Synthesis with silicon derivatives: non symmetrical derivatization of symmetrical diamines

0040-4039/82/090979-04$03.00/0

Tetrahedron Letters,Vol.23,No.9,pp 979-982,1982 PrInted In Great Britain

01982

Pergamon Press Ltd.

SYNTHESISWITH SILICON DERIVATIVES. NONSYMMETRICAL DERIVATIZATIONOF SYMMETRICAL DIAMINES Eduard Schwartzand Abraham Shanzer* Department of Organic Chemistry The Weizmann Institute

Summary nitrogen

The conversion

compounds as intermediates

The conversion problem,

of symmetrical

the synthesis

of spermidlne

former case,

the preparation

butane and 1 equivalent material

unreacted

symmetrlcal alternative

equlmolar

of symmetrical Into

cyclic

as well

and symmetrical Leznoff

et al

prlnclple

(5,6)

dlamlnes

of the first

A solution

of 0.0077

1s carried another

M cyclic ml/mln

In order

temperature,

In this

and gives

as major

blocklng

groups,

communication

silazane

of the second

procedure

with

slllcon-nitrogen

compound as

allowlng

mixture subsequently Stlrrlng

1s added dropwlse at room temperature

of the reagent

of the reagent

fluoride.

is

979

of

cooled

with Ice

1s continued

phase 1s dried

to a The reactlon

with a syringe

completed, for

30 ml of 5% aqueous bicarbonate.

the organic

and

the preparation

1s as follows

and the addition

the addition

of 30 ml chloroform

on the

Subsequent reactlon

of the cyclic

In 25 ml tetrahydrofuran

bottle

of hydrogen

an

and wish to report

The method 1s based on transforrmng

In 10 ml tetrahydrofuran

and the mixture poured into

with 3 portions

In the

the two amino groups have become interdependent

30 mln and the reaction

of a 40% aqueous solution

Examples are (3).

the problem of non-

as selective

derlvatlves

a difficult

butane from 1,4-dlarmno (2,4)

to solve

polymers

We wish to describe

In the formation

experimental

After

slllcon-

monoamldes.

M acyl halide

out In a polyethylene

at a speed of 0.15 for

dlamlde introduced

group causes deactivation

The detalled

alkaloids

N-acetyl-1,4-dlamlno

compounds as Intermediates. gives

lntermedlate,

of 0.0077

spermldlne

is

products.

In only 22-23% yield

to mono annoes

sillcon-nitrogen

In this

monoderlvatlves. solution

occurs

derivatives

of many natural

as many cyclic

anhydrlde

The key of the method resides reaction

to non-symmetrical synthesis

of the key precursor,

amounts of acyl halides

lntermedlate.

Israel

to monoamldes via the use of cyclic

method which 1s based on the use of slllcon

conversion dlamlnes

(1,Z)

derlvatlzation,

ma!-.lng use of the dllutlon

dlamlnes

in the total

acetlc

dlamine

dlamines

Rehovot,

is described.

of symmetrical

which IS encountered

of Science,

stlrring and treated

pump

is

continued

with 1 ml

30 mln at room After

extraction

over magnesium sulfate,

filtered

980

and concentrated. concentrated. AG M-50,

The aqueous phase is extracted

The oily

resrdue

is subsequently

100-200 mesh hydrogen form. elution

diamrde by-products, the Individual

with chloroform, separated

Elutlon

dried,

filtered

and

on an Ion exchange resrn,

with methanol provdes

small

amounts of the

with 0.5% NH4GHin methanol the monoamides. The yrelds

examples and the spectroscopic

and physical

properties

for

of the products

are swnmarlzed in Table 1.

(CH&

$-CO-R’

TN\

+ MeaSi(NEt&--

(CHaIn LN/S~Msa

\NH ;

I.R’COCI (CHa), 2 rlFag \Nti

k I,

k

na2,RgEt

&,n=2,R=

Bz

&J R’=Ph

-5on=Z,R’Et

4b,R:

_5&n =2,Ra

Bu

J.n*3,RuEt

evrdent

As

with allphatrc alrphatlc

acyl halides

dramides

are obtained

The reaction phlllc mediate

attack

substltuents

however,

(See footnote

$ilazanes

of the sllazane

and to allphatlc

no dlamrdes are formed,

as by-products

of cyclic

nitrogen

Gn*2,R=Bz

R’=Ph

e

R’=Bu

“= 2,R.Bz

Gn=3,R=Et

R’=Ph

2

R’eBu

n=3,R*Et

and aromatlc

while with aromatrc may be visualized

-N\

(CH2jn

7 _SMe,

+ R’COCI

-

With

acyl halides

some

to occur by nucleo-

carbon to give the non-symmetrical

I.

‘:

to dramines

acyl halrdes.

In Table 1).

with acyl halldes on the acyl

R’s BU

the method IS applrcable

from the examples given In the Table, and aromatic

R’.Ph Et

7

NCOR’

(CH21n

-

N-St-Cl

ADMfJ I

inter-

w

AND

72f

61d

7a

7b

1.74(s)

1.62(e)

1.98(a)

234

2oc

3500 3300 1630 3470 3300 1635

1.5(s)

1.53(s)

1.6(s)

HN..

310

344

186

Spectra

a

(m) 4.56(s) 4.59(s)

(m) 3.71(e) 3.75(s)

(m)

(m)

3.1-3.6

(m)

2.4-2.

3.2-3.6

1.9-3.2 (m)

(m) 2.5-2.9

(m) 4.64 (broad 3.2-3.6

(m) 3.4-3.7

3.4-3.7

(m)

2.7-2.9

3.3-3.5

(m)

(m)

2.5-2.8

2.9-3.5

(m)

e.)

2.23(t)

(m)

2.1-2.5

2.3(t)

-COCHt

Spectrab

b (ppm) -CONCHa-

‘H-NMR

2.2-2.6

HNCH2-

OF MONOAMIDES

3480 3305 1640

3500 3310 1630

1630

3280

3480

220

m/e

Mass

PROPERTIES

-

7.36(s)

7.15” 7.53(m)

7.49(m)

7.23-

O_.72-l.

7.13(e)

e,

21%

f,

19%.

17

34

35(m)

0.75-l. 1.35-l.

;

35(m) 9(m)

1.35-1.9(m)

1.0-l.

(m)

0.9-l. 00 (m) 1.36-1.4

(m)

(2t) 1.25-1.8

0.86-l.

(2t)

others

-ArH

b The NMRSprctra were recorded In CDCl, o1 a Varlan 6OMHz aThe IR -Spectra were recorded in KBr pellets. instrument except for 5a, the spectrum of which was recorded in CC14 on a Vdrlan 60MHe Instrument. Chemical shift8 are given relative to internal TMS. The yields of the corresponding dlamlden were : c, 2274 d, undetectable

60d

69e

6a

6b

5$

5b

3500 3310 1630

y(cm-‘)

%

75=

IR -Spectraa

Yield

SPECTROSCOPIC

5a

Compound

YIELDS

Table

982

‘lhe electronegative

chlorine

substituent

second amino group which becomes resistant silicon-nitrogen

in an earlier

reactivity

out,

compounds towards organic with trn-nitrogen

substrates

tin has to be used since

group.

functions

We are currently

derivatives

between the silicon

as both,

and for

protecting

in progress

the synthesis

for

anunes and tin

ready availability, for

method and the polymer-method group,

nitrogen For dials,

while

the method for occuring

is

the polymer only the preparation

nitrogen

tin-oxygen

that the

as protecting of mixed

compounds.

References 1.

C.W. Tabor, H. Tabor and U Bachrach,

2.

E.L. Jackson,J. Org

3

M Hesse and H. Schmidt,

in oInternational

Two”, Vol.

9, Alkaloids,

ed. Wiesner,

4.

A. Hessing

and R. Eckard,

5.

C.C. Leznoff,

6.

D.M Dixlt

7

A. Shanzer,

a

For the preparation

Chem., 21,

Leznoff,

Tetrahedron

Chem , 23J, 2194 (1964).

1374 (1956).

Chem. Ber.,

Chem. Rev , 3,

and C.C

J. Biol.

Review of Science,

Butterworth,

Organic

Chemistry Series

London, p. 265 (1976).

103, 534 (1970).

309 (1974). Chem Commun., 798 (1977)

Letters,

of silazanes

221 (1980) see

E.W. Abel and R.P. Bush, J. Organomet

Chem., 5,

245 (1965) . 9.

10.

K. Jones and M.F. Lappert,

in “Organotin

Dekker, Inc.,

509 (1971)

A J

New York, p

Bloodworth

and A.G. Davies,

ibid.,

(Received in UK 21 December 198)

Compounds”, Vol. Vol

1, p.

153.

2 a ed

as

when compared

amines.

inert,

dials

the chemical

(10).

and activating of applying

for

of silicon

compounds are rather

of naturally

of the

but based on considering

with their

substrates

cleavage

of the

the mono amides.

the element of choice

silicon-oxygen

the reactivity

Subsequent

The high reactivity

(8) together

towards organic

‘the major difference

attack.

of silicon

derivative

make silicon

I reduces

provides

(7) is not arbitrary,

metalloid

compounds (9))

compounds are reactive silicon

that the selection

publication

of the respective

however,

to further

bond with aqueous hydrogen fluoride

It should be pointed reported

in intermediate

A. K. Sawyer, Marcel