Fluoride-catalyzed nucleophilic perfluoroalkylations of acetylenic ketones or aldehydes

Article abstract of DOI:10.1135/cccc20021296

Reactions of 4-phenylbut-3-yn-2-one (1a) and phenylpropynal (1b) with trimethyl(perfluoroalkyl)silanes (Me₃SiR_f) (R_f = CF₃, C₂F₅, n-C₆F₁₃, n-C₇F₁₅

Full text of DOI:10.1135/cccc20021296

1296
Manandhar, Singh, Shreeve:
FLUORIDE-CATALYZED NUCLEOPHILIC PERFLUOROALKYLATIONS
OF ACETYLENIC KETONES OR ALDEHYDES
1
2
3,
Sudha MANANDHAR , Rajendra P. SINGH and Jean’ne M. SHREEVE *
Department of Chemistry, University of Idaho, Moscow, ID 83844-2343, U.S.A.;
1
2
3
e-mail: sudhaneeraj@hotmail.com, rsingh@uidaho.edu, jshreeve@uidaho.edu
Received April 15, 2002
Accepted Jun e 5, 2002
Dedicated to the memory of Professor MiloŠ Hudlický – one of fluorine chemistry’s finest gentlemen.
Reaction s of 4-ph en ylbut-3-yn -2-on e (1a ) an d ph en ylpropyn al (1b ) with trim eth yl-
(perfluoroalkyl)silan es (Me3SiRf) (Rf = CF3, C2F5, n -C6F13, n -C7F15, n -C8F17) in th e presen ce
of catalytic am oun ts of cesium fluoride (CsF) h ave been studied. Com poun ds 1a, 1b were re-
acted with 0.5 equivalen t excess of Me3SiRf in eth ylen e glycol dim eth yl eth er (m on oglym e)
at 25 °C for Rf = CF3, C2F5 an d at 50 °C for Rf = n -C6F13, n -C7F15, n -C8F17 to give th e corre-
spon din g perfluoroalkylated alcoh ols in good yields after acid h ydrolysis. Th e n ew com -
poun ds were ch aracterized by IR, NMR (1H, 19F, 13C), MS an d elem en tal an alysis. In th ese
reaction s, tetrabutylam m on ium fluoride (TBAF) is also effective as th e fluoride catalyst. Th e
alcoh ols with CF3 or C2F5 are viscous liquids wh ereas th ose with n -C6F13, n -C7F15 or n -C8F17
are solids. Th ey are soluble in com m on organ ic solven ts an d stable to air an d m oisture.
Keyw ord s: Fluoride; Nucleoph ilic addition s; Perfluoroakylation s; Keton es; Aldeh ydes; Al-
kyn es; Trim eth yl(perfluoroalkyl)silan es.
Th e perfluoroalkyl group is a h igh ly im portan t substituen t in th e field of
organ ofluorin e com poun ds. Th e in troduction of a fluorin e atom or fluori-
n ated group in to an organ ic com poun d can brin g about som e rem arkable
ch an ges in th e ph ysical, ch em ical an d biological properties th at result in
n ew com poun ds/m aterials suitable for diverse application s in th e areas of
m aterials scien ce, agroch em istry an d in dustry1–5. Th e powerful electron -
with drawin g ability an d relatively sm all size of th e fluorin e atom lead to
sign ifican t ch an ges in th e ch em istry of substituted com poun ds wh en com -
pared with th eir n on fluorin ated an alogues. Th e in fluen ce of a perfluoro-
alkyl group in biologically active m olecules is often associated with th e
in creased lipoph ilicity6 th at gives active ph arm aceutical an d agroch em ical
com poun ds with im proved tran sport ch aracteristics. Am on g oth er th in gs,
th is property facilitates lower dose rates. Wh ile oth er m eth ods h ave been
Collect. Czech. Chem. Commun. (Vol. 67) (2002)
doi:10.1135/cccc20021296

Perfluoroalkylations of Acetylenic Ketones or Aldehydes
1297
developed for th e in troduction of perfluoroalkyl groups in to organ ic com -
poun ds7, th e utilization of trim eth yl(perfluoroalkyl)silan es (Me3SiRf) as
n ucleoph ilic perfluoroalkylatin g reagen t is rapidly becom in g th e m eth od of
ch oice8. Recen tly, we an d oth ers h ave reported th e reaction s of keto com -
poun ds with Me3SiCF3 in th e presen ce of fluoride ion s8. However, little ef-
fort h as been devoted to th e tran sfer of lon ger perfluoroalkyl groups in to a
n on activated carbon yl system . We becam e in terested in th e n ucleoph ilic
perfluoroalkylation reaction s of carbon yl com poun ds wh ile exam in in g vari-
ous fluoride ion sources as catalysts. Here we report th e fluoride-catalyzed
perfluoroalkylation s of 4-ph en ylbut-3-yn -2-on e an d ph en ylpropyn al with
trim eth yl(perfluoroalkyl)silan e. To our kn owledge, th is is th e first report of
th e tran sfer of th e h igh er perfluoroalkyl groups in to a sim ple acetylen ic ke-
ton es or aldeh ydes system utilizin g fluoride ion catalysis.
RESULTS AND DISCUSSION
Nucleoph ilic tran sform ation of th e lon ger perfluoroalkyl groups with sim -
ple carbon yl com poun ds usin g fluoride ion catalysis is un kn own . Nearly a
decade ago reaction s were reported th at in volved trim eth yl(perfluoro-
alkyl)silan e an d h igh ly activated carbon yl com poun ds with very stron g
electron -with drawin g perfluoroalkyl groups, catalyzed by cesium fluoride or
potassium fluoride9 (Sch em e 1). Recen tly, we h ave carried out a large vari-
ety of fluoride catalyzed reaction s8. Here we report our study of th e
n ucleoph ilic perfluoroalkylation s of acetylen ic keton es or aldeh ydes, with
trifluorom eth yl an d h igh er perfluoroalkyl h om ologues. Th e details of th e
ch em istry are described below.
O
OH
Rf3SiMe3
Rf1
Rf3
Rf1
Rf2
Rf2
MF
(M = K, Cs)
Rf1
n-C8F13
(CF3)2CHO(CF2)4
Rf2
Rf3
CF3
n-C6F13
n-C6F13
CF3
SCHEME 1
Reaction s of trim eth yl(trifluorom eth yl)silan e (2c) with 4-ph en yl-
but-3-yn -2-on e (1a) an d ph en ylpropyn al (1b) in th e presen ce of a catalytic
am oun t of cesium fluoride in m on oglym e proceeded sm ooth ly at 25 °C to
give th e correspon din g (trifluorom eth yl)silyl eth er derivatives in quan tita-
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Manandhar, Singh, Shreeve:
tive yields. Hydrolysis of th e silyl eth er in term ediates with aqueous h ydro-
ch loric acid form ed th e (ph en yleth yn yl)(trifluorom eth yl)m eth an ols 3h , 3i
in 88% isolated yields. Un der sim ilar reaction con dition s, wh en trim eth yl-
(pen tafluoroeth yl)silan e (2d ) was reacted with 1a an d 1b, (pen tafluoro-
eth yl)(ph en yleth yn yl)m eth an ols 3j, 3k were obtain ed in >80% isolated
yield. Th ese reaction s are n ot surprisin g, an d gave a sim ple route to th e
trifluorom eth yl an d pen tafluoroeth yl com poun ds in very good yields.
Wh en 1a was reacted with 2e in m on oglym e at 25 °C in th e presen ce of a
catalytic am oun t of CsF, or TBAF after 24 h , th e reaction was foun d to be
in com plete with ca 25% of 1a rem ain in g un reacted. Heatin g th e reaction
m ixture at 50 °C for 15 h com pleted th e con version of 1a. Hydrolysis with
aqueous HCl produced 3l in 60% isolated yield. Un der sim ilar reaction con -
dition s, 1b reacted with 2e to yield 3m in 55% isolated yield (Sch em e 2).
Th us, th e reaction of 1a, 1b with 2f, 2g produced 3n –3q in good isolated
yields after acid h ydrolysis (Table I).
1. CsF (cat.),
monoglyme
O
OH
C R
Rf
+
C R
Me3SiRf
2. H3O+
2c–2g
3h–3q
1a, 1b
SCHEME 2
In all th ese reaction s, TBAF was also foun d to be a suitable fluoride ion
catalyst to produce th e fin al products in com parable yields. For Me3SiCF3
an d Me3SiC2F5, th e correspon din g silyl eth er in term ediate was foun d to be
stable wh ile for Me3SiRf (Rf = n -C6F13, n -C7F15, n -C8F17) th e correspon din g
silyl eth er in term ediates were un stable an d were n ot isolated. Tetrah ydro-
furan was also foun d to be a suitable solven t for th e above ch em istry.
Th e n ucleoph ilic reaction m ech an ism s for trifluorom eth ylation an d
pen tafluoroeth ylation of acetylen ic keton es or aldeh ydes with Me3SiRf (Rf =
CF3, C2F5) are assum ed to be th e sam e as th at reported for keton es an d alde-
h ydes10. Th e reaction was in itiated by fluoride ion to form perfluoro-
alkylated oxyan ion s wh ich catalyze subsequen t reaction .
With th e exception of 3h –3k th at are viscous liquids, th e n ew
(perfluoroalkyl)(ph en yleth yn yl)m eth an ols (Table I) are solids. Th ey are sol-
uble in com m on organ ic solven ts (dich lorom eth an e, ch loroform , aceton e,
dieth yl eth er, m on oglym e, etc.) an d h ave poor solubility in pen tan e an d
h exan e. Th ey all are stable to m oisture an d air. Th e solid com poun ds 3l–3q
are crystallizable in a m ixture of pen tan e/dich lorom eth an e at –15 °C. Th e
in frared spectra of all th e com poun ds h ave a broad peak in th e region 3 200–
3 400 cm –1 assigned to ν(OH) and a sharp peak in the region 2 200–2 300 cm –1
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Perfluoroalkylations of Acetylenic Ketones or Aldehydes
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TABLE I
Nucleoph ilic perfluoroalkylation of acetylen ic keton e/aldeh ydea
Me3SiRf
Acetylen ic keton e/aldeh yde
Product
Yield, %
Rf
OH
O
C
CH3
C CH3
CF3
CF3
2c
88
90
1a
3h
O
OH
C
H
C H
CF3
CF3
2c
1b
3i
3j
O
C
OH
CH3
C2F5
2d
C
CH3
85
C2F5
1a
O
OH
C
H
C H
C2F5
C2F5
2d
83
1b
3k
O
OH
CH3
C
CH3
n-C6F13
C
60
2e
n-C6F13
1a
3l
O
OH
C
H
n-C6F13
2e
C H
55
n-C6F13
1b
3m
3n
O
OH
C
CH3
n-C7F15
2f
C
CH3
62
n-C7F15
1a
O
OH
C
H
n-C7F15
2f
C H
53
n-C7F15
1b
3o
3p
OH
O
C
CH3
n-C8F17
2g
C CH3
62, 60c
n-C8F17
1a
O
OH
C
H
n-C8F17
2g
58
C H
1b
n-C8F17
3q
a
All reaction s were carried out with 2 m m ol of acetylen ic keton e/aldeh yde an d 2.5 m m ol of
b
c
Me3SiRf in 3 m l of m on oglym e. Isolated. Usin g a catalytic am oun t of TBAF in THF.
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Manandhar, Singh, Shreeve:
assign ed to ν(C≡C). In th e 19F NMR spectra, a peak due to th e CF3 m oiety
appeared in th e ran ge of –70 to –80 ppm . Th e CF2 groups appeared as a
1
m ultiplet in th e region of –119 to –127 ppm . Th e H NMR spectra of all th e
products clearly sh ow th e presen ce of proton s of h ydroxy groups. Th is reso-
n an ce disappeared upon treatin g with D2O. In th e 13C NMR spectra, th e
peak assign ed to th e carbon yl carbon th at appeared at about 190 ppm in
th e startin g m aterials 1a, 1b, sh ifted upfield to ca 60–70 ppm . Th is sh ift re-
sulted from in troduction of th e perfluoroalkyl group an d h ydroxy group on
th e sam e carbon .
In con clusion , we h ave described a useful m eth od to prepare lon ger ch ain
(perfluoroalkyl)(ph en ylpropyn yl)m eth an ols in good yields by fluoride-
catalyzed reaction s of 4-ph en ylbut-3-yn -2-on e an d ph en ylpropyn al with
trim eth yl(perfluoroalkyl)silan e.
EXPERIMENTAL
All th e reaction s were perform ed un der dry n itrogen . Th e (perfluoroalkyl)trim eth ylsilan es
were prepared by publish ed procedures11. Cesium fluoride was m ain tain ed at 200 °C an d re-
peatedly groun d un til it rem ain ed as a fin ely divided powder. On ce th is stage is reach ed, it
can be stored at th is tem perature in its fin ely divided state an d used in defin itely. Th e
4-ph en ylbut-3-yn -2-on e an d ph en ylpropyn al (Aldrich ) were used as received. Eth ylen e glycol
dim eth yl eth er (m on oglym e) of h igh purity (Aldrich ) was used as solven t. 1H, 19F, an d 13C
NMR spectra were recorded in CDCl3 on a spectrom eter operatin g at 300, 282, an d 75 MHz,
respectively. Ch em ical sh ifts are reported in ppm (δ-scale) relative to th e appropriate stan -
dard, CFCl3 for 19F, an d TMS for 1H an d 13C NMR spectra. Couplin g con stan ts (J) are given
in Hz. IR spectra (waven um bers in cm –1) were recorded usin g NaCl plates. Mass spectra were
m easured on an electron -im pact 70 eV spectrom eter. Elem en tal an alyses were perform ed at
th e Sh an gh ai In stitute of Organ ic Ch em istry, Ch in a.
Gen eral Procedure for Perfluoroalkylation of Ph en ylpropyn al (1a) an d
4-Ph en ylbut-3-yn -2-on e (1b) with Trim eth yl(trifluorom eth yl)silan e (2c) an d
Trim eth yl(pen tafluoroeth yl)silan e (2d )
In a typical experim en t, 1a or 1b (2 m m ol) an d 2c or 2d (2.5 m m ol) were dissolved in
m on oglym e (3 m l). A catalytic am oun t of cesium fluoride/tetrabutylam m on ium fluoride (0.1
m m ol) was added at 25 °C. Reaction occurred with th e gen eration of h eat an d color ch an ge
to dark brown . Progress of th e reaction was m on itored by GC-MS. Glym e an d excess Me3SiRf
were rem oved at reduced pressure an d THF (2 m l) was added to th e residue followed by 4
M
HCl (8 m l). Volatile m aterials were rem oved un der reduced pressure an d th e product was ex-
tracted with m eth ylen e ch loride. Purification was accom plish ed via th in layer ch rom atogra-
ph y usin g m eth ylen e ch loride/pen tan e m ixtures (1 : 1) to yield 3h –3k in good to excellen t
yields.
1,1,1-Trifluoro-2-methyl-4-phenylbut-3-yn-2-ol12 (3h ). Yield 88%; yellowish viscous liquid. IR
(NaCl film ): 3 412, 2 958, 2 240, 1 491, 1 708, 1 491, 1 445, 1 296, 1 261, 1 188, 1 154, 1 105,
958, 905, 756, 690. 1H NMR (CDCl3): 1.68 (s, 3 H); 2.87 (s, 1 H );7.2–7.4 (m , 5 H). 19F NMR
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Perfluoroalkylations of Acetylenic Ketones or Aldehydes
1301
(CDCl3): –82.67 (s, 3 F). 13C NMR (CDCl3): 23.49, 69.52 (q, JC-C-F = 33, COHCF3); 85.12,
86.64, 121.6, 124.5 (q, JC-F = 278, CF3); 128.8, 129.7, 132.3. MS (EI), m/z (species, rel. in t.):
214 (M+, 25), 197 (M+ – OH, 31), 145 (M+ – CF3, 79), 129 [M+ – (CF3 + CH3 + H), 94], 115
(Ph CCCH2+, 51), 102 (Ph CCH, 22), 77 (Ph +, 20), 69 (CF3+, 14), 43 (CH3CO+, 100).
1,1,1-Trifluoro-4-phenylbut-3-yn-2-ol13 (3i). Yield 90%; yellowish viscous liquid. IR (NaCl
film ): 3 379, 3 063, 2 241, 1 678, 1 599, 1 491, 1 445, 1 353, 1 272, 1 186, 1 140, 1 073,
981, 838, 756, 690. 1H NMR (CDCl3): 2.93 (s, 1 H); 4.86 (q, 1 H, J = 5.7); 7.1–7.4 (m , 5 H).
19F NMR (CDCl3): –79.78 (d, 3 F, J = 5.3). 13C NMR (CDCl3): 63.3 (q, JC-C-F = 36, COHCF3);
80.9, 88.3, 121.4, 123.3 (q, JC-F = 279, CF3); 128.9, 129.9, 132.5. MS (CI), m/z (species, rel.
in t.): 201 (M+ + H, 100), 200 (M+, 13), 183 (M+ – OH, 4), 131 (M+ – CF3, 18).
4,4,5,5,5-Pentafluoro-3-methyl-1-phenylpent-1-yn-3-ol (3j). Yield 85%; yellowish viscous
liquid. IR (NaCl film ): 3 423, 3 061, 3 009, 2 243, 1 491, 1 445, 1 342, 1 273, 1 215, 1 197,
1 117, 1 089, 1 010, 956, 889, 756. 1H NMR (CDCl3): 1.75 (s, 3 H); 2.46 (s, 1 H); 7.23–7.45
(m , 5 H). 19F NMR (CDCl3): –78.4 (s, 3 F); –123.6 (d, 1 F, J = 270); –125.3 (d, 1 F, J = 270).
13C NMR (CDCl3): 23.65 (m ); 69.25 (t, J = 26.9, COHCF2CF3); 84.58 (m ); 87.1 (t, J = 0.6 );
113.15 (t of q, J = 262.8, CF2CF3, J = 0.37); 119.38 (q of t, J = 289, CF2CF3, J = 35.9); 121.1,
128.393, 129.3, 131.8. MS (EI), m/z (species, rel. in t.): 264 (M+, 17), 247 (M+ – OH, 84), 145
(M+ – CF2CF3, 100), 129 [M+ – (C2F5 + CH3 + H), 60], 115 (CCCOCHCF2+, 29), 102 (Ph CCH,
13), 77 (Ph +, 8), 43 (CH3CO+, 60). For C12H9F5O (264.2) calculated: 54.56% C, 3.43% H;
foun d: 54.47% C, 4.87% H.
4,4,5,5,5-Pentafluoro-1-phenylpent-1-yn-3-ol (3k). Yield 83%; yellowish viscous liquid. IR (NaCl
film ): 3 392, 2 240, 1 659, 1 598, 1 491, 1 445, 1 193, 1 140, 1 078, 953, 804, 757. 1H NMR
(CDCl3): 2.54 (d, 1 H, J = 8.6); 4.97 (m , 1 H); 7.28–7.6 (m , 5 H). 19F NMR (CDCl3): –81.5 (s,
3 F); –123.2 (dd, 1 F, J = 270, J = 8.0); –128.02 (dd, 1 F, J = 270, J = 13). 13C NMR (CDCl3):
62.7 (t, JC-C-F = 26.0, COHCF2CF3); 80.3, 89.4, 113.50 (t of q, J = 258, CF2CF3, J = 35.5);
120.0 (q of t, J = 286.5, CF2CF3, J = 35.5); 121.3, 128.9, 130.0, 132.4. MS (EI), m/z (species,
rel. in t.): 250 (M+, 23), 233 (M+ – OH, 35), 131 (M+ – CF2CF3, 100), 114 [M+ – (OH +
CF2CF3), 12], 77 (C6H5, 22), 69 (CF3, 2).
Gen eral Procedure for Perfluoroalkylation of 4-Ph en ylbut-3-yn -2-on e (1a) an d
Ph en ylpropyn al (1b) with Me3SiRf (Rf = n -C6F13, n -C7F15, n -C8F17) (2e–2f)
Reaction s were carried out un der sim ilar con dition s as reported for 3h –3k except in th e
presen t case th e reaction m ixture was h eated at 50 °C for 15 h .
4,4,5,5,6,6,7,7,8,8,9,9,9-Tridecafluoro-3-methyl-1-phenylnon-1-yn-3-ol (3l). Yield 60%; very
ligh t viscous liquid. IR (NaCl film ): 3 433, 2 243, 1 491, 1 445, 1 357, 1 238, 1 205, 1 145,
959, 831, 754. 1H NMR (CDCl3): 1.74 (s, 3 H); 2.74 (s, 1 H); 7.19–7.41 (m , 5 H). 19F NMR
(CDCl3): –81.35 (t, 3 F, J = 9.8); –119.0 to –126.75 (m , 10 F). 13C NMR (CDCl3): 23.9, 77 (t,
JC-C-F = 30, COHCF2); 85.0, 87.7, 106.2–121 (m ); 121.2, 128.4, 129.4, 131.8. MS (CI), m/z
(species, rel. in t.): 465 (M+ + H, 2), 447 (M+ – OH, 58), 145 (M+ – C6F13, 100), 129 [M+
–
(C6F13 + CH3 + H), 23], 43 (CH3CO+, 24). For C16H9F13O (464.2) calculated: 41.40% C,
1.95% H; foun d: 41.39% C, 2.22% H.
4,4,5,5,6,6,7,7,8,8,9,9,9-Tridecafluoro-1-phenylnon-1-yn-3-ol (3m ). Yield 55%; yellowish
solid, m .p. 34 °C. IR (KBr film ): 3 389, 2 235, 1 666, 1 600, 1 493, 1 446, 1 359, 1 145, 1 070,
894, 755. 1H NMR (CDCl3): 2.66 (d, 1 H, J = 8.8); 5.05 (t of d, 1 H, J = 8.5, 3.5); 7.28–7.44
(m , 5 H). 19F NMR (CDCl3): –81.35 (t, 3 F, J = 8.6); –121.6 to –126.8 (m , 10 F). 13C NMR
(CDCl3): 63.2 (t, JC-C-F = 27, COHCF2); 80.4, 89.4, 105.0–120 (m ); 121.3, 128.8, 129.9, 132.4.
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Manandhar, Singh, Shreeve:
MS (CI), m/z (species, rel. in t.): 451 (M+ + H, 1), 450 (M+, 6), 433 (M+ – OH, 4), 131 (M+
C6F13, 100), 103 (Ph CHCH, 40), 102 (Ph CCH, 23), 77 (C6H5+, 45), 69 (CF3+, 16). For
–
C
15H7F13O (450.2) calculated: 40.02% C, 1.57% H; foun d: 40.22% C, 1.79% H.
4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Pentadecafluoro-3-methyl-1-phenyldec-1-yn-3-ol (3n ). Yield
62%; very ligh t yellowish solid, m .p. 35 °C. IR (KBr film ): 3 428, 3 062, 3 009, 2 954, 2 243,
1 953, 1 884, 1 806, 1 757, 1 668, 1 598, 1 492, 1 445, 1 350, 1 245, 1 006, 957, 899, 864,
824, 754. 1H NMR (CDCl3): 1.78 (s, 3 H); 2.66 (s, 1 H); 7.25–7.50 (m , 5 H). 19F NMR
(CDCl3): –81.10 (t, 3 F, J = 9.5); –126.48 to –117.26 (m , 12 F). 13C NMR (CDCl3): 24.1, 70.5
(t, JC-C-F = 30.16, COHCF2); 84.9, 87.6, 107.0–199.3 (m ); 121.4, 128.6, 129.6, 132.1. MS (CI),
m/z (species, rel. in t.): 515 (M+ + H, 1), 498 (M+ + H – OH, 8), 497 (M+ – OH, 41), 178 [M+
–
(C6F13 + OH), 15], 146 (M+ + H – C7F15, 14), 145 (M+ – C7H15, 100), 129 (Ph CCCO+, 23), 69
(CF3+, 4), 43 (CH3CO+, 47 ). For C17H9F15O (514.2) calculated: 39.71% C, 1.76% H; foun d:
39.78% C, 1.90% H.
4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Pentadecafluoro-1-phenyldec-1-yn-3-ol (3o). Yield 53%;
yellowish solid, m .p. 38 °C. IR (KBr film ): 3 369, 3 065, 2 932, 2 243, 1 660, 1 600, 1 490,
1 442, 1 351, 1 240, 1 207, 1 135, 1 072, 1 017, 972, 836, 882, 796, 754, 690. 1H NMR
(CDCl3): 2.75 (d, 1 H, J = 8.8 ); 5.09 (m , 1 H); 7.23–7.48 (m , 5 H). 19F NMR (CDCl3): –81.09
(t, 3 F, J = 9.7); –126.4 to –119.2 (m , 12 F). 13C NMR (CDCl3): 63.2 (t, JC-C-F = 22.6,
COHCF2); 80.4, 89.4, 105–119 (m ); 121.3, 128.8, 130.4, 132.4. MS (CI), m/z (species, rel.
in t.): 501 (M+ + H, 11), 500 (M+, 3), 483 (M+ – OH, 14), 182 [M+ – (C6F13 + H), 4], 181 [M+
–
(C6F13 + 2 H), 3], 164 (C6H5CCCHCF2+, 24), 132 (M+ + H – C7F15, 11), 131 (M+ – C7F15, 100),
103 (Ph C2H2+, 31), 102 (Ph C2H+, 13), 77 (C6H5+, 16), 69 (CF3+, 4). For C16H7F15O (500.2)
calculated: 38.42% C, 1.41% H; foun d: 38.47% C, 1.56% H.
4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-Heptadecafluoro-3-methyl-1-phenylundec-1-yn-3-ol (3p ).
Yield 62%; very ligh t yellowish solid, m .p. 33 °C. IR (KBr film ): 3 433, 2 243, 1 492, 1 445,
1 351, 1 240, 1 209, 1 150, 958, 892, 754. 1H NMR (CDCl3): 1.73 (s, 3 H); 2.64 (s, 1 H);
7.24–7.41 (m , 5 H). 19F NMR (CDCl3): –81.66 (t, 3 F, J = 11.28); –119.19 to –126.95 (m , 14 F).
2
13C NMR (CDCl3): 24.1, 70.72 (t, JC-C-F = 27, COHCF2); 84.9, 87.6, 117–118 (m ); 121.6,
128.7, 129.7, 132.2. MS (CI), m/z (species, rel. in t.): 565 (M+ + H, 1), 548 (M+ + H – OH, 5),
547 (M+ – OH, 23), 146 (M+ + H – C8F17, 14), 145 (M+ – C8F17, 100), 129 [M+ – (C8F17 + CH3
+
H), 17], 102 (Ph C2H+, 2), 69 (CF3+, 3), 43 (CH3CO+, 31). For C18H9F17O (564.2) calculated:
38.32% C, 1.61% H; foun d: 38.41% C, 1.66% H.
4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-Heptadecafluoro-1-phenylundec-1-yn-3-ol (3q ). Yield
58%; wh ite solid, m .p. 43 °C. IR (KBr film ): 3 382, 2 212, 1 655, 1 491, 1 445, 1 147, 1 080,
999, 949, 756. 1H NMR (CDCl3): 2.64 (d, 1 H, J = 8.8); 5.05 (t of d, 1 H, J = 8.5, 3.5); 7.20–7.50 (m ,
5 H). 19F NMR (CDCl3): –80.98 (t, 3 F, J = 9.8); –119.0 to –126.5 (m , 14 F). 13C NMR (CDCl3):
2
63.2 (t, JC-C-F = 30.1, COHCF2); 80.5, 89.4, 105.0–122.0 (m ); 121.3, 128.8, 129.1, 132.4. MS
(EI), m/z (species, rel. in t.): 551 (M+ + H, 24), 164 [M+ – (OH + C7F15), 21], 131 (M+ – C8F17+
,
,
100), 105 (Ph C2H4+, 34), 104 (Ph C2H3+, 2), 103 (Ph C2H2+, 20), 102 (Ph C2H+, 7), 77 (C6H5
3), 69 (CF3+, 1). For C17H7F17O (550.2) calculated: 37.11% C, 1.28% H; foun d: 37.29% C,
1.41% H.
This work was supported by National Science Foundation (Grant No. CHE-9720365) and donors of
the American Chemical Society Petroleum Research Fund. We thank Dr A. Blumenfeld for NMR mea-
surements.
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