Reaction of C-silyl-P-chloro-alkylidenephosphoranes with carbonyl compounds

Article abstract of DOI:10.1080/10426507.2015.1054932

Reaction of P-chloroylides with carbonyl compounds leads to the formation of four-membered phosphorus heterocycles - 2⁵-chloro-2,2-oxaphosphetanes. The 2-chloro-2,2-oxaphosphetanes depending on substituent R at α;-atom carbon, rearrange with formation of 2-chloroalkylphosphonates (R = H, Alk, Ar) or with elimination of trimethylchlorosilane (R = Me₃Si) convert into trans-phosphorylated alkenes.

Full text of DOI:10.1080/10426507.2015.1054932

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Reaction of C-silyl-P-chloro-
alkylidenephosphoranes with carbonyl
compounds
Olga O. Kolodiazhna & Oleg I. Kolodiazhnyi
To cite this article: Olga O. Kolodiazhna & Oleg I. Kolodiazhnyi (2016) Reaction of C-silyl-P-
chloro-alkylidenephosphoranes with carbonyl compounds, Phosphorus, Sulfur, and Silicon and
the Related Elements, 191:2, 322-328, DOI: 10.1080/10426507.2015.1054932
To link to this article: http://dx.doi.org/10.1080/10426507.2015.1054932
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Date: 03 March 2016, At: 12:46

PHOSPHORUS, SULFUR, AND SILICON
, VOL. , NO. , –

http://dx.doi.org/./..
Reaction of C-silyl-P-chloro-alkylidenephosphoranes with carbonyl compounds
Olga O. Kolodiazhna and Oleg I. Kolodiazhnyi
Institute of Bioorganic Chemistry and Petrochemistry of National Academy of Sciences of Ukraine, Kiev, Ukraine
ABSTRACT
ARTICLE HISTORY
Received  March 
Accepted  May 
Reaction of P-chloroylides with carbonyl compounds leads to the formation of four-membered phospho-
5
rus heterocycles—2λ -chloro-2,2-oxaphosphetanes. The 2-chloro-2,2-oxaphosphetanes depending on sub-
stituent R at α-atom carbon, rearrange with formation of 2-chloroalkylphosphonates (R = H, Alk, Ar) or with
KEYWORDS
C-silylated
alkylphosphonites;
elimination of trimethylchlorosilane (R = Me Si) convert into trans-phosphorylated alkenes.
3
C-silyl-P-ylides;


,λ -oxaphosphetanes;
vinylphosphonates;
dienephosphonates;
vinylphosphine oxides
GRAPHICAL ABSTRACT
Introduction
chemical transformations. They react with methanol convert-
ing into trimethylsilylphosphonates and enter to the [2+2]-
cycloaddition reaction with carbonyl compounds with forma-
Phosphorus ylides play important roles in modern organic
synthesis due to their wide spectrum of synthetic applica-
tions.1 Among the different classes of phosphorus ylides, P-
halogeneylides are versatile and powerful tools for the synthe-
sis of various compounds.3 P-halogenylides exhibit specific
properties which permit to prepare from them synthetically
important compounds unavailable through the use of triph-
5
tion of 2-chloro-1,2λ -oxaphosphetanes—in general case unsta-
–3
7
ble intermediates. The stability of 2-chlorooxaphosphetanes
depends on nature of substituents at C-4 atoms. The 2-chloro-
,4
5
1
,2λ -oxaphosphetanes bearing H, Alk, or Ar at C-4 atom are
unstable, though can be registered by NMR at low tempera-
ture. In this case, oxaphosphetanes rearrange to convert into 2-
cloroalkylphosphonates 4.5d At the same time, oxaphosphetanes
bearing trimethylsilyl group at C-3 atom with elimination of
trimethylchlorosilane converted into phosphorylated alkenes 5
5
enylphosphonium ylides. For example, phosphorus ylides con-
taining chlorine atoms at the phosphorus atom, so-called P-
chloroylides, have attracted chemist’s attention by their availabil-
ity, and high reactivity, as well as by interesting chemical proper-
ties. 4 The labile chlorine atom at the phosphorus determine
unusual properties of these compounds that are interesting in
theoretical, and in preparative relations.5
(
Scheme 1).
a,5a
The oxaphosphetanes 3a-d bearing electronegative CF3 sub-
stituent at C-4 are more stable and can be isolated and ana-
lyzed by NMR (Scheme 2). For example, the oxaphosphetanes
3
a-d were isolated and their structures were confirmed by
NMR spectroscopy and chemical reactions. The NMR spectra
of these compounds reveal signals at 0.15–0.20 ppm, singlet
Result and discussion
8–11
(
Me3Si), at 5.4 ppm (PCH), at 7.3–7.8 (aromatic protons).
C-Silyl-P-chloroylides 2, which possess high stability, owing to
stabilizing effect of trimethylsilyl group represents the particular
interest. The ylides 2 can be obtained by reaction of alkylphos-
3
1
5
The P NMR signals of 2-chloro-1,2λ -oxaphosphetanes 3a-
1
d at δP +48 ppm (3, R = i-PrO) and at δP = +60 ppm (3,
1
R = Et2N) respond to tetracoordinate phosphorus included
6
phonites 1 with CC14. They were purified by distillation under
12,13
in four-membered phosphetane cycle.
It is interesting
vacuum and isolated as pure compounds. The ylides 2 repre-
sent fuming, flammable on air colorless liquids and very active
compounds in the chemical relation. They enter into various
5
that the δP of 2-chloro-1,2λ -oxaphosphetane 3d (R = t-Bu)
depends on polarity of solvent (Table 1). In nonpolar solvents
CONTACT Oleg I. Kolodiazhnyi
 Taylor & Francis Group, LLC
olegkol@rambler.ru
Institute of Bioorganic Chemistry, Murmanskaia Street, , Kyiv , Ukraine.
©

PHOSPHORUS, SULFUR, AND SILICON
323

Scheme . Convertions of -chloro-,λ -oxaphosphetanes 3.

Scheme . Chemical properties of -chloro-,λ -oxaphosphetanes 3a-d.
(
hexane), the δP = 10 ppm of 3d is typical for phosphorane P(V)- were registered by means of 31P NMR spectroscopy. For exam-
1
2
structures. In medium-polar solvents (chloroform, acetonitrile), ple, the oxaphosphetane 3b (R = i-PrO, R = H) was registered
the δP are shifted to weak fields, +40 to +50 ppm, because of by signal at δ +40 ppm, which disappeared in course of reac-
P
oxaphosphetane dissociation 3A ꢀ 3B. The addition of chloride tion, and instead of this signal a new signal at δ +17 ppm was
P
aluminium into a solution of oxaphosphetane shifts the value registered. This signal belongs to vinylphosphonate 5b which
5
δP to +100 ppm, because of full ionization of 2-chloro-1,2λ - was isolated and analyzed. At heating (40–50°C) the 3b con-
oxaphosphetane 3d with formation of tetracoordinated P(IV) verts readily and completely into a corresponding vinylphos-
5f
structure (see ).
phonate 5. The oxaphosphetane 3b in aqueous ether in the pres-
5
The 2-chloro-1,2λ -oxaphosphetanes 3a-d after evaporation ence of triethylamine was hydrolyzed with formation of crys-
of solvent were obtained as colorless oils. The compounds 3a- talline 2-trifluoromethyl-2-hydroxyphosphonate 6b in good
d at room temperature slowly, and at heating faster, eliminates yield.
trimethylchlorosilane to convert into alkenephosphonates 5,
The P-chloroylides 2 react with carbonyl compounds at
which were isolated in good yields and were purified by distil- equimolecular ratio of reagents in ether solution or without sol-
5
lation under vacuum. The 2-chloro-1,2λ -oxaphosphetanes not vent to give alkenes 7a-l in good yield. The course of reac-
containing CF3 group are unstable, though in certain cases they tion was monitored by TLC or NMR. The reaction products
were purified by distillation under vacuum or by column chro-
matography with silica gel. The reaction can be carried out as

Table . Effect of solvents on the δP of -chloro-,λ -oxaphosphetane 3d.
a one pot two-step synthesis starting from phosphines, CCl4
Solvent
Pentane
.
CCl
.
CDCl
.
CD CN
CDCl /AlCl
and aldehydes without the isolation of ylides. This reaction is
a convenient method for the preparation of phosphorylated
trans-alkenes (Table 2).



δ
.
.
P

3
24
O. O. KOLODIAZHNA AND O. I. KOLODIAZHNYI
Table . The synthesis of phosphorylated alkenes 7a-l.
Reaction conditions
ꢀ
Yield (%)a
Entry
R
R
Time (h)
(t°C)
Solvent
Product
b)

t-Bu
EtO
EtO
Ph
Ph
.

–





–
–
–



7a







e)
c)






Ether
Ether
Ether
Ether
Ether
Ether
7b
e)
d)
-BrC H
7c


e)
d)
i-PrO
Ph
Ph
7d
Et N
7e
7f
7g

Et N
-FC H

 
Et N
CH = CHPh


Et N


THF
7h



EtO


THF
7i







Et N
C H CHO-p






THF
THF
THF
7j




 
Et N
R P(O)CH = CHC H
7k





e)
i-PrO
R P(O)CH = CHC H
7l


a) Yield of the isolated product; (b) without solvent; (c) ref.–; (d) ref.,; (e) ref. ; (f) ref. .


(e) After evaporation of solvent the reaction mixture was heated up to °C.
The assignment of the stereochemistry of the double bond of Experimental
diethyl E-1-alkenylphosphonates 7a-l was based on the values
1H and 13C NMR spectra were recorded a Varіan VXR-300
3
3
of vicinal proton–proton ( JHH) and proton–phosphorus ( JHP)
1
13
31
(
300 MHz for H, 60 MHz for C, 126.16 ( P) MHz) spectrom-
3
coupling constants. Thus, the values of constants JHH = 17–
1
13
31
eter relative to Me4Sі ( H, C) or 85% H3PO4 ( P) using CDCl3
as solvent. Coupling constants (J) are reported in Hertz (Hz).
Analytical TLC was carried out on Merck Silica gel 60 F254 plates
with detection by UV light, anisaldehyde stain solution. Sol-
vents were preliminarily distilled in an inert atmosphere: diethyl
ether, hexane, benzene, and carbon tetrachloride over phospho-
rus pentoxide, methanol, and triethylamine over sodium, and
ethyl acetate over calcium chloride. Reagents were purchased
from Merck (Germany), Fluka (Buchs, Switzerland), and Acros
and were used without further purification. Melting points are
uncorrected.
3
1
8 Hz and JHP = 18–22 Hz for E-1-alkenylphosphonates 7a-
3
l, whereas for Z-7 vicinal-coupling constants Jhh = 11–14 Hz,
3
and JHP are around 47–51 Hz. These results are in agreement
with the literature data.1
4–19
The trans-vinylphosphonates 7a-d,
7
l were earlier synthesized by other methods and their spectro-
scopic and physical data are identical to those reported in the
references cited.1
5–19
The reaction of ylides with aldehydes is regioselective. For
example, the reaction of 2c with terephthalic aldehyde depend-
ing on a ratio of initial reactants led to the formation of
1
,4-bis-vinylphosphonobenzene 7k,l or phosphonovinylben-
zaldehydes 7j, that represent interest as reactants for organic
synthesis.
Diethyl trimethylsilylmethylphosphonite (1a)
A solution of trimethylsilylmethylenemagnesium chloride
(
0.1 mol) in diethyl ether was added at −20°C and stirring to
a solution of diethylchlorophosphite (0.1 mol) in diethyl ether
ca.100 mL) After complete addition, the reaction mixture was
Conclusion
(
In conclusion, we have studied the reaction of C-silyl- heated to room temperature and the mixture was stirred for
P-chloroylides 2 with aldehydes leading to the formation 1 h, a precipitate of magnesium dichloride was filtered off. After
5
5
of 2-chloro-1,2λ -oxaphosphetanes 3. The 2-chloro-1,2λ - filtration, residual MgCl2 was washed thoroughly with ether
3
oxaphosphetanes 3 were registered by NMR. The compounds (3 × 30 cm ), the extracts were combined and solvent was
3
, depending on substituent R at α-carbon atom, rearranged to removed under reduced pressure to afford crude phosphonite
2
-chloroalkylphosphonates 4 (R = H, Alk, Ar) or with elimina- 1a. Distillation at reduced pressure yields pure 1a as a colorless
1
tion of trimethylchlorosilane (R = Me3Si) converted into trans- liquid. Bp 85–90°C (12 mmHg). Yield 75%. H NMR (CDCl3):
3
3
phosphorylated alkenes 5. The reaction is a convenient method δ 0.01 s (9H, CH3Si); 1.32 d.t ( JHH = 6.5 Hz, JPH = 1.0 Hz, 6H,
3
for the preparation of phosphorylated alkenes and can be useful CH3); 1.50 d ( JPH = 13 Hz, 2H, PCH2); 3.90 m (4H, OCH2).
for fine organic synthesis.22
31
P NMR (CDCl3), δP 184.9 ppm.6

PHOSPHORUS, SULFUR, AND SILICON
325
Anal. Calcd for C8H21O2PSi: C, 46.13; H, 10.16; P, 14.87. Diisopropoxychlorphosphonium trimethylsilylmethylide
Found: C, 46.45; H, 10.32; P, 14.61.
(2b)
In a flask with a magnetic stirrer was placed a solution of diiso-
propyl (trimethylsilyl)methylphosphonite (0.02 mol) in 20 mL
of diethyl ether and at cooling to −70°C. the carbon tetrachlo-
ride (0.04 mol) was added dropwise. Then, the reaction mixture
was heated to room temperature and was stirred for 3 h. The sol-
vent was evaporated and the residue was distilled under vacuum.
Diisopropyl (trimethylsilyl)methylphosphonite (1b)
The phosphonite 1b was prepared from (i-PrO)2PCl and
trimethylsilylmethylenemagnesium chloride analogously to 1a.
1
Yield 75%, bp 80–90°C (12 mmHg). H NMR (CDCl3): δ 0.01 s
3
3
(
9H, CH3Si); 1.40 d ( JPH = 15 Hz, 2H, PCH2); 1.25 d.d ( JHH
1
Yield 80%, bp 65°C (0.06 mmHg). H NMR (CDCl3): δ 0.30 d
3
31
=
6.0 Hz, JPH 1.0, 12H, CH3); 4.20 m (2H, OCH). P NMR
4
3
(
JPH = 0.3 Hz, 9H, CH3Si); 0.48 d ( JPH = 3 Hz, 1H, P = CH);
(
CDCl3): δP 185.0 ppm.
3
3
1
.65 d.d [ JHH = 6.5 Hz, JPH = 1.0 Hz, 12H (CH3)2CH]; 4.92 m
Anal. Calcd for C10H25O2PSi: C 50.81; H 10.66; P 13.10.
13 3
(
2H, OCH). C NMR (C6D6): δ 0.89 d ( JPC = 6.0 Hz, CH3Si);
Found: C 50.99; H 10.88; P 12.91.
1
3
1
5.00 d ( JPC = 155 Hz, P = C); 21.30 d ( JPC = 6 Hz, CH3C);
2 31
7
1.55 d ( JPC 9 = Hz, OCH). P NMR (CDCl3): δP +59.00 ppm.
Anal. Calcd for: C10H24ClO2PSi: Cl 13.09; P 11.44%. Found:
Bis(diethylamido) trimethylsilylmethylphosphonite (1c)
Cl 12.79; P 11.58.
The phosphonite 1c was prepared from (Et2N)2PCl and
trimethylsilylmethylenemagnesium chloride analogously to 1a.
13
Yield 65%, bp 110°C (10 mmHg). C NMR (CDCl3):
Bis(diethylamino)chlorphosphonium trimethylsilylmeth
ylide (2c)
3
1
δ −0.1 d ( JPC = 7 Hz, CH3Si); 14.5 d ( JPC = 28 Hz, PC); 15.1 d
3
2
31
(
JPC = 5.0, CH3); 43.3 d ( JPC = 15.0, NC). P NMR (CDCl3):
In a flask with a magnetic stirrer was placed a solu-
tion of bis(diethylamino) (trimethylsilyl)methylphosphonite
δP 85.7 ppm.
Anal. Calcd for C12H31N2PSi: C, 54.92; H, 11.91; P, 11.80.
Found: C, 54.09; H, 11.96; P, 11.87.
(
0.02 mol) in diethyl ether (20 mL) and dropwise the carbon
tetrachloride (0.04 mol) was added at cooling to −70°C. Then,
the reaction mixture was heated to room temperature and was
stirred for 0.5 h. The solvent was evaporated and the residue was
Di-tert-butyl(trimethylsilylmethyl)phosphine (1d)
1
distilled under vacuum. Yield 70%, bp 105°C (0.08 mmHg). H
To a solution of di-tert-butylchlorophosphine (0.1 mol) in pen-
tane (ca.100 mL) in a flask equipped with a water-cooled reflux
condenser was added a solution of trimethylsilylmethyllithium
4
NMR (CDCl3): δ 0.03 d ( JPH = 0.3 Hz, 9H, 9H, CH3Si); 1.30 d
3
3
(
JPH = 3 Hz, 1H, P = CH); 1.41 t ( JHH = 6.5 Hz, 12H, CH3);
3
3
.54 m (8H, OCH2). 13C NMR (C6D6): δ 2.16 d ( JPC = 6.0 Hz,
(
0.1 mol) in pentane at −20°C and stirring. After complete addi-
1
CH3Si); 12.64 s (CH3); 20.30 d ( JPC = 144 Hz, P = C); 39.60 d
tion, the reaction solution was refluxed for 1.5 h, then the reac-
tion mixture was cooled to room temperature and the mixture
was filtered off. After filtration, residual LiCl was washed thor-
3
31
(
JPC = 4.0 Hz, CH2N). P NMR (CDCl3): δP +75.6 ppm.
3
oughly with hexane (3×30 cm ), the extracts combined and
2
-Chloro-2,2-bis(diethylamino)-2,2-dihydro-4-phenyl-4-
solvent removed under reduced pressure to afford crude phos-
(
(
trifluoromethyl)-3-(trimethylsilyl)-1,2λ5-oxaphosphetane
3c)
phine. Distillation at reduced pressure yields pure 1d as a col-
1
orless liquid. Bp 100–104°C (10 mmHg). Yield 75%. H NMR
3
To
a
solution of bis(diethylamino) trimethylsilyl-
(
CDCl3): δ −0.01 s (9H, CH3Si); 1.15 d ( JPH = 10 Hz, 18H,
3
31
methylchlorophosphorane (0.02 mol) in diethyl ether (20 mL),
was added CCl4 (0.04 mol) dropwise, at stirring and cool-
ing to −70°C. Then, the reaction mixture was heated to
room temperature and was stirred for 20 min. The 2,2,2-
trifluoroacetophenone (0.025 mol) was added to the solution
and the reaction mixture was stirred for 1–2 h. The course of
CH3); 1.70 d ( JPH = 15 Hz, 2H, PCH2). P NMR (CDCl3): δP
−
37.6 ppm.
Anal. Calcd for C12H29PSi: C 62.01; H 12.50; P 13.33. Found:
C 62.42; H 12.95; P 13.01.
Diethoxychlorphosphonium trimethylsilylmethylide (2a)
31
reaction was monitored by P NMR. The solvent was removed
under vacuum and at temperature below 0°C. Yield ∼ 90%.
In a flask equipped with a magnetic stirrer was placed a solution
of diethyl trimethylsilylmethylphosphonite (0.02 mol) in diethyl
ether (20 ml), and the carbon tetrachloride (0.04 mol) was added
dropwise at stirring and cooling to −70°C. Then, the solvent was
removed under reduced pressure to afford crude ylide. The dis-
tillation at reduced pressure yields pure 2a as a colorless liquid.
1
Yellowish oil. H NMR (CDCl3): δ 0.15 C (9H, CH3Si); 1.10 t
3
2
(
JHH = 7.0 Hz, 12H, CH3C); 3.20 m (8H, NCH2); 5.4 d ( JPH
19
=
16.0 Hz, 1H, PCH); 7.30 m; 7.80 m (5H, C6H5). F NMR
(
CDCl3): δF −70.40. 31P NMR (CDCl3): δP +60 ppm.
6
Yield 70%, bp 60°C (0.06 mmHg).
2
-Chloro-2,2-diisopropoxy-2,2-dihydro-4-phenyl-4-
1
4
H NMR (CDCl3): δ 0.01 d ( JPH = 0.3 Hz, 9H, CH3Si); 0.50 d
(
(
trifluoromethyl)-3-(trimethylsilyl)-1,2λ5-oxaphosphetane
3b)
(3
JPH = 3 Hz, 1H, P = CH); 1.25 d.d ( JHH = 6.5 Hz, JPH = 1.0,
13 3
3
3
6
H, CH3); 4.20 m (4H, OCH2). C NMR (C6D6): δ 0.85 d ( JPC
1
3
=
6.0 Hz, CH3Si); 15.00 d ( JPC = 160 Hz, P = C); 21.30 d ( JPC The oxaphosphetane 3b was prepared from diisopropyl
2 31
=
6 Hz, CH3C); 71.55 d ( JPC = 9 Hz, OCH). P NMR (CDCl3): trimethylsylilmethylphosphonite 1b, CCl4 and 2,2,2-
trifluoroacetophenone analogously to 3c. Yield 90%, oil.
δ +65.00 ppm.

3
26
O. O. KOLODIAZHNA AND O. I. KOLODIAZHNYI
1
H NMR (CDCl3): δ: 0.20 s (9H, CH3Si); ·0.90 d ( JHH = ( JHH = 18 Hz, 1H, C = CH); 7.8 m (5H, C6H5). 31P NMR
3
3
2
6
.0 Hz, 12H, CH3C); 1.95 d ( JPH = 18.0 Hz, 1H, PCH); 4.20 m (CDCl3): δ 50 ppm.
19
(
2H, OCH); 7.30 m; 7.80 m (5H, C6H5). F NMR (CDCl3), δF
Anal. Calcd for: C16H25OP. C 72.70; H 9.53; P 11.72%. Found:
−
68.40. 31P NMR (CDCl3): δP +48.3 ppm.
C 72.70; H 9.53; P 11.72%
Diisopropyl 2-phenyl-2-(trifluoromethyl)
ethenylphosphonate (5b)
Diethyl (E)-(2-phenylethenyl)phosphonate (7b)
7
b was prepared analogously to 7a.
Oxaphosphetane 3b was heated at 60°C for 0.5 h, then the reac-
Yield 60%, bp 122°C (0.06 mmHg).13–15 1H NMR (CDC13):
3
3
tion mixture was distilled under vacuum. Yield 77%, bp 130 δ 1.28 t ( JHH = 7.0 Hz, 3H); 1.30 t ( JHH = 7.0 Hz, 3H, CH3);
3
3
(
0.07 mmHg). The mixture of E and Z-isomers is in ratio 7:1. 4.15 d.q ( JHH = 7.0 Hz, JPH = 11.0 Hz, 4H, OCH2), 6.30 d.d
3
2
3
We suppose that the major isomer is E-alkene 5b, because δH of ( JHH = 17.2 Hz, JPH = 17.2 Hz, lH, CH = C), 7.10 d.d ( JHH =
3
vinyl proton and δP of this compound are shifted to down field 17.2 Hz, JPH = 22 Hz, 1H, C = CH), 7.10–7.40 m (5H, C6H5).
relative to those of minor Z-isomer (in all 3 P NMR spectra, the
1
13
C NMR (CDCl3): δ 16.30, 61.6 d ( JCP = 6 Hz), 110.70 d ( JCP
2
1
2
signals of the Z-isomers 5 appear at higher field than the ones of = 190 Hz, CH), 128.00, 129.00, 131.10, 136.10, 149.20 d ( JCP =
the E-5).1
2,13,22,23a–c
6.1 Hz, CH). P NMR (CDCl3): δP +18.00 ppm.
31
1
3
(
E-isomer): H NMR (CDCl3): δ 1.03 d ( JHH = 6.4 Hz, 6H,
3
CH3C); 1.12 d ( JHH = 6.2 Hz, 6H, CH3C); 4.45 m (2H, OCH);
Diethyl (E)-[2-(2-bromphenyl)ethenyl]phosphonate (7c)
4
2
6
(
.44 d.q ( JFH = 1.5 Hz, JPC = 12.0 Hz, 1H, PCH = C); 7.30 m
5H, C6H5). 19F NMR (CDCl3), δF −68.40. P NMR (CDCl3): The vinylphosphonate 7c was prepared from 1b analogously to
31
16
δP 9.3 ppm.
7b. Yield 75%, mp 82°C (ref. mp 82°C).
1
3
1
3
(
Z-isomer): H NMR (CDCl3): δ 1.28 d ( JHH = 6.5 Hz, 6H,
H NMR (CDC13): δ 1.29 t ( JHH = 7.0 Hz, 6H, CH3). 4.07 m
3
3
3
2
CH3C); 1.32 d ( JHH = 6 Hz, 6H, CH3C); 4.75 m (2H, OCH); ( JHH = 7.5 Hz, 4H, CH2O); 6.18 d.d ( JHH = 17.5 Hz, JHP =
2
31
3
6
.20 d ( JPH = 8.8 Hz, 1H, PCH = C); 7.30 m (5H, C6H5).
P
17.0 Hz, 1H, PCH = C); 7.30 d ( JHH = 8.5 Hz, 2H, C6H4);
3
3
NMR (CDCl3): δP 7.68 ppm.
7.37 d.d ( JHH = 17.5 Hz, JHP = 18.2 Hz, 1H, PC = CH); 7.46 d
3 13
Anal. Calcd for: C15H20F3O3P: C 53.57; H 5.99; P 9.21. Found ( JHH = 8.5 Hz, 2H, o-BrC6H4). C NMR (C6D6): δ 16.40, d (JPC
2
2
C 54.27; H 5.95; P 9.43.
= 7.0 Hz, CH3); 61.90 d ( JPC = 5.6 Hz, CH2O); 114.80 d ( JPH
3
=
192.0 Hz, PC = C); 124.40; 128.50; 132.60; 133.70 d ( JPC =
2
31
2
4.0 Hz), 147.30 d ( JPC = 6.9 Hz, PC = C). P NMR (CDCl3):
Bis(diethylamid) 2-phenyl-2-(trifluoromethyl)ethenylphos-
phonate (5c)
δP +19.06 ppm.
Anal. Calcd for: C12 H16 BrO3P. C 45.16; H 5.05; P 9.71.
The vinylphosphonate 5c was prepared from 1c analogously to Found: C 45.22; H 9.65; P 11.42.
1
5
a. Yield 70%, b.p. 150°C (0.07 mmHg). H NMR (CDCl3): δ
3
3
1
.38 t ( JHH = 7 Hz, 12H, CH3); 3.27 d.q ( JPH = 10 Hz, 8H,
Diisopropyl (E)-(2-phenylethenyl)phosphonate (7d)
2 4
CH2N); 6.80 d.q ( JPH = 12 Hz, JHF = 1.5 Hz, 1H, C = CH);
.60 m (5H, C6H5). 19F NMR (CDCl3): δF −68.11. P NMR The vinylphosphonate 7d was prepared analogously to 7b. Yield
31
7
13 1
(
CDCl3): δP 23.50; 16.20 ppm.
60%, b. p.122°C (0.06 mmHg). H NMR (CDC13): δ 1.24 d.d
3
3
Anal. Calcd for: C17H26F3N2OP: C 56.35; H 7.23; P 8.55. ( JHH 6.0 Hz, JPH 2.5 Hz, 12H, CH3C); 4.33 m (2H, OCH);
3
2
Found, %: C 56.35; H 7.23; P 8.55.
6.10 d.d JHH (17.5 Hz, JPH 18 Hz, 1H, PCH = C); 7.70 d.d
3
3
3
(
JHH 17.5 Hz, JPH 19 Hz, 1H, PC = CH); 7.10 m (5H, C6H5).
1
2
C NMR (C6D6): δ 23.60, 23.80; 70.21 d ( JCP 6 Hz, 2H, OCH),
Diisopropyl (1–trimethylsilyl-2-hydroxyphenyl-3,3,
1
1
20.80 d ( JCP 190 Hz), 128.35, 129.00, 131.10, 136.10, 149.20 d
3
-trifluoro)propylphosphonate (6b)
2
31
(
JCP = 6.1 Hz, CH). P NMR (CDCl3): δP +16.00 ppm.
1
Yield 80%, bp 118°C (0.04 mmHg). H NMR (CDCl3): δ 0.5 s
2
(
9H, CH3Si); 0.92 m (12H, CH3C); 2.82 d ( JPH = 21.0 Hz, 1H,);
Bis(diethylamido) (E)-(2-phenylethenyl)phosphonate (7e)
2
2
.87 d ( JPH = 20.0 Hz, 1H, PCH): 4.48 m; 4.85 m (CHO+OH),
.17–7.51 m (5H, C6H5). 19F NMR (CDCl3): δF −77.60.
31
P
7
To a solution of ylide 1c (0.01 mol) at −70°C was added ben-
NMR (CDCl3): δP +18.70 ppm.
zaldehyde (0.015 mol), the reaction mixture was heated to room
Anal. Calcd for: C18H30F3O4P. C 50.69; H 7.09. Found C temperature and the mixture was stirred for 14 h. The reaction
4
9.97; H 6.89.
mixture was evaporated in vacuo at +20°C, then the residue was
heated at 100°C for 15 min under vacuum (0.05 mm Hg) and the
1
residue was recrystallized in hexane. Yield 80%, mp 103.5°C. H
Di-tert.–butyl(2-phenylethenyl)phosphine oxide (7a)
3
NMR (CDCl3): δ 1.38 t ( JHH 7 Hz, 12H, CH3CH2); 1.38 ·d.q
3
3
3
The ylide (I) (0.01 mol) was mixed with benzaldehyde (0.01 mol) ( JHH 7 Hz, JPH 11 Hz, 8H, CH2N); 6.60 d.d ( JHH 17.2 Hz,
and the mixture was heated at 150°C for 30–40 min to the end
2
3
3
JPH 18 Hz, 1H, PCH = C); 7.75 d.d ( JHH 17.5 Hz, JPH 19 Hz,
13
of trimethylchlorosilane emission. The residue was cooled and 1H, C = CH); 7.65 m (5H, C6H5). C NMR (C6D6): δ 13.70;
1
recrystallized from heptane. Yield 80%, mp 138°C (heptane).
41.85; 114.50, d ( JPC 152.0 Hz, PCH = C); 128.70; 131.66 d
1
3
2
3
31
H NMR (CDCl3): δ 1.53 d ( JHH = 13.7 Hz, 9H,CH3C); ( JPC 24.0 Hz, PC = C), 144.17, 161.90 d ( JPC 30 Hz). P NMR
.08 d.d ( JHH = 18 Hz, JPH = 22.5 Hz, 1H, PCH = C); 7.95 d.d (CDCl3): δP +24.50 ppm.
3
2
7

PHOSPHORUS, SULFUR, AND SILICON
327
Bis(diethylamid) (E)-[2-(2-fluorophenyl)
ethenyl]phosphonate (7f)
(0.025 mol) in THF (3 mL) at 0°C. The reaction mixture was
left for a night. Then, the solvent was evaporated under reduced
pressure (10 mmHg). The residue was recrystallized in a mixture
of ether/pentane at 0°C. Yield 50%, mp 92.5–94°C. After second
Analogously to 7b, the vinylphosphonate 7f was prepared from
1
2
c. Yield 60%, b.p. 130°C (0.1 mmHg), m.p. 114°C (hexane). H
1
recrystallization in hexane, mp 98°C. H NMR (CDCl3): δ 1.40 t
3
3
NMR (CDC13): δ 1.08 t ( JHH 7.0 Hz, 12H, CH3). 3.08 m ( JHH
3
3
3
(
JHH 7 Hz, 12H, CHзCH); 3.41 dd ( JHH 7 Hz, JPH 10.5 Hz,
3
2
7.5 Hz, 4H, CH2N); 6.25 d.d ( JHH 17.5 Hz, JHP 17.0 Hz, 1H,
2
1
8
H, CH2N); 8.10 d.d (4H, C6H4); 6.80 d.d ( JHH 17.5 Hz, JPH
3
3
PCH = C); 7.03 m (2H, C6H4); 7.40 d.d (1H, J 17.5 Hz, JHP
3
3
1
7.5 Hz, 1H, PCH = C); 7.85, d.d ( JHH 17.5 Hz, JPH 19, 1H,
3
13
1
8.0 Hz, PC = CH); 7.46 d ( J 8.5 Hz, 2H, C6H4). C NMR
4
C = CH); 8.00 d; 8.10 d ( JHH 9 Hz, 4H, C6H4); 10.30 s (1H,
1
(
C6D6): δ 13.77; 37.9; 114.50, 118.10 (d, JPC 152.0 Hz, P–CH =
13
C(O)H). C NMR (CDCl3): δ 14.01; 41.7 d (J 6 Hz); 105.2 d
2
C); 128.70; 131.66 d ( JPC 24.0 Hz, PC = C), 144.17, 161.90 d
1
2
(
JPC 160 Hz); 130.1; 131.5; 136.0; 142.5; 154.2 d ( JPC 32 Hz);
2
31
(
JCF 247.5 Hz). P NMR (CDCl3): δP +19.06 ppm.
1
91.5. 31P NMR (CDCl3): δ 23.7 ppm.
Anal. Calcd for C16H26FN2OP: C 61.52; H 8.39; P 9.92.
Anal. Calcd. for C17H27N2O2P: C 63.34; H 8.44; P 9.61.
Found: C 61.81; H 8.42; P 9.61.
Found: C 63.13; H 8.41; P 9.52.
Bis(diethylamid) 4-phenyl-(1E,3E)-butadienylphosphonate
ꢀ
(
1E,1 E)-Bis-1,4-(tetraethyldiamidophosphono)
(
7g)
ethenyl)benzene (7k)
To a solution of ylide 1c (0.02 mol) in diethyl ether (10 ml)
was added cinnamic aldehyde (0.02 mol) at 0 to +5°. The mix-
ture was left for 18 h at room temperature and then was evap-
orated under vacuum. Yield 70%, bp 170–175°C (0.06 mmHg).
A solution of ylide 1c (0.025 mol) in diethyl ether (10 ml) was
added dropwise at −20°C to a solution of terephthalic aldehyde
(0.01 mol) in THF. The temperature was raised to a room and the
reaction mixture was left for a night. The solvent was evaporated,
the residue was recrystallized in heptane to give a yellow crys-
talline product in yield of 50%. After second recrystallization
1
3
3
H NMR (CDCl3): δ 1.4 t ( JHH 7 Hz, 12H, CH3); 3.30 d.q ( JPH
1
0 Hz, 8H, CH2N); 6.30 m; 7.30 m (4H, CH = CH); 7.80 m (5H,
31
C6H5). P NMR (CDCl3): δP +23.30 ppm.
Anal. Calcd. for C18H29N2OP: C 67.47; H 9.12; P 9.67. Found
C 67.77; H 9.20; P 9.66.
1
3
in heptane mp 188.5–190°C. H NMR (CDCl3): δ 1.05 t ( JHH
3
3
7
6
1
, 24H, CH3CH,); 3.03 d.q ( JHH 7 Hz, JPH 11, 16H, NCH2);
3
2
3
.33 d.d ( JHH 17 Hz, JPH 17 Hz, 2H, PCH = C); 7.30 d.d ( JHH
7 Hz, JPH 19 Hz, 2H, C = CH); 7.44 m (4H, C6H4). C NMR
3
13
3
2
(
CDCl3): δ 14.00 d ( JPC 8 Hz); 41.80 d ( JPC 6 Hz); 105.70 d
Bis(diethylamid) (E)-2-(1,3-benzodioxol-5-yl)
ethenylphosphonate (7h)
1
2
31
(
JPC 180 Hz, PCH = ); 129.80; 137.70; 154.20 d ( JPC 32 Hz). P
NMR (CDCl3), δP 24.80 ppm. Anal. Calcd. for C20H48H2O2P2:
The vinylphosphonate 7h was prepared from 2c, analogously to
C 61.16; H 9.47; N 10.97. Found C 61.31; H 9.66; N10.85.
7
b, bp 115–135°C(0.1 mmHg). The product was recrystallized
1
3
in heptane at −20°C. H NMR (CDCl3): δ 1.08 t ( JHH 7 Hz,
ꢀ
(
1E,1 E)-Bis-1,4-(diisopropylphosphono)ethenyl)-benzene
7l)
1
2H, CH3); 3.07 m (4H, CH2N); 5.96 s (2H, OCH2O); 6.14 d.d
3
2
(
(
JHH 17 Hz, JPH 17.5 Hz, 1H, PCH = C); 6.78–7.32 m (6H,
13
PC = CH + C6H5). C NMR (CDCl3): δ 13.86; 38.00, 100.94;
7
l was prepared analogously to 7k. Yield 50%. Solid, mp
1
05.63, 107.97; 115.39, 116.63; 122.69, 129.93, 130.03; 145.00,
47.76, 148.32. 31P NMR (CDCl3), δP 24.00 ppm.
20
140–145°C (heptane).
1
1
2
H NMR (CDCl3): δ 1.25 d ( JHP = 6.5 Hz, 12H, CH3); 1.30 d
Anal. Calcd. for C17H27N2O3P: C 60.34; H 8.04; P 9.15.
(2
2
JHP = 6.5 Hz, 12H, CH3), 4.6 m (4H, OCH), 6.16 dd ( JHP =
Found: C 60.66; H 8.21; P 9.05.
3
3
1
7.0 Hz, JHH 17.0 Hz, 2H, PCH = C), 7.30 d.d ( JHP = 22.3 Hz,
3
13
JHH 17.0 Hz, 2H, C = CH), 7.44 s (4H, H-Ar). C NMR
1
(CDCl3): δ 23.60; 23.80; 70.5; 120.0 d ( JPC = 180.5 Hz), 130.0,
Diethyl [(E)-2-(1,3-benzodioxol-5-yl)ethenylphosphonate
3
31
136.0 d ( JPC = 25 Hz), 148.5. P NMR (CDCl3): δ 18.1 ppm.
(7l)
Yield 65%; bp 135 (0.1 mmHg).21
1
3
References
H NMR (CDCl3): δ = 1.30 t ( JHH = 7.0 Hz, 6 H, CH3CH2);
.23 m (2H, CH2O), 4.28 m (2H, CH2O); 6.00 s (2H, CH2O2);
4
6
6
1
1
1
2
. Wittig, G. Science 1980, 210, 600.
3
2
.1 d.d ( JHH = 17.0 Hz, JHP = 17.0 Hz, 1H, PCH = C);
. (a)Taillefer, M.; Cristau, H.-J. Top. Curr. Chem. 2003, 229, 41-73;
(b)Kolodiazhnyi, O. I. Russ. Chem. Rev. 1997, 225-254; (c)A. E. Nako,
A. J. P.; White, M. R.; Crimmin, M. R. Chem. Sci., 2013, 4, 691-
695; (d)Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 863-927;
13
.78–7.32 m (4H, PC = CH + C6H5). C NMR (CDCl3): δ =
1
6.2, 61.9, 101.25, 106.78, 109.2, 119.1 d ( JCP = 185 Hz, PCH),
3
31
23.54, 130.94 d ( JCP = 20.0 Hz), 147.9, 147.8, 150.1. P NMR
(
e)Edmonds, M.; Abell, A. The Wittig Reaction In:T. Takeda (Ed.),
(
CDCl3): δP = 20.01 ppm.
Modern Carbonyl Olefination: Methods and Applications; Wiley-VCH:
Weinheim, 2004; pp. 1-17.
. Kolodiazhnyi, O. I. Phosphorus Ylides. Chemistry and Application in
Organic Synthesis. John Wiley-VCH: Weinheim, 1999; 565 p.
3
Bis(diethylamid) (Е)-[2-(4-formylphenyl)
ethenyl]phosphonate (7j)
4. (a)Kolodiazhnyi, O. I. Tetrahedron Lett. 1981, 22, 1231-1234;
b)Kolodiazhnyi, O. I.; Grishkun, E. V. Heteroatom. Chem., 1998, 9,
19-228; (c)Kolodiazhnyi, O. I. Hermann/Brauer. In:H. H. Karsch
(Ed.), Synthetic Methods of Organometallic and Inorganic Chemistry,
(
2
A solution of ylide 1c (0.02 mol) in diethyl ether (10 ml)
was added at stirring to a solution of terephthalic aldehyde

3
28
O. O. KOLODIAZHNA AND O. I. KOLODIAZHNYI
Stuttgart: Thieme, 1996, Vol. 3, p. 90. (d)Fluck, E.; Heckmann, G.;
Plass, W.; Spahn, M.; Borrmann, H. J. Chem. Soc, Perkin Trans. 1, 1990,
13. Gorenstein, D. G. (Ed.). Phosphorous-31 NMR Principles and Applica-
tions. Academic Press: New York, 1984; 604 p.
14. Lazrek, H.B.; Witvrouw, M.; Pannecouque, C.; De Clerq, E. Tetrahe-
dron 1998, 54, 3807-3816.
15. Zhong, P.; Xiong, Z. X.; Huani, X. Synth. Commun. 2000, 30,
273-278.
16. Xu, Y.; Flavin, M. T.; Xu, Z.-Q. J. Org. Chem. 1996, 61, 7697-7701.
17. Blaszczyk, R.; Gajda, T. Heteroatom Chem. 2007, 18, 732-739.
18. Brunner, H.; Le Cousturier de Courcy, N.; Genêt, J.-P. Synlett 2000,
201-204.
1
223-1224; (e)Soleilhavoup, M.; Baceiredo, A.; Bertrand, G. Angew.
Chem., Int. Edit. Engl. 1993, 32, 1167-1169; (f)Igau, A.; Baceiredo, A.;
Grutzmacher, H.; Pritzkow, M.; Bertrand, G. J. Am. Chem. Soc. 1989,
1
11, 6853-6854.
5
. (a)Kolodiazhnyi, O. I. Rus. J. Gen. Chem. 2005, 75, 1017-1039;
(
(
b)Kolodiazhnyi, O. I.; Schmutzler, R. Synlett 2001, 1065-1078;
c)Kolodiazhnyi, O. I.; Golokhov, D. B. Russ. J. Gen. Chem. 1989, 59,
2
93-306; (d)Kolodiazhnyi, O. I. Russ. J. Gen. Chem. 1986, 56, 283-298.
. Kolodiazhnyi, O. I.; Golokhov D. B. Russ. J. Gen. Chem. 1987, 57,
640-2642.
6
7
19. Al-Maksoud, W.; Mesnager, J.; Jaber, F.; Pinel, C.; Djakovitch, L. J.
Organometal. Chem. 2009, 694, 3222-3231.
2
. Robiette, R.; Richardson, J.; Aggarwal, V. K.; Harvey, J. N. J. Am. Chem.
Soc. 2006, 128, 2394-2409.
20. Jouvin, K.; Coste, A.; Bayle, A.; Legrand, F.; Karthikeyan, G.; Tadi-
parthi, K.; Evano, G. Organometallics, 2012, 31, 7933-7947.
21. Krawczyk, H.; Łukasz, A. Synthesis 2005, No. 17, 2887-2896.
22. Keglevich G.; Szelke H.: Alk-1-enyl Phosphorus Compounds.
In:Molander G. A. (Ed.), Science of Synthesis, Vol. 33; Thieme
Verlag: Stuttgart, 2007, pp. 737-771.
23. (a)Cristau, H-J.; Pirat, J-L.; Drag, M.; Kafarski, P. Tetrahedron. Lett.
2000, 41, 9781-9785; (b)Cristau, H-J.; Mbianda, X. Y.; Beziat, Y.; Gasc,
M. B. J. Organomet. Chem. 1997, 529, 301-311; (c)Sainz-Dıaz, C. I.;
Galvez-Ruano, E.; Hernandez-Laguna, A.; Bellanato, J. J. Org. Chem.
1995, 60, 74-83.
8
9
. Vedejs, E.; Marth. C. F. J. Am. Chem. Soc., 1990, 112, 3905-3909
. Bangerter, F.; Karpf, M.; Meier, L. A.; Rys, P.; Skrabal, P. J. Am. Chem.
Soc. 1998, 120, 10653-10659.
1
0. Lopez, J. G.; Ramallal, A. M.; Gonzalez, J.; Roces, L.; García-Granda,
S.; Iglesias, M. J.; Ona-Burgos, P.; Ortiz. F. L. J. Am. Chem. Soc. 2012,
1
34, 19504-19507.
1
1
1. Vedejs, E. J. Org. Chem. 2004, 69, 5159-5167.
2. Kühl O. Phosphorus-31 NMR Spectroscopy; Springer: Berlin, 2008; pp.
3
1-35.