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The porphyrin handbook - Kadish K.M.

Kadish K.M. The porphyrin handbook - Academic press, 2000. - 368 p.
Download (direct link): kadishsmishgulilard2000.djvu
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polymerizations has been successfully extended to the synthesis ol a
copolymer of 11 and 18 rich in the cross-propagation sequence.''' Anionic
eopolymerizalion of 11 and 18 usually gives a copolymer rich in Ihe homo-
propagalion sequence.
since the latter is much more reactive than Ihe former towards
nucleophiles and is polymerized preferentially over the former al the
initial stage. This is also the case for the eopolymerizalion of 11 and
18 with 5g in the dark, where a copolymer with a lower content of the
cross propagation sequence is formed, [n contrast, under irradiation with
visible light, the reaction of the zinc alcoholate growing species
(originating from epoxide) with 18 is accelerated.
142
Aida and Inoue
Table 4. Selected 'H NMR Data for Reactive Ends of Living Polymers with
Aluminum and Zinc Porphyrins in CDCI3 at Room Temperature
Monomer Reactive end
Chemical shift in S (ppm)
Reference


11 (R = H) CH,

i
a b
;ai-0-ch2ch2-o-

o
11 (R = Me) CH2CH3


11 (R = Et) C(CH3)3

I
I
I

CH3

Al- O-CHCH2 O-
(13C: 60)
a
CH2CH3
;ai 2-o-
11 (R = Bu)

13 (R = H)
J
I
1

a

C(CH3)3 'AI-0 CHCH2 -O-
a b
Al--C-CH2CH2-0-C-
II II

(13C: 165.7)
H3C -< >-0

13 (R = Me)
I
1
CH3
Al- CH2CH-0-C
II II

(13: 163.6)
-
14
15

I

I
abed

;ai--2222--



^1--22222--
3
-<
-
3
16

I


3
3

AI-0-CH-----

II d II

: - 1.4 (), -0.1 ()
: - 0.45 (), 0.67 (b) [C6D6] EtioP: - 0.98 (), 0.46 (b) [C6D61
: -2.0
: - 1.8 ()
: - 1.58 ()
: -0.66 (), 1.90 ()
: -0.2 ()
: -1.34(a), -1.80(b). -0.71(c), -1.0(c)
: -1.09(a)
: -1.56(a), -1.95(b), -0.97(c), - 3.95 (d)
30, 81 58
30, 59, 81 81 81
13-15, 74
13-15
16
17
D,C=C

-OCH3

21-d5(R = CH3)

1
CD3
Al-o-c^c-cd2-
OCH3 a
TPP: 0.53-0.62 (a) [C6D6] EtioP: 0.18-0.33 (a) [C6D6]
58

21 (R = Bu)
I
I

Me
0"rtBu AI-0 C-C CH2

OC(CH3)3
TPP: - 0.33 (a) [C6D6]
82
42 / Metalloporhpyrins as Catalysts
143
Table 4. (continued)
Monomer Reactive end Chemical shift in & (ppm) Reference
CH3 Me^Zn-O a TPP: - 1.17 (a), -0.35 (b),
\7 CH3
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