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ANTIFUGAL COMPOUNDS FOR LEATHER Part 1. SYNTHESIS OF SOME

BENZOTHIAZOLES BIOCIDE FOR BOVINE HIDES

Conference Paper · April 2009

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Assist. Prof. Dr. M. Mete MUTLU
Assist. Prof. Dr. Ahmet ASLAN
Dr. Luminita ALBU
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Ege University (TURKEY)
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Ege University (TURKEY)
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Prof. Dr. Ayşen ERDİNÇLER Bogazici University (TURKEY)
Indian Shoe Federation (INDIA)
Assoc. Prof. Dr. Kadir ALP Istanbul Technical University (TURKEY)
The University of Northampton (ENGLAND)
Dr. Volkan ÇANDAR Pulcra Kimya San. ve Tic. A.Ş. (TURKEY)
Ege University (TURKEY)
Dr. Chellappa MURALIDHARAN Central Leather Research Institute (INDIA)
Engineering School of Igualada (SPAIN)
Dr. Mwinyikione MWINYIHIJA Ministry of Livestock Development (KENYA)
Bahçeşehir Univarsity (TURKEY)
Assoc. Prof. Dr. İsmet HAKİMOĞLU AR-TU Kimya ve San. Tic. A.Ş. (TURKEY)
Tomas Bata University (CZECH REPBLIC)
Budapesti Műszaki Főiskola University (HUNGARY)
Budapesti Műszaki Főiskola University (HUNGARY)
Ege University (TURKEY)
Ege University (TURKEY)
Engineering School of Igualada (SPAIN)
Ege University (TURKEY)
Ege University (TURKEY)
Leather and Footwear Research Institute (ROMANIA)
Leather and Footwear Research Institute (ROMANIA)
III IV
 I. International Leather Engineering Symposium,
April 29th-May 1st, 2009, Izmir, TURKEY

ANTIFUGAL COMPOUNDS FOR LEATHER

Part 1. SYNTHESIS OF SOME BENZOTHIAZOLES BIOCIDE FOR
BOVINE HIDES

Maria-Marcela ŢÂRLEA1), Mete Mehmet MUTLU2), Behzat Oral BĐTLĐSLĐ2), Bahri BAŞARAN2), Arife Candaş
ADIGÜZEL ZENGĐN2)

1)
I N C D T P – Division Leather and Footwear Research Institute, Bucharest, RO
2)
Ege University Faculty of Engineering Leather Engineering Department,Izmir, TR

ABSTRACT

The paper presents a synthesis of four new products, derivatives of 2-amino-benzothiazoles-6–substituted with
methyl, methoxy, chlorine and nitro with sulphonic anionic group in molecule, which confers them an increased
water solubility and ionic lacing to –NH3+ group of bovine hides, ensuring them an antifungal protection. The new
benzothiazole biocide products were characterized by: melting, UV,IR, MS, RMN spectra, HPLC chromatography.

Key words: 6–substituted 2-amino-benzothiazoles, sulphonation, melting point, spectra, HPLC chromatography,
bovine hides.

INTRODUCTION
During processing and marketing, especially in shipping of wet blue, must ensure a protection
against the main species of fungi that grows on the skins. Antifungal protection of wet-blue
bovine hides must be ensured during the classical processing. Fungicides are part of the category
of substances harmful to humans and the environment, generically called biocides, whose
production and marketing is regulated by Directive 67/548/EEC [1]. In Romania, the
DIRECTIVE was adopted by Government Decision no. 956/2005 concerning placing on the
market of dangerous chemicals, including biocides [2].
Most currently used fungicides accepted as being less harmful, used to antifungal protect of wet-
blue bovine hides, are those with Heterocyclic based chemical structure: benzothiazole,
glyoxaline, 2-n-Octyl-4-izotiazolin-3-ona, triazoles [3-10], but with some drawbacks, namely:
- they have low water solubility, thus they requiring large operation fleet;
- no link to reactive groups of the hide and they are washing in the subsequent technological
steps. New benzothiazole Biocides synthesized are derivatives of 2-aminobenzothiazoles 6-
substituted with methyl, methoxy, chloro, nitro chemically modified by sulphonation process by
which a single sulphonic group enters into the molecule which gives them some advantages:
- they have a higher water solubility, because the sulphonic group in molecule;- they bind of the
substrate by the reaction of -NH3+ hide group with a group -SO3, which it owns, similarly to
anionic charge auxiliary materials: synthetic tanning materials, oils and dyes;
- the size of molecular weight is between 244-275, considered the optimum size to enter into the
intermolecular spaces of chromed collagen macromolecule.

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Commercial antifungal products are generally a mixture of two or more chemicals to act on a
greater range of fungi and are dispersed in a surfactant for the dispersion in the processing
environs of support, water in the case of hide. [11-12]
EXPERIMENTAL
Materials and methods
The Basic materials are 2-aminobenzothyazoles-6-substitiuiţi with methyl, methoxy, chlorine
and nitro, 22% oleum and ethyl alcohol p.a. 95-96%.
Method of sulphonation
They have been used a laboratory elctro-mechanical stirrer VELP SCIENTIFIC srl Italy BS type
and a sulphonation ballon with three heat-resistant glass flask necks of 500 ml, equipped with
thermometer, ascending refrigerator and water bath, where is introduces 150 g oleum 22 - 24%.
Under stirring is added in portions of 0.2 mol 2-aminobenzothiazole – 6 - substituted in about 2
h, so the temperature does not exceed 25-28°C. In succession, the temperature rises to 40°C, and
then at 75 - 85°C, which is maintained for 8 h under stirring. The sulphonation reaction is
considered complete when a drop of sulphide mass is totally solubilized in about 10 ml of water.
After completing the reaction, sulphomass is passing on 400 g shredded ice in a Berzelius glass
of 500 ml under stirring. In about an hour, precipitate 2- aminobenzothiazoles substituted-6-
sulfonated. To obtain benzothiazolic biocid products as sodium salts or triethanolamine, the
sulphomass is pouring out over sodium chloride or triethanolamine deposited on the ice. It is
washed with three portions of 2000 ml of water up to 4.0 - 4.5 pH. The dried product is then
crystalline transformated of 95% ethyl alcohol and it results about 25g. It is filtered and dried at
the 65°C.
The sulphonation of heterocyclic amines, 2-aminobenzothiazoles-6-substituted by – CH3, –
OCH3, – Cl and –NO2 was done with 22-24% oleum, differs in the temperature and times of
maintenance for each substitute.After the sulphonation reaction is resulted mixtures of euphonic
acids isomers and for 2- aminobenzotiazol-6-nitro a unitary product was obtained, according to
the reaction in Figure 1 and to the compounds in Figure 2. [13-14]
Due to electronic effect induced in the molecule of 2-substituent aminobenzothiazole by the
substitute in position 6, sulphonation should take place in positions 5 and 7 when into the
position 6of the benzothiazolic ring are graft first order substitutes: – CH3, – OCH3, – Cl.
It can be estimated that if sulphonation of 2-aminobenzotiazolului-6-methyl, a sulphonic group
enters at position 5, achieving B type compounds in Figure 2.
Similarly, the sulphonic group can enter in the position 5in both 2-amino benzotiazolului-6-
methoxy and 2-aminobenzotiazolului-chloro-6, achieving B type compounds in Figure 2.
Equally well however, the sulphonic group may be grafted in position 7, achieving the C type
compounds in Figure 2.
The – NO2 substitute is of the second order and it can target the sulphonic group substitution
at position 4, so at the sulphoning of this compound should result in a unitary product, the 2-
aminobenzothiazole-6-nitro-4-sulphonic acid, composed of A type, in Figure 2 .

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There may be exceptions due to steric or conjugation effects.

R S
6 NH2 (A)
N
4
SO3H
Oleum cu
R 7 SO3 22-24% R S
S
6 40- 95 oC 6 NH2
NH2 (B)
5 N
5 N - H2O
HO3S
4
SO3H
R 7
S
6 NH2 (C)
N

Figure 1. The sulphoning reaction of -6-substitiuted 2-aminobenzothiazoles

where R = – CH3 ; – OCH3 ; –Cl ; –NO2 .

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7 1 7 1
H 3C S H 3C S
6 2 6 2
NH2 NH2
5 5
N HO3S N
4 3 4 3
SO3H
1A 1B
SO3H
7 1 1
H3CO S H3CO 7
S
6 2 6 2
NH2 NH2
5
N 5 N
HO3S 4 3 4 3

2B 2C
SO3H
7 1 7 1 1
Cl Cl S Cl 7
S S
6 2 6 2 6 2
NH2 NH2 NH2
5 5
N N 5 N
4 3
HO3S 4 3 4 3
SO3H
3A 3B 3C

7 1
O2N S
6 2
NH2
5
N
4 3
SO3H
4A

Figure 2. Chemical formula and isomers of biocide benzothiazolic products

Methods for characterization of sinthetized biocidal benzothiazolic products
Benzothiazolic Biocides obtained in the sulphonic acids form, were washed with distilled water
up to pH = 4,0-4,5 and purified with alcohol p.a. of 96% and characterized as any organic pure
substance.
Melting points were executed using Boetzius device, Germany.
UV spectra of 2-aminobenzotiazolilor-6-substitution with –CH3, – OCH3, – Cl, – NO2,
sulphonic acids purified and dissolved in ethylic alcohol p.a., at the concentration of 2x10-4 mol /
L, were done with a JASCO UV 540 Japan spectrophotometer. [16]
IR spectra of 2-aminobenzotiazoles-6-substituted with –CH3, – OCH3, – Cl, – NO2, mixture of
purified sulphonic acid isomers at a concentration of 2 x 10-3 mol / l, were done by reflection
technique in KBr with a EQUINOX 55 – USA spectrometer.
Since from the sulphoning reaction results mixtures of isomers, for the substitutes methyl-,
methoxy- and, chloro- in the IR spectra are complicated and the tasks are risky. It recognizes,
however, some bands characteristic of sulphonic group located in the 1040-1060 cm-1 area, for
the symmetric valence vibration and 1170-1190 cm-1 for the asymmetric one. The switterion

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form NH3 + group respectively, is confirmed by the presence of an intense band at about. 3020-
3040 cm-1, and also of a medium intensity one between the 1570-1595 cm-1, attributed to
valence angle deformation. The bands corresponding to the amino benzothiazolic vibration
system undergoes less displace according to the position in which sulphonic grouping was
grafted.
Mass spectra of 2-aminobenzotiazoli-6-substituted by –CH3, –OCH3, – Cl, – NO2 products in
the form of sulphonic acids have been recorded in solution of water / methanol (1 / 1, v / v)
containing 0.25% of trietilamina at a concentration of 50µg/mL were obtained by turbospray MS
method. have been used An instrument of triple quadrupol type API 2000 LC / MS / MS Perkin-
Elmer Sciex with the turbospray ionization source and the analyte was introduced in the source
by flow injection. [16]
The first quadrupol scan (MS scan) the expected molecular ion was obtained in conditions of
ionizing with negative ions (M-1). The fragments observed in MS / MS (product ion scan)
confirms the structure of these intermediates.
RESULTS AND DISCUSSION
Biocides no.1. The mixture of sulphonic acid isomers derivatives of 2-amino benzothiazole-
6-methyl, noted as 1A and 1B, has an expected molecular mass of 244.28 and a negative ion
molecular weight founded (M-1) is 243.4. In the MS / MS spectrum of the isomer, corresponding
to the first chromatographic pick we meet the fragment with m / z 163, characteristic to the 2-
aminobenzotiazol-6-methyl ion, which means the loss of SO3H at ionization. With a high
intensity the ion characteristic of the sulfonic group (m / z 80) appears and at m / z 146.2 we
have the benzothiazole-6-methyl ion. The second isomer shows a different fragmentation,
probably through the division of benzothiazolic cycle with the elimination of HCN and obtaining
of ionic fragment with m / z 216.
Biocides no. 2. The mixture of two sulphonic acids isomers derivatives of 2-
aminobenzothiazole-6-methoxy noted as 2B and 2C has an expected molecular mass of
260.28 and the molecular weight found of negative ion (M-1) is 259.9. In the MS / MS spectrum
of the mixture of sulphonic acid isomers derivatives of 2-amino-6-methoxy-benzothiazole, the
ion is also be observed with m / z 244, this suggesting the loss first of amino group in
compounds of this type.
Biocides no.3. The mixture of three sulphonic acids isomers derivatives of 2-
aminobenzothiazole-6-methoxy noted as 3B and 3C has an expected molecular mass of 264.7
and a molecular weight found of negative ion (M-1) is 263 for 35Cl and 265 for 37Cl. In the MS /
MS spectrum of the mixture of sulphonic acid isomers derivatives of 2-aminobenzothiazole-
chloro-6 in MS scan is observed in the area of molecular ion two picks separated by two atomic
mass units, corresponding to two isotopes of chlorine atom. Both masses were used in MS / MS,
achieving two spectra showing the same difference of two units between the most significant
fragments. At this compound the ionization process occurs likely with the division of
benzothiazolic cycle and the elimination of HCN, as suggested by the fragment from m / z 236
(238 if 37Cl isotope).

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Biocides no 4. The 2-aminobenzotiazol-6-nitro-4-sulphonic acid, noted as 4A, has an

expected molecular mass of 275.25 and a molecular weight found of negative ion (M-1) is 274.
A similar fragmentation is observed at the product 4, respectively the appearing of a pick at m / z
246.8 assuming elimination of HCN. The ion with m / z 194, corresponding to 2-
aminobenzotiazolului-nitro-6 is also present, which means the elimination of sulfonic group in
the basic structure, so a fragmentation in two ways is possible.
The HPLC chromatography preparative of 2-aminobenzothiazoles-6-substitution with-CH3,-
OCH3,-Cl,-NO2, sulfonated and purified, was performed on an Agilent 1100 type liquid
chromatograph equipped with a fraction collector and a ZORBAX SB – C18 9.4 mm x 25 cm
chromatography column, with reverse phase, which allows achieving semipreparative
separations getting limited substances, then analyzed by various spectroscopic methods. For the
separation of semipreparative an injection loop of 500 µL have been used. Since the specific
literature indicates for the separation of sulphonic acid type compounds and sulphonic azoic dyes
the use of methanol in combination with cushion disodium phosphate solutions (100 mM, pH =
6.7) it began with the same type of solvents mixture, which was modified on the way to achieve
a best possible separation for each of the compounds analyzed. [17-20]
In Figure 3, are played the HPLC cromatograms obtained by preparative variant for each of the
three sulphonic acid mixture of isomers derived from 2-aminobenzothiazoles-6-substituted with
methyl, methoxy- and chloro- groups and 2-aminobenzothiazole-6-nitro-4-sulfonic , simplified
reproduced and noted as 1,2,3,4.
At the HPLC chromatography to the preparative of the sulphonic acids isomers mixture
obtained by sulphoning of 2-aminobenzothiazole-6-methyl, the product 1, has resulted in
two fractions corresponding to two isomers of which one with a sulphonic group certain in the
position 5 and another probably in the position 4 :
- peak no. 1, represents 61.48% it eluates after 6.7 minutes and is probably the 2-
aminobenzothiazole-6-methyl-4-sulfonic acid isomer;
- peak no. 2, represents 35.4% it eluates after 7.1 minutes and is probably the 2-
aminobenzothiazole-6-methyl-5-sulfonic acid isomer. Both sulphonic acid isomers derivatives of
2-aminobenzotiazol methyl-6-sulfonic with the sulphonic group at position 4 or 5 represent
96.9%in all, the rest are probably traces of unreacted amine.
At the HPLC preparative cromatography of the sulphonic acids isomers mixture obtained
by sulphonation of 2-aminobenzothiazole-6-methoxy product 2 were obtained two fractions
corresponding for the two isomers, one with a sulfonic group at position 5 and another one with
sulphonic group in the position 7:
- peak no. 1 represents 60.6%, it eluates after 6.347 minutes, and is possible to represent the
sulphonate isomer at position 5;
- peak no. 2 represents 37, 4%, it eluates after 13 minutes and is probably represent the
sulphonate isomer in position 7. Both derivative sulphonic acid isomers of 2-aminobenzothiazole
methoxy-6-sulfonic with sulphonic group in position 5 or 7 represents in all 98.1%, the rest are
probably traces of unreacted amine;

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At the HPLC chromatography of the three sulphonic acids isomers mixture obtained by
sulphonation of 2-aminobenzothiazole-6-chloro, the product 3, has resulted three fractions,
one for the isomer with sulfonic group at position 4 or 5 or 7.
After the chromatogram examination results:
- peak no. 1, representing 28.8%, it eluates after 7.2 minutes and it is probably an derivative acid
isomer of 2-aminobenzothiazole-6-chloro-4-sulphonic and together with it also comes out the
same isomer obtained 37Cl;
- peak no. 2, represents 22.4%, it eluates after 10.02 minutes and is likely to represent sulphonic
acid isomer with the sulfonic group at position 5 and and together with it appears the obtained
isomer pick 37Cl after the 10.5 minutes;
- peak no. 3, represents 11.68% it eluates after 11.1 minutes and it is probably the isomer with
sulfonic group at position 7. All the isomers 35Cl probably give a proportion of 62.88%, plus 37Cl
isomers about 20%, so this mixture contains a mixture of six sulphonic acids isomers in the
proportion of 82.65%, the rest being probably traces of unreacted amine.
At the HPLC preparative cromatography of the product 2-aminobenzothiazole-6-nitro-4
sulphonic, product 4, has resulted a single peak, which represents 96%. it eluates after 5.9
minutes and at the same time it also expresses the purity of unitary product, the rest being
probably traces of unreacted amine.

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Figure 3. chromatograms HPLC of biocides derived from 2-aminobenzothiazoles-6-substituted

with sulphonic groups in positions 4, 5 or 7 R = – CH3 (1A and 1B), – OCH3 (2B and 2C), – Cl
(3A, 3B, 3C), and - NO2 (4)
The nuclear magnetic resonance spectra of (1H-NMR and 13C-NMR) of 2-
aminobenzothiazoles-6-substitution with-CH3,-OCH3,-Cl,-NO2 in the form of purified sulphonic
acids were done using a VARIAN GEMINI 2000 - 300 MHz spectrometer, at ambient
temperature, the chemical displacements being in values of δ comparing with the used solvent.
dimethilsulfoxid. [16]
Physico-chemical and spectral characteristics of benzothiazolic biocides synthesized and
purified in the form of powders
1. The isomers mixture: 2-aminobenzothiazole-6-methyl, 4 and 5 sulphonic: C8H8N2S2O3;
molecular mass = 244.28, melting point = 265-270 oC; solubility g / L: H2O = 0.60, in EtOH=
0125, MeOH = 0100; UV: λ max (1) = 266 nm, a = 0.9722, λ max (2) = 223 nm, a = 2.9777, IR
(KBR, cm -1): 3395, 2744, 2870, 3052, 1637, 1540, 1467, 910, 891, 1306, 1280.
- retention time in ZORBAX C18 column: (1) = 6.75 minutes (1B) = 7.15 minutes.

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From the integrals report results the isomers report A / B = 0.4 / 0.2, and 2:1 respectively.
1.1. Aminobenzothiazole-6-methil-4-sulphonic (1A)
1
H-RMN(dmso-d6, δ ppm, J Hz): 7,71(m H-5); 7,46 (m H-7); 2,36 (s 6-R); 9,51[sl NH2 (NH3 +
)].
13
C-RMN(dmso-d6 , δ ppm): 168,53 (C-2); 126,17(C-4); 124,02(C-5); 131,38(C-6); 126,07(C-
7);134,06(C-8); 145,49(C-9); 20,83 (C-6R=-CH3 ).
1.2. Aminobenzothiazole-6-methil-5-sulphonic (1B)
1
H-RMN(dmso-d6, δ ppm, J Hz): 7,83(s H-4);7,59(s H-7); 2,55 (s 6-R=-CH3 ); 9,51[sl NH2
(NH3+)]
13
C-RMN(dmso-d6, δ ppm): 169,47(C-2);113,57(C-4); 124,26(C-5); 131,92(C-6); 123,92(C-7);
134,06(C-8); 145,49(C-9); 20,05(C-6R=-CH3).
2. The mixture of two isomers: 2-aminobenzothiazole-6-metoxy, 5 and 7 sulphonic:
C8H8N2S2O4; molecular mass =260,28; melting point oC =270-275; solubility, g/L: H2O=1,55;
EtOH=0,50; MeOH=0,125; UV: λ max (1) = 264 nm, a =1,3029; λ max (2) = 223 nm, a =
3,3138;
IR ( KBr, cm -1): 3388; 2839; 2745; 3107; 1645; 1548; 1464; 905; 847; 1179; 1338; 1278.
- retention times in column ZORBAX de proton spectra results the molar report B/C= 0,6/0,4.
2.1. Aminobenzothiazol-6-methoxy-5-sulphonic (2B)
1
H-RMN (dmso-d6, δ ppm, J Hz): 7,82(s H-4); 7,58(s H-7); 3,73(s 6-R= CH3 ); 9,56 [sl NH2
(NH3+)]
13
C-RMN(dmso-d6 , δ ppm): 168,71(C-2); 115,26(C-4); 126,40(C-5); 153,73(C-6); 106,58(C-7);
131,34(C-8); 135,30(C-9); 56,30(C-6R=-OCH3).
2.2. Aminobenzothiazole-6-methoxy-7-sulphonic (2C)
1
H-RMN(dmso-d6, δ ppm, J Hz): 7,43(d H-4); 7,17(d H-5); 3,77(s C-6R=-OCH3 ); 9,53[sl NH2
(NH3+)].
13
C-RMN(dmso-d6, δ ppm): 170,33(C-2); 115,26(C-4); 113,13(C-5); 153,78(C-6); 123,70(C-7);
131,61(C-8); 135,30(C-9); 56,30(C-R=-OCH3).
3. The mixture of three isomers: 2-aminobenzothiazole-6-chloro, 4 and 5 and 7 sulphonic:
C7H5N2S2O3Cl; molecular mass =264,7; melting point oC=280-285; solubility, g/L: H2O = 0,50;
EtOH=0,125; MeOH=0,100; UV : λ max (1) = 264 nm, a =1,4439; λ max (2) = 224 nm, a
=3,314.
IR(KBr, cm -1): 3458; 3093; 1636; 1539; 1448; 892; 861; 702; 1338; 1278.
- retention times in column ZORBAX C18: (3A) = 7,22 minutes; (3B) =10,03 minutes; (3C)
=12,06 minute.

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From the integral curves report results: A/B/C = 0,6 / 0,3 / 0,1.
3.1. 2-Aminobenzothiazole-6-chloro-4-sulphonic (3A)
1
H-RMN(dmso-d6, δ ppm, J Hz): 8,04 (d H-5); 7,58 (s H-7); 9,62 [sl NH2 (NH3+)].
13
C-RMN(dmso-d6 , δ ppm): 170,16(C-2); 134,15(C-4); 123,82(C-5); 128,00(C-6); 125,07(C-7);
132,63(C-8); 143,85(C-9).
3.2. 2-Aminobenzothiazole-6-chloro-5-sulphonic (3B)
1
H-RMN(dmso-d6, δ ppm, J Hz): 7,94 (s H-4); 7,59 (s H-7); 9,62 [sl NH2 (NH3+)].
13
C-RMN(dmso-d6, δ ppm): 169,24(C-2); 115,35(C-4); 132,63(C-5); 125,22(C-6); 125,22(C-
7); 132,63(C-8); 141,42(C-9);
3.3. 2-Aminobenzothiazole-6-chloro-7-sulphonic (3C)
1
H-RMN(dmso-d6, δ ppm, J Hz): 7,51 (s H-4); 7,42 (s H-5); 9,62 [sl NH2 (NH3+)].
13
C-RMN(dmso-d6, δ ppm): 171,10(C-2); 130,28(C-4); 123,92(C-5); 125,72(C-6); 137,90(C-7);
132,90(C-8); 141,48(C-9).
4. 2-Aminobenzotiazol-6-nitro-4-sulfonic (4A)
C7H5N3S2O5; molecular mass = 275,25; p.t. oC = 300-305; solubility, g/L: H2O= 0,75;
EtOH=0,125; MeOH=0,100; UV: λ max (1) =360 nm, a=1,85153; λ max (2) = 231 nm, a
=3,06814
IR ( KBr, cm -1): 3462; 3044; 1654; 1534; 1491; 915; 886; 1124; 1305.
- retention times in column ZORBAX C18 of the unitary product (4A)=5,93 minutes;
1
H-RMN(dmso-d6, δ ppm, J Hz): 8,88 (d H-5); 8,37 (d H-7); 9,85 [sl NH2 (NH3+)]
13
C-RMN(dmso-d6, δ ppm): 171,94(C-2); 126,89(C-4);120,72(C-5);139,71(C-6); 120,24(C-7);
133,32(C-8); 142,79(C-9).
5. The antifungal activity of the four new benzothiazolic biocides have been demonstrated
separately for two species of fungi: Aspergillus niger, Trichoderma viridae in Part II [22] .
CONCLUSIONS
1. The objective of the paper was to obtain biocidal benzothiazolic derivatives products of
aminobenzothiazoles-2-6-substituted by– CH3, – OCH3, – Cl, – NO2 in the form of sulphonic
acids, for antifungal treatment of bovine hides. Separation of isomers from the mixture, is a
costly technological operation, maybe even impossible, therefore biocides were used in the
treatment of bovine hides in the form of isomers mixtures.
2. At sulphonation of 2-aminobenzothiazole-6-methyl-2 isomers are formed: one with sulfonic
group at position 5 (1A), in proportions of 62% and second isomer has the sulphonic group at
position 4 (1B), which represents about 30 %. The substituent-CH3-SO3H leads the substitution
in the benzothiazolic nucleus different from that of the benzene nucleus, so the methyl substitute
behaves as the order I and II.

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3. At the sulphonation of 2-aminobenzotiazolului-6-methoxy, two isomers was formed: one with

sulphonic group at position 5 (2B) at a proportion of 60% and the second one at position 7 (2C)
in the proportion of 40%. The substitute-OCH3-SO3H leads the substitution of –SO3H in the
benzotiazolic nucleus similarly to that of benzene nucleus, so of the order I.
4. At sulphonation of 2-aminobenzothiazole-chloro-6, three isomers are formed: one with
sulphonic group at position 4 (3A) at 60%proportion, second one in position 5 (3B) in
proportion of 30% and third one with the sulphonic group in position 7 (3C) in the proportion of
10%. The substitute-Cl lead the substitution of –SO3H in the benzotiazolic nucleus similarly
with the benzene nucleus in positions 5 and 7, so as a substitute of order I and different from
benzene nucleus at position 4, as an order II substitute.
5. At the sulphonation of 2-aminobenzothiazole-6-nitro, an unitary product was formed with the
sulphonic group at position (meta) 4 (4A) in the proportion of 96%. The substitute-NO2 lead the
substitution –SO3H in the benzothiazolic nucleus as a substitute of the order II.
6. In all four substitution cases of the sulphonic group by mass spectra was demonstrated that in
the benzothiazole molecule enters one single - SO3H group.
Bibliografy
[ 1] Directive 67/548/EEC. Chemicals classified by the EU and placed on Annex 1 to the Directive 67/548 of 27
June 1967.
[ 2] X X X Hotărârea de Guvern nr. 956 din 18 august 2005 privind plasarea pe piaţă a produselor bioxide, M.Of.
nr.852/21 september 2005.
[ 3] Cristiane Hauber, Heinz-Peter German. Lederinstitut Gerberschule Reutlingen Deutschaland. The addition of
fungicides in chrome taanage and their penetration, absorbtion and distribution in the wet-blue. International
Congress on the Leather Shoe Industries, Budapest, 7-9.10. 1998, vol.II, Proceedings, p.256.
[ 4] Admis U., Huynh C., Money C.A. The need for improved fungicides for wet-blue. Journal of.the Society of
Leather Tehnologists and Chemists, Vol.86, 2002, p.118.
[ 5] Stosic R.G., Covington A.D., Alexander K.T.W. Tannerry scale application of isothiazoline microemulsion
fungicide. JALCA, vol.88, N0.5,MAY 1993, p.171-177.
[ 6]Adam Hughens.A novel fungicide delivery system LEATHER INTERNATIONAL,July, 2005, p.17.
[ 7] Karsa, D. Ashworth D.Industrial Biocides, 2002,John Wiley, London. ISBN 0 85404 805 7.
[ 8] Hughes N., Patent G.B. 1.594.002/ 30.07, 1981.
[ 9] Shoko Okawa.Ibaraki. Japan. Industrial prezervative antifungal compozition and underwater antifouling
compoziţion. U.S.Patent no.5.741.483, 21 April 1998. Rohm and Haas Company, Philadelphia, Pa.
[10] Antoni-Zimmer5mann, Rudger baum, Thomas Wunder, hans-Jürgen Schimidt, Unied States Patent
no.6,846,777 B2/25 january 2005, Synergetic biocidal compozition.
[11]X X X ARACIT 4A.TFL Ledertechnik GmbH, am Schwrzenbach 2, 79575 WEIL AM RHEIN, Germany,
2003.
[12]X X X TANACIDE TPG, LAMIRSA, LABORATORIES MIRET, S.A. NUEVA TANEX S.A., Barcelaona
Spain, 2005
[13] Maria-Marcela Ţârlea. Application for a patent to OSIM no A 2006.10.10 / 00 767. Method of obtaining some
biocidal products for the bovine hides preservation on the basis of 2-aminobenzothiazoles-6-substituted with
methyl, methoxy, chlorine, nitro, sulphonates, used as intermediates for acid benzothiazolic dyes [14] Maria-

149
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29 Nisan-1 Mayıs, 2009, Đzmir, TÜRKĐYE

Marcela Ţârlea; C.Cincu, G.Marton.C.Drăghici, L.Tarko. New Sulphonic Acids Derivates Obtained by
Sulphonation of 6-substituted-2-aminobenzothiazoles. REVISTA DE CHIMIE, vol.58, nr.2, 2007, p. 218-223,
ISSN 0034-7752.
[15] Ţârlea Maria-Marcela, Mete Mehmet Mutlu. 12CB Romania-Turky 2008-2009. Studies on the synthesis of a
new benzothiazole biocide class and its application in the preservation of bovine wet-blue leather.
[16] Balaban A.T., Banciu M., Pogany I. Aplicaţii ale metodelor fizice în chimia organică. Editura Ştiinţifică şi
Enciclopedică, Bucureşti 1983.
17] Ţârlea Maria-Marcela, Corneliu Tărăbăşanu-Mihăilă, George Marton, Nicoleta Grigoriu, Roxana Niţă.
Phisical-chemical characterization of 2-aminobenzohtiazoles 6 – substituted with –CH3 , -OCH3 , -Cl, -NO2 .
REVISTA DE CHIMIE vol.57, nr.12, 2006, p.1265-1268
[18] Grossenbacher H., J. Chromatography 360, 1986, 219 – 223, ISSN 0034-7752.
[19] X X X. HPLC Liquid Chromatography. MACHEREY – NAGEL.HPLC Catalogue e 1/10/0/5.1995 PD. Printed
in Germany,1995.
[20] X X X. Separation Sciences. MACHEREY – NAGEL. HPLC. Specialists e6/5/0/4.1995 PD. Printed in
Germany.
[21] X X X The „Turneul European Agilent INNOVATION TOUR 2008” Symposium, 23 september 2008,
Bucharest, Romania.
[22] Ţârlea Maria-Marcela - Mete Mehmet Mutlu şi altii. Antifungal compound for leather part II. Testing of
antifungal activity Ist INTERNATIONAL LEATHER ENGINEERING SYMPOSIUM”LEATHER INDUSTRY-
ENVIROMENT and PROGRESSIVE TECHNOLOGIES”, April 29-May 1, 2009, IZMIR-TURKIYE.

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