A methodology for synthesis of primary o-phenylenebisphosphines and o-chlorophenylphosphines

Article abstract of DOI:10.1134/S1070363206060089

On the basis of the reaction of ethynediylbisphosphonates and chloroethynylphosphonates with classical donor alka-1,3-dienes, a general strategy for synthesis of o-bisphosphanylbenzenes and o- chlorophosphanylbenzenes, which includes two consecutive steps

Full text of DOI:10.1134/S1070363206060089

ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 6, pp. 885 894.
Pleiades Publishing, Inc., 2006.
Original Russian Text
S.N. Tverdomed, A.V. Dogadina, B.I. Ionin, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76, No. 6, pp. 925 934.
A Methodology for Synthesis of Primary
o-Phenylenebisphosphines and o-Chlorophenylphosphines
S. N. Tverdomed, A. V. Dogadina, and B. I. Ionin
St. Petersburg State Institute of Technology (Technical University)
Moskovskii pr. 26, St. Petersburg, 190013 Russia
e-mail: bi@thesa.ru
Received April 11, 2006
Abstract On the basis of the reaction of ethynediylbisphosphonates and chloroethynylphosphonates with
classical donor alka-1,3-dienes, a general strategy for synthesis of o-bisphosphanylbenzenes and o-chlorophos-
phanylbenzenes, which includes two consecutive steps: Diels Alder condensation
aromatization of the
carbocyclic phosphonate (bisphosphonate) formed reduction of the phosphonate groups, was developed.
Convenient procedures are devised for aromatization of phosphorus-containing cyclohexa-1,4-dienes and for
reduction of o-phenylenebisphosphonates and o-clorophenylphosphonates to primary phosphines. A series of
new alkylsubstituted phosphonic chlorides were prepared, and a possibility of functionalization of methyl-
substituted o-phenylenebisphosphonates and o-clorophenylphosphonates by the methyl groups is demonstrated.
DOI: 10.1134/S1070363206060089
Primary ring-substituted o-bisphosphanylbenzenes
are of special interest for the coordination chemistry
as polydentate ligands [1]. The simplest representative
of this class of compounds, 1,2-bisphosphanylbenzene,
o-C6H4(PH2)2, has been prepared by reduction of
corresponding o-bisphosphorylated arenes: tetraethyl
o-phenylenebisphosphonate with LiAlH4 [2]; tetra-
methyl o-phenylenebisphosphonate with LiAlH4/
Me3SiCl [3] or Ph2SiH2 [4], as well as o-phenylene-
bis(dichlorophosphane) o-C6H4(PCl2)2 by LiAlH4
[5, 6]. Methods for formation of aromatic precursors
are mostly complicated, give hardly separable mix-
tures, and, as a result, afford low yields. One of the
methods involves substitution of halogens in 1,2-di-
halobenzenes. For example, o-phenylenebisphospho-
nates can be synthesized by a photocatalytic reaction
of dialkyl phosphites with 1-bromo-2-iodo- and 1-
chloro-2-iodobenzene [7] and by photo- [8] or Ni(II)-
catalyzed [9] reactions of trialkyl phosphites with the
above-mentioned 1-iodo-2-halobenzenes or o-dichlo-
robenzene [3]. Another synthetic route to aromatic o-
bisphosphines is based on nucleophilic substitution of
halogens in 1-iodo-2-halobenzenes with Na, K, Li, or
Ca phosphides. Depending on the phosphide used,
secondary or tertiary o-bisphosphanylbenzenes have
been obtained [10 22].
phosphonic acid with some active cyclic dienes
( -pyrone [23], cyclohexa-1,3-diene [24]) with a fixed
cis configuration. The process involves thermal eli-
mination of low-molecular compounds (CO2, C2H4),
resulting in ring aromatization. In the case of 1-phos-
phono-2-propynoic acid as dienophile [25], a high
regioselectivity was noted in the reaction with 1-sub-
stituted butadienes. In all the cases, the initial Diels
Alder adduct was not registered, and compounds
formed by subsequent aromatization of carbocyclic
phosphonates were only described. We earlier re-
ported [26, 27] that 2-chloro- and 2-bromoethynyl-
phosphonates, like ethynediylbisphosphonates, are
active dienophiles in reactions with donor alka-1,3-
dienes (butadiene, isoprene, piperylene, and 2,3-di-
methylbuta-1,3-diene).
In this communication we consider in more details
a general method for synthesis of phenylphosphonates
and o-phenylenebisphosphonates, related dichlorides,
phosphanylbenzenedicarboxylates, and primary phos-
phines, in which the ortho position of two phosphorus
or phosphorus and chlorine substituents is provided
by the formation of a six-membered ring in the Diels
Alder reaction of ethynediylbisphosphonates or halo-
ethynylphosphonates with donor open-chain alka-1,3-
dienes. Ethynediylbisphosphonates are most active in
these reactions. Therewith, the process proceeds
readily at room temperature or under heating at 140
150 C [28].
The Diels Alder reaction provides an alternative
synthetic route to o-phenylenebisphosphonates. Its
classical form (donor diene and acceptor acetylene)
has been realized in the reaction of ethynediylbis-
885

886
TVERDOMED et al.
R1
R1
R1
3
3
4 R2
R3
4 R2
R3
P(O)(OMe)2
||
(MeO)2(O)P 2
(MeO)2(O)P
(MeO)2(O)P 2
(MeO)2(O)P
R2
R3
[O]
+
5
1
5
1
P(O)(OMe)2
6
6
Ia Id
IIa IId
I, R1 = R2 = R3 = H (a); R1 = Me, R2 = R3 = H (b); R1 = R3 = H, R2 = Me (c); R1 = H, R2 = R3 = Me (d).
As objects for study we used tetramethyl ethyne-
air oxygen and, probably, by bromine in catalytic
amounts. With the bisphosphonates prepared from di-
chloroacetylene, such spontaneous aromatization did
not occur. Chloroethynylphosphonates are less active
as dienophiles, but they, too, form corresponding car-
bocyclic o-halophosphonates while at higher tempera-
tures ( 180 200 C) and longer time (8 12 h).
diylbisphosphonate that forms products with lower
boiling points. Carbocyclic bisphosphonates Ia Id
formed by the reaction of the bisphosphonate prepared
from dibromoacetylene undergo partial spontaneous
aromatization at room temperature to form aromatic
bisphosphonates IIa IId; the reaction is promoted by
R1
R1
6
5 R2
R3
P(O)(OMe)2
R2
(MeO)2(O)P 1
X
||
+
4
2
R3
X
3
Ie Ig
I, R1 = H, R2 = R3 = Me (e); R1 = H, R2 = H, R3 = Me (f); R1 = H, R2 = Me, R3 =H (g); X = Cl (Br) [26].
The synthesis proceeds better in ampules sealed
under argon, in the presence of an inhibitor of poly-
merization (1,4-hydroquinone). Phosphonates Ie Ig
are high-boiling viscous stable liquids. Bromoethynyl-
phosphonates can also be used in this reaction.
traced the reaction regioselectivity with unsymmetrical
2-substituted dienes. Isoprene forms a mixture of
4-methyl- and 5-methyl-substituted (2-chlorocyclo-
hexa-1,4-dien-1-yl)phosphonates in a 3:1 ratio. The
predominant formation of isomer Ie corresponds to
polarization of the components and provides evidence
for the electronic reaction control.
With chloroethynylphosphonate as example, we
6
6
P(O)(OMe)2
||
5 CH3
(MeO)2(O)P 1
Cl
(MeO)2(O)P 1
5
+
+
+
4
Cl
2
4
2
CH3
Cl
3
+
CH3
3
If
Ig
The structure of isomers If and Ig is unambiguogly
established by their 13C NMR spectra. Ceratin reaction
regioselectivity is observed with 1-substituted alka-
1,3-dienes: With piperylene, only one isomer is
formed, which corresponds to the electronic control
of reaction regioselectivity [25]:
We failed to involve alkyl- and arylethynylphos-
phonic esters to the Diels Alder reaction even by
heating to 240 C. However, the more acceptor di-
chlorophosphinoyl group strongly enhances the polar-
ity of the adjacent triple bond, and the condensation
occurs successfully at 140 160 C and features a high
regioselectivity. Noteworthy, the reactions of (3,3-di-
methylbut-1-ynyl)phosphonic dichloride with alka-1,3-
dienes involves cleavage of the phosphonate group to
form corresponding benzene derivatives [27].
CH3
CH3
P(O)(OMe)2
||
(MeO)2(O)P
Cl
+
+
Cl
+
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A METHODOLOGY FOR SYNTHESIS OF PRIMARY o-PHENYLENEBISPHOSPHINES
887
temperatures, both competing reactions decelerated,
but the product yields did not improved. Using Lewis
acids (FeCl3, AlCl3, SnCl4, ZnCl2) and transition
metal salts (CuCl2, NiCl2, PdCl2) as catalysts and
performing the reaction under conditions of high dilu-
tion, too, proved unsuccessful. Acceptor alka-1,3-di-
enes, such as 1,4-diphenylbuta-1,3-diene, 2,3-bis(di-
chlorophosphinoyl)buta-1,3-diene, and 2,3-bis(di-
phenylphosphanyl)buta-1,3-diene, do not undergo the
diene synthesis even under rigid conditions: We failed
to detect even traces of cyclocondensation products in
the reactions in solvents (toluene, o-xylene, nitroben-
zene) or in their absence, at temperatures ranging from
120 C to 250 C, or in the presence of the above-menti-
oned catalysts. Probably, the key factors responsible
for the negative result here were both steric hindrances
and insufficient reactivity of the ethynylbisphospho-
nate.
R3
R2
R1
P(O)Cl2
||
P(O)Cl2
R4
R2
R1
+
R
R1, R2, R3 = H, CH3; R = Ph, t-Bu, CH3.
As known, ethyl (diethoxyphosphinoyl)ethynylcar-
boxylate (EtO)2P(O)C CCO2Et enters the diene syn-
thesis with furan to form the corresponding carbo-
cyclic o-carboxyphosphonate [25]. Tetramethyl
ethynediylbisphosphonate, too, reacts with furan but
under more rigid conditions (200 C, 8 h). The initial
condensation product was not registered, and the re-
action resulted in exclusive formation of phenolic
bisphosphonate IIhe via cleavage of the C O bond.
P(O)(OMe)2
||
(MeO)2(O)P
As known, 1,4-cyclohexadienes can be dehydro-
genated to obtain substituted benzenes, using a wide
range of reagents: Pd/C at 300 C [29], benzaldehyde
or nitrobenzene [30], MnO2 in boiling benzene [31],
and KMnO4 in the presence of dicyclohexyl-18-
crown-6 [32]. 1,4-Dihydropyridine can be dehydro-
genated by the reaction with the KMnO4 Al2O3 sys-
tem in aqueous benzene under reflux [33]. We found
that 2-chlorocyclohexadienylphosphonates Ie Ig and
cyclohexadienediylbisphosphonates Ib Id are also
readily dehydrogenated affording chlorophenylphos-
phonates IIe IIg and o-phenylenebisphosphonates
IIb IId. In our hands, the KMnO4 Al2O3 system in
acetone at 0 C proved the most convenient. Com-
pounds IIb IIg were obtained in good yields (50
70%) without admixtures of by-products.
O
+
O
(MeO)2(O)P
OH
P(O)(OMe)2
(MeO)2(O)P
(MeO)2(O)P
IIh
The reaction involved profound polymerization of
furan. Compound IIh was identified in the reaction
mixtures by spectroscopy. With highly reactive elec-
tron-donor dienes, 1-dimethylamino- and 1-ethoxy-
buta-1,3-dienes, only traces of adducts (1 2%)
and much polymerization products of the diene com-
ponent were detected by 1HNMR spectroscopy. At low
R1
R1
R1
3
R2
R3
R2
R3
R2
X
Cl
KMnO4/Al2O3
(MeO)2(O)P
(MeO)2(O)P
KMnO4/Al2O3
2
4
R3
(MeO)2(O)P 1
(MeO)2(O)P
5
6
Ib Id
IIb IIg
Ie Ig
II, R1 = Me, R2 = R3 = H, X = P(O)(OMe)2 (b); R1 = R3 = H, R2 = Me, X = P(O)(OMe)2 (c); R1 = H, R2 = R3 = Me,
X = P(O)(OMe)2 (d); R1 = H, R2 = R3 = X = Cl (e); R1 = H, R2 = Me, R3 = H, X = Cl (g).
With KMnO4 without Al2O3, the yield is reduced
(30 40%), and the consumption of KMnO4 is in-
creased. Other reagents (sulfur without solvent, SeO2
in dioxane, benzoquinone in THF, or Pd/C in ethanol)
can also be used for aromatization, but the expected
phosphonates always formed in lower yields and were
contaminated with hardly separable by-products (such
as, respectively, phosphonothioaates, phosphonic acids,
hydroquinone, or cyclohexylphosphonates). Phos-
phonates IIb IIg are stable high-boiling viscous
liquids, compounds IIc IIe afford crystals on
prolonged keeping.
Phosphonic halides are known to be more suitable
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888
TVERDOMED et al.
starting materials for preparing aromatic phosphines
than corresponding dialkyl phosphonates [34, 35].
Moreover, the presence of mobile halide atoms at
phosphorus allows functionalization and modification
of the phosphorus-containing part of the molecule.
Dimethyl alkylphosphonates are readily transformed
into chlorides by treatment with PCl5 POCl3 [36].
We found that o-phenylenebisphosphonates IIb IId
and o-chlorophenylphosphonates IIe IIg, too, react
with PCl5 POCl3 to form o-phenylenebis(phosphonic
dichlorides) IIIb IIId and o-chlorophenylphosphonic
dichlorides IIIe IIIg [28] very readily and in high
yields (60 85%).
R1
R1
R1
R2
R3
R2
R3
R2
R3
Cl
(CH3O)2(O)P
X
X
PCl5/POCl3
30 40%
PCl5/POCl3
60 85%
Cl2(O)P
(CH3O)2(O)P
IIb IIg
IIIb IIIg
Ib Ig
III, R1 = Me, R2 = R3 = H, X = P(O)Cl2 (b); R2 = Me, R1 = R3 = H, X = P(O)Cl2 (c); R1 = H, R2 = R3 = Me, X =
P(O)Cl2 (d); R1 = H, R2 = R3 = Me, X = Cl (e); R1 = H, R2 = H, R3 = Me, X = Cl (f); R1 = H, R2 = Me, R3 = H,
X = Cl (g).
Phosphonic dichlorides IIIb IIIg are also directly
available by the reactions of (cyclohexa-1,4-diene-1,2-
diyl)bisphosphonates Ia Id and (2-chlorocyclohexa-
1,4-dien-1-yl)phosphonates Ie Ig with phosphorus
pentachloride taken in a 1.5 molar excess, in the pre-
sence of phosphorus oxychloride. The reaction is ac-
companied by strong tarring, and the product yields
are fairly low (30 40%). In general, this route proved
to be less suitable, because the final chlorides were
strongly contamined with isomeric cyclohexa-1,3- and
cyclohexa-1,4-dienylphoshonic chlorides, which could
not be removed by repeated high-vacuum distillation.
Chlorides IIIb IIIg are low-melting white crystalline
substances with an unpleasant odor, easily hydrolyzed
by air moisture.
For revealing pathways for further functionalization,
we oxidized the methyl groups in o-phenylenebis-
phosphonate IId and o-chlorophenylphosphonate IIe
with KMnO4 into carboxy groups to obtain earlier
unknown phosphorus-containing phthalic acids: 4,5-
diphosphonophthalic (IVd) and 4-chloro-5-phospho-
nophthalic (IVe) acids.
KMnO4/
C5H5N H2O
KMnO4/
C5H5N H2O
6
3
CH3
CH3
(HO)2(O)P
(CH3O)2(O)P
Cl
COOH
COOH
CH3
CH3
(CH3O)2(O)P
(CH3O)2(O)P
1
5
X
4
2
IId
IVd, IVe
X = P(O)(OH)2 (d), Cl (e).
IIe
The oxidation requires rather rigid conditions.
Therefore, attempted aromatization of Id and Ie and
subsequent oxidation of the methyl groups without
isolation of phosphonates IId and IIe resulted in
polymerization of the starting carbocyclic compounds
and tarring. By contrast, phosphonates IId and IIe
could be easily and effectively oxidized in boiling
pyridine. A significant excess of KMnO4 is required,
because it is also consumed to oxidize the methanol
formed by hydrolysis of the ester. Acids IVd and IVe
can also be prepared in aqueous medium but in a
considerably lower yield. The phosphonophthalic
acids obtained are high-melting white crystalline
substances very well soluble in water and methanol.
Compounds IIb IIg can be reduced to the
corresponding aromatic phosphines [37]. o-Phenylene-
bisphosphonates IIc, IId and 2-chlorophenylphos-
phonate IIe react with LiALH4 in the presence of
AlCl3 in diethyl ether to form substituted o-phenylene-
bisdiphosphines Vc, Vd and 2-chlorophenylphosphine
(Ve), respectively.
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A METHODOLOGY FOR SYNTHESIS OF PRIMARY o-PHENYLENEBISPHOSPHINES
889
R1
R1
3
P(O)(OMe)2
H2P
X
R2
R3
R2
R3
H3C
H3C
LiAlH4/AlCl3
(C5H5)2O
(MeO)2(O)P
(MeO)2(O)P
LiAlH4/AlCl3
(C5H5)2O
2
4
Cl
5
1
6
IIc, IId
Vc Ve
IIe
V, R2 = Me, R1 = R3 = H, X = PH2 (c); R1 = H, R2 = R3 = Me, X = PH2 (d); R1 = H, R2 = R3 = Me, X = Cl (e).
With LiAlH4 in ether or THF and with LiAlH4
Me
Me
(CH3)3SiCl in THF, the reduction requires prolonged
boiling, which results in formation of a great amount
of polyphosphoric by-products and oxidation of the
main product; the phosphines formed are difficult to
isolate. We found that dimethyl (2-chloro-4,5-dime-
thylphenyl)phosphonate (IIe) is reduced with trichlo-
rosilane in benzene to form phosphine Ve in higher
yield and fairly pure.
CH3
PH2
H2P
PH2
Ar H
H2P
Cl
CH3
CH3
CH3
CH3
(MeO)2(O)P
Cl
SiHCl3
C6H6
IIe
Ve
Phenylenebisphosphonates IIc, IId under the same
conditions form with SiHCl3 a hardly controlled
7.5
7.0
4.5
4.0
3.5
2.0
, ppm
mixture of polyphosphoryl compounds (
60 ppm).
40 to
P
1
H NMR spectrum of (4,5-dimethyl-o-phenylene)bis-
phosphine (Vd).
Attempts to prepare phosphines Vc Ve by reduc-
tion of phosphonic chlorides IIIc IIIe were less suc-
cessful, since the latter were extremely poorly soluble
in diethyl ether, especially below zero. This wiped out
the effect of the high reactivity of chlorides in this
reaction and made them much less suitable synthons
for preparing primary phosphines than dialkyl aryl-
phospohnates IIc IId.
phosphine) allows preparation of ring-substituted o-
phenylenebisphosphines and o-chlorophenylphosphi-
nes, earlier unavailable synthons for polydentate
ligands.
EXPERIMENTAL
Bisphosphine Vc is a colorless labile liquid with a
very unpleasant odor, and compounds Vd and Ve are
low-melting white crystalline substances. In the H
All reagents and solvents were of chemical grade.
Synthesis and all operations with phosphines were
performed under oxygen-free argon of ultrapure grade.
1
NMR spectrum, the phosphine proton signals appear
1
The H, 13C and 31P NMR spectra were registered on
in the high field as a multiplet assignable to an A2X
1
3
a Bruker AC-200 instrument at 200.05 (1H), 50.328
(13C), and 81 MHz (31P), solvents CDCl3, CCl4, C6D6,
XA2 spin system [ 4.0 ppm, JHP 200 210 Hz, JHP
23 Hz (see figure)] arising as a result of equal chemical
shifts of two phosphorus and four proton signals at
unequl JHP constants.
1
and D2O. The H and 13C chemical shifts referred to
TMS were measured using internal CDCl3, and the
31P chemical shifts, using external 85% H3PO4. The
starting compounds: tetramethyl ethynediylbisphos-
phonate, dimethyl chloroethynylphosphonate, and 1,3-
dienes were prepared by known procedures [38 46].
The proton-decoupled 31P NMR spectra of unsym-
metrical bisphosphine Vc, like those of starting phos-
phonate IIc and chloride IIIc containing nonequi-
valent phosphorus nuclei, shows a typical AB system
3
with JPP 38.9 Hz.
Tetramethyl (cyclohexa-1,4-diene-1,2-diyl)bis-
phosphonate (Ia). Tetramethyl ethynediylbisphos-
phonate, 12.1 g (0.05 mol), was placed in a cooled
The proposed synthetic strategy (cyclohexa-1,4-di-
enylphosphonate
phenylphosphonate
phenyl-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 6 2006

890
TVERDOMED et al.
2
3
50-ml ampule, after which 16.6 ml (0.2 mol) of
freshly distilled and cooled ( 30 C) buta-1,3-diene
and 3 5 mg of hydroquinone were added. The ampule
was sealed and heated at 120 125 C for 10 h. The
191.44 Hz , JCP 15.2 Hz), 120.81 d (C4,5 , JCP
4.2 Hz), 52.37 s (Ci), 36.10 d (C3,6 , JCP 12.9 Hz),
2
17.17 s (C7,8). H NMR spectrum, , ppm: 3.34 d
1
3
(12H, JHP 8.8 Hz), 2.68 (m, 4H), 1.32 (s, 6H).
1
reaction progress was monitored by H NMR spectro-
Dimethyl (2-chloro-4,5-dimethylcyclohexa-1,4-
dien-1-yl)phosphonate (Ie) was prepared similarly
to Ia from 8.4 g (0.05 mol) of dimethyl (chloroethy-
nyl)phosphonate and 12.3 ml (0.15 mol) of 2,3-di-
methylbuta-1,3-diene. The reaction was performed at
160 170 C for 8 h. Yield 60%, bp 98 100 C (1 mm
scopy. After the reaction had been complete, excess
buta-1,3-diene was distilled off at reduced pressure,
and the residual oil was distilled in a vacuum. Yield
55%, bp 143 145 C (1 mm Hg). 31P NMR spectrum,
P, ppm (CDCl3): 15.23 s. 13C NMR spectrum,
,
C
1
2
ppm: 137.85 d.d (C1,2, JCP 191.69 Hz, JCP 17.3 Hz),
Hg). 31P NMR spectrum, P, ppm (CCl4): 16.20 s.
13C NMR spectrum, C, ppm: 139.80 s (C2), 122.10
3
2
121.69 d (C4,5, JCP 4.5 Hz), 52.31 d (Ci, JCP
2
1
3.8 Hz), 29.43 d (C3,6, JCP 12.7 Hz). H NMR spec-
s (C5), 120.40 s (C4), 119.80 d (C1, JCP 141.93 Hz),
1
3
trum, , ppm: 5.20 m (2H), 3.34 d (12H, JHP
51.13 d (Ci, JCP 6.5 Hz), 41.30 d (C6, 2JCP 15.1 Hz),
2
8.1 Hz), 2.54 (m, 4H).
36.0 d (C3, JCP 10.0 Hz), 16.47 s (C8), 16.36 s (C7).
3
Tetramethyl (3-methylcyclohexa-1,4-diene-1,2-
diyl)bisphosphonate (Ib) was prepared similarly to
Ia from 12.1 g (0.05 mol) of tetramethyl ethynediyl-
bisphosphonate and 20 ml (0.2 mol) of piperylene.
The reaction was performed at 165 C for 12 h. Yield
50%, bp 150 154 C (1 mm Hg). 31P NMR spectrum,
1H NMR spectrum, , ppm: 3.35 d (6H, JHP 9.4 Hz),
3
2.56 (m, 4H), 1.22 (s, 6H).
Dimethyl (2-chloro-4-methylcyclohexa-1,4-dien-
1-yl)phosphonate (If) was prepared similarly to Ia
from 8.4 g (0.05 mol) of dimethyl (chloroethynyl)-
phosphonate and 25.0 ml (0.25 mol) of isoprene. The
reaction was performed at 180 200 C for 12 h. Yield
50% (together with isomer Ig), bp 90 94 C (1 mm
Hg). Content in the mixture 65 mol %. 31P NMR
P, ppm (CDCl3): 15.99 s. 13C NMR spectrum,
,
C
1
ppm: 143.25 d (C1, JCP 187.16 Hz), 138.03 d (C2,
3
1JCP 190.6 Hz), 128.91 d (C4, JCP 7.9 Hz), 120.46
3
2
d (C5, JCP 8.7 Hz), 51.98 d (Ci, JCP 4.7 Hz), 33.25
spectrum, P, ppm (CCl4:) 16.49 s. 13C NMR spec-
trum, C, ppm: 139.60 s (C2), 128.10 s (C4), 120.15
d.d (C3, JCP 16.05 Hz , JCP 10.07 Hz), 29.61 d.d,
C6, JCP 16.05 Hz, JCP 10.07 Hz), 20.70 s (C7). H
2
3
2
3
1
d (Ci, JCP 186.20 Hz), 116.34 d (C5, JCP 11.1 Hz),
1
3
NMR spectrum, , ppm: 5.37 m (2H), 3.42 d (12H,
3
3JHP 10.5 Hz), 2.69 m (4H), 0.81 d (3H, JHH
50.96 d (Ci, JCP 4.3 Hz), 39.36 d (C6, 2JCP 12.0 Hz),
2
8.4 Hz).
30.2 d (C3, JCP 10.0 Hz), 20.69 s (C7). H NMR
3
1
3
Tetramethyl (4-methylcyclohexa-1,4-diene-1,2-
diyl)bisphosphonate (Ic) was prepared similarly to
Ia from 12.1 g (0.05 mol) of tetramethyl ethynediyl-
bisphosphonate and 12.5 ml (0.13 mol) of isoprene.
The reaction was performed at 140 160 C for 6 h.
Yield 70%, bp 155 158 C (1 mm Hg). 31P NMR
spectrum, P, ppm (CDCl3): 16.07 s. 13C NMR spec-
spectrum, , ppm: 4.87 m (1H), 3.23 d (6H, JHP
11.8 Hz), 2.23 (m, 4H), 1.15 (s, 3H).
Dimethyl (2-chloro-4-methylcyclohexa-1,4-dien-
1-yl)phosphonate (Ig) formed together with Ie in the
preceding experiment, content in the mixture 35 mol%.
31P NMR spectrum, P, ppm (CCl4): 16.24 s. 13C
NMR spectrum, C, ppm: 140.10 s (C2), 129.23 d
1
2
trum, C, ppm: 137.55 d.d (C1,2, JCP 189.6 Hz, JCP
18.3 Hz), 127.97 d (C5, JCP 3.9 Hz), 115.06 d (C4,
(C5, JCP 11.1 Hz), 120.05 d (Ci, JCP 186.20 Hz),
3
3
1
3JCP 13.1 Hz), 51.39 d (Ci, JCP 5.8 Hz), 33.27 d.d
2
115.50 s (C4), 51.96 d (Ci, JCP 4.3 Hz), 35.80 d
2
(C6, 2JCP 13.1 Hz , JCP 13.1 Hz), 29.97 d.d (C3, 2JCP
3
(C6, 2JCP 12.0 Hz), 34.0 d (C3, 3JCP 10.0 Hz), 20.96 s
13.1 Hz JCP 13.1 Hz), 20.88 s (C7). H NMR spec-
3
1
(C7). 1H NMR spectrum, , ppm: 4.64 m (1H), 3.23 d
3
3
trum, , ppm: 5.10 m (1H), 3.55 d (12H, JHP
(6H, JHP 11.8 Hz), 2.23 (m, 4H), 1.15 (s, 3H).
8.4 Hz), 2.80 m (2H), 2.75 m (2H), 1.20 s (3H).
Tetramethyl (3-methyl-o-phenylene)bisphos-
phonate (IIb). a. To 31.6 g (0.1 mol) of KMnO4/
Al2O3 (1:1) suspended in 100 ml of anhydrous ace-
tone, a solution of 15.5 g (0.05 mol) of Ib in 80 ml of
acetone was added under cooling and vigorous stirring.
The reaction mixture was kept for 4 h at room tem-
perature and 2 h under reflux. After cooling, the sus-
pension was filtered, the solid was carefully washed
with acetone, and the combined filtrate was evapo-
Tetramethyl (4,5-dimethylcyclohexa-1,4-diene-
1,2-diyl)bisphosphonate (Id) was prepared similarly
to Ia from 12.1 g (0.05 mol) of tetramethyl ethynedi-
ylbisphosphonate and 9.0 ml (0.08 mol) of 2,3-di-
methylbuta-1,3-diene. The reaction was performed at
120 140 C for 5 h. Yield 78%, bp 163 167 C (1 mm
Hg). 31P NMR spectrum, P, ppm (CDCl3): 15.90 s.
1
13C NMR spectrum, C, ppm: 137.94 d.d (C1,2, JCP).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 6 2006

A METHODOLOGY FOR SYNTHESIS OF PRIMARY o-PHENYLENEBISPHOSPHINES
891
rated. The residue was fractionated in a vacuum
(1.0 mm Hg).
12.5 g (0.05 mol) of Ie under the action of 28.4 g
(0.09 mol) of KMnO4/Al2O3 (1:1) (procedure a), or
21.3 g (0.14 mol) of KMnO4 (procedure b). Yield
64% (a), 42% (b). bp 105 108 C (1 mm Hg). 31P
NMR spectrum, P, ppm (CDCl3): 18.14 s. 13C NMR
b. A solution of 24.8 g (0.08 mol) of Ib in 100 ml
of anhydrous acetone was slowly added under cooling
and vigorous stirring to a solution of 38.4 g (0.24 mol)
of KMnO4 in 200 ml of acetone. The reaction mixture
was kept at room temperature for 4 h and under reflux
for 2 h. The product was isolated as described in
procedure a. Yield 42% (a), 29% (b). bp 160 162 C
(1 mm Hg). 31P NMR spectrum, P, ppm (CDCl3):
18.70 s. 13C NMR spectrum, C, ppm: 140.80 d.d (C6,
4
spectrum, C, ppm: 142.38 d (C4, JCP 2.2 Hz),
2
2
136.06 d (C6, JCP 8.2 Hz), 134.15 d (C5, JCP
13.7 Hz), 132.73 d (C2, JCP 3.0 Hz), 130.67 d (C3,
2
3JCP 10.5 Hz), 122.35 d (C1, JCP 193.5 Hz), 52.11 d
1
(Ci, JCP 4.1 Hz), 18.97 s (C7), 18.24 s (C8). 1H NMR
2
3
spectrum, , ppm: 7.49 m (1H, JHP 15.0 Hz), 6.98
m (1H, JHP 6.2 Hz), 3.56 d (6H, JHP 13.0 Hz), 2.04
3
3
2JCP 8.8 Hz, JCP 12.7 Hz), 134.12 d (C4, JCP
4
3
13.1 Hz), 132.68 d.d (C3, 2JCP 9.3 Hz, JCP 12.2 Hz),
3
s (6H).
3
1
131.26 d (C5, JCP 12.9 Hz), 127.22 d.d (C2, JCP
2
1
Dimethyl (2-chloro-4-methylphenyl)phosphonate
(IIf) was prepared similarly to IIb from 18.2 g of the
mixture of isomers If and Ig under the action of
60.8 g (0.192 mol) of KMnO4/Al2O3 (1:1) (procedure
a) or 45.6 g (0.29 mol) of KMnO4 (procedure b).
Yield (together with isomer IIg) 50% (procedure a) or
31% (procedure b). Content in the mixture 65 mol%.
bp 85 92 C (1 mm Hg). 31P NMR spectrum, P, ppm
188.30 Hz, JCP 9.6 Hz), 121.13 d.d (Ci, JCP
2
2
192.4 Hz, JCP 10.3 Hz), 51.46 d (Ci, JCP 4.2 Hz),
1
19.30 s (C7). H NMR spectrum, , ppm: 7.53 d.d
3
3
(1H, JHP 17.8 Hz, JHH 7.7 Hz), 7.21 m (1H), 6.79
d (1H, JHH 7.1 Hz), 3.46 d (12H, JHP 6.88 Hz),
3
3
1.90 s (3H).
Tetramethyl (4-methyl-o-phenylene)bisphos-
phonate (IIc) was prepared similarly to IIb from
15.5 g (0.05 mol) of Ic under the action of 28.4 g
(0.09 mol) of KMnO4/Al2O3 (1:1) (procedure a) or
of 21.3 g (0.135 mol) of KMnO4 (procedure b). Yield
62% (a), 37% (b). bp 163 166 C (1 mm Hg). 31P
NMR spectrum, P, ppm (CDCl3): 18.01, 18.36 (AB
system), JPP 14.14 Hz. 13C NMR spectrum, C, ppm:
(CDCl3): 18.48 s. 13C NMR spectrum, C, ppm:
2
2
139.80 d (C2, JCP 2.1 Hz), 131.80 d (C6, JCP
8.4 Hz), 128.70 d (C3, JCP 2.9 Hz), 126.10 d (C4,
3
4JCP 10.2 Hz), 125.20 d (C5, JCP 14.4 Hz), 119.60
3
d (C1, JCP 196.6 Hz), 52.60 d (Ci, JCP 6.3 Hz),
1
2
18.50 s (C7). H NMR spectrum, , ppm: 7.54 d.d
1
3
2
141.59 m (C4, JCP 12.1 Hz), 135.16 d.d (C6, JCP
3
3
(1H, JHP 15.79 Hz, JHH 5.2 Hz), 7.12 s (1H), 6.80
d (1H, JHH 7.7 Hz), 3.51 d (6H, JHP 12.1 Hz), 2.08
8.5 Hz, JCP 13.6 Hz ), 134.51 d.d (C3, JCP 9.1 Hz,
3
2
3
3
3JCP 13.3 Hz), 131.36 d (C5, JCP 13.4 Hz), 128.90
3
s (3H).
d.d (C2, 1JCP 189.0 Hz, JCP 10.7 Hz), 125.74 d.d (Ci,
2
1JCP 191.7 Hz, 2JCP 9.7 Hz), 51.87 d (Ci, JCP1 3.8 Hz),
2
Dimethyl (2-chloro-5-methylphenyl)phosphonate
(IIg) formed together with If in the preceding experi-
ment, content in the mixture 35 mol%. bp 85 92 C
51.79 d (Ci, JCP 4.6 Hz), 20.51 s (C7). H NMR
2
3
3
spectrum, , ppm: 7.51 d.d (1H, JHP 14.0 Hz, JHH
7.6 Hz), 7.46 d (1H, JHP 20.0 Hz), 6.98 d (1H, JHH
7.8 Hz), 3.50 d (12H, JHP 7.41 Hz), 2.20 s (3H).
(1 mm Hg). 31P NMR spectrum, P, ppm (CDCl3):
18.53 s. 13C NMR spectrum, C, ppm: 132.70 d (C6,
3
3
3
3
Tetramethyl (4,5-dimethyl-o-phenylene)bis-
phosphonate (IId) was prepared similarly to IIb from
16.2 g (0.05 mol) of Id under the action of 23.7 g
(0.08 mol) of KMnO4/Al2O3 (1:1) (procedure a) or
17.8 g (0.11 mol) of KMnO4 (procedure b). bp 170
174 C (1 mm Hg). Yield 70% (a), 40% (b). 31P NMR
spectrum, P, ppm (CDCl3): 18.95 s. 13C NMR spec-
2JCP 9.1 Hz), 131.30 d (C5, JCP 13.7 Hz), 127.30 d
(C4, 4JCP 3.71 Hz), 126.79 d (C2, 2JCP 4.7 Hz), 124.40
3
1
d (C3, JCP 7.3 Hz), 122.35 d (C1, JCP 187.7 Hz),
51.90 d (Ci, JCP 5.8 Hz), 18.70 s (C7). H NMR
spectrum, , ppm: 7.47 d (1H, JHP 14.90 Hz), 7.02
d.d (1H, JHP 3.80 Hz, JHH 6.90 Hz), 6.91 d (1H,
3JHH 6.7 Hz), 3.62 d (6H, JHP 10.2 Hz), 2.20 s (3H).
2
1
3
4
3
3
4
trum, C, ppm: 140.06 d.d (C4,5 , JCP 10.9 Hz, JCP
3
4.2 Hz), 136.06 d.d (C3,6
,
2JCP 11.7 Hz, JCP
3
11.7 Hz), 126.12 d.d (C1,2, JCP 190.1 Hz, JCP
1
2
(3-Methyl-o-phenylene)bis(phosphonic dichlo-
ride) (IIIb). To a solution of 15.4 g (0.05 mol) of IIb
in 16.5 ml (0.18 mol) of POCl3, 45.9 g (0.22 mol) of
ground PCl5 was added in small portions under cool-
ing and stirring. The mixture was stirred under reflux
for 4 h, phosphorus oxychloride was then distilled off,
and the residue was distilled in an oil-pump vacuum.
8.1 Hz), 51.77 s (Ci), 18.5 s (C7,8). H NMR spec-
1
3
trum, , ppm: 7.50 m (2H, JHP 16.0 Hz), 3.37 d
(12H, JHP 9.6 Hz), 1.90 (s, 6H).
3
Dimethyl (2-chloro-4,5-dimethylphenyl)phos-
phonate (IIe) was prepared similarly to IIb from
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 6 2006

892
TVERDOMED et al.
4
Yield 69%, bp 146 150 C (0.05 mm Hg), 31P NMR
17.8 Hz), 7.22 d (1H, JHP 8.8 Hz), 2.24 s (3H), 2.19
spectrum, P, ppm (CDCl3): 31.32 d, 31.14d, JPP
s (3H).
12.60 Hz. 13C NMR spectrum, C, ppm: 146.30 d (C6,
(2-Chloro-4-methylphenyl)phosphonic dichlo-
ride (IIIf) was prepared similarly to IIIb from 11.7 g
of the mixture of isomers IIf and IIg under the action
of 22.9 g (0.11 mol) of PCl5 in the presence of 8.3 ml
(0.09 mol) POCl3 for 4 h. Yield 76% (together with
2
3
2JCP 9.9 Hz), 135.40 d.d (C3, JCP 10.4 Hz, JCP
12.30 Hz), 135.20 d.d (C2, JCP 185.5 Hz, JCP
1
2
7.9 Hz), 134.81 d (C5, JCP 13.8 Hz), 134.34 d (C4,
3
1
2
3JCP 13.80 Hz), 131.10 d.d (C1, JCP 187.7 Hz, JCP
isomer IIg) 65 mol%. bp 87 90 C (0.05 mm Hg). 31P
8.1 Hz), 20.40 s (C7). H NMR spectrum, , ppm:
1
NMR spectrum, P, ppm (CDCl3): 28.88 s. 13C NMR
3
3
7.86 d.d (1H, JHP 18.1 Hz, JHH 8.3 Hz), 7.74 m
(1H), 7.12 d (1H, JHH 9.2 Hz), 2.38 (s, 3H).
spectrum, C, ppm: 147.23 d (C2, JCP 2.77 Hz),
2
3
136.20 d (C4, JCP 2.61 Hz), 133.76 d (C6, JCP
4
2
10.52 Hz), 132.15 d (C3, 3JCP 15.4 Hz), 128.14 d (Ci,
(4-Methyl-o-phenylene)bis(phosphonic dichlo-
ride) (IIIc) was prepared similarly to IIIb from
15.4 g (0.05 mol) of IIc under the action of 45.9 g
(0.22 mol) of PCl5 in the presence of 16.5 ml
(0.18 mol) of POCl3 for 3 h. Yield 72%, bp 151
155 C (0.05 mm Hg). 31P NMR spectrum, P, ppm
(CDCl3): 31.41 d, 31.11 d, JPP 16.20 Hz. 13C NMR
1JCP 164.1 Hz), 127.39 d (C5, JCP 15.80 Hz), 21.04
3
s (C7). H NMR spectrum, , ppm: 7.99 d.d (1H,
1
3JHP 17.21 Hz, JHH 7.81 Hz), 7.39 s (1H), 7.37 d
3
3
(1H, JHH 10.0 Hz), 2.40 (s, 3H).
(2-Chloro-5-methylphenyl)phosphonic dichlo-
ride (IIIg) formed together with isomer IIIf in the
proceding experiment, content in the mixture
35 mol%. bp 87 90 C (0.05 mm Hg). 31P NMR spec-
trum, P, ppm (CDCl3): 28.88 s. 13C NMR spectrum,
3
spectrum, C, ppm: 145.98 m (C4, JCP 11.8 Hz),
1
2
135.70 d.d (C2, JCP 185.1 Hz, JCP 8.3 Hz), 134.98
d.d (C6, JCP 13.1 Hz, JCP 13.1 Hz), 134.79 d (C5,
2
3
3JCP 19.1 Hz), 134.60 d (C3, JCP 10.2 Hz), 132.15
2
1
2
C, ppm: 136.55 d (C5, JCP 14.95 Hz), 135.21 d
3
d.d (C1, JCP 188.4 Hz, JCP 7.5 Hz), 20.55 s (C7). 1H
4
2
3
(C4, JCP 4.83 Hz), 134.26 d (C6, JCP 10.71 Hz),
NMR spectrum, , ppm: 8.18 d.d (1H, JHP 29.02 Hz,
3JHH 7.8 Hz), 8.09 d (1H, JHP 29.21 Hz), 7.67 d
(1H, JHH 7.8 Hz), 2.52 (s, 3H).
2
3
3
132.23 d (C2, JCP 5.99 Hz), 131.45 d (C3, JCP
1
3
11.98 Hz), 130.68 d (C1, JCP 159.49 Hz), 20.33 s
1
3
(C7). H NMR spectrum, , ppm: 7.93 d (1H, JHP
3
(4,5-Dimethyl-o-phenylene)bis(phosphonic
dichloride) (IIId) was prepared similarly to IIIb from
16.1 g (0.05 mol) of IId under the action of 45.9 g
(0.22 mol) of PCl5 in the presence of 16.5 ml
(0.18 mol) of POCl3 for 3 h. Yield 75%, bp 164
169 C (0.05 mm Hg). 31P NMR spectrum, P, ppm
16.61 Hz), 7.41 d (1H, JHH 7.00 Hz), 7.27 d.d (1H,
4JHP 4.6 Hz, JHH 8.2 Hz), 2.37 (s, 3H).
3
4,5-Diphosphonophthalic acid (IVd). To a solu-
tion of 9.7 g (0.03 mol) of IId in 50 ml of boiling
50% aqueous pyridine, KMnO4 was added very
slowly and carefully until the violet color no longer
disappeared (a total of about 57 g). The reaction mix-
ture was then refluxed for 2 h and then filtered. The
precipitate of MnO2 was washed with 50 ml of hot
water. The filtrate was made strongly acidic with conc.
HCl (by universal indicator), evaporated to dryness at
reduced pressure, and dried. The dry residue was ex-
tracted with hot dioxane (3 30 ml), the solvent was
distilled off, and the residue was dried for 8 h at
120 130 C and recrystallized from dioxane MeOH
(CDCl3): 31.08 s. 13C NMR spectrum, C, ppm:
3
2
144.23 d (C4,5, JCP 12.3 Hz), 135.42 d (C3,6 , JCP
16.1 Hz, JCP 16.1 Hz), 132.48 d.d (C1,2, JCP
187.88 Hz, JCP 11.2 Hz), 19.87 s (C7,8). H NMR
3
1
2
1
3
spectrum, , ppm: 8.03 d (2H, JHP 16.01 Hz), 2.44
s (6H).
(2-Chloro-4,5-dimethylphenyl)phosphonic di-
chloride (IIIe) was prepared similarly to IIIb from
12.4 g (0.05 mol) of IIe under the action of 22.9 g
(0.11 mol) PCl5 in the presence of 8.3 ml (0.09 mol)
POCl3 for 3 h. Yield 85%, bp 88 93 C (0.05 mm Hg).
31P NMR spectrum, P, ppm (CDCl3): 29.12 s. 13C
NMR spectrum, C, ppm: 145.83 d (C4, 4JCP 4.6 Hz),
(3:1). mp 332 335 C (decomp.). Yield 60%. 31P
NMR spectrum, P, ppm (D2O): 6.22 s. 13C NMR
spectrum, C, ppm: 173.92 s (C7,8), 140.60 d.d (C1,2,
1JCP 172.34 Hz, JCP 10.4 Hz), 141.47 d (C4,5, JCP
2
3
3
2
135.62 d (C5, JCP 16.0 Hz), 134.34 d (C6, JCP
11.3 Hz), 135.04 d.d (C3,6 , JCP 9.3 Hz, JCP 9.3 Hz).
2
3
12.4 Hz), 132.30 d (C3, 3JCP 12.5 Hz), 132.03 s (C2),
1H NMR spectrum, , ppm: 8.64 m (2H, JHP
3
127.87 d (C1, JCP 161.5 Hz), 19.45 s (C8), 18.68 s
1
15.2 Hz), 4.60 (s, 6H, H2O).
(C7). H NMR spectrum, , ppm: 7.76 d (1H, JHP
4-Chloro-5-phosphonophthalic acid (IVe) was
1
3
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A METHODOLOGY FOR SYNTHESIS OF PRIMARY o-PHENYLENEBISPHOSPHINES
893
prepared similarly to IVd from 7.4 g (0.03 mol) of IIe
under the action of 47.4 g (0.3 mol) KMnO4. Yield
75%, mp 310 314 C (decomp.) from dioxane MeOH
IIe under the action of 2.8 g (0.08 mol) of LiAlH4
and 4.0 g (0.03 mol) of AlCl3, followed by treatment
with 1.5 ml (0.08 mol) of oxygen-free water. Yield
53%.
(3:1). 31P NMR spectrum, P, ppm (D2O): 5.97 s. 13C
NMR spectrum, C, ppm: 171.92 s (C8), 171.44 s
b. To a solution of 16.3 g (0.12 mol) of SiHCl3 in
70 ml of anhydrous benzene cooled to 0 C, a solution
of 7.5 g (0.03 mol) of IIe in 50 ml of benzene was
quickly added. The solution was stirred under reflux
for 12 h, cooled to 0 C, and a solution of 0.4 mol of
NaOH in 100 ml of water distilled under argon was
added. The mixture was kept heated at 60 C until the
amorphous precipitate formed had dissolved com-
pletely. The organic layer was separated, and the
aqueous layer was extracted with two portions of
benzene. The combined organic extract was dried over
Na2SO4, the solvent was distilled off, and the residue
was distilled in a vacuum. Yield 60%, bp 80 83 C
(1 mm Hg). 31P NMR spectrum, P, ppm (C6D6):
129.19 s. 13C NMR spectrum, C, ppm: 138.39 s
3
1
(C7), 140.77 d (C5, JCP 4.9 Hz), 137.40 d (Ci, JCP
178.1 Hz), 137.08 s (C4), 135.39 d (C6, 2JCP 8.8 Hz),
131.66 d (C3, JCP 8.7 Hz), 129.93 d (C2, JCP
11.8 Hz). H NMR spectrum, , ppm: 8.33 d (1H,
3JHP 14.04 Hz), 7.71 d (1H, JHP 4.9 Hz), 4.80 s (4H,
3
2
1
4
H2O).
(4-Methyl-o-phenylene)bisphosphine (Vc).
To a vigorously stirred and cold ( 70 C) suspension
of 5.7 g (0.15 mol) of LiALH4 in 100 ml of anhydrous
ether, 8.0 g (0.06 mol) of AlCl3 was quickly added
and then a solution of IIc in 50 ml of ether was added
dropwise at 60 C. After stirring for 4 h at room
temperature and 1 h under reflux, the mixture was
cooled to 30 C, and 2.8 ml (0.15 mol) of water pre-
liminarily distilled under argon was added dropwis.
The mixture was allowed to warm to room tempera-
ture, and then it was refluxed for 2 h and filtered. The
filtrate was dried over Na2SO4 and evaporated. The
residue was distilled in a vacuum. Yield 50%, bp 86
3
(C4), 136.25 d (C3, JCP 10.8 Hz), 134.90 d (C2, 2JCP
3
4.6 Hz), 134.77 d (C5, JCP 7.9 Hz), 129.62 s (C6),
1
126.64 d (C1, JCP 9.6 Hz), 18.99 s (C7), 18.60 s
1
3
(C8). H NMR spectrum, , ppm: 7.29 d (1H, JHP
4
1
6.2 Hz), 7.13 d (1H, JHP 2.7 Hz), 3.98 d (2H, JHP
209.0 Hz), 2.23 (s, 6H).
90 C (1 mm Hg). 31P NMR spectrum, P, ppm (C6D6):
3
125.47, 123.50 (AB system, JPP 38.9 Hz). 13C
REFERENCES
NMR spectrum, C, ppm: 139.07 d (C5, 3JCP 4.07 Hz),
1. Reddy, S., Katti, K.V. and Barnes, C.L., J. Chem.
Soc., Dalton Trans., 1996, vol. 7, p. 1301; Bader, A.
and Lindner, E., Coord. Rev., 1991, vol. 108, p. 27;
Braunstein, P. and Naud, F., Angew. Chem., 2001,
vol. 113, p. 703.
2
3
135.89 d.d (C3, JCP 3.9 Hz, JCP 13.5 Hz ), 135.40
d.d (C6, JCP 3.9 Hz, JCP 13.6 Hz), 134.42 d.d (Ci,
2
3
2
1
1JCP 15.1 Hz, JCP 6.8 Hz), 130.29 d.d (C2, JCP
14.9 Hz, JCP 6.9 Hz), 128.98 d (C4, JCP 5.4 Hz),
2
3
20.70 s (C7). H NMR spectrum, , ppm: 7.44 d.d
2. Issleib, K., Liessring, E. and Meyer, H., Tetrahedron
Lett., 1981, vol. 22, p. 4475.
1
3
3
3
(1H, JHP 9.6 Hz, JHH 3.0 Hz), 7.38 d (1H, JHH
3.7 Hz), 7.02 d (1H, JHP 8.0 Hz), 4.04 d.d (4H, JHP
208.1 Hz, JHP 6.0 Hz), 2.31 s (3H).
3
1
3. Kyba, E.P., Liu, S-T. and Harris, R.L., Organometal-
lics, 1983, vol. 2, no. 12, p. 1877.
4
4. Fritzsche, K. and Hasserodt, M., Chem. Ber., 1965,
(4,5-Dimethyl-o-phenylene)bisphosphine (Vd)
was prepared similarly to Vc from 9.7 g (0.03 mol)
of IId under the action of 5.7 g (0.15 mol) of LiALH4
and 8.0 g (0.06 mol) of AlCl3. Yield 55%, bp 103
vol. 98, p. 1681.
5. Drewelies, K. and Latscha, H.P., Angew. Chem., 1982,
vol. 94, p. 642.
106 C (1 mm Hg). 31P NMR spectrum, P, ppm
(C6D6): 126.11 m. 13C NMR spectrum, C, ppm:
6. Worz, H.-J. and Quien, E., Z. Naturforsch. B, 1984,
vol. 39, p. 1706.
2
3
136.93 d (C3,6, JCP 9.1 Hz), 136.73 d (C4,5, JCP
7. Bard, R.R. and Bunnett, J.F., J. Org. Chem., 1979,
vol. 44, p. 4918.
10.2 Hz), 130.99 d.d (C1,2, JCP 6.6 Hz, JCP 6.6 Hz),
19.07 s (C7,8). H NMR spectrum, , ppm : 7.34 d.d
(2H, JHP 4.8 Hz, JHP 4.8 Hz), 4.01 d.d (4H, JHP
207.5 Hz, JHP 22.8 Hz), 2.21 s (6H).
1
2
8. Obrycki, R. and Griffin, C.E., Tetrahedron Lett., 1966,
1
p. 5049.
3
4
1
9. Tavs, P., Chem. Ber., 1970, vol. 103, p. 2428.
4
10. Mann, F.G. and Mercer, A.J.H., J. Chem. Soc., Perkin
Trans. 1, 1972, p. 1631.
(2-Chloro-4,5-dimethylphenyl)phosphine (Ve).
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