Benzothiazole derivatives of the formula ##STR1## with the substituent meanings mentioned in the description, are starting compounds for the preparation of new azo dyestuffs. Some methods of preparing the new benzothiazole derivatives are described.

The invention relates to benzothiazole derivatives of the formula 
##STR2## 
wherein R=OH, OX, NH.sub.2 NHX, NX.sub.2, NHSO.sub.2 X 
X=alkyl, alkenyl, cycloalkyl, aryl, aralkyl, or hetaryl, 
R.sup.1 =H, alkyl, alkoxy or halogen 
A=SO.sub.2 or CO and 
n=0, 1 or 2 
it being possible for the abovementioned radicals to contain ionic or 
nonionic substituents customary in dyestuff chemistry, including in 
particular SO.sup.3 H and COOH, to their preparation and to their use as 
intermediates for preparing dyestuffs. 
Examples of suitable alkyl radicals are those having 1 to 12 C atoms. 
Examples of suitable alkenyl radicals are those having 2 to 5 C atoms. 
Suitable cycloalkyl radicals are in particular cyclopentyl and cyclohexyl. 
Examples of suitable aralkyl radicals are C.sub.1 -C.sub.3 -alkylphenyl 
radicals which can be substituted in the phenyl nucleus, for example by 
Cl, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy. 
Suitable aryl radicals are in particular phenyl radicals which can be 
substituted in corresponding manner. 
Suitable hetaryl radicals are 5- or 6-membered quasi-aromatic N-, O- and/or 
S-containing heterocyclic ring systems. 
Preferred compounds are those of the formula 
##STR3## 
wherein A=SO.sub.2, CO 
R.sup.2 =NR.sub.5 R.sub.6, OH, NHSO.sub.2 R.sub.5 
R.sup.3 =H, CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5, Cl 
R.sup.4 =H, CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5, Cl 
R.sup.5, R.sup.6 =hydrogen; a C.sub.1 -C.sub.8 -alkyl radical which is 
substituted by hydroxyl, amino, C.sub.1 -C.sub.4 -alkylamino, C.sub.1 
-C.sub.4 -dialkylamino, C.sub.1 -C.sub.4 -trialkylammonium, halogen, 
cyano, C.sub.1 -C.sub.4 -alkoxy, carboxyl, aminocarbonyl or C.sub.1 
-C.sub.4 -alkoxycarbonyl; a C.sub.2 -C.sub.4 -alkenyl radical; a 
cyclohexyl radical which is optionally substituted by C.sub.1 -C.sub.4 
-alkyl; a phenyl, benzyl or phenylethyl radical which is optionally 
substituted by halogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 
-dialkylamino, C.sub.1 -C.sub.4 -trialkylammonium or C.sub.1 -C.sub.4 
-alkoxy; or a C.sub.1 -C.sub.4 -alkyloxycarbonyl, mono- or di-C.sub.1 
-C.sub.4 -alklyaminocarbonyl, aminocarbonyl, mono- or di-C.sub.1 -C.sub.4 
-alkylaminosulphonyl, 2-thienyl, 2-furyl, 2-tetrahydrofuryl, amino, 
C.sub.1 -C.sub.4 -alkylamino, di-(C.sub.1 -C.sub.4 -alkyl)-amino or 
optionally C.sub.1 -C.sub.4 -alkyl- or C.sub.1 -C.sub.4 
-alkoxy-substituted phenylamino or benzylamino radical, or 
R.sup.5 and R.sup.6, together with the N atom, form a 5- or 6-membered ring 
which optionally contains a further N or O atom. 
Additionally preferred compounds are those of the formula 
##STR4## 
wherein A, R.sup.2, R.sup.3 and R.sup.4 have the meaning indicated in the 
formula II. 
The invention also relates to a process for preparing the compounds (I), 
characterised in that 3- or 4-nitrobenzoyl chlorides of the formula 
##STR5## 
are reacted with 2-aminothiophenol derivatives of the formula 
##STR6## 
or with reaction products of 2-nitrohalogenobenzenes of the formula 
##STR7## 
with sulphur alkali metal compounds (NaHS, Na.sub.2 S, K.sub.2 S); the 
intermediates--optionally without isolation--are cyclised and reduced or 
converted to compounds of the formula I; and the intermediates--if desired 
without isolation--are reduced and cyclised to compounds of the formula I. 
In the formulae (IV) to (VI), R, R, R.sup.1 and n have the meaning 
indicated in the formula (I) and Halogen stands for fluorine, chlorine or 
bromine. 
The reductions are preferably carried out with sulphidic reducing agents. 
The cyclisations are preferably carried out under acid conditions, but can 
also be carried out under neutral or alkaline conditions. 
The process according to the invention is carried out in detail by first 
converting a 3- or 4-nitrobenzoic acid of the general formulae VII with 
excess thionyl chloride or another acid-halogenating compound, such as 
phosgene, phosphorus trichloride, phosphorus pentachloride, or phosphorus 
oxychloride in a manner known per se (cf. Houben-Weyl, Methoden der 
Organischen Chemie [Methods of Organic Chemistry], 4th edition, volume 8, 
page 467 (1952); German Reich Pat. No. 1,026,750) into the corresponding 
3- or 4-nitrobenzoyl chlorides of the general formula IV: 
##STR8## 
This reaction is generally carried out in the presence of small amounts of 
an organic nitrogen compound as a catalyst, preferably in the presence of 
dimethylformamide or pyridine, and at rising temperature, preferably from 
20.degree. to 100.degree. C. The reaction of the 3- or 4-nitrobenzoic acid 
VII to the corresponding 3- or 4-nitrobenzoyl chloride IV is preferably 
carried out in the absence of a solvent, but it can also be carried out in 
inert organic solvents, for example methylene chloride, chloroform, carbon 
tetrachloride, dichloroethane, trichloroethane, n-hexane, cyclohexane, 
toluene, xylene, monochlorobenzene or o-dichlorobenzene. 
The resulting melt or solution of the 3- or 4-nitrobenzoyl chloride (III) 
is--preferably without further purification--condensed with an aqueous 
suspension or solution of the aminothiophenol of the formula V. 
The condensation reaction is normally carried out at pH 1-10, preferably 
5-9, and at temperatures of from -10.degree. to =100.degree. C., 
preferably 50.degree. to 80.degree. C. 
To maintain the optimal pH of 1 to 10, preferably 5 to 9, for the 
condensation reaction, it is possible to add, before or during the 
reaction, bases suitable for binding the hydrogen chloride which is 
liberated, for example sodium hydroxide, sodium carbonate, sodium 
hydrogencarbonate, sodium acetate, trisodium phosphate, disodium 
phosphate, monosodium phosphate, sodium formate or sodium propionate. The 
preferred solvent is water. 
However, the aqueous reaction medium can also contain water-miscible 
solvents, for example alcohols such as methanol, ethanol or isopropanol, 
or non-water-miscible solvents, for example methylene chloride, 
chloroform, carbon tetrachloride, dichloroethane, tichloroethane, 
n-hexane, cyclohexane, toluene, xylene, monochlorobenzene or 
o-dichlorobenzene. 
Furthermore, it is possible to add to the reaction medium used in the 
condensation reactions surfactants, for example an anionic surfactant, 
cationic surfactants, amphoteric surfactants or nonionic surfactants (cf. 
Ullmanns Enzyclopadie der technischen Chemie [Ullmann's Encyclopedia of 
Chemical Technology], volume 16, pages 724-748 (1965) or "Surface 
Activity" by J. L. Moilliet, B. Collie and Black, 2nd edition, chapters 
10-15). The addition of surfactants raises the rate of reaction of the 
condensation reactions. The condensation reactions are normally complete 
at 50.degree. C. to 80.degree. C. within 1 to 6 hours. 
The initial products in this condensation reaction are compounds of the 
formula 
##STR9## 
which are cyclised to benzothiazoles of the formula 
##STR10## 
and are then reduced to benzothiazoles of the formula I. 
The cyclisation of VIII and/or IX is preferably carried out at pH 0-5. 
In a preferred embodiment of the present invention, the reaction steps of 
condensation, cyclisation and reduction are combined into a single process 
step. 
In this preferred process variant (a), the condensation products of the 
formula IV are reduced with sulphidic reducing agents, such as, for 
example, hydrogen sulphide, alkali metal sulphides or alkali metal 
polysulphides, in particular with an alkali metal hydrogensulphide, for 
example of technically customary hydrosulphide solution (sodium 
hydrogensulphide). 
In a particularly preferred embodiment of the present invention, the 
primary adducts VIII and/or IX are first reduced to the amino compounds 
##STR11## 
and these are then cyclised, preferably at pH 0-5, to give the 
benzothiazole derivatives of the formula I. 
In this process variant the condensation products of the formula VIII/IX 
can likewise be converted without isolation of intermediates into the end 
products of the formula (I) using a so-called single-vessel method. In 
this method, the heterocyclic amines of he formula (I) are likewise 
obtained in excellent quality and in high yields, which is surprising in 
view of the process which proceeds via a plurality of stages without 
intermediate isolation and purification of the intermediate stages which 
occur. 
In a very particularly preferred embodiment (b) of the present invention, 
nitrobenzoyl chlorides of the formula IV are made to react with reaction 
products of nitrohalogen compounds of the formula VI with sulphur alkali 
metal compounds. The products of reacting VI with sulphur alkali metal 
compounds are, depending on reaction conditions and substituents, 
aminotiophenols of the formula V and/or disulphides and polysulphides of 
the formula XIII (cf. German Offenlegungsschriften Nos. 2,127,989, 
2,053,715 and 2,503,164; J. Mech. Chem. 14 248 et seq. (1971), Monatshefte 
f. Chem. 56 365 et seq. (1930)). 
##STR12## 
wherein m can be=0 to 10, preferably 0 to 2. 
It is surprising that not only mixtures of V and XIII but also XIII alone 
react or reacts with nitrobenzoyl chlorides of the formula IV with 
subsequent reduction and cyclisation on the one hand or cyclisation and 
reduction on the other in high yields and high purity to give 
benzothiazole derivatives of the formula I. In this very particularly 
preferred process variant, the reaction steps of reaction with sulphur 
alkali metal, reaction with nitrobenzoyl chlorides, reduction and 
cyclisation are combined into a single process step. The 
reduction-cyclisation or cyclisation-reduction of this process variant (b) 
are subject to the same remarks as process variants (a). In the formulae 
VII to XIII, A, R, R.sup.1 and n have the meaning indicated in the formula 
I. 
Nitrobenzoic acids of the formula VII, aminothiophenols of the formula V 
and nitrohalogenobenzenes of the formula VI are known, as are disulphides 
and polysulphides of the formula XIII, and/or can be prepared by methods 
described in the literature. 
Examples of 3- or 4-nitrobenzoic acids (VII) which can be used for 
preparing the 3- or 4-nitrobenzoyl chlorides IV required for the 
condensation reaction are: 
Table 1 
4-Nitrobenzoic acid 
2-Methyl-4-nitrobenzoic acid 
3- Methyl-4-nitrobenzoic acid 
3,5-Dimethyl-4-nitrobenzoic acid 
2-Ethyl-4-nitrobenzoic acid 
2-Methoxy-4-nitrobenzoic acid 
3-Methoxy-4-nitrobenzoic acid 
2,3-Oimethoxy-4-nitrobenzoic acid 
3,5-Oimethoxy-4-nitrobenzoic acid 
2-Methyl-5-methoxy-4-nitrobenzoic acid 
3-Ethoxy-4-nitrobenzoic acid 
3-Methyl-6-methoxy-4-nitrobenzoic acid 
2-Chloro-4-nitrobenzoic acid 
3-Chloro-4-nitrobenzoic acid 
2-Bromo-4-nitrobenzoic acid 
3-Bromo-4-nitrobenzoic acid 
3-Nitrobenzoic acid 
2-Methyl-3-nitrobenzoic acid 
4-Methyl-3-nitrobenzoic acid 
5-Methyl-3-nitrobenzoic acid 
6-Methyl-3-nitrobenzoic acid 
5-Ethyl-3-nitrobenzoic acid 
2,4-Dimethyl-3-nitrobenzoic acid 
4,6-Dimethyl-3-nitrobenzoic acid 
2-Methoxy-3-nitrobenzoic acid 
4-Methoxy-3-nitrobenzoic acid 
6-Methoxy-3-nitrobenzoic acid 
4-Ethoxy-3-nitrobenzoic acid 
5-Methyl-6-methoxy-3-nitrobenzoic acid 
4-Methoxy-5-methyl-3-nitrobenzoic acid 
4-Methyl-6-methoxy-3-nitrobenzoic acid 
5,6-Dimethoxy-3-nitrobenzoic acid 
2,4-Dimethoxy-3-nitrobenzoic acid 
2,5-Dimethoxy-3-nitrobenzoic acid 
4,5-Dimethoxy-3-nitrobenzoic acid 
2-Chloro-3-nitrobenzoic acid 
4-Chloro-3-nitrobenzoic acid 
5-Chloro-3-nitrobenzoic acid 
6-Chloro-3-nitrobenzoic acid 
2,5-Dichloro-3-nitrobenzoic acid 
2,6-Dichloro-3-nitrobenzoic acid 
4,6-Dichloro-3-nitrobenzoic acid 
2-Bromo-3-nitrobenzoic acid 
4-Bromo-3-nitrobenzoic acid 
5-Bromo-3-nitrobenzoic acid 
6-Bromo-3-nitrobenzoic acid 
4,5-Dibromo-3-nitrobenzoic acid 
3-Ethyl-4-nitrobenzoic acid 
3-n-Butyl-4-nitrobenzoic acid 
3-Ethoxy-4-nitrobenzoic acid 
3-n-Butoxy-4-nitrobenzoic acid 
To prepare amines of the formula I in accordance with the invention, use is 
preferably made of such 3- and 4-nitrobenzoic acid derivatives of the 
formula VII in which R.sup.1 is hydrogen, methyl, methoxy or chlorine. 
Examples of aminothiophenols which can be used are those of Table 2 below. 
TABLE 2 
______________________________________ 
##STR13## V 
A = SO.sub.2 or CO 
##STR14## 
##STR15## 
##STR16## 
##STR17## 
##STR18## 
##STR19## 
______________________________________ 
The nitrohalogenobenzenes of the formula VII used can be compounds in which 
A stands for CO or SO.sub.2, R has the meanings indicated in Table 2 and 
Halogen stands for fluorine, chlorine or bromine. 
The new compounds I, furthermore, are intermediates for the preparation of 
azo dyestuffs and can be diazotised in conventional manner and reacted 
with coupling components.

EXAMPLE 1 
2-(4'-Aminophenyl)-benzothiazole-5-sulphonic acid 
158 g of the sodium salt of 4-chloro-4-nitro benzenesulphonic acid 
(technical, about 83% pure) are dissolved at about 80.degree. C. in 400 ml 
of water. 180 ml of 30% strength aqueous sodium hydrogen sulphide solution 
(technical) are added dropwise in the course of about 30 minutes. The 
mixture is then stirred at 90.degree. C. for one hour and is then cooled 
down to 70.degree. C., and at at this temperature 93 g of 4-nitrobenzoyl 
chloride are added. The pH of the mixture is held at 8 by addition of 
sodium hydroxide solution. As soon as the pH remains constant, 180 ml of 
30% strength aqueous sodium hydrogen sulphide solution are added, and the 
reaction mixture is boiled under reflux for one hour. The reaction mixture 
is then brought to pH 1 with hydrochloric acid and is boiled under reflux 
for 5 hours. After cooling down, the precipitated product is isolated. The 
crude product is heated to 90.degree. C. in a mixture of 300 ml of water 
and 150 ml of 20% strength ammonia water. The mixture is filtered while 
still hot, and 50 g of sodium chloride are added to the filtrate while 
still hot. On cooling down, 125 g of pure product of the formula 
##STR20## 
crystallise out. 
NMR (DMSO) .delta.=3.40 (s, 2H), 6.70 (d, 2H), 7.65 (d, 1H), 7.78 (d, 2H), 
7.95 (d, 1H), 8.12 (s, 1H). 
EXAMPLE 2 
158 g of sodium 4-chloro-3-nitrobenzenesulphonate are reacted with NaHS 
solution as described in the example. A solution of 93 g of nitrobenzoyl 
chloride in 130 ml of toluene is added at 70.degree. C. pH 8 is maintained 
with sodium hydroxide solution. As soon as the pH of the mixture remains 
constant, 180 ml of 30% strength aqueous sodium hydrogensulphide solution 
are added. The reaction mixture is then heated to from 100.degree. to 
105.degree. C., and the starting toluene is recovered by distillation. 
After the toluene has been distilled off, the mixture is brought to pH 1 
with hydrochloric acid and is boiled under reflux for a further 3 hours. 
Isolation and separation from sulphur are carried out as in Example 1. The 
result obtained is 120 g of product which is identical to that of Example 
1. 
EXAMPLE 3 
158 g of the sodium salt of 4-chloro-3-nitrobenzenesulphonic acid 
(technical, about 83% pure) are dissolved at 80.degree. C. in 400 ml of 
water. A solution of 130 g of Na.sub.2 S.times.3H.sub.2 O and 16 g of 
sulphur in 100 ml of water is added dropwise in such a way that the 
reaction mixture boils lightly under reflux. After this the mixture is 
boiled for a further 2 hours. The mixture is then reacted at 70.degree. C. 
and pH 8 as described in Example 1 with 83 g of 4-nitrobenzoyl chloride, 
which is followed by reduction with 180 ml of 30% strength NaHS solution 
and cyclisation under acid conditions. Isolation and purification are 
carried out as described in Example 1. The result obtained is 90 g of 
product which is identical to that of Example 1. 
EXAMPLE 4 
93 g of 4-nitrobenzoyl chloride are added at 70.degree. C. to 103 g of 
2-aminothiophenol-4-sulphonic acid in 400 ml of water. pH 8 is maintained 
by addition of sodium hydroxide solution. As soon as the pH of the 
reaction mixture remains constant, 180 ml of 30% strength NaHS solution 
are added as in Example 1, which is followed by cyclisation under acid 
conditions and working up as described in Example 1. The result obtained 
is 135 g of product which is identical to that of Example 1. 
EXAMPLE 5 
158 g of the sodium salt of 4-chloro-3-nitrobenzenesulphonic acid are 
reacted at pH 7.5 to 8.5 with NaHS solution and 4-nitrobenzoyl chloride as 
described in Example 1. As soon as the pH of the reaction mixture remains 
constant, the mixture is brough to pH 1 with HCL and is boiled under 
reflux for one hour. Cooling down is followed by isolation and washing 
with H.sub.2 O. The moist paste of the product of the formula 
##STR21## 
is suspended in 500 ml of water and, starting at 80.degree. C., 180 ml of 
30% strength NaHS solution are added. The mixture is boiled under reflux 
for 1 hour and is brought to pH 1 with hydrochloric acid, and the product 
is isolated. The crude product is heated to 90.degree. C. in a solution of 
20 g of NaOH in 500 ml of water, and is filtered, the filtrate is brought 
to pH 1 with HCL, and is stirred until cold, and the product is isolated, 
washed and dried. This gives 120 g of product of the formula 
##STR22## 
If the instructions of Examples 1 to 6 are followed using in place of 
4-nitrobenzoyl chloride the acid chlorides of the nitrobenzoic acids 
listed in Table 1 of this application, this produces correspondingly 
substituted benzothiazole-5-sulphonic acid derivatives. 
EXAMPLE 6 
115 g of product of the formula 
##STR23## 
prepared from 4-chloro-3-nitrobenzenesulphonyl chloride and "Amin Z" 
[amine Z], are reacted in 300 ml of water with 20 g of sodium carbonate 
and 130 ml of 30% strength NaHS solution analogously to Example 1. At 
75.degree. C., 65 g of 4-nitrobenzoyl chloride are added, pH 8 is 
maintained with sodium hydroxide solution, stirring follows for 1 hour, 
130 ml of 30% strength NaHS solution are then added, which is followed by 
boiling under reflux for 1 hour, adjustment to pH 1 with hydrochloric 
acid, boiling under reflux for 2 hours, cooling down, removal of 
precipitated sulphur by filtration and setting of filtrate at pH 11 with 
NaOH. The product initially appears in the form of an oil, but later, 
after stirring, in the form of crystals. Isolation and drying gives 80 g 
of product of the formula 
##STR24## 
NMR (DMSO): 1.70 (m, 2H), 2.20 (s, 6H), 2.35 (t, 2H), 3.33 (m, 2H), 5.86 
(s, 2H), 6.65 (d, 2H), 7.75 (m, 3H), 8.02 (d, 1H), 8.32 (s, 1H), 8.55 (s, 
1H). 
EXAMPLE 7 
180 g of product of the formula 
##STR25## 
are reacted with 180 ml of 30% strength NaHS solution as described in 
Example 6. 110 g of 3-nitro-4-methoxybenzoyl chloride are then added at 
70.degree. C. and pH 8 is maintained with NaOH. As soon as the pH remains 
constant, the mixture is brought to pH 1 with HCl and is boiled under 
reflux for 2 hours. After cooling down, the product is isolated and 
recrystallised from DMF. This gives 110 g of the product of the formula 
##STR26## 
110 g of this product are reduced at 65.degree. C. in 500 ml of ethanol 
with hydrogen in the presence of Raney nickel. Separation from the Raney 
nickel and isolation gives 80 g of product of the formula 
##STR27## 
EXAMPLE 8 
83 g of product of the formula 
##STR28## 
prepared from 4-chloro-3-nitrobenzoyl chloride and "Amin Z" [amine Z], are 
reacted in 300 ml of water with 25 g of sodium carbonate and 95 ml of 30% 
strength NaHS solution. analogously to Example 1. 55 g of 4-nitrobenzoyl 
chloride are then added at 70.degree. C., pH 8 is maintained with sodium 
hydroxide solution, and boiling at reflux for 1 hour with 100 ml 30% 
strength NaHS solution is followed by setting of pH 1 with hydrochloric 
acid, boiling under reflux for a further 3 hours, cooling down, removal of 
precipitated sulphur by filtration, and setting of pH 11 with sodium 
hydroxide solution. The product initially appears in the form of an oil, 
but later, on stirring, in the form of crystals. Isolation and drying 
gives 75 g of product of the formula 
##STR29## 
NMR (DMSO): 1.84 (m, 2H), 2.62 (s, 6H), 2.90 (m, 4H), 6.05 (s, 2H), 6.70 
(d, 2H), 7.75 (3 H), 7.90 (s, 1H), 8.20 (d, 2H). 
EXAMPLE 9 
52 parts of 3-nitro-4-chlorobenzoic acid are dissolved at 80.degree. C. in 
200 parts of water and 10 parts of sodium hydroxide. 90 ml of 30% strength 
NaHS solution are added dropwise at 80.degree.-85.degree. C. in the course 
of 30 minutes. 44 parts of sodium dithionite are then added, which is 
followed by boiling under reflux for 2 hours. 47 parts of 4-nitrobenzoyl 
chloride are then added at 70.degree. C., and pH 8 is maintained with 
sodium hydroxide solution. The mixture is stirred for 1 hour and 90 parts 
of 30% strength NaHS solution are then added. After one hour of refluxing 
the mixture is brought to pH 1 with hydrochloric acid and is boiled under 
reflux for a further 3 hours. After cooling down, the solids are isolated 
and washed with water. To separate off the sulphur, the moist crude 
product is suspended in 400 parts of water, the suspension is brought to a 
pH 10 with sodium hydroxide solution and heated to 90.degree.-95.degree. 
C., and the sulphur is filtered off. On cooling down, 55 parts of product 
of the formula 
##STR30## 
crystallise out. 
NMR (DMSO): 5.80 (s, 2H), 6.62 (d, 2H), 7.68 (d, 2H), 7.85 (m, 2H), 8.30 
(s, 1H). 
EXAMPLES 10-15 
The method of Example 1 is used to prepare: 
______________________________________ 
##STR31## 
Example NH.sub.2 R 
______________________________________ 
10 4' 3'-CH.sub.3 
11 3' 4'-CH.sub.3 
12 3' 4'-OCH.sub.3 
13 3' 4'-OC.sub.2 H.sub.5 
14 4' 3'-OCH.sub.3 
15 4' 2',5'-OCH.sub.3 
______________________________________ 
EXAMPLES 16-21 
The method of Example 9 is used to prepare the corresponding 
benzothiazole-5-carboxylic acids: 
______________________________________ 
##STR32## 
Example NH.sub.2 R 
______________________________________ 
16 4' 3'-CH.sub.3 
17 3' 4'-CH.sub.3 
18 3' 4'-OCH.sub.3 
19 3' 4'-OC.sub.2 H.sub.5 
20 4' 3'-OCH.sub.3 
21 4' 2',5'-OCH.sub.3 
______________________________________ 
EXAMPLES 22-36 
The method of Example 7 is used to prepare the following compounds: 
______________________________________ 
##STR33## 
##STR34## 
Exam- 
ple NH.sub.2 
R R.sup.1 R.sup.2 
______________________________________ 
22 4' H H H 
23 4' H H CH.sub.3 
24 4' H CH.sub.3 
CH.sub.3 
25 3' H H H 
26 4' H H 
##STR35## 
27 4' 3'-CH.sub.3 
H 
##STR36## 
28 4' 3'-OCH.sub.3 
C.sub.2 H.sub.4 OC.sub.2 H.sub.4 
29 4' H H 
##STR37## 
30 4' H H 
##STR38## 
31 4' H H 
##STR39## 
32 4' H R.sup.1 + R.sup.2 
##STR40## 
33 4' H C.sub.2 H.sub.4OC.sub.2 H.sub.4 
34 3' 4'-OCH.sub.3 
CH.sub.3 
CH.sub.3 
35 3' 4'-CH.sub.3 
H 
##STR41## 
36 3' 4'-OCH.sub.3 
R.sup.1R.sup.2 
C.sub.2 H.sub.4 OCH.sub.3 
37 4' H H SO.sub.2 CH.sub.3 
38 4' H H 
##STR42## 
______________________________________ 
EXAMPLES 39-52 
Analogous 4-chloro-3-nitrobenzenecarboxamides are used analogously to 
Examples 22-39 to prepare the corresponding 
2-(aminophenyl)-benzothiazole-5-carboxamides.