Porphyrin synthesis from nitrocompounds

0@4&i02@90 53.09+.00 @ 1990 Pergamon Pms pk

'Ie1rohrdronVol.46.No.21.~.7483-7496.1990 Brimin

PtinmdinGreat

PORPHYRIN

SYNTHESIS

On**,

Hisayuki

and Kazuhiro

Maruyama

Noboru

Department

FROM NITROCOMPOUNDS

of Chemistry,

University,

Kyoto

Masahiro

Kawamura, *

Faculty

Bougauchi,

of Science,

Kyoto

606, Japan

(Received in USA 5 February 1990)

Abstract: their

A new

equivalents

coproporphyrin, 2,7,12,f7

synthesis

is described.

materials

nitromethane,

such

in organic new

group.* Such

use of the nitro

organic

synthesis.

synthetic

Namely,

and radical carbon,

Recently

formed

a new with

reactions

role:

as an activating

synthesis

and readily

case

where

directly,

Knorr reaction,

and various

of the pyrrole

substituents rinq

organic

system. 7483

group

group

to

complex

of the reaction Pyrroles

were

to nitroalkenes group. The sequence

function

group5

were

reactions

of the nitro

consists

By this

this

in

for preparing

of the nitro

group.

as a

of the nitro

strategy

the nitro

function

the Diels-Alder

displacement

which

We

a new area

many

addition,

or a trifluoromethyl

pyrroles

the nitro

activates

and their

documented.'

has opened

of isocyanoacetates

and as a leaving

chains4

well

has been developed.3

and elimination

to the conventional

intermediates

using

of pyrroles

addition

Compared

and 4 positions

yield

nitroethane,

or elimination

a very effective

is a typical

long alkyl

Subsequent

isocyanoacetates

by cyclization

these

having

group

and heteroatoms

via the Michael

followed

from

has been

function

the Michael

reactions.

bonds

of nitroalkenes

methods

the nitro

condensation,

provides molecules. 2

organic

acid,

in good

are valuable

synthesis

leaving

by hydrogen,

or

octaethylporphyrin,

octapropionic

1 -nitroproQane,

as

and nitroalkenes

potential

give double

For example,

are prepared

have been developing

reaction,

from nitroalkenes

and aldehydes.

Nitroalkanes

such as the aldol

starting

porphyrin-1,2,3,4,5,6,7,8

tetraarylporphyrin

available

preparative

porphyrin

plays

method, have

method readily

pyrroles

been

gave

of

a dual

prepared.

n-free

introduced

at the 3

7484

N. ONO er al.

R2

R’CHO +

1) DBU -

R’CH =CyR2 2) -H,O

R2CH2N02

R’

CNCH2C02Et C02Et

DBU

‘NO, 1

2

In this starting

paper

from

of nitroalkenes Although well

our laboratory.

Synthesis

models

methods from

reaction are

and

porphyrins

(OEP) is one of the most of porphyrin

chemistry.

in Scheme starting

7-ene

ethyl

intermediate,

propionaldehyde

converted Mannich

in

The

nitro

OEP was carried

were

B-nitro

start

is prepared

in preparing

by

starting

of the pyrrole modified A new

yields

ring by many

method, in every

which case.

l-nitropropane,propionaldehyde,

are all commercially

ethyl

aldol

high

numerous

2,4_pentanedione.

is still difficult.

available.

3,4-diethyl-2-pyrrolecarboxylate

of

acetate

condensation

by acetylation

with

out in various

into OEP via deethoxycarbonylation

(s),

of 3-acetoxy-4-nitrohexane

in the presence

requisite

followed

reaction.8

group

and widely

of these

which

have been extensively

by the reaction

isocyanoacetate

by the conventional

of sinto

which

in 86% yield

(DBu).~

with

1, gave reproducibly materials

Therefore,

to difficulties

the 5-methyl

of OEP

isocyanoacetate,

The key

with

due

the procedures

is summarized

prepared

has been

are difficult

important

pyrrole,

of ethyl-propionylacetate inconvenient

The

and ethyl

which

so far. 8 Most

OEP have been devised

workers, 8 the preparation

requisite

(Eq 1).

reaction

from .2__hasjust started

gave novel

in transforming

Although

system.

isocyanoacetates

methods.5'7

for the study

methods

materials

was

of porphyrins

by the reaction

of Octaethylporphyrin.

to prepare

the Knorr

of porphyrins

prepared

by the Knorr

2-ethoxycarbonyl-3,4-diethyl-5-methyl

These

synthesis

with

prepared

Our new method

by other

a new

in turn were

equivalents

synthesis

Octaethylporphyrin used

to report

which

of pyrroles

established,6

1.

(3

(1) or their

conversion

to prepare

we wish

pyrroles

(G1

1,8-diazabicyclo[5.4.O]undec-

(21

was

prepared

of l-nitropropane acetic

in 80%

yield

with

anhydride.'

Conversion

ways. For example,2&was of the ester

function

and the

7485

Porphyrin synthesis from nitrocompounds

EtCH,NO,

+ EtCHO

OAC

i

-

II

Et-CH-CkEt

.. COPEt

k0, la .&X 7

2,

I i) EtBN ; Ac20-H,S04

iii

ii) CNCHzCOIEt iii)

3

Scheme

we could

due to the instability convenient

procedure

treatment

with

an acid

The yield

of OEP depended

increased equivalent readily

agent

was carried

by this procedure

found a more

temperature

as formaldehyde

starting

in lo-55% especially

for a long time,

with

LiAlH4."

group

at the

Thus, OEP was materials.

When

yields. those

to produce

of

n-position

prepared

was

of to produce

of pyrroles

additional

The results

was

2-ethoxycarbonylpyrrole

The conditions

methylal

the

the reduction

were also important

by an acid catalyst,

is

of 2-hydroxymethyl-

in good yield.

of OEP. Alternatively,

of formaldehyde.

gave OEP

conditions,

out at low temperature

of 2-hydroxymethylpyrrole

the yield

We have

and the tetramerization

to 2-methylpyrrole

available

in good yields

on the reaction

in good yield. The hydroxymethyl eliminated

(OEP).

2a the procedure - into OEP. Additionally Reduction of 2a with LiAlH4 followed by

2-hydroxymethylpyrrole

tetramerization

OEP

and an oxidizing

LiA1H4

out at higher

reduced

Octaethylporphyrin

not prepare

simple.

The reduction

intermediate carried

with

of

of 3,4_diethylpyrrole.

quite

pyrrole.

; H +; [ 0 ]

to convert

experimentally

the reduction

LiAIH,

, DBU

OEP Preparation

1.

However,

was

06%

OEP

was

formaldehyde

used as an

by simple

procedures

are summarized

and

in Table

7486

N. ONOet al.

Table

1 .

Reduction

Preparation

of

OEP

from

Cyclization

of 3

2a . Oxidation

Yield of OEP, (%)

2h

Ac20

02

25 “C

8 h

AcPO

02

trace

0°C

2h

, p-TsOH

02

23

02

52

0°C

CH&I,

30

0°C

2h

CH2C12 , p-TsOH CH,(OMe),, (3 equiv)

0°C

2h

CH2C12, p-TsOH CH2(0Me)2, (3 equiv)

chloranil

55

0°C

2h

MeOH,

chloranil

14

HCOOH

CH2WW

The present porphyrins

which

procedure

have

the same

example,

1-nitro-cyclohexene

as shown

in Eq 2.

NO2

was

extended

to the general

substituents

was

converted

I -

C02Et

i ) ii )

CNCH2C02Et, LiAIH,

; H

DBU l

; [ 0 ]

Pb, WV

80 %

at the

synthesis

U-positions.

to porphyrin

of

For

3b in good yield PU.1

7487

Porphyrinsynthesis from nitrocompounds

Synthesis

2.

of Coproporphyrin

octapropionic

Porphyrins porphyrins.

acid

with

propionic

They are not only

the study of porphyrin

model

to study

metals."

over a broad pyrroles

which

appropriate tedious paper and

lengthy

we wish

esters

sequences to report

active

octaesters

prepared

to prepare a simple

preparation

starting Michael

material reaction

is summarized was methyl

in Scheme

02NCH2CH2CH2C02CH3i)

reaction

with

methyl

methods

coproporphyrin

octamethyl

ester

which

was prepared

acrylate.

iii)

CH3CHdHCH2CH2C02CH,

-

CH3

I\ LL

N H

5 -’

C02Et -+C,H.O

C ~;O,.H,_+ ::

H

H 6 65% vy:

70 %

i) CH3CH0, ii)

DBU ( 0.1 equiv) /CH3CN

Ac20-H2S04

i ii)

CNCH2C02C4H9-t, DBU (2 equiv), THF, 25°C , 10 h iv) CH2(OCH3)2, p-TsOH ( 0.1 equiv), CH2C12, 25°C) 18 h v) CF,CO,H , 25°C , 5 min , CH(OCH3)3 , benzoquinone 25”C, 10h;

P = CH2CH2C02CH3

Scheme

2 .

Synthesis

of

Coproporphyrin

require

porphyrins. l3 In this

d AC P

from

between

these

NO2

ii)

mesophases prepared

2 and 3, respectively.

4-nitrobutyrate,

of nitromethane

have been

to synthesize acid

of several

descotic

However,

porphyrin-1,2,3,4,5,6,7,8-octapropionic

Their

aggregation

the desired

method

in

have

and tetrameric

exhibit

by the Knorr

useful

such porphyrins

porphyrins

and b -diketones.

in natural

but are also

trimeric,

of the enforced

range. l2 These

in turn were

3-keto

are found

For example,

of dimeric,

porphyrin

temperature

side chains

biologically

the effect

Furthermore,

acid

systems.

been used for the construction porphyrins

and Porphyrin-1,2,3,4,5,6,7,8-

(7) . H

(7J

(2).

The common by the

N.ONO er al.

Nitro

aldol

condensation

of methyl

gave the nitroalcohol,

which

overall

4_,was treated

yield. Acetate

presence

was converted

of DBU to give the

converted

*free

into dipyrromethane

of p-toluenesulfonic

was obtained

in 25% yield

from

followed

by treatment

with

prepared

from

available

acrylate,

pyrrole

with

into the acetate t-butyl

acid

5 in 70% yield.

(Q-TsOH).

6,by reaction

methyl

4 in 70% in the

Pyrrole with

Finally

with

orthoformate.

materials

acetaldehyde

isocyanoacetate

6 in 85% yield on treatment

the presence

readily

with

4-nitrobutyrate

methylal

coproporphyrin

trifluoroacetic

Thus,

5 was

7, was methyl

and acetaldehyde.

02NCH&H,CH,C0,CH,

-

i)

OHCCH,CH,CO,CH,

OAc P- CH - &f -P

ii)

-

iii)

NO,

P

8

90 %

&

70 %

$

75%

P

10 -

75%

P

P 12

P= CH&H,C02CH3 E= CO,C,Hg-t

ii) 0,NCH2CH2CH2C02CH3,

i) KOH-MeOH , KMn04 iii) CNCH2C02C4Hg-t iv) v)

CH,(OCH& CF3C02H, 10h

Scheme

;

, DBU (2 equiv), THF , 25 “C,

, p-TsOH ( 0.1 equiv), 25 ‘C,

5 min ; CH(OCH&

benzoquinone

3.

DBU ; Ac*O, H2S04 10 h .

CH,C12 , 25 “C,

18 h .

, CHpC12 , 25 “C ,

.

Synthesis

of

Porphyrin-l

octapropionic

,2,3,4,5,6,7,8-

Acid Octamethyl

Ester

(2.

7 ,,,

acid,

COQrOQOrQhyriXI

such as nitromethane,

in

7489 Porphyrin synt~~sis~omni~~om~unds

Porphyrin J,2,which has eight propionic acid side chains, was also prepared from methyl 4-nitrobutyrate as shown in Scheme

3. The requisite. aldehyde 0 was prepared by the Nef reaction of methyl 4-nitrobutyrate.'4

Nitro aldol reaction of 8 with methyl 4-nitrobutyrate followed by acetylation gave 9 in 75% yield. The same procedures as in the synthesis of 7,gave porphyrin 12, The present method for the synthesis of _7_and j2_ is far superior to the conventional method which starts from the corresponding pyrroles via the Knorr reacti.ons.l5 3.

Synthesis of 1,3,5,7-Tetraarylporphyrins: New Sterically Hindered Porphyrins. Recently,sterically

hindered tetraaryl porphyrins have become the

principal species used not only to model biomimetic transformations, but also to investigate catalytic oxygen transfer and solar energy conversion by synthetic metalloporphyrins.16 Steric bfocking in the porphyrin ring inhibits dimerization and various bimolecular decomposition reactions. Thus, hindered porphyrins are more stable to intramolecular oxidative decomposition than unhindered porphyrins. Unfortunately, hindered porphyrins are generally obtained in low yields,l' and furthermore most known hindered porphyrins have bulky aryl groups in the meso t Q, R, yI

61 positions, which causes deviations from planarity of

the porphyrin ring. Such porphyrins behave in an unusual manner compared with those that are naturally occurring and the usual model compounds with fi-substituents.' In this paper we report the synthesis of a new type of sterically hindered porphyrin with B-aryl substituents which may be more suitable models than meso-tetraarylporphyrins The nitroalkenes (z)

(Scheme 4).

were prepared in 60-808 yield by refluxing a

mixture of the aldehyde, nitroethane, methylamine hydrochloride, potassium acetate, and methyl orthoformate in MeOH."

Such hindered aldehydes as

mesitaldehyde and 2,6-dichlorobenzaldehyde gave &in

good yields by this

procedure. The reaction of 12 with ethyl isocyanoaeetate gave E in 70-80% yield. Here again steric hindrance has no effect on the transformation. The reduction of l&with

LiAlH4 followed by tetramerization with p-TsOH and

oxidation with chforanil gave the porphyrins (15J in SO-708 yield. In general, tetramerization of monopyrroles with an acid induces the rearrangement of substituents to give four possible isomers of porphyrins."

7490

N. ONOer al.

ArCH =C

Me

3402

Ar ii)

1) _ / \ n N

‘Me

CO,Et

13

Ar ;

I) CNCH2C02E1, DBU, THF, 25X, 2 h ; Ii) LiAlH4 , THF, 5X, pTsOH , CH2C12 , 25°C , 24 h ; Chloranll , CH2Cl2 , 25°C , 5 h

Scheme

4 .

However, serious

problem,

porphyrins

were

Synthesis

if the aryl selectively

12,

and ?S_j. The results are

and meso-H

become more those

large.

bulky

formed

are

resonances

are sterically

hindered.

in the preparation

summarized

in Table

Namely,

type

I

of 1_5&.,1.5_$,15e,

2, where

are not much affected

are

The W-Visible

of OEP. These

in these range

is not a

that this type of rearrangement groups

shifts

arylgroups.

aryl groups porphyrin

(15) -

some

spectral

shown.

The NH chemical B-Me

of 1,3,5,7-Tetraarylporphyrin

we have found

data

for 24 h.

shifted

to higher

absorption

maxima

The absorption

maxima

data

show

that

in 1.5.change

with

increasing

15c, However, hindered

field

because

steric

as the aryl

are also blue of

1

Scare

the out-of-plane

the planarity

porphyrins,

6 -3.3 to -3.5.

by the arylgroups,

angles

and approach

of the porphyrin the NH resonances

groups

shifted

very close

rotation

bulk

ring

but

with to of the

90' in

is maintained

all appear

in the

7401

Porphyrin synthesisfrom nirrocompounds

Table

2.

Yield of 15.

‘/%!P

46%

1%

50%

Preparation NMR

of

2

and

Spectral

8”

&,,.,J

-3.45 (8, 2H), 2.68 (s,llH), 3.60 (s,llH), 7.66 (d, 8H), 8.06 (d, 8H), 10.15 (s,4H) -3.34 (s, 2H), 2.lO(m,llH),

data

of

them .

nm ( CH2C12 )

MS b,

418, 506, 540, 572, 626

727

410, 501, 536,

727

3.47 (s,l2H), 7.6-8.0 (16H ), 9.80 (8, 4H)

568, 622

1%

55%

-3.38 (s, 2H), 2.10 (s,l2H), 2.17 (I, 24H), 3.24 (s,l2H), 7.28 (8, 8H), 9.60 (I, 4H)

403, 499, 531, 565, 620

819

12

48%.

-3.46 (s, 2H), 3.60 (s,lH), 7.5-7.7 (m, 16H), 10.08 (8, 4H)

418, 506, 540, 572, 626

809

E

50%

-3.38 (8, 2H), 3.41 (8, 12H), 7.5-7.7 (m, 16H), 9.85 (8, 4H )

406, 500, 535, 568, 621

809

ISJ

70%

-3.35 (8, 2H), 3.37 (8, 12H), 7.6-7.7 (m, 12H), 9.71 (s, 4H)

404, 500, 533, 566, 621

947

133

56%

-3.41 (s, PH), 3.67 (8, 12H), 416, 507, 542, 4.09 (8, 12H), 7.75 (m, 16H), 573, 624 10.12 (8, 4H)

791

15h

56%

-3.41 (8, 2H), 3.40 (s, 12H), 4.09 (s, 12H), 7.6 (m, 16H), 9.97 (s, 4H)

409, 505, 540, 573, 624

791

15i -

55%

-3.25 (s, 2H), 3.30 (8, 12H), 3.73 (8, 24H), 7.02 (d, 8H), 7.62 (d, 4H), 9.77 (s, 4H)

407, 504, 539, 572, 624

911

-3.44 (8, 2H), 3.62 (s,lZH), 4.05 (s,24H), 6.84 (s,4H), 7.32 (s, 8H), 10.22 (8, 4H)

417, 505, 540, 573, 624

911

-3.27, (8, 2H), 3.50 (8, 12H), 7.7-8.8 (m, 28H), 10.23 (s, 4H)

411, 507, 542, 573, 627

863

151

‘I

lJ$

50%

65%

-3.22 (8, PH), 3.20 (s, 12H), 7.7-8.5 (m, 28H), 9.55 (8, 4H)

60%

a) NMR data were temperature

recorded

wlth Me&I

409, 504, 538, 571, 624

In CDCI~ (5~10~ 3 W) at 400 MHz at room as Internal

nhmnw.

b) Mass spectra were measured by FAB techniques, appsmd as parent ions.

where M + 1 peaks

863

N. ONOer al.

Thus, various Compared

compounds. following Since

porphyrins

are readily

to conventional

(1) (I -free pyrroles

merits:

nitroalkenes

are prepared

at the B-position

may be changed

Ethyl

isocyanoacetate

nitration

Other

0.087 mol),

and dried

with

with

anhydrous

magnesium

(silica

gel/CH2C12-hexane) cm-'.

NMR

(CDC13)

9.28 (1 H, br s). Found:

nitroalkenes

g, 8 mmol) mmol)

were

was

3). The extract

was

anhydrous

magnesium

pressure,

and

ml, 9.6 mmol) solution was out either oxidation

CH2C12

was extracted

with

sulfate.

After

evaporation

chromatography

added.

prepared

into

To this

The yield

were

procedure,

used.

mixture

(0.32

was

by the addition

saturated

ethyl

NH4C1

acetate

(10 ml x

and dried

under

solution

methylal

added,

mixture

of the solvent,

the residue

(0.7

and the was carried

of OEP was not affected

with

with

reduced

for 12 h. Oxidation

the reaction

gel/CH2C12)

by this

of &a_ (0.657 g, 3.2

destroyed

with

for CllH17N02:

of LiA1H4

layer was dried

(silica

IR (neat)

(1 H, d, J = 3 Hz),

NaCl solution

temperature

oxidation,

and the organic

6.70

was removed

(0.11 g, 0.65 mmol)

at room

by air or chloranil.

After

saturated

The solvent

(15 ml) was

and p-TsOH stirred

method.

aq NaHC03,

washed

under

as oil.

a solution

poured

mixture

removed

66% yield)

at O-5 "C. The resulting

the mixture

water

chromatography

mixture

was

The reaction

was

M

with

to column

of DBU was

LiA1H4

solution.

column

pyrroles

added

at

(9 H, t), 2.40 (2 H, q, J = 7 Hz),

then

acetate,

washed

H, 8.72: N, 7.05%. Calcd

in dry THF (15 ml) was

(9.8 g,

stirred

containing1

were

The solvent

at O-5 OC for 2 h. Excess

of ethyl

sulfate.

The extracts

used, 1 equivalent

in THF (5 ml) dropwise

stirred

in THF (100 ml) was

-1.42

by

of 3-acetoxy-

isocyanoacetate

22 (14.2 g,

Al.05

prepared by the

(22). A mixture ethyl

(OEP). To a stirred

Octaethylporphyrin

were

available.

sulfate.

C, 67.42;

were

(2)

substituents

prepared

4.24 (2 H, q, J = 7 Hz),

C, 67.66; H, 8.78; N, 7.17. Other but when

step;

are commercially

was subjected

to give

(2 H, q, J = 7 Hz),

was

was pouredintowater

and the residue

pressure,

1680

mixture

ethyl acetate.

reduced

3340,

materials

(26.4 g, 0.17 mol)

20°C for 12 h. The reaction HCl and extracted

2.60

isocyanoacetate

(?a_, 16.3 g, 0.083 mol), and DBU

in one

of reactions,

nitro

has the

Section

3,4-diethylpyrrole-2-carboxylate

4-nitrohexane

from

method

systematically.

and t-butyl

of cyclohexene.

Ethyl

are prepared

1 -Nitrocyclohexene

methods.21

starting

the present

by a variety

Experimental

the literature

prepared

methods,

was washed

anhydrous was

by the with

magnesium subjected

to

to give OEP. Recrystallization

7493

Porphyrin synthesis fi-om nitrocompounds

from

CH2C12-MeOH

gave

pure

OEP,

0.24 g (55% yield).

(s, 2 HI, 1.93 (t, 24 HI, 4.11 (q, 16 H), 10.11 398, 497, 532, 564, 619 nm. These authentic

3b was

mp 320-325

from

method

t-butyl

a mixture

(_6_] by stirring and

p-TsOH

OC, Yield

pyrrole

(0.1 g) in CH2C12

(0.11 g, 1 mmol) neutralized

subjected 286-289

was

removed

reflux,

and reflux

by washing

sulfate

to column

chromatography

H, J = 7 Hz),

3.675

= 7 Hz), 10.10

fs, 4 H). A max

Octaethyl

Porphyrin

Ester Methyl

reaction bp 82

of

'C/17

HI. The nitro nitrobutyrate

under

6-3.75

was

layer was dried

was removed.

(CDC13)

To this mixture

solution

to give porphyrin

tCH2C12)

for

g, s

with

The residue

L(O.11

was

g, 25%), mp

Is, 2 H), 3.31 ft, 8

(Me, s, 12 H), 4.45 (t, 0 H, J

401,

499,

534,

7,2,3,4,5,6,7,8-octapropionic

569,

620 nm.

acid

(Ik).

methyl mmHq aldol

(9

was prepared

I-nitrobutyrate

; NMR

to

the

with

a mixture

with

acetic

procedure: 21

3 HI, 9.75

methyl

4-

of methyl

4-

8 (2.1 g, 18.1 mmol),

acetylaed

by the Nef

modified

(m, 4 H), 3.64 k,

out by stirring

was

in 90% yield

of this aldehyde

(2.54 g, 17.3 mmol), product

according

(CDC13) $2.3-2.8

condensation

was carried

$5 ml). The

-6f0.48

by p-benzoquinone

The organic

s, 12 H1, 3.652

4-oxobutyrate

nitrobutyrate THF

(OMe,

oxidized

and the solvent

oC).'3 NMR

132-

(0.62 g, 6 mmol)

for 12h. The

20% NaHC03.

to column

solid, mp

pressure.

orthoformate

continued

with

magnesium

of

subjected

(6 ml) and then

under reduced

was

temperature

H, 8.76; N, 5.68. Calcd

acid

the mixture

OC (lit. 286-288

Synthesis

was

6 as a white

C, 72.22;

1.56

td, 1 H,

(2.0 g, 26.3

N2 at room

H, 8.77; N, 5.80. Dipyrromethane

(50 ml) and methyl

24 h at

product

to give

(4) by

(CDC13)6

into dipyrromethane

methylal

(50 ml) under

in trifluoroacetic

acid

CH2C12

acetate

of 22. NMR

was converted

up, the crude

1.7 g (70%). Found:

trifluoroacetic

N2, After

work

C, 72.17;

was disolved

added

566, 619 nm. Fab

and $-nitro

of 5 (2.3 g, 10 mmol),

usual

C2gH42N204:

398, 499, 535,

(m, 4 H), 3.70 (s, 3 H), 6.72

(silica gel/CH2C12)

anhydrous

as described

in the preparation

for 48 h. After

was

procedure

17).

chromatography

mmol)

those of an

(s, 2 H), 2.56 (br, 16 H), 4.18

isocyanoacetate

as described

9.15 (s, 1 H). This

J = 3 Hz),

134

with

526.

(s, 9 HI, 1.93 (s, 3 H), 2.5-2.7

mmol),

(s, 4 H). ~~ax(CH2Cl2)

4-(2-methoxycarbonylethyl~-3-methylpyrrole-2-carboxylate

prepared

the same

requires

L-3.45

(CH2C12)

of Coproporphyrin

t-Butyl (,5) was

s-3.74

identical

by the same

(CDC13)

(s, 4 H). :max

527. C36H38N4 Synthesis

prepared

'C. NMR

(br, 16 H), 10.10 Mass

were

(CDCl3)

sample.

Porphyrin above:

data

NMR

and DBU

anhydride

and

(s,

1

(0.1 gl in H2S04

to

N. ONOet al.

give 9,in

75% yield.

NMR

(CDC13)

61.9-2.6 (m, 8 H), 2.21 (s, 3 H), 3.75 (s,

3 H), 4.82 (m, 1 H), 5.40 (m, 1 H). The pyrrole

10, dipyrromethane

porphyrin

as the preparation

l-2 were

prepared

and .?_,respectively.

2.77 (t, 2 H, J = 7 Hz),

3.65

(m, 8 H), 2.72

(s, 3 H), 3.68 (CDC13)

Mass

999.

reported

(s, 2 H), 3.30

(s, 4 H). imax

H). 11: NMR

of5*,_6, (m, 4 H),

(CDC13)61.60

3.00

(s, 18

(t, 4 H, J = 7 Hz), 9.42

(s, 2 H). 12:

(t, 16 H, J = 8 Hz), 3.64 (s, 24 H), 4.40

(CH2C12)

requi;;s

C52H62N40,6

in the

1

9.42 (s,

(t, 4 H, J = 7 Hz),

and

3.67 (s, 3 H), 3.68 (s, 3

(s, 3 H), 6.75 (d, 2 H, J = 8 Hz),

5-3.79

(t, 16 H), 10.09

manner

(CDC13) c‘1.58 (s, 9 H), 2.53-2.63

3.00 (t, 2 H, J = 7 Hz),

(d, 1 H, J = 3 Hz),

H), 6.67

H), 2.4-2.63 NMR

in the same

19.: NMR

11,

406,

998. These

502,

data

537,

were

573,

627

identical

nm. Fab

with

those

literature.

Synthesis

of Porphyrin (15&) -as a Typical Procedure: l-(2,6-dimethoxyphenyl)-2-nitropropene (13-k). A mixture 45 mmol),

(3.4 g,

g, 35 mmol),

methylamine

orthoformate

(10 ml),

The reaction After

2,6_dimethoxybenzaldehyde

mixture

the usual

and methanol was poured

work

(30 ml) was

into water

up, the crude

7.5 g (80%). mp

product

to give

102-103

3.84

(s, 6 H), 6.48 (d, 2 H, J = 10 Hz),

of

42 mmol),

(3.4 g, 35 mmol),

Et20 1

z,

hydrochloride

(7.0 g,

stirred

at reflux with

was recrystallized (CDCl,)a 1

7.20 (t,

(2.4

methyl

and extracted

'C. NMR

nitroethane CH3C02K

for 7 h.

ethyl from

2.06

ether. MeOH-

(s, 3 H),

H, J = 8 Hz),

7.72 (s,

HI. 2-Ethoxycarbonyl-3-(2,6-dimethoxyphenyl)-4-methylpyrrole

To a cooled

solution

(4.5 g, 40 mmol) reaction After

in THF

mixture

usual

work

of 13_i.(7.0 g,

31.4 mmol)

(60 ml) was added

was stirredat

and

(14i). . .isocyanoacetate

ethyl

DBU (6.1 g, 40 mmol).

"C for 12 h and poured

up, the crude material

was recrystallized

give

12_i, 6.5 g (73%). mp 112-113

Hz),

1 76 (s, 3 H), 3.64 (s, 6 H), 4.00 (9, 2 H, J = 8 Hz),

H, J = 8 Hz), 1 H). Found:

6.66

OC. NMR

(d, 1 H, J = 3 Hz),

C, 66.29;

in dry THF (30 ml) was

in THF

(5 ml) dropwise

O-5 'C for 2 h. After of OEP,

the crude

gel/CH2C12) in Table

2. Other

preparation

the same

15i,

mixture

treatment

was purified

were

9.36

was

at

in the preparation

data

the same

mmol)

stirred

chromatography

spectral

(s,

C, 66.43;

(0.32 g, 8

mixture

by column in

(d, 2

of 14i (0.89 g, 3.1

as described

prepared

6.44

H, J = 8 Hz),

1

EtOH to

1.00 (t, 3 H, J = 8

of LiAlH4

a solution

0.36 g (50%). The

porphyrins

of !5&

added

from

for C16HlgN04:

at O-5 oC. The resulting

product

to give

7.08 (t,

H, 6.69; N, 4.81. Calcd

H, 6.57; N, 4.84. Porphyrin (l-5!.).To a stirred mmol)

(CDC13)E

The

into water.

are

(silica

summarized

way as the

7495

ieferences

E. W. Calvin, F. Lehr, T. Weller, Chimia 33, 1 (1979); N.

11 1. Seebach,

3no and A. Kaji, Yoshikoshi Barret

Kaqaku

M. Miyasita,

and G. G. Graboski, Synthesis,

R. Ballini, 2)

Yukiqosei

and

J. Ono and A. Kaji,

Kyoukaishi,Q,l15

(19801;

833 (19881.

Synthesis,

693

(1986);

N. One,

"Nitro

Compounds:

Recent Advances in Synthesis and Chemistry" VCH Publisher, 3) 3. H. R. Barton

and

A.

l8, 284 (1985); A. G. M. Act. Chem. w, ~-86, 751 (1986); G. Rosini and Chem, Rev.,

S. Z. Zard,

J._ -Chem.

N. Y.,

(1980).

1098

Sot., ------.-%t Chem. Commun

(1985).

and K. Maruyama,

4) \I.Ono 5) +. One,

Bull. --Chem. Soc.Jpn., 61, 4470 (1988). and K. Maruyama, Bull. Chem. Soc.J=, 62, 3386 ____----

H. Kawamura,

(1989). 6) "Porphyrins

Amsterdam

and Metalloporphyrins,"

ed by K. M. Smith,

Elsevier,

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Pree,

New York (1976). 7) U. Ono, H. Kawamura,

M. Bougauchi,

Chem. Commun., 1580 (1989). -8) J. B. Pain III, W. B. Krishner, 41, 3857

and K. Maruyama,

and D. W. Moskovitz,

J-Chem. ---

J. Org. Chem., --

(1976).

9) "Methoden

der

Stuttgart

Organichen

Chemie,"

Vol.

in Houben-Wey

XI,

and

11) A. Hamilton,

J. M. Lehn, and J. L. Sessler, J. Chem. --Am. -_

(1986);

S. Theodoropules,

A. C. Cowan,

Harrison,

J. Chem. -

and A. D. Hamilton, references

J. K. M. Sanders,

J. Chem. Sot., Chem.

(1987) and

and

A. H. Jackson,

G.

(1963).

s,

108,

and

R. J.

M. Dubowchik

., 665 (19861, and

Commun

references

references

151 B.

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Appl. Chem.,

Act. Chem Res ---..--_~I 58, 1493 (1986);

82, 4327

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Sot., Perkin

L,

therein.

in ref. 1.

16) J. P. CoIlman,

Sot., -.-.--z_ Chem

J. Am. -Chem. &, and J. Wass, J- --Chem.

S. F. MacDonald,

G. W. Kenner,

(19721, and

references

3052

G. S. Beddard, (1987);

Chem. -therein.

14) References Frank,

55

Commun.,

Sot., Chem.

M. A. Fox, and A. J. Bard, &

1134

13) F. Morsingh

1475

J. --_.._%I28, - Org.Chem

therein.

12) B. A. Gregg, Commun.,

10 MulIer,

(1971).

10) R. L. Hinman 5158

Sot.

3,

265

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B. Meunier,

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M. Momenteau,

Pure

Bull. Sot. Chim. &, --__-

and S. Quici, J. Orq, -2r Chem

53,

758

N. ONOer al.

2863

(1988),

17) T. G. Groves S. Lindsey

references T. E.

and

18) E. McDonald 19) N. Ono

and and

I?. W. Wagner,

and R. T. Martin,

and K. Maruyama,

20) G. D. Hartman 21) N. Kornblum,

263

Chem.

J. Am. -_&I Chem sot 105, 6243 (1983); J. Org. -zr Chem 54, 828 (1989). Tetrahedron Lett.,

and L. M. Weinstock, A. S. Erickson,

Chem 47, 4534 (1982). -_--_I 22) B. Franck, G. Bringmann, Chem -_I

therein.

Nemo,

(1980).

1237

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W. J. Kelley,

C. Wegner,

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VI, 620

H. Hengreler,

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Lebigs,

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