Efficient intramolecular [2 + 2] photocycloaddition of styrene derivatives toward new crown ethers

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EFFICIENT INTRAMOLECULAR C2 + 23 PHOTOCYCLOADDITION OF STYRENE DERIVATIVES TOWARD NEV CROWN ETHERS') Seiichi Department

Inokuma, of

Takamasa

Chemistry,

Yamamoto.

Faculty

Tenjin-cho,

of

and Jun Nishimura*

Engineering,

Kiryu

376,

Gunma University,

Japan

Abstract: New crown

ethers, exhibiting high Li+ -selectivity on the extraction, were prepared from I,@-bisfp-vinylphenyl)oligo(oxyethylenes) title reaction in excellent yields. Recently give

bis(vinylaryl)alkanes

cyclophanes

yields2).

having

cyclobutane

The photophysical

is

an efficient

photoreaction

of

cyclophanes.

like

phanes,

and so

This ties

such the

photoreaction Scheme

with

their

to our of

synthesis

by this

aromatic

as shown

in Scheme

of

excellent

revealed

ca.

O.43).

that

Several

biphenylophanes,

to prepare ring

systems, of

this

a new kind which sort

Cram’)

communication

this

the

crown

of

have

it kinds

naphthaleno

have

and #isumi61

ethers

ethers,

many

designed

we would

obtained

crown

some possibili-

do not

In of

like

and to

by the

1.

1

L

2 -

a: n=3 b: n=4

h3 0280 nm) Solv. (MEF4) under N2

1

66 Odd L4 c6” 0

0

+

0

O

5

a: n=3

NaOH/dioxane.

0

H

00

a: n=3

b) NaBH4/EtOH. 97

0

n

0

n

b: n=4

b: n=4 TsOfC2H40),+1Ts.

a: n=3 b: n=4

H

al

and sometimes

cycloaddition

survey,

ethers.

to

method2*4).

Crown ethers

and properties

photoirradiation

reasonable this

metacyclophanes,

literature

crown

under

quantum yields

can be applied

properties.

a kind

in of

high

prepared

oriented

According

examples. prepared report

were

face-to-face

to modify

ring(s)

paracyclophanes,

forth,

cyclized

investigation

photocycloaddition

possessing

were

solid-liquid by the

z

a: n=3 b: n=4

cl TsO-HPy+/benzene.

98

Styrene yields)

by

derivatives the

with

pyridinium

out

in methanol,

of

tosylate,

Olefinb)

3a

2 3

shown

Reaction

reasonable

trile of

1.

with

Crown

Time

with

and without

60% overall and dehydration7) was carried

an alkali

metal

fluoro-

3 and sa).

Conv. e, (min)d)

(ca. NaBH4,

The photoreaction

Ethers

conditions

Add. ‘1

yields

reduction

Scheme

in

Preparation

I.

in

formation,

and acetoni

Solv. 1

prepared

ether as

benzene, Table

Entry

3 were

sequence

Yield

(%)e)

(X)

4

5

98

67

3

NeOH

-

20

3a

HeCN

-

30

100

91

2

3a

PhH

-

30

100

74

10

4

3a

MeOH

LiBF4

30

100

a2

11

5

3a

HeOH

NaBF4

40

100

86

14

6

3a

MeOH

KBF4

50

100

88

7

7

b

MeOH

-

30

100

93

7

8

3b

MeCN

-

30

100

95

5

9

3b

MeOH

LiBF4

20

100

94

6

10

a

MeOH

NaBF4

20

100

93

7

11

3b

MeOH

KBF4

30

100

91

9

a) A 400W high-pressure mercury lamp was set at a distance of 5 cm from Pyrex test tubes (15 ml) which contained the reaction mixture (10 ml) under b) 2 mM. c) 40 mH. d) At around maximum a nitrogen atmosphere at r.t. yields. e) Determined by GLC, using tetraethylene glycol bis-p-ethylphenyl ether as an internal standard. Table

II.

Physical

Compd Mp; Anal.

Calcd

‘H-NHR Chemical

and Analytical (Found)‘); shift

Data MS(H+);

6 (intensity,

of

Products

IR(u~=~

4 and 5.

and/or

multiplicity,

Y~_~). J in Hzlb).

4a

c 72.34(71.85), H 7.59f7.23). 44.0 - 45.0 ‘C; 6.62(48, A&. 8.81, 4.06(4H. 6.77(4H. ABq, 8.81, bs), 2.41(4H, m). m), 3.62(88,

3.92(2H,

m),

3.75

(4H,

&

43.5 - 44.5 “C; C 70.57(70.06). H 7.74f7.68); m/z 442; (C-0) 6.77(4H, ABq, 8.81, 6.63(4H, ABq, 8.81, 4.03(4H. ml, 3.92(2H. bs). 2.39(4H, m). m). 3.65(128,

1180 m),

cm-‘. 3.76

(4H,

&X

78.0 - 79.0 ‘C; C 69.89(70.06), H 6.84c6.75). 7.11(2H, ABq, 8.7); 6.99(2H, 8.03flH. Ad. 8.71, 6.18~1~. Xd, 2.51, 4.28(2H, m). 4.09(1H, 2.5). am), 2.34(2H, mm). 3.58flOH. m). 2.75(2H,

m

H 7.07(7.391; m/z 456; CC=01 1670, (C-01 1185 Cm81.0 - 82.0 Oc; c 68.40(69.00), 8.04flH. Ad, 8.7). 7.04(2H, 4Bq. 8.71, 7.00(2H. A&q, 8.7). 6.8OflH. Mdd, 8.7 8 6.24(18. xd, 2.51, 4.21(2H. m), 4.10flH. Xm), 3.99(2H, m), 3.86 (2H. m), 2.51, 3.63(14H. m), 2.65(2H, am). 2.38(2H. ABm).

a) Microanalysis Varian Gemini-200 s tandard.

Faculty of Center, FT NHR spectrometer.

m),

A&, 8.71, 6.78(1H. Mdd. &ml. 4.02(2H, m). 3.86(2H,

Engineering, Gunma University. In deuterochloroform using

b) Taken TMS as an

8.7 8 m).

on a internal

99

under

borate,

the

u-Crown yields

ethers

from

They

showed

(&I

and

Table

the

if

most

I where

predominantly

by

the

signal

of

results and

column

are

data

also

isolated

in

chromatography

more

methine

aromatic

protons

of

ethers

crown

listed.

(SiO2.

u-cyclobutane

high-field-shifted

‘H NHR spectroscopic

efficient

in

they

According

the

increase

of the

the

moment .

Crown

yield

in

ethers

Even

Figure

though

reaction

1.

than

75%

acetone/benzene).

protons

caused 4 are

Products

summarized

in and

oxygen

crown

ethers.

which

ethers

Table

III.

Salts

by Ethers

Solubilization

Ether

Amount Molar

of

by

at the

63.92

layered

summarized

in

of

to

can

effects metal is

are were

out

after

be

by

of

the

removed the

oxidation

of

cyclohexenone

moiety

support

structure

bind was

their

alkali determined

photo-

then

decreases,

metal

are

ions

from

as

the

the

maxima. gas

and

into

gave

a radical

reaction

system. whose

substituted

this

under

IR spectrometries,

three

The

data

aromatic easily

found

in

in

Scheme

as

nitrogen

are

ring

depicted well

the

Solvents at

nitrogen place

the

in

around

took

from

yield

resulted

clear

and

bubbling

photo-oxidation formed

at

the

glycols.

stable

read

yields, of

the

effect.

a maximum

I,

one

on

not

not

is

ion

template

origin to

Table

not

the

oligoethylene

the

high

which

from

moiety

be

considerably

solvent alkali

the

‘H NHR, HS, and

ability

1.

conventional content

of

the

Thiocyanate

Methylene

solubilized ratio

due

carried

to

clearly

prepared binding

into

in

could

of

an

increases

30 min,

by

which

The

4

An AHX pattern

II.

of

1).

was

5 seem

an ABCDX pattern

‘H NMR spectra, The

of

least

determined

Table

and

although

listed

at

compounds

a cyclobutane

experiment

5. 5 was

6 vs.

in

cyclization8)

template

addition

yield

obtained

Okahara

crown

extent,

Yields,

every

with of

4 to

some the

for

intermediate structure

of The

4 having

mixture

cyclohexenones

I).

were

of

small

(entry to

Eventually

shown

crown

Table

ethers

those

obtained,

reaction

irradiation.

crown

with methods

data (see

affected

their

I the

compared

synthetic

to

protons

Table

are

recognized

the

Table

II.

even

as

and

in

formed

mixture multiplet

UW4’

nuclei.

As shown

are

shown

4 were

reaction

a typical

4.03

aromatic

conditions

Chloridea). thiocyanatesb)

HSCN/ether

KSCN

NaSCN

4a

0 .-1

0.3

1

3a

0.1

0.4

1

4b

0.3

0.3

1

3b

0.1

0.1

1

LiSCN

a) Experimental conditions: Cpolyetherl, 0.25 mmo1/5 ml of methylene chloride; HSCN, 7.5 mmol; stirred at r-t. for 24 h. b) From nitrogen content in the organic which was determined by the layer, elemental analysis.

30

60 Time

Figure

1.

120

(min)

Time course of the photocycloaddition. See Table I for details.

180

100

organic

layer,

salts

after

(HSCN)

summarized

in

in

the

prolonged

methylene

Table

III.

Not

effectively

extracted

the

selectivity

for

under

since

lithium

electric

metal

power

acetophenone did

not

mental

any

ethers

ti-phenethyl

studies

under

on ring-opening

photoirradiation, at and

reported

their

of

metal

their

hydrophilic

applications

and

their

Nishimura.

Y.

Nishimura.

H. Doi,

J.

5293

the

same

6’) experi-

transport’*).

and

hydrophobic

are

now

in

Nishimura,

Horikoshi,

A.

5)

R. C.

6)

N. Kawashima,

structural

progress

and

Helgeson.

0

the and from supports.

Part

H. Takahashi, A.

7.

Part

6 of

Tetrahedron

Ohbayashi.

and

this

Lett A,

A.

Oku.

Ito,

A.

J.

series,

in

press.

Am. A Chem

Sot -,

Y.

Wada,

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Oku,

29,

Lett., H. Doi.

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Tsuchida.

M. Yamamoto,

(1988).

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and

A.

H. Timko,

D. J.

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Chem.

Ber..

121.

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A.

Talma,

G.

T.

L.

Tarnowski,

T.

Kawashima,

H. van

Vossen, 1986.

Reinhoudt.

Synthesis,

P.-L.

H. Hiki , and

Kuo,

K. Hiratani

and

linear

alkali acid.

On the

high

selectivity,

K. Hiratani,

12)

J.

S.

ions

and

Cram,

J.

Am.

Chem.

Sot.,

other

Otubo,

E.

J.

all, hand,

using K. Taguchi,

and

S.

Misumi.

R. Rudhblter,

J.

Tetrahedron van

Lett.,

Eerden,

and

D. N.

680. J.

-Chem

Bull.

like at

T.

H. Okahara,

Aiba,

polyethers

metal

11)

J.

(1977).

1978,

1976

00

will

(1988). 6411

The

Ueda,

Tetrahedron A.

Nishimura.

99,

and

E.

Ohbayashi,

Y. Nishijima.

2019

H

H

(1987).

J.

9)

like

oxacyclophane

under

cyclobutane

ion

C2 + 23 photocycloaddition,”

J.

4)

10)

ethers

Notes

J.

and

8)

and

notable,

future

&

“Intramolecular

109,

7)

the

other

2,

high

are

as

chloride

3

show

results

derivatives

methylene

thiocyanat

are

ethers

both

elsewhere.

References

3)

linear and

The

This work was supported in part by grants from Ministry of Education, Science, and Culture, Japan, Toray Science Foundation. We are indebted for their

2)

also

chloride,

alcohol into

ground

Results

conditions”).

uni ts12),

1)

finely

in many fields such 11) , etc. However,

fusion

ions

3 with method’).

applied”).

attracted

metal

of

3 but

methylene

by nuclear 1,

h)

reported

conditions

much

alkali

(24

the

crown

into

the

very

derivatives

modifications be

is

by

only

salts

generation

extract

Further ring

LiSCN

contact

chloride,

styrene

sot . . Chem . Commun..

Jon.,

Sot.

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using

their

crown

ethers

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Chem.

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H. Sugihara,

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2657

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504.

(1984).

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1978.

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to an ion

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(1984).

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in

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I