619-44-3

Basic information

• Product Name: Methyl 4-iodobenzoate
• Synonyms: ASISCHEM Z27958;METHYL-P-IODOBENZOATE;METHYL 4-IODOBENZENECARBOXYLATE;METHYL 4-IODOBENZOATE;4-IODOBENZOIC ACID METHYL ESTER;P-IODOBENZOIC ACID METHYL ESTER;RARECHEM AL BF 0710;4-iodo-benzoicacimethylester
• CAS NO: 619-44-3
• Molecular Formula: C₈H₇IO₂
• Molecular Weight: 262.04
• EINECS: 210-597-1
• Product Categories: Aromatic Esters;Acids & Esters;Iodine Compounds;Isoxazoles
• Mol File: 619-44-3.mol
• Article Data: 93

Chemical Properties

• Melting Point: 113-117 °C
• Boiling Point: 278.5°C (rough estimate)
• Flash Point: 120.8 °C
• Appearance: Beige to pale pink/Crystalline Powder
• Density: 2.0200
• Vapor Pressure: 0.00491mmHg at 25°C
• Refractive Index: 1.597
• Storage Temp.: Keep in dark place,Sealed in dry,Room Temperature
• Sensitive: Light Sensitive
• CAS DataBase Reference: Methyl 4-iodobenzoate(CAS DataBase Reference)
• NIST Chemistry Reference: Methyl 4-iodobenzoate(619-44-3)
• EPA Substance Registry System: Methyl 4-iodobenzoate(619-44-3)

Safety Data

• Hazard Codes: Xi,N
• Statements: 36/37/38-51/53
• Safety Statements: 37/39-26-61
• RIDADR: UN 3082
• WGK Germany: 3
• TSCA: Yes
• HazardClass: IRRITANT
• Hazardous Substances Data: 619-44-3(Hazardous Substances Data)

Usage

Chemical Properties

beige to pale pink crystalline powder

Uses

suzuki reaction

Synthesis Reference(s)

Tetrahedron Letters, 35, p. 5539, 1994 DOI: 10.1016/S0040-4039(00)77241-8

InChI:InChI=1/C8H7IO2/c1-11-8(10)6-2-4-7(9)5-3-6/h2-5H,1H3

Synthetic route

methanol (67-56-1) + 4-iodobenzoic acid (619-58-9) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
With acetyl chloride at 60℃; for 12h;	100%
With sulfuric acid for 30h; Reflux;	99%
With sulfuric acid Reflux;	99%

sodium (¹²⁵I)iodide + methyl 4-tri-n-butylstannylbenzoate (91734-76-8) + sodium iodide (7681-82-5) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
With N-chloro-succinimide In methanol; acetic acid to a soln. of Sn-compd. in MeOH was added NaI in MeOH, then Na(125)I was added (10% stoichiometric amount of NaI/Na(125)I), addn. of AcOH followed by addn. of NCS in MeOH, the mixture was stirred at 25°C for 20 min; the reaction was monitored by use of HPLC equipped with a UV detector, the yield was calculated by HPLC analysis of a solution of known concn., the established yield is the radiochemical yield;	98%
With N-chloro-succinimide In methanol; acetic acid to a soln. of Sn-compd. in MeOH was added NaI in MeOH, then Na(125)I was added (100% stoichiometric amount of NaI/Na(125)I), addn. of AcOH followed by addn. of NCS in MeOH, the mixture was stirred at 25°C; the reaction was monitored by use of HPLC equipped with a UV detector, the yield was calculated by HPLC analysis of a solution of known concn., the established yield is the radiochemical yield;	98%

4-(Pyrrolidin-1-ylazo)-benzoic acid methyl ester → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
With iodine In various solvent(s) at 100℃; for 9h;	97%

methyl 4-(3,3-diethyltriaz-1-en-1-yl)benzoate (77726-96-6) + methyl iodide (74-88-4) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
at 110 - 120℃; for 6h;	97%

methanol (67-56-1) + p-(iodophenyl)carboxaldehyde (15164-44-0) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
With dihydrogen peroxide at 20℃; for 20h;	97%
With oxygen; potassium carbonate at 65℃; for 3h; Catalytic behavior;	82 %Chromat.

sodium (¹²⁵I)iodide + sodium iodide (7681-82-5) + 4-methoxycarbonylphenylboronic acid (99768-12-4) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
With N-chloro-succinimide In methanol; acetic acid to a soln. of B-compd. in MeOH was added NaI in MeOH, then Na(125)I was added (100% stoichiometric amount of NaI/Na(125)I), addn. of AcOH followed by addn. of two equivalents of NCS in MeOH, the mixture was stirred at 25°C for 24 h; the reaction was monitored by use of HPLC equipped with a UV detector, the yield was calculated by HPLC analysis of a solution of known concn., the established yield is the radiochemical yield;	96%
With N-chloro-succinimide In methanol; acetic acid to a soln. of B-compd. in MeOH was added NaI in MeOH, then Na(125)I was added (100% stoichiometric amount of NaI/Na(125)I), addn. of AcOH followed by addn. of NCS in MeOH, the mixture was stirred at 25°C for 20 h; the reaction was monitored by use of HPLC equipped with a UV detector, the yield was calculated by HPLC analysis of a solution of known concn., the established yield is the radiochemical yield;	70%
With N-chloro-succinimide In methanol; acetic acid to a soln. of B-compd. in MeOH was added NaI in MeOH, then Na(125)I was added (100% stoichiometric amount of NaI/Na(125)I), addn. of AcOH followed by addn. of NCS in MeOH, the mixture was stirred at 25°C for 3 h; the reaction was monitored by use of HPLC equipped with a UV detector, the yield was calculated by HPLC analysis of a solution of known concn., the established yield is the radiochemical yield;	60%
With N-chloro-succinimide In methanol; acetic acid to a soln. of B-compd. in MeOH was added NaI in MeOH, then Na(125)I was added (10% stoichiometric amount of NaI/Na(125)I), addn. of AcOH followed by addn. of NCS in MeOH, the mixture was stirred at 25°C for 20 min; the reaction was monitored by use of HPLC equipped with a UV detector, the yield was calculated by HPLC analysis of a solution of known concn., the established yield is the radiochemical yield;	>99

methanol (67-56-1) + 4-iodo-N,N-bis(pyridin-2-ylmethyl)benzamide (1314659-41-0) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
With copper(II) bis(trifluoromethanesulfonate) at 20℃; for 16h;	96%

methanol (67-56-1) + C10H7IN2O3 → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
With triethylamine at 100℃; for 24h; Inert atmosphere;	96%

chloro-trimethyl-silane (75-77-4) + 4-iodobenzoic acid (619-58-9) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
In methanol at 20℃;	95%

methanol (67-56-1) + 4-iodobenzoic acid chloride (1711-02-0) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
With triethylamine In dichloromethane at 0℃; for 0.5h;	93%
Stage #1: 4-iodobenzoic acid chloride With pyridine In dichloromethane at 20℃; for 16h; Stage #2: With pyridinium p-toluenesulfonate In toluene at 50℃; for 16h; Stage #3: methanol With sodium amide In tetrahydrofuran for 0.5h; Further stages.;

4-iodobenzoic acid (619-58-9) + tris(o-methoxyphenyl)phosphine (4731-65-1) → methyl 4-iodobenzoate (619-44-3) + 2-((2-hydroxyphenyl)(2-methoxyphenyl)(methyl)phosphonio)phenolate

Conditions	Yield
With dirhodium tetraacetate In cyclohexane at 120℃; for 12h; Reagent/catalyst; Schlenk technique; Inert atmosphere;	A 93% B 89%

di-tert-butyl dicarbonate (24424-99-5) + 2-(4-iodophenyl)-5,5-dimethyl-1,3,2-dioxaborinane (5572-94-1) + methyl iodide (74-88-4) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
Stage #1: di-tert-butyl dicarbonate; 5,5-dimethyl-2-(4-iodophenyl)-1,3,2-dioxaborinane With 4,4'-dimethyl-2,2'-bipyridines; lithium methanolate; copper(l) chloride In N,N-dimethyl acetamide at 30℃; for 6h; Inert atmosphere; Schlenk technique; Stage #2: methyl iodide In N,N-dimethyl acetamide at 30℃; for 2h; Schlenk technique;	92%

methanol (67-56-1) + carbon monoxide (201230-82-2) + μ-oxobis[(trifluoromethanesulfonato)(phenyl)iodine] (88016-29-9) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
palladium diacetate In N,N-dimethyl-formamide under 760 Torr; for 0.5h; Ambient temperature;	91%

4-iodobenzoic acid (619-58-9) + tris(o-methoxyphenyl)phosphine (4731-65-1) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
With dirhodium tetraacetate In cyclohexane at 120℃; for 12h; Schlenk technique; Inert atmosphere;	91%

methyl 4-tri-n-butylstannylbenzoate (91734-76-8) + sodium iodide (7681-82-5) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
With N-chloro-succinimide In methanol; acetic acid to a soln. of Sn-compd. in MeOH was added one equivalent NaI in MeOH/AcOH and one equivalent NCS, the mixture was stirred for 15 min at 25°C; the reaction was monitored by use of HPLC equipped with a UV detector, the yield was calculated by HPLC analysis of a solution of known concn.;	90%

4-methoxycarbonylphenylboronic acid (99768-12-4) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
With iodine; potassium carbonate In acetonitrile at 80℃; for 8h; Inert atmosphere; Schlenk technique; Sealed tube;	90%
With 1,10-Phenanthroline; oxygen; potassium iodide; copper(ll) bromide In N,N-dimethyl-formamide at 80℃; for 20h;	88%
With copper(I) oxide; ammonium hydroxide; oxygen; potassium iodide In water at 25℃; for 24h;	80%
With copper(l) iodide; N-iodomorpholine-hydrogen iodide In methanol at 20℃; for 24h;

sodium (¹²⁵I)iodide + p-(methoxycarbonyl)phenylmercuric chloride (20883-45-8) + sodium iodide (7681-82-5) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
With N-chloro-succinimide In methanol; acetic acid to a soln. of Hg-compd. in MeOH was added NaI in MeOH, then Na(125)I was added (10% stoichiometric amount of NaI/Na(125)I), addn. of AcOH followed by addn. of NCS in MeOH, the mixture was stirred at 25°C for 20 min; the reaction was monitored by use of HPLC equipped with a UV detector, the yield was calculated by HPLC analysis of a solution of known concn., the established yield is the radiochemical yield;	89%
With N-chloro-succinimide In methanol; acetic acid to a soln. of Hg-compd. in MeOH was added NaI in MeOH, then Na(125)I was added (100% stoichiometric amount of NaI/Na(125)I), addn. of AcOH followed by addn. of NCS in MeOH, the mixture was stirred at 25°C for 72 h; the reaction was monitored by use of HPLC equipped with a UV detector, the yield was calculated by HPLC analysis of a solution of known concn., the established yield is the radiochemical yield;	60%
With N-chloro-succinimide In methanol; acetic acid to a soln. of Hg-compd. in MeOH was added NaI in MeOH, then was Na(125)I added (100% stoichiometric amount of NaI/Na(125)I), addn. of AcOH followed by addn. of NCS in MeOH, the mixture was stirred at 25°C for 20 h; the reaction was monitored by use of HPLC equipped with a UV detector, the yield was calculated by HPLC analysis of a solution of known concn., the established yield is the radiochemical yield;	40%

4-iodobenzoic acid (619-58-9) + methyl iodide (74-88-4) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
With potassium carbonate In dimethyl sulfoxide	88%
With N'',N'''''-1,8-naphthalenediyl bis[N,N,N',N'-tetramethyl]guanidine In N,N-dimethyl-formamide at 20℃; Kinetics;
With potassium carbonate In N,N-dimethyl-formamide

4-iodobenzoic acid (619-58-9) + bis-(2-methoxy-phenyl)-phenyl-phosphane (36802-41-2) → methyl 4-iodobenzoate (619-44-3) + 2-((2-hydroxyphenyl)(methyl)(phenyl)phosphonio)phenolate

Conditions	Yield
With dirhodium tetraacetate In cyclohexane at 160℃; for 12h; Schlenk technique; Inert atmosphere;	A 87% B 86%

chlorido(η-cycloocta-1,5-diene)[tris(2-methoxyphenyl)phosphine]rhodium (102844-63-3) + 4-iodobenzoic acid (619-58-9) → methyl 4-iodobenzoate (619-44-3) + 2-((2-hydroxyphenyl)(2-methoxyphenyl)(methyl)phosphonio)phenolate + 2-(bis(2-methoxyphenyl)(methyl)phosphonio)phenolate

Conditions	Yield
In cyclohexane at 120℃; for 12h; Schlenk technique; Inert atmosphere;	A 85% B 82% C 5%

methanol (67-56-1) + 4-iodo-benzyl alcohol (18282-51-4) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
With Oxone; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; tetrabutylammomium bromide at 60℃; for 48h; Sealed tube;	77%
With oxygen; potassium carbonate at 60℃; under 750.075 Torr; for 24h; Schlenk technique; Green chemistry;	94 %Chromat.
With carbon-nitrogen embedded cobalt nanoparticles (800); air In hexane at 25℃; under 760.051 Torr; for 96h;	> 99 %Chromat.
With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; (2-((2-(diphenylphosphanyl)ethyl)(quinolin-2-ylmethyl)amino)ethyl)diphenylphosphine oxide; potassium carbonate In n-heptane at 120℃; for 16h;	35 %Chromat.

methanol (67-56-1) + carbon monoxide (201230-82-2) + (4-nitro-phenyl)-phenyl-iodonium ; bromide (4072-48-4) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
palladium diacetate In N,N-dimethyl-formamide under 760 Torr; for 1h; Ambient temperature;	76%

Monomethyl terephthalate (1679-64-7) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
With N-iodo-succinimide; [4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridine-N1,N1′]bis{3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-κN]phenyl-κC}iridium(III) hexafluorophosphate; iodine; caesium carbonate In 1,2-dichloro-ethane at 50℃; for 24h; Inert atmosphere; Irradiation; Sealed tube;	76%
With tris-(dibenzylideneacetone)dipalladium(0); 1-iodo-butane; N,N,N',N'-tetramethyl-1,8-diaminonaphthalene; chloro-N,N,N',N'-bis(tetramethylene)formamidinium hexafluorophosphate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In toluene at 120℃; for 16h; Sealed tube; Inert atmosphere;	63%

methanol (67-56-1) + carbon monoxide (201230-82-2) + phenyl(4-methoxyphenyl)iodonium triflate (115298-63-0) → 1,4-benzenedicarboxylic acid dimethyl ester (120-61-6) + methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
palladium diacetate In N,N-dimethyl-formamide under 760 Torr; for 0.5h; Ambient temperature;	A 13% B 72%
palladium diacetate under 760 Torr; Ambient temperature;	A 13% B 72%

4-Methoxycarbonylbenzoyl chloride (7377-26-6) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
With tris-(dibenzylideneacetone)dipalladium(0); 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In toluene at 100℃; for 12h;	68%

4-methoxycarbonyl aniline (619-45-4) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
Stage #1: 4-methoxycarbonyl aniline With sulfuric acid; sodium nitrite at 0℃; for 5h; Sandmeyer Reaction; Stage #2: With potassium iodide In water at 20℃; Sandmeyer Reaction;	66%
Stage #1: 4-methoxycarbonyl aniline With tert.-butylnitrite; methanesulfonic acid In dimethyl sulfoxide at 20℃; for 0.045h; Flow reactor; Stage #2: With tetra-(n-butyl)ammonium iodide In dimethyl sulfoxide at 20℃; for 0.333333h; Solvent; Flow reactor;
With iodine; sodium nitrite

C13H16BO5(1-)*K(1+) → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
With chloroamine-T; sodium iodide In tetrahydrofuran; water at 50℃; for 0.5h;	64%

tributylphenylstannane (960-16-7) + MeO-PEG5000 bound para-iodobenzoate → methyl 4-iodobenzoate (619-44-3) + MeO-PEG5000-(4-phenylbenzoate)

Conditions	Yield
With lithium chloride; tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran for 24h; Stille coupling; Heating;	A 63% B 7%

tris(2,4,6-trimethoxyphenyl)phosphine (91608-15-0) + 4-iodobenzoyl fluoride → methyl 4-iodobenzoate (619-44-3)

Conditions	Yield
In toluene at 130℃; for 24h; Schlenk technique; Inert atmosphere;	63%

methyl 4-iodobenzoate (619-44-3) + phenylacetylene (536-74-3) → methyl 4-(phenylethynyl)benzoate (42497-80-3)

Conditions	Yield
With copper(l) iodide; triethylamine; triphenylphosphine In water at 60℃; for 24h; Sonogashira Cross-Coupling; Schlenk technique; Inert atmosphere;	100%
With potassium hydroxide In N,N-dimethyl-formamide at 135℃; for 2h; Sonogashira Cross-Coupling; Inert atmosphere;	100%
With copper(l) iodide; iron; caesium carbonate; triphenylphosphine In N,N-dimethyl-formamide at 110℃; for 1h; Sonogashira coupling; Inert atmosphere;	99%

methyl 4-iodobenzoate (619-44-3) + trimethylsilylacetylene (1066-54-2) → 4-trimethylsilanylethynyl-benzoic acid methyl ester (75867-41-3)

Conditions	Yield
With triethylamine; bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide In tetrahydrofuran at 20℃; for 8h;	100%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine In N,N-dimethyl-formamide at 20℃; for 3h; Inert atmosphere;	100%
With copper(l) iodide; N-ethyl-N,N-diisopropylamine; bis-triphenylphosphine-palladium(II) chloride In tetrahydrofuran at 60℃; for 18h; Castro-Stephens/Sonogashira coupling;	98%

methyl 4-iodobenzoate (619-44-3) + 2-methyl-but-3-yn-2-ol (115-19-5) → methyl 4-(3-hydroxy-3-methylbut-1-ynyl)benzoate (33577-98-9)

Conditions	Yield
With copper(l) iodide; (Ph3)2PdCl2; triphenylphosphine; triethylamine for 68h; Sonogashira reaction; Heating;	100%
With copper(l) iodide; trans-bis(triphenylphosphine)palladium dichloride; triethylamine at 20℃; Inert atmosphere;	96.07%
With copper(l) iodide; triethylamine; polymer-bound Pt(0)-phoshine In water; acetonitrile at 55℃; for 8h;	95%

methyl 4-iodobenzoate (619-44-3) + 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; tetrakis(triphenylphosphine) palladium(0); tri-tert-butyl phosphine In 1,1,1,2,3,3,3-Heptafluoropropane; ethanol; 1,1,1,3,3-pentafluorobutane at 20℃; for 24h; Suzuki-Miyaura cross-coupling reaction; Inert atmosphere;	99%

1-ethynyl-2-methoxybenzene (767-91-9) + methyl 4-iodobenzoate (619-44-3) → methyl 4-((2-methoxyphenyl)ethynyl)benzoate (229174-44-1)

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran at 60℃;	100%
With copper(l) iodide; bis(triphenylphosphine)palladium(II) chloride; triethylamine In tetrahydrofuran at 0 - 20℃; for 1h; Sonogashira Cross-Coupling; Inert atmosphere;	90%
With pyridine; bis-triphenylphosphine-palladium(II) chloride at 80℃; for 1h; Sonogashira Cross-Coupling; Inert atmosphere; Schlenk technique;	73%
With copper(l) iodide; tris(2,4,6-trimethylphenyl)phosphine; tetra-(n-butyl)ammonium iodide; N-ethyl-N,N-diisopropylamine; tris(dibenzylideneacetone)dipalladium(0) chloroform complex In N,N-dimethyl-formamide at -20℃; for 0.333333h; Yield given;

bis(4-tert-butylphenyl) diselenide (71518-97-3) + methyl 4-iodobenzoate (619-44-3) → 4-(4-tert-butyl-phenylselanyl)-benzoic acid methyl ester

Conditions	Yield
With polymer supported borohydride; bis(bipyridine)nickel(II) bromide In ethanol at 70℃; for 16h; Substitution;	100%

methyl 4-iodobenzoate (619-44-3) + N-benzyl 4-cyclohexylidene-2-propylacrylamide (463930-76-9) → N-benzyl (4-(4-methoxycarbonylphenyl)-3-propyl-1-oxa-spiro[4,5]dec-3-enylidene) amine

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; potassium carbonate In toluene at 70℃; for 44h;	100%

methyl 4-iodobenzoate (619-44-3) + propargyl alcohol methyl ether (627-41-8) → methyl 4-(3-methoxy-1-propynyl)benzoate (827028-02-4)

Conditions	Yield
With triethylamine; bis-triphenylphosphine-palladium(II) chloride In N,N-dimethyl-formamide at 80℃; for 6h;	100%

tert-Butyl acrylate (1663-39-4) + methyl 4-iodobenzoate (619-44-3) → (E)-methyl 4-(3-(tert-butoxy)-3-oxoprop-1-en-1-yl)benzoate (683246-09-5)

Conditions	Yield
With C36H36Cl2N6Pd; triethylamine In methanol at 70℃; for 24h; Heck Reaction;	100%
With C43H54NO5P; palladium diacetate; triethylamine In water at 40℃; for 12h; Heck Reaction;	92 %Spectr.

methyl 4-iodobenzoate (619-44-3) + N-tosyl-N-allylpropargylamine (133886-40-5) → methyl 4-(3-((N-allyl-4-methylphenyl)sulfonamido)prop-1-yn-1-yl)benzoate

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 50℃;	100%

methyl 4-iodobenzoate (619-44-3) + 4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)aniline (214360-73-3) → methyl 4’-amino-[1,1’-biphenyl]-4-carboxylate (5730-76-7)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 100℃; for 10h;	100%

methyl 4-iodobenzoate (619-44-3) → 4,4'-biphenyldicarboxylic acid dimethyl ester (792-74-5)

Conditions	Yield
With caesium carbonate; hydroquinone; palladium diacetate In N,N-dimethyl acetamide at 75℃; for 2h; Ullmann coupling;	99%
With dipotassium hydrogenphosphate; digold(I)bis(diphenylphosphinomethane)dichloride; triethylamine In methanol; acetonitrile at 20℃; for 16h; Inert atmosphere; UV-irradiation;	91%
With Palladacycle; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 100℃; for 12h;	76%

styrene (292638-84-7) + methyl 4-iodobenzoate (619-44-3) → (E)-methyl 4-styrylbenzoate (1149-18-4)

Conditions	Yield
With palladium diacetate; triethylamine In N,N-dimethyl-formamide at 20℃; for 24h; Heck Reaction; Inert atmosphere; Schlenk technique; Irradiation;	99%
With triethylamine In water; N,N-dimethyl-formamide at 90℃; for 21h; Heck Reaction;	96%
With tributyl-amine; Si-SH-Pd(0) In xylene at 100℃; for 6h;	91%

methanol (67-56-1) + carbon monoxide (201230-82-2) + methyl 4-iodobenzoate (619-44-3) → 1,4-benzenedicarboxylic acid dimethyl ester (120-61-6)

Conditions	Yield
With potassium hydroxide at 100℃; under 5171.62 Torr; for 6h; Autoclave;	99%
With palladium/palladium oxide-supported N-doped carbon at 120℃; under 15001.5 Torr; for 24h; Autoclave; Sealed tube;	55%
palladium diacetate In N,N-dimethyl-formamide under 760 Torr; for 0.5h; Ambient temperature;

methyl 4-iodobenzoate (619-44-3) + 4-n-methylphenylacetylene (766-97-2) → 4-[2-(4-methylphenyl)ethynyl]benzoic acid methyl ester

Conditions	Yield
With 1,4-diaza-bicyclo[2.2.2]octane In water; acetonitrile at 90℃; for 7h; Heck Reaction; Sealed tube;	99%
With copper(l) iodide; tris(2,4,6-trimethylphenyl)phosphine; tetra-(n-butyl)ammonium iodide; N-ethyl-N,N-diisopropylamine; tris(dibenzylideneacetone)dipalladium(0) chloroform complex In N,N-dimethyl-formamide at -20℃; for 1.33333h;	86%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine In dimethyl sulfoxide at 70℃; for 0.441667h; Sonogashira Cross-Coupling; Flow reactor;	154 mg

methyl 4-iodobenzoate (619-44-3) → 3-bromo-4-iodobenzoic acid methyl ester (249647-24-3)

Conditions	Yield
With N-Bromosuccinimide; sulfuric acid at 20℃; for 15h; Bromination;	99%

methyl 4-iodobenzoate (619-44-3) + hex-1-yne (693-02-7) → 1-(4-methoxycarbonylphenyl)-1-hexyne (462637-32-7)

Conditions	Yield
With piperidine; copper(l) iodide; polystyrene-N(CH2PPh2)2PdCl2 In 1,4-dioxane at 60℃; for 8h; Sonogashira coupling reaction;	99%
Sonogashira coupling; Inert atmosphere;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 20℃; Sonogashira Cross-Coupling; Inert atmosphere;

di-tert-butyl 1-phenylhydrazine-1,2-dicarboxylate (65578-58-7) + methyl 4-iodobenzoate (619-44-3) → C6H5NN(C(CH3)3CO2)2C6H4COOCH3

Conditions	Yield
With copper(l) iodide; 1,10-Phenanthroline; caesium carbonate In N,N-dimethyl-formamide at 80℃; for 3h;	99%

methyl 4-iodobenzoate (619-44-3) + N,N-dimethylethylenediamine (108-00-9) → methyl 4-{[2-(dimethylamino)ethyl]amino}benzoate (956427-71-7)

Conditions	Yield
With caesium carbonate; copper(l) iodide; 2-acetylcyclohexanone In N,N-dimethyl-formamide at 90℃; for 18h;	99%
With caesium carbonate; tris-(dibenzylideneacetone)dipalladium(0); 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In 1,4-dioxane at 100 - 110℃; Sealed tube;

methyl 4-iodobenzoate (619-44-3) + hexamethyldistannane (661-69-8) → (4-carbomethoxyphenyl)trimethylstannane (65488-27-9)

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride In 1,4-dioxane at 60℃; for 15h; Inert atmosphere;	99%
dichloro bis(acetonitrile) palladium(II) In N,N-dimethyl-formamide byproducts: (CH3)3SnI; Me6Sn2, p-MeO2CC6H4I dissolved in DMF in a flask, catalyst added with stirring, reacted for 15 min at 20°C; water added, extracted with ether, extracts filtered, washed with water, dried with Na2SO4, chromy.(silica gel, hexane/ether 2:1);	97%
With tetrakis(triphenylphosphine) palladium(0) In 1,4-dioxane at 100℃; for 18h; Inert atmosphere;	83%

4-tert-Butylphenylacetylene (772-38-3) + methyl 4-iodobenzoate (619-44-3) → C20H20O2 (1038987-07-3)

Conditions	Yield
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine at 20℃; Inert atmosphere;	99%

methyl 4-iodobenzoate (619-44-3) + dimethyl methane phosphonate (756-79-6) → lithio dimethyl [2-(4-iodophenyl)-2-oxoethyl]phosphonate

Conditions	Yield
With lithium hexamethyldisilazane In tetrahydrofuran Barbier reaction; Cooling with ice; Inert atmosphere;	99%

Cyclopropylacetylene (6746-94-7) + methyl 4-iodobenzoate (619-44-3) → 4-(methoxycarbonyl)phenylethynylcyclopropane (1057284-07-7)

Conditions	Yield
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); diisopropylamine In tetrahydrofuran at 20℃; Sonogashira coupling; Inert atmosphere;	99%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 20℃; for 5.66667h; Sonogashira Cross-Coupling;	98%
With copper(l) iodide; trans-bis(triphenylphosphine)palladium dichloride; triethylamine at 0 - 20℃; Inert atmosphere;	90.21%

2-(diisopropylsilyl)pyridine (1232692-92-0) + methyl 4-iodobenzoate (619-44-3) → C19H25NO2Si (1312936-25-6)

Conditions	Yield
With potassium phosphate; di-μ-chlorobis(norbornadiene)dirhodium(I) In 1,4-dioxane at 20℃; Inert atmosphere;	99%

methyl 4-iodobenzoate (619-44-3) + phenylpropyolic acid (637-44-5) → methyl 4-(phenylethynyl)benzoate (42497-80-3)

Conditions	Yield
With copper(l) iodide; potassium carbonate; triphenylphosphine In dimethyl sulfoxide at 90℃; for 24h; Inert atmosphere;	99%
With copper(l) iodide; potassium carbonate; triphenylphosphine In dimethyl sulfoxide at 100℃; for 24h; Inert atmosphere;	99%
With bis-triphenylphosphine-palladium(II) chloride; (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; 1,8-diazabicyclo[5.4.0]undec-7-ene In diethylene glycol dimethyl ether at 80℃; for 4h; Mechanism; Temperature; Time;	98%

methyl 4-iodobenzoate (619-44-3) + [1-methoxyprop-1-enyloxy]trimethylsilane (34880-70-1) → C12H14O4

Conditions	Yield
With (R)-1-(bis(4-methoxy-3,5-dimethylphenyl)phosphano)-2-((S)-1-(dicyclohexylphosphano)ethyl)ferrocene; palladium diacetate; thallium(I) acetate In toluene at 70℃; for 6h; optical yield given as %ee; enantioselective reaction;	99%

methyl 4-iodobenzoate (619-44-3) + Trimethyl-((E)-1-propoxy-propenyloxy)-silane (88584-69-4) → C14H18O4

Conditions	Yield
With (R)-1-(bis(4-methoxy-3,5-dimethylphenyl)phosphano)-2-((S)-1-(dicyclohexylphosphano)ethyl)ferrocene; palladium diacetate; thallium(I) acetate In toluene at 70℃; for 6h; optical yield given as %ee; enantioselective reaction;	99%

3-phenyl-1,1-di(pyridin-2-yl)prop-2-yn-1-ol (87446-01-3) + methyl 4-iodobenzoate (619-44-3) → methyl 4-(1-oxo-3-phenyl-8a-(pyridin-2-yl)-1,8a-dihydroindolizin-2-yl)benzoate (1383711-46-3)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In acetonitrile at 90℃; for 13h;	99%

Upstream product

• 67-56-1 methanol 
• 619-58-9 4-iodobenzoic acid 
• 186581-53-3 diazomethane 
• 201230-82-2 carbon monoxide 
• 143360-88-7 N-(2-(hex-1-yn-1-yl)phenyl)-2,2,2-trifluoroacetamide 
• 696-62-8 para-iodoanisole 
• 77726-96-6 methyl 4-(3,3-diethyltriaz-1-en-1-yl)benzoate 
• 74-88-4 methyl iodide 
• 829-77-6 4-dichloroiodanyl-benzoic acid methyl ester 
• 66003-76-7 Diphenyliodonium triflate 
• 88016-29-9 μ-oxobis[(trifluoromethanesulfonato)(phenyl)iodine] 
• 4072-48-4 (4-nitro-phenyl)-phenyl-iodonium ; bromide 
• 115298-63-0 phenyl(4-methoxyphenyl)iodonium triflate 
• 960-16-7 tributylphenylstannane 

Downstream Products

• 561023-21-0 1-iodo-4-(prop-1-en-2-yl)benzene 
• 92-92-2 biphenyl-4-carboxylic acid 
• 102554-79-0 4-(1-nitro-carbazol-9-yl)-benzoic acid methyl ester 
• 17104-75-5 4,4',4''-nitrilo-tri-benzoic acid trimethyl ester 
• 39115-95-2 4-iodobenzohydrazide 
• 792-74-5 4,4'-biphenyldicarboxylic acid dimethyl ester 
• 829-77-6 4-dichloroiodanyl-benzoic acid methyl ester 
• 25069-30-1 4-(diphenylamino)benzoic acid methyl ester 
• 17104-81-3 4-[(4-(methoxycarbonyl)phenyl)amino]benzoic acid methyl ester 
• 21250-03-3 1,3-Bis-<4-methoxycarbonyl-phenyl>-perfluorpropan 
• 13710-46-8 perfluoroheptylbenzoic acid 
• 52392-55-9 n-Butyl methyl terephthalate 
• 110396-61-7 4-(1,1-Dioxo-2,5-dihydro-1H-1λ⁶-thiophen-3-yl)-benzoic acid methyl ester 
• 42497-80-3 methyl 4-(phenylethynyl)benzoate 

Relevant articles and documents

Flexible bifunctional monoethylphosphonate/carboxylates of Zn(ii) and Co(ii) reinforced with DABCO co-ligand: paradigmatic structural organization withpcutopology

Two novel isostructural phosphonate-monoethylcarboxylate MOFs with the structural formula of [M2(EtBCP)2(DABCO)0.5]·2DMA (M = Zn (2), Co (3); H2EtBCP =O-ethyl-P-(4-carboxyphenyl)phosphonic acid, DABCO = 1,4-diazabicyclo[2.2.2]octane, DMA =N,N-dimethylacetamide) were synthesized and characterized. The frameworks of2and3are sustained by {Zn2(PO2(OEt))2}nmetal-phosphonate- and DABCO-extended {Zn2(COO)4(DABCO)}npaddle-wheel carboxylate chain-SBUs. The chains providing connectivity in three, mutually orthogonal directions are running parallel and are combined in a framework, which could be interpreted as having apcutopology. The simple structure-organization principle, which suggests the possibility of the elongation of the bifunctional ligand with scaling in two directions, allows to view the structures of2and3as prototypes for an isoreticular series. The porosity of both compounds, based on a relatively short ligand, is low: no adsorption of N2was registered, however, CO2is adsorbed readily allowing to estimate the surface area at ～330 m2g?1(～900-1060 m2g?1geometric estimate). The compounds demonstrate a two-step CO2adsorption isotherm both at 195 K (0-1 bar) and 298 K (0-20 bar). The adsorption isotherms are characterized by a gradual (type “F-I”), albeit still relatively steep onset of the second step, associated with structural flexibility/bistability. The estimated pore volumes at the start of the transformation (195 K) for2and3are ～0.11 (0.08P/P0) and 0.12 cm3g?1(0.12P/P0) respectively, which corresponds considerably well to the geometrically calculated accessible volume of ～0.07 cm3g?1for the experimental structure (3.3 ? probe diameter). The structural prerequisites of the observed flexibility of the framework, which might be associated with the non-planarity of the metal-phosphonate moieties, acting as ‘levers’ for propagating mechanical stress, are discussed.

Field-induced single-ion magnets exhibiting tri-axial anisotropy in a 1D Co(ii) coordination polymer with a rigid ligand 4,4′-(buta-1,3-diyne-1,4-diyl)dibenzoate

Herein a 1D Co(ii) coordination polymer of formula [Co(η1-L1)(η2-L1)(py)2(H2O)]n (CoCP) has been synthesised using the rigid H2L1 proligand, containing a long spacer bearing two triple bonds. Single-crystal X-ray diffraction showed that Co(ii) adopts a distorted octahedral geometry. The state-averaged complete active self-consistent field (SA-CASSCF) calculation showed that the ground state of CoCP is a high spin quartet with a highly multiconfigurational character of its electronic structure. Due to the large intra- and intermolecular distances between the spin carriers, the magnetic interactions are negligible and the zero-field splitting (ZFS) effects of cobalt(ii) ions are predominant. This behavior was confirmed by direct current (DC) magnetic measurements and theoretical calculations using the broken-symmetry approach. Quantum chemical calculations indicate that CoCP has a negative axial component possessing mixed tri-axial anisotropy. The DC magnetic susceptibility data were fitted with a Griffith-Figgis Hamiltonian and the obtained parameters are in good agreement with those simulated by the ab initio calculation. Alternating current (AC) magnetic measurements showed a field induced slow magnetic relaxation in CoCP, which is attributed to the hyperfine interaction effects.

Method for preparing iodo-benzoic acid (ester) by improving moral Michael reaction

The invention discloses a method for preparing iodo-benzoic acid (ester) by improving a moral reaction, and belongs to the technical field of organic synthesis. The method comprises the following steps: preparing and separating the diazonium tetrafluoroborate through diazotization of aminobenzoic acid (ester) and then performing iodination reaction with the iodinated reagent in an organic medium to obtain the corresponding iodo carboxylic acid (ester). The iodo-benzoic acid (ester) prepared by the method has high purity. The method has the advantages of good quality and simple post-treatment, and the product yield reaches 70 - 90%.