Diisopropylamine: Difference between revisions

{{distinguish|Diisopropanolamine}}

|Verifiedfields = changed

|Watchedfields = changed

|verifiedrevid = 440520163

|ImageFile = Diisopropylamine.png

|ImageFile_Ref = {{chemboximage|correct|??}}

|ImageSize = 100

|ImageName = Skeletal formula of diisopropylamine

|PIN = ''N''-(Propan-2-yl)propan-2-amine

|OtherNames = Di(propan-2-yl)amine<br>''N''-Isopropylpropan-2-amine<br>(Diisopropyl)amine<br>(The name diisopropylamine is deprecated.)

|Section1={{Chembox Identifiers

|CASNo = 108-18-9

|CASNo_Ref = {{cascite|correct|CAS}}

|PubChem = 7912

|ChemSpiderID = 7624

|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}

|UNII = BR9JLI40NO

|UNII_Ref = {{fdacite|correct|FDA}}

|EINECS = 203-558-5

|UNNumber = 1158

|RTECS = IM4025000

|Beilstein = 605284

|SMILES = CC(C)NC(C)C

|StdInChI = 1S/C6H15N/c1-5(2)7-6(3)4/h5-7H,1-4H3

|StdInChI_Ref = {{stdinchicite|correct|chemspider}}

|StdInChIKey = UAOMVDZJSHZZME-UHFFFAOYSA-N

|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}

}}

|Section2={{Chembox Properties

|C=6 | H=15 | N=1

|Appearance = Colorless liquid

|Odor = Fishy, ammoniacal

|Density = 0.722 g mL⁻¹

|MeltingPtK = 212.15

|BoilingPtK = 356 to 358

|VaporPressure = 9.3 kPa (at 20°C)<ref name="pubchem">{{pubchem|7912}}</ref>

|pKa = 11.07 (in water) (conjugate acid)

|pKb = 3.43<ref name="pubchem" />

|RefractIndex = 1.392–1.393

|Solubility = miscible<ref name=PGCH/>

}}

|Section3={{Chembox Thermochemistry

|DeltaHf = −173.6 to −168.4 kJ mol⁻¹

|DeltaHc = −4.3363 to −4.3313 MJ mol⁻¹

}}

|Section4={{Chembox Hazards

|GHSPictograms = {{gHS flame}} {{gHS corrosion}} {{gHS exclamation mark}}

|GHSSignalWord = '''DANGER'''

|HPhrases = {{h-phrases|225|302|314|332}}

|PPhrases = {{p-phrases|210|280|305+351+338|310}}

|NFPA-H = 2

|NFPA-F = 3

|NFPA-R = 0

|FlashPtC = −17

|AutoignitionPtC = 315

|ExploLimits = 1.1–7.1%<ref name=PGCH/>

|LD50 = {{unbulleted list|770 mg kg⁻¹ <small>(oral, rat)</small>|>10 g kg⁻¹ <small>(dermal, rabbit)</small>}}

|PEL = TWA 5 ppm (20 mg/m³) [skin]<ref name=PGCH>{{PGCH|0217}}</ref>

|IDLH = 200 ppm<ref name=PGCH/>

|REL = TWA 5 ppm (20 mg/m³) [skin]<ref name=PGCH/>

|LC50 = 1140 ppm (rat, 2 hr)<br/>1000 ppm (mouse, 2 hr)<ref name=IDLH>{{IDLH|108189|Diisopropylamine}}</ref>

|LCLo = 2207 ppm (rabbit, 2.5 hr)<br/>2207 ppm (guinea pig, 80 min)<br/>2207 ppm (cat, 72 min)<ref name=IDLH/>

}}

|Section5={{Chembox Related

|OtherFunction_label = amines

|OtherFunction = {{unbulleted list|[[Dimethylamine]]|[[Diethylamine]]}}

|OtherCompounds = {{unbulleted list|[[Triisopropylamine]]|[[N,N-Diisopropylethylamine]]}}

}}

'''Diisopropylamine''' is a [[secondary amine]] with the [[chemical formula]] (Me₂CH)₂NH (Me = [[methyl]]). Diisopropylamine is a colorless liquid with an ammonia-like odor. Its lithium derivative, [[lithium diisopropylamide]], known as '''LDA''' is a widely used reagent.

==Reactions and use==

Diisopropylamine is a common amine nucleophile in [[organic synthesis]].<ref>{{cite journal |doi=10.15227/orgsyn.056.0036|title=Conversion of Nitro to Carbonyl by Ozonolysis of Nitronates: 2,5-Heptanedione|journal=Organic Syntheses|year=1977|volume=56|page=36|author=John E. McMurry, Jack Melton}}</ref> Because it is bulky, it is a more selective nucleophile than other similar amines, such as [[dimethylamine]].<ref>{{cite journal |pmid=34526731| doi=10.15227/orgsyn.096.0400|title=Preparation of a Diisopropylselenophosphoramide Catalyst and its Use in Enantioselective Sulfenoetherification|year=2019|last1=Denmark|first1=Scott|first2=Pavel|last2=Ryabchuk|first3=Hyung |last3=Min Chi |first4=Anastassia|last4=Matviitsuk|journal=Organic Syntheses|volume=96|pages=400–417| pmc=8439352|doi-access=free}}</ref>

It reacts with organolithium reagents to give [[lithium diisopropylamide]] (LDA). LDA is a [[strong base|strong]], [[non-nucleophilic base]]<ref>{{cite journal |doi=10.15227/orgsyn.064.0118|title=α-Hydroxy Ketones from the Oxidation of Enol Silyl Ethers with m-Chloroperbenzoic Acid: 6-Hydroxy- 3,5,5-trimethyl-2-cyclohexen-1-one|author=George M. Rubottom, John M. Gruber, Henrik D. Juve, Jr, , Dan A. Charleson|journal=Organic Syntheses|year=1986|volume=64|page=118}}</ref>

The main commercial applications of diisopropylamine is as a precursor to the herbicide, diallate and triallate as well as certain [[sulfenamide]]s used in the [[vulcanization]] of rubber.<ref>{{cite encyclopedia |first1=Karsten | last1=Eller | first2=Erhard | last2=Henkes | first3=Roland | last3=Rossbacher | first4=Hartmut | last4=Höke | title=Amines, Aliphatic | journal=Ullmann's Encyclopedia of Industrial Chemistry | date=2000-06-15 | publisher=[[Wiley-VCH]] | isbn = 978-3527303854 | ol = OL9052422M | doi=10.1002/14356007.a02_001 | df=dmy-all}}</ref>

It is also used to prepare [[N,N-Diisopropylethylamine|N,N-Diisopropylethylamine (Hünig's base)]] by alkylation with [[diethyl sulfate]].<ref name="Hünig1958">{{cite journal | last1 = Hünig | first1 = Siegfried | last2 = Kiessel | first2 = Max | date = 1958-04-01 | title = Spezifische Protonenacceptoren als Hilfsbasen bei Alkylierungs- und Dehydrohalogenierungsreaktionen | trans-title = Specific proton acceptors as auxiliary bases in alkylation and dehydrohalogenation reactions | language = de | journal = [[Chemische Berichte]] | publisher = [[Wiley-VCH]] |volume = 91 | issue = 2 | pages = 380{{hyphen}}392 | doi = 10.1002/cber.19580910223 | issn = 0009-2940 | oclc = 889715844 | df=dmy-all}}</ref>

The [[bromide]] [[salt (chemistry)|salt]] of diisopropylamine, diisopropylammonium bromide, is a room-temperature organic [[ferroelectric]] material.<ref name="2013_Science">{{cite journal | last1= Fu | first1= Da-Wei | last2= Cai | first2= Hong-Ling | last3= Liu | first3= Yuanming | last4= Ye | first4= Qiong | last5= Zhang | first5= Wen | last6= Zhang | first6= Yi | last7= Chen | first7= Xue-Yuan | last8= Giovannetti | first8= Gianluca | last9= Capone | first9= Massimo | last10= Li | first10= Jiangyu | last11= Xiong | first11= Ren-Gen | display-authors= 5 |date= 2013-01-25 |title= Diisopropylammonium Bromide Is a High-Temperature Molecular Ferroelectric Crystal |journal= [[Science (journal)|Science]] |language= en |volume= 339 |issue= 6118 |pages= 425{{hyphen}}428 |doi= 10.1126/science.1229675 | pmid= 23349285 | bibcode= 2013Sci...339..425F | s2cid= 12389978 |issn= 0036-8075 | eissn= 1095-9203 |lccn= 17024346 |oclc= 1644869 | df=dmy-all}}</ref>

== Preparation ==

Diisopropylamine, which is commercially available, may be prepared by the [[reductive amination]] of [[acetone]] with [[ammonia]] using a modified [[copper oxide]], generally [[copper chromite]], as a [[catalysis|catalyst]]:<ref>{{cite journal | journal = [[Chemische Berichte|Berichte der Deutschen Chemischen Gesellschaft]] |volume = 43 | issue = 2 | pages = 2031–2035 | doi = 10.1002/cber.191004302145 | title = Über eine neue Bildungsweise primärer und sekundärer Amine aus Ketonen | trans-title = About a new way of forming primary and secondary amines from ketones | language = de | first1 = Karl | last1 = Löffler|date = 1910-04-01 | issn = 0365-9496 | oclc = 219854722 |url = https://zenodo.org/record/1426399 | df=dmy-all }}</ref><ref>{{cite patent|inventor = Willard Bull | title = One-step process for preparing diisopropylamine|country = US | number = 2686811}}</ref>

: {{chem2|NH3 + 2 (CH3)2CO + 2 H2 -> C6H15N + 2 H2O}}

Diisopropylamine can be dried by distillation from [[potassium hydroxide]] ({{Chem2|KOH}}) or drying over [[sodium]] wire.<ref>{{cite book | last1 = Armarego | first1 = W. L. F. | last2 = Perrin | first2 = D. D. | title = Purification of Laboratory Chemicals | edition = 4th | publisher = [[Butterworth-Heinemann]] | date = 1996-10-16 | isbn = 978-0750628396 | oclc = 762966259 | ol = OL722457M | lccn = 97109714 | df= dmy-all}}</ref>{{rp|page=186}}

== Toxicity ==

Diisopropylamine causes burns by all exposure routes. Inhalation of high concentrations of its vapor may cause symptoms like headache, dizziness, tiredness, nausea and vomiting.

==References==

{{reflist}}

[[Category:Alkylamines]]

[[Category:Diisopropylamino compounds]]

[[Category:Secondary amines]]