Phosphorofluoridic acid ammonium salts and acids: Synthesis, NMR properties, and application as acid catalysts

Article abstract of DOI:10.1002/hc.20700

Phosphoric acid alkyl diphenyl esters were prepared by reacting diphenyl phosphoryl chloride with alcohols in the presence of amines, and then subjected to fluorinative hydrolysis with Bu₄ NF to give phosphorofluoridic acid ammonium salt monoes

Full text of DOI:10.1002/hc.20700

Heteroatom Chemistry
Volume 22, Number 3/4, 2011
Phosphorofluoridic Acid Ammonium Salts
and Acids: Synthesis, NMR Properties, and
Application as Acid Catalysts
Toshiaki Murai, Yusuke Tonomura, and Toru Takenaka
Department of Chemistry, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, Japan
Received 29 August 2010; revised 7 November 2010
than that of other halogen-substituted phosphor-
ABSTRACT: Phosphoric acid alkyl diphenyl esters
ates. Therefore, phosphoric acid derivatives bearing
were prepared by reacting diphenyl phosphoryl chlo-
a P F bond have been used as key intermediates to
ride with alcohols in the presence of amines, and
lead to biologically interesting molecules. Addition-
then subjected to fluorinative hydrolysis with Bu4 NF
ally, a 19F nucleus can be a probe for disclosing some
to give phosphorofluoridic acid ammonium salt mo-
interaction between phosphoric acid derivatives and
noesters in moderate to high yields. The salts were
biologically relevant molecules. Metal fluorides such
converted to the corresponding acids by treatment
as KF [4,5] and AgF [6,7], hydrogen fluoride/amine
with Amberlyst 15. The NMR properties of a series
complexes [8,9], and diethylaminosulfur trifluoride
of organophosphorus compounds are presented. The
(DAST) [10] are used as fluorinating agents for phos-
catalytic activities of the acids for the condensation
phorus chlorides and esters. Tetrabutylammonium
reaction of α-bromobutanoic acid and 3-hexyne-2-ol
fluoride (TBAF) has also been used to introduce fluo-
ꢀ
C
were tested.
2011 Wiley Periodicals, Inc. Heteroatom
rine atom to the phosphorus atom [5]. TBAF-t-BuOH
adduct has recently been applied to the fluorination
of phosphoryl chlorides [11]. Despite recent progress
on the introduction of fluorination, the applicability
of these methods is still limited, and new types of
fluorinated organophosphorus compounds are de-
manded. In this regard, in our studies on compounds
with P Se bonds [12–22], we also found that phos-
phoric acid phenyl esters undergo fluorinative hy-
drolysis with a THF solution of TBAF [23]. We report
herein the details of this reaction leading to phos-
phorofluoridic acid ammonium salt monoesters and
their conversion to the corresponding acids. The ap-
plication of these acids to the condensation reaction
of carboxylic acids and alcohols is described.
Chem 22:417–425, 2011; View this article online at wiley-
onlinelibrary.com. DOI 10.1002/hc.20700
INTRODUCTION
Introduction of a fluorine atom to organophospho-
rus compounds adds unique properties to the re-
sulting compounds [1–3]. For example, fluorinated
phosphoric acids are expected to be more acidic than
the nonfluorinated corresponding acids, whereas
fluorinated phosphorates are less basic and less
nucleophilic than the corresponding phosphorates.
The stability of fluorinated phosphorates is higher
Dedicated to Professor Kin-ya Akiba on the occasion of his 75th
birthday.
Correspondence to: Toshiaki Murai; e-mail: mtoshi@gifu-u.ac
.jp.
RESULTS AND DISCUSSION
Contract grant sponsor: Grant-in-Aid for Scientific Research
on Innovative Area (“Integrated Organic Synthesis”) from the
Ministry of Education, Culture, Sports, Science and Technology,
Initially, phosphoric acid alkyl diphenyl esters 3
were synthesized by reacting diphenyl phosphoryl
chloride (1) with alcohols 2 (Table 1). As a com-
bination of a solvent and base, THF/Et3N or
417
Japan.
c
ꢀ
2011 Wiley Periodicals, Inc.

418 Murai, Tonomura, and Takenaka
TABLE 1 Phosphorylation of Alcohols
O
P
O
P
O
P
– PhO–
–OH
PhO
PhO
HO
O
O
P
PhO
OR
HOR
OR
OR
PhO
PhO
PhO
PhO
F
F
P
6
5
F–
3
Cl
OR
1
3
PhO–
+
+
PhOH
H2O
Bu4N+
Bu4N+
Alcohol
2
Conditions
Entry
Yield
O
O
P
Bu4NF
DMAP
CH2Cl2
rt, 6 h
Ph
Bu4N+–
O
PhO
PhO
HO
Ph
1
2
P
OR
O
2a
F
4
3a
87%
95%
Et3N
THF
reflux
8 h
O
SCHEME 1
PhO
P
HO
PhO
O
3b
2b
2c
and new doublet signals corresponding to phospho-
rus atoms bearing a fluorine atom became larger
in 31P NMR spectra of the reaction mixture. When
the signals due to 3 had completely disappeared,
which required 5–20 h, the reaction mixture was
poured onto H2O and initially extracted with Et2O.
The aqueous layer was then extracted with CH2Cl2
and the organic layers were dried over MgSO4, fil-
tered, and concentrated to give phosphorofluoridic
acid salt monoesters 4. Generally, with this workup,
the salts were efficiently isolated with a purity of
greater than 90%. Excess TBAF was removed by ex-
tracting a CH2Cl2 solution of 4 with aqueous solution
of NaOH several times.
A plausible reaction pathway for the reaction in
Table 2 is proposed in Scheme 1. Fluoride ion may
initially attack the phosphorus atom in 3, followed
by the elimination of phenolate ion to generate phos-
phoryl fluorides 5. The fluorides 5 were then sub-
jected to the substitution reaction with hydroxyl ion
generated from the phenolate ion and H2O to form
acids 6, which are further deprotonated to lead to
ammonium salts 4.
DMAP
CH2Cl2
rt
O
P
PhO
PhO
3
4
5
O
HO
5 h
3c
86%
DMAP
CH2Cl2
Ti(OiPr)4
(10 mol%)
rt
O
P
PhO
PhO
O
HO
2 h
2d
2e
3d 84%
DMAP
CH2Cl2
rt
O
PhO
PhO
P
6 h
O
HO
3e
90%
O
DMAP
CH2Cl2
rt
PhO
PhO
O
O
P
O
HO
HO
6
7
5 h
OBn
OBn
OBn
OBn
3f
O
O
O
84%
2f
O
P
O
DMAP
CH2Cl2
rt
PhO
PhO
O
O
O
3g
2g
6 h
O
88%
O
P
DMAP
CH2Cl2
rt
8
PhO
PhO
HO
Some of the salts were reacted with methyl io-
dide and proton sources. Salts 4b and 4d were re-
acted with methyl iodide, with Et2O as a solvent
(Scheme 2). Even in the reaction with excess methyl
86%
2h
3h
5 h
CH2Cl2/DMAP was used [24]. The reaction in the
presence of Et3N in THF required reflux temperature
(entry 2), whereas the reaction with DMAP as a base
in CH2Cl2 was complete at room temperature (en-
tries 1, 3–8). As primary alcohols, 2-phenylethyl (2a)
[25], 2-naphthylethyl (2b), and adamantylmethyl
(2c) alcohols, as secondary alcohols, (l)-menthol
(2d), 2-adamantanol (2e), and O-benzyl dianhydro-
D-glucitols (2f) and (2g), and as a tertiary alcohol,
1-adamantanol, were used. No difference was ob-
served in the efficiency of the condensation reactions
between these alcohols 2 and phosphoryl chloride 1.
Next, phosphoric esters 3 were stirred with
TBAF in THF at room temperature. The signals
due to the starting esters 3 gradually disappeared
MeI
O
P
F
O
P
(4 equiv)
Ar
Ar
Bu4N+–
O
MeO
O
O
F
Et2O
rt
6 h
4b
16%
7b
Ar = 2-naphthyl
MeI
(4 equiv)
O
P
O
P
Bu4N+–
O
MeO
O
O
Et2O
rt
4 h
F
F
23%
4d
7d
SCHEME 2
Heteroatom Chemistry DOI 10.1002/hc

Synthesis, NMR Properties, and Application of Phosphorofluoridic Acid Ammonium Salts and Acids 419
TABLE
2 Fluorinative Hydrolysis of Phosphoric Acid
O
P
Amberlyst15 (H+)
CH2Cl2, rt, 2 h
O
P
Diphenyl Esters
Bu4N+ -
O
O
OR1R2
OR1R2
HO
F
F
O
P
O
PhO
P
Bu4NF
OR
PhO
OR
O
P
THF, time
F
4
3
Ph
O
P
P
HO
O
HO
F
O
F
HO
Alcohol
2
O
Entry
Yield
Time
8a
F
8c
91%
84%
8d
71%
O
P
O
P
PhO
PhO
Ph
Bu4N+–
O
16 h
Ph
1
2
O
O
F
O
3a
O
P
87%
4a
P
HO
O
O
5 h
O
P
F
HO
F
O
PhO
PhO
F
P
2-naphthyl
2-naphthyl
86%
Bu4N+–O
84%
8h
O
O
81%
8e
3b
4b
SCHEME 3
O
P
O
8 h
PhO
PhO
P
Bu4N+ –
O
O
3
4
5
O
F
3c
63%
70%
found in biologically important molecules [3,10,27–
31].
4c
O
P
O
P
15 h
Bu4N+–
The NMR properties of a series of organophos-
phorus compounds 3, 4, and 8 are listed in Ta-
ble 3. The relative trends in the chemical shifts of
3, 4, and 8 are consistent and independent of the
substituents on the oxygen atom in 31P NMR spec-
tra. Among these, the signals of 3 were observed in
the highest regions, whereas those of 4 were in the
lowest regions. The signals of 8 were midway be-
tween those of 3 and 4. All of the signals in the 19F
PhO
PhO
O
O
O
O
F
3d
4d
O
P
3e
8 h
7 h
O
PhO
PhO
P
Bu4N+ –
O
O
F
98%
4e
O
O
PhO
PhO
O
P
O
P
Bu4N+ –
O
O
O
6
7
F
3f
OBn
OBn
98%
4f
O
O
O
TABLE 3 NMR Spectra of a Series of Organophosphorus
Compounds 3, 4, and 8
O
P
O
7 h
PhO
PhO
O
O
Bu4N+–
O
P
O
O
F
3g
O
P
3
O
P
O
P
OBn
94%
OBn
4g
O
OR
PhO
PhO
Bu4N+ –
O
HO
OR
OR
OR
F
F
4
8
O
O
P
1JP-F
(Hz)
1JP-F
(Hz)
31P
( )
31P 19F
31P 19F
( ) ( )
20 h
Bu4N+ –
PhO
PhO
8
P
O
O
O
( )
( )
F
3h
100%
4h
a
c
Ph
–4.7
O
–77.5 923.6 –7.7
–79.0 918.0 –6.6
–74.7 919.5 –7.8
–11.5
–80.6 950.0
–81.3 945.4
–77.5 945.4
–3.6
–5.4
–11.0
–11.9
O
iodide, methylation was not efficient and the methy-
lated products 7 were obtained in only low yields,
although the salts were completely dissolved in Et2O
and the reaction mixture was homogeneous. Acid hy-
drolysis of the salts 4 with an Et2O solution of HCl
also proceeded sluggishly and gave the desired acids
in moderate yields. Instead, the salts 4 were stirred
with Amberlyst 15 in CH2Cl2 for 2 h (Scheme 3).
Filtration and concentration of the reaction mix-
ture gave the desired acids 8 in good to excellent
yields. Much less attention has recently been paid to
phosphorofluoridic acids with simple carbon skele-
tons [2,26], but phosphorofluoridic acid moieties are
d
O
–4.7
–8.3
–73.6 918.3 –8.6
–67.0 919.7 –10.1
–12.0
–16.4
–77.8 945.4
–71.4 944.3
e
h
O
O
Heteroatom Chemistry DOI 10.1002/hc

420 Murai, Tonomura, and Takenaka
TABLE
4 Reaction of 2-Bromobutanoic Acid (9) with
tion of 10 (entries 3 and 9), whereas acids 8c and 8e
that were derived from secondary alcohols appear to
catalyze both condensation and dehydration (entries
4 and 8). Notably, in the acid 8d-catalyzed reaction,
the starting acid 9 was completely consumed and
the product 11 was the major component of the re-
action mixture (entry 5). The reaction mixture was
then purified by column chromatography on silica
gel to give the ester 11 in 70% isolated yield.
3-Hexyne-2-ol (10) in the Presence of Acid Catalystsa
O
O
cat.
+
HO
OH
9
O
6 h
Et
11
Br
10
1.5 equiv
Br
Et
2 mmol
Entry
Acid Catalyst Temperature
9
10
11
1
2
3
4
5
6
7
8
9
140°C
140°C
140°C
140°C
140°C
100°C
120°C
140°C
140°C
1
0
0
0
0
1
1
1
1
1
1
1
H2SO4
TsOH
8a
CONCLUSION
1
The fluorinative hydrolysis of phosphoric acid alkyl
diphenyl esters was demonstrated. The reaction took
7–20 h, but the starting esters were selectively con-
verted to the corresponding phosphorofluoridic acid
salt monoesters. Acid hydrolysis of the salts was
achieved by treating the salts with Amberlyst 15.
The NMR properties of a series of organophosphorus
compounds were presented. Finally, the catalytic ac-
tivities of phosphorofluoridic acids were examined
in the condensation reaction of α-bromobutanoic
acid and 3-hexyne-2-ol, and were found to depend
on the structure of the alkyl groups in the acid
catalysts.
1.2
1
0.55
0.78
0.10
2.9
8c
b
0
(70%)
8d
3.3
2
8e
2.7
8e
0.89
1
0.67
0.45
8e
8h
a Relative ratios of 9 10, and 11 as determined by 1H NMR
spectra.
b Isolated yield.
EXPERIMENTAL
NMR spectra were observed at −67 to −81 ppm and
the protonation of 4 slightly shifted the signals to
a higher region by 2.3–4.1 ppm. In all cases, the 1-
adamantyl group affected the signals of 3h, 4h, and
8h, which slightly differed from the mean values of
other derivatives. In contrast, the 1-adamantyl group
Typical Procedure for the Synthesis of
Phosphoric Acid Alkyl Diphenyl Esters
Synthesis of Phosphoric Acid 1-tricyclo
[3.3.1.13,7]dec Diphenyl Ester (3h). To a CH2Cl2
solution (20 mL) of diphenylphosphoryl chloride (1)
(2.1 mL, 10 mmol), 1-adamantanol (1.5 g, 10 mmol)
and DMAP (2.4 g, 20 mmol) were added under an
Ar atmosphere. The resulting solution was stirred
at room temperature for 5 h and concentrated in
vacuo. The reaction mixture was purified by column
chromatography on silica gel (EtOAc : hexane = 1:3,
Rf = 0.45) to give the corresponding ester 3h (3.31
g, 86%) as a colorless oil.
1
had no effect on the J coupling constants between
phosphorus and fluorine atoms. The coupling con-
stants of 8 were greater than those of 4 by around
27 Hz.
Finally, the catalytic activities of acids 8 in the
condensation reaction between acid 9 and propar-
gyl alcohol 10 were tested under solvent-free condi-
tions [32] because the development of reactions un-
der solvent-free conditions is an important subject
in synthetic chemistry [33]. The results are shown in
Table 4. The reaction of 9 and 10 in the presence of a
catalytic amount of H2SO4 or TsOH at 140◦C did not
give the desired product 11 (entries 1 and 2). This re-
sult is probably due to the fact that these acids pre-
dominantly mediate dehydration of the alcohol 10
to mainly give the enyne. Phosphorofluoridic acids
8 were then used as an acid catalyst. Phosphoroflu-
oridic acids 8 catalyzed the condensation regardless
of the substituents attached to the oxygen atom of 8,
but the efficiency of the reaction highly depended on
the substituents. On the basis of relative ratio of 9,
10, and 11, acids 8a and 8h facilitate the dehydra-
IR (neat): 3069, 2913, 2854, 2684, 1942, 1738,
1592, 1490, 1456, 1371, 1357, 1592, 1490, 1456,
1371, 1357, 1284, 1224, 1191, 1163, 1105, 1051,
1018, 945, 903, 849, 814, 775, 712, 689, 642, 617,
587, 558, 525, 515, 506, 488, 478, 459, 445, 433,
420, 411, 402 cm−1; H NMR (CDCl3): δ 1.58–1.69
1
(m, 6H, OCCH2CHCH2), 2.09–2.17 (m, 6H, OCCH2),
4.04–4.20 (m, 3H, OCCH2CH), 7.14–7.35 (m, 10H,
Ph); 13C NMR (CDCl3): δ 31.2 (OCCH2CH), 35.5
3
(OCCH2CHCH2), 43.3 (d, JC-P = 4.1 Hz, OCCH2),
85.1 (d, 2 JC-P = 8.3 Hz, OCCH2), 120.0, 120.1, 124.9,
129.5, 150.8, 150.9 (Ph); 31P NMR (CDCl3): δ −16.4;
MS (EI) 384 m/z (M+); HRMS Calcd. for C22H25O4P
(M+): 384.1490. Found: 384.1480.
Heteroatom Chemistry DOI 10.1002/hc

Synthesis, NMR Properties, and Application of Phosphorofluoridic Acid Ammonium Salts and Acids 421
2374, 2331, 2265, 2232, 2140, 1983, 1955, 1924, 1866,
1790, 1727, 1685, 1591, 1492, 1452, 1385, 1366, 1358,
1344, 1280, 1193, 1114, 1102, 1068, 1043, 869, 830,
817, 772, 739, 688, 637, 616, 586, 543, 521, 511, 500,
Phosphoric Acid 2-Naphthylethyl Diphenyl Ester
(3b). Colorless solid; mp: 62–63◦C; IR(KBr): 3100,
3051, 3015, 2955, 2929, 2892, 2414, 2318, 1959, 1930,
1876, 1811, 1739, 1589, 1488, 1456, 1392, 1365, 1312,
1272, 1233, 1192, 1166, 1070, 1023, 1023, 960, 905,
870, 822, 762, 689, 648, 616, 576, 545, 536, 503, 466,
411 cm−1; 1H NMR (CDCl3): δ3.17 (t, J = 6.8 Hz, 2H,
OCH2CH2), 4.53 (dt, J = 6.9 Hz, 6.9 Hz, 2H, OCH2),
7.10–7.82 (m, 17H, Ar); 13C NMR (CDCl3): δ 36.8 (d,
1
456, 445, 418 cm−1; H NMR (CDCl3): δ 1.50–1.53
(m, 2H), 1.71–1.73 (m, 4H), 1.81–1.86 (m, 4H), 2.02–
2.05 (m, 2H), 2.10 (br, 2H), 4.79–4.82 (m, 1H, OCH),
7.15–7.35 (m, 10H, Ph); 13C NMR (CDCl3): δ 26.7,
27.1, 31.1, 33.3 (d, J = 4.1 Hz), 36.3, 37.3, 84.0 (d,
2 JC-P = 7.4 Hz, OCH), 120.2 (d, J = 5.0 Hz), 125.1,
129.7, 150.9 (d, J = 5.8 Hz) (Ph); 31P NMR (CDCl3):
δ −12.0; MS (EI): m/z: 384 (M+); HRMS Calcd. for
C22H25O4P: 384.1490. Found: 384.1498.
2
3 JC-P = 7.0 Hz, OCH2CH2), 69.4 (d, JC-P = 6.6 Hz,
OCH2), 119.99, 120.04, 125.3, 125.7, 126.1, 127.2,
127.6, 127.65, 127.71, 128.3, 129.7, 132.4, 133.5,
134.2, 150.4, 150.5 (Ar); 31P NMR (CDCl3): δ −11.8;
MS (EI) m/z 404 (M+); HRMS Calcd. for C24H21O4P:
404.1177. Found: 404.1160.
Phosphoric
Acid
1,4:3,6-Dianhydro-5-O-
benzylglucide Diphenyl Ester (3f). Colorless oil;
IR (neat): 3919, 3887, 3862, 3823, 3761, 3737, 3691,
3649, 2925, 1590, 1488, 1456, 1286, 1189, 1163,
1024, 953, 756, 688, 616, 573, 560, 520, 499, 486,
476, 463, 444, 431, 409 cm−1;1H NMR (CDCl3): δ 3.62
(t, J = 8.0 Hz, 1H), 3.88 (m, 1H), 4.04–4.20 (m, 3H),
4.56–4.60 (m, 2H), 4.70–4.72 (m, 1H, POCH), 4.78
(d, J = 12.2 Hz, 1H), 5.06–5.08 (m, 1H), 7.01–7.38
(m, 15H, Ph); 13C NMR (CDCl3): δ 70.4, 72.5, 74.0 (d,
J = 4.1 Hz), 79.0, 80.5, 82.7 (d, J = 6.6 Hz), 86.2 (d,
J = 6.6 Hz), 120.0, 125.5, 127.9, 128.0, 128.5, 129.8,
137.5, 150.2, 150.3; 31P NMR (CDCl3): δ −12.5; MS
(EI) m/z 468 (M+); HRMS Calcd. for 468.1357.
Phosphoric Acid Tricyclo[3.3.1.13,7]dec-1-methyl
Diphenyl Ester (3c). Colorless oil; IR (neat): 3904,
3868, 3841, 3674, 3631, 3495, 3070, 2892, 2754,
2678, 2659, 2575, 2409, 1939, 1784, 1737, 1593,
1494, 1453, 1388, 1365, 1345, 1294, 1193, 1108,
942, 905, 863, 808, 768, 754, 689, 661, 617,
606, 578, 567, 538, 502, 486, 450, 437, 414,
400 cm−1; 1H NMR (CDCl3): δ 1.47–1.57 (m, 6H,
OCH2CCH2CHCH2), 1.66 (d, J = 28.8 Hz, 3H,
CCH2CHCH2 and d, J = 52.7 Hz, 3H, CCH2CHCH2),
1.85–2.04 (m, 3H, CCH2CH), 3.81 (d, J = 5.4 Hz,
2H, OCH2CCH2), 7.14–7.42 (m, 10H, Ph); 13C NMR
(CDCl3): δ 27.8 (OCH2CCH2CH), 34.0 (OCH2CCH2),
36.8 (OCH2CCH2CHCH2), 38.6 (OCH2CCH2CH),
Phosphoric
Acid
1,4:3,6-Dianhydro-2-O-
2
benzylglucide Diphenyl Ester (3g). Colorless oil;
IR (neat): 3435, 3066, 2925, 2873, 1951, 1735, 1685,
1590, 1490, 1456, 1372, 1293, 1220, 1190, 1164,
1071, 1026, 955, 833, 773, 690, 634, 617, 577, 517,
479, 469, 461, 452, 438, 424, 415, 403 cm−1; 1H NMR
(CDCl3): δ 3.71 (dd, J = 6.3 Hz, 1H), 3.82–3,88 (m,
2H), 3.97–4.11 (m, 2H), 4.49–4.55 (m, 3H), 4.72–4.74
(m, 1H), 4.95–5.01 (m, 1H, POCH), 7.13–7.29 (m,
15H, Ph);13C NMR (CDCl3): δ 70.1 (d, J = 6.6 Hz),
71.4, 73.5, 78.1 (d, J = 5.8 Hz), 80.6 (d, J = 4.1 Hz),
83.2, 86.1, 120.1, 125.4, 127.7, 127.9, 128.5, 129.7,
137.4, 150.3; 31P NMR (CDCl3): δ −11.6; MS (EI)
m/z 468 (M+); HRMS Calcd. for C25H25O7P (M+):
468.1338. Found 468.1324.
78.6 (d, JC-P = 7.4 Hz, OCH2CCH2), 120.1, 125.2,
129.7, 150.6 (Ph); 31P NMR (CDCl3): δ −11.0; MS
(EI) m/z 398 (M+); HRMS Calcd. for C23H27O4P (M+):
398.1647. Found: 398.1651.
Phosphoric Acid l-Menthyl Diphenyl Ester (3d).
IR(neat): 3070, 3044, 2955, 2870, 2366, 1941,
1720, 1592, 1490, 1456, 1388, 1370, 1349, 1289,
1223, 1193, 1163, 1110, 1061, 1016, 947, 903,
882, 829, 807, 774, 689, 617, 589, 546, 526, 511,
448, 432, 410 cm−1; 1H NMR (CDCl3): δ 0.73 (d,
J = 6.8 Hz, 3H, OCHCH2CHCH3), 0.86 (d, J =
6.8 Hz, 3H, OCHCHCH[CH3)2], 0.90 [d, J = 6.8 Hz,
3H, OCHCHCH(CH3)2], 0.80–1.06 (m, 2H), 1.19 (q,
J = 11.7 Hz, 1H), 1.38–1.46 (m, 2H), 1.66 (br d,
J = 11.2 Hz, 2H), 1.99–2.06 [m, 1H, CH(CH3)2], 2.23
(br d, J = 12.2 Hz, 1H), 4.43 (ddt, J = 11.2 Hz,
6.8 Hz, 4.4 Hz, 1H, OCH), 7.15–7.36 (m, 10H,
Ph); 31P NMR (CDCl3): δ −11.9; MS (EI) m/z 388
(M+); HRMS Calcd. for C22H29O4P: 388.1803. Found:
388.1789.
Typical Procedure for Fluorinative Hydrolysis of
Alkyl Diphenyl Phosphoric Acid Esters
Synthesis of N,N,N-Tributyl-1-butanaminium 2-
Phenylethylphosphorofluoridate (4a). To a THF so-
lution (8 mL) of ester 3a (709 mg, 2.0 mmol), tetra-
butylammonium fluoride (1.0 M, THF) (4.0 mL,
4.0 mmol) was added at room temperature under an
Ar atmosphere. The mixture was stirred for 16 h at
room temperature. The reaction mixture was poured
Phosphoric Acid 2-Adamantyl Diphenyl Ester
(3e). Colorless solid; mp: 58◦C–59◦C; IR(KBr): 3097,
3067, 3042, 3015, 2899, 2854, 2679, 2637, 2431, 2398,
Heteroatom Chemistry DOI 10.1002/hc

422 Murai, Tonomura, and Takenaka
13C NMR (CDCl3): δ 13.7 (CH3), 19.7 (CH2CH3), 24.0
(CH2CH2CH3), 28.2 (OCH2CCH2CH), 33.8 (d, 3 JC-P
into water and extracted with Et2O (40 mL). The or-
ganic layer was washed with water (40 mL × 2).
The water layer was extracted with CH2Cl2 (120 mL
× 3) and 15% aqueous sodium hydroxide (20 mL).
The organic layer was dried over MgSO4, filtered,
and concentrated in vacuo to give an ammonium
salt 4a (861 mg, 97%) as a colorless solid; mp: 101–
102◦C◦ IR (KBr): 3626, 3594, 3567, 3478, 3446, 3393,
3331, 3313, 3263, 2874, 2365, 1644, 1488, 1281, 1118,
1034, 885, 798, 763, 747, 699, 669, 638, 593, 578, 563,
535, 503, 495, 482, 461, 450, 440, 427, 408 cm−1; 1H
NMR (CDCl3): δ 0.98 (t, J = 7.3 Hz, 12H, CH3), 1.42
(sext, J = 7.3 Hz, 8H, CH2CH3), 1.58–1.62 (m, 8H,
NCH2CH2), 2.98 (t, J = 7.3 Hz, 2H, OCH2CH2Ph),
3.27 (t, J = 8.3 Hz, 8H, NCH2CH2), 4.15 (q, J =
7.8 Hz, 2H, OCH2CH2Ph), 7.03–7.25 (m, 5H, Ph);
13C NMR (CDCl3): δ 13.6 (CH3), 19.7 (CH2CH3), 24.0
=
8.3 Hz, OCH2CCH2), 37.2 (OCH2CCH2CHCH2), 39.0
(OCH2CCH2CH), 58.7 (NCH2), 76.0 (d, 2 JC-P = 6.6 Hz,
1
OCH2CCH2); 31P NMR (CDCl3): δ −3.64 (d, JP-F
=
=
1
917.7 Hz); 19F NMR (CDCl3): δ −79.0 (d, JP-F
918.2 Hz); MS (FAB) m/z 247 (M+ Bu4N).
N,N,N-Tributyl-1-butanaminium
L-Menthyl
Phosphorofluoridate (4d). Colorless solid; mp:
48–49◦C; IR (KBr): 2967, 2872, 2733, 2360, 2341,
1645, 1487, 1383, 1281, 1179, 1151, 1094, 1078,
1060, 1028, 1000, 931, 884, 825, 807, 750, 552, 520,
1
495, 453, 413 cm−1; H NMR (CDCl3): δ 0.70–0.77
(m, 1H), 0.74 (d, J = 7.2 Hz, 3H, OCHCH2CHCH3),
0.79 (d, J = 6.8 Hz, 3H, OCHCHCH(CH3)2), 0.80 (d,
J = 7.2 Hz, 3H, OCHCHCH(CH3)2), 0.86–1.02 (m,
1H), 0.94 (t, J = 7.4 Hz, 12H, CH2CH3), 1.16–1.23
(m, 1H), 1.38 (sex, J = 7.3 Hz, 8H, CH2CH3),
1.33–1.63 (m, 4H, CH2 and/or CH), 1.53–1.63 (m,
8H, CH2CH2CH3), 2.25–2.28 (m, 2H), 3.24–3.28
(m, 8H, NCH2), 3.93–4.01 (m, 1H, OCH); 13C NMR
(CDCl3): δ 13.6 (CH2CH3), 15.8, 19.6 (CH2CH3),
21.2, 22.1, 22.9, 23.9 (CH2CH2CH3), 25.2, 31.4, 34.5,
43.0, 48.8 (d,J = 7.2 Hz), 58.6 (NCH2), 75.7 (d,
2 JC-P = 6.3 Hz, OCH); 19F NMR (CDCl3): δ −74.7
3
(NCH2CH2), 37.3 (d, JC-P = 6.6Hz, OCH2CH2Ph),
2
58.7 (NCH2), 66.5 (d, JC-P = 6.6Hz, OCH2CH2Ph),
125.9, 128.1, 129.0, 138.8 (Ph); 31P NMR (CDCl3): δ
−4.71 (d, 1 JP-F = 923.6 Hz); 19F NMR (CDCl3): δ −77.5
(d, 1 JP-F = 923.5 Hz); MS (FAB) m/z 203 (M+ Bu4N).
N,N,N-Tributyl-1-butanaminium 2-(2-Naphthyl)
ethylphosphorofluoridate (4b). Colorless liquid; IR
(neat): 3052, 2962, 2875, 2193, 1632, 1601, 1508,
1469, 1382, 1113, 1067, 1038, 931, 887, 856, 819, 784,
731, 640, 533, 498, 478 cm−1; 1H NMR (CDCl3): δ 0.98
(t, J = 7.4 Hz, 12H, CH2CH3), 1.40 (sex, J = 7.4 Hz,
8H, CH2CH3), 1.55–1.63 (m, 8H, CH2CH2CH3), 3.15
(t, J = 7.4 Hz, 2H, OCH2CH2), 3.20–3.25 (m, 8H,
NCH2), 4.27 (dt, J = 7.6 Hz, 7.5 Hz, 2H, OCH2),
7.38–7.79 (m, 7H, Ar); 13C NMR (CDCl3): δ 13.7
(CH2CH3), 19.7 (CH2CH3), 24.0 (CH2CH2CH3), 37.4
1
(d, JP-F = 919.5 Hz); 31P NMR (CDCl3): δ −5.4 (d,
1 JP-F = 919.5 Hz); MS (FAB−): m/z: 237 (M−); Anal
Calcd for C26H55FO3P·0.5H2O (479.3904): C, 63.62;
H, 11.71; N, 2.74. Found: C, 63.90; H, 11.55; N,
2.87.
N,N,N-Tributyl-1-butanaminium
2-Tricyclo
3
[3.3.1.13,7]decphosphorofluoridate (4e). Colorless
solid; mp: 151–153◦C; IR (KBr): 2979, 2672, 1456,
1382, 1272, 1120, 1080, 1056, 981, 954, 861, 814,
777, 670, 639, 619, 544, 503, 449, 405 cm−1; 1H
NMR (CDCl3): δ 0.97 (t, J = 7.3 Hz, 12H, CH2CH3),
1.42 (sex, J = 7.3 Hz, 8H, CH2CH3), 1.58–1.65 (m,
8H, NCH2CH2), 1.65–1.73 (m, 10H), 2.08 (br, 2H),
2.19–2.22 (m, 2H), 4.38–4.42 (m, 1H, OCH); 13C
NMR (CDCl3): δ 13.6 (CH2CH3), 19.7 (CH2CH3), 24.0
(NCH2CH2), 27.2, 27.5, 31.3, 33.3 (d, J = 4.9 Hz),
(d, JC-P = 6.8 Hz, OCH2CH2), 58.8 (NCH2), 66.5 (d,
2 JC-P = 5.4 Hz, OCH2), 125.1, 125.7, 127.3, 127.6,
127.7, 127.9, 132.1, 133.6, 136.5 (Ar); 19F NMR
1
(CDCl3): δ −78.0 (d, JP-F = 923.2 Hz); 31P NMR
1
(CDCl3): δ −5.0 (d, JP-F = 923.2 Hz); Anal Calcd.
for C28H47FO3P·1H2O (495.3278): C, 65.52; H, 9.51;
N, 2.87. Found: C, 65.47; H, 9.62; N, 2.73.
N,N,N-Tributyl-1-butanaminium
Tricyclo
[3.3.1.13,7] dec-1-methyl Phosphorofluoridate (4c).
Colorless solid; mp: 155–156◦C◦ IR (neat): 3902,
3842, 3798, 3729, 3674, 3439, 2905, 2849, 2676,
1638, 1593, 1490, 1465, 1383, 1363, 1345, 1273,
1189, 1156, 1112, 1047, 989, 941, 921, 884, 849, 806,
772, 693, 608, 577, 521, 499, 480, 468, 444, 427,
2
36.5, 37.8, 78.5 (d, JC-P = 6.6 Hz, OCH); 19F NMR
1
(CDCl3): δ −73.6 (d, JP-F = 918.3 Hz); 31P NMR
1
(CDCl3): δ −4.7 (d, JP-F = 918.3 Hz); MS (FAB−):
m/z: 233 (M−).
1
409 cm−1; H NMR (CDCl3): δ 1.00 (t, J = 7.3 Hz,
N,N,N-Tributyl-1-butanaminium 1,4:3,6-Dian-
12H, CH3), 1.45 (sext, J = 7.3 Hz, 8H, CH2CH3),
1.51–1.57 (m, 6H, OCH2CCH2CHCH2), 1.61–1.74 (m,
8H, NCH2CH2 and m, 6H, CCH2CHCH2), 1.86–1.94
(dr, 3H, CCH2CHCH2), 3.33 (t, J = 8.3 Hz, 8H,
NCH2CH2), 3.54 (d, J = 5.4 Hz, 2H, OCH2CCH2);
hydro-2-O-benzylglucidephosphorofluoridate
(4f).
Colorless oil; [α]2D5 = +24.0 (c = 1.0, CHCl3); IR
(neat): 3410, 2960, 2873, 1648, 1458, 1383, 1291,
1208, 1093, 1017, 979, 933, 887, 855, 829, 776, 739,
700, 611, 538, 500, 478, 466, 454, 429, 415 cm−1; 1H
Heteroatom Chemistry DOI 10.1002/hc

Synthesis, NMR Properties, and Application of Phosphorofluoridic Acid Ammonium Salts and Acids 423
NMR (CDCl3) δ 0.92 (t, J = 7.3 Hz, 12H, CH3), 1.35
Typical Procedure for Methylation of the Salts:
Synthesis of a Mixture of Diastereomers of
Phosphorofluoridic Acid and l-Menthyl Methyl
Ester (7d)
(sext, J = 7.3 Hz, 8H, CH2CH3), 1.52–1.56 (m, 8H,
NCH2CH2), 3.22 (t, J = 8.3 Hz, 8H, NCH2CH2), 3.62–
3.70 (m, 1H), 3.88 (d, J = 2.9 Hz, 2H), 3.94–3.99
(m, 2H), 4.44–4.52 (m, 3H), 4.58–4.60 (m, 1H),
4.71–4.81 (m, 1H, POCH), 7.16–7.29 (m, 5H, Ph);13C
NMR (CDCl3): δ 13.7 (CH3), 19.7 (CH2CH3), 24.0
(NCH2CH2), 58.7 (NCH2), 69.8 (d, J = 5.8 Hz),
71.4, 73.3, 75.4 (d, J = 5.8), 81.2 (d, J = 5.0 Hz),
84.1, 85.5, 127.6, 127.7, 128.4, 137.7 (Ph); 31P NMR
To an Et2O solution (3 mL) of the ammonium
salt 4d (170 mg, 0.35 mmol), iodomethane (89 μL,
1.4 mmol) was added under an Ar atmosphere. Af-
ter the addition was complete, the mixture was
stirred for 4 h at room temperature. The reaction
mixture was poured into water and extracted with
Et2O. The organic layer was dried over MgSO4, fil-
tered, concentrated in vacuo, and purified by col-
umn chromatography on silica gel (ethyl acetate:
hexane = 1:3, Rf = 0.53) to give to give diastere-
omeric mixture (51:49) 7d (21 mg, 24%) as a col-
orless oil. IR (neat): 2958, 2872, 1458, 1304, 1025,
1
(CDCl3): δ −5.90 (d, JP-F = 929.6 Hz); 19F NMR
(CDCl3): δ −75.6 (d, 1 JP-F = 931.1 Hz); MS (FAB) m/z
317 (M+ Bu4N).
N,N,N-Tributyl-1-butanaminium 1,4:3,6-Dian-
hydro-2-O-benzylglucidephosphorofluoridate
(4g).
Colorless oil; [α]2D5 = +54.1 (c = 1.0, CHCl3); IR
(neat): 3402, 2962, 2875, 1647, 1465, 1382, 1280,
1119, 1078, 1007, 886, 822, 745, 701, 604, 511, 472,
460, 443, 433, 422, 409 cm−1; 1H NMR (CDCl3):
δ 0.97 (t, J = 7.3 Hz, 12H, CH3), 1.41 (sext, J =
7.4 Hz, 8H, CH2CH3), 1.58–1.62 (m, 8H, NCH2CH2),
3.26 (t, J = 8.3 Hz, 8H, NCH2CH2), 3.53 (t, J =
8.3 Hz, 1H), 3.82 (t, J = 7.8 Hz, 1H), 3.94–4.04 (m,
2H), 4.13–4.19 (m, 1H), 4.52 (d, J = 11.7 Hz, 1H),
4.58–4.62 (m, 1H), 4.62–4.66 (m, 1H), 4.72 (d, J =
11.7 Hz, 1H), 4.76–4.81 (m, 1H), 7.24–7.32 (m, 5H,
Ph); 13C NMR (CDCl3): δ 13.6 (CH3), 19.7 (CH2CH3),
24.0 (NCH2CH2), 58.7 (NCH2), 69.6, 72.3, 75.1 (d,
J = 4.1 Hz), 79.5, 79.9, 80.0 (d, J = 3.0 Hz), 87.2
(d, J = 7.4 Hz), 127.8, 128.0, 128.4, 129.2, 137.8
(Ph); 31P NMR (CDCl3): δ −6.58 (d, J = 926.6 Hz);
19F NMR (CDCl3): δ −74.7 (d, 2 JP-F = 928.1 Hz); MS
(FAB) m/z 317 (M+ Bu4N).
1
878, 788, 430, 418 cm−1; H NMR (CDCl3): δ 0.75
(d, J = 6.8 Hz, 3H, OCHCH2CHCH3), 0.76 (d, J =
7.2 Hz, 3H, OCHCH2CHCH3), 0.86 (d, J = 6.8 Hz,
6H, OCHCHCH(CH3)2), 0.87 (d, J = 6.0 Hz, 6H,
OCHCHCH(CH3)2), 0.78–1.01 (m, 2H, m, 2H), 1.01–
1.20 (m, 1H, m, 1H), 1.31–1.42 (m, 2H, m, 2H), 1.60–
1.63 (m, 2H, m, 2H), 2.00–2.04 (m, 1H, m, 1H), 2.12–
2.16 (m, 1H, m, 1H), 3.81 (d, J = 11.2 Hz, 3H, OCH3),
3.82 (d, J = 11.6 Hz, 3H, OCH3), 4.22–4.31 (m, 1H,
OCH, m, 1H, OCH); 13C NMR (CDCl3): δ 15.6, 15.7,
20.8, 20.8, 21.9, 21.9, 23.0, 23.0, 25.7, 25.8, 31.5, 31.5,
33.8, 33.8, 42.2, 42.3, 48.2, 48.3, 55.2 (d, J = 6.6 Hz,
2
OCH3), 55.3 (d, J = 5.8 Hz, OCH3), 82.08 (d, JC-P
2
= 6.6 Hz, OCH), 82.14 (d, JC-P = 5.8 Hz, OCH); 19F
1
NMR (CDCl3): δ −79.6 (d, JP-F = 976.9 Hz), −81.8
1
(d, JP-F = 976.9 Hz); 31P NMR (CDCl3): δ −7.7 (d,
1 JP-F = 976.9 Hz), −8.1 (d, 1 JP-F = 976.9 Hz).
Phosphorofluoridic Acid Methyl 2-Naphthylethyl
Ester (7b). IR (neat): 3402, 2960, 1602, 1509, 1458,
1313, 1192, 1115, 1029, 948, 887, 822, 749, 619, 521,
N,N,N-Tributyl-1-butanaminium
1-Tricyclo
[3.3.1.13,7]decphosphorofluoridate (4h). Viscous
solid; IR (neat): 3925, 3903, 3882, 3856, 3845, 3755,
3738, 3693, 3679, 3402, 2912, 2681, 2343, 1637,
1604, 1592, 1489, 1458, 1382, 1368, 1357, 1260,
1184, 1151, 1119, 1101, 1067, 1029, 998, 984, 961,
934, 885, 838, 813, 773, 711, 695, 643, 618, 592,
1
481, 411, 402 cm−1; H NMR (CDCl3): δ 3.10 (t, J =
6.8 Hz, 2H, OCH2CH2), 4.32 (dt, J = 7.8 Hz, 7.3 Hz,
2H, OCH2), 7.12–7.77 (m, 7H, Ar); 13C NMR (CDCl3):
δ 39.0 (d, J = 6.6 Hz, OCH2CH2), 78.2 (dd, J = 1.7 Hz,
J = 1.7 Hz, OCH2), 126.1, 128.4, 128.5, 141.1 (Ar); 19
F
NMR (CDCl3): δ −77.8 (d, 1 JP-F = 945.8 Hz); 31P NMR
542, 508, 479, 467, 454, 441, 419 cm−1; H NMR
1
1
(CDCl3): δ −8.4 (d, JP-F = 945.8 Hz); MS (EI): m/z:
(CDCl3): δ 1.00 (t, J = 7.3 Hz, 12H, CH3), 1.45
(sext, J = 7.8 Hz, 8H, CH2CH3), 1.54–1.71 (m, 8H,
NCH2CH2, m, 6H, OCCH2CHCH2), 2.05–2.15 (m,
6H, OCCH2), 2.15–2.24 (m, 3H, OCCH2CH), 3.32
(t, J = 8.3 Hz, 8H, NCH2CH2); 13C NMR (CDCl3): δ
268 (M+); HRMS Calcd for C13H14FO3P: 268.0659,
Found: 268.0640.
Typical Procedure for the Acid Hydrolysis of
Phosphorofluoridic Acid Salt Monoesters
13.7 (CH3), 19.7 (CH2CH3), 24.0 (CH2CH2CH3), 31.0
3
(OCCH2CH), 36.2 (OCCH2CHCH2), 43.3 (d, JC-P
=
4.1 Hz, OCCH2), 58.8 (NCH2), 68.0 (OCCH2); 31P
Synthesis Phosphorofluoridic Acid 2-Phenylethyl
Ester (8a). To a CH2Cl2 solution (7 mL) of tetra-
butylammonium salt 4a (446 mg, 1.0 mmol),
Amberlyst15 H+ (2.92 g) was added at room
1
NMR (CDCl3): δ −8.27 (d, JP-F = 920.7 Hz); 19F
1
NMR (CDCl3): δ −67.0 (d, JP-F = 919.7 Hz); MS
(FAB) m/z 233 (M+ Bu4N).
Heteroatom Chemistry DOI 10.1002/hc

424 Murai, Tonomura, and Takenaka
636, 526, 497, 446, 438, 426 cm−1; 1H NMR (CDCl3):
δ 1.52–1.55 (m, 2H), 1.68–1.71 (m, 4H), 1.81–1.88
(m, 4H), 2.07–2.10 (m, 4H), 4.60 (br, 1H, OCH), 8.39
temperature. The mixture was stirred for 2 h at room
temperature. The reaction mixture was filtered and
washed with CH2Cl2 (10 mL). The filtrate was dried
over MgSO4, filtered, and concentrated in vacuo to
give phosphorofluoridic acid 8a (186 mg, 91%) as a
colorless oil. IR (neat): 3031, 2967, 1698, 1497, 1472,
1455, 1217, 1057, 903, 749, 700, 590, 576, 527, 494,
439, 427, 417, 401 cm−1; 1H NMR (CDCl3): δ 2.10 (1H,
POH), 2.96 (t, J = 7.1 Hz, 2H, CH2CH2O), 4.26 (q,
J = 7.3 Hz, 2H, CH2CH2O), 7.10–7.26 (m, 5H,
(br, 1H, OH); 13C NMR (CDCl3): δ 26.6, 27.0, 30.9,
2
33.1 (d, J = 9.6 Hz), 36.2, 37.2, 84.5 (d, JC-P
=
=
=
1
6.6 Hz, OCH); 19F NMR (CDCl3): δ −77.8 (d, JP-F
1
945.4 Hz); 31P NMR (CDCl3): δ −8.6 (d, JP-F
945.4 Hz); MS (EI) m/z 234 (M+) HRMS. Calcd for
C10H16NO3P: 234.0821, Found: 234.0819.
3
Ph); 13C NMR (CDCl3): δ 36.4 (d, JC-P = 7.4 Hz,
Phosphorofluoridic Acid 1-Tricyclo[3.3.1.13,7]
dec Ester (8h). Colorless oil; IR (neat): 3988, 3966,
3954, 3932, 3922, 3911, 3900, 3886, 3858, 3820, 3805,
3790, 3762, 3749, 3735, 3719, 3708, 3620, 3608, 3453,
3431, 3341, 2842, 2663, 1616, 1593, 1519, 1453, 1419,
1384, 1353, 1335, 1315, 1301, 1281, 1227, 1174, 1116,
1088, 1038, 1014, 982, 927, 891, 813, 776, 755, 723,
643 cm−1; 1H NMR (CDCl3): δ 1.56–1.65 (m, 6H,
OCCH2CHCH2), 1.71 (d, J = 9.3 Hz, 6H, OCCH2),
2.10–2.15 (m, 3H, OCCH2CH), 3.20–3.22 (br, 1H,
POH); 13C NMR (CDCl3): δ 30.7 (OCCH2CH), 35.5
(OCCH2CHCH2), 36.0 (OCCH2), 45.2 (OCCH2); 31P
OCH2CH2Ph), 69.8 (d, 2 JC-P = 5.8 Hz, OCH2CH2Ph),
127.0, 128.6, 128.9, 136.1 (Ph); 31P NMR (CDCl3):
1
δ −7.66 (d, JP-F = 950.3 Hz); 19F NMR (CDCl3): δ
1
−80.6 (d, JP-F = 949.4 Hz); MS (EI) m/z 204 (M+);
HRMS Calcd for C8H10FO3P-H+ (M+) 203.0273,
Found 203.0284.
Phosphofluoridic Acid Tricyclo[3.3.1.13,7]dec-1-
methyl Ester (8c). Viscous colorless solid; IR (neat):
2906, 2850, 2678, 2305, 1698, 1453, 1390, 1365, 1345,
1264, 1155, 1037, 945, 928, 893, 831, 803, 719, 648,
599, 504, 480, 468, 440, 428, 406 cm−1;1H NMR
(CDCl3): δ 1.47–1.57 (m, 6H, OCH2CCH2CHCH2),
1.67 (d, J = 23.4 Hz, 3H, CCH2CHCH2 and d,
J = 47.3 Hz, 3H, CCH2CHCH2), 1.95–2.05 (m,
3H, OCH2CCH2CH), 3.70 (d, J = 5.8 Hz, 2H,
OCH2CCH2), 6.54 (s, 1H, POH);13C NMR (CDCl3):
δ 27.8 (OCH2CCH2CH), 34.0 (OCH2CCH2), 36.7
(OCH2CCH2CHCH2), 38.4 (OCH2CCH2CH), 79.1 (d,
2 JC-P = 6.6 Hz, OCH2CCH2); 31P NMR (CDCl3: δ
1
NMR (CDCl3): δ −10.1 (d, JP-F = 944.4 Hz); 19F
NMR (CDCl3): δ −71.4 (d, 1 JP-F = 944.1 Hz); MS (EI)
m/z 234 (M+); HRMS Calcd. for C10H16FO3P (M+)
234.0821. Found 234.0854.
2-Methyl-3-hexyne 2-Bromobutyrate (11)
Phosphoric acid l-menthyl ester 8e (24 mg,
0.10 mmol), 2-bromobutyric acid (9) (0.21 mL,
2.0 mmol), and 3-hexyn-2-ol (10) (294 mg, 3.0 mmol)
were added to a reaction tube. The resulting solution
was stirred at 140◦C◦ or 6 h. The reaction mixture
was purified by column chromatography on silica
gel (EtOAc : hexane = 1:10, Rf = 0.45) (column size:
φ25 mm, height: ca 25 cm) to give the corresponding
ester 11 (346 mg, 70%) as a colorless oil.
1
−6.58 (d, JP-F = 944.4 Hz); 19F NMR (CDCl3) δ
1
−81.3 (d, JP-F = 946.4 Hz); MS (EI) m/z 249 (M+);
HRMS Calcd for C11H18FO3P-H+ (M+) 247.0899,
Found 247.0877.
Phosphorofluoridic Acid L-Menthyl Ester (8d).
Colorless oil; IR (neat): 3432, 2958, 2872, 2619,
2197, 1672, 1457, 1389, 1371, 1350, 1240, 1030, 978,
941, 902, 861, 819, 802, 595, 540, 511, 480, 451,
440, 402 cm−1; 1H NMR (CDCl3): δ 0.79 (d, J =
6.8 Hz, 3H, OCHCH2CHCH3), 0.90 (d, J = 7.4 Hz,
3H, OCHCHCH(CH3)2), 0.92 (d, J = 7.8 Hz, 3H,
OCHCHCH(CH3)2), 0.78–1.05 (m, 3H), 1.22 (q, J =
11.9 Hz, 1H), 1.37–1.44 (m, 2H), 1.62–1.70 (m, 2H),
2.06–2.18 (m, 2H), 4.21–4.29 (m, 1H, OCH); 13C NMR
(CDCl3): δ 15.6, 20.8, 21.9, 23.0, 25.6, 31.6, 33.9, 42.1,
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