A general synthesis of thiophosphates containing an α,β-unsaturated carbonyl moiety

Article abstract of DOI:10.1055/s-1999-3477

The O-silylated dienolates of α,β-unsaturated ketones and aldehydes can be thiophosphorylated using O,O-dialkyl chlorothiophosphonates and O,O- dialkyl bromodithiophosphonates to give a new class of compounds thio- and dithiophosphates 1-4 in high yield.

Full text of DOI:10.1055/s-1999-3477

844
PAPER
A General Synthesis of Thiophosphates Containing an a,b-Unsaturated
Carbonyl Moiety
Piotr Dybowski, Marek Koprowski, Iwona Maciπgiewicz, Aleksandra SkowroÒska*
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, 90-363 £ódü, Sienkiewicza 112, Poland
Fax +48(42)6847126; E-mail: askow@bilbo.cbmm.lodz.pl
Received 9 November 1998; revised 5 January 1999
Abstract: The O-silylated dienolates of a,b-unsaturated ketones
and aldehydes can be thiophosphorylated using O,O-dialkyl chlo-
rothiophosphonates and O,O-dialkyl bromodithiophosphonates to
give a new class of compounds thio- and dithiophosphates 1–4 in
high yield.
Key words: unsaturated ketones, aldehydes, O-silylated dienolates,
thiophosphates, dithiophosphates
Scheme 1
Recently, we have reported a methodology1 for the stere-
oselective synthesis of various Z-alkenes based on inter-
mediate S-(b-oxoalkyl) thiophosphates2 and Se-(b-
oxoalkyl) selenophosphates3 (Scheme 1).
phosphorylthio) substituent in position 1 and a dialkoxy-
phosphoryloxy substituent in position 2.5,6
Exploring the scope of our approach further we decided to
extend it to intermediates thio- 1–2 and dithiophosphates
3–4 containing an a,b-unsaturated carbonyl moiety. As
we already knew, compounds 1–4 are of considerable in-
terest due to their value as synthetic intermediates in the
preparation of substituted vinylthiiranes4 and diversely
substituted buta-1,3-dienes including 2-cyanobuta-
1,3-dienes4 as well as (Z)-1,2-diheterosubstituted
1,3-dienes containing an alkylthio (acylthio, dialkoxy-
In this paper we report a general and efficient synthesis of
previously unknown thiophosphates 1–2 and dithiophos-
phates 3–4. These compounds have been prepared in a
two step procedure from the appropriate a,b-unsaturated
carbonyl compounds in high yield. The corresponding ke-
tones 5 and aldehydes 6 are converted into O-silylated di-
enolates 7 and 8 using trimethylsilyl chloride in the
Table 1 Thiophosphates 1 and Dithiophosphates 3 from a, b-Unsaturated Ketones
1, 3
R
R1
R2
R3
R4
X
Yielda
(%)
d
31P NMR
(ppm) (CDCl3)
JPSCH
(Hz)
1a
1b
1cb
1d
1e
1f
1g
1h
1i
Et
Et
Et
Et
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
i-Pr
i-Pr
H
H
O
O
O
O
O
O
O
O
O
O
O
O
S
90
100
93
100
83
84
91
42
88
87
87
83
80
25.20
26.80
26.86c
25.19
26.48
20.13
26.86
25.66
27.11
27.24
19.80
25.18
93.99
98.16
13.9
13.5
13.5
14.0
14.7
14.6
13.7
14.0
13.2
12.5
13.4
16.4
16.2
16.0
Me
i-Pr (H)
Ph
Ph
Ph
H (i-Pr)
H
H
H
Me
H
H
H
H
Me
H
Et
-CH2C(Me)2CH2-
Et
Et
Et
Me
MeO
-(CH2)3-
-(CH2)4-
-OCH=CH-
H
H
H
H
H
H
1j
Et
1k
1ld
3a
3b
-CH2C(Me)2CH2-
Et
Et
Me
CH2-
Ph
Me
-C(Me)2
H
H
Me
S
62
a
Yields have not been optimized and refer to analytically pure compounds.
mixture of (E) and (Z) isomers 75:25.
main isomer .
b
c
d
isophorone ring.
Synthesis 1999, No. 5, 844–848 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Synthesis of Thiophosphates Containing an a,b-Unsaturated Carbonyl Moiety
845
presence of sodium iodide and triethylamine in acetoni- phates 3,4 and assigned structures using spectroscopic
trile solution.7–9 A mixture of (E) and (Z) diastereoisomers data (Table 1 and 2, as well as the experimental part).
(75:25) is only obtained in the case of dienolate 7c, (E)/
(Z) ratio is the same as in starting ketone (Table 1, entry
In conclusion, the synthetic protocol described here pro-
vides access from readily available starting materials to
c). Then addition of phosphorus S-electrophiles O,O-di-
novel thio- and dithiophosphates 1–4 containing an
alkylchloro thiophosphonates (RO)2P(O)SCl10 9 and O,O-
a,b unsaturated carbonyl moiety. Compounds 1–4 are in-
dialkylbromo dithiophosphonates (RO)2P(S)SBr11,12 10 to
teresting precursors of alkenes. Further applications of 1–
7 and 8 afforded compounds 1–2 and 3–4 respectively
4 are currently under investigation.
(Scheme 2). Compounds 9 and 10 can be readily prepared
from commercial materials and used without isolation.
1H, 13C, and 31P NMR spectra were obtained on Bruker Instruments
AC-200, MSL-300 and DRX-500 using internal TMS (1H and 13C)
and external 85% H3PO4 (31P) as reference and on JEOL FX-60
without solvent using TMS and 85% H3PO4 as external reference.
Mass spectra (EI, CI-isobutane) were recorded on Finnigan MAT
95 and LKB 2091 spectrometer. IR spectra were recorded on ATI
Mattson Infinity Series 60 AR FT IR Spectrometer and Specord 71
IR instruments. Microanalyses obtained on a Carlo Erba CHNS-O
EA1108 Elemental Analyzer: C± 0.34 except 1d (+0.41), 3c
(–0.41); H± 0.35; S± 0.40 except 1b (–0.89) - S determined only for
1b, 1c, 1d, 1f, 1k; O± 0.39 except 1g (+0.75) - O determined only
for 1e, 1g, 1i. Phosphorus microanalyses: P± 0.35 except 1f (+0.37),
1g (–0.49), 3b (–0.39). All reactions were performed under Ar. Sil-
ica gel (70–230 mesh Merck) was used for chromatographic sepa-
rations. Silyl enol ethers 7 and 8,7–9 dialkylchloro thiophosphonates
910 and dialkylbromo dithiophosphonates 1011,12 were prepared ac-
cording to the published procedures.
Thiophosphates 1 and 2; General Procedure
A solution of SO2Cl2 (0.05 mol) in CH2Cl2 (20 mL) was added drop-
wise to the triethyl thionophosphate (0.05 mol) in CH2Cl2 (20 mL)
Scheme 2
at –5 °C. Stirring was continued for 20 min at r.t. After removal of
about 80% of solvent the crude thiophosphonate 9 was added drop-
wise to a stirring solution of freshly prepared o-silylated dienolate 7
or 8 in CH2Cl2 (100 mL) at –78 oC. Stirring was continued at r.t. for
an additional 1 h. The solvent and trimethylsilyl halide were re-
moved under reduced pressure to give crude 1 or 2, which were pu-
rified by column chromatography on silica gel (eluent: from C6H6
to C6H6/EtOAc 1:1) or by crystallization. In the case of compounds
1b, 1d, 2a and 2b 5–10% of excess of O-silylated dienolates 7 or 8
was used. Their purification after removing excess of 7 or 8 in vac-
uo (0.01 mmHg) is not necessary. The compound 1h was obtained
using 10% excess of O-silylated dienolate and immediately after re-
moving of the excess of O-silylated dienolate purified by column
chromatography.
In most cases thiophosphorylation of O-silylated dieno-
lates 7 and 8 is fully chemoselective. Dienolates 7 un-
doubtedly react with electrophiles at C-1 giving the
compounds 1 and 3 in which the thio- and dithiophosphate
groups are situated in the b-position in relation to the car-
bonyl function. Only dienolate 7c was attacked by electro-
philes at C-4 and in very low yield (~1%). In the case of
the dienolates 8 however, the thiophosphorylation reac-
tion proceeds exclusively at a terminal unsaturated bond
(at C-4 or C-6, Table 2). Thiophosphorylation of 7 and 8
is also stereoselective. In fact, the stereochemistry of di-
enolates is fully preserved in the final products. With this
procedure we obtained various thio- 1,2 and dithiophos-
Dithiophosphates 3 and 4; General Procedure
To a solution of bis(dialkoxythiophosphoryl) disulfides (0.05
mmol) in CH2Cl2 (40 mL) was added dropwise with stirring at –80
Table 2 Thiophosphates 2 and Dithiophosphate 4 from a,b-Unsaturated Aldehydes
2, 4
R
n
X
Yielda
(%)
d
31P NMR
(ppm) (CDCl3)
JPSCH
(Hz)
2a
2b
2c
4a
Et
1
1
2
1
O
O
O
S
100
100
84
26.20
20.34
26.31
94.40
16.5
16.6
16.0
17.0
-CH2C(Me)2CH2-
Et
Et
73
aYields have not been optimized and refer to analytically pure compounds.
Synthesis 1999, No. 5, 844–848 ISSN 0039-7881 © Thieme Stuttgart · New York

846
P. Dybowski et al.
PAPER
°C a solution of anhyd bromine (0.05 mol) in CH2Cl2 (10 mL). The
stirring was continued at r.t. for 20 min. After removing of 80% of
solvent the crudedithiophosphonates 10 was added dropwise to a
stirring solution of freshly prepared dienolates 7 or 8 in CH2Cl2 (100
mL) at –78 °C. Further workup was the same as described above.
31P NMR (CDCl3, 81.0 MHz): d = 26.05.
13C NMR (CDCl3, 50.32 MHz, DEPT): d = 15.21 and 15.35
(CH3CH2O); 20.42 and 20.58 [(CH3)2CH]; 30.36 and 30.58
[(CH3)2CH]; 37.99 and 38.04 (CH2SP); 63.03 and 63.14
(OCH2CH3); 127.76 and 153.59 (CH=CH); 192.08 and 192.17
(C=O).
Yields of analytically pure compounds 1–4 are listed in the Table 1
and 2.
IR (neat): n = 1694 (vs) (C=O), 1626 (m) (C=C), 1257 (vs) (P=O).
O,O-Diethyl S-(2-Oxobut-3-enyl) Thiophosphate (1a)
Yield 90%, colorless liquid.
O,O-Diethyl S-(1,1 Dimethyl-4-oxopent-2-enyl) Thiophosphate
(1c')
1H NMR (CDCl3, 300.13): d = 1.34 (t, 6H, J = 7.0 Hz, OCH2CH3);
3.89 (d, 2H, J = 13.9 Hz, C(O)CH2SP); 4.15 (m, 4H, OCH2CH3);
ABX: 5.92 (1H, JAX = 10.35, JBX = 1.0, HX-trans to C=O); 6.34 (1H,
JAB = 17.6, JBX = 1.0, HB-cis to C=O); 6.47 (1H, JAB = 17.6, JAX
10.35, HA-gem. to C=O).
Yield 1%, brownish oil, product from enoxysilane (CH3)2C=CH-
CH=C(CH3)OSi(CH3)3.
1H NMR (CDCl3, 200 MHz): d = 1.33 (td, 6H, J = 7.2, J2 = 1.0 Hz,
CH3CH2O); 1.66 [2s=d, 3H+3H, J = 2 Hz, (CH3)2CSP]; 2.29 (s, 3H,
CH3C=O); 4.10 (m, 4H, OCH2CH3); 6.08 (d, 1H, J = 16.1 Hz,
CH=CHC=O); 7.05 (d, 1H, J = 16.1 Hz, CH=CHC=O).
=
31P NMR (CDCl3, 24.3 MHz): d = 25.20.
13C NMR (CDCl3, 50.32 MHz, DEPT): d = 15.29 and 15.44
(POCH2CH3); 37.67 and 37.73 (PSCH2C=O); 63.28 and 63.38 and
63.47 (POCH2CH3); 129.67 (CH2=CH); 133.66 (CH2=CH); 192.37
and 192.46 (C=O).
31P NMR (CDCl3, 81.0 MHz): d = 23.42.
IR (neat): n = 1679 (vs) (C=O), 1624 (m) (C=C), 1260 (vs) (P=O).
O,O-Diethyl S-[(E)-2-Oxo-4-phenylbut-3-enyl] Thiophosphate
(1d)
Yield 100%, light yellowish oil.
1H NMR (CDCl3, 300.13 MHz): d = 1.39 (td, 6H, J = 7.0 Hz, Dn =
1.0, CH3CH2O); 3.97 (d, 2H, J = 14.0, CH2SP); 4.21 (m, 4H,
CH3CH2O); 6.87 (d, 1H, J = 16.0 Hz, PhCH=CH); 7.40 (m, 2H, o-
ring protons), 7.66 (d, 1H, J = 16.0 Hz, PhCH=).
IR (neat): n = 1721 (vs) (C=O), 1639, 1617 (m) (C=C), 1253 (vs)
(P=O).
(neat, Specord 71 IR): n = 1705 (vs) (C=O), 1630 (s) (C=C), 1270
(vs) (P=O).
O,O-Diethyl S-(2-Oxopent-3-enyl) Thiophosphate (1b)
Yield 100%, colorless oil.
31P NMR (EtOAc, 24.3 MHz): d = 25.18, (CDCl3, 81.0 MHz):
1H NMR (CDCl3, 200 MHz): d = 1.35 (td, 6H, J = 7.0, J2 = 1.0 Hz,
OCH2CH3); 1.93 (dd, 3H, J = 7.0, J2 = 1.5 Hz, CH3CH=); 3.86 (d,
2H, JPH = 13.5 Hz, CH2SP); 4.16 (m, 4H, OCH2CH3); 6.24 (dq, 1H,
d = 25.19.
13C NMR (CDCl3, 50.32 MHz, DEPT): d = 15.47 and 15.65 and
15.80 (OCH2CH3), 40.14 and 40.19 (CH2SP), 63.57, 63.66 and
64.33, 64.44 (OCH2CH3), 121.59 and 144.16 (CH=CH), 126.70,
127.45, 127.66, 127.88, 128.23, 130.54 (ipso-C6H5), 199.98 and
200.06 (C=O).
Jtrans = 15.5, J2 = 1.6 Hz, =CHC=O); 6.97 (dq, 1H, Jtrans= 15.5, Jvic =
6.9 Hz, CH3CH=).
31P NMR (CDCl3, 81.0 MHz): d = 26.80.
13C NMR (CDCl3, 50.32 MHz, DEPT): d = 15.01 and 15.16
(CH3CH2O); 17.54 (CH3CH=); 37.57 (SPCH2); 62.82 and 62.93
(OCH2CH3); 128.77 (=CHCH3); 144.22 (=CHC=O); 191.36 and
191.46 (C=O).
IR (neat, Specord 71 IR): n = 1700 (vs) (C=O), 1628 (s) (C=C),
1255 (vs) (P=O).
O,O-Diethyl S-(1-Isopropyl-4-phenyl-2-oxobut-3-enyl) Thio-
phosphate (1e)
IR (neat): n = 1693 (vs) (C=O), 1676, 1632 (m) (C=C), 1255 (vs)
Yield: 83%, yellowish solid mass, mp = 55–57 °C (EtOAc/C6H6).
(P=O).
3
1H NMR (CDCl3, 200 MHz): d = 1.06 [d, 3H, JHH = 6.7,
O,O-Diethyl S-(5-Methyl-2-oxohex-3-enyl) Thiophosphate (1c)
Yield 93%, light orange oil, mixture of (E) and (Z) 75:25.
CH(CH3)2], 1.13 [d, 3H, 3JHH = 6.7, CH(CH3)2], 1.29 (dt, 3H, 4JPH
=
3
4
3
0.9, JHH = 7.1, OCH2CH3), 1.33 (dt, 3H, JPH = 0.9, JHH = 7.1,
3
4
3
OCH2CH3), 2.24 [dd sept, 1H, JHH = 6.7, JPH = 1.3, JHH = 8.0,
isomer (E):
CH(CH3)2], 4.01 (dd, 1H, 3JHH = 8.0, 3JPH = 14.7, CHS), 4.01–4.26
1H NMR (CDCl3, 200 MHz): d = 1.08 [d, 6H, J = 7.1 Hz,
(CH3)2CH]; 1.35 (td, 6H, J = 7.0, J2 = 1.0 Hz, CH3CH2OP); 2.49 [oct
d, 1H, J = 7.1, J2 = 1.8 Hz, (CH3)2CH]; 3.90 (d, 2H, JPH = 13.5 Hz,
3
(m, 4H, 2¥OCH2), 7.01 (d, 1H, JHH = 15.9, =CH), 7.32–7.45 (m,
3H, meta-C6H5, para-C6H5), 7.55–7.62 (m, 2H, ortho-C6H5), 7.74
(d, 1H, 3JHH = 15.9, =CHPh).
CH2SP); 4.20 (m, 4H, OCH2CH3); 6.17 (dd, 1H, Jtrans= 16.5, JPH
=
31P NMR (CDCl3, 81.0 MHz): d = 26.48.
13C NMR (CDCl3, 50.32 MHz): d = 15.71 (d, JPC=7.2,
1.5 Hz, =CHCO); 6.92 (dd, 1H, Jtrans = 16.5, Jvic= 7.0 Hz,
CH=CHCO).
3
2¥OCH2CH3), 19.62 [s, CH(CH3)2], 20.60 [s, CH(CH3)2], 30.43 [d,
3JPC=6.8, CH(CH3)2], 59.52 (s, CHS), 63.63 (d, 2JPC=6.1, 2¥OCH2),
123.54 (s, =CH), 128.34 (s, meta-C6H5), 128.74 (s, ortho-C6H5),
130.57 (s, para-C6H5), 134.17 (s, ipso-C6H5), 143.99 (s, =CHPh),
195.85 (s, C=O).
31P NMR (CDCl3, 81.0 MHz): d = 26.86.
13C NMR (CDCl3, 50.32 MHz, DEPT): d 15.21 and 15.35
(CH3CH2O); 20.42 and 20.58 [(CH3)2CH]; 30.36 and 30.58
[(CH3)2CH]; 37.99 and 38.04 (CH2SP); 63.03 and 63.14
(OCH2CH3); 124.60 and 154.98 (CH=CH); 192.08 and 192.17
(C=O).
MS (CI-isobutane) (Finnigan MAT 95): m/z = 357 [100.00,
M(+H)],
253
[3.53,
M(PhCH=CH)],
225
[2.39,
IR (neat): n = 1700 (vs) (C=O), 1676 (m) (C=C), 1257 (vs) (P=O).
M(PhCH=CHC(O)], 186 [6.90, M(HSP(O)(OEt)2)], 169 [0.33,
(SP(O)(OEt)2)], 131 [2.20, (PhCH=CHC(O)].
isomer (Z):
1H NMR (CDCl3, 200 MHz): d = 1.34 (tdd, 6H, J = 7.0, J2 = 3.0, J3
= 1.0 Hz, CH3CH2OP); 1.80 [dd, 6H, J = 6.7, J2 = 1.2 Hz,
(CH3)2CH]; 2.49 [oct d, 1H, J = 7.0, J2 = 1.5 Hz, (CH3)2CH]; 3.90
(d, 2H, JPH = 13.5 Hz, CH2SP); 4.20 (m, 4H, OCH2CH3); 4.83 (dd=t,
1H, Jcis = Jvic = 11.8 Hz, CH=CHCO); 5.17 (d quin, 1H, Jcis = 11.8,
J2 = 1.0 Hz, =CHCO).
(E)-4-[(5,5-Dimethyl-2-oxido-1,3,2-dioxaphosphinan-2-yl)sul-
fanyl]-5-methyl-1-phenylhex-1-en-3-one (1f)
Yield 84%, yellow needles, mp = 93–95 ∞C (CH2Cl2/pentane).
1H NMR (CDCl3, 300.13 MHz): d = 0.84 and 1.25 [s, 3H,
(CH3)2CCH2O]; 1.07 and 1.12 [d, 3H, J =6.9, (CH3)2CH]; 2.31 [oct,
Synthesis 1999, No. 5, 844 –848 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Synthesis of Thiophosphates Containing an a,b-Unsaturated Carbonyl Moiety
847
1H, J =7.0, (CH3)CH]; 3.65–4.18 [mc=9d with J =1.5, 4H,
OCH2C(CH3)2]; 4.25 (dd, 1H, JPH = 14.7, Jvic = 7.3, CHSP); 6.99 (d,
1H, Jtrans = 15.0, PhCH=CH); 7.35 (m, 3Harom); 7.55 (m, 2Harom);
7.72 (d, 1H, Jtrans = 15, PhCH=).
phate (1j)
Yield 78%, colorless liquid.
1H NMR (CDCl3, 300.13 MHz): d = 1.18 (td, 6H, J1 = 7.1, J2 = 0,9
Hz, OCH2CH3); 1.45 (m, 4H, CH2CH2CH2CH2); 2.09 (m, 4H,
CH2CH2CH2CH2); 3.88 (d, 2H, JPH = 12.5 Hz, CH2SP); 4.00 (m,
4H, OCH2CH3); 6.81 (m (7 lines), 1H, = CH).
31P NMR (CDCl3, 81.0 MHz): d = 20.30.
13C NMR (CDCl3, 50.32 MHz, DEPT): d = 19.69 and 20.36 and
20.76 and 22.00 [(CH3)C< and (CH3)2CH]; 30.81 and 30.93
[(CH3)2CH]; 32.33 and 32.47 [(CH3)C<]; 58.12 (CHSP); 77.49 and
77.62 and 77.79 and 78.20 (POCH2); 124.16 and 144.56 (CH=CH);
128.34, 128.70,129.00, 130.89, 131.54, 134.32 – C–4∞ (Ph); 196.05
(C=O).
31P NMR (CDCl3, 81.0 MHz): d = 27.24.
13C NMR (CDCl3, 50.32 MHz, DEPT): d = 15.07 and 15.21
(OCH2CH3); [20.50; 20.91; 22.39; 2529 (CH2CH2CH2CH2)]; 35.85
(CH2SP); 62.76 and 62.87 (OCH2CH3); [136.96 (C-4∞) and 141.36
C-olef.]; 192.41 (d, J =5.14, C=O).
IR (KBr): n = 1686 (vs) (C=O), 1655, 1609 (m) (C=C), 1281 (vs)
(P=O).
IR (neat, Specord 71 IR): n = 1690–1700 (vs) (C=O), 1640 (m)
(C=C), 1260 (vs) (P=O).
O,O-Diethyl S-(4-Methyl-2-oxopent-3-enyl) Thiophosphate (1g)
Yield: 91%, colorless oil.
2-[(5,5-Dimethyl-2-oxido-1,3,2-dioxaphosphinan-2-yl)sulfa-
nyl]-1-furan-2-ylethanone (1k)
Yield 87%, yellow needles, mp = 58–61∞C (EtOAc/C6H6).
3
1H NMR (CDCl3, 500 MHz): d = 1.35 (t, 6H, JHH = 7.0,
2¥OCH2CH3), 1.93 (s, 3H, CH3C=), 2.17 (s, 3H, CH3C=), 3.71 (d,
2H, 3JPH = 13.7, CH2S), 4.15 (q, 2H, 3JHH = 7.0, OCH2), 4.20 (q, 2H,
3JHH = 7.0, OCH2), 6.17 (s, 1H, =CH).
1H NMR (CDCl3, 200 MHz): d = 0.86 and 1.25 [s, 3H,
(CH3)2CCH2O]; 3.87 and 4.21 [ddt, 2H, J = 25.5, J2 = 11.4, J3 = 1.5]
and [dd, 2H, J = 10.8, J2 = 3.4, O(CH2)2C]; 4.25 (d, 2H, JPH = 13.4,
CH2SP); 6.55 [dd, 1H, J1 = 3.7 J2 = 2.0, C(O) COCH=CHCH=];
7.32 [dd, 1H, J1 = 3.7 J2@1.0, C(O) COCH=CHCH=]; 7.61 [dd, 1H,
J1 = 1.7 J2@1, C(O) COCH=CH-CH=].
31P NMR (CDCl3, 81.0 MHz): d = 26.86.
13C NMR (CDCl3, 50.32 MHz): d = 15.45 (d, JPC = 7.1,
3
2¥OCH2CH3), 20.48 (s, CH3C=), 27.27 (s, CH3C=), 41.03 (d, 2JPC
2
= 2.7, CH2S), 63.22 (d, JPC = 5.6, 2¥OCH2), 120.87 (s, =CH),
31P NMR (CDCl3, 81.0 MHz): d = 19.80.
158.26 [s, =C(CH3)2], 191.92 (d, 3JPC = 5.0, C=O).
13C NMR (CDCl3, 50.32 MHz, DEPT): d = 20.03 and 21.69
[(CH3)2C<]; 32.15 and 32.27 [(CH3)2C<]; 35.37 (CH2SP); 76.36
and 77.00 and 77.64 and 77.89 (CH2OP); 112.58 and 118.86 and
147.34 and 150.57-C4∞ (furyl carbons); 181.20 (C=O).
MS (15eV): 266 (8.59, M), 251 [0.16, M(Me)], 238 [8.02, M(Et,
+H)], 221 [1.35, M(OEt)], 211 [1.33, (C(O)CH2SP(O)(OEt)2)], 184
[8.00, (CH2SP(O)(OEt)2)], 171 [4.16, (H+HSP(O)(OEt)2)], 155
[2.79, (H+HP(S)(OEt)2)], 137 [2.74, (HP(O)(OEt)2)], 128 [3.27,
M(HP(O)(OEt)2)], 96 [11.92, M(HSP(O)(OEt)2)], 83 [100.00,
M(CH2SP(O)(OEt)2)], 55 [62.60, M(C(O)CH2SP(O)(OEt)2)].
IR (KBr): n = 1667 (vs) (C=O), 1568 (l), 1473 (s), 1395 (m) - furan
ring, 1270 (vs) (P=O).
O,O-Diethyl S-(4,6,6-Trimethyl-2-oxocyclohex-3-enyl) Thio-
phosphate (1l)
IR (neat): n = 1688 (vs) (C=O), 1621 (m) (C=C), 1255 (vs) (P=O).
O,O-Diethyl S-(4-Methoxy-2-oxobut-3-enyl) Thiophosphate
Yield 83%, colorless oil.
(1h)
1H NMR (CDCl3, 300.13 MHz): d = 1.09 and 1.21 (s, 3H, (CH3)2C);
Yield 42%, brown oil.
1.36 (tdd, 6H, J =7, Dn = 2, J2 = 1.0, CH3CH2O); 1.95 (d, 3H, J =
1H NMR (CDCl3, 200 MHz): d = 1.35 (td, 6H, J = 7.2 J2 = 1Hz,
OCH2CH3); 3.42 (d, 3H, J = 2.2 Hz, CH3O); 3.90 (d, 2H, J = 14.0
Hz, CH2SP); 4.20 (m, 4H, OCH2CH3); 5.60 (d, 1H, J = 12.5 Hz,
CH=CH); 7.75 (d, 1H, J = 12.5 Hz, CH=CH).
1.0, CH3C = CH); 2.30 (m, 2H, ring CH2); 3.77 (d, 1H, JPSCH
=
3
16.4, CHSP); 4.20 (m, 4H, OCH2CH3); 5.96 (q, 1H, J = 1.0,
CH3C=CH).
31P NMR (C6H6, 24.3 MHz): d = 25.18 (78%) and 21.65 (22%).
31P NMR (CDCl3, 81.0 MHz): d = 25.66.
IR (neat, Specord 71 IR): n = 1685 (vs) (C=O), n=1635 (s) (C=C),
n=1260 (vs) (P=O).
13C NMR (CDCl3, 50.32 MHz, DEPT): d = 14.87 and 15.78 and
15.92 (OCH2CH3); 29.77 (CH2SP); 55.04 (OCH3); 63.59 and 64.19
(OCH2CH3); 104.13 (=CHC=O); 128.25 (MeOCH=); 196.79
(C=O).
O,O-Diethyl S-[(E)-2-Oxo-4-phenylbut-3-enyl] Dithiophos-
phate (3a)
Yield 80%, brown oil.
IR (neat): n = 1719 (vs) (C=O), 1679 (m) (C=C), 1258 (vs) (P=O).
1H NMR (CDCl3, 300.13 MHz): d = 1.33 (td, 6H, J1 = 7.1, J2 = 0.8
Hz, OCH2CH3); 3.96 (d, 2H, J = 16.2 Hz, CH2SP); 4.17 (m (19
lines), 4H, OCH2CH3); 6.87 (d, 1H, J = 16.1 Hz, PhCH=CH); 7.38
(m, 3Harom.); 7.55 (m, 2Harom.); 7.67 (d, 1H, J = 16.1 Hz, PhCH=).
S-(2-Cyclopent-1-en-1-yl-2-oxoethyl) O,O-Diethyl Thiophos-
phate (1i)
Yield: 87%, colorless oil.
1H NMR (CDCl3, 200 MHz): d = 1.34 (dt, 6H, 4JPH = 0.9, 3JHH = 7.1,
2◊OCH2CH3), 1.85–2.05 (m, 2H), 2.52–2.64 (m, 4H, 2¥CH2C=),
4.03 (d, 2H, 3JPH = 13.2, CH2S), 4.05–4.30 (m, 4H, 2¥OCH2), 6.84–
6.89 (m, 1H, =CH).
31P NMR (CDCl3, 81.0 MHz): d = 93.99.
13C NMR (CDCl3, 50.32 MHz): d = 16.27 and 16.43 (OCH2CH3);
42.425 (d, J =2.4 Hz, CH2SP); 65.00 and 64.88 (OCH2CH3); 124.26
(=CHCO); [129.09; 129.58; 131.54; 134.59 (Carom)]; 145.10
(PhCH=); 193.18 (d, J = 4.8, C=O).
31P NMR (CDCl3, 81.0 MHz): 27.11.
3
13C NMR (CDCl3, 50.32): d = 15.49 (d, JPC = 7.1, 2¥OCH2CH3),
IR (neat, Specord 71 IR): n = 1695 (vs) (C=O), 1630 (s) (C=C).
22.09 (s), 30.36 (s), 33.75 (s), 37.04 (d, 2JPC = 2.6, CH2S), 63.33 (d,
2JPC = 5.5, 2¥OCH2), 143.29 (s), 145.51 (s, = CH), 190.46 (d, 3JPC
= 5.3, C=O).
O,O-Dimethyl S-(4-Methyl-2-oxopent-3-enyl) Dithiophosphate
(3b)
Yield 62%, light orange oil.
MS (70 eV): 278 (8.21, M), 171 (21.24, (H+HSP(O)(OEt)2)), 108
(69.75, M(HSP(O)(OEt)2)), 95 (100.00, M(CH2SP(O)(OEt)2)).
1H NMR (CDCl3, 300.13 MHz): d = 1.91 and 2.14 (s, 3H,
3
(CH3)2C=); 3.69 (d, 2H, JPSCH = 16.0 Hz, CH2SP); 3.76 (d, 6H,
S-(2-Cyclohex-1-en-1-yl-2-oxoethyl] O,O-Diethyl Thiophos-
3JPOCH = 15.2 Hz, POCH3); 6.14 (br s, 1H, =CHC=O).
Synthesis 1999, No. 5, 844–848 ISSN 0039-7881 © Thieme Stuttgart · New York

848
P. Dybowski et al.
PAPER
31P NMR (CDCl3, 121.49 MHz): d = 98.16; (neat 24.3 MHz): 98.66.
IR (neat, Specord 71 IR): n = 1695 (vs) (C=O), 1610 (s) (C=C).
J3>1.0 Hz, PSCH2CH=); 6.87 (dt, 1H, J = 16.2, J2 = 7 Hz, =CH-
CHO); 9.43 (d, 1H, J = 7.0 Hz, CHO).
31P NMR (CDCl3, 121.49): d = 94.40.
O,O-Diethyl S-[(E)-4-Oxobut-2-enyl] Thiophosphate (2a)
Yield 100%, yellow oil.
IR (neat, Specord 71 IR): n = 1695 (vs) (C=O);,1650 (s) (C=O).
1H NMR (CDCl3, 300.13 MHz): d = 1.30 and 1.31 (t, 6H, J = 7.0
Hz, CH3CH2O); 3.65 (ddd, 2H, J = 16.5, J2 = 7.0, J3 = 1.5 Hz,
CH2SP); 4.13 (m, 4H, OCH2CH3); 6.20 (ddt, 1H, J = 15.5, J2 = 7.5,
J3 = 1.25 Hz, PSCH2CH=); 6.84 (dt, 1H, J = 15.5, J2 = 7.0 Hz,
=CHCHO); 9.42 (d, 1H, J = 7.0 Hz, CHO).
Acknowledgement
We gratefully acknowledge financial support from the Polish State
Committee for Scientific Research (KBN) Grant No 3 T09A 029
15.
31P NMR (neat, 24.3 MHz): d = 25.48; (CDCl3, 81.0 MHz): 26.20.
IR (neat, Specord 71 IR): n = 1695 (vs) (C=O), 1650 (s) (C=C),
1240 (vs) (P=O).
References
(E)-4-[(5,5-Dimethyl-2-oxido-1,3,2-dioxaphosphinan-2-yl)sul-
fanyl]but-2-enal (2b)
Yield 100%, brownish solid mass.
1H NMR (CDCl3, 200 MHz): d = 0.82 and 1.20 [s, 3H,
(CH3)CCH2O]; 3.67 (ddd, 2H, JPH = 16.6 Jvic = 7.1, J3 = 1.4 Hz,
PSCH2); 3.87 (ddt, 2H, Dn = 23.7, J1 = 11.2, J2 = 1.4 Hz, OCH2);
4.04 (broad dd, 2H, J1 = 10.8, J2 = 4.0 Hz, OCH2); 6.16 (ddt, 1H,
(1) Dybowski, P.; SkowroÒska, A. Tetrahedron Lett. 1991, 32,
4385.
(2) Dybowski, P.; SkowroÒska, A. Synthesis 1990, 609.
(3) Dybowski, P.; Krawczyk, E.; SkowroÒska, A. Synthesis 1992,
601.
(4) Maciπgiewicz, I.; Dybowski, P.; SkowroÒska, A., Tetrahe-
dron Lett. in press.
(5) SkowroÒska, A.; Dybowski, P.; Koprowski, M.; Krawczyk, E.
Tetrahedron Lett. 1995, 36, 8129.
Jtrans = 15.3, Jvic = 7.7 J3 = 1.0 Hz, =CHCHO); 6.82 (dt, 1H, Jtrans
15.3, Jvic = 7.7 Hz, SCH2CH=); 9.50 (d, 1H, J = 7.7 Hz, CHO).
=
(6) Skowroñska, A.; Dybowski, P.; Koprowski, M.; Krawczyk, E.
Tetrahedron Lett. 1995, 36, 8133.
(7) (a) Cazeau, P.; Duboudin, F.; Moulines, F.; Babot, O.; Dun-
ogues, J. Tetrahedron 1987, 43, 2075.
(b) Brownbridge, P. Synthesis 1983, 1 and references cited
therein.
(8) Cazeau, P.; Duboudin, F.; Moulines, F.; Babot, O.; Dunogues,
J. Tetrahedron 1987, 43, 2089.
(9) House, H. O.; Czuba, L. J.; Gall, M.; Olmstead, H. O.
J. Org. Chem. 1969, 2325.
(10) SkowroÒska, A.; Dembiñski, R.; Gwara, J.; Michalski, J.
Phosphorus Sulfur 1988, 39, 119 and references therein.
(11) (a) £opusiÒski, A.; Potrzebowski, M. Phosphorus Sulfur
1987, 32, 5564.
(b) £opusiÒski, A.; £uczak, L.; Michalski, J. Phosphorus Sul-
fur 1988, 40, 233.
(12) Michalski, J.; Potrzebowski, M.; £opusiÒski, A. Angew.
Chem., Int. Ed. Engl. 1982, 94, 135.
31P NMR (CDCl3, 81.0 MHz): d = 20.34.
IR (neat): n = 1690 (vs) (C=O), 1645 (m) (C=C), 1280 (vs) (P=O).
O,O-Diethyl S-[(2E,4E)-6-Oxohexa-2,4-dienyl] Dithiophos-
phate (2c)
Yield 84%, light yellow oil.
1H NMR (CDCl3, 300.13 MHz): d = 1.15 (t, 6H, J = 7.0,
CH3CH2O); 3.41 (dd, 2H, 3JPSCH = 16.0, J2 = 7.4, PSCH2CH=); 3.97
(m, 4H, CH3CH2O); 5.95 (dd, 1H, J = 15.4, J2 = 7.9, =CHCHO);
6.12 (dt, 1H, J = 15.0, J2 = 7.4, SCH2CH=); 6.31 (dd, 1H, J = 15.0,
J2 = 10.8, SCH2CH=CH); 6.99 (dd, 1H, J = 15.4, J2 = 10.8,
CH=CHCHO); 9.37 (d, 1H, J = 7.9, CHO).
31P NMR (neat, 24.3 MHz): d = 25.99; (CDCl3, 81.0 MHz): 26.31.
IR (neat, Specord 71 IR): n = 1675 (vs) (C=O), 1640 (s), 1600 (s)
(C = C), 1245 (vs) (P=O).
O,O-Diethyl S-[(E)-4-oxobut-2-enyl] Dithiophosphate (4a)
Yield 73%, brown oil.
1H NMR (CDCl3, 300.13 MHz): d = 1.28 and 1.29 (t, 6H, J = 7.0
Hz, CH3CH2O); 3.64 (ddd, 2H, JPH = 17.0, J2 = 7.5, J3 = 1.5 Hz,
CH2SP); 4.07 (m, 4H, OCH2CH3); 6.23 (ddt, 1H, J = 16.2, J2 = 7.5,
Article Identifier:
1437-210X,E;1999,0,05,0844,0848,ftx,en;P05998SS.pdf
Synthesis 1999, No. 5, 844 –848 ISSN 0039-7881 © Thieme Stuttgart · New York