The crystal structure of dimethyl 4-methoxy-2,3,5,6-tetrachlorophenyl phosphate

Article abstract of DOI:10.1023/A:1009583531502

The crystal structure of dimethyl 4-methoxy-2,3,5,6-tetrachlorophenyl phosphate was determined by X-ray analysis. It crystallized in the space group P2₁/c (#14) with a = 9.446(2), b = 11.977(2), c = 12.306(2) A, β = 96.55(1)°, V = 1383.1(4) A³, D_calc = 1,665 5/cm³, and Z = 4.

Full text of DOI:10.1023/A:1009583531502

Journal of Chemical Crystallography, Vol. 29, No. 4, 1999
Notes
The crystal structure of dimethyl 4-methoxy-2,3,5,6-
tetrachlorophenyl phosphate
Min Shi(1)
Received November 23, 1998
The crystal structure of dimethyl 4-methoxy-2,3,5,6-tetrachlorophenyl phosphate was deter-
mined by X-ray analysis. It crystallized in the space group P21/c (#14) with a ϭ 9.446(2),
3
b ϭ 11.977(2), c ϭ 12.306(2) A, ͱ ϭ 96.55(1)Њ, V ϭ 1383.1(4) A , Dcalc ϭ 1,665 5/cm3, and
˚
˚
Z ϭ 4.
KEY WORDS: Chloranil; phosphite; phosphate; hydroquinone.
Introduction
It is well known that the reaction of triisopropyl
phosphite with chloranil afforded the corresponding
benzoquinone (1), while the reaction of trimethyl
phospite or triethyl phospite with chloranil gave hy-
droquinone monoalkyl ether (2) or (3) (Scheme 1).1
The reaction difference between the two phosphites
has been explained by the fact that the attack of
the bulky tetrachlorophenoxide ion on a secondary
carbon would be more difficult than on a primary
carbon.1c However, the real structure of 2 has not
Fig. 1. Molecular structure of 2.2
Scheme 1
(1) Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, 354 Fenglin Lu, Shanghai 200032, China.
been previously disclosed. Herein, we wish to report
the X-ray crystal structure of 2.
497
1074-1542/99/0400-0497$16.00/0  1999 Plenum Publishing Corporation

498
Shi
Table 1. Crystal data and summary of intensity data collection
Table 2. Atomic coordinates and Biso/Beq
and structure refinement
a
Atom
x
y
z
Beq
Empirical formula
CCDC deposit no.
Formular weight
Crystal color, habit
Crystal Dimensions
Crystal system
C9H9Cl4O5P
CCDC-1003/5550
369.95
colorless, prismatic
0.20 ϫ 0.20 ϫ 0.30 mm
monoclinic
C1(1)
C1(2)
C1(3)
C1(4)
P(1)
0.51115(7)
0.56216(8)
0.85745(8)
0.82154(8)
0.86705(7)
0.6412(2)
0.7306(2)
0.9324(2)
0.8063(2)
0.9724(2)
0.6683(2)
0.6101(2)
0.6326(2)
0.7129(2)
0.7688(3)
0.7484(3)
0.7476(4)
0.7157(4)
0.9335(4)
0.751(4)
0.45844(6)
0.22029(6)
0.40335(6)
0.64000(6)
0.14174(5)
0.6399(1)
0.2194(1)
0.1687(2)
0.0235(2)
0.1547(2)
0.5363(2)
0.4421(2)
0.3366(2)
0.3245(2)
0.4178(2)
0.5235(2)
0.6797(3)
Ϫ0.0340(3)
0.1223(3)
0.629(3)
0.23921(6)
0.14516(6)
Ϫ0.15730(5)
Ϫ0.05384(6)
Ϫ0.00129(5)
0.1265(2)
Ϫ0.0413(1)
0.1072(1)
Ϫ0.0255(2)
Ϫ0.0894(1)
0.0872(2)
0.1311(2)
0.0891(2)
0.0026(2)
Ϫ0.0438(2)
Ϫ0.0002(2)
0.2111(3)
0.0432(4)
Ϫ0.2013(3)
0.273(3)
3.91(2)
3.88(2)
3.54(2)
3.91(2)
2.84(1)
3.57(4)
2.81(4)
3.99(4)
4.15(5)
3.46(4)
2.75(5)
2.66(5)
2.53(5)
2.50(5)
2.53(5)
2.72(5)
4.30(8)
4.85(9)
4.29(8)
5.4(8)
O(1)
O(2)
O(3)
O(4)
O(5)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
H(1)
H(2)
H(3)
H(4)
H(5)
H(6)
H(7)
H(8)
H(9)
Lattice type
Primitive
Lattice parameters
˚
a, A
9.446(2)
˚
b, A
11.977(2)
12.306(2)
96.55(1)
˚
c, A
ͱ, Њ
V, A
3
˚
1383.1(4)
P21/c (#14)
4
Space group
Z value
Dcalc
F(000)
Ȑ (MoKͰ)
Diffractometer/scan
Radiation, graphite
monochromator
Temperature
1.776 g/cm3
744.00
9.80 cmϪ1
Rigaku AFC7R
˚
0.834(4)
0.717(4)
0.765(4)
0.640(5)
0.722(5)
0.852(6)
0.935(4)
0.997(4)
0.683(3)
0.755(3)
0.008(3)
0.005(4)
Ϫ0.100(4)
0.156(4)
0.043(3)
0.179(3)
0.227(3)
0.111(3)
0.023(4)
6.9(10)
6.1(8)
6.9(9)
7(1)
9(1)
11(1)
6.8(10)
6.4(10)
MoKͰ (␭ ϭ 0.71069 A)
20.0ЊC
50.0Њ
(1.78 ϩ 0.30 tan ␪)Њ
0.03
0.032; 0.045
2␪
max
0.031(4)
Scan width
␳-factor
Residuals: R; Rw
Ϫ0.232(4)
Ϫ0.207(3)
Ϫ0.237(3)
0.146(3)
8
3
a Beq
ϭ
ȏ2(U11(aa*)2 ϩ U22(bb*)2 ϩ U33(cc*)2 ϩ 2U12aa*bb**
cos Ͳ ϩ 2U13aa*cc* cos ͱ ϩ 2U23bb*cc* cos Ͱ).
The mass spectrum was recorded with a JMS D-300
instrument. CHN microanalysis was carried out with
a Perkin-Elmer Model 240 analyzer.
A single crystal of this compound could be ob-
tained by recrystallization from ethyl acetate and hex-
ane (1 : 1). The X-ray crystal structure of 2 is shown
in Fig. 1 and the X-ray data are summarized in Table
1. Atomic coordinates are given in Table 2.
Experimental
Compound 2 was obtained from the reaction of
trimethyl phosphite (1.0 g, 8.2 mmol) with chloranil
(2.0 g, 8.2 mmol) in benzene under reflux for 4 h.
After the benzene was removed under reduced pres-
sure, 2 was obtained as a colorless solid m.p. 92–94ЊC;
UV (MeCN) ␭ ϭ 276 nm (⑀ ϭ 1120 dm3 molϪ1
max
cmϪ1); IR (KBr) ␯ 1290 cmϪ1 (PuO); ͳH (CDCl3) 3.90
(3H, s, Me), 3.98 (6H, d, J 11.7 Hz, OMe); ͳc (CDCl3)
55.60, 55.66, 60.82, 126.36, 126.40, 128.04, 142.05,
142.12, 151.322; ͳP (CDCl3, 85% H3PO4)—4.46;
MS (FAB) m/z 371 (Mϩ ϩ 1); (Found: C, 29.24; H,
2.40. Calc. for C9H9Cl4O5P requires C, 29.22; H,
2.45%).
Results
Compound 2 was readily synthesized by the reac-
tion of chloranil with trimethyl phosphite in benzene
under reflux and was readily characterized by 1H nmr,
13C nmr, 31P nmr, mass spectroscopy, and micro-
analysis.
The CUC bond lengths of the six-membered
ring are essentially equivalent (1.383U1.390 A) and
the benzene ring is completely planar. The bond
The melting point was obtained with a Yanagi-
moto micro melting point apparatus and is uncor-
1
13
rected. H and C nmr spectra were determined for
a solution in CDCl3 with tetramethylsilane as an in-
ternal standard on a JNM-GX 270 spectrometer. The
31P nmr spectrum was recorded on the same spec-
trometer using 85% H3PO4 as an external standard.
˚
lengths of C1UO1 and C4UO2 are 1.367 and 1.388
˚
A, respectively. They are the CUO single bonds.

Dimethyl 4-methoxy-2,3,5,6-tetrachlorophenyl phosphate
499
The four Cl atoms are located at the 2,3,5,6-position
of the benzene ring and the methoxy group and phos-
phate group are on the 1,4-positions, respectively.
All of the bond lengths and bond angles are normal.
Thus, the structure of 2 was clearly elucidated by X-
ray analysis.
References
1. (a) Reetz, T. U.S. Patent 2935518, 19609, CA 54, 19598, 1960;
(b) Reetz, T.; Powers, J.F.; Grahan, G.R. Abstract of papers
for the 134th meeting; Am. Chem. Soc.: Chicago, 1958; p 86;
(c) Ramirez, F.; Chen, E.H.; Dershowitz, S. J. Am. Chem. Soc.
1959, 81, 4338.