Aminobenzophenones have the formula ##STR1## where the ring A may be benzofused, PA1 X.sup.1 is hydrogen or hydroxysulfonyl, PA1 X.sup.2 is hydrogen, hydroxysulfonyl, hydroxysulfonylphenyl, hydroxysulfonylbenzyl or hydroxysulfonylphenylethyl, PA1 R.sup.1, R.sup.2 and R.sup.3 are each independently of the others hydrogen, halogen, C.sub.1 -C.sub.12 -alkyl, cyclohexyl or C.sub.1 -C.sub.4 -alkoxy, or one of them may also be the radical of the formula ##STR2## where L is a chemical bond, C.sub.1 -C.sub.4 -alkylene or --O--CH.sub.2 -- and Y.sup.1, Y.sup.2 and Y.sup.3 are each independently of the others hydrogen, halogen, C.sub.1 -C.sub.12 -alkyl or C.sub.1 -C.sub.4 -alkoxy and R.sup.4, X.sup.1, X.sup.2 and the ring A are each as defined above, and PA1 R.sup.4 is hydrogen or chlorine, with the proviso that X.sup.1 and X.sup.2 are not both hydrogen, their intermediates having the formula ##STR3## where L is as defined above.

The present invention relates to novel aminobenzophenones of the formula I 
##STR4## 
where the ring A may be benzofused, 
X.sup.1 is hydrogen or hydroxysulfonyl, 
X.sup.2 is hydrogen, hydroxysulfonyl, hydroxysulfonylphenyl, 
hydroxysulfonylbenzyl or hydroxysulfonylphenylethyl, 
R.sup.1 , R.sup.2 and R.sup.3 are identical or different and each is 
independently of the others hydrogen, halogen, C.sub.1 -C.sub.12 -alkyl, 
cyclohexyl or C.sub.1 -C.sub.4 -alkoxy, or one of them may also be the 
radical of the formula 
##STR5## 
where L is a chemical bond, C.sub.1 -C.sub.4 -alkylene or a radical of the 
formula --O--CH.sub.2 --, Y.sup.1, Y.sup.2 and Y.sup.3 are identical or 
different and each is independently of the others hydrogen, halogen, 
C.sub.1 -C.sub.12 -alkyl or C.sub.1 -C.sub.4 -alkoxy, and R.sup.4, 
X.sup.1, X.sup.2 and the ring A are each as defined above, and 
R.sup.4 is hydrogen or chlorine, 
with the proviso that X.sup.1 and X.sup.2 are not both hydrogen. 
The present invention also relates to novel doubled aminobenzophenones of 
the formula II 
##STR6## 
where L is a chemical bond, C.sub.1 -C.sub.4 -alkylene or a radical of the 
formula --O--CH.sub.2 --, preferred compounds of the formula II being 
those in which each carbonyl group is meta or para to NH.sub.2. 
The novel doubled aminobenzophenones are useful intermediates for preparing 
aminobenzophenones of the formula I. 
The novel aminobenzophenones of the formula I have been specified in the 
form of the free acid. Of course, their salts should also be deemed to be 
included. 
These salts are metal or ammonium salts. Metal salts are in particular the 
lithium, sodium or potassium salts. Ammonium salts for the purposes of the 
present invention are those salts which contain either substituted or 
unsubstituted ammonium cations. Substituted ammonium cations are for 
example monoalkylammonium, dialkylammonium, trialkylammonium, 
tetraalkylammonium or benzyltrialkylammonium cations or those cations 
which are derived from nitrogen-containing five- or six-membered saturated 
heterocycles, such as pyrrolidinium, piperidinium, morpholinium, 
piperazinium or N-alkyl-piperazinium cations or their N-monoalkyl- or 
N,N-di-alkyl-substituted products. By alkyl is meant here in general 
straight-chain or branched C.sub.1 -C.sub.20 -alkyl which may be 
substituted by hydroxyl and/or interrupted by oxygen. 
EP-A-302,401 discloses aminobenzophenones which, however, have no acid 
group in the molecule. 
It is an object of the present invention to provide novel 
aminobenzophenones having at least one hydroxysulfonyl group. 
We have found that this object is achieved by the aminobenzophenones of the 
formula I defined at the beginning. 
Any alkyl or alkylene appearing in the above mentioned formula I may be 
either straight-chain or branched. 
R.sup.1, R.sup.2, R.sup.3, Y.sup.1, Y.sup.2 and Y.sup.3 are each for 
example fluorine, chlorine, bromine, methyl, ethyl, propyl,isopropyl, 
butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, 
hexyl, 2-methylpentyl, heptyl, 2-methylhexyl, octyl, isooctyl, 
2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl (the 
above designations isooctyl, isononyl and isodecyl are trivial names 
derived from oxo process alcohols - cf. Ullmanns Encyklophdie der 
technischen Chemie, 4th edition, Volume 7, pages 215 to 217, and Volume 
11, pages 435 and 436), methoxy, ethoxy, propoxy, isopropoxy, butoxy, 
isobutoxy or sec-butoxy. 
L is for example methylene, ethylene, 1,2- or 1,3-propylene, isopropylidene 
or 1,2-, 1,3-, 2,3- or 1,4-butylene. 
Preference is given to aminobenzophenones of the formula Ia 
##STR7## 
where X.sup.1 is hydrogen or hydroxysulfonyl, 
X.sup.2 is hydrogen or hydroxysulfonyl and 
R.sup.1, R.sup.2 and R.sup.3 are each independently of the others hydrogen, 
halogen, C.sub.1 -C.sub.6 -alkyl, cyclohexyl or C.sub.1 -C.sub.4 -alkoxy, 
or one of them may also be the radical of the formula 
##STR8## 
where L is a chemical bond, C.sub.1 -C.sub.4 -alkylene or a radical of the 
formula --O--CH.sub.2 --, Y.sup.1, Y.sup.2 and Y.sup.3 are each 
independently of the others hydrogen, halogen, C.sub.1 -C.sub.5 -alkyl or 
C.sub.1 -C.sub.4 -alkoxy, and S.sup.1 and X.sup.2 are each as defined 
above. 
Preference is further given to aminobenzophenones of the formula I where 
one of X.sup.1 and X.sup.2 is hydrogen and the other is hydroxysulfonyl. 
Emphasis must be given to aminobenzophenones of the formula I where 
R.sup.1, R.sup.2 and R.sup.3 are each independently of the other hydrogen, 
chlorine, C.sub.1 -C.sup.4 alkyl, in particular methyl or ethyl, methoxy 
or ethoxy, or one of them may also be a radical to the formula 
##STR9## 
where L and X.sup.1 are each as defined above. 
Of particular importance are aminobenzophenones of the formula 
##STR10## 
where one of H.sup.1 and X.sup.2 is hydrogen and the other is 
hydroxysulfonyl and 
R.sup.1 is chlorine, C.sub.1 -c.sub.4 -alkyl, in particular methyl or 
ethyl, methoxy or ethoxy, or the radical of the formula 
##STR11## 
where L, X.sup.1 and X.sup.2 are each as defined above and where each 
carbonyl group is para to NH.sup.2 or X.sup.1. 
Of particular importance are furthermore aminobenzophenones of the formula 
Ic or Id 
##STR12## 
where one of X.sup.1 and X.sup.2 is hydrogen and the other is 
hydroxysulfonyl and 
R.sup.1 and R.sup.2 are each independently of the other chlorine, C.sub.1 
-C.sub.4 -alkyl, in particular methyl or ethyl, methoxy or ethoxy, and 
where each carbonyl group is para to NH.sub.2 or X.sup.1. 
The aminobenzophenones of the formula I according to the present invention 
can be obtained in a conventional manner. 
For instance, by treating a benzophenone derivative of the formula III 
##STR13## 
where Z is amino or nitro and Q.sup.1, Q.sup.2 and Q.sup.3 are identical 
or different and each is independently of the others hydrogen, halogen, 
C.sub.1 -C.sub.12 -alkyl, cyclohexyl or C.sub.1 -C.sub.4 -alkoxy, or one 
of them may also be a radical of the formula 
##STR14## 
where R.sup.4, Z, L, Y.sup.1, Y.sup.2, Y.sup.3 and the ring A are each as 
defined above, with a suitable sulfonating agent in a conventional manner. 
Suitable sulfonating agents are for example sulfuric acid, chlorosulfonic 
acid, oleum and mixtures In general, 1 mol of the sulfonating agent is 
used per mole equivalent of hydroxysulfonyl to be introduced. 
The sulfonation is in general carried out at from 20.degree. to 200.degree. 
C., preferably from 50 to 180.degree. C. 
A solvent may be used. Suitable solvents are for example inert organic 
solvents, such as o-dichlorobenzene or trichlorobenzene, but also excess 
sulfonating agent. 
If an aminobenzophenone derivative of the formula III (Z =amino) is to be 
sulfonated, the sulfonation is preferably carried out in the absence of an 
inert organic solvent but in the presence of a small excess of sulfonating 
agent (about 0.01-0.3 mol per mole of benzophenone III). 
After the sulfonation reaction has ended, the product is worked up in a 
conventional manner. For instance, after any inert organic solvent has 
been removed by steam distillation, by dissolving the residue in water and 
salting out with for example sodium chloride at a pH which in general is 
less than 1. 
If the sulfonation is carried out on nitrobenzophenone derivatives of the 
formula III (Z =nitro), the nitro group must subsequently be converted 
into an amino group by reduction. This may be achieved in a conventional 
manner, for example with hydrogen in the presence of a catalyst. Suitable 
catalysts are for example Raney nickel and palladium on carbon. 
The benzophenones of the formula II or III are likewise prepared in a 
conventional manner. For instance, a benzoyl chloride of the formula IV 
##STR15## 
where r.sup.4 is as defined above, can be reacted under the reaction 
conditions of a Friedel-Crafts acylation with an aromat of the formula V 
##STR16## 
where W.sup.1, W.sup.2 and W.sup.3 are identical or different and each is 
independently of the others hydrogen, halogen, C.sub.1 -C.sub.12 -alkyl, 
cyclohexyl or C.sub.1 -C.sub.4 -alkoxy or one these substituents can also 
be a radical of the formula 
##STR17## 
where L, Y.sup.1, Y.sup.2, Y.sup.3 and the ring A are each as defined 
above, and the resulting benzophenone is reduced if necessary. 
The aminobenzophenones of the formula I according to the present invention 
are useful intermediates for the synthesis of dyes and active substances. 
The Examples which follow are intended to illustrate the invention in 
greater detail.

EXAMPLE 1 
105.5 g of 4-amino-4,-methylbenzophenone were suspended in 500 ml of 
o-dichlorobenzene. 62g g of sulfuric acid (96 % strength by weight) were 
then added, and the mixture was heated to the boil 
(175.degree.-180.degree. C.), and the refluxed o-dichlorobenzene was 
passed through a water separator in which the water of reaction and the 
water present in the sulfuric acid were separated off. After about 1 hour 
there was no further water to be separated off. The water-moist 
o-dichlorobenzene condensate was then passed over dry silica gel. (It is 
also possible to use fresh, dry o-dichlorobenzene instead.) In this way 
the conversion into 4-amino-4,-methylbenzophenone-3-sulfonic acid 
##STR18## 
was virtually quantitative. 
After the reaction had ended (after about 5-hours), the o-dichlorobenzene 
was separated off by steam distillation. The residue was dissolved in 
water with the said of 50% strength by weight sodium hydroxide solution, 
and the solution was clarified with 1 g of active charcoal. The filtrate 
was adjusted to a pH less than 1 with concentrated hydrochloric acid and 
cooled down to room temperature. Filtering off with suction, washing with 
a little highly dilute hydrochloric acid and drying left 120 g of 
4-amino-4'-methylbenzophenone -3-sulfonic acid. 
Melting point: 280.degree. C. (dec.). .lambda..sub.max (measured in 
N,N-dimethylformamide): 332 nm 
EXAMPLE 2 
241 g of 4-methyl-4'-nitrobenzophenone were added at room temperature to 
700 g of oleum (24% strength by weight). The temperature of the mixture 
was then raised to 65.degree. C. and maintained at that level while the 
mixture was stirred for 5 hours. The reaction had then ended. The mixture 
was cooled down to room temperature and discharged onto 1600 ml of 
ice-water, 150 g of sodium chloride were added, and the mixture was cooled 
down to room temperature. The precipitated product of the formula 
##STR19## 
was filtered off with suction, washed with a little ice-cold, dilute 
hydrochloric acid and dried. This gave 240 g of 
4-methyl-4'-nitrobenzophenone-3-sulfonic acid. 
This product was suspended in 1500 ml of methanol and 100 ml of water, 
brought to pH 5.5 with 50% strength by weight sodium hydroxide solution 
and then hydrogenated with hydrogen at 40.degree.-50.degree. C. and 
atmospheric pressure in the presence of 3 g of finely divided Raney 
nickel. 
After the nickel had been separated and the methanol distilled off, the 
mixture was acidified to about pH 0.5, and the amino compound of the 
formula 
##STR20## 
was isolated by salting out as described in Example 1. 
Yield: 208 g, melting point: &gt;300.degree. C; .lambda..sub.max (measured in 
water: 336, 252 nm). 
EXAMPLE 3 
Example 1 was repeated, except that the benzophenone used was 105.5 g of 
the amine of the formula 
##STR21## 
and the sulfonating agent used was 74 g of concentrated sulfuric acid. 
This gave a product of the formula 
##STR22## 
.lambda..sub.max (measured in N,N-dimethylformamide): 331 nm. 
EXAMPLE 4 
4.78 kg of 4-amino-4'-isopropylbenzophenone were admixed at 120.degree. C. 
in the course of 30 minutes with 2100 g of 96% strength by weight sulfuric 
acid by stirring. this produced a freely stirrable, homogeneous mixture, 
which was head to 165.degree.-175.degree. c. in the course of 3 hours and 
was converted at that temperature into 
4-amino4'-isopropylbenzophenone-3-sulfonic acid of the formula 
##STR23## 
by baking with nitrogen. 
The conversion was quantitative. (Even if stoichiometric amounts of 
sulfuric acid (2050 g) were used, only traces of unsulfonated starting 
material were found.) 
The produce was a gray powder which was soluble in water in the presence of 
sodium hydroxide without leaving a residue. 
.lambda..sub.max (measured in N,N-dimethylformamide): 332 nm, yield: 6.76 
kg. (The product still contained 416 g of sulfuric acid.). 
The same methods were used to obtain the benzophenone derivatives listed in 
Tables 1 and 2. 
TABLE 1 
______________________________________ 
##STR24## 
Ex. 
No. L.sup.1 L.sup.2 L.sup.3 
______________________________________ 
5 CH.sub.3 CH.sub.3 H 
6 C.sub.2 H.sub.5 
H H 
7 C.sub.4 H.sub.9 (n) 
H H 
8 CH.sub.3 CH.sub.3 SO.sub.3 H 
9 H Cl H 
10 CH.sub.3 H CH.sub.3 
11 H CH.sub.3 Cl 
12 Cl CH.sub.3 H 
13 OCH.sub.3 CH.sub.3 H 
14 OCH.sub.3 CH.sub.3 SO.sub.3 H 
15 H 
##STR25## H 
16 H C.sub.6 H.sub.13 (n) 
H 
______________________________________ 
TABLE 2 
______________________________________ 
##STR26## 
Ex. 
No. L.sup.1 L.sup.2 L.sup.3 L.sup.4 
______________________________________ 
17 H CH.sub.3 CH.sub.3 SO.sub.3 H 
18 CH.sub.3 SO.sub.3 H 
H CH.sub.3 
19 OCH.sub.3 SO.sub.3 H 
H CH.sub.3 
20 CH.sub.3 H OCH.sub.3 
SO.sub.3 H 
21 H H Cl SO.sub.3 H 
22 H H C.sub.2 H.sub.5 
SO.sub.3 H 
23 H H C.sub.4 H.sub.9 (n) 
SO.sub.3 H 
24 H H C.sub.6 H.sub.13 (n) 
SO.sub.3 H 
25 H Cl CH.sub.3 SO.sub.3 H 
______________________________________ 
EXAMPLE 26 
a) 320 g of aluminum chloride were introduced into 800 ml of dry methylene 
chloride at not more than 20.degree. C. Then 372 g of p-nitrobenzoyl 
chloride were added a little at a time with thorough stirring at not more 
than 20.degree. C., followed by 256 g of anhydrous naphthalene. The 
mixture evolved hydrogen chloride. This was followed by stirring at room 
temperature for 3 hours and the melt was then decomposed on water and ice. 
After phase separation the organic phase was extracted once with water and 
the methylene chloride was then removed by distillation The residue was 
boiled up with methanol, cooled down to room temperature and adjusted with 
sodium carbonate to pH 7-9. The crystalline precipitate was filtered off 
with suction, washed and dried, leaving 519 g of the compound of the 
formula 
##STR27## 
(The product still contained a small amount of the naphthophenone of the 
formula 
##STR28## 
b) The product mixture was suspended in 2500 ml of isobutanol together with 
30 ml of glacial acetic acid and a catalytic amount of activated nickel 
powder and was hydrogenated at 60.degree. C. with hydrogen with very 
thorough stirring to the corresponding amine of the formula 
##STR29## 
(The product still contained a small amount of the corresponding isomer.) 
Isolation in a conventional manner left 445 g of product. 
c) After addition of 192 g of 96% strength sulfuric acid and intensive 
mixing, the mixture obtained under b) was subjected to baking at 
200.degree. c. under nitrogen. This produced 589 g of the compound of the 
formula 
##STR30## 
.lambda..sub.max (measured in water at pH 7-9: 333 nm). (shoulder at 242 
nm). 
The UV spectrum has a minimum at 276 nm. 
This novel diazo component still contained a small amount of the compound o 
the formula 
##STR31## 
EXAMPLE 27 
320 g of aluminum chloride were introduced into 800 ml of dry methylene 
chloride at not more than 20.degree.C. Then 372 g of m-nitrobenzoyl 
chloride were added a little at a time with thorough stirring at 
.ltoreq.20.degree. C., followed by 256 g of anhydrous naphthalene. The 
mixture was reacted and worked up as described in Example 26. 
##STR32## 
EXAMPLE 28 
150 g of 4-amino-1-naphthophenone-3-sulfonic acid were introduced into 400 
g of oleum (25% strength by weight) at not more than 40.degree. C. The 
reaction mixture was stirred at room temperature for 5 ours and at 
80.degree. C. for 4 hours. Then the mixture was stirred onto ice. A 
solution was obtained of the diazo component of the formula 
##STR33## 
After neutralization with sodium hydroxide solution and removal of 
precipitated sodium sulfate, the solution of the diazo component (in the 
form of the disodium slat) had an absorption maximum in the UV spectrum at 
330 nm. 
EXAMPLE 29 
251 g of 2,4-dimethyl-4'-nitrobenzophenone were sulfonated inoleum and then 
educed o the diazo component of the formula 
##STR34## 
both steps being carried out as described in example 2. 
The same method as can also be used to obtain the following components: 
__________________________________________________________________________ 
Example No. 
__________________________________________________________________________ 
30 
##STR35## .lambda..sub.max (measured in 
water at pH .gtoreq.7): 334 nm 
31 
##STR36## .lambda..sub.max (measured in 
water at pH .gtoreq.7): 327 nm 
32 
##STR37## .lambda..sub.max (measured in 
water at pH .gtoreq.7): 335 nm 
33 
##STR38## 
34 
##STR39## .lambda..sub.max (measured in 
water at pH 7): 326 nm 
35 
##STR40## 
36 
##STR41## .lambda..sub.max (measured in 
water at pH 7): 330 nm 
37 
##STR42## 
38 
##STR43## 
39 
##STR44## 
40 
##STR45## .lambda..sub.max (measured in 
water at pH 7): 238 nm, 268 nm 
325 nm (low) 
41 
##STR46## .lambda..sub.max (measured in 
water at pH 7): 237 nm 267 nm 
42 
##STR47## Melting point &gt;300.degree. C. 
43 
##STR48## .lambda..sub.max (measured in 
water at pH 8): 299 nm 
44 
##STR49## 
45 
##STR50## 
46 
##STR51## .lambda..sub.max (measured in 
water at pH .gtoreq.7): 263 nm, 
328 nm, 246 nm 
47 
##STR52## .lambda..sub.max (measured in 
water at pH 8): 293 nm 
48 
##STR53## .lambda..sub.max (measured in 
water at pH 7): 239 nm, 268 nm, 
326 nm 
49 
##STR54## .lambda..sub.max (measured in 
water: 336 nm) Melting point: 
330.degree. C. (decom- position) 
50 
##STR55## .lambda..sub.max (measured in 
water at pH 7): 330 
__________________________________________________________________________ 
nm 
EXAMPLE 51 
480 g of dry aluminum chloride powder were introduced into 2500 ml of 
anhydrous methylene chloride at room temperature, followed by 600 g of 
p-nirogenzoyl chloride added a little at a time. The mixture was then 
admixed with 274 g of anhydrous 1,2-diphenylethane and stirred at 
35.degree. C. overnight. The mixture was then decomposed onto water, the 
upper, aqueous phase was separated off, the organic phase was extracted 
twice with water (pH about 7) and then the organic solvent was distilled 
off. Filtering off with suction, washing and drying left 680 g of the 
compound of formula 
##STR56## 
360 g of this produce were hydrogenated with hydrogen in 2500 ml of 
N,N-dimethylformamide and 30 ml of hydrogen and glacial acetic acid at 
80.degree. C. with the said of a nickel catalyst. After the uptake of 
hydrogen had ended, the catalyst was separated off and the diamine of the 
formula 
##STR57## 
was precipitated with water, giving 310 g of product. 
EXAMPLE 52 
Example 51 was repeated, except that the p-nitrobenzoyl chloride was 
replaced by the same amount of m-nitrobenzoyl chloride. 
Similar amounts of products of the formulae 
##STR58## 
(.lambda..sub.max (methanol): 244, 335 nm) were obtained.