Site directed synthesis of mono and disubstituted SF5-polyfluoroalkyl benzenes

Site directed synthesis of mono and disubstituted SF5-polyfluoroalkyl benzenes

Journal of Fluorine Chemistry 126 (2005) 1202–1214 www.elsevier.com/locate/fluor Site directed synthesis of mono and disubstituted SF5-polyfluoroalky...

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Journal of Fluorine Chemistry 126 (2005) 1202–1214 www.elsevier.com/locate/fluor

Site directed synthesis of mono and disubstituted SF5-polyfluoroalkyl benzenes R.W. Winter a, R. Dodean a, J.A. Smith a, Anilkumar R. b, D.J. Burton b,**, G.L. Gard a,* a

Department of Chemistry, Portland State University, Portland, OR 97207, USA b Department of Chemistry, University of Iowa, Iowa City, IA 52242, USA

Received 20 April 2005; received in revised form 31 May 2005; accepted 31 May 2005 Available online 1 July 2005

Abstract A novel method for the preparation of o-, m-, p-SF5CF2CFYC6H4X (Y = Br, F and X = m-Br, p-Br, Cl, CH3, CF3, NO2, o-NO2, F, CF3, CH(CH3)2) derivatives was devised by a two-step reaction: SF5Br-addition to o-, m-, p-CF2 CFC6H4X followed by reaction of AgBF4 with the o-, m-, p-SF5CF2CFBrC6H4X adducts. Additional studies have been carried out with several derivatives and includes the preparation of SF5CF2C(O)C6H5, p-CF3CFBrC6H4NO2, SF5CF2CF2C6H3(NO2)2, SF5CF2CF2C6H3(NH2)2, and an SF5CF2CF2-containing polyimide and dye. The complete characterization (IR, NMR, and MS) of these compounds is given. # 2005 Elsevier B.V. All rights reserved. Keywords: SF5-fluoroalkyl aromatics; Sulfur hexafluoride derivatives; Trifluorostyrenes

1. Introduction The properties of organic compounds are often significantly enhanced or modified by the incorporation of perfluoroalkyl groups [1–3]. Although a large body of work has been published with compounds containing perfluoroalkyl groups, only a small number of compounds containing an F5S-group or F5S(CF2)n-groups have been prepared and investigated, even though useful properties ranging from the fields of liquid crystals to pesticides to dielectrics are enhanced by incorporation of the F5S-moiety [4]. The F5S-group as a polar terminal group has produced a new class of liquid crystals that have very strong dielectric anisotropy with some having monotropic nematic and smectic phases [5,6]. The first reported organic superconductor contained an F5S-group [7]. Since this initial report, a number of F5Scontaining materials having properties ranging from superconductivity to metallic conductivity to semiconductivity * Corresponding author. Fax: +1 503 725 9525. ** Corresponding author. Fax: +1 319 335 1270. E-mail addresses: [email protected] (D.J. Burton), [email protected] (G.L. Gard). 0022-1139/$ – see front matter # 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.jfluchem.2005.05.009

have been reported [8,9]. Polymeric F5S-containing imides with low dielectric constants (2.51–3.00) have potential use in the electronics industry [10]. When the surfactant properties of the F5S-group have been compared to similar F3C-containing analogs, the F5S-group has been found to be superior for lowering aqueous surface tension [11], and polymers containing the F5S-moiety have exhibited fluorinated surfaces with low wettability [12,13]. There are many known meta-, para- and several orthoderivatives of SF5C6H5 [14–16]. However, only a relatively small number of meta-F5SCF2CF2C6H4X derivatives has been prepared; there were no known ortho- or paraderivatives [17,18] previous to this work.

2. Results The above limitations prompted us to seek a new, more general route to functionalized o-, m-, p-F5SCF2CF2C6H4X derivatives. The recent report of a low-cost general route for the preparation of o-, m-, and p-trifluorostyrene derivatives [19] suggested a general entry into the preparation of o-, m-, and p-F5SCF2CF2C6H4X (cf. Eqs. (1) and (2)). Since the substituent in the styrene precursor can be ortho, meta or

R.W. Winter et al. / Journal of Fluorine Chemistry 126 (2005) 1202–1214

para, the F5S-analogs can contain a variety of ortho, meta or para atoms or groups. Interestingly, no deactivating effect of ortho substituents in either reaction scheme was observed.

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yield. Its formation is rationalized by the following mechanism:

F2 C¼CFC6 H4 X þ SF5 Br hn;0  C

!

CH2 Cl2 ð1751 hÞ

SF5 CF2 CFðBrÞC6 H4 X

(1)

ð2282% yieldsÞ

SF5 CF2 CFðBrÞC6 H4 X þ AgBF4 ð78 to 138  CÞ

!

CH2 Cl2 ð344 hÞ

SF5 CF2 CF2 ðBrÞC6 H4 X

(2)

ð3882% yieldsÞ

(X = m-Br, p-Br, p-Cl, p-CH3, p-CF3, p-NO2, o-F, o-CF3, oCH(CH3)2). The actual yields are given in Table 1.

For both reaction steps, a range of reactivities was found, estimated by reaction times and temperatures for complete reaction. The addition of SF5Br to the trifluorostyrenes proceeded fast with alkyl or halogen substituents ( p-CH3, oCH(CH3)2, o-F, m-Br, p-Br and p-Cl) and less readily with electron withdrawing substituents (o-CF3, p-CF3, p-NO2). Similar reactivity patterns were found in the fluorination step. Additional reactions of SF5CF2CFYC6H4X (Y = Br, F and X = H, NO2) have led to several interesting products: p-SF5 CF2 CFðBrÞC6 H4 NO2 þ AgF

rt

!

CH3 CN; 10d

p-CF3 CFðBrÞC6 H4 NO2 þ SF4

(3)

19ð98% yieldÞ

Interestingly, treatment of SF5CF2CF2C6H5 with BF32CH3COOH, produced SF5CF2C(O)C6H5 (20) in 36%

A by-product, CF3C(O)C6H5, was formed in 8% yield; a trace product, possibly the result of the acetylation of SF5CF2C(O)C6H5, was detected in GC–MS. The condensation of SF5CF2CF2C6H4NH2 with Fischer’s aldehyde, followed by heating gave the following red dye product:

The above reaction was carried in absolute ethanol, heated to 50 8C for 15 min, diluted with water (50 8C), acidified with HCl(aq.) and stirred overnight. The red-brown product was heated in vacuo to 100 8C and recrystallized from ethanol. A piece of paper that was treated with acetone solution of the SF5CF2CF2-dye repelled water. While past work has produced several mono substituted derivatives SF5CF2CF2C6H4X [17,18] there have been no reports of disubstituted products. Treatment of SF5CF2CF2C6H5 with HNO3/H2SO4 gave the expected 3,5SF5CF2CF2C6H3(NO2)2 product, (22) in 19% yield; reduction of the dinitro-derivative with iron in aqueous HCl produced 3,5-SF5CF2CF2C6H3(NH2)2, (23) in 48% yield. The 3,5-diaminoderivative when combined with the dianhydride ‘‘6-FDA’’ formed the corresponding polyimide polymer:

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R.W. Winter et al. / Journal of Fluorine Chemistry 126 (2005) 1202–1214

Table 1 Yields of SF5CF2CFBrC6H4X (1–9) and SF5CF2CF2C6H4X (10–18)

3. Experimental

SF5CF2CFBrC6H4X (1–9)

The reactant SF5Br was prepared from SF4, BrF3, Br2 and CsF via a method previously described by us [22]. The a,b,b-trifluorostyrene derivatives were prepared according to literature method. AgBF4 was prepared from AgF and BF3 in benzene [23]. The infrared spectra of the reactants and products were obtained on a Perkin-Elmer 2000 FTIR spectrometer operating at 1.0 cm1 resolution using KBr windows. The NMR spectroscopy values were obtained by use of the following instruments: 19F Varian EM-390 (84.7 MHz) and 1H Bruker (500 MHz) in CDCl3 with CCl3F and Si(CH3)4 as internal standards. Gas chromatography–mass spectroscopy (GC–MS) results were obtained using a Hewlett-Packard HP5890 series II gas chromatograph equipped with a HP5890 mass selective detector (operating at 70 eV) and a DB5, 30 m column; the temperature profile used was 50 8C for 2 min, then 11 8C min1 up to 280 8C. The HRMS values were determined on a Kratos MS 50TC; chemical ionization with methane.

SF5CF2CF2C6H4X (10–18)

Entry

X

Yields (%) a

Entry

X

Yields (%)a

1 2 3 4 5 6 7 8 9

m-Br p-Br p-Cl p-CH3 p-CF3 p-NO2 o-F o-CF3 o-CH(CH3)2

53 53 52 41 22 c 80 82 74 67

10 11 12 13 14 15 16 17 18

m-Br p-Br p-Cl p-CH3 p-CF3 p-NO2 o-F o-CF3 o-CH(CH3)2

99 98 97 38b 96 67 93 99 89

a b c

Isolated yields. Low yield due to loss in the filtration process. Low yield due to volatility of product.

The light yellow solid product was formed by mixing the reactants together in N,N-dimethylacetamide for 24 h. The polymer was cured at 100–180 8C for 4 h. The infrared (IR) spectral data for the new compounds are listed in Section 3. With the exception of pCF3CFBrC6H4NO2 and SF5CF2C(O)C6H5, all compounds contained the SF5CF2CF(Y)-group (Y = Br, F). The IR spectra showed significant bands in the 846–937 cm1 region and are attributed to the S–F stretching modes; bands found in the 596–610 cm1 region are due to one of the S–F deformation modes. Cross and coworkers reported that the most intense bands for compounds containing the SF5grouping appears in the 850–920 cm1 region (S–F stretching modes) and in the 600 cm1 region (one of the S–F deformation modes [20]. The strong absorption peaks in the 1100–1400 cm1 are assigned to the C–F stretching mode [21]. For all SF5CF2CF2-compounds the 19F NMR spectra contain an AB4 pattern: A (nine-line pattern) at dA = 65.4–67.5 ppm and B (d or m-d) at 45.2–46.2 ppm. The chemical shifts of the CF2 fluorines adjacent to the SF5group are located in the range d = 93.6 to 95.8 ppm. The CF2 fluorines adjacent to the benzene ring are present at 107.2 to 114.3 ppm; the fluorine of the CFBr is found at 121.7 to 132.6 ppm. The results are in agreement with the literature [17,18]. The 1H and 19F NMR data are given in Tables 2–5. The major mass spectral peaks contain the parent ion; additional peaks are found supporting the assigned structure. In conclusion, this work has developed a simple, general route to SF5CF2CF2C6H4X derivatives, where X can be a variety of o, m, p atoms or groups. This methodology avoids S2F10, by-passing the use of SF5CF2CF2I, and since S2F10 is prepared from SF5Br, saves one additional step, avoids the use of C2F4, and provides entry to any pattern of aromatic substitution. Also, this work has expanded the scope of SF5(CF2)2-aromatic chemistry to include a new SF5aromatic ketone, a dye, and several disubstituted products from which an interesting polymer can be prepared.

3.1. Preparation of SF5CF2CFBrC6H4X derivatives (general procedure) The reactions were carried out in a 30 mL Carius tube equipped with a Kontes Teflon valve and a Teflon coated stirring bar. After evacuation, the Carius tube was filled with argon. The trifluorostyrene derivatives were dissolved in pentane (1–2 g of the styrene in 3–5 mL pentane), and CH2Cl2 (5 ml). After cooling to 196 8C, the vessel was evacuated and up to 2 mol-equivalents of SF5Br were added via vacuum transfer. The Carius tube was then placed in a 0 8C circulating water bath under three 90 W sunlamps at a distance of 15–20 cm. Completion of the reaction was marked by a change of color from light yellow to red-brown. The absence of a vinyl stretching frequency (1756– 1790 cm1) in the infrared spectrum confirmed the total consumption of the trifluorostyrene derivative. The pentane and CH2Cl2 were removed by rotary evaporation and the product isolated by silica gel chromatography (hexane as eluant). Hexane and any residual solvents were removed under vacuum to give the pure product. In this manner the following compounds were prepared. 3.2. 3-Bromo-1-(2-pentafluorosulfanyl-1bromotrifluoroethyl)benzene (1) Following the general procedure given above, mCF2 CFC6H4Br (0.99 g, 4.18 mmol) dissolved in 3 ml pentane, 5 ml CH2Cl2, and 1.14 g (5.51 mmol) SF5Br were added to a 30 ml Carius tube. The mixture was irradiated for 18 h at 0 8C. The product was isolated by silica gel chromatography; 0.98 g, 2.21 mmol, yield was 53%. IR spectrum (cm1): C–H, 3072 (vw); C–F, 1197 (m-s); S–F, 877 (vs), 857 (m-s); 597 (m-s).

Table 2 1 H NMR data

d2

m-Br (1)

7.74, s 1.0H

p-Br (2)

7.59, 1.0H 7.54, 1.0H 7.48, 1.0H 7.72, 1.0H 8.32, 1.0H

p-Cl (3) p-CH3 (4) p-CF3 (5) p-NO2 (6) o-F (7) o-CF3 (8) o-CH(CH3)2 (9)

d3

d J23 = 8.39, d J23 = 8.39, d J23 = 7.94, d J23 = 9.31, d J23 = 8.70,

7.46, d J23 = 8.39, 1.0H 7.43, d J23 = 8.39, 1.0H 7.23, d J23 = 7.94, 1.0H 7.74, d J23 = 9.31, 1.0H 8.70, d J23 = 8.70 1.0H 7.17, d-d, J34 = 8.24, J3Fc = 11.6, 1.0H 7.88, d J34 = 8.24, 1.0H 7.57, d J34 = 7.93, 1.0H

d4

d5

d6

7.54, d J45 = 8.09, 1.0H

7.33, t J45 = 8.09 J56 = 8.09, 1.0H 7.46, d J56 = 8.39, 1.0H 7.43, d J56 = 8.39, 1.0H 7.23, d J56 = 7.94, 1.0H 7.74, d J56 = 9.31, 1.0H 8.70, d J56 = 8.70, 1.0H 7.25, t J45 = 7.86, 1.0H 7.58, t J45 = 7.71, 1.0H 7.21, t J45 = 7.33, 1.0H

7.60, d J56 = 8.09, 1.0H

7.57, t J45 = 7.86, 1.0H 7.64, t J45 = 7.71, 1.0H 7.41, t J45 = 7.33, 1.0H

d7

d8

7.59, d J56 = 8.39, 1.0H 7.54, d J56 = 8.39, 1.0H 7.48, d J56 = 7.94, 1.0H

2.39, s (CH3) 3.0H

7.72, d J56 = 9.31, 1.0H 8.32, d J56 = 8.70, 1.0H 7.79, m J56 = 7.94, 1.0H 7.81, d J56 = 7.93, 1.0H 7.46, t J56 = 7.93, 1.0H

3.65, br.sept (CH) J78 = 6.26, 1.0H

1.27, d-d or t (CH3) J78 = 6.26, 6.0H

R.W. Winter et al. / Journal of Fluorine Chemistry 126 (2005) 1202–1214

X

1205

1206

Table 3 19 F NMR data

dA (ppm)

dB (ppm)

da (ppm)

db (ppm)

dc (ppm)

67.50, t-nine lines JaA = 5.10, JAB = 150.01 1.0F 68.56, nine lines JaA = 4.79, JAB = 152.46 1.0F 68.10, nine lines JaA = 4.79, JAB = 151.52 1.0F 67.83, nine lines JaA = 5.64, JAB = 151.89 1.0F 67.47, nine lines JaA = 4.24, JAB = 148.13 1.0F 67.37, t-nine lines JaA = 4.89, JAB = 148.13 1.0F 67.83, t-nine lines JaA = 5.65, JAB = 148.88 1.0F

47.50 m-d JbB 12, JaB = 14.12 JAB = 150.01, 4.0F 48.17, d JbB = 11.29, JaB = 14.12 JAB = 152.46, 4.0F 47.70, m-d JbB = 11.29, JaB = 14.96 JAB = 151.52, 4.0F 47.50, m-d JbB = 11.99, JaB = 16.38 JAB = 151.89, 4.0F 47.63, m-d JbB = 12.99, JaB = 16.00 JAB = 148.13, 4.0F 47.77, m-d JbB = 12.85, JaB 17 JAB = 148.13, 4.0F 45.17, m-d JbB = 11.29, JaB = 16.94 JAB = 148.88, 4.0F

131.83, p (poorly resolved) Jb 13 (from 19F-sp) 1.0F 131.33, p (poorly resolved) JbB = 11.29 1.0F 131.77, p (poorly resolved) JbB = 11.29 1.0F 131.00, p (poorly resolved) JbB = 11.99 1.0F 132.37, p JbB = 12.99 1.0F

64.40, s 3.0F

67.40, t-nine lines JaA = 5.65, JAB = 147.75 1.0F 68.27, t-nine lines JaA = 4.94, JAB = 150.95 1.0F

47.53, m-d JbB = 11.29, JaB = 15.81 JAB = 147.75, 4.0F 47.77, m-d (poorly resolved) JAB = 150.95, 4.0F

AB system of d-p: 86.33, 85.33, JaA = 5.10 JaB = 14.12, 2.0F AB system of p: 86.33, 84.33, JaA = 4.79, JaB = 14.12 2.0F AB system of d-p: 86.97, 84.97, JaA = 4.79 JaB = 14.96, 2.0F AB system of p: 86.33, 85.67, JaA = 5.64, JaB = 16.38 2.0F AB system of p: 86.42 85.42, JaA = 4.24, JaB = 16.00 2.0F 86.07, d-p JaA = 4.89, JaB = 14.79 2.0F AB system of d-d-p: 87.58, 84.08, Jac = 4.59 JaA = 5.65, JaB = 16.94, 2.0F AB system of p: 84.63, 83.63, JaA = 5.65, JaB = 15.81 2.0F 84.07, d-m, (poorly resolved) JaA = 4.94, 2.0F

p-Br (2) p-Cl (3) p-CH3 (4) p-CF3 (5) p-NO2 (6) o-F (7)

o-CF3 (8) o-CH(CH3)2 (9)

132.57, p JbB = 12.85 1.0F 129.67, d-p (poorly resolved) JbB = 11.29, Jbc = 19.76, 1.0F

107.00, m Jac = 4.59, Jbc = 19.76 1.0F

129.47, p-q JbB = 11.29, Jbc = 46.30 1.0F 121.73, broad m (poorly resolved) 1.0F

59.07, d Jbc = 46.30 3.0F

R.W. Winter et al. / Journal of Fluorine Chemistry 126 (2005) 1202–1214

X m-Br (1)

Table 4 1 H NMR data

d2

m-Br (10)

7.78, s 1.0H

p-Br (11)

7.67, 1.0H 7.55, 1.0H 7.45, 1.0H 7.75, 1.0H 7.84, 1.0H

p-Cl (12) p-CH3 (13) p-CF3 (14) p-NO2 (15) o-F (16)

d3

d J23 = 8.09, d J23 = 8.55, d J23 = 7.94, d J23 = 8.39, d J23 = 8.77,

7.47, 1.0H 7.49, 1.0H 7.23, 1.0H 7.79, 1.0H 8.24,

d4

d5

d6

7.55, d J45 = 7.93, 1.0H

7.74, d J56 = 8.24, 1.0H

d J23 = 8.09,

7.39, t J45 = 7.93, J56 = 8.24 1.0H 7.47, d J56 = 8.09, 1.0H

7.67, d J56 = 8.09, 1.0H

d J23 = 8.55,

7.49, d J56 = 8.55, 1.0H

7.55, d J56 = 8.55, 1.0H

d J23 = 7.94,

7.23, d J56 = 7.94, 1.0H

7.45, d J56 = 7.94, 1.0H

d J23 = 8.39,

7.79, d J56 = 8.39, 1.0H

7.75, d J56 = 8.39, 1.0H

d J23 = 8.77, 1.0H

8.24, d J56 = 8.77, 1.0H

7.84, d J56 = 8.77, 1.0H

7.28, J = 7.78, 1.0H

7.55, d-overlap J56 = 7.02, 1.0H 7.92, d-d J56 5.8, J46 4.3 1.0H 7.51, unresolved 1.0H

o-CF3 (17)

7.20, d-d J34 = 8.85, J3Fc = 10.53 1.0H 7.76, broad m 1.0H

7.58, t-overlap J = 7.78, 1.0H 7.69, m-overlap 1.0H

7.71, m-overlap J56 5.8, 1.0H

o-CH(CH3)2 (18)

7.51, unresolved 1.0H

7.78, d-t 1.0H

7.51, unresolved 1.0H

d7

d8

2.39, s (CH3) 3.0H

3.37, sept (CH) J78 = 6.86, 1.0H

1.26, d-d or t (CH3) J78 = 6.86, 6.0H

R.W. Winter et al. / Journal of Fluorine Chemistry 126 (2005) 1202–1214

X

1207

1208

Table 5 19 F NMR data

dA (ppm)

m-Br (10)

66.63, t-nine lines JAB = 151.71 1.0F 66.87, t-nine lines JAB = 151.61 1.0F 66.93, t-nine lines JAB = 151.71 1.0F 67.27, t-nine lines JAB = 149.07 1.0F 66.33, t-nine lines JAB = 149.63 1.0F 66.00, t-nine lines JAB = 152.27 1.0F 67.17, t-nine lines JAB = 150.01 1.0F 66.67, t-nine lines JAB = 151.33 1.0F 67.17, t-nine lines JAB = 151.71 1.0F

p-Br (11) p-Cl (12) p-CH3 (13) p-CF3 (14) p-NO2 (15) o-F (16) o-CF3 (17) o-CH(CH3)2 (18)

JaA = 4.23, JaA = 4.52, JaA = 5.08, JaA = 4.91, JaA = 4.24, JaA = 4.52, JaA = 4.24, JaA = 5.65, JaA = 5.36,

dB (ppm)

da (ppm)

db (ppm)

45.60, m-d JbB = 13.27, JaB = 14.96 JAB = 151.71, 4.0F 45.76, m-d JbB = 12.71, JaB = 15.53 JAB = 151.61, 4.0F 45.76, m-d JbB = 12.70, JaB = 16.23 JAB = 151.71, 4.0F 45.67, m-d JbB = 11.99, JaB = 15.30 JAB = 149.07, 4.0F 45.50, m-d JbB = 12.70, JaB = 15.53 JAB = 149.63, 4.0F 45.83, m-d JbB = 12.48, JaB = 15.25 JAB = 152.27, 4.0F 45.50, m-d JbB = 12.71, JaB = 17.65 JAB = 150.01, 4.0F 45.83, m-d JaB = 14.12, JbB = 14.96 JAB = 151.33, 4.0F 45.17, m-d JbB = 12.99, JaB = 14.11 JAB = 151.71, 4.0F

95.57, d-p JaA = 4.23, JaB = 14.96 2.0F 95.73, d-p JaA = 4.52, JaB = 15.53 2.0F 95.57, d-p JaA = 5.08, JaB = 16.23 2.0F 95.43, d-p JaA = 4.91, JaB = 15.30 2.0F 95.57, d-p JaA = 4.24, JaB = 15.53 2.0F 95.53, broad m JaA = 4.53, JaB = 15.25 2.0F 95.83, d-d-p Jac = 16.94, JaA = 4.24, JaB = 17.65 2.0F 93.60, q-p JaA = 5.65, Jac = 12.71 JaB = 14.12 2.0F 94.50, p JaA = 5.36, JaB = 14.11 2.0F

113.90, p JbB = 13.27 2.0F

dc (ppm)

113.93, p JbB = 12.71 2.0F 113.57, p JbB = 12.70 2.0F 113.90, p JbB = 11.99 2.0F 114.20, p JbB = 12.70 2.0F

64.66, m-s 3.0F

114.33, broad m JbB = 12.48 2.0F 112.50, d-p JbB = 12.71, Jbc = 21.46 2.0F 108.83, p-q JbB = 13.27, JbB = 14.96 Jbc = 19.76, 2.0F 107.17, p JbB = 12.99 2.0F

113.83, m Jac = 16.94, Jbc = 21.46 1.0F 59.57, t-t Jac = 12.71, Jbc = 19.76 3.0F

R.W. Winter et al. / Journal of Fluorine Chemistry 126 (2005) 1202–1214

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GC–MS (m/z, ion, rel. %): 446, 444, 442 (M)+ (7, 13, 7); 319, 317, 315 (M–SF5)+ (4, 10, 5); 238, 236 (M–SF5–Br)+ (95, 100); 89 (SF3)+ (12). 3.3. 4-Bromo-1-(2-pentafluorosulfanyl-1bromotrifluoroethyl)benzene (2) Following the general procedure given above, pCF2 CFC6H4Br (1.49 g, 6.28 mmol) dissolved in 3 ml pentane, 5 ml CH2Cl2, and 2.52 g (12.2 mmol) SF5Br were added to a 30 ml Carius tube. The mixture was irradiated for 25 h at 0 8C. The product was isolated by silica gel chromatography; 1.49 g, 3.34 mmol, yield was 53%. IR spectrum (cm1): C–H, 3101 (vw); C–F, 1230 (w-m), 1199, 1189 (m); S–F, 917 (s), 877 (vs), 855 (m-s); 596 (s). GC–MS (m/z, ion, rel. %): 446, 444, 442 (M)+ (2, 4, 2); 319, 317, 315 (M–SF5)+ (4, 8, 4); 238, 236 (M–SF5–Br)+ (98, 100); 89 (SF3)+ (8). 3.4. 4-Chloro-1-(2-pentafluorosulfanyl-1bromotrifluoroethyl)benzene (3) Following the general procedure given above, pCF2 CFC6H4Cl (1.08 g, 5.61 mmol) dissolved in 3 ml pentane, 5 ml CH2Cl2, and 1.20 g (5.80 mmol) SF5Br were added to a 30 ml Carius tube. The mixture was irradiated for 20 h at 0 8C. The product was isolated by silica gel chromatography; 1.17 g, 2.92 mmol, yield was 52%. IR spectrum (cm1): C–H, 2975, 2941 (w); C–F, 1201, 1188, 1102 (s); S–F, 919 (vs), 907 (s), 881 (vs), 858 (s), 597 (s). GC–MS (m/z, ion, rel. %): 400, 398 (M)+ (2, 2); 273, 271 (M–SF5)+ (7, 5); 192 (M–SF5–Br)+ (100); 89 (SF3)+ (4). 3.5. 4-Methyl-1-(2-pentafluorosulfanyl-1bromotrifluoroethyl)benzene (4) Following the general procedure given above, pCF2 CFC6H4CH3 (1.00 g, 5.81 mmol) dissolved in 3 ml pentane, 5 ml CH2Cl2, and 1.80 g (8.70 mmol) SF5Br were added to a 30 ml Carius tube. The mixture was irradiated for 48 h at 0 8C. The product was isolated by silica gel chromatography; 0.910 g, 2.40 mmol, yield was 41%. IR spectrum (cm1): C–H, 3042, 2929 (w); C–F, 1204 (s), 1191 (vs), 1159 (w-m); S–F, 921 (vs), 905 (s), 879 (vs), 857 (s), 596 (s). GC–MS (m/z, ion, rel. %): 380, 378 (M)+ (1, 1); 299 M– + Br (47); 253 251 (M–SF5)+ (5, 5); 172 (M–SF5–Br)+ (100); 89 (SF3)+ (4). 3.6. 4-Trifluoromethyl-1-(2-pentafluorosulfanyl-1bromotrifluoroethyl)benzene (5) Following the general procedure given above, pCF2 CFC6H4CF3 (0.50 g, 2.21 mmol) dissolved in 3 ml pentane, 5 ml CH2Cl2, and 1.22 g (5.89 mmol) SF5Br were

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added to a 30 ml Carius tube. The mixture was irradiated for 20 h at 0 8C. The product was isolated by silica gel chromatography; 0.209 g, 0.482 mmol, yield was 22%; low yield due to volatility of product. IR spectrum (cm1): C–H, 3124, 3088, 2932 (vw); C–F, 1328 (vs), 1204 (m), 1195 (m), 1176 (m), 1141 (m); S–F, 921 (m-s), 912 (m), 881 (vs), 865 (s), 597 (m-s). GC–MS (m/z, ion, rel. %): 434, 432 (M)+ (0.1, 0.1); 353 (M–Br)+ (31); 307, 305 (M–SF5)+ (10, 11); 226 (M–SF5– Br)+ (100); 195 (C8H4F5)+ (93); 89 (SF3)+ (6). 3.7. 4-Nitro-1-(2-pentafluorosulfanyl-1bromotrifluoroethyl)benzene (6) Following the general procedure given above, pCF2 CFC6H4NO2 (4.30 g, 21.17 mmol) dissolved in 3 ml pentane, 5 ml CH2Cl2, and 8.7 g (42.0 mmol) SF5Br were added to a 30 ml Carius tube. The mixture was irradiated for 51 h at 0 8C. The product was isolated by silica gel chromatography; 6.95 g, 16.94 mmol, yield was 80%. IR spectrum (cm1): C–H, 3122, 3087 (w), 3061, 2867 (vw); C–F, 1352 (s), 1212 (m), 1199 (s), 1188 (m-s); S–F, 920, 879, 870 (vs), 853 (s), 597 (s). GC–MS (m/z, ion, rel. %): 395, 393 (M)+ (0.4, 0.4); 330 (M–Br)+ (33); 282, 284 (M–SF5)+ (8, 8); 203 (M–SF5–Br)+ (100); 89 (SF3)+ (31). 3.8. 2-Fluoro-1-(2-pentafluorosulfanyl-1bromotrifluoroethyl)benzene (7) Following the general procedure given above, oCF2 CFC6H4F (1.0 g, 10.10 mmol) dissolved in 3 ml pentane, 5 ml CH2Cl2, and 1.40 g (6.76 mmol) SF5Br were added to a 30 ml Carius tube. The mixture was irradiated for 17 h at 0 8C. The product was isolated by silica gel chromatography; 1.78 g, 4.65 mmol, yield was 82%. IR spectrum (cm1): C–H, 3095, 2969 (vw); C–F, 1285 (w-m), 1251 (m-s), 1193 (s); S–F, 921 (s), 907 (s), 876 (vs), 849 (s), 597 (s). GC–MS (m/z, ion, rel. %): 384, 382 (M)+ (0.3, 0.4); 257, 255 (M–SF5)+ (7, 7); 176 (M–SF5–Br)+ (100); 89 (SF3)+ (6). 3.9. 2-Trifluoromethyl-1-(2-pentafluorosulfanyl-1bromotrifluoroethyl)benzene (8) Following the general procedure given above, oCF2 CFC6H4CF3 (1.55 g, 6.85 mmol) dissolved in 3 ml pentane, 5 ml CH2Cl2, and 1.22 g (5.89 mmol) SF5Br were added to a 30 ml Carius tube. The mixture was irradiated for 18 h at 0 8C. The product was isolated by silica gel chromatography; 1.55 g, 3.58 mmol, yield was 74%. IR spectrum (cm1): C–H, 3064, 2923 (vw); C–F, 1309 (m), 1294, 1283, 1198, 1177 (m), 1156 (m-s); S–F, 915 (m), 876 (vs), 849 (m), 598 (m-s).

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GC–MS (m/z, ion, rel. %): 434, 432 (M)+ (0.04, 0.04); 353 (M–Br)+ (33); 307, 305 (M–SF5)+ (14, 15); 226 (M– SF5–Br)+ (83); 195 (C8H4F5)+ (100); 89 (SF3)+ (6). 3.10. 2-Isopropyl-1-(2-pentafluorosulfanyl-1bromotrifluoroethyl)benzene (9) Following the general procedure given above, oCF2 CFC6H4CH(CH3)2 (1.40 g, 6.99 mmol) dissolved in 3 ml pentane, 5 ml CH2Cl2, and 1.69 g (8.17 mmol) SF5Br were added to a 30 ml Carius tube. The mixture was irradiated for 18 h at 0 8C. The product was isolated by silica gel chromatography; 1.91 g, 4.69 mmol, yield was 67%. IR spectrum (cm1): C–H, 3073, 3031 (w), 2967 (s), 2935, 2875 (m); C–F, 1367 (m), 1185 (vs), 1097 (s); S–F, 916, 878, 846 (vs), 598 (s). GC–MS (m/z, ion, rel. %): 406, 407, 408 (M)+ (1, 0.2, 1); 327 (M–Br)+ (100); 281 (M–SF5)+ (0.1); 200 (M–SF5–Br– CH3)+ (37); 89 (SF3)+ (11). 3.11. Preparation of SF5CF2CF2C6H4X derivatives (general procedure) To a 30 mL Carius tube equipped with a Kontes Teflon valve and a Teflon coated stirring bar, was added AgBF4. Anhydrous CH2Cl2 (5 ml) was transferred to the Carius tube under vacuum, and a 0.5 molar equivalent amount of o-, p-, m-SF5CF2CF(Br)C6H4X was added under an argon atmosphere. The reaction mixture was usually stirred at room temperature or with heating. When GC–MS analysis indicated total consumption of the reactant bromide, the reaction mixture was cooled to room temperature, the solid phase removed by vacuum filtration and the solid washed with 2–3 ml of CH2Cl2. The CH2Cl2 fractions were combined and separated by silica gel chromatographysolvent removed under vacuum to give pure o-, p-, mSF5CF2CF2 C6H4X products which were characterized by IR, 19F, 1H NMR and HRMS. 3.12. 3-Bromo-1-(2-pentafluorosulfanyltetrafluoroethyl) benzene (10) Following the general procedure above, mSF5CF2CFBrC6H4Br (0.68 g, 1.53 mmol) dissolved in 5.2 ml CH2Cl2, and 0.59 g (3.03 mmol) AgBF4 were added to a 30 ml Carius tube under an argon atmosphere. The reaction mixture was stirred for 44 h at room temperature; the solid phase was removed by vacuum filtration and washed with small amounts of CH2Cl2. The filtrate was passed through a short column of silica gel in order to remove any polar constituents and the eluate was concentrated under vacuum at 24 8C; 0.580 g, 1.52 mmol, yield was 99%. IR spectrum (cm1): C–H, 3076 (w); C–F, 1283 (m-s), 1262, 1199 (vs), 1161 (s), 1121 (vs); S–F, 909 (s), 875 (vs), 831 (s), 817 (vs), 608 (vs).

GC–MS (m/z, ion, rel. %): 384, 382 (M)+ (31, 31); 257, 255 (M–SF5)+ (10, 9); 207, 205 (M–SF5CF2)+ (97, 100); 126 (C6H4CF2)+ (29); 107 (C6H4CF)+ (4); 89 (SF3)+ (11); 75 (C6H3)+ (6). HRMS: calcd for C8H4F9S81Br 383.90529 found 383.90529. 3.13. 4-Bromo-1-(2-pentafluorosulfanyltetrafluoroethyl) benzene (11) Following the general procedure above, pSF5CF2CFBrC6H4Br (0.99g, 2.23 mmol) dissolved in 5.2 ml CH2Cl2, and 0.65 g (3.34 mmol) AgBF4 were added to a 30 ml Carius tube under an argon atmosphere. The reaction mixture was stirred for 0.4 h at 0 8C and 20.5 h at room temperature; the solid phase was removed by vacuum filtration and washed with small amounts of CH2Cl2. The filtrate was passed through a short column of silica gel in order to remove any polar constituents and the eluate was concentrated under vacuum at 24 8C; 0.834 g, 2.18 mmol, yield was 98%. IR spectrum (cm1): C–H, 3106, 2868 (vw); C–F, 1403 (s), 1275 (vs), 1257 (w-m), 1245 (m), 1201 (vs), 1159 (s); 1147 (m-s), 1117 (vs), 1110 (s); S–F, 909 (s), 877 (vs), 606 (vs). GC–MS (m/z, ion, rel. %): 384, 382 (M)+ (23, 21); 257, 255 (M–SF5)+ (7, 7); 207, 205 (M–SF5CF2)+ (100, 99); 126 (C6H4CF2)+ (30); 107 (C6H4CF)+ (5); 89 (SF3)+ (3); 75 (C6H3)+ (6). HRMS: calcd for C8H4F9S79Br 381.90734 found 381.90709. 3.14. 4-Chloro-1-(2pentafluorosulfanyltetrafluoroethyl)benzene (12) Following the general procedure above, pSF5CF2CFBrC6H4Cl (0.80g, 2.00 mmol) dissolved in 5.2 ml CH2Cl2, and 0.63 g (3.24 mmol) AgBF4 were added to a 30 ml Carius tube under an argon atmosphere. The reaction mixture was stirred for 0.4 h at 0 8C and 20.5 h at room temperature; the solid phase was removed by vacuum filtration and washed with small amounts of CH2Cl2. The filtrate was passed through a short column of silica gel in order to remove any polar constituents and the eluate was concentrated under vacuum at 24 8C; 0.660 g, 1.95 mmol, yield was 97%. IR spectrum (cm1): C–H, 2929 (vw); C–F, 1275 (s), 1245 (w-m), 1200, 1161 (s), 1147 (m-s), 1117 (vs); S–F, 908 (m-s), 877 (vs), 836, 825 (s), 607 (s). GC–MS (m/z, ion, rel. %): 338 (M)+ (20); 211 (M–SF5)+ (9); 192 (M–SF5–F)+ (3); 163, 161 (M–SF5CF2)+ (34, 100); 126 (C6H4CF2)+ (6); 125 (C6H3CF2)+ (5); 107 (C6H4CF)+ (3); 89 (SF3)+ (2); 75 (C6H3)+ (5). HRMS: calcd for C8H4F9S35Cl 337.95785 found 337.95752.

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3.15. 4-Methyl-1-(2-pentafluorosulfanyltetrafluoroethyl) benzene (13) Following the general procedure above, pSF5CF2CFBrC6H4CH3 (0.72 g, 1.90 mmol) dissolved in 5.2 ml CH2Cl2, and 0.47 g (2.41 mmol) AgBF4 were added to a 30 ml Carius tube under an argon atmosphere. The reaction mixture was stirred for 0.66 h at 80 8C; the solid phase was removed by vacuum filtration and washed with small amounts of CH2Cl2. The filtrate was passed through a short column of silica gel in order to remove any polar constituents and the eluate was concentrated under vacuum at 24 8C; 0.230 g, 0.724 mmol, yield was 38% (low yield due to loss in filtration). IR spectrum (cm1): C–H, 3043, 2929 (vw); C–F, 1203, 1189 (s) 1159 (w-m); S–F, 917 (s), 904 (m-s), 877 (vs), 856 (s), 597 (s). GC–MS (m/z, ion, rel. %): 318 (M)+ (20); 191 (M–SF5)+ (8); 172 (M–SF5–F)+ (3); 141 (M–SF5CF2)+ (100); 140 (M– SF5CF2–H)+ (7); 91 (C6H4CH3)+ (7); 89 (SF3)+ (3); 75 (C6H3)+ (1). HRMS: calcd for C9H7F9S 318.01248 found 318.01056. 3.16. 4-Trifluoromethyl-1-(2pentafluorosulfanyltetrafluoroethyl)benzene (14) Following the general procedure above, pSF5CF2CFBrC6H4CF3 (0.36 g, 0.83 mmol) dissolved in 5.2 ml CH2Cl2, and 0.34 g (1.75 mmol) AgBF4 were added to a 30 ml Carius tube under an argon atmosphere. The reaction mixture was stirred for 28 h at 100 8C; the solid phase was removed by vacuum filtration and washed with small amounts of CH2Cl2. The filtrate was passed through a short column of silica gel in order to remove any polar constituents and the eluate was concentrated under vacuum at 24 8C; 0.298 g, 0.801 mmol, yield was 96%. IR spectrum (cm1): C–H, 3059, 2989, 2933 (vw); C–F, 1328 (vs), 1277 (m), 1203, 1178 (s) 1143, 1120, 1112 (vs); S–F, 911 (m), 883 (vs), 849 (s), 597 (s). GC–MS (m/z, ion, rel. %): 372 (M)+ (8); 353 (M–F)+ (8); 245 (M–SF5)+ (11); 226 (M–SF5–F)+ (2); 195 (M–SF5CF2)+ (100); 176 (M–SF5CF3)+ (5); 145 (C6H4CF3)+ (13); 125 (C6H3CF2)+ (3); 107 (C6H4CF)+ (0.8); 89 (SF3)+ (2); 75 (C6H3)+ (2). HRMS: calcd for C9H4F12S 371.98421 found 371.98416. 3.17. 4-Nitro-1-(2pentafluorosulfanyltetrafluoroethyl)benzene (15) Following the general procedure above, p-SF5CF2CFBrC6H4NO2 (0.72 g, 1.76 mmol) dissolved in 5.2 ml CH2Cl2, and 1.01 g (5.19 mmol) AgBF4 were added to a 30 ml Carius tube under an argon atmosphere. The reaction mixture was stirred for 46 h at 138 8C (boiling xylene); the solid phase was removed by vacuum filtration and washed with small amounts of CH2Cl2. The filtrate was passed

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through a short column of silica gel in order to remove any polar constituents and the eluate was concentrated under vacuum at 24 8C; 0.410 g, 1.18 mmol, yield was 67%. IR spectrum (cm1): C–H, 3123, 3091, 3064, 2879 (vw); C–F, 1355, 1275 (s), 1244 (m), 1201, 1166 (s), 1122 (vs); S– F, 912 (s), 880, 860 (vs), 607 (s). GC–MS (m/z, ion, rel. %): 349 (M)+ (14); 333 (M–O)+ (2); 303 (M–NO2)+ (4); 222 (M–SF5)+ (8); 176 (M–NO2– SF5)+ (15); 172 (CF2C6H4NO2)+ (100); 126 (C6H4CF2)+ (27); 89 (SF3)+ (4); 75 (C6H3)+ (6). HRMS: calcd for C8H4F9SNO2 348.98190 found 348.98096. 3.18. 2-Fluoro-1-(2pentafluorosulfanyltetrafluoroethyl)benzene (16) Following the general procedure above, oSF5CF2CFBrC6H4F (0.98 g, 2.56 mmol) dissolved in 5.2 ml CH2Cl2, and 0.89 g (4.57 mmol) AgBF4 were added to a 30 ml Carius tube under an argon atmosphere. The reaction mixture was stirred for 22.5 h at 0 8C; the solid phase was removed by vacuum filtration and washed with small amounts of CH2Cl2. The filtrate was passed through a short column of silica gel in order to remove any polar constituents and the eluate was concentrated under vacuum at 24 8C; 0.770 g. 2.39 mmol, yield was 93%. IR spectrum (cm1): C–H, 3097, 3055, 2961, 2919 (vw); C–F, 1296 (vs), 1254 (s), 1235, 1201 (vs), 1167, 1159 (s), 1126, 1109 (vs); S–F, 909 (s), 878, 833 (vs), 607 (vs). GC–MS (m/z, ion, rel. %): 322 (M)+ (18); 195 (M–SF5)+ (10); 176 (M–SF5-F)+ (3); 145 (M–SF5CF2)+ (100); 125 (C6H3CF2)+ (4); 89 (SF3)+ (2); 75 (C6H3)+ (4). HRMS: calcd for C8H4F10S 321.98740 found 321.98634. 3.19. 2-Trifluoromethyl-1-(2pentafluorosulfanyltetrafluoroethyl)benzene (17) Following the general procedure above, oSF5CF2CFBrC6H4CF3 (1.02 g, 2.36 mmol) dissolved in 5.2 ml CH2Cl2, and 0.67 g (3.44 mmol) AgBF4 were added to a 30 ml Carius tube under an argon atmosphere. The reaction mixture was stirred for 3 h at 100 8C; the solid phase was removed by vacuum filtration and washed with small amounts of CH2Cl2. The filtrate was passed through a short column of silica gel in order to remove any polar constituents and the eluate was concentrated under vacuum at 24 8C; 0.8652 g, 2.32 mmol yield was 99%. IR spectrum (cm1): C–H, 3059 (v-m), 2969 (vw); C–F, 1310 (s), 1296 (s), 1260, 1207 (m), 1175, 1151 (s), 1121 (m), 1104 (s); S–F, 912 (w-m), 878 (vs), 607 (m). GC–MS (m/z, ion, rel. %): 372 (M)+ (4); 245 (M–SF5)+ (12); 226 (M–SF5–F)+ (2); 195 (M–SF5CF2)+ (100); 176 (M–SF5CF3)+ (3); 145 (C6H4CF3)+ (10); 125 (C6H3CF2)+ (3); 107 (C6H4CF)+ (1); 89 (SF3)+ (2). HRMS: calcd for C9H4F12S 371.98421 found 371.98490.

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3.20. 2-Isopropyl-1-(2pentafluorosulfanyltetrafluoroethyl)benzene (18)

3.22. Difluoro-SF5-methylphenyl ketone, SF5CF2C(O)C6H5 (20)

Following the general procedure above, o-SF5CF2 CFBrC6H4CH(CH3)2 (1.00 g, 2.46 mmol) dissolved in 5.2 ml CH2Cl2, and 0.81 g (4.17 mmol) AgBF4 were added to a 30 ml Carius tube under an argon atmosphere. The reaction mixture was stirred for 4.5 h at 78 8C warmed to room temperature; the solid phase was removed by vacuum filtration and washed with small amounts of CH2Cl2. The filtrate was passed through a short column of silica gel in order to remove any polar constituents and the eluate was concentrated under vacuum at 24 8C; 0.756 g, 2.18 mmol, yield was 89%. IR spectrum (cm1): C–H, 3079 (vw-w), 3022 (w), 2970 (m), 2936, 2876 (w); C–F, 1245 (s), 1198 (vs), 1170 (s), 1142 (vs-s), 1118 (vs); S–F, 879 (vs), 607 (s-vs). GC–MS (m/z, ion, rel. %): 346 (M)+ (100); 331 (M– CH3)+ (89); 223 (C10H7F5)+ (51); 203 (M–SF5–H–CH3)+ (31); 183 (M–SF6–CH5)+ (95); 169 (M–SF5CF2)+, (27); 153 (M–SF5CF2–CH4)+ (43); 119 (M–SF5CF2CF2)+ (9); 104 (M–SF5CF2–CH3)+ (7); 89 (SF3)+ (7); 75 (C6H3)+ (4). HRMS: calcd for C11H11F9S 346.04378 found 346.04361.

v-SF5-perfluoroethylbenzene (2.13 g, 7.0 mmol) and 20 ml of BF32CH3COOH were heated in a 75-ml Carius tube with stirring in such a manner that the oil of the heating bath was the same as the liquid level inside the Carius tube. At 135 8C there was virtually no reaction in 2 h, but at 155– 160 8C only a trace of starting material remained after 5 h. There was very little if any pressure in the reaction vessel after cooling. Three products were present; a trace quantity with a mass of 324 was detected in the GC–MS. Pouring the mixture into 100 ml of cold water and extracting with ether (3 ml 20 ml), removing the ether of the united fractions in the cold under vacuum, the mixture was separated by chromatography on silica gel (25 g) with a 5:95 (by volume) mixture of CH2Cl2 and hexane; first fraction, yellowish oil, 0.71 g; second fraction 0.10 g, a volatile oil. A mixed fraction was discarded. Washing out the column with acetone resulted in about 0.2 g material that was not examined further. First fraction, SF5CF2C(O)C6H5, 0.71 g, 2.52 mmol, yield was 36%. IR spectrum (cm1): C–H, 3075 (w); C O, 1715 (s-vs); C–F, 1283 (m), 1201 (s-vs), 1187 (sh, s-vs), 1175 (vs); S–F, 915 (s), 866 (vs), 610, (w-m).

3.21. 4-Nitro-1-(1-bromotetrafluoroethyl)benzene (19) p-NO2–C6H4CFBrCF2SF5 (1.01 g, 2.46 mmol), AgF (0.50 g, 3.94 mmol) and 3 ml of CH3CN are stirred in a 75 ml Carius tube for 10 days at ambient temperature. Complete conversion of the starting compound had taken place after this time ( 95% after 7 days), as determined by GC–MS. The product was isolated by filtration, removal of the solid residue by washing with ether, evaporation of the filtrate (rotary evaporator) and passing the crude product through a short column of Kieselgel in methylene chloride. After removal of the solvent a yellow oil was present, 0.73 g, 2.42 mmol, yield was 98%. A GC–MS spectrum showed the product to be pure. 1

H NMR-spectrum (CDCl3): d2,6 = 7.81 ppm, d, 2H; d3,5 = 8.32, d, 2H, J = 8.9 (av.). 19 F NMR-spectrum (CDCl3), X3Y-type: dX = 82.2 ppm, d, 3F; dY = 133.3, q, 1F; JXY = 9.7 Hz. IR spectrum(cm1): Neat sample on NaCl: C–H, 3120 (w), 3089 (w-vw), 3060 (vw), 2870 (vw); asym/sym NO2, 1533 (vs) 1351 (vs); C–F, 1351 (vs) 1308 1296 (m-s) 1279 (s-vs) 1209 (vs) 1192 (vs). GC–MS: (m/z, ion, rel.%): 301, 303 (M)+ (1, 1); 222 (M– Br)+ (100); 176 (C6H4CFCF3)+ (18); 164 (C8H3FNO)+ (13); 126(C4H2F4)+ (14); 125 (C4H3F4)+ (10); 107 (C6H4CF)+ (10); 81 (C2F3)+ (4); 69 (CF3)+ (2); 57 (C3H2F)+ (2); 46 (NO2)+ (0.7); 30 (NO)+ (9). HRMS: calcd for C8H4F4O279BrN 300.93615 found 300.93718.

1

H NMR spectrum (CDCl3): d2,6 = 8.09 ppm, d, J = 7.93 Hz, 3H; d3,5 = 7.55 ppm, t, J = 7.63 ( 1/2(7.92 + 7.32)), 2H; d4 = 7.71 ppm, t, J = 7.32, 1H. 19 F NMR-spectrum (CDCl3), AB4X2-type: dA = 67.8 ppm, 9 lines, each split into a triplet, 1F; dB = 43.4 ppm, skewed d, 4F; dX2 = 88.6, d-p, 2F. JAB = 147 Hz, JAX2 4.5 Hz (measured in A), 4.1 (measured in X2), JB4X2 = 11.3 Hz. GC–MS (m/z, ion, rel.%): Rt = 7.7 min.: 282 (M)+ (1); 127 (SF5)+ (3); 105 (C6H5CO)+ (100); 89 (SF3)+ (7); 77 (C6H5)+ (57); 51 (C4H3)+ (14). HRMS: calcd for C8H5F7SO 281.99493 found 281.99534. Second fraction, CF3C(O)C6H5, 0.10 g, 0.544 mmol, yield was 8%. GC–MS: (m/z, ion, rel. %): Rt = 5.09 min.: 174 (M)+ (11); 105 (C6H5CO)+ (100); 77 (C6H5)+ (82); 51 (C4H3)+ (17); 50 (C4H2)+ (10). An authentic commercial sample showed an identical retention time and fragmentation. 3.23. 3-[2-(1,3,3-trimethyl-2indolinylidene)ethylidenamino]-1-[2pentafluorosulfanyltetrafluoroethyl] benzene (21) A 100-ml round bottom flask, equipped with a Teflon coated stirring bar, was charged with 0.4086 g (1.276 mmol) of m-SF5(CF2)2C6H4NH2, 0.2568 g (1.276 mmol) of Fischer’s aldehyde and 4.0 ml of 100% ethanol. The mixture was heated to 50 8C with stirring for 15 min. Preheated

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water (4.0 ml, 50 8C) was then added dropwise, followed by the dropwise addition of 1.2 ml of 37% HCl and 2.5 ml of water. The mixture was stirred overnight at room temperature. The HCl and solvents were removed via vacuum distillation. The remaining red-brown solid was then heated to 100 8C under vacuum in order to remove water and HCl; a dark red-brown liquid solidified on cooling. The solid was recrystallized from 95% ethanol and gave a reddish solid product (0.251 g, 0.498 mmol, mp 195– 200 8C), 39% yield. The IR spectrum (cm1): N–H, 3404 (w, b); C–H, 3067 (w), 2975 (w), 2873 (w), 2814 (m), 2803 (w); C N or N–H, 1643 (vs), 1590 (s), 1560 (vs), 1485 (s); C–F, 1360 (ms), 1328 (s), 1305 (s), 1278 (s), 1235 (s), 1204 (s), 1154 (ms), 1116 (vs); S–F, 881 (vs), 609 (m). The 19F NMR spectrum (CDCl3) of FA–SF4B–CF2aCF2b– C6H4X exhibited the following peaks: dA 67.5 ppm (nine line pattern, 1F); dB 46.2 ppm (d, 4F); da 95.0 ppm (p, d, 2F), db 113.1 (p, 2F). GC–MS (m/z, ion, rel. %): 502 (M)+ (29), 487 (M–CH3)+, (5); 375 (M–SF5)+, (5); 309 (SF5CF2CF2C6H4)+, (8); 275 (SF5CF2CF2)+, (3); 184 (M–SF5(CF2)2C6H4N)+, (40); 169 (M–SF5(CF2)2C6H4NCH)+, (8); 154 (M–SF5(CF2)2C6H4NCHCH)+, (3). HRMS: calcd for C21H19F9SN2 502.11252; found 502.11168. 3.24. 3,5-Dinitro-1-(2pentafluorosulfanyltetrafluoroethyl)benzene (22) A 100-ml round bottom flask, equipped with a stir bar, was charge with 25 ml of conc. H2SO4 and 15 ml of 90% HNO3. To this mixture, 4.0 g (13.15 mmol) of SF5(CF2)2 C6H5 was added dropwise. The flask was placed into a sand bath and a condenser was attached. The mixture was stirred at room temperature for 2 h and at 140 8C for 3 days. The mixture was cooled to room temperature and carefully poured into 60 ml of water/ice solution. The organic phase was extracted with 4 ml 50 ml of CH2Cl2, and dried over anhydrous MgSO4. The extracted product was nitrated two more times after which TLC showed essentially no starting SF5(CF2)2C6H5. The dried organic phase was extracted with 3 ml 50 ml of heptane, washed with 3 ml 20 ml of water and dried over MgSO4. The heptane was removed via vacuum rotary evaporation. A pure white solid, 3,5-SF5(CF2)2C6H3(NO2)2, 0.96 g (2.43 mmol) was obtained with a mp of 67 8C; yield 18.5%. The IR spectrum (cm1): C–H, 3111–2888 (w-vw); N–O asym/sym, 1563 (m), 1350 (vs); C–F, 1329 (m), 1281 (m), 1208 (m), 1175 (ms), 1145 (m), 1125 (s); S–F, 921 (ms), 911 (m), 877 (vs), 861 (s), 609 (wm). The 19F NMR spectrum (CDCl3) of FA–SF4B–CF2aCF2b– C6H3(NO2)2 exhibited the following peaks: dA 65.4 ppm (nine line spectrum, 1F), dB 46.1 ppm (d, 4F), da 95.7 ppm (p, d, 2F), db 113.1 ppm (p, 2F). The 1H NMR spectrum

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(CDCl3, 500 MHz): d2 = d6 9.29 ppm (s, 2H); d4 8.81 ppm (s, 1H). GC–MS (m/z, ion, rel. %): 394 (M+), (2); 301 (M–N2O4– + H) (11); 267 (M–SF5)+, (16); 217 (M–SF5–CF2)+, (100); 171 (M–SF5–CF2–NO2)+, (16); 125 (M–SF5–CF2–N2O4)+, (22). HRMS: calcd for C8H3F9SN2O4 393.96698, found 393.96752. 3.25. 3,5-Diamino-1-(2pentafluorosulfanyltetrafluoroethyl)benzene (23) A 100 ml three neck round bottom flask equipped with a Teflon-coated stirring bar and a condenser was charged with 0.50 g (1.27 mmol) of 3,5-SF5(CF2)2C6H3(NO2)2, 15 ml of ethanol and 2.5 ml of conc. HCl. The mixture was heated to reflux, then 0.85 g (15.22 mmol) of Fe powder was added in small increments over a period of 30 min. The green-yellow mixture was stirred for 2 h at reflux temperature. The excess Fe was removed by vacuum filtration. The reaction mixture was poured into 50 ml of ice water and neutralized with 10% NaOH solution. The organic phase was extracted 4 5 ml of diethyl ether, washed with 100 ml of water and dried over anhydrous MgSO4. The ether was removed via rotary evaporation; the remaining product was separated by column chromatography using CH2Cl2 as the eluant. The CH2Cl2 was removed via rotary evaporation and via pumping on through a trap connected to a vacuum line. The product, 3,5-SF5(CF2)2C6H3(NH2)2 was obtained as a white solid, mp 85 8C; 0.203 g, 0.609 mmol, yield was 48%. IR spectrum (cm1): N–H, 3486 (wm), 3356 (ms), 3224 (wm); C–F, 1370 (wm), 1341 (wm), 1207 (s), 1150 (s), 1110 (s); S–F, 903 (wm), 871 (vs), 858 (vs), 597 (wm). The 19F NMR spectrum (CDCl3) FA–SF4B–CF2aCF2b– C6H3(NH2)2 2 exhibited the following peaks: dA 67.5 ppm (nine line spectrum, 1F), dB 45.2 ppm (d, 4F), da 95.2 ppm (p, d, 2F), db 114.2 ppm (p, 2F). The 1H NMR spectrum (CDCl3, 500 MHz): d2 = d6 6.29 ppm (s, 2H); d4 6.14 ppm (s, 1H); d(NH2) 3.72 ppm (s, 4H). GC–MS (m/z, ion, rel. %): 334 (M+), (80); 207 (M–SF5)+, (33); 187 (M–SF5—H)+, (10); 157 (M–SF5–CF2)+, (100); 129 (C8N2H5)+, (13); 89 (SF3)+, (3); 75 (C6H3)+, (12). HRMS: calcd for C8H7F9SN2 334.01938 found 334.01862. 3.26. SF5CF2CF2-polyimide (24) A 25-ml round bottom flask, equipped with a Teflon stirring bar, was charged with 0.076 g (0.227 mmol) of 3,5SF5(CF2)2C6H3(NH2)2, 1.0 g (11.5 mmol) of N,N-dimethylacetamide and 0.100 g (0.225 mmol) of 4,40 -hexafluoro(isopropylidene) diphthalic anhydride (6-FDA). The mixture was stirred at room temperature for 4 days. The color of the mixture (brownish solution) did not change with stirring at room temperature but the solution became more viscous. The polymer mixture was cured at 100–180 8C for 4 h. The

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resulting solid, 0.170 g, darkened but did not melt up to 360 8C. The polymer is soluble in acetone. IR spectrum (cm1): N–H, 3489 (w, b); C–H, 2957, 2931, 2862 (w, b); C O 1730 (vs); C–F, 1356 (m), 1258 (s, sh at 1246), 1222 (s), 1144 (ms), 1157 (sh, w), 1120 (m); S–F, 882 (vs), 860 (s), 610 (w).

Acknowledgments We (PSU, UI) are grateful to the National Science Foundation (CHE-9904316 and CHE-9820769) for support of this work. We wish to thank Jeff Morre´ (Mass Spectrometry Laboratory, Oregon State University, Corvallis, Oregon) for obtaining the high resolution mass spectra (HRMS).

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