Diisopropylamine

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.

Not to be confused with Diisopropanolamine.
Diisopropylamine
Names
Preferred IUPAC name
N-(Propan-2-yl)propan-2-amine
Other names
Di(propan-2-yl)amine
N-Isopropylpropan-2-amine
(Diisopropyl)amine
(The name diisopropylamine is deprecated.)
Identifiers
3D model (JSmol)
Abbreviations DIPA
605284
ChemSpider
ECHA InfoCard 100.003.235
EC Number
  • 203-558-5
RTECS number
  • IM4025000
UNII
UN number 1158
Properties
C6H15N
Molar mass 101.193 g·mol−1
Appearance Colorless liquid
Odor Fishy, ammoniacal
Density 0.722 g mL−1
Melting point −61.00 °C; −77.80 °F; 212.15 K
Boiling point 83 to 85 °C; 181 to 185 °F; 356 to 358 K
miscible[1]
Vapor pressure 9.3 kPa (at 20°C)[2]
Acidity (pKa) 11.07 (in water) (conjugate acid)
Basicity (pKb) 3.43[2]
1.392–1.393
Thermochemistry
−173.6 to −168.4 kJ mol−1
−4.3363 to −4.3313 MJ mol−1
Hazards
GHS pictograms
GHS Signal word Danger
H225, H302, H314, H332
P210, P280, P305+351+338, P310
NFPA 704 (fire diamond)
Flammability code 3: Liquids and solids that can be ignited under almost all ambient temperature conditions. Flash point between 23 and 38 °C (73 and 100 °F). E.g. gasolineHealth code 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformReactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
3
2
0
Flash point −17 °C (1 °F; 256 K)
315 °C (599 °F; 588 K)
Explosive limits 1.1–7.1%[1]
Lethal dose or concentration (LD, LC):
  • 770 mg kg−1 (oral, rat)
  • >10 g kg−1 (dermal, rabbit)
1140 ppm (rat, 2 hr)
1000 ppm (mouse, 2 hr)[3]
2207 ppm (rabbit, 2.5 hr)
2207 ppm (guinea pig, 80 min)
2207 ppm (cat, 72 min)[3]
NIOSH (US health exposure limits):
PEL (Permissible)
 TWA 5 ppm (20 mg/m3) [skin][1]
REL (Recommended)
 TWA 5 ppm (20 mg/m3) [skin][1]
IDLH (Immediate danger)
 200 ppm[1]
Related compounds
Related amines
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YN ?)
Infobox references

Reactions and use

Diisopropylamine is a common amine nucleophile in organic synthesis.[4] Because it is bulky, it is a more selective nucleophile than, say, dimethylamine.[5]

It reacts with organolithium reagents to give lithium diisopropylamide (LDA). LDA is a strong, non-nucleophilic base[6]

The main commercial applications of diisopropylamine is as a precursor to two herbicides, diallate and triallate, as well as certain sulfenamides used in the vulcanization of rubber.[7]

It is also used to prepare N,N-Diisopropylethylamine (Hünig's base) by alkylation with diethyl sulfate.[8]

The bromide salt of diisopropylamine, diisopropylammonium bromide, is a room-temperature organic ferroelectric material.[9]

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 catalyst:[10][11]

NH
3 + 2(CH
3)
2CO + 2H
2 → C
6H
15N + 2H
2O


Diisopropylamine can be dried by distillation from potassium hydroxide (KOH) or drying over sodium wire.[12]{{rp|page=186}

Toxicity

Causes burns by all exposure routes. Inhalation of high vapor concentrations may cause symptoms like headache, dizziness, tiredness, nausea and vomiting.[13]

References
  1. NIOSH Pocket Guide to Chemical Hazards. "#0217". National Institute for Occupational Safety and Health (NIOSH).
  2. CID 7912 from PubChem
  3. "Diisopropylamine". Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  4. John E. McMurry, Jack Melton (1977). "Conversion of Nitro to Carbonyl by Ozonolysis of Nitronates: 2,5-Heptanedione". Organic Syntheses. 56: 36. doi:10.15227/orgsyn.056.0036.
  5. Denmark, Scott; Ryabchuk, Pavel; Min Chi, Hyung; Matviitsuk, Anastassia (2019). "Preparation of a Diisopropylselenophosphoramide Catalyst and its Use in Enantioselective Sulfenoetherification". Organic Syntheses. 96: 400–417. doi:10.15227/orgsyn.096.0400.
  6. George M. Rubottom, John M. Gruber, Henrik D. Juve, Jr, , Dan A. Charleson (1986). "α-Hydroxy Ketones from the Oxidation of Enol Silyl Ethers with m-Chloroperbenzoic Acid: 6-Hydroxy- 3,5,5-trimethyl-2-cyclohexen-1-one". Organic Syntheses. 64: 118. doi:10.15227/orgsyn.064.0118.CS1 maint: multiple names: authors list (link)
  7. Eller, Karsten; Henkes, Erhard; Rossbacher, Roland; Höke, Hartmut (15 June 2000). "Amines, Aliphatic". Ullmann's Encyclopedia of Industrial Chemistry. Wiley-VCH. doi:10.1002/14356007.a02_001. ISBN 978-3527303854. OL 9052422M.
  8. Hünig, Siegfried; Kiessel, Max (1 April 1958). "Spezifische Protonenacceptoren als Hilfsbasen bei Alkylierungs- und Dehydrohalogenierungsreaktionen" [Specific proton acceptors as auxiliary bases in alkylation and dehydrohalogenation reactions]. Chemische Berichte (in German). Wiley-VCH. 91 (2): 380–392. doi:10.1002/cber.19580910223. ISSN 0009-2940. OCLC 889715844.
  9. Fu, Da-Wei; Cai, Hong-Ling; Liu, Yuanming; Ye, Qiong; Zhang, Wen; et al. (25 January 2013). "Diisopropylammonium Bromide Is a High-Temperature Molecular Ferroelectric Crystal". Science. 339 (6118): 425–428. doi:10.1126/science.1229675. eISSN 1095-9203. ISSN 0036-8075. LCCN 17024346. OCLC 1644869. PMID 23349285. S2CID 12389978.
  10. Löffler, Karl (1 April 1910). "Über eine neue Bildungsweise primärer und sekundärer Amine aus Ketonen" [About a new way of forming primary and secondary amines from ketones]. Berichte der Deutschen Chemischen Gesellschaft (in German). 43 (2): 2031–2035. doi:10.1002/cber.191004302145. ISSN 0365-9496. OCLC 219854722.
  11. US 2686811, Willard Bull, "One-step process for preparing diisopropylamine"
  12. Armarego, W. L. F.; Perrin, D. D. (16 October 1996). Purification of Laboratory Chemicals (4th ed.). Butterworth-Heinemann. ISBN 978-0750628396. LCCN 97109714. OCLC 762966259. OL 722457M.
  13. "SAFETY DATA SHEET--Triethylamine". ThermoFisher Scientific. Jan 17, 2018. Retrieved June 18, 2020.
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