Notes
J . Org. Chem., Vol. 62, No. 6, 1997 1879
removed. The crude porphyrin was crystallized from CH
2
Cl
2
/
singlet, 8H), 10.12, 10.14, 10.15, 10.16 (each s, 4H); UV λmax (ꢀ)
hexane. Obtained 240 mg, 91%. No satisfactory melting point
398 nm (136 000), 498 (14 800), 532 (11 000), 568 (7 400), 622
1
+•
could be obtained for this compound. The H NMR matched
(6 400); (MH ) 683). Anal. Calcd for C38
H
42
N
4
O
8
: C, 66.85;
1
3,14
+•
published values.
consistent with 4. Anal. Calcd for C36
.15; N, 9.00. Found: C, 69.16; H, 6.33; N, 8.75. 4 could be
quatitatively converted to the zinc complex 12 using the zinc
The mass specrum (MH ) 582) was also
H, 6.20; N, 8.21. Found: C, 66.82; H, 6.37; N, 8.02.
H
38
N
4
O
6
: C, 69.44; H,
2,4-Bis[3-(m eth oxycar bon yl)-2-pr open yl]-6,7-bis[2-(m eth -
oxyca r bon yl)eth yl]-1,3,5,8-tetr a m eth ylp or p h yr in Isom er s
10a -d . To 2,4-Bis(formylmethyl)-6,7-bis[2-(methoxycarbonyl)-
ethyl]-1,3,5,8-tetramethylporphyrin 4 (100 mg; 0.161 mmol) and
methyl (triphenylphosphoranylidene)acetate (17) (215 mg; 0.643
6
2
4
acetate method.
2
,4-Bis(2-h yd r oxyet h yl)-6,7-b is[2-(m et h oxyca r b on yl)-
eth yl]-1,3,5,8 tetr a m eth ylp or p h yr in (5). Starting with 200
mg of 1 the above procedure for the synthesis of 4 was followed
but without isolation of 4. 4 was redissolved in 50% MeOH/
2 2
mmol) was added dry CH Cl (10 mL). After 4 h stirring at room
temperature, the volume was reduced under vacuum and hexane
added to precipitate the porphyrin. After a second recrystalli-
zation the crude mixture was purified by flash chromatography
2 2 4
CH Cl , and NaBH was added. After 10 min, reaction was
quenched with glacial acetic acid, the porphyrin washed three
times with water, and solvent removed. The crude porphyrin
using a step gradient of 0, 0.2, 0.3, 0.4% MeOH/CH
2 2
Cl . Obtained
a trace (<1 mg) of putative cic/cis isomer 10a : mp 182-184 °C;
1
was recrystallized from MeOH/CH
2
Cl
2
/hexane and dried under
3
H NMR (CDCl ): δ -3.75 (s, 2H), 3.29 (m, 4H), 3.62-3.66
1
4
high vacuum to obtain 197 mg, 93%: mp 224-226 °C (lit. mp
(overlaping s, 18H), 4.04 (s, 6H), 4.42 (m, 4H), 5.52 (d, 4H), 6.06
(d, 2H, J ) 11.3 Hz), 6.85 (m, 2H, J ) 11.3 Hz), 10.09, 10.10,
10.21, 10.22 (each s, 4H); insuficient material was available to
measure UV-vis extinction coefficients accurately or to perform
1
13,14
2
22-226 °C); H NMR matched published values.
The mass
+
•
spectrum (MH ) 624) was also consistent with 5.
,4-Bis[2-(m et h oxyca r b on yl)et h en yl]-6,7-b is[2-(m et h -
oxyca r bon yl)eth yl]-1,3,5,8-tetr a m eth ylp or p h yr in (6). To
,4-diformyldeuteroporphyrin dimethyl ester 3 (282 mg; 0.474
mmol) and methyl (triphenylphosphoranylidene)acetate (17)
637 mg; 1.90 mmol) was added dry CH Cl (125 mL). The
2
+
•
elemental analysis (MH ) 735).
2
Next was obtained the putative mixed mono cis/mono trans
1
isomers 10b and 10c, 20 mg, 17%: mp 161-166 °C; H NMR
(CDCl ): δ -3.74 (s, 2H), 3.28 (m, 4H), 3.56-3.65 (overlaping s,
3
(
2
2
solution was refluxed for 42 h and cooled, the solvent volume
was reduced under vacuum, and then hexanes were added to
precipitate the porphyrin. The collected porphyrin was recrys-
18H), 4.04 (s, 6H), 4.42 (m, 4H), 4.95 (d, 2H), 5.53 (d, 2H), 5.95
(d, 1H, J ) 15.7 Hz), 6.07 (d, 1H, J ) 11.3 Hz), 6.84 (m, 1H, J
) 11.3 Hz), 7.74 (m, 1H, J ) 15.7 Hz), 9.95, 10.10, 10.21, 10.24
(s, 4H); UV λmax (ꢀ) 400 nm (159 000), 498 (15 300), 532 (10 800),
tallized from CH
2 2
Cl /hexanes a second time. Obtained 321 mg,
1
8
1
+•
9
6%: mp 253-255 °C (lit. mp 259-261 °C); H NMR matched
568 (6 300), 572 (6 500), 622 (6 300); (MH ) 735). Anal. Calcd
+
•
published data; (MH ) 707). Anal. Calcd for C40
7.97; H, 5.99; N, 7.93. Found: C, 67.83; H, 6.17; N, 7.69.
Cop r op or p h yr in III Tet r a m et h yl E st er (7). 2,4-Bis[2-
methoxycarbonyl)ethenyl]-6,7-bis[2-(methoxycarbonyl)ethyl]-
,3,5,8-tetramethylporphyrin (6) (100 mg; 0.141 mmol) and 10%
H
42
N
4
O
8
: C,
46 4 8
for C42H N O : C, 68.65; H, 6.31; N, 7.62. Found: C, 68.61;
H, 6.38; N, 7.50.
After the elution of an impure fraction composed of mixed
mono cis/mono trans isomers and trans/trans isomer 10b, 10c,
6
(
1
and 10d (6 mg, 5%) was obtained pure putative trans/trans
1
Pd on activated carbon (100 mg) were added to a 100 mL flask
under argon. A 96% formic acid solution (70 mL) was added
isomer 10d 73 mg (61%): mp 190-192 °C; H NMR (CDCl
3
): δ
-3.87 (s, 2H), 3.25 (t, 4H), 3.39, 3.40 (each s, 6H), 3.52-3.58
(singlets, 12H), 3.64 (s, 6H), 4.33 (m, 4H), 4.70 (m, 4H), 5.87
(overlapping d, 2 H, J ) 15.7 Hz), 7.64 (m, 2H, J ) 15.7 Hz),
9.40-10.10 (singlets, 4H); UV λmax (ꢀ) 400 nm (178 000), 498
and the flask placed under a H
was filtered and most of the solvent removed. The remaining
solution was diluted with CH Cl and washed once with water,
and then MeOH was added to the organic phase. The solution
was briefly treated with ethereal CH and the reaction
2
balloon. At 14 h the solution
2
2
+
•
(17 500), 532 (12 300), 572 (7 400), 622 (6 600); (MH ) 735).
Anal. Calcd for C, 68.65; H, 6.31; N, 7.62.
Found: C, 68.64; H, 6.45; N, 7.42.
2
N
2
42 46 4 8
C H N O :
quenched with acetic acid and then washed twice with water.
The solvent was removed, and the porphyrin was purified by
Zn -2,4-Bis(oxir a n ylm eth yl)-6,7-bis[2-(m eth oxyca r bon -
yl)eth yl]-1,3,5,8-tetr a m eth ylp or p h yr in (13). To the zinc
complex of 2,4-bis(formylmethyl)-6,7-bis[2-(methoxycarbonyl)-
ethyl]-1,3,5,8-tetramethylporphyrin (12) (100 mg; 0.147 mmol)
in dry DMSO (10 mL) was added a solution of dimethyloxo-
sulfonium methylide (20) (1.9 mL of an ∼0.160 M solution in
DMSO, ∼0.304 mmol). After 45 min the solution was diluted
preparative TLC on silica gel with 4% MeOH/CH
2
Cl
2
. Obtained
1
8
8
1
0 mg, 80%, (77% from diformyl): mp 173-175 °C (lit. mp
1
+•
75-176 °C); H NMR matched published; (MH ) 711). Anal.
: C, 67.59; H, 6.52; N, 7.88. Found: C,
7.57; H, 6.72; N, 7.59.
,4-Bis[2-(ter t-bu toxyca r bon yl)eth en yl]-6,7-bis[2-(m eth -
Calcd for C40
46 4 8
H N O
6
2
oxyca r bon yl)eth yl]-1,3,5,8-tetr a m eth ylp or p h yr in (8). 2,4-
Diformyldeuteroporphyrin dimethyl ester 3 (300 mg; 0.504
mmol) and [(tert-butoxycarbonyl)methylene]triphenylphosphorane
2 2
with CH Cl , washed three times with water and the solvent
removed. The crude mixture was purified by flash chromatog-
raphy using a step gradient of 0, 0.5, 0.6, 0.8% MeOH/CH Cl
2
2
.
(18) (760 mg; 2.02 mmol) were refluxed in dry CH
2
Cl
2
(125 mL)
The compound was unstable to TFA-demetalation conditions and
for 42 h. The reaction was cooled and the solvent volume
reduced under vacuum. Hexane was added and the precipitate
was characterized as the zinc complex. Obtained 9 mg, 8.6%:
1
mp 223-225 °C; H NMR (CDCl
3
): δ 2.51-2.67 (m, 4H), 3.17
collected. The solid was twice more precipitated from CH
2
Cl
2
(m, 4H), 3.24-3.32 (overlaping s and m, 8H), 3.47 (s, 6H), 3.67
with hexane and dried. Obtained 339 mg, 85%: mp 226-228
(s, 6H), 3.87-3.99 (m, 4H), 4.27 (m, 4H), 9.32, 9.47, 9.54, 9.62
1
13
°
(
2
4
(
C; H NMR (CDCl
3
): δ -4.14 ppm (s, 2H), 1.79 (s, 18H), 3.24
3
(each s, 4H); C NMR (CDCl ): δ 11.33, 11.47, 21.27, 29.07,
m, 4H), 3.56-3.67 (overlapping s, 18H), 4.34 (m, 4H), 6.99 (d,
36.97, 47.33, 51.69, 52.90, 96.13-96.76, 134.1-147.2, 173.6; UV
+
•
H, J ) 16 Hz), 9.17 (d, 2H, J ) 16 Hz), 9.87 (s, 4H); UV λmax (ꢀ)
λ
max (ꢀ) 398 (140 000), 532 (13 900), 568 (18 700); (MH ) 712).
24 nm (148 000), 516 (17 800), 552 (17 200), 584 (10 000), 638
Anal. Calcd for C38 Zn: C, 63.91; H, 5.65; N, 7.85.
40 4 6
H N O
+
•
8 500); (MH ) 791). Anal. Calcd for C46
H, 6.88; N, 7.08. Found: C, 69.88; H, 7.06; N, 6.86.
,4-Bis(2-ca r b oxyet h yl)-6,7-b is[2-(m et h oxyca r b on yl)-
H
54
N
4
O
8
: C, 69.85;
Found: C, 63.53; H, 5.75; N, 7.55.
Tr ea tm en t of 2,4-Bis(for m ylm eth yl)-6,7-bis[2-(m eth oxy-
ca r bon yl)eth yl]-1,3,5,8-tetr a m eth ylp or p h yr in (4) w ith Di-
a zom eth a n e to Yield 22a -d . To 2,4-bis(formylmethyl)-6,7-
bis[2-(methoxycarbonyl)ethyl]-1,3,5,8-tetramethylporphyrin (4)
2
eth yl]-1,3,5,8-tetr a m eth ylp or p h yr in (9). To 2,4-Bis[2-(tert-
butoxycarbonyl)ethenyl]-6,7-bis[2-(methoxycarbonyl)ethyl]-1,3,5,8-
tetramethylporphyrin (8) (100 mg; 0.126 mmol) and 10% Pd on
activated carbon (100 mg) under argon was added 96% formic
(100 mg; 0.161 mmol) dissolved in 20% MeOH/CH
was added 5 mL of an ethereal solution of CH . Glacial acetic
acid (2 drops) was added after 1 h. After another 5 min the
solution was diluted with CH Cl and washed three times with
2 2
Cl (25 mL)
2
N
2
acid (60 mL). The reaction was stirred 15 h under a H
The mixture was filtered, the catalyst was washed with 10%
MeOH/CH Cl , and the solvent was removed. The solid was
dissolved CH Cl and washed twice with water, and the solvent
was removed. The crude mixture was purified by flash chro-
matography using a step gradient of 5, 8, and 10% MeOH/CH Cl
followed by elution with 10% MeOH/CH Cl /0.2% glacial acetic
2
balloon.
2
2
2
2
water. Solvent was removed, and then flash chromatography
was performed using a step gradient of 0, 0.2, 0.3, 0.4% MeOH/
CH Cl . Five fractions were obtained all of which contained
2 2
2
2
2
2
more than one component. The most mobile fraction was mainly
composed of a very small amount of diepoxide 22a while the
least mobile was composed mostly of diketone 22d . Intermediate
2
2
acid. The eluted fraction was washed once with water and the
1
solvent removed. Obtained 67 mg, 78%: mp 250-254 °C dec;
fractions contained 22b and 22c as well. Comparison of the H
1
H NMR (CDCl
3
): δ 3.27 (m, 8H), 3.66 (s, 18H), 4.43 (broad
NMR of the first and last fractions allowed tentative assign-