The preparation of alkylaryldichlorocyclopropanol phosphates

Article abstract of DOI:10.1080/10426500307780

In the present article we report the preparation of alkylaryldichlorocyclopropanol phosphates by the addition of dichlorocarbene to enol phosphates of propiophenone and cyclohexanone with steric hinderance. The stereoselectivity of enol phosphates and the effect of substituents on the carbene addition rate are discussed.

Full text of DOI:10.1080/10426500307780

This article was downloaded by: [George Mason University]
On: 25 December 2014, At: 06:44
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK
Phosphorus, Sulfur, and Silicon and the Related
Elements
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/gpss20
The Preparation of Alkylaryldichlorocyclopropanol
Phosphates
Qi Xi a , Xingji Lin b , Jianhua Chang a & Yixiang Ding b
a Northwest University , Xian
b Chinese Academic of Science , Shanghai
Published online: 27 Oct 2010.
To cite this article: Qi Xi , Xingji Lin , Jianhua Chang & Yixiang Ding (2003) The Preparation of Alkylaryldichlorocyclopropanol
Phosphates, Phosphorus, Sulfur, and Silicon and the Related Elements, 178:1, 47-54, DOI: 10.1080/10426500307780
To link to this article: http://dx.doi.org/10.1080/10426500307780
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions

Phosphorus, Sulfur and Silicon, 2003, Vol. 178:47–54
C
Copyright 2003 Taylor & Francis
1042-6507/03 $12.00 + .00
DOI: 10.1080/10426500390170147
THE PREPARATION OF
ALKYLARYLDICHLOROCYCLOPROPANOL
PHOSPHATES
Qi Xi,a Xingji Lin,b Jianhua Chang,a and Yixiang Ding b
Northwest University, Xiana and Chinese Academic of Science,
Shanghaib
(Received July 9, 2002)
In the present article we report the preparation of alkylaryldichlorocy-
clopropanol phosphates by the addition of dichlorocarbene to enol phos-
phates of propiophenone and cyclohexanone with steric hinderance. The
stereoselectivity of enol phosphates and the effect of substituents on the
carbene addition rate are discussed.
Keywords: Addition; carbene; enol phosphate
Cyclopropanol is an important structure for the enzyme inhibitor,1 its
phosphates may be potential bioactive compounds. The easiest syn-
thetic method is carbene addition to enol phosphates.
Due to the electron-withdrawing effect of the phosphoryl and phenyl
group, aryl substituted enol phosphates can be regarded as electron-
poor alkenes and relatively unreactive substrances, the carbene addi-
tion produces a complicated situation and gives a poor yield. Selms2
obtained the dichlorocyclopropanol phosphates in an average yield of
25% by addition of carbene, generated from sodium trichloroacetate, to
enol phosphates. Dichlorocarbene generated by phase-transfer reaction
is exceptionally reactive toward substrates which hardly react.3 To im-
prove the addition reaction, Toke4 studied the dichlorocarbene addition
to enol phosphate under PTC condition.
In this article, we report on the addition of dichlorocarbene to more
sterically hindered enol phosphates of propiophenone 2a–j and cyclo-
hexanone 2k by the Toke method to prepare alkyl and aryl substituted
cyclopropanol phosphates. The stereoselectivity of enol phosphates and
the effect of substituents on the carbene addition rate are discussed.
Address correspondence to Yixiang Ding, Shanghai Institute of Organic Chemistry,
354 Feng Liu Lu, Shanghai 200032, China. E-mail: dingyx@pub.sioc.ac.cn
47

48
Q. Xi et al.
a
b
c
d
e
f
g
h
i
j
X
H
4-Me 4-MeO 4-Cl 2,4-Me2 H 4-Me 4-MeO 4-Cl 2,4-Me2
Me Me Me Et Et Et Et Et
R Me Me
RESULTS AND DISCUSSION
All enol phosphates used in the present work were prepared by re-
action of dialkyl phosphorochloridate with enolate anion that formed
from phenyl ethyl ketone and LDA under kinetically controlled condi-
tion as shown in Table I. LiBu and NEt3 as base or the Atherton-Todd
procedure gave poorer results.
We found that all of the propiophenones listed in Table I, except
for compounds 2e and 2j, formed Z-isomers under the given condi-
tions in a highly stereoselective manner. The structures of the products
TABLE I Preparation of Enol Phosphates
No.
Yield (%)a of 2
Z:Eb of 2
Yield (%)a of 3
a
b
c
d
e
f
g
h
i
70
65
58
72
59
56
54
75
90
69
78
>95:5
>95:5
>95:5
>95:5
4:6
>95:5
>95:5
>95:5
>95:5
4:6
57
70
98
60
59c
68
63
98
54
50c
75
j
k
aIsolated yield.
bThe Z:E ratios were determined by 1H-NMR
analyses of the vinyl proton peaks of reaction
products in the crude reaction mixture.
cThe ratios of cis and trans isomers of
cyclopropanol phosphates 3e or 3j are 3:7, the
difference with 2e and 2j may be contributed to
experimental and NMR error.

Enol Phosphates
49
were assigned on the basis of 1H-NMR spectral analysis; the spec-
trum did not show the vinyl proton peak of the E isomer. TLC mon-
itoring did not show the presence of other products. In each case, this
analysis was carried out on the crude product prior to purification by
chromatography.
The stereoselectivity can be rationalized by the CIPE hypothesis
(complex-induced proximity effect).5 The more stable cis-conformation
of propiophenones would lead to the formation of predominantly Z-
isomer6 of enol phosphates. In order to have more precise geometries
PM3 semiempirical quantum mechanics calculation was performed.
The binding energy and the heat of formation of cis conformations of the
phenone 2d are 2129.986 kcal/mol and 32.177 kcal/mol respectively;
that of gauche conformation are 2125.623 kcal/mol and 36.540 kcal/
mol. Cis-conformation is proved to be more stable than gauche.
In carbene addition reaction phase transfer catalysis was used to
generate dichlorocarbene. A solution of the enol phosphates and TEBAC
in chloroform was stirred with 50% aqueous sodium hydroxide at room
temperature resulting in the formation of the adducts 3 as summarized
in Table I.
1
The H NMR spectra of all compounds showed that the two alkyl
groups of phosphates are magnetic nonequivalent, because of the dif-
ferent relative position to the magnetically anisotropic benzene ring.7
Because the dichlorocarbene is a strong electronphile, electron-
withdrawing group will decrease the reaction rate, but the range of
relative rates is not great.8 We examined relative rates of addition of
dichlorocarbene to enol phosphates by the competing reaction, the re-
sults are shown in Table II, X represents the group at the benzene ring.
The experimental results were consistent with the expectation.
EXPERIMENTS
All melting points were uncorrected. IR spectra were measured with
1
a Shimadzu IR-440 spectrometer. H-NMR spectra were recorded on
TABLE II Relative Addition Rates of
Dichlorocarbene to Enol Phosphates
No.
X
Relative rates (GC)
3f
3g
3h
3i
H
1.00
1.04
1.27
0.91
3.78
4-methyl
4-methoxyl
4-chloro
3j
2,4-dimethyl

50
Q. Xi et al.
AM-300 or DPX-400 using TMS as internal standard and CDCl3 as sol-
vent. Mass and HRMS spectra were taken on a Finnigan GC-MS-4021
spectrometer. Elemental analyses were done by the Elemental Analy-
ses Group of SIOC. The known compounds were identified in agreement
with the literature data, and only the NMR data are reported here.
Phenyl ethyl ketones and diethyl phosphochloriate were prepared by
known methods with purity of >97% (GC).
General Procedure for the Preparation
of Enol Phosphates
Under nitrogen atmosphere a multi-necked round bottom flask was
charged with dry THF and HN(i-Pr)2. The mixture was stirred and
cooled to 0 C. The BuLi solution in hexane (1.5 M) was added. 30 min.
Later, a solution of propiophenone in THF was added dropwise at
78 C. After 1 h phosphochloridate was added. The reaction tempera-
ture was allowed to warm to rt. When the reaction was completed as
determined by TLC (about 2 h), the reaction mixture was neutralized
with acetic acid and then filtered. The filtrate was washed with water,
dried over Na2SO4, and concentrated in vacuo to give an oil. The pure
product was obtained after flash chromatography on silica gel (using
petroleum ether and ethyl acetate as eluent).
2a: 1H NMR (300 MHz) : 7.49 (d, J = 7.8 Hz, 2H), 7.64 (m, 3H), 5.67
(q, J = 7.0 Hz, 1H), 3.72 (d, J = 11 Hz, 6H), 1.88 (d, J = 7.0 Hz, 3H). m/z:
242 (M+, 19.50), 131 (1.49), 127 (100.00), 115 (65.34), 116 (34.13), 109
(13.58), 91 (4.28), 77 (13.97). IR (film): 2959, 2858, 1667, 1447, 1578,
1040, 852, 520 cm 1. Anal. calcd. For C11H15O4P: C, 54.55; H, 6.20.
Found: C, 54.28; H, 6.40.
2b: 1H NMR (300 MHz) : 7.38 (d, J = 7.4 Hz, 2H), 7.15 (d, J = 7.4 Hz,
2H), 5.14 (q, J = 7.0 Hz, 1H), 3.74 (d, J = 11 Hz, 6H), 2.34 (s, 3H), 1.87
(d, J = 7.0 Hz, 3 H). m/z: 257 (M+ + 1, 26.11), 256 (M+, 59.29), 245
(4.69), 130 (76.98), 127 (100.00), 115 (64.49), 109 (16.09), 91 (20.81). IR
(film): 2958, 2858, 1668, 1513, 1277, 1035, 852, 525 cm 1. Anal. cacld.
for C12H17O4P: C, 56.25; H, 6.64. Found: C, 56.07; H, 6.92.
2c: 1H NMR (300 MHz) : 7.42 (d, J = 7.0 Hz, 2H), 6.85 (d, J = 7.0 Hz,
2H), 5.53 (q, J = 7.0 Hz, 1H), 3.75 (d, J = 11 Hz, 6H), 3.70 (s, 3H), 1.86
(d, J = 7.0 Hz, 3H). m/z: 272 (M+, 24.32), 146 (100.00), 131 (45.31),
127 (20.75), 115 (9.40), 109 (14.19), 103 (39.02), 91 (5.82). IR (film):
2959, 2857, 1669, 1513, 1251, 1033, 850, 590 cm 1. Anal. cacld. For
C12H17O5P: C, 52.94; H, 6.25. Found: C, 53.52; H, 6.46.
1
2d: H NMR (300 MHz) : 7.39 7.44 (m, 4H), 5.67 (q, J = 7.1 Hz,
1H), 3.73 (d, J = 11 Hz, 6H), 1.84 (d, J = 7.1 Hz, 6 H). m/z: 276

Enol Phosphates
51
(M+, 7.72), 241 (2.04), 150 (11.58), 127 (100.00), 115 (37.37), 109
(27.69), 95 (4.36), 79 (5.25). IR (film): 2959, 2858, 1666, 1492, 1278,
1036, 852, 508 cm 1. HRMS cacld. for C11H14ClO4P: 276.0318; Found:
276.0325.
1
2e: H NMR (300 MHz) : 6.70 7.71 (m, 3H), 5.63 (q, J = 7.0 Hz,
0.4 1H), 5.13(q, J = 7.0 Hz, 0.60 1H), 3.58 (d, J = 11 Hz, 0.40 6H),
5.07 (d, J = 11 Hz, 0.60 6H), 2.25 2.29 (m, 6H), 1.79 (d, J = 7.0 Hz,
0.60 3H), 1.44 (d, J = 7.0 Hz, 0.40 3H). m/z: 270 (M+, 9.40), 144
(73.86), 130 (13.67), 129 (100.00), 127 (36.95), 115 (9.63), 105 (5.68),
1
77 (5.36). IR (film): 2957, 2858, 1615, 1450, 1280, 1041, 851, 570 cm
.
Anal. cacld. For C13H19O4P: C, 57.78; H, 7.04. Found: C, 57.61; H,
7.13.
1
2f9: H NMR (300 MHz) : 7.51 7.24 (m, 5H), 5.65 (q, J = 7.0 Hz,
1H), 4.06 (m, 4H), 1.87 (d, J = 7.0 Hz, 3H), 1.20 (m, 6H).
2g: 1H NMR (300 MHz) : 7.33 (d, J = 12 Hz, 2H), 7.07 (d, J = 12 Hz,
2H), 5.57 (q, J = 7.0 Hz, 1H), 4.01 (m, 4H), 2.27 (s, 3H), 1.80 (d,
J = 7.0 Hz, 3H), 1.19 (m, 6H). m/z: 284 (M+, 25.17), 257 (3.09), 155
(100.00), 129 (57.97), 127 (50.33), 115 (52.61), 99 (49.12), 91 (28.35). IR
(film): 2984, 2934, 1668, 1445, 1270, 1031, 815, 519 cm 1. HRMS cacld
for C14H21O4P: 284.1178; Found: 284.1174.
2h: 1H NMR (300 MHz) : 7.38 (d, J = 6.9 Hz, 2H), 6.79 (d,
J = 6.9 Hz, 2H), 5.47 (q, J = 7.0 Hz, 1H), 4.06 (m, 4H), 3.74 (s, 3H),
1.81 (d, J = 7.0 Hz, 3H), 1.20 (m, 3 H). m/z: 306 (M+, 6.92), 155
(11.11), 146 (100.00), 131 (43.49), 115 (8.71), 103 (30.30), 99 (8.75),
77 (12.28). IR (film): 2986, 2840, 1668, 1610, 1513, 1250, 1032, 797
cm 1. Anal. cacld. For C14H21O5P: C, 56.00; H, 7.00. Found: C, 55.98; H,
7.05.
2i: 1H NMR (300 MHz) : 7.20 7.39 (m, 4H), 5.60 (q, J = 7.0 Hz, 1H),
4.03 (m, 4H), 1.82 (d, J = 7.0 Hz, 3H), 1.19 (m, 6H). m/z: 306 (M+
+
2, 16.08), 304 (M+, 19.95), 277 (12.50), 155 (100.00), 127 (51.04), 115
(50.49), 99 (47.26), 81 (13.71). IR (film): 2894, 1666, 1492, 1396, 1270,
1093, 1031, 819 cm 1. Anal. cacld. For C13H18ClO4P: C, 51.15; H, 5.90.
Found: C, 50.83; H, 6.22.
1
2j: H NMR (300 MHz) : 6.91 7.17 (m, 3H), 5.67 (q, J = 7.0 Hz,
0.4 1H), 5.13 (q, J = 7.0 Hz, 0.60 1H), 3.93 (m, 4H), 2.27 (m,
6H), 1.81 (d, J = 7.0 Hz, 0.60 3H), 1.45 (d, J = 7.0 Hz, 0.40
3H), 1.18 (m, 6H). m/z: 299 (M+, 11.57), 298 (14.62), 238 (5.54), 155
(100.00), 144 (61.93), 129 (83.19), 127 (20.36), 91 (7.91). IR (film): 2985,
1616, 1445, 1273, 1032, 969, 818, 543 cm 1. Anal. cacld. For C15H23O4P:
C, 60.40; H, 7.72; Found: C, 60.48; H, 7.67.
2k9: 1H NMR (300 MHz) : 5.42 (m, 1H), 4.10 (m, 4H), 2.0–2.3, 1.5–1.9
(m, 8H), 1.35 (t, 6H, J = 7 Hz).

52
Q. Xi et al.
General Procedure for the Preparation of
1-Aryl-2,2-dichlorocyclopropanol Phosphates
The solution of 2.4 mmol enol phosphate in 5 ml chloroform was added
dropwise to the mixture of 0.11 g (0.50 mmol) of TEBAC, 10 ml of chlo-
roform and 8 ml (50% NaOH) at rt. The mixture was stirred and fol-
lowed by TLC until the reaction was finished. The organic layer was
washed and dried. After concentration in vacuo the crude product was
purified by flash column chromatography using a mixture of petroleum
ether (bp 60–90 C) and ethyl acetate as eluent to give the desired
products.
3a: 1H NMR (300 MHz) : 7.58 (m, 2H), 7.43 (m, 3H), 3.63
(d, J = 11 Hz, 3H), 3.23 (d, J = 11 Hz, 3H), 2.25 (q, J = 6.6 Hz, 1H), 1.52
(d, J = 6.6 Hz, 3H). m/z: 325 (M+, 1.50), 289 (5.80), 253 (8.42), 200 (3.32),
163 (100.00), 127 (50.45), 109 (38.01), 77 (35.90). IR (film): 2958, 1450,
1281, 1047, 1005, 854, 702, 486 cm 1. Anal. cacld. For C12H15Cl2O4P:
C, 44.33; H, 4.65. Found: C, 44.49; H, 4.86.
3b: 1H NMR (300 MHz) : 7.47 (d, J = 7.4 Hz, 2H), 7.22 (d, J = 7.4 Hz,
2H), 3.65 (d, J = 11 Hz, 3H), 3.26 (d, J = 11 Hz, 3H), 2.36 (s, 3H), 2.23 (q,
J = 6.6 Hz, 1H), 1.50 (d, J = 6.6 Hz, 3H). m/z: 339 (M+, 0.78), 303 (5.31),
267 (6.80), 214 (4.30), 177 (100.00), 155 (38.12), 91 (22.30), 77 (3.25).
1
IR (film): 2958, 1616, 1452, 1280, 1045, 1280, 1045, 848, 729, 538 cm
.
Anal. cacld. For C13H17Cl2O4P: C, 46.02; H, 5.01; Found: C, 46.24; H,
5.27.
3c: 1H NMR (400 MHz) : 7.42 (d, J = 6.5 Hz, 2H), 6.83 (d, J = 6.5 Hz,
2H), 3.69 (s, 3H), 3.56 (d, J = 11 Hz, 3H), 3.18 (d, J = 11 Hz, 3H),
2.13 (q, J = 6.6 Hz, 1H), 1.39 (d, J = 6.6 Hz, 3H). m/z: 355 (M+,
4.88), 319 (33.57), 283 (5.75), 230 (4.96), 193 (100.00), 158 (4.36), 127
1
(30.88). IR (film): 2958, 1612, 1517, 1255, 1045, 1001, 848, 512 cm
.
Anal. cacld. For C13H17Cl2O5P: C, 43.96; H, 4.82. Found: C, 44.23; H,
5.05.
3d: 1H NMR (400 MHz) : 7.46 (d, J = 8.6 Hz, 2H), 7.33 (d, J = 8.6 Hz,
2H), 3.57 (d, J = 11 Hz, 3H), 3.26 (d, J = 11 Hz, 3H), 2.15 (q, J = 6.6 Hz,
1H), 1.42 (d, J = 6.6 Hz, 3H). m/z: 359 (M+, 32.3), 323 (10.71), 287
(13.57), 235 (16.38), 197 (100.00), 127 (26.75), 109 (4.63), IR (film):
2958, 1598, 1493, 1294, 1047, 1005, 849, 514 cm 1. Anal. cacld. For
C12H14Cl3O4P: C, 40.06; H, 3.90. Found: C, 40.15; H, 4.12.
3e: 1H NMR (400 MHz) : 7.00 7.28 (m, 3H), 3.69, 3.71 (2d,
J = 11 Hz, cis/trans = 3/7, 3H), 3.08, 3.18 (2d, J = 11 Hz, cis/trans, 3H),
2.50, 2.49 (2s, cis/trans, 3H), 2.32 (s, 3H), 2.25 (q, J = 6.6 Hz, 1H), 1.52
(d, J = 6.6 Hz, trans, 0.7 3H), 1.46 (d, J = 6.6 Hz, cis, 0.3 3H). m/z:
353 (M+, 1.51), 317 (5.10), 281 (11.74), 228 (2.64), 191 (100.00), 155
(7.31), 105 (2.30). IR (film): 2958, 1616, 1451, 1281, 1041, 1002, 854,

Enol Phosphates
53
493 cm 1. Anal. cacld. For C14H19Cl2O4P: C, 47.62; H, 5.42. Found: C,
47.78; H, 5.57.
3f: 1H NMR (300 MHz) : 7.58 (m, 2H), 7.40 (m, 3H), 4.00 (m,
2H), 3.73 3.80 (m, 2H), 2.51 (q, J = 6.5 Hz, 1H), 1.33 (d, J = 6.5 Hz,
3H), 0.98 (m, 6H). m/z: 353 (M+, 4.41), 317 (6.58), 281 (7.73), 263
(1.86), 200 (2.24), 163 (100.00), 155 (23.28), 77 (23.13). IR (film): 2986,
1450, 1275, 1034, 886, 702, 512 cm 1. Anal. cacld. For C14H19Cl2O4P:
C, 47.61; H, 5.42. cacld: C, 47.60; H, 5.49.
3g: 1H NMR (400 MHz) : 7.45 (d, J = 7.4 Hz, 2H), 7.22 (d, J = 7.4 Hz,
2H), 4.00 (m, 2H), 3.70 (m, 1H), 3.51 (m, 1H), 3.15 (s, 3H), 2.22
(q, J = 6.6 Hz, 1H), 1.49 (d, J = 6.6 Hz, 3H), 1.28 (m, 3H), 1.01
(m, 3H). m/z: 367 (M+, 7.50), 3.31 (7.51), 295 (5.04), 277 (1.48), 214
(3.87), 177 (100.00), 155 (38.12), 91 (22.30). IR (film): 2985, 1454, 1275,
1034, 1002, 886, 729, 539 cm 1. Anal. cacld. For C15H21Cl2O4P: C, 49.06;
H, 5.76. Found: C, 49.05; H, 5.86.
3h: 1H NMR (400 MHz) : 7.45 (d, J = 7.4 Hz, 2H), 6.86 (d, J = 7.4 Hz,
2H), 3.94 (m, 2H), 3.74 (s, 3H), 3.64 (m, 1H), 3.49 (m, 1H), 2.11 (q,
J = 6.6 Hz, 1H), 1.42 (d, J = 6.6 Hz, 3H), 1.17 (t, J = 7.0 Hz, 3H), 0.95
(t, J = 7.0 Hz, 3H). m/z: 383 (M+, 6.65), 374 (17.55), 311 (2.75), 230
(1.11), 193 (100.00), 155 (11.52), 135 (1.42). IR (film): 2985, 1612, 1517,
1254, 1033, 1000, 886, 519 cm 1. Anal. cacld. For C15H21Cl2O5P: C,
47.01; H, 5.53. Found: C, 46.98; H, 6.05.
3i: 1H NMR (400 MHz) : 7.41 (d, J = 8.5 Hz, 2H), 7.28 (d, J = 8.5 Hz,
2H), 3.92 (m, 2H), 3.64 (m, 1H), 3.51 (m, 1H), 2.11 (q, J = 6.5 Hz, 1H),
1.39 (d, J = 6.5 Hz, 3H), 1.14 (t, J = 4.3 Hz, 3H), 0.93 (t, J, = 4.3 Hz,
3H). m/z: 387 (M+, 31.51), 351 (14.81), 315 (14.95), 297 (1.19), 234 (2.07),
197 (100.00), 155 (29.50). IR (film): 2986, 1599, 1494, 1274, 1033, 1004,
885, 514 cm 1. Anal. cacld. For C14H18Cl3O4P: C, 43.53; H, 4.65. cacld.:
C, 43.36; H, 4.86.
3j: 1H NMR (400 MHz) : 6.98 7.28 (m, 3H), 4.07 (m, 2H), 3.54 (m,
1H), 3.24 (m, 1H), 2.49, 2.48 (2s, cis/trans, 3H), 2.32 (s, 3H), 2.24 (q,
J = 6.6 Hz, 1H), 1.51 (d, J = 6.6 Hz, trans, 0.7 3H), 1.45 (d, J = 6.6 Hz,
cis, 0.3 3H), 1.30 (t, J = 7.1 Hz, 3H), 0.91 (t, J = 7.1 Hz, 3H). m/z: 381
(M+, 1.73), 345 (3.30), 329 (9.01), 228 (2.37), 191 (100.00), 155 (17.07),
1
105 (4.29). IR (film): 2984, 1616, 1452, 1274, 1033, 999, 882, 501 cm
.
Anal. cacld. For: C16H23Cl2O4P: C, 50.41; H, 6.08, cacld.: C, 49.77; H,
6.37.
3k: 1H NMR (400 MHz) : 4.11 (m, 4H), 2.35–2.10 (m, 4H), 1.51–1.65
(m, 2H), 1.32 (t, 3H). m/z: 315 (M+ 1, 1062), 281 (6.67), 233 (100), 205
(29.82), 177 (29.80), 155 (17.35), 127 (23.24), 99 (42.39). IR (film): 2984,
1589, 1473, 1270, 1063, 1040. Anal. cacld. For: C11H19C12O4P: C, 41.64;
H, 5.99. Cacld: C, 41.59; H, 5.99.

54
Q. Xi et al.
REFERENCES
[1] W. O. Foye, T. L. Lemke, and D. A. Williams, Priciples of Medicinal Chemistry
(Williams & Wilkins, 1995), 4th ed.
[2] R. C. De Selms and T. W. Lin, Tetrahedron, 23, 1479 (1967).
[3] E. V. Dehmlow, Angew. Chem. Internat. Edit., 13, 170 (1974).
[4] I. Petnehazy, G. Keglevich, and L. Toke, Phosphorus and Sulfur, 33, 77 (1987).
[5] P. Beak, A. Basn, D. J. Gallagher, Y. S. Park, and S. Thayumanavan, Acc. Chem. Res.,
29, 552 (1996).
[6] Y. X. Ding and X. G. Huang, Heteroatom Chem., 10, 55 (1999).
[7] C. Y. Yuan, Y. X. Ding, H. Y. Long, and S. S. Li, Acta Chimica Sinica, 71 (1983).
[8] a) D. Seyferth, J. Y.-P. Mui, and R. Damrauer, J. Am. Chem. Soc., 90, 6182 (1968);
b) I. H. Sadler, J. Chem. Soc. B, 1969, 1024.
[9] T. Hayashi, T. Fujiwa, Y. Okamoto, Y. Katsuro, and M. Kamada, Synthesis, 1001
(1981).