Organic Chemistry III

Organic Dye Chemistry

Organic Chemistry Division

Chemistry Study Program
Pakuan University
Muhamad Alif Hamimdal, Ssi., MEng
References

Gordon, P.F., and Gregory, P., Organic Chemistry in Colour, Berlin Heidelberg:
Springer-Verlag, 1987.

Christie, R. M., Colour Chemistry 2nd Ed., Cambridge: Royal Society of Chemistry,
2015.

McMurry, J. Organic Chemistry 8th Ed., California: Brooks/Cole, 2012.

Komiya, N., Kashiwabara, T, Iwata, S., Naota, T. , J. Organomet. Chem. 2013, 738,
66–75.
The Concept of Color – Colored Objects

Object

In colored objects, the color we see is actually the combination of un-absorbed visible
lights that pass through or reflected by a certain object. The appeared color is called
complimentary color.

Phenolphthalein
λABS = ~553 nm (green)
Color: Red-Purple

Light absorption is strongly related with the structure of a molecule. Especially if it has a
conjugated π-bonds. The absorption wavelength can be measured by a
spectrophotometer.
 The Concept of Color – Color-Changing Moieties

Electron-donor groups: -CH3, -OH, -OCH3, -NH2, -N(CH3)2, etc.

Electron-accepting groups: -CF3, -COOH, -COOCH3, -SO3, etc.
The compound parts that are responsible to the visibility of colors are called chromophores.
Addition of auxochromes to the chromophores lead
to the shift of colors, and sometimes the shift is
closely related to the auxochrome position.

λABS = ~486 nm λABS = ~501 nm

Color: Greenish-blue Color: Blue
 The Concept of Color – Color-Changing Explanation
The Valence Bond (VB) Theory

Without electron donor(s) or acceptor(s), the chromophores can perform resonance in order
to stabilize itself by delocalizing electrons.

8 e-

-N(Me)2 give their electrons to the chromophores to make resonance easier. Such species is
called electron donor.
 The Concept of Color – Color-Changing Explanation
The Valence Bond (VB) Theory

6 e-

-NO2 pulls the electrons to itself. This action also makes the resonance easier. Such species is
called electron acceptor.

λABS = ~320 nm λABS = ~385 nm λABS = ~332 nm

- Effect of electron donor and acceptor can be seen here; Both donor and acceptor addition in
one ring leads to the bathochromic shift from the original azo dye.
- The effect of donor is bigger here, because carbon in the far right is still having 8 electrons.
- In –NO2-attached dye, the carbon in far right is having an electron deficiency, thus unstable.
 The Concept of Color – Color-Changing Explanation
The HOMO-LUMO Theory
Energy
-1.60 eV
LUMO

ΔE = 3.39 eV, ~366 nm

HOMO
-4.99 eV

- Every molecule has its HOMO (highest occupied molecular orbital) and LUMO (lowest
unoccupied molecular orbital). Electron excitation from HOMO to LUMO requires energy.
If the absorbed energy is in the range of visible light, we can see color.
- Usually, HOMO is related with the electron/charge donor, while the LUMO is related with
the charge/electron acceptor.
 The Concept of Color – Color-Changing Explanation
The HOMO-LUMO Theory
Energy
-1.55 eV
LUMO

ΔE = 3.09 eV, ~401 nm

HOMO
-4.64 eV

Addition of electron donor or acceptor can change the energy of HOMO and/or LUMO.
 The Concept of Color – Color-Changing Explanation
The HOMO-LUMO Theory
Energy

LUMO LUMO
-1.60 eV -1.55 eV
ΔLUMO = 0.05 eV

b
a ΔE = 3.09 eV,
LUMO HOMO
ΔE = 3.39 eV, ~401 nm
Contributor Contributor
~366 nm
HOMO ΔHOMO = 0.35 eV
Electron -4.64eV
donor HOMO
-4.99 eV
Electron
donor
LUMO HOMO
contributor contributor
- Addition of electron donor in HOMO contributor greatly increase the energy of HOMO.
- Addition of electron donor in LUMO contributor partly increase the energy of LUMO.
- The opposite effect happens in electron acceptor group
 The Concept of Color – Tinctorial Strength

- Tinctorial strength is a strength of observed color. It is economically important because it

can reduce the amount of dyes used for the same color.
- Tinctorial strength can be seen in its absorption spectra. If the spectrum has a wide area
(like Dye B), it has a stronger tinctorial strength, even though its intensity (ε) is sometimes
lower than dye A.
- Tinctorial strength can be increased by creating a long donor-acceptor system in a
molecule because the dipole moment will be stronger.
Azo Dyes – Structure

Aniline yellow Butter yellow Chrysodine Methyl red

(for oil colorant or lacquer) (paper or leather colorant) (you know what it is for)

- By far the most used dyes, with approximately 50% of the available dye in the
market, because of their strong, various, and durable color and easiness to prepare.
- Known for the red, yellow, and orange dyes
- However, they have some drawbacks such as duller shade, especially for blue color.

cis- isomer Trans-isomer Bismarck brown

(leather, wool, and cotton colorant)
A diazo compound

- Azo dyes must have N=N bond with at least 1 benzene rings.
- Typically more stable in its trans- form than its cis- form. Why?
Azo Dyes – Substitution Effects
a. b. c.

λmax = ~320 nm λmax = ~387 nm λmax = ~414 nm

d. e.

λmax = ~439 nm λmax = ~486 nm

The general phenomenon can be seen as follows:

- Azo dyes without substituents usually has the lowest λabs
- Addition of electron-donating group in 1 ring (compare a to b) increases the λabs
- Addition of electron-donating group with hydrogen-bond ability (compare a, b, and
c) increases the λabs even more
- Addition of electron donor and acceptor in different rings (d) give a complete donor-
acceptor system, thus the λabs becomes much higher
- Usage of a stronger electron donor (e) also makes the λabs even higher. The opposite
effect happens in weaker donor/acceptor groups.
Synthesis of Azo Dyes – Sandmeyer Reaction
Anthraquinone Dyes – Structure

CI Disperse Blue CI Acid Blue Alizarin CI Acid Violet

- The second-popular dyes after azo
due to economic reasons
- Famous for its excellent property for
bright blue colorant
- Known as a dye with outstanding
light fastness ability
- Slightly more difficult to synthesize
than azo
- Most absorbance of plain
anthraquinone lies on UV region or
stronger
- The absorption that is responsible
for yellow color is located above
400 nm. This is too small that
sometimes undetected by workers
Anthraquinone Dyes – Substitution Effects
- Anthraquinone gives more response
to 1-substitution than 2-substitution
- The addition of strong electron
donor gives a stronger effect on
increasing the λmax
- The addition of electron acceptor
gives weaker effect, compared to
electron donor species

- Addition of two or more electron

donor species gives an even stronger
bathochromic effect
- Attaching electron donor and
acceptor in the same ring disrupts
the electron-donating ability, thus
reduce the bathochromic effect
Anthraquinone Dyes – Synthesis
Anthracene Oxidation Route (HNO3 or H2CrO4)

[O]

Friedl-Craft Acillation Route

heat
AlCl3 H2SO4

oleum oleum
120 °C 120 °C
Indigo Dyes – Structure

Indigo Thioindigo Tyrian purple

- One of the oldest known dyes

- Popular dyes in jeans, because it is easy to fade, but still showing blue color
- Poor solubility and high boiling point (390–392 °C)

Indigo dye is unique because it shows different colors in different phases

Indigo Dyes – Substitution Effect

Electron donor in 5,5’ gives stronger bathochromic effect, while electron accepting
group does that in 6,6’ position.
Indigo Dyes – Synthesis
N-Cyanomethyl Route

Friedl-Craft Acillation
Nitro and Nitroso-Derived Dyes – Stucture

Picric acid Martius yellow Naphthol yellow S Fast disperse yellow 2 K

(dye for HCN analysis) (dye for erythrocyte analysis) (used to be a food colorant) (fiber colorant)
explosive
Nitro-based dyes are small molecules with 1 to 3 benzene rings attached to nitro (–NO2)
group(s), accompanied by –OH and/or –NH2 groups. Usually providing yellow, brown, and
orange colors.

Nitroso-based dyes are a metal complex of ortho-nitroso naphtols and/or phenols.

These types of dyes are not commonly used anymore because of low tinctorial strength
caused by its low absorbance intensity.
Nitro-Derived Dyes – Substitution Effects

Nitro-diphenylamine dyes can also change color depending on the location of -NO2
group. Here, nitro-diphenylamines are compared with their analogue: aniline.
Nitro-Derived Dyes – Substitution Effects

Absorption Spectra of selected nitro-diphenylamines. The hidrogen bond between –NO2

and NH in ortho-position stabilizes the LUMO, thus the HOMO-LUMO gap gets closer
Nitro-Derived Dyes - Synthesis

Picric acid

Maritus yellow

Some simple nitro dyes can be made by electrophilic substitution reaction (OrgChem I).
The reactions shown above is a reverse-thinking method of synthesis.

Attachment of aniline can be made by nucleophilic substitution reaction.

Nitro-Derived Dyes – Some Exceptions

Some of these nitro dyes do not follow the common VB rule; -NH2 group in meta-
position of –NO2 group makes the λmax higher, while the –NH2 group in ortho- and
para- position lowers the λmax.
Other Types of Dyes
Diphenylmethane

Michel’s hydrol blue Bindschedler’s green

Auramine O
λmax = ~607.5 nm λmax = ~725 nm
λmax = ~430 nm
εmax = 147500
Used for dyeing ink, leather, and paper

Triphenylmethane

Malachite green Phenolphthalein

λmax = ~621 nm λmax = ~553 nm
εmax = 104000
Other Types of Dyes
Xanthene

Such compound are

famous for their strong
fluorescence ability,
but their light fastness
are poor
Fluorescein
Rhodamine 6G
λmax = ~490 nm
λmax = ~535 nm