Synthesis of phosphirenium salts

Tetrahedron Letters,Vol.24,No.6,pp Printed in Great Britain

SYNTHESIS

K.S. Fongers,

Abstract:

OF PHOSPHIRENIDM

H. Hogevce?

Nijenborgh

16, 9747 AG Groningen,

presence

of aluminum

selenirenium

characterized.

Although

metal carbonyl X-ray analysis. synthesis

?(

complexes

of phosphirenium

however,

in the

three-membered

are selenirene

derivatives4

prompts

of which

salts, obtained

been shown to be capable

type intermediates

have now been the postu-

unambiguously

et. a1.6 prepared (M=W, R=Rl=C,HS)

by formal addition

ring

l1 and thiirene

have appeared,

by spec-

phosphirene

was proven by

us to report our preliminary

results

on the

of "Rp Cl" to alkynes.

of addition

to alkenes8,

a reaction

have been suggested.

H3cyc;;F~ ““y:“,:,, R’vR’ I +

AH3

of a 1 molar

solution

of 2-butyne

643

Rpl,0i

5

5

I

3

2

After addition

have been

dichlorides

ion 4', all of which

Mathey

C6H6 1

described,

have not been demonstrated

2, the structure

This observation

\s/

examples

ion 3' and thiirenium

Very recently,

phosphiranium

success;

reports on phosphirene

The "R? Cl" ion has already in which

type not previously

the search for unsaturated

for these compounds

evidence5.

The Netherlands

of alkynes with phosphonous

has met with remarkable

2' as well as

The University

trichloride.

During the past several years

troscopic

Chemistry,

salts, a compound

by the reaction

lated structures

and R.F. Kingma

of Organic

prepared

0040-4039/83,'060643-04$03.00/O 01983 Pergamon Press Ltd.

SALTS

Department

Phosphirenium

heterocycles

643-646,1983

(1 equiv.)

in methylene

chloride

644

to a 1 molar methylene termined

solution

chloride

of methylphw_phonous

at -3O'C a colorless

from the 'H-NMR spectrum,

dichloride/aluminum solution

is obtained,

a new compound,

which

13

frommethylene

chloride yields

a white

solid hygroscopic

ambiguously

of phosphirenium

demonstrates

15.1 Hz) absorption

product

salt -6a (see below). The

the presence

of the AlC14@

at 102.9 ppm (lit.l':102.4

27

(1:l) in

contains,

as de-

two sharp doublets

of this product

C- and 31 P-NMR data (Tables 1 and 2) for the addition

with our assignment

which

exhibits

(3 = 22.9 and 18.0 Hz) in the ratio 2:l. Crystallization perature

trichloride

at low tem-

material'.

The 'H-,

are fully in accord Al-NMR

ion by a narrow

spectrum

un-

(5.2 Hz; lit."

ppm). R'

R' +

R'PCI, l Al'&

R'-E-R'

.,c,p

V

-

R’ 6a -6b

ride is possible; demonstrated

variation

by NMR spectroscopy.

CH,

CHa

CHa

H

CHa

H

H

60

CsHs

CH,

CHs

sr

C,Hs

CH,

H

70

H

H

50

C6HS

the formation

of -6a (isolated y'ield after crystallization for the phosphirenium

structure

the 31 P-NMR spectra observed

to the almost quantitative

92.4%).

1 and 2. First the large values of the coupling

Hz) and cyclopropenium

-12 ions

shifts

also in other small ring phosphorus

constants

data lJ

=CH

to those found in cyclopropenes12

(around 260 Hz). Second,

in 6a-f show upfield

byproduct

is based on the spectroscopic

(232 to 241 Hz) in --6b, 6c, 6e and 6f are comparable (213-255

dichlo-

salts 6 has been

In the case of -6c and -6f considerable

formation

in Tables

and the phosphonous

of phosphirenium

as compared

(%)

70

90

lowers the yield of these products

summarized

>90

CH,

formation

The evidence

yield”

CH,

with regard to the alkyne

in all instances

R3

-6c -6d -6f Some structural

R2

the absorptions

(-57.3 to -69.2 ppm), which

compounds

13

(e.g. phosphiranes

in

have been around

645

-200 ppm). Third the values of the chemical and -6f

shifts of phenyl-Cl

(aver. 115 PPm, 114 HZ) are in agreement

(C6H5)3?R (118 ppm, 90 Hz), compare

Carbons

between

and

phosphorus

salts

2 14

, e.g.

(137.1 ppm, 12.4 Hz). Last, but not

constants

and the protons

have the same order of magnitude

in E,

1

with those in phosphonium

to (C6H5)3P

least, the values found for the coupling

1 JPC

and

between

directly

as those predicted

phosphorus

attached

and the ring

to the ring carbons 15: 1J

by calculations

PC,calcd=

4.1 and -1.0, 'Jpc exp = 6.6 to 15.3; *J PH,calcd = 2.6 and 3.3, *Jp,,, exp - = 10.4 to 12.2. 3 * Table

I

:

aP-

Salt

and ‘H- NMR

dataa

of

=C-CHJ

6 ,I,”

phosphirenium

salts

+J,,,

&&

P-CH)

t?J,,,l

%!

-57.3

2 60

td. 22.9)

2.92

td.18.0)

$&d

- 62.2

2.70

Ld.23

2.90

td.18.1)

SC

- 68.L

3.26

ld.18.3)

6d

- 58 0

2.69

&C

- 57.9

2.95

ti

- 69.2

a. Spectra b.“P

-

c. nP-1H

shifts

coupled

in CH&

spectra

couplings:

c. Long-

coupling

Table

2

:

‘k-NMR

of

:

data

solutions

relative &

of

phosphirenium

t57.6:1~03 18.9

; 134)

(61.1 ;140)

5,, :

7.6-8.2

lbr)

9.00

7.4

tbr)

9.28 td.ll.5)

Cl (lJpc’

bl(’

:l6.6:

at

have Table

spectra.

co (

?QJC”,

CP

cnl [ ?I,,; ‘JC”’

!Icl4 1 ( LJpc:

-

142.8

; 141)

been 1

the ‘H-NMR

-30%.

0.00 ppm.

-_)

(13.2:

241)

113.0

shifts a)

(below

Hg04at

154.1

(12.5;232)

116.6

l89;-

1

131.0

152.6

(15.3

note

from

andf 80%

:- )

133.7

; 13L)

chemical

be expected

to

wab

f109.l)

measured

: 238) relative

114.6

1

111.2

b.See

to

for 3.E

and converted

(d.10.4)

- 1.3 Hz

tlL.5:23L):l8.5:-

a %

82

tcmperature.ercept at 19.90ppm’6

-

3 tbrJ

VS.8 (7.4

11.2 (1.6

td.12.2)

-

c-c (

18.9 (64.1

td.10.5)

9.51

-

splittings

salts

19.3

: 135)

8.89

1.4 Hz.

bCH)

‘!lpc:

the

-

7.6-8

at wm

‘JHccc,,

tzJP,,

-

to tNPCl21

show

:

z 0.9 Hz

P-CH,

: ‘Jc,, 1

13.L Il.7

CO&l,

S.&and

LJHccc,-.::

11.2 (2.1

or

?&PcH

=C-CH, ‘!$,c

td. 22.9)

have been measured

d. Long-range range

Id. 23 1)

-

are recorded

chemical

2)

=CH

CE.H~

132 7

(111 I

t11.5:170)

111.8

133.2

(118.7) to

129.8

132.6 (16.5 ;168)

CH2C12

at

135.8

; 168)

(5.3:1681

129.8

136.2

Ll&5:169)

(5.3

130.6

(17.2 ;172) 53.4 ppm

t 20.4

and

(21.5 converted

:160) 137.2

; 1681 to tCH,tSi

(5.5;173) at O.Mppm

646

Investigations

concerning

of the phosphirenium

This investigation

Research

the Advancement

7

and the chemistry

by the Netherlands

aid from the Netherlands

Foundation

Organization

for

(ZWO).

and Notes:

1.

J. Laureni,

2.

G.H. Schmid,

3.

a)

G. Capozzi,

b)

M. Torres,

a)

E.W. Koos, J.P. VanderKooi,

4.

of "RPCl"

was supported

(SON) with financial

for Pure Research

References

@

structure

salts are in progress.

Acknowledgements: for Chemical

the detailed

A. Krantz, R.A. Hajutu, D.G. Garrett,

0. De Lucchi, A. Clement,

J.Am.Chem.Soc.,

-98, 7872 (1976). Lett., 3991 (1975).

Tetrahedron

V. Lucchini,

G. Modena,

Tetrahedron

J.E. Bertie, J.Org.Chem.,s, E.E. Green,

Lett., 2603 (1975).

2490 (1982).

J.K. Stille, J.C.S. Chem.Comm.,1085

(1972,). b)

A.M. Torgomy,

M.Zh. Ovakimyan,

C.A. 92, 6622a c)

N.M. Kansal,

M.G.

Indzhikyan,

Arm.Khim.Zh.,

2,

288 (1979);

(1980).

S. Verma,

R.S. Mishra,

M.M. Bokadia,

Indian J.Chem.,

-19B, 610

(1980);C.A. -94, 15817mand 15818n (1981). 5.

The experimental between

data given in the publications

phosphirenes

and vinyl-phosphorus

Ref. 4a were proven to be incorrect.

of Ref.4 do not allow distinction

type structures.

The results

See: H. Quast, M. Heuschmann,

given in

J.C.S.

Chem.

conull.,390 (1979). 6.

A. Marinetti,

7.

C.Symmes

F. Mathey,

8.

A. Rudy, Y. Kashman,

9.

M.P. 108-109°C;

J.Am.Chem.Soc.,

Jr., L.D. Quin, J.Org.Chem., Tetrahedron

Microelemental

Al 8.87 %, Cl 58.24 %; found

104,

4484 (1982).

43, 1250 (1978).

Lett.,-2209 analysis:

(1978).

calcd. for C5HgA1C15P

870, 915 (br), 1065, 1135, 1370, 2915 cm-l. UV(CH2C12):Amax 10. R.G. Kidd, D.R. Truax, J.Am.Chem.Soc.,

-90, 6867 (1968).

11. Appoximate

by examining

yields

have been determined

12. See J.B. Stothers, 13.

"Carbon-13

C 19.73 %, H 2.98 %,

C 19.81 %, H 3.11 %, Al 8.88 %, Cl 57.78 %. IR(CH2C12):

NMR Spectroscopy",

W.J. Richter, Angew.Chem.Int.Ed.

the

< 230 nm.

1 31 P-NMR spectra. H- and

Academic

Press,

1972, pp.336,344.

(Engl.), -21, 292 (1982).

14. a) Ref. 12, p. 380. b) T.A. Albright, 15. T.A. Albright,

W.J. Freeman,

Org.Magn.Res.,

16. V. Mark, C. Dungan, Vol. 5, Interscience

E.E. Schweizer,

J.Am.Chem.Soc.,

_104, 2872 (1982).

8, 489 (1976).

M. Crutchfield, Publishers,

J. van Wazer

p. 392.

(Received in UK 29 November 1982)

in "Topics

in Phosphorus

Chemistry",