3585-33-9

Basic information

• Product Name: LITHIUM DIMETHYLAMIDE
• Synonyms: LITHIUM DIMETHYLAMIDE;LITHIUM DIMETHYLAMIDE, 5 WT. % SUSPENSIO N IN HEXANES;Lithiumdimethylamide,95%;Methanamine, N-methyl-, lithium salt;lithium dimethylamide preparation;(Dimethylamino) lithium;Dimethylaminolithium;Dimethyllithioamine
• CAS NO: 3585-33-9
• Molecular Formula: C₂H₆LiN
• Molecular Weight: 51.02
• EINECS: 222-714-3
• Product Categories: Chemical Synthesis;Organic Bases;Synthetic Reagents;metal amide
• Mol File: 3585-33-9.mol
• Article Data: 13

Chemical Properties

• Boiling Point: 68-70 °C
• Flash Point: -23 °C
• Appearance: White/Slurry
• Density: 0.68 g/mL at 25 °C
• Vapor Pressure: 1520mmHg at 25°C
• Water Solubility: Reacts violently with water.
• Sensitive: Air & Moisture Sensitive
• BRN: 3618233
• CAS DataBase Reference: LITHIUM DIMETHYLAMIDE(CAS DataBase Reference)
• NIST Chemistry Reference: LITHIUM DIMETHYLAMIDE(3585-33-9)
• EPA Substance Registry System: LITHIUM DIMETHYLAMIDE(3585-33-9)

Safety Data

• Hazard Codes: F,C,N,Xn
• Statements: 17-34-67-65-62-51/53-48/20-11-36/38
• Safety Statements: 9-16-26-29-33-36/37/39-45-62-27-61-36/37
• RIDADR: UN 3394 4.2/PG 1
• WGK Germany: 3
• F: 1-10
• HazardClass: 4.2
• PackingGroup: I
• Hazardous Substances Data: 3585-33-9(Hazardous Substances Data)

Usage

Uses

It is used in the synthesis of some d0 organoimido complexes of the early transition metals and in meta rearrangement in the reaction of triphenyl-(p-bromophenyl)-silane.

InChI:InChI=1/C2H6N.Li/c1-3-2;/h1-2H3;/q-1;+1

Synthetic route

trityllithium (733-90-4) + dimethyl amine (124-40-3) → triphenylmethane (519-73-3) + lithium dimethylamide (3585-33-9)

Conditions	Yield
In tetrahydrofuran at 30℃; Equilibrium constant;

1-cyclopentenyllithium (67788-09-4) + 3,4-dimethoxy-3-cyclobutene-1,2-dione (5222-73-1) + C5H10LiN → lithium dimethylamide (3585-33-9) + (3aS,5aR,8aS)-3a-Hydroxy-2,3-dimethoxy-4-methylene-4,5,5a,6,7,8-hexahydro-3aH-cyclopenta[c]pentalen-1-one + (3aS,3bR,6aS,7aR)-7a-Dimethylaminomethyl-3a-hydroxy-2,3-dimethoxy-3a,3b,4,5,6,6a,7,7a-octahydro-cyclopenta[a]pentalen-1-one + (3aS,3bR,6aR,7aR)-7a-Dimethylaminomethyl-3a-hydroxy-2,3-dimethoxy-3a,3b,4,5,6,6a,7,7a-octahydro-cyclopenta[a]pentalen-1-one

Conditions	Yield
Mechanism; other squarates, other alkenyllithium compounds, other 2-lithioallylamines, multistep reaction, 1.) THF, pentane, 1 h, 2.) THF, pentane, -78 deg C -> room temperature;

dimethyl amine (124-40-3) → lithium dimethylamide (3585-33-9)

Conditions	Yield
With n-butyllithium
With n-hexyllithium In tetrahydrofuran; hexane at 10℃;
With n-butyllithium In hexane for 1h; Cooling with ice;

n-hexyllithium (21369-64-2) + dimethyl amine (124-40-3) → lithium dimethylamide (3585-33-9)

Conditions	Yield
In tetrahydrofuran; hexane at 10℃;

Mo(NMe2)6Li2(THF)2 → lithium dimethylamide (3585-33-9)

Conditions	Yield
In not given dissocn. in soln.;

Mo(NMe2)6Li2(THF)2 → lithium dimethylamide (3585-33-9) + tetrakis(dimethylamido)molybdenum(IV) (100207-68-9)

Conditions	Yield
In benzene
In toluene

N,N-dimethylammonium chloride (506-59-2) → lithium dimethylamide (3585-33-9)

Conditions	Yield
With n-butyllithium In tetrahydrofuran at -78 - 20℃; for 14h; Inert atmosphere;

n-butyllithium (109-72-8, 29786-93-4) + dimethyl amine (124-40-3) → lithium dimethylamide (3585-33-9)

Conditions	Yield
In hexane; toluene at -20 - -15℃;

bis(dimethylamino)chlorocarbenium trifluoroacetate + lithium dimethylamide (3585-33-9) → hexamethylguanidinium trifluoroacetate

Conditions	Yield
In acetonitrile at 20℃; for 5h;	99.2%

bis(dimethylamino)chlorocarbenium trifluoroacetate + lithium dimethylamide (3585-33-9) → hexamethylguanidinium trifluoroacetate

Conditions	Yield
In acetonitrile	99.2%

lithium dimethylamide (3585-33-9) + diphenyltin(IV) dichloride (1135-99-5) → bis(dimethylamido)diphenyltin(IV) (1087-64-5)

Conditions	Yield
In benzene under inert conditions, 1 equiv. of Sn-compd was added to an ice-cooled suspension of 2.2 equiv. of LiNMe2 in benzene, stirring at room temp. for 2 d; mixt. was filtered, volatiles were removed in vac.;	99%
In not given

(p-Me2NC6H4)2SnCl2 (56541-98-1) + lithium dimethylamide (3585-33-9) → (p-Me2NC6H4)2Sn(NMe2)2 (880475-50-3)

Conditions	Yield
In benzene under inert conditions, 1 equiv. of Sn-compd was added to an ice-cooled suspension of 2.2 equiv. of LiNMe2 in benzene, stirring at room temp. for 2 d; mixt. was filtered, volatiles were removed in vac.;	99%

lithium dimethylamide (3585-33-9) + di(p-tolyl)tin dichloride (32538-29-7) → (p-MeC6H4)2Sn(NMe2)2 (952516-08-4)

Conditions	Yield
In benzene under inert conditions, 1 equiv. of Sn-compd was added to an ice-cooled suspension of 2.2 equiv. of LiNMe2 in benzene, stirring at room temp. for 2 d; mixt. was filtered, volatiles were removed in vac.;	99%

dichloro[bis(p-methoxyphenyl)]stannane (56541-97-0) + lithium dimethylamide (3585-33-9) → (p-MeOC6H4)2Sn(NMe2)2 (952516-06-2)

Conditions	Yield
In benzene under inert conditions, 1 equiv. of Sn-compd was added to an ice-cooled suspension of 2.2 equiv. of LiNMe2 in benzene, stirring at room temp. for 2 d; mixt. was filtered, volatiles were removed in vac.;	99%

lithium dimethylamide (3585-33-9) + bis(4-fluorophenyl)tin dichloride (17236-61-2) → (p-FC6H4)2Sn(NMe2)2 (952516-10-8)

Conditions	Yield
In benzene under inert conditions, 1 equiv. of Sn-compd was added to an ice-cooled suspension of 2.2 equiv. of LiNMe2 in benzene, stirring at room temp. for 2 d; mixt. was filtered, volatiles were removed in vac.;	99%

di(4-trifluoromethylphenyl)tindichloride (77459-83-7) + lithium dimethylamide (3585-33-9) → (p-CF3C6H4)2Sn(NMe2)2 (952516-13-1)

Conditions	Yield
In benzene under inert conditions, 1 equiv. of Sn-compd was added to an ice-cooled suspension of 2.2 equiv. of LiNMe2 in benzene, stirring at room temp. for 2 d; mixt. was filtered, volatiles were removed in vac.;	99%

(C5(CH3)5)TaCl2(C6H5C)2 (75522-28-0) + lithium dimethylamide (3585-33-9) → (C5(CH3)5)Ta(C6H5CCC6H5)(N(CH3)2)Cl + (C5(CH3)5)Ta(C6H5CCC6H5)(N(CH3)2)2

Conditions	Yield
In toluene under N2; addn. of 2 equiv LiNMe2 to the soln. of the Ta-complex in toluene, mixt. stirred (room temp., 8 h); filtered (Celite), filtrate concd., layered with hexane, crystn. (24 h), elem. anal.;	A 98.7% B 0%

Hexamethylcyclotrisiloxane (541-05-9) + lithium dimethylamide (3585-33-9) → lithium (dimethylamino)dimethylsilanolate

Conditions	Yield
In tetrahydrofuran for 4h;	98%

Salen((t)Bu)AlCl (182315-48-6) + lithium dimethylamide (3585-33-9) → ((CH3)2N)Al((CH2NCHC6H2(C(CH3)3)2O)2) (182315-57-7)

Conditions	Yield
In toluene stirring (35°C, 24 h); filtering, evapn. (reduced pressure); elem. anal.;	98%

quinuclidine dichlorogallane adduct + lithium dimethylamide (3585-33-9) → [HGa(NMe2)2]2 (676995-07-6)

Conditions

Yield

In diethyl ether byproducts: LiCl, quinuclidine; under N2; to a stirred slurry of Li-contg. compd. (81.5 mmol) in Et2O at-78°C was added dropwise a soln. of Ga-contg. compd. (40.7 mmol) in Et2O; the mixt. was allowed to warm to room temp. and stirred for 17 h; volatiles were removed under vac.; pentane was added and the resulting slurry was filtered to sep. LiCl and a filtrate; the filtrate was concd. and stored at -20°C overnight; elem. anal.;

97%

lithium dimethylamide (3585-33-9) + 1-Chlor-N,N,N',N'-tetramethylformamidinium-trifluormethansulfonat (105142-17-4) → N,N,N',N',N'',N''-hexamethylguanidinium triflate

Conditions	Yield
In acetonitrile at 20℃; for 12h;	96.7%

lithium dimethylamide (3585-33-9) + 1-Chlor-N,N,N',N'-tetramethylformamidinium-trifluormethansulfonat (105142-17-4) → hexamethyl guanidinium trifluoromethane sulfonate

Conditions	Yield
In diethyl ether; acetonitrile	96.7%

bis(dimethylamino)chlorocarbenium tosylate + lithium dimethylamide (3585-33-9) → hexamethylguanidinium tosylate

Conditions	Yield
In acetonitrile at 20℃; for 5h;	96.6%

bis(dimethylamino)chlorocarbenium tosylate + lithium dimethylamide (3585-33-9) → hexamethylguanidinium tosylate

Conditions	Yield
In acetonitrile	96.6%

pentacarbonyl(1,4-diethoxy-4-methylpentynylidene)chromium + lithium dimethylamide (3585-33-9) → pentacarbonyl{(2E)-3-(dimethylamino)-1,4-diethoxy-4-methylpentenylidene}chromium + pentacarbonyl{3-(dimethylamino)-4-ethoxy-4-methyl-1,2-pentadienylidene}chromium

Conditions	Yield
In diethyl ether addn. of the Li-amide in Et2O to the Cr-complex in Et2O under N2 at 20°C, stirred for 30 min; evapd. (vac.), chromy.;	A 0% B 96%

tetrahydrofuran (109-99-9) + lithium dimethylamide (3585-33-9) + zirconium(IV) chloride (10026-11-6) → 2Li(1+)*6C2H6N(1-)*Zr(4+)*2C4H8O

Conditions	Yield
With lithium chloride In toluene at 20℃; for 12h; Inert atmosphere;	96%

2,4-dicarba-closo-heptaborane (20693-69-0) + lithium dimethylamide (3585-33-9) → 2,4-dicarba-nido-hexaborate(8)(1-) (39394-97-3)

Conditions	Yield
In acetonitrile N2-atmosphere, condensing C2B5H7 to Li-compd. in NMR-tube (vac., -195°C), warming (room temp.), shaking, standing (2 min), cooling (-195°C), addn. of MeCN, warming (ambient temp.), standing (room temp., 2 months); not isolated; (11)B-NMR;	95%

Cp*TiCl3 (12129-06-5) + lithium dimethylamide (3585-33-9) → mono(pentamethylcyclopentadienyl)tris(dimethylamido)titanium(IV)

Conditions	Yield
In hexane suspn. of Ti-complex and LiNMe2 is stirred in hexane (under Ar) for 15 h; filtn., concn. the volume, cooling to -40°C for 24 h, elem. anal.;	95%

1,2-Mo2Br2(CH2SiMe3)4 (75059-90-4) + lithium dimethylamide (3585-33-9) → 1,2-bis(dimethylamido)tetrakis(trimethylsilylmethyl)dimolybdenum(Mo-Mo) + 1,1-bis(dimethylamido)tetrakis(trimethylsilylmethyl)dimolybdenum(Mo-Mo) (75059-94-8)

Conditions	Yield
In hexane byproducts: LiCl; react. at -50°C, then warming to 0°C over 2 h; filtration, solvent stripped, products are not sepd., detected by NMR, elem. anal.;	A 5% B 95%
In hexane byproducts: LiBr; filtration, removal of solvent in vac.;

[Zr(η5-C5Me4SiMeH-η1-NBu-t)Cl2] (570401-34-2) + lithium dimethylamide (3585-33-9) → [Zr(η5-C5Me4SiMeH-η1-NBu-t)(NMe2)2] (570401-37-5)

Conditions	Yield
In toluene toluene was added at -78°C to a mixt. of compounds, warmed to room temp., stirred for 21 h (Ar); solvent was removed under reduced pressure, extd. with hexane, filtered,evapd.; elem. anal.;	95%

[(tert-butylcalix[4]arene methyl ether)chlorotitanium(IV)] toluene + lithium dimethylamide (3585-33-9) → [(tert-butylcalix[4]arene methyl ether)(dimethylamido)titanium(IV)] (850538-56-6)

Conditions	Yield
In toluene N2, to a soln. of 1.15 equiv. of Li compd. added at room temp. a soln., of Ti compd., stirred for 12 h; filtered (Celite), volatiles removed (vac.), suspnd. (hexane), ppt. collected, dried (vac.); elem. anal.;	95%

TaCl(dimethylamide)3(1,1-dimethyl-2-(trimethylsilyl)hydrazide) + lithium dimethylamide (3585-33-9) → Ta(dimethylamide)4(1,1-dimethyl-2-(trimethylsilyl)hydrazide) (1233220-56-8)

Conditions	Yield
In pentane byproducts: LiCl; addn. of LiN(CH3)2 to Ta complex in pentane at -30°C, slow warming to room temp., stirring for 24 h; filtration, extn. with pentane, concn., storage at -30°C, isolation of solid;	95%

bis(dimethylamino)chlorocarbenium thiocyanate + lithium dimethylamide (3585-33-9) → 1,1,2,2,3,3-Hexamethylguanidiniumthiocyanat (68897-49-4)

Conditions	Yield
In acetonitrile at 20℃; for 5h;	94.8%

bis(dimethylamino)chlorocarbenium thiocyanate + lithium dimethylamide (3585-33-9) → hexamethylguanidinium thiocyanate

Conditions	Yield
In acetonitrile	94.8%

aluminium trichloride (7446-70-0) + lithium dimethylamide (3585-33-9) + tris(benzyl)aluminum (14994-03-7) → [(C6H5CH2)2AlN(CH3)2]2

Conditions	Yield
In toluene byproducts: LiCl; inert atmosphere; treatment of Al(CH2Ph)3 with AlCl3, suspending in PhMe, addn. of LiNMe2 at 25°C, stirring for 12 h; removal of volatiles, extn. into PhMe, filtration, evapn.;	94%

Diethylcyanamide (617-83-4) + lithium dimethylamide (3585-33-9) + zinc(II) chloride (7646-85-7) + lithium hexamethyldisilazane (4039-32-1) → [zinc(μ-1,1-dimethyl-3,3-diethylguanidine)(N(SiMe3)2)]2 (1000163-77-8)

Conditions	Yield
In diethyl ether byproducts: LiCl; (Ar); Li-dialkylamide dissolved in ether; equimolar cyanamide added dropwise; stirred for 30 min; equimolar LiN(SiMe3)2 and ZnCl2 added; stirredfor 24 h; centrifuged; soln. concd.; cooled to -35°C; elem. anal.;	94%

(η(5)-indenyl)trichlorotitanium (84365-55-9) + lithium dimethylamide (3585-33-9) → [Ti(η5-Ind)(NMe2)Cl2]

Conditions	Yield
In toluene to stirred suspn. of Ti-complex in toluene at -80°C was added dropwise suspn. of LiNMe2 in toluene, warmed to room temp., stirred overnight under Ar; solvent was evapd. to dryness, washed with hexane, extd. with toluene, cooled to -20°C; elem. anal.;	93%

1,3-dimethyl-2-chloroimidazolidinium nitrate + lithium dimethylamide (3585-33-9) → 1,3-dimethyl-2-dimethylaminoimidazolidinium nitrate

Conditions	Yield
In acetonitrile at 20℃; for 5h;	92.2%

Upstream product

• 506-59-2 N,N-dimethylammonium chloride 
• 109-72-8 n-butyllithium 
• 124-40-3 dimethyl amine 
• 21369-64-2 n-hexyllithium 
• 67788-09-4 1-cyclopentenyllithium 
• 5222-73-1 3,4-dimethoxy-3-cyclobutene-1,2-dione 
• 733-90-4 trityllithium 

Downstream Products

• 3275-24-9 tetrakis(dimethylamino)titanium 
• 705277-84-5 2-{[3-tert-butyl-1-(2-methylphenyl)-1H-pyrazol-5-yl]amino}-4-(dimethylamino)benzoic acid 
• 68897-49-4 1,1,2,2,3,3-Hexamethylguanidiniumthiocyanat 
• 4207-54-9 5-chloro-2,2-dimethylpentanenitrile 
• 1624-01-7 tetrakis(dimethylamino)silane 
• 330942-05-7 betrixaban 
• 229635-34-1 [Ta(C₅(CH₃)5)(CH₃)(N(CH₃)2)(NC₆H₃(CH₃)2)] 
• 19756-04-8 tetrakis(dimethylamido)zirconium 
• 7313-22-6 N,N,N'N'-tetramethyl malonamide 
• 6526-66-5 2-amino-N,N-dimethylbenzamide 
• 51579-87-4 N,N-dimethyl-2-oxo-2-phenylacetamide 
• 611-74-5 N,N-dimethylbenzamide 
• 74484-51-8 [(2-Butylsulfanyl-phenyl)-phenyl-methyl]-dimethyl-amine 
• 86046-32-4 (R)-2-benzyl-N,N-dimethylpyrrolidine-2-carboxamide 

Relevant articles and documents

Evaluation of Amino Substituants as Nucleofugal Controllers of Regioselectivity and as Chelate Modulators of Stereoselectivity in Squarate Ester Cascades

The tandem addition of an alkenyllithium reagent and a 2-lithioallylamine to squarate esters has been systematically examined. The effect of the sequencing of this twofold addition has been investigated. The extent to which the amino group is eliminated was found to be dependent on the structural features of the companion nucleophile. Also assessed was the comparative ease with which the amino and methoxy groups experience competitive β-elimination from the highly reactive, medium-ring dianionic intermediates. Attempts were made to curtail the level of competing 1,4-addition, and success was achieved by increasing the effective size of the O-alkyl groups in the squarate ester. The highly stereocontrolled transformations described represent a notably direct means for producing highly fused polycyclic compounds. Mechanistic considerations surrounding these reactions, which are characterized by an impressive enhancement of molecular scaffolding, are discussed.

A nickel(II) guanidinate compound and its potential as CVD precursor for nickel related films

In this study, a nickel(II) compound with guanidinate ligand of the general form [((Me)2NC(iPrN)2)2Ni] has been synthesized and isolated from the reaction of NiCl2 with the corresponding lithium salt of guanidinate ligand [(Me)2NC(iPrN)2Li] at 70 °C. Its structure was determined by 1H NMR, elemental analysis, and single crystal X-ray diffraction. Thermogravimetric analysis (TGA) was employed to study the thermal properties (including thermal stability, volatility, vapor pressure and transport behavior) of compound. Furthermore, a deposition experiment was made to examine the compound's potential as CVD precursor, and a Ni metal film was successfully deposited. These preliminary results illustrate the potential of this compound to act as CVD precursor.

Mesoporous Silica-Supported Amidozirconium-Catalyzed Carbonyl Hydroboration

The hydroboration of aldehydes and ketones using a silica-supported zirconium catalyst is reported. Reaction of Zr(NMe2)4 and mesoporous silica nanoparticles (MSN) provides the catalytic material Zr(NMe2)n@MSN. Exhaustive characterization of Zr(NMe2)n@MSN with solid-state (SS)NMR and infrared spectroscopy, as well as through reactivity studies, suggests its surface structure is primarily ≡ SiOZr(NMe2)3. The presence of these nitrogen-containing zirconium sites is supported by 15N NMR spectroscopy, including natural abundance 15N NMR measurements using dynamic nuclear polarization (DNP) SSNMR. The Zr(NMe2)n@MSN material reacts with pinacolborane (HBpin) to provide Me2NBpin and the material ZrH/Bpin@MSN that is composed of interacting surface-bonded zirconium hydride and surface-bonded borane ≡ SiOBpin moieties in an approximately 1:1 ratio, as well as zirconium sites coordinated by dimethylamine. The ZrH/Bpin@MSN is characterized by 1H/2H and 11B SSNMR and infrared spectroscopy and through its reactivity with D2. The zirconium hydride material or the zirconium amide precursor Zr(NMe2)n@MSN catalyzes the selective hydroboration of aldehydes and ketones with HBpin in the presence of functional groups that are often reduced under hydroboration conditions or are sensitive to metal hydrides, including olefins, alkynes, nitro groups, halides, and ethers. Remarkably, this catalytic material may be recycled without loss of activity at least eight times, and air-exposed materials are catalytically active. Thus, these supported zirconium centers are robust catalytic sites for carbonyl reduction and that surface-supported, catalytically reactive zirconium hydride may be generated from zirconium-amide or zirconium alkoxide sites.