl-formamide at 90℃; for 6h; Suzuki coupling; Inert atmosphere;	99%

chlorobenzene (108-90-7) + phenylboronic acid (98-80-6) → biphenyl (92-52-4)

Conditions	Yield
With Cs2O3; PCy3 adduct of cyclopalladated ferrocenylimine In 1,4-dioxane at 100℃; for 15h; Suzuki cross-coupling reaction;	100%
With dichloro(cycloocta-1,5-diene)palladium (II); 2,2-[μ-(N,N'-piperazindiyl)dimethyl]-bis(4,6-di-tert-butyl-phenol); potassium carbonate In methanol for 0.166667h; Suzuki cross-coupling reaction; Microwave irradiation; Inert atmosphere;	100%
With potassium carbonate In methanol at 100℃; for 0.0833333h; Suzuki-Miyaura Coupling; Microwave irradiation;	100%

4-iodobenzoic acid (619-58-9) + phenylboronic acid (98-80-6) → biphenyl-4-carboxylic acid (92-92-2)

Conditions	Yield
With potassium phosphate monohydrate; 4,4'-di-tBu-2,2'-dipyridylpalladium(II) dichloride In methanol; water at 80℃; for 2h; Suzuki-Miyaura Coupling;	100%
With potassium carbonate; palladium dichloride In water at 20 - 90℃; Suzuki coupling; Inert atmosphere;	99%
With potassium carbonate In water at 90℃; for 0.25h; Suzuki reaction; Inert atmosphere;	99%

2-bromo-5-nitrotoluene (7149-70-4) + phenylboronic acid (98-80-6) → 2-methyl-4-nitrobiphenyl (91718-52-4)

Conditions	Yield
With trans-dibromobis(1-butyl-3-methylimidazol-2-ylidene)palladium(II); sodium hydrogencarbonate In ethylene glycol at 110℃; for 1h; Catalytic behavior; Suzuki-Miyaura Coupling; Schlenk technique;	100%
With tetrabutylammomium bromide; sodium carbonate In water at 100℃; for 2h; Suzuki coupling;	99%
With sodium carbonate In 1,2-dimethoxyethane; water for 16h; Heating / reflux;	86%

2-bromo-6-nitrotoluene (55289-35-5) + phenylboronic acid (98-80-6) → 2-nitro-6-phenyltoluene (107622-50-4)

Conditions	Yield
With potassium carbonate; copper-palladium In N,N-dimethyl-formamide at 110℃; for 4h; Suzuki cross-coupling;	100%
With tetra-butylammonium acetate; Pd EnCat-30TM In ethanol at 120℃; for 0.166667h; Suzuki cross-coupling; microwave irradiation;	97%
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,2-dimethoxyethane; water at 100 - 102℃; Suzuki Coupling; Inert atmosphere;	93%

phenylboronic acid (98-80-6) + 3-Iodobenzoic acid (618-51-9) → 3-phenylbenzoic acid (716-76-7)

Conditions	Yield
With sodium hydroxide; palladium dichloride In water for 0.166667h; Product distribution; Ambient temperature; other reagents, reaction times;	100%
With sodium hydroxide; palladium diacetate In water at 20℃; for 2h; Suzuki reaction;	100%
With disodium hydrogenphosphate; Pd(OAc)2(2-amino-4,6-dihydroxypyrimidine disodium salt)2 In water at 120℃; for 0.166667h; Suzuki-Miyaura coupling; Microwave irradiation;	98%

bromochlorobenzene (106-39-8) + phenylboronic acid (98-80-6) → 4'-biphenyl chloride (2051-62-9)

Conditions	Yield
With potassium carbonate In ethanol at 80℃; for 36h; Suzuki-Miyaura Coupling; Inert atmosphere;	100%
With C28H38Cl2N2O6PdS2(2-)*2Na(1+); tetrabutylammomium bromide; potassium carbonate In water at 75℃; Suzuki coupling; Inert atmosphere;	99%
With Br(1-)*C28H29BrN5O2Pd(1+); potassium carbonate In methanol; water at 100℃; for 3h; Suzuki-Miyaura coupling;	99%

bromobenzene (108-86-1) + phenylboronic acid (98-80-6) → biphenyl (92-52-4)

Conditions	Yield
With potassium carbonate; {1,3-di[(R)-1-PhEt]imidazolin-2-ylidene}(PPh3)PdI2 In xylene at 130℃; for 13h; Suzuki-Miyaura cross-coupling reaction;	100%
With potassium phosphate; triphenylphosphine; Ni(II) complexes of bidentate carbene; phosphine ligand In toluene at 80℃; Suzuki cross-coupling;	100%
With [PdCl2(2-ethyl-2-oxazoline)2]; potassium carbonate In toluene at 110℃; for 3h; Suzuki reaction;	100%

1-bromo-4-methoxy-benzene (104-92-7) + phenylboronic acid (98-80-6) → 4-methoxylbiphenyl (613-37-6)

Conditions	Yield
With potassium carbonate; {1,3-di[(R)-1-PhEt]imidazolin-2-ylidene}(PPh3)PdI2 In xylene at 130℃; for 14h; Suzuki-Miyaura cross-coupling reaction;	100%
With 1,2-bis(diphenylphosphino)-1'-(diisopropylphosphino)-3',4-di-tert-butyl ferrocene; potassium carbonate; bis(η3-allyl-μ-chloropalladium(II)) In xylene at 130℃; for 20h; Suzuki cross-coupling;	100%
With 1,4-diaza-bicyclo[2.2.2]octane; PEG-400; potassium carbonate; palladium diacetate at 110℃; for 2h; Suzuki-Miyaura cross-coupling reaction;	100%

iodobenzene (591-50-4) + phenylboronic acid (98-80-6) → biphenyl (92-52-4)

Conditions	Yield
With potassium carbonate; copper-palladium In N,N-dimethyl-formamide at 110℃; Kinetics; Product distribution; Further Variations:; Catalysts; Reaction partners; Suzuki cross-coupling;	100%
With sodium hydroxide; Pd-dodecanethiolate nanoparticles In tetrahydrofuran at 20℃; for 24h; Suzuki-Miyaura cross-coupling;	100%
With sodium carbonate; 1-butyl-3-methylimidazolium Tetrafluoroborate; 2C10H15N2(1+)*Cl4Pd(2-) In water at 110℃; for 12h; Conversion of starting material; Suzuki Coupling;	100%

2-bromoanisole (578-57-4) + phenylboronic acid (98-80-6) → 2-methoxy-1,1'-biphenyl (86-26-0)

Conditions	Yield
With di-tert-butyl(4-sulfonatobenzyl)phosphonium; palladium diacetate; sodium carbonate In water at 50℃; for 24h; Solvent; Temperature; Reagent/catalyst; Suzuki Coupling; Inert atmosphere; Glovebox;	100%
With di-tert-butyl(4-sulfonatobenzyl)phosphonium; palladium diacetate; sodium carbonate In water at 50℃; Reagent/catalyst; Solvent; Temperature; Suzuki Coupling; Inert atmosphere; Glovebox;	100%
With sodium carbonate In water at 100℃; Suzuki-Miyaura reaction;	99.1%

para-bromotoluene (106-38-7) + phenylboronic acid (98-80-6) → 4-Methylbiphenyl (644-08-6)

Conditions	Yield
With potassium phosphate; (η5-C5H5)Re(NO)(P(C6H5)3)(C(CH3)3)2; palladium diacetate In toluene at 100℃; for 1h; Suzuki cross-couplings reaction;	100%
With N,N-dicyclohexyl-2-(dicyclohexylphosphanyl)benzenesulfonamide; tris(dibenzylideneacetone)dipalladium (0); caesium carbonate In 1,4-dioxane at 80℃; for 3h; Suzuki-Miyaura cross coupling;	100%
With potassium phosphate; 3-(2,6-diisopropylphenyl)-1-(2-diphenylphosphanylbenzyl)-3H-imidazol-1-ium chloride; bis(η3-allyl-μ-chloropalladium(II)) In 1,4-dioxane at 80℃; for 12h; Product distribution; Further Variations:; Catalysts; Reagents; Solvents; Suzuki cross-coupling;	100%

2-methylphenyl bromide (95-46-5) + phenylboronic acid (98-80-6) → 2-methylbiphenyl (643-58-3)

Conditions	Yield
With [Pd(1-butylimidazole)2Cl2]; potassium hydroxide In water; isopropyl alcohol at 40℃; for 1h; Suzuki-Miyaura reaction; Under air;	100%
With caesium carbonate In water; isopropyl alcohol at 80℃; for 3h; Suzuki-Miyaura reaction; Inert atmosphere;	100%
With potassium hydroxide In propan-1-ol; water at 60℃; for 1h; Reagent/catalyst; Suzuki-Miyaura Coupling; Schlenk technique;	100%

1-Bromonaphthalene (90-11-9) + phenylboronic acid (98-80-6) → 1-phenylnaphthalene (605-02-7)

Conditions	Yield
With C31H26N6O4Pd; potassium carbonate In water at 100℃; for 3h; Suzuki-Miyaura coupling;	100%
With potassium phosphate; 1,1'-bis(4-methoxyphenyl)-3,3'-methylene-diimidazoline-2,2'-diylidene-palladium(II)-dibromide In toluene at 40℃; for 2h; Reagent/catalyst; Temperature; Time; Suzuki-Miyaura Coupling; Inert atmosphere;	100%
With C16H21ClN2Pd; sodium carbonate In methanol at 85℃; for 1h; Reagent/catalyst; Suzuki-Miyaura Coupling;	100%

2-Bromo-6-methoxynaphthalene (5111-65-9) + phenylboronic acid (98-80-6) → 2-methoxy-6-phenylnaphthalene (59115-43-4)

Conditions	Yield
With potassium phosphate; (η5-C5H5)Re(NO)(P(C6H5)3)P(C6H5)2; palladium diacetate In toluene at 100℃; for 0.25h; Suzuki cross-couplings reaction;	100%
With palladium diacetate; tetrabutylammomium bromide; potassium carbonate In water at 70℃; for 1h;	99%
With potassium fluoride; o-(dicyclohexylphosphino)diisopropylbenzamide; tris(dibenzylideneacetone)dipalladium (0) In N,N-dimethyl-formamide at 80℃; for 40h; Suzuki cross-coupling;	98%

4-methoxycarbonylphenyl bromide (619-42-1) + phenylboronic acid (98-80-6) → methyl 4-phenylbenzoate (720-75-2)

Conditions	Yield
With potassium phosphate; second generation phosphine dendrimer-stabilized palladium In 1,4-dioxane for 20h; Suzuki coupling; Heating;	100%
With potassium phosphate; silica gel; palladium In toluene at 110℃; for 5h; Suzuki-Miyaura reaction;	100%
With potassium phosphate tribasic heptahydrate In 1,4-dioxane for 20h; Suzuki coupling; Reflux;	100%

para-iodoanisole (696-62-8) + phenylboronic acid (98-80-6) → 4-methoxylbiphenyl (613-37-6)

Conditions	Yield
With 1,4-diaza-bicyclo[2.2.2]octane; potassium carbonate; palladium diacetate In acetone at 110℃; for 2h; Suzuki-Miyaura cross-coupling reaction;	100%
With sodium hydroxide; Pd-dodecanethiolate nanoparticles In tetrahydrofuran at 20℃; for 17h; Suzuki-Miyaura cross-coupling;	100%
With caesium carbonate; (1-adamantylisonitrile)2PdCl2 In 1,4-dioxane for 18h; Product distribution; Further Variations:; Catalysts; Suzuki-Miyaura reaction; Heating;	100%

Upstream product

• 60-29-7 diethyl ether 
• 688-74-4 boric acid tributyl ester 
• 2674-04-6 diphenyl cadmium 
• 2622-89-1 diphenylborinic acid 
• 31044-59-4 diethyl phenylboronate 
• 587-85-9 diphenylmercury(II) 
• 121-43-7 Trimethyl borate 
• 873-51-8 phenylborondichloride 
• 7732-18-5 water 
• 13471-35-7 dimethyl phenylboronate 
• 108-86-1 bromobenzene 
• 71-43-2 benzene 
• 100-59-4 phenylmagnesium chloride 
• 629-05-0 n-octyne 

Downstream Products

• 5747-23-9 2-phenyl-1,3,2-benzodioxaborole 
• 2479-64-3 2-phenyl-2,3-dihydro-1H-benzo[1,3,2]diazaborole 
• 98109-89-8 bis(s-butyloxy)phenyl borane 
• 7330-48-5 dibutoxyphenylborane 
• 13471-35-7 dimethyl phenylboronate 
• 31044-59-4 diethyl phenylboronate 
• 6638-75-1 (2R,3R,4R,5R)-1:2,3:4,5:6-O¹:O²,O³:O⁴,O⁵:O⁶-tris(phenylboranato)-D-mannitol 
• 6638-75-1 O¹,O²;O³,O⁴;O⁵,O⁶-tris-phenylboranediyl-D-glucitol 
• 6638-75-1 O¹,O²;O³,O⁴;O⁵,O⁶-tris-phenylboranediyl-galactitol 
• 59024-15-6 diisobutyl phenylborate 
• 6638-66-0 phenylboronic acid 1,3-butanediol ester 
• 65796-77-2 N-methyldiethanolamine phenylboronic ester 
• 7462-37-5 (3aR,6aS)-2-phenyl-hexahydrocyclopenta[d][1,3,2]dioxaborole 
• 96080-52-3 dipropyl phenylboronate 

Relevant articles and documents

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Novel biscapped and monocapped tris(dioxime) Mn(II) complexes: X-ray crystal structure of the first cationic tris(dioxime) Mn(II) complex [Mn(CDOH)3BPh]OH (CDOH2 = 1,2-cyclohexanedione dioxime)

This report describes the synthesis and characterization of a series of novel biscapped and monocapped tris-(dioxime) Mn(II) complexes [Mn(dioxime) 3(BR)2] and [Mn(dioxime)3BR]+ (dioxime = cyclohexanedione dioxime (CDOH2) and 1,2-dimethylglyoxyl dioxime (DMGH2); R = Me, n-Bu, and Ph). All tris(dioxime) Mn(II) complexes have been characterized by elemental analysis, IR, UV/vis, cyclic voltammetry, ESI-MS, and, in the cases of [Mn(CDOH)3BPh] OH·CHCl3 and [Mn(CDO)(CDOH)2(BBu(OC 2H5))2], X-ray crystallography. It was found that biscapped Mn(II) complexes [Mn(dioxime)3(BR)2] are not stable in the presence of water and readily hydrolyze to form monocapped cationic complexes [M(dioxime)3BR]+. This instability is most likely caused by mismatch between the size of Mn(II) and the coordination cavity of the biscapped tris(dioxime) ligands. In contrast, monocapped cationic complexes [M(dioxime)3BR]+ are very stable in aqueous solution even in the presence of PDTA (1,2-diaminopropane-N,N,N′,N′- tetraacetic acid) because of the kinetic inertness imposed by the monocapped tris(dioxime) chelators that are able to completely wrap Mn(II) into their N6 coordination cavity. [Mn(CDO)3BPh]OH has a distorted trigonal prismatic coordination geometry, with the Mn(II) being bonded by six imine-N donors. The hydroxyl groups from three dioxime chelating arms form very strong intramolecular hydrogen bonds with the hydroxide counterion so that the structure of [Mn(CDOH)3BPh]OH can be considered as being the clathrochelate with the hydroxide counterion as a cap .

Fourth subgroup metal complex with rigid annular bridging structure and application of fourth subgroup metal complex

The invention belongs to the technical field of olefin polymerization catalysts, and particularly relates to a fourth subgroup metal complex with a rigid annular bridging structure and an application of the fourth subgroup metal complex. The fourth subgroup metal complex provided by the invention has a structure represented by a formula (A) or a formula (B), X is halogen or alkyl; and M is titanium, zirconium or hafnium. On the basis of a non-metallocene catalyst, a bridging structure in catalyst molecules is improved and upgraded, and a brand-new metal complex with excellent catalytic performance and good high-temperature tolerance is designed; when the fourth subgroup metal complex is used as a main catalyst to catalyze olefin polymerization reaction, under the activation action of a small amount of mixed cocatalyst, the fourth subgroup metal complex can efficiently catalyze the copolymerization reaction of ethylene and alpha-olefin to obtain polyolefin with high molecular weight and high comonomer insertion rate.

Boronic Ester Based Vitrimers with Enhanced Stability via Internal Boron-Nitrogen Coordination

Boron-containing polymers have many applications resulting from their prominent properties. Organoboron species with reversible B-O bonds have been successfully employed for the fabrication of various self-healing/healable and reprocessable polymers. However, the application of the polymers containing boronic ester or boroxine linkages is limited because of their instability to water. Herein, we report the hydrolytic stability and dynamic covalent chemistry of the nitrogen-coordinating cyclic boronic diester (NCB) linkages, and a new class of vitrimers based on NCB linkages is developed through the chemical reactions of reactive hydrogen with isocyanate. Thermodynamic and kinetic studies demonstrated that NCB linkages exhibit enhanced water and heat resistance, whereas the exchange reactions between NCB linkages can take place upon heating without any catalyst. The model compounds of NCBC-X1 and NCBC-X2 containing a urethane group and urea group, respectively, also showed higher hydrolytic stability compared to that of conventional boronic esters. Polyurethane vitrimers and poly(urea-urethane) vitrimers based on NCB linkages exhibited excellent solvent resistance and mechanical properties like general thermosets, which can be repaired, reprocessed, and recycled via the transesterification of NCB linkages upon heating. Especially, vitrimers based on NCB linkages presented improved stability to water and heat compared to those through conventional boronic esters because of the existence of N → B internal coordination. We anticipate that this work will provide a new strategy for designing the next generation of sustainable materials.