A new synthetic route to donor-acceptor porphyrins

Article abstract of DOI:10.1016/S0040-4020(02)00109-6

Some new donor-acceptor porphyrins have been prepared based on a metallated bis(ethynyl) porphyrin core. 4-(Dimethylamino)phenyl was used as the donor group and 4-nitrophenyl, 4-cyanophenyl and 5-nitrothiazoyl as the acceptor groups. Dipyrrylmethane was used for large scale porphyrin ring synthesis because the absence of methylene substituents reduces the difficulty of substituent scrambling that occurs during porphyrin synthesis.

Full text of DOI:10.1016/S0040-4020(02)00109-6

TETRAHEDRON
Pergamon
Tetrahedron 58 (2002) 2405±2413
A new synthetic route to donor±acceptor porphyrins
a,p
M. John Plater, Stuart Aiken and Grant Bourhill
a
b,²
a
Department of Chemistry, University of Aberdeen, Meston Building, Room G103, Meston Walk, Aberdeen, Scotland AB24 3UE, UK
b
Defence Science and Technology Laboratory, Great Malvern, St Andrews Road, Worcs WR14 3PS, UK
Received 5 November 2001; revised 19 December 2001; accepted 24 January 2002
AbstractÐSome new donor±acceptor porphyrins have been prepared based on a metallated bis(ethynyl) porphyrin core. 4-(Dimethyl-
amino)phenyl was used as the donor group and 4-nitrophenyl, 4-cyanophenyl and 5-nitrothiazoyl as the acceptor groups. Dipyrrylmethane
was used for large scale porphyrin ring synthesis because the absence of methylene substituents reduces the dif®culty of substituent
scrambling that occurs during porphyrin synthesis. q 2002 Elsevier Science Ltd. All rights reserved.
1
. Introduction
zinc(II) possesses by far the largest b value or ®rst order
hyperpolarisability yet measured for an organic based chro-
5
mophore. The pioneering synthesis of ethynyl substituted
New generations of optoelectronic devices for tele-
communications, optical switching and information storage
require the development of materials with exceptional
porphyrins was a key step towards the development of
conjugated porphyrin chromophores. Alkynyl groups
6
1
±3
nonlinear optical (NLO) responses.
This is because an
allow conjugation to the central porphyrin whereas other
groups such as aryl rings and alkenes are twisted which
reduces their ability to be conjugated to the central
porphyrin. Our interest in these compounds stems from
the potential use of porphyrins in optical limiting devices
for the attenuation of short laser pulses, owing to their desir-
able reverse saturation absorption characteristics, and their
potential use in optical limiters for the attenuation of con-
tinuous wave laser beams, owing to their large b values and
NLO chromophore with a very large ®rst-order hyper-
polarisability would be desirable for incorporation into
electric ®eld poled-polymeric systems and serve as the
basis for frequency doubling materials and for devices
that function as waveguide switches, modulators, ®lters
and optical limiting devices. The general approach to
designing NLO chromophores with large molecular ®rst
order hyperpolarisabilities involves coupling an electron
donor (D) and acceptor (A) to an organic framework that
provides moderately strong electronic coupling between D
and A. Previous studies have illustrated that macrocycles
with extensive p-conjugation can provide a basis from
which to construct D±A molecules with interesting NLO
7
±8
dipole moments. This paper reports improved synthetic
routes to D±A porphyrins that allows the donor and
acceptor groups to be varied more easily. The solubility of
the chromophores is increased by using 3,5-di-tert-butyl-
phenyl side groups. Two D±A porphyrins are also described
which possess different electron acceptor groups and D±D
and A±A porphyrins are described.
4
properties. Recently very large ®rst-order hyperpolaris-
abilities have been measured in a new class of asymmetric
D±A porphyrin. These molecules are based on a porphyrin
centred 5,15-bis(arylethynyl) linker topology with donor
and acceptor groups attached to the ethynyl groups. One
such compound [5,15-bis-(phenyl)-10-(4-N,N-dimethyl-
aminophenylethynyl)-20-(4-nitrophenylethynyl)porphinato]-
2. Results and discussion
The key building block [5,15-bis-bromo-10,20-bis-(3,5-bis-
2 2 2 6 4
Scheme 1. Reagents and conditions: (i) NBS, (PhCO) O 50% (125 g); (ii) (CH ) N , c. HCl 82% (79 g).
Keywords: porphyrins and analogues; palladium and compounds.
Corresponding author. Tel.: 144-1224-272-943; fax: 144-1224-272-921; e-mail: m.j.plater@abdn.ac.uk
Fax: 144-1865-747719.
p
²
0040±4020/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(02)00109-6

2406
M. J. Plater et al. / Tetrahedron 58 (2002) 2405±2413
tert-butylphenyl)porphinato]zinc(II) 9 and the related
uncatalysed reaction between pyrrole and thiophosgene.
Porphyrin 7 was prepared on a 26 g scale by acid catalysed
condensation of dipyrrylmethane 6 with 3,5-di-tert-butyl-
compound
have been described previously.
5,15-bis-bromo-10,20-bis-(phenyl)porphyrin
A variation on a
9
,10
9
synthetic route to it which can be performed on a large
scale is reported here. 3,5-Di-tert-butylbenzaldehyde 3
was prepared from 3,5-di-tert-butyl(bromomethyl)benzene
benzaldehyde 3 in a similar manner to a literature protocol.
An advantage of porphyrin synthesis using dipyrrylmethane
6 is the absence of unwanted side products arising as a
consequence of acid catalysed scrambling of sub-
2
by oxidation with hexamethylenetetraamine (Scheme 1).
The intermediate 3,5-di-tert-butyltoluene 1 was prepared by
1
6,17
stituents
which can occur when methylene substituted
1
1±12
Friedel±Crafts tert-butylation of toluene.
This is an
dipyrrylmethanes are used. Substituent scrambling requires
a reversal of bond formation with the formation of a pyrrylic
carbocation intermediate. For porphyrin syntheses using
dipyrrylmethane this fragmentation does not occur because
there is no extra group to stabilise the pyrrylic carbocation.
Porphyrin 7 was easily metallated by heating with Zn(OAc)2
in DMF. The two meso positions were then brominated by
treatment with NBS to give the dibrominated porphyrin 9. It
was found to be more satisfactory to brominate the metal-
lated porphyrin 8 rather than the unmetallated porphyrin 7
interesting reaction since the methyl group activates the
ortho and para sites of toluene. The isolation of the meta
functionalised product indicates the reversibility of the
reaction and that the de-tert-butylation of the meta isomer
is presumably slower than that of the ®rst formed ortho or
para isomers. The second key building block for porphyrin
1
3
synthesis, dipyrrylmethane 6, was prepared by reduction
of dipyrrylketone 5 with NaBH (Scheme 2). Thione 4
1
4
4
1
required to prepare dipyrryl ketone 5 was prepared by an
5
Scheme 2. Reagents and conditions: (i) CSCl
CF CO H, CH Cl , 0.01M then DDQ 51% (26 g); (v) Zn(OAc)
Pd(PPh Cl , CuI, Et N, THF, 16 h 91% (13.2 g); (viii) Bu NF, CHCl
2
, Et
2
O, 08C 52% (80 g); (ii) H
, DMF, D 3 h 98% (16 g); (vi) NBS, CH
3
90% (8.8 g); (ix) LiHMDS/THF then ( Pr) SiCl 48% (0.3 g).
2
O
2
, KOH, MeOH/H
2
O 70% (44 g); (iii) NaBH
4 2
, EtOH/H O 66% (27 g); (iv) 3,
3
2
2
2
2
2
Cl , 5 min, acetone 90% (8.8 g); (vii) TMSCCH,
2
i
3
)
2
2
3
4
3

M. J. Plater et al. / Tetrahedron 58 (2002) 2405±2413
2407
3 2 2 4 3 2 2
Scheme 3. Reagents and conditions: (i) 14, Pd(PPh ) Cl , CuI, pyrrolidine, 20 min 80% (1.0 g); (ii) Bu NF, THF 95% (0.73 g); (iii) 17, 18 or 19, Pd(PPh ) Cl ,
CuI, Et N, THF, 20 79% (82 mg), 21 19% (22 mg), 22 30% (35 mg).
3
as reported previously for a related preparation of 5,15-bis-
9
766(4.9) nm. The D±A compound similar to porphyrin 20
studied by Therien, in which the 3,5-di-tert-butylphenyl
5
bromo-10,20-bis-(phenyl)porphyrin. The bis(trimethylsilyl-
ethynyl) porphyrin 11 was prepared by palladium catalysed
coupling of dibrominated porphyrin 9 with trimethylsilyl-
acetylene 10 on a 13 g scale. It was not necessary to use
trimethylsilylethynylzinc chloride as reported previously by
Therien on a small scale for the preparation of [5,15-bis-
groups are replaced by phenyl groups, was prepared
previously by palladium catalysed coupling of [5,15-bis-
bromo-10,20-bis-(phenyl)porphinato]zinc(II) ®rstly with
para-(dimethylamino)phenylacetylene followed by para-
nitrophenylacetylene. This route necessitates the synthesis
of ethynyl derivatised donor and acceptor building blocks.
The route published here is a more convergent approach
making use of readily available bromo- and iodo- aromatic
acceptors 20±22 for palladium coupling reactions. The
D±D and A±A porphyrins 25 and 26, respectively, were
prepared in a similar manner by palladium catalysed
coupling reactions of the bis(ethynyl) building block 12
with either 4-iodo-N,N-dimethylaniline 14 or 4-iodonitro-
benzene 17, respectively.
18
(phenyl)-10,20-bis-trimethylsilylethynylporphinato]zinc(II).
This route into bis(ethynyl) porphyrins was found by trial
and error to be the most satisfactory for preparing multigram
quantities of material. The two silyl groups of compound 11
were easily removed with Bu NF to give the bis(ethynyl)
4
porphyrin 12. This was monolithiated and quenched with
triisopropylchlorosilane to give the mono-protected
porphyrin 13 following a procedure developed by
1
9
Anderson. The coupling of dibromoporphyrin 9 with tri-
isopropylsilylacetylene using Pd(PPh ) Cl was unsuccess-
3
2
2
ful presumably owing to the steric bulk of the silyl group.
Porphyrin 13 was used as a key building block to access
donor±acceptor porphyrins. Palladium catalysed coupling
2
0
with 4-iodo-N,N-dimethylaniline 14 gave the donor func-
tionalised porphyrin 15 (Scheme 3). This was desilylated
with ¯uoride to give porphyrin 16 which was then coupled
with three different acceptors to give the novel D±A
porphyrins 20±22. The D±A porphyrin 20 was also
prepared by palladium catalysed coupling of mono-
protected porphyrin 13 with 4-iodonitrobenzene 17 to give
the acceptor functionalised porphyrin 23. This was subse-
quently deprotected with ¯uoride to give porphyrin 24 then
coupled with 4-iodo-N,N-dimethylaniline 14 to give the
same D±A porphyrin 20. This variation on the route
appeared to offer no particular advantages. D±A porphyrins
2
0 and 21 show similar long wavelength UV absorptions at
79(4.9) and 674(5.2) nm, respectively, while D±A
6
porphyrin 22 containing the nitrothiazoyl acceptor group
showed a long wavelength UV absorption red shifted to

2408
M. J. Plater et al. / Tetrahedron 58 (2002) 2405±2413
Melting points were carried out using a Ko¯er hot-stage
microscope and are uncorrected. Starting materials were
supplied by Aldrich and Lancaster Synthesis. Pyrrole,
Et N, Et NH and pyrrolidine were dried by distillation
3
2
from CaH . Solvents were used as supplied unless otherwise
2
stated. THF was dried under nitrogen over CaH and LiAlH
2
4
using triphenylmethane as an indicator.
1
1
3
(
1
(
.1.1. 3,5-Di-tert-butyltoluene 1. Aluminium trichloride
20 g, 0.14 mol) was added in 2 g portions, over a period of
2 h, to a rapidly stirred solution of 2-chloromethylpropane
400 g, 4.3 mol) in toluene (200 g, 2.1mol) in a 1L round
bottomed ¯ask ®tted with a silicon oil bubbler. After a
further 12 h, water was added and the product was extracted
into Et O. The solvent was removed under reduced pressure
2
and the residue puri®ed by Vigreux distillation. The distil-
late was collected in 30 mL portions, which were subse-
quently stored in the cold for 24 h. The crude crystalline
product (220 g, 50%) was ®ltered and used without further
puri®cation. An analytical sample was puri®ed by crystal-
lisation from methanol. (Found: C, 88.1; H, 12.3. C H
1
5
24
requires C, 88.2; H, 11.8%.)
1
2
3.1.2. 3,5-Di-tert-butyl(bromomethyl)benzene 2.
A
mixture of 3,5-di-tert-butyltoluene 1 (90 g, 0.44 mol),
N-bromosuccinimide (135 g, 0.66 mol) and benzoyl-
peroxide (1g, 4 mmol) in CCl (800 mL) was re¯uxed for
4
3
h. The solution was cooled, ®ltered and concentrated
under reduced pressure. The crude product (125 g) was
used without further puri®cation in the next step.
2
1
Palladium catalysed self coupling of porphyrin 13 gave
the dimer 27 which has recently been studied as a template
for the supramolecular assembly of a six particle
3.1.3. 3,5-Di-tert-butylbenzaldehyde 3. A mixture of 3,5-
di-tert-butyl(bromomethyl)benzene 2 (crude weight 125 g,
0.44 mol) and hexamethylenetetraamine (256 g, 1.83 mol)
in methanol/water (500 mL, 1:1) was re¯uxed for 4 h.
Concentrated aqueous HCl (150 mL) was added dropwise
and the mixture re¯uxed for a further 0.5 h. The solution
was cooled and extracted into CH Cl (3£350 mL), the
2
2
hydrogen bonded aggregate using 4(3H)pyrimidone.
This report was the ®rst example of a prototype aggregate
that was co-operatively stabilised by both hydrogen bonding
4 H-bonds) and reversible pyridyl nitrogen±zinc bonding
4 N±zinc bonds).
(
(
2
2
solvent removed under reduced pressure and the residue
recrystallised from EtOH/water to give the title compound
(79 g, 82%) as a white crystalline solid, mp 88±898C (sub-
In summary a new improved approach to bis(ethynyl)
porphyrins has been developed and some new D±A
porphyrins have been synthesised. Their NLO properties
are currently under evaluation.
1
2
limation) (lit. 82±838C) (Found: C, 82.7; H, 10.2. C H O
1
5
22
requires C, 82.5; H, 10.2%); l
3.2); nmax (KBr) (cm ) 3365m, 2962vs, 2904s, 2866s,
(CHCl ) (nm) 296 (log 1
3
max
2
1
2
1
815s, 2733s, 1689vs, 1601s, 1463s, 1388s, 1364s,
324vs, 1304m, 1278m, 1249s, 1190vs, 1126w, 998w,
3. Experimental
947m, 899m, 882s, 817m, 706s and 514m; d
CDCl ) 1.35 (18H, s, t-Bu), 7.71(3H, m, o and p-Ph) and
(250 MHz;
H
3
3
.1. General
10.00 (1H, s, CHO); d
(62.9 MHz; CDCl ) 31.4, 35.0,
C 3
1
24.2, 128.9, 136.2, 151.9 and 193.3; m/z 219.1 (M 1H,
1
100%) and 203 (M 2Me, 5).
1
Ultraviolet spectra were recorded on a Perkin±Elmer
Lambda 15 UV±VIS spectrophotometer using dichloro-
methane or THF as the solvent. Infrared spectra were
3.1.4. 2,2-Dipyrrylthione 4. A solution of pyrrole (116 g,
1
recorded on an ATI Mattson FTIR spectrometer. H and
C NMR spectra were obtained at 250 and 62.9 MHz,
1.74 mol) in dry Et
stirred solution of thiophosgene (100 g, 0.87 mol) in dry
Et O (300 mL) at 08C under argon. After 30 min, MeOH
2
O (300 mL) was added dropwise to a
1
3
respectively, on a Brucker AC 250 spectrometer. Chemical
shifts, d, are given in ppm relative to the residual solvent.
Coupling constants J are given in Hz. Low resolution mass
spectra were obtained using electrospray ionisation on a
Finnigan Navigator Mass Spectrometer and accurate mass
at the University of Wales, Swansea using fast atom
bombardment methods. Butterworth Laboratories, using a
PE 2400 CHN analyser, conducted elemental analyses.
2
(200 mL) was added and stirring was continued for a further
30 min. The solvent was removed under reduced pressure
and the residue dissolved in CHCl before ®ltering through a
3
short plug of silica. The solvent was removed under reduced
pressure to give the title compound (80 g, 52%) as a deep
purple crystalline solid. An analytical sample was puri®ed
by ¯ash chromatography on silica gel using toluene/CHCl
3

M. J. Plater et al. / Tetrahedron 58 (2002) 2405±2413
2409
(
(
(
1
9
6
9:1) as eluent, mp 98±998C (ether/light petroleum 60±80)
(CHCl ) (nm) 404 (log 1 4.5); n
3 max
s, N±H), 1.57 (36H, s), 7.83 (2H, t, Jˆ1.8 Hz, p-Ph), 8.16
(4H, d, Jˆ1.8 Hz, o-Ph), 9.17 (4H, d, Jˆ4.8 Hz), 9.42 (4H,
1
lit 96±988C); l
4
max
2
1
KBr) (cm ) 3394s, 3344s, 3115m, 1523vs, 1405vs,
d, Jˆ4.8 Hz) and 10.33 (2H, s, meso); d (62.9 MHz;
C
386vs, 1284s, 1234w, 1129w, 1101vs, 1060m, 1028vs,
85w, 935w, 906m, 878m, 832w, 773w, 748vs, 701m,
36s and 585vs; d (250 MHz; CDCl ) 6.40 (2H, m), 7.04
CDCl ) 31.8, 35.1, 105.1, 120.5, 121.1, 130.3, 131.3,
3
1
131.5, 140.4, 145.0, 147.5 and 149.1; m/z 687.0 (M ,
1
50%), 499.6 (M 2di-tert-BuPh1H, 100).
H
3
(
(
2H, m), 7.19 (2H, m) and 9.76 (2H, s, N±H); dC
62.9 MHz; CDCl ) 112.5, 114.8, 127.7, 138.4 and 193.2;
3.1.8.
[5,15-Bis-(3,5-bis-tert-butylphenyl)porphinato]-
3
1
10
m/z 176.0405 (M C H SN requires 176.0408); m/z 177.0
9
zinc(II) 8. A suspension of 5,15-bis-(3,5-bis-tert-butyl-
phenyl)porphyrin 7 (15 g, 22 mmol) and Zn(OAc) ´2H O
8
2
1
1
(
M , 100%) and 110.1 (M 2C H N, 6).
4 4
2
2
(
48 g, 220 mmol) in DMF (900 mL) was re¯uxed for 3 h.
0
0%) was added dropwise to a solution of KOH (100 g,
.8 mol) and 2,2 -dipyrrylthione 4 (80 g, 0.4 mol) in 95%
3
3
1
.1.5. 2,2 -Dipyrrylketone 5. Hydrogen peroxide (330 mL,
Water (1L) was added and the precipitate ®ltered and
washed with water, MeOH and acetone. The residue was
dissolved in CHCl and ®ltered, MeOH was added and the
0
3
aqueous MeOH (2.5 L) at 08C. The mixture was re¯uxed for
min then cooled. Water (4 L) was added and the solution
volume reduced to precipitate the product. Filtration give
the title compound (16 g, 98%) as a purple solid,
mp.2508C (dichloromethane/methanol). lmax (CHCl )
5
chilled. The product was ®ltered and dried to give the title
compound (44 g, 69%) as pale yellow needles, mp 159±
3
1
2
(nm) 412 (log 1 5.6) and 540 (4.3); nmax (KBr) (cm )
2958vs, 2903s, 2867s, 2362m, 2363m, 1652s, 1589s,
1517w, 1469m, 1424m, 1389s, 1360s, 1287m, 1244s,
1213m, 1059s, 987s, 926w, 855m, 822w, 784s, 707m and
670w; d (250 MHz; CDCl ) 1.58 (36H, s, t-Bu), 7.85 (2H,
1
608C (sublimation) (lit. 160±1618C) (Found: C, 67.6;
5
1
H, 5.0; N, 17.5. C H N O requires C, 67.5; H, 5.0; N,
9
8
2
1
(
7.5%); l
cm ) 3413s, 3364s, 3126m, 1726w, 1568vs, 1545s,
(CHCl ) (nm) 333 (log 1 4.5); n
(KBr)
max
max
3
2
1
H
3
1
7
405vs, 1120m, 1101s, 1056m, 1032s, 882m, 839vs,
53vs and 577s; d (250 MHz; CDCl ) 6.34 (2H, m), 7.08
t, Jˆ1.8 Hz, p-Ph), 8.15 (4H, d, Jˆ1.8 Hz, o-Ph), 9.20 (4H,
d, 4.7), 9.44 (4H, d, 4.7) and 10.31 (2H, s, meso); dC
(62.9 MHz; CDCl ) 31.8, 35.1, 106.0, 120.8, 121.4, 130.1,
H
3
(2H, m), 7.16 (2H, m) and 10.09 (2H, s, N±H); dC
(62.9 MHz; CDCl ) 111.0, 116.2, 124.2, 130.6 and 173.1;
3
1
131.6, 132.8, 141.7, 148.7, 149.4 and 150.4; m/z 749.3 (M ,
100%).
3
1
1
m/z 161.1 (M , 100%) and 94.1 (M 2C H N, 4).
4
4
0
0
3
.1.6. 2,2 -Dipyrrylmethane 6. A mixture of 2,2 -dipyrryl-
ketone 5 (44 g, 0.27 mol) and sodium borohydride (100 g,
.7 mol) in aqueous EtOH (500 mL, 95%) was brought to
3.1.9.
[5,15-Bis-bromo-10,20-bis-(3,5-bis-tert-butyl-
1
0
phenyl)porphinato]zinc(II) 9. NBS (3.84 g, 22 mmol)
was added to a stirred solution of porphyrin 8 (8.1g,
11 mmol) in DCM (400 mL). After 5 min the reaction was
quenched with acetone (50 mL), MeOH was added and the
solvent was reduced to a small volume. The solution was
then ®ltered and the residue was washed with MeOH to give
the title compound (8.8 g, 90%) as a purple powder and a
single spot by TLC, mp.2508C (tetrahydofuran/light
petroleum); (Found: C, 63.3; H, 5.6; N, 6.0; Br, 17.0.
C H Br N Zn requires C, 63.5; H, 5.5; N, 6.2; Br,
2
re¯ux. After 3 h, water (300 mL) was added and the EtOH
removed under reduced pressure. The remaining solution
was extracted with Et O (4£300 mL). The solvent was
2
removed under reduced pressure and the residue extracted
with light petroleum 40±60 until only a small amount of a
dark coloured oil remained. The solvent was removed under
reduced pressure in base washed glassware to yield the title
compound (26.5 g, 66%) as a cream powder, mp 73±748C
4
8
64
2
4
1
3
(
(
2
1
1
light petroleum 60±80) (lit. 72±738C); lmax (CHCl )
3
17.6%); l
(CHCl ) (nm) 426 (log 1 5.6); n
3
(KBr)
max
max
2
nm) 334 (log 1 3.1) and 449 (3.0); nmax (KBr) (cm )
1
21
(cm ) 3456br, 2959s, 2862m, 1590m, 1470w, 1385m,
1360m, 1286m, 1260s, 1097s, 1074s, 1005s, 795s and
715w; dH (250 MHz; THF-d ) 1.64 (36H, s, t-Bu), 7.99
896m, 1716w, 1656w, 1562m, 1469m, 1438m, 1423m,
403m, 1330m, 1261w, 1245w, 1224w, 1181m, 1112s,
093s, 1024vs, 884m, 803vs, 726vs and 664s; dH
8
(2H, t, Jˆ1.8 Hz, p-Ph), 8.14 (4H, d, Jˆ1.8 Hz, o-Ph),
(
250 MHz; CDCl ) 3.92 (2H, s, CH ), 6.07 (2H, bs), 6.19
3
8.96 (4H, d, Jˆ4.9 Hz) and 9.73 (4H, d, Jˆ4.9 Hz); d
2
C
(
CDCl ) 53.6, 106.6, 108.3, 117.5 and 129.3; m/z 147.1
2H, m), 6.60 (2H, m) and 7.62 (2H, m); dC (62.9 MHz;
(62.9 MHz; THF-d ) 33.4, 37.1, 106.4, 123.4, 125.6,
8
132.2, 134.8, 135.6, 144.2, 150.9, 152.3 and 153.4; m/z
927/929/931(M , 100%).
3
1
M , 100%).
1
(
1
0
3
.1.7. 5,15-Bis-(3,5-bis-tert-butylphenyl)porphyrin 7.
A
3.1.10. Trimethylsilylacetylene 10. A suspension of
sodium acetylide (80 g, 18% w/w in xylenes, 0.3 mol) was
added to chlorotrimethylsilane (32.5 g, 0.3 mol) in THF
(100 mL) under argon. The mixture was stirred for 24 h,
the solution distilled, and the fraction boiling between 50
and 808C collected. The crude product was washed with
solution of dipyrrylmethane 6 (21.7 g, 0.15 mol) and 3,5-di-
tert-butylbenzaldehyde 3 (33 g, 0.15 mol) in DCM (20 L)
was stirred for 3 h, under argon, in the presence of tri¯uoro-
acetic acid (10 mL). The reaction was quenched by the
addition of DDQ (51g, 0.23 mol) and stirring continued
for 0.5 h. The mixture was basi®ed with Et N (50 mL)
3
water, dried over MgSO and redistilled. The fraction boil-
4
and ®ltered through silica. The solvent was removed
under reduced pressure to give the title compound (26 g,
ing between 50 and 658C was collected, washed with water,
dried over MgSO and ®ltered to give the title compound
4
5
4
2
1
7
1%) as a purple solid, mp.2508C; l
(CHCl ) (nm)
3
(22 g, 75%) as a colourless oil which was spectroscopically
identical to a commercial sample (Aldrich).
max
2
1
09 (log 1 5.7); nmax (KBr) (cm ) 3292m, 3067vs,
959s, 2865s, 1588s, 1536w, 1469s, 1410s, 1359s,
245vs, 1197m, 1143w, 1053w, 959m, 912m, 846s,
86vs, 737s and 686m; d (250 MHz; CDCl ) 23.02 (2H,
3.1.11. [5,15-Bis-(3,5-bis-tert-butylphenyl)-10,20-bis-tri-
methylsilylethynylporphinato]zinc(II) 11. Triethylamine
H
3

2410
M. J. Plater et al. / Tetrahedron 58 (2002) 2405±2413
(
35 mL) was distilled, from CaH under argon, into a stirred
2
1.55 (36H, s, t-Bu), 4.13 (1H, s, CCH), 7.81 (2H, bs, p-Ph),
8.04 (4H, bs, o-Ph), 8.98 (4H, d, Jˆ4.6 Hz), 9.71(2H, d,
solution of dibromoporphyrin
trimethylsilylacetylene 10 (6 g, 60 mmol), Pd(PPh ) Cl
2
(
9 (14 g, 15.4 mmol),
1
Jˆ4.6 Hz) and 9.77 (2H, d, Jˆ4.6 Hz); m/z 954.6 (M ,
3
2
600 mg, 0.84 mmol) and CuI (150 mg, 0.78 mmol) in
100%).
THF (700 mL). The resulting solution was stirred for 16 h,
the solvent was removed under reduced pressure and the
residue, dissolved in light petroleum 60/80±CH Cl (1:1),
3.1.14. 4-Iodo-N,N-dimethylaniline 14. Ground mercury-
(II)chloride (67 g, 248 mmol) was added to a solution of
N,N-dimethylaniline (30 g, 248 mmol) in CH Cl (1L).
2
2
was ®ltered through silica. The solvent was removed under
reduced pressure and the butadiynyl compound formed as a
side product was removed by sublimation. The residue was
recrystallised from DCM/acetonitrile to yield the title
compound (13.2 g, 91%) as a deep purple crystalline solid
which was spectroscopically identical to the compound
2
2
Iodine (31g, 12 4 mmol) was added and the mixture stirred
rapidly for 9 h. The solid was removed by ®ltration and
washed with sodium thiosulphate (500 mL, 0.1M) and
saturated KI solution (500 mL). The organic layer was
dried over Na SO and the solvent removed under reduced
2
4
1
9
reported previously, mp.2508C; (Found: C, 74.3; H,
7
pressure to give the title compound (30 g, 22%) as white
2
0
.4; N, 6.0. C H N Si Zn requires C, 73.9; H, 7.3; N,
5
plates, mp 81±828C (ethanol) (lit 79±80.58C); nmax (KBr)
1
8
68
4
2
2
5
nmax (KBr) (cm ) 2960vs, 2139s, 1590m, 1498w, 1470m,
.9%); lmax (CHCl ) (nm) 434 (log 1 5.8) and 633 (4.8);
(cm ) 2979w, 2929m, 2888m, 2853m, 2802m, 1586s,
1553m, 1498s, 1444m, 1354s, 1312m, 1227s, 1192m,
1165m, 1123m, 1062m, 983w, 942w, 801vs, 743w, 691w,
565w and 502s; d (250 MHz; CDCl ) 2.91(6H, s, N-Me),
3
2
1
1
1
423w, 1360m, 1288m, 1248s, 1211s, 1163w, 1063w,
005s, 794s, 758m and 712s; dH (250 MHz; CDCl ) 0.60
3
H
3
(
18H, s, Si-Me), 1.55 (36H, s, t-Bu), 7.82 (2H, t, Jˆ1.8 Hz,
6.48 (2H, d, Jˆ9 Hz) and 7.46 (2H, d, Jˆ9 Hz); d
1
z247.9 (M , 100%) and 122.1 (M 2I, 22).
C
p-Ph), 8.04 (4H, d, Jˆ1.8 Hz, o-Ph), 8.97 (4H, d, Jˆ4.8 Hz)
(62.9 MHz; CDCl ) 40.4, 77.5, 114.8, 137.6 and 150.0; m/
3
1
and 9.71(4H, d, Jˆ4.8 Hz); d (62.9 MHz; CDCl ) 0.4,
C
3
3
1
1.8, 35.1, 101.3, 101.8, 107.5, 121.1, 124.1, 129.8, 131.2,
33.1, 141.1, 148.8, 150.6 and 152.2; m/z 941.4352
3.1.15. [5,15-Bis-(3,5-bis-tert-butylphenyl)-10-(4-N,N-
1
(
(
M 1H. C H N Si Zn requires 941.4352), 941.3
5
dimethylaminophenylethynyl)-20-triisopropylsilylethynyl-
porphinato]zinc(II) 15. Porphyrin 13 (1g, 1mmol) was
dissolved in pyrrolidine (30 mL, freshly distilled from
8
69
4
2
1
M 1H, 100%).
3
.1.12.
ethynylporphinato]zinc(II) 12.
uoride (50 mL, 0.5 M in THF) was added to a stirred
solution of porphyrin 11 (11.62 g, 12.3 mmol) in CH Cl
[10,20-Bis-(3,5-bis-tert-butylphenyl)-5,15-bis-
CaH ), under argon. Bis-(triphenylphosphine)palladium
2
1
9
Tetrabutylammonium
dichloride (5 mg, 7 mmol), CuI (5 mg, 26 mmol) and
4-iodo-N,N-dimethylaniline 14 (60 mg, 0.24 mmol) were
added. The solution was stirred for 20 min and the solvent
removed under reduced pressure. The residue was puri®ed
by ¯ash chromatography twice on silica using light
petroleum 60/80±THF (4:1) as eluent. The crude product
was crystallised from CH Cl ±methanol to give the title
¯
2
2
(
(
350 mL). After 5 min acetic acid (2 mL) and MeOH
600 mL) were added and the solution chilled (,2208C).
After 1h the precipitate was ®ltered and washed with
MeOH to give the title compound (8.8 g, 90%) as a purple
powder, mp.2508C; (Found: C, 77.8; H, 6.6; N, 6.8.
C H N Zn requires C, 78.2; H, 6.6; N, 7.0%); l
max
2
2
compound (0.9 g, 80%) as a deep green, almost black,
crystalline solid, mp.2508C; (Found: C, 77.0; H, 7.4; N,
6.5. C H N SiZn requires C, 77.2; H, 7.6; N, 6.5%); l
5
2
52
4
2
1
(
CHCl ) (nm) 432 (log 1 5.8); n
3
(KBr) (cm ) 3300m,
max
69 81
5
max
2
1
9
958vs, 2865m, 2089w, 1590s, 1499w, 1469m, 1423w,
391w, 1361m, 1287m, 1245m, 1209m, 1062m, 1003m,
32m, 880w, 821w, 792s, 711m and 651w; d (250 MHz;
H
(CHCl ) (nm) 454 (log 1 5.8) and 658 (5.2); n
3
(KBr)
max
2
1
(cm ) 2958vs, 2863s, 2183m, 2136m, 1601s, 1520s,
1468m, 1360s, 1287w, 1245w, 1213s, 1164w, 1113m,
1066m, 1005m, 929w, 882w, 821w, 796m, 739w, 713m
CDCl ) 1.59 (36H, s, t-Bu), 4.63 (2H, s, CC±H), 7.92 (2H, s,
3
p-Ph), 8.10 (4H, s, o-Ph), 8.90 (4H, d, Jˆ4.6 Hz) and 9.68
and 678w; dH (250 MHz; THF-d ) 1.48 (21H, m, i-Pr),
8
(
4H, d, Jˆ4.6 Hz); d (62.9 MHz; CDCl ) 32.2, 35.9, 85.4,
1.57 (36H, s, t-Bu), 3.09 (6H, s, N-Me), 6.91(2H, d,
Jˆ8.8 Hz), 7.89 (4H, m), 8.08 (4H, d, Jˆ1.8 Hz, o-Ph),
8.83 (2H, m, Jˆ4.6 Hz), 8.84 (2H, d, Jˆ4.6 Hz), 9.65
C
3
8
1
7.3, 100.7, 122.0, 124.6, 130.9, 131.7, 133.6, 143.0, 149.7,
51.6 and 153.2; m/z 798.3 (M , 100%).
1
(
2H, d, Jˆ4.6 Hz) and 9.72 (2H, d, Jˆ4.6 Hz); d
C
3
2
.1.13. [5,15-Bis-(3,5-bis-tert-butylphenyl)-10-ethynyl-
A
(62.9 MHz; THF-d ) 13.1, 19.7, 32.2, 35.9, 40.4, 64.4,
8
0-triisopropylsilylethynylporphinato]zinc(II) 13.
92.1, 97.2, 99.6, 100.5, 104.5, 111.8, 112.1, 113.1, 122.0,
124.7, 130.6, 131.3, 131.6, 133.0, 133.6, 143.2, 149.7,
151.2, 151.3, 151.7, 152.6 and 153.6; m/z 1073.5 (M ,
solution of lithium bis(trimethylsilyl)amide (0.9 mL, 1M
in THF, 0.9 mmol) was added to a rapidly stirred solution
of porphyrin 12 (0.50 g, 0.6 mmol) in dry THF (60 mL)
under an argon atmosphere. After 10 min chlorotriiso-
propylsilane (0.4 mL, 1.8 mmol) was added. Stirring was
continued for 30 min and aqueous KOH (1M, 30 mL)
was added. The solution was poured into CH Cl and
1
100%).
3.1.16. [5,15-Bis-(3,5-bis-tert-butylphenyl)-10-ethynyl-
20-(4-N,N-dimethylaminophenylethynyl)porphinato]-
zinc(II) 16. Tetrabutylammonium ¯uoride (0.4 mL, 0.10 M
in THF) was added to a stirred solution of porphyrin 15
(40 mg, 0.04 mmol) in THF (30 mL). The solvent was
removed under reduced pressure and the resulting solid
washed with MeOH, ®ltered, dried to give the title
compound (31mg, 90%) which was used without further
2
2
washed with water. The solvent was removed under reduced
pressure and the residue puri®ed by ¯ash chromatography
using light petroleum/CH Cl ±pyridine (70:10:2) as eluent.
2
2
Recrystallisation from CH Cl /MeOH gave the title
2
2
compound (0.30 g, 48%) as a purple solid, mp.2508C;
lmax (CHCl ) (nm) 434 (log 1 5.4), 445 (5.2), 580 (4.2)
puri®cation; lmax (CHCl ) (nm) 456 (log 1 5.6) and 666
3
3
and 629 (4.4); dH (250 MHz; CDCl ) 1.44 (21H, m, i-Pr),
3
(4.6).

M. J. Plater et al. / Tetrahedron 58 (2002) 2405±2413
2411
1
3
dimethylaminophenylethynyl)-20-(4-nitrophenylethynyl)-
.1.17.
[5,15-Bis-(3,5-bis-tert-butylphenyl)-10-(4-N,N-
151.6 and 152.1; m/z 1016.4478 (M C H N Zn requires
67 64 4
1
1016.4484); m/z 1017.3 ([M1H] , 20%).
porphinato]zinc(II) 20. Method 1: Triethylamine (2 mL)
was distilled, from CaH under argon, into a mixture of
3.1.19. [5,15-Bis-(3,5-bis-tert-butylphenyl)-10-(4-N,N-di-
methylaminophenylethynyl)-(2-(5-nitrothiazoyl)ethynyl)-
20-porphinato]zinc(II) 22. A mixture of porphyrin 13
(100 mg, 0.1 mmol), 2-bromo-5-nitrothiazole 19 (100 mg,
0.5 mmol), Pd(PPh ) Cl (5 mg, 7 mmol), CuI (5 mg,
26 mmol) and triethylamine (2 mL, distilled from CaH2
under argon) in dry THF (20 mL) was stirred for 12 h.
The solvent was removed under reduced pressure and the
residue, extracted into light petroleum 60/80±THF (3:1,
pyridine (1%)), was chromatographed on silica with light
petroleum±THF (3:1, pyridine (1%)). The green brown
band was collected and the solvent removed under reduced
pressure. The residue was triturated successively with
MeOH and then chloroform to give the title compound
(35 mg, 30%) as a deep green powder, mp.2508C; lmax
2
porphyrin 16 (100 mg, 0.1 mmol), 4-iodonitrobenzene 17
(
30 mg, 0.12 mmol), Pd(PPh ) Cl (5 mg, 7 mmol) and
3 2 2
CuI (5 mg, 26 mmol) in THF (20 mL) with stirring. Stirring
was continued for 20 h. The solvent was removed under
reduced pressure and the residue, extracted into light
petroleum 60/80±THF (4:1), chromatographed on silica
with light petroleum/THF (3:1) as eluent to give the title
compound (82 mg, 79%) as a deep green powder,
mp.2508C; (Found: C, 75.4; H, 6.7; N, 6.9.
C H N O Zn´C H O requires C, 75.7; H, 6.5; N, 7.6%);
3
2
2
6
6
64
6
2
4
8
lmax (CHCl ) (nm) 458 (log 1 5.4) and 679 (4.9); n (KBr)
max
3
2
cm ) 2957s, 2905m, 2868m, 2180s, 1590s, 1515s, 1361m,
1
(
1
1
336vs, 1286m, 1261m, 1246m, 1208m, 1191m, 1109m,
066w, 1006m, 929m, 851m, 793s and 712m; dH
(
250 MHz; CDCl ) 1.65 (36H, s, t-Bu), 3.07 (6H, s,
3
(CHCl ) (nm) 288 (log 1 5.5), 468 (5.2) and 766 (4.9);
3
2
1
NMe), 6.89 (2H, d, Jˆ8.2 Hz), 7.89 (2H, d, Jˆ8.0 Hz),
nmax (KBr) (cm ) 711m, 790m, 929w, 1004w, 1108m,
1205s, 1280m, 1351s, 1513s, 1513s, 1596vs, 2176m,
2858m, 2912m, 2952vs, 3397s, 3428s and 3498s; dH
(250 MHz; CDCl (1% pyridine d )) 1.58 (36H, s, t-Bu),
7
8
d
1
1
1
.97 (2H, s, o-Ph), 8.19 (4H, s), 8.24 (2H, d, Jˆ8.2 Hz),
.42 (2H, d, Jˆ8.0 Hz), 8.95 (4H, m) and 9.78 (4H, m);
(62.9 MHz; THF-d ) 32.1, 37.1, 93.3, 96.7, 100.0,
C
8
3
5
01.4, 106.7, 113.1, 114.3, 123.2, 126.2, 126.5, 127.3,
32.4, 132.9, 133.0, 133.5, 134.2, 134.3, 135.1, 135.2,
44.2, 149.3, 151.0, 152.4, 152.7, 153.0 and 154.6 (two
3.09 (6H, s, N-Me), 6.86 (2H, d, Jˆ8.8 Hz), 7.26 (1H, s,
C±H), 7.81(2H, t, Jˆ3.8 Hz), 7.90 (2H, d, Jˆ8.8 Hz), 8.07
(4H, t, Jˆ3.8 Hz), 8.88 (2H, d, Jˆ4.3 Hz), 8.97 (2H, d,
Jˆ4.3 Hz), 9.72 (2H, d, Jˆ4.3 Hz), and 9.86 (2H, d,
Jˆ4.3 Hz); d (62.9 MHz; CDCl /1% pyridine d ) 31 .8,
1
resonances are missing); m/z 1036.4390 (M .
C H N O Zn requires 1036.4382); m/z 1036.3 (M ,
1
from CaH under argon into a mixture of porphyrin 24
(
(
1
6
6
64
6
2
C
3
5
00%). Method 2. Triethylamine (20 mL) was distilled
35.1, 40.4, 82.2, 88.7, 91.7, 98.3, 103.6, 111.2, 112.2,
120.8, 124.4, 130.0, 130.4, 130.7, 132.4, 132.8, 133.3,
141.8, 148.5, 150.0, 150.3, 150.4, 151.6 and 153.2 (3
2
40 mg, 0.04 mmol), 4-iodo-N,N-dimethylaniline 14
20 mg, 0.08 mmol), Pd(PPh ) Cl (5 mg, 7 mmol) and
1
resonances are missing); m/z 1044 (M , 25%).
3
2
2
CuI (5 mg, 26 mmol) in THF (20 mL) with stirring.
Stirring was continued for 5 h. The solvent was removed
under reduced pressure and the residue, extracted into
light petroleum 60/80±THF (3:1), chromatographed on
silica with light petroleum 60/80±THF (3:1) as eluent to
give the title compound (34 mg, 75%) as a deep green
powder.
3.1.20. [5,15-Bis-(3,5-bis-tert-butylphenyl)-10-(4-nitro-
phenylethynyl)-20-triisopropylsilylethynylporphinato]-
zinc(II) 23. Bis-(triphenylphosphine)palladium dichloride
(5 mg, 7 mmol), CuI (5 mg, 26 mmol) and 4-iodonitro-
benzene (60 mg, 0.24 mmol) and Et N (5 mL) were added
3
to a solution of porphyrin 13 (50 mg, 0.05 mmol) in THF
(40 mL). The solution was stirred for 40 min and the solvent
3
.1.18. [5,15-Bis-(3,5-di-tert-butylphenyl)-10-(4-cyano-
removed under reduced pressure. The residue was puri®ed
by ¯ash chromatography four times on silica using light
petroleum 60/80±THF (4:1) as eluent. The fraction
phenylethynyl)-20-(4-N,N-dimethylphenylethynyl) por-
phinato]zinc(II) 21. A mixture of porphyrin 16 (100 mg,
0
Pd(PPh ) Cl (5 mg, 7 mmol), CuI (5 mg, 26 mmol) and
triethylamine (2 mL, distilled from CaH under argon) in
2
dry THF (20 mL) was stirred for 12 h. The solvent was
removed under reduced pressure and the residue, extracted
into light petroleum 60/80±THF (3:1, pyridine (1%)), chro-
matographed on silica with light petroleum/THF (3:1,
pyridine (1%)) as eluent to give the title compound
.1mmol), 4-bromobenzonitrile 18 (100 mg, 0.6 mmol),
R ,0.83 was crystallised from THF±propanol to give the
f
title compound (39 mg, 80%) as a green solid, mp.2508C;
lmax (CHCl ) (nm) 453 (log 1 5.7) and 653 (4.6); n (KBr)
3
2
2
3
max
2
1
(cm ) 3640s, 2958vs, 2868s, 2185w, 2139w, 1750w,
1697w, 1592m, 1519w, 1433s, 1393m, 1363m, 1342m,
1311m, 1230s, 1154s, 1120m, 859m, 771m, 575w and
502w; dH (250 MHz; CDCl ) 1.43 (21H, m, i-Pr), 1.56
3
(36H, s, t-Bu), 7.83 (2H, t, p-Ph), 7.92 (2H, d, Ph), 8.05
(4H, d, o-Ph), 8.36 (2H, d, Ph), 8.96 (2£2H, 2£d, b-pyr-
rolic), 9.54 (2H, d, b-pyrrolic) and 9.72 (2H, d, b-pyrrolic);
(
lmax (CHCl ) (nm) 457 (log 1 5.7) and 674 (5.2); n (KBr)
22 mg, 19%) as a deep green±blue powder, mp.2508C;
3
max
2
1
cm ) 709w, 792s, 875w, 931w, 1008m, 1062m, 1108m,
(
dC (62.9 MHz; CHCl ) 11.9, 19.1, 31.8, 35.1, 94.5, 97.2,
3
1
2
203m, 1255m, 1351s, 1508s, 1598vs, 2179s, 2863m,
902m, 2954s, 3411s, 3467s and 3554m; dH (250 MHz;
98.9, 99.6, 121.2, 124.0, 124.6, 129.5, 131.4, 131.8, 133.2,
133.4, 133.5, 141.1, 148.8, 150.4, 150.8, 151.8 and 152.3
(four resonances are missing); m/z 1075 (M 1H, 100%).
1
CDCl ) 1.55 (36H, s, t-Bu), 3.08 (6H, s, N-Me), 6.84 (2H,
3
d, Jˆ8.8 Hz), 7.81(6H, m), 8.02 (6H, m), 8.89 (4H, 2 £d,
Jˆ4.6 Hz), 9.62 (2H, d, Jˆ4.6 Hz) and 9.72 (2H, d,
Jˆ4.6 Hz); d (62.9 MHz; CHCl ) 31.8, 35.1, 91.6, 94.3,
3.1.21. [5-Ethynyl-10,20-bis-(3,5-bis-tert-butylphenyl)-
15-(4-nitrophenylethynylporphinato]zinc(II) 24. Tetra-
butylammonium ¯uoride (0.3 mL, 0.10 M in THF) was
added to a stirred solution of porphyrin 23 (15 mg,
0.016 mmol) in THF (20 mL). The solvent was removed
C
3
9
1
1
7.7, 98.5, 99.0, 103.9, 110.8, 111.2, 112.2, 118.9, 120.8,
24.5, 129.9, 130.8, 131.7, 132.3, 132.5, 132.8, 133.1,
41.7, 148.3, 148.6, 148.8, 149.2, 150.1, 150.3, 150.5,

2412
M. J. Plater et al. / Tetrahedron 58 (2002) 2405±2413
under reduced pressure and the residue crystallised from
THF±propanol to give the title compound (15 mg, 90%)
as a green powder, mp.2508C (THF±propanol) (Found:
C, 76.3; H, 6.4; N, 7.4. C H N O SiZn requires C, 75.8;
Jˆ4.6 Hz) and 9.86 (4H, d, Jˆ4.6 Hz); d (62.9 MHz;
C
THF-d ) 33.7, 37.1, 97.2, 100.7, 102.0, 123.4, 126.2,
8
127.0, 132.9, 132.8, 133.2, 134.4, 135.3, 135.3, 144.0,
149.6, 151.2, 153.0, 153.1 and 154.2; m/z (FAB) 1040.3
5
8
55
5
2
1
1
H, 6.0; N, 7.6%); l
(
(CHCl ) (nm) 449 (log 1 5.7); n
3
(M , 100%) EI 1038.3815 (M C H N O Zn requires
64 58 6 4
max
max
2
KBr) (cm ) 3296w, 2958s, 2866w, 2187m, 1592s, 1514m,
1
1038.3811).
1
8
338vs, 1288w, 1210m, 1104w, 1065w, 1006m, 934m,
51m, 793m and 711m; d (250 MHz; CDCl ) 1.52 (36H,
0
3.1.24. [5,5 -Bis-[10,20-bis(3,5-di-tert-butylphenyl)-15-
triisopropylsilylethynyl-porphinyl]-1,3-butyn-1,4-diyl]-
dizinc(II) 27. Porphyrin 13 (250 mg, 0.3 mmol),
H
3
s), 4.14 (1H, s), 7.78 (2H, t, Jˆ1.8 Hz), 7.99 (4H, d,
Jˆ1.8 Hz), 8.09 (2H, d, Jˆ2.1Hz), 8.37 (2H, d,
Jˆ2.1Hz), 8.90 (4H, m) and 9.65 (4H, m); d (62.9 MHz;
Pd(PPh
)
3
2
Cl
0.15 mmol) and Et
2
(108 mg, 0.15 mmol), CuI (30 mg,
N (1mL) in dry THF (40 mL) were
C
CHCl ) 31.8, 35.0, 122.8, 123.2, 123.5, 124.1, 130.0, 131.8,
3
3
1
and 149.8 (®ve resonances are missing); m/z 919.2 (M ,
33.0, 133.2, 135.0, 135.4, 135.8, 141.5, 148.6, 149.0, 149.4
stirred at room temperature for 1h. The solvent was
removed under reduced pressure and the residue, dissolved
in DCM±light petroleum (1:6) ®ltered through a short plug
of silica. The solvent was removed under reduced pressure
1
1
00%).
3
1
2
0
.1.22. [5,15-Bis-(4-N,N-dimethylaminophenylethynyl)-
0,20-bis-(3,5-bis-tert-butylphenyl)porphinato]zinc(II)
5. Tetrakis(triphenylphosphine)palladium(0) (34 mg,
.03 mmol) and CuI (5 mg, 0.03 mmol) were added to a
and the residue crystallised from CH Cl ±MeOH to give the
2 2
title compound (240 mg, 95%) as a green solid with a metal-
lic lustre, mp.3008C; (Found: C, 76.2; H, 7.8; N, 5.8.
C
H
(CHCl
N
) (nm) 455 (log 1 5.7), 491(5.3), 727 (5. 1) ;
Si
Zn requires C, 76.8; H, 7.5; N, 5.9%); lmax
2 2
122
142
8
stirred solution of porphyrin 12 (65 mg, 0.08 mmol) and
-iodo-N,N-dimethylaniline 14 (40 mg, 0.16 mmol) under
3
n
max
2
1
4
(KBr) (cm ) 622w, 707m, 792m, 829w, 881w, 1002m,
1062w, 1207s, 1245w, 1284m, 1357w, 1461m, 1492m,
1589m, 2130m, 2861s, 2954vs, 3413s, 3469s and 3546m;
argon in pyrrolidine (20 mL) freshly distilled from CaH2.
The solution was stirred for 1h and the solvent removed
under reduced pressure. The residue was chromatographed
on silica using light petroleum 60/80±THF (3:1) as eluent.
d (250 MHz; CDCl ) 1.44 (42H, m, i-Pr), 1.57 (72H, s,
H 3
t-Bu), 7.84 (4H, bs), 8.09 (8H, bs), 8.98 (4H, d,
Jˆ4.6 Hz), 9.06 (4H, d, Jˆ4.6 Hz), 9.74 (4H, bd,
(62.9 MHz;
C
The fraction R ,0.7 was collected, the solvent removed
f
under reduced pressure and the product washed with three
portions of MeOH to give the title compound (58 mg, 69%)
as a green powder, mp.2508C; lmax (THF) (nm) 467 (log 1
Jˆ4.3 Hz) and 9.92 (4H, bd, Jˆ4.3 Hz); d
CDCl ) 11.9, 19.1, 31.8, 35.1, 82.4, 87.6, 98.8, 99.8,
3
102.4, 109.2, 121.2, 124.6, 129.6, 130.9, 131.3, 133.2,
133.6, 141.1, 148.8, 150.4, 150.8, 152.3 and 153.0; m/z
2
1
5.5) and 683 (5.1); nmax (KBr) (cm ) 2957s, 2901m,
2865m, 2182m, 1603vs, 1521s, 1444m, 1358m, 1285w,
1245w, 1211m, 1190m, 1109m, 1062w, 1006w, 933w,
8
1
1908 (M , 100%).
17w, 794m and 713w; dH (250 MHz; THF-d ) 1.59
8
(
36H, s, t-Bu), 3.09 (6H, s, N-Me), 6.91(4H, d,
Acknowledgements
Jˆ8.9 Hz), 7.88 (6H, m), 8.11 (4H, d, Jˆ8.6 Hz), 8.84
(
(
4H, d, Jˆ4.3 Hz) and 9.70 (4H, d, Jˆ4.3 Hz); d
We are grateful to the EPSRC national mass spectrometry
service center for mass spectra.
C
62.9 MHz; THF-d ) 32.4, 36.0, 40.6, 92.3, 99.1, 103.5,
8
1
1
12.5, 113.2, 121.9, 124.6, 131.2, 131.4, 133.2, 133.7,
43.4, 149.8, 151.1, 151.7 and 153.0; m/z (FAB) 1035.4
1
21
1
(M , 100%) and 517 (M , 70) EI 1034.4931 (M
C H N Zn requires 1034.4953).
References
6
8
70
6
1
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2
2. Prasad, P. N.; Williams, D. J. Introduction to Nonlinear
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(
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®
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7
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1
1
514m, 1423w, 1338s, 1289w, 1258m, 1208m, 1102w,
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8
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1