Nucleophilic Fluorination of Glyoxal Hydrates
J . Org. Chem., Vol. 67, No. 6, 2002 1923
δ -109.54 (m, 2F), -110.78 (ABX pattern, 4F, J F-F ) 268 Hz),
-145.43 (doublet of multiplets, 2F, J ) 60 Hz); 1H NMR
(CDCl3) δ 5.66 (doublet of multiplets, 2H, J ) 60 Hz), 7.0 (m,
4H), 7.32 (m, 4H); 13C NMR (CDCl3) δ 103.4 (doublet of triplets,
J ) 237.5, 41.5 Hz), 115.3, 115.4, 116.0 (triplet of doublets,
of multiplets, 1F, J ) 62 Hz), -146.40 (doublet of multiplet,
1F, J ) 62 Hz); 1H NMR (CDCl3) δ 3.78 (s, 3H), 5.57 (doublet
of multiplets, 1H, J ) 62 Hz), 5.77 (doublet of multiplets, 1H,
J ) 62 Hz), 6.84 (d, 2H, J ) 8.9 Hz), 6.99 (m, 1H), 7.16 (m,
1H), 7.30 (d, 2H, J ) 8.9 Hz), 7.41 (dd, 1H, J ) 1.2, 5 Hz); MS
(EI) m/z (species, rel int) 370 (M+, 20), 351 (M+ - F, 1), 332
(M+ - 2F, 1), 157 (MeOC6H4CF2+, 100), 133 (C5H3F2+, 13).
Anal. Calcd for C15H12F6O2S: C, 48.65; H, 3.27. Found: 48.47;
H, 3.13.
J ) 246.0, 30.0 Hz), 128.8 (t, J ) 9.0 Hz); MS (EI) m/z (species,
rel int) 370 (M+, 7), 177 (FC6H4CF2CFH+, 7), 145 (FC6H4CF2
,
+
100), 127 (FC6H4CF+ + H, 27), 95 (FC6H4+, 6); HRMS calcd
for C16H10F8O 370.0604, found 370.0581.
Bis(2-ph en yl-1,2,2-tr iflu or oeth yl)eth er (m eso) (7e): yield
45%; IR (KBr film) 2945, 1604, 1595, 1450, 1409, 1346, 1300,
2-Th ien yl-2′-(4-m eth ylp h en yl)bis(1,2,2-tr iflu or oeth yl)-
eth er (9i): yield 23%; viscous liquid; IR (KBr pellet): 1612,
1519, 1430, 1300, 1288, 1250, 1209, 1175, 1091, 1031, 988, 930,
1278, 1137, 1060, 983, 847, 761, 698 cm-1 19F NMR (CDCl3)
;
713 cm-1 19F NMR (CDCl3) δ -101.00 (s, 2F), -111.25 (ABX
;
δ -110.99 (ABX pattern, 4F, J F-F ) 268 Hz), -138.31 (doublet
of multiplets, 2F, J ) 59 Hz); 1H NMR (CDCl3) δ 5.63 (doublet
of multiplets, 2H, J ) 59 Hz), 7.2-7.5 (m, 10H); 13C NMR
(CDCl3) δ 107.1 (doublet of triplets, J ) 236.8, 41.1 Hz), 116.
8 (triplet of doublets, J ) 246.2, 30 Hz), 126.4 (t, J ) 3.8 Hz),
128.2, 130.3 (t, J ) 23.2 Hz), 130.9; MS (EI) m/z (species, rel
int) 334 (M+, 10), 159 (PhCF2CFH+, 12), 127 (PhCF2, 100), 109
(PhCHF+, 27), 77 (Ph+, 10); HRMS calcd for C16H12F6O
334.0793, found 334.0786.
pattern, 2F, J F-F ) 288 Hz), -145.85 (doublet of multiplets,
1F, J ) 60 Hz), -146.47 (doublet of multiplet, 1F, J ) 60 Hz);
1H NMR (CDCl3) δ 2.34 (s, 3H), 5.56 (doublet of multiplets,
1H, J ) 60 Hz), 5.79 (doublet of multiplets, 1H, J ) 60 Hz),
6.80-7.55 (m, 7H); MS (EI) m/z (species, rel int) 354 (M+, 5),
165 (C4H3SCF2CFH, 1), 141 (MeC6H4CF2+, 100), 91 (MeC6H4,
13). 83 (C4H3S + H, 6). Anal. Calcd for C15H12F6OS: C, 50.84;
H, 3.42. Found: 50.50; H, 3.60
Bis(2-p h en yl-1,2,2-tr iflu or oeth yl)eth er (r a cem ic) (8e):
yield 46%; IR (KBr film) 2963, 104, 1595, 1445, 109, 1368,
2-Met h yl-2′-(4-m et h oxyp h en yl)b is(1,2,2-t r iflu or oet h -
yl)eth er (9j): yield 18%; viscous liquid; IR (KBr pellet) 2950,
1296, 1278, 1133, 1060, 983, 843, 761, 689 cm-1 19F NMR
;
1615, 1512, 1438, 1290, 1250, 1200, 1190, 1039, 976, 722 cm-1
;
(CDCl3) δ -111.43 (ABX pattern, 4F, J F-F ) 268 Hz), -145.73
(doublet of multiplets, 2F, J ) 60 Hz); 1H NMR (CDCl3) δ 5.65
(doublet of multiplets, 2H, J ) 60 Hz), 7.0-7.5 (m, 10H); 13C
NMR (CDCl3) δ 103.5 (doublet of triplets, J ) 236.6, 42 Hz),
116.5 (triplet of doublets, J ) 246.1, 30.0 Hz), 126.5 (t, J )
6.3, Hz), 127.9, 130.3 (t, J ) 23.2 Hz), 130.8; MS (EI) m/z
(species, rel int) 334 (M+, 9), 159 (PhCF2CFH+, 10), 127
(PhCF2+, 100), 109 (PhCHF+, 26), 77 (Ph+, 10); HRMS calcd
for C16H12F6O 334.0793, found 334.0791.
19F NMR (CDCl3) δ -107.00 (m, 2F), -110.40 (ABX pattern,
2F, J F-F ) 278 Hz), -139.50 (doublet of multiplets, 1F, J )
58 Hz), -145.88 (doublet of multiplet, 1F, J ) 60 Hz); 1H NMR
(CDCl3) δ 1.50 (m, 3H), 3.34 (s, 3H), 5.54 (m, 1H), 5.65 (m,
1H), 7.37 (d, 2H, J ) 8.8 Hz), 7.93 (d, 2H, J ) 8.8 Hz); MS
(EI) m/z (species, rel int) 302 (M+, 5), 283 (M+ - F, 1), 263
[M+ - (HF + H), 1], 189 (MeOC6H4CF2CF2H+, 4), 157
(MeOC6H4CF2+, 60), 59 (C2FO+, 100). Anal. Calcd for C12H12
F6O2: C, 47.69; H, 4.00. Found: 47.57; H, 4.12.
-
Bis(2-th ien yl-1,2,2-tr iflu or oeth yl)eth er (m eso) (7f): yield
44%; IR (KBr film) 2950, 1535, 1433, 1355, 1283, 1257, 1134,
3-Oxo-3′,2,2′,3,3′-Tetr a flu or oh yd r in d a n tin (12): yield
65%; mp 176 °C; IR (KBr pellet) 1750, 1600, 1465, 1339, 1273,
1103, 1049, 952, 847, 826, 714 cm-1 19F NMR (CDCl3) δ
;
1190, 1087, 1028, 993, 933, 894, 837, 771, 710 cm-1 19F NMR
;
-100.30 (ABX pattern, 4F, J F-F ) 273 Hz), -137.70 (doublet
of multiplets, 2F, J ) 60 Hz); 1H NMR (CDCl3) δ 5.66 (doublet
of multiplets, 2H, J ) 60 Hz), 7.01 (m, 2H), 7.26 (m, 2H), 7.42
(doublet of doublets, 2H, J ) 5, 1.2 Hz); 13C NMR (CDCl3) δ
106.6 (doublet of triplets, J ) 237.5, 41 Hz), 115.06 (triplet of
doublets, J ) 245, 31.5 Hz), 127.06, 128.97, 129.16 (t, J ) 6
Hz), 131.1 (t, J ) 29 Hz); MS (EI) m/z (species, rel int) 346
(M+, 23), 133 (SCHdCHCHdCCF2+, 100), 165 (SCHdCHCHd
CCF2CFH+, 8), 146 (SCHdCHCHdCCF2CH+, 8), 115 (SCHd
CHCHdCCF + H, 18); HRMS calcd for C12H8F6OS2 345.9921,
found 345.9917.
(CDCl3) δ -111.48 (s, 1F), -181.09 (s, 1F); 1H NMR (CDCl3) δ
7.77 (m, 2H), 7.95(m, 6H); 13C NMR (CDCl3) δ 96.0 (doublet of
doublet, J ) 219.5, 31.5 Hz), 97.7 (doublet of doublet, J )
219.5, 31.5 Hz), 115.9, 117.9, 124.8, 133.3, 138.0, 143.9, 186.29
(doublet, J ) 8.5 Hz), 186.39 (doublet, 8.5 Hz); MS (EI) m/z
(species, rel int) 348 (M+, 44), 329 (M+ - F, 1), 272 [M+
-
(3F + HF), 1], 197 (M+ - C8H4FO2, 1), 151 (C8H4FO2+, 100).
Anal. Calcd for C18H8F4O3: C, 62.08; H, 2.32. Found: C, 61.89;
H, 2.12. X-ray crystallographic data: crystal system, mono-
clinic; space group, C2/c; unit cell dimensions, a ) 15.338(2)
Å, b ) 7.7419(12) Å, c ) 14.017(2) Å, R ) 90°, â ) 118.66(3)°,
λ ) 90°; Z ) 4; F(000) ) 704; crystal size ) 0.22 × 0.10 × 0.08
mm3; R1 (all data) ) 0.1201, wR2 ) 0.1105. Selected bond
lengths (Å): F(1)-C(8) ) 1.359(3), F(1)-C(9) ) 1.380(3), O(2)-
C(8) ) 1.392(3), C(8)-C(5) ) 1.533(4). Selected bond angles
(deg): C(8)-O(2)-C(831) ) 113.1(3), O(1)-C(1)-C(9) ) 123.4-
(3), C(2)-C(1)-C(9) ) 106.6(3), F(1)-C(8)-O(2) ) 107.2(2),
O(2)-C(8)-C(7) ) 113.8(2), F(1)-C(8)-C(9) ) 111.7(3), F(2)-
C(9)-C(1) ) 110.7(2).
Bis(2-th ien yl-1,2,2-tr iflu or oeth yl)eth er (r a cem ic) (8f):
yield 46%; IR (KBr film) 2962, 1535, 1433, 1281, 1132, 1094,
1045, 950, 823, 712 cm-1 19F NMR (CDCl3) δ -100.74 (ABX
;
pattern, 4F, J F-F ) 273 Hz), -145.73 (doublet of multiplets,
1
2F, J ) 60 Hz); H NMR (CDCl3) δ 5.73 (doublet of triplets,
2H, J ) 60 Hz), 7.00 (m, 2H), 7.22 (m, 2H), 7.42 (dd, 2H, J )
5, 1.2 Hz); 13C NMR (CDCl3) δ 103.1 (doublet of triplets, J )
237.3, 41 Hz), 115.0 (triplet of doublets, J ) 245, 30 Hz), 127.0,
128.97, 129.1 (t, J ) 6 Hz), 131.3 (t, J ) 29 Hz); MS (EI) m/z
+
(species, rel int) 346 (M+, 25), 133 (SCHdCHCHdC-CF2
,
1,1,1,5,5,5-Hexa flu or o-4-bis(m eth oxyeth yl)a m in o-3-en -
100), 165 (SCHdCHCHdCCF2CFH+, 7), 146 (SCHdCHCHd
CCF2CH+, 6), 115 (SCHdCHCHdCCF + H, 20). Anal. Calcd
for C12H8F6OS2: C, 41.62; H, 2.33. Found: 41.71; H, 2.50.
Bis(2-m eth yl-1,2,2-tr iflu or oeth yl)eth er (m eso) (7g): 19F
2-on e (13): yield 60%; viscous liquid; IR (KBr pellet) 2895,
1670, 1559, 1455, 1254, 1191, 1139, 1057, 794, 737 cm-1 19F
;
NMR (CDCl3) δ -63.88 (s, 3F), -77.22 (s, 3F); 1H NMR (CDCl3)
δ 3.24 (s, 6H), 3.42 (t, 4H, J ) 5.2 Hz), 3.61 (t, 4H, J ) 5.2
Hz), 5.90 (s, 1H); MS (EI) m/z (species, rel int) 324 (M+ + H,
1), 278 (M+ - CH3OCH2, 52), 59 (CH3OCH2CH2+, 100), 58
(CH3OCH2CH+, 44), 45 (CH3OCH2+, 19). Anal. Calcd for
1
NMR (CDCl3) δ -108.45 (m, 4F), -121.22 (m, 2F); H NMR
(CDCl3) δ 1.56 (m, 6H), 5.68 (m, 2H,); MS (EI) m/z (species,
rel int) 210 (M+, 1), 194 [M+ - (CH3 + H), 1], 97 (CH3CF2-
CFH+, 100).
C
11H15F6NO3: C, 40.87; H, 4.68. Found: C, 40.72; H, 4.80.
Bis(2-m eth yl-1,2,2-tr iflu or oeth yl)eth er (r a cem ic) (8g):
19F NMR (CDCl3) δ -110.26 (m, 4F), -131.72 (m, 2F); 1H NMR
(CDCl3) δ 1.60 (m, 6H), 5.85 (m, 2H); MS (EI) m/z (species, rel
int) 210 (M+, 1), 194 [M+ - (CH3 + H), 2], 97 (CH3CF2CFH+,
100).
Rea ction of Glyoxa l Hyd r a tes w ith Deoxoflu or in
Dilu te Solu tion s. An arylglyoxal hydrate (1 mmol) was
dissolved in dichloromethane (200 mL), and Deoxofluor (2.5
mmol) was added neat dropwise under vigorous stirring. The
reaction mixture was stirred at 25 °C for 4 h. The reaction
was quenched with aqueous NaHCO3 solution. The dichlo-
romethane layer was separated, dried over anhydrous MgSO4,
and filtered. The product was purified by flash chromatogra-
phy using dichloromethane and pentane (1:1) solution as the
solvent.
2-Th ien yl-2′-(4-m eth oxyp h en yl)bis(1,2,2-tr iflu or oeth -
yl)eth er (9h ): yield 26%; viscous liquid; IR (KBr pellet): 1616,
1517, 1434, 1308, 1280, 1257, 1209, 1178, 1134, 1091, 1032,
983, 937, 716 cm-1 19F NMR (CDCl3) δ -101.01 (m, 2F),
;
-110.43 (ABX pattern, 2F, J F-F ) 290 Hz), -145.68 (doublet