Synthesis of the new adducts of imines and enamines with PH acids and their derivatives

Article abstract of DOI:10.1002/hc.20513

Nucleophilic or radical addition of esters of trivalent organophosphorus acids with PH fragments to various imines and enamines is proposed as convenient methods for the synthesis of new substituted aminomethyl organophosphorus compounds with three-, four-, and five-coordinated phosphorus. Also the new functionalized derivatives of these compounds with acyl and methanesulfonyl moieties are synthesized, and some properties of the obtained compounds are presented. 2009 Wiley Periodicals, Inc.

Full text of DOI:10.1002/hc.20513

Heteroatom Chemistry
Volume 20, Number 2, 2009
Synthesis of the New Adducts of Imines and
Enamines with PH Acids and Their Derivatives
Andrey A. Prishchenko, Mikhail V. Livantsov, Olga P. Novikova,
Ludmila I. Livantsova, and Elena R. Milaeva
Department of Chemistry, M. V. Lomonosov Moscow State University, Moscow, 119991 Russia
Received 18 September 2008
ing adducts in high yield. Further acylation of these
ABSTRACT: Nucleophilic or radical addition of es-
adducts with NH fragments yields the new amides
ters of trivalent organophosphorus acids with PH frag-
and sulfonylamides of functionalized aminomethyl
ments to various imines and enamines is proposed
organophosphorus acids as promising substances
as convenient methods for the synthesis of new sub-
especially with antioxidative fragments of 2,6-di-
stituted aminomethyl organophosphorus compounds
tert-butyl-4-methylphenol and oleic acid (cf. [5–7]).
with three-, four-, and five-coordinated phosphorus.
Also the new functionalized derivatives of these com-
pounds with acyl and methanesulfonyl moieties are
RESULTS AND DISCUSSION
synthesized, and some properties of the obtained
In the present work, we showed that the reaction
of alkyl or trimethylsilylhypophosphites A with var-
ious imines is a convenient route to functionalized
aminomethylphosphonites 1–6. So hypophosphites
A readily reacts with imines in the presence of boron
trifluoride diethyl etherate as a catalyst exclusively
by the regioselective addition involving the PH frag-
ment to give phosphonites 1–5 in high yield. Note
that the phosphonite 6 is obtained without a cata-
lyst, but this reaction proceeds during 24 h (Eq. (1);
cf. [8,9]). It is necessary to remove the catalyst from
the reaction mixture before its distillation using
diethylamine.
ꢀ
C
compounds are presented.
2009 Wiley Periodicals,
Inc. Heteroatom Chem 20:70–80, 2009; Published online
in Wiley InterScience (www.interscience.wiley.com). DOI
10.1002/hc.20513
INTRODUCTION
The reaction of PH-containing esters of trivalent
organophosphorus acids with organic compounds,
containing multiple bonds, provides a convenient
synthetic route to various aminomethyl organophos-
phorus compounds, which present a great interest as
promising polydentate ligands and biologically ac-
tive compounds [1–4]. In the present work, we re-
port here the results of the nucleophilic or radical
addition of the esters of trivalent organophospho-
rus acids with PH fragments to various imines and
enamines, resulting in the formation of correspond-
Ph
BF3 Et2O
R1O(R2O)PH + PhCH=NX
R1O(R2O)PCHNHX
(1)
A
1-6
R1=R2= Bu (1), Me3Si (4-6); R1 = Et (2), Bu (3); R2 = Me3Si (2,3); X = Me (1-4), t-Bu(5), Me3Si (6).
It is necessary to remove the catalyst from
the reaction mixture before its distillation us-
ing diethylamine. Trimethylsilyl hypophosphite
B formed from ammonium hypophosphite and
chlorotrimethylsilane easily reacts with 2 equiv-
alents of aromatic imines in methylene chloride
and provides aryl-substituted bis(aminomethyl)-
phosphinates C as intermediates. The corresponding
Dedicated to Professor Ivan F. Lutsenko (1912–1993).
Correspondence to: Andrey A. Prishchenko; e-mail: aprish
chenko@yandex.ru
Contract grant sponsor: Russian Foundation for Basic
Research.
Contract grant number: 08-03-00282.
2009 Wiley Periodicals, Inc.
c
ꢀ
70

Synthesis of the New Adducts of Imines and Enamines with PH Acids and Their Derivatives 71
phosphinic acids 7–9 were isolated in high yield by
additional treatment of the reaction mixture with
excess of ethanol (Eq. (2); cf. [10]).
Under the same condition, the reaction of excess
diethyl phosphite with N-trimethylsilylbenzalimine
D [12] is more complicated, and phosphonate 21
Me3SiCl
2ArCH=NX
EtOH
HOP[C1H(NHX)Ar]2
NH4H2PO2
Me3SiOP(O)H2
Me3SiOP[CH(NHX)Ar]2
−NH4Cl
−Me3SiOEt
O
O
B
C
7–9
(2)
t−Bu
HO
Ar = Ph (7), 4–MeOC6H4 (8),
(9); X = Me (7,8), Ph (9).
t−Bu
is isolated after distillation of the reaction mixture.
The proposed scheme of this reaction includes the
desilylation of starting imine D and the formation of
dimer E, which adds diethyl phosphite, and the final
phosphonate 21 is formed via the elimination of am-
monia from intermediate F by distillation (Eq. (5);
cf. [13]).
In contrast, the addition of bis(trim-
ethylsiloxy)phosphine to enamines proceeds
A
only in the presence of azobis(isobutironitrile) at
100–120◦C to give phosphonites 10–13 in high yields
(Eq. (3)). Note that the influence of dialkylamino
fragments on the orientation of the radical addition
in these reactions is more preferable (cf. [11]).
(EtO)2P(O)H
PhCH=NH
3 (EtO)2POH + 2 PhCH=NSiMe3
PhCH=NH
PhCH=NCHPh
−2 (EtO)2POSiMe3
NH2
D
E
Ph
Ph
(5)
(EtO)2PCHN=CHPh
O
(EtO)2PCHNHCHPh
−NH3
O
NH2
F
21
The excess diethyl phosphite slowly added to
phosphonate 21 giving bisphosphonate 22, but af-
ter distillation of the reaction mixture the starting
compounds were obtained (Eq. (6)).
R
(Me3SiO)2PH + R1CH=CHNR2
(Me3SiO)2PCHNR2
CH2R1
A
10–12
Ph
(EtO)2POH
(6)
NH
2
(EtO)2PCH
O
21
−(EtO)2POH
1
R
R N = Et N (10),
= Me2(NC)C ,
N (11),
N (12);
O
R = Me (11), Et (12)
2
2
22
R
(Me3SiO)2P-C
(3)
N
A +
O
N
Also we have developed the methods for the
13
synthesis of new phosphoranes with aminomethyl
fragments via smooth addition of hydrospirophos-
phorane G to enamines. Thus phosphorane G eas-
ily adds to enamines in methylene chloride to give
aminomethyl phosphoranes 23–25 in high yield (Eq.
(7); cf. [14,15]).
Diethyl phosphite and O-ethyl methylphosphite
containing PH fragments easily add to aromatic
imines without any catalyst by heating to 90–100◦C
to give the corresponding aminomethylphospho-
nates 14–18 and phosphinates 19,20 with NH frag-
ments (Eq. (4); cf. [1]).
O
O
O
O
O
O
O
O
O
N
CH
O
P
+
RCH=CHN
P
CH2R
X
X
(7)
H
(EtO)2P(O)H
Me
Me(EtO)P(O)H
(EtO)2PCHNHR
XCH=NR
PCHNHR
G
23–25
EtO
O
O
14–18
19,20
R = Me (23), Et (24), Ph (25).
(4)
(17,20),
(18);
X = Ph (14–16,19),
No doubt, this reaction takes place due to reac-
tive phospholane H, which is in tautomeric equi-
librium with phosphorane G [16]. The proposed
O
N
R = Me (14,17–20), CH2=CHCH2 (15), t−Bu (16).
Heteroatom Chemistry DOI 10.1002/hc

72 Prishchenko et al.
scheme (Eq. (8)) consist of formation of highly reac-
tive aminomethylating cations I and following for-
mation of phosphoranes 23–25.
thesis and present certain interest as effective lig-
ands and biologically active compounds [1,2]. Also
phosphorus-containing amides and their deriva-
O
O
O
O
O
O
RCH=CHNR2
+
−
O RCH=CHNR2H
P
P O
OH
P O
O
O
H
G
H
(8)
O
O
O
O
O
+
O
O
O
O
+
CHNR2
CH2R
P
CHNR2
CH2R
−
P
O RCH2CHNR2
P O
−
O
23–25
I
NR2 =
N
O.
Note the similar reaction of phosphorane G with
cyclic enamine proceeds as a slow redox process un-
der the same conditions, yielding bisphosphorane 26
and bisphospholane 27 (Eq. (9); cf. [16,17]).
tives, including a PCHN fragment with a chi-
ral carbon atom, are promising organophosphorus
biomimetics of amino acids and can be used in
various stereoselective processes [3,18,19]. We have
O
2
N
O
O
O
O
O
O
O
O
O
O
O
O
O
+
4
P
P
P
O
O
O
O
P
P
O
O
O
−2
O
N
H
(9)
27
G
26
Another route of this reaction may be accounted
for the attack of sterically hindered cation I is more
preferable at P H bond of hydrospirophosphorane
E. The following symmetrization of intermediate J
yields the final products 26 and 27 (Eq. (10)).
proposed facile synthetic routes to new representa-
tives of this type of compounds—the phosphorus-
containing carboxamides and also methane sul-
fonamides, based on readily accessible adducts of
imines and PH acids with NH fragments. Thus
O
O
P
O
O
O
O
O
O
O
+
O
O
H
−
+
P
−
O
P O
O
P
O
P O
N
O
O
N
I
+
P
O
O
O
O
O
O
−
O
O
O
O
O
O
O
O
O
O
−
+
P
O
P
O
O
P O
P
O
O
P
O
O
O
O
O
O
27
J
(10)
O
O
O
O
O
O
O
P
O
P
O
O
26
Organophosphorus-substituted carboxamides of
various structures are widely used in organic syn-
adducts 14,15,17 with NH fragment are readily
formylated and acylated to give amides 28–33, and
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of the New Adducts of Imines and Enamines with PH Acids and Their Derivatives 73
in the presence of triethylamine the former smoothly
Ar
(1) RC(O)Cl; (2) H2O
reacts with cyclopropylcarbonyl and methanesul-
fonyl chlorides yielding amide 34 and sulfonamides
35–38 (Eq. (11)).
HOP[CHNC(O)R]2
7–9
−Py
HCl
O
X
43–45
t−Bu
OH (45);
t−Bu
(CH2)7CH3
H
(CH2)7
H
(14)
R =
Ar = Ph (43), 4−MeC6H4 (44),
;
X
R
X
R
X
R
HCOOH
Ac2O
−AcOH
(EtO)2PCHNCHO
(EtO)2PCHNH
O
(EtO)2PCHNAc
−H2O
O
O
X = Me (43,44), Ph (45).
(11)
28–30
14,15,17
31–33
The synthesized compounds 28–45 are promis-
ing ligands and biologically active substances, for
example, antioxidants 9,42,45; also phosphorus-
substituted oleamides 43–45 can be applied as
micelle-forming agents.
The structures of organophosphorus-substituted
amines and amides 1–45 were confirmed by the 1H,
13C, and 31P NMR spectra, which show characteris-
tic signals of the PCHN and PCHNC(O) fragments
and signals of substituted aromatic fragments (see
Tables 1 and 2). The elemental analysis data of syn-
thesized compounds are summarized in Table 3.
C(O)Cl
, B
X Me
(EtO)2PCHNC
X Me
(EtO)2PCHNSO2Me
MeSO2Cl , B
14,17
−B
HCl
−B
HCl
O
O
O
35,36
34
X
X
Me
Me
MeSO2Cl , B
PCHNH
PCHNSO2Me
EtO
−B
EtO
HCl
Me
O
Me
O
19,20
37,38
R = Me (28,30,31,33), CH2=CHCH2 (29,32);
X = Ph (28,29,31,32,35,37),
(30,33,34,36,38); B = Et3N.
O
In contrast, under similar conditions adduct 16
reacts with acetic anhydride via elimination of tert-
butyl group in intermediate K giving phosphorus-
containing acetamide 39 (Eq. 12).
EXPERIMENTAL
The 1H, 13C, and 31P NMR spectra were registered on
the Varian VXR-400 and Bruker Avance-400 spec-
trometer (400, 100, and 162 MHz, respectively) in
CDCl3 (1–6, 10–45), CD3COOD (7–9) or D2O (14)
against TMS (1H and 13C) and 85% H3PO4 in D2O
(31P). All reactions were carried out under dry argon
in anhydrous solvents. The starting hypophospites
A, imines, and enamines were prepared as described
in [20,21].
Ph
Ph
+
Ac2O
(EtO)2PCHNHBu−t AcO−
16
(EtO)2PCHNHAc
(12)
−Me2C=CH2, −AcOH
O
Ac
O
K
39
The several phosphorus-substituted amides
of acetic and oleic [(Z)-octadec-9-enoic] acids
are synthesized on the basis of arylsubsti-
tuted bis(aminomethyl)phosphinic acids 7–9. So
phosphorus-substituted acetamides 40–42 were pre-
pared in high yields by heating a mixture of amines
7–9 with excess acetic anhydride followed by the
treatment of the reaction mixture with water and
recrystallization of the product in aqueous ethanol
(Eq. (13)).
O,O-Dibutyl N-Methylamino(phenyl)methylpho-
sphonite (1). To a stirred mixture of dibutoxyphos-
phine (3.6 g) and benzal(methyl)imine (2.4 g), boron
trifluoride diethyl etherate (0.1 g) was added. The
mixture was stirred for 0.5 h, and the solution di-
ethylamine (3 g) in 40 mL of pentane was added,
and the mixture was boiled for 0.5 h. The precipitate
that formed was filtered off, the solvent was distilled
off, and the residue was distilled to obtain 4.9 g of
phosphonite 1.
Ar
Ar
1) Ac2O; 2) H2O
HOP[CHNH]2
HOP[CHNAc]2
−AcOH
O
X
O
X
Phosphonites 2–6 were synthesized by the same
method. Phosphonite 6 was synthesized without a
catalyst; this reaction mixture was left for 24 h.
(13)
7−9
40−42
t−Bu
OH (42);
t−Bu
Ar = Ph (40), 4–MeC6H4 (41),
X = Me (40,41), Ph (42).
Bis[N-methylamino(phenyl)methyl]phosphinic
Acid (7). A mixture of 8.3 g of ammonium hy-
pophosphite, 25.2 g of benzal(methyl)imine, and
17 g of chlorotrimethylsilane in 60 mL of methylene
chloride was heated under reflux with stirring for
2 h. Ammonium chloride was filtered off, the solvent
The reaction of amines 7–9 with excess oleoyl
chloride in the presence of pyridine under the same
conditions gave phosphorus-substituted oleamides
43–45 in high yield (Eq. (14)).
Heteroatom Chemistry DOI 10.1002/hc

74 Prishchenko et al.
b
P
J
f
a
J
a
g
g
J
n
i
e
e
d
d
d
h
f
g
g
g
g
J
J
c
c
c
g
g
g
g
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of the New Adducts of Imines and Enamines with PH Acids and Their Derivatives 75
b
J
P
J
k
J
J
J
J
J
k
l
l
l
J
J
J
J
n
l
l
l
J
X
B
J
g
g
g
X
A
J
B
j
J
A
J
B
J
A
J
J
D
J
n
J
a
b
c
d
e
f
g
h
i
j
k
l
Heteroatom Chemistry DOI 10.1002/hc

76 Prishchenko et al.
c
P
J
d
d
d
d
d
d
a
b
b
b
b
b
b
b
J
a
J
J
J
e
D
n
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of the New Adducts of Imines and Enamines with PH Acids and Their Derivatives 77
c
P
J
f
f
f
J
f
f
f
f
f
f
f
J
J
J
J
J
J
J
J
J
J
D
n
J
J
J
a
b
c
d
e
f
Heteroatom Chemistry DOI 10.1002/hc

78 Prishchenko et al.
was removed in a vacuum, and 60 mL of ethanol
was added to the residue. The mixture was heated
to boil; the precipitate that formed was filtered off
and washed with 20 mL of ethanol and 20 mL of
ether. The resulting white fine crystals were kept in
vacuum of 1 mmHg for 1 h to obtain compound 7,
yielding 28 g.
crystals were filtered off and washed with 3 mL of
hexane and then were kept in a vacuum of 1 mmHg
for 0.5 h to obtain 3 g of bisphosphorane 26, yielding
92%, mp 152◦C. In 1H NMR spectrum, δ (ppm):
3.5–3.7 m (cyclic CH2, 16H), 3.9–4.0 m (bridged
CH2, 4H). In 13C NMR spectrum, δ (ppm): 60.08
2
d (cyclic CH2, JPC 7.9 Hz), 66.87 t (bridged CH2,
3
The acids 8,9 were prepared by the same proce-
dure.
2 JPC = JPC 14.7 Hz). In 31P NMR spectrum, δ (ppm):
−27.44. The solvent was removed from combined
ether solutions, the residue was distilled to obtain
1.4 g of bisphospholane 27, yielding 65%, bp 120◦C
O,O-Bis(trimethylsilyl) 1-(diethylamino)butylpho-
sphonite (10). A mixture of 7.2 g of bis(trimethyl-
n20
under 0.05 mmHg, D 1.4890. In 1H NMR spectrum,
siloxy)phosphine, 3.5
g
of 1-(diethylamino)-1-
δ (ppm): 3.55–3.65 m (cyclic CH2, 8H), 3.80–3.95 m
butene, and 0.1 g of azobis(isobutyronitrile) was
heated to 110–130◦C for 2.5 h and then distilled in a
vacuum to obtain 7.4 g of phosphonite 10.
(bridged CH2, 4H). In 13C NMR spectrum, δ (ppm):
2
64.86 d (cyclic CH2, JPC 8.9 Hz), 62.68 dd (bridged
2
3
CH2, JPC = 11.9 Hz, JPC = 4.2 Hz,). In 31P NMR
Phosphonites 11–13 were prepared similarly.
spectrum, δ (ppm): 134.46.
The constants and NMR spectral data of com-
pounds 26 and 27 are coincided with the data from
the literature [16,17,22].
O,O-Diethyl N-Methylamino(phenyl)methylpho-
sphonate (14). A mixture with 25.7 g of diethyl
phosphite and 13.8 g of benzal(methyl)imine was
heated at 90–100◦C for 1 h, and the mixture was left
for 48 h at 20◦C, then was distilled, yielding 26.3 g of
phosphonate 14.
O,O-Diethyl N-Formyl-N-methylamino(phenyl)-
methylphosphonate (28). A mixture of 12 g of phos-
phonate 14 and 3.5 g of 95% formic acid in 35 mL
of toluene was refluxed with a water trap until water
no longer separated. The solvent was then removed,
and the residue was distilled to obtain 10 g of phos-
phonate 28.
The compounds 15–21 were prepared similarly.
Bis[diethoxyphosphoryl(phenyl)methyl]amine (22).
A mixture of 2.9 g of diethyl phosphite and 6.7 g
of phosphonate 21 was left for 1 month at 20◦C,
then was kept in vacuum of 1 mmHg for 2 h to
obtain amine 22, yielding 9.5 g. According to 31P
NMR data, amine 22 contains as impurity of diethyl
phosphite, 3%.
Compounds 29–33 and 39 were obtained simi-
larly.
O,O-Diethyl N-(Cyclopropylcarbonyl)-N-methyl-
amino(2-furyl)methylphosphonate (34). A solution
of 3.8 g of cyclopropylcarbonyl chloride in 10 mL of
diethyl ether was added dropwise with stirring and
cooling to 10◦C to a solution of 8.7 g of phospho-
nate 17 and 5 g of triethylamine in 25 mL of diethyl
ether. The mixture was allowed to stand at 20◦C for
12 h, the precipitate that formed was filtered off, the
solvent was removed, and residue was distilled to
obtain 9.2 g of phosphonate 34.
5-(1-Morpholinopropyl)-1,4,6,9-tetraoxa-5-pho-
sphaspiro[4.4]nonane (23). 1-Morpholino-1-pro-
pene having a weight of 6.9 g was added to a solution
of 4.1 g of hydrospirophosphorane G in 5 mL of
methylene chloride. The mixture was left for 24 h.
Then solvent was removed, and 50 mL of hexane
was added to the residue. The white crystals were
filtered off and washed with 10 mL of hexane, then
were kept in a vacuum of 1 mmHg for 1 h to obtain
6.9 g of compound 23.
Sulfonamides 35–38 were obtained similarly.
The compounds 24 and 25 were prepared
similarly.
Bis[N-acetyl-N-methylamino(phenyl)methyl]pho-
sphinic Acid (40). A mixture of 3.1 g of amine 7,
15 mL of acetic anhydride, and 20 mL of methylene
chloride was heated under reflux with stirring for
2 h, after which 20 mL of water was added, and
the mixture was heated to boil. The solvents were
then removed in a vacuum. Twenty milliliters of
water, 5 mL of ethanol, and 5 mL of ether were
added to the residue, and the crystals were filtered
off, washed with ether, and exposed to a vacuum of
1 mmHg for 1 h to obtain 3.2 g of acid 40.
1,2-Bis(1,4,6,9-tetraoxa-5-phosphaspiro[4.4]non-
5-yloxy)ethane (26) and 1,2-bis(1,3,2-dioxaphos-
pholan-2-yloxy)ethane (27). Twelve grams of
1-Morpholino-1-cyclohexene was added to a solu-
tion of 5.5 g of hydrospirophosphorane G in 5 mL
of methylene chloride. This mixture was left for
2 weeks, then solvent was removed, and 5 mL of
diethyl ether was added to the residue. The white
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of the New Adducts of Imines and Enamines with PH Acids and Their Derivatives 79
TABLE 3 Elemental Analyses Data of Compounds 1–45a
Calcd (%)
Found (%)
Compound No
Empirical Formula
C16H28NO2P
Formula Weight
C
H
C
H
1
2
3
4
5
6
7
8
297.38
285.40
313.45
329.52
371.61
387.69
304.33
364.38
684.89
337.58
335.56
351.56
377.60
257.27
283.31
299.35
247.23
258.26
227.24
217.21
331.35
469.46
279.28
293.30
307.33
285.28
311.32
275.25
299.30
325.34
289.28
315.31
335.36
325.33
305.33
295.30
285.28
388.40
448.45
768.97
610.81
670.87
991.38
64.62
54.71
57.48
51.03
54.95
49.57
63.15
59.33
73.66
49.81
50.11
47.83
50.90
56.02
59.35
60.19
48.58
60.46
58.14
49.77
65.25
56.29
47.31
49.14
50.81
54.73
57.87
48.00
56.18
59.07
49.82
53.33
46.56
40.61
47.20
40.67
54.73
61.85
58.92
71.85
70.79
68.03
75.12
9.49
8.48
9.00
8.56
9.22
8.84
6.96
6.92
8.39
64.35
54.59
57.19
50.90
54.71
49.40
62.97
59.12
73.52
49.70
49.95
47.68
50.74
55.89
59.16
60.02
48.43
60.28
58.98
49.68
65.12
55.93
47.58
48.90
51.00
54.60
57.66
47.86
55.88
58.93
49.59
53.02
46.35
40.38
47.02
40.52
54.92
61.68
58.72
71.64
70.65
67.82
74.89
9.33
8.39
9.12
8.49
9.18
8.79
7.09
6.97
8.26
10.66
10.09
9.59
9.52
7.78
7.64
8.65
7.26
8.03
7.92
7.30
6.52
6.91
8.08
8.35
8.54
6.98
7.01
6.47
7.27
7.30
6.68
6.91
6.49
6.03
6.42
6.01
7.02
6.52
6.59
8.07
8.94
8.74
9.03
C
C
13H24NO2PSi
15H28NO2PSi
C
C
C
14H28NO2PSi2
17H34NO2PSi2
16H34NO2PSi3
C16H21N2O2P
C18H25N2O4P
9
C42H57N2O4P
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
C
14H36NO2PSi2
14H34NO2PSi2
14H34NO3PSi2
16H36NO3PSi2
10.75
10.21
9.75
9.61
7.84
7.83
8.76
7.34
8.20
7.98
7.43
6.69
7.08
7.94
8.25
8.53
7.07
7.12
6.59
7.41
7.44
6.97
7.03
6,61
6.20
6.60
6.14
7.07
6.49
6.52
8.00
9.07
8.86
9.25
C
C
C
C12H20NO3P
C14H22NO3P
C15H26NO3P
C10H18NO4P
C
C
13H21N2O3P
11H18NO2P
C9H16NO3P
18H22NO3P
NO6P2
C
C
22 33
H
C
H NO5P
11 22
C12H24NO5P
C13H26NO5P
C13H20NO4P
C15H22NO4P
C11H18NO5P
C14H22NO4P
C16H24NO4P
C12H20NO5P
C14H22NO5P
C13H22NO5PS
C11H20NO6PS
C
C
12H20NO4PS
10H18NO5PS
C13H20NO4P
C
C
C
20H25N2O4P
22H29N2O6P
46H61N2O6P
C36H55N O P
C
C
38H59N22O46P
62H91N2O6P
aThe compounds 26 and 27 were described earlier in [16,17,22].
Compounds 41 and 42 were synthesized by the
same procedure.
milliliters of water 10 mL of hexane and 3 mL of
ether were added to the residue, and the mixture
was stirred for 0.5 h. Hexane was separated, and
water was distilled off in a vacuum of 1 mmHg for
1 h to obtain 4.9 g of acid 43.
Bis[N-methyl-N-oleoylamino(phenyl)methyl]pho-
sphinic Acid (43). To a cooled (10◦C) and stirred
mixture of 3.1 g of amine 7, 5 mL of pyridine, and
30 mL of methylene chloride, 7.7 g of oleoyl chloride
in 10 mL of methylene chloride was added. The
mixture was heated for 3 h and was left to stand for
12 h. The precipitate was filtered off. The filtrate was
diluted with 20 mL of water and heated for 1 h. The
solvents were then removed in a vacuum. Twenty
Compounds 44,45 were prepared by the same
method.
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