Naphthalenetetracarboxylic dianhydride

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Naphthalenetetracarboxylic dianhydride
Naphthalenetetracarboxylic dianhydride.svg
Names
Preferred IUPAC name
Naphtho[1,8-cd:4,5-cd′]dipyran-1,3,6,8-tetrone
Other names
  • 1,4,5,8-Naphthalenetetracarboxylic dianhydride
  • Naphthalene-1,4,5,8-tetracarboxylic anhydride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.001.221 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • C1=CC2=C3C(=CC=C4C3=C1C(=O)OC4=O)C(=O)OC2=O
Properties
C14H4O6
Molar mass 268.180 g·mol−1
AppearanceBeige powder
Melting point >300 °C (572 °F; 573 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Naphthalenetetracarboxylic dianhydride (NTDA) is an organic compound related to naphthalene. The compound is a beige solid. NTDA is most commonly used as a precursor to naphthalenediimides (NDIs) (such as napthalenetetracarboxylic diimide), a family of compounds with many uses. [1]

Contents

Synthesis and structure

Synthesis of NTDA NaphDianhydeSyn.png
Synthesis of NTDA

Naphthalenetetracarboxylic dianhydride is prepared by oxidation of pyrene. Typical oxidants are chromic acid and chlorine. The unsaturated tetrachloride hydrolyzes to enols that tautomerize to the bis-dione, which in turn can be oxidized to the tetracarboxylic acid. [2]

Structure of NTDA. Distances in angstroms: O1 - C4, 1.182; O2 - C4, 1.375; O2 - C5, 1.365; O3 - C5, 1.189; C4 - C6, 1.494; C5 - C7, 1.494. Ntda crys struc.jpg
Structure of NTDA. Distances in angstroms: O1 – C4, 1.182; O2 – C4, 1.375; O2 – C5, 1.365; O3 – C5, 1.189; C4 – C6, 1.494; C5 – C7, 1.494.

Naphthalene diimides

Symmetrical naphthalene diimides are synthesized by the condensation reaction of primary amines and the dianhydride. Unsymmetrical derivatives, i.e. those derived from two different amines, are obtained by hydrolysis of one of the two anhydride groups prior to the condensation with the first amine.

These diimides are members of a broader class of compounds called rylenes, oligomers of naphthalene with bonds between the 1 and 1' and 8 and 8' positions. The resulting materials have rigidly planar, highly conjugated cores. They exhibit good processing characteristics for fabrication of soft electronic devices. Aside from the NDIs, other members include the diimide derivatives of perylene-3,4:9,10-tetracarboxylic dianhydride and terrylene-3,4:11,12-tetracarboxylic dianhydride. [4]

Synthesis of symmetric and unsymmetric NDIs NDIpreps.png
Synthesis of symmetric and unsymmetric NDIs

Naphthalene diimides (NDIs) are often fluorescent, although the intensity is sensitive to substituents. NDIs are also redox-active, forming stable radical anions near -1.10 V vs. Fc/Fc+. [1] Their ability to accept electrons reflects the presence of an extended conjugated ring system and the electron withdrawing groups (carbonyl centers). NDIs are used in supramolecular chemistry due to their tendency to form charge-transfer complexes with crown ethers, e.g. to give rotaxanes and catenanes. As another consequence of their planar structure and electron-acceptor properties, NDIs intercalate into DNA.

A range of amines can be condensed with the dianhydride. For example, two useful pigments of the perinone class are generated by condensation with phenylenediamine. A variety of ligands with NDI backbones have also been prepared. [5]

Related Research Articles

In chemistry, amines are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia, wherein one or more hydrogen atoms have been replaced by a substituent such as an alkyl or aryl group. Important amines include amino acids, biogenic amines, trimethylamine, and aniline. Inorganic derivatives of ammonia are also called amines, such as monochloramine.

<span class="mw-page-title-main">Amide</span> Organic compounds of the form RC(=O)NR′R″

In organic chemistry, an amide, also known as an organic amide or a carboxamide, is a compound with the general formula R−C(=O)−NR′R″, where R, R', and R″ represent any group, typically organyl groups or hydrogen atoms. The amide group is called a peptide bond when it is part of the main chain of a protein, and an isopeptide bond when it occurs in a side chain, such as in the amino acids asparagine and glutamine. It can be viewed as a derivative of a carboxylic acid with the hydroxyl group replaced by an amine group ; or, equivalently, an acyl (alkanoyl) group joined to an amine group.

Ferrocene is an organometallic compound with the formula Fe(C5H5)2. The molecule is a complex consisting of two cyclopentadienyl rings bound to a central iron atom. It is an orange solid with a camphor-like odor, that sublimes above room temperature, and is soluble in most organic solvents. It is remarkable for its stability: it is unaffected by air, water, strong bases, and can be heated to 400 °C without decomposition. In oxidizing conditions it can reversibly react with strong acids to form the ferrocenium cation Fe(C5H5)+2.

<span class="mw-page-title-main">Porphyrin</span> Heterocyclic organic compound with four modified pyrrole subunits

Porphyrins are a group of heterocyclic macrocycle organic compounds, composed of four modified pyrrole subunits interconnected at their α carbon atoms via methine bridges (=CH−). In vertebrates, an essential member of the porphyrin group is heme, which is a component of hemoproteins, whose functions include carrying oxygen in the bloodstream. In plants, an essential porphyrin derivative is chlorophyll, which is involved in light-harvesting and electron transfer in photosynthesis.

<span class="mw-page-title-main">Imine</span> Organic compound or functional group containing a C=N bond

In organic chemistry, an imine is a functional group or organic compound containing a carbon–nitrogen double bond. The nitrogen atom can be attached to a hydrogen or an organic group (R). The carbon atom has two additional single bonds. Imines are common in synthetic and naturally occurring compounds and they participate in many reactions.

<span class="mw-page-title-main">Imide</span> Class of chemical compounds

In organic chemistry, an imide is a functional group consisting of two acyl groups bound to nitrogen. The compounds are structurally related to acid anhydrides, although imides are more resistant to hydrolysis. In terms of commercial applications, imides are best known as components of high-strength polymers, called polyimides. Inorganic imides are also known as solid state or gaseous compounds, and the imido group (=NH) can also act as a ligand.

<span class="mw-page-title-main">Polyimide</span> Class of polymers

Polyimide is a polymer containing imide groups belonging to the class of high-performance plastics. With their high heat-resistance, polyimides enjoy diverse applications in roles demanding rugged organic materials, e.g. high temperature fuel cells, displays, and various military roles. A classic polyimide is Kapton, which is produced by condensation of pyromellitic dianhydride and 4,4'-oxydianiline.

<span class="mw-page-title-main">1,8-Bis(dimethylamino)naphthalene</span> Chemical compound

1,8-Bis(dimethylamino)naphthalene is an organic compound with the formula C10H6(NMe2)2 (Me = methyl). It is classified as a peri-naphthalene, i.e. a 1,8-disubstituted derivative of naphthalene. Owing to its unusual structure, it exhibits exceptional basicity. It is often referred by the trade name Proton Sponge, a trademark of Sigma-Aldrich.

<span class="mw-page-title-main">Michael addition reaction</span> Reaction in organic chemistry

In organic chemistry, the Michael reaction or Michael 1,4 addition is a reaction between a Michael donor and a Michael acceptor to produce a Michael adduct by creating a carbon-carbon bond at the acceptor's β-carbon. It belongs to the larger class of conjugate additions and is widely used for the mild formation of carbon-carbon bonds.

<span class="mw-page-title-main">Organic acid anhydride</span> Any chemical compound having two acyl groups bonded to the same oxygen atom

An organic acid anhydride is an acid anhydride that is also an organic compound. An acid anhydride is a compound that has two acyl groups bonded to the same oxygen atom. A common type of organic acid anhydride is a carboxylic anhydride, where the parent acid is a carboxylic acid, the formula of the anhydride being (RC(O))2O. Symmetrical acid anhydrides of this type are named by replacing the word acid in the name of the parent carboxylic acid by the word anhydride. Thus, (CH3CO)2O is called acetic anhydride.Mixed (or unsymmetrical) acid anhydrides, such as acetic formic anhydride (see below), are known, whereby reaction occurs between two different carboxylic acids. Nomenclature of unsymmetrical acid anhydrides list the names of both of the reacted carboxylic acids before the word "anhydride" (for example, the dehydration reaction between benzoic acid and propanoic acid would yield "benzoic propanoic anhydride").

<span class="mw-page-title-main">Benzil</span> Chemical compound

Benzil (i.e. Bz2, systematically known as 1,2-diphenylethane-1,2-dione) is the organic compound with the formula (C6H5CO)2, generally abbreviated (PhCO)2. This yellow solid is one of the most common diketones. Its main use is as a photoinitiator in polymer chemistry.

<span class="mw-page-title-main">Fluorene</span> Chemical compound

Fluorene, or 9H-fluorene is an organic compound with the formula (C6H4)2CH2. It forms white crystals that exhibit a characteristic, aromatic odor similar to that of naphthalene. It has a violet fluorescence, hence its name. For commercial purposes it is obtained from coal tar. It is insoluble in water and soluble in many organic solvents. Although sometimes classified as a polycyclic aromatic hydrocarbon, the five-membered ring has no aromatic properties. Fluorene is mildly acidic.

In chemistry, transfer hydrogenation is a chemical reaction involving the addition of hydrogen to a compound from a source other than molecular H2. It is applied in laboratory and industrial organic synthesis to saturate organic compounds and reduce ketones to alcohols, and imines to amines. It avoids the need for high-pressure molecular H2 used in conventional hydrogenation. Transfer hydrogenation usually occurs at mild temperature and pressure conditions using organic or organometallic catalysts, many of which are chiral, allowing efficient asymmetric synthesis. It uses hydrogen donor compounds such as formic acid, isopropanol or dihydroanthracene, dehydrogenating them to CO2, acetone, or anthracene respectively. Often, the donor molecules also function as solvents for the reaction. A large scale application of transfer hydrogenation is coal liquefaction using "donor solvents" such as tetralin.

<span class="mw-page-title-main">Organocopper chemistry</span> Compound with carbon to copper bonds

Organocopper chemistry is the study of the physical properties, reactions, and synthesis of organocopper compounds, which are organometallic compounds containing a carbon to copper chemical bond. They are reagents in organic chemistry.

<span class="mw-page-title-main">DOTA (chelator)</span> Chemical compound

DOTA (also known as tetraxetan) is an organic compound with the formula (CH2CH2NCH2CO2H)4. The molecule consists of a central 12-membered tetraaza (i.e., containing four nitrogen atoms) ring. DOTA is used as a complexing agent, especially for lanthanide ions. Its complexes have medical applications as contrast agents and cancer treatments.

Organosodium chemistry is the chemistry of organometallic compounds containing a carbon to sodium chemical bond. The application of organosodium compounds in chemistry is limited in part due to competition from organolithium compounds, which are commercially available and exhibit more convenient reactivity.

<span class="mw-page-title-main">Rylene dye</span> Dye based on the rylene framework of naphthalene units

A rylene dye is a dye based on the rylene framework of naphthalene units linked in peri-positions. In homologues additional naphthalene units are added, forming compounds — or poly(peri-naphthalene)s — such as perylene, terrylene and quarterrylene.

<span class="mw-page-title-main">Pyromellitic dianhydride</span> Chemical compound

Pyromellitic dianhydride (PMDA) is an organic compound with the formula C6H2(C2O3)2. It is the double carboxylic acid anhydride that is used in the preparation of polyimide polymers such as Kapton. It is a white, hygroscopic solid. It forms a hydrate.

<span class="mw-page-title-main">Naphthalenetetracarboxylic diimide</span> Chemical compound

Naphthalenetetracarboxylic diimide (NTCDI) is a solid organic compound and one of the simplest naphthalenediimides (NDIs). NTCDI is produced from the parent naphthalene via an intermediate compound naphthalenetetracarboxylic dianhydride.

Non-fullerene acceptors (NFAs) are types of acceptors used in organic solar cells (OSCs). The name Fullerene comes from another type of acceptor-molecule which was used as the main acceptor material for bulk heterojunction Organic solar cells. Non-fullerene acceptors are thus defined as not being a part of this sort of acceptors.

References

  1. 1 2 Bhosale, Sheshanath V; Jani, Chintan H; Langford, Steven J (2008). "Chemistry of naphthalene diimides". Chem. Soc. Rev. 37 (2): 331. doi:10.1039/b615857a. PMID   18197349.
  2. F. Röhrscheid "Carboxylic Acids, Aromatic" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2012. doi : 10.1002/14356007.a05_249
  3. Yasutake, Mikio; Fujihara, Takashi; Nagasawa, Akira; Moriya, Keiichi; Hirose, Takuji (2008). "Synthesis and Phase Structures of Novel π-Acceptor Discotic Liquid Crystalline Compounds Having a Pyrenedione Core". European Journal of Organic Chemistry. 2008 (24): 4120. doi:10.1002/ejoc.200800360.
  4. Zhan, Xiaowei; Facchetti, Antonio; Barlow, Stephen; Marks, Tobin J; Ratner, Mark A; Wasielewski, Michael R; Marder, Seth R (2011). "Rylene and Related Diimides for Organic Electronics". Advanced Materials. 23 (2): 268. doi:10.1002/adma.201001402. PMID   21154741.
  5. Pan, Mei; Lin, Xiao-Ming; Li, Guo-Bi; Su, Cheng-Yong (2011). "Progress in the study of metal–organic materials applying naphthalene diimide (NDI) ligands". Coordination Chemistry Reviews. 255 (15–16): 1921. doi:10.1016/j.ccr.2011.03.013.