Tetrapropylammonium

Tetrapropylammonium
Names
	IUPAC name N,N,N-Tripropylpropan-1-aminium
	Other names Tetrapropylammonium; Tetrapropylazanium; Tetra-n-propylammonium; TPA
Identifiers
CAS Number	13010-31-6 ;
3D model (JSmol)	Interactive image;
Beilstein Reference	1748523
ChEBI	CHEBI:55319;
ChEMBL	ChEMBL2074857;
ChemSpider	9184;
PubChem CID	9559;
CompTox Dashboard (EPA)	DTXSID6047026 ;
	InChI InChI=1S/C12H28N/c1-5-9-13(10-6-2,11-7-3)12-8-4/h5-12H2,1-4H3/q+1 Key: OSBSFAARYOCBHB-UHFFFAOYSA-N;
	SMILES [N+](CCC)(CCC)(CCC)CCC;
Properties
Chemical formula	C12H28N+
Molar mass	186.362 g·mol−1
Structure
Molecular shape	Tetrahedral
Related compounds
Other cations	Tetramethylammonium [N(CH3)]+4; Tetraethylammonium [N(C2H5)4]+; Tetrabutylammonium [N(C4H9)4]+;
Related compounds	Trimethylamine N(C3H7)3; Tetrapropylammonium perruthenate N(C3H7)4RuO4;
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Tetrapropylammonium (TPA) is a quaternary ammonium cation with the formula [N(C₃H₇)₄]⁺, also denoted [NPr₄]⁺ (where Pr = propyl group). It is a precursor to several significant industrial and laboratory catalysts.

Properties

TPA is chemically similar to other quaternary ammonium cations with saturated alkyl groups. As such, it is highly electrochemically stable, degrading only in the presence of particularly strong bases and nucleophiles.^[1]

It is isoelectronic with tetrapropyltin and the tetrapropylboranuide anion.

Synthesis

Like other quaternary ammonium cations, TPA is prepared by the alkylation of the corresponding ammonia analogue, tripropylamine. Treatment of the amine with a primary propyl halide such as n-bromopropane yields the corresponding TPA halide salt in a Menshutkin reaction:

(C₃H₇)₃N + C₃H₇Br → (C₃H₇)₄N⁺Br⁻

The halide salts are then converted to the more industrially valuable hydroxide by reaction with aqueous silver oxide, electrolysis, ion-exchange resin, or electrodialysis.^[2]

Applications

The tetrapropylammonium cation is used as a structure-directing agent in the production of synthetic zeolites, in particular ZSM-5^[3] and titanium-bearing TS-1 catalysts.^[4] After synthesis, TPA is removed by thermolysis.^[5]

The TPA salt tetrapropylammonium perruthenate (TPAP) is an effective and highly selective oxidiser, with numerous applications in organic synthesis.^[6]^[7] Combined with a cooxidant, it serves as a catalyst for the oxidation of primary and secondary alcohols to aldehydes and ketones.

References

^ Mousavi, Maral P. S.; Kashefolgheta, Sadra; Stein, Andreas; Bühlmann, Philippe (2016). "Electrochemical Stability of Quaternary Ammonium Cations: An Experimental and Computational Study". Journal of the Electrochemical Society. 163 (2): H74–H80. doi:10.1149/2.0671602jes. hdl:11858/00-001M-0000-0029-2301-3.
^ Shen, Jiang-nan; Yu, Jie; Huang, Jie; Van Der Bruggen, Bart (2013), "Preparation of highly pure tetrapropyl ammonium hydroxide using continuous bipolar membrane electrodialysis", Chemical Engineering Journal, 220: 311–319, Bibcode:2013ChEnJ.220..311S, doi:10.1016/j.cej.2013.01.040
^ Li, Teng; Krumeich, Frank; Chen, Ming; Ma, Zhiqiang; Van Bokhoven, Jeroen A. (2020). "Defining aluminum-zoning during synthesis of ZSM-5 zeolites". Physical Chemistry Chemical Physics. 22 (2): 734–739. Bibcode:2020PCCP...22..734L. doi:10.1039/C9CP05423E. hdl:20.500.11850/383611. PMID 31832632.
^ Yang, Zhenyuan; Guan, Yanan; Xu, Lei; Zhou, Yangtao; Fan, Xiaolei; Jiao, Yilai (2023). "Tetrapropylammonium Hydroxide Treatment of Aged Dry Gel to Make Hierarchical TS-1 Zeolites for Catalysis". Crystal Growth & Design. 23 (3): 1775–1785. doi:10.1021/acs.cgd.2c01291. PMC 9983304. PMID 36879771.
^ Choudhary, V. (1985). "Influence of decomposition conditions of TPA-ZSM-5 on surface and catalytic properties of the resulting H a Na-ZSM-5". Journal of Catalysis. 94 (2): 573–575. doi:10.1016/0021-9517(85)90224-6.
^ Ley, Steven V.; Norman, Joanne; Griffith, William P.; Marsden, Stephen P. (1994). "Tetrapropylammonium Perruthenate, Pr₄N⁺RuO₄ ^-, TPAP: A Catalytic Oxidant for Organic Synthesis". Synthesis. 1994 (7): 639–666. doi:10.1055/s-1994-25538.
^ Langer, Peter (2000). "Tetra-n-propyl Ammonium Perruthenate (TPAP) - an Efficient and Selective Reagent for Oxidation Reactions in Solution and on the Solid Phase". Journal für Praktische Chemie. 342 (7): 728–730. doi:10.1002/1521-3897(200009)342:7<728::AID-PRAC728>3.3.CO;2-I.

[1] Mousavi, Maral P. S.; Kashefolgheta, Sadra; Stein, Andreas; Bühlmann, Philippe (2016). "Electrochemical Stability of Quaternary Ammonium Cations: An Experimental and Computational Study". Journal of the Electrochemical Society. 163 (2): H74–H80. doi:10.1149/2.0671602jes. hdl:11858/00-001M-0000-0029-2301-3.

[2] Shen, Jiang-nan; Yu, Jie; Huang, Jie; Van Der Bruggen, Bart (2013), "Preparation of highly pure tetrapropyl ammonium hydroxide using continuous bipolar membrane electrodialysis", Chemical Engineering Journal, 220: 311–319, Bibcode:2013ChEnJ.220..311S, doi:10.1016/j.cej.2013.01.040

[3] Li, Teng; Krumeich, Frank; Chen, Ming; Ma, Zhiqiang; Van Bokhoven, Jeroen A. (2020). "Defining aluminum-zoning during synthesis of ZSM-5 zeolites". Physical Chemistry Chemical Physics. 22 (2): 734–739. Bibcode:2020PCCP...22..734L. doi:10.1039/C9CP05423E. hdl:20.500.11850/383611. PMID 31832632.

[4] Yang, Zhenyuan; Guan, Yanan; Xu, Lei; Zhou, Yangtao; Fan, Xiaolei; Jiao, Yilai (2023). "Tetrapropylammonium Hydroxide Treatment of Aged Dry Gel to Make Hierarchical TS-1 Zeolites for Catalysis". Crystal Growth & Design. 23 (3): 1775–1785. doi:10.1021/acs.cgd.2c01291. PMC 9983304. PMID 36879771.

[5] Choudhary, V. (1985). "Influence of decomposition conditions of TPA-ZSM-5 on surface and catalytic properties of the resulting H a Na-ZSM-5". Journal of Catalysis. 94 (2): 573–575. doi:10.1016/0021-9517(85)90224-6.

[6] Ley, Steven V.; Norman, Joanne; Griffith, William P.; Marsden, Stephen P. (1994). "Tetrapropylammonium Perruthenate, Pr₄N⁺RuO₄ ^-, TPAP: A Catalytic Oxidant for Organic Synthesis". Synthesis. 1994 (7): 639–666. doi:10.1055/s-1994-25538.

[7] Langer, Peter (2000). "Tetra-n-propyl Ammonium Perruthenate (TPAP) - an Efficient and Selective Reagent for Oxidation Reactions in Solution and on the Solid Phase". Journal für Praktische Chemie. 342 (7): 728–730. doi:10.1002/1521-3897(200009)342:7<728::AID-PRAC728>3.3.CO;2-I.

[1]

[2]

[3]

[4]

[5]

[6]

[7]