1,2-Dialkoxycarbonylhydrazine derivatives of pyrroles and indolizines. A new synthesis of cycl[3.2.2]azines

Tetr&e&on LetteraVol. 21, pp 3675 - 3676 OPergamonPressLtd.

oo40-403?/WwV-3~73#o2.

1,2-DIALKOXYCARBONYLHYDRAZINE

A NEW

INDOLIZINNS.

Wilhelm

Flitsch=

Orlgans-Ring

Summary:

The

sines

5 and

obtained

reaction

and

2-

6 are

The

2

reaction

by

5 with

ever,

we have

been

and

(R = i-C

H 37

2

temperature

the

mam+

and

from for

(I? = i-C

) under

only The

(51,

to

Extensive

this

(Western

diieopropyl

3-

route.

diethyl

(I).

and

Germany)

azodicarboxylate 1,3-substituted

Cyc1[3.2.2]aeinem

substituted

yields

from

decomposition

derivatives

a reaction taking

place

the

reaction

of

2,5-dimethyl

formation

conditions

which,

hydraeino-1,2_dicarboxylate and 3

follows

unabiguously

of 2 (R = CI13) from 2

2

R R=H,Me R’= I-C3H7

3

3673

(R = CH3).

at

room

simultaneously

cotnes from

reaction

a5o

in methanol

the

of 2

been

and 3 from 1

2

by

diisopropyl

1 have

techniques, how-

chromatographic

pyrroles

same

2 indoli-

has been reported

the

the

MLinster,

axodicarboxylate

Using

R'O$-N=N-C4R'

1

Universitgt

of

constitution

and the

der

acetylenedicarborylate.

isolate

an oxidation

indication H 37

to

) in moderete

12,31.

originate

leads

able

1 with

dimethyl

of pyrroles

Jiirgen Heinrich

Miinster

derivatives.

lead to no isolable products

to

D-4400

of pyrroles

formed

and

und

AND

OF PYRROLES

OF CYCL[ 3.2.23AZIIUES

Institut

23,

2,5-substituted

from

DERIVATIVES

SYNTHESIS

Organisch-Chemisches

yields

DQ/o

lgao.Printedin~tBritain

compound

2

pyrrole

besides

may

(4).

An

with

2

decomposition,

(48 %I. from

the

iM-NMR-spectra

A substitution indolixines vatives

which

in better

in a two-step

in

operation

hydrofurane

dimethyl

temperature

in benzene

of the previously reactions

more

of

of &

to

obtained

2

with

1,3-hydrazino

the latter

indoliaine

have

from which

compounds

deri-

being

(45.2 96) and 5

and 2

(RI = C2H3)

into

the l-position

been

reported

no product

we have

for 5 hours

described

proceeds

(17 !%I

in tetra-

(2,s).

acetylenedicarboxylate

the educts

of 3- and

described,

(6.7). We

reaction

nixture

to that of pyrrole

formation

to achieve substitution

tion of a complex

are

The

from a reaction

at room

Attempts

logoue

yields.

of type 1 and i has been

formed one

is similar

to result

(7).

able however

derivative

7c

using in the fonna-

was isolated

been

cyclC3.2.2Jazine

of 2

to obtain

5.6 96

(8). The ana-

(8) (32 $1 and & to give E

give 2

Refluxing

(2,51

(66

Cage

_

96)

efficient.

HN-C+Et $--C%Et

Me%C

HN-C%Et 5a b

7a

R=H R=

Since

C&

6

3-hydrazinoindolizine

(8 + 21~ cycloadditian Boekelheide's

method

as 8X components

(8).

derivatives

to electron in which

deficient

3-unsubstituted

R=H,

d=H

b

R q Hi RI= NP+Et)NHC%Et

c

R=C6Hsi

are readily acetylenee

RI=

H

accessible nicely

indolizines

have

the

complements functioned

3675

It has dlalkyl

been

briefly

acetylenedicarboxylate

insensibility eines

reported

of

the

is noteworthy

a future

also

reaction (10).

that

to

3-cyano

yields

indolizine

the

on

reaction

cycl[3.2.2]azine

substituents

in position

This

observation

will

be

this

work

Minister

(9). The

2

3 of

discussed

the

in

with

indoli-

details

in

communication.

Financial Forechung

dea

support

(1)

0.

Die18

(2)

All

new

Landes

and

of

by

the

Nordrhein-Westfalen

gratefully

REFBRENCES

AND

NOTES

Liebigz

Ann.

Chem.

K. Alder,

cdmpounde

is

showed

fiir Wissenschaft

satisfactory

,

und

acknowledged.

237 (1926),

C,H,N-analyses

and

spectral

data. (3)

1

3.9 %; 4 (R =

5.6 96;2 (R = CH$:

(R = H):

H):

3.8 %; 4 (R = CH3):

11.5 96. (4)

Other the 3018

(5)

1

1

oxidation

reactions of

of

alkyl

hydroquinonee

azodicarboxylatee

see:

0.

are

For

known.

Diels and P. Fritsche,

Ber.

44,

( 19 1%) .

H-NMR-spectra: (R = H)

2H) ; k

oxidation

CDC13:

4.92 (m, 2H);

(R = H)

(d,

8 = 7.02

12H,

CDC13:

4.99 b,

& =

(d,

1H);

(s,

1H);

6H,

(d,

6.87

(t,

6.5 Hz);

J =

6.82 (8. 1H);

6.5 Hz); 1.12

J =

6 = 6.92

1.30

(s,

6.01

12H,

J =

Hz).

2

(R = CH3)

6 =

(m,

4H);

3.50 (6, 3H)i 1.27 (d, 12H.

6.2

Hz)-

&

d6-Acetone:

CDC13;

S = 8.76

1.i8

(d, 4.92

6.5 Hz).

2

2H1; 3.59 (6, 3H): 1.27 (d. 6H,

6.2

J = 2.6

Is, 2H);

6.52 (t, lH, J = 2.4 Ha);

J =

lH,

J =

Hz);

6.00

6~, J = 6.5 Hz). (m,

4s);

(R = CH3)

(a, NH);

1.23

CDC13:

6.06 (d, ZH, J = 2.4 Hz); 6.2 HZ):

1.20

(d,

6.94 (s, 2H); 6.06 (s, 2H); J =

(a,

6.2 Hz):

1.20

8.25 (a, H

5'

6H,

4.99

(d,

lW,

J =

J =

6.8 Hz);

7.39 fd, ITS, J = 8.8 Hz); 6.74 (m, Hz);

(q, W,

J = 7.0

1.25

H51;

Hsl. 2 d6-Acetone: J = 0.9

(m, (6)

&I):

Is,

P. Benin

and

and R-K.

Rievi,

(8)

The eyntheeis has been

J. Am. Chem. has been

4.00

(8,

Y.

Yamachita, from

Xyokai

Shi a,

739

and U. Krlmer,

K. Matsumoto,

Y-B.

of the

being

Vol.

(1977) Adv.

2

dG-Acetone:

C.M.

4.24

Gupta

57.

787 11979). acetylenedicarboxylate

an intermediate

of the

and Y. Boekelheide,

Barnes

of

of

cyclC3.2.2lazines

Heterocyclic

Compounds

30, p. 246, 1977, J. Wiley Yulci

and J. Yamanichi,

[Chem.

Abstr.

Heterocycl.

and L.A.

(1964);

14B,

dfmethyl

Paquette,

T. Uchida

88,

3764d

and

Gosei

1197811. -

Chem. 22,

322 (1978).

Synthesis

1979,

and L.A. Paquette,

(8 + 2)fi cycloaddition

of

the

and ethylenes

746 and Hetero-

and S. Xanemase,

in

Garmmy

Chem.

955

19 Pebrueuy

depend

reaction

to electron

strongly

on the rrubstitu-

(81. See also:

indolieines

Heterocycl.. Chem. is, (Received

509

l2,

Chemistry

T. Uohida

Kemi-Kono,

acetylenes

pattern

gaeshi

1976,

and

The

(la, 12H).

103 (19801.

l4,

The yielda

t&on

B.

94,

R.A.

and E.G. Taylor),

T. Uchida

deficient

Sect.

indolieine

A. Taurins:

6.85 (I , HZ);

(la, 6~).

453 (1961). The chemietry

see. fQ,

K. Matsumoto,

cycles

1.28

Ital.

Small,

Hz);

1.12

fleterocycles

Th.

1.2

J = 7.8 Hz); 7.89 (8, H31;

a dihydroderivative

Galbraith,

=

8H);

3H);

Chim.

J. Chem.

- K. Matawnoto,

W. Flitsch

(f0)

3H);

reviewed:

N.Y.

Kagaku

(9, R6'

of z

(A. Weissbgrger

Sons,

8.05

reported, A.

tm,

4.17

Gazz.

J

J = 9.4,

H7);

Ind.

and

reaction:

8.85 (6, NH); 8.63 IS, NH); 8.22 Id, ~5, J = cd, H8,

A. Honti,

1.19 Ct, PH, J = 7.0

(t, 3H, J = 7.0 Hz);

6.64 (m, ~6);

4.05

M. Masumura

=

7.56

8.46 (m, 4,

(7)

(9)

&

Hz);

6.81 (m, H7); 6 =

6.61 (t, H6, J = 6.8 ,

H7);

6.18 (d, WI, J = 4.2 He); 4.19 (q, 214, J = 7.0 Hz); 4.17

J = 6.6

7.5,

HZ,

Lett.

(1978). 19SO)

1976,

S. Ikeda,

S.

Kaje-

367. - E.X. Pohjole,

J.