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LIBRARY
Michigan State
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This is to certify that the
thesis entitled

PHOTOCYCLIZATION OF SUBSTITUTED a-(O-
ETHYLPHENYL)ACTETOPHENONES AND a-(O-
TOLYL)ACETOPHENONES

presented by

Linging Wang

has been accepted towards fulﬁllment
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Master of degree in Department of Chemistry

 

 

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2/05 c:/CIRC/DateDue.indd-p.15

PHOTOCYCLIZATION OF SUBSTITUTED
a-(O—ETHYLPHENYL)-ACETOPHENONES AND
(HO-TOLYL)ACETOPHENONES

By

Lingling Wang

A THESIS

Submitted to
Michigan State University
In partial fulfillment of the requirements
for the degree of

MASTER OF SCIENCE
Department of Chemistry

2005

Abstract

PHOTOCYCLIZATION OF SUBSTITUTED
q-(O-ETHYLPHENYL)-ACETOPHENONES AND
(HO-TOLYL)ACETOPHENONES

By
Lingling Wang
The photochemistry of several substituted d-arylacetophenones was
investigated. These ketones undergo intramolecular 6-hydrogen abstraction to
form 1, 5 biradicals, which upon cyclization form indanols as photoproducts.
The intramolecular OH-to-benzene ring hydrogen bonding in the preferred
conformation of such 1,5 biradical intermediate effects the photochemical
behavior of these ketones. Tuning up the strength of such intramolecular
hydrogen bonding is achieved by putting different ring substituents on the
benzene ring. It turns out that an electron-donating methoxy group increases
the product diastereoselectivity of the substituted q-(o-ethylphenyl)
acetophenone by strengthening the above-mentioned hydrogen-bonding in
reaction intermediate, while an electron-withdrawing cyanide group has
exactly the opposite effect on diastereoselectivity. Temperature also effects
product diastereoselectivity of these ketones.
Substituent also has an effect on steady-state photokinetics of
d-arylacetophenones. The electron-donating methoxy group tends to increase
the quantum yield and fasten the hydrogen abstraction while

electron-withdrawing cyanide group has the opposite effects.

ACKNOWLEDGMENTS

First, i would like to give my warmest thanks to my advisor Prof. Peter J.
Wagner. Thanks a lot for his help and guidance throughout my graduate study,
both academic and personal.

Then, I also appreciate the National Science Foundation and Michigan State
University for financial support in forms of teaching and research
assistantships.

Special thanks also go to all the people working in Wagner’s lab: Yana,
Jason and Ali. I sincerely thank these group members for their warm help and
advice on my project.

I’d also like to thank the amazing friends I’ve made here, especially Zhenjie,
Yu, Ziyang, Jun, Lei, meng and Xiaoyu. Those pleasant moments shared with
you will always be shining in my memory.

Finally, I extend the most sincere gratitude to my family, my husband Haojun,
my parents and my two cousins and their family members. Without their
unfailing support and love, I would not have been able to go through the over

two years of research and study and finish this thesis.

TABLE OF CONTENTS

LIST OF FIGURES ........................................................................... iv
LIST OF TABLES ............................................................................ v
LIST OF SCHEMES ......................................................................... vii
INTRODUCTION .............................................................................. 1

l. BIRADICAL BEHAVIOR DURING PHOTOCYCLIZATION OF
a-ARYLACETOPHENONES ............................................................... 1
II. GOALS OF RESEARCH ................................................................. 5
RESULTS ....................................................................................... 7
I. GENERAL PREPARATION OF THE KETONES ................................... 7
II. IRRADIATION OF KETONES .......................................................... 7
III. STEADY-STATE PHOTOKINETICS ................................................. 13
DISCUSSION .................................................................................. 15
I. THE REASON FOR NON-REACTIVITY OF a-(2-ETHYL-5-NlTRO-PHENYL)
ACETOPHENONE TOWARD IRRADIATION ................................................. 15

II. TEMPERATURE AND SUBSTITUENT EFFECT ON PRODUCT
DIASTEREOSELECTIVITY IN PHOTOCYCLIZATION OF

a-(O-ETHYLPH ENYL)ACETOPH ENON ES .................................................... 17
Ill. SUBSTITUENT EFFECT ON STEADY-STATE PHOTOKINETICS OF 0-
(O-ETHYLPHENYL)- ACETOPHENONES AND

a-(O-TOLYL)-ACETOPHENON ES ................................................................. 1 9
EXPERIMENTAL21
I. GENERAL PROCEDURES ......................................................................... 21
II. PREPARATION OF STARTING KETONES .............................................. 21
a-(2-Ethyl-5-nitrophenyl)acetophenone ...................................................... 21
q-(5-Cyano-2-ethylphenyl)acetophenone ................................................... 24
a-(2-Ethyl-5-methoxyphenyl)acetophenone ................................................ 27
q-(5-Cyano-2-methylphenyl)acetophenone ................................................ 32
q-(2-Methyl-S-methoxyphenyl)acetophenone ............................................. 35
III. PHOTOCHEMICAL EXPERIMENTS AND PROCEDURES ...................... 41
A. Purification of Chemicals .......................................................................... 41
B. Equipment and procedures ...................................................................... 41
C. Identification of photoproducts ................................................................. 42
D. Quantitative Measurements ..................................................................... 53
REFERENCES ............................................................................................... 63

List of Figures
Figure 1. 1H NMR of d-(5-Cyano-2-ethylphenyl)acetophenone Before and After
Irradiation in Benzene-d6 (A> 290 nm) ............................................................. 45

Figure 2. 1H NMR of d-(2-Ethyl-5-methoxyphenyl)acetophenone Before and
After Irradiation in Benzene-d6 (A> 290 nm) .................................................... 48

Figure 3. 1H NMR of a-(5-Cyano-2-methylphenyl)acetophenone Before and
After Irradiation in Benzene-d6 (A> 290 nm) .................................................... 50

Figure 4. 1H NMR of d-(2-Methyl-5-methoxyphenyl)acetophenone Before and
After Irradiation in Benzene-d6 (A> 290 nm) .................................................... 52

Figure 5. Stern-Volmer Plot from Quenching Study of
a-(5-Cyano-2-ethylphenyl)acetophenone ....................................................... 59

Figure 6. Stern-Volmer Plot from Quenching Study of
d-(2-Ethyl-5-methoxyphenyl)acetophenone ................................................... 60

Figure 7. Stern-Volmer Plot from Quenching Study of
a-(5-Cyano-2-methylphenyl)acetophenone .................................................... 61

Figure 8. Stern-Volmer Plot from Quenching Study of
a-(2-Methyl-5-methoxyphenyl)acetophenone ................................................ 62

List of Tables

Table 1. Solvent effect on cyclization diastereoselectivity of
a—(o-Ethylphenyl)acetophenone ....................................................................... 3

Table 2. Chemical yields and ratios of photoproducts from ketone 2 in
benzene-d6 at various temperatures (A>290 nm) ........................................... 11

Table 3. Chemical yields and ratios of photoproducts from ketone 3 in
benzene-d5 at various temperatures (A>290 nm) ........................................... 12

Table 4. Lifetimes of Triplet Acetophenones in Benzene ............................... 14

Table 5. Quantum Yields of Photoproducts from Acetophenones in Benzene
(measured at 313nm) ..................................................................................... 14

Table 6. Arrhenius Data from Graph 1 ........................................................... 19
Table 7. Cyclization quantum yield and rate of hydrogen abstraction of
non-substituted and some substituted d-(o-Ethylphenyl)- acetophenones and

(MO -Tolyl)acetophenones ............................................................................ 20

Table 8. Product Quantum Yield of d-(5-Cyano-2-ethylphenyl)acetophenone in
Benzene ......................................................................................................... 55

Table 9. Product Quantum Yield of q-(2-Ethyl-5-methoxyphenyl)acetophenone
in Benzene ..................................................................................................... 56

Table 10. Product Quantum Yield of d-(5-cyano-2-methylphenyl)acetophenone
in Benzene ..................................................................................................... 57

Table 11. Product Quantum Yield of d-(5-methoxy-2-methylphenyl)
acetophenone in Benzene ............................................................................. 58

Table 12. Quenching of the Indanol Formation in o-(5-Cyano-2-ethylphenyl)
acetophenone ................................................................................................ 59

Table 13. Quenching of the Indanol Formation in d-(2-Ethyl-5-methoxyphenyl)
acetophenone ................................................................................................ 60

Table 14. Quenching of the Indanol Formation in o-(5-Cyano-2-methylphenyl)
acetophenone ................................................................................................ 61

vi

Table 15. Quenching of the Indanol Formation in d-(2-Methyl-S-methoxyphenyl)
acetophenone ................................................................................................ 62

vii

List of Schemes

Scheme 1. Formation of 2-Phenyl-2-indanol from Irradiation of a—(o—Tolyl)
acetophenone ................................................................................................ 1

Scheme 2. Formation of Z- and E-1-Methyl-2-phenyI-2-indanol from Irradiation
of a-(o-Ethylphenyl)acetophenone ................................................................. 2

Scheme 3. Biradical Conformations during Cyclization of o-(o-Ethylphenyl)
acetophenone ................................................................................................. 4

Scheme 4. Chemical Shifts ( in CDCI3)of Methyls Trans and Cis to Phenyl in
Five-Membered Rings ..................................................................................... 9

Scheme 5. Photochemistry of d-(S-Cyano-Z—ethylphenyl)acetophenone ...... 10
Scheme 6. Photochemistry of a-(2-Ethyl-5-methoxyphenyl)acetophenone...11
Scheme 7. Photochemistry of d-(5-Cyano-2-methylphenyl)acetophenone....13
Scheme 8.Photochemistry of q-(5-Methoxy-2-methylphenyl)acetophenone..13

Scheme 9. Disproportionation of 1,5 biradical to the Ground State Ketone

during Irradiation of a-(2-Ethyl-S-nitrophenyl)acetophenone .......................... 16
Scheme 10. Preparation of a-(2-EthyI-5-nitrophenyl)acetophenone .............. 22
Scheme 11. Preparation of q-(S-Cyano-2-ethylphenyl)acetophenone ........... 24

Scheme 12. Preparation of q-(2-Ethyl-5-methoxyphenyl)acetophenone ....... 28
Scheme 13. Preparation of q-(5-Cyano-2-methylphenyl)acetophenone ........ 32

Scheme 14. Preparation of d-(2-Methyl-S-methoxyphenyl)acetophenone ..... 36

viii

INTRODUCTION

l. Biradical Behavior during Photocyclization of a-Arylacetophenones
It has been reported by Wagner et. al. that a—(o—tolyl)acetophenone undergoes
very efficient n,1T* triplet state cyclization in benzene via 6-hydrogen atom

abstraction to form 2-phenyI-2-indanol with quantum yield equal to unity. ‘

 

 

 

Disproportionation

II
0 0* '
CH2
Ph Ph 6-H dro e
O m 0 abstraction

1,5-biradical

Ill
H-O

 

 

OH Coupling
, <
O .3.

Scheme 1. Formation of 2-PhenyI-2-indanol from Irradiation of a-(o-Tolyl)

 

acetophenone.
The 100% quantum yield indicates that the 1, 5-biradical intermediate

undergoes no reactions that compete effectively with cyclization. The preferred

conformation of the 1, 5-biradical intermediate is stabilized by intramolecular OH-

2 as shown in scheme 1, and this

to-benzene ring hydrogen bonding
conformation can prevent reversion of the biradical intermediate to the ground
state ketone via disproportionation. Thus high quantum efficiency of cyclization
was observed.

a-(o-Ethylphenyl)acetophenone, however, undergoes photocyclization with
quantum yield smaller than 100%,3 which indicates that disproportionation back

to the ground state ketone is now competing with cyclization process for the

corresponding 1, 5-biradical intermediate.

0 O 0 HO
Ph Ph 6-Hydrogen JrPh
pm 0 abstraction> I \
/

 

 

1,5-biradical
CH3 pol—'3 Cou Iin
OH OH
Z-1-methyI-2-phenyI-2-lndanol E-1 -methyl-2-phenyI-2-indanol

Scheme 2. Formation of Z- and E-1-MethyI-2-phenyl-2-indanol from

Irradiatlon of a—(o-Ethylphenyl)acetophenone.

Furthermore, the diastereoselectivity of the two cyclization products is
solvent-dependent, as shown in table 1, with the one having its methyl and
phenyl group trans to each other being favored.

Table 1. Solvent effect on cyclization diastereoselectivity‘ of a-(o-

Ethylphenyl)acetophenone 3' 4

 

 

 

Solvent Z-indanoll E-indanol Ratio
Benzene 14.6:1 (0.48)b
Methanol 2:1

 

 

 

 

aIrradiation under room temperature.

b Product quantum yield in parentheses.

Analysis of the possible biradical conformations indicates that in the biradical
intermediate, the stereochemistry is set prior to cyclization,5 as shown in scheme

3:

HO

.uPh
@ﬂ-Cw

H

Z-1-methyl-2-phenyl-2-Indanol

 

Ph

ﬁnIOH
; CH3
Fl

E-1-methyl-2-phenyI-2-Indanol
Scheme 3. Biradical Conformations during Cyclization of a-(o-Ethylphenyl)
acetophenone.
In the above scheme, BRz, BR; and BRx are computed to be the three
minimum energy geometries of the intermediate 1, 5-biradical. BRz and
BRE can undergo least motion cyclization to Z and E indanols, respectively,

while BRx must rotate into one of the other two in order to cyclize.

Furthermore, BRz is calculated to be 1.6 kcanol more stable than BRE.

This can be understood by both steric and electronic point of views:

1) Sterically speaking, the phenyl group on one radical center prefers to be
twisted away from the central benzene ring and the methyl group on the other
radical center prefers to be twisted away from the large ortho substituent, so
they tend to end up trans to each other when the two biradical ends rotate
together.

2) Electronically speaking, the intramolecular O-H-to-benzene ring hydrogen
bonding in the BRz conformation helps stabilize the BRz conformer. 6' 7
There is no such hydrogen bonding in BRE conformer.

The first point was supported by the fact that diastereoselectivity decreases

dramatically when solvent changing from benzene to methanol. Since in

methanol, the OH group is solvated by hydrogen bonding, it is now comparable
in size to the phenyl group such that the two rotamers (BRz and BRE) are nearly

equal in energy.

II. Goal of Research

The goal of this research work is to get experimental results to support
the hypothesis that O-H-to-benzene ring hydrogen bonding in the biradical
conformations formed during irradiation of a-arylacetophenones have

stabilization effect for the conformers.

To achieve this goal, changes of the strength of the abovementioned
intramolecular hydrogen bonding have been made by putting different ring
substituents onto the a-aryl ring, both electron-withdrawing and electron-donating.

Diastereoselectivity of the photocyclization products have been measured for
two substituted a-(o-Ethylphenyl) acetophenones. And the results have been
compared to the product diastereoselectivity of their non-substituted analog to
see the effect of hydrogen bonding on product diastereoselectivity.

Since this kind of intramolecular hydrogen bonding can prevent reversion of
the biradical intermediate to the ground state ketone via disproportionation, the
quantum yield of photocyclization is also expected to be effected when the
strength of this intramolecular hydrogen bonding changes. So quantum yields of
cyclization have been measured for the abovementioned two substituted d-(o-
ethylphenyl)acetophenones and the results have been compared with their non-
substituted analog. At the same time, cyclization quantum yields of two
substituted d-(o-tolyl) acetophenones have also been measured to see if the
values change in the same trend as their a-(o—ethylphenyl) analogs.

Furthermore, different substituents on the a-aryl ring can also affect the rate of
hydrogen abstraction. 5 So the rates have been calculated for those substituted
d-(o-ethylphenyl)-and a-(o-tolyl)acetophenones by measuring triplet lifetimes of

biradicals using quenching study.

RESULTS

I. General Preparation of the Ketones

Substituted a-(o-Ethylphenyl)-acetophenones and d-(o-tolyl)acetophenones
were similarly prepared from the corresponding substituted 2-bromo-1-
ethylbezne and 2-bromotoluene by coupling with acetophenone using palladium

( ll) catalyst. 8-9 As a result, the following compounds were prepared and used in

this study.
Ph Ph Ph
0 o O o D 0
N02 CN OMe
1 2 3

Ph Ph
0 0 O 0
CN OMe
4 5

ll. Irradiation of ketones
NMR scale irradiations were carried out on 0.1M solutions of ketones in

deuterated benzene. In order to achieve n, rt* excitation, the ketones were

irradiated through Pyrex (>290 nm) filter. A medium pressure mercury arc lamp
served as the light source. For substituted d-(o-ethylphenyl)-acetophenones, 2
and 3, they were irradiated at 0°C, room temperature (25 °C ), 45 °C and 75 0C to
determine the effect of temperature on product ratios. The desired temperatures
were attained by ice-water, water (at room temperature) and heated silicon oil
baths, respectively. For substituted a-(o—TolyI)-acetophenones, they were only
irradiated at room temperature( 25 °C ). In most cases, the starting ketones
disappeared within 24 hours’ irradiation with the apprearance of corresponding 2-
phenyl-2-indanols as the photoproducts and material balance were > 95%.
Ketone 1 is an exception, after irradiation for 20 days at room temperature, no
change in 1HNMR was observed.

Chemical yields were measured by irradiating 0.02M solutions of ketones in
purified benzene at room temperature (25°C). Silica gel column chromatography
was used to separate and purify the photoproducts.

For substituted q-(o-Ethylphenyl)-acetophenones 2 and 3, the structure
assignments of the diastereomeric photoproducts were straightfonivard. Methyl
doublet at 0.6-1.5ppm were most informative since it is generally accepted that a
methyl cis to the phenyl is significantly shielded relative to one trans, as
previously observed in a number of such products. ‘0' "' ‘2 For example, in
photoproducts from d—(o-Ethylphenyl)-acetophenone, the chemical shifts of
methyl group of E isomer was shifted much more upfield than that of Z isomer, as

shown in scheme 4 .

00 °“ 00
.. ,

H ’CH3 CH3
3.32ppm 0.72ppm 3.47ppm 1 .16ppm
E-isomer Z-isomer

Scheme 4. Chemical Shifts ( in CDCI3)of Methyls Trans and Cis to Phenyl in

Five-Membered Rings.

1. a-(2-EthyI-5-nitrophenyl)acetophenone (1)
After 20 days’ irradiation at room temperature in benzene, no significant

change in 1H NMR compared with the ketone reactant was observed.

2. a-(S-Cyano-z-ethylphenyl)acetophenone (2)

Under various irradiation temperatures, the starting ketone disappeared after
15-24 hours’ irradiation with the corresponding appearance of diastereomeric
mixtures of 2-phenyl-2-indanols. Quantitative analysis of chemical yields and
photoproduct ratios were achieved by NMR analysis of the resulting mixtures.

Preparative scale irradiation of 2 followed by column chromatography on silica
resulted in separation of the two products which were identified as two isomeric
2-phenyl-2-indanols ( 2indZ and 21ndE) by their NMR spectra in CDCI3

(Scheme 5).

 

 

Ph NC
0 Benzener - P“ + O. ph

H EH3

CN / \ / H C\H
3.46ppm 0.80ppm 3.58ppm 1.27ppm
2 2indE 2indZ

Scheme 5. Photochemistry of a-(5-Cyano-2-ethylphenyl)acetophenone.
NOE experiments also confirmed this assignment. For the photoproduct having
methyl doublet at 0.80ppm, this doublet was irradiated and enhancement
resonance of aromatic protons was observed. It indicates that the methyl and
phenyl ring are cis to each other in this product. The methyl doublet at 1.27ppm
for the other photoproduct was also irradiated and no such enhancement was
observed. Instead, irradiation of the methine quartet at 3.58ppm leaded to
enhancement resonance of aromatic protons, which indicates the hydrogen in
methine and the phenyl ring are cis to each other.
Quantitative analysis of product ratio at several temperatures was achieved by
irradiating 0.1M solution of 2 in benzene-d6 through a Pyrex filter followed by

NMR analysis. Table 2 shows the result of temperature effect study for ketone 2.

10

Table 2. Chemical yields and ratios of photoproducts from ketone 2 in

benzene-dc at varlous temperatures (It>290 nm)

 

 

 

 

 

Temperature(°C) %2indE %2indZ 2/ E ratio
0 9.9 89.3 9.0
25 10.4 89.2 8.6
45 1 1.9 87.6 7.4
75 14.1 85.6 6.1

 

 

 

 

 

 

3. a-(2-Ethyl-5-methoxyphenyl)acetophenone (3)

Irradiation of a 0.1 M solution of 3 in benzene-d6 resulted in formation of two
isomeric 2-phenyl-2-indanols (31ndZ and 3indE, Scheme 6). Preparative scale
irradiation of 2 in benzene followed by column chromatography on silica resulted
in separation of the two products, which were identified from their corresponding
NMR spectra in CDCI3, each isomer showing a methyl doublet, a methine quartet
and an AB quartet signal with coupling constants similar to previously identified
indanols. 3' ‘3' 14The NMR signal of the cis methyl appears at 1.21ppm while that

of the trans methyl appears at 0.77ppm.

00 °” ..
Benzene - 9P“ + “pr.

 

H I’CH3 ’
3.35ppm 077me 3.51 ppm 1.21 ppm
3 3indE 3in¢ﬂ

Scheme 6. Photochemistry of a-(2-EthyI-5-methoxyphenyl)acetophenone.

11

NOE experiments also confirmed this assignment. For the photoproduct having
methyl doublet at 0.77ppm, this doublet was irradiated and enhancement
resonance of aromatic protons was observed. It indicates that the methyl and
phenyl ring are cis to each other in this product. The methyl doublet at 1.21ppm
for the other photoproduct was also irradiated and no such enhancement was
observed. Instead, irradiation of the methine quartet at 3.51ppm led to
enhancement resonance of aromatic protons, which indicates the hydrogen in
methine and the phenyl ring are cis to each other.

The product ratios were determined by intergration of the methyl doublet signals
of each isomer. Chemical yields and product ratios under several reaction

temperatures are listed in Table 3.

Table 3. Chemical yields and ratios of photoproducts from ketone 3 in

benzene-dc at various temperatures (b290 nm)

 

 

 

 

 

Temperature(°C) %3indE %3indZ Z/E ratio
0 4.6 94.4 20.5
25 5.1 94.0 18.3
45 5.9 93.7 16.0
75 6.0 93.4 15.7

 

 

 

 

 

 

4. a-(5-Cyano-2-methylphenyl)acetophenone (4)

12

Irradiation of 0.1M solution of 4 in benzene-d6 at room temperature results in
formation of 5-cyano-2-phenyl-indan-2-ol (4ind, Scheme 7) as the only

photoproduct in a quantitative way.

Ph
D hv mum
o = O
Benzene Ph

CN

 

4 4ind

Scheme 7. Photochemistry of a-(5-Cyano-2-methylphenyl)acetophenone.

5. a-(5-Methoxy-2-methylphenyl)acetophenone (5)
Irradiation of 0.1M solution of 5 in benzene-d6 at room temperature results in
formation of 5-methoxy-2-phenyl-indan-2-ol (5ind, Scheme 8) as the only

photoproduct in a quantitative way.

 

Ph
0 “V mono”
o > O
Benzene Ph

5 5ind
Scheme 8. Photochemistry of a-(5-Methoxy-2-methylphenyl)acetophenone.

Ill. Steady-State Photokinetics.

13

The quantum yields were measured by irradiation of degassed solutions of
ketones in tubes containing a fixed amount of internal standard parallel to
valerophenone actinometer15 at 313nm. For quenching studies, these tubes also
contained varying amounts of 2,5-dimethyl-2,4-hexadiene quencher. ‘6 Product
yields around 10% to 20% were measured using GC analysis and were
converted to quantum yields. Stern-Volmer plots ‘7 were linear with slopes equal
to M. The kinetic data are listed in table 4 and 5. Triplet lifetimes, based on a Kq
value of 6x109M“S",18 are also listed. The errors represent deviation of 2-4
measured values from the average.

Table 4. Lifetimes of Triplet Acetophenones in Benzene

 

 

 

 

 

 

Ketones qu , M'1 UT, 109 SI
2 14.49 :I: 0.6 0.41
3 2.54 t 0.1 2.36
4 53.12105 0.11
5 14.89 :I: 0.4 0.40

 

 

 

 

Table 5. Quantum Yields of Photoproducts from Acetophenones in

Benzene (measured at 313nm)

 

 

 

 

 

 

Ketones ‘ ¢cyc.
2 0292:0013
3 0.601 :I:0.013
4 034210.002
5 097810.012

 

 

 

14

 

DISCUSSION

l. The Reason for Non-reactivity of a-(2-Ethyl-5-nitrophenyl)acetophenone
(1) toward Irradiation

UV experiments showed that for 4-ethyI-nitrobenzene, £313nm=132.8, while for
ketone 1, £313nm=241.5 and for a—(o-Ethylphenyl)acetophenone, £313nm=116.9.
The ratio of the values between 4-ethyl-nitrobenzene and ketone 1 is about 55:
100. It indicates that for ketone 1, among every 100 protons it absorbs, there are
55 photons being absorbed by the N02 chromophore, instead of being absorbed
by the carbonyl group. Furthermore, the strong electron-withdrawing effect of the
nitro substituent on o—ethylphenyl ring decreases the nucleophilicity of the
benzene ring thus weaken the OH-to-benzene ring hydrogen bonding in BRz
conformation. The biradical is now easier to reverse back to ground state ketone
via disproportination than when there is strong intramolecular hydrogen bonding
in BRz conformation. These reasons explain partially why photolysis of ketone 1

proceeded at such a slow rate.

15

 

 

 

DIsproportIonationI

 

o 0 \EH HO
Ph Ph

Irradiation 5‘” drogen
" abstraction

.Ph

no2 N02 No2

1 ,5-biradical

 

 

 

Scheme 9. Disproportionation of 1,5 biradical to the Ground State Ketone

during Irradiation of d-(2-Ethyl-5-nitrophenyl)acetophenone.

II. Substituent and Temperature Effect on Product Diastereoselectivity in

Photocyclization of a-(5-Cyano-2-ethylphenyl)acetophenone (2) and q-(2-

Ethyl-S-methoxyphenyl)acetophenone(3)

16

 

1. Substltuent Effect on Product Diastereoselectivity in Photocyclization of
some a-(o-Ethylphenyl)acetophenones

Ali R. Zand studied for the product diastereoselectivity of q-(o-
ethylphenyl)acetophenone. 3 The ratio of Z/E-indanol equals to 14.6 at room
temperature. Having an electron-withdrawing group substituted on the
ethylphenyl ring, a-(5-Cyano-2-ethylphenyl)acetophenone (2) gives a lower
product ratio of 8.6 under same reaction temperature. On the other hand, for a-
(2-Ethyl-5-methoxyphenyl)acetophenone(3), this ratio increases to 18.3.

These experimental results support the hypothesis mentioned in the
introduction part that intramolecular O-H-to-benzene ring hydrogen bonding can
stabilize the BRz conformation shown in scheme Ill. Since electron donating
substituents like methoxy group will increase the nucleophilicity of the benzene
ring and thus enhance the strength of the O-H-to-benzene ring hydrogen bonding,
BRz is more favored over BRE than in the case when there is no substituent on
the benzene ring. So the stereoselectivity of cyclization was enhanced. On the
other hand, an electron withdrawing substituent such as a cyanide group will
have exactly the opposite effect resulting in weaker O-H-to-benzene ring

hydrogen bonding and lower product stereoselectivity.

2. Temperature effect on product Diastereoselectivity
For ketone 2 and 3, the same trend of temperature effect was observed on
photoproduct diastereoselectivity. That is, the selectivity decreases when

temperature goes up. The same trend was also observed for non-substituted

17

 

ketone, d-(o-ethylphenyl)acetophenone, which was studied by Dr. Zand. 3These
results indicate that not only the activation enthalpy difference in BRz and BRE,
but also the entropies may be responsible for the observed diasteroselectivity.
Since BRE conformer is the one with higher rotational freedom, it might be more
favored at higher temperature than when the reaction is running under lower

temperature.

 

F
I:l——'———i"'ﬂﬂiﬂ"—’T’l Orketone 2

L I ketone 3

 

 

 

1nZ/E
T‘IT‘E—‘NNNNNPD
OWNQDP-‘CADUWNLDr—i
I

 

2. 8 3 3. 2 3. 4 3. 6
1000/T

Graph 1. Arrhenius plot of temperature effect for ketones 2 and 3.

Graph 1 shows the Arrhenius plot of ketones 2 and 3 under various irradiation
temperature. According to the Arrhenius equation, K= Ae'Ea/RT, the following
Arrhenius data can be obtained in table 6.

Table 6. Arrhenius Data from Graph 1.

 

 

 

 

Ketone AzlAE AEa, Kcallmole
2 Az/AE=1 .5 EE-Ez=1 .02
3 Az/AE=5.4 EE-Ez=0.73

 

 

 

18

 

III. Substituent Effect on Steady-state Photokinetics of a-(o-Ethylphenyl)
acetophenones and a-(o -Tolyl)acetophenones

When comparing cyclization quantum yields of three d-(o-Ethylphenyl)
acetophenones as shown in Table 6, an obvious trend can be observed. Ketone
2, with an electron-withdrawing cyanide group substituted on the ethylphenyl ring,
has a lower cyclization quantum yield than its non-substituted analog, while
ketone 3 with an electron-donating methoxy group substituted on the same
position has a higher value. A similar trend can be found by comparing
cyclization quantum yields of three a-(o —Tolyl)acetophenones which are also
listed in table 6.

These results again support the hypothesis mentioned in the introduction part
that intramolecular O-H-to—benzene ring hydrogen bonding can stabilize the BRz
conformation shown in scheme 3. The electron-withdrawing cyanide group in
ketones 2 and 4 decreases nucleophilicity of the benzene ring and results in
weaker Hydrogen bonding. An electron donating methoxy group in ketones 3 and
5, on the other hand, strengthen the hydrogen bonding by donating electron
density into the benzene ring. Since such kind of intramolecular hydrogen
bonding can prevent reversion of the biradical intermediate back to the ground
state ketone via disproportionation, a stronger hydrogen-bonding results in a
higher Cyclization quantum yield.

Since the reactive n, n* triplet is a very electron-deficient species, electron-
withdrawing substituents near the C-H bond being attacked strongly decrease

the rate constant and electron-donating substituents increase rate constant. 5

19

That’s exactly what can be seen from the results in table 6. ketones 2 and 4 with

electron-withdrawing cyanide substituted have slower hydrogen abstraction rate

than their non-substituted analog, while ketones 3 and 5 abstract hydrogen faster

than their non-substituted analog.

Table 7. Cyclization quantum yield and rate of hydrogen abstraction of non-

substituted and some substituted a-(o-Ethylphenyl)- acetophenones and a-

(o -Tolyl)acetophenones

 

 

 

 

 

 

 

 

Ketones <1)on 1/r, 109 S‘1
a-(o-Ethylphenyl)acetophenonej 0.48 1 .08
2 0.29 0.41
3 0.60 2.36
u-(o -Tolyl)acetophenone ‘ 1.00 0.16
4 0.34 0.1 1
5 0.98 0.40

 

 

 

20

 

EXPERIMENTAL
I. General Procedures
1H NMR and “’0 NMR spectra were recorded primarily on Varian Unity+-500
and Varian Gemini-300 NMR spectrometers in CDCI3 except where noted. IR
spectrum on a Nicolet lR/42 spectrometer, UV spectra on either a Shimadza UV-
160 or a Hewlett Packard 8453 spectrometer, GC analyses on either a Varian

1400 or a Hewlett Packard 5890 Series II Gas Chromatography.

II. Preparation of Starting Ketones

All new compounds were analyzed by CHN elemental analysis on a Perkin
Elmer Series II CHN S/O Analyser 2400 instrument or by high resolution mass
spectra on a Joel JMS-HX110 Mass spectrometer in the MSU Mass
Spectroscopic facility.
a-(2-Ethyl-5-nItrophenyl)acetophenone (1)

4-nitroethylbezene (Alfa Aesar) was brominated with bromine catalyzed by
iron powder. ‘9 The resulting bromide was coupled with acetophenone using

palladium (ll) catalysis to form ketone 1. 2°

21

Pd(OAC)2(2°/o), PPh3(8°/ )

Br2 ,Fe (cat), 60°C B k
0 (540/0) 0 K2003 (2 SQUIV.),

Acetophenone(1 equiv.)
N02 N02 o-Xylene, A
( 53%)

 

 

N02
1
Scheme 10. Preparation of a-(2-Ethyl-5-nitrophenyl)acetophenone.
2-bromo-4-nltroethylbezene
To a 100mL three-necked round bottom flask equipped with a thermometer, a
condenser, a magnetic stir bar and purged with nitrogen gas, 20.0 grams (0.132
moles) of 4-nitroethylbenzene and 0.6 grams (0.0107mol) of iron (reduced by
hydrogen) was added. The flask was wrapped with aluminum foil and the
reaction was allowed to run in the dark to avoid radical reactions. When
temperature increased to 40°C, 21.6 grams (0.135 moles) of bromine was added
from syringe drop by drop to the flask with stirring. The mixture was allowed to
stir at 60°C for 60 hours. Then the reaction mixture was extracted by ether three
times. The combined ether layer was washed by brine and dried over anhydrous
sodium sulfate. Solvent was then removed to afford 27.02g brown oil. Analysis of
the oil showed it to contain the desired product, the starting material and some

poly-brominated byproducts. Fractional distillation resulted in recovery of 7.8g

22

starting material and 10.09 of desired product (54% yield, based on recovery) as
yellow oil.
1H NMR (CDCI3): 61.24( t, J: 7.5 Hz, 3 H ), 2.83( q, J = 7.5 Hz, 2 H ), 7.38( d, J
= 4.5 Hz, 1 H ), 8.09( d, J: 8.4 Hz, 1 H), 8.38(s, 1 H).
a-(2-EthyI-5-nItrophenyl)acetophenone

To a 100mL three-necked round bottom flask equipped with a thermometer, a
condenser, a magnetic stir bar and purged with nitrogen gas, 0.090 grams
(0.0004 moles) of palladium (ll) acetate, 0.42 grams (0.0016 moles) of
triphenylphosphine and 5.53 grams (0.04 moles) of potassium carbonate was
added. Then 50mL of o-xylene was added by syringe. With stirring, 4.6 grams
(0.02 moles) of 2-bromo-4-nitroethylbezene dissolved in 5 mL of o-xylene was
added by syringe, followed by 2.4 grams (0.02 moles) of acetophenone. The
mixture was refluxed for 96 hours. Then the reaction mixture was extracted by
ether three times. The combined ether layer was washed by brine and dried over
anhydrous sodium sulfate. Solvent was then removed to afford a mixture of
yellow oil. Analysis of the oil showed it to contain the desired product and the
starting materials. After silica gel chromatography (using 15:1 hexane/ethyl
acetate solution as eluent), 2.22 grams of the desired ketone was obtained (53%
yield, based on recovery) together with 1.02 grams of the starting bromide.
1H NMR(CDCI3): 61.21( t, J: 7.5 Hz, 3 H ), 2.63 ( q, J= 7.5 Hz, 2 H ), 4.43( s, 2
H), 7.39(d, J=8.5 Hz, 1 H), 7.51 (t, J=7.5 Hz, 2 H), 7.62(t, J=7.5 Hz,1

H), 8.00-8.04( m, 3 H), 3.10 (dd, J: 8.5, 2 Hz. 1 H)

23

‘30 NMR(CDCI3): 514.5, 26.4, 42.8, 122.8, 128.1, 128.5, 129.2, 129.4, 134.0,
1346,1366, 1464,1509, 196.3

IR (0014): 1688, 1518, 1348, 1211cm"

m.p.: 83.3—84.7 °C

HRMS (FAB): m/z 270.1129 (MH+).

q-(5-Cyano-2-ethylphenyl)acetophenone (2 )

4-Ethylbenzioc acid (Aldrich) was first transformed to the corresponding acyl
chloride with thionyl chloride. 4-Ethylbenzamide was then obtained by reacting
the acyl chloride with aqueous ammonia (3M).21 Dehydration of this amide
furnished 4-ethyloenzonitrile.22 Bromination of the nitrile 23 followed by coupling

with acetophenone using palladium (ll) catalysis 2° gave ketone 2.

 

 

1) 90012
O 2) NH4OH‘ O 500'2' A _ NBS, sto.)
(94%) (78%) (90%)

 

COOH Czo
l
NH2
Br Pd(OAc)2(2%), PPh3(8°/:)
K2003 (2 equiv. ),
Acetophenone(1 equiv.)
CEN o-Xylene, A

Scheme 11. Preparation of a-(5-Cyano-2-ethylphenyl)acetophenone.

24

4-Ethylbenzamide

To a 100 mL round bottom flask equipped with a condenser, a magnetic stir
bar and purged with nitrogen gas, 10 grams of 4-ethylbenzioc acid was added.
The flask was then heated in a water bath. When the temperature of the water
bath reached 50°C, 9 mL of thionyl chloride and 20 drops of dimethylfomamide
were added dropwise with stirring. Then the mixture was stirred for 15 minutes
at 50-60°C until all acid was dissolved. The mixture was then added drop by drop
into 200 mL ice-cold ammonium hydroxide (3M) with stirring. Suction filtration of
the mixture afforded 9.37 grams (94% yield) of product as white solid. This solid
was used without further purification in the next step.
1H NMR (00013): 5 1.13 (t, J: 7.5 Hz, 3 H ), 2.58 (q, J: 7.5 Hz, 2 H), 5.90-6.10

(bs,2H),7.15(d,J=8.4 Hz,2H),7.62(d,J=8.1Hz,2H)

4-ethylbenzonltrile

To a 50 mL round bottom flask equipped with a condenser, a magnetic stir bar
and purged with nitrogen gas, 9.37 grams (0.063 moles) of 4-Ethylbenzamide
and 7 mL (0.096 moles) of thionyl chloride were added. The mixture was refluxed
for 1 hour. The excess thionyl chloride was removed by rotatory evaporator.
Vacuum distillation afforded 6.7g crude product (b.p. = 64-67°C/3mmHg). After
silica gel chromatography (using 80:1 hexane/ethyl acetate solution as eluent),
6.54 grams (78% yield) of pure product was obtained.
1H NMR (00013): 5 1.22 (t, J: 7.5 Hz, 3 H ), 2.68 (q, J: 7.5 Hz, 2 H ), 7.26 (d, J

=7.8Hz,2H),7.53(d,J=8.1Hz,2H)

25

3-bromo-4-ethylbenzonitrile

To a 100 mL round bottom flask equipped with a magnetic stir bar, 6.54
grams (0.050 moles) of 4-ethylbenzonitrile and 30 mL of sulfuric acid aqueous
solution (concentrated sulfuric acid :water = 1:1,v/v) were added. The flask was
wrapped with aluminum foil and the reaction was allowed to run in the dark to
avoid radical reaction. After the mixture was stirred for 10 minutes, 8.9 grams
(0.050 moles) of N-bromo-succinimide was added to the flask slowly over 20
minutes. The mixture was stirred at room temperature for 2 days. Then the
reaction mixture was extracted by ether three times. The combined ether layer
was washed with brine and dried over anhydrous sodium sulfate. Solvent was
removed to afford crude product as a pale-yellow solid. After silica gel
chromatography (using 80:1 hexane/ethyl acetate solution as eluent), 9.43 grams
(90% yield) of pure product was obtained.
1H NMR (CDCI3): o 1.22 (t, J: 7.5 Hz, 3 H ), 2.79 (q, J: 7.5 Hz, 2 H), 7.31 (d, J

=7.8Hz,1H)7.52(d,J=7.2Hz,1H),7.80(s,1H)

a-(5-Cyano-2-ethylphenyl)acetophenone

To a 250 mL three-necked round bottom flask equipped with a thermometer, a
condenser, a magnetic stir bar and purged with nitrogen gas, 0.198 grams
(0.00088 moles) of palladium (ll) acetate, 0.923 grams (0.00352 moles) of
triphenylphosphine and 12.2 grams (0.088 moles) of potassium carbonate was

added. Then 80 mL of o-xylene was added by syringe. With stirring, 9.24 grams

26

(0.044 moles) of 3-bromo-4-ethylbenzonitrile dissolved in 10 mL of o-xylene was
added by syringe, followed by 5.29 grams (0.044 moles) of acetophenone. The
mixture was refluxed for 3 days. Then the reaction mixture was extracted by
ether three times. The combined ether layer was washed with brine and dried
over anhydrous sodium sulfate. Solvent was then removed to afford a mixture of
compounds as a yellow oil. Analysis of the oil showed it to contain the desired
product and the starting materials. After silica gel chromatography (using 40:1
hexane/ethyl acetate solution as eluent), 1.77 grams of the desired ketone was
obtained (30% yield, based on recovery) together with 4.26 grams of the starting
bromide. A

1H NMR(CDCI3): 5 1.19 (t, J: 7.5 Hz, 3 H ) 2.60 (q, J: 7.5 Hz, 2 H ), 4.37 ( s, 2
H ), 7.33 ( d, J: 8.1 Hz, 1 H ), 7.40 ( d, J: 1.5 Hz, 1 H ), 7.48-7.54 (m, 3 H),
7.59 (t, J: 2 Hz, 1H ), 7.99-8.02 ( m, 2 H)

13C NMR(CDCI3): 6 13.9, 25.8, 42.0, 109.6, 118.8, 128.0, 128.6, 128.8, 130.8,
133.4, 133.9, 135.9, 148.2, 196.0

IR (001.): 2228, 1690 cm“

m.p.: 92.9-93.5 °C

HRMS (FAB): m/z 250.1233 (MH+)

a-(2-Ethyl-5-methoxyphenyl)acetophenone (3)
Reduction of 2-bromo-4-nitroethylbenzene formed the corresponding aniline, 2“
which was then subjected to a Sandmeyer reaction to obtain 3-bromo-4-ethyl-

phenol.25 Methylation of the phenol with potassium hydroxide and methyl iodide

27

afforded 3-bromo-4-ethyI-anisole 2° which was coupled with acetophenone using

palladium (II) catalysis 2° to furnish ketone 3.

ET SD, HCI Br 1) H2304, NaNO2O Br Mel, KO:
0 A O 2) ”20 A DMSO

 

 

 

 

°o (70%) 59%
Br Pd(OAc)2(2%), PPh3(8°/:) O
O K2003 (2 equiv. ), 090
Acetophenone(1 equiv.)
OMe o-Xylene, A
(49%) 3

Scheme 12. Preparation of a-(2-EthyI-5-methoxyphenyl)acetophenone.

3-bromo-4-ethyI-aniline

To a 100 mL three-necked round bottom flask equipped with a thermometer, a
condenser, a magnetic stir bar and purged with nitrogen gas, 6.50 grams ( 0.055
moles) of finely divided tin powder and 5.65 grams ( 0.0246 moles) of 2-bromo-4-
nitroethylbenzene was added. The flask was cooled by an ice-water bath while
20 mL of concentrated hydrochloric acid was added dropwise with stirring. The
rate of acid addition was controlled so that the temperature was maintained
below 60 °C. After the initial exothermic portion of the reaction was complete, the

ice water bath was removed and the reaction mixture was refluxed for 40 minutes.

28

After the mixture cooled down to room temperature, 10 M aqueous NaOH
solution was added to make it basic. The organic layer was extracted by other
three times. The combined other layer was washed with brine and dried over
anhydrous sodium sulfate. Solvent was then removed to afford 4.08 grams (81%
yield) of the product as a yellow oil.
1H NMR(CDCI3): 5 1.16, (t, J = 7.5 Hz, 3 H, ), 2.63 (q, J = 7.5 Hz, 2 H ), 3.48-
3.62 ( bs, 2 H), 6.58 (dd, J: 8.4, 2.4 Hz, 1 H ), 6.87 ( d, J: 2.4 Hz, 1 H), 6.98
(d,J=8.1Hz1 H)
3-bromo-4-ethyI-phenol

To a 250 mL three-necked round bottom flask equipped with a thermometer, a
magnetic stir bar and purged with nitrogen gas, 4.97 grams (0.025 moles) of 3-
bromo-4-ethyl-aniline was added. To it was added the hot diluted acid obtained
by adding 4.5 mL of concentrated sulfuric acid into 12.5 mL of water. The clear
solution was stirred and cooled to 15°C. Then 10 grams of ice was added. As
soon as the temperature had dropped below 5°C, a solution of 2.01 grams (0.029
moles) of sodium nitrite in 6 mL of water was added from a syringe, the needle of
which extended below the surface of the liquid. The temperature of the solution
was kept below 5°C during addition. The solution was stirred for 5 minutes after
addition. Then 5 mL of cold water, 0.19 grams of urea and 10 grams of cracked
ice were added successively. The solution was kept in an ice water bath until
used. To another 250 mL three-necked round bottom flask equipped with a
condenser, a magnetic stir bar and purged with nitrogen gas, 9.4 grams of

anhydrous sodium sulfate, 12.5 mL of concentrated sulfuric acid and 6 mL of

29

water were added. The mixture was boiled, them the solution of diazonium salt
was added in portions. The mixture was refluxed for 1 hour. After it was cooled
down to room temperature, the reaction mixture was extracted with two100 mL
portions of ether, and the combined extracts were washed successively with 100
mL of water and 100 mL of 10% sodium bicarbonate solution. The phenol was
then extracted from the ether layer by use of one 100 mL and two 50 mL portions
of 10% NaOH solution. The combined alkaline solutions were acidified, with
cooling, by the addition of 100 mL of concentrated hydrochloric acid. The phenol
was then extracted with one 100 mL and two 50 mL portions of ether. The
combined other layer was washed with brine and dried over anhydrous sodium
sulfate. Solvent was then removed to afford crude product as a brown oil. After
silica gel chromatography (using 6:1 hexane/ethyl acetate solution as eluent),
3.45 grams (70% yield) of the product was obtained.

1H NMR(CDCI3): 5 1.17, (t, J = 7.5 Hz, 3 H ), 2.66 (q, J = 7.5 Hz, 2 H), 5.4-6.0

(bs, 1H ), 6.73 (dd, J: 8.1, 2.4 Hz, 1 H ), 7.04-7.07 ( m, 2 H)

3-bromo-4-ethylanlsole

To a 100 mL round bottom flask equipped with a magnetic stir bar and purged
with nitrogen gas, 3.92 grams (0.07 moles) of powdered potassium hydroxide
and 50 mL of dimethyl sulfoxide were added. After stirring for 5 minutes, 3.45
grams (0.017 moles) of 3-bromo-4-ethyl-phenol was added, followed immediately
by 4.97 grams (0.035 moles) of methyl iodide. Stirring was continued for 3 hours.

Then the mixture was poured into 200 mL of water and extracted three times with

30

100 mL portions of dichloromethane. The combined organic extracts were
washed with brine and dried over anhydrous sodium sulfate. Solvent was then
removed to afford crude product as a brownish red oil. After silica gel
chromatography (using 80:1 hexane/ethyl acetate solution as eluent), 2.17 grams
(59% yield) of the product was obtained.

1H NMR(CDCI3): 6 1.18 (t, J: 7.5 Hz, 3 H, ), 2.68 (q, J: 7.5 Hz, 2 H ), 3.76 ( s,
3 H), 6.79(dd, J=8.6, 2.7 Hz, 1 H), 7.08(d, J=2.7 Hz, 1 H ), 7.11 (d, J=8.4

Hz,1H)

a-(2-EthyI-5-methoxyphenyl)acetophenone

To a 100 mL three-necked round bottom flask equipped with a thermometer, a
condenser, a magnetic stir bar and purged with nitrogen gas, 0.045 grams
(0.0002 moles) of palladium (II) acetate, 0.210 grams (0.0008 moles) of
triphenylphosphine and 2.76 grams (0.02 moles) of potassium carbonate was
added. Then 40 mL of o-xylene was added by syringe. With stirring, 2.17 grams
(0.01 moles) of 3-bromo-4-ethylanisole dissolved in 5 mL of o-xylene was added
by syringe, followed by 1.20 grams (0.01 moles) of acetophenone. The mixture
was refluxed for 24 hours. Then the reaction mixture was extracted with ether
three times. The combined ether layer was washed with brine and dried over
anhydrous sodium sulfate. Solvent was then removed to afford a yellow solid.
Analysis of the solid showed it to contain the desired product and the starting
materials. After silica gel chromatography (using 40:1 hexane/ethyl acetate

solution as eluent), 1.25 grams of the product was obtained (49% yield).

31

1H NMR(CDCI3): 5 1.16 (t, J: 7.5 Hz, 3 H, ), 2.53 (q, J: 7.5 Hz, 2 H ), 3.74 ( s,
3H ), 4.29 (s, 2H ), 6.68 (d, J: 1.5 Hz, 1 H ), 6.78 (dd, J: 8.5, 1.5 Hz, 1 H),
7.15 ( d, J=8.0 Hz, 1 H ), 7.47 ( t, J=7.5 Hz, 2 H ), 7.57 (t, J: 7.5 Hz, 1 H),
8.01 (d, J: 7.0 Hz, 2 H)

‘30 NMR(CDCI3): 5 15.3, 25.5, 43.3, 55.4, 112.9, 116.4, 128.6, 128.9, 129.6,
133.4,134.0,134.9,137.1, 157.9, 197.9lR (001.): 1690, 1261 cm"

m.p.: 53.8-54.5 °c

Anal. Calcd for C17H1302 :C, 80.28; H, 7.13. Found: C, 80.40; H, 7.25.
a-(5-Cyano-2-methylphenyl)acetophenone(4)

p-Toluic acid (Aldrich) was first transformed to the corresponding acyl chloride
with thionyl chloride. p-Toluamide was then obtained by reacting the acyl chloride
with aqueous ammonia (3M).21 Dehydration of this amide furnished p-tolunitrile. 22
Bromination of the nitrile 23 followed by coupling with acetophenone using

palladium (ll) catalysis2° gave ketone 4.

 

 

 

1)SOCb
O 2) NH4OH‘ O SOCI2,A O NBS, st0.,_
(86%) (80%) (69%)
COOH : _
C'; O C:N
NH2
Br Pd(OAc)2(1%), PPh3(4%) O
O . ’ O o
K2003 (2 equ1v.),
= Acetophenone(1 equiv.) CEN
CTN o-Xylene, A
(35%) 4

Scheme 13. Preparation of a-(5-Cyano-2—methylphenyl)acetophenone.

32

p-toluamide

To a 100 mL round bottom flask equipped with a condenser, a magnetic stir
bar and purged with nitrogen gas, 13.6 grams (0.1 moles) of p-Toluic acid was
added. The flask was then heated in a water bath. When the temperature of the
water bath reached 50°C, 13 mL (0.18 moles) of thionyl chloride and 20 drops of
dimethylfomamide were added dropwise with stirring. Then the mixture was
stirred for 15 minutes at 50-60°C until all of the acid was dissolved. The mixture
was then added drop by drop into 100 mL ice-cold ammonium hydroxide (3M)
with stirring. Suction filtration of the mixture afforded 11.62 grams (86% yield) of
the product as white solid. This solid was used without further purification in the
next step.
1H NMR(CDCI3): 5 2.38 ( s, 3 H ), 5.40-6.20 (bs, 2 H ), 7.23 (d, J: 7.5 Hz, 2 H ),

7.68(d,J=8.1Hz,2H)

p-talunitrlle

To a 50 mL round bottom flask equipped with a condenser, a magnetic stir bar
and purged with nitrogen gas, 11.62 grams (0.086 moles) of 4-Ethylbenzamide
and 30 mL of thionyl chloride were added. The mixture was refluxed for 1 hour.
The excess thionyl chloride was removed by rotatory evaporator. Vacuum
distillation afforded 8.07 grams of product (b.p. = 75-80°C/5mmHg) as a pale
yellow oil (80% yield). This oil was used without further purification in the next

step.

33

1H NMR (CDCI3): 5 2.39 ( s, 3 H ), 7.24 ( d, J: 7.8 H22 H), 7.51 (d, J: 8.1

HLZH)

2-bromo-4-cyanotoluene

To a 250 mL round bottom flask equipped with a magnetic stir bar, 16.8 grams
(0.143 moles) of p-tolunitrile and 80 mL of aqueous sulfuric acid solution
(concentrated sulfuric acid :water = 1:1,v/v) were added. The flask was wrapped
with aluminum foil and the reaction was allowed to run in the dark to avoid radical
reactions. After the mixture was stirred for 10 minutes, 25.6 grams of N-bromo-
succinimide (0.143 moles) was added to the flask slowly over 20 minutes. The
mixture was stirred at room temperature for 3 days. Then the reaction mixture
was extracted by other three times. The combined ether layer was washed with
brine and dried over anhydrous sodium sulfate. Solvent was removed to afford
the crude product as a white solid. After silica gel chromatography (using 40:1
hexane/ethyl acetate solution as eluent), 19.44 grams (69% yield) of pure
product was obtained.
1H NMR (CDCI3): 5 2.44 ( s, 3 H ), 7.30 (d, J = 7.8 Hz,1 H ), 7.47 ( dd, J = 8.0,

1.5 Hz, 1 H), 7.78(d,J= 1.5 Hz, 1 H)

a-(5-Cyano-2-methylphenyl)acetophenone
To a 250 mL three-necked round bottom flask equipped with a thermometer, a
condenser, a magnetic stir bar and purged with nitrogen gas, 0.135 grams

(0.0006 moles) of palladium (ll) acetate, 0.630 grams (0.0024 moles) of

34

triphenylphosphine and 16.6 grams (0.12 moles) of potassium carbonate was
added. Then 80 mL of o-xylene was added by syringe. With stirring, 11.82 grams
(0.06 moles) of 2-bromo-4-cyanotoluene dissolved in 20 mL of o-xylene was
added by syringe, followed by 7.21 grams (0.06 moles) of acetophenone. The
mixture was refluxed for 12 days. Then the reaction mixture was extracted by
ether three times. The combined ether layer was washed with brine and dried
over anhydrous sodium sulfate. Solvent was then removed to afford a yellow oil.
Analysis of the oil showed it to contain the desired product and the starting
materials. After silica gel chromatography (using 10:1 hexane/ethyl acetate
solution as eluent), 1.60 grams of the product was obtained (35% yield, based on
recovery) together with recovery of 7.98 grams of the starting bromide.

1H NMR(CDClg): 5 2.28 (s, 3 H), 4.33 ( s, 2 H ), 7.29 ( d, J = 7.5 Hz, 1 H ), 7.40
(s, 1 H ), 7.46 to 7.52 (m, 3 H), 7.61 (t, J: 7.5 Hz, 1 H ), 7.99 to 8.03 (m, 2 H)
130 NMR(CDC13): 5 19.8, 42.6, 109.6, 118.6, 127.9, 128.5, 130.6, 130.7, 133.4,
133.6, 134.6, 136.0, 142.8, 195.6

IR (001.): 2227, 1685 cm"

m.p.: 116.4-117.3 °C

Anal. Calcd for C16H13N02: C, 81.68; H, 5.57; N, 5.95. Found: C, 81.12; H, 5.48;

N, 5.91.
q-(2-Methyl-5-methoxyphenyl)acetophenone (5)

p-Nitrotoluene (Aldrich) was brominated by NBS in concentrated sulfuric acid. 23

Reduction of 2-bromo-4-nitrotoluene 2‘ formed the corresponding aniline, which

35

was then taken in a Sandmeyer reaction to give 3-bromo-4-methyI-phenol.25

Methylation of the phenol with potassium hydroxide and methyl iodide afforded 3-
bromo-4-methyl-anisole,2° which was then coupled with acetophenone using

palladium (ll) catalysis 2° to furnish ketone 5.

 

 

 

 

NBS, H2804 Br SR, HCI Bf
o 0 0
No2 No2 ( °) NH2
1) H2304, NaN02 Br Mel, KOH Br
2) H20, A r DMSO 0
(82 4) OH (87%) We
Pd(OAc)2(2%), PPh3(8%) O

 

K2C03 (2 equiv), O o

Acetophenone(1 equiv.)
o-Xylene, A OMe

(43%) 5

Scheme 14. Preparation of a-(2-MethyI-5-methoxyphenyl)acetophenone.

2-bromo-4-nitrotoluene

To a 250 mL round bottom flask equipped with a magnetic stir bar, 10.0 grams
(0.073 moles) of p-Nitrotoluene and 80 mL of aqueous sulfuric acid solution
(concentrated sulfuric acid :water = 1:1,v/v) were added. The flask was wrapped

with aluminum foil and the reaction was allowed to run in the dark to avoid radical

36

reactions. After the mixture was stirred for 10 minutes, 13.0 grams of N-bromo-
succinimide (0.073 moles) was added to the flask slowly over 20 minutes. The
mixture was stirred at room temperature for 24 hours. Then the reaction mixture
was extracted by other three times. The combined ether layer was washed with
brine and dried over anhydrous sodium sulfate. Solvent was removed to afford
14.66 grams (93% yield) of the product as a yellow solid.

1H NMR (00013): 5 2.48 ( s, 3 H ), 7.38 ( d, J = 8.4 Hz, 1 H), 8.04 (dd, J = 8.3,

2.4 Hz, 1 H), 8.37(d, J=2.4 Hz, 1 H)

3-bromo-4-methyl-aniline

To a 100 mL three-necked round bottom flask equipped with a thermometer, a
condenser, a magnetic stir bar and purged with nitrogen gas, 9.69 grams
(0.0816 moles) of finely divided tin powder and 7.95 grams ( 0.0368 moles) of 2-
bromo-4-nitrotoluene was added. The flask was cooled by an ice-water bath
while 25 mL of concentrated hydrochloric acid was added dropwise with stirring.
The rate of acid addition was controlled so that the temperature was maintained
below 60 °C. After the initial exothermic portion of the reaction was complete, the
ice water bath was removed and the reaction mixture was refluxed for 1 hour.
After the mixture cooled down to room temperature, 20 M aqueous NaOH
solution was added to make it basic. The organic layer was extracted by other
three times. The combined ether layer was washed with brine and dried over
anhydrous sodium sulfate. Solvent was then removed to afford 5.48 grams (80%

yield) of the product as a yellow oil.

37

‘H NMR(CDCI3): 5 2.28 ( s, 3 H ), 3.5-3.6 ( bs, 2H ), 6.52 (dd, J = 8.1, 2.4 Hz, 1

H), 6.88(d, J=2.1 Hz, 1 H), 6.98(d, J=8.1 Hz, 1 H)

3-bromo-4-methyI-phenol

To a 250 mL three-necked round bottom flask equipped with a thermometer, a
magnetic stir bar and purged with nitrogen gas, 5.48 grams (0.0295 moles) of 3-
bromo—4-methyl-aniline was added. To it was added the hot diluted acid obtained
by adding 6 mL of concentrated sulfuric acid into 15 mL of water. The clear
solution was stirred and cooled to 15°C. Then 10 grams of ice was added. As
soon as the temperature had dropped below 5°C, a solution of 2.42 grams (0.035
moles) of sodium nitrite in 7 mL of water was added from a syringe, the needle of
which extended below the surface of the liquid. The temperature of the solution
was kept below 5°C during addition. The solution was stirred for 5 minutes after
addition. Then 6 mL of cold water, 0.24 grams of urea and 15 grams of cracked
ice were added successively. The solution was kept in an ice water bath until
used. To another 250 mL three-necked round bottom flask equipped with a
condenser, a magnetic stir bar and purged with nitrogen gas, 11.2 grams of
anhydrous sodium sulfate, 15 mL of concentrated sulfuric acid and 7.5 mL of
water were added. The mixture was boiled, then the solution of diazonium salt
was added in portions. The mixture was refluxed for 2 hours. After cooled down
to room temperature, the reaction mixture was extracted with two100 mL portions
of ether, and the combined extracts were washed successively with 100 mL of

water and 100 mL of 10% sodium bicarbonate solution. The phenol was then

38

extracted from the ether layer with one 100 mL and two 50 mL portions of 10%
NaOH solution. The combined alkaline solutions were acidified, with cooling, by
the addition of 100 mL of concentrated hydrochloric acid. The phenol was then
extracted with one 100 mL and two 50 mL portions of ether. The combined ether
layer was washed with brine and dried over anhydrous sodium sulfate. Solvent
was then removed to afford 4.50 grams (82% yield) of the product as a brownish
red oil.

1H NMR(CDCI3): 5 2.28 ( s, 3 H ), 6.68 ( dd, J = 8.4, 2.7 Hz, 1 H ), 7.04 (d, J =

2.4 Hz, 1 H), 7.05(d, J=8.1 Hz, 1 H)

3-bramo-4-methoxytoluene

To a 100 mL round bottom flask equipped with a magnetic stir bar and purged
with nitrogen gas, 5.39 grams (0.096 moles) of powdered potassium hydroxide
and 50 mL of dimethyl sulfoxide were added. After stirring for 5 minutes, 4.5
grams (0.024 moles) of 3-bromo-4-methyI-phenol was added, followed
immediately by 6.83 grams (0.048 moles) of methyl iodide. Stirring was
continued for 4 hours. Then the mixture was poured into 200 mL of water and
extracted three times with 200 mL portions of dichloromethane. The combined
organic extracts were washed with brine and dried over anhydrous sodium
sulfate. Solvent was then removed to afford 4.23 grams (87% yield) of product as
a brownish red oil.
1H NMR(CDCI3): 5 2.31 (s, 3 H ), 3.76 (s, 3 H ), 6.75 (dd, J = 8.3, 2.4 Hz, 1 H),

7.08-7.12 ( m, 2 H)

39

a-(2-Methyl-5-methoxyphenyl)acetophenone

To a 100 mL three-necked round bottom flask equipped with a thermometer, a
condenser, a magnetic stir bar and purged with nitrogen gas, 0.081 grams
(0.00036 moles) of palladium (ll) acetate, 0.38 grams (0.0014 moles) of
triphenylphosphine and 4.95 grams (0.036 moles) of potassium carbonate was
added. Then 30mL of o-xylene was added by syringe. With stirring, 3.6 grams
(0.018 moles) of 3-bromo-4-methoxytoluene dissolved in 5 mL of oxylene was
added by syringe, followed by 2.15 grams (0.018 moles) of acetophenone. The
mixture was refluxed for 3 days. Then the reaction mixture was extracted by
ether three times. The combined other layer was washed by brine and dried over
anhydrous sodium sulfate. Solvent was then removed to afford a yellow oil.‘
Analysis of the oil showed it to contain the desired product and the starting
materials. After silica gel chromatography (using 20:1 hexane/ethyl acetate
solution as eluent), 1.70 grams (43% yield) of the product was obtained.
1H NMR(CDCI3): 5 2.18 ( s, 3 H ), 3.74 ( s, 3 H ), 4.25 ( s, 2 H ), 6.68 ( d, J = 2.5
Hz, 1 H), 6.73 (dd, J: 8.5, 2.5 Hz, 1 H), 7.10 ( d, J = 8.0 Hz, 1 H ), 7.44-7.46
(m,2H), 7.56(t,J=7.5 Hz, 1 H), 8.00(d,J=7.0 Hz,2H)
130 NMR(CDC13): 5 19.0, 43.8, 55.4, 112.5, 116.2, 128.5, 128.8, 129.0, 131.3,
133.4, 134.6, 137.0, 158.0, 197.5
11:1 (001.): 1688 cm"
m.p.: 68.4-70.1 °C

Anal. Calcd for C16H1602 :C, 79.97; H, 6.71. Found: C, 79.64; H, 6.52

40

III. Photochemical Experiments and Procedures

A. Purification of Chemicals

1. Solvent

1.5 liter of reagent grade benzene was mixed with 0.2 liter of concentrated
sulfuric acid and the mixture was stirred for 2 days. The benzene layer was
separated and was washed with 100 mL portions of concentrated sulfuric acid
several times until the sulfuric acid layer did not turn yellow. The benzene was
then washed with distilled water and saturated sodium bicarbonate solution. The
benzene was separated, dried over anhydrous sodium sulfate and filtered into a
2 liter round bottom flask. Phosphorous pentoxide (50 grams) was added and the
solution was reflux for 2 days. After refluxing, the benzene was distilled through a

one meter column. The first and last 10% were discarded. (b.p.: 78°C)

2. Internal Standard

Eicosane(C20) was purified by recrystallization from methanol.

8. Equipment and Procedures

1. Glassware

All photolysis glassware (Pyrex culture tubes, syringes, volumetric flasks, etc.)

were rinsed with reagent grade acetone and distilled water and boiled in a

41

solution of Alconox laboratory detergent in distilled water for 2 days. They were
rinsed with water and boiled in distilled water for another 2 days. After a final
rinse with distilled water, the glassware was oven dried overnight and cooled to
room temperature before use.

Tubes used for irradiation were made from 13x100 mm Pyrex culture tubes by
flame heating them approximately 2 cm from the top with an oxygen-natural gas

torch and drawing them into a uniform 15 cm length.

2. Sample Preparations
All solutions were prepared by directly weighing the desired material into
volumetric flasks or by dilution of stock solutions. Equal volumes (2.8 mL) of

sample were placed via syringes into each tube

3. Degasslng Procedure
Irradiation tubes were attached to a vacuum line. The tubes were degassed by
three consecutive freeze-pump-thaw cycles. The tubes were then sealed with an

oxygen-natural gas torch while still under vacuum.

4. Irradiatlon Procedures
Small scale irradiations were made by irradiating 0.1 M degassed solutions of
the sample in NMR tubes. A medium pressure mercury arc lamp served as the

light source. The light from the source was filtered through a Pyrex glass.

42

C. Identification of Photoproducts

1. Products From a-(5-Cyano-2-ethylphenyl)acetophenone (2)

0.1 M solution of a-(5-Cyano-2-ethylphenyl)acetophenone in 0.7 mL of
benzene-d6 was irradiated through Pyrex filter (A > 290 nm) at room temperature
for 12 hours. The signals of two products were detectable by NMR. The effect of
temperature on product ratios was studied by doing the photochemistry in ice-
water, water, and silica oil baths. The diasteromeric ratio of the products were
determined by NMR integration of the methyl doublet signals corresponding to
each isomer. Large scale irradiation using 0.3 grams of d-(5-Cyano-2-
ethylphenyl)acetophenone in 100 mL of benzene was performed until no trace of
starting material could be observed by NMR. The product mixture was then
separated by silica gel chromatography (using 20:1 hexane/ethyl acetate solution
as eluent) to get two indanols. The Z-indanol was eluted before the E-indanol.
The products were recovered as solids.

(AS-cyanod -methyl-2-phenyl-Indan-2-ol

1H NMR (00013) 5 1.27 (d, J=7.0 Hz, 3 H ), 3.19, 3.48 (AB quartet, J: 16.8 Hz.
2 H ), 3.58 (quartet, J: 7.5 Hz, 1H), 7.27-7.32 (m, 2 H ), 7.39 (t, J :7.0 Hz, 2
H ), 7.51-7.58 ( m, 4 H);

1H NMR (Benzene-d6) 5 0.95 (d, J=6.9 Hz, 3 H ), 2.64, 2.95 (AB quartet, J =
16.6 Hz, 2 H), 3.03 (quartet, J= 6.6 Hz, 1H), 6.61 (d, J=7.8 Hz, 1 H ), 6.84 ( s,

1 H), 7.21-7.40(m, 3 H ), 8.07-8.10 (m, 3 H). A doublet ( J: 7.2 Hz ),

43

13C NMR (00013) 5 10.3, 48.9, 50.7, 85.6, 110.9, 119.6, 124.6, 125.5, 127.7,
128.4,128.7, 131.7, 141.9, 143.7, 151.3

m.p. 99.9-101.4 °C

IR ( 001. ) 3476, 2228 cm'1

MS (FAB) m/z 250.1233 (MH+).

(ﬁt5-cyano-1-methyI-2-phenyl-indan-2-ol
1H NMR (CDCI3) 6 0.80 (d, J =8.0 Hz, 3 H ), 3.20, 3.79 (AB quartet, J = 16.5 Hz,

2 H ), 3.46 (quartet, J: 7.5 Hz, 1H ), 7.28-7.43 ( m, 6 H), 7.52 (d, J=8.0 Hz, 1
H), 7.58(s, 1H)

130 NMR (0001.) 5 17.0, 43.6, 52.0, 85.6, 110.2, 119.1, 124.7, 125.7, 127.5,
128.0,128.1, 131.0, 141.1, 142.2, 152.5

m.p. 103.6-105.1°C

11=1 ( 001. ) 3453, 2228 cm"

Anal. Calcd for C(7H15NO: C, 81.90; H, 6.06; N 5.62. Found: C, 81.16; H, 5.86; N,

5.66

44

Ph NC
0 Benzene-d6 -, II)“ + D. Ph

CN H CH3 H ’CH3

 

 

 

 

 

 

'I
I
—a

10 ,9 8 7 6 5 4 3 2 1 0 ppm

Figure 1. 1H NMR of a-(5-Cyano-2-ethylphenyl)acetophenone Before and

After Irradiation in Benzene-d5 (A> 290 nm)

45

2. Products From a-(2-Ethyl-5-methoxyphenyl)acetophenone (3)

0.1 M solution of q-(2-Ethyl-5-methoxyphenyl)acetophenone in 0.7 mL of
benzene-d6 was irradiated through Pyrex filter (A > 290 nm) at room temperature
for 6 hours. The signals of two products were detectable by NMR. The effect of
temperature on product ratios was studied by doing the photochemistry in ice-
water, water, and silica oil baths. The diasteromeric ratio of the products were
determined by NMR integration of the methyl doublet signals corresponding to
each isomer. Large scale irradiation using 0.3 grams of d-(2-Ethyl-5-
methoxyphenyl)acetophenone in 100 mL of benzene was performed until no
trace of starting material could be observed by NMR. The product mixture was
then separated by silica gel chromatography (using 20:1 hexane/ethyl acetate
solution as eluent) to get two indanols. The Z-indanol was eluted before the E-

indanol. The products were recovered as solids.

Z 5-methox -1-meth I-2- hen l-indan-2-ol

1H NMR (00013) 5 1.21 (d, J=6.9 Hz, 3 H ), 3.11, 3.48 (AB quartet, J: 16.8 Hz,
2 H), 3.51 (quartet, J: 7.5 Hz, 1H ), 3.80 ( s, 3 H), 6.78-6.82(m,2 H), 7.09 ( d,
J=8.1 Hz, 1 H), 7.28-7.41 (m, 3 H ), 7.60 (d, J: 7.8 Hz, 2 H)

1H NMR (Benzene-d6) 5 1.11 (d, J: 7.2 Hz, 3 H ), 2.90, 3.27 (AB quartet, J =
16.6 Hz, 2 H), 3.30 (quartet, J: 7.2 Hz, 1H ), 3.73 ( s, 3 H), 6.71 (s, 1 H), 6.79
(dd, J: 2.7, 8.4 Hz, 1 H), 6.93 (d, J: 7.8 Hz, 1 H ), 7.18-7.24 ( m, 2 H), 7.51-

7.55 ( m, 2 H), 8.07-8.11 (m, 1 H)

46

130 NMR (00013) 5 10.9, 49.6, 50.0, 55.7, 85.8, 111.0, 112.9, 124.6, 125.6,
127.2, 128.4, 137.4, 141.8, 144.4, 159.5
m.p. 49.3-50.5 °0
IR ( 001. ) 3492, 1248 cm"
Anal. Calcd for C17H1302! C, 80.28; H, 7.13. Found: C, 80.45; H, 7.22

E -5-methox -1-meth l-2- hen l-indan-2-ol ‘
1H NMR (00013) 5 0.77 (d, J=7.2 Hz, 3 H ), 3.15, 3.73 (AB quartet, J = 16.2 Hz,
2 H), 3.35 (quartet, J: 7.2 Hz, 1H ), 3.80 ( s, 3 H ), 6.76 ( d, J: 8.7 Hz, 1H ),
6.87 ( s, 1 H ), 7.10 (d, J: 7.8 Hz, 2 H ), 7.27-7.45 ( m, 4 H)
130 NMR (00013) 5 18.0, 45.1, 51.9, 55.7, 86.7, 110.8, 112.9, 125.2, 126.4,
127.6, 128.4, 139.1, 141.7, 143.4, 159.3
m.p. 52.9-53.6 °C
IR ( 001. ) 3427, 1249 cm“

Anal. Calcd for C17H1302 :C, 80.28; H, 7.13. Found: C, 80.57; H, 7.34

47

Ph OMe OH 0 Me

0 * I . O‘
Ph
Benzene-d6 . Ph

a +
H CH3 ,
0M8 H CH3

 

 

 

 

 

 

 

fTTIr'YITT—rI[IIIV'I’FFTIFﬁIIIIKTIITrTYIIIII’

1o 9 .8 7 6 5 ' 4 3 2 -1 0 ”9'"

Figure2. 1H NMR of a-(2-Ethyl-5-methoxyphenyl)acetophenone Before and

After Irradiation in Benzene-d5 (A> 290 nm)

48

3. Product From a-(5-Cyano-2-methylphenyl)acetophenone(4)

0.1 M solution of a-(5-cyano-2-methylphenyl)acetophenone in 0.7 mL of
benzene-05 was irradiated through Pyrex filter (A > 290 nm) at room temperature.
Only one photoproduct was observed in both 1H NMR and GC spectrum, and the
reaction completed within 5 hours. Large scale irradiation using 0.3 grams of 01-
(5-Cyano-2-methylphenyl)acetophenone in 100 mL of benzene was performed
until no trace of starting material could be observed by NMR. The product was
then purified by silica gel chromatography (using 10:1 hexane/ethyl acetate
solution as eluent).
5-Cyano-2-phenyl-indan-2-ol
1H NMR (00013) 5 2.22 ( br s, 1 H), 3.29, 3.50 (AB quartet, J : 16.2 Hz, 4 H),
7.30-7.40 ( m, 4 H ), 7.46-7.54 (m, 4 H)

130 NMR (00013) 5 48.1, 48.6, 82.9, 110.1, 119.2, 124.8, 125.3, 127.3, 128.0,
128.2, 130.8, 142.2, 144.4, 146.8

IR ( 001. ) 3458, 2228 cm"

m.p.: 123.6-124.3 °C

Anal. Calcd for C16H13N02: C, 81.68; H, 5.57; N, 5.95. Found: C, 81.08; H, 5.44;

N, 5.90

49

 

CN

 

 

 

 

 

 

Figure 3. 1H NMR of a-(S-Cyano-z-methylphenyl)acetophenone Before and

After Irradiation in Benzene-ds (A> 290 nm)

50

4. Products From a-(2-MethyI-5-methoxyphenyl)acetophenone(5)

0.1 M solution of a-(2-Methyl-5-methoxyphenyl)acetophenone in 0.7 mL of
benzene-d5 was irradiated through Pyrex filter (A > 290 nm) at room temperature.
Only one photoproduct was observed in both 1H NMR and GC spectrum, and the
reaction completed within 3 hours. Large scale irradiation using 0.3 grams of 01-
(2-Methyl-5-methoxyphenyl)acetophenone in 100 mL of benzene was performed
until no trace of starting material could be observed by NMR. The product was
then purified by silica gel chromatography (using 10:1 hexane/ethyl acetate

solution as eluent).

5-Methoxy-2-phenyl-indan-2-ol
1H NMR ( benzene-d6) 5 2.96, 3.21 (A6 quartet, J : 15.8 Hz, 4 H ), 3.34 ( s, 3

H ), 6.69 (s, 1 H ), 6.73 (dd, J: 2.5, 8.0 Hz, 1 H ), 6.92 ( d, J: 8.5 Hz, 1 H),
7.05-7.17 ( m, 3 H ), 7.42-7.44 (m, 2 H)

130 NMR (benzene-d6) 5 49.2, 50.2, 54.8, 83.3, 110.7, 112.9, 125.3, 125.5, 126.9,
128.2, 133.3, 142.9,146.9, 159.7

IR ( 001. ) 3469, 1282 cm"

mp 66.5-68.1 °0

Anal. Calcd for C16H1502 :C, 79.97; H, 6.71. Found: C, 79.58; H, 6.58

51

 

. hv 4 M90 OH
O Benzene-d5 V 0. Ph

 

 

 

 

 

 

 

OMe
_ ’ 'r
r r '
.1” .II I f A .1 J
I IILI . ' '- -
{7]I-T‘ITYETTITIITTTTgitII{1T1 ITIWIIPIFTIIIW—TfrrijTlrrrlITjV
10. 8 ' 6 4 2

Figure 4. 1H NMR of q-(2-Methyl-5-methoxyphenyl)acetophenone Before

and After Irradiation in Benzene-d5 (A> 290 nm)

52

D. Quantitative Measurements

1. Ouanntum Yield Measurements

Quantum yields for cyclization product formation were measured by irradiating
solutions of desired precursor parallel to 0.01 M valerophenone samples in
sealed, degassed tubes. Quantum yields were calculated from the following
equation, 27

def Number of molecules of product produced
— Number of photons of light absorbed

 

= [PP]/I

Equation 1
where [PP] is the concentration of photoproduct and I is the intensity of light
absorbed by the sample.

The value of l was determined by 0.01 M valerophenone actinometer irradiated
parallel with the samples to be analyzed. The irradiation was stopped after less
than 10% conversion of valerophenone and the sample was analyzed for
presence of acetophenone. Acetophenone’s concentration was then determined
from Equation 2:

[AP] = Rf x[Std] x AA): /As(d
Equation 2

where [AP] is the concentration of acetophenone, Rf is the instrument
response factor for acetophenone, AM is the integrated area for acetophenone,
[Std] is the concentration of internal standard, and A...) is the integrated area for

internal standard. The intensity of the light, I, can then be calculated using the

53

acetophenone concentration base on <I>Ap = 0.33 (when A=313nm in benzene
solution), ‘5 thus,
I : [AP] / 0.33
The concentration of photoproduct, [PP], can be calculated using Equation 3.
[PP] = qup) x[Std] x App /As(d
Equation 3

Where Rf(pp) is the instrument response factor for the photoproduct and App is
the integrated area for the photoproduct. The instrument response factor for the
photoproduct were obtained using equation 4:

RflPP) = (IPP I/[StdII X (Astd / APP)

Equation 4

2. Quenching Studies

Stern-Volmer quenching studies were performed by irradiating sealed degassed
tubes containing the ketone and various amounts of quencher (2,5-dimethyl-2,4-
hexadiene). The quenching is assumed to be diffusion-controlled with a rate
constant equals to 6x10 9M“S". ‘8 The results of these experiments are

summarized below.

54

GC analysis: VG-TRIO-I
Carrier Gas: Helium

Pressure of Carrier Gas: 7.5 Psi

Initial column temp.: 80°C

Initial col. Hold time: 2 min.
Final col. Temp.: 280°C

Rate: 15°C/min., Hold time: 2 min.

Table 8. Product Quantum Yield of
d-(5-Cyano-2-ethylphenyl)acetophenone in Benzene

 

 

 

 

 

 

 

 

 

Photoproduct A(product) A(std.) Concentration (D
Indanols 1 8309680 29293936 3.1 48e-4M 0.296
Indanols 2891 0406 49055424 2.970e-4M 0.279
Indanols 25537978 40793400 3.154e-4M 0.296
Indanols 41549092 66075024 3.169 e-4M 0.298

‘ “ ' ' " 029210.013

lndanols( avg.) E

 

 

 

 

[Ketone]=1.7346-3M, 8315,4;28263025159."5‘97e-5M, Ftf '“°5“°'t:5.25
[VP] :1 0005-2111, [020] =1 .092e-3M, RtAP : 4.01
Irradiation source=Mercury Arc Lamp, A=313nm, Irradiation Time = 6hrs

55

 

..EI II ‘9II’Q‘,.II‘I ' '. " I "ll’l'.l_°l‘l 3."?I'l'l’

GC analysis: VG-TRIO-1
Carrier Gas: Helium
Pressure of Carrier Gas: 7.5 Psi.
Initial column temp.: 80°C
Initial col. Hold time: 2 min.

Final col. Temp.: 280°C

Rate: 15°C/min., Hold time: 2 min.

Table 9. Product Quantum Yield of a-(2-Ethyl-5-
methoxyphenyl)acetophenone In Benzene

 

 

 

 

 

 

 

 

 

 

     

Photoproduct A(product) A(std.) Concentratio O
n
Indanols 8228722 1 38054041 6 2.4686-4M 0.595
Indanols 7543025 1 279699840 2.440e-4M 0.588
Indanols 4547281 738286208 2.550e-4M 0.614
Indanols 7147236 1 1 76859264 2.514e-4M 0.606

 

 

 

 

[Ketone]=2.402e-3IIII, £313nm=2L089[C20]=T270;-21IIIF1) '"°a"°'°=3.26
[VP] =1.031e-2M, [0201:1 .971e-3M, Ft,AP = 4.01
Irradiation source=Mercury Arc Lamp, A=313nm, Irradiation Time = 3hrs.

56

 

° '.' EI'HII‘I .‘l’vl

GC analysis: VG-TRIO-1
Carrier Gas: Helium

Pressure of Carrier Gas: 7.5 Psi.

Initial column temp.: 80°C

Initial col. Hold time: 2 min.
Final col. Temp.: 280°C

Rate: 15°C/min., Hold time: 2 min.

Table 10. Product Quantum Yield of
a-(5-cyano-2-methylphenyl)acetophenone In Benzene

 

 

 

 

 

 

 

 

 

 

 

 

Photoproduct A(product) A(std.) Concentration 1D
Indanols 9283746 24575364 2.292e-4M 0.340
Indanols 21464002 56255476 2.3156-4M 0.343
Indanols 23432908 61 783584 2.301 e-4M 0.341
Indanols 1 7551 224 461 14864 2.3096-4M 0.342

lndanols( avg.) . " " ‘ WWW] 034210.002

 

[Ketone]=2.094e-3M, s313.m=243.5, [02.]:9.92'8me-51111,WFI. '“da“°‘s:6.1 1
[VP] =1.037e-2M, [Czo]=1.234e-3M, H." = 4.01

Irradiation source=Mercury Arc Lamp, A=313nm, Irradiation Time = 4hrs

57

 

GC analysis: VG-TRIO-t
Carrier Gas: Helium

Pressure of Carrier Gas: 7.5 Psi.

Initial column temp.: 80°C

Initial col. Hold time: 2 min.
Final col. Temp.: 280°C

Rate: 15°C/min., Hold time: 2 min.

Table 11. Product Quantum Yield of a-(5-methoxy-2-
methylphenyl)acetophenone in Benzene

 

 

 

 

 

 

 

 

Photoproduct A(product) A(std.) Concentration 41
Indanols 242569008 38959971 2 5.4686-4M 0.973
Indanols 292571 168 466273312 5.51 1e-4M 0.980
Indanols 1 39761 936 220447024 5.5686-4M 0.990
Indanols 1 66798384 2691 20448 5.4439-4M 0.968

lndanols(avg)E ., .. W. 0978:0012

 

 

 

 

 

 

[Ketone]=2.6506-3M,831311111498. 3,[0201=3.404e-4M F11'"da"°'s :2. 58

[VP] =1.072e-2M, [C20]=8.8656-4M, F11AP

= 4.01

Irradiation source=Mercury Arc Lamp, A=313nm, Irradiation Time = 3.3hrs

58

Table 12. Quenching of the Indanol Formation in a-(5-Cyano-2-ethylphenyl)

 

 

 

 

 

 

acetophenone
[Q] A (Product )IA(std.) <D°I<D
0.00 0.880 1 .00
0.00780 0.785 1.12
0.0304 0.619 1.42
0.0508 0.503 1 .75

 

 

 

[Ketone]=0.064M, Quencher=2, 5-dimethyI-2, 4-hexadiene

 

 

kq'r: 14.5
2 - Ph
0
I 5 7 CN
Q 1 ,
°e
y=14.49X+1.00
0.5 *
O l 1 i l L I
0 O. 01 O. 02 0. 03 O. 04 O. 05 0. 06

[0]
Figure 5. Stern-Volmer Plot from Quenching Study of a-(5-Cyano-2-

ethylphenyl) acetophenone

59

 

Table 13. Quenching of the Indanol Formation in d-(2-EthyI-5-

methoxyphenyl) acetophenone

 

 

 

 

 

 

[Q] A (Product )IA(std.) ¢°I<D
0.00 1 .500 1 .00
0.0173 1.438 1.04
0.0464 1.338 1.12
0.0653 1.288 1.16

 

 

 

[Ketone]=0.075M, Quencher=2, 5-dimethyl-2, 4-hexadiene

qu= 2.54

  
 

 

 

1 12 ” OMe
Q 11;); ’
0
° =2. 4 1.
9 1.06 y 5 x+ 00
1.04
1.02
1 I
0.98 L 1 1 J
O O. 02 O. 04 0. 06 0. 08

[0]

Figure 6 Stern-Volmer Plot from Quenching Study of a-(2-EthyI-5-

methoxyphenyl) acetophenone

60

 

Table 14. Quenching of the Indanol Formation in 01-(5-Cyano-2-

methylphenyl) acetophenone

 

 

 

 

 

 

[Q] A (Product )IA(std.) 3%
0.00 0.667 1.00
0.00944 0.439 1.52
0.0132 0.388 1.72
0.0187 0.338 1.97

 

 

 

[Ketone]=0.032M, Quencher=2, 5-dimethyl-2, 4-hexadiene

Ph
0

CN

kq1= 53.1

2.5[

  
 

 

y=53.12 x+1.00

 

 

0 0. 005 0. 01 0.015 0.02
[0]
Figure 7. Stern-Volmer Plot from Quenching Study of u-(5-Cyano-2-

methylphenyl) acetophenone

61

 

 

Table 15. Quenching of the Indanol Formation in 01-((2-Methyl-5-

methoxyphenyl) acetophenone

 

 

 

 

 

[Q] A (Product )IA(std.) (Du/(D
0.00 0.387 1 .00
0.00581 0.358 1.08
0.0198 0.296 1.31
0.0535 0.216 1.79

 

 

 

 

[Ketone]=0.068M, Quencher=2, 5-dimethyl-2, 4-hexadiene

qu = 14.9

 

 

 

e
‘8 0,3 _ y=14.89x+1.00
0.5 ~
0.4 —
0.2 -
o I I I 1 I A
0 0.01 0.02 0.03 0.04 0.05 0.06
[0]

Figure 8. Stern-Volmer Plot from Quenching Study of a-(2-Methyl-5-

methoxyphenyl)acetophenone

62

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64

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