676-58-4

Basic information

• Product Name: Methylmagnesium chloride
• Synonyms: chloromethyl-magnesiu;METHYLMAGNESIUM CHLORIDE;METHYLMAGNESIUM CHLORIDE, 2.5M SOLUTIONIN BUTYL DIGLYME;METHYLMAGNESIUM CHLORIDE, 3.0M SOLUTION IN TETRAHYDROFURAN;METHYLMAGNESIUM CHLORIDE SOLUTION, ~3 M IN THF;METHYLMAGNESIUM CHLORIDE, 3.0M SOLUTION;Methylmagnesium Chloride 1.5 M In Butyl Diglyme;Methylmagnesium Chloride 1.5 M in n-Butyl Ether
• CAS NO: 676-58-4
• Molecular Formula: CH₃ClMg
• Molecular Weight: 74.79
• EINECS: 211-629-7
• Product Categories: Organometallics;GRIGNARD REAGENTS;AlkylChemical Synthesis;Grignard Reagents;Organic Bases;Organometallic Reagents;Synthetic Reagents;grignard reagent
• Mol File: 676-58-4.mol
• Article Data: 8

Chemical Properties

• Boiling Point: 66 °C
• Flash Point: −1 °F
• Appearance: Pale brown to dark green/Liquid
• Density: 1.013 g/mL at 25 °C
• Storage Temp.: Flammables + water-Freezer (-20°C)e area
• Solubility: Miscible with diethyl ether and tetrahydrofuran.
• Water Solubility: reacts
• Sensitive: Air & Moisture Sensitive
• BRN: 3587199
• CAS DataBase Reference: Methylmagnesium chloride(CAS DataBase Reference)
• NIST Chemistry Reference: Methylmagnesium chloride(676-58-4)
• EPA Substance Registry System: Methylmagnesium chloride(676-58-4)

Safety Data

• Hazard Codes: F,C
• Statements: 11-14/15-34-19-15-37-14
• Safety Statements: 26-30-36/37/39-43-45-7/8-33-29-16
• RIDADR: UN 3399 4.3/PG 2
• WGK Germany: 1
• F: 1-3-10
• TSCA: Yes
• HazardClass: 4.3
• PackingGroup: I
• Hazardous Substances Data: 676-58-4(Hazardous Substances Data)

Usage

Uses

Methylmagnesium chloride is used as a Grignard reagent and an alkylating agent in organic synthesis.

Definition

ChEBI: Methylmagnesium chloride is an alkylmagnesium halide and a one-carbon compound. available as a solutionin tetrahydrofuran.

Hazard

Flammable, dangerous fire and explosionrisk.

InChI:InChI=1/CH3.ClH.Mg/h1H3;1H;/q;;+1/p-1/rCH3Mg.ClH/c1-2;/h1H3;1H/q+1;/p-1

Synthetic route

methylene chloride (74-87-3) → methylmagnesium chloride (676-58-4)

Conditions	Yield
With magnesium In tetrahydrofuran
With magnesium In solid matrix at -258.2℃;
With magnesium; lithium chloride In tetrahydrofuran at 0 - 20℃; Inert atmosphere;

methylene chloride (74-87-3) + magnesium → methylmagnesium chloride (676-58-4)

Conditions	Yield
With diethyl ether

methylmagnesium chloride (676-58-4) + heptan-3-one (106-35-4) → 3-methyl-3-heptanol (5582-82-1)

Conditions	Yield
In diethyl ether at 0 - 20℃;	100%

8-bromo-2-tetralone (117294-21-0) + methylmagnesium chloride (676-58-4) → 8-bromo-2-hydroxy-2-methyl-1,2,3,4-tetrahydronaphthalene (127810-66-6)

Conditions	Yield
With titanium tetrachloride In tetrahydrofuran; dichloromethane at 0℃; for 2h;	100%

methylmagnesium chloride (676-58-4) + methyl 6-<2-(7-acetamidoheptyl)-1,3-dioxolan-2-yl>hexanoate (119947-11-4) → N-<7-<2-(6-hydroxy-6-methylheptyl)-1,3-dioxolan-2-yl>heptyl>acetamide (119947-12-5)

Conditions	Yield
In tetrahydrofuran for 12h;	100%

methylmagnesium chloride (676-58-4) + dimethyl (RS)-6,6'-dibromobiphenyl-2,2'-dicarboxylate (156749-48-3) → 6,6'-dibromobiphenyl-2,2'-di(1-methylethanol) (156749-47-2)

Conditions	Yield
In tetrahydrofuran for 3h; Heating;	100%

methylmagnesium chloride (676-58-4) + 2,2-Dimethyl-propionic acid (2S,3S)-4-hydroxy-2-methyl-6-(tetrahydro-pyran-2-yl)-3-(2-trimethylsilanyl-ethoxymethoxy)-hexyl ester → 2,2-Dimethyl-propionic acid (2S,3S)-4-hydroxy-2,4-dimethyl-6-(tetrahydro-pyran-2-yl)-3-(2-trimethylsilanyl-ethoxymethoxy)-hexyl ester

Conditions	Yield
In tetrahydrofuran	100%

methylmagnesium chloride (676-58-4) + 3-(6',6'-dimethyl-2'-methylenecyclohexyl)propan-1-al (76337-22-9) → 4-(6',6'-dimethyl-2'-methylenecyclohexyl)butan-2-ol (13720-13-3)

Conditions	Yield
	100%

methylmagnesium chloride (676-58-4) + C6H4(CH2CH2C(O)O) (119-84-6) → 4-(2-hydroxyphenyl)-2-methyl-2-butanol (4167-73-1)

Conditions	Yield
In tetrahydrofuran at 0 - 20℃;	100%
In tetrahydrofuran Ambient temperature;	6.25 g
In tetrahydrofuran; (2S)-N-methyl-1-phenylpropan-2-amine hydrate; water
Stage #1: methylmagnesium chloride; C6H4(CH2CH2C(O)O) In tetrahydrofuran for 18.6667h; Stage #2: With water In tetrahydrofuran Cooling;

methylmagnesium chloride (676-58-4) + (3R,5R)-3,5-Bis-benzyloxy-2,2,6,6-tetramethyl-heptanedial → (4SR,6SR)-4,6-bis(benzyloxy)-3,3,7,7-tetramethylnonane-2,8-diol

Conditions	Yield
In tetrahydrofuran at -20 - 20℃;	100%
at -20℃; for 0.0833333h; pH=13; Grignard reaction;

phenyl(tetrahydro-2H-pyran-2-yl)methanone (73504-72-0) + methylmagnesium chloride (676-58-4) → (R*,S*)-2-(1'-hydroxy-1'-phenyl)ethyloxane

Conditions	Yield
In tetrahydrofuran; diethyl ether at 20℃; for 2h; Addition;	100%

methylmagnesium chloride (676-58-4) + 8-(tert-butyl-dimethyl-silanyloxy)-8-imidazol-1-yl-octan-2-one (410097-80-2) → 8-(tert-butyl-dimethyl-silanyloxy)-8-imidazol-1-yl-2-methyl-octan-2-ol (410097-88-0)

Conditions	Yield
In tetrahydrofuran	100%

methylmagnesium chloride (676-58-4) + (+)-(3aR,4R,6aS)-4-tert-butoxymethyl-3,3a,4,6a-tetrahydrocyclopenta[b]furan-2-one (479041-69-5) → ((1S,4S,5R)-5-tert-Butoxymethyl-4-methyl-cyclopent-2-enyl)-acetic acid (479041-70-8)

Conditions	Yield
With copper(I) bromide dimethylsulfide complex In tetrahydrofuran	100%

methylmagnesium chloride (676-58-4) + (+/-)-(3aR,4R,6aS)-4-tert-butoxymethyl-3,3a,4,6a-tetrahydrocyclopenta[b]furan-2-one → ((1R,4R,5S)-5-tert-Butoxymethyl-4-methyl-cyclopent-2-enyl)-acetic acid

Conditions	Yield
With copper(I) bromide dimethylsulfide complex In tetrahydrofuran	100%

4,4-dimethoxy-5,6-dihydro-2H-pyran-3(4H)-one (693245-80-6) + methylmagnesium chloride (676-58-4) → C8H16O4 (693248-63-4)

Conditions	Yield
In diethyl ether at 0℃; for 3h;	100%

isovanillin (621-59-0) + methylmagnesium chloride (676-58-4) → 3-(α-hydroxyethyl)-6-methoxyphenol (29866-05-5)

Conditions	Yield
In tetrahydrofuran at 0 - 20℃; for 4.08333h;	100%
In tetrahydrofuran at 5 - 20℃; Grignard addition;	85%

[3-(2-ethoxy-2-oxoethyl)phenyl]acetic acid (113520-28-8) + methylmagnesium chloride (676-58-4) → 2-[3-(2-hydroxy-2-methylpropyl)phenyl]acetic acid (808768-96-9)

Conditions	Yield
Stage #1: [3-(2-ethoxy-2-oxoethyl)phenyl]acetic acid; methylmagnesium chloride In tetrahydrofuran at 0 - 20℃; Stage #2: With hydrogenchloride In tetrahydrofuran; water Product distribution / selectivity;	100%
Stage #1: [3-(2-ethoxy-2-oxoethyl)phenyl]acetic acid; methylmagnesium chloride In tetrahydrofuran at 0℃; for 18h; Stage #2: With hydrogenchloride; water In tetrahydrofuran	100%
In tetrahydrofuran at 0 - 20℃; Inert atmosphere;	100%

N-(4-acetyl-3-methoxyphenyl)acetamide (51410-08-3) + methylmagnesium chloride (676-58-4) → N-[4-(1-Hydroxy-1-methyl-ethyl)-3-methoxy-phenyl]-acetamide (865306-00-9)

Conditions	Yield
Stage #1: N-(4-acetyl-3-methoxyphenyl)acetamide; methylmagnesium chloride In tetrahydrofuran at 0 - 20℃; for 2.91667h; Stage #2: With ammonium chloride In tetrahydrofuran	100%
In tetrahydrofuran at 0 - 20℃; for 1.91667h;	100%

1-(3-chlorophenyl)-1H-pyrazole-4-carbaldehyde (400877-26-1) + methylmagnesium chloride (676-58-4) → 1-[1-(3-chlorophenyl)-1H-pyrazol-4-yl]ethanol (863609-08-9)

Conditions	Yield
Stage #1: 1-(3-chlorophenyl)-1H-pyrazole-4-carbaldehyde; methylmagnesium chloride In tetrahydrofuran; diethyl ether at 0 - 20℃; for 2.25h; Stage #2: With water; ammonium chloride In tetrahydrofuran; diethyl ether	100%

methylmagnesium chloride (676-58-4) + 2-(3-chloro-phenyl)-2H-[1,2,3]triazole-4-carbaldehyde (41886-28-6) → 1-[2-(3-chlorophenyl)-2H-1,2,3-triazol-4-yl]ethanol (863609-09-0)

Conditions	Yield
Stage #1: methylmagnesium chloride; 2-(3-chloro-phenyl)-2H-[1,2,3]triazole-4-carbaldehyde In tetrahydrofuran; diethyl ether at 0 - 20℃; for 1.5h; Stage #2: With water; ammonium chloride In tetrahydrofuran; diethyl ether	100%

3-Ethyl-N-methoxy-N-methyl-1-{[2-(trimethylsilyl)ethoxy]methyl}-1H-indazole-6-carboxamide (885132-75-2) + methylmagnesium chloride (676-58-4) → 1-(3-Ethyl-1-{[2-(trimethylsilyl)ethoxy]methyl}-1H-indazol-6-yl)ethanone (885132-76-3)

Conditions	Yield
In tetrahydrofuran at -78 - 20℃;	100%
Stage #1: 3-ethyl-N-methoxy-N-methyl-1-[(2-(trimethylsilyl)ethoxy)methyl]-1H-indazole-6-carboxamide; methylmagnesium chloride In tetrahydrofuran at -78 - 20℃; Stage #2: With water; ammonium chloride In tetrahydrofuran at 20℃;	100%

N-methoxy-N-methylisoquinoline-1-carboxamide (866328-99-6) + methylmagnesium chloride (676-58-4) → 1-acetylisoquinoline (58022-21-2)

Conditions	Yield
Stage #1: N-methoxy-N-methylisoquinoline-1-carboxamide; methylmagnesium chloride In tetrahydrofuran at 0℃; for 1.16667h; Stage #2: With water; ammonium chloride In tetrahydrofuran	100%

3,7-dimethyl-2,6-octadienal (141-27-5) + ammonium chloride + methylmagnesium chloride (676-58-4) → 1-methylgeraniol (853065-81-3)

Conditions	Yield
In hexane; tert-butyl methyl ether	100%

(E)-N-butyl-1-(2-chloro-6-fluorophenyl)methanimine (945408-07-1) + methylmagnesium chloride (676-58-4) → butyl-[1-(2-chloro-6-methyl-phenyl)-meth-(E)-ylidene]-amine (945408-08-2)

Conditions	Yield
With manganese(ll) chloride In tetrahydrofuran at 0 - 40℃; for 0.5h;	100%

methylmagnesium chloride (676-58-4) + (5-bromo-pentyl)-dimethyl tin (1+); bromide (61222-13-7) → (5-bromo-pentyl)-trimethyl stannane (61222-07-9)

Conditions	Yield
In diethyl ether	100%

methylmagnesium chloride (676-58-4) + copper(l) chloride + phosphorous acid trimethyl ester (121-45-9) → CH3Cu{P(OCH3)3}3

Conditions	Yield
In tetrahydrofuran under N2, MeMgCl reacted with CuCl, P(OMe)3 was added, stirred for 30 min at 0°C; not isolated;	100%

methylmagnesium chloride (676-58-4) + copper(l) chloride → Mg(2+)*4Cu(1+)*6(CH3)(1-) = {(CH3)3Cu2}2Mg

Conditions	Yield
With N,N,N,N,N,N-hexamethylphosphoric triamide In tetrahydrofuran under N2, soln. of MeMgCl was added to a stirred suspn. of CuCl at -10°C (ratio MeMgCl/CuCl = 3/2), stirred for 30 min at 0°C; not isolated;	100%

methylmagnesium chloride (676-58-4) + copper(l) chloride → Mg(2+)*2{CH3CuCl}(1-) = Mg{CH3CuCl}2

Conditions	Yield
With N,N,N,N,N,N-hexamethylphosphoric triamide In tetrahydrofuran under N2, soln. of MeMgCl was added to a stirred suspn. of CuCl at -10°C, HMPT was also added, stirred for 30 min at 0°C; not isolated;	100%

Ti(η(5):η(1):η(1)-C5Me4SiMe2NCH2CH2OMe)Cl2 (166987-94-6, 174898-32-9) + methylmagnesium chloride (676-58-4) → Ti(η(5):η(1)-C5Me4SiMe2NCH2CH2OMe)Me2 (166987-98-0, 219947-10-1)

Conditions	Yield
In not given	100%

methylmagnesium chloride (676-58-4) + N-methoxy-N-methyl-3-(1-(tert-butoxycarbonyl)piperidin-4-yl)propionamide (301186-40-3) → tert-butyl 4-(3-oxobutyl)piperidine-1-carboxylate

Conditions	Yield
Stage #1: methylmagnesium chloride; N-methoxy-N-methyl-3-(1-(tert-butoxycarbonyl)piperidin-4-yl)propionamide In tetrahydrofuran at 0 - 20℃; for 4h; Stage #2: With ammonium chloride In tetrahydrofuran; water for 0.166667h;	100%

({2-[3-methoxy-4-(4-methyl-imidazol-1-yl)-phenylamino]-6-methyl-pyrimidin-4-yl}-methyl-amino)-acetic acid benzyl ester (1185019-50-4) + methylmagnesium chloride (676-58-4) → 1-({2-[3-methoxy-4-(4-methyl-imidazol-1-yl)-phenylamino]-6-methyl-pyrimidin-4-yl}-methyl-amino)-2-methyl-propan-2-ol (1185015-50-2)

Conditions	Yield
Stage #1: ({2-[3-methoxy-4-(4-methyl-imidazol-1-yl)-phenylamino]-6-methyl-pyrimidin-4-yl}-methyl-amino)-acetic acid benzyl ester; methylmagnesium chloride In tetrahydrofuran at 20℃; for 2.16667h; Cooling with ice; Stage #2: With water In tetrahydrofuran Hydrolysis;	100%

3-(3-methoxypropoxy)-4-[(triisopropylsilyl)oxy]benzaldehyde (960409-26-1) + methylmagnesium chloride (676-58-4) → 1-{3-(3-methoxypropoxy)-4-[(triisopropylsilyl)oxy]phenyl}ethanol (960409-28-3)

Conditions	Yield
Stage #1: 3-(3-methoxypropoxy)-4-[(triisopropylsilyl)oxy]benzaldehyde; methylmagnesium chloride In tetrahydrofuran at 0 - 20℃; Stage #2: With water; ammonium chloride In tetrahydrofuran at 0℃;	100%

Upstream product

• 74-87-3 methylene chloride 

Downstream Products

• 1084-78-2 (1RS,2SR)-(+/-)-1,2-diphenyl-1,2-propandiol 
• 1084-78-2 (1RS,2RS)-(+/-)-1,2-diphenyl-1,2-propandiol 
• 4613-11-0 2,3-diphenylbutane 
• 2726-21-8 2,3-diphenylbutane 
• 92551-16-1 1-chloro-1,2-diphenylpropane 
• 2532-58-3 cis-1,3-dimethylcyclopentane 
• 1759-58-6 trans-1,3-dimethylcyclopentane 
• 75-77-4 chloro-trimethyl-silane 
• 594-82-1 tetramethyl-2,2,3,3 butane 
• 2344-80-1 Chloromethyltrimethylsilane 
• 1825-61-2 Trimethylmethoxysilane 
• 1112-39-6 dimethyldimethoxysilan 
• 23171-85-9 2,3,3-Trimethyl-2-pentanol 
• 29772-39-2 2,2,3,4-tetramethyl-3-pentanol 

Relevant articles and documents

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Chemical synthesis

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