Synthesis and polymerization of some ethynyl trifluoromethyl napthhalenes

Journal ofFluorine

139

Chemistry,38(1988)139-152

Received: March 10,1987;accepted: October15,1987

SYNTHESIS

AND POLYMERIZATION

OF SOME ETHYNYL

TRIFLUOROMETHYL

NAPHTHALENES

T. OKANO,+

K. ITO, K. KODAIRA,

K. HOSOKAWA,

M. NISHIDA,

T. UEDA

and H. MURAMATSU*

Government

Industrial

Hirate-cho,

Kita-ku,

Research Nagoya

Institute,

462

Nagoya,

(Japan)

SUMMARY

Some

bromonaphthoic

acids

were

bromo(trifluoromethyl)naphthalenes. Grignard yield

reagent

of a

lithio

derivatives

gave the desired

in improved

of the vinylic

halogens

acetylenes

catalyst

Although

of one of the bromides

with

with a

SF

to

4

reaction

C12C=CF2

gave

of low

(dichlorofluorovinyl)(trifluoromethyl)naphthalene,

naphthalenes

the

fluorinated

ethynyl(trifluoromethyl)-

after

subsequent

with g-butyllithium.

carried

was

to yield

yields

out with

high-molecular-weight

eliminations

Polymerization

photo-activated

of

W(COj6

polymers.

INTRODUCTION

We

have

aromatic

containing tions

recently

[ll.

reported

acetylene

In this paper,

the syntheses compounds

we report

ethynyl(trifluoromethyl)naphthalenes reported

erization.

Okuhara

naphthalene

from Grignard

C12C=CF2

t Present Faculty 464

(2) [21.

adress:

Institute

of Engineering,

Nagoya

and their

polymeriza-

the synthesis

of

some

and their polym(la-d) -the preparation of l-ethynyl-

reagent

However,

of some fluorine-

of

1-bromonaphthalene

some different

of

Applied

University,

reactivities

Organic

with were

Chemistry,

Chikusa-ku,

Nagoya

(Japan).

0022-1139/88/S3.50

OElsevier Sequoia/Printed inThe Netherlands

140

observed

in the similar

naphthalenes alyst

reactions

bromo(trifluoromethyl)-

Photochemically

(a-Cl.

effected

of

the polymerization

to high-molecular-weight

activated

CXH

R1 R2

CXH

3a

3h

3c

3d

CXH

Br

Br

Br

Br

CF3H

CF3 H

H

H

CF3

H

H

H

CF3 H

H

H

R4

H

H

CF3 H

H

H

CF3

H

R5

H

H

H

CF3 H

H

H

CF3

H

of Bromo(trifluoromethyl)naphthalenes

4-Bromo-I-naphthoic methylnaphthalene yield.

(a)

Similarly,

naphthoic

acid

(a)

(4a) was prepared from 1-bromo-4[3] by bichromate oxidation in 43 %

I-bromo-2-naphthoic

probably

(a)

because

another

position,

reaction

had given

had

be

to

methyl

ester

(Scheme

I)

[5].

though only

by sulfur

5-bromo-2-naphthoic by an isomer

there were

5- brominated

by successive

followed

by alkaline

of these

70°C for 20 h in an autoclave

acid

reports

that claimed [5,61.

recrystallizations hydrolysis

acids

in anhydrous to afford

(4cJ),

brominated

product

bromonaphthoic

tetrafluoride

(4&j was prepared

(6a) gave only 5-bromo-lbromination of 2-naphthoic

However, the pure

acid

(31 %) 141.

acid

of contamination

purified

Fluorination

(2)

of 1-naphthoic

did not give

(3).

acid

I-bromo-2-methylnaphthalene Bromination

out

CXH

Id

AND DISCUSSION

(I) Preparation

acid

_l_

H

R3

from

cat-

polymers.

la lb lc ___-----

RESULTS

W(CO16

of the naphthylacetylenes

again

4

hydrogen

was

at the

Thus,

fi

of

its

to

a.

carried

fluoride

bromo(trifluoromethyl)-

at

CCOH

a3

z!

s -

L!!J

R=M3

fjb R=H -

Scheme

I

naphthalenes

(a-d)

HF

the

lowered

fluorination

in moderate reaction

of nitronaphthoic

temperature,

no

tractable

(Table

tar

no trifluoride

expected I,

yields

temperature acids

product

(Table

[71.

Addition with

At a higher

was isolated

The methyl

9).

I).

in comparison

ester

reaction

from of u

of the

the

in-

also gave

3d -.

(II) Introduction

of Ethynyl

Group

into Trifluoromethvl-

naphthalenes. In

a

magnesium reported

to

olefin

reagent

give

by

II).

substitution coupling

This

the introduction

group.

A

selectivity

more

the

reaction

of

the

yield

of

a-naphthyl

change

However,

derivative

product reaction

&

&

reaction

the

to the binaphthyl

which

gave

of

Grignard the

(15 %) 8

was probably

of an electron-withdrawing

suitable

reaction

afforded

in low yield

of the reactivity

was lithiation

(2) was

dichlorofluorovinylated

of the similar

a-naphthyllithium.

trifluoromethyl

an unexpected

(Scheme

[21,

good yield

2 and

of

corresponding to

paper

and 1,1-dichloro-2,2-difluoroethylene

in spite of the lower

product the

previous bromide

due

(26 %) caused

trifluoromethyl higher

with g-butyllithium

yields

(diethyl

and ether

142 TABLE

I

Fluorination

of Bromonaphthoic

acids -4

(trifluoromethyl)naphthalenes

Acid

Product

4a --

3a

4b --

Reaction

3b

Yield

Temp.

c

gx

No identifiable

solution)

in

7o"c

66 % a

mp; 61-3'C

7o"c

62 %

mp;

37-8.5'C

5o"c

38 %

bp;

lO6-7“C/5

mm

70°c

48 % a

addition

of

b

product.

ether

Methyl

were

The

reaction

except

2 although

&

the

Higher

reaction solution

in the ratio

2

causes

:

==9:1

:

1)

(1 h at -7O'C)

a longer

was decreased

temperature

increase

this

-3 were converted to the (trifluoroby-products,

the

similar

required

reactivity

g-hexane

the protonated

were

which

because

In

chloro(trifluoromethyl)naphthalenes

(1 :

not separable

for

slow

2 at the same temperature.

2 and

times

96-8'C/4

of a.

at -7O'C and subsequent

precursors

methyljnaphthalenes

bp;

ester

way, bromo(trifluoromethyl)naphthalenes

lo,

mm

66 % 77 %

dichlorodifluoroethylene

acetylene

(bp)

7o"c

80°Cb a

mp

9o”c

130°c

-4c

Bromo-

to

3

or

use

the decrease

of the halogen

time

in

(2 h

(Scheme

II).

each

case

at

-7O'C)

by

steric

hindrance.

of

"-butyllithium

of the selectivity exchanged

(trifluoromethyl)naphthalenes

2.

products

in

due to B

and

1*3

1) Mg/THF

z

*g+

2) C12C=CF2

Q \

(2) 53-PC

3 ti

s

CF3

3 1) n-BuLi (ether)

I

2) C12C=CF2 (2) / -70'~

FC=CC12

dcF+

QJ$ 3 z-BuLi (n-hexane)

z

+ 4

Qjj lo

cF3

CF3

-7OOC I

Scheme

TABLE

II.

II

Conversion

of Bromo(trifluoromethyl)naphthalenes

to Ethynyl(trifluoromethyl)naphthalenes

Bromide

Acetylene

-la

Yield

48 %

2

1

'H-NMR(CCl4)

3.49

(s, IH), 7.4-8.6

(m, 6H)

J.!?

47 %

3.70

(s, IH), 7.4-8.5

(m, 6H)

Ic

60 %

3.34

(s, IH), 7.1-8.6

(m, 6H)

X!

69 %

3.36

(s, IH), 7.2-8.5

(m, 6H)

144 Conversion was

performed

ether

amounts

at -70°C,

parative

HPLC

47-69

(Si02,

give

mono-

cular-weight

or

disubstituted

polyacetylenes

photochemically

activated

polymerization

of

Polymerization

of the

achieved

comparison,

Yields were

more

given

weights

the

observed

to give

benzene

lenes

with

which

have

in Ccl4

monomer

at

3o"c.

IJ,

which

under

conditions,

of

reduced

the

yields

are summarized.

and

monomers con-

gave no polymer

under

The decrease

Such

For

catalyst

by the steric

of the

hindrance

polymerof the two

polymerizability

was

2,6-bis(trifluoromethyl)phenylon the steric

that prevents [8].

their

effects

of

cyclotrimerization

However,

of the monomers

of

in Table

the polymer III.

a trifluoromethyl

naphthylacetylene.

for

there

which

seems

to be a

polymerize

with

catalysts.

weight

similar

that

effective

of the naphthylacetylene

derivatives

as shown

for

high-mole-

we reported was

polymers

has reported

of bulkiness metal

into

was also polymerized

conditions.

Masuda

Molecular monomer

al.

III, the reaction

for monomer

acetylenes

the transition

et

catalysts

in CC1

of the formed

in the case

[91.

limitation

Masuda

metal

Recently,

90 % at appropriate

reaction

monomer

polymers,

[la].

of -lb was affected o- position substituents.

acetylene

not

1 was

izability

also

do

(trifluoromethyl)naphthylacetylenes

of polymerization

except

1

II).

4 (trifluoromethyljphenylacetylenes

In Table

than

centrations the

[81.

a-naphthylacetylene

and molecular

2 (Table

acetylenes

W(CO)6

in

by pre-

acetylenes

with the same catalyst

same conditions.

separated

1.

transition

efficient

solution)

of the acetylenes

of substituted

higher-molecular-weight

reported

converting

also

Yields

bromides

of the Acetylenes

polymerizations

being

1

mixtures

products

(E-hexane

mixtures

E-hexane).

acetylenes

1 to

of the resulting

% from the corresponding

Although

have

olefins

of n-butyllithium

the reaction

(III) Polymerization

always

precursor

by treatment

2-molar

with

were

of these

or higher Similar

is a

Especially, group

tend

molecular results

function

of

the

the naphthylacetyto

weight were

afford than the observed

polymers parent in

the

145

TABLE

III

Polymerization

of Ethynylnaphthalenes

1.

W(CO)6-CC+hv

[Ml Monomer

l-ethynylnaphthalene

x 10

Mw 3

x 10

96

12.1

la

0.33

60

100

32.6

-lb

0.30

60

0

Ic

1.09

60

77

20.2

46.3

0.49

60

97

11.7

30.2

0.065

60

44

9.9

35.1

0.49

6

12

66.9

181

0.55

60

93

42.5

147

parent

of

that

monomer

concentration. ization

parent

concentration

Similar

results

of the fluorinated polynaphthylacetylene

291-344'C

introduction experimental.

of

108

-

-

weight and with

[la].

were

was

it in-

polymerThermal

all comparable

not

the

catalyst

in the

(decomposition

group

with

decreasing

were obtained

polymers

of &,

increased

in air or in N2) and the apparent trifluoromethyl

and

In the polymerization

of o-(trifluoromethyl)phenylacetylene

stabilities

=

[la,81.

the molecular

3

39.4

(trifluoromethyl)phenylacetylene

phenylacetylene

observed

creasing

the

Mn

(%I

60

polymerization

Td

Yield

mmolll

0.67

Id

was

w(co)6

mol/l

to

temperature; effect found;

of see

146

As

described

above,

some novel

naphthalenes

were

prepared

thoic

and

polymerized

acids

ethynyl(trifluoromethyl)-

from the

molecular-weight

polymers

2-trifluoromethyl

derivative

with

corresponding W(CO)6

except

bromonaph-

catalyst

to

for the sterically

high-

hindered

j&.

EXPERIMENTAL

Melting

points

Riken's

micro

were

point

IR spectra

corrected.

1

spectrophotometer. Hitachi ment

R-22

nal

MHz,

were

obtained 19

tube

on

apparatus

on a JASCO

F-NMR

spectra

IR-810

were

at 90 MHz and a Hitachi and chemical

respectively,

Mitamura

a

un-

and were

infrared

recorded

on a

instru-

R-20B shifts

were

re-

interper million (6) relative to Me4Si as an 1 H and to CF3COOH as an external standard for for

in parts

standard

"F .

Mass

and GC-MS

spectra

Shimazu

GC-MS

7000

17).

"-Butyllithium

Okuhara's

procedure

conducted

under

ether. Toyo

measurement

H- and

instrument

at 56.45

ported

in a sealed

taken

melting

weights GPC

was used

temperatures

Seiko

thermal

was

with

on

silicone

by were

uses of sodium-dried were

estimated

the molecular

measurement

a OV-

prepared

and the calibration

(Td) of polymers

gravity

with

of n-butyllithium

of polymers

(THF),

to calculate

composition TG-20

solution)

atmosphere,

performed

were

packed

All reactions

nitrogen

HLC-802A

polystyrene

(ether

[21.

The molecular Soda

analyses

2 m column

(column;

were

with a

curve

analysed

apparatus

for De-

weights. with

a

in air and in

N2. 4-Bromo-I-naphthoic

acid

(4a).

1-Bromo-4-methylnaphthalene dispersed the 18

mixture atm).

water

and

chloric Free

in aq.

was heated cooled

The then

acid.

acid

Na2Cr207*2H20

4a

in an autoclave mixture

the mixture

The

(2)

formed

at 25O'C

was acidified

precipitates

(lit. 217-22O'C

0.23 mol)

was

150 ml),

and

(2.7 M,

was dissolved

was recrystallized

43 %): mp 220-4OC

(50.0 g,

solution

were

for 20 h (max.

with with

1000 cont.

filtered

from acetic [3a], 212'C

acid [3bl).

ml

of

hydro-

and dried. (24.8

g,

147 I-Bromo-2-naphthoic

Reaction 0.23

mol)

described

acid

of

with above

1-bromo-2-methylnaphthalene

aq.

Na2Cr20,*2H20

gave

acid &

5-Bromo-l-naphthoic

acid

cording

to Hausmann's

5-Bromo-2-naphthoic

not give

(lit.

under

and was poured

the mixture mixture

with

of esters.

afforded (lit.

in cont.

reduced

H2S04

(500

mixture

to -ca. 100 extraction of

After

gave a solid

recrystallizations

MS, m/z

mol) acids

The cooled

of the solvent

-1

0.29

brominated

to concentrate

5-bromo-2-naphthoate

3H);

(s,

ac-

(25 ml) and methanol

(1000 ml).

IR (KBr) 1725 cm

3.92

(50.0 g, of

for 5 h.

evaporation

Successive

t61);

(a)

pressure

into water

pure methyl 73'C

acid

The mixture

was refluxed

ether,

out

[S].

of 2-naphthoic

and the mixture

(6a) was carried -

(4d).

pure acid $J.

was evaporated

acid

procedure

(51.9 g) was dissolved

6H),

g,

150 ml) as

(4~).

acid

Bromination

ml,

(50.0

(2.7 M,

(17.9 g, 31 %): mp 182-186°C

of 1-naphthoic

Bromination

ml),

(2)

solution

[41).

186OC

did

(4b).

1

;

from methanol

(25.5 g); NMR

(%) 266

(Ccl41

(M++2,

mp 73-4'C 8.5-7.2

(m,

99), 264

(M+,

to

NaOH

100). 5-bromo-2-naphthoate

Methyl solution The

(2.5 M,

resulting

yielding pure

250 ml), clear

a precipitate

General

acid a):

procedure

To a mixture and

anhydrous

which

of Hastelloy

400

mm011

was

acid

filtered

cooling

under

with

with

reduced

HCl,

33

%

to give from

2-

161).

acids.

acid

(40 ml)

for 3 h.

cont.

of bromonaphthoic

of a bromonaphthoic

C under

refluxing

(fi) (24.0 g,

fluoride

aq.

off and dried

(lit. 27O'C

for fluorination

added

under

was acidified

was

mp 250-5'C

hydrogen

made

and stirred

solution

5-bromo-2-naphthoic

naphthoic

was dissolved

(4) (ca. in a 100 ml

liquid pressure.

N2,

100

SF4 The

mmol)

autoclave (43.2 g, reaction

148

was heated

vessel

The cooled

was poured

combined

The

ether.

at 70°C for 20 h (max.

mixture

dried

KOH solution, pressure

to give

pressure

(a,

extracts

with

and evaporated was distilled

or recrystallized

from ethanol

18.5 195

3080,

840,

987,

1573,

765 cm J=2.2

(d,

(M+-Br,

-1

Hz);

92),

with water

which

175

;

1340,

1512,

'H-NMR

(cc14)

MS m/z

(%) 276

(39), 126

under

1305,

(3b, &I.

1268,

(M++2,

66 %; IR

1142,

99), 274

(29): Analysis:

965,

1600,

820,

(CC14)

17.2

(M+-Br,

1465,

758,

745 cm

(s);

MS m/z

-1

;

'H-NMR

(%) 276

(CC14)

(M++2,

2.15 %: C11H6BrF3

requires

C, 48.03;

C, 47.86;

(KBr) 3070,

1573,

690 cm J=2.0

(d,

(M+-Br, 47.93;

-1

;

Hz);

96),

1503,

(CC14)

MS m/z

(%) 276

175

7.2-8.4 (M++2,

3070, 892,

1075,

NMR

(CC14)

195

(M+-Br,

15.0

1602,

of

Griqnard

Reagent

mmol)

1314, (CC14)

175

(%) 276 (M++2,

prepared

a stirred

1140,

C, 48.03;

from

mixture THF

1115,

(CC14)

18.7

(M+, IOO), Found:

195 C,

H, 2.20 %.

1265,

49 %; IR

1200,

7.3-8.3

951, 274

(36), 126 (30): Analysis: requires

H,

64 %; IR

(3d): nc, yield

1355,

and anhydrous and THF

95),

1155,

(ml; "F(M+, 1001,

Found:

C, 47.81;

H, 2.20 %.

1,1-dichloro-2,2-difluoroethvlene

Reaction

To

1155,

274

'H-NMR

H, 2.20 %: 'II H6BrF3

mmol)

1202,

1504,

MS m/z

195

C, 47.76;

(m); "F-NMR

840, 795 cm-'; (s);

96),

Found:

C, 48.03;

I-Bromo-6-(trifluoromethyl)naphthalene (neat film)

(m); "F-NMR

(39), 145 (25), 97 (26): Analysis: requires

1100,

(M+, loo),

(3~): nc, yield 1232,

1310,

'H-NMR

H, 2.29 %: CllH6BrF3

1130,

7.4-8.4

98), 274

67 %; IR

1130,

H, 2.20 %.

I-Bromo-5-(trifluoromethyl)naphthalene

800,

1155,

1120, (CC14)

(M+, lOO),

Found:

1248,

(31), 126 (27): Analysis:

175

97),

1786,

1337,

aq.

reduced

(m); "F-NMR

8.2-7.3

with

reduced

under

H, 2.01 %: CllH6BrF3 requires C, 48.03; H, 2.20 %. I-Bromo-2-(trifluoromethyl)naphthalene (3b): nc, yield (KBr) 3060,

atm).

and

(3a): nc, yield

I-Bromo-4-(trifluoromethyl)naphthalene (neat film)

16

and extracted

were washed

Na2S04,

a residue,

x)

pressure;

into ice-water

(2)

and

the

g,

165

3a.

of magnesium

(IO ml),

(300 ml) was added

turnings

a mixture dropwise

of &

(4.00

(39.37 g, 143

in 1 h under

gentle

149 The mixture

reflux. 2

h

and

was

completely

stirred

mixture

with

cont.

The

combined

solution

several

for an additional

the

portions

bromide

&

was

1 ,I -dichloro-2,2-

of

680 mmol) were added to the -ca. was refluxed at 53-5'C for 10 h. The

was poured

hydrochloric

and dried

into ice-water

acid

extract

chromatography

reflux

After

(2) (60 ml,

and the mixture

solution,

under

red-brown.

consumed,

difluoroethylene

cooled

was

then

was washed

with water

with Na2S04.

on a silica

(400

Removal

gel column

acidified

ml),

(40 ml), and extracted

with

and

sat.

of the

ether. NaHC03

solvent

(n-hexane)

gave

and

I-(2',2'-

dichloro-l'-fluorovinyl)-4-(trifluoromethyl)naphthalene (6.78

g,

15

(7.25 g, 26 %), and other 2:

nc,

1522,

bp 102-6'C

1318,

(CC14)

(M++2,

17), 308

(loo),

204

C13H6C12F4

(28):

765 cm

252

(40),

requires

-1

(s,

;

3F),

C, 67.70;

2920,

8.5-7.3

n-butyllithium at

-7O'C

-7O'C

mixture 36 mmol)

in diethyl

in 30 min,

for additional

-7OOC

added

H,

1578,

1506,

(m); "F-NMR

C, 67.70;

1.80

%:

1330,

1262,

(CC14)

20.2

321 (60), 320

H, 3.10 %: C22H12F6

(I) from Bromo(trifluoro-

bromo(trifluoromethyl)naphtha-

in anhydrous

diethyl

(I M, 40 ml,

and the resulting After

1 h.

at -7O'C

for 1 h further

of a

ether

dichloro-2,2_difluoroethylene carefully

310

(3).

a stirred

(2) (IO g,

(m);

(%)

(M+, 65), 238

50.53;

390 (M+, IOO),

24), Found:

Ethynyl(trifluoromethyl)naphthalenes

To

1594,

H, 3.10 %.

methyl)naphthalenes

lene

MS m/z

23), 273

C,

1655, 8.4-7.6

H, 1.96 %.

(CC14)

(M++l,

3070,

(CC14)

IF);

(M++2-Cl,

IR (KBr) 3060,

(%) 391

(s,

(a)

fractions.

; 'H-NMR

Found:

C, 50.52;

(48): Analysis:

-1

-6.7

Analysis:

'H-NMR

minor

IR (neat film)

762 cm

(M+, 27), 275

requires

MS m/z

(s);

(3 mmHg);

19.6

8: nc, mp 152-4'C; 1118,

unseparable

968, 942, 778,

"F-NMR

(7a)

bis-1,1-[4-(trifluoromethyl)naphthyll

%),

(2) (10 ml,

in 15 min.

(100 ml), was added

mixture

completion

(2 h for 3&),

ether

40 mmol) was

stirred

of lithiation,

-ca. The mixture

at l,l-

110 mmol) was stirred

and then allowed

to warm

was at to

150 room

temperature,

poured

rochloric

acid

(2 ml),

extracts

were

washed

dried

with

into water,

and extracted with

water

Removal

Na2S04.

(l10°C/0.2

mixture

(2',2'-dichloro-I'

naphthalene

(z),

with

mmHg)

oil

anhydrous

ether

solution, the

mixture.

mixture

was poured

hydrochloric combined

extracts

and again the

acid

with

solvent

(Waters

a

mixture

of

(100 ml),

preparative 5OOA;

221

(M++l,

Analysis: 70.91;

220

13), Found:

H, 3.20

3 Na SO Evaporation of 2 4' HPLC on a SiO2 packed column

Prep

PAK-SOO/SILICA)

658 cm

17),

220

Found:

C,

elution (1)

and

and

chloro-

-1

;

"F-NMR loo),

70.79;

H,

1582,

(Ccl,) 219

nc, 1518,

19.0

(30), 201

3.32 %:

colorless 1328,

1312,

(s); MS m/z

(%)

(26), 170 (42):

C13H6F3

requires

C,

%.

IR (KBr) 3305, 825,

on

(2)

(la):

2100,

I-Ethynyl-2-(trifluoromethyl)naphthalene -1

The

solution,

with

3070,

(M+,

C,

cont.

(10).

32951,

764 cm

to

blue

ether.

sat. NaHCO

(trifluonomethyl)naphthalene

844,

with

with

ethynyl(trifluoromethyl)naphthalene

(neat film)

1124,

1264,

the dark

acidified

with water,

I-Ethynyl-4-(trifluoromethyl)naphthalene IR

pale

a

in lh at -7O'C

for 2 h,

and extracted

and dried

(trifluoromethyljnaphthalene

oil;

9:1:1

(2) (m/z 196) and

dropwise

at -7O'C

into water

water,

give

a

(m/z 230) as

(lo,

added

to pH = 3,

LC/System

with g-hexane

was

stirring

were washed

and

Prep

gave

(ca 10 g) was dissolved in _. and c-butyllithium (1.60 M n-hexane

64 mmol)

After

and

Kugel-rohr

and

The mixture

(100 ml),

40 ml,

solution

of the residue

(trifluoromethyl)naphthalene

(ca. 10 g).

hyd-

The combined

ether.

solvent

cont.

-fluorovinyl)(trifluoromethyl)-

chloro(trifluoromethyl)naphthalene yellow

with

NaHC03

and sat.

of the

distillation of

acidified

3070, ;

(M+,

2115,

"F-NMR

70.87;

(CC14) 219

loo), H,

1598,

17.1

(33),

3.08 %:

(lb):

1472,

201

1345,

nc, 1298,

(s); MS m/z

mp 36-8'C; 1175,

(%I 221

1130, (M++l,

(31), 170 (35): Analysis:

C13H6F3

requires

C,

70.91;

H,

3.20 %. I-Ethynyl-5-(trifluoromethyl)naphthalene

(1~):

nc,

colorless

oil;

IR (neat film) 3200, 3060, 2100, 1584, 1512, 1312, 1122, -1 792 cm ; "F-NMR (CC14) 19.5 (s); MS m/z (%) 221 (M++l, 13), 220

(M+,

C, 70.88;

IOO),

219

(31), 201

H, 3.23 %: C,3H6F3

(13), 170

requires

(42): Analysis:

C, 70.91;

Found:

H, 3.20 %.

151

I-Ethynyl-6-(trifluoromethyl)naphthalene oil;

IR -1

798

cm

220

(M+,

(neat film) ;

"F-NMR loo),

3300,

(CC14) 219

3055, 16.7

H, 3.17 %: C13H6F3

C, 70.94;

Polymerization

of W(COj6

acetylene

was conducted was

were

requires

by addition

1582,' 1500,

(25 ml) was

irradiated

solution.

304'C 662 cm

(N2); -1 .

(100 ml).

to constant

319OC (air), -1 774 cm .

1578,

1508,

IR (KBr)

(N2);

700 cm

-1

1580,

3000,

3OO'C

a

then

The precipi-

343OC

(N2);

Td 29l'C 1325,

1305,

IR

(air), 842,

1105,

(air), 786,

1112,

.

Poly[l-ethynyl-6-(trifluoromethyl)naphthalene]:

894,

and

Td 306'C

1508,

with

weight.

Poly[l-ethynyl-5-(trifluoromethyl)naphthalenel: 344OC

Found:

The polymerization

Td

3000,

15),

Polymerization

Poly[l-ethynyl-4-(trifluoromethyl)naphthalenej_: IR (KBr)

(M++l,

H, 3.20 %.

C, 70.91;

of methanol

1392,

1122,

1308,

(1).

to this

off and dried

Poly(l-ethynylnaphthalene): (KBr) 3020,

colorless

lamp at 30°C for 30 min,

_l_was added

filtered

1470,

(%) 221

in the dark at 30°C for 24 h.

terminated

tates

nc,

(27), 170 (25): Analysis:

in Ccl4

100-W high-pressure-mercury

1596,

MS m/z

of ethynylnaphthalenes

A solution

monomer

2100,

(s):

(30), 201

(Id):

(N2);

IR (KBr) 3020,

826, 796,

755, 738 cm

-1

1626,

1588,

Td 321°C

1464,

1302,

1106,

(air), 1070,

.

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