51-80-9

Basic information

• Product Name: N,N,N',N'-TETRAMETHYLDIAMINOMETHANE
• Synonyms: ((CH3)2N)2CH2;Dimethyl[(dimethylamino)methyl]amine;Methylenebis(dimethylamine);Methylenediamine, N,N,N',N'-tetramethyl-;N,N,N',N'-Tetramethyldiaminomethan;n,n,n’,n’-tetramethyldiaminomethan;n,n,n’,n’-tetramethyl-methanediamin;NA 9069
• CAS NO: 51-80-9
• Molecular Formula: C₅H₁₄N₂
• Molecular Weight: 102.18
• EINECS: 200-124-7
• Mol File: 51-80-9.mol
• Article Data: 21

Chemical Properties

• Melting Point: -55°C
• Boiling Point: 85 °C(lit.)
• Flash Point: 9 °F
• Appearance: Clear colorless/Liquid
• Density: 0.749 g/mL at 25 °C(lit.)
• Refractive Index: n20/D 1.401(lit.)
• Storage Temp.: Flammables area
• PKA: 7.67±0.10(Predicted)
• Water Solubility: Fully miscible in water.
• Stability: Stable, but highly flammable. Incompatible with acids, acid chlorides, acid anhydrides, strong oxidizing agents, carbon dioxide.
• BRN: 1731946
• CAS DataBase Reference: N,N,N',N'-TETRAMETHYLDIAMINOMETHANE(CAS DataBase Reference)
• NIST Chemistry Reference: N,N,N',N'-TETRAMETHYLDIAMINOMETHANE(51-80-9)
• EPA Substance Registry System: N,N,N',N'-TETRAMETHYLDIAMINOMETHANE(51-80-9)

Safety Data

• Hazard Codes: F,C
• Statements: 11-34
• Safety Statements: 16-26-36/37/39-45
• RIDADR: UN 2733 3/PG 2
• WGK Germany: 3
• RTECS: PA6700000
• TSCA: Yes
• HazardClass: 3
• PackingGroup: II
• Hazardous Substances Data: 51-80-9(Hazardous Substances Data)

Usage

Chemical Properties

slightly yellow liquid

Uses

N,N,N',N'-Tetramethylmethylenediamine is a reagent used as a convenient source of the Mannich intermediate.

Safety Profile

Poison by intraperitoneal route. Flammable liquid and very dangerous fire hazard when exposed to powerful oxidizers, heat or open flame. When heated to decomposition it emits toxic fumes of NOx. See also AMINES.

Synthetic route

formaldehyd (50-00-0) + dimethyl amine (124-40-3) → bis-(dimethylamino)methane (51-80-9)

Conditions	Yield
In water at 0 - 20℃;	92%
With potassium hydroxide at 20 - 25℃;	89%
Cooling with ice;	81%

(Me2N)2Zr[iPrNC(NMe2)NiPr]2 + oxygen (80937-33-3) → bis-(dimethylamino)methane (51-80-9) + Zr(=O)[iPrNC(NMe2)NiPr]2 + {Zr(μ-O)[iPrNC(NMe2)NiPr]2}2 + {Zr(μ-O)[iPrNC(NMe2)NiPr]2}n + dimethyl amine (124-40-3)

Conditions	Yield
In toluene at 90℃; under 760.051 Torr; for 40h; Kinetics; Temperature; Reagent/catalyst; Solvent; Schlenk technique;	A n/a B n/a C n/a D 62% E n/a

Zr(NMe2)2[MeC(NiPr)2]2 + oxygen (80937-33-3) → bis-(dimethylamino)methane (51-80-9) + {(μ-O)Zr[MeC(NiPr)2]2}n + {(μ-O)Zr[MeC(NiPr)2]2}2 + dimethyl amine (124-40-3)

Conditions	Yield
In benzene-d6 at 70℃; Concentration; Temperature;	A 1.09 mg B 58.4% C n/a D 0.125 mg

Zr(NMe2)2[MeC(NiPr)2]2 + oxygen (80937-33-3) → bis-(dimethylamino)methane (51-80-9) + {(μ-O)Zr[MeC(NiPr)2]2}2 + {(μ-O)Zr[MeC(NiPr)2]2}n + dimethyl amine (124-40-3)

Conditions	Yield
In benzene-d6 at 70℃; under 760.051 Torr; for 288h; Inert atmosphere;	A 1.1 mg B n/a C 58% D 0.13 mg

(Me2N)2Hf[iPrNC(NMe2)NiPr]2 + oxygen (80937-33-3) → bis-(dimethylamino)methane (51-80-9) + {Hf(μ-O)[iPrNC(NMe2)NiPr]2}2 + {Hf(μ-O)[iPrNC(NMe2)NiPr]2}n + dimethyl amine (124-40-3)

Conditions	Yield
In benzene-d6 at 70℃; under 760.051 Torr; for 45h; Reagent/catalyst; Schlenk technique;	A n/a B n/a C 40% D n/a

N-Methoxy-N-chloro-N',N'-dimethylurea (88470-22-8) + dimethyl amine (124-40-3) → bis-(dimethylamino)methane (51-80-9) + tetramethylurea (632-22-4)

Conditions	Yield
at 0℃; for 1h;	A 26.4% B 9.1%

1,4-dioxane (123-91-1) + dimethylchloroamine (1585-74-6) + diethylmagnesium (557-18-6) + dimethyl amine (124-40-3) → bis-(dimethylamino)methane (51-80-9)

dimethylchloroamine (1585-74-6) → bis-(dimethylamino)methane (51-80-9)

Conditions	Yield
With silver

dimethylaminomethanol (14002-21-2) → bis-(dimethylamino)methane (51-80-9)

Conditions	Yield
bei der Destillation;
With potassium hydroxide
With dimethyl amine

dichloromethane (75-09-2) + dimethyl amine (124-40-3) → bis-(dimethylamino)methane (51-80-9)

Conditions	Yield
at 70℃;
at 70℃;

N,N-dimethyl-formamide (68-12-2, 33513-42-7) → bis-(dimethylamino)methane (51-80-9) + trimethylamine (75-50-3)

Conditions	Yield
With sodium tetrahydroborate; bis(cyclopentadienyl)titanium dichloride at 95℃; for 1h; Mechanism; effect of titanium complex concentration on the induction period;
With sodium tetrahydroborate; bis(cyclopentadienyl)titanium dichloride at 87℃; for 1h;

N,N-dimethyl-(3,5-di-tert-butyl-4-hydroxybenzyl)amine (88-27-7) → bis-(dimethylamino)methane (51-80-9) + 2,6-di-tert-butyl-4-(3,5-di-tert-butyl-4-hydroxy-benzylidene)-cyclohexa-2,5-dienone (4359-97-1) + 1,2-di(3',5'-di-tert-butyl-4'-hydroxyphenyl)ethene (2950-01-8) + 4-(dimethylamino)methylene-2,6-di-tert-butylcyclohexa-2,5-dien-1-one (17329-93-0) + dimethyl amine (124-40-3) + 3,5-di-t-butyl-4-hydroxybenzaldehyde (1620-98-0)

Conditions	Yield
With water In xylene at 125℃; for 7h; Product distribution; Rate constant; Thermodynamic data; effect of addition of stearic acid or TFA; Ea; other solvent, temperature;

tetra-N-ethyl-2-methyl-2-nitro-propanediyldiamine (704915-64-0) + Raney nickel → bis-(dimethylamino)methane (51-80-9)

Conditions	Yield
Hydrogenation;

diethyl ether (60-29-7) + dimethylchloroamine (1585-74-6) + copper bronze → bis-(dimethylamino)methane (51-80-9) + 1.3.5-trimethyl-hexahydro-1.3.5-triazine

dimethylchloroamine (1585-74-6) + silver → bis-(dimethylamino)methane (51-80-9) + N,N-dimethylammonium chloride (506-59-2)

ethanol (64-17-5) + N,N,S-trimethyldithiocarbamate (3735-92-0) + sodium → bis-(dimethylamino)methane (51-80-9) + trimethylamine (75-50-3) + sodium thiomethoxide (5188-07-8) + Na2S

2,2-bis-dimethylaminomethyl-3-hydroxy-propionaldehyde ; dihydrochloride + sodium amalgam → formaldehyd (50-00-0) + bis-(dimethylamino)methane (51-80-9) + 1,1-Bis(dimethylaminomethyl)-2-ethanol (261528-91-0)

Conditions	Yield
in schwach saurer Loesung;

Zr(NMe2)2[MeC(NiPr)2]2 + {(μ-η2:η2-O2)Zr[MeC(NiPr)2]2}3 → bis-(dimethylamino)methane (51-80-9) + {(μ-O)Zr[MeC(NiPr)2]2}2 + {(μ-O)Zr[MeC(NiPr)2]2}n + dimethyl amine (124-40-3)

Conditions	Yield
In benzene-d6 Inert atmosphere;

Zr(NMe2)2[MeC(NiPr)2]2 + dihydrogen peroxide (7722-84-1) → bis-(dimethylamino)methane (51-80-9) + {(μ-O)Zr[MeC(NiPr)2]2}2 + {(μ-O)Zr[MeC(NiPr)2]2}n + dimethyl amine (124-40-3)

Conditions	Yield
In benzene-d6 Inert atmosphere;

triethylsiloxymethyl-N,N-dimethylamine (1353053-97-0) + diethylamine (109-89-7) → bis-(dimethylamino)methane (51-80-9) + bis-(diethylamino)methane (102-53-4) + N'-N-Diethyl-N'-,N'-dimethyl-methanediamine (85413-87-2)

Conditions	Yield
In benzene-d6 Sealed tube; Inert atmosphere;

formaldehyd (50-00-0) + N,N-dimethylammonium chloride (506-59-2) → bis-(dimethylamino)methane (51-80-9)

Conditions	Yield
In water at 20℃; for 0.5h; Cooling with ice;

bis-(dimethylamino)methane (51-80-9) → N,N-dimethyl(methylene)ammonium chloride (30354-18-8)

Conditions	Yield
With acetyl chloride In diethyl ether for 2h;	100%
With acetyl chloride In diethyl ether at 20℃; Cooling with ice;	90%
With acetyl chloride In tert-butyl methyl ether at 0 - 30℃; for 0.5h; Inert atmosphere;	83.7%

bis-(dimethylamino)methane (51-80-9) + 6-Bromo-2-[(4-chloro-phenylamino)-methyl]-5-hydroxy-1-methyl-1H-indole-3-carboxylic acid ethyl ester (132629-08-4) → 6-Bromo-2-[(4-chloro-phenylamino)-methyl]-4-dimethylaminomethyl-5-hydroxy-1-methyl-1H-indole-3-carboxylic acid ethyl ester

Conditions	Yield
In 1,4-dioxane Heating;	100%

bis-(dimethylamino)methane (51-80-9) + tetraethylcyclohexane-trans-1,2-bis(aminomethylphosphonate) → [(3aS,7aS)-3-(Diethoxy-phosphorylmethyl)-octahydro-benzoimidazol-1-ylmethyl]-phosphonic acid diethyl ester

Conditions	Yield
at 80℃;	100%

4-(1H-benzoimidazole-5-carbonyl)-piperazine-1-carboxylic acid tert-butyl ester (251106-06-6) + bis-(dimethylamino)methane (51-80-9) → 4-(3-dimethylaminomethyl-3H-benzoimidazole-6-carbonyl)-piperazine-1-carboxylic acid tert-butyl ester (1254162-61-2)

Conditions	Yield
With succinic acid anhydride; potassium carbonate In dichloromethane at 20 - 23℃; for 6h;	100%

bis-(dimethylamino)methane (51-80-9) + 4-Vinylbenzyl chloride (1592-20-7) → N,N'-(methylene)bis(N,N-dimethyl-1-(4-vinylphenyl)methanaminium) chloride

Conditions	Yield
In acetonitrile at 50℃; for 48h; Inert atmosphere;	100%

bis-(dimethylamino)methane (51-80-9) + phenylacetylene (536-74-3) → N,N-dimethyl-3-phenyl-2-propyn-1-amine (2568-65-2)

Conditions	Yield
With C14H20Cu2I2N2O2S2 In toluene Reagent/catalyst;	99.8%
With samarium nitrate at 80℃; for 6h; Reactivity; Reagent/catalyst; Solvent; Inert atmosphere; neat (no solvent);	98%

bis-(dimethylamino)methane (51-80-9) + phenol (108-95-2) → ortho-dimethylaminomethylphenol (120-65-0)

Conditions	Yield
	99.5%

bis-(dimethylamino)methane (51-80-9) + phenol (108-95-2) → 2,6-bis-<(dimethyamino)methyl>phenol (15827-34-6)

Conditions	Yield
	99.5%

bis-(dimethylamino)methane (51-80-9) + 3H-2,1-benzoxathiolan-3-one 1-oxide (91837-36-4) → N,N-dimethylmethyleneimmonium salt of dimethylamide of 0-(oxysulfinyl)isobutyric acid

Conditions	Yield
In diethyl ether at 4℃; Acylation;	99%

bis-(dimethylamino)methane (51-80-9) + urea (57-13-6) → N,N′-bis[(dimethylamino)methyl]urea (52663-01-1)

Conditions	Yield
With SmCl3*6H2O In ethanol; chloroform at 20℃; for 1h; Reagent/catalyst; Solvent; Time;	99%
With samarium(III) chloride hexahydrate In ethanol for 8h;	99%

bis-(dimethylamino)methane (51-80-9) + thiourea (17356-08-0) → N,N′-bis[(dimethylamino)methyl]thiourea (98425-53-7)

Conditions	Yield
With SmCl3*6H2O In ethanol; chloroform at 20℃; for 1h;	99%
With samarium(III) chloride hexahydrate In ethanol; chloroform for 8h; Heating;	99%

1-(4-fluorophenyl)-2-[5-(trifluoromethyl)-2-pyridyl]ethanone (145834-67-9) + bis-(dimethylamino)methane (51-80-9) → 1-(4-fluorophenyl)-2-[5-(trifluoromethyl)-2-pyridyl]prop-2-en-1-one

Conditions	Yield
With acetic anhydride In dichloromethane at -15℃; for 0.0833333h; Inert atmosphere;	99%
With acetic anhydride at 0℃; for 0.0833333h;	1.4 g

bis-(dimethylamino)methane (51-80-9) + 7-hydroxy-3-(4-methoxyphenyl)-8-methyl-4H-chromen-4-one (116718-51-5) → 6-[(N,N-dimethylamino)methyl]-7-hydroxy-3-(4-methoxyphenyl)-8-methyl-4H-chromen-4-one

Conditions	Yield
In 2-methoxy-ethanol at 70 - 124℃; for 16h;	99%

bis-(dimethylamino)methane (51-80-9) + ethyl 6-bromo-5-hydroxy-2-(((3-hydroxyphenyl)thio)methyl)-1-methyl-1H-indole-3-carboxylate → ethyl 6-bromo-4-((dimethylamino)methyl)-5-hydroxy-2-(((3-hydroxyphenyl)thio)methyl)-1-methyl-1H-indole-3-carboxylate

Conditions	Yield
In dichloromethane for 3.5h; Inert atmosphere; Reflux;	99%
In dichloromethane for 3.5h; Inert atmosphere; Reflux;	34 mg

bis-(dimethylamino)methane (51-80-9) + C14H22O5 → C15H22O5

Conditions	Yield
With acetic anhydride; acetic acid In dichloromethane at 20℃; for 10h; Cooling with ice; Inert atmosphere;	99%
With acetic anhydride; acetic acid In dichloromethane at 20℃; for 10h; Cooling with ice;	99%

bis-(dimethylamino)methane (51-80-9) + trichlorophosphazotrichlorooxoethane (14335-48-9) → dimethylamidodichlorophosphazotrichlorooxoethane

Conditions	Yield
In benzene for 1h;	98%

bis-(dimethylamino)methane (51-80-9) + Diphenyl phosphorochloridite (5382-00-3) → O,O-diphenyl N-dimethylamidophosphite (19620-78-1)

Conditions	Yield
In benzene	98%

3-benzyloxy-2-methyl-1H-pyridin-4-one (61160-18-7) + bis-(dimethylamino)methane (51-80-9) → 2-methyl-3-benzyloxy-5-(N,N-dimethyl)aminomethyl-pyridin-4-one (174095-91-1)

Conditions	Yield
In ethanol for 20h; Heating;	98%

bis-(dimethylamino)methane (51-80-9) + 3-(2,3-dihydro-1,4-benzodioxin-6-yl)-7-hydroxyisoflavone (96754-91-5) → 3-(2,3-dihydro-1,4-benzodioxin-6-yl)-8-[(N,N-dimethylamino)methyl]-7-hydroxy-4H-chromen-4-one

Conditions	Yield
In 1,4-dioxane Heating;	98%
In isopropyl alcohol Reflux;

bis-(dimethylamino)methane (51-80-9) + (S)-2-Benzyl-4-methyl-1,2-dihydro-2,4a,9-triaza-anthracene-3,10-dione (194925-84-3) → (1S,4S)-2-Benzyl-1-dimethylaminomethyl-4-methyl-1,2-dihydro-2,4a,9-triaza-anthracene-3,10-dione

Conditions	Yield
With trifluoroacetic acid at 65℃; for 3.5h;	98%

bis-(dimethylamino)methane (51-80-9) + (4S)-2,4-dimethyl-2,4-dihydro-(1H)-pyrazino<2,1-b>quinazoline-3,6-dione (54799-50-7) → (1S,4S)-1-Dimethylaminomethyl-2,4-dimethyl-1,2-dihydro-2,4a,9-triaza-anthracene-3,10-dione

Conditions	Yield
With trifluoroacetic acid at 65℃; for 3.5h;	98%

6,12,18,24-tetramethoxy-2,8,14,20-tetrapentylresorcin[4]arene + bis-(dimethylamino)methane (51-80-9) → C64H100N4O8

Conditions	Yield
Stage #1: bis-(dimethylamino)methane With potassium carbonate; acetyl chloride In dichloromethane for 0.5h; Stage #2: 6,12,18,24-tetramethoxy-2,8,14,20-tetrapentylresorcin[4]arene In dichloromethane at 20℃; for 120h;	98%

bis-(dimethylamino)methane (51-80-9) + n-octyne (629-05-0) → N,N-dimethyl-N-(non-2-yn-1-yl)amine (1150626-72-4)

Conditions	Yield
With copper dichloride at 80℃; for 6h; Reactivity; Solvent; Reagent/catalyst; Inert atmosphere; neat (no solvent);	98%

bis-(dimethylamino)methane (51-80-9) + prop-2-yn-1-yl 3-methylbutanoate (1289157-09-0) → 4-(dimethylamino)but-2-yn-1-yl 3-methylbutanoate (1289157-13-6)

Conditions	Yield
With copper(l) chloride at 80℃; for 6h; Inert atmosphere; Neat (no solvent);	98%

1-butanethiol (109-79-5) + bis-(dimethylamino)methane (51-80-9) → 1-(butylsulfanyl)-N,N-dimethylmethanamine (62142-30-7)

Conditions	Yield
With samarium(III) chloride hexahydrate at 60℃; for 1.5h; Inert atmosphere; chemoselective reaction;	98%

n-pentanethiol (110-66-7) + bis-(dimethylamino)methane (51-80-9) → N,N-dimethyl-1-(pentylsulfanyl)methaneamine (1369272-96-7)

Conditions	Yield
With samarium(III) chloride hexahydrate at 60℃; for 1.5h; Inert atmosphere; chemoselective reaction;	98%

heptanethiol (1639-09-4) + bis-(dimethylamino)methane (51-80-9) → 1-(heptylsulfanyl)-N,N-dimethylmethanamine (1369272-97-8)

Conditions	Yield
With samarium(III) chloride hexahydrate at 60℃; for 1.5h; Inert atmosphere; chemoselective reaction;	98%

bis-(dimethylamino)methane (51-80-9) + C22H21N3O7S → C23H21N3O7S

Conditions	Yield
With acetic anhydride In acetonitrile at 23℃;	98%

bis-(dimethylamino)methane (51-80-9) + 1-4,6-dihydroxy-2-methoxy-3-methylphenylbutan-1-one (478-48-8) → 1-[3-((dimethylamino)methyl)-2,4-dihydroxy-6-methoxy-5-methylphenyl]butan-1-one

Conditions	Yield
In dichloromethane at 20℃; for 2h;	98%
In dichloromethane at 20℃;

triethylsilane (617-86-7) + bis-(dimethylamino)methane (51-80-9) → 1,1,1-triethyl-N,N-dimethylsilylamine (3550-35-4) + trimethylamine (75-50-3)

Conditions	Yield
With nickel at 140 - 150℃;	A 97% B n/a

Upstream product

• 123-91-1 1,4-dioxane 
• 1585-74-6 dimethylchloroamine 
• 557-18-6 diethylmagnesium 
• 124-40-3 dimethyl amine 
• 68-12-2 N,N-dimethyl-formamide 
• 88-27-7 N,N-dimethyl-(3,5-di-tert-butyl-4-hydroxybenzyl)amine 
• 704915-64-0 tetra-N-ethyl-2-methyl-2-nitro-propanediyldiamine 
• 60-29-7 diethyl ether 
• 64-17-5 ethanol 
• 3735-92-0 N,N,S-trimethyldithiocarbamate 
• 80937-33-3 oxygen 
• 50-00-0 formaldehyd 
• 506-59-2 N,N-dimethylammonium chloride 
• 1353053-97-0 triethylsiloxymethyl-N,N-dimethylamine 

Downstream Products

• 23580-89-4 methyl-(3-phenyl-propyl)-amine 
• 1467-79-4 NCNMe₂ 
• 22711-72-4 N-bromomethyl-N,N-dimethylamine 
• 6912-12-5 dimethylamine hydrobromide 
• 23562-77-8 2-(dimethylaminomethyl)-4-methoxyphenol 
• 2543-57-9 1-Dimethylamino-3-butanon 
• 5419-02-3 1-dimethylaminomethyl-naphthalen-2-ol 
• 108851-11-2 3-dimethylamino-1-(4-methoxy-phenyl)-2-methyl-propan-1-ol 
• 39943-37-8 1-Dimethylaminomethylcyclopentancarboxaldehyd 
• 2404-03-7 diethyl N,N-dimethylphosphoramide 
• 1670-17-3 N,N-dimethyl-2,4-dinitroaniline 
• 918-05-8 N,N-dimethylmethanesulfonamide 
• 120-65-0 ortho-dimethylaminomethylphenol 
• 5468-76-8 2,2-dichloro-N,N-dimethylacetamide 

Relevant articles and documents

Siloxymethylamines as Aminomethylation Reagents for Amines Leading to Labile Diaminomethanes That can be Trapped as Their [Mo(CO)4] Complexes

Compound Et3SiOCH2NMe2 transfers Me2NCH2 to R2NH (R2=Et2, PhMe, [Cr(η6-C6H5)(CO)3]Me, PhH) to form previously unknown diaminomethanes, Me2NCH2NR2 and, in the case of R2=PhH, the triamine Me2NCH2N(Ph)CH2NMe2. The diaminomethanes exhibit an unreported disproportionation to a mixture of (R2N)2CH2, (Me2N)2CH2, and Me2NCH2NR2, which can be trapped as their [Mo(CO)4(diamine)] complexes. Whereas PhMeNCH2NMe2 is a labile material, the metal-substituted ([(η6-C6H5)Cr(CO)3]MeNCH2NMe2 is a stable material. The triamine Me2NCH2N(Ph)CH2NMe2 is unstable with respect to transformation to 1,3,5-triphenyltriazine, but is readily trapped as the bidentate-triamineMo(CO)4. All metal complexes were characterized by single-crystal X-ray diffraction.

Reactions of zirconium amide amidinates with dioxygen. Observation of an unusual peroxo intermediate in the formation of oxo compounds

Reaction of d0 Zr(NMe2)2[MeC(N iPr)2]2 (1) with O2 at -30°C gives three Zr containing products: a peroxo trimer {(μ-η2: η2-O2)Zr[MeC(NiPr)2] 2}3 (2), an oxo dimer {(μ-O)Zr[MeC(N iPr)2]2}2 (3), and an oxo polymer {(μ-O)Zr[MeC(NiPr)2]2}n (4). 2 is a rarely observed peroxo complex from the reaction of a d0 complex with O2. This journal is the Partner Organisations 2014.