Bis (3-aminopropyl) amine

Structural formula
General
Surname	Bis (3-aminopropyl) amine
other names	4-azaheptane-1,7-diamine; N - (3-aminopropyl) propane-1,3-diamine; 3,3'-diaminodipropylamine; 1,5,9-triazanonane; Dipropylenetriamine; Norspermidine;
Molecular formula	C 6 H 17 N 3
Brief description	colorless to light yellow liquid
External identifiers / databases
EC number	200-261-2
ECHA InfoCard	100,000,238
PubChem	5942
Wikidata	Q3878510
properties
Molar mass	131.22 g mol −1
Physical state	liquid
density	0.938 g cm −3 at 25 ° C
Melting point	−14 ° C ; −16 ° C ;
boiling point	151 ° C at 67 h Pa ; 235 ° C ;
Vapor pressure	0.05 h Pa (20 ° C); 1.15 h Pa (50 ° C);
pK s value	12 at 20 ° C
solubility	miscible with water, soluble in diethyl ether and ethanol
Refractive index	1.481 (20 ° C)
safety instructions
H and P phrases	H: 302-311-314-317-330-341-373
	P: 260-280-303 + 361 + 353-304 + 340 + 310-305 + 351 + 338-403 + 233
Toxicological data	738 mg kg −1 ( LD 50 , rat , oral ) ; 100 mg kg −1 ( LD 50 , rabbit , transdermal ) ;
	As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions . Refractive index: Na-D line , 20 ° C

Bis (3-aminopropyl) amine is a polyamine that has one secondary and two primary amino groups and has a strongly basic reaction in aqueous solution. Like other polyamines, dipropylenetriamine is used as a hardener for epoxy resins and as a starting material for vulcanization accelerators , emulsifiers and corrosion inhibitors . Some derivatives have antibacterial and anti-cancer properties in vitro .

Occurrence and representation

In contrast to the asymmetrical polyamine spermidine, bis (3-aminopropyl) amine (norspermidine) does not occur in animal cells, but only in simple organisms such as e.g. B. Bacteria.

Addition of acrylonitrile to ammonia gives bis (2-cyanoethyl) amine in yields of over 90% if the process is carried out appropriately (30% strength aqueous ammonia solution).

The catalytic hydrogenation of the two nitrile groups yields dipropylenetriamine.

The reactive distillation of propane-1,3-diamine with hydrogen at elevated pressures (5 to 10 bar) and temperatures (140 to 160 ° C.) in the presence of palladium on zirconium dioxide as the hydrogenation catalyst produces dipropylenetriamine with selectivities above 70% and 1.3 - Diaminopropane conversions greater than 50%.

By reactive distillation, the formation of higher propyleneamines such. B. tris (3-aminopropyl) amine, suppressed.

properties

Bis (3-aminopropyl) amine is an amine-like smelling clear liquid that mixes completely with water and is soluble in diethyl ether and ethanol . Compared to the homologous spermidine, norspermidine is very toxic and probably mutagenic.

Applications

The trifunctional polyamine dipropylenetriamine (DPTA) is used - mostly together with other polyvalent amines - as a hardener for epoxy resins, e.g. B. in floor coatings.

As reducing agents in the vulcanization of synthetic rubber and natural rubber , polyamines, such as. B. Dipropylenetriamine used.

Amphiphilic derivatives of bis (2-aminoethyl) amine with long (C ₁₂ - C ₁₈ ) side chains z. B. dodecyldipropylenetriamine, are bactericidal or antimicrobial. They inhibit the formation of biofilms and are used as disinfectants and biocides .

Polynuclear complexes of norspermidine with bivalent platinum Pt (II) and in particular bivalent palladium Pd (II) have tumor-inhibiting properties on breast cancer cells.

Bis (2-aminoethyl) amine is the starting compound for the bicyclic fused guanidine - Base Triazabicyclodecen TBD.

Individual evidence

↑ ^a ^b ^c ^d ^e ^f ^g data sheet bis (3-aminopropyl) amine, 98% from Sigma-Aldrich , accessed on November 25, 2018 ( PDF ).
↑ ^a ^b ^c ^d ^e ^f ^g ^h ⁱ Entry on 4-azaheptane-1,7-diamine in the GESTIS substance database of the IFA , accessed on November 25, 2018(JavaScript required) .
↑ ^a ^b Entry on 3,3'-Diaminodipropylamine Template: link text check / apostrophe at TCI Europe, accessed on November 25, 2018.
↑ Entry on dipropylenetriamine in the Classification and Labeling Inventory of the European Chemicals Agency (ECHA), accessed on December 30, 2018. Manufacturers or distributors can expand the harmonized classification and labeling .
↑ ^a ^b B. Brycki, I. Kowalczyk, J. Werner, T. Pospieszny, A. Kozirog: Synthesis and structural analysis of novel norspermidine derivatives . In: Int. J. Org. Chem. Volume 7 , no. 2 , 2017, p. 106-139 , doi : 10.4236 / ijoc.2017.72010 .
↑ ^a ^b T.M. Silva, S. Andersson, SK Sukumaran, MP Marques, L. Persson, S. Oredsson: Norspermidine and novel Pd (II) and Pt (II) polynuclear complexes of norspermidine as potential antineoplastic agents against breast cancer . In: PLOS ONE . tape 8 , no. 2 , 2013, p. e55651 , doi : 10.1371 / journal.pone.0055651 .
^ AJ Michael: Polyamines in eukaryotes, bacteria, and archaea . In: J. Biol. Chem. Volume 291 , no. 29 , 2016, p. 14896-14903 , doi : 10.1074 / jbc.R116.734780 .
↑ Patent US4055586 : Process for the manufacture of bis- (2-cyanoethyl) -amine. Applied on October 20, 1976 , published on October 25, 1977 , applicant: Ruhrchemie AG, inventor: H. Feichtinger, W. Payer, B. Cornils, J. Weber. ‌
↑ Patent US6342492B1 : Anti-viral triaza compounds and compositions. Filed February 16, 1996 , published January 29, 2002 , applicant: The Research Foundation of State University of New York, inventor: TW Bell. ‌
↑ RJ Bergeron, JR Garlich: Amines and polyamines from nitriles . In: Synthesis . tape 9 , 1984, pp. 782-784 , doi : 10.1055 / s-1984-30973 .
↑ Patent WO2006082203A1 : Process for the production of bis (3-aminopropyl) amine (dipropylenetriamine, DPTA). Registered on February 1, 2006 , published on August 10, 2006 , applicant: BASF AG, inventor: J.-P. Melder, T. Krug. ‌
↑ MC-DUR rapid primer component B. (PDF; 203nbsp; KB) In: mc-bauchemie.de. MC-Bauchemie Müller GmbH & Co. KG, accessed on December 1, 2018 .
↑ Patent DE4037814B4 : Process for vulcanizing rubber latex with peroxide using acrylate ester as an accelerator. Applied on November 28, 1990 , published on August 25, 2005 , Applicants: Japan Atomic Energy Research Institute, Inventors: K. Makkuuchi, F. Yoshii, I. Ishigaki, S. Iskandar. ‌
↑ Triameen Y12D-30. (PDF; 60nbsp; KB) In: akzonobel.com/sc. AkzoNobel Surface Chemistry AB, accessed December 1, 2018 .
↑ Triameen Y12D - The high-performing, non-sensitizing biocide without MRL. (PDF; 90nbsp; KB) In: akzonobel.com/sc. AkzoNobel Surface Chemistry AB, accessed December 1, 2018 .
↑ S. Usachev, A. Gridnev: Convenient preparation of bicyclic guanidines . In: Synth. Commun. tape 41 , no. 24 , 2011, p. 3683-3688 , doi : 10.1080 / 00397911.2010.519848 .

[Sigma-1] ↑ ^a ^b ^c ^d ^e ^f ^g data sheet bis (3-aminopropyl) amine, 98% from Sigma-Aldrich , accessed on November 25, 2018 ( PDF ).

[GESTIS-2] ↑ ^a ^b ^c ^d ^e ^f ^g ^h ⁱ Entry on 4-azaheptane-1,7-diamine in the GESTIS substance database of the IFA , accessed on November 25, 2018(JavaScript required) .

[TCI-3] Entry on 3,3'-Diaminodipropylamine Template: link text check / apostrophe at TCI Europe, accessed on November 25, 2018.

[CLP_100.000.238-4] Entry on dipropylenetriamine in the Classification and Labeling Inventory of the European Chemicals Agency (ECHA), accessed on December 30, 2018. Manufacturers or distributors can expand the harmonized classification and labeling .

[Brycki-5] B. Brycki, I. Kowalczyk, J. Werner, T. Pospieszny, A. Kozirog: Synthesis and structural analysis of novel norspermidine derivatives . In: Int. J. Org. Chem. Volume 7 , no. 2 , 2017, p. 106-139 , doi : 10.4236 / ijoc.2017.72010 .

[Silva-6] T.M. Silva, S. Andersson, SK Sukumaran, MP Marques, L. Persson, S. Oredsson: Norspermidine and novel Pd (II) and Pt (II) polynuclear complexes of norspermidine as potential antineoplastic agents against breast cancer . In: PLOS ONE . tape 8 , no. 2 , 2013, p. e55651 , doi : 10.1371 / journal.pone.0055651 .

[7] AJ Michael: Polyamines in eukaryotes, bacteria, and archaea . In: J. Biol. Chem. Volume 291 , no. 29 , 2016, p. 14896-14903 , doi : 10.1074 / jbc.R116.734780 .

[8] Patent US4055586 : Process for the manufacture of bis- (2-cyanoethyl) -amine. Applied on October 20, 1976 , published on October 25, 1977 , applicant: Ruhrchemie AG, inventor: H. Feichtinger, W. Payer, B. Cornils, J. Weber. ‌

[9] Patent US6342492B1 : Anti-viral triaza compounds and compositions. Filed February 16, 1996 , published January 29, 2002 , applicant: The Research Foundation of State University of New York, inventor: TW Bell. ‌

[10] RJ Bergeron, JR Garlich: Amines and polyamines from nitriles . In: Synthesis . tape 9 , 1984, pp. 782-784 , doi : 10.1055 / s-1984-30973 .

[11] Patent WO2006082203A1 : Process for the production of bis (3-aminopropyl) amine (dipropylenetriamine, DPTA). Registered on February 1, 2006 , published on August 10, 2006 , applicant: BASF AG, inventor: J.-P. Melder, T. Krug. ‌

[12] MC-DUR rapid primer component B. (PDF; 203nbsp; KB) In: mc-bauchemie.de. MC-Bauchemie Müller GmbH & Co. KG, accessed on December 1, 2018 .

[13] Patent DE4037814B4 : Process for vulcanizing rubber latex with peroxide using acrylate ester as an accelerator. Applied on November 28, 1990 , published on August 25, 2005 , Applicants: Japan Atomic Energy Research Institute, Inventors: K. Makkuuchi, F. Yoshii, I. Ishigaki, S. Iskandar. ‌

[14] Triameen Y12D-30. (PDF; 60nbsp; KB) In: akzonobel.com/sc. AkzoNobel Surface Chemistry AB, accessed December 1, 2018 .

[15] Triameen Y12D - The high-performing, non-sensitizing biocide without MRL. (PDF; 90nbsp; KB) In: akzonobel.com/sc. AkzoNobel Surface Chemistry AB, accessed December 1, 2018 .

[16] S. Usachev, A. Gridnev: Convenient preparation of bicyclic guanidines . In: Synth. Commun. tape 41 , no. 24 , 2011, p. 3683-3688 , doi : 10.1080 / 00397911.2010.519848 .