Scope and limitation of the reactions of 3-imino derivatives of pentane-2,4-diones with organophosphorus reagents

Article abstract of DOI:10.1080/10426507.2011.642432

3-(Hydroxyimino)pentane-2,4-dione reacts with phosphonium ylides, Wittig-Horner reagents, trialkyl phosphites, and Lawesson's reagents to give the olefinic and cyclic products, the phosphonate adducts, the dialkyl phosphate products, the phosphinodithioic acid, and 2,4-dithione products, respectively. Furthermore, the reaction of 3-(phenylimino)pentane-2,4-dione with Wittig, Wittig-Horner reagents and trialkyl phosphite resulted in the formation of 2,5-diendioate, diethoxy phosphoryl hexanoate and the phosphate products. Possible reaction mechanisms are considered and the structural assignments are based on analytical and spectroscopic results. The antibacterial and antifungal activities for some of the new compounds are also reported. Copyright

Full text of DOI:10.1080/10426507.2011.642432

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Phosphorus, Sulfur, and Silicon and the
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Scope and Limitation of the Reactions
of 3-Imino Derivatives of Pentane-2,4-
Diones with Organophosphorus Reagents
Leila S. Boulos a , Hoda A. Abdel-Malek a , Naglaa F. El-Sayed a
Maysa E. Moharam b
&
a Department of Organometallic and Organometalloid Chemistry ,
NRC , Dokki , Cairo , Egypt
b Department of Microbial Chemistry , NRC , Dokki , Cairo , Egypt
Accepted author version posted online: 04 Jan 2012.Published
online: 05 Apr 2012.
To cite this article: Leila S. Boulos , Hoda A. Abdel-Malek , Naglaa F. El-Sayed & Maysa E. Moharam
(2012) Scope and Limitation of the Reactions of 3-Imino Derivatives of Pentane-2,4-Diones with
Organophosphorus Reagents, Phosphorus, Sulfur, and Silicon and the Related Elements, 187:6,
697-710, DOI: 10.1080/10426507.2011.642432
To link to this article: http://dx.doi.org/10.1080/10426507.2011.642432
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Phosphorus, Sulfur, and Silicon, 187:697–710, 2012
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2011.642432
SCOPE AND LIMITATION OF THE REACTIONS OF
3-IMINO DERIVATIVES OF PENTANE-2,4-DIONES
WITH ORGANOPHOSPHORUS REAGENTS
Leila S. Boulos,1 Hoda A. Abdel-Malek,1 Naglaa F. El-Sayed,1
and Maysa E. Moharam2
1Department of Organometallic and Organometalloid Chemistry, NRC, Dokki,
Cairo, Egypt
2Department of Microbial Chemistry, NRC, Dokki, Cairo, Egypt
GRAPHICAL ABSTRACT
O
O
CH3
OH
CH3
N
O
O
P
R1
OR1
OR1
CH3
R1O
R2
O
OR1
OR1
N
P
OH CH3
O
12a, R1=CH3
b, R1= C2H5
1 =C2H5, R2=OC2H5
10a,
R
10b,R1=CH3, R2 = OCH3
O
O
OH CH3
S
O
P
N
O
R2
CH3
O
CH3
CH3
OR1
SH
N
P
H3C
O
O
OR1
13
16, R1 = C2H5
R2= OC2H5
Abstract 3-(Hydroxyimino)pentane-2,4-dione reacts with phosphonium ylides, Wittig–Horner
reagents, trialkyl phosphites, and Lawesson’s reagents to give the olefinic and cyclic products,
the phosphonate adducts, the dialkyl phosphate products, the phosphinodithioic acid, and
2,4-dithione products, respectively. Furthermore, the reaction of 3-(phenylimino)pentane-2,4-
dione with Wittig, Wittig–Horner reagents and trialkyl phosphite resulted in the formation of
2,5-diendioate, diethoxy phosphoryl hexanoate and the phosphate products. Possible reaction
mechanisms are considered and the structural assignments are based on analytical and spec-
troscopic results. The antibacterial and antifungal activities for some of the new compounds
are also reported.
Keywords 3-Substituted pentane-2,4-diones; alkyl phosphites; ylides; Wittig–Horner reagents;
Lawesson’s reagent
Received 27 September 2011; accepted 12 November 2011.
Address correspondence to Leila S. Boulos, Department of Organometallic and Organometalloid Chemistry,
NRC, Dokki, Cairo, Egypt. E-mail: leilagoubran@yahoo.com
697

698
L. S. BOULOS ET AL.
INTRODUCTION
Several different nitrogen—containing heterocycles such as oxazolines, ox-
azines, and isoquinolines were synthesized directly from the reaction of α-
benzoinmonoxime with stabilized—and reactive ylides.1 Furthermore, the reaction
of 2-phenylimino–1,2,3–indantrione with phosphonium ylides gave the new phosphorane
products.2 Recently, several nitrogen containing heterocycles were synthesized from
the reaction of triketoindane-2-oxime with different types of phosphoryl carbanions.3
In view of this and in continuation of our work in organophosphorus chemistry,4–12
it was of considerable interest to investigate the behavior of 3-(hydroxyimino)-(1a),
3-(phenylimino)pentane-2,4-diones (1b) toward phosphonium ylides 2a–d, Wittig–Horner
reagents 3a–c, trialkyl phosphites 4a, b, and Lawesson’s reagents 5a, b (Scheme 1). The
purpose of this study was to determine the preferential site of attack by these reagents and
to synthesize new phosphonate adducts with anticipated biological activities.
O
O
Ph3P=CHCOR
Ph3P=N-Ph
CH3
CH3
X
2a, R= OC2H5
b, R= OCH3
c, R= CH3
2d
1a, X= NOH
, X= N-Ph
b
(R1O)2P(O)CH2R2
R1
R1
O
4a, R1=CH3
b, R1= C2H5
3a, R1= C2H5, R2 = COOC2H5
b, R1= CH3, R2 = COOCH3
c, R1= C2H5, R2 = CN
OR1
P:
O
S
S
Ar
P
P
S
Ar
S
5 a, Ar = 4 - H3COC6H5
b, Ar = S - C6H5
(also named Japanese reagent)
Scheme 1
RESULTS AND DISCUSSION
We have found that 3-(hydroxyimino)pentane-2,4-dione (1a) reacted with two mol
equivalents of ethoxycarbonylmethylenetriphenylphosphorane (2a) in refluxing toluene to

SCOPE AND LIMITATION OF THE REACTIONS OF 3-IMINO DERIVATIVES
699
give chromatographically pure adducts formulated as ethyl-4-(hydroxyimino)-3-methyl-5-
oxohex-2-enoate (6a) (25% yield), and 3-acetyl-4-methyl-6H-1,2-oxazin-6-one (7) (65%,
yield). Triphenylphosphane oxide was also isolated from the reaction medium and identified
(Scheme 2).
O
H3C
O
N
Ph3P=CHCOR
O
CH3
Ph3P=O
+
+
CH
C
H3C
2a, R= OC2H5
2b, R= OCH3
O
CH3
N
O
OH
6a, R=OC2H5
R
7
-
RH
6b, R= OCH3
O
CH3
O
O
O
NOH
1a
PH3P=CHCOCH3
CH3
H3C
+
Ph3P=O
H3C
CH3
2c
NOH
8
O
CH3
Ph3P=O
+
PH3P=N-Ph
H3C
N
2d
NOH
9
Scheme 2
Similarly, methoxycarbonylmethylenetriphenylphosphorane (2b) reacts with (1a)
(2b:1a = 2:1), in refluxing toluene to give products 6b (30% yield) and 7 (60% yield).
Triphenylphosphane oxide was also isolated from the reaction mixture (Scheme 2).
Structures 6a, 6b, and 7 were deduced from correct microanalysis, IR, 1H, 13C NMR,
and mass spectral (MS) data (cf. Experimental). We propose the reaction course depicted in
Scheme 2. The reaction was assumed to form the olefinic compounds 6a, b with expulsion
of triphenylphosphane oxide. Then, the reaction was accompanied by elimination of one
molecule of alcohol under the applied reaction conditions to afford the cyclic 3-acetyl-4-
methyl-6H-1,2-oxazin-6-one (7). Worthy to mention is that only one isomer of 6a and 6b
was isolated. The course of cyclization of 6a and 6b to 7 suggested the cis isomer since the
cyclization process occurs only in case of E-isomer.13 Furthermore, when 6a or 6b were
heated in refluxing xylene for 4 h, product 7 was obtained in 75% yield.
Next, when 1a was treated with 1 mol equivalent of acetylmethylenetriphenyl-
phosphorane (2c) in refluxing toluene for 8 h, product 8 along with triphenylphosphane

700
L. S. BOULOS ET AL.
oxide were isolated from the reaction medium (Scheme 2). Compound 8 was obtained
irrespective of whether one or two mol equivalents of 2c were used. Structural elucidation
of 5-(hydroxyimino)-4-methylhept-3-ene-2,6-dione (8) is based upon elemental and spec-
1
troscopic data (IR, H, 13C, 31P–NMR and MS, cf. Experimental). When 1a was allowed
to react with 1 mol equivalent of N-(triphenylphosphoranylidene)aniline (2d) in reflux-
ing toluene for 3 h, product 9 was isolated in 80% yield. Triphenylphosphane oxide was
also isolated from the reaction mixture and identified. The structure of 3-(hydroxyimino)-4-
(phenylimino)pentane-2-one (9) was deduced on the basis of elemental analysis and spectral
studies (Scheme 2, cf. Experimental). In addition, the reaction of 3-(hydroxyimino)pentane-
2,4-dione (1a) with Wittig–Horner reagents 3a–b was studied too. When 1a was treated
with 1 mol equivalent of triethylphosphonoacetate (3a), in the presence of alcoholic sodium
ethoxide solution at reflux temperature for 2 h, adduct 10a was isolated (Scheme 3).
O
O
CH3
OH
(R1O)2P(O)CH2COR2
CH3
R1O
R2
3a, R1=C2H5, R2 =OC2H5
b, R1=CH3, R2=OCH3
OR1
OR1
N
P
O
1 =C H , R2=
OC2H5
2 5
10a,
R
10b,R1=CH3, R2 = OCH3
O
O
NOH
1a
CH3
CH3
NOH
(C2H5O)2P(O)CH2CN
O
NC
CN
+ (C2H5O)2P-H
3c
CH3
CH3
11
Scheme 3
The structure of methyl 2-(diethoxyphosphoryl)-3-hydroxy-4-(ethoxyimino)-3-
1
methyl-5-oxohexanoate (10a) was assigned from its analysis, IR, H, 13C, 31P NMR, and
MS data. The Infrared (IR) spectrum of 10a revealed the presence of strong absorption
bands at 3498 cm−1 (OH), 1252 cm−1 (P O),14 1129 cm−1 (P O C2H5), and 1739 cm−1
(C O, ester), 1683 cm−1 (COCH3). The product 10a possesses a positive shift in its 31P
NMR spectrum (δ = 20.2, 85% H3PO4) and absorbs in the region characteristic for this
class of compounds.15–17 The structure of compound 10a was also confirmed from its 1H,
13C–NMR, and MS data, cf. Experimental). Similarly, trimethylphosphonoacetate (3b) re-
acts with 1a in the presence of methanolic sodium methoxide solution at reflux temperature
for 3 h to give methyl 2-(dimethoxyphosphoryl)-3-hydroxy-4-(methylimino)-3-methyl-5-
oxohexan-oate 10b in 75% yield (Scheme 3). Due to the bulky of the phosphonate groups

SCOPE AND LIMITATION OF THE REACTIONS OF 3-IMINO DERIVATIVES
701
in compound 10a, b, trans configuration was suggested. The spectroscopic data of product
10b were in good agreement with the proposed structure (cf. Experimental).
Moreover, when 3-(hydroxyimino)pentane-2,4-dione (1a) was treated with 2 mol
equivalent of diethyl(cyanomethylene)phosphonate (3c) in the presence of ethanolic sodium
ethoxide solution at 60–70 ◦C for 5 h, adduct 11 was isolated in good yields (Scheme 3).
The structure of 4-(hydroxyimino)-3,5-dimethylhepta-2,5-dienedinitrile (11) was deduced
from its analysis, IR, 1H, 13C NMR, and MS data (cf. Experimental).
The reaction of 1a with trialkyl phosphites was also investigated. We have found that
the reaction with trimethyl-(4a) and/or triethyl (4b) phosphites in refluxing benzene gave
dimethyl(3-(methyl(hydroxyl)amino-4-oxopent-2-en-2-yl) phosphate 12a and diethyl(3-
(ethyl(hydroxy)amino)-4-oxopent-2-en-2-yl) phosphate 12b. This is simply explained of
initial nucleophilic attack by phosphorus on the carbonyl oxygen, forming zwitterion in-
termediate of which undergo intramolecular alkyl group transfer to yield products 12a and
12b, respectively (Scheme 4).18,19 Physical and spectroscopic data in Experimental Section.
CH3
O
O
O
O
P
:P(OR1)3
OR1
OR1
+
R1
O
CH3
CH3
N
NOH
4a, R1=CH3
b, R1= C2H5
OH
CH3
1a
12a, R1=CH3
b, R1= C2H5
Scheme 4
We have also investigated the reaction of 1a with Lawesson’s and Japanese reagents
5a, b. When 3-(hydroxyimino)pentane-2,4-dione (1a) was reacted with Lawesson’s reagent
5a in dry benzene at room temperature for 1 h, the corresponding (((2,4-dioxopentan-3-
ylidene)amino)oxy)(4-methoxyphenyl)phosphinodithioic acid (13) was only obtained in
1
good yield. The elemental microanalysis, H, 13C, 31P NMR, and MS data agreed with
structure 13 (Scheme 5).
The IR spectrum of 13 revealed the absence of =NOH band that appeared in the
starting material at v = 3384 and showed bands at 625 cm−1 (P S), 1654 cm−1 (C N),
1673 cm−1 (2 CH3CO), 2320 cm−1 (SH). The 1H NMR shifts of compound 13 were 2.05
(s, 6H, 2CH3), 3.75 (s, 3H, OCH3), 3.3 (s, 1H, SH, exchangeable with D2O), and 6.94–7.28
(m, 4H, aromatic). The 31P NMR of 13 appeared at δ 18.78 ppm.20 The structure assigned
for 13 was based on 13C NMR spectra that indicates the presence of signals at δ = 55.70
(OCH3), 30.15 (2CH3), 121.5 (P C Ph, d, 1JCP = 115.3 Hz), 132.5 (d, 2C C P, 2JCP
=
22.0 Hz), 113.97 (d, 2C C C P, 3JCP = 15.7 Hz), and 161.86 (C OCH3), corresponding
to the carbon atoms of the methoxy phenyl ring attached to the phosphorous, 143.9 (C N)
and 195.821 (2H3C C O).21 Compound 13 is formed by the addition of oxime 1a to the
monomer of LR followed by migration of a proton to the sulfur anion.22,23 The reaction
of 1a with Japanese reagent 5b was also investigated. We have found that reaction with
Japanese reagent 5b affect thionation of 1a to form 3-(hydroxyimino)pentane-2,4-dithione

702
L. S. BOULOS ET AL.
S
S
P
S
P
Ar
S
O
Ar
P
S
Ar
S
P
N
O
S
O
CH3
Ar =
5a
SH
OCH3-Ph
H3C
O
CH3
13
O
O
H3C
CH3
NOH
1a
S
P
S
P
S
S
S
S
P
S
S
Ph
S
S
Ph
S
Ph
H3C
CH3
NOH
5b
14
Scheme 5
CH3
CH3
2a
C2H5OOC
COOC2H5
-TPPO
N
15
O
O
OH CH3
O
O
3a
CH3
CH3
C2H5
CH3
N
OC2H5
N
P
O
OC2H5
1b
16
O
CH3
O
P
4a
OCH3
OCH3
CH3
O
NH
17
Scheme 6

SCOPE AND LIMITATION OF THE REACTIONS OF 3-IMINO DERIVATIVES
703
(14) as a the sole reaction product (Scheme 5). The spectroscopic data of product 14 were
in good agreement with the proposed structure (cf. Experimental).
Furthermore, this study has been extended to include the reaction of 3-
(phenylimino)pentane-2,4-dione (1b) with phosphonium ylide 2a, Wittig–Horner
reagent 3a, and trialkyl phosphite 4a to establish whether they would behave in a similar
manner. We have found that 3-(phenylimino)pentan-2,4-dione (1b) reacts with one mol
equivalent of 2a in refluxing toluene to give diehyl-3,5-dimethyl-4-(phenylimino)hepta-
2,5-dienedioate (15) in 40% yield. Triphenylphosphane oxide was also isolated and
identified (Scheme 6). When 1b was treated with 2 mol equivalents of 2a in refluxing
toluene, the new olefinic 15 was isolated in a good yield together with triphenylphos-
1
phane oxide. The elemental analysis, IR, H, 13C NMR, spectra and molecular weight
determination (MS) were in good agreement with structure 15 (cf. Experimental).
Moreover, the reaction product of 1b with triethylphosphonoacetate 3a in the presence
of alcoholic sodium ethoxide solution at reflux temperature for 4 h afforded compound 16
on the basis of spectroscopic evidences (Scheme 6, cf. Experimental). Moreover, trimethyl
phosphite 4a reacted with 1b in refluxing toluene to give dimethyl-(4-oxo-3(phenylamino)
pent-2-en-2-yl) phosphate (17) (Scheme 6). The structure of 17 was assigned on the basis
of IR, 1H, 13C, 31P NMR, and MS data (cf. Experimental).
CONCLUSION
From the results of the present investigation, it could be concluded that the reaction
of 3-(hydroxyimino)pentane-2,4-dione 1a and 3-(phenylimino)pentane-2,4-dione 1b with
phosphonium ylide 2a–c proceeds according to the Wittig reaction to give the olefinic
products 6, 8, 9, 15. Moreover, the reaction of 3-substituted-2,4-pentanediones 1a, b with
Wittig–Horner reagents 3 led to different products 10a–b, 11, 16 depending on the nature of
the phosphonate anion used as well as the stability of the addition products. In the reaction
of 1a, 1b with trialkyl phosphites 4a–b, the dialkyl phosphate adducts 12a–b, 17 were
the sole reaction products. The reaction of LR 5a with 1a represents an interesting ap-
proach to the construction of new bioactive compound containing phosphorus and sulfur as
2,4-dioxopentan-3-ylidene)aminooxy)4-methoxyphenyl)phosphinodithioic acid (13). This
finding clearly indicated that Lawesson’s reagent preferentially attacked the =NOH rather
than the carbonyl carbon. On the other hand, Japanese reagent 5b reacted with 1a to give the
dithione product 14 through thionation reaction. These processes can be considered as new
and simple routes for the preparation of different organophosphorus and cyclic compounds
that cannot be obtained by other conventional methods.
BIOLOGICAL EVALUATION OF THE TESTED COMPOUNDS
Biological Screening
The antibacterial and antifungal activities were carried out in the Microbial Chemistry
Department, National Research Centre, using the diffusion plate method.24–27
Antibacterial and Antifungal Activities
Evaluation. [The antimicrobial activity of the tested compounds were examined
against Gram positive bacteria Bacillus subtilis, Bacillus cereus, and Staphylococcus au-
reusand Gram negative bacteria Escherichia coli, Pseudomonas aeruginoseand fungus

704
L. S. BOULOS ET AL.
Candida albicans. The obtained results are compared with reference antibiotics24–27 that
were purchased from Egyptian markets].
Conclusion. All the biologically active compounds exceeds the values of the start-
ing material 1a which means that improvement of compounds takes places raising their
medical value.
EXPERIMENTAL
Melting points were measured by means of an electrothermal melting points appara-
tus. Starting materials 1a, b were prepared according to reference,28,29 respectively. The IR
spectra were measured in KBr pellets with a Perkin–Elmer Infrared Spectrometer Model
157. The 1H and 13C NMR spectra were recorded in CDCl3 or DMSO on a Jeol spectrometer
at 500 and 125 MHz respectively and the chemical shifts were recorded in δ values relative
to tetramethylsilane (TMS) as internal reference. The 31P NMR (200 MHz) spectra were
recorded in CDCl3 or DMSO on a Jeol-500 spectrometer, too. The MS were recorded at
70 eV with a kratosMS equipment or Varian MAT311A Spectrometer. Elemental analyses
were performed using the Elementarvaru EL-Germany Instrument. Their values agreed
favorably with the calculated ones. The using reported yields are of pure isolated materials
obtained by column chromatography silica gel 60 (Merk).
Reaction of Phosphonium Ylide (2a) with
3-(Hydroxyimino)Pentane-2,4-Dione (1a)
A mixture of 1.36 g 2a (4 mmol) and 0.26 g (2 mmol) of 1a in dry toluene (30 mL)
was refluxed for 2 h. The volatile material was evaporated under reduced pressure. The
residue was subjected to silica gel column chromatography to give product 6a [ethyl-4-
(hydroxyimino)-3-methyl-5-oxohex-2-enoate] (6a, C9H13NO4) and product 7 [3-acetyl-4-
methyl-6H-1,2-oxazin-6-one] (7, C7H7NO3). Triphenylphosphane oxide was also isolated
and identified.
◦
6a: Eluent: petroleum ether (60–80 C)/ethyl acetate (90/10, v/v), product 6a was
separated as pale yellow crystals, yield 25%, m.p. 99–101 C. IR [v,KBr, cm−1]: 1653
◦
(C N), 1672 (COCH3), 1720 (CO, ester), 3520 (OH).1H NMR (500 MHz, δ ppm, CDCl3):
1.27 (t, 3H, CH3 ethyl), 2.23 (s, 3H, CH3 C CH), 2.39 (s, 3H, CH3 C O), 4.17 (q,
2H, CH2 ethyl), 5.64 (s, 1H, CH), 8.56 (s, 1H, OH). 13C NMR (125 MHz, δ ppm, CDCl3):
14.1 (CH3 C CH), 17.5 (CH3, ethyl), 25.9 (CH3 C O), 60.4 (CH2, ethyl), 121.6 (CH),
145.9 (C N), 158.8 (C C), 165.7 (C O, ester), 195.4 (CH3 C O). MS m/z (%) 199
[M+] (100), 154 [M+-OC2H5] (30), 126 [M+-COOC2H5] (40). Anal. Calcd for C9H13NO4
(199.2): C, 54.26; H, 6.58; N, 7.03. Found: C, 54.66; H, 6.56; N, 7.2.
7: Eluent: petroleum ether (60–80 ◦C)/ethyl acetate (95/5, v/v), product 7 was sep-
◦
arated as pale yellow crystals, yield 65% and m.p. 85–86 C. IR [v, KBr, cm−1]: 1658
(C N), 1680 (CO), 1737(CO, lactone). 1H NMR (500 MHz, δ ppm, CDCl3): 2.38 (s, 3H,
CH3 C CH) 2.60 (s, 3H, CH3 C O), 6.47 (s, 1H, CH). 13C NMR (125 MHz, δ ppm,
CDCl3): 14.8 (CH3), 29.77 (CH3 C O), 122.7(C C), 147.4 (C N), 166.3 (C CH3),
169.9 (C O, lactone), 195.3 (C O). MS m/z (%) 153 [M+] (100), 110 [M+-COCH3] (40).
Anal. Calcd for C7H7NO3 (153.14): C, 54.90; H, 4.61; N, 9.15. Found: C, 54.63; H, 4.31;
N, 9.33.

SCOPE AND LIMITATION OF THE REACTIONS OF 3-IMINO DERIVATIVES
705
Reaction of Phosphonium Ylide 2b
with 3-(Hydroxyimino)Pentane-2,4-Dione (1a)
A mixture of 1.32 g 2b (4 mmol) and 0.26 g (2 mmol) of 1a in dry toluene (30 mL)
was refluxed for 4 h. The volatile material was evaporated under reduced pressure. The
residue was subjected to silica gel column chromatography to give product 6b methyl-4-
(hydroxyimino)-3-methyl-5-oxohex-2-enoate (6b, C8H11NO4) (elution of the column with
◦
petroleum ether (60–80 C)/ethyl acetate (90/10, v/v) and product 7 3-acetyl-4-methyl-
6H-1,2- oxazin-6-one (7, C7H7NO3) (elution of the column with petroleum ether (60–80
◦C)/ethyl acetate (95/5, v/v), (mixed melting points and comparative IR spectra with au-
thentic samples previously obtained). Triphenylphosphane oxide was also isolated and
identified. When compound 6a or 6b were heated in refluxing xylene for 4 h, compound 7
was obtained in good yield via expulsion of alcohol.
◦
6b: Eluent: petroleum ether (60–80 C)/ethyl acetate (90/10, v/v), product 6b was
separated as pale yellow crystals, yield 30%, m.p. 147–149 C. IR [v, KBr, cm−1]: 1678
◦
(COCH3), 1728 (CO, ester), 3527 (OH). 1H NMR (500 MHz, δ ppm, CDCl3): 1.60 (s, 3H,
CH3C C), 2.40 (s, 3H, CH3 C O), 3.72 (s, 3H, OCH3), 5.63 (s, 1H, CH), 8.58 (s, 1H,
OH). 13C NMR (125 MHz, δ ppm, CDCl3): 14.8 (CH3 C CH), 26.9 (CH3 C O),
52.6 (OCH3), 122.0 (CH), 145.4b (C N), 159.0 (C C), 166.5 (C O, ester), 195.3
(CH3 C O). MS m/z (%) 185 [M+] (100), 154 [M+-OCH3] (35), 126 [M+-COOCH3]
(53). Anal. Calcd for C8H11NO4 (185.18): C, 51.89; H, 5.99; N, 7.56. Found: C, 51.99; H,
5.63; N, 7.27.
Reaction of Acetylmethylenetriphenylphosphorane (2c)
with 3-(Hydroxyimino)Pentane-2,4-Dione (1a)
A mixture of 0.6 g 2c (2 mmol) and 0.26 g (2 mmol) of 1a in dry toluene (30 mL) was
refluxed for 8 h. The volatile material was evaporated under reduced pressure. The residue
was subjected to silica gel column chromatography to give product 8 [5-(hydroxyimino)-4-
methylhept-3-ene-2,6-dione] (8, C8H11NO3). Triphenylphosphane oxide was also isolated
and identified.
Eluent: petroleum ether (60–80 ◦C)/ethyl acetate (90/10, v/v), product 8 was separated
as colorless crystals, yield 85%, m.p. 110–111 ◦C. IR [v, KBr, cm−1]: 1653 (C N), 1681
(COC C), 1684 (CO C N), 3518 (OH). 1H NMR (500 MHz, δ ppm, CDCl3): 2.19 (s, 3H,
CH3COCH), 2.26 (s, 3H, CH3 C CH), 2.39 (s, 3H, CH3COCN), 6.00 (s, 1H, CH), 8.22 (s,
1H, OH). 13C NMR (125 MHz, δ ppm, CDCl3): 17.8 (CH3 C C), 26.0 (CH3 C O), 32.2
(CH3COCN), 128.0 (CH), 143.7 (C N), 159.0 (C C), 195.3(C OCH3), 198.4 (COC C).
MS m/z (%) 169 [M+] (100), 127 [M+-COCH3] (32).Anal. Calcd for C8H11NO3 (169.18):
C, 56.80; H, 6.55; N, 8.28. Found: C, 56.62; H, 6.22; N, 8.43.
Reaction of N-(Triphenylphosphoranylidene) Aniline (2d)
with 3-(Hydroxyimino)-Pentane-2,4-Dione (1a)
A mixture of 0.7 g (2 mmol) of 2d and 0.26 g (2 mmol) of 1a was refluxed 3 h in 30
mL dry toluene. The volatile material was evaporated under reduced pressure. The residue
was subjected to silica gel column chromatography to give product 9 [3-(hydroxyimino)-4-
(phenylimino)pentan-2-one] (9, C11H12N2O2). Triphenylphosphane oxide was also isolated
and identified.
◦
Eluent: petroleum ether (60–80 C)/ethyl acetate (90/10,v/v), product 9 was sepa-
rated as colorless crystals yield, 87%, m.p. 219–221 ◦C. IR [v, KBr, cm−1]: 1655 (2C N),

706
L. S. BOULOS ET AL.
1680 (COCH3), 3523 (OH). 1H NMR (500 MHz, δ ppm, CDCl3): 2.43 (s, 3H, CH3CNPh),
2.45 (s, 3H, CH3CO), 7.61(m, 5H, aromatic), 8.60 (s, 1H, OH).13C NMR (125 MHz, δ
ppm, CDCl3): 26.1 (CH3 C N), 31.4(CH3C O), 118,122,124,128,129 (aromatic car-
bon), 140.2 (C NOH), 153.1 (C N Ph), 192.0 (C OCH3). MS m/z (%) 204 [M+] (100),
127 [M+-Ph] (30). Anal. Calcd for C11H12N2O2 (204.23): C, 64.69; H, 5.92; N, 13.72.
Found: C, 64.99; H, 5.73; N, 14.02.
Reaction of Triethoxyphosphonate (3a) with
3-(Hydroxyimino)Pentane-2,4-Dione (1a)
A solution of sodium ethoxide (0.136 g, 2 mmol) in absolute ethanol (30 mL) was
treated with an equimolar amount of triethoxyphosphonate (3a) (0.44 g, 2 mmol) then
1 mol of 1a (0.26 g, 2 mmol) was added and the resulting reaction mixture was refluxed for
2 h (TLC). Then, poured on a small amount of water, extracted with ethyl acetate, dried and
the extracts were evaporated under reduced pressure. The residue was applied to silica gel
column chromatography to give product 10a [methyl 2-(diethoxyphosphoryl)-3-hydroxy-
4-(ethoxyimino)3-methyl-5-oxo-hexanoate] (10a, C15H28NO8P).
◦
Eluent: petroleum ether (60–80 C) : ethyl acetate (60/40, v/v), product 10a was
separated as pale yellow crystals, yield (71%), m.p. 212–214 ◦C. IR (v, KBr, cm−1): 1129
1
(P O C2H5), 1252 (P O),14 1683 (COCH3), 1739 (C O, ester), 3498(OH). H NMR
(500 MHz, δ ppm, CDCl3): 1.03 (t, 3H, NOCH2CH3), 1.04, 1.05 (2t, 6H, PO(OCH2CH3)2,
JHP = 11.0 Hz), 1.10 (t, 3H, COOCH2CH3), 2.68 (s, 3H, CH3C OH), 2.72 (s, 3H, CH3CO),
3.40 (s, 1H, OH, exchangeable with D2O), 3.35 (q, 2H, CH2, NOCH2CH3),3.47 (d, 1H, CH,
2JHP = 18.0 Hz), 3.85, 3.87 (2q, 2CH2, P O(OCH2CH3)2), 3.88 (q, 2H, COOCH2CH3).
13C NMR (125 Hz, δ ppm,CDCl3): 14.4 (s, CH3CH2ON), 15.3 (s,CH3CH2COO), 16.1, 16.3
(d, 3JCP = 11.0 Hz(CH3CH2O)2P O), 22.3 (d, 3JCP = 10.0 Hz, CH3COH), 33.7 (CH3CO),
2
1
51.2(C OH, d, JCP = 23.0 Hz), 52.3 (CHPO, JCP = 105.0 Hz), 61.7(COOCH2CH3),
62.6, 62.6 ((CH3CH2O)2PO), 63.4 (C NOCH2CH3), 148.2 (CN), 167.5 (C O, ester)
195.0 (COCH3). 31P NMR (125 MHz, δ ppm, CDCl3): 20.2. MS m/z (%): 381 [M+] (100).
Anal. Calcd for C15H28NO8P (381.36): C, 47.24; H, 7.40; N, 3.67; P, 8.12, Found: C, 46.98;
H, 7.73; N; 4.00; P, 8.33.
Reaction of Trimethoxyphosphonate 3b with
3-(Hydroxyimino)Pentane-2,4-Dione (1a)
A solution of sodium methoxide (0.108 g, 2 mmol) in absolute methanol (30 mL) was
treated with an equimolar amount of trimethyoxyphosphonate (3b) (0.36 g, 2 mmol) then
1 mol of 1a (0.26 g, 2 mmol) was added and the resulting reaction mixture was refluxed
for 3 h (TLC). Then, poured on a small amount of water, extracted with ethyl acetate,
dried, and the extracts were evaporated under reduced pressure. The residue was applied to
silica gel column chromatography to give product 10b [methyl 2-(dimethoxyphosphoryl)-
3-hydroxy-4-(methoxyimino) 3-methyl-5-oxohexanoate] (10b, C11H20NO8P).
◦
Eluent: petroleum ether (60–80 C): ethyl acetate (60:40, v:v), product 10b was
separated as pale yellow crystals, yield (75%), m.p. 205–206 ◦C. IR (v, KBr, cm−1): 1129
1
(P O CH3), 1252 (P O),14 1688 (COCH3), 1742(C O, ester), 3502 (OH). H NMR
(500 MHz, δ ppm,CDCl3): 2.33 (s, 3H, CH3C OH), 2.96 (s, 3H, CH3CO), 3.00 (s, 1H,
OH, exchangeable with D2O), 3.70 (s, 3H, CH3COO), 3.73 (s, 3H, NOCH3), 3.78 (d, 1H,

SCOPE AND LIMITATION OF THE REACTIONS OF 3-IMINO DERIVATIVES
707
CH, 2JHP = 18.0 Hz), 3.80, 3.85 (2d, 6H, JHP = 11.0 Hz, P O(OCH3)2). 13C NMR (125
Hz, δ ppm, CDCl3): 14.7 (CH3COH), 26.7 (CH3CO), 51.7 (s, CH3ON), 51.2 (C OH,
2
1
2
d, JCP = 23.0 Hz), 52.3 (CHP O, JCP = 102.0 Hz), 52.86, 52.9 ((CH3O)2PO, JCP
=
22.3 Hz), 150.6 (C N), 166.1 (C O, ester), 196.3 (COCH3); 31P NMR (125 Hz, δ ppm,
CDCl3): 20.2. MS m/z (%) 325 [M+] (100). Anal. Calcd for C11H20NO8P (325.25): C,
40.62; H, 6.20; N, 4.31; P, 9.52, Found: C, 40.22; H, 6.25; N; 3.98; P, 9.19.
Reaction of Diethyl (Cyanomethylene)Phosphonate (3c)
with 3-(Hydroxyimino)Pentane-2,4-Dione (1a)
A solution of sodium ethoxide (0.136 g, 2 mmol) in absolute ethanol (30 mL) was
treated with an equimolar amount of diethyl(cyanomethylene)phosphonate (3c) (0.35 g,
2 mmol) then 1a (0.13 g◦, 1 mmol) was added and the resulting reaction mixture was
refluxed for 5 h at 60–70 C (TLC). Then, poured on a small amount of water, extracted
with ethyl acetate, dried, and concentrated under reduced pressure. The precipitate was
filtered off and recrystallized from benzene to afford product 11 [4-(hydroxyimino)-3,5-
dimethyl-hepta-2,5-dienedinitrile] (11,C9H9N3O).
Crystallized from benzene, 11 as colorless crystals, yield 85%, m.p. 145–147 ◦C. IR
1
[v, KBr, cm−1]: 2228 (C N), 3502 (OH). H NMR (500 MHz, δ ppm, CDCl3): 2.31 (s,
6H, 2CH3), 5.85 (s, 2H, 2CH), 6.21 (s, 1H, OH).13C NMR (125 MHz, δ ppm, CDCl3):
22.4 (2CH3), 112.4 (2CH), 123.04 (2C N), 158.2 (2C C), 170.0 (C N). MS m/z (%) 174
[M+] (100), 149 [M+-CN] (32), 122 [M+-2C N). Anal. Calcd for C9H9N3O (175.19): C,
61.7; H, 5.18; N, 23.99. Found: C, 62.01; H, 5.37; N, 23.83.
General Procedure for the Reaction of Trialkyl Phosphites 4a–b
with 3-(Hydroxyimino)Pentane-2,4-Dione (1a)
Trimethyl phosphite 4a (0.24 g, 2 mmol) and/or triethyl phosphite 4b was added drop-
wise to a solution of compound 1a (0.26 g, 2 mmol) in dry benzene (30 mL), and the reaction
mixture was refluxed for 12 h. After evaporation of the volatile material under reduced pres-
sure, the residue was applied to silica gel column chromatography. Elution of the column
◦
with petroleum ether (60–80 C) : ethyl acetate (50: 50, v:v) afforded 12a [dimethyl(3-
(hydroxy(methyl)amino)-4-oxopent-2-en-2-yl) phosphate] (12a, C8H16NO6P) and/or 12b
[diethyl (3-(hydroxy (ethyl)amino)-4-oxopent-2-en-2-yl) phosphate] (12b, C8H16NO6P).
◦
12a: pale yellow crystals, yield 62%, m.p. 162–164 C, IR [v, KBr, cm−1]: 1118
(P O CH3), 1260 (P O), 1675 (C O), 3492 (OH). 1H NMR (500 MHz, δ ppm, CDCl3):
2.56 (s, 3H, N CH3), 2.79 (s, 1H, OH, exchangeable with D2O), 2.83,2.85 (2s, 6H, 2CH3),
3
3.74, 3.87 (2d, 6H, JHP = 11.5 Hz, P(OCH3)2)). 13C NMR (125 MHz, δ ppm, CDCl3):
22.5 (s, CH3C O), 31.1 (s, CH3C O), 54.3, 54.5 (2d, 2JCP = 29.30 Hz, P (OCH3)2), 113.0
(C N), 190.3 (C O), 194.0 (C O). 31P NMR (125 MHz, δ ppm, CDCl3): 2.1. MS m/z
(%): 253 [M+] (100). Anal. Calcd for C8H16NO6P (253.19): C, 37.95; H, 6.37; N, 5.53; P,
12.23. Found: C, 37.88; H, 6.21; N, 5.82; P, 12.35.
◦
12b: Pale yellow crystals, yield 60%, m.p. 170–172 C, IR [v, KBr, cm−1]: 1123
1
(P O C2H5), 1263 (P O), 1669 (C O), 3494 (OH). H NMR (500 MHz, δ ppm,
CDCl3): 1.27 (t, 3H, NCH2CH3), 1.30, 1.33 (2t, 6H, PO(OCH2CH3)2), 2.35 (s, 1H, OH,
exchangeable with D2O), 2.51, 2.63 (2s, 6H, 2CH3), 2.69 (q, 2H,NCH2CH3), 4.10, 4.18 (2q,
4H, 3JHP = 10.5 Hz,PO(OCH2CH3)2). 13C NMR (125 MHz, δ ppm, CDCl3): 14.2

708
L. S. BOULOS ET AL.
(N CH3 CH2), 16.2, 16.5 (2CH3CH2O), 22.8 (s, CH3C O), 30.1 (s, CH3C O), 52.6
(N CH3 CH2), 64.3, 64.4 (2d, 2Jcp = 28.5 Hz, P O CH2), 113.2 (C N), 190.3 (C O),
193.4 (C O). 31P NMR (125 MHz, δ ppm, CDCl3): 2.15. MS m/z (%) 295 [M+] (100).
Anal. Calcd for C11H22NO6P (295.27): C, 44.74; H, 7.51; N, 4.74; P, 10.49. Found: C,
44.71; H, 7.82; N, 4.70; P, 10.21.
Reaction of Lawesson’s Reagent 5a with 3-(Hydroxyimino)-2,4-
Pentanedione (1a)
A mixture of 0.8 g (2 mmol) of 5a and 0.26 g (2 mmol) of 1a was stirred for 1 h in dry
benzene. The volatile material was evaporated under reduced pressure. The precipitate was
filtered off and washed with cyclohexane then recrystallized from methanol to afford product
13 (((2,4-dioxopentan-3-ylidene)amino)oxy)(4-ethoxyphenyl)phosphinodithioic-acid (13,
C12H14NO4PS2).
Crystallized from methanol, 13 as buff crystals, yield 85%, m.p. 170–172 ◦C. IR [v,
KB, cm−1]: 625 (P S), 1654 (C N), 1673 (CH3CO), 2320 (SH). 1H NMR (500 MHz, δ
ppm, DMSO): 2.05 (s, 6H, 2CH3), 3.30 (s, 1H, SH, exchangeable with D2O), 3.75 (s, 3H,
OCH3), 7.11 (m, 4H, aromatic). 13C NMR (125 MHz, δ ppm, DMSO): 30.2 (2CH3), 55.7
(OCH3), 114.0 (d, 2C C C P, 3JCP = 15.7 Hz), 121.5 (d, P C Ph, 1JCP = 115.3 Hz),
132.5 (d, 2C C P, 2JCP = 22.0 Hz), 143.9 (C N), 195.8 (2C O). 31P NMR (125 MHz,
δ ppm, DMSO): 18.7. MS m/z (%) 331 [M+] (100), 300 [M+-OCH3] (47). Anal. Calcd for
C12H14NO4PS2 (331.35): C, 43.50; H, 4.26; N, 4.23;P, 9.35; S, 19.35. Found: C, 43.82; H,
4.37; N, 4.52; P, 9.01 S, 19.0.
Reaction of Japanese Reagent 5b with
3-(Hydroxyimino)Pentane-2,4-Dione (1a)
A mixture of 0.8 g (2 mmol) of 5b and 0.26 g (2 mmol) of 1a was stirred for 1 h in dry
benzene. The volatile material was evaporated under reduced pressure. The precipitate was
filtered off and washed with benzene then recrystallized from methanol to afford product
14 [3-(hydroxyimino) pentane-2.4-dithione] (14, C5H7NOS2).
Crystallized from methanol, 14 as colorless crystals, yield, 75%, m.p. 172–174 ◦C.
1
IR [v, KBr, cm−1]: 1255 (C S), 1652 (C N), 3511(OH). H NMR (500 MHz, δ ppm,
DMSO): 1.01 (s, 6H, 2CH3), 8.021 (s, 1H, OH, exchangeable with D2O). 13C NMR (125
MHz, δ ppm, DMSO): 28.1 (2CH3), 143.5 (C N), 205.2 (2C S). MS m/z (%) 161 [M+]
(45). Anal. Calcd for C5H7NOS2 (161.25): C, 37.24; H, 4.38; N, 8.69; S, 39.77. Found: C,
37.01; H, 4.72; N, 8.52; S, 40.00.
Reaction of Phosphonium Ylide 2a with
3-(Phenylimino)Pentane-2,4-Dione (1b)
A mixture of 0.68 g 2a (2 mmol) and 0.38 g (2 mmol) of 1b in dry toluene
(30 mL) was refluxed for 4 h. The volatile material was evaporated under reduced
pressure. The residue was subjected to silica gel column chromatography to give 15
[diehyl-3,5-dimethyl-4-(phenylimino)hepta-2,5-dienedioate] (15,C19H23NO4). Triphenyl-
phosphane oxide was also isolated and identified. When compound 1b was treated with
two mol equivalents of 2a in refluxing toluene, compound 15 was obtained in good yield
and triphenylphosphane oxide was also isolated.

SCOPE AND LIMITATION OF THE REACTIONS OF 3-IMINO DERIVATIVES
709
◦
Eluent: petroleum ether (60–80 C)/ethyl acetate (90/10, v/v), compound 15 was
separated as pale yellow crystals, yield 40%, m.p. 135-137 C, IR [v, KBr, cm−1]: 1735
(CO, ester). H NMR (500 MHz, δ ppm, CDCl3): 1.24-1.25 (2t, 6H, 2CH3 ethyl), 2.01,
◦
1
2.438 (2s, 6H, 2CH3), 4.17,4.35 (2q, 4H, 2CH2, ethyl), 6.19, 6.24 (2s, 2H, 2CH), 6.95 (m,
5H, aromatic). 13C NMR (125 MHz, δ ppm, CDCl3): 14.2, 14.4 (2CH3), 19.1, 29.4 (2CH3,
ethyl), 60.3, 60.6 (2CH2, ethyl), 126.1, 126.8, (2CH), 119.1–150.3 (aromatic carbon),
151.1, 151.3 (2C CH), 165.9 (C N), 166.43, 168.42 (2C O, ester). MS m/z (%) 329
[M+] (100). Anal. Calcd for C19H23NO4 (329.39): C, 69.28; H, 7.04; N, 4.25. Found: C,
69.5; H, 7.22; N, 4.01.
Reaction of Triethoxyphosphonate 3a with
3-(Phenylimino)Pentane-2,4-Dione (1b)
A solution of sodium ethoxide (0.136 g, 2 mmol) in absolute ethanol (30 mL) was
treated with an equimolar amount of triethoxyphosphonoacetate (3a) (0.44 g, 2 mmol)
then 1b (0.38 g, 2 mmol) was added and the resulting reaction mixture was refluxed for
4 h (TLC). Then, poured on a small amount of water, extracted with ethyl acetate, dried,
and the extracts were evaporated under reduced pressure. The residue was applied to silica
gel column chromatography to give product 16 [ethyl2-(diethoxyphosphoryl)-3-hydroxy-
3-methyl-5-oxo-4-(phenylimino)hexan◦oate] (16,C19H28NO7P).
Eluent: petroleum ether (60–80 C)/ethyl acetate (50/45, v/v), 16 was separated as
◦
yellow crystals, yield (60%), m.p. 193–194 C, IR (v, KBr, cm−1): 1132 (P O C2H5),
1256 (P O),14 1682 (COCH3), 1754 (C O, ester), 3418(OH). 1H NMR (500 MHz, δ ppm,
CDCl3):1.24, 1.39 (2t, 6H, PO(OCH2CH3)2, JHP = 10.83 Hz), 1.59 (t, 3H, COOCH2CH3),
2.17 (s, 3H, CH3C OH), 2.22 (s, 3H, CH3CO), 3.00, 3.01 (2q, 4H, 2CH2,3JHP = 11.00 Hz,
P O(CH2CH3)2), 3.72 (d, 1H, CH, 2JHP = 20.2 Hz), 3.82 (s, 1H, OH, exchangeable with
D2O), 3.88 (q, 2H, COOCH2CH3), 7.03 (m, 5H, aromatic). 13C NMR (125 Hz, CDCl3,
δ ppm): 13.2 (s, CH3CH2COO), 14.3,19.9 (d, (CH3CH2)2PO), 29.8 (CH3COH), 30.4
(CH3CO), 45.7 (COH, d, 2JCP = 22.0 Hz), 52.7(CHPO, 1JCP = 114.0), 64.2 (COOCH2CH3),
65.0, 66.4 ((CH3CH2O)2PO), 65.2 (C OH, 2JCP = 36.9 Hz), 113.8–129.5 (aromatic car-
bon), 164.2 (CN), 174.0 (C O), 195.00 (COCH3). 31P NMR (125Hz, δ ppm, CDCl3): 18.7.
MS m/z (%) 413[M+] (100). Anal. Calcd for C19H28NO7P (413.40): C, 55.20; H, 6.83; N,
3.39; P, 7.49. Found: C, 55.58; H, 7.02; N; 3.33; P, 7.83.
Reaction of Trimethyl Phosphite (4a) with
3-(Phenylimino)Pentane-2,4-Dione (1b)
Trimethyl phosphite (4a) (0.24 g, 2 mmol) was added dropwise to a solution of
compound 1b (0.38 g, 2 mmol) in dry toluene (30 mL), and the reaction mixture was
refluxed for 6 h. After evaporation of the volatile material under reduced pressure, the
residue was applied to silica gel column chromatographyto afford 17 [dimethyl (4-oxo-3-
(phenylamino)pent-2-en-2-yl) phosphate (17, C13H18NO5P).
◦
Eluent: petroleum ether (60–80 C) : ethyl acetate (30 : 70, v:v), 17 was separated
as yellow crystals, yield 62%, m.p. 162–164 C. IR [v, KBr, cm−1]: 1118 (P O CH3),
◦
1264 (P O),14 1677 (C O), 3500 (NH). 1H NMR (500 MHz, δ ppm, CDCl3): 2.10, 2.23
(2s, 6H, 2CH3), 3 (s, 1H, NH, exchangeable with D2O), 3.75, 3.77 (2d, 6H, 3JHP = 11.00
Hz, PO(OCH3)2)), 7.16(m, 5H, aromatic).13C NMR (125 MHz, δ ppm, CDCl3): 22.5 (s,
CH3C O), 30.3 (s, CH3C O), 54.2, 54.3(2d, 2JCP = 29.0 Hz, PO(OCH3)2), 116.5 (C N),

710
L. S. BOULOS ET AL.
119.00–142.9 (aromatic carbon), 192.2 (C O), 193.4 (C O).31P NMR (125 MHz, δ ppm,
CDCl3): 5.8.MS m/z (%)299[M+] (100). Anal. Calcd for C13H18NO5P (299.26): C, 52.18;
H, 6.06; N, 4.68; P, 10.35. Found: C, 52.08; H, 6.21; N, 5.75; P, 10.15.
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