Synthesis of hydroxyisoxazolidines on adsorbents

Tetrahedron Letters, Vo1.30, No.1, pp 117-120, 1989 Printed in Great Britain

SYNTHESIS

OF

I.A.blotorina*, Chair

of

Organic

HYDROXYISOXAZOLIDINES

L.A.Sviridova,

Chemistry,

Chemical

Department,

5-hydroxyisoxazolidines and on the surface depends on regioselectivity

to

they

are

very

w ter

method It

of

compounds

have

a

and

most

the

the

oases

aryl

only

acids

presence

of

State

University,

the

alkenals

and

in

products we

have

has

3-

and

and

of

cyclic

their

the

been 1.

As

structure,

elimination

described

an

of

efficient

5-hydroxyisoxazolidines3

d,p

heterophase

yielding

in The used.

5-hydroxyisoxazolidines fragment

undescribed

(TEAE-cellulose) on

la mi nes or

hemiacetal

arylhydroxamic in

3-

Recently

previously

that

interact

in

isolated2.

Moscow

can be synthesized of an adsorbent. the type of adsorbent

of or

Yu.G,Bundel.

USSR

hydroxy

formation hemfaminal

be

synthesizing

ethylcellulose depending

the

can

found

N-substituted

with

unstable

molecule

WI9

of

re,?ction

proceed

corapounds

these

a

119899,

3; And solution

The shown

ON ADSORBEWTS

G.A.Golubeva,

MOSC ow , Abstract.

0040-4039/89 $3.00 + .OO Pergamon Press plc

-unsaturated catalyst

compounds

1

carbonyl triethylanino-

or 2

(see

Scheme)

substituent4. RI

ArCONHOW

R Ho

F&&H-C

HO

‘R2

Rl,R2=H,CH3

Ar=CGH2(CH3)3-2,4,5;

Ar=CDHd)(-p X=OCH3,

I X=H,Br,N02

%&X-P

The solution

interaction yields

mixture

of

3-

tautomerism

Ring-chain The

benzohydroxamic

of a

present

note

is

devoted

(98:4) is

acid and

and

characteristic to

the

crotonaldehyde

5-hydroxyisoxazolidines

comparison

of of

the

CH3,

in

methanol

(=.$A)

compounds

_l_

reaction

of

5 and

. 2.

hydro-

aldehydes in solution and in an adsorbed d#P -unsaturated in the absence of any solvent. that adsorption causes an acceleration of the Our experiments have shown

xamic acids and state

H

reaction.

Thus,

the

complete

conversion

117

into

2-benzoyl-3-hydroxy-5-methyl-

118

isoxazolidine

under

cellulose

catalysis)

the

of

yield

conversion

conditions

(OoC,

methanol

solution,

an adsorbed

only after prolonged stirring (5-7 h) and and purification is about 60%. The same (20 oC, si02)6 is complete within 30-40

state

( yie Id 90%).

Quite

surprisingly

it

turned

out

that

the

isolated

product

(3- or S-isomer) depends on the type of adsorbent (see sup posed that these results can be ex;?la ined by the properties of adsorbents.

Table

Table

reaction

1.

Effect

CH3CI-!=CH-CHO +

of

adsorbent

on the

composition

of

Total

Neutral

alumina

Neutral

alumi na/KF

the

products*.

HO

yield,%

3-OH isomer,

isomer,

5-O”

% total

% total

70-75

80-85

20-15 25-20

70

75-80

Ml-70

85-80

15-20

1

50-70

85-90

15-10

68

32

loo

0

Silica

AB

73

gel

80-90

Cellulose

43

75

25

CM-cellulose

41

70

30

DEAE-cellulose

95-98

a

100

TEAE-cellulose

9s

0

100

ric

It

was found

of

2-benzoyl-3-hydroxy-5-methylisoxazoli

pair

of

may be

in basic

alumina

Inerton

case

It

C6HgCONHOH

Adsorbent

Florisi

structure

1).

difference

HgC

Acid

TEA!? -

is achieved after isolation

product

in

mi nutes

conventional

that

different

diastereomers

form dine,

2-benzoyl-5-hydroxy-3-methylisoxazolidine

in equal

amounts

%

in the

but only

one diastereome-

forms

on DEAE-cellulo-

se7. Further showed

that

*-Reaction

investigation for

al 1

was carried

of starting out

the

reactions

hydroxamic

at 2DoC,

reaction

on

DEAE-cellulose

acids time

and

carbonyl

in all

cases

as adsorbent compounds was 15-16

h.

119

(acrol

ei n,

crotona

(overnight

yie Id

comparison

with

in

that On the

other

2 h,

a mixture

of

3-

the

reaction

time

on the

formed

the

even

led

The

inversion

hand,

when

the

the

of

on prolonged

was transformation in

reaction

addition

solution

good

direction for

in and

X=H,Br

was reduced

time

obtained of

in

zform

observed

to

l-

(see Table 2). Increasing 3-hydroxyisoxazolidines

Nevertheless,

an adsorbent.

stirring

adducts

of was

solution

and 5-isomers

to

surface

only

nylketone),

methanol

Ar=C6H2(CH3)3.

5-isomer

methylvi

ldehyde, incubation).

(20-40

products

::z.;s)

Por

X=r102,

to not

2 are

.:r

and

Ar=C#2(Cl-!3)3.

Table

The

2.

correlation

between

reaction

time

and amounts

of

isomers.

&f&

PhCONHOH + CH3CH=CH-CHO -

Reaction

conditions

Time

Ratio

of

products,

3-OH isomer(la)

?$

5-014 isomer(a)

methanol

solution

5h

98

methanol

solution

30 days

95-98

adsorbed

state,

30 nin

100

0

adsorbed

state,

DEAE-cellulose

1 h

6U

40

adsorbed

state,

DEAE-cellulose

6h

4

90

These dines

is

data

gel

support

reversible

reaction, xazoli

silica

dine

but

into

the

and

also

the

the

a)

Y.YaI:!ada,

(1973); 2. a)

b)

A.Belly,

(1972);

b)

Cl.Noda, J.E.Van

Ii. Epp,

R.Jacquier, A.Belly,

the of

ly more

and

Okada,

formation catalyzes

transformation

thermodynamical

Notes 1.

that

fact

OEAE-cellulose

the

stable

of 3==hydroxyisoxazolinot

only

the

addition

kinetic product 5-isomerS.

3-hydroxyiso-

Biolog. 40, 1727

J7,

references.

Agricul.

and

Diss. Abstr. x.,B, -F.Petrus, J.Verducci,

F.Petrus,

2 2-5

J.Verducci,

Bull u.

Chem., (1979).

. sot. E.

Q&g. u.

N9, France,

France,

2201, 330 1395

(1973). 3.

K.N.Zelenin,

I.A.hlotori

A.Yu.Ershov,

Yu.G.Bundel,

na,

L.A.Sviridova, Khim.

Geterotsikl.

G.A.Golubeva, m.

, N9,

I.P*Bezhan, 1270 (1987).

120

4.

The

reaction

5.

the

structure

The

carried

MS

catalysis,

of

17.7 :-:I

77-D2 and

ppm,

The

general

procedure methanol

"Chenapol

’

c> neutral neutral

alumina

and

1

and

for

evaporated

with

under (act-01

hove

0~1 ,‘-‘-;

:n t-?rtcPi c.1 c ,

heniaminal

carbon

more

‘,- 7:~ s tic*

C(3)--

being

detailed

;jr ; ;,R

chemidel

atom

5-hydroxyisoxazolidines

redused

being

thoroughly from

e)

Servacel some

at

5,2-5,8

information

20

see

also

TEAE,

mmoles

of

volume

of

adsorbent

(a)

‘Reanal’, of

as

large

stirred

by CHC13 and

Hungary;

as during

purified

of

,

f> DEAE-

that

of min.

was

carbonyl stabilized

adsorbent,

30-40

d)

solvent

-unsaturated

nylketonef

portion

Poland

Hungary; The

d ,p

Si lpearl

pH 5-7,

adsorbents).

another

and

5 minimum

pit 9-lD,‘Reanal”,

methylvi

times

the

I Drockman,

5 mmoles

the

follows: in

dried

other

ldehyde, on

as

activity

Brockman,

and

mixed

adsorbent

was dissolved

previously

pressure.

crotone

an adsorbent

extracted

to II

5% KF;

adsorbed

was

was alcfiJi n:,

, Hungary

ws

Everything

reaction

added b) acid

ei n,

hydroquinone, of

the asid

activity

‘Reanal”

compound

by

the

the

total

reagents. The

product

by recrystallization

or

chromatography.

7.

The

existence

8.

As follows

and

di n2=3

For

of

, CSSF!, or alumina,

cellulose,

column

znli 1 ppn,

values

hydroxamic

anhydrous

t~s

%, _ - :‘;~r:ro::yiooxo

TEAE-cellulose

3.

p-substituted

mass

D-5oc,

h.

’ n 3 d ’ .i?S ~~~i;~3b~i) 0:; ^, 5 ClP

c~;,ounds

analogous

solution,

5-29

ppm correspondingly.

reference 6.

methanol

being

pro-b::n .3t .5,5-S,

the

95-100

in

time

the

1 :I Liri cl 1”3 C cla tz . shifts

out

reaction

of

dias tereoi

different

Somers

WSS

estimated

from

NAIR ‘H

13C spectra. from

simultaneously isomers

(Received

the and

is

about

in

kinetic the

ratio

data of

5.4.

UK 16 October

1988)

3-OH and

production

S-OH rates

isomers between

are 3-OH

prodused and

5-OH