Preparative synthesis of vinyl diamondoids

Article abstract of DOI:10.1080/00397911.2012.667491

We describe a convenient four-step preparation of 1-vinyl adamantane, 1-vinyl diamantane, and 4,9-divinyl diamantane from the respective diamondoid acetic acids in 50-80% isolated yields involving esterification, reduction, and hydrobromination/dehydrobromination. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications to view the free supplemental file.

Full text of DOI:10.1080/00397911.2012.667491

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Preparative Synthesis of Vinyl Diamondoids
a b
a
a
a
Andrey A. Fokin , Ekaterina D. Butova , Anastasiya V. Barabash , Nhan N. Huu
,
b
b
b
Boryslav A. Tkachenko , Natalie A. Fokina & Peter R. Schreiner
a
Department of Organic Chemistry, Kiev Polytechnic Institute, Kiev, Ukraine
b
Institute of Organic Chemistry, Justus-Liebig University, Giessen, Germany
Accepted author version posted online: 27 Dec 2012.
To cite this article: Andrey A. Fokin , Ekaterina D. Butova , Anastasiya V. Barabash , Nhan N. Huu , Boryslav A. Tkachenko ,
Natalie A. Fokina & Peter R. Schreiner (2012): Preparative Synthesis of Vinyl Diamondoids, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, DOI:10.1080/00397911.2012.667491
To link to this article: http://dx.doi.org/10.1080/00397911.2012.667491
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PREPARATIVE SYNTHESIS OF VINYL DIAMONDOIDS
1
,2
1
1
1
Andrey A. Fokin , Ekaterina D. Butova , Anastasiya V. Barabash , Nhan N. Huu ,
2
2
2,
Boryslav A. Tkachenko , Natalie A. Fokina , Peter R. Schreiner
1
2
Department of Organic Chemistry, Kiev Polytechnic Institute, Kiev, Ukraine, Institute
of Organic Chemistry, Justus-Liebig University, Giessen, Germany
Institute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 58, D-
3
5392 Giessen, Germany Fax: +49-0641-99-34309 E-mail: aaf@xtf.kpi.ua,
prs@org.chemie.uni-giessen.de
Abstract
We describe a convenient four-step preparation of 1-vinyl - adamantane, 1-
vinyldiamantane, and 4,9-divinyl-diamantane from the respective diamondoid acetic
acids in 50–80% isolated yields involving esterification, reduction, and
hydrobromination/dehydrobromination.
Supplemental materials are available for this article. Go to the publisher’s online edition
of Synthetic Communications® to view the free supplemental file.
4
steps
R
CO H
R
=
2
50–80%
KEYWORDS: diamondoids, diamondoid acetic acids, vinyl derivatives
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INTRODUCTION
Diamondoids belong to a class of polycyclic hydrocarbons that not only reproduce part of
the diamond crystal lattice, but also resemble the fragments of the hydrogen-terminated
diamond surface.[1-3] The growing interest to diamondoid derivatives was triggered by
[4]
[5]
[6]
their isolation from natural sources and by their potential use as ligands, polymers,
and pharmaceuticals.[7, 8] It was shown recently that diamondoid thiols are able to form
self-assembled monolayers on metal surfaces.[9] The material thus obtained may be used
for the construction of monochromatic photocathodes, reproducing the negative electron
affinity of natural diamond, but with much higher quantum efficiency.[9, 10]
Unsaturated functional groups are often used for the deposition of organic molecules onto
semiconductor surfaces (Si or Ge).[11] Thus, the development of new methods for the
preparation of unsaturated diamondoid derivatives (primarily vinylic and acetylenic) is of
great importance for developments in nanoelectronics. Unfortunately, despite substantial
efforts, the convenient preparation of vinyl diamondoids has not been developed yet.
Several procedures were suggested for the preparation of 1-vinyl adamantane (1) and all
of them are problematic for laboratory practice. For instance, dehydrogenation of 1-ethyl
[
12]
adamantane in the presence of Fe
2
O
3
-K
2
CO
3
-Cr
2
O
3
or Cr-Al catalyst at 520 °С in the
gas phase gave the desired product in very low yields.[13] The synthesis of 1 from
adamantane 1-carbaldehyde through Wittig reaction[14] or through the reduction of 1-
ethinyl adamantane with diisobutyl aluminium hydride[15] is cumbersome. Compound 1
was also obtained from the oxime of methyl 1-adamantyl ketone in low yield,[16] through
the pyrolysis of N,N-dimethyl adamantylethyl amine with 30% Н
2
О
2
in presence of
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[
17]
palladium at 200 °С, or through the reductive cleavage of adamantane-containing
phenyl sulfones.[18] Alternatively, procedures based on the thermal decomposition of l-
(
adamantyl)ethyl S-methyl xanthate,[19, 20] pyrolysis of adamantane-containing alcohols in
presence of boric acid,[21] or reaction of 1-propenyl adamantane with ethylene in the
presence of ruthenium and aluminum oxides were utilized.[22]
RESULTS AND DISCUSSION
We suggest two new methods for the preparation of 1 (Scheme 1) and its higher
congeners based on the respective diamondoidyl carboxylic or acetic acids. The later
approach is characterized by a number of substantial advantages over all existing
procedures and may be recommended as a general way for the preparation of vinyl
diamondoids. We tested the first method for the preparation of 1 starting from
commercially available 1-adamantane carboxylic acid (2). The reduction of 2 through the
respective methyl ester gave alcohol 3 followed by the oxidation to aldehyde 4.[14]
Further Corey methylenation gave oxirane 5, whose ring opening with excess HBr gave
dibromide 6. The debromination of 6 with Zn-powder in DMF under heating gave the
desired 1 in total 54 % yield (from 2). Method А, despite the high preparative yield and
its potential scalability, still contains some bottleneck steps, e. g., the instability of
aldehyde 4, utilization of the chromium-containing oxidant (PCC), and the high
temperature required for the 6 → 1 debromination.
We therefore developed an alternative way (Method B, Scheme 2) starting from the
methyl esters of commercially available 1-adamantyl acetic acid (7) and 1-diamantyl
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acetic acid (8) prepared in accordance to the literature procedure.
[23]
The transformations
include the acid-catalyzed esterification of 7 and 8, reduction to the respective alcohols 9
and 10, exchange for halogen with 45% HBr in the presence of catalytic amounts of
H SO that gives the respective bromides 11 and 12. These three steps proceed with
2
4
quantitative yields. Dehydrobrominations of bromides 11 and 12 with tBuOK in DMSO
or in t-BuOH gave vinyl diamondoids 1 and 13 in, respectively, 90 and 65 % yield.
We also extended out protocol for the incorporation of the two vinyl fragments into the
diamondoid cage. The resulting structures may potentially be used as nanowires for
connecting semiconductor contact surfaces. We started from the 4,9-diamantane diacetic
acid, which was prepared from 4,9-dihydroxy diamantane (14) through the reaction with
[
24]
CH =CCl /H SO . Methylation gave methyl diester 15, which, after reduction to 16,
2
2
2
4
hydrobromination to 17 and dehydrobromination, gave 4,9-divinyl diamantane (18) in
3% preparative yield (Scheme 3).
7
In summary, we developed a simple and effective new procedure for the preparation of
diamondoid mono- and divinyl derivatives that is characterized by high preparative
yields. It allows the incorporation of unsaturated substituents even into the sterically
hindered 1-positions of the diamondoid cages as it was shown on the example of 1-
vinyldiamantane (13) preparation. We currently examine the properties of semiconductor
surfaces modified with vinyl diamondoids that are now available in multigramm
quantities through the procedure described in Schemes 2 and 3.
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EXPERIMENTAL
General
The NMR spectra were recorded with a Bruker Advance II spectrometer, the chemical
shifts are given in ppm relative to TMS. GC–MS analyses were performed with an
HP5890 GC with an HP5971A mass-selective detector. High resolution mass spectra
were recorded on a Finnigan MAT 95 instrument. The full experimental details with
spectroscopic characterization of new compounds are provided in the Supplementary
Information, available online.
General Procedure For Esterification Of Carboxylic Acids
A solution of 10 mmol of the respective acid in 30 mL of dry methanol and 1 mL of 95%
H SO stirred under reflux for 10 h, most of the methanol was evaporated in vacuum, the
2
4
residue was diluted with 10 mL of water, extracted with ether (3 х 15 mL). The combined
extracts were washed with water, brine, and dried over Na SO . Evaporation of the
2
4
solvent gave the respective methyl ester (99%) that was used for further transformations
without additional purifications.
General Procedure For The Reduction Of Methyl Esters (Preparation Of Hydroxy-
Derivatives 9, 10, And 16)
A solution of the respective methyl ester (10 mmol or 5 mmol in case of diester 15) in the
minimal amount of dry ether was added dropwise under stirring and cooling to the
suspension of 40 mmol of LiAlH in 100 mL of dry ether. The reaction mixture was
4
stirred under reflux for 20 h, cooled and quenched with 5% HCl under stirring and
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cooling. The reaction mixture extracted with ether (5 х 20 mL), the combined extracts
were washed with water, brine, and dried over Na SO . Evaporation gave the respective
2
4
alcohols in > 98% yields.
General Procedure For Hydrobromination Of Alcohols (Preparation Of Bromides
1, 12, And 17)
1
A mixture of the respective hydroxy-derivatives (5 mmol), 20 mL of 45% HBr, and 1 mL
of 95% H SO was stirred under reflux for 10 h. The cooled mixture was diluted with 10
2
4
mL of water and extracted with hexane (3 х 15 mL). The combined extracts were
washed with water, brine, and dried over Na SO . The residue after the evaporation of the
2
4
solvent was filtered through the layer of silica (hexane) to give 98% of the respective
bromides as white crystalline solids.
General Procedure For Dehydrobromination Of Bromides (Preparation Of Vinyl
Derivatives 1, 13, And 18)
A mixture of 2 mmol of the respective bromide (1 mmol of dibromide 17), 8 mmol of t-
BuOK (2 mmol for bromide 11) in 10 mL of dry DMSO or t-BuOH was stirred at 80 °С
for 1–24 h. After cooling, dilution with 10 mL of water the reactions mixture was
extracted with hexane (3 х 20 mL). The combined extracts were washed with water,
brine, and dried over Na
2
SO . The residue after the evaporation of the solvent was
4
filtered through the layer of silica (pentane) to give the respective vinyl derivative 1, 13,
or 18.
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ACKNOWLEDGMENT
This work was supported by the Ukrainian Basic Research Foundation, Ministry of
Science and Education of Ukraine, and the Department of Energy, Office of Basic
Energy Sciences, Division of Materials, Science and Engineering under Contract DE-AC-
76SF00515.
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[
[
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Scheme 1. The preparation of 1-vinyl adamantane (1) from adamantane-1-carboxylic
acid (2) (Method A).
O
+
1
. CH OH, H
3
S
2
. LiAlH
PCC
4
O
O
OH
OH
Br
2
5
3
6
4
1
HBr, H SO
Zn
2
4
DMF
Br
O
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1
0

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Scheme 2. The preparation of 1-vinyl adamantane (1) and 1-vinyl diamantane (13) from
the respective 1-diamondoid acetic acids 7 and 8.
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1
1

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Scheme 3. The preparation of 4,9-divinyl diamantane (18).
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1
2