Synthesis and molecular design of 4,8-diaryl- and 4,8-di(arylethynyl) pyrido[4,3-d]pyrimidines: Potential applications in nonlinear optics. Diazines part 49

Article abstract of DOI:10.1002/jhet.5570450219

(Chemical Equation Presented) Using metallation and cross-coupling reactions, we report the synthesis of a new series of push-pull compounds with a pyrido[4,3-d]pyrimidine system as the central core. Two of them were tested and their NLO properties highlighted. Incorporation of triple and double bonds as spacer between the central core and the substituted aryl groups has been performed to allow an extension of conjugation.

Full text of DOI:10.1002/jhet.5570450219

Mar-Apr 2008
417
Synthesis and Molecular Design of 4,8-Diaryl- and 4,8-
Di(arylethynyl)pyrido[4,3-d]pyrimidines: Potential Applications in
Nonlinear Optics. Diazines Part 49.
Alexandrine Busch, Alain Turck, Nelly Plé*
Laboratoire de Chimie Organique Fine et Hétérocyclique, UMR 6014
IRCOF-INSA, B.P. 08, 76131 Mont-Saint-Aignan Cedex (France)
nelly.ple@insa-rouen.fr.; Tel +33-2-35-52-29-02 ; Fax +33-2-35-52-29-62
Received May 15, 2007
Ar'
( )n
O
N
O
N
Cl
N
cross-coupling
reaction
cross-coupling
reaction
N
N
N
Chlorination
t-Bu
N
NH
N
NH
N
N
t-Bu
t-Bu
t-Bu
I
(
)
n
(
)
( ) n
n
Ar
Ar
Ar
n = 0, 1
Using metallation and cross-coupling reactions, we report the synthesis of a new series of push-pull
compounds with a pyrido[4,3-d]pyrimidine system as the central core. Two of them were tested and their
NLO properties highlighted. Incorporation of triple and double bonds as spacer between the central core
and the substituted aryl groups has been performed to allow an extension of conjugation.
J. Heterocyclic Chem., 45, 417 (2008).
INTRODUCTION
RESULTS AND DISCUSSION
Organic molecules with delocalized π-electron systems
which may have applications in nonlinear optics (NLO)
and electrooptics (EO) materials were extensively studied
for their applications in optical data storage, telecommun-
ications and optical signal processing.
In previous papers the synthesis of new materials with
NLO properties comprising a cinnoline or quinazoline
moiety [8] have been reported. In continuation of our
work dealing with the functionalization of benzo- and
pyridodiazines, we describe herein the synthesis, structure
determination and potential optoelectronic properties of
novel 4,8-diaryl pyrido[4,3-d]pyrimidines I and 4,8-
diarylethynylpyrido[4,3-d]pyrimidines II (Scheme 1). In
this last series an extension of the conjugation can be
obtained via incorporation of ethynyl linkages between
the central core and phenyl moieties substituted by
electron-donor or acceptor groups.
A typical NLO chromophore consists of an electron-
withdrawing group (A) and an electron-donating group
(D) connected by a π-conjugated system. There is
widespread interest in the synthesis and study of
optoelectronic properties of new conjugated oligoarenes
containing electron-deficient heterocycles in the backbone
or as pendant groups [1]. Azaheterocycles can be used as
an electron-deficient unit in π-conjugated materials [2].
So it was established that pyridine [3], pyrimidine [4],
quinoline [5] and 1,3,5-triazine [6] units improve electron
characteristics compared to their phenylene analogues.
Moreover, the introduction of aromatic rings improves the
transparency-non linearity trade-off and the thermal
stability, both factors being critical for electro-optical
applications [7].
In order to find relations between NLO properties and
chemical structures, theoretical calculations have been
performed to investigate the role of the different parts (A,
D, π-system) in the molecule. The main goal of this work is
to evaluate the quadratic NLO interest of structures I and II
and not to optimize the values of the quadratic
hyperpolarizability β. Standard donor (OMe, NMe2) and
acceptor groups (CN) have been used to compare properties
Scheme 1
tBu
N
tBu
N
N
N
N
(D) or (A)
(D) or (A)
(A) or (D)
(A) or (D)
N
II
I

418
A. Busch, A. Turck, N. Plé
Vol 45
of various systems. These properties have been also
compared to those of p-nitroaniline (PNA), as a reference
molecule in the field of quadratic NLO (Scheme 2).
Similar properties were observed for molecules A and
B, which have the same backbone but differ only by the
substituent at C2. This result indicates that the presence of
Scheme 2
CN
CN
OMe
CN
CN
OMe
CN
NO2
NH2
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
tBu
tBu
N
tBu
N
tBu
tBu
N
tBu
NMe2
CN
NMe2
NMe2
NMe2
CN
NMe2
PNA
A
B
C
D
F
G
E
a bulky and non polar substituent such as the tert-butyl
group at C2 position does not modify significantly the
properties of these molecules.
Calculated hyperpolarizabilities values of structures A-
G were established on the classical two-level model [9]
and reported in Table 1.
Molecule C presents the weakest static β0 value of
8.10-30 esu, identical to the PNA molecule.
Introduction of alkynyl linkages at C4 and C8 positions
D-G increases by two to three times the values of
quadratic hyperpolarizability β0.
We can note that for molecules A-D the quadratic
hyperpolarizability β0 and the linear absorption are
influenced by the position of the electron-donor group.
When this one is at C8 on the pyridine moiety, the values
of β0 and λmax are higher than when it is at C4, fixed to the
more π-deficient pyrimidine moiety. Moreover, the red-
shift absorption becomes more important between B and
E (Δλ= 73 nm) than between C and D (Δλ=42 nm).
Comparison between structures E, F and G shows the
influence of the position of the nitrogen atom on the
pyridine moiety. For these molecules similar maximum
absorption wavelengths were calculated whereas the best
Table 1
Theoretical NLO properties for structures A-G: maximum absorption
wavelength (λmax), dipole moment (µ), dipole moment difference (Δµ)
between the ground and the first excited charge transfer states and first-
order hyperpolarizability (β0).
Structure
λmax
(nm)
µ
(D)
Δµ (D)
β0
(10-30 esu)
PNA
A
310
361
357
343
385
430
426
420
8.2
9.1
9.2
8.2
9.6
5.6
9.0
4.1
6.8
8
11.6
10.4
1.6
15
15
8
B
C
D
1.8
23
43
53
36
E
19.4
13.7
11.2
F
G
Scheme 3
O
N
O
N
1) LTMP (8 eq.)/ THF/-20°C/1h
2) I2 (8eq.)/THF/-78°C/1h
N
NH
N
NH
t-Bu
t-Bu
Ar'
I
2
1
( )n
O
O
Cl
cross-coupling
reaction
cross-coupling
reaction
N
N
N
NH
Chlorination
N
NH
N
N
N
t-Bu
N
t-Bu
N
t-Bu
N
t-Bu
I
(
)
(
)
( ) n
n
n
2
Ar
Ar
Ar
n = 0, 1

Mar-Apr 2008
Potential Applications in Nonlinear Optics. Diazines Part 49
419
value of β0 was predicted for F when the nitrogen atom
was at C5.
Experimental results for
β
showed values
approximately twice as high as the theoretical data.
As was predicted by calculation, we observed a
higher value for β when the electron-donor group
was at C8 on the pyridine moiety.
We report here the synthesis of several molecules with
a pyrido[4,3-d]pyrimidine as central core comprising one
electron-rich aryl substituted by an electron-donor (D)
while the other aryl group has a reduced electronic density
resulting of substitution with an electron-withdrawing
group (A) or is a π-deficient heteroarene. These aryl
substituents are directly attached or connected by a triple
bond to the core of the molecule.
Table 2
Theoretical and experimental data PNA, 9 and 12: maximum absorption
wavelength (λmax) and first-order hyperpolarizability (β0).
exp
λth
λexp
εexp
β0th
β0
According to the general synthetic route, the target
compounds I and II were obtained using cross-coupling
reactions from 2-tert-butyl-8-iodopyrido[4,3-d]pyrimidin-
4(3H)-one 2 as starting material (Scheme 2). The key
intermediate 2 was synthesized via metallation reaction of
Compound
max
max
(nm)
312
343
357
(nm)
310
333
397
(10-30 esu)
(10-30 esu)
PNA
9
-
8
8
7
13
33
14418
6394
12
15
2-tert-butyl-pyrido[4,3-d]pyrimidin-4(3H)-one
1
with
A new series of pyrido[4,3-d]pyrimidines bearing one
or two arylethynyl groups at C8 or at C4 and C8 positions
were also synthesized by Pd-catalyzed Sonogashira
coupling reaction. Starting from compound 2 a first
coupling reaction was performed at C8 position leading to
compounds 13-16. As previously, reaction with
phosphorus oxychloride gave the C4 chlorinated
compounds 17-19 which underwent a further coupling
reaction to give the diarylethynyl compounds 20 and 21
(Scheme 5).
lithium tetramethylpiperidide (LTMP) at low temperature
(-20°C), followed by reaction with iodine as the
electrophile (Scheme 3) [10]
Synthesis of the 4,8-diaryl pyrido[4,3-d]pyrimidines I
involves formation of the first aryl-aryl bond at the C8
position obtained by a Suzuki cross-coupling reaction of 2
leading to compounds 3-5. The 4-oxo derivatives were
converted with phosphorus oxychloride to their 4-chloro
analogues 6-8. In a last step these compounds reacted
with arylboronic acid to give the expected compounds 9-
12 (Scheme 4).
When the second Sonogashira coupling was
performed with the difluoro derivative 19 and 2-
Scheme 4
Y
O
N
O
N
Cl
N
X-PhB(OH)2/Pd(Ph3)4
Y-PhB(OH)2/Pd(Ph3)4
N
NH
POCl3/!
N
NH
N
N
N
N
DME/K2CO3/!
DME/K2CO3/!
t-Bu
t-Bu
N
t-Bu
t-Bu
I
2
9
X = CN
Y = OMe 76%
3
4
5
X = CN
X = OMe 65%
X = NMe2 55%
67%
6
7
8
X = CN
X = OMe 66%
X = NMe2 65%
63%
10 X = OMe Y = CN 73%
11 X = NMe2 Y = OMe 99%
12 X = NMe2 Y = CN 40%
X
X
X
Starting from 2-tert-butylpyrido[4,3-d]pyrimidin-
4(3H)-one 1, four new push-pull compounds 9-12 were
obtained in four steps with an overall yield varying
from 14 to 33%. These compounds present a high
thermal stability with melting points between 171°C
and 232°C.
Theoretical and experimental NLO properties of
PNA and compounds 9 and 12 could be compared
(Table 2).
pyridylethyne, the compound 22 bearing an arylethynyl
group and an arylvinyl group was obtained in 51%
1
yield. The H NMR spectrum presents two signals at
8.54 and 8.35 ppm which were assigned to the vinylic
protons. The coupling constant of 14.7 Hz was
attributed to an E configuration for the double bond. To
determine which triple bond had been reduced, a
NOESY NMR experiment was performed, the
correlations between H5 (9.72 ppm) the pyridyl H3'
(7.60 ppm) with the two vinylic protons respectively at
8.54 and 8.35 ppm indicated that the double bond was
located between the pyridine ring and the
pyridopyrimidine moiety (Scheme 6).
The hyperpolarizability value β0 was calculated
and measured using the EFISH method for
compounds
9 and 12 which present a higher
quadratic hyperpolarizability than p-nitroaniline.

420
A. Busch, A. Turck, N. Plé
Vol 45
Scheme 5
R'
O
N
Ar
O
N
Cl
Ar
CuI/ Pd(PPh3)2Cl2/ NEt3
CuI/ Pd(PPh3)2Cl2/ NEt3
POCl3/!
N
NH
N
NH
N
N
N
N
THF/!
THF/!
t-Bu
t-Bu
N
t-Bu
N
t-Bu
I
2
13 R = H
88%
17 R = H
18 R = OMe 53%
19 R = 2,4 F 71%
68%
14 R = OMe 89%
15 R = NMe2 79%
16 R = 2,4 F 61%
20 R = H
R' = OMe 76%
21 R = OMe R = H
84%
R
R
R
Scheme 6
Scheme 7
Me
Me
N
Me
H3'
N
N
19
20
23
H
Cl
N
F
N
H
N
H5
N
7
8
N
N
N
F
N
Bond length: 1.195 A
Bond order: 2.788
Orb. Coeff. : C19 : -0.2485
C20 : 0.1539
t-Bu
CuI/Pd(PPh3)2Cl2/NEt3
N
F
t-Bu
F
THF / !
Bond length: 1.195 A
Bond order: 2.776
51%
Orb. Coeff. : C7 : 0.1885
C8 : -0.1122
19
22
F
F
and could explain the better reactivity of this bond
towards the reduction reaction.
To explain the regioselective reduction of the triple
bond fixed at the C4 position a semi-empirical calculation
using PM3 method has been performed with the
hypothetical compound 23 bearing two triple bonds.
Geometry optimization obtained with PM3 method
reveals a planar structure for molecule 23 without sterical
hindrance (Figure 1).
CONCLUSION
Using metallation and cross-coupling reactions, we
have synthesized a new series of push-pull compounds
with a pyrido[4,3-d]pyrimidine system as central core.
Two of these compounds were tested and have
highlighted NLO properties. In addition, incorporation of
triple and double bonds as spacer between the central core
and the substituted aryl groups allowed an extension of
conjugation which could improve NLO properties.
Synthesis of similar compounds with various central cores
and substituted aryl groups are in progress and their NLO
properties will be studied in the future.
Figure 1
Bond length, bond order and orbital coefficients in the
LUMO have been calculated for each triple bond and
reported (Scheme 7).
The bond lengths of the two triple bonds are identical, a
slightly higher value of bond order is observed for the
triple bond between the central core and the pyridine
moiety. Comparison of the orbital coefficients in the
LUMO for the carbon atoms of the triple bonds reveals
higher values for the triple bond fixed on the pyridine ring
EXPERIMENTAL
The geometry of the molecules was optimized by using Sybyl,
i.e. Tripos force field and PM3 from MOPAC package [11]. The
experimental quadratic hyperpolarizability was determinated by
using the well-known EFISH (Electric Field Induced Second
Harmonic) method [12] at the wavelength of 1.907 µm.
Melting points were determined on a Kofler hot-stage. The ir
spectra were obtained as potassium bromide pellets with a
Perkin-Elmer Paragon 500 spectrophotometer. The H, 13C and
1

Mar-Apr 2008
Potential Applications in Nonlinear Optics. Diazines Part 49
421
19F nmr spectra were recorded on a Bruker AC 300 (300 MHz
1H, 75 MHz 13C, 282 MHz 19F) instrument. Mass spectra were
recorded on a JEOL JMS AX500. Microanalyses were
performed on a Carlo Erba CHNOS 1160 apparatus.
δ 12.36 (s, 1H, NH); 9.22 (s, 1H, H5); 8.88 (s, 1H, H7); 7.78 (d, J
= 8.3 Hz, 2H, H2'/6'); 7.06 (d, J = 8.7 Hz, 2H, H3'/5'); 3.84 (s, 3H,
OCH3); 1.34 (s, 9H, 3 CH3 tert-butyl); 13C nmr (dimethyl sulfoxide-
d6) : δ 166.9 (C2), 162.0 (C4), 159.1, 152.4 (C7), 150.1, 147.8
(C5), 131.7 (C2',C6'), 131.4, 126.8, 116.5 (C4a), 113.4 (C3',C5'),
55.2 (OCH3), 38.1 (C tert-butyl), 27.6 (3 CH3 tert-butyl). Anal. Calcd
for C18H19N3O2 (309.37) : C, 69.88; N, 13.58; H, 6.19. Found: C,
69.49; N, 13.29; H, 6.23.
All reagents were of commercial quality and were purchased
from Acros, Aldrich Chemical Co. or Avocado. The Pd(0)-
catalyst Pd(PPh3)4 was prepared according to the literature. 4-
Methoxyphenyl-, 4-N,N-dimethylaminophenyl- and 4-cyano-
phenylboronic acids were synthesized by halogen-metal
exchange followed by reaction with trimethylborate or triiso-
propylborate from the commercially available 4-bromoanisole,
4-bromo-N,N-dimethylaniline or 4-bromobenzonitrile.
General cross-coupling procedure A of arylboronic acid
with heteroaryl halide. A mixture of the heteroaryl halide (2
mmol), the arylboronic acid (1.3 equiv.), Pd(PPh3)4 (0.05
equiv.), aqueous 2M sodium carbonate (2 equiv.) and water (2
mL) in degassed dimethoxyethane (15 mL) was heated under
reflux and under nitrogen for 40-60 hours. After cooling to room
temperature, the organic solvent was evaporated under reduced
pressure, the residue was diluted with water and extracted with
dichloromethane (3x15 mL), the combined organic extracts were
dried over magnesium sulfate and evaporated. The crude product
was purified by column chromatography on silica gel.
General cross-coupling procedure B of alkynes with
heteroaryl halide. To a mixture of the heteroaryl halide,
copper(I) iodide (0.03 equiv.), bis(triphenylphosphine)pallad-
ium(II) chloride (0.03 equiv.), in degassed tetrahydrofuran,
triethylamine (2.5 equiv.) and alkyne (1.2 equiv) were added
under nitrogen. The mixture was heated under reflux for 24-60
hours. After cooling to room temperature, the organic solvent
was evaporated under reduced pressure, the residue was diluted
with water and extracted with dichloromethane (3x15 mL), the
combined organic extracts were dried over magnesium sulfate
and evaporated. The crude product was purified by column
chromatography on silica gel.
2-tert-Butyl-8-(4'-N,N-dimethylaminophenyl)pyrid-[4,3-d]-
pyrimidin-4(3H)-one (5). Coupling of 4-N,N-Dimethylamino-
phenylboronic acid (1.3 equiv.) with 2 (747 mg, 2 mmol)
according to the general procedure A (t = 40 hours) gave after
purification by column chromatography (silica gel, eluent : ethyl
acetate) 355 mg (55%) of 5 as a yellow solid, mp >250°C; ir :
3175, 3040, 2965, 2908, 1683, 1609, 1522, 1460, 1390, 1156,
818 cm-1;1H nmr (deuteriochloroform) : δ 11.14 (s, 1H, NH);
9.39 (s, 1H, H5); 8.92 (s, 1H, H7); 7.73 (d, J = 8.7 Hz, 2H, H2'/6');
6.83 (d, J = 8.7 Hz, 2H, H3'/5'); 3.04 (s, 6H, N(CH3)2); 1.47 (s,
9H, 3 CH3 tert-butyl); 13C nmr (deuteriochloroform) : δ 166.0 (C2),
164.1 (C4), 153.1 (C7), 151.0 (C8a or C4'), 150.3 (C8a or C4'),
148.0 (C5), 132.9 (C8), 131.6 (C2',C6'), 122.5 (C1'), 116.4 (C4a),
112.0 (C3',C5'), 40.5 (2 CH3), 38.6 (C tert-butyl), 28.3 (3 CH3 tert-butyl);
ms (IC) : 323 (MH+). Anal. Calcd for C19H22N4O (322.41) : C,
70.78; N, 17.28; H, 6.88. Found: C, 70.58; N, 16.87; H, 6.82.
2-tert-Butyl-4-chloro-8-(4'-cyanophenyl)pyrido[4,3-d]pyr-
imidine (6). Reaction of 3 (400 mg, 1.3 mmol) in POCl3 (20
mL) under reflux for 5 hours, followed by removal of excess of
POCl3 under reduced pressure and partitionning of the residue
between CH2Cl2 and cold aqueous Na2CO3 solution, gave after
purification by column chromatography (silica gel, eluent :
petroleum ether:ethyl acetate (4:6)) 264 mg (63%) of 6 as a
yellow solid, mp >250°C; ir : 3042, 2965, 2854, 2230, 1593,
1
1558, 1460, 1341, 1143, 838 cm-1; H nmr (deuteriochloroform):
δ 9.63 (s, 1H, H5); 8.99 (s, 1H, H7); 7.91 (d, J = 8.3 Hz, 2H,
H2'/6'); 7.79 (d, J = 8.3 Hz, 2H, H3'/5'); 1.40 (s, 9H, 3 CH3 tert-butyl); 13C
nmr (deuteriochloroform) : δ 177.6 (C2), 163.2 (C4), 151.8 (C8a),
151.3 (C5), 151.1 (C7), 139.1 (C1'), 132.1 (C3',C5'), 131.5 (C2',C6'),
131.1 (C8), 118.9 (CN), 117.6 (C4a), 112.4 (C4'), 40.9 (C tert-butyl),
29.3 (3 CH3 tert-butyl). Anal. Calcd for C18H15ClN4 (322.80) : C,
66.98; N, 17.36; H, 4.68. Found: C, 67.34; N, 17.97; H, 5.18.
2-tert-Butyl-4-chloro-8-(4'-methoxyphenyl)pyrido[4,3-d]-
pyrimidine (7). Reaction of 4 (350 mg, 1.1 mmol) in POCl3 (20
mL) under reflux for 6 hours, followed by removal of excess of
POCl3 under reduced pressure and partitionning of the residue
between CH2Cl2 and cold aqueous Na2CO3 solution, gave after
purification by column chromatography (silica gel, eluent:
petroleum ether:ethyl acetate (8:2)) 238 mg (66%) of 7 as a yellow
oil; ir : 1502, 1574, 1556, 1461, 1341, 1250, 1180, 1143, 1035,
830, 808 cm-1;1H nmr (deuteriochloroform) : δ 9.53 (s, 1H, H5);
8.98 (s, 1H, H7); 7.78 (d, J = 8.3 Hz, 2H, H2'/6'); 7.04 (d, J = 8.7 Hz,
2H, H3'/5'); 3.88 (s, 3H, OCH3); 1.44 (s, 9H, 3 CH3 tert-butyl); 13C nmr
(deuteriochloroform) : δ 176.8 (C2), 163.1 (C4), 160.0 (2 Cq),
151.9, 150.3 (C5 or C7), 149.1 (C5 or C7), 132.1 (C2',C6'), 126.4
(2 Cq), 113.8 (C3',C5'), 55.4 (OCH3), 40.7 (C tert-butyl), 29.2 (3 CH3
tert-butyl). Anal. Calcd for C18H18ClN30 (327.82) : C, 65.95; N,
12.82; H, 5.53. Found: C, 65.55; N, 12.92; H, 5.96.
2-tert-Butylpyrido[4,3-d]pyrimidin-4(3H)-one (1) [10] mp
248-249°C, mp(litt) 248-249°C .
2-tert-Butyl-8-iodopyrido[4,3-d]pyrimidin-4(3H)-one (2) [10]
mp > 250°C, mp(litt) > 250°C.
2-tert-Butyl-8-(4'-cyanophenyl)pyrido[4,3-d]pyrimidin-4(3H)-
one (3). Coupling of 4-cyanophenylboronic acid (1.3 equiv.)
with 2 (747 mg, 2 mmol) according to the general procedure A (t
= 40 hours) gave after purification by column chromatography
(silica gel, eluent:petroleum ether:ethyl acetate (6:4)) 408 mg
(67%) of 3 as a slight yellow solid, mp >250°C; ir : 3191, 3106,
2970, 2905, 2226, 1711, 1698, 1586, 1489, 1465, 1388, 835, 811
1
cm-1; H nmr (deuteriochloroform) : δ 11.41 (s, 1H, NH); 9.53
(s, 1H, H5); 8.91 (s, 1H, H7); 7.86 (d, J = 8.3 Hz, 2H, H2'/6'); 7.78
(d, J = 8.3 Hz, 2H, H3'/5'); 1.45 (s, 9H, 3 CH3 tert-butyl); 13C nmr
(deuteriochloroform) : δ 167.2 (C2), 163.4 (C4), 153.8 (C7),
151.5 (C8a), 150.9 (C5), 140.0 (C1'), 132.1 (C3',C5'), 131.6
(C2',C6'), 131.4 (C8), 119.2 (CN), 116.7 (C4a), 112.1 (C4'), 38.9 (C
tert-butyl), 28.5 (3 CH3 tert-butyl); ms (IC) : 305 (MH+). Anal. Calcd
for C18H16N4O (304.35) : C, 71.04; N, 18.41; H, 5.30. Found: C,
70.91; N, 18.74; H, 5.39.
2-tert-Butyl-8-(4'-methoxyphenyl)pyrido[4,3-d]pyrimidin-
4(3H)-one (4). Coupling of 4-methoxyphenylboronic acid (1.3
equiv.) with 2 (747 mg, 2 mmol) according to the general
procedure A (t = 40 hours) gave after purification by crystal-
lization in dichloromethane, 359 mg (58%) of 4 as a beige solid,
mp >250°C; ir : 3189, 1693, 1593, 1514, 1463, 1390, 1293,
2-tert-Butyl-4-chloro-8-(4'-N,N-dimethylaminophenyl)pyr-
ido[4,3-d]pyrimidine (8). Reaction of 5 (355 mg, 1.1 mmol) in
POCl3 (20 mL) under reflux for 4 hours, followed by removal of
excess of POCl3 under reduced pressure and partitionning of the
residue between CH2Cl2 and cold aqueous Na2CO3 solution, gave
1
1
1247, 1178, 833, 812 cm-1; H nmr (dimethyl sulfoxide-d6) :
377 mg (65%) of 8 as an orange solid; H nmr (deuteriochloro-

422
A. Busch, A. Turck, N. Plé
Vol 45
form): δ 9.49 (s, 1H, H5); 9.00 (s, 1H, H7); 7.82 (d, J = 8.7 Hz,
2H, H2'/6'); 6.85 (d, J = 8.7 Hz, 2H, H3'/5'); 3.06 (s, 3H, N(CH3)2);
1.47 (s, 9H, 3 CH3 tert-butyl); 13C nmr (deuteriochloroform):
δ 175.2, 162.0, 150.8 (C8a or C4'), 149.6 (C8a or C4'), 149.3 (C5 or
C7), 147.3 (C5 or C7), 131.8 (C8), 130.8 (C2',C6'), 120.7 (C1'),
116.7 (C4a), 111.0 (C3',C5'), 39.7 (C tert-butyl), 39.5 (2x CH3), 28.4
(3xCH3 tert-butyl). Anal. Calcd for C19H21ClN4 (340.86) : C, 66.95;
N, 16.44; H, 6.21. Found: C, 66.65; N, 15.92; H, 6.06.
according to the general procedure A (t = 48 hours) gave after
purification by column chromatography (silica gel, eluent:
petroleum ether:ethyl acetate (6:4)) 326 mg (40%) of 12 as a
yellow solid, mp 228°C; ir : 2226, 1610, 1584, 1542, 1525,
1466, 1379, 1359, 1202, 1160, 851, 826, 811 cm-1; 1H nmr
(deuteriochloroform) : δ 9.23 (s, 1H, H5); 8.94 (s, 1H, H7); 7.97
(d, J = 8.3 Hz, 2H, H2'/6'); 7.86 (m, 4H, H2''/6''/3'/5'); 6.86 (d, J = 8.7
Hz, 2H, H3''/5''); 3.05 (s, 6H, N(CH3)2, 1.49 (s, 9H, 3 CH3 tert-butyl);
13C nmr (deuteriochloroform): δ 176.4 (C2), 167.1 (C4), 152.0
(C8a), 150.7 (C4''), 149.0 (C7), 148.8 (C5), 141.3 (C1'), 133.4 (C8),
132.7 (2xCHAr), 132.0 (2xCHAr), 131.3 (C2'/6'), 122.2 (C1''), 118.5
(CN), 116.5 (C4a), 114.4 (C4'), 112.1 (C3'',C5''), 40.9 (C tert-butyl),
40.6 (2 CH3), 29.7 (3 CH3 tert-butyl); Anal. Calcd for C26H25N5
(407.21) : C, 76.63; N, 17.19; H, 6.18. Found: C, 76.59; N,
16.92; H, 6.65.
2-tert-Butyl-8-(4''-cyanophenyl)-4-(4'-methoxyphenyl)pyr-
ido[4,3-d]pyrimidine (9). Coupling of 4-methoxyphenylboronic
acid (1.3 equiv.) with 6 (646 mg, 2 mmol) according to the
general procedure A (t = 48 hours) gave after purification by
column chromatography (silica gel, eluent:petroleum ether:ethyl
acetate (6:4)) 600 mg (76%) of 9 as a yellow solid, mp 171°C; ir :
1
2223, 1605, 1544, 1470, 1380, 1254, 1175, 843, 830 cm-1; H
nmr (deuteriochloroform) : δ 9.55 (s, 1H, H5); 8.92 (s, 1H, H7);
8.00 (d, J = 8.3 Hz, 2H, H2''/6''); 7.91 (d, J = 8.7 Hz, 2H, H2'/6'); 7.82
(d, J = 8.3 Hz, 2H, H3''/5''); 7.14 (d, J = 8.7 Hz, 2H, H3'/5'); 1.47 (s,
9H, 3 CH3 tert-butyl); 13C nmr (deuteriochloroform): δ 177.3 (C2),
168.7 (C4), 162.3 (C4'), 152.9 (C5), 152.1 (C8a), 149.5 (C7), 140.2
(C1''), 132.7 , 132.1 , 131.8 , 131.4 (C8), 129.1 (C1'), 119.3 (CN),
116.7 (C4a), 114.7 , 112.0 (C4''), 55.9 (OCH3), 40.9 (C tert-butyl), 29.7
(3xCH3 tert-butyl). Anal. Calcd for C25H22N4O (394.48): C, 76.12;
N, 14.20; H, 5.62. Found: C, 76.37; N, 13.88; H, 5.35.
2-tert-Butyl-8-(phenylethynyl)pyrido[4,3-d]pyrimidin-
4(3H)-one (13). Coupling of phenylacetylene (1.2 equiv.) with 2
(373 mg, 1 mmol) according to the general procedure B (t = 24
hours) gave after purification by column chromatography (silica
gel, eluent:petroleum ether:ethyl acetate (6:4)) 267 mg (88%) of
13 as a yellow solid, mp >250°C; ir : 2210, 1707, 1585, 1493,
1
1395, 1160, 813, 760, 690 cm-1; H nmr (deuteriochloroform): δ
10.15 (s, 1H, NH); 9.38 (s, 1H, H5); 9.01 (s, 1H, H7); 7.62 (m,
2H, H2'/6'); 7.39 (m, 3H, H3'/4'/5'); 1.52 (s, 9H, 3 CH3 tert-butyl); 13
C
2-tert-Butyl-4-(4'-cyanophenyl)-8-(4''-methoxyphenyl)pyr-
ido[4,3-d]pyrimidine (10). Coupling of 4-cyanophenylboronic
acid (1.3 equiv.) with 7 (655 mg, 2 mmol) according to the
general procedure A (t = 60 hours) gave after purification by
column chromatography (silica gel, eluent:petroleum ether:ethyl
acetate (8:2)) 576 mg (73%) of 10 as a yellow solid, mp 232°C;
ir : 2228, 1590, 1570, 1547, 1468, 1381, 1252, 1178, 831, 812
nmr (deuteriochloroform): δ 167.8 (C2), 163.4 (C4), 156.3 (C7),
154.4 (C8a), 149.1 (C5), 132.0 (C2',C6'), 129.0 (C4'), 128.6
(C3',C5'), 123.0 (C4'), 117.9, 116.1, 98.4, 83.4, 38.6 (C tert-butyl),
28.3 (3 CH3 tert-butyl). Anal. Calcd for C19H17N3O (303.37) : C,
75.23; N, 13.85; H, 5.65. Found: C, 75.12; N, 13.68; H, 5.92.
2-tert-Butyl-8-(4'-methoxyphenylethynyl)pyrido[4,3-d]pyr-
imidin-4(3H)-one (14). Coupling of 4-methoxyphenylethyne
[13] (1.2 equiv.) with 2 (373 mg, 1 mmol) according to the
general procedure B (t = 24 hours) gave after purification by
column chromatography (silica gel, eluent:petroleum ether:ethyl
acetate (6:4)) 297 mg (89%) of 14 as a yellow solid, mp
>250°C; ir : 3178, 2209, 1677, 1563, 1510, 1465, 1253, 1164
1
cm-1; H nmr (deuteriochloroform) : δ 9.31 (s, 1H, H5); 8.95 (s,
1H, H7); 7.99 (d, J = 8.3 Hz, 2H, H2'/6'); 7.91 (d, J = 8.7 Hz, 2H,
H3'/5'); 7.85 (d, J = 8.7 Hz, 2H, H2''/6''); 7.07 (d, J = 8.7 Hz, 2H,
H3''/5''); 3.90 (s, 3H, OCH3); 1.49 (s, 9H, 3 CH3 tert-butyl); 13C nmr
(deuteriochloroform) : δ 176.6 (C2), 171.3 (C4), 167.1, 160.0,
151.8, 149.7 (C5), 149.4 (C7), 141.0, 132.9, 132.6 (C2''/6''), 132.2
(C3',C5'), 131.2 (C2'/6'), 126.9, 118.3, 116.3, 114.4, 113.8 (C3'',C5''),
55.4 (OCH3), 40.8 (C tert-butyl), 29.5 (3 CH3 tert-butyl). Anal. Calcd
for C25H22N4O (394.48): C, 76.12; N, 14.20; H, 5.62. Found:
C,75.91; N, 13.99; H, 5.82.
1
1029, 825, 808 cm-1; H nmr (deuteriochloroform): δ 11.13 (s,
1H, NH); 9.37 (s, 1H, H5); 8.99 (s, 1H, H7); 7.56 (d, J = 8.7 Hz,
2H, H2'/6'); 6.92 (d, J = 8.7 Hz, 2H, H3'/5'); 3.85 (s, 3H, OCH3);
1.55 (s, 9H, 3 CH3 tert-butyl); 13C nmr (deuteriochloroform): δ 167.4
(C2), 163.0 (C4), 160.3 (C4'),156.1 (C7), 154.2 (C8a), 148.7 (C5),
133.6 (C2',C6'), 118.2 (C8), 116.1 (C4a), 115.1 (C1'), 114.3 (C3',C5'),
98.7, 82.2, 55.5 (OCH3), 38.5 (C tert-butyl), 28.3 (3 CH3 tert-butyl). Anal.
Calcd for C20H19N3O2 (333.39) : C, 72.05; N, 12.60; H, 5.74.
Found: C, 71.66; N, 12.45; H, 5.89.
2-tert-Butyl-8-(4''-N,N-dimethylaminophenyl)-4-(4'-meth-
oxyphenyl)pyrido[4,3-d]pyrimidine (11). Coupling of 4-meth-
oxyphenylboronic acid (1.3 equiv.) with 8 (681 mg, 2 mmol)
according to the general procedure A (t = 48 hours) gave after
purification by column chromatography (silica gel, eluent:
petroleum ether:ethyl acetate (6:4)) 800 mg (97%) of 11 as a
yellow solid, mp 203°C; ir : 1613, 1586, 1544, 1526, 1484,
2-tert-Butyl-8-(4'-N,N-dimethylphenylethynyl)pyrido[4,3-d]-
pyrimidin-4(3H)-one (15). Coupling of 4-N,N-dimethyl-amino-
phenylethyne [13, 14] (1.2 equiv.) with 2 (373 mg, 1 mmol)
according to the general procedure B (t = 24 hours) gave after
purification by column chromatography (silica gel, eluent:
petroleum ether:ethyl acetate (7:3)) 274 mg (79%) of 15 as a
yellow solid, mp >250°C; ir : 3177, 2201, 1673, 1607, 1586, 1558,
1
1466, 1380, 1253, 1174, 1159, 1030, 827, 812 cm-1; H nmr
(deuteriochloroform) : δ 9.39 (s, 1H, H5); 8.92 (s, 1H, H7); 7.90
(m, 4H, H2'/6'/2''/6''); 7.12 (d, J = 8.7 Hz, 2H, H3'/5'); 6.89 (d, J = 8.7
Hz, 2H, H3'/5'); 6.89 (d, J = 8.7 Hz, 2H, H3''/5''); 3.93 (s, 3H,
OCH3), 1.52 (s, 9H, 3 CH3 tert-butyl); 13C nmr (deuteriochloroform):
δ 176.2 (C2), 168.4 (C4), 162.0 (C4'), 152.2 (C8a), 150.6 (C4''),
150.1 (C5 or C7), 148.7 (C5 or C7), 133.1 (C8), 132.6 (2xCHAr),
132.0 (2xCHAr), 129.7 (C1'), 123.0 (C1''), 116.9 (C4a), 114.5
(C3',C5'), 112.2 (C3'',C5''), 55.9 (OCH3), 40.8 (C tert-butyl), 40.7 2x
CH3), 29.9 (3xCH3 tert-butyl). Anal. Calcd for C26H28N4O (412.54) :
C, 75.70; N, 13.58; H, 6.84. Found: C, 75.77; N, 13.25; H, 6.91.
2-tert-Butyl-4-(4'-cyanophenyl)-8-(4''-N,N-dimethylamino-
phenyl)pyrido[4,3-d]pyrimidine (12). Coupling of 4-cyano-
phenylboronic acid (1.3 equiv.) with 8 (681 mg, 2 mmol)
1
1520, 1462, 1391, 1359, 1222, 1151, 1115, 810 cm-1; H nmr
(dimethyl sulfoxide-d6): δ 12.41 (s, 1H, NH); 9.12 (s, 1H, H5);
8.89 (s, 1H, H7); 7.40 (d, J = 8.7 Hz, 2H, H2'/6'); 6.77 (d, J = 8.7 Hz,
2H, H3'/5'); 3.98 (s, 6H, N(CH3)2); 1.42 (s, 9H, 3 CH3 tert-butyl); 13
C
nmr (deuteriochloroform): δ 168.0 (C2), 161.9 (C4), 154.4 (C7),
153.1 (C8a), 150.4 (C4'), 147.4 (C5), 132.5 (C2',C6'), 117.4, 116.3,
112.0 (C3',C5'), 108.2 (C1'), 99.4, 82.1, 38.0 (C tert-butyl), 30.7
(N(CH3)2), 28.3 (3 CH3 tert-butyl). Anal. Calcd for C21H22N4O
(346.44) : C, 72.81; N, 16.17; H, 6.40. Found: C, 72.47; N,
15.89; H, 6.03.

Mar-Apr 2008
Potential Applications in Nonlinear Optics. Diazines Part 49
423
2-tert-Butyl-8-(2',4'-difluorophenylethynyl)pyrido[4,3-d]-
pyrimidin-4(3H)-one (16). Coupling of 2,4-difluorophenyl-
ethyne (1.2 equiv.) with 2 (373 mg, 1 mmol) according to the
general procedure B (t = 48 hours) gave after purification by
column chromatography (silica gel, eluent:petroleum ether:ethyl
acetate (6:4)) 207 mg (61%) of 16 as a brown solid, mp >250°C;
ir : 2318, 1722, 1704, 1587, 1509, 1397, 1267, 1093, 966, 849,
(deuteriochloroform): δ -105.0 (d, J = 9.7 Hz, 1F), -106.3 (d, J =
9.7 Hz, 1F); 13C nmr (deuteriochloroform) : δ 177.9 (C2), 164.2
(d, J = 46.2 Hz, CF), 154.2 (C8a), 154.0 (C7),149.8 (C5), 134.6
(dd, J = 40.4 and 11.5 Hz, C6'), 117.7, 117.3, 112.0 (dd, J = 89.5
and 17.3 Hz, C5'), 107.3 (dd, J = 60.7 and 14.4 Hz, C1'), 104.6 (t,
J = 98.2 Hz, C3'), 91.4, 82.5, 40.7 (C tert-butyl), 29.1 (3 CH3 tert-butyl).
Anal. Calcd for C19H14ClF2N3 (357.79) : C, 63.78; N, 11.74; H,
3.94. Found: C, 64.15; N, 11.38; H, 4.11.
1
810 cm-1; H nmr (dimethyl sulfoxide-d6): δ 12.46 (s, 1H, NH);
9.21 (s, 1H, H5); 8.99 (s, 1H, H7); 7.71 (m, 1H, H6'); 7.49 (m,
2-tert-Butyl-4-(4'-methoxyphenyl)-8-(phenylethynyl)pyr-
ido[4,3-d]pyrimidine (20). Coupling of 4-methoxyphenyl-
ethyne (1.2 equiv.) with 17 (322 mg, 1 mmol) according to the
general procedure B (t = 40 hours) gave after purification by
column chromatography (silica gel, eluent: petroleum ether:ethyl
acetate (8:2)) 351 mg (84%) of 20 as a yellow green solid, mp
180°C; ir : 2198, 1602, 1511, 1462, 1252, 1170, 1030, 820, 806,
754, 690 cm-1; 1H nmr (deuteriochloroform) : δ 9.64 (s, 1H, H5);
9.06 (s, 1H, H7); 7.71 (d, J = 8.7 Hz, 2H, H2'/6'); 7.66 (m, 2H,
H2''/6''); 7.41 (m, 3H, H3''/4''/5''); 6.96 (d, J = 8.7 Hz, 2H, H3'/5'); 3.87
(s, 3H, OCH3); 1.58 (s, 9H, 3 CH3 tert-butyl); 13C nmr (deuterio-
chloroform): δ 178.2 (C2), 161.7 (C4'), 153.9 (C4), 153.3 (C7),
153.1 (C8a), 150.7 (C5), 134.8 (C2',C6'), 132.1 (C2'',C6''), 129.1
(C4''), 128.7 (C3'',C5''), 123.1 (C1''), 118.3 (C8 or C4a), 115.6 (C1'),
114.6 (C3',C5'), 112.8 (C8 or C4a), 100.8 , 99.1, 84.3, 83.3, 55.6
(OCH3), 40.8 (C tert-butyl), 29.6 (3 CH3 tert-butyl). Anal. Calcd for
C28H23N3O (417.52) : C, 80.55; N, 10.06; H, 5.55. Found: C,
80.68; N, 9.88; H, 5.82.
1H, HPh-F2); 7.23 (m, 1H, HPh-F2); 1.39 (s, 9H, 3 CH3 tert-butyl); 19
F
nmr (dimethyl sulfoxide-d6) : δ -105.0 (d, J = 9.7 Hz, 1F), -106.3
(d, J = 9.7 Hz, 1F); 13C nmr (dimethyl sulfoxide-d6): δ 168.7
(C2), 164.2 (m, CF), 161.6, 155.4 (C7), 154.6 (C8a), 148.9 (C5),
144.1, 134.8 (d, J = 37.6 Hz, C6'), 116.5, 115.9, 112.8 (dd, J =
80.9 and 14.5 Hz, C5'), 107.3, 105.0 (t, J = 98.2 Hz, C3'), 89.0,
82.5, 38.1 (C tert-butyl), 27.6 (3 CH3 tert-butyl). Anal. Calcd for
C19H15F2N3O (339.35) : C, 67.25; N, 12.38; H, 4.46. Found: C,
67.03; N, 11.85; H, 4.21.
2-tert-Butyl-4-chloro-8-(phenylethynyl)pyrido[4,3-d]pyr-
imidine (17). Reaction of 13 (303 mg, 1 mmol) in POCl3 (20
mL) under reflux for 6 hours, followed by removal of excess of
POCl3 under reduced pressure and partitioning of the residue
between CH2Cl2 and cold aqueous Na2CO3 solution, gave after
purification by column chromatography (silica gel, eluent:
petroleum ether:ethyl acetate (6:4)) 219 mg (68%) of 17 as a
yellow solid, mp 133°C; ir : 2218, 1592, 1554, 1492, 1460,
1
1347, 1147, 850, 759, 690 cm-1; H nmr (deuteriochloroform): δ
2-tert-Butyl-8-(4'-methoxyphenylethynyl)-4-phenyl-
ethynyl-pyrido[4,3-d]pyrimidine (21). Coupling of
phenylacetylene (1.2 equiv.) with 18 (351 mg, 1 mmol)
according to the general procedure B (t = 60 hours) gave after
purification by column chromatography (silica gel,
eluent:petroleum ether:ethyl acetate (8:2)) 317 mg (76%) of 21
as a yellow solid, mp 191°C; ir : 2208, 1605, 1579, 1538, 1509,
1464, 1247, 1170, 1153, 1030, 836, 821, 804, 762, 690 cm-1; 1H
nmr (deuteriochloroform): δ 9.62 (s, 1H, H5); 9.03 (s, 1H, H7);
7.76 (dd, J = 7.9 et 1.5 Hz, 2H, H2'/6'); 7.61 (d, J = 8.7 Hz, 2H,
H2''/6''); 7.50-7.43 (m, 3H, H3'/4'/5'); 6.92 (d, J = 8.7 Hz, 2H, H3''/5'');
3.85 (s, 3H, OCH3); 1.58 (s, 9H, 3 CH3 tert-butyl); 13C nmr
(deuteriochloroform): δ 178.0 (C2), 160.3 (C4''), 153.6 (Car), 153.0
(C7 et Car), 150.1 (C5), 133.7 (C2'',C6''), 132.9 (C2',C6'), 129.1 (C4''),
128.9 (C3',C5'), 120.9 (C1'), 118.6 (Car), 118.4 (Car), 115.1 (C1''),
114.3 (C3'',C5''), 99.6, 99.5, 84.7, 82.2, 55.5 (OCH3), 40,8 (Ctert-butyl),
29,6 (3 CH3tert-butyl). Anal. Calcd for C28H23N3O (417.52) : C, 80.55;
N, 10.06; H, 5.55. Found: C, 80.38; N, 9.92; H, 5.74.
9.39 (s, 1H, H5); 9.01 (s, 1H, H7); 7.54 (m, 2H, H2'/6'); 7.30 (m,
3H, H3'/4'/5'); 1.49 (s, 9H, 3 CH3 tert-butyl); 13C nmr (deuteriochloro-
form): δ 177.4 (C2), 162.7 (C4), 156.3 (C7), 154.1 (C8a), 149.1
(C5), 131.8 (C2',C6'), 129.0 (C4''), 128.3 (C3',C5'), 123.0 (C4'),
118.0, 117.1, 99.2, 82.8, 40.6 (C tert-butyl), 29.1 (3 CH3 tert-butyl).
Anal. Calcd for C19H16ClN3 (321.81) : C, 70.91; N, 13.06; H,
5.01. Found: C, 71.00; N, 12.58; H, 5.39.
2-tert-Butyl-4-chloro-8-(4'-methoxyphenylethynyl)pyrido-
[4,3-d]pyrimidine (18). Reaction of 14 (333 mg, 1 mmol) in
POCl3 (20 mL) under reflux for 7 hours, followed by removal of
excess of POCl3 under reduced pressure and partitionning of the
residue between CH2Cl2 and cold aqueous Na2CO3 solution, gave
after purification by column chromatography (silica gel,
eluent:petroleum ether:ethyl acetate (6:4)) 186 mg (53%) of 18
as a yellow solid, mp 163°C; ir : 2213, 1605, 1588, 1555, 1501,
1252, 1168, 1038, 837, 812, 798 cm-1; 1H nmr (deuterio-
chloroform): δ 9.45 (s, 1H, H5); 9.05 (s, 1H, H7); 7.54 (d, J = 8.7
Hz, 2H, H2'/6'); 6.88 (d, J = 8.7 Hz, 2H, H3'/5'); 3.82 (s, 3H,
OCH3); 1.53 (s, 9H, 3 CH3 tert-butyl); 13C nmr (deuteriochloroform):
δ 177.4 (C2), 162.8 (C4), 160.4 (C4'),154.1 (C8a), 153.5 (C7),
148.9 (C5), 133.6 (C2',C6'), 114.8 (C8, C4a, C1'), 114.2 (C3',C5'),
99.7, 81.9, 55.4 (OCH3), 40.7 (C tert-butyl), 29.2 (3 CH3 tert-butyl).
Anal. Calcd for C20H18ClN3O (351.11) : C, 68.28; N, 11.94; H,
5.16. Found: C, 68.56; N, 12.22; H, 5.48.
2-tert-Butyl-8-(2',4'-difluorophenylethynyl)-4-(2'-pyridyl)-
pyrido[4,3-d]pyrimidine (22). Coupling of 2-pyridylethyne (1.2
equiv.) with 19 (351 mg, 1 mmol) according to the general
procedure B (t = 48 hours) gave after purification by column
chromatography (silica gel, eluent:petroleum ether:ethyl acetate
(8:2)) 217 mg (51%) of 22 as a brown solid, mp 188°C; ir: 2219,
1584, 1539, 1506 1465, 1266, 1142, 1103, 967, 850, 812 cm-1;
1H nmr (deuteriochloroform): δ 9.72 (s, 1H, H5); 9.04 (s, 1H,
H7); 8.73 (d, J = 3.8 Hz, 1H, H6'); 8.54 (d, J = 14.7 Hz, 1H,
CH=CH); 8.35 (d, J = 14.7 Hz, 1H, CH=CH); 7.78 (dt, J = 7.5
and 1.9 Hz, 1H, H4'); 7.60 (m, 2H, H3' and HPhF2); 7.31 (m, 1H,
2-tert-Butyl-4-chloro-8-(2',4'-difluorophenylethynyl)pyr-
ido[4,3-d]pyrimidine (19). Reaction of 16 (339 mg, 1 mmol) in
POCl3 (20 mL) under reflux for 6 hours, followed by removal of
excess of POCl3 under reduced pressure and partitioning of the
residue between CH2Cl2 and cold aqueous Na2CO3 solution, gave
after purification by column chromatography (silica gel, eluent:
petroleum ether:ethyl acetate (6:4)) 254 mg (71%) of 19 as an
orange solid, mp 153°C; ir : 2225, 1591, 1556, 1506, 1269,
H5'); 6.96-6.89 (m, 2H, 2HPhF2); 1.59 (s, 9H, 3 CH3 tert-butyl); 19
F
nmr (deuteriochloroform): δ -104.8 (d, J = 8.5 Hz, 1F), -106.4
(d, J = 8.5 Hz, 1F); 13C nmr (deuteriochloroform) : δ 177.7 (C2),
165.0 (m, C2''), 162.4 (C4), 161.6 (m, C4''), 154.3 (Car), 153.8
(Car), 152.9 (C7), 150.4 (C6''), 149.0 (C5), 139.6 (CHCH=CH), 137.1
(C4'), 134.8 (C6''), 125.2 (CH), 124.3 (CH), 123.7 (CH), 117.9
(C8), 116.4 (C4a), 112.0 (m, CHPhF2), 108.3 (m, CPhF2), 104.6 (t, J
1
1150, 1106, 967, 888, 849, 815 cm-1; H nmr (deuteriochloro-
form) : δ 9.47 (s, 1H, H5); 9.06 (s, 1H, H7); 7.60-7.53 (m, 1H,
H6'); 6.94-6.85 (m, 2H, H2'/5'); 1.50 (s, 9H, 3 CH3 tert-butyl); 19F nmr

424
A. Busch, A. Turck, N. Plé
Vol 45
C.; Batsanov, A. S.; Fearn, M.; Franck, S.; Bryce, M. R.; Perepichka, F.;
Monkman, A. P.; Lyons, B. P. Org. Biomol. Chem. 2003, 1, 3069.
[5] Zhang, X.; JeneKhe, S. A. Macromolecules 2000, 33, 2069.
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L. J. Mater. Chem. 2000, 10, 867. [b] Pang, J.; Tao, Y.; Freiberg, S.;
Yang, X. P.; D'Iorio, M.; Wang, S. J. Mater. Chem. 2002, 12, 206.
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Bräuchle, C.; Reisner, A.; Jones, P. G. Angew. Chem. Int. Ed. Engl.
1995, 34, 1485. [b] Grahn, W.; Bahl, A.; Link, S.; Stader, S.; Dietrich,
R.; Meerholz, K.; Bräuchle, C. Proc. SPIE, 1997, 3147, 62-73. [c]
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= 98.2 Hz, CHPhF2), 90.7, 88,5, 40,8 (Ctert-butyl), 29,6 (3 CH3
butyl). Anal. Calcd for C26H20F2N4 (426.47): C, 73.27; N, 13.14;
H, 4.73. Found: C, 73.52; N, 12.96; H, 4.82.
tert-
Acknowledgements. We thank Dr. C. Andraud (ENS Lyon)
for her collaboration and the determination of the theoretical and
experimental values of first-hyperpolarisability (β0) by the
EFISH method.
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