Inorganic Fluorine Chemistry - American Chemical Society

Chapter 8 6

Functionalization of Pentafluoro-λ -sulfanyl (SF ) Olefins a n d Acetylenes Downloaded by UNIV OF CALIFORNIA SANTA BARBARA on September 10, 2015 | http://pubs.acs.org Publication Date: April 29, 1994 | doi: 10.1021/bk-1994-0555.ch008

5

Rolf Winter and Gary L. Gard Portland State University, Portland, OR 97207-0751 In this review, the synthesis of SF -olefins and acetylenes and their conversion to compounds with new functional groups are described. It will be seen that there are only few reactions that allow the introduction of an SF -group, and that there are also only few reactions which lead to derivatives of unsaturated compounds. The chemical transformations of these simple unsaturated compounds into a number of useful and exciting products will be described. 5

5

The outstanding chemical stability of sulfur hexafluoride is to some degree carried over to its organic derivatives. Various methods are at hand to effect such a derivatization, e.g., treatment of disulfides, mercaptans or sulfides with fluorine (7), electrochemical fluorination (2), oxidation of aromatic disulfides with silver(II)fluoride (5). SF X (X = Cl,Br,SF ) adds across multiple bonds and forms adducts. Furthermore, tetrafluorosulfur ylides (F S=CR R ) add HF to form SF -compounds; however, as most of these ylides are formed from SF compounds, this method is only of limited value (4). The simple organic derivatives can undergo further reactions; in particular, the primary addition products of SF X and alkenes or alkynes can be dehydrohalogenated to yield alkenes or alkynes. Over 70 different compounds that contain both the SF -substituent and a double or triple bond were synthesized in the last thirty years and are listed in Table I. The high thermal, radiative and chemical stability of the pentafluorothio group make these compounds attractive as replacements for compounds that contain a trifluoromethyl group. The electronegativity value of the SF -group appears to be very high; by examining the C n.m.r. chemical shifts of a number of fluorosultones, a Pauling electronegativity of 3.62 is found (5). It is, however, comparatively more difficult to introduce this group into a molecule than a CF 5

5

4

1

2

5

5

5

5

5

13

3

Note: A common name for the SF group is pentafluorothio and will be used throughout the text. 5

0097-6156/94/0555-0128$08.00/0 © 1994 American Chemical Society In Inorganic Fluorine Chemistry; Thrasher, J., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1994.

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8.

6

Pentafluoro-\ -sulfanyl Olefins and Acetylenes

WINTER AND GARD

129

Table I. SF Alkenes Derivatives 5

Compound (Two-Carbon Alkenes)

IR(C=C) (CM* ) 1

BD

CO

Reference

...

41

(27)

SF CH=CHF

...

...

(29)

3.

SF CH=CHC1

1615

65-67

(20)

4.

SF C(C1)=CH

1616

64

(40)

5.

SF CH=CF

1748

28.1

(32,72)

6.

cis/trans SF CF=CHF

...

...

(17)

7.

SF CH=CFC1

8.

SF CF=CF

1.

SF CH=CH

2.

5

2

5

5

5

5

2

2

5

(48)

5

5

2

(27,31,72)

1786

19

(40)

9.

SF C(C1)=CF

2

1721

...

10.

SF CH=CHBr

1611

86±2

(20b)

11.

SF C(Br)=CH

...

86

(20)

12.

£/Z-SF CH=CFP(0)(OH)

1649

66(mp)

(61)

13.

cis/trans SF C(Br)=CHCl

50/52mm

(20)

14.

£-SF CF=CFP(0)(OH)

5

5

5

2

5

2

5

101(mp)

(61)

55 ±1/48mm

(20b)

1672

48

(43)

SF C(Br)=CH(SF )

1610

...

(22)

(SF ) C=CF

1706

88

(33,34)

5

2

...

15.

cis/trans SF C(Br)=CH(Br) 1573

16.

SF CF=CFI

17. 18.

5

5

5

5

5

2

2

Continued on next page

In Inorganic Fluorine Chemistry; Thrasher, J., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1994.

130

I N O R G A N I C F L U O R I N E C H E M I S T R Y : T O W A R D T H E 21ST C E N T U R Y


Table I. Continued

Compound

IR(C=C)

(Three-Carbon Alkenes) 1.

SF5CH2CH=CH2

2.

1

(CM" )

Reference

BD(°C)

80-82

(27)

cis/trans SF CH=CHCH 1663

80-82

(27)

3.

rô-SF CH=CHOCH

1672

50/20mm

(20)

4.

ira>w-SF CH=CHOCH

1639

115

(20)

5.

SF CH=C(C1)CH

1653

92

(27)

1640

59/158mbar

(42)

1643

109±2

(23)

—

5

3

5

3

5

3

5

3

6.

SF CH C(C1)=CH

7.

SF CH=C(CH )Br

8.

SF C(CF )=CF

9.

SF CF C(C1)=CF

10.

£/Z-SF CH=C(CF )Br

5

2

5

2

3

5

3

5

2

5

2

2.

SF CH=C(CH ) 5

3

(32,49) (41)

1630/1637

93 ± 1

(22,23)

IR (C=C) 2

SF CH CHFCH=CH 5

47 ...

3

Compound (Four-Carbons) 1.

1722 ...

2

2

2

Bp(°C)

Reference

1668

102-106

(33)

...

...

a

...

...

(27) (20)

3.

SF CH CH(C1)CH=CH

4.

SF CH=CHCH=CHC1

...

—

5.

SF C(CH )=C(Cl)OCH

...

40-45/20mbar (24)

6.

SF CH=C(Br)OCH

1620 sh. at 15901

—

(26b)

7.

SF CF=CFCH CH I

...

...

(29)

8.

(SF CF=CF )

—

...

(52)

a

See M. Tremblay (8) reference in the cited literature.

5

2

5

5

3

5

5

2

5

2

2

2

3

2


8. WINTER AND GARD

6



Table I. Continued

Compound (Five or More Carbons)

IR (C=C)

Bp(°C)

1.

SF C(CH )=C(Cl)OC H

—

45/20mbar

(24)

2.

£/Z-SF CH=CFP(0)(OEt)

1655/1630

—

(61)

3.

SF CF=CFP(0)(OEt)

1666

3870.04mm

(60)

4.

[SF CF=CFPMe ] BF -

1660

159°(mp)

(43)

5.

£/Z-SF CH=CFP(0)(OSiMe )

1660/1640

—

(61)

6.

SF (CF ) CH OC(0)CH=CH

—

...

a

7.

SF CF=CFP(0)(OSiMe )

1665

7270.1mm

(60)

a

See J.C. Hansen and P.M. Savu (7) reference in the cited literature.

5

3

2

5

5

5

5

+

3

2

2

4

5

5

2

3

4

2

5

3

2

2

2

Reference

SF Cyclic, Heterocyclic, Aromatic Derivatives g

Compound (Mono SF )

IR(C=C) (cm' ) 1

5

F,S

Reference

Bp(°C)

72.0/48mm ( X = H ) (3,20) a

O

HC-CSF

o 5

II II

HC

161°

(27)

62°C/15mm

(33)

68-69°(mp) (R=H)

(20)

SF>

SF C-CH 5

• "

Ν

-

(R=C(0)N(CH ) ) 3

2

V

R

SF C = C-H 5

/ CH?

\

CR

\

1686(C=C) 48-50/10mm (R=H) 1652(CH=C-S)

(20)

CHo

/

= CR

1661

6574mm (R=CH ) 3



131


132

INORGANIC FLUORINE CHEMISTRY: TOWARD THE 21ST CENTURY

Table I. Continued

SF Cyclic, Heterocyclic, Aromatic Dervatives, cont'd. S

HC-CSFc

197-198°(mp)(R=H) (21) 78-78.5 (mp)(R=CH C(0)) 200-201 (mp) (R=C H NHC(0)) 116-117 (mp)(R=NH ) 3

CFLC Ν

V

6

5

2

SF,

7.

120°

CH =CH?

8.

SF C = CCF 5

3

\ / NiX,

a

1890/1865

-

(X=CO)

(26)

1750

137°C(mp) (X=P(C H ) ) 6

5

3

Numerous derivatives with X = m-N0 , /?-N0 , m-NH , p-NH2, m-OH, p-OH, m-C0 H, p-C0 H, m-CH=CH , etc. 2

2

2

2

2

2

See Reference Banks et al (7) in the cited literature.


6

Pentafluoro- X -sulfanyl Olefins and Acetylenes

WINTER AND GARD

Table I. Continued Compound (poly SF )


S

Compound fpolv SF )

IR(C=C) Reference

?

SF, 1.

(73)

SR

γ-c

H

88/1.6mm ( X - N O J (3) (X=NH ) 80.7-81.5°(mp) (X=NH · HC1)

2.

2

X

2

SF, 3.

(7*)

SF. CH. ^

c - A CTL

ο = c-o 4.

N

163-164°(mp)

S F

SF (0>- = N-(0) 5

(3)

5

CH SF 2

5

(35) F SCH 5

2

Ο

4l

F S^^SF 5

7.

126-127°(mp)

(25)

5

SF^ 6°

(25)

SF« F,S



134

INORGANIC FLUORINE CHEMISTRY: TOWARD THE 21ST CENTURY

Table I. Continued

SF Alkvne Derivatives Downloaded by UNIV OF CALIFORNIA SANTA BARBARA on September 10, 2015 | http://pubs.acs.org Publication Date: April 29, 1994 | doi: 10.1021/bk-1994-0555.ch008

g

Compound

IR(C=C) fern' )

BpfQ

1

Reference

1.

SF C=CH

2118

6°C

(20,21)

2.

SF OCLi

...

...

(25)

3.

SF C=CCH

2661

65-70°C

(27)

4.

SF OC-OCH

2260

57.6°

(26)

5.

SF OC-Cl

...

-69°

(25)

6.

SF OC-CF

2295

14.4°

(22)

7.

SF OC-Br

...

-65°

(25)

8.

(CH ) SiOCSF

-8.5°C (mp) 96.9°

(25)

9.

SF CH=C(Br)OCH

...

(26)

10.

SF OC-Ag

2062

...

(20)

11.

SF OC-I

...

-52°(mp)

(25)

12.

SF OCSF

2220

51°

(22)

13.

IMg(OCSF )

...

...

(25)

14.

SF OC-OCSF

2180

5

5

5

3

5

5

5

3

5

3

3

5

2120 ( O C )

5

1620, sh. at 1590 (C=C) 5

5

5

5

5

5

5

15.

Co (CO) (HC=C-SF )

...

16.

Hg(OCSF )

...

17.

Co (CO) ((CH ) SiOC-SF )

2

6

5

5

2

2

6

3

3

5

18.

Co (CO) (HC=C-SF )

19.

Co (CO) (SF OCSF )

2

5

2

5

6

5

5

20.

Co (CO) (HOC-SF )

21.

C H HgOCSF

2

6

4

5

2

...

5

5

3

...

105°

(26b)

47°(mp)

(25)

—

(25)

135°(mp)

(25)

74°(mp)

(25)

149°(mp)

(25)

108°(mp)

(25)

100°(mp)

(25)


8.

6


WINTER AND GARD

135

group, or generally, C F -group, and also rather more expensive. It is envisioned that SF -compounds could be useful dielectrics, replacements for fluorochlorohydrocarbons, very resistant polymers, fuel cell electrolytes with advantageous properties, blood substitutes, surfactants, high energy materials (explosives and rocket fuels (6)) or pesticides. In several cases, these expectations are seen to be fulfilled (7). In order to allow for ready access to these compounds, it was necessary to devise acceptably simple syntheses of both SF C1 and SF Br, which form an SF -C bond by addition across double and triple bonds. The use of S F has been described, either alone (8) or as a mixture with iodine (9); product mixtures were obtained with olefins and only selected olefins yielded any SF -compounds at all. n

2n+1

5


5

5

5

2

10

5

The Synthesis of Pentafluorothio Halides (SF X) 5

Pentafluorothio chloride can be obtained by several different methods, the oldest one being first heating SF with cesium fluoride (at ca 150°C), potassium fluoride (300°C) or silver fluoride (300°C) and then treating the intermediate MSF with chlorine (M = Cs ca. 75% yield, Κ = 5-10 %, Ag =22 %) (10). The less expensive K F can be used instead at lower temperature (200-225°C) in a more cumbersome process and yields are also apparently very good (ca 80%) (77). The easiest method consists of allowing a frozen equimolar mixture of SF and C1F in the presence of a small amount of CsF to attain room temperature slowly (72). Care has to be taken that the C1F is completely free of C1F (C1F is prepared by heating C1F and Cl ). This can be achieved through low temperature distillation at -140°C; otherwise, dangerous explosive reactions can occur. The yield is almost quantitative. The compound SF Br was first obtained by heating a mixture of Br , BrF and SF (10% yield) (75), then by heating Br and S F (

Inorganic Fluorine Chemistry - American Chemical Society

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