Synthese et etude conformationnelle par RMN (1H, 13C, 31P) et DFT des cycloalcoxyphosphinallenes et des hydrazones β-cycloalcoxyphosphonatees

Article abstract of DOI:10.1080/10426507.2012.700348

The addition of hydrazine and its derivatives to cycloalkoxyphosphinallenes leads to β-(5,5-dialkyl-2-oxo-1,3,2-dioxaphosphoranyl)-hydrazones in good yields. The structure of the obtained compounds were elucidated by the NMR (¹H, ¹³C

Full text of DOI:10.1080/10426507.2012.700348

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Phosphorus, Sulfur, and Silicon and the
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Synthese et Etude Conformationnelle
Par RMN (1H, 13C, 31P) et DFT des
Cycloalcoxyphosphinallenes et des
Hydrazones β-Cycloalcoxyphosphonatees
Nessrine Salah a , Youssef Arfaoui a b , Mohamed Bahri c , Mohamed
Lotfi Efrit a & Azaiez Ben Akacha a
a Laboratoire de Synthèse Organique et Hétérocyclique,
Département de Chimie, Faculté des Sciences de Tunis , Université
de Tunis El Manar, Campus Universitaire El Manar , Tunisie
b Faculté des Sciences et de l’Art Erras , Université el Qasim , Arabie
Saoudite
c Laboratoire de Spectroscopie Atomique, Moléculaire et
Applications. Département de Physique, Faculté des Sciences de
Tunis , Université de Tunis El Manar, Campus Universitaire El Manar ,
Tunisie
Accepted author version posted online: 22 Jun 2012.Published
online: 31 May 2013.
To cite this article: Nessrine Salah , Youssef Arfaoui , Mohamed Bahri , Mohamed Lotfi Efrit &
Azaiez Ben Akacha (2013) Synthese et Etude Conformationnelle Par RMN (1H, 13C, 31P) et DFT des
Cycloalcoxyphosphinallenes et des Hydrazones β-Cycloalcoxyphosphonatees, Phosphorus, Sulfur, and
Silicon and the Related Elements, 188:5, 609-622, DOI: 10.1080/10426507.2012.700348
To link to this article: http://dx.doi.org/10.1080/10426507.2012.700348
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Phosphorus, Sulfur, and Silicon, 188:609–622, 2013
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2012.700348
SYNTHESE ET ETUDE CONFORMATIONNELLE PAR RMN
(1H, 13C, 31P) ET DFT DES
CYCLOALCOXYPHOSPHINALLENES ET DES
HYDRAZONES β-CYCLOALCOXYPHOSPHONATEES
Nessrine Salah,1 Youssef Arfaoui,1,2 Mohamed Bahri,3
Mohamed Lotfi Efrit,1 and Azaiez Ben Akacha1
1Laboratoire de Synthe`se Organique et He´te´rocyclique, De´partement de Chimie,
Faculte´ des Sciences de Tunis, Universite´ de Tunis El Manar, Campus Universitaire
El Manar, Tunisie
2Faculte´ des Sciences et de l’Art Erras, Universite´ el Qasim, Arabie Saoudite
3Laboratoire de Spectroscopie Atomique, Mole´culaire et Applications.
De´partement de Physique, Faculte´ des Sciences de Tunis, Universite´ de Tunis El
Manar, Campus Universitaire El Manar, Tunisie
GRAPHICAL ABSTRACT
Abstract The addition of hydrazine and its derivatives to cycloalkoxyphosphinallenes leads
to β-(5,5-dialkyl-2-oxo-1,3,2-dioxaphosphoranyl)-hydrazones in good yields. The structure of
the obtained compounds were elucidated by the NMR (1H, 13C, 31P) spectroscopy and density
functional theory (DFT) calculations at B3LYP/6-311++G (2d, 2p) level of theory.
Keywords 5; 5-Dialkyl-1; 3; 2-dioxaphosphoranylallene; hydrazine derivatives; β-(5; 5-
dialkyl-1; 3; 2-dioxaphosphoranyl)-hydrazone; 13C; 1H; and 31P NMR; DFT
INTRODUCTION
Les organophosphore´s constituent une classe importante de compose´s utilise´s dans
le domaine pharmaceutique comme agents the´rapeutiques,1 anti-inflammatoires2 et anti-
cance´reux.3,4 Ils sont aussi utilise´s en agrochimie en tant que pesticides,1,5 insecticides,6–8
herbicides9 et fongicides.10,11 Depuis plusieurs anne´es notre laboratoire s’est inte´resse´ a` la
synthe`se de mole´cules comportant le motif phosphonyle.12–17
Received 10 January 2012; accepted 16 May 2012.
Address correspondence to Azaiez Ben Akacha, Laboratoire de Synthe`se Organique et He´te´rocyclique,
De´partement de Chimie, Faculte´ des Sciences de Tunis, Universite´ de Tunis El Manar, Campus Universitaire El
Manar 2092, Tunisie. E-mail: azaiezbenakacha@yahoo.fr
609

610
N. SALAH ET AL.
Dans le pre´sent travail, nous nous sommes inte´resse´s a` la synthe`se et a` l’e´tude
ste´re´ochimique en solution et a` l’e´tat solide par les techniques d’analyses spectroscopiques
RMN (1H, 13C, 31P), me´thodes de calcul density functional theory (DFT) avec la fonction-
nelle B3LYP et la base 6-311G++(2d, 2p), de compose´s organophosphore´s contenant un
cycle 1,3,2-dioxaphosphoranyle.18
RESULTATS ET DISCUSSIONS
Synthe`se des 1-(5,5-dialkyl-2-one-1,3,2-dioxaphosphoranyl) propa-1,2-
die´ne 1a–f
L’action du 2-chloro-5,5-dialky-1,3,2-dioxaphosphorinane sur les de´rive´s d’alcools
propargyliques en pre´sence de la trie´thylamine (Et3N) dans le THF anhydre pendant 1
heure, conduit a` la formation des cyclophosphoalle`nes 1 avec un rendement variant entre
50 a` 80% (Sche´ma 1).
Sche´ma 1
Etude Spectroscopique
La RMN du phosphore (31P) des compose´s 1a-f met en e´vidence l’existence d’un
seul signal. Les valeurs des de´placements chimiques varient entre 6 et 9 ppm selon la nature
des substituants R1 et R2. Les re´sultants sont regroupe´s dans le Tableau 1.
Le carbone C2 hybride´ sp re´sonne entre 205 et 215 ppm caracte´ristique d’un carbone
alle´nique. Pour les compose´s 1a2 et 1a4, ils re´sonnent sous forme de doublet provenant du
2
couplage avec le phosphore et la valeur de la constante de couplage JPC est faible. Les
carbones C1 et C3 re´sonnent tous sous forme de doublets entre 80 et 104 ppm et la constante
de couplage 1JPC1 varie entre 100 et 200 Hz. Ces re´sultats sont en accord avec les donne´es
spectroscopiques de la litte´rature.19–21
Nous avons e´tudie´ l’effet des substituants sur les valeurs de constantes de couplage
scalaire du syste`me de spin de la partie CH2–C–CH2 (syste`me ABCD) du cycle 1,3,2-
1
dioxaphosphorinane22 par RMN H. Les re´sultats ainsi obtenus sont consigne´s dans le
Tableau 2.

SYNTHESE ET ETUDE CONFORMATIONNELLE PAR RMN (1H, 13C, 31P)
611
Tableau 1 RMN du 13C et 31P (CDCl3): δ en ppm, nJPC en Hz, des compose´s 1a–f
1
a
b
c
d
e
f
C-1 2JPC
C-2 2JPC
C-3 3JPC
31P
78.4
113.2
214.8
82.5
189.4
213.3
1.5
95.9
16.6
6.6
78.0
180.2
207.8
81.4
213.3
213.0
1.5
102.7
17.4
6.7
77.7
191.7
214.5
82.7
190.2
213.2
76.2
8.3
103.8
16.6
8.8
76.1
15.8
8.9
95.8
16.6
7.2
Etude par DFT
Des e´tudes ante´rieures par diffe´rentes techniques re´alise´es sur les structures de
type 1,3,2-dioxaphoshoranyl ont montre´ que la conformation du groupe lie´ au phosphore
de´pendent de plusieurs facteurs.23–26
Les compose´s phosphonate´s 1 peuvent exister sous forme de deux isome`res et le
groupe (–CH=C=CH–) se trouvent soit en position e´quatoriale (structure a) soit en position
axiale (structure b). Des calcules the´oriques avec le programme Gaussian 03 effectue´s au
niveau DFT (The´orie de la fonctionnelle de densite´) avec la base 6-311G++ (2d,2p) et la
fonctionnelle B3LYP22 confirment la stabilite´ de la structure a.
Synthe`se des hydrazones β-cyclophosphonate´es 2a–n
Les hydrazones phosphonate´es 2 sont obtenues par addition des de´rive´s de l’hydrazine
sur les phosphoalle`nes 112,13,16,27–29 (Sche´ma 2).
Les hydrazones existent sous la forme de deux isome`res cis (Z) et trans (E).30–32 Le
carbone en α de (C=N) de la forme cis est plus blinde´ que celui de la forme trans.33–35
Etude Spectroscopique
L’analyse des spectres de RMN 31P re´alise´s dans le CDCl3 des compose´s 2a–n nous
a permis de repe´rer les signaux correspondants. L’ensemble des re´sultats sont regroupe´s
dans le Tableau 3.

612
N. SALAH ET AL.
Sche´ma 2
Les spectres de RMN 31P, montrent que ces compose´s existent sous forme de deux
ste´re´oisome`res Z et E en e´quilibre. La forme Z est toujours pre´ponde´rante que la forme E.
Ce re´sultat est appuye´ par la pre´sence de la liaison hydroge`ne intramole´culaire PO···NH
qui stabilise d’avantage la forme Z (Tableau 3).
Le spectre de RMN 13C permet de repe´rer les de´placements chimiques de certains
carbones. Les carbones C=N apparaissent dans la zone comprise entre 136 et 170 ppm
2
couple´s avec le phosphore avec une constante de couplage J variant de 3 a` 13 Hz. Le
carbone (Cα) du groupe me´thyle`ne (P–CH2–) apparait sous forme de doublet; ceci est
duˆ au couplage avec le phosphore (1JPCα = 130 Hz). Nous signalons que le de´placement
chimique de chaque doublet de´pend de l’environnement chimique autour de ce carbone.
Tableau 2 Constantes de couplage scalaire JHH (en Hz) calcule´es et expe´rimentales relative aux cyclophospho-
alle`nes
JHH
1a
1f
1e
Exp.
JAB
JAC
JAD
JBC
JBD
JCD
−11.015
1.677
−1.263
−1.263
0.318
−10.953
1.932
−1.168
−1.152
0.517
−10.960
1.912
−1.181
−1.169
0.522
−11.29 0.04
1.48 0.04
−1.35 0.04
−1.60 0.04
1.35 0.04
−11.010
−10.689
−10.68
−11.09 0.04

SYNTHESE ET ETUDE CONFORMATIONNELLE PAR RMN (1H, 13C, 31P)
613
Tableau 3 RMN du δ 31P (ppm) (CDCl3) et% (Z/E)
2
Z
E
%Z
%E
a
b
c
d
e
f
g
h
i
j
k
l
m
n
20.9
21.2
22.0
20.7
20.4
18.2
19.0
20.4
21.6
21.6
21.3
21.2
19.8
20.0
20.7
–
–
20.2
–
19.5
–
75
100
100
86
100
44
100
100
56
49
46
86
44
25
–
–
14
–
56
–
–
–
21.6
21.6
21.0
20.9
19.3
19.0
44
51
54
14
56
12
88
Dans le cas des hydrazones 2a et 2f, le carbone (Cα) de la forme Z apparait vers 26.2 ppm
(2a) et 29.3 ppm (2f). Ce meˆme carbone re´sonne vers 26.4 ppm (2a) et 35.1 ppm (2f) pour
l’isome`re E. Ces re´sultats sont en accord avec les donne´es de la litte´rature.16,28,36
1
Ils sont en outre appuye´s par l’analyse des spectres de RMN H, sur les quels on
remarque un de´doublement des signaux. On attribue le signal le plus intense a` l’isome`re Z
comme il a e´te´ indique´ en RMN 13C. Les valeurs des de´placements chimiques des protons
porte´s par le carbone (C=N) sont en accord avec les donne´es de la litte´rature.16,36,37 En
effet, ces protons apparaissent sous forme d’un doublet duˆ au couplage avec le phosphore.
Lorsque ces protons sont en position cis par rapport au motif NHR,4 ils apparaissent plus
de´blinde´s que ceux en trans. Par exemple, pour le compose´ 2i, δ(P–CH2) cis = 2.92 ppm
et δ(P–CH2) trans = 2.83 ppm. Une bande large entre 4 et 10 ppm relative au proton mobile
du groupe NHR.4
Une e´tude the´orique par le programme Gaussian 03 me´thode DFT a e´te´ re´alise´e sur
le compose´ 2f montre la pre´fe´rence de la forme Z. La liaison hydroge`ne intramole´culaire
PO···NH a e´te´ confirme´e par une e´tude de diffraction des rayon-X38 (Sche´ma 3).
Sche´ma 3

614
N. SALAH ET AL.
PARTIE EXPERIMENTALE
Les spectres de RMN 1H, 13C et 31P ont e´te´ enregistre´s dans une solution de CDCl3 sur
un spectrome`tre Bruker AC 300 MHz. Les de´placements chimiques sont exprime´s en ppm
par rapport au TMS pris comme re´fe´rence interne pour le 1H et le 13C et par rapport a` H3PO4
a` 85% comme re´fe´rence externe pour le 31P. Les constantes de couplage he´te´ronucle´aires
et homonucle´aires (J) sont exprime´es en Hz. La multiplicite´ des signaux en RMN du 1H est
indique´e par les abre´viations suivantes: s (singulet), d (doublet), t (triplets), q (quadruplet),
m (multiplet), ma (multiplet massif), mc (multiplet centre´).
Les e´nergies potentielles et les constantes de couplage scalaire ont e´te´ calcule´es par
le programme Gaussian 03, me´thode DFT et une base (B3LYP/6-311++g (2d,2p)).
Les points de fusion (tempe´rature de fusion) exprime´s en degre´ Celsius sont
de´termine´s par la me´thode des capillaires avec un appareil Buchi.
Pre´paration de 2-Chloro-5,5-dime´thyl (ou 5,5-Die´thyl)-1,3,2-
dioxaphosphorinane39
Dans un ballon, et sous atmosphe`re d’azote on introduit une solution de 0.25 mol de
trichlorure ◦de phosphore (21.83 mL) dans 400 mL d’e´ther anhydre et on ajoute goutte a`
goutte a` 0 C (glace + sel) et sous agitation me´canique une solution contenant 0.25 mol
de 2,2-dime´thyl (ou die´thyl) propan-1,3-diol et 0.54 mol de trie´thylamine (75.12 mL)
dans environ 150 mL d’e´ther anhydre. A basse tempe´rature, un solide blanc de chlorhy-
drate de trie´thylamine apparait progressivement. Une fois l’addition termine´e, le me´lange
re´actionnel est laisse´ sous agitation me´canique continue pendant 2 h jusqu’au retour a` sa
tempe´rature ambiante. Le pre´cipite´ re´sultant est ensuite filtre´ et lave´ a` l’e´ther anhydre.
Le filtrat est concentre´ sous vide puis distille´ sous pression re´duite. On obtient un liquide
visqueux incolore.
2-Chloro-5,5-dime´thyl-1, 3,2-dioxaphosphorinane
M = 168.4 g/mol, Rdt = 43%, Te´b = 70–125 ◦C. RMN 31P: δ = 146.6. RMN 1H: δ
= 0.76 (s, 3H, CH3), 1.2 (s, 3H, CH3), 3.46–4.29 (m, 4H, ABCD). RMN 13C: δ = 22.37
(CH3), 22.39 (CH3), 32.8 (d, 3JPC = 4.5 Hz, –C–), 70.9 (d, 2 JPC = 3.0 Hz, CH2–O–P).
2-Chloro-5, 5-die´thyl-1, 3, 2-dioxaphosphorinane
M = 196.4 g/mol, Rdt = 38%, Te´b = 80–125 ◦C. RMN 31P: δ = 149.4. RMN 1H: δ =
0.81 (m, 3H, CH3–C), 0.89 (m, 3H, CH3–C), 1.16 (m, 2H, C–CH2), 1.73 (m, 2H, C–CH2),
3.67–4.32 (m, 4H, ABCD). RMN 13C: δ = 6.2 (CH3–C), 7.3 (CH3–C), 22.7 (C–CH2), 25.0
(C–CH2), 37.6 (d, 3J = 4.5 Hz, –C–), 68.4 (d, 2J = 2.26, CH2–O–P).
Pre´paration de 1-(5,5-Dialkyl-2-oxo-1,3,2-dioxaphosphoranyl)-propa-1,
2-die´ne 1a–f36,40–44
A une solution de 0.03 mol d’alcool α-ace´tyle´nique (5.05 g) et 0.031 mol de
trie´thylamine (4.3 mL) dans environ 150 mL de THF anhydre et sous atmosphe`re d’azote,
on ajoute goutte a` goutte a` une tempe´rature voisine de 0 ◦C et sous agitation magne´tique,

SYNTHESE ET ETUDE CONFORMATIONNELLE PAR RMN (1H, 13C, 31P)
615
0.03 mol de 2-chloro-5,5-dime´thyl-1,3,2-dioxaphosphorinane 1a (ou die´thyl 1b) dans en-
viron 15 mL de THF anhydre. A basse tempe´rature, du chlorhydrate de trie´thylamine se
forme. A la fin de l’addition, on porte le me´lange re´actionnel au reflux de THF et sous
agitation continue pendant environ une ou deux heures. Le pre´cipite´ blanc ainsi forme´ est
ensuite filtre´ et lave´ par du THF anhydre. Le filtrat est par la suite concentre´ sous vide.
Les produits obtenus sont traite´s par l’e´ther ou l’e´ther de pe´trole et recristallise´s dans
l’hexane.
1-(5,5-Dime´thyl-2-oxo-1,3,2-dioxaphosphoranyl)-propa-1,2-die`ne (1a)45
◦
1
M = 188 g/mol, Rdt = 80%, Tf = 118 C. RMN 31P: δ = 8.3 RMN H: δ = 0.98
(s, 3H, CH3), 1.21 (s, 3H, CH3), 3.9–4.10 (m, 4H, ABCD), 5.08 (dd, 4JPH = 15 Hz, 4JHH
= 6 Hz, 2H, =CH2), 5.39 (m, 1H, P–CH=). RMN 13C: δ = 20.9 (CH3), 21.7 (CH3), 32.5
3
2
1
(d, JPC = 6.79 Hz, –C–), 76.2 (=CH2), 76.5 (d, CH2–O–P, JPC = 6 Hz), 78.4 (d, J =
113,2 Hz, P–CH=), 214.8 (=C=).
1-(5,5-Dime´thyl-2-oxo-1,3,2-dioxaphosphoranyl)-3-phe´nyl-propa-1,2-
die`ne (1b)
M = 264 g/mol, Rdt = 75%, Tf = 104 ◦C. RMN 31P: δ = 6.4. RMN 1H: δ = 0.79 (s,
3H, CH3), 1.15 (s, 3H, CH3), 3.8–4.03 (m, 4H, ABCD), 5.78 (m, 1H, =CH–C6H5), 6.47
2
4
(dd, JPH = 12 Hz, JHH = 6 Hz, 1H, P–CH=), 7.27 (mc, 5H, arom-H). RMN 13C: δ =
20.65 (CH3), 21,68 (CH3), 32.4 (d, 3JPC = 6.8 Hz, –C–), 76.9 (d, 2JPC = 6 Hz, CH2–O–P),
82.7 (d, 1J = 189.4 Hz, P–CH=), 95.89 (d, 3JPC = 16.6 Hz, =CH–C6H5), 127.2 (d, 6JPC
= 2.3 Hz, CH=arom), 128.2 (d, 7J = 1.5 Hz, CH=arom), 129.0 (d, 5J = 1.5 Hz, CH=arom),
130.9 (d, 4J = 8.3 Hz, –C=arom), 213.2 (d, 2J = 1.5 Hz, =C=).
1-(5,5-Dime´thyl-2-oxo-1,3,2-dioxaphosphoranyl)-3-cycohexyl-propa-1,2-
die´ne (1c)
M = 256 g/mol, Rdt = 54%, Tf = 86 ◦C. RMN 31P: δ = 8.8. RMN 1H: δ = 0.97 (s,
3H, CH3), 1.25 (s, 3H, CH3), 4.0–4.5 (m, 4H, ABCD), 1.5–2.4 (ma, 10H, Hcyclo), 5.2 (ma,
1H, P–CH=). RMN 13 C: δ = 20.8 (CH3), 21.7 (CH3), 25.7–29.8 (CH2 cyclo), 32.3 (d, 3JPC
= 4.52 Hz, –C–), 74.8 (d, 2JPC = 8.3 Hz, CH2–O–P), 82.0 (d, 1JPC = 182.0 Hz, P–CH=),
103.8 (d, 3JPC = 16.6 Hz, –C=cyclo), 207.8 (=C=).
1-(5,5-Dime´thyl-2-oxo-1,3,2-dioxaphosphoranyl)-3-me´thyl-3-phe´nyl-
propa-1,2-die´ne (1d)
M = 256 g/mol, Rdt = 67%. RMN 31P: δ = 6.7. RMN 1H: δ = 0.79 (s, 3H, CH3),
1.17 (s, 3H, CH3), 2.18 (dd, 5JPH = 6.0 Hz, 3JHH = 3.0 Hz, CH3–C=), 3.88–3.99 (m, 4H,
ABCD), 5.69 (ma, 1H, P–CH=), 7.35 (mc, 5H, arom-H). RMN 13C: δ = 17.3 (CH3–C=),
20.1 (CH3), 20.6 (CH3), 32.5 (d, 3JPC = 6.0 Hz, –C–), 76.1 (d, 2JPC = 6.0 Hz, CH2–O–P),
1
3
6
81.4 (d, JPC = 213.3 Hz, P–CH=), 102.7 (d, JPC = 17.4 Hz, =C–), 125.9 (d, JPC
=

616
N. SALAH ET AL.
2.3 Hz, =CHarom), 127.9 (d, 7JPC = 1.5 Hz, =CHarom), 128.7 (d, 5JPC = 1.5 Hz, =CHarom),
134.0 (d, 4JPC = 7.6 Hz, –C=) 213.0 (d, 2JPC = 1.5 Hz, =C=).
1-(5,5-Die´thyl-2-oxo-1,3,2-dioxaphosphoranyl)-propa-1,2-die´ne (1e)
◦
1
M = 216 g/mol, Rdt = 55%, Tf = 93 C. RMN 31P: δ = 8.9. RMN H: δ = 0.78
(m, 3H, CH3), 0.82 (m, 3H, CH3), 1.25 (m, 2H, CH2), 1.6 (m, 2H, CH2), 3.94–4.11 (m,
4H, ABCD), 5.03 (m, 2H, =CH2), 5.32 (m, 1H, P–CH=). RMN 13C: δ = 6.9 (CH3–C),
7.0 (CH3–C), 22.2 (C–CH2), 22.9 (C–CH2), 37.3 (d, 3JPC = 6.0 Hz, –C–), 74.2 (d, 2JPC
=
1
3
6.8 Hz, CH2–O–P), 77.7 (d, JPC = 191.7 Hz, P–CH=), 76.1 (d, J = 15.8 Hz, =CH2),
214.5 (=C=).
1-(5,5-Die´thyl-2-oxo-1,3,2-dioxaphosphoranyl)-3-phe´nyl-propa-1,2-die´ne (1f)
M = 292 g/mol, Rdt = 48%, Tf = 107 ◦C. RMN 31P: δ = 7.2. RMN 1H: δ = 0.67 (m,
3H, CH3–C), 0.80 (m, 3H, CH3–C), 1.13 (m, 2H, C–CH2), 1.59 (m, 2H, C–CH2), 3.89–4.12
2
4
(m, 4H, ABCD), 5.76 (m, 1H, =CH–C6H5), 6.45 (dd, JPH = 15.0 Hz, JHH = 6.0 Hz,
P–CH=), 7.24 (ma, 5H, arom-H). RMN 13C: δ = 6.9 (CH3), 7.1 (CH3), 22.4 (CH2), 22.9
(CH2), 37.3 (d, 3JPC = 6.0 Hz, –C–), 74.2 (d, 2JPC = 6.8 Hz, CH2–O–P), 82.7 (d, 1JPC
=
190.2 Hz, P–CH=), 95.8 (d, 3JPC = 16.6 Hz, =CH–C6H5), 127.2 (d, 5JPC = 3.0 Hz, C-o),
128.1 (d, 6JPC = 1.5 Hz, C-m), 128.9 (d, 7JPC = 1.5 Hz, C-p), 131.0 (d, 4JPC = 8.3 Hz, C-i)
213.2 (d, 2JPC = 1.5 Hz, =C=).
Pre´paration des Hydrazones β-Cyclophosphonate´es 2a–n
A une solution de 0.5 × 10−2 mol de cycloalcoxyphosphinalle`nes 1 dans environ
35 mL de chloroforme, on ajoute goutte a` goutte a` tempe´rature ambiante une quantite´
le´ge`rement en exce`s de de´rive´s de l’hydrazine dans 5 mL de chloroforme. Le me´lange est
porte´ au reflux pendant 6 heures. La solution est par la suite concentre´e sous vide et le
re´sidu obtenu est traite´ par l’e´ther die´thylique ou l’e´ther de pe´trole. Le solide obtenu est
recristallise´ dans l’hexane.
Hydrazone de la 1-(5,5-Dime´thyl-2-oxo-1,3,2-dioxaphosphoranyl)-3-
phe´nyl-propanone (2a)
Solide, M = 296 g/mol, Rdt = 50%, Tf = 150 ◦C. Forme Z : RMN 31P: δ = 20.9. RMN
1H: δ = 0.89 (s, 3H, CH3), 0.92 (s, 3H, CH3), 3.29 (d, 2JPH = 24.0 Hz, 2H, PCH2), 3.48
(s, 2H, CH2–C6H5), 3.7–4.2 (m, 4H, ABCD), 4.99 (s, 2H, NH2), 7.29 (mc, 5H, arom-H).
RMN 13C: δ = 21.0 (CH3), 21.6 (CH3), 26.2 (d, 1JPC = 126.0 Hz, PCH2), 32.4 (d, 3JPC
=
7.5 Hz, –C–), 44.0 (CH2–C6H5), 76.3 (d, 2JPC = 6.8 Hz, CH2–O–P), 126–130 (CH-arom),
136.2 (–C=arom), 161.8 (d, 2JPC = 3.0 Hz, CN). Forme E: RMN 31P: δ = 20.7. RMN 1H: δ
= 1.11 (s, 3H, CH3), 1.14 (s, 3H, CH3), 3.19 (d, 2JPH = 24.0 Hz, 2H, PCH2), 3.43 (s, 2H,
CH2–C6H5), 3.7–4.2 (m, 4H, ABCD), 4.97 (s, 2H, NH2), 7.29 (mc, 5H, arom-H). RMN
13C: δ = 21.4 (CH3), 21.5 (CH3), 26.4 (d, 1JPC = 127.0 Hz, P–CH2), 32.3 (d, 3JPC = 7.0 Hz,
–C–), 43.7 (CH2–C6H5), 75.7 (d, 2JPC = 6.8 Hz, CH2–O–P), 126–130 (CH-arom), 136.6
(–C=arom), 169.9 (d, 2JPC = 3.0 Hz, CN).

SYNTHESE ET ETUDE CONFORMATIONNELLE PAR RMN (1H, 13C, 31P)
617
Hydrazone de la 1-(5,5-Dime´thyl-2-oxo-1,3,2-dioxaphoaphoranyl)-3-
me´thyl-3-phe´nyl-propanone (2b)
1
Paˆteux, M = 310 g/mol, Rdt = 66%. RMN 31P: δ = 21.2. RMN H: δ = 0.97 (s,
2
3H, CH3), 1.08 (s, 3H, CH3), 1.42 (m, 3H, CH3–C–), 2.58 (dd, JPH = 24.0 Hz, 2JHH
=
15.0 Hz, 1H, P–CH), 3.00 (dd, JPH = 24.0 Hz, 2JHH = 15.0 Hz, P–CH), 3.60–3.82 (m,
2
1H, –CH–), 4.1–4.2 (m, 4H, ABCD), 5.86 (s, 2H, NH2), 7.24 (m, 5H, arom-H). RMN 13C:
1
δ = 19.5 (CH3–C), 21.1 (CH3), 21.5 (CH3), 25.8 (d, JPC = 133.6 Hz, P–CH2), 32.6 (d,
3JPC = 6.0 Hz, –C–), 47.6 (d, 3JPC = 2.3 Hz, –CH–), 75.3 (d, 2JPC = 4.5 Hz, CH2–O–P),
126–129 (arom-CH), 143.2 (d, 4JPC = 1.5 Hz, C-i), 146.2 (d, 2JPC = 11.3 Hz, CN).
Hydrazone de la 1-(5,5-Dime´thyl-2-oxo-1,3,2-dioxaphoaphoranyl)-3-
cyclohexyl-propanone (2c)
Solide, M = 287 g/mol, Rdt = 74%, Tf = 150 ◦C. RMN 31P: δ = 22.0. RMN 1H: δ
= 0.98 (s, 3H, CH3), 1.17 (s, 3H, CH3), 1.2–2.3 (m, 11H, Hcyclo), 2.99 (d, 2JPH = 21.0 Hz,
P–CH2), 3.7–4.5 (m, 4H, ABCD), 5.59 (s, 2H, NH2). RMN 13C: δ = 21.2 (CH3), 21.8
(CH3), 25.8 (d, 1JPC = 134.3 Hz, P–CH2), 26–30.5 (CHcyclo), 32.7 (d, 3JPC = 6.0 Hz, –C–),
46.3 (d, 3J = 2.3 Hz, CHcyclo), 75.1 (d, 2JPC = 6.8 Hz, CH2–O–P), 148.7 (d, 2JPC = 12.0 Hz,
CN).
Hydrazone de la N-Phe´nyl-1-(5,5-dime´thyl-2-oxo-1,3,2-
dioxaphosphoranyl)-3-phe´nyl-propanone (2d)
◦
Solide, M = 372 g/mol, Rdt = 97%, Tf = 155 C. Forme Z : RMN 31P: δ = 20.7.
RMN 1H: δ = 0.98 (s, 3H, CH3), 1.05 (s, 3H, CH3), 2.91 (d, 2JPH = 24.0 Hz, P–CH2), 3.47
(s, 2H, CH2–C6H5), 3.7–4.24 (m, 4H, ABCD), 7.2 (mc, 5-H, arom-H), 8.60 (s, 1H, NH).
RMN 13C: δ = 21.1 (CH3), 21.6 (CH3), 26.7 (d, 1JPC = 134.3 Hz, P–CH2), 32.6 (d, 3JPC
= 6.0 Hz, –C–), 44.7 (d, 3JPC = 3.0 Hz, CH2–C6H5), 75.5 (d, 2JPC = 6.0 Hz, CH2–O–P),
4
2
113.0–129.5 (CH-arom), 137.0 (d, JPC = 2.3 Hz, C–i), 139.1 (d, JPC = 12.0 Hz, CN),
146.2 (N–C=arom). Forme E: RMN 31P: δ = 20.2. RMN 1H: δ = 0.90 (s, 3H, CH3), 1.02
(s, 3H, CH3), 3.03 (d, 2JPH = 24.0 Hz, P–CH2), 3.32 (s, 2H, CH2–C6H5), 3.6–4.24 (m, 2H,
CH2–O–P), 7.2 (mc, 5H, arom-H), 8.0 (s, 1H, NH). RMN 31C: δ = 21.2 (CH3), 21.6 (CH3),
28.0 (d, 1JPC = 134.0 Hz, P–CH2), 32.6 (d, 3JPC = 6.0 Hz, –C–), 44.0 (d, 3JPC = 3.0 Hz,
CH2–C6H5), 75.7 (d, 2JPC = 6.8 Hz, CH2–O–P), 112–129.5 (CH-arom), 136.4 (d, 4JPC
2.3 Hz, C-i), 138.2 (d, 2JPC = 12.0 Hz, CN), 145.0 (N–C=arom).
=
Hydrazone de la N-Me´thyl-1-(5,5-dime´thyl-2-oxo-1,3,2-
dioxaphosphoranyl)-3-me´thyl-3-phe´nyl-propanone (2e)
Paˆteux, M = 324 g/mol, Rdt = 74%. RMN 31P: δ = 20.4. RMN 1H: δ = 0.98 (s, 3H,
2
CH3), 1.01 (s, 3H, CH3), 1.45 (m, 3H, CH3–C), 2.80 (d, JPH = 24.0 Hz, P–CH2), 3.00
(s, 3H, –NCH3), 3.7–3.8 (m, 1H, –CH–), 4.0–4.3 (m, 2H, CH2–O–P), 6.0 (s, 1H, –NH),
7.3 (mc, 5H, arom-H). RMN 31C: δ = 20.0 (CH3–C), 21.0 (CH3), 21.6 (CH3), 26.1 (d,
1JPC = 117.7 Hz, P–CH2), 32.3 (d, 3JPC = 5.3 Hz, –C–), 38.1 (d, 3JPC = 5.3 Hz, –CH–),
47.4 (–NCH3), 74.7 (d, 2JPC = 7.5 Hz, CH2–O–P), 126–128 (CH-arom), 143.3 (–C=arom),
142.1 (d, 2JPC = 11.3 Hz, –C=N).

618
N. SALAH ET AL.
Hydrazone de la N-Carbe´thoxy-1-(5,5-dime´thyl-2-oxo-1,3,2-
dioxaphosphoranyl)-propanone (2f)
◦
Solide, M = 292 g/mol, Rdt = 77%, Tf = 170 C. Forme Z : RMN 31P: δ = 18.2.
RMN 1H: δ = 1.13 (s, 3H, CH3), 1.14 (s, 3H, CH3), 1.31 (m, 3H, CH3–C–O), 2.14 (d, 4JPH
2
= 3.0 Hz, 3H, CH3–CN), 3.01 (d, JPH = 21.0 Hz, P–CH2), 3.68–4.05 (m, 4H, ABCD),
4.25 (m, 2H, O–CH2), 9.19 (s, 1H, NH). RMN 31C: δ = 14.6 (CH3–C–O) 16.2 (CH3–CN),
21.5 (CH3), 21.7 (CH3), 32.5 (d, 3JPC = 6.8 Hz, –C–), 29.3 (d, 1JPC = 131.3 Hz, P–CH2),
2
61.6 (O–CH2), 75.8 (d, JPC = 6.8 Hz, CH2–O–P), 145.1 (CN), 155.1 (C=O). Forme E:
1
RMN 31P: δ = 19.5. RMN H: δ = 1.00 (s, 3H, CH3), 1.04 (s, 3H, CH3), 1.29 (m, 3H,
CH3–C–O), 2.04 (d, 4JPH = 3.0 Hz, CH3–CN), 3.05 (d, 2JPH = 21.0 Hz, P–CH2), 3.84–4.08
(m, 4H, ABCD), 4.28 (m, 2H, O–CH2), 8.12 (s, 1H, NH). RMN 31C: δ = 14.5 (CH3–C–O),
16.2 (CH3–CN), 21.0 (CH3), 21.2 (CH3), 35.1 (d, 1JPC = 131.3 Hz, P–CH2), 32.7 (d, 3JPC
2
= 6.0 Hz, –C–), 61.8 (O–CH2), 76.2 (d, JPC = 6.8 Hz, CH2–O–P), 144.1 (CN), 154.2
(C=O).
Hydrazone de la N-Carbe´thoxy-1-(5,5-dime´thyl-2-oxo-1,3,2-
dioxaphosphoranyl)-3-phe´nyl-propanone (2g)
Solide, M = 368 g/mol, Rdt = 54%, Tf = 115 ◦C. RMN 31P: δ = 19.0. RMN 1H: δ
= 0.99 (s, 3H, CH3), 1.01 (s, 3H, CH3), 1.30 (m, 3H, CH3–C–O), 2.84 (d, 2JPH = 24.0 Hz,
2H, P–CH2), 3.74 (s, 2H, CH2–C6H5), 3.68–4.05 (m, 4H, ABCD), 4.25 (m, 2H, O–CH2),
7.29 (mc, 5H, arom-H), 9.63 (s, 1H, NH). RMN 13C: δ = 14.6 (CH3–C–O), 21.2 (CH3),
1
3
21.4 (CH3), 26.8 (d, JPC = 132.0 Hz, P–CH2), 32.5 (d, JPC = 3.0 Hz, –C–), 44.8 (d,
3JPC = 3.0 Hz, CH2–C6H5), 61.6 (O–CH2), 75.8 (d, 2JPC = 6.0 Hz, CH2–O–P), 127–127.5
(CH-arom), 135.9 (d, 4JPC = 1.5 Hz, C-i), 145.8 (d, 2JPC = 10.6 Hz, CN), 155.1 (C=O).
Hydrazone de la N-Carbetoxy-1-(5,5-dime´thyl-2-oxo-1,3,2-
dioxaphoaphoranyl)-3-cyclohexyl-propanone (2h)
Solide, M = 359 g/mol, Rdt = 90%, Tf = 110 ◦C. RMN 31P: δ = 20.4. RMN 1H: δ =
1.03 (s, 3H, CH3), 1.16 (s, 3H, CH3), 1.28 (m, 3H, CH3–C–O), 1.5–2.0 (ma, 11H, Hcyclo),
2.98 (d, 2JPH = 24.0 Hz, P–CH2), 3.93 (m, 2H, O–CH2), 4.23 (mc, 4H, ABCD), 9.57 (s,
1H, NH). RMN 13C: δ = 14.6 (O–C–CH3), 21.1 (CH3), 21.4 (CH3), 25.8–30.2 (CH2cyclo),
28.8 (d, 1JPC = 172.0 Hz, P–CH2), 32.7 (d, 3JPC = 6.0 Hz, –C–), 47.0 (d, 3JPC = 3.0 Hz,
CHcyclo), 61.4 (O–CH2), 75.7 (d, 2JPC = 6.0 Hz, CH2–O–P), 150.7 (d, 2J = 11.3 Hz, CN),
155.1 (C=O).
Hydrazone de la 1-(5,5-Die´thyl-2-oxo-1,3,2-dioxaphosphoranyl)-
propanone (2i)
Solide, M = 248 g/mol, Rdt = 74%, Tf = 160 ◦C. Forme Z : RMN 31P: δ = 21.62.
1
RMN H: δ = 0.80 (m, 3H, CH3–C), 0.82 (m, 3H, CH3–C), 1.24 (m, 2H, C–CH2), 1.55
4
2
(m, 2H, C–CH2), 1.93 (d, JPH = 3.0 Hz, CH3–CN), 2.92 (d, JPH = 21.0 Hz, P–CH2),
4.03 (mc, 4H, ABCD), 5.42 (s, 2H, NH2). RMN 13C: δ = 7.0 (CH3–C), 7.1 (CH3–C), 22.4
(C–CH2), 22.5 (C–CH2), 24.6 (CH3–CN), 28.1 (d, 1JPC = 125.0 Hz, P–CH2), 37.3 (d, 3JPC
= 5.3 Hz, –C–), 73.3 (d, 2J = 5.3 Hz, CH2–O–P), 159.0 (d, 2J = 6.8 Hz, CN). Forme E:
RMN 31P: δ = 21.57. RMN 1H: δ = 0.83 (s, 3H, CH3–C), 0.85 (s, 3H, CH3–C), 1.33 (m,

SYNTHESE ET ETUDE CONFORMATIONNELLE PAR RMN (1H, 13C, 31P)
619
2H, C–CH2) 1.43 (m, 2H, C–CH2), 1.84 (d, 4JPH = 3.0 Hz, 3H, CH3–CN), 2.83 (d, 2JPH
=
21.0 Hz, 2H, P–CH2), 4.03 (mc, 2H, CH2–O–P), 5.09 (s, 2H, NH2). RMN 13C: δ = 6.96
1
(CH3–C–), 7.01 (CH3–C–), 22.7 (C–CH2), 23.0 (C–CH2) 24.1 (CH3–CN), 28.7 (d, J =
127.0 Hz, P–CH2), 37.2 (d, 3J = 6.0 Hz, –C–), 73.8 (d, 2J = 6.8 Hz, CH2–O–P), 156.7 (d,
2J = 3.0 Hz, CN).
Hydrazone de la 1-(5,5-die´thyl-2-oxo-1,3,2-dioxaphosphoranyl)-3-
phe´nyl-propanone (2j)
◦
Solide, M = 324 g/mol, Rdt = 70%, Tf = 144 C. Forme Z : RMN 31P: δ = 21.7.
RMN 1H: δ = 0.77 (m, 3H, CH3–C), 0.80 (m, 3H, CH3–C), 1.18 (m, 2H, C–CH2), 1.51 (m,
2H, C–CH2), 2.79 (d, 2JPH = 24.0 Hz, 2H, P–CH2), 3.52 (d, 4JPH = 3.0 Hz, CH2–C6H5),
3.76–4.15 (mc, 4H, ABCD), 5.23 (s, 2H, NH2), 7.17 (mc, 5H, arom-H). RMN 31C: δ
1
= 7.1 (CH3–C), 7.2 (CH3–C), 23.0 (C–CH2), 22.7 (C–CH2), 25.0 (d, JPC = 133.6 Hz,
P–CH2), 34.5 (d, 3JPC = 9.0 Hz, –C–), 43.9 (d, 3JPC = 3.0 Hz, CH2–C6H5), 72.9 (d, 2JPC
= 6.8 Hz, CH2–O–P), 126–129 (CH-arom), 135 (d, 4JPC = 2.3 Hz, C-i), 143.4 (d, 2JPC
=
1
10.6 Hz, CN). Forme E: RMN 31P: δ = 21.6. RMN H: δ = 0.75 (m, 3H, CH3–C), 0.73
2
(m, 3H, CH3–C), 1.28 (m, 2H, C–CH2), 1.38 (m, 2H, C–CH2), 2.76 (d, JPH = 21.0 Hz,
2H, P–CH2), 3.66 (d, 4JPH = 3.0 Hz, CH2–C6H5), 3.76–4.15 (m, 4H, ABCD), 5.61 (s, 2H,
NH2), 7.17 (mc, 5H, arom-H). RMN 13C: δ = 7.0 (CH3–C), 7.2 (CH3–C), 22.6 (C–CH2),
23.1 (C–CH2), 33.0 (d, 1JPC = 132.8 Hz, P–CH2), 37.4 (d, 3JPC = 9.0 Hz, –C–), 44.3 (d,
3JPC = 3.0 Hz, CH2–C6H5), 72.7 (d, 2JPC = 6.8 Hz, CH2–O–P), 126.0–129.6 (CH-arom),
136.2 (d, 4JPC = 1.5 Hz, C-i), 143.8 (d, 2JPC = 11.3 Hz, CN).
Hydrazone de la N-Phe´nyl-1-(5,5-die´thyl-2-oxo-1,3,2-
dioxaphosphoranyl)-propanone (2k)
◦
Solide, M = 324 g/mol, Rdt = 83%, Tf = 135 C. Forme Z : RMN 31P: δ = 21.3.
1
RMN H: δ = 0.73 (m, 3H, CH3–C), 0.75 (m, 3H, CH3–C), 1.30 (m, 2H, C–CH2), 1.31
(m, 2H, C–CH2), 2.04 (d, 3JPH = 3.0 Hz, CH3–CN), 2.97 (d, 2JPH = 24.0 Hz, 2H, P–CH2),
3.85–4.22 (m, 4H, ABCD), 7.17 (mc, 5H, arom-H), 7.50 (s, 1H, NH). RMN 13C: δ = 6.9
1
(CH3–C), 7.0 (CH3–C), 22.5 (C–CH2), 23.1 (C–CH2), 25.0 (CH3–CN), 29.0 (d, JPC
=
3
2
132.8 Hz, P–CH2), 37.6 (d, JPC = 5.3 Hz, –C–), 73.0 (d, JPC = 6.0 Hz, CH2–O–P),
113.0–128.6 (CH-arom), 136.9 (d, 5JPC = 11.3 Hz, C-i), 145.8 (d, 2JPC = 10.6 Hz, CN).
Forme E: RMN 31P: δ = 21.6. RMN 1H: δ = 0.75 (m, 3H, CH3–C), 0.78 (m, 3H, CH3–C),
3
1.42 (m, 2H, C–CH2) 1.43 (m, 2H, C–CH2), 1.95 (d, JPH = 3.0 Hz, CH3–CN), 2.94 (d,
2JPH = 21.0 Hz, P–CH2), 3.85–4.22 (m, 4H, ABCD), 7.00 (s, 1H, NH). RMN 13C: δ =
7.09 (CH3–C), 7.11 (CH3–C), 22.8 (C–CH2), 23.1 (C–CH2), 25.0 (CH3–CN), 35.0 (d, 1JPC
3
2
= 132.1 Hz, P–CH2), 37.4 (d, JPC = 6.0 Hz, –C–), 73.2 (d, JPC = 6.0 Hz, CH2–O–P),
112–120 (CH-arom), 138.3 (d, 5JPC = 12.8 Hz, C-i), 145.0 (d, 2JPC = 10.6 Hz, CN).
Hydrazone de la N-Phe´nyl-1-(5,5-die´thyl-2-oxo-1,3,2-
dioxaphosphoranyl)-3-phe´nyl-propanone (2l)
◦
Solide, M = 400 g/mol, Rdt = 70%, Tf = 104 C. Forme Z : RMN 31P: δ = 21.2.
1
RMN H: δ = 0.77 (m, 3H, CH3–C), 0.72 (m, 3H, CH3–C), 1.30 (m, 2H, C–CH2), 2.80
(d, 2JPH = 21.0 Hz, 2H, P–CH2), 3.62 (d, 4JPH = 3.0 Hz, CH2–C6H5), 3.63–4.13 (m, 4H,
ABCD), 7.00 (mc, arom-H), 8.58 (s, 1H, NH). RMN 31C: δ = 6.9 (CH3–C) 7.1 (CH3–C),

620
N. SALAH ET AL.
22.6 (C–CH2), 23.1 (C–CH2), 26.6 (d, 2JPC = 134.3 Hz, P–CH2), 37.4 (d, 3JPC = 5.3 Hz,
–C–), 44.8 (d, 3JPC = 3.0 Hz, CH2–C6H5), 73.0 (d, 2JPC = 6.0 Hz, CH2–O–P), 113.6–129.4
5
5
(CH-arom), 137.1 (d, JPC = 2.3 Hz, C-i), 139.1 (d, JPC = 12.0 Hz, N–C=arom), 146.3
(CN). Forme E: RMN 31P: δ = 20.9. RMN H: δ = 0.75 (m, 3H, CH3–C), 0.78 (m, 3H,
1
CH3–C), 1.41 (m, 2H, C–CH2), 2.92 (d, 2JPH = 21.0 Hz, P–CH2), 3.71 (d, 4JPH = 3.0 Hz,
CH2–C6H5), 3.63–4.13 (m, 4H, ABCD), 7.20 (mc, 5H, arom-H), 8.00 (s, 1H, NH). RMN
13C: δ = 7.1 (CH3–C), 8.5 (CH3–C), 22.9 (C–CH2), 33.3 (d, JPC = 131.3 Hz, P–CH2),
2
3
2
35.4 (d, JPC = 5.0 Hz, –C–), 45.8 (CH2–C6H5), 73.3 (d, JPC = 6.8 Hz, CH2–O–P),
113.0–129.2 (CH-arom), 134.8 (–C=), 138,0 (d, 5JPC = 11.3 Hz, N–C=arom), 145.1 (CN).
Hydrazone de la N-Carbe´thoxy-1-(5,5-die´thyl-2-oxo-1,3,2-
dioxaphosphoranyl)-propanone (2m)
◦
Solide, M = 320 g/mol, Rdt = 74%, Tf = 102 C. Forme Z: RMN 31P: δ = 19.8.
1
RMN H: δ = 0.69 (m, 3H, CH3–C), 0.71 (m, 3H, CH3–C), 1.15 (m, 2H, C–CH2), 1.15
4
(m, 2H, C–CH2), 1.32 (m, 3H, CH3–C–O), 1.98 (d, JPH = 3.0 Hz, CH3–CN), 2.90 (d,
2JPH = 21.0 Hz, P–CH2), 3.87–4.20 (m, 6H, ABCD et O–CH2), 9.12 (s, 1H, NH). RMN
13C: δ = 6.89 (CH3–C), 6.91 (CH3–C), 14.4 (O–C–CH3), 22.4 (C–CH2), 22.5 (C–CH2)
1
3
25.1 (CH3–CN), 29.0 (d, JPC = 130.6 Hz, P–CH2), 37.3 (d, JPC = 6.0 Hz, –C–), 61.4
(O–CH2) 73.5 (d, 2JPC = 6.0 Hz, CH2–O–P), 145.2 (CN), 155.0 (C=O). Forme E: RMN
31P: δ = 19.3. RMN H: δ =0.74 (m, 3H, CH3–C), 0.76 (m, 3H, CH3–C), 1.14 (m,
1
4
2H, C–CH2), 1.14 (m, 2H, C–CH2), 1.41 (m, 3H, CH3–C–O), 1.90 (d, JPH = 3.0 Hz,
2
CH3–CN), 2.89 (d, JPH = 24.0 Hz, P–CH2), 3.87–4.20 (m, 6H, ABCD et O–CH2),
8.29 (s, 1H, NH). RMN 13C: δ = 6.8 (CH3–C), 7.0 (CH3–C), 16.2 (CH3–C–O), 22.4
(C–CH2), 22.7 (C–CH2), 25.1 (CH3CN), 34.9 (d, 1JPC = 130.6 Hz, P–CH2) 37.5 (d, 3JPC
=
2
5.3 Hz, –C–), 61.5 (O–CH2), 73.3 (d, JPC = 6.8 Hz, CH2–O–P), 145.1 (–C=N), 154.0
(C=O).
Hydrazone de la N-Carbe´ttoxy-1-(5,5-die´thyl-2-oxo-1,3,2-
dioxaphosphoranyl)-3-phe´nyl-propanone (2n)
◦
Solide, M = 396 g/mol, Rdt = 82%, Tf = 136 C. Forme Z: RMN 31P: δ = 20.0.
RMN 1H: δ = 0.80 (m, 3H, CH3–C), 0.82 (m, 3H, CH3–C), 1.28 (m, 3H, CH3–C–O), 1.33
2
(m, 2H, C–CH2), 2.78 (d, JPH = 24.0 Hz, P–CH2), 3.72 (s, 2H, CH2–C6H5), 4.04–4.27
(m, 4H, CH2–O–P et O–CH2), 7.26 (mc, 5H, arom-H), 9.55 (s, 1H, NH). RMN 13C: δ =
7.1 (CH3–C), 6.9 (CH3–C), 14.5 (CH3–C–O), 22.6 (C–CH2), 23.0 (C–CH2) 26.8 (d, 1JPC
3
= 132.8 Hz, P–CH2), 37.4 (d, JPC = 6.0 Hz, –C–), 44.9 (CH2–C6H5), 61.6 (O–CH2),
2
73.2 (d, JPC = 6.8 Hz, CH2–O–P), 127.0–129.5 (CH-arom), 136.0 (–C=arom), 145.8
2
1
(d, JPC = 10.6 Hz, CN), 155.1 (C = O). Forme E: RMN 31P: δ = 19.0. RMN H: δ
= 0.77 (m, 3H, CH3–C–), 0.79 (m, 3H, CH3–C–), 1.18 (m, 3H, CH3–C–O), 1.55 (m,
2
2H, C–CH2), 2.99 (d, JPH = 21.0 Hz, 2H, P–CH2), 3.69 (s, 2H, CH2–C6H5), 4.04–4.27
(m, 6H, ABCD et O–CH2), 7.26 (mc, 5H, arom-H), 8.19 (s, 1H, NH). RMN 13C δ = 8.6
(CH3–C), 9.1 (CH3–C), 15.2 (CH3–C–O), 22.5 (C–CH2), 33.9 (d, 1JPC = 233.2 Hz, P–CH2),
3
2
35.4 (d, JPC = 6.0 Hz, –C–), 44.9 (CH2–C6H5), 61.6 (O–CH2), 73.7 (d, JPC = 6.8 Hz,
CH2–O–P), 128.5–129.5 (CH-arom), 136.0(–C=arom), 145.8(d, 2JPC = 10.6Hz, CN), 155.1
(C=O).

SYNTHESE ET ETUDE CONFORMATIONNELLE PAR RMN (1H, 13C, 31P)
621
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