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October 2006 University of Sharjah Journal of Pure & Applied Sciences Volume 3, No. 3 25

SYNTHESIS, CHARACTERIZATION AND KINETIC

STUDIES OF ETHYLENE-[1,3]OXAZINAN -4,6-

DIONE, CARBONYL-[1,3]OXAZINAN-4,6-DIONE AND

THIOCARBONYL-[1,3]OXAZINAN-4,6-DIONEFROM REACTION OF SCHIFF-BASES OF

ETHYLENE DIAMINE, UREA AND THIOUREA WITH

MALONIC ANHYDRIDE

Mohammed A. Al-HadithiChemistry Department, College of Science, University of Al-Anbar, Iraq

ABSTRACT

N-benzylidene2-({2-[(2-hydroxy-benzylidene)-amino]-ethylimino}-methyl)- phenol,1,3-Bis-(2-hydroxy-benzylidene)-urea and1,3-Bis-(2-hydroxy-benzylidene)-Thiourea (Schiff bases) were prepared by condensation of Ethylenediamine,urea and thiourea with Salicylaldehyde and 4-dimethyl aminebenzaldhyde. These Schiff bases were reacted with Malonic anhydride byrefluxing it in absolute ethanol at 78C for 1,3 and 2 hrs. respectively to give asix-membered heterocyclic ring system; 2-(2-hydroxy-phenyl)-3-{2-[2-(2-hydroxy-

phenyl)-4,6-dioxo-[1,3]oxazinan-3-yl]-ethyl}-[1,3]oxazinan-4,6-dione,2-(2-hydroxy-phenyl)-3-[2-hydroxy-phenyl)-4,6-dioxo-[1,3]oxazinan-3-carbonyl]-[1,3]oxazinan-4,6-dione and 2-(2-hydroxy-phenyl)-3-[2-hydroxy-phenyl)-4,6-dioxo-[1,3]oxazinan-3-thiocarbonyl]-[1,3]oxazinan-4,6-dione.

The costants of reaction velocity for the compounds (Schiff-bases) with

(malonic anhydride) were studied and showed that the reaction was a first-orderone. Some of the thermodynamic characteristics were evaluated and showeddifferences among the prepared compounds. The final products were identified bytheir melting points, elemental analysis, IR,

1H NMR and UV-Visible spectra.

Keywords: Schiff bases; oxazinan; synthesis; properties; kinetic studies.

-4,)(

78.(-6,4--(-3-}2-]2-)2--:2-)2)2(

-(-3-]2-)2--,2-)2-6,4-]{-]3,1-]--3]-]3,1

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Synthesis, Characterization and Kinetic Studies of Ethylene-[1,3]Oxazinan -4,6-Dione, Carbonyl-[1,3]Oxazinan-

4,6-Dione and Thiocarbonyl-[1,3]Oxazinan-4,6-Dione from Reaction of (Schiff-Bases) of Ethylene Diamine,Urea and Thiourea with Malonic Anhydride

University of Sharjah Journal of Pure & Applied Sciences Volume 3, No. 3 October 200626

---)2-6-4-]--3]3-]11-6(-4-.-6-4-]--3]3-]11-6(-4--(-3-]2-)2

.IR,,1HNMR.UV)(

, .

1. INTRODUCTION

The sixmembered heterocyclic ring system: 1,3-oxazine hasalready been reported and thoroughly reviewed in the literature [1-4].

Maleic, arylmaleic and substituted maleic anhydrides react withtrimethylsilyl azide to give 4- and 5-substituted "oxauraciles": dihydro-

1,3-oxazine-2,6-diones [5,6].

Both 2-methoxypyrroline and 2-methoxypiperdinine react withdiketene under netural conditions at 0C to give the corresponding,2-

methoxydihydro 1,3-oxazine-4-ones [7,8].

Diketene reacts with N,N-diphenyl guanidine to give the tranquilizer

ketazolam and N- substituted tetrahydro-1,3-oxazine-4-one respectively

[9-10]. The reaction of diketene with isocyanic acid, cyanamides andflourosulphinyl isocyanate afforded the corresponding 1,3-oxazine-2,4-

diones [11,13].

Ethyl benzimidate,and ethyl butyrimidate react with diketene to give

2-ethoxy-1,3-oxazine- 4-ones [14]. Imines and N-acyl imines react with

diketen to give tetrahydro-1,3-oxazine-4-ones [15,16].

N-acyl imines undergo [4+2] cycloaddition with both-C=C- and

heterodienes. For instance, isolable bis(trifluoromethyl)acyl imine,reactswith 2,2-dimethylethylene to give 1,3-oxazine.

N-acyl Ammonium ions have been the most commonly used dienes

to effect [4+2] cycloaddition as 4 components with substituted 1,3- butadienes. It is found that N-acylimimes or immonium ions that are

capable of tautomerization undergo intramolecular Diels-alder reactionto give dihydro-1,3-oxazines [17].

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Mohammed A. Al-Hadithi (25- 45)


The reaction of N-benzylidene 1,5-dimethyl-2-phenylpyrazolonamines

(Schiff bases with cyclopentane -1,1-dicarboxylic anhydride to give 2-aryl-

3-3(1,5-dimethyl-2-phenylpyrazolo)-1-(5) spirocyclopentyltetra hydro-1,3-

oxazine-4,6-diones [18].

Synthesis and characterization of 8-(4-dimethyl amino-phenyl)-9-(6-

R- benzothiazol-2-yl)-7-oxa-9-aza-spiro[4.5]decane-6,10-dione [19].

2. EXPERIMENTAL METHODS

Melting points were recorded with Gallenkamp Melting point

Apparataus and were uncorrected. Elemental analysis were carried out

with perkin-Elmer,2400;CHN Elemental Analyzer. FT-IR spectra were

recorded on FT-IR spectrophotometer -8400s Shimadza (KBr) and UV-

Visible spectra were recorded (in ethanol) on Schimadza Reco- 160Spectrophotometer. Their H-NMR spectra were recorded with

BRUKERAC200MHZFT NMR spectrophotometer.

Preparation of N-(4-Dimethylamino-benzylidene)-N`-(4-

Dimethylamino-benzylidene)-ethan-1,2 diamine: A mixture of 0.01

mole (0.6 g) of ethylene diamine and 0.01 mole (1.66 g) of 4-

dimethylamino benzaldehyde in 10 ml of absolute ethanol, was refluxed in

a water bath for 30 min, then left to cool in icewater bath whereby yellow

crystalline solid was precipitated. The solid was filtered, washed with

2%HCl, then with water and recrystallized twice from ethanol.

Preparation of 1,3-Bis-(2-hydroxy-benzylidene)-urea: A mixture

of 0.01 mole (0.6 g) of urea and 0.01 mole (1.22 g) of o-

hydroxybenzaldehyde in 10 ml of absolute ethanol, was refluxed in a

water bath for 45 min, then left to cool in icewater bath whereby yellow



Preparation of 1,3-bis-(2-hydroxy-benzylidene)-thiourea: A

mixture of 0.01 mole (0.76 g) of thiourea and 0.01 mole (1.22 g) of o-

hydroxybenzaldehyde in 10 ml of absolute ethanol, was refluxed in a

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water bath for 1hr, then left to cool in icewater bath whereby yellow



Preparation of 3-{2-[(2-hydroxy-benzylidene)-amino]-ethyl}-2-(2-hydroxy-phenyl)-[1,3]oxazinan-4,6-dione: In a 100 ml round

bottom flask equiped with a double surface condenser fitted with

calcium chloride guard tube, was placed a mixture of 0.01mol (2.68 g)

of (4-2-({2-[(2-hydroxy-benzylidene)-amino]-ethylimino}-methyl)-

phenol and 0.01 mol (0.86 g) of malonic anhydride in 20ml of absolute

ethanol. The reaction mixture was refluxed in water bath at 78C for

2hr., the solvent was then removed and the resulting solid was

recrystallized from anhydrous THF.

Preparation of 2-(2-hydroxy-phenyl)-3-{2-[2-(2-hydroxy-phenyl)-

4,6-dioxo-[1,3]oxazinan-3-yl]-ethyl}-[1,3]oxazinan-4,6-dione: In a 100

ml round bottom flask equiped with a double surface condenser fitted

with calcium chloride guard tube, was placed a mixture of 0.01mol (2.68

g) of 3-{2-[(2-hydroxy-benzylidene)-amino]-ethyl}-2-(2-hydroxy-phenyl)-

[1,3]oxazinan-4,6-dione and 0.01 mol (0.86 g) of malonic anhydride in

20ml of absolute ethanol. The reaction mixture was refluxed in water bath

at 78C for 2hr., the solvent was then removed and the resulting solid was

recrystallized from anhydrous THF.

Preparation of 2-(4-dimethylamino-phenyl)-4,6-dioxo-[1,3] oxazinan

-3-carboxylicacid-4-dimethylaminobenzylideneamide: In a 100 mlround bottom flask equiped with a double surface condenser fitted with

calcium chloride guard tube, was placed a mixture of 0.01 mol (3.22 g) of

1,3-bis-(4-dimethylamino-benzylidene)-urea and 0.01 mol (0.86 g) of

malonic anhydride in 20ml of absolute ethanol. The reaction mixture was

refluxed in water bath at 78C for 3hr., the solvent was then removed and

the resulting solid was recrystallized from anhydrous 1,4-dioxan.

Preparation of 2-(4-dimethylamino-phenyl)-3-[2-(4-dimethylamino -

phenyl)-4,6-dioxo-[1,3]oxazinan-3-carbonyl]-[1,3]oxazinan-4,6-dione:

In a 100 ml round bottom flask equiped with a double surface condenser

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fitted with calcium chloride guard tube, was placed a mixture of 0.01mol

(4.085 g) of 2-(4-dimethylamino-phenyl)-4,6-dioxo-[1,3]oxazinan-3-

carboxylicacid-4-dimethylaminobenzylideneamide and 0.01 mol (0.86 g)

of malonic anhydride in 20ml of absolute ethanol. The reaction mixture

was refluxed in water bath at 78C for 3hr., the solvent was then removed

and the resulting solid was recrystallized from anhydrous 1,4-dioxan.

Preparation of 2-(4-Dimethylamino-phenyl)-4,6-dioxo-[1,3]oxazinan

-3-carbothioicacid-4-dimethylaminobenzylideneamide: In a 100 ml

round bottom flask equiped with a double surface condenser fitted with

calcium chloride guard tube, was placed a mixture of 0.01 mol (3.38 g)

of 1,3-bis-(4-dimethylamino-benzylidene)-thiourea and 0.01 mol (0.86

g) of malonic anhydride in 20ml of absolute ethanol.

The reaction mixture was refluxed in water bath at 78C for 3hr., the

solvent was then removed and the resulting solid was recrystallized fromanhydrous THF.

Preparation of 2-(4-dimethylamino-phenyl)-3-[2-(4-dimethylamino -

phenyl)-4,6-dioxo-[1,3]oxazinan-3-thiocarbonyl]-[1,3]oxazepane-4,7-

dione: In a 100 ml round bottom flask equiped with a double surface

condenser fitted with calcium chloride guard tube, was placed a mixture

of 0.01mol (4.24g) of 2-(4-dimethylamino-phenyl)-4,6-dioxo-

[1,3]oxazinan-3-carbothioicacid-4-dimethylaminobenzylideneamide

and 0.01 mol (1.0 g) of succinic anhydride in 20ml of absolute ethanol.

The reaction mixture was refluxed in water bath at 78C for 3hr., the

solvent was then removed and the resulting solid was recrystallized fromanhydrous 1,4-dioxan.

3. DISCUSSION

It is known that Schiff bases react smoothly with acid chlorides and

anhydrides to give the corresponding addition products[20-22].

The reaction is followed by the appearance of (N=CH) absorption

band at (1600-1610) cm-1 the disappearance of both (C=O) absorption

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HO N

N OH

C O

C

O

O

CO

C

O

O[11A]

O

O

O

HO N

N OH

C O

C

O

O

CO

C

O

O

HO N

N OH(Z)

(Z)

[11B]

Ethanol

water bath/ reflx

band at (1670-1685) cm-1 and (-NH2) absorption bands at (3400,3650)

cm-1 in their IR spectra.

In this paper,the reaction of the malonic anhydride with(4-2-({2-[(2-

hydroxy-benzylidene)-amino]-ethylimino}-methyl)-phenol gives thedipolar intermediate [11A] which collapses to the 6-membered

hetrocyclic ring system [11B] is presented.

This is indicated by the appearance of the characteristic C=O

(lacton-lactam) absorption band at 1700cm-1 in the IR spectra of the

addition products [11B].

It is impressive to note that the two absorption band at (1800-

1950)cm-1 in the IR spactra of pure malonic anhydride and 2-Oxa-

spiro[3.4] octane-1,3-dione (anhydride) have disappeared when the

anhydride became part of the 6-membered ring system of the 2-(2-

hydroxy-phenyl)-3-{2-[2-(2-hydroxy-phenyl)-4,6-dioxo-[1,3]oxazinan-

3-yl]-ethyl}-[1,3]oxazinan-4,6-dione and 6-(4-dimethylamino-phenyl)-

7-{2-[2-(4-dimethylamino-phenyl)-4,6-dioxo-[1,3]oxazinan-3-yl]-

ethyl}-5-oxa-7-aza-spiro[2.5]octane-4,8-dione.

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Table 1. Melting points, yield, molecular formula [M.F], elemental analysis and UV-Visible

absorption maxima (nm) of ethylene [1,3] oxazinan-4,6-dione (1-8).

Calculated FoundNo. M.P/C Yield% M.F.

C% H% N% C% H% N%

UV-Visible absorption

Maxima(nm)

1 192-194

66 C12H14N2O4 57.59 5.64 11.19 57.66 5.70 11.31 482,454,3,51,301,224,202

2 204-206

73 C19H18N2O5 64.40 5.12 7.91 64.35 15.20 7.74 485,459,375,310,225,205

3 210-212

80 C22H20N2O8 60.00 4.58 6.36 59.89 4.62 6.23 346, 315,289,2,75,252,207

4 160-

162

77 C14H19N3O3 60.63 6.91 15.15 60.71 7.02 15.11 478,345,312,286,250,224

5 166-168

69 C23H28N4O3 67.63 6.91 13.72 67.60 7.00 13.59 474,376,300,299,264,223,

6 167-169

82 C26H30N4O6 63.15 6.11 11.33 63.10 5.99 11.23 471,340,311,291,257,220

7 126-128

69 C23H22N2O8 60.79 4.88 6.16 60.81 5.00 6.10 445,430,398,368,264,232

8 174-176

75 C27H32N4O6 63.77 6.34 11.02 63.59 6.33 11.00 456,326,288,261,249,227

Table 2. The major IR absorptions (cm-1) of ethylene [1,3]oxazinan-4,6-dione (1-8).

No. OHstr.

phenol

NH2 C-H str.

benzylic

C=Ostr.

Lacton

C=Ostr.

Lactam

C=Nstr.

Imine

C=Cstr.

Aromatic

C-O str.

Lacton

CH bend.

Aromatic

1 3470 3450,3420 3230 1690 1645 1610 1560 1330 760

2 3480 - 3220 1690 1650 1600 1570 1320 780

3 - 3440,3410 3220 1695 1650 1610 1570 1310 780

4 - - 3230 1700 1650 1610 1560 1300 770

5 3475 - 3225 1695 1640 1605 1590 1320 780

6 - - 3225 1680 1640 1600 1580 1285 760

7 3490 - 3200 1690 1645 1610 1580 1300 760

8 - - 3200 1685 1640 1600 1570 1310 770

Table 3. The major1

H NMR absorptions (ppm) of ethylene [1,3] oxazinan-4,6-dione (1-8).Benzene

ringCOCH2

H2C

C O

NCH3H3C

OHO

CH2

N

CO

CH2

CO

N CH2

CH2

N

-NH2No.

6.5-7.0_-4.87.23.02.8, 3.52.11

6.5-7.1_-4.97.23.13.5, 3.7-2

6.5-7.0_2.75-7.23.02.75, 3.42.13

6.5-7.5_2.75-7.13.052.75, 3.4-4

6.5-7.5_-4.97.23.13.4-5

6.5-7.0_2.75-7.223.13.41, 3.72-6

6.5-7.12.5_4.857.23.153.41, 3.72-7

6.5-7.12.512.75-7.23.153.43-8

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absorption maxima (nm) of carbonyl [1,3]oxazinan-4,6-dione (9-16).

Calculated Found

No. M.P/C

Yield%

M.F.C% H% N% C% H% N%

UV-Visible absorptionMaxima (nm)

9 214-216

57 C11H10N2O5 52.80 4.03 11.20 52.77 4.00 11.15 389,336,322,277,248,221

10 208-210

66 C18H14N2O6 61.02 3.98 7.91 60.98 4.03 7.88 393,345,303,235,223,213

11 190-192

67 C13H15N3O4 56.31 5.45 15.15 56.42 5.56 15.12 386,358,317,282,249,225

12 125-127

68 C22H24N4O4 64.69 5.92 13.72 64.76 6.04 13.65 412,396,375,266,246,220

13 136-138

67 C21H16N2O9 57.28 3.66 6.36 57.34 3.73 6.33 460,404,377,332,269,225

14 200-202

70 C22H18N2O9 58.15 3.99 6.17 58.00 4.11 6.04 463,419,384,334,246,228

15 128-130

59 C25H26N4O7 60.72 5.30 11.33 60.80 5.34 11.25 400,383,349,291,254,226

16 146-148

63 C26H28N4O7 61.41 5.55 11.02 61.44 5.60 11.00 397,354,323,277,235,222

Table 5. The major IR absorptions (cm-1) of carbonyl [1,3]oxazinan-4,6-dione (9-16).

No. OHstr.Phenol

NH2 C-H str.benzylic

C=Ostr.Lacton

C=Ostr.Lactam

C=Nstr.Imine

C=Cstr.Aromatic

C-O str.Lacton

CH bend.Aromatic

9 3490 3460,3410 3240 1700 1640 1600 1580 1300 770

10 3495 - 3220 1680 1650 1620 1590 1310 760

11 - 3475,3400 3225 1680 1640 1610 1580 1320 760

12 - - 3240 1675 1655 1610 1575 1320 780

13 3480 - 3200 1690 1645 1600 1575 1300 760

14 3475 - 3240 1670 1635 1600 1580 1310 760

15 - - 3210 1685 1640 1615 1590 1290 780

16 - - 3210 1670 1650 1600 1570 1290 770

Table 6. The major1H NMR absorptions (ppm) of carbonyl [1,3] oxazinan-4,6-dione (9-16).

No. NH2 CO

CH2

CO

OCH2

N

OH NCH3H3C

COCH2

H2C

C O

Benzenering

9 5.7 3.20 7.2 4.8 2.7 - 6.4-7.5

10 - 3.12 7.1 4.75 2.77 - 6.5-7.5

11 5.8 3.22 7.2 4.9 2.75 - 6.44-7.7

12 - 3.15 7.15 4.8 2.68 - 6.4-7.5

13 - 3.11 7.2 4.8 2.78 - 6.4-7.8

14 - 3.20 7.2 4.75 2.84 - 6.4-7.5

15 - 3.17 7.22 4.8 2.75 2.46,2.5 6.4-7.5

16 - 3.18 7.2 4.85 2.75 2.44,2,5 6.5-7.4

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absorption maxima (nm) of thiocarbonyl[1,3] oxazinan-4,6-dione (17-24).

Calc. FoundNo. M.P/C Yield%

M.F.C% H% N% C% H% N%

UV-Visible absorptionMaxima (nm)

17 178-180 62 C11H10N2O4S 49.62 3.79 10.52 49.73 384 10.45 425,367,291,249,220,20318 184-186 66 C18H14N2O5S 58.37 3.81 7.56 58.46 4.00 7.34 436,402,286,255,231,22319 124-126 59 C13H15N3O3S 53.23 5.15 14.32 53.42 5.22 14.20 389,352,320,284,247,22720 236-138 58 C22H24N4O3S 62.24 5.70 13.20 62.34 5.83 13.11 403,387,355,321,285,22421 136-138 67 C21H16N2O8S 55.26 3.53 6.14 55.36 3.60 6.04 430,386,361,342,288,234,22222 129-131 70 C22H18N2O8S 56.17 3.86 5.95 56.23 4.00 5.91 410,379,346,275,249,22623 140-142 64 C25H26N4O6S 58.81 5.13 10.97 60.00 5.25 1082 416,390,361,282,237,22924 158-160 60 C24H24N4O6S 58.05 4.87 11.28 85.11 5.01 11.12 400,369,345,289,264,235,220

Table 8. The major IR absorptions (cm-1) of thiocarbonyl [1,3]oxazinan-4,6-dione (17-24).

No. OH str.phenol

NH2 C-H str.Benzylic

C=O str.Lacton

C=O str.Lactam

C=N str.Imine

C=C str.Aromatic

C-O str.Lacton

CH bend.Aromatic

17 3500 3480,3410 3310 1685 1655 1605 1595 1290 76018 3490 - 3220 1690 1650 1605 1590 1300 76019 - 3495, 3420 3200 1680 1650 1610 1580 1310 77020 - - 3230 1685 1640 1620 1570 1300 790

21 3495 - 3200 1670 1640 1610 1570 1320 79022 3505 - 3200 1670 1640 1600 1655 1320 78023 - - 3210 1685 1645 1620 1670 1310 760

24 - - 3230 1680 1650 1625 1675 1320 760

Table 9. The major1H NMR absorptions (ppm) of thiocarbonyl [1,3] oxazinan-4,6-dione (17-24).

No. -NH2

CO

CH2

CO

OCH2

N

OH

NCH3H3C

COCH2

H2C

C O

Benzenering

17 2.2 3.2 7.2 4.9 - - 6.4-7.218 - 3.05 7.15 4.9 - - 6.5-7.319 2.2 3.07 7.2 - 2.66 - 6.5-7.220 - 3.05 7.11 - 2.65 - 6.5-7.8

21 - 3.1 7.05 4.8 - - 6.5-7.822 - 3.2 7.15 - 2.7 - 6.6-7.623 - 3.2 7.2 4.8 - 2.55 6.5-7.824 - 3.15 7.2 - 2.65 2.52 6.5-7.8

4. CALCULATION OF THE REACTION VELOCITY

A first-order reaction equation was applied to the reaction of Schiff-bases

with Malonic anhydride. It proves to be useful to calculation of the reactions

velocity under vaying temperatures (213-253)K with (10) K increase.

The value of the reaction velocity K was calculated for all reactions

by drawing the relation between ln At/A with time.

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The relation between lnK and 1/T was then drawn. It shows the

effect of temperature on the reaction velocity in order to obtain the ideal

temperature for the reaction. It was noticed that velocity increases with

temperature and that the velocity is stable at (353) k.

From the Tables (10-21) we notice that the values ofH, S, and

G are positive. This proves that the reactions are endothermic and

spontaneous. We also notice that the activation energy H starts to

increase with different used compounds. So the (Ethylene Schiff-bases)

compounds are less than those of (thiourea schiff-bases), which are in

turn, less than the (Urea Schiff-bases) compounds. This is due to group

C=S and group C=O which reduce the electronic density on C=N group,

and consequently, it takes more energy and longer time for the reaction.

Table 10. Thermodynamic values for the reaction of (A) with malonic anhydride calculated fromthe effect of temperature on K, Ea, H, S and G value (1).

T [K] K,h-1

Ea / J mol-1

H Jmol-1

S J.K-1mol-1

G K,mol-1

313 0.0413 3137.4 539.5 -281.868 88764.16

323 0.0519 3137.4 488.8 -282.366 91693.018333 0.068 3137.4 373.5 -282.86 94565.88

343 0.084 3137.4 290.5 -283.362 131783.66

353 0.1112 3137.4 207.5 -283.86 100410.08

Table 11. Thermodynamic values of reaction of (B) with malonic anhydride calculated from the

effect of temperature on K, Ea, H, S and G value (2).

T [K] K,h-1

Ea / J mol-1

H Jmol-1

S J.K-1mol-1

G K,mol-1

313 0.0533 3304.4043 706.504 -283.86 89554.684

323 0.0651 3304.4043 623.504 -284.35 92468.554333 0.0891 3304.4043 540.504 -284.939 95425.191

343 0.1342 3304.4043 457.504 -285.354 98333.926353 0.1831 3304.4043 374.504 -285.935 101309.559

Table 12. Thermodynamic values of reaction of (C) with malonic anhydride calculated from theeffect of temperature on K, Ea, H, S and G value (4).

T [K] K,h-1

Ea / J mol-1

H Jmol-1

S J.K-1mol-1

G K,mol-1

313 0.0579 3292.7345 694.8349 -282.615 89153.3299323 0.0691 3292.7345 611. 8349 -284.441 92486.2779

333 0.0899 3292.7345 523. 8349 -283.03 94772.8249343 0.162 3292.7345 445. 8349 -283.528 97695.9389

353 0.1997 3292.7345 362. 8349 -284.026 100624.0129

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Table 13. Thermodynamic values of reaction of (D) with malonic anhydride calculated from the


T [K] K,h-1

Ea / J mol-1

H Jmol-1

S J.K-1mol-1

G K,mol-1

313 0.0521 3322.8469 742.9469 -284.026 89643.0849

323 0.0623 3322.8469 641. 9469 -284.275 92462.7719

333 0.0711 3322.8469 558. 9469 -285.105 95498.9119343 0.0834 3322.8469 475. 9469 -285.603 98437.77

353 0.123 3322.8469 392. 9469 -286.018 101357.3009

Table 14. Thermodynamic values of reaction of (E) with malonic anhydride calculated from theeffect of temperature on K, Ea, H, S and G value (17).

T [K] K,h-1

Ea / J mol-1

H Jmol-1

S J.K-1mol-1

G K,mol-1

313 0.0031 5710.4084 3112.5083 -297.876 96347.6963

323 0.0060 5710.4084 3029. 5083 -280.042 93483.0743333 0.020 5710.4084 2946. 5083 -280.955 96504.5233

343 0.0332 5710.4084 2863. 5083 -281.453 99401.8873353 0.0411 5710.4084 2780. 5083 -281.951 102309.2113

Table 15. Thermodynamic values of reaction of (F) with malonic anhydride calculated from theeffect of temperature on K, Ea, H, S and G value (18).

T [K] K,h-1

Ea / J mol-1

H Jmol-1

S J.K-1mol-1

G K,mol-1

313 0.0037 5884.7083 3286.8083 -281.785 91485.5133323 0.0081 5884.7083 3203. 8083 -281.204 94032.7003

333 0.0301 5884.7083 3120. 8083 -281.702 96927.5743343 0.0421 5884.7083 3037. 8083 -282.2 99832.4083

353 0.0562 5884.7083 2954. 8083 -282.615 102717.9033

Table 16. Thermodynamic values of reaction of (G) with malonic anhydride calculatedcalculated from the effect of temperature on K, Ea, H, S and G value (19).

T [K] K,h-1

Ea / J mol-1

H Jmol-1

S J.K-1mol-1

G K,mol-1

313 0.0043 5667.2566 3069.3566 -280.125 90748.4816

323 0.0076 5667.2566 2986. 3566 -280.623 93627.5856333 0.0312 5667.2566 2903. 3566 -281.121 96516.6496343 0.042 5667.2566 2820. 3566 -281.702 99444.1426

353 0.0558 5667.2566 2737. 3566 -282.117 102324.6576

Table 17. Thermodynamic values of reaction of (K) with malonic anhydride calculated from the


T [K] K,h-1

Ea / J mol-1

H Jmol-1

S J.K-1mol-1

G K,mol-1

313 0.0038 5730.3283 3132.4283 -280.042 90785.5743

323 0.0068 5730.3283 3049. 4283 -280.623 93690.229333 0.0214 5730.3283 2966. 4283 -279.71 96109.8583

343 0.0396 5730.3283 2883. 4283 -281.619 99478.7453353 0.0498 5730.3283 2800. 4283 -282.034 102358.4303

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Table 18. Thermodynamic values of reaction of (L) with malonic anhydride calculated from the


T [K] K,h-1

Ea / J mol-1

H Jmol-1

S J.K-1mol-1

G K,mol-1

313 0.0013 7924.8566 5326.9566 -279.129 92694.3336

323 0.0032 7924.8566 5243. 9566 -279.627 95563.4776

333 0.011 7924.8566 5160. 9566 -280.125 98442.5816

343 0.029 7924.8566 5077. 9566 -280.623 101331.6456

353 0.031 7924.8566 4994. 9566 -281.121 104230.669

Table 19. Thermodynamic values of reaction of (M) with malonic anhydride calculated from theeffect of temperature on K, Ea, H, S and G value (10).

T [K] K,h-1

Ea / J mol-1

H Jmol-1

S J.K-1mol-1

G K,mol-1

313 0.0018 7543.0566 4945.1566 -279.544 92442.4286

323 0.0041 7543.0566 4862. 1566 -280.042 95315.7226

333 0.018 7543.0566 4779. 1566 -280.623 98226.625

343 0.03 7543.0566 4696. 1566 -281.121 101263.0046

353 0.038 7543.0566 4613. 1566 -281.536 103995.3646

Table 20. Thermodynamic values of reaction of (N) with malonic anhydride calculated from theeffect of temperature on K, Ea, H, S and G value (11).

T [K] K,h-1

Ea / J mol-1

H Jmol-1

S J.K-1mol-1

G K,mol-1

313 0.0015 8099.9866 5502.0866 -280.208 93207.1906

323 0.0033 8099.9866 5419. 0866 -280.789 96113.9336

333 0.018 8099.9866 5336. 0866 -266.45 94063.9366

343 0.03 8099.9866 5253. 0866 -281.785 101905.3416

353 0.033 8099.9866 5170. 0866 -282.366 104845.2846

Table 21. Thermodynamic values of reaction of (O) with malonic anhydride calculated from the


T [K] K,h-1

Ea / J mol-1

H Jmol-1

S J.K-1mol-1

G K,mol-1

313 0.0016 7834.1376 5236.2376 -280.208 92941.3416

323 0.0039 7834.1376 5153. 2376 -280.457 95740.8486

333 0.019 7834.1376 5070. 2376 -280.955 98628.2526

343 0.032 7834.1376 4987. 2376 -281.536 101554.0856

353 0.038 7834.1376 4904. 2376 -281.951 104277.266

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Figures 1, 2 and 3 show the reaction velocity for different compounds.

0.0028 0.0029 0.0030 0.0031 0.0032 0.0033 0.0034 1/T " Temperature"

-3.4

-3.2

-3.0

-2.8

-2.6

-2.4

-2.2

-2.0

-1.8

-1.6

lnK

Y = -378.515 * X + 34.5918R-squared = 0.976341Y = -398.121 * X + 48.9335

R-squared = 0.985927Y = -396.715 * X + 48.7871R-squared = 0.952944

Y = -400.343 * X + 31.8692

R-squared = 0.969376

Reaction of (A) with malonic anhydride

Reaction of (B) with Malonic anhydride

Reaction of (C) with Malonic anhydride

Reaction of (D) with Malonic anhydride

Figure1. The relationship between lnK and 1/T of reaction A,B,C and Dwith malonic anhydride.

0.0029 0.0031 0.0033 0.0028 0.0030 0.0032 0.0034

1/T "Temperature"

-6.0

-5.5

-5.0

-4.5

-4.0

-3.5

-3.0

-2.5

lnK

Y = -682.802 * X + 113.334R-squared = 0.979861

Y = -690.401 * X + 114.623R-squared = 0.955656

Y = -688.001 * X + 114.056R-squared = 0.9425

Y = -709.001 * X + 117.956R-squared = 0.927366

Reaction of (E) with Malonic anhydride

Reaction of (F) with Malonic anhydride

Reaction of (G) with Malonic anhydride

Reaction of (K) with malonic anhydride

Figure 2. The relationship between lnK and 1/T of reaction E,F,G and K with malonic anhydride.

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0.0028 0.0029 0.0030 0.0031 0.0032 0. 0033

1/T "Temperature"

-7.0

-6.5

-6.0

-5.5

-5.0

-4.5

-4.0

-3.5

-3.0

-2.5

lnK

Y = -954.802 * X + 142.244R-squared = 0.945648

Y = -908.802 * X + 134.554R-squared = 0.952513

Y = -978.902 * X + 146.581R-squared = 0.938231

Y = -943.872 * X + 140.585R-squared = 0.935367

Reaction of (L) with Malonic anhydride

Reaction of (M) with Malonic anhydride

Reaction of (N) with malonic anhydride

Reaction of (O) with Malonic anhydride

Figure 3. The relationship between lnK and 1/T of reaction L,M,N and O with malonic anhydride.

5. CONCLUSIONS

1-The Schiff bases prepared in this research were verified by

elemental analysis, IR, 1H NMR and UV-Visible spectra.

2-The Oxazinans prepared in this research were verified by

elemental analysis, IR,1H NMR and UV-Visible spectra.

3- A first-order reaction equation was applied to the reaction of

Schiff-bases with malonic anhydride. It proves to be useful for the

calculation of the reactions velocity under varying temperatures (213-

253)K with (10) K increase.

4- The values ofH, S, and G are positive. This proves that the

reactions are endothermic and spontaneous.

5- The (Ethylene Schiff-bases) compounds are needs less energy than

those of (Thiourea schiff-bases), which are in turn, less energy than the

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(Urea Schiff-bases) compounds. This is due to group C=S and group C=O

which reduce the electronic density on C=N group, and consequently, it

needs more energy and takes longer time for the reaction.

Table 22. The Schiff bases prepared in this research.

Reaction No. Compound Name Structure

A 2-[(2-amino-ethylimino)-methyl]-phenolHO N

NH2

(Z)

B2-({2-[(2-hydroxy-benzylidene)-amino]-ethylimino}-methyl)-phenol

HO N

N OH(Z)

(Z)

CN,N-(3-dimethylamino-benzylidene)-ethane-1,2-diamine

N

H2N

N

(Z)

DN-(4-dimethylamino-benzylidene)-N'-(4-dimethylamino-benzylidene)-ethane-1,2 -diamine N

N

NN

(Z)

(Z)

E (2-hydroxy-benzylidene)-thioureaN

S

NH2

HO(Z)

F 1,3-bis-(2-hydroxy-benzylidene)-thiourea NS

N OHOH(Z)

(E)

G (4-dimethylamino-benzylidene)-thioureaN

SH2N N

(Z)

K 1,3-bis-(4-dimethylamino-benzylidene)-thiourea

N

S

N

N

N(Z)

(Z)

L (2-hydroxy-benzylidene)-ureaN

O

NH2

HO(Z)

M 1,3-bis-(2-hydroxy-benzylidene)-urea NO

N OHOH(Z)

(E)

N (4-dimethylamino-benzylidene)-ureaN

OH2N N

(Z)

O 1,3-bis-(4-dimethylamino-benzylidene)-urea

N

O

N

N

N(Z)

(Z)

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Table 23. The oxazinanes prepared in this research.

No Name Structure

13-(2-Amino-ethyl)-2-(2-hydroxy-

phenyl)-[1,3]oxazinane-4,6-dione O N

OO

HONH2

23-{2-[(2-Hydroxy-benzylidene)-amino]-

ethyl}-2-(2-hydroxy-phenyl)-[1,3]oxazinane-4,6-dione

ON

O

O

OH

NHO(Z)

33-(2-Amino-ethyl)-2-(4-dimethylami

no-phenyl)-[1,3]oxazinane-4,6-dioneO

NO

O

N

NH2

43-(2-Amino-ethyl)-2-(4-dimethylami

no-phenyl)-[1,3]oxazinane-4,6-dione

ON

O O

O N

O O

HO

OH

53-(2-Amino-ethyl)-2-(2-hydroxy- henyl

)-[1,3]oxazinane-4,6-dione

O

NO

O

NN

N

(Z)

62-(4-dimethylamino-phenyl)-3-{2-[2-(4-dimethy lamino-phenyl)-

4,6-dioxo-[1,3]oxazinan-3-yl] -ethyl}-[1,3]oxazinane-4,6-dione

O

NO

O

O

N

O

O

N

N

7

2-(2-Hydroxy- henyl)-3-{2-[2-(2-hydroxy-

phenyl)-4,6-dioxo-[1,3]oxazinan-3-yl]

-ethyl}-[1,3]oxazepane-4,7-dione

ON

OO

O N

O O

HO

OH

8

2-(4-Dimethylamino-phenyl)-3-{2-[2-(4-dimethyl

amino-phenyl)-4,6-dioxo-[1,3]oxazinan-3-yl]-

ethyl}-[1,3]oxazepane-4,7-dione O

N

O

O

O

N

O

O

N

N

9

2-(2-Hydroxy-phenyl)-4,6-dioxo

-[1,3]oxazinane-3-carboxylic

acid amide O N

O

NH2

O O

HO

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Table 23. Continued.

No Name Structure

102-(2-Hydroxy-phenyl)-4,6-dioxo-[1,3]oxazinane-3-carboxylic acid

2-hydroxy-benzylideneamide O N

O

N

HOO O

HO

(E)

112-(4-Dimethylamino-phenyl)-4,6-dioxo

-[1,3]oxazinane-3-carboxylic acid

amide O

N

OH2N

O

O

N

12

2-(4-Dimethylamino-phenyl)-4,6-dioxo-

[1,3]oxazinane-3-carboxylic acid -4-

dimethylamino-benzylideneamide

N

O

O N

N

O

O

N (E)

13

2-(2-Hydroxy-phenyl)-3-[2-(2-hydroxy-

phenyl)-4,6-dioxo-[1,3]oxazinane-3-

carbonyl]-[1,3]oxazinan-4,6-dione

ON

O

O

O

ON

OO

OHHO

14

2-(2-Hydroxy-phenyl)-3-[2-(2-hydroxy-

phenyl)-4,6-dioxo-[1,3]oxazinane-3-

carbonyl]-[1,3]oxazepane-4,7-dione ON

O O

OONO

O

HO

OH

15

2-(4-dimethylamino- henyl)-3-[2-(4-Dimethyl

amino-phenyl)-4,6-dioxo-[1,3]oxazinane-3-

carbonyl]-[1,3]oxazinan-4,6-dione O

N

O

O

O

ON

OO

NN

16

2-(4-Dimethylamino-phenyl)-3-[2-(4-dimethyl

amino-phenyl)-4,6-dioxo-[1,3]oxazinane-3-

carbonyl]-[1,3]oxazepane-4,7-dione ONO O

O

O NO

O

NN

172-(2-Hydroxy-phenyl)-4,6-dioxo-[1,3]oxazinane-3-carbothioic acid amide O N

S

NH2

O O

HO

18

2-(2-Hydroxy- henyl)-4,6-dioxo-[1,3

]oxazinane-3-carbothioic acid

2-hydroxy-benzylideneamide O N

S

N

HOO O

HO

(E)

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Table 23. Continued.

No Name Structure

192-(4-Dimethylamino-phenyl)-4,6-dioxo-[1,3]oxazinane-3-carbothioic acid

amide O

N

S

H2N

O

O

N

20

2-(4-Dimethylamino- henyl)-4,6-

dioxo- [1,3]oxazinane-3-carbothioic acid

4-dimethylamino-benzylideneamide

N

O

S N

N

O

O

N (E)

212-(2-Hydroxy- henyl)-3-[2-(2-hydroxy- henyl)

-4,6-dioxo-[1,3]oxazinane-3-thiocarbonyl]

-[1,3]oxazinan-4,6-dione

ON

O

O

S

ON

OO

OHHO

22

2-(2-Hydroxy-phenyl)-3-[2-(2-hydroxy-p

henyl)-4,6-dioxo-[1,3]oxazinane-3-

thiocarbonyl]-[1,3]oxazepane-4,7-dione ONO O

SONO

O

HO

OH

23

2-(4-dimethylamino-phenyl)-3-[2-(4-Dimethylamino-phenyl)-4,6-dioxo-[1,3]oxazinane

-3-thiocarbonyl]-[1,3]oxazinan-4,6-dione O

N

O

O

S

ON

OO

NN

242-(4-Dimethylamino-phenyl)-3-[2-(4-dimeth

ylamino-phenyl)-4,6-dioxo-[1,3]oxazinane-3

- thiocarbonyl]-[1,3]oxazepane-4,7-dione ON

O O

S

O NO

O

NN

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