Synthesis of cyclohexa-1,4-dienephosphonoyl dichlorides

Full text of DOI:10.1134/S1070363213110315

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 11, pp. 2122–2124. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © K.S. Titov, B.I. Ionin, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 11, pp. 1932–1934.
LETTERS
TO THE EDITOR
Synthesis of Cyclohexa-1,4-dienephosphonoyl Dichlorides
K. S. Titov and B. I. Ionin†
St. Petersburg State Technological Institute (Technical University),
Moskovskii pr. 26, St. Petersburg, 190013 Russia
e-mail: kstitov@mail.ru
Received September 30, 2013
DOI: 10.1134/S1070363213110315
Cyclohexadiene fragment is a part of many natural
compounds and synthetic drugs. Cyclohexadienes can
be subjected to aromatization; therefore they can be
used as reducing agents in biochemical processes
[1, 2].
addition of conjugated dienes to the acetylenes con-
taining acceptor substituents (the Diels–Alder reaction).
The Diels–Alder reaction of dimethyl chloroacetyl-
enephosphonate and tetramethyl acetylenediphosphonate
with some dienes leads to formation of the phos-
phorus-containing 1,4-cyclohexadiene derivatives [4–6].
1,4-Cyclohexadiene and similar hydrocarbons can
be prepared via the Birch reduction of aromatic hydro-
carbons with metals in liquid ammonia [3]. However,
this approach is limitedly applicable in the cases of
functionalized derivatives. One of the convenient me-
thods to prepare 1,4-cyclohexadiene derivatives is cyclo-
Aiming to obtain new phosphorus-containing
cyclohexanes, we performed the Diels–Alder reaction
between phenylacetylenephosphonic acid dichloride II
and several dienes: 1,3- and 2,3-dimethyl-1,3-diene,
isoprene and piperylene (Ia–Id).
R1
R1
Ph
R2
R3
Ph
R2
+
R3
POCl2
POCl2
Ia_Ic
IIIa_IIIc
II
R1 = H, R2 = R3 = Me (а); R1 = R3 = H, R2 = Me (b); R1 = Me, R2 = R3 = H (c); R1 = R3 = Me, R2 = H (d).
The reactions resulted in the corresponding sub-
stituted 1,4-cyclohexadienephosphonoyl dichlorides
IIIa–IIId. The reactions of phenylacetylenephos-
phonic acid dichloride II with 1,3-dimethyl-1,3-diene,
isoprene, and piperilene proceeded with low regio-
selectivity to give isomeric mixtures of methyl-
substituted 1,4-cyclohexadienephosphonoyl dichlo-
rides IIIb–IIId and IVa–IVd.
IIId were isolated as mixtures of isomers. The result-
ing compounds were viscous liquids, which were
isolated by vacuum distillation. They were unstable
and partially aromatized during storage.
The structures of the new phosphorus-containing
carbocyclic compounds IIIa–IIId were confirmed by
1H, 13C, and 31P NMR spectroscopy method.
General procedure for preparation of III and
IV. A mixture of 0.053 mol of phenylacetylene-
phosphonic acid dichloride, 0.06 mol of the cor-
responding diene IIa–IId, and 3.5 mg of hydroquinone
was placed into an ampoule. The ampoule was flushed
with argon and sealed. The mixture was heated at 140–
The reactions occurred under harsh conditions, at
140–160°C in the absence of any solvent, to form the
corresponding adducts IIIa–IIId. Compounds IIIb–
† Deseased.
2122

2123
SYNTHESIS OF CYCLOHEXA-1,4-DIENEPHOSPHONOYL DICHLORIDES
160°C during 10 h. The reaction products were
isolated by distillation under high vacuum.
spectrum, δ, ppm: 1.87 s (3Н, СН3), 3.07 d (2Н, С3Н2,
3JHH 8.0 Hz), 3.25–3.35 m (2Н, С6Н2), 5.47–5.53 m
3
(1Н, С4Н), 7.28 t (2Н, С3'HAr, C5'HAr, JHH 8.0 Hz),
4,5-Dimethyl-2-phenylcyclohexa-1,4-dienephos-
7.38–7.44 m (3Н, C4'HAr, С2'HAr, C6'HAr). 13С NMR
phonoyl dichloride (IIIа). Yield 78%, yellowish
3
spectrum, δС, ppm: 22.80 (CH3), 32.87 d (C3H2, JCP
1
viscous liquid, bp 150–154°С (1 mm Hg). H NMR
2
1
15.3 Hz), 38.16 d (C6H2, JCP 19.4), 126.80 (C1, JCP
spectrum, δ, ppm: 1.78 s (3Н, СН3С4), 1.89 s (3Н,
187.3 Hz), 127.04 (Сmeta), 128.28 (Сpara), 128.38
2
СН3С5), 3.12 and 3.14 (2Н, С6НАНВ, АВ-system, JHH
(Cortho), 129.89 (C5), 130.32 (C4), 140.23 (Cipso, JCP
3
3
= JHР = 8.0 Hz), 3.21 and 3.26 (2Н, С3НАНВ, АВ-
9.1 Hz), 155.66 (С2, JCP 9.1 Hz). 31P NMR spectrum:
2
2
3
system, JHH 8.0 Hz), 7.34 t (2Н, С3'НAr, С5'НAr, JHH
δP 33.49.
8.0 Hz), 7.47 t (1Н, С4'HAr, JHH 8.0 Hz), 7.53 d (2Н,
3
С2'HAr, C6'HAr, JHH 8.0 Hz). 13С NMR spectrum, δС,
3
4-Methyl-2-phenylcyclohexa-1,4-dienephosphonoyl
dichloride (IVc). Content in the mixture was of 35%.
1H NMR spectrum, δ, ppm: 1.78 s (3Н, СН3), 3.07 d
ppm: 17.85 (СН3С4), 18.25 (СН3С5), 34.85 d (С3Н2,
3JCP 15.5 Hz), 43.65 d (С6Н2, JCP 19.5 Hz), 122.09
2
(Сmeta), 122.27 (Сmeta), 125.46 (С4), 127.13 (С5),
3
(2Н, С3Н2, JHH 8.0 Hz), 3.25–3.35 m (2Н, С6Н2),
127.23 d (С1Р, JCP 185.1 Hz), 128.67 (Сpara), 129.04
1
5.60–5.66 m (1Н, С4Н), 7.27 t (2Н, С3'HAr, C5'HAr,
3JHH 8.0 Hz), 7.38–7.44 m (3Н, C4'HAr, С2'HAr, C6'HAr).
13С NMR spectrum, δС, ppm: 22.29 (CH3), 29.48 d
(Сortho), 140.03 d (Сipso, 3JCP 9.4 Hz), 155.85 d (С2, 2JCP
10.1 Hz). 31P NMR spectrum: δP 33.99 ppm.
3
2
(C3, JCP 16.1 Hz), .61 (С6, JCP 19.4 Hz), 127.01 (C1,
6-Methyl-2-phenylcyclohexa-1,4-dienephosphonoyl
dichloride (IIIb). Yield 73% (along with the isomer
IVb), yellowish viscous liquid, bp 146–150°С (1 mm
1JCP 187.8 Hz), 127.04 (Сmeta), 128.28 (Сpara), 128.38
(Cortho), 129.89 (C4), 130.18 (C5), 140.13 (Cipso, JCP
3
10.0 Hz), 155.48 (C2, JCP 10.0 Hz). 31P NMR
2
1
Hg), content in the mixture was 75%. H NMR spec-
trum, δ, ppm: 0.99 d (3Н, CH3, 3JHH 8.0 Hz), 3.10–3.17
m (2Н, С3Н2), 3.18–3.23 m (1Н, С6Н), 5.72 d (1Н,
С5Н, 3JHH 8.0 Hz), 5.81 t (1Н, С4Н, 3JHH 8.0 Hz), 7.37
spectrum: δP 33.85 ppm.
3,5-Dimethyl-2-phenylcyclohexa-1,4-dienephospho-
noyl dichloride (IIId). Yield 76% (along with the
isomer IVd), yellowish viscous liquid, bp 149–152°С
3
t (2Н, С3'HAr, C5'HAr, JHH 8.0 Hz), 7.47 t (1Н, C4'HAr,
3
3JHH 8.0 Hz), 7.53 d (2Н, С2'HAr, C6'HAr, JHH 8.0 Hz).
1
(1 mm Hg), content in the mixture was of 35%. H
13С NMR spectrum, δС, ppm: 20.16 (CH3), 28.38 d
3
NMR spectrum, δ, ppm: 1.37 d (3Н, С3СН3, JHH
3
2
(С3Н2, JCP 17.1 Hz), 39.46 d (С6Н, JCP 18.1 Hz),
8.5 Hz), 1.84 s (3Н, С5СН3), 3.20 s (2Н, С6Н), 3.27–
3.31 m (1Н, С3Н), 5.67 s (1Н, С4Н), 7.35 t (2Н, С3'HAr,
121.32 (Сmeta), 121.46 (Сmeta), 127.33 d (С1Р, JCP
1
181.1 Hz), 128.01 br (Сpara, C4), 129.06 (Сortho), 129.36
d (С5 8.01 Hz), 138.86 d (Сipso, 3JCP 10.1 Hz), 160.06 d
(С2, 2JCP 8.5 Hz). 31P NMR spectrum: δP 33.60 ppm.
3
3
C5'HAr, JHH 8.0 Hz), 7.42 t (1Н, C4'HAr, JHH 8.0 Hz),
7.59 d (2Н, С2'HAr, C6'HAr, 3JHH 8.0 Hz). 13С NMR spec-
trum, δС, ppm: 22.76 (С5СН3), 22.87 (С3СН3), 33.04 d
(С6Н2, JCP 17.5 Hz), 38.16 d (С3Н, JCP 15.0 Hz),
3
3-Methyl-2-phenylcyclohexa-1,4-dienephosphonoyl
126.42 (Сmeta), 126.33 d (С1Р, JCP 187.1 Hz), 128.40
1
dichloride (IVb). Content in the mixture was of 25%.
(Сpara), 129.79 (С4), 128.93 (Сortho), 129.16 d (С5, JCP
3
3
1H NMR spectrum, δ, ppm: 1.40 d (3Н, СН3, JHH
8.5 Hz), 139.10 (Сipso, 3JCP 17.5 Hz), 156.27 d (С2, 2JCP
10.0 Hz). 31P NMR spectrum: δP 33.76 ppm.
8.0 Hz), 3.25–3.29 m (2Н, С6Н2), 3.30–3.36 m (1Н,
С3Н), 5.77–5.81 m (1Н, С4Н), 5.84–5.89 m (1Н, С5Н),
3
7.38 t (2Н, С3'HAr, C5'HAr, JHH 8.0 Hz), 7.47 t (1Н,
4,6-Dimethyl-2-phenylcyclohexa-1,4-dienephospho-
3
3
C4'HAr, JHH 8.0 Hz), 7.63 d (2Н, С2'HAr, C6'HAr, JHH
8.0 Hz). 13С NMR spectrum, δС, ppm: 22.83 (СН3),
33.57 d (С6Н2, JCP 17.1 Hz), 37.08 d (С3Н, 2JCP 15.1 Hz),
noyl dichloride (IVd). Content in a mixture was of
1
35%. H NMR spectrum, δ, ppm: 1.02 d (3Н, С6СН3,
3JHH 8.0 Hz), 1.75 s (3Н, С4СН3), 3.10 s (2Н, С3Н),
3.25–3.34 m (1Н, С6Н), 5.77 s (1Н, С5Н), 7.29 t (2Н,
127.67 (Сpara), 127.93 d (С1Р, JCP 176.1 Hz), 128.78
1
(С4), 128.40 (Сmeta), 128.90 (Сortho), 140.9 d (С5, JCP
3
3
3
С3'HAr, C5'HAr, JHH 8.0 Hz), 7.45 t (1Н, C4'HAr, JHH
9.05 Hz), 155.73 (Сipso, JCP 18.1 Hz), 156.14 d (С2,
3
8.0 Hz), 7.57 d (2Н, С2'HAr, C6'HAr, JHH 8.0 Hz). 13С
3
2JCP 10.1 Hz). 31P NMR spectrum: δP 34.39 ppm.
NMR spectrum, δС, ppm: 20.93 (С6СН3), 22.35
3
5-Methyl-2-phenylcyclohexa-1,4-dienephosphonoyl
dichloride (IIIc). Yield 69% (along with the isomer
IVc), yellowish viscous liquid, bp 144–148°С (1 mm
(С4СН3), 29.87 (С3Н2, JCP 16.8 Hz), 39.07 d (С6Н,
2JCP 17.4 Hz), 127.11 (Сmeta), 127.15 d (С1Р, 1JCP 186.8
Hz), 128.28 (Сpara), 128.40 (Сortho), 129.08 (С4),
129.92 d (С5, 3JCP 8.5 Hz), 140.19 (Сipso, 3JCP 12.5 Hz),
1
Hg), content in the mixture was of 65%. H NMR
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 11 2013

2124
TITOV, IONIN
2
160.07 d (С2, JCP 8.5 Hz). 31P NMR spectrum: δP
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33.23 ppm.
The NMR spectra in CDCl3 were registered with
Bruker Avance 400 spectrometer operating at 400.13
(1Н), 100.61 (13С) and 161.98 (31Р) МHz relative to
internal HMDS (1Н) or 85% H3PO4 (31P).
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 11 2013