![IOSR Journal of Applied Chemistry (IOSR-JAC)
e-ISSN: 2278-5736.Volume 10, Issue 5 Ver. I (May. 2017), PP 37-46
www.iosrjournals.org
DOI: 10.9790/5736-1005013746 www.iosrjournals.org 37 |Page
Synthesis, Identification and Surface Active Properties of Some
Nonionic Surfactants Containing Quinazolinone Ring.
Suaad M.H. Al-Majidi and Haider M.M. Al-tamimy
Department of Chemistry, College of Science / University of Baghdad, Iraq
Abstract: This research includes synthesis of new heterocyclic derivatives of quinazolinone and studying the
possibility for their application as surfactants. The preparation process started by the reaction of pentadecanoyl
chloride with anthranilic acid gave 2-pentadecyl-4H-benzo[3,1]oxazin-4-one [1] which was used as starting
material to synthesis some heterocyclic compounds by a reaction with nitrogen nucleophiles. Compound [1] as
starting material reacted by three ways. The first way react Compound [1] with semicarbazide,
thiosemicarbazide and phenylsemicarbazide in pyridine as solvent to obtained [1-(4-oxo-2-
pentadecylquinazolin-3(4H)-yl) urea [2], thiourea [3], phenylthiourea [4] respectively]. The second way
include the reaction of Compound [1] with 99% hydrazine hydrate to produce 3-amino-2-pentadecylquinazolin-
4(3H)-one [5], then converted to amino derivatives [6-8] by the reaction of Compound [5] with different
halogenated compounds such as (benzoyl chloride, acetyl chloride and chloro acetyl chloride ) in DMF and
pyridine as catalyst. The third way include the reaction of compound [1] with different substituted amine and
amide compounds (thiourea, hydroxylamine hydrochloride, glycine, ammonium acetate and phenyl hydrazine)
respectively to obtain derivatives of quinazoline [9-14]. The produced compounds [2,4,5,7 and 12] react with
propylene oxide in different moles (n=3, 5 and7) to yield novel groups of nonionic compounds having a function
as surface active agents. The surface active properties like surface tension and interfacial tension, wetting time,
cloud point, emulsion stability, foam height and CMC of these compounds were measured and showed a
pronounced surface activity, good emulsifying properties and highly foaming in some of these compounds.
Newly synthesized compounds were identified via spectral methods; their [FTIR and some of them by 1
HNMR,
13
C-NMR] and measurements of some of its physical properties.
Keywords: Quinazolinone derivatives, surface active agent, nonionic surfactant,
I. Introduction
Nonionic surfactant is one of the most important groups of surfactant with growing industrial interest
and can by synthesized by the ethoxylation or propxylation (addition of ethylene oxide or propylene oxide) of
hydrophobic organic compounds containing active hydrogen in the presence of catalyst such as KOH.(1)
Quinazolinone derivatives which may have pharmaceutical and industrial applications (2)
. These
derivatives are the subject of many research studies due to their widespread potential biological activities such
as antimicrobial (3)
, anti-inflammatory (4)
, antitumor (5)
anticancer (6)
corrosion inhibitors (7)
and anti-oxidant (8)
.
This led us to synthesis of novel group of nonionic surfactant containing this nucleus from long chain fatty acid
(palmitic acid). Some of the synthesized compounds which have active hydrogen atom were subjected to react
with propylene oxide by different moles (n=3, 5 and7) to produce nonionic compounds.
The main objective of this investigation is to synthesis and identification of new surface active agents
containing quinazolinone nuclei and studies the surface active properties as surface tension and interfacial
tension, wetting time, cloud point, emulsion stability, foam height and CMC.
II. Experimental
2.1 Materials and Instruments
Chemicals used in this work are supplied from BDH, Fluka, Merck and Sigma Aldrich companies and
used without further purification. Melting points were uncorrected and registered via digital Stuart scientific
SMP3 melting point device .Thin layer chromatography (TLC) used to check purity and homogeneity of
synthesis compounds. FTIR spectra of the compounds in the (4000-600) cm-1
spectral range were recorded on
SHIMAZU FTIR-8400 Fourier transform Infrared spectrophotometer using KBr discs. 1
HNMR and 13
CNMR
spectra were recorded on Bruker, Ultrasheild (300) MHz in Jordan and (500) MHz in Iran,using TMS as internal
reference and DMSO-d6 as a solvent.
2.1.1 Synthesis of 2-pentadecyl-4H-benzo[1,3]oxazin-4-one (9)
[1].
To a stirred solution of anthranilic acid (1.37gm, 0.01mole) in dry acetone, palmitoyl chloride (3ml,
0.01mole) was added in presence of pyridine as solvent. The mixture was refluxed for 3hrs then concentrated
under vacuum. The solid product that separated on cold was filtrated off, dried and crystallized from petroleum-](https://image.slidesharecdn.com/f1005013746-170704101730/85/Synthesis-Identification-and-Surface-Active-Properties-of-Some-Nonionic-Surfactants-Containing-Quinazolinone-Ring-1-320.jpg)
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DOI: 10.9790/5736-1005013746 www.iosrjournals.org 38 |Page
ether. The product was heated for 4 hrs under reflux in acetic anhydride then concentrated under vacuum.
Physical properties of compound [1] are listed in Table (1).
2.1.2 Synthesis of 1-(4-oxo-2-pentadecylquinazolin-3(4H)-yl) urea [2], thiourea [3], phenyl thiourea(10)
[4]:
To a solution of compound [1] (3.57gm, 0.01mole) in 30ml pyridine, (semi carbazide,
thiosemicarbazide and phenylsemicarbazide) respectively (0.01 mole) were added and the reaction mixture was
heated under reflux for (6-8hrs), and poured into cold diluted HCl. the crud solid product that separated was
filtered off, washed with water, dried and recrystallized from ethanol to give crystals. Physical properties of
compounds [2-4] are listed in Table (1).
2.1.3 Synthesis of 3-amino-2-pentadecylquinazolin-4(3H)-one(11)
[5]:
Compound [1] (3.57gm, 0.01mole) in (10 ml) dimethylformamide (DMF) as solvent; excess of 99%
hydrazine hydrate in ethanol (30ml) was added to the reaction mixture and reflexed for (6 hrs.). Finally, the
reaction mixture cooled to room temperature, poured on ice-cold water, stirred and filtered. The precipitate was
recrystallized from ethanol to give off white crystals. Physical properties of compound [5] are listed in Table
(1).
2.1.4 Synthesis of N-(4-oxo-2-pentadecylquinazolin-3(4H)-yl) benzamide(12)
[6].
Compound [5] (3.68 gm, 0.01mole) in dry acetone (40ml) containing a catalytic amount of pyridine
(3drops), (1.2ml, 0.01mole) benzoyl chloride was added in drop wise maintaining the temperature near 8° C for
(1 hrs.). The reaction mixture was refluxed for another (3hrs.), and then cooled at room temperature. The
separated solid product was filtered off and recrystallized from ethanol. Physical properties of compound [6] are
listed in Table (2).
2.1.5 Synthesis of N-(4-oxo-2-pentadecylquinazolin-3(4H)-yl) acetamide(12)
[7].
A solution of compound [5] (3.68 gm, 0.01mole) in dry acetone (40ml) and acetyl chloride (0.8ml,
0.01mole) in pyridine (20 ml) was refluxed for (5 hrs.). The cold mixture was poured into ice/water. The
separated solid was filtered off, dried and recrystallized from benzene-hexane. Physical properties of compound
[7] are listed in Table (2).
2.1.6 Synthesis of N-(4-oxo-2-pentadecylquinazolin-3(4H)-yl)-2-chloro acetamide(14)
[8].
A mixture of compound [5] (3.68 gm, 0.01mole) in dry acetone and chloroacetyl chloride (0.8ml, 0.01
mole) was refluxed for 6 hrs. The mixture was then poured into cold water (30 ml) and the precipitated solid
was filtered off, dried and recrystallized from benzene. Physical properties of compound [8] are listed in Table
(2).
2.1.7 Synthesisof N-(4-oxo-2-pentadecylquinazoline-3(4H)-yl) carbothioamide[9], carboxamide (15)
[10].
Compound [1] (3.57gm, 0.01mole) in (15 ml) dimethylformamide (DMF) as solvent; was refluxed with
(0.8gm, 0.01 mole) (thiourea and urea) respectively in (40 ml) dry acetone containing a catalytic amount of
pyridine (3drops), for (10hrs.). The reaction mixture cooled to room temperature, poured on ice-cooled water,
the formed precipitate was filtered and recrystallized from ethanol. Physical properties of compounds [9] and
[10] are listed in Table (3).
2.1.8 Synthesis of 3-hydroxy-2-pentadecylquinazolin-4(3H)-one(16)
[11].
A solution of compound [1] (3.57gm, 0.01mole) in in (20 ml) dimethylformamide (DMF) and
hydroxylamine hydrochloride (0.7gm, 0.01mole) in pyridine (25ml) was refluxed for (16hrs.). The reaction
mixture was cooled and poured into a crushed ice water. The solid that separated was filtered off, washed with
water, dried and then recrystallized from dioxane to give the required products. Physical properties of compound
[11] are listed in Table (3).
2.1.9 Synthesis of 2-(4-oxo-2-pentadecylquinazolin-3(4H)-yl)acetic acid (17)
[12].
To a solution of compound [1] (3.57gm, 0.01mole) in (25ml) dimethylformamide (DMF), (0.75gm,
0.01mole) glycine in dry pyridine (20ml) was added and the heated under reflux for (4hrs.) then left to cool at
room temperature. The reaction mixture was poured into ice/HCl to reveal the solid product, which was filtered
off, washed with water, dried and recrystallized from ethanol. Physical properties of compound [12] are listed in
Table (3).](https://image.slidesharecdn.com/f1005013746-170704101730/85/Synthesis-Identification-and-Surface-Active-Properties-of-Some-Nonionic-Surfactants-Containing-Quinazolinone-Ring-2-320.jpg)
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DOI: 10.9790/5736-1005013746 www.iosrjournals.org 39 |Page
2.1.10 Synthesis of 2-pentadecylquinazolin-4(3H)one(18)
[13].
compound [1] (3.57gm, 0.01mole) was fused with of ammonium acetate (3gm, 0.04mole) heated in an oil bath
in temperature (160-170) o
C for (2hrs.), then cooled, water is added, the solid product obtained after filtration
and recrystallized from methanol. Physical properties of compound [13] are listed in Table (3).
2.1.11 Synthesis of 2-pentadecyl-3-(phenylamino)quinazolin-4(3H)-one(19)
[14].
Compound [1] (3.57gm, 0.01mole) and phenyl hydrazine (1.08gm, 0.01mole) were dissolved in
absolute ethanol (50ml). This solution was refluxed for (12hrs.). Concentrated, cooled and poured into crushed
ice and filtered. The solid thus obtained was purified by recrystallization from ethanol. Physical properties of
compound [14] are listed in Table (3).
2.2 Conversion of the prepared compounds to nonionic surfactants (20)
:
They are prepared by the addition of (n) moles of propylene oxide (n = 3, 5, 7) to one mole of
synthesized compounds (2, 4, 5, 7 and 12) by mixed with KOH (0.1 wt %) The mixture was heated up to 130o
C
and a rapid stream of N2 gas was passed continuously for about 20 min to exclude the oxygen and water vapors.
And the product was characterized by FT-IR spectrophotometer. The addition of propylene oxide gave a
mixture of propenoxylated products whose structures were shown through IR spectra to be two broad bands at
1100 and 950 cm-1
and by 1
HNMR spectra showed δ= (3.2 – 3.7) ppm.
2.3 Determination of the performance properties
1. Surface and interfacial tensions:
Surface and interfacial tensions were measured with a Du-Nouy tensiometer (Kruss, Type 8451) using an
aqueous solution of surfactants (0.1 wt %) at room temperature (25 o
C) (21)
.
2. Cloud point:
Cloud point was determined by gradually heating a surfactant solution (1.0 wt %) in a temperature controlled
bath, and recording the temperature at which the clear, or nearly clear solutions become definitely turbid. The
reproducibility of this temperature was checked by cooling the solutions until they became clear again (21)
.
3. Wetting time:
Wetting time was determined by immersing a sample of cotton fabric in a (1.0 wt %) aqueous solution of
surfactants (21)
.
4. Foaming properties:
Foaming properties were measured according to El-Sukkary et al (1987). In this procedure a 25 ml solution (1.0
wt %) was shaken vigorously for 10 seconds in a 100 ml graduated cylinder with glass stopper at 25 o
C. The
solution was allowed to stand for 30 seconds, and then, the foam height was measured (22)
.
5. Emulsification stability:
Emulsification stability was prepared from 10 ml of a 20 mmol aqueous solution of surfactant and 5 ml of
toluene at 40 o
C. Emulsion stability was determined as the time it took 9 ml of an aqueous layer to separate
from the emulsion once shaking had stopped (23)
.
6. Determination of CMC of Surfactant by Surface Tension Method:
Surface tension measurements were done by applying du Nouy ring method using Du-Nouy (Kruss,
Type 8451) tensiometer and platinum ring at room temperature (25˚C). Stock solution of 5% (v/v) of
synthesized nonionic surfactant in aqua was prepared in 1 L volumetric flask. First of all, the surface tension of
pure water in a glass vessel was noted. The surface tensions were measured by a dilution method in which a 5%
(v/v) of synthesized nonionic surfactant stock solution was gradually diluted by deionized water. After each
dilution the solution was stirred for 30 s, and then left for 2 min before reading the surface tension value. All
surface tension measurements were done at least three times or up to obtaining repeated value. The CMC values
were determined by plotting surface tension versus concentrations of surfactant (23)
.
Table (1) : Physical properties and FT-IR spectral data cm-1
of the synthesized compounds (1-5).
Com.
No.
Physical Properties Major FT-IR Absorption cm-1
Structures M.P
°C
Yield
%
Color (C-H)
arom.
(C-H)
aliph.
(C=O) (C=C)
aromati
c
Others
1 48 -50 75 Pale
yellow
3030 2920
2850
1764 1598
1533
1487
(C=N)
1641](https://image.slidesharecdn.com/f1005013746-170704101730/85/Synthesis-Identification-and-Surface-Active-Properties-of-Some-Nonionic-Surfactants-Containing-Quinazolinone-Ring-3-320.jpg)
![Synthesis, Identification And Surface Active Properties Of Some Nonionic Surfactants Containing
DOI: 10.9790/5736-1005013746 www.iosrjournals.org 41 |Page
14 90-91 75 red 3050 2955
2850
1679
amid 1595
1565
1490
NH 3340
(C=N)
1606
III. Results And Discussion
The synthetic sequences for preparation of series new 2-pentadecyl quinazolinone compounds by
reaction of pentadecanoyl chloride with anthranilic acid gave 2-pentadecyl-4H-benzo[3,1]oxazin-4-one [1]
which was used as starting material to synthesis some quinazolinone compounds by a reaction with nitrogen
nucleophiles (e.g., semicarbazide, thiosemicrabazide, phenylsemicarbazide and hydrazine hydrate) are show in
scheme(1).
Scheme (1): Synthesis of new derivatives of quinazolinone (1-5)
Physical properties of compounds [2, 3, 4 and 5] are listed in Table (1). FTIR spectrum of prepared
compounds [2, 3, 4 and 5] showed appearance of absorptions at (3425-3396) cm-1
and at (3286-3226) cm-1
of
NH2 asym. and sym. respectively. (3358, 3298) cm-1
of NH group, Also it showed shift in the C=O band
from (1764cm-1
) of cyclic ester to (1690- 1645 cm-1
) of amide. FTIR spectral data are listed in Table (1). 1
H-
NMR spectrum of compound [3] showed triplet signal at δ= (0.85) ppm due to (-CH3) protons, multiplet signal
at δ= (1.2 – 2.66) ppm due to (C-H) protons of long chain 14CH2, signals at δ= (7.11 -7.60) ppm due to aromatic
rings protons, singlet signal at δ= (8.09- 8.51) ppm due to (-NH2) protons, and singlet signal at δ= (11.1) ppm
due to (N-H) proton as shown in Table (4). 13
C-NMR spectrum of compound [3] showed signals at δ= (22-27)
ppm, δ= (122-133) ppm, δ= (147) ppm, δ= (162.29) ppm and δ= (174.5) ppm belong to long chain (C15H31), (C-
aromatic), (C=N) imine, (C=O) ester and (C=S) respectively. 13
CNMR spectral data of compound [3] is listed
in Table (5).
Table (4) 1
H-NMR spectral data (ppm) for selected compounds.
Comp.
No.
Structures 1
HNMR Spectral data(ᵟppm)
1 δ 0.85 (t,3H, CH3), δ 1.59 – 2.69 (m, 28H, 14CH2), δ 7.1 -8.5(m, 4H,ArH)
3 δ 0.85 (t, 3H, terminal CH3), δ 1.2 – 2.66 (m, 28H, 14CH2), δ 7.11 -7.60(m, 4H,ArH),
δ8.09- 8.51 (s, 2H,NH2), δ 11.1 (s,1H, NH)
6 δ 0.84 (t,3H, CH3), δ 1.22 – 2.50 (m, 28H, 14CH2), δ 6.51 -7.84 (m, 9H,ArH) , δ 9.10(
s, 1H ,N-NH)
7 δ 0.83 (t, 3H, terminal CH3), δ 1.27 – 2.4 (m, 28H, 14CH2),δ3.47 (s,3H, O=C-CH3), δ
7.01 -8.51(m, 4H,ArH)](https://image.slidesharecdn.com/f1005013746-170704101730/85/Synthesis-Identification-and-Surface-Active-Properties-of-Some-Nonionic-Surfactants-Containing-Quinazolinone-Ring-5-320.jpg)
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DOI: 10.9790/5736-1005013746 www.iosrjournals.org 42 |Page
9 δ 0.85 (t,3H, CH3), δ 1.8 – 2.38 (m, 28H, 14CH2), δ 7.11 -7.9(m, 4H,ArH), δ 8.5-
9.14( s, 2H ,NH2)
Table (5) : 13
C-NMR spectral data (ppm) for selected compounds.
Com.
No
structure 13CNMR Spectral data(ᵟppm)
1 22-27 (Long chain C7); 122(C1); 127(C2)134(C4), 147(C3); 148(C6);
162.4(C5).
3 22-27 (Long chain C7); 123(C1); 128(C2); 133(C4),147(C6); 162.92(C5);
174.5(C8)
6 22-27 (Long chain C7); 122(C1); 126(C2); 132(C4); 145 ( C3 and C9) ;
146(C6); 162 (C5); 168 (C8)
7 22-27 (Long chain C7); 58 (C9) ; 121(C2); 128(C4); 133.4(C1); 145(C3);
154(C6); 161 (C5); 169 (C8)
9 17-27 (Long chain C7); 121(C1); 125(C2); 134(C4); 148(C6); 164 (C5);182
(C8)
Compound [5] allowed to react with halogenated compounds such as benzoyl chloride, acetyl chloride
and chloro acetyl chloride by nucleophilic substitution reaction to synthesis newly derivatives of quinazolinone
compounds [6], [7] and [8]. This reaction carried out in presence of catalytic amount of pyridine and DMF. The
synthetic sequences for preparation of new N-(4-oxo-2-pentadecylquinazolin-3(4H)-yl) benzamide [6],
acetamide [7] and chloro acetamide [8] was performed as outlined in scheme (2).
Scheme (2)
Physical properties of compounds [6], [7] and [8] listed in Table (2). FTIR spectrum of compound [6],
[7] and [8] showed disappearance of ν (NH2) absorption band at 3496 and 3245 cm-1
and appearance of
characteristic absorption bands at ν cm-1
3329 for ν (N-H), 3030 for C-H aromatic; 2910 and 2850 for C-H aliph](https://image.slidesharecdn.com/f1005013746-170704101730/85/Synthesis-Identification-and-Surface-Active-Properties-of-Some-Nonionic-Surfactants-Containing-Quinazolinone-Ring-6-320.jpg)
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; 1689 for C=O (amide) ; 1604 for C=N of compound[6]; 1697 for C=O (amid) of compound[7]; and 1685for
C=O (amide) of compound[8]; C=N (1604 - 1635) cm-1
. 1
H-NMR spectrum data of compound [6] showed
triplet signal at δ= (0.84) ppm due to (-CH3) protons, multiplet signal at δ= (1.22 – 2.50) ppm due to (C-H)
protons of long chain 14CH2, signals at δ= (6.51 -7.84) ppm due to aromatic rings protons, singlet signal at δ=
(9.10) ppm due to (N-H) proton. 1
H-NMR Spectral data of compounds [6] are listed in Table (4). 13
C-NMR
spectrum of compound [6] showed signals at δ= (22-27) ppm, δ= (126 -135) ppm, δ= (146) ppm and δ= (168)
ppm belong to long chain (C15H31), (C-aromatic), (C=N) imine and (C=O) ester respectively. 13
CNMR spectral
data of compound [6] are listed in Table (5). While 1
H-NMR spectrum data of compound [7] showed triplet
signal at δ= (0.83) ppm due to (-CH3) protons, multiplet signal at δ= (1.27 – 2.4) ppm due to (C-H) protons of
long chain 14CH2, singlet signal at δ= (3.47) ppm due to (O=C-CH3) proton, signals at δ= (7.01 -8.51) ppm due
to aromatic rings protons. 1
H-NMR Spectral data of compounds [7] are listed in Table (4). 13
C-NMR spectrum
of compound [7] showed signals at δ= (22-27) ppm, δ= 58 ppm, δ= (128-134) ppm, δ= (145) ppm, δ= (154)
ppm, δ= (161) ppm and δ= (169) ppm belong to long chain (C15H31), (O=C-CH3), (C- aromatic), (C=N) imine ,
(C=O) ester (C=O-CH3) respectively. 13
CNMR spectral data of compound [7] are listed in Table (5). The
syntheses of different new quinazolinone compounds by reaction of compound [1] with different substituted
amine compounds. These different synthesized compounds that are presented in Scheme (3).
Scheme (3)
Reaction of compound [1] with thiourea and urea in presence catalytic amount of pyridine afforded the
product N-(4-oxo-2-pentadecylquinazoline-3(4H)-yl) carbothioamide [9], carboxamide [10] respectively.
Physical properties of compounds [9] and [10] are listed in Table (3). FTIR spectrum of prepared compounds
[9-10] showed appearance of absorptions at (3440-3320) cm-1
, (3040) cm-1
, (2960, 2860) cm-1
, (1699 and
1677) cm-1
, (1608) cm-1
due to ν –NH2, ν C-H aromatic, ν C-H aliphatic, ν C=O for amide, ν C=N of
compounds (9 and 10), in addition (1413) cm-1
for ν C=S of compound [9]. In the other hand1
HNMR spectra
data of compound (9) δ ppm in DMSO-d6 solvent showed singlet signal at δ= (0.85) ppm due to (-CH3) protons,
multiplate signale at δ= (1.18-2.38) due to long chain (14CH2), signals at δ= (7.9-7.11) ppm due to aromatic ring
protons and δ= (8.5-9.14) ppm due to (-NH2) protons. As listed in table (4). 13
C-NMR spectrum data of
compound [9] showed signals at δ= (17-27) ppm, δ= (121-134) ppm, δ= (148) ppm, δ= (164.07) ppm and δ=
(182.3) ppm belong to long chain (-C15H31), (C-aromatic), (C=N), (C=O) amide and (C=S)
respectively.13
CNMR spectral data of compound [9] is listed in Table (5).. the synthesized quinazolinone
derivatives bearing an active hydrogen atom such as (-NH, -OH, -COOH and - NH2) and the structure of a
surface active agent requires a hydrophilic component. This is accomplished through the condensation of
propylene oxide with different moles, (3, 5 and 7) moles in the presence of KOH as catalyst at any active
hydrogen atom of synthesized compounds [2, 4, 5, 7 and 12] which contain one or more active hydrogen atoms
to yield novel groups of nonionic surfactant (2(a-c), 4(a-c), 5(a-c), 7(a-c) and 12(a-c)) respectively that showed
in scheme (4).](https://image.slidesharecdn.com/f1005013746-170704101730/85/Synthesis-Identification-and-Surface-Active-Properties-of-Some-Nonionic-Surfactants-Containing-Quinazolinone-Ring-7-320.jpg)
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DOI: 10.9790/5736-1005013746 www.iosrjournals.org 45 |Page
Table (6) surface properties of synthesized compounds (2(a-c), 4(a-c), 5(a-c), 7(a-c) and 12(a-c))
compd No of
moles
Surface
Tension
(dyne/cm)
0.1wt%
Interfacial
tension
(dyne/cm)
0.1wt%
Cloud point
C
0.1wt%
Wetting
time (Sec)
0.1wt%
Emulsion
stability (Min)
25 mmole
Foam height
(mm)
0.1wt%
CMC × 10-3
2(a-c) 3
5
7
32
33
35
10
11
13
58
64
73
43
32
21
92
85
74
85
115
135
3.6
4.1
4.3
4(a-c) 3
5
7
30
33
34
9
11
12
67
75
84
46
28
20
94
84
71
90
105
130
3.8
4.0
4.2
5(a-c) 3
5
7
28
30
32
8
10
12
74
91
98
41
33
24
101
95
75
95
110
140
3.9
4.1
4.3
7(a-c) 3
5
7
32
33
35
9
11
13
68
82
91
49
35
26
96
85
78
105
135
150
4.0
4.1
4.4
12(a-c) 3
5
7
33
34
35
10
13
14
72
76
81
40
31
21
112
93
87
95
120
135
3.4
3.6
3.9
The reaction condition of propenoxilated compounds are illustrated in table (7).
Table (7) reaction condition of propenoxilated compounds
compd Catalyst,wt% Temp C Propenoxylated compounds Yield% Degree of
propenoxylation
color
2 KOH, 0.01wt% 130 2(a-c) 55-60 3,5 and 7 brown cream
4 4(a-c) 60-65 Pale brown cream
5 5(a-c) 70-74 Yellow white
Cream
7 7(a-c) 63-68 Pale brown cream
12 12(a-c) 72-75 Yellow white
Cream
1
H-NMR spectra data of compound [4(a-c) and 5(a-c)] showed disappearance peaks –NH of compound [4] and
–NH2 of compound [5]. And appearance multiplate signal at δ= (3.2 – 3.7) ppm due to the protons of
propenoxy groups (-CH2-CH-(CH3)-O)- beside other characteristic bands as listed in table (8) and shown in
Figure (1 and 2).
Table (8): 1
H-NMR spectral data δ ppm for compound [4(a-c) and 5(a-c)]
Comp. No. Structures 1
HNMR Spectral data(ᵟppm)
4(a-c) δ 0.83 (t,3H, CH3),
δ 1.8 – 2.38 (m, 28H, 14CH2),
δ 3.2-3.7( m, (-CH2-CH-(CH3)-O)-)
δ 7.11 -7.9(m, 9H,ArH)
5(a-c) δ 0.85 (t,3H, CH3),
δ 1.8 – 2.38 (m, 28H, 14CH2),
δ 3.2-3.7( m, (-CH2-CH-(CH3)-O)-)
δ 7.11 -8.3(m, 4H,ArH)
Figure (1) 1
H-NMR spectrum of compound [5(a-c)]](https://image.slidesharecdn.com/f1005013746-170704101730/85/Synthesis-Identification-and-Surface-Active-Properties-of-Some-Nonionic-Surfactants-Containing-Quinazolinone-Ring-9-320.jpg)
![Synthesis, Identification And Surface Active Properties Of Some Nonionic Surfactants Containing
DOI: 10.9790/5736-1005013746 www.iosrjournals.org 46 |Page
Figure (2) 1
H-NMR spectrum of compound [4(a-c)]
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Synthesis, Identification and Surface Active Properties of Some Nonionic Surfactants Containing Quinazolinone Ring.
- 1. IOSR Journal of Applied Chemistry (IOSR-JAC) e-ISSN: 2278-5736.Volume 10, Issue 5 Ver. I (May. 2017), PP 37-46 www.iosrjournals.org DOI: 10.9790/5736-1005013746 www.iosrjournals.org 37 |Page Synthesis, Identification and Surface Active Properties of Some Nonionic Surfactants Containing Quinazolinone Ring. Suaad M.H. Al-Majidi and Haider M.M. Al-tamimy Department of Chemistry, College of Science / University of Baghdad, Iraq Abstract: This research includes synthesis of new heterocyclic derivatives of quinazolinone and studying the possibility for their application as surfactants. The preparation process started by the reaction of pentadecanoyl chloride with anthranilic acid gave 2-pentadecyl-4H-benzo[3,1]oxazin-4-one [1] which was used as starting material to synthesis some heterocyclic compounds by a reaction with nitrogen nucleophiles. Compound [1] as starting material reacted by three ways. The first way react Compound [1] with semicarbazide, thiosemicarbazide and phenylsemicarbazide in pyridine as solvent to obtained [1-(4-oxo-2- pentadecylquinazolin-3(4H)-yl) urea [2], thiourea [3], phenylthiourea [4] respectively]. The second way include the reaction of Compound [1] with 99% hydrazine hydrate to produce 3-amino-2-pentadecylquinazolin- 4(3H)-one [5], then converted to amino derivatives [6-8] by the reaction of Compound [5] with different halogenated compounds such as (benzoyl chloride, acetyl chloride and chloro acetyl chloride ) in DMF and pyridine as catalyst. The third way include the reaction of compound [1] with different substituted amine and amide compounds (thiourea, hydroxylamine hydrochloride, glycine, ammonium acetate and phenyl hydrazine) respectively to obtain derivatives of quinazoline [9-14]. The produced compounds [2,4,5,7 and 12] react with propylene oxide in different moles (n=3, 5 and7) to yield novel groups of nonionic compounds having a function as surface active agents. The surface active properties like surface tension and interfacial tension, wetting time, cloud point, emulsion stability, foam height and CMC of these compounds were measured and showed a pronounced surface activity, good emulsifying properties and highly foaming in some of these compounds. Newly synthesized compounds were identified via spectral methods; their [FTIR and some of them by 1 HNMR, 13 C-NMR] and measurements of some of its physical properties. Keywords: Quinazolinone derivatives, surface active agent, nonionic surfactant, I. Introduction Nonionic surfactant is one of the most important groups of surfactant with growing industrial interest and can by synthesized by the ethoxylation or propxylation (addition of ethylene oxide or propylene oxide) of hydrophobic organic compounds containing active hydrogen in the presence of catalyst such as KOH.(1) Quinazolinone derivatives which may have pharmaceutical and industrial applications (2) . These derivatives are the subject of many research studies due to their widespread potential biological activities such as antimicrobial (3) , anti-inflammatory (4) , antitumor (5) anticancer (6) corrosion inhibitors (7) and anti-oxidant (8) . This led us to synthesis of novel group of nonionic surfactant containing this nucleus from long chain fatty acid (palmitic acid). Some of the synthesized compounds which have active hydrogen atom were subjected to react with propylene oxide by different moles (n=3, 5 and7) to produce nonionic compounds. The main objective of this investigation is to synthesis and identification of new surface active agents containing quinazolinone nuclei and studies the surface active properties as surface tension and interfacial tension, wetting time, cloud point, emulsion stability, foam height and CMC. II. Experimental 2.1 Materials and Instruments Chemicals used in this work are supplied from BDH, Fluka, Merck and Sigma Aldrich companies and used without further purification. Melting points were uncorrected and registered via digital Stuart scientific SMP3 melting point device .Thin layer chromatography (TLC) used to check purity and homogeneity of synthesis compounds. FTIR spectra of the compounds in the (4000-600) cm-1 spectral range were recorded on SHIMAZU FTIR-8400 Fourier transform Infrared spectrophotometer using KBr discs. 1 HNMR and 13 CNMR spectra were recorded on Bruker, Ultrasheild (300) MHz in Jordan and (500) MHz in Iran,using TMS as internal reference and DMSO-d6 as a solvent. 2.1.1 Synthesis of 2-pentadecyl-4H-benzo[1,3]oxazin-4-one (9) [1]. To a stirred solution of anthranilic acid (1.37gm, 0.01mole) in dry acetone, palmitoyl chloride (3ml, 0.01mole) was added in presence of pyridine as solvent. The mixture was refluxed for 3hrs then concentrated under vacuum. The solid product that separated on cold was filtrated off, dried and crystallized from petroleum-
- 2. Synthesis, Identification And Surface Active Properties Of Some Nonionic Surfactants Containing DOI: 10.9790/5736-1005013746 www.iosrjournals.org 38 |Page ether. The product was heated for 4 hrs under reflux in acetic anhydride then concentrated under vacuum. Physical properties of compound [1] are listed in Table (1). 2.1.2 Synthesis of 1-(4-oxo-2-pentadecylquinazolin-3(4H)-yl) urea [2], thiourea [3], phenyl thiourea(10) [4]: To a solution of compound [1] (3.57gm, 0.01mole) in 30ml pyridine, (semi carbazide, thiosemicarbazide and phenylsemicarbazide) respectively (0.01 mole) were added and the reaction mixture was heated under reflux for (6-8hrs), and poured into cold diluted HCl. the crud solid product that separated was filtered off, washed with water, dried and recrystallized from ethanol to give crystals. Physical properties of compounds [2-4] are listed in Table (1). 2.1.3 Synthesis of 3-amino-2-pentadecylquinazolin-4(3H)-one(11) [5]: Compound [1] (3.57gm, 0.01mole) in (10 ml) dimethylformamide (DMF) as solvent; excess of 99% hydrazine hydrate in ethanol (30ml) was added to the reaction mixture and reflexed for (6 hrs.). Finally, the reaction mixture cooled to room temperature, poured on ice-cold water, stirred and filtered. The precipitate was recrystallized from ethanol to give off white crystals. Physical properties of compound [5] are listed in Table (1). 2.1.4 Synthesis of N-(4-oxo-2-pentadecylquinazolin-3(4H)-yl) benzamide(12) [6]. Compound [5] (3.68 gm, 0.01mole) in dry acetone (40ml) containing a catalytic amount of pyridine (3drops), (1.2ml, 0.01mole) benzoyl chloride was added in drop wise maintaining the temperature near 8° C for (1 hrs.). The reaction mixture was refluxed for another (3hrs.), and then cooled at room temperature. The separated solid product was filtered off and recrystallized from ethanol. Physical properties of compound [6] are listed in Table (2). 2.1.5 Synthesis of N-(4-oxo-2-pentadecylquinazolin-3(4H)-yl) acetamide(12) [7]. A solution of compound [5] (3.68 gm, 0.01mole) in dry acetone (40ml) and acetyl chloride (0.8ml, 0.01mole) in pyridine (20 ml) was refluxed for (5 hrs.). The cold mixture was poured into ice/water. The separated solid was filtered off, dried and recrystallized from benzene-hexane. Physical properties of compound [7] are listed in Table (2). 2.1.6 Synthesis of N-(4-oxo-2-pentadecylquinazolin-3(4H)-yl)-2-chloro acetamide(14) [8]. A mixture of compound [5] (3.68 gm, 0.01mole) in dry acetone and chloroacetyl chloride (0.8ml, 0.01 mole) was refluxed for 6 hrs. The mixture was then poured into cold water (30 ml) and the precipitated solid was filtered off, dried and recrystallized from benzene. Physical properties of compound [8] are listed in Table (2). 2.1.7 Synthesisof N-(4-oxo-2-pentadecylquinazoline-3(4H)-yl) carbothioamide[9], carboxamide (15) [10]. Compound [1] (3.57gm, 0.01mole) in (15 ml) dimethylformamide (DMF) as solvent; was refluxed with (0.8gm, 0.01 mole) (thiourea and urea) respectively in (40 ml) dry acetone containing a catalytic amount of pyridine (3drops), for (10hrs.). The reaction mixture cooled to room temperature, poured on ice-cooled water, the formed precipitate was filtered and recrystallized from ethanol. Physical properties of compounds [9] and [10] are listed in Table (3). 2.1.8 Synthesis of 3-hydroxy-2-pentadecylquinazolin-4(3H)-one(16) [11]. A solution of compound [1] (3.57gm, 0.01mole) in in (20 ml) dimethylformamide (DMF) and hydroxylamine hydrochloride (0.7gm, 0.01mole) in pyridine (25ml) was refluxed for (16hrs.). The reaction mixture was cooled and poured into a crushed ice water. The solid that separated was filtered off, washed with water, dried and then recrystallized from dioxane to give the required products. Physical properties of compound [11] are listed in Table (3). 2.1.9 Synthesis of 2-(4-oxo-2-pentadecylquinazolin-3(4H)-yl)acetic acid (17) [12]. To a solution of compound [1] (3.57gm, 0.01mole) in (25ml) dimethylformamide (DMF), (0.75gm, 0.01mole) glycine in dry pyridine (20ml) was added and the heated under reflux for (4hrs.) then left to cool at room temperature. The reaction mixture was poured into ice/HCl to reveal the solid product, which was filtered off, washed with water, dried and recrystallized from ethanol. Physical properties of compound [12] are listed in Table (3).
- 3. Synthesis, Identification And Surface Active Properties Of Some Nonionic Surfactants Containing DOI: 10.9790/5736-1005013746 www.iosrjournals.org 39 |Page 2.1.10 Synthesis of 2-pentadecylquinazolin-4(3H)one(18) [13]. compound [1] (3.57gm, 0.01mole) was fused with of ammonium acetate (3gm, 0.04mole) heated in an oil bath in temperature (160-170) o C for (2hrs.), then cooled, water is added, the solid product obtained after filtration and recrystallized from methanol. Physical properties of compound [13] are listed in Table (3). 2.1.11 Synthesis of 2-pentadecyl-3-(phenylamino)quinazolin-4(3H)-one(19) [14]. Compound [1] (3.57gm, 0.01mole) and phenyl hydrazine (1.08gm, 0.01mole) were dissolved in absolute ethanol (50ml). This solution was refluxed for (12hrs.). Concentrated, cooled and poured into crushed ice and filtered. The solid thus obtained was purified by recrystallization from ethanol. Physical properties of compound [14] are listed in Table (3). 2.2 Conversion of the prepared compounds to nonionic surfactants (20) : They are prepared by the addition of (n) moles of propylene oxide (n = 3, 5, 7) to one mole of synthesized compounds (2, 4, 5, 7 and 12) by mixed with KOH (0.1 wt %) The mixture was heated up to 130o C and a rapid stream of N2 gas was passed continuously for about 20 min to exclude the oxygen and water vapors. And the product was characterized by FT-IR spectrophotometer. The addition of propylene oxide gave a mixture of propenoxylated products whose structures were shown through IR spectra to be two broad bands at 1100 and 950 cm-1 and by 1 HNMR spectra showed δ= (3.2 – 3.7) ppm. 2.3 Determination of the performance properties 1. Surface and interfacial tensions: Surface and interfacial tensions were measured with a Du-Nouy tensiometer (Kruss, Type 8451) using an aqueous solution of surfactants (0.1 wt %) at room temperature (25 o C) (21) . 2. Cloud point: Cloud point was determined by gradually heating a surfactant solution (1.0 wt %) in a temperature controlled bath, and recording the temperature at which the clear, or nearly clear solutions become definitely turbid. The reproducibility of this temperature was checked by cooling the solutions until they became clear again (21) . 3. Wetting time: Wetting time was determined by immersing a sample of cotton fabric in a (1.0 wt %) aqueous solution of surfactants (21) . 4. Foaming properties: Foaming properties were measured according to El-Sukkary et al (1987). In this procedure a 25 ml solution (1.0 wt %) was shaken vigorously for 10 seconds in a 100 ml graduated cylinder with glass stopper at 25 o C. The solution was allowed to stand for 30 seconds, and then, the foam height was measured (22) . 5. Emulsification stability: Emulsification stability was prepared from 10 ml of a 20 mmol aqueous solution of surfactant and 5 ml of toluene at 40 o C. Emulsion stability was determined as the time it took 9 ml of an aqueous layer to separate from the emulsion once shaking had stopped (23) . 6. Determination of CMC of Surfactant by Surface Tension Method: Surface tension measurements were done by applying du Nouy ring method using Du-Nouy (Kruss, Type 8451) tensiometer and platinum ring at room temperature (25˚C). Stock solution of 5% (v/v) of synthesized nonionic surfactant in aqua was prepared in 1 L volumetric flask. First of all, the surface tension of pure water in a glass vessel was noted. The surface tensions were measured by a dilution method in which a 5% (v/v) of synthesized nonionic surfactant stock solution was gradually diluted by deionized water. After each dilution the solution was stirred for 30 s, and then left for 2 min before reading the surface tension value. All surface tension measurements were done at least three times or up to obtaining repeated value. The CMC values were determined by plotting surface tension versus concentrations of surfactant (23) . Table (1) : Physical properties and FT-IR spectral data cm-1 of the synthesized compounds (1-5). Com. No. Physical Properties Major FT-IR Absorption cm-1 Structures M.P °C Yield % Color (C-H) arom. (C-H) aliph. (C=O) (C=C) aromati c Others 1 48 -50 75 Pale yellow 3030 2920 2850 1764 1598 1533 1487 (C=N) 1641
- 4. Synthesis, Identification And Surface Active Properties Of Some Nonionic Surfactants Containing DOI: 10.9790/5736-1005013746 www.iosrjournals.org 40 |Page 2 N N O C15H31 N H O NH2 94-96 80 White 3061 2918 2849 1676 amid 1645 amid 1575 1531 1490 NH 3298 νNH2 asym 3425 sym 3226 (C=N) 1676 3 99-100 80 White 3062 2918 2850 1676 amid 1585 1537 1494 (C=S) 1409 NH 3358 νNH2 asym3358 sym3286 (C=N)1635 4 117- 118 80 White 3052 2922 2855 1678 amid 1648 amid 1590 1538 1494 NH 3358 (C=N) 1604 5 98-100 80 Off white 3062 2916 2850 1674 amid 1590 1537 1491 νNH2 asym3396 sym3245 (C=N) 1601 Table (2) : Physical properties and FT-IR spectral data cm-1 of the synthesized compounds (6-8). Com. No. Physical Properties Major FT-IR Absorption cm-1 Structures M.P °C Yield % Color (C-H) arom. (C-H) aliph. (C=O) (C=C) aromatic Others 6 88 -90 85 White 3030 2910 2850 1689 amid 1580 1540 1492 NH 3329 (C=N) 1604 7 102- 104 85 White 3035 2911 2849 1697 amid 1585 1541 1488 NH 3329 (C=N) 1608 8 104- 106 85 Off white 3030 2910 2850 1685 amid 1705 amid 1585 1555 1490 NH 3329 (C=N) 1635 Table (3) : Physical properties and FT-IR spectral data cm-1 of the synthesized compounds (9-14). Com. No. Physical Properties Major FT-IR Absorption cm-1 Structures M.P °C Yield % Color (C-H) arom. (C-H) aliph. (C=O) (C=C) aromatic Others 9 90 -91 75 White 3040 2920 2860 1677 amid 1600 1565 1494 NH2 3440,3336 (C=S) 1413.7 (C=N) 1606.5 10 88-90 75 White 3040 2960 2860 1699 amid 1677 amid 1585 1555 1490 NH2 3421,3320 (C=N) 1608 11 72 -73 70 off White 3067 2920- 2850 1685 amid 1605 1550 1492 OH 3420 (C=N) 1604 12 92-93 75 White 3060 2945 2850 1732 acid 1697 amid 1595 1565 1490 OH 3340 (C=N) 1608 13 114 - 115 70 White 3036 2920- 2850 1681 amid 1605 1550 1492 NH 3168 (C=N) 1604
- 5. Synthesis, Identification And Surface Active Properties Of Some Nonionic Surfactants Containing DOI: 10.9790/5736-1005013746 www.iosrjournals.org 41 |Page 14 90-91 75 red 3050 2955 2850 1679 amid 1595 1565 1490 NH 3340 (C=N) 1606 III. Results And Discussion The synthetic sequences for preparation of series new 2-pentadecyl quinazolinone compounds by reaction of pentadecanoyl chloride with anthranilic acid gave 2-pentadecyl-4H-benzo[3,1]oxazin-4-one [1] which was used as starting material to synthesis some quinazolinone compounds by a reaction with nitrogen nucleophiles (e.g., semicarbazide, thiosemicrabazide, phenylsemicarbazide and hydrazine hydrate) are show in scheme(1). Scheme (1): Synthesis of new derivatives of quinazolinone (1-5) Physical properties of compounds [2, 3, 4 and 5] are listed in Table (1). FTIR spectrum of prepared compounds [2, 3, 4 and 5] showed appearance of absorptions at (3425-3396) cm-1 and at (3286-3226) cm-1 of NH2 asym. and sym. respectively. (3358, 3298) cm-1 of NH group, Also it showed shift in the C=O band from (1764cm-1 ) of cyclic ester to (1690- 1645 cm-1 ) of amide. FTIR spectral data are listed in Table (1). 1 H- NMR spectrum of compound [3] showed triplet signal at δ= (0.85) ppm due to (-CH3) protons, multiplet signal at δ= (1.2 – 2.66) ppm due to (C-H) protons of long chain 14CH2, signals at δ= (7.11 -7.60) ppm due to aromatic rings protons, singlet signal at δ= (8.09- 8.51) ppm due to (-NH2) protons, and singlet signal at δ= (11.1) ppm due to (N-H) proton as shown in Table (4). 13 C-NMR spectrum of compound [3] showed signals at δ= (22-27) ppm, δ= (122-133) ppm, δ= (147) ppm, δ= (162.29) ppm and δ= (174.5) ppm belong to long chain (C15H31), (C- aromatic), (C=N) imine, (C=O) ester and (C=S) respectively. 13 CNMR spectral data of compound [3] is listed in Table (5). Table (4) 1 H-NMR spectral data (ppm) for selected compounds. Comp. No. Structures 1 HNMR Spectral data(ᵟppm) 1 δ 0.85 (t,3H, CH3), δ 1.59 – 2.69 (m, 28H, 14CH2), δ 7.1 -8.5(m, 4H,ArH) 3 δ 0.85 (t, 3H, terminal CH3), δ 1.2 – 2.66 (m, 28H, 14CH2), δ 7.11 -7.60(m, 4H,ArH), δ8.09- 8.51 (s, 2H,NH2), δ 11.1 (s,1H, NH) 6 δ 0.84 (t,3H, CH3), δ 1.22 – 2.50 (m, 28H, 14CH2), δ 6.51 -7.84 (m, 9H,ArH) , δ 9.10( s, 1H ,N-NH) 7 δ 0.83 (t, 3H, terminal CH3), δ 1.27 – 2.4 (m, 28H, 14CH2),δ3.47 (s,3H, O=C-CH3), δ 7.01 -8.51(m, 4H,ArH)
- 6. Synthesis, Identification And Surface Active Properties Of Some Nonionic Surfactants Containing DOI: 10.9790/5736-1005013746 www.iosrjournals.org 42 |Page 9 δ 0.85 (t,3H, CH3), δ 1.8 – 2.38 (m, 28H, 14CH2), δ 7.11 -7.9(m, 4H,ArH), δ 8.5- 9.14( s, 2H ,NH2) Table (5) : 13 C-NMR spectral data (ppm) for selected compounds. Com. No structure 13CNMR Spectral data(ᵟppm) 1 22-27 (Long chain C7); 122(C1); 127(C2)134(C4), 147(C3); 148(C6); 162.4(C5). 3 22-27 (Long chain C7); 123(C1); 128(C2); 133(C4),147(C6); 162.92(C5); 174.5(C8) 6 22-27 (Long chain C7); 122(C1); 126(C2); 132(C4); 145 ( C3 and C9) ; 146(C6); 162 (C5); 168 (C8) 7 22-27 (Long chain C7); 58 (C9) ; 121(C2); 128(C4); 133.4(C1); 145(C3); 154(C6); 161 (C5); 169 (C8) 9 17-27 (Long chain C7); 121(C1); 125(C2); 134(C4); 148(C6); 164 (C5);182 (C8) Compound [5] allowed to react with halogenated compounds such as benzoyl chloride, acetyl chloride and chloro acetyl chloride by nucleophilic substitution reaction to synthesis newly derivatives of quinazolinone compounds [6], [7] and [8]. This reaction carried out in presence of catalytic amount of pyridine and DMF. The synthetic sequences for preparation of new N-(4-oxo-2-pentadecylquinazolin-3(4H)-yl) benzamide [6], acetamide [7] and chloro acetamide [8] was performed as outlined in scheme (2). Scheme (2) Physical properties of compounds [6], [7] and [8] listed in Table (2). FTIR spectrum of compound [6], [7] and [8] showed disappearance of ν (NH2) absorption band at 3496 and 3245 cm-1 and appearance of characteristic absorption bands at ν cm-1 3329 for ν (N-H), 3030 for C-H aromatic; 2910 and 2850 for C-H aliph
- 7. Synthesis, Identification And Surface Active Properties Of Some Nonionic Surfactants Containing DOI: 10.9790/5736-1005013746 www.iosrjournals.org 43 |Page ; 1689 for C=O (amide) ; 1604 for C=N of compound[6]; 1697 for C=O (amid) of compound[7]; and 1685for C=O (amide) of compound[8]; C=N (1604 - 1635) cm-1 . 1 H-NMR spectrum data of compound [6] showed triplet signal at δ= (0.84) ppm due to (-CH3) protons, multiplet signal at δ= (1.22 – 2.50) ppm due to (C-H) protons of long chain 14CH2, signals at δ= (6.51 -7.84) ppm due to aromatic rings protons, singlet signal at δ= (9.10) ppm due to (N-H) proton. 1 H-NMR Spectral data of compounds [6] are listed in Table (4). 13 C-NMR spectrum of compound [6] showed signals at δ= (22-27) ppm, δ= (126 -135) ppm, δ= (146) ppm and δ= (168) ppm belong to long chain (C15H31), (C-aromatic), (C=N) imine and (C=O) ester respectively. 13 CNMR spectral data of compound [6] are listed in Table (5). While 1 H-NMR spectrum data of compound [7] showed triplet signal at δ= (0.83) ppm due to (-CH3) protons, multiplet signal at δ= (1.27 – 2.4) ppm due to (C-H) protons of long chain 14CH2, singlet signal at δ= (3.47) ppm due to (O=C-CH3) proton, signals at δ= (7.01 -8.51) ppm due to aromatic rings protons. 1 H-NMR Spectral data of compounds [7] are listed in Table (4). 13 C-NMR spectrum of compound [7] showed signals at δ= (22-27) ppm, δ= 58 ppm, δ= (128-134) ppm, δ= (145) ppm, δ= (154) ppm, δ= (161) ppm and δ= (169) ppm belong to long chain (C15H31), (O=C-CH3), (C- aromatic), (C=N) imine , (C=O) ester (C=O-CH3) respectively. 13 CNMR spectral data of compound [7] are listed in Table (5). The syntheses of different new quinazolinone compounds by reaction of compound [1] with different substituted amine compounds. These different synthesized compounds that are presented in Scheme (3). Scheme (3) Reaction of compound [1] with thiourea and urea in presence catalytic amount of pyridine afforded the product N-(4-oxo-2-pentadecylquinazoline-3(4H)-yl) carbothioamide [9], carboxamide [10] respectively. Physical properties of compounds [9] and [10] are listed in Table (3). FTIR spectrum of prepared compounds [9-10] showed appearance of absorptions at (3440-3320) cm-1 , (3040) cm-1 , (2960, 2860) cm-1 , (1699 and 1677) cm-1 , (1608) cm-1 due to ν –NH2, ν C-H aromatic, ν C-H aliphatic, ν C=O for amide, ν C=N of compounds (9 and 10), in addition (1413) cm-1 for ν C=S of compound [9]. In the other hand1 HNMR spectra data of compound (9) δ ppm in DMSO-d6 solvent showed singlet signal at δ= (0.85) ppm due to (-CH3) protons, multiplate signale at δ= (1.18-2.38) due to long chain (14CH2), signals at δ= (7.9-7.11) ppm due to aromatic ring protons and δ= (8.5-9.14) ppm due to (-NH2) protons. As listed in table (4). 13 C-NMR spectrum data of compound [9] showed signals at δ= (17-27) ppm, δ= (121-134) ppm, δ= (148) ppm, δ= (164.07) ppm and δ= (182.3) ppm belong to long chain (-C15H31), (C-aromatic), (C=N), (C=O) amide and (C=S) respectively.13 CNMR spectral data of compound [9] is listed in Table (5).. the synthesized quinazolinone derivatives bearing an active hydrogen atom such as (-NH, -OH, -COOH and - NH2) and the structure of a surface active agent requires a hydrophilic component. This is accomplished through the condensation of propylene oxide with different moles, (3, 5 and 7) moles in the presence of KOH as catalyst at any active hydrogen atom of synthesized compounds [2, 4, 5, 7 and 12] which contain one or more active hydrogen atoms to yield novel groups of nonionic surfactant (2(a-c), 4(a-c), 5(a-c), 7(a-c) and 12(a-c)) respectively that showed in scheme (4).
- 8. Synthesis, Identification And Surface Active Properties Of Some Nonionic Surfactants Containing DOI: 10.9790/5736-1005013746 www.iosrjournals.org 44 |Page Scheme (4) The study of the surface active properties of the polypropenoxy compounds has been done in an aqueous solution (1wt %, pH = 7) at 25o C. The surface activity and related properties of the synthesized compounds including surface tension and interfacial tension, wetting time, cloud point, foaming height, emulsification properties and CMC are given in Table (6). The surface and interfacial tension of the synthesized compounds are shown in Table (6). It can be observed that the nonionic surfactants have pronounced surface activity. The surface and interfacial tension increase with an increase in the molecular weight of the hydrophobic moiety. The data given in Table (6) shows that the values of surface and interfacial tension increased with the increase in the number of propylene oxide units added to the molecule. (24) A very important factor in making the most efficient use of nonionic surfactants in an aqueous system is an understanding of the property called cloud point. All synthesized compounds showed high cloud points which gave performance in hot water and it was increased by increasing the number of the propoxy group. All the synthesized compounds showed a decrease in wetting time with an increase in the number of propylene oxide units in the molecule. Moreover, the presence of propylene oxide in different moles caused a reduction in wetting time, i.e. improving their wetting properties which make widely applicable in the textile industry. (25) Nonionic surfactants containing an aromatic ring such showed poor foaming properties. The foam height of the prepared surfactants increases with an increase in the number of propylene oxide units per molecule of surfactant. The low foaming power could have an application in the dyeing auxiliary industry Emulsification is one of the most important Properties of surfactants. In many textile processes such as scouring and dyeing, it is necessary to introduce surfactants into the bath to remove oily impurities from the fibers. On the other hand, nonionic surfactants with good emulsion stability have been used in such fields as, shampoos, cosmetics, emulsion paints and the textile industry. The results in Table (6) showed that the emulsion stability increases by decreasing the number of propylene oxide units.
- 9. Synthesis, Identification And Surface Active Properties Of Some Nonionic Surfactants Containing DOI: 10.9790/5736-1005013746 www.iosrjournals.org 45 |Page Table (6) surface properties of synthesized compounds (2(a-c), 4(a-c), 5(a-c), 7(a-c) and 12(a-c)) compd No of moles Surface Tension (dyne/cm) 0.1wt% Interfacial tension (dyne/cm) 0.1wt% Cloud point C 0.1wt% Wetting time (Sec) 0.1wt% Emulsion stability (Min) 25 mmole Foam height (mm) 0.1wt% CMC × 10-3 2(a-c) 3 5 7 32 33 35 10 11 13 58 64 73 43 32 21 92 85 74 85 115 135 3.6 4.1 4.3 4(a-c) 3 5 7 30 33 34 9 11 12 67 75 84 46 28 20 94 84 71 90 105 130 3.8 4.0 4.2 5(a-c) 3 5 7 28 30 32 8 10 12 74 91 98 41 33 24 101 95 75 95 110 140 3.9 4.1 4.3 7(a-c) 3 5 7 32 33 35 9 11 13 68 82 91 49 35 26 96 85 78 105 135 150 4.0 4.1 4.4 12(a-c) 3 5 7 33 34 35 10 13 14 72 76 81 40 31 21 112 93 87 95 120 135 3.4 3.6 3.9 The reaction condition of propenoxilated compounds are illustrated in table (7). Table (7) reaction condition of propenoxilated compounds compd Catalyst,wt% Temp C Propenoxylated compounds Yield% Degree of propenoxylation color 2 KOH, 0.01wt% 130 2(a-c) 55-60 3,5 and 7 brown cream 4 4(a-c) 60-65 Pale brown cream 5 5(a-c) 70-74 Yellow white Cream 7 7(a-c) 63-68 Pale brown cream 12 12(a-c) 72-75 Yellow white Cream 1 H-NMR spectra data of compound [4(a-c) and 5(a-c)] showed disappearance peaks –NH of compound [4] and –NH2 of compound [5]. And appearance multiplate signal at δ= (3.2 – 3.7) ppm due to the protons of propenoxy groups (-CH2-CH-(CH3)-O)- beside other characteristic bands as listed in table (8) and shown in Figure (1 and 2). Table (8): 1 H-NMR spectral data δ ppm for compound [4(a-c) and 5(a-c)] Comp. No. Structures 1 HNMR Spectral data(ᵟppm) 4(a-c) δ 0.83 (t,3H, CH3), δ 1.8 – 2.38 (m, 28H, 14CH2), δ 3.2-3.7( m, (-CH2-CH-(CH3)-O)-) δ 7.11 -7.9(m, 9H,ArH) 5(a-c) δ 0.85 (t,3H, CH3), δ 1.8 – 2.38 (m, 28H, 14CH2), δ 3.2-3.7( m, (-CH2-CH-(CH3)-O)-) δ 7.11 -8.3(m, 4H,ArH) Figure (1) 1 H-NMR spectrum of compound [5(a-c)]
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