Hexahelicene

1.Introduction

Hexahelicene (Phenanthro[3,4-c]phenanthren; [6]Helicene) is a molecule composed of six ortho-

condensed benzene rings. The rings aren’t arraigned planar, because the terminal benzenes occupy
the same room (the image above isn’t correct). They are constructed as a helix and so they get the
name “Helicene”. The structure allows the molecule to do a left- or a right turn.

Another nomenclature for helicenes, which only consists of carbon-atoms, is all-benzene-helicene.

In this case it is possible to name it by indicating the number of benzene rings in box brackets and
ending with the structure description “Helicene”.
To differentiate the enantiomers it is necessary to use the CIP-nomenclature

The two enantiomers of [6]Hexahelicene (1):

It is important to look at the helix

axes to define chirality. If it turns to
the left, away from the viewer, it is
a M (minus) helix. If it turns to the
right, it is a P (plus) helix. It is a
special feature of helicenes to be
chiral, without having a chirality
center.

Author: Kerstin Bathon, Christin Hamm, Ruven Jilly, Benjamin Betz

The orientation of [6]helicene could be shown schematic by using three levels (2).

X-ray crystallography illustrates an angel

between the blue and the red level of
58.5°. In the molecule-core the six carbon-
carbon bounds are 1.437+0.004 Å, in
opposite to the carbon-carbon bounds,
which are parallel and peripheral, they are
1.334+0.007 Å long.

2. Physical Dates

Molecular formula: C26H16

Molar mass: 328,413 g/mol
Melting point: 230 + 1°C
Density: 1.2715 + 0.0035 g/ml
Crystal structure: Rhombic
Amount of rotaion [α]D25°C: 3640° (-)
in CHCl3 3707° (+)

CAS-No.: 187-83-7

Author: Kerstin Bathon, Christin Hamm, Ruven Jilly, Benjamin Betz

3. Synthesis of hexahelicene

This paragraph shows us different synthesizes for preparing hexahelicene.

The first helicene was synthesized by Melvin S. Newman and Daniel Lednicer in 1955:

The condensation of 1-naphthaldehyde with Diethylmanolate afforded (2) in 70% yield. The yields
of (3) by addition of the grignard reagent from 1-bromonaphthalene to (2) varied unpredictably
between 35% and 56%. Reduction of (3) afforded pure (4) in 90% yield. Conversion of the latter to
(6) was carried out in high over-all yield without purification of (5) or the corresponding dinitrile.
Interestingly, the hydrolysis of the dinitrile by sulfuric in acetic acid was incomplete even after
prolonged refluxing. However, alkine hydrolysis for one hour in ethylen glycol at reflux afforded
the acid (6) in high yield. Cyclization of (6) to (7) bye anhydrous hydrogen fluoride proceeded in

Author: Kerstin Bathon, Christin Hamm, Ruven Jilly, Benjamin Betz

65-70% yield, the remaining product being a neutral glass. When pure (7) was dissolved in
hydrogen fluoride it could be quantitatively recovered. The only fair yield obtained in this type of
cyclization which ordinarily proceeds in high yield foreshadowed the increasing difficulties which
were to be met in the synthesis because of the increasing steric strains gradually being introduced
into the molecule.
The ketoacid (7) was reduced to (8) in 87% yield by the Huang-Minlon procedure. There was found
in this case, as well as in several others, that the long periods of heating often recommended are not
necessary.
The cyclization of the reduced acid (8) proved difficult. The ring closure of the acid chloride of (8)
to (9) in 55% yield was finally accomplished by heating at 90° for one hour with stannic chloride in
ODCB.
The conversion of (9) to hexahelicene (11) was effected by several different routes, the best of
which comprised reduction to the hexahydro derivative (10) followed by hydrogen transfer to
benzene over 5% rhodium-on-alumina at 300°.
The arise from (7), they must have the same stereochemistry unless isomerism occurred during the
reaction of (7), a possibility that is unlikely.

Eleven years later, Bogaert-Verhoogen and Martin synthesized [6] helicene by using liquid
potassium, as you see at the illustration.

The reagent could be made by an

addition reaction from 2-(3-
Phenanthro)-aceticacid and
1-bromnaphthalene-2-aldehyde
in sodium acetate. In this case the yield
is 44%

Today hexahelicene is synthesized with higher yield by an oxidation photocyclization of a stilbene-

type in phenanthrene. This reaction was discovered by Wood and Mallory in 1964 and was the
breakthrough for preparing [6] helicene in a important scale.

This illustration shows the photocyclization of hexahelicene:

Author: Kerstin Bathon, Christin Hamm, Ruven Jilly, Benjamin Betz

In the year 2005 Shawn K. Collins, Alain Grandboi, Martin P. Vachon and Jolie Côté synthesized
hexahelicene by using metathesis reaction for ring closure.
In a simple way metathesis can be pictured like this:

A-B + C-D → A-D + C-B

It is necessary to use a catalytic transition-metal-complex to reach this reaction. Robert Grubbs

developed an air stable Grubbs-Catalyst. This metathesis-reaction is an important tool for organic-
chemistry.

The illustration shows the reaction to hexahelicene with the metathesis-reaction.

In CH2Cl2 under microwave irradiation

60min, 80% yield

in Benzene at 40°C, 24h, 70% yield

The rate is 100% (identified by NMR) with a yield of 80%/70%

Author: Kerstin Bathon, Christin Hamm, Ruven Jilly, Benjamin Betz

4. Dividing the racemates

A special optical active π-complexing-agent were synthesized to divide both racemates: TAPA
(Tetranitrofluorenylidenaminooxypropionic acid). This molecule forms a charge-transfer-complex
with electron-rich aromatic compounds.

The making of TAPA:

TAPA only builds charge-transfer-complexes with (+)-hexahelicene and stays in a solution of

benzene/ethanol. The opposite is (-)-hexahelicene. It is indissoluble.

References:

- K. Peter C. Vollhardt, Organische Chemie; 1 Auflage; 1988; page 1189

- R. H. Martin, Angew. Chem. 1974, 86, 727; Angew. Chem.-Int. Edit. Engl. 1974, 13, 649
- http://www.uni- saarland.de/uploads/media/Aromaten_und_Heteroaromaten_WS_2008-
2009.pdf
- http://www.chemgapedia.de/vsengine/vlu/vsc/de/ch/12/oc/vlu_organik/stereoch
emie/weitere_chiralitaetselem.vlu/Page/vsc/de/ch/12/oc/stereochemie/helicale_
chiralitaet/helicale_chiralitaet.vscml.html
- Journal; Hahn; ACCRA9; Acta Crystallographica; 11; 1958; 825; DOI:
10.1107/S0365110X58002310; ISSN: 0365-110X
- Newman, M.S. &Lednicer, D. (1956). J. Amer.Chem. Soc. 78, 4765
- Angew. Chem. Int. Ed. 2006, 45, 2923 –2926

Author: Kerstin Bathon, Christin Hamm, Ruven Jilly, Benjamin Betz