p-Toluenesulfonyl esters of perfluorinated tertiary alcohols: crystal structure determination of the absolute configuration of C6F5(CF3)2COSO2C6H4CH3

ELSEVIER

p-Toluenesulfonyl esters of perfluorinated tertiary alcohols: crystal structure determination of the absolute configuration of

C,Fs( CF, >,?COSO&,H&H, Burkhard

Krumm, Ashwani Vij, Robert L. Kirchmeier, Jean’ne M. Shreeve I~qJ(i/‘rlr?crrr (I/(‘lrr/irr.\rr-~, l!,lilY~l \,I, Cl/I(irilr,l. M,l\l~flli~. II)x.Ix4I-_‘.Cl.~, 1!SA Recei\txl 0 .lu~le I Wh. xxp~ed

*

24 Ocroher 1997

Abstract Selected

pertluorinated

tertiary

C,,Fi(CF,),COS()IC,,H,CH, The absolute contiguration

alcohols

can

be reacted

with

/,-toluell~~ul~onyl

chloride

to form

their

/,-toluene~ulf~~nyl

e,terh

(3).

( 1). CF,C,,F,OC,,F,( C;FT J (C,F,, )C’OSO,C,,H,CH, (2) and (CF,C,F,OC,,F, )?( C,F,i)COSO,C,,H,CH, 0 1098 Elxevier Science S.A. All right5 reserved. of 1 is established hy X-ray dit’ftxtic~n.

k’r\~~w~-~/.\: Pcrlluorinnlell tertiwy alcohols: /~-Toluene~ull~~n~l cskm. ,I- I’~~luene~ul tonyt chlol-ide

1. Introduction Perfluorinatcd

tertiary

class of compounds.

alcohols

represent

The increased

acidity

gen enables

them

compounds.

The fact that they normally

to he important

cous

oils

solid

state. II-Toluenesulfonyl

prepared The

or noncrystalline

solids

ester

these

highly

vents.

The

miscibility

solids,

alcohols

alcohols

in organic

show

solvent5

crystalline

enhanced

of vix-

in the

are easily materials. solubility

in common

organic

decreasing

solubility

a\ a function

of CFI group”

studies

of alcohol\

form

provide

usually

to a variety

exist as liquids,

precludes

esters

also

fluorinated

tent. i.e., the number

2.

precursors

1 I 1, and usually

derivatives

an interesting

of the OH hydro-

of Huorinc

01 sol01 toll-

C7F1s

( highly

Unfortunately.

ester 2

do not form

any crystalline

viscous

oil)

and 3 (powder)

materials.

present.

Results and discussion The isolation The derivatization

hols

of selected

perfluorinated

I2,3] to form their I,-toluenesulfonyl

by heating

the alcohols

in the presence

an excess of p-toluenesulfonyl

tertiary

alco-

esters is achicvcd of triethylamine

and

us to carry compare

secondary

and tertiary

fluorinated

by X-ray

p-CH7C6H~S0~CIMEt~ * CHzClz OTCHCIq (reflus)

RFOSO~

CH!

made

to determine

ment

of Flack’s

coordinates. 0. I

( 2 ) which

figuration.

inversion,

suggests

alcohols

1 allowed

analysis

PM?,.

configuration.

required

inversion

Flack’s

the correctness

and

esters

of

] which were

14,s

Because

space group

its absolute

for

structural

p-toluenesulfonyl

diffraction.

parameter

Upon

crystals

X-ray

to other

the non-centrosymmetric R,.OH

quality

crystal

its structure

characterized

chloride.

of diffraction

out its single

I crystallizes an attempt Initial

in was

refine-

of the atomic

parameter

retined

of the absolute

to con-

1.43 l(7) A is similar to the bond lengths found in A3 and A4 but shorter than in Al and A2. and in (?-norbornenyl-) ( CIF,)COSO,C,H,H, ( 5 1. The S I-OIA bond length of 1.613( 5) A in 1 is longer than the bond lengths obser\,ed in to the prcsencc A3 and A4 ( - I .61 A). Thi\ can be attributed of a more electron

electron

dcticient

withdrawing

groups

l’ortnation where

with

respect

largest

and the smallest this difference

bending IA)

l.h33(5)

O( I B )-St

I )--(I(

I(’ J

IB,

1.113(5)

O( IB)-St

I )kOt

IA)

S( I )-(I(

I(‘1

1.119(5)

Of ICI-St

I I-0(

IA1

relieved

SC I )&CC I J

1.71ito)

O( IA)-SI

I1M.t

I)

lOY.Y(7)”

01 IAk(‘(X)

I .43 I t 7 I

ot I B I-SI

I ,k(‘(

I i

c‘( I )Klh)

I ..ihh( x 1

O( I(‘,kSl

I lk(‘(

I)

C(I)-(‘I71

1.5oxt

C(XIkOI

C‘(S)-C‘thl

1.373(Y)

C(Zl-(‘I

I )bS( 1)

l.ciflS(

IO)

C(h)-Cl

I )-St

l.53Y(

I I)

C(6)M.l

I l-C(2)

IO)

(‘~X)~(‘(ll)

1.53Y(X)

ot IAk(‘(X)-C‘rYl

1.?07(‘))

O( IA-(‘iX)-(‘t

IO) II 1

IOB)

1.311(‘J)

O( IAI-(‘tX)bC‘t

(‘I 16)-F(

IhI

l.M>((l)

C~Io)-CIx)--C(Y)

from

107.5(6)“

for

There

-

I /2+

:),

the

two in

C 1 I,

group.

CF;

sotne

group4

are

1 is increased

to

the c-axis

is shown

in

of the pentafluorophenyl

1 along

groups

in

lattice.

fluorine/oxygen

to

the

Inter-

i.c.. H7C,‘.FY”=

and HS...01B1’==2.SSY

leading

in interaC8. thereby

Conseyucntly,

angle

are two hydrogen

seen in the crystal I, :)

a reduction

in A4.

diagram

the ~rh plane.

in the Ph-O-

pentafluorophcnyl

between

I 1.5” and

A4 by a pen-

in

crowded

group.

is the

By com-

13.5”. A3

group

from

CF,-CX-CF,

is a stacking

(tr=.r.~,-

C(Y)-E(YB) CI IO)-I‘(

the

Fig. 3. There

actions

I)

ofthc

interactions and

The packing

I I

C(X)-C‘(Y) CfX)K(

repulsive

CX is 13.0”.

the sterically

the p-toluencsulfonyl

S( I j-01

IAJ-SI

around

angle

between

1 c;lu\es ;I decrease

in

the &o-carbon

Si I)-()(

atom. CX. deviates

compt-esscd

around

angle. This results

repulsions

towards

most

of the phenyl

group

SOJ?,H,CH, tomic

Al and A2, the S-

is in A I 9.6”. A2

13.-l”. Substitution

tafluorophcnyl

con-

In the C;IW

and the difference

angle

three

eclipsed

at _ I .S8 A.

carbon

The

( 102.5(5)“).

parison,

bearing

bond\.

as in

shorter

the tertiary

geometry.

OIA-C&Cl0

I21

is staggered

around

tetrahedral

carbon

and S-C

is comparatively

The geometry from

A4

to S-O

the conformation

0 bond length

tertiary

and to a partially

formation

of

2.535

A

I -.t-, 1 -J\‘.

r\ (/I=

a chiral

crystal

structure.

C( I I)-cl8,kC(Y) cc I I )&CC x ,-C(

IO 1

C( 16)bc‘I

I I )kCl

XI

(‘I Ih)&C(

II)b(‘(

12)

Tables ters.

F(YB)~CtY)-l-(94) F( lb,-Cc

Ihl-C‘(

listing

bond

equivalent

I I I

cients,

sulfonyl the

1 shows

the molecular

structure

isotropic

and

hydrogen

and the pentafluorophenyl

expected

anti

group as

position.

available

of 1. The II-toluene-

is

the

are not present case

for

Furthermore,

a mean plane

least square analysis

from

the fluorine

effects

between

position

and

the

atomic

anisotropic

displacetnent

and isotropic

and calculated

the authors

parame-

coordinates, coeffi-

displacement

structure

factors.

are

upon request.

in

revcats

3.

Experimental

that

( 5.3~3 )“). Table 1 lists selected bond lengths and bond angles for 1. All C-F distances are in the range of I .307( Y )-I .346( 6) A. The CCF, bond distances, i.e.. CX-CY and C8-C IO are 1.565( IO) and 1.539 ( 1 1 ) A. are similar to those found in A4 ( I.559 ( Y) and I .536( 9) A). The CX-C I 1 bond length of 1.5.19( 8) A in 1 is longer than the non-fluorinated phenyl analoguc A4 ( 1.S 10( 8) A) probably resulting because of steric crowding in

and processing

angles,

atom coordinates

observed from

bond

C,Hi-

(CF,)(R)COSO,C,H,CHj 141 (R=H (Al). CH, (A2), CN ( A3) and CF, (A4) ) where an anti-conformation exists. the aryl groups

data collection and

coefficients, Fig.

full

distances

1 are almost coplanar

atoms on the phenyl the aromatic CF,

groups.

fluorine The

group

and/or

atoms C-O

repulsive

in the r~tlro-

bond

length

of

Infrared

spectra

are recorded

IR spectrometer

between

as nujol

‘H and

Bruker

mulls. AC200

Chemical

shifts

tisches fonyl

analyses

Laboratorium. chloride

17 IO FTor solids

spectra

instrument

are reported

mass spectrometer

on a Perkin-Elmer plates as neat liquids

‘“F NMR

FT-NMR

CFCI {. Mass spectra Elemental

KBr

with

are obtained using

using CDCI, respect

with

electron

Giittingen.

by

or

VG 7070 HS

(El)

techniques.

Beller

Germany. from

on a

as solvent.

to (CH,),Si

a Varian

impact

are performed

is recrystallized

are obtained

MikroanalyI’-Toluenesul-

petroleum

ether.

and

21

triethylamine R,.OH

is distilled

are prepared

prior to use. The tertiary

according

to literature

methods

alcohols

chloroform

[ 7.3 1.

monitored volatile

is heated under reflux by “‘F NMR

materials.

extracted

several

the

32.1. R,. = C’,>F,(CF,),C (I) A mixture

consisting

of 2.4 mmol

3.7 mmol p-toluenesulfonyl lamine

in 30 ml dichloromethane

days. The reaction of all volatile extracted

several

leum

ether

remove

Spectral

1532s.

are IR

-

1495s.

1386s.

1276~

131.3 (2-F,

-

is then

-

(CF,.

C,F,(

to

ppm; MS (El)

CF, )2COSOIlSY7m.

1185s.

113%.

(3-H,

Iwz/r (species)

(C,F,(CF,),C+)

4. 298

54Sm. S36m, 5 IXm.

d, 2H).

(C,F’

) 3. IS5 (C,F,’ Yl

) 95,

l3Y

(CH,C,H,+)

(C,F,+)

2.

(HSO,‘)

23. Anal.

69

A mixture toluenesulfonyl

consisting chloride

of02

-

mmol R,OH

122.1

(CF,.

F, br, 2F),

139.3

-

-

1.54.6 (2’-F. Hz).

(EI)

H-C&)

100.963

’) + ) I. 262

7. 8 I4 IS5

data

are

H.

lh4Sm.

1600~.

br. 2F).

6 7.84

(2-H.

61 Xw. S63m.

t. 6F, ‘.I,. ~,.= 22.3

13 1. I .S mmol II-

hr. -IF),

-

Anal.

834m.

8 l6w,

‘: “‘F NMR

hr.

772~. 6 56.3

I 147s. 7 I7tn.

(4’~CF,,

I, 3F. ‘J,: ,. = 9.5 Hz),

-- 126.4

(.3-F.

for

H. 0.66.

1656~.

1226s

l16.7(CFJ,br.2F),

l3Y.3

~78, Calcd.

(CF,C,F,OC,,F,):-

1335s.

br. 2F). -

(.%I+-

(M +-ZF-C,F,)

(Nujol/KBr)

- 8 I. I ( CF,,

(CF,.

br,3F).

for

‘./,,_ ppm;

5, II33

24. 982

IR

1488s.

5SOm cm

Hz).

I II.O(CFI.hr.~F). 123.0

follows

X77m.

d. 2H. 5, 3H)

Found: C. 30.7Y:

(3).

Y72m.

m. ?F),

(MI-H)

’ ) 92.

H. 0.61. as

12X.7 (2.

(3-F.

(4-CH,, II51

br. 3F),

-

( CF,C,F,OC,F.,CO

(CH,C,H,

15 15s.

(2).

134.0 (2-F.

154.5

I I. 945

3) 2 I, 309

C. 39.35:

-

HL). t, 3F. ‘.I,.

(CF2.

hr. 2F),

2.45

intensity1

C. 33.35;

-

133.0 -

’ -HF-C,F,)

(M

(C7Fli)COSOIChH1CH?

in 5 ml

SS7m. S30m

10X.0( CFI.

IO19 (M+-HF-0-CO-CF,)

65

-

-

m, 2F).

d. 2H).

’ ) YS. 91

YY9m.

-

ICFI,

‘H NMR

(3-H.

( M ’ -F-C,F,

Spectral

127.2

(3’-F.

[III/P (species)

(C,F,

1077w,

br, 2F). -

br, 2F);

7.36

6.

and I .O mmol triethylamine

6 l3w,

-121.S(CF2.br.2F).-I21.8(CF,.

br, 2F),

,,=X.3

1397s.

1. 3F. ‘J,. ,.-2X

( CFI. hr, 3F),

~ 126.4 (CF:,

668m.

R,. = CE‘IC;,F,OC,F,(C.,~‘,)(C,~F,,)C (CF,C,F,OC,I;,I,(C-E‘,~~C (31

(4’.CF,.

-

-l17.8(CFI,br,2F). hr. 2F).

2962~.

IOOOm. Y77m.

,.=X.9

(4-C%,.

H. 1.60.

3.2.2.

7 I8m. 7OSm. 667m.

105.9

C iF,)--

3076~.

t, 3F, “.I,. k = I I .4 HI ). - 8 I. I (CF,.

Hz).

(70-230

) ; 67% (3)

16OOm. 1516s. 1488s. 1432m.

6 56.3

70.

)

gel

- 80.8 (CF,,

+ ) 2. I I7

(CF,’

Calcd. for C,,H,F,,O$:

1.45. Found: C, 39.05:

‘“F NMR

‘:

is repeat-

for CF.,C,F,OC,F,(

( liquid/KBr)

166lm.

C,,H,F,,O,S:

(CH,C,H,SO 100.

1641s.

silica

viscous oil

1223s hr. I 145s hr. 107J111, IOSOm.

(M--F)

(C,F,(CF,),(“)7,217(C,F:+)6.19S(C’,F,CO’)Y.Ih7

on

1345s.

MS

3X8 (M

(C,F,(CF,),C

IR

and

using dichlorome-

793Sm.

(2.

C, 7.82

2.47

intensity]

(2).

Hz.

‘J,. ,.=21.6

‘H NMR

as eluent

data are as follows

vacuum

165%~.

tt, IF.

m, 2F):

7.38

Spectral

COSO,C,H,CH,

is

of all

in ether

The crude product

chromatography

). Yields are 65% C2) (colorless ( m.p. 3436°C. colorless powder j

Cl11

t. 6F. ‘.l, _, = 17.8 H/).

147.2 (4-F,

H. d. 2H. ‘al,,_,, = 8.2 Hz).

mixtures

removal

The ether layer is then

mesh

9OSw, X77m. 826m,

gives colorlc\\

1236s br, I l98s,

159.7 (3-F.

thanc/hexane

After

is dissolved

water.

Na,SO.,.

by column

from petro-

997s, 963s. 826s. 7XSm, 757s. 737m.

671.3

m. 2F).

Hz).

for

3104~.

SY8m, S77m. 554m.

‘: “‘FNMR

“.II._,.=6.3

14, 317

high

chloride

as follows

104Ys, 1025m.

cm

s. 3H)

removal

in ether and

The ether layer

for 24 h under

(Nujol/KBr)

724s, 67Sm. 637~. 356m

After

Recrystallization

I?-toluenesulfonyl

data (I).

109Sm.

triethy-

( 1 ) ( 77%. m.p. 95-‘37°C)

crystals of

C,H,CH,

water.

Na,SO,.

and pumping

residual

by ‘“F NMR.

the residue is dissolved

times with

dried over anhydrous

and 7.5 mmol

with

edly purified

is heated under reflux for 3

is monitored

materials,

[ 7 I.

C,FS( CF>) ,COH

chloride

residue

times

dried over anhydrous

for 3 days. The reaction

until complete.

m,4F).

-

122.O(CF,,

(CFz, -

br. 2F). 154.0

(2’-

F, hr. 4F).

-

154.6 (3-F, m. 4F): ‘H NMR

‘JI, ,, = 8.3 Hz),

‘H. ppm:

MS

1 I66

( M + -3F-C,H,CH,

55,

(El)

7.34 (3-H.

I 114

[ rntz/c,(species)

(M

>) 8 I. 907

HF-CF,-C,F,,)

CO’

1395 (M’

100.

I55

(C,F,

39.

‘)

SO, 91 C. 37.46;

409

based

-F)

7.

reflections.

3)

omega

I 105 ( M +-2F( M r-

C. 37.5 I

the

The X-ray ;I Siemens

54.73”)

diffraction 3-circle

equipped

with

1 are collected

data for

diffractometer a

CCD

detector

are determined

from

collecting

60 ten-second

frames

is fixed

maintained

reflection

data obtained

at ;t detector

resolution

tile

contains

it is used for is solved

SHELXTL

Version

at

the absolute

structure

crystallires

in

hy

parameter

refined

of

determination structure Fourier peraturc

5.03

space

of the absolute

density

Lpldecay.

correction.

using

The

SHELXS-90

[9 ]

method

using

P~tr2,.

resulting

of

are located

maps and refined

The

Flack’s

in an accurate

configuration

atoms

and

2. Determinalion

out since thi, compound

group

( 2) thereby

at

directional

1IO 1. The finnl data collection

the polar

electron

for

about

least-squares

is also carried

01‘ 1. Hydrogen

decay is

collected

data using SAINT

corrected

arc listed in Table

to 0. I

set of SO

Data reduction

absorption

methods

by the full-matrix

parameters

collection.

information

empirical

by direct

SO frameh

on

for a total

[ 7 ] The crystal

file

arc

is scanned

frames

the frames

the raw

structure

refinement

01‘ data

data from

by processing to give

values

sets plus ;t tinal

and at the end ofdata

cosines.

at

( 61. The initial cell

- S4.3( 2 )“C. using the w-scan technique constants

at 299( 2) K

(X-axis

reflection

raw

and relined

hemisphere

software

from

unit-cell

of all of the observed

a run time of ten-second in three

[ 81 software Since

final

collected

is accomplished

:

the

refinement

the SMART

the beginning

H. 0.54.

on

with

using

monitored

) 18. Anal. Found:

However,

A complete

(0.3”)

frames

98, 823

(CH&H,’

pixels.

on the least square

of 1271 frames

(CF,C,F,OC,F,-

H. 0.54.

5 I3 X.512

s, 3H)

) 16. 856

74. 855 (M+-H-HF-CF;-C;F,,)

for C,,H,F,,O$:

(3-H% d.

( M t -OSO&H,CH

’ -2F-C7F,S

,-OSO,C,H,CH,)

) 34.

Calcd.

(M

6 7.70

7.35 (4CH,.

intensity]

) 13, I I33

’ -F-OSO,C,H,CH,)

OSO&H,CH ( M ’ -C,F,

d, ZH),

of the crystal from

with

difference

isotropic

tem-

factors.

Conlpound I

Acknowledgements We are grateful research.

We thank

to British Dr.

Nuclear

Gary

Knerr

Fuels for support for obtaining

of this

the mas5

spectral data. The single crystal CCD X-ray facility at the University of Idaho was established with the assistance of the NSF-Idaho EPSCoR program under NSF OSR-9350539 and the M.J. Murdock Charitable Trust. Vancouver. WA.

References III 121 131 I-11 151 Ihl I71 1x1 191

1101