Reaction of dibenzylphosphine oxide with α,β-unsaturated O-methyloximes

Article abstract of DOI:10.1023/A:1023902621846

The reaction of dibenzylphosphine oxide with O-methyloximes of some α,β-unsaturated ketones results in the phosphorylation at the β-carbon atom to form methoxyiminophosphine oxides, whereas the reaction of dibenzylphosphine oxide with O-methyloximes of α,β-unsaturated aldehydes affords aminodihydrophosphole oxides.

Full text of DOI:10.1023/A:1023902621846

624
Russian Chemical Bulletin, International Edition, Vol. 52, No. 3, pp. 624—629, March, 2003
Reaction of dibenzylphosphine oxide with α,βꢀunsaturated Oꢀmethyloximes
ꢀ
V. D. Kolesnik and А. V. Tkachev
N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences,
9 prosp. Akad. Lavrent´eva, 630090 Novosibirsk, Russian Federation.
Fax: +7 (383 2) 34 4855. Eꢀmail: atkachev@nioch.nsc.ru
The reaction of dibenzylphosphine oxide with Oꢀmethyloximes of some α,βꢀunsaturated
ketones results in the phosphorylation at the βꢀcarbon atom to form methoxyiminophosphine
oxides, whereas the reaction of dibenzylphosphine oxide with Oꢀmethyloximes of α,βꢀunsaturꢀ
ated aldehydes affords aminodihydrophosphole oxides.
Key words: α,βꢀunsaturated oximes, dibenzylphosphine oxide, phosphorylation, phosphoꢀ
rusꢀcontaining heterocycles, phosphine oxides.
In the 1970s, Polish scientists showed the promising
The structures of methoxyiminophosphine oxides 3
and 4 were proved by spectroscopic methods. The chemiꢀ
cal shifts of signals for the phosphorus atom in the
31P NMR spectra of compounds 3 and 4 indicate that
phosphorus exists in the phosphine oxide form and is not
use of dibenzylphosphine oxide as a phosphorylating agent
for olefins activated with respect to nucleophilic addiꢀ
tion.1,2 A great advantage of this reagent is its ability to
afford, in some cases, derivatives of phosphorusꢀcontainꢀ
ing heterocycles, viz., phospholanes. This possibility was
demonstrated for unsaturated ketones and esters.
1
incorporated in the ring. The H and 13C NMR spectra
exhibit signals for the methoxy group, and the 13C NMR
spectrum contains a signal for the C=N—O fragment,
proving that the methoxyimino group is retained in the
molecules.
We succeeded to include α,βꢀunsaturated nitriles in
the scope of substrates for this method of synthesis of
phosphorusꢀcontaining heterocycles.3,4 At the same time,
nucleophilic addition of phosphorus reactants to derivaꢀ
tives of unsaturated carbonyl compounds, viz., unsaturꢀ
ated oximes, remained virtually unstudied. A few pubꢀ
lished reactions of oximes with phosphorus reagents reꢀ
sult, as a rule, in the reduction of the oxime group.5,6
We studied the reactions of dibenzylphosphine oxide
with ethers of unsaturated ketoximes and aldoximes in the
presence of sodium hydride. Evidently, it is senseless to
introduce oximes themselves into this reaction, because
they would form salts under these conditions, and their
ability of adding nucleophiles would strongly decrease.
This reaction turned out to be very sensitive to the subꢀ
strate structure. For example, phosphorylation of ketꢀ
oximes was successful only with pinocarvone Oꢀmethylꢀ
oxime 1 and benzylideneacetone Oꢀmethyloxime 2
(Scheme 1). The double bond of pinocarvone oxime 1 is
very accessible and favorable for the nucleophilic attack
and, in the case of benzylideneacetone oxime 2, the double
bond is additionally activated by the phenyl group. Phosꢀ
phine oxides 3 and 4, respectively, were isolated as the
reaction products. Attempts to involve oximes of other
ketones in this reaction (carenone oxime 5 and carvone
oxime 6, oximes 7 and 8) were unsuccessful, although the
ketones themselves react readily with dibenzylphosphine
oxide to form oxophosphine oxides: in the reaction,
oximes 7 and 8 decomposed, and oximes 5 and 6 reꢀ
mained unchanged.
According to the data from the 1H and 13C NMR
spectra, phosphine oxides synthesized from pinocarvone
oxime 1 are epimeric derivatives of pinocamphone oxime
3 with a ratio of isomers of 3 : 1.
The signals in the 13C and 1H NMR spectra of 3 were
1
assigned from the 2D H—1H and 13C—1H correlation
spectra.
The configuration of the C(2) atom in the pinane
skeleton was determined from comparison of the chemiꢀ
cal shifts of the carbon atoms in compound 3 with the
shifts for isopinocamphone oxime7 and isomeric pinoꢀ
camphone.8 Based on this comparison, we concluded that
the main isomer belongs to the isopinanocamphane series.
Phosphine oxide 4 was synthesized from benzylꢀ
idenecetone oxime 2 as a mixture of E/Z isomers
with respect to the oxime group in a ratio of 5 : 3 in
favor of the E isomer (according to the 13C NMR
spectrum).
It is well known that the nucleophilic addition of phosꢀ
phorus reagents to α,βꢀunsaturated aldehydes, unlike unꢀ
saturated ketones, occurs almost always on the carbonyl
group.9 Therefore, it was of interest to compare the reacꢀ
tivity of ethers of unsaturated ketoximes and aldoximes.
For this purpose, we studied the reactions of dibenzylꢀ
phosphine oxide with myrtenal (9), cinnamal (10), citral
(11), and 2ꢀmethylpentꢀ2ꢀenal Oꢀmethyloximes (12)
(Scheme 2).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 598—602, March, 2003.
1066ꢀ5285/03/5203ꢀ624 $25.00 © 2003 Plenum Publishing Corporation

Phosphorylation of α,βꢀunsaturated oximes
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 3, March, 2003
625
Scheme 1
i.
, dioxane/NaH.
Scheme 2

626
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 3, March, 2003
Kolesnik and Tkachev
Scheme 3
The reactions of dibenzylphosphine oxide with these
phosphole oxide, and (2) elimination of the cyanide ion
to form vinylphosphine oxide and the addition of the
second equivalent of the phosphorus reagent to form
bisphosphine oxide provided the substrate structure is faꢀ
vorable.
As can be seen, this scheme explains the formation of
both aminodihydrophosphole oxides and unsaturated
phosphine oxides along with bisphosphine oxide.
Thus, we have found that ethers of aliphatic and aroꢀ
matic α,βꢀunsaturated ketoximes can react in some cases
with dibenzylphosphine oxide in the presence of a base to
form methoxyimino derivatives of phosphine oxides. The
reactivity of α,βꢀunsaturated aldoxime ethers in the reacꢀ
tion with dibenzylphosphine oxide much exceeds that of
unsaturated ketoximes. Unlike ketoximes, the reactions
of aldoxime ethers produce aminodihydrophosphole oxꢀ
ides, phosphoolefins, or bisphosphine oxides.
compounds do not afford methoxyimino derivatives of
phosphine oxides. The products of the reactions of
dibenzylphosphine oxide with citral (11) and 2ꢀmethylꢀ
pentꢀ2ꢀenal Oꢀmethyloximes (12) are aminodihydroꢀ
phosphole oxides 16 and 17, respectively. The reaction
with cinnamal Oꢀmethyloxime gave bisphosphine oxꢀ
ide 15. Unsaturated phosphine oxide 14 is formed along
with aminodihydrophosphole oxide 13 as the reaction
product with myrtenal Oꢀmethyloxime (Scheme 2).
The structure of compound 14 was established by
NMR spectroscopy. According to the elemental analysis
and 13C NMR spectroscopic data, one carbon atom is
absent from the pinane framework. The chemical shift of
the phosphorus atom indicates that phosphorus in the
molecule is represented by phosphine oxide and is not
incorporated into the ring. The 13C NMR spectrum shows
that the molecule contains the trisubstituted double bond
with phosphorus as one of the substituents. The hydrogen
atom is bound to another olefinic carbon atom. At the
Experimental
1
same time, the patterns of the H and 13C NMR spectra
All solvents were distilled before use. Thin layer chromatogꢀ
raphy (TLC) was performed on Silufol plates with a fixed SiO2
layer. To detect substances, the plates were sprayed with
ethanolic solutions of vanillin (2 g of vanillin + 5 mL of conc.
H2SO4 in 150 mL of EtOH) or iron chloride (10% solution of
FeCl3•6H2O in EtOH) and heated. Silica gel (KSK, particle
size 0.140—0.315 mm) activated at 140 °C for 6—7 h was used
for column chromatography. IR spectra were recorded on a
Bruker Vectorꢀ22 instrument. Mass spectra were obtained on a
Finnigan MAT 8200 spectrometer (50—100 °C, EI, 70 eV).
1H and 13C NMR spectra were recorded on a Bruker DRXꢀ500
spectrometer (500.13 and 125.75 MHz) for solutions in CDCl3
with concentrations of 70—100 mg mL–1 at 25—27 °C. The
signals from the solvent were used as the internal standards:
chloroformꢀd (δ = 76.90, δ = 7.24). 31P NMR spectra were
suggest that the pinane skeleton is retained on the whole.
It is noteworthy that aminodihydrophosphole oxides
13, 16, and 17 and bisphosphine oxide 15 have previously
been synthesized by the reactions of dibenzylphosphine
oxide with the corresponding nitriles.3,4 This suggests the
intermediate formation of nitriles from oxime ethers in
the transformation under study. The plausible mechaꢀ
nism of the reaction of aldoxime ethers with dibenzylꢀ
phosphine oxide is presented in Scheme 3.
According to this mechanism, sodium hydride induces
the elimination of the methoxide anion to form unsaturꢀ
ated nitrile followed by the addition of dibenzylphosphine
oxide. Further, two reaction routes become possible:
(1) deprotonation of the methylene group of the benzyl
fragment and attack of the benzyl anion followed by ring
closure with the nitrile group to form aminodihydroꢀ
С
Н
recorded under the same conditions on a Bruker ACꢀ200 instruꢀ
ment (81.015 MHz, 80% H3PO4 as the external standard, δ 0.0).
P
Signals were assigned using the 13С NMR spectra recorded in
the Jꢀmodulation regime (noise proton decoupling, opposite

Phosphorylation of α,βꢀunsaturated oximes
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 3, March, 2003
627
phase for signals for atoms with even and odd numbers of atꢀ
tached protons with adjusting to the constant J = 135 Hz) and
from data from the twoꢀdimensional spectra: (1) 1H—1H homoꢀ
nuclear correlation, (2) 13C—1H heteronuclear correlation
with direct spinꢀspin coupling constants (J = 135 Hz), and
(3) 13C—1H heteronuclear correlation with longꢀrange spinꢀ
spin coupling constants (J = 10 Hz). Optical rotations were
measured on a Polamat A polarimeter for solutions in CHCl3.
Melting points were determined on a Koffler stage.
Synthesis of Oꢀmethyloximes (general procedure). To a soluꢀ
tion of an oxime (0.02 mol) in benzene (70 mL), TEBAC
(1—2 mg) and a 30% solution of NaOH (30 mL) were added.
Dimethyl sulfate (0.03 mol) was added dropwise with intense
stirring to the resulting mixture. The mixture was stirred at ∼20 °C
until the oxime disappeared (TLC monitoring). The reaction
mixture was diluted with water (70 mL). The organic phase was
separated and dried with sodium sulfate, and the solvent was
distilled off. The resulting Oꢀmethyloxime was purified, if
necessary, by percolation or distillation in a vacuum of an
oil pump.
Pinocarvone (E)ꢀOꢀmethyloxime (1). Highꢀresolution mass
spectrum, found: m/z 179.13122. C11H17NO. Calculated:
M = 179.13101. MS, m/z (Irel(%)): 179 (23), 164 (21), 148 (14),
136 (100), 104 (29), 91 (46), 79 (22), 77 (25), 69 (18), 53 (27).
IR (in thin layer), ν/cm–1: 2980—2810, 1050, 900, 820.
1H NMR, δ: 0.74 (s, 3 H, H(8)); 1.12 (d, 1 H, H(7α), J =
9.2 Hz); 1.25 (s, 3 H, H(9)); 2.00 (m, 1 H, H(5)); 2.43—2.58
(m, 4 H, H(1), H(4), (7β)); 3.86 (s, 3 H, OMe); 4.60 (d, 1 H,
H(10a), J = 2.0 Hz); 5.62 (d, 1 H, H(10b), J = 2.0 Hz).
13C NMR, δ: 21.17 (C(8)); 26.21 (C(9)); 29.45 (C(4)); 31.31
(C(7)); 37.96 (C(5)); 40.43 (C(6)); 49.95 (C(1)); 61.64 (OMe);
107.74 (C(10)); 145.18 (C(2)); 152.38 (C(3)).
2ꢀAcetylꢀ6,6ꢀdimethylbicyclo[3.1.0]hexꢀ2ꢀene Oꢀmethylꢀ
oxime (7), [α]22
+8.6 (c 21.28). Highꢀresolution mass specꢀ
578
trum, found: m/z 179.13086.
C11H17NO. Calculated:
M = 179.13101. MS, m/z (Irel(%)): 179 (70), 164 (97), 148 (80),
132 (72), 118 (24), 107 (42), 91 (100), 79 (33), 65 (26), 42 (30).
IR (in thin layer), ν/cm–1: 3100—2700, 1450, 1370, 1270, 1050,
900, 870, 790. 1H NMR, δ: 0.75 (s, 3 H, H(7)); 1.08 (s, 3 H,
H(8)); 1.27 (ddm, 1 H, H(5), J = 6.4, 6.4 Hz); 1.89 (s, 3 H,
H(10)); 2.04 (dd, 1 H, H(1), J = 6.4, 3.2 Hz); 2.15 (dm, 1 H,
H(4a), J = 19.0 Hz); 2.52 (ddd, 1 H, H(4b), J = 19.0, 7.3,
3.0 Hz); 3.87 (s, 3 H, OMe); 5.73 (m, 1 H, H(3)). 13C NMR, δ:
11.57 (C(10)); 12.87 (C(7)); 18.73 (C(6)); 26.47 (C(8)); 28.36
(C(5)); 32.52 (C(4)); 36.05 (C(1)); 61.49 (OMe); 132.35 (C(3));
141.80 (C(2)); 152.50 (C(9)).
1,1´ꢀBi(cyclopentyliden)ꢀ2ꢀone Oꢀmethyloxime (8). Highꢀ
resolution mass spectrum, found: m/z 179.13122. C11H17NO.
Calculated: M = 179.13101. MS, m/z (Irel(%)): 179 (52), 153
(27), 148 (100), 120 (88), 105 (13), 94 (28), 91 (30), 81 (12), 79
(28), 77 (19), 53 (15). IR (in thin layer), ν/cm–1: 3000—2800,
1420, 1050, 870, 850. 1H NMR, δ: 1.70 (m, 6 H, H(4), H(8),
H(9)); 2.30 and 2.50 (both m, 4 H each, H(3), H(5), H(7),
H(10)). 13C NMR, δ: 22.13, 26.06, 27.06, 28.83, 31.44, 33.67,
33.78 (C(3), C(4), C(5), C(7), C(8), C(9), C(10)); 61.53 (OMe);
125.41 (C(1)); 144.09 (C(6)); 161.83 (C(2)).
Myrtenal Oꢀmethyloxime (9), [α]22 –34.1 (c 3.28). Highꢀ
578
resolution mass spectrum, found: m/z 179.13104. C11H17NO.
Calculated: M = 179.13101. MS, m/z (Irel(%)): 179 (47), 148
(54), 136 (100), 132 (29), 121 (23), 105 (52), 95 (50), 91 (47), 79
(50), 77 (55), 67 (29), 55 (25), 53 (34), 41 (64). IR (in thin
layer), ν/cm–1: 3000—2800, 1680, 1620, 1450, 1050, 870.
1H NMR, δ: 0.81 (s, 3 H, H(8)); 1.14 (d, 1 H, H(7α), J = 9 Hz);
1.33 (s, 3 H, H(9)); 2.12 (m, 1 H, H(5)); 2.33—2.61 (m, 3 H,
H(4), H(7β)); 2.82 (ddd, 1 H, H(1), J = 5.7, 5.7, 1.4 Hz); 3.79
(s, 3 H, OMe); 5.75 (m, 1 H, H(3)); 7.55 (s, 1 H, H(10)).
13C NMR, δ: 20.98 (C(8)); 26.16 (C(9)); 31.18, 32.34 (C(7) and
C(4)); 40.26 (C(6)); 40.46, 40.85 (C(1) и C(5)); 61.33 (OMe);
129.78 (C(3)); 143.34 (C(2)); 149.24 (C(10)).
Benzylideneacetone Oꢀmethyloxime (2). The spectra of the
sample were identical to the published data.10
2ꢀCarenꢀ4ꢀone (E)ꢀOꢀmethyloxime (5), [α]24
+182.4
578
(c, 1.93). Highꢀresolution mass spectrum, found: m/z 179.13160.
C11H17NO. Calculated: M = 179.13101. MS, m/z (Irel(%)): 179
(36), 164 (30), 137 (73), 132 (32), 121 (17), 119 (23), 106 (100),
93 (52), 91 (52), 53 (13). IR (in thin layer), ν/cm–1: 3000—2800,
1050, 900. 1H NMR, δ: 0.76 (s, 3 H, H(8)); 0.99 (dd, 1 H, H(6),
J = 8.1, 8.1 Hz); 1.10 (s, 3 H, H(9)); 1.11 (m, 1 H, H(1)); 1.79
(s, 3 H, H(10)); 2.48 (dd, 1 H, H(5α), J = 20.0, 8.5 Hz); 2.74 (d,
1 H, H(5β), J = 20.0 Hz); 3.82 (s, 3 H, OMe); 5.96 (d, 1 H,
H(2), J = 4.5 Hz). 13C NMR, δ: 13.85 (C(8)); 18.16 (C(10));
18.62 (C(5)); 20.80 (C(6)); 23.16 (C(7)); 23.33 (C(1));
27.85 (C(9)); 61.55 (OMe); 128.45 (C(3)); 129.81 (C(2));
153.42 (C(4)).
Cinnamal Oꢀmethyloxime (10). The spectra of the sample are
identical to the published data.11
3,7ꢀDimethyloctaꢀ2,6ꢀdienal Oꢀmethyloxime (11). Highꢀ
resolution mass spectrum, found: m/z 181.14609. C11H19NO.
Calculated: M = 181.14666. MS, m/z (Irel(%)): 181 (8), 113
(10), 82 (20), 69 (100), 53 (13), 41 (68). IR (in thin layer),
ν/cm–1: 3000—2800, 1720, 1650, 1440, 1380, 1050. 1H NMR, δ:
1.58 and 1.66 (both s, 3 H each, H(8) and H(9)); 1.83 (s, 3 H,
H(10)); 2.12 (m, 4 H, H(4), H(5)); 3.78 (s, 3 H, OMe); 5.04 (m,
1 H, H(6), W1/2 = 10.3); 5.84 (dm, 1 H, H(2), J = 10 Hz); 7.88
(d, 1 H, H(1), J = 10 Hz). 13C NMR, δ: 17.69 (C(9)); 24.15
(C(10)), 25.65 (C(8)); 26.78 (C(5)); 32.73 (C(4)); 61.21 (OMe);
118.48 (C(6)); 123.52 (C(2)); 131.78 (C(7)); 145.72 (C(3));
146.54 (C(1)).
2ꢀMethylpentꢀ2ꢀenal Oꢀmethyloxime (12). Highꢀresolution
mass spectrum, found: m/z 127.09971. C7H13NO. Calculated:
M = 127.09971. MS, m/z (Irel(%)): 127 (70), 112 (29), 100 (14),
96 (71), 94 (25), 81 (93), 69 (21), 67 (32), 55 (30), 53 (38), 41
(100). IR (in thin layer), ν/cm–1: 3000—2800, 1460, 1060, 900.
1H NMR, δ: 1.00 (t, 3 H, H(5), J = 7.5 Hz); 1.77 (m, 3 H, H(6),
W1/2 = 3); 2.17 (qdm, 2 H, H(4), J = 7.3 Hz, 7.3); 3.78 (s, 3 H,
OMe); 5.59 (tm, 1 H, H(3), J = 7.3 Hz); 7.53 (s, 1 H, H(1)).
13C NMR, δ: 11.32 (C(6)); 13.61 (C(5)); 21.42 (C(4)); 61.28
(OMe); 130.50 (C(2)); 139.43 (C(3)); 152.64 (C(1)).
Carvone (E)ꢀOꢀmethyloxime (6), [α]22
–13.3 (c 1.95).
578
Highꢀresolution mass spectrum, found: m/z 179.13122.
11H17NO. Calculated: M = 179.13101. MS, m/z (Irel(%)): 179
C
(62), 151 (12), 148 (39), 138 (100), 132 (34), 124 (13), 119 (28),
107 (99), 105 (74), 93 (40), 91 (61), 79 (67), 55 (50), 53 (79),
41(68). IR (in thin layer), ν/cm–1: 3100—2750, 1650, 1450,
1370, 1052, 900. 1H NMR, δ: 1.72 (s, 3 H, H(10)); 1.79 (s, 3 H,
H(9)); 1.83—2.38 (m, 4 H, Hax(4), Heq(4), H(5), Hax(6));
3.07 (ddd, 1 H, Heq(6), J = 16.5, 5.5, 1.7 Hz); 3.84 (s, 3 H,
OMe); 4.72 (m, 2 H, H(8), W1/2 = 2.7); 5.91 (m, 1 H, H(3),
W1/2 = 10.9). 13C NMR, δ: 17.65 (C(10)); 20.74 (C(9)); 27.85
(C(4) or C(6)); 30.36 (C(4) or C(6)); 40.43 (C(5)); 61.47 (OMe);
110.02 (C(8)); 130.90 (C(2)); 131.36 (C(3)); 147.70 (C(7));
155.28 (C(8)).

628
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 3, March, 2003
Kolesnik and Tkachev
Reaction of dibenzylphosphine oxide with Oꢀmethyloximes
14.45 (C(1), E isomer); 20.97 (C(1), Z isomer); 29.88 (C(3),
Z isomer); 34.13 (CH2Ph, JC,P = 60.6 Hz); 34.90 (CH2Ph,
JC,P = 60.5 Hz); 35.48 (C(3), E isomer); 42.11 (C(4), Z isomer),
JC,P = 60.3 Hz), 42.56 (C(4), E isomer, JC,P = 60.6 Hz), 60.99
(OCH3, Z isomer); 61.04 (OCH3, E isomer); 126.93 (Cp); 127.24
(C(8)); 128.34 (C(7)); 128.58 (Cm); 129.47 (C(6), JC,P = 5.5 Hz);
(general procedure). To a solution of dibenzylphosphine oxide
(3.0 mmol) in anhydrous dioxane (25 mL), NaH (the content of
NaH 60%, 6.0 mmol) was added. The reaction mixture was
heated to boiling, and a solution of an Oꢀmethyloxime (2.0 mmol)
in anhydrous dioxane (10 mL) was added dropwise with stirring.
The mixture was refluxed with stirring until the initial oxime
disappeared (TLC monitoring), cooled to ∼20 °C, poured into a
saturated solution of NaCl (100 mL), and extracted with ethyl
acetate (50 mL). The extract was dried with Na2SO4 and the
solvent was evaporated in vacuo. The residue was dried in a
vacuum of an oil pump. The product was purified by flash chroꢀ
matography or recrystallization.
129.86 (Co, JC,P = 5.6 Hz); 132.04 (Cipso, Z isomer, JC,P
=
6.7 Hz); 132.08 (Cipso, E isomer, JC,P = 6.5 Hz); 135.98 (C(5),
Z isomer, JC,P = 5.3 Hz); 136.54 (C(5), E isomer, JC,P = 4.8 Hz);
153.67 (C(3), E isomer, JC,P = 12.6 Hz); 155.29 (C(3), Z isoꢀ
mer, JC,P = 12.2 Hz).
3ꢀAminoꢀ5ꢀbenzylꢀ9,9ꢀdimethylꢀ5ꢀoxoꢀ4ꢀphenylꢀ5ꢀ
phosphatricyclo[6.1.1.02,5]decꢀ3ꢀene (13) was isolated as a light
crystalline substance using column chromatography of the prodꢀ
uct prepared from myrtenal Oꢀmethyloxime 9 (0.60 g, 3.4 mmol).
The yield was 0.30 g (24%). The substance was identical to the
sample obtained previously from myrtenonitrile.4
10ꢀ(Dibenzylphosphinoylmethyl)isopinocamphone (E)ꢀOꢀmeꢀ
thyloxime (3a) and 10ꢀ(dibenzylphosphinoylmethyl)pinocamphone
(E)ꢀOꢀmethyloxime (3b) (a mixture of С(2) isomers, 3 : 1) were
isolated by chromatography of the product (1.15 g) prepared
from pinocarvone Oꢀmethyloxime 1 (0.5 g, 2.8 mmol). The yield
was 0.63 g (55%). White crystalline powder, m.p. 98—102 °C
(from ButOMe). Highꢀresolution mass spectrum, found
m/z 409.21775. C25H32NO2P. Calculated: M = 409.21707. MS,
m/z (Irel(%)): 409 (23), 378 (31), 337 (14), 318 (23), 286 (11),
244 (7), 180 (26), 148 (53), 139 (18), 121 (9), 91 (100). IR
(c = 2%, CHCl3), ν/cm–1: 3100—2800, 1600, 1450, 1245, 1050,
3ꢀDibenzylphosphinoylꢀ10ꢀnorꢀαꢀpinene (14) was isolated by
column chromatography on silica gel of the product prepared
from myrtenal Oꢀmethyloxime 9 (0.60 g, 3.4 mmol). The yield
was 0.30 g (26%). Yellowish crystals with m.p. 127—130 °C
(from ButOMe), [α]24
–53.6 (c 2.09). MS, m/z (Irel(%)):
578
350.18173 (59%, calculated for C23H27OP 350.17995), 309 (18),
307 (13), 259 (14), 139 (24), 120 (10), 91 (100). IR (c = 2%,
CHCl3), ν/cm–1: 3090, 1600, 1495, 1455, 1190, 825. 31P NMR,
1
830. Spectroscopic data for 3a. 31P NMR, δ: 43.97. H NMR, δ:
1
0.67 (s, 3 H, H(8)); 0.91 (d, 1 H, H(7α), J = 10.5 Hz); 1.11 (s,
3 H, H(9)); 1.72 (ddd, 1 H, H(10a), J = 15.2, 14.0, 9.0 Hz); 1.86
(m, 1 H, H(5)); 2.12 (m, 1 H, H(2)); 2.31 (ddd, 1 H, H(10b),
J = 15.3, 6.8, 3.4 Hz); 2.35 (dddd, 1 H, H(7β), J = 10.5, 6.2, 6.2,
2.7 Hz); 2.47 (ddd, 1 H, H(4α), J = 18.8, 3.0, 3.0 Hz); 2.71 (dd,
1 H, H(4β), J = 18.8, 3.0 Hz); 2.81 (m, 1 H, CH2Ph); 3.03 (m,
1 H, CH2Ph); 3.10 (m, 1 H, H(1)); 3.26 (m, 2 H, CH2Ph); 3.86
(s, 3 H, OCH3); 7.34—7.17 (m, 10 H, Ph). 13C NMR, δ: 21.63
(C(8)); 26.90 (C(9)); 30.91 (C(10), JC,P = 64.2 Hz); 31.09
(C(4)); 32.97 (C(7)); 36.45 (CH2Ph, JC,P = 71.0 Hz); 36.52
(CH2Ph, JC,P = 69.6 Hz); 37.44 (C(5)); 38.37 (C(6)); 39.52
(C(1), JC,P = 3.2 Hz); 44.36 (C(2), JC,P = 2.2 Hz); 61.27
δ: 32.98. H NMR, δ: 0.49 (s, 3 H, H(8)); 0.84 (d, 1 H, H(7α),
J = 8.3 Hz); 1.18 (s, 3 H, H(9)); 2.09 (m, 1 H, H(5)); 2.20 (m,
4 H, H(1), H(4) and H(7β)); 2.88—3.29 (m, 4 H, CH2Ph); 6.98
(dd, H(2), J = 16.0, 6.3 Hz); 7.14—7.34 (m, 10 H, Ph).
13C NMR, δ: 20.90 (C(8)); 25.86 (C(9)); 30.65 (C(7), JC,P
3.2 Hz); 31.22 (CH2Ph, JC,P = 63.8 Hz); 31.27 (CH2Ph, JC,P
=
=
63.8 Hz); 31.85 (C(4) JC,P = 8.6 Hz); 38.10 (C(6), JC,P = 2.8 Hz);
40.70 (C(5), JC,P = 8.6 Hz); 42.62 (C(1), JC,P = 12.3 Hz);
126.41 (C(3), JC,P = 93.3 Hz); 126.54 (Cp, JC,P = 2.6 Hz);
126.61 (Cp, JC,P = 2.4 Hz); 128.29 (Cm, JC,P = 2.2 Hz); 128.42
(Cm, JC,P = 2.0 Hz); 129.65 (Co, JC,P = 5.2 Hz); 129.72 (Co,
JC,P = 5.4 Hz); 131.84 (Cipso, JC,P = 7.3 Hz); 131.92 (Cipso
JC,P = 7.3 Hz), 154.06 (C(2), JC,P = 3.9 Hz).
,
(OCH3); 126.66 (Cp)); 128.43 and 128.53 (Cm); 129.83 (JC,P
=
5.2 Hz), 129.93 (JC,P = 5.2 Hz) (Co); 131.9 (JC,P = 7.3 Hz),
132.49 (JC,P = 6.9 Hz) (Cipso); 159.30 (C(3), JC,P = 9.5 Hz).
[1,2ꢀBis(dibenzylphosphinoyl)ethyl]benzene (15) was isolated
as a light crystalline substance by recrystallization from acetoniꢀ
trile of the product prepared from cinnamal Oꢀmethyloxime
(10) (0.37 g, 2.3 mmol). The yield was 0.67 g (52%). The prodꢀ
uct was identical to the substance obtained from cinnamonitrile.3
3ꢀAminoꢀ1ꢀbenzylꢀ5ꢀmethylꢀ5ꢀ(4ꢀmethylpentꢀ3ꢀenyl)ꢀ1ꢀoxoꢀ
2ꢀphenylꢀ4,5ꢀdihydroꢀ1Hꢀphosphole (16) was synthesized as a
light crystalline substance from citral Oꢀmethyloxime (11)
(0.45 g, 2.5 mmol). The yield was 0.47 g (50%). The substance
was identical to the product synthesized from geranylnitrile.3
3ꢀAminoꢀ1ꢀbenzylꢀ5ꢀethylꢀ4ꢀmethylꢀ1ꢀoxoꢀ2ꢀphenylꢀ4,5ꢀ
dihydroꢀ1Hꢀphosphole (17) was synthesized as a light crystalline
substance from 2ꢀmethylpentꢀ2ꢀenal Oꢀmethyloxime (12) (0.3 g,
2.4 mmol). The yield was 0.24 g (30%). The substance was
identical to the sample synthesized from 2ꢀmethylpentꢀ2ꢀ
enonitrile.3
1
Spectroscopic data for 3b. 31P NMR, δ: 43.22. H NMR, δ: 0.72
(s, H(8)); 0.84 (H(7α); 1.15 (s, H(9)); 2.17 (m, H(7β)); 3.84 (s,
OCH3). 13C NMR, δ: 19.38 (C(8)); 26.29 (C(9)); 27.67 (C(7));
37.11 (C(5)); 38.50 (C(6)); 43.67 (C(2)); 158.71 (C(3)) (other
signals of isomer 3a are not seen because they overlap with the
signals of the main isomer).
4ꢀDibenzylphosphinoylꢀ4ꢀphenylbutanꢀ2ꢀone Oꢀmethyloxime
(4) (a mixture of E/Z isomers, 5 : 3) was isolated by recrystallizaꢀ
tion from benzene of the product (0.60 g) prepared from
benzylideneacetone Oꢀmethyloxime 2 (0.30 g, 1.7 mmol). The
yield was 0.34 g (50%). Yellowish crystals with m.p. 150—152 °C.
Highꢀresolution mass spectrum, found: m/z 405.18540.
C
25H28NO2P. Calculated: M = 405.18577. MS, m/z (Irel(%)):
405 (35), 374 (23), 314 (28), 176 (100), 144 (38), 139 (13), 121
(10), 104 (14), 103 (10), 91 (93), 65 (10). IR (c = 2%, CHCl3),
ν/cm–1: 3100—2820, 1715, 1495, 1455, 1215, 1057, 730, 700,
670. 31P NMR, δ: 44.19 (E isomer), 44.17 (Z isomer). 1H NMR,
δ: 1.34 (s, H(1), Z izomer); 1.48 (s, H(1), E isomer); 2.55—2.75
(m, H(3)); 2.76 and 3.04 (both m, CH2Ph); 3.35 (m, H(4),
Z isomer); 3.38 (m, H(4), E isomer); 3.70 (s, OCH3, E isomer);
3.79 (s, OCH3, Z isomer)); 7.10—7.30 (m, Ph). 13C NMR, δ:
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 01ꢀ03ꢀ32369)
and the Presidium of the Siberian Division of the Rusꢀ
sian Academy of Sciences (Grant for Young Scientists
of 2000).

Phosphorylation of α,βꢀunsaturated oximes
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 3, March, 2003
629
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Received February 18, 2002;
in revised form September 24, 2002