4,4'-(1,6-Hexanediyl)dioxydianiline
[CAS# 47244-09-7]

Identification

• Classification: Pharmaceutical intermediate >> Diphenylamine intermediate
• Name: 4,4'-(1,6-Hexanediyl)dioxydianiline
• Synonyms: 4-[6-(4-aminophenoxy)hexoxy]aniline
• Molecular Formula: C₁₈H₂₄N₂O₂
• Molecular Weight: 300.40
• CAS Registry Number: 47244-09-7
• EC Number: 637-158-0
• SMILES: C1=CC(=CC=C1N)OCCCCCCOC2=CC=C(C=C2)N

Properties

• Density: 1.1±0.1 g/cm³ Calc.^*
• Boiling point: 518.7±35.0 ºC 760 mmHg (Calc.)^*
• Flash point: 289.2±19.6 ºC (Calc.)^*
• Index of refraction: 1.591 (Calc.)^*

^* Calculated using Advanced Chemistry Development (ACD/Labs) Software.

Safety Data

Hazard Classification

Hazard	Class	Category Code	Hazard Statement
Acute hazardous to the aquatic environment	Aquatic Acute	1	H400
Specific target organ toxicity - single exposure	STOT SE	3	H335
Skin irritation	Skin Irrit.	2	H315
Serious eye damage	Eye Dam.	1	H318

Discovory and Applicatios

4,4'-(1,6-Hexanediyl)dioxydianiline is an aromatic diamine monomer characterized by a flexible aliphatic linker connecting two p-aminophenoxy groups. Its molecular formula is C₁₈H₂₄N₂O₂, and it contains a six-carbon hexamethylene spacer between the two ether-linked aromatic rings. Each aromatic ring carries a primary amino group at the para position, making the molecule bifunctional and reactive in step-growth polymerization reactions. The combination of rigid aromatic rings and a flexible aliphatic linker allows the monomer to impart both mechanical strength and flexibility to polymers derived from it.

Compounds like 4,4'-(1,6-Hexanediyl)dioxydianiline belong to the class of aromatic diamines with ether linkages, which are widely used in the synthesis of high-performance polymers such as polyimides, polyamides, and poly(ether imide)s. The primary amino groups react readily with diacid chlorides, dianhydrides, or diisocyanates to form amide, imide, or urea linkages during polymerization. The ether linkages in the monomer contribute to increased solubility and processability of the resulting polymers, while the aliphatic hexamethylene spacer reduces chain rigidity relative to entirely aromatic diamines, allowing for tailored flexibility and thermal behavior in the polymer.

The synthesis of 4,4'-(1,6-Hexanediyl)dioxydianiline typically involves the formation of ether bridges through nucleophilic aromatic substitution or Williamson ether synthesis, followed by reduction of nitro precursors to yield the diamine. For example, 4,4'-(1,6-hexanediyl)dinitrophenoxy derivatives can be reduced using catalytic hydrogenation to generate the corresponding diamine. Analytical techniques such as nuclear magnetic resonance spectroscopy and elemental analysis are used to confirm the structure and purity of the synthesized compound.

In materials science, this monomer is primarily used as a research chemical to produce specialty polymers with desired mechanical and thermal properties. Its bifunctional nature and flexible spacer make it suitable for creating polymers with improved solubility, controlled flexibility, and thermal resistance. Incorporation of the hexamethylene-linked aromatic diamine into polyimides or polyamides allows chemists to tune properties such as glass transition temperature, crystallinity, and chain mobility, making it a valuable tool in advanced polymer design.

Beyond polymer synthesis, the primary amino groups in 4,4'-(1,6-Hexanediyl)dioxydianiline can be derivatized to produce imines, amides, or other functionalized molecules, expanding its utility in organic synthesis and materials research. Its combination of aromatic rigidity, ether linkages, and flexible aliphatic segments exemplifies the design principles used to balance thermal stability, mechanical strength, and processability in high-performance polymer chemistry.

Overall, 4,4'-(1,6-Hexanediyl)dioxydianiline is a versatile bifunctional aromatic diamine monomer. Its structure, featuring para-substituted amino groups on ether-linked aromatic rings connected by a six-carbon aliphatic spacer, enables its use in advanced polymer synthesis and research applications where tailored mechanical, thermal, and solubility properties are desired.

References

2021. Self-assembly of bis-[1]rotaxanes based on diverse thiourea-bridged mono-functionalized dipillar[5]arenes. Journal of Inclusion Phenomena and Macrocyclic Chemistry, 100(3-4).
DOI: 10.1007/s10847-021-01103-4

2009. 4,4'-(Hexane-1,6-diyldi-oxy)dianiline. Acta Crystallographica Section E, 65(5).
DOI: 10.1107/s160053680901321x