15N and 31P NMR spectroscopy of triclorophosphazopolyfluoroaryls.

Joumaloft;luon’neChemistry, 17 (1981)103-111 0 Elsevier Sequoia S.A., Iausanne - Printed in theNetherlands

103

Received: March3, 1980

15N

AND

31P

NMR

SPEC.TROSCOPY

OF

TRICLOROPHOSPHAZO-

POLYFLUOROARYUS.

A. I. REZVIJKHIN

Institute

and

of Organic

G. G. FURIN

Chemistry,

Novosibirsk,

(U. S. S. R. )

630090

SUMMARY 15

31

“I arid the

P N MR

obtained

by

benzene

( Kirsanov

spectra

interaction

of trichlorophosphazopolyfluoroaryls

between

reaction

polyfluoroanilines

) have

slons of monomeric and dimeric 31 P NMR are also shown. by

been

forms

and

investigated.

PC15

The

in

interconver-

of trichlorophosphazopolyfluoroaryls

INTRODUCTION

The

lnvestlgation

compounds very

exf

mainly

with the

ensively ,

by

of the help

and

studying

of thelr

to depend

melting their

or the

total

of dlmer nuclei

and

can

the

the

solution

and forms.

shifts

various

thoroughly

as

for

forms at

the

a

the

and

to the

heavy

polar

present

of

spectral

represent

time.

spectrostructural an

Therefore

important

problem.

group.

The

leads

either

to

equilibrium mixture 15 N and 31P on the

lnvestlgation structures

developed

can’t the

aryl

solvents

values

correlation

out

made

of an

of the

of trichlorophosphazoaryls

carried

been

1

formation

the

far

1 . The ability of I: monomer form has been

insufficiently

nuclei,

in phosphazonot been

so

of the

establishment

Owing

establishment data

In non-

or to the

has

it have

effects

electronic

bonds

spectroscopy 1,2 . NMR c I convenient method for the

for

the

P

behavior

in dimer

of dimers

monomer

serve

monomer

chemical

on

about

chemical exist

depolymerizatlon

transformations and

to

of N-

methods

conclusions

trichlorophosphazoaryls shown

nature

of physical

theory

of chemical be

shifts

of for

predicted

accumulation from

Of such of dimer

N MR

and 15

N and

31P

104 RESULTS

AND

In this and

31 P

reveal

paper

spectra

the

we

nitrogen

and

dimer

undertaken

series

forms

N MR

an

the

chemical

spectra

and

shifts

the

of the

showing

the of

influence !7I

substitution of varying

of the

to

phosphorus

of the

monomer

Study

of the

4-

of trlchlorophosphazoaryls.

constant

15N

of NM R

stability

of trichlorophosphazopolyfluoroaryls

because

substituted

1s of particular

situation

close

substituents

as

to the

a

interest,

group

relationship

P =N, to the

- conjugation.

Trichlorophosphazopolyfluoroaryls reaction

investigation

of trichlorophosphazopolyfluoroaryls

determining

in the

derivatives

have

in a

factors

and

effects

DISCUSSION

of the

corresponding

were

polyfluorinated

synthetized anllines

by

the

Kirsanov

with PC15

in

benzene. PC1

PC15 ArFNH2

ArFN

___?r

= PC13

Ar

+

C6H6 Ia-

ArF

r

IIa-

= 4-N(C2H5)2C6F4 4-

CH30C6F4

4-

CH3C6F4

4-H-

(II,11 1 ),

4-

(Ih,IIh,IIIh),

C6F4

(Iq,IIq

4-

C6F4 ),

F

),

solutions Therefore

to

exist

in nonthe

ln the polar

establishment

phosphazocompounds 31 P spectra of the from

anilInes

individual

solvents

( Ia-

was

carried

f ),

are

observed

( Table

and

monomer

( IIa-

IIf ),

4-

CH3S02-C6F4

5-

CF3-C6F3

),

out for

)

been

shown

earlier

as

dlmer

(IIIg ),

whereas

structures

of the

each

which

e ) forms.

electroncan

be

donor

form

in our in

( IIg ) p-

4.

synthethized

compound.

In the

to the

NMR

obtained

substltuents,

attributed

),

),

has

to monomer

(Ig,IIg,IlIg

CN-C6F4

(Ip,IIp

(Ir,IIr

state

C6F5 4-

(In,IIn

of trich!orophosphazocompounds

containing 1 ),

(Id,IId,IIId),

(Ik,IIk

2

It revert;

of the

solutions

),

(Ib,IIb,IIIb),

C6F4

(I f,

CF3C6F4

2- N02-

Trlchlorophosphazopentaduorophenyl laboratory

C

N-

CI-C6F4

(Im,IIm

(10,110

e

4-N(CH3)2C6F4

4-

(Ie,IIe,IIIe),

NArF

3

IIIa-

(Ia,IIa,IIIa),

4- NO2-

‘? ‘PC<

r

(Ic,IIc,IIIc),

C6F4

2 - NO2-

N/ F

two

dlmer

signals

(III a-

e )

105 TABLE 1. 31 P and l5 N N MR benzene

at

data

of trichlorophosphazopolyfluoroaryls

30°.

;hemicaI Compounds

85

IIa

33.6

II b

33.5

II c

32.4

IId

33.5

II e IIf

1

p-pm % H3PO4*

; 15N

from

*1

.J

15N_ 31p*Hz

CH3N02

251.4

22.5

32.9

245.5

21.4

29.G

244.9

20.1

II g

30.3

252.0

20.1

II h

3016

II k

22.8

245.5

16.3

II 1

19.9

244.4

16.4

II m

18.6

245.5

16.3

[6]

II n

17.6

II 0

22.0

244.3

12.6

II P

21.5

248.6

11.3

II 4

16.5

242.2

17.6

II r

22.2

243.6

15.1

III a

71.0

III b

68.7

III c

71.8

III d

70.1

III e

73.0

+ Chemical

shifts

Chemical

**

fact

that

( Table

2 ),

factors.

At

the

shift, from

Y31P

The

in

strong

the

relation

proves the

containing

strong group,

dimer-

that this

same

electron-

(II k- n ) are

P ln high field from 85 % H3P04 are positive 15 N in high field from CH3N02 are positive.

shifts

the

amino

31

time

the

donor electron-

only

obtained

is

proportion

substituents. acceptor

monomer under

monomer

relation

the

depends

on

the

controlled

by

thermodynamic

of dimer

form

In the substltuents

forms action

case

temperature.

increases

for

of polyfluoroanilines

in the

para

position

of trichlorophosphazopolyfluoroaryls of PC15

on

;

the

former.

to

106

TABLE The

2.

influence

for

of the

temperature

on the

trichlorophosphazopolyfluoroaryls

60

30

79

21

84

16

82

18

95

5

30 60

[l ( II

aromatic

only

of

II p

2- nitro-

atom

is

) would

trifluoroaniline

( II p ) really

an

be

by

their

important

parameter

has

monomeric

form.

been

shown

( II q ) and

(II r ) in the

of PC1 5 with

the forms

to fadlitate

Therefors

the

formation

monomeric 4- amino-

form

known

to

of PC15

the

in the

2- nitro-

The

form

spectral

substituent relative

blpreferable

compounds

of trichlorodata.

at the

stability

The

reaction

5- trifluoro-

in benzene.

and

of the

determining

are

action

to occur

monomeric

properties

character

factor

PC15

to the

chemical

acceptor

the

of phosphazocompounds

expected

(I p ) with

correspond

group

under

( I o ) and

trichlorophosphazocompounds

reaction

ortho - nitro

forms

tetrafluoroaniline

electron

various

an

monomer

respectively

phosphazoaryls The

of the

3,4,5,6-

3,4,6-

( II o ) and

containing

trichlorophosphazoaryls

formation

O,

methyl-

amines

monomeric

I-The and

dimer

78

60

The

%

30

I

II b

form

mixture,

60

I

II e

equilibrium

monomer

OC

II a

monomer

Reaction

Temperature,

Compound

dimer-

in benzene.

nitrogen

of the

increase formation

of that of the

of trichlorophosphazocompounds could

2,3,5,6-

be

predicted

in the

tetrafluoropyridine

( I q ) and

5 - aminononafluoroindane ( I r ). That prediction was proved experimentally, 31 P and l5 N N MR data for trichlorophosphazoaryls have been shown

in the

depends the must

on

increase be

of

paid

and

dimeric

with

respect

shift

In

the

Table the

1.

The

change

distribution electron-

to the forms

of the donating

presence

in the electron power

chemical

shifts

density

in the

of the

of phosphorus

substituent.

signals

of trichlorophosphazopolyfluoroaryls

to their spectrum

hydrocarbon of a

solution

analoques

k

for

both

The

31P

of trichlorophosphazophenyl

with

Attention of monomeric

at lower ].

phosphorus

molecule

field

chemical in

107 tetrachloroethane 80.2

ppm

form

of the

known 73.0

-

for

dimeric

the

the

atom

P =N

nature

phosphorus

4-

of the

the

by

30.3

ppm

, while

it is

equal

the

greater

for

atom

greater

9

the

additive

on

the

double

bond

phenyl

effects

of former

substituents

conceptions

about

of the

and

the

in which of the

at the

character

screening

character

-

substituent

of the

direction

to

68. 7-

to the

displaced to upper field. 31 P NMR data for monomeric

of the

the

stronger

bond

trichlorophosphazotetrafluorophenyls

substituent

to

$-

constant

double

same

a

the

theoretical

L-1

in the

be

exhibit

while of a

with the

shift

to

one

for

electron

relative

electronegativity

to a

increase must

known

case

of

lead

chemical

is

the

In agreement

must

substituents

phenyl

decreasing must

consideration

substituted

caused

ring

than

the

atom

The

is

of polyfluoroaryl

atom

bond. 31 of P

phosphorus the

This

8 . Therefore

nitrogen

of the

).

Cl

negligible

is

of trichlorophosphazoaryls

1

character

phosphorus at

forms,

pentafluorophenyi

acceptor

are

monomeric form equal to 47.6 pp m and 31 one. The P c:?omical shift of the monomeric

( II g ) in benzene

properties

The

the

dimeric

( Table

withdrawal group.

for

compound

ppm

@-

is

signal

forms the

P =N

of

influence

bond

is

ST- conjugation effects shows that electron31 shift the P signal to the lower field relative

withdrawing

substituents

to

donating

ones.

substituent

the

Thus P-N

substituent of

the

decreased

fragment in the

Kirsanov

properties.

10

3 Our

data

in the

percentage

The

to a

benzene

ring

leads

P=N

and

bond

than ionic

the

for

dimerization

conclusion,

form

lower and

of the

the

ionic

c bond

can

allows

is

be

bond

field

dimerization

11

shift

the

The is

such

fact

more

us

by

with the

to

respect

that

the

confirm for

the

to

trichlorophosphazotetracoordina-

preferable

the

P =N

in the

character between 33. of P signal.The

with

of

necessary

caused

donating

promote

substituent

character

phosphorus one

P-N

electron-

substituent

of double

disadvantageous.

latter

aryl

withdrawing

degree

of trichlorodonating

2 ).

to the lower

pentavalent

The

more

with

donating

conclusions

elecrton-

the

( Table

more

and

of the

strong

of trichlorophosphazoaryls

electron-

pentacoordinated

form.

to the

of the

with

due

conjugation

electron-

according

that

case

becomes the

character

monomeric

In that

compounds

polyfluoroaryls state

to a

of

’ It leads

of conjugation strong

nitrogen

has

unsubstituted

ted

support

aryl

presence

facilitating

substltuents

molecules

Increasing due

phosphorus

to the

of dimerlc

fragment

of the

with the

ring.

1

c containing

substituents

degree

observed

benzene

et.al.

phosphazoaryls

greater

is

electron-

of

energetically

that

a

existence

greater

highly of

electronegati-

108

vity

of the

action

aryl

of the

substituent

strong

strong

as

the

CF3-group

shift

are

present (II o-

Hammett

instance ring

electron-

correlation

and

for

withdrawing

compounds

satisfactory

chemical

whole,

containing

1 ). The

A

a

electron-

phosphazocompounds

( Table

as

just

be

constants

result

as

the

All

monomeric

to

of the trichloro-

substltuents

of course,

noticed

of

a

substituents.

withdrawing

r ) are

must

as

also exist

substituents

as

form

monomers. between

in the

the

31P

compounds

(Ia-n).

s

=

31P

r =

The

G

11.1 =

0.967,

s

2.12,

signals

of phosphorus

trichlorophosphazoaryls spin-

spin

of the

increase

of

the

series

the

compounds The

is

( Table

1

c Therefore

12

1 the

are

sensitive

to

observed

signal

not

1

substituent

determlned.

They

decreased

[131 * constants.

cyclic

Thus,

can forms

and

6.9

Hz

of that

form

The

with the respectively

coupling

for

respectively. of trichlorophospha-

for

[14,15]

which

the

ortho to

the

.

the

1 ). At spin-

absolute

electron-

found

to be

to have -

16.3 presence

and Hz

same

coupling

values

substltuted The

fragment

less

time

the

between

constants

of these

have

coupling ( Table

substituents

in accordance upon

are

interaction

withdrawing

respectively. of P=N

the

data,

of substituents

influence

para-

our

spin

of the

electronegativity

is

seem

to the signs

strong

also

12.6

indicate

the

( Table

due The

to the

ones

from

influence

doublet

for

one

bis(pentafluorophenyl)fluorophosphazo-

Nevertheless,

factors

changes

constant

observed

Hz

dimeric

to the atoms.

equal to 65.6 and 80.0 pp m respectively. 31 P may indicated the assignment of the of

atoms.

sensitive

to weak Sterlc

tant

a

phosphorus

are

respect

shifts

gives

constants are

of the

4.4

due

to monomeric or dimeric forms. 15 N nuclei, as follows from shifts of

ring

and

been

signal

is

values

and

of

fluorine

( 6. 2, 6.5,

). The 5.6

forms

to triplets ortho-

constants

NO2

11 [ to be

chemical

chemical

nitrogen

split and

substituent

( II r ) are

atom

known

phosphazocompounds The

be

monomeric

observed in the upper field with respect to the monomeric 31 ). The P shifts of the dimeric forms of pentafluorophenyl-

difluorophosphazomethyl methyl

to

coupling of

( II g ) and

in the

phosphorus

CH3SO2<

phosphorus

zoaryls

atom

corresponding

CF3(

12

found

between

electronegativity

for

2.0

n -

are

coupling

increase

+

para

the

with

the

values

derivatives value being

1 ). with

data

of these the

cons-

of that higher

for

the

109 EXPERIMENTAL 19

at

F NM R spectra

56.4

were

MHz

recorded

on a

respectively. into

a

The

as

a

HX-

into

90

a

3 s.

The

the

The

sweep

For

l5 N nuclei

pulse

width

laboratory and

was

the

2OJs

the

from

compounds 95-

compounds

96

used

anilines

by

with

% ) [16].

has

been

was

for

30

of polyfluorinated

physical

constants in Table

and

The

17 r.s

next

), the

used

for

the

of work

were

used

for

), the

delay

tlme-

equal

Hz

: sweep

delay

put

of latter

regime

was

6000

MHz

were

signal

optimal

cases

9.12

in benzene

accumulation

by

degree

equal

to 8

was

width

time-8

s.

used

6024

k. ).

Hz,

The

Fourier-

transformation

N NMR

spectra

15N

to 95-

96

analytical

data

of

% by

PC15 of all

15NH3

( enrichment

enrichment

been

with

were

of polyfluorinated

solution of

have

anillnes

15

of

lnteractlon

% aqueous

The

Trlchlorophosphazocompounds reaction

listed

36.4

parameters

recording

obtained

found

and

spectra

D20.

pulse-

the

3Ops

spectrometer

N MR

spectra.

compounds

aromatic 15N

of

data

were

12

-

A

15N

at

with

following ( 90°

60156

solutions

mm one

( In some

pulse-

B-NC

optimization

synthethlzed

Hz

parameters ( 90°-

computer

Labeled

s

for

3000

A and

stabilization.The The

of memory

31P

spectrometer

10

of deuterium

width

);

or their

of the spectrometer was used. 31 P spectra : pulse width 12r value

on Varian

C6F6

compounds

placed

signal

recorded

internal

Bruker

pure

5 mm tube

served

were

( p p m from

mass-

prepared

obtalned

spectral by

in benzene new

of

method.

known

[ 5 1. The

compounds

have

been

3.

REFERENCES

1

G, I. Derkach A,

1965 ,p. 2

, I.N.

S. Shtepanek,

Yu.P.Egorov,

Yu.

G.

I.F.

G.G.

T. D. Petrova, Izv.

V.I.

Shevchenko,

, Naukova

Akad.

Exp.

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V. E. Platonov,

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Yu.Ya.

Tslmbal, Theor.

Shermolovich

G.G.Furln, 4

Kirsanov,

Dumka

,

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177.

V.G.Yurchenko, 3

, A.V.

Zhmurova

Phosphazocompounds

S.S.S.R.,

Borovikov,

Khlm.,

Polumbrik, Zh.Org. T.I. Ser.

15

I.N.

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13

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L. M. Meshdkine.,

( 1978

) 2635.

‘Saenko,,

TABLE

3.

(IIr)

C9CI3F9NP

relative intensity

(IIq)

C5C13FqN2P

The

(11~)

C7CI3F6N202P

+

(110)

(IIm)

(111)

(IIe)

C6C13F4N202P

C7C13FqN2P

C7H3C13F4NP

of

signal

104-106

35-86

114-115

has

(6)

(3)

(3)

(3)

(3)

150-152 150-152

(3)

118-120

(7)

(3)

(3) 121

152-154

120-

92-93

(IId )

(11~)

C llH10C13F4N2P

C7H3CI3F4NOP

9::- 93, (3 )

(IIb)

C8H6C13F4N2P

and

11.0

.:4

19.80 24.94

-74.1,-14.3 - 57.5(2),-

95 0 ti

noted

in brackets.

- 30.7(l),- 21.5(l)

- 36.1(l),- 33.6(2),

56.5(2),

_40.7,-

95

21.09

20.71

-19.7,-16.2,-13.~

94

21.6,-13.f

20.62

- 14.5,-14.2

- 3.2

25.70

- 27.Q,-15.6

90

26.58

- 17.4,-11.3

F

%

05

39.31

25.00

28.64

2L.80

21.74

23.

24.00

19.62

212.34

22.90

Found,

25.30

27

C

97

l-

90

I PPm*

34.20

- ll.O,-3.0

-

19F

anaI,rtic~l properties.

-11.0

80

88

75

field

been

(pressure)

physical

B.p.

trichlorophosphazocompounds-

Compound

New

7.00

10.1

7.70

8.02

8.53

9.4(

9.53

7.83

9.02

9.l"i

P

25.09

19.90

21.24

20.34

25.81

26.71

34.42

25.42

i7.95

39.72

25.21

28.82

22.00

23.35

24.16

19.82

23.r)O

22.13

F

Calcd. %

7.20

10.28

7.84

8.97

9.52

9.85

8.08

9.38

9.02

P

111 5

Yu. G.

Shermolovich,

G.G.Furin, ( 1980 K.

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Ulvary,

H. A. 8

R. Filler,

J.R.

11

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J.H.

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Nauk

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Chemistry

York,

1977,

( 1974

Rev.,

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vol. 8 ,

p.l.

in M. Grayson

Chemistry,

vol.

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E. J. Griffith

Interscience

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Klrsanov, T.

99

aIIg.

Fluorine

Letcher,

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Zh.

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Stankiewicz,

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30 -

( 1960

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