Reaction of enehydrazines with acetylenecarboxylic esters

Tetrahedron Letters,Vo1.23,No.48,pp Printed In Great Britain

0040-4039/82/485025-02$03.00/O 01982 Pergamon Press Ltd.

5025-5026,1982

REACTION OF ENEHYDRAZINES WITH ACETYLENECARBOXYLIC ESTERS '

Wolfgang Sucrow*, Wolfgang Turnschek and Ulrlch Wolf Fachbereich

Chemle,

Eight products

Abstract formylacetate

Recent

of Paderborn,

from reactions

dlmethylhydrazones

have been characterized

University

with

Interest

of acetylacetone-,

dlmethyl

by the usual

D-4790

Paderborn,

methyl

acetoacetate-

acetylenedlcarboxylate

spectroscopic

in the electrophlllc

methods

Germany

and

and, partly,

substitution

and methyl

methyl structure

of enehydrazlnes'

proplolate analyses.

prompts

us to

report on own results with the title reactions. Acetylacetone ethanol

to give a

(2,3-E)-isomer

12

deuterochloroform

dlmethylhydrazone'

5 l-mixture

of the

can be crystallized equilibrates

the hydrogen

bridge were

Additionally,

the constitution

reacts with

stereolsomerlc

(diisopropylether),

back to the above mixture.

tentatively

assigned

5.82

acetylenedlcarboxylate 12 and

mp 67°C.

&

nmr data

indicated

by a structure

/\C/

and lk and

at the formulae.

analysis.

6.85

5.73

E\C/H

L

/CH3 C\ \D ,!,N,H

'

II

,COCH3

CH3

E+ 12'.4

E H

H3C

3

C'

':H

kKH3)Z

N(CH312 ip

5.83

6.80 H

H3C

E/

:

II \CiE II

H +NH 3

(CH3)2 E = C02CH3

E\C/H

i&E 7.25 9.90

,,/CiC/E 1 H+H

h(CH3)2 2

4

5025

5 =

in the

of pure lc in

of &

H\,JE II

from which

A solution

The configurations

by the

of 1~ has been confirmed

6 94

dlmethyl

compounds

9.15

i(CH3)2

5026

Compounds isomeric

pyrazoles

formation

15 and !k

i&k

of la,,b are the

cyclobuta[l,2-dlpyrroline

dated by an X-ray analysis From 76-78°C

methyl

could be

dimethylhydrazine its reaction figuration

product

of

hydrazone

(with

with a second molecule

a nice coupling

constant

pattern

proplolate

results

in ethanol.

analysis.

ketone cleavage, Only traces

e.g.

n H3C

reaction

4, mp

proplolate

with

dimethylhydrazone5 5, mp 45-46°C.

and

The E-con-

of H-2 to that of 12,

of

pyrldone

H\c/E

II

II

acetylacetone

with a having

The structure

E-l/H

2, how-

of

dlmethylhydrazone

relation lost a

of

H3C fl

CH3CO-group

8 could be detected

6 =

to

ln the

by an

X-ray

by nmr.

H\C/E

i

H3C-C

:\,

H3C n

0

1

proplolate

Q was confirmed

c\H

HjC

CH2E r N(CH3)2

shift

most of them

of the acetyl contalnlng

H

propiolate,

cyclic products

$I and l.

E

HjC

has been elucl-

J2 3 = 16.5 cps. fro; the

Only

E\C/H II

methyl

in the

crystalline

Methyl

formylacetate

chemical

larger than 1 could be isolated,

sense of a

of which

in THF only the

methyl

of

By-products

the other 4,5-trans-isomer.

acetylenedlcarboxylate).

from the similar

to give the stereo-

yield.

2 the structure

dlmethylhydrazone4 dlmethyl

in THF

moderate

of 2, probably

ether gave both the known

A complex methyl

acetoacetate

0 was deduced

ever, exhibits

with

and a stereoisomer

obtained in

react with monomethylhydrazlne

( bp 95 and 125"C/O.l mm Hg) in

0

r

N(CH3)2

N(CH3)2

7 =

8 E = C02CH3

The leading

N,N-bond

may

to a number of pyndlnes A more detailed

analyses

will be given

also be

cleaved

and a pyrrole

discussion

of the

during the

reaction

with

methyl

propiolate

ln trace amounts. reactions

presented

here

and of the structure

in the full paper.

REFERENCES 1. Communication

No. 33 in the series

2. K.Grohe and H.Heitzer, 3. N.A.Domnln Yakimovlch

"Enehydrazlnes".

Lleblgs Ann.Chem.

1982, 884, 894.

and S.I.Yaklmovlch, Zh.Org.Khim. 1, 658 (1965), engl. 2537. and F.Ya.Perveev, ibid. 8, 2488 (7972), engl

S.I.Yaklmovlch 4. T.A.Favorskaya, Ahlbrecht and H.Henk, Chem.Ber.

and V.A.Khrustalev, -108, 1659 (1975).

658,

K.G.Golodova,

ibid. 8, 2250 (1972), engl.

S.1

2298, H.

5. S.A.Glller, A.V.Eremeev, I.Ya.Kalvlnsh, V.G.Semenlkhlna, E.E.Llepinsh, T.M.Kupch and I.S. Khim.Geterots.Soedln. 3, 396 (1976), engl. 337, S.I.Yakimovlch, I.V.Zerova Yankovskaya, and N.A.Starygina, Zh Org.Khlm. 13, T168 (1977), engl. 1075. Acknowledgements. the performance Industrle (Received

We thank Prof.C.Kruger, of structure

and the Scherlng In

Germany

analyses.

AG Berlin 13

Mulhelm -

1s gratefully

September

1982)

a d.Ruhr,

Financial

and Dr.H.D'Amour,

support

acknowledged.

Paderborn,

for

of the Fonds der Chemlschen