CA1251466A - 5-amino-2-substituted phenyl 2-hydroxyethyl sulphone intermediates for dyestuffs - Google Patents

Abstract

ABSTRACT
The invention relates to an amino compound of the general formula V

(V) wherein X is NR3, O or S;
R3 is H, C1-C4-alkyl, C1-C4-alkyl substituted by SO3H, OSO3H, COOH, OH or OCH3; and Y is C2-C6-alkylene, C2-C6-alkylene substituted or inter-rupted in the alkylene chain by OSO3H, O, SO2, NH, S or -NCH3.
These compounds of formula V are useful as intermediates in pre-paring triphendioxazine dyestuffs.

Description

~2~

The present divisional application is divided out of parent application ~erial No. 473,856 filed on February 8, 1985.
According to one aspect of the invention of the present divisional application there is provided an amino compound of the general formula V

H2N ~ ~ X-Y-OH (V) wherein X is NR3, O or S;
R3 is H, cl-c4-alkyl ~ cl-c4-alkyl substituted by SO3H
OS03H, COOH, OH or OCH3; and Y is C2-C6-alkylene, C2-C6-alkylene substituted or inter-rupted in the alkylene chain by OS03H, , S2, NH, S or -NCH3.
The invention of the parent application relates to a triphendioxazine dyestuff of the general formula I
H03SO-Y-X ~ 0~,~,S2 ` `Z

~N~\O~ X-Y-0$03H

wherein Rl and R2 are each independently H, F, Cl, Br, Cl-C4-alkyl, Cl-C4-alkoxy, phenoxy, Cl-C4-alkylcarbonylamino, benzoyl-amino or carboxamido;
X is NR3, O or S;

~s~

- 2 - 23189-5908D

R3 is H, Cl-C4-alkyI, Cl-C4-alkyl substituted by SO3H, OSO3H, COOH, OH or OCH3;
Y is C2-C6-alkylene, C2-C6~alkylene substituted or inter-rupted in the alkylene chain by OSO3H, O, SO2, NH, S or -NCH3;
Z is -CH = CH2 or -CH2-CH2-W
wherein

3 ~ 3H, OPO3H2, -ocl-c4-alkyl-carbonyl and wherein the -SO2Z radicals are in the o-position relative to the -X-Y-OSO3H group.
The -SO2Z radicals in the formula are preferably in the o-position relative to the -X-Y-OSO3H group.
Preferred dyestuffs of the formula (I) have the f'ormula HO SO-Y-HN ~1 S2 Z
3 \ ~ o ~ ~N ~ (II~

~ N ~ O ~ NH-Y-OSO3H
Z -O2S ~2 wherein Rl, R2 and Y are as defined above and Zl denotes -CH2-CH2-OSO3H or -CH=CH2, or the formula Cl SO2-CH2-CH2-OSO3H

HO3SO~Y'-HN ~ ~ ~N ~ (III) 3 2 H2 O2S ~ NH-~I~-OSO3H

wherein Y' denotes C2-C4 alkylene.

lZ~;14~

Examples of R3 are methyl, ethyl, l-propyl, 2-propyl, l-butyl, 2-butyl and 2-methylpropyl, all of which can be substitut-ed by the water-solubilising or hydrophilic groups SO3H, OSO3H, COOH, OH or OCH3.
Examples of suitable alkylene radicals Y are:

-CH2)2-6, -CH2-CH2-CH- , -CH2-CH- , --CH-CH-,H3 1C~I3 ,CH3 2 , 2 ' ,C CH2- , -CH2-C-CH2- , -CH -C-CH -2 , CH2 , -CH2-CH-CH2OSO3H , -C-CH -CH

OSO3H C~I3 -CH2-CH2-0-CH2-CH2- , -CH2-CH2-S02-CH2-C~I2- ~

-CH2-C~2-NH-CH2-CH2- , -CH2-cH2-(o-cH2-cH2)l or 2' -CH2CH2-S-CH2CH2- ~ -CH CH `N-CH CH -Compounds ~ re preferably prepared by condensing 1,4-benzoquinones of the formula 1 ~ T
T2 ~R2 o wherein Tl and T2 each denote hydrogen, F, Cl, Br, O-alkyl or lZS~

- 4 - 23189-5908D

O-aryl and Rl and R2 are as defined above, with compounds of the formula H2N ~ 2 C 2 2 (V) : X-Y-OH:
wherein :X and Y are as defined above, to form compounds of the formula HO-CH -CH -O S R
2 2 2 ~ HN ~ O ~ X-Y~-O~
HO-Y-X ~ O ~ NH ~ ~S2-cH2-cH2~

wherein Rl, R2, X and Y are as defined a~ove, followed by a ring closure reaction in a strongly acid medium and, if desired the -SO2CH2CH2OSO3H groups resulting if the reaction is conducted in oleum are then converted into -SO2CH=CH2 or SO2CH2CH2W groups wherein W is -SSO3H, OPO3H2, -OCl-C4-alkyl-carbonyl.
The ring closure of condensation products (VI) can be effected, for example, by mekhod.s of the type described in German Offenlegungsschriften 2,122,262, 2,124,080, 2,302,382, 2,344,781, 2,503,611 and 2,823,828 and in British Patent Specifi-cation 2,019,872, in particular in concentrated sulphuric acid or especially in oleum having an SO3 concentration of 1-50%, at temperatures of 10-80, if desired particularly advantageously in the presence of oxidising agents, such as potassium peroxodisulphate, ~ZSl~
....

- 5 - 23189-5908D

ammonium peroxodisulphate or organic peroxides.
The new dyestuffs produce bright dvelngs on cellulose and natural and synthetic polyamide materials. The~ are distin-~uished by high tinctorial strength.
As water-soluble reactive dyestuffs, the new dyestuffs are preerably of interest for dyeing hydroxyl- and amide-containing textile materials, in particular materials made of natural and regenerated cellulose and of nylon and polyurethane fibres, wool and silk.
Said materials are dyed or tinted by the methods which are common knowledge and industrially customary for water-soluble reactive dyestuffs. Light- and wet-fast brilliant dyeings and prints are then obtained.
The temperatures in the Examples are given in C. The formulae of the water-soluble reactive dyestuffs in the description and in the Examples are those of the free acids. The dyestuffs are generally isolated and used in -the form of their alkali metal salts, in particular the lithium, aodium or potassium salts.
The indicator numbers with which the hue is character-ised in the Examples refer to the Colour Index hue indication chart.
As mentioned above, the invention of this divisional application relates to new amino compounds of the structure S02CH2C~12H
H2N ~X-Y-OH (V) wherein z~
- 5a - 231$9-5908D

X and Y are as defined above~ of these, preference is given to amino compounds of the formula ~ S02CH2CH20H

2N ~ ~ Xl-~E~CH-2~ (VII) wherein Xl = NX, G or S.
The present invention also relates to processes for pre-paring (V). In one process, 2-halogeno-5-nitrophenyl ~-hydroxy-ethyl sulphones 2 ~ EJal (VIII) wherein Hal = F, C1, Br or I, which can be prepared by ethoxylating 2-halogeno-5-nitrobenzene-sulphinic acids under neutral aqueous conditions~ are reacted with compounds of the structure HX-Y-OH (IX) under heat and if desired under pressure, H-Hal being eliminated, and the resulting nitro-sulphones of the formula S02CH2CHz 02N-g--X-Y-OH (X) are subsequently, if possible without prior isolation, reduced to (V) .

~Z5~4~i~

- 5b ~ 23189-5908D

~ he condensation with the nucleophilic reac-tants (IX) is carried out above 70C, most advantageously between 75 and 120, i~ desired under pressure. The reaction medium can be water, any organic water-soluble ~ZS14~i~
, . .

- 6 -solvent, for example any alcohol~ DMF or DMSO, or a mix-ture of the t~o. If HX-Y-OH is present ;n excess it is also possible to dispense with a solvent altogether.
To neutralise the hydrogen hal;de ~hich is liberated~ it is possible to add an auxiliary base, for exa~ple a ter-tiary amine, in particular a ~rialkylamine such as tri-ethyLamine, sod;um hydrogencarbonate or sodiuo carbonate, or, if HNR3-Y-oH ;s used, to use about t~ice the equi-molar amount of this hydroxyalkylamirle.
The concLuding reduct;on can be effected catalyti-cally tfor example hydrogen/catalyst~, with metal/acid (for exa~ple iron/acetic acid) or ~ith other customary re-ducing agen~s for aromatic nitro compounds.
In another process, the alkali metal salts of the 2-halogeno-5-nitrobenzenesulphin;c ac;ds are condensed ~ith HX-Y-OH compounds at above 80C in an aqueous reac-tion med;um, if des1red under pressure, and the condensa-tion products f 02M
02N ~ -X-Y-OH tXI) M = L;~ Na or K
are alkylated uith ethylene oxide or chloroethanol under heat, pressure and neutral conditions. To keep the pH
constant, an inorganic acid, for example sulphuric ac;d, is metered ;n cQnt;nuously, or the react;on is carried out in a phosphate-buffered solution~ The corresponding ni-trosulphones (X) are then reduced to the corresponding amino compounds (V) as described in the first preparation process.
The compounds ~X) can also be prepared by acyla-ting o-substituted sulphones of the for~uLa Le A 22 904 ~;'3~
' SO~ C~2 CH2 ~

~-X-Y OH (XII~

t~ice on the 0 and if desired the N, nitrating ~ith sul-phuric acid/nitric acid under relatively miLd conditions, and finally deacylating by acid hydrolysis (cf. US Patent S 2~784~204).
Example 1 20.0 9 of a chloroanil condensation product of the formula -25 ~ ~ Cl ~ -CH2-CH2-O~

~ 2-C~2 HN O &2 ~ ~ ~

are added at 10-20 to 50 ml of 20X strength oleum in the course of about an hour. To effect complete solution the m;xture is after~ards stirred for 30 to 60 minutes, and the viscous mass then has added to it at 20-25 vith slight external cooling 15.6 9 of potassium peroxodisul-phate in the course of about ~5 minutes~ 30 Minutes after this addition the reaction has ended. The reaction mix-ture is stirred into 40D g of ;ce, and the resuLting blue solution then has added to it drop~ise first 2.5 9 of trisodiu~ phosphate in 20 ml of water and then about 46û ml of 4 N sodium hydroxide solution with cooling and thorough stirr;ng unt;l the pH is 4.5 to SØ The dye-stuff, ~hich has come out of solut;on in the form of a pasty precip;tate, is filtered off with suction, is washed with sod;um chloride solution and is dried at 50 in a circulat;ng air cab;netO The dyestuff has the formula Le A 22 904 .
.. ~
~1 HO3 ~ ~ HN ~ ~ ~ ~ S02~H2 ~ ~3H

~a3 ~ ~ -2~ ~ ~ ~ NH ~ ~ ~3H
C.I. indicator number 13 It dyes cotton at 4~ to 60 from a long liquor in deep, somewhat reddish blue shades having excellent fastness properties.
The chloroanil condensation product used at ~he start of Example 1 is prepared as follous:
35 g of 5-nitro-2-~-hyroxyethylaminophenyl ~-hydroxyethyl sulphone are suspended in 200 ml of metha-nol in an autoclave. After add;tion of 2 9 of Raney nickel, 10 to 20 bar of hydrogen are injected, and the mixture is heated at 45 until there ;s no further con-sumption of subsequentLy injscted hydrogen. The resulting solution or suspension is freed at 50 from the liquor by filtration, the filter res~due ;s washed ~lth a little ~ater, and the f1ltrate has added to lt 14.4 9 of 2,3,5,6-tetrachloroquinone and 1~ g of anhydrous sodium acetate.
The mixture is then refluxed for 2 hours until tetrachloro-qu;none is no longer detectable. The condensation pro-duct~ which has come out of solut;on in the form of a brown precipitate, ;s filtered off ~;th suction, is ~ashed with ~ethanol or methanol/~ater and is dried at 60 in a circulating air cabinet.
1t ;s also poss;ble to evaporate the methanol solution obtained at the end of the catalytic reduction, to dissolve the residue of 5-amino~2-~-hydroxyethylamino phenyl ~-hydroxyethyl sulphone in Yater, and to condense the solution at 45 with the chloroanil whi~le the pH

is maintained at 5.5 to 5.8 ~ith 2 N sod;um carbonate solution. Under these cond;tions the condensation is com-plete atter about an hour. The likewise precipitated brown sediment is filtered off ~ith suction and washed Le A 22 90~
:

_ 9 _ with ~ater.
Example 2 If the ox;dati~e ring closure of Example 1 is car-ried out not at 20 to 25 with 50 ml of 2ûX strength oleum but ~ithout the presence of peroxodisulphate in 30%
strength oleum at 5û~, this produces, on isolation from the react;on m;xture, a similar dyestuff ~hich dyes cellu-lose fibres in blue shades.
Further similar blue dyes of C.I. indicator number 13 are obtained ~hen the 5-am;no-2-thydroxyalkyla~ino)-phenyl ~-hydroxyethyl sulphones tY~ of the subsequent Table are condensed ~ith the ind;cated 1,4-benzoquinones tIV~ and the condensation products are cycl;sed and sul-phated ;n the manner descr;bed.

Le A 22 90~
.

1~51~

Starting compounds_V __ ~en20quinone IY

~ 2 Cl ~
o 5~2~2~2~H
¢~) 2 2, ~3 CH2-cH2-oH
H2N-~-NH~2 C~3 S02-CH2~20H

CH2 2 2-CH2~ n 52~2~?2C~H
CH2--CH2 S~2~2~2H n H2N ~{~H2~H2-~8~OH n S02~ CH2~0H

~2N-~N-CH2-CH2-OH N

Le A 22 904 -Startin~ compounds V _ __ 8enzoquinone IV

. .

~o2~2~

C~H3 502-CH2~2-OH
H2N ~/NR-C (CH3) ;~-CH2C)H

2-cH2-( H2~
H n 0~1 S02~2~2~)H
PzN--~ n CH2~

I ~ 502-CH2~-OH
~3 CH;! 6 n ~2N ~ ' ~3 O

Le A 22 904 Startin~ compounds V _ 8enzoquinone IV

C H2~2 aH o ~NH~2~2ff~ ¢~

n Cl ~H3 H3~ ) 3 1 n ~ ~ 3 CH3C~HN Cl HSC6 ~OC6H5 H5C6 K~6H5 " H3C~3 F~F
F O F

Br ~r Br Br Le A 22 904 Exa~ple 3:
5-Aminou?(2-hydroxyethyl?aminophenyl 2-hydroxrethyl sulphone ~09 g of a moist paste of sodium 2-chLoro-5-nitro-benzenesulphinate (58.4X strength) are d;ssolved in 250 ml of water. The pH should be between 7 and 8. The reaction vessel is flushed with nitrogen while the soLution is raised to 60C. Under compliance ~ith the prescribed safety regulations, ethyLene oxide is slo~ly passed at pH

7-9 into the sealed reaction vesseL, together with 25X
strength sulphuric acid. A total of 11D to 120 9 of ethy-lene oxide and about 204 9 of sulphuric acid are consumed for pH control. As soon as no starting material is de-tectable, the mixture is heated at pH 7 to 85C for 1 hour, and the apparatus is subsequently flushed ~ith nitrogen. When cooled down to room temperature, the mix-ture is filtered ~ith suction, and the filter residue is ~ashed ~ith about 200 ml of water and ls dried at 70C
~n vacuo. 118 9 of crystalline 2-chloro-5-nltrophenyl 2-hydroxyethyl ~ulphone are isolated.
93 9 of 2-chloro-5-nitrophenyl 2-hydroxyethyl sul-phone are heated to the boil in 84 ml of isopropanol. The heat supply ;s cut back, and 50 9 of ethanolamine are ad-ded ;n the course of 15 minutes. The resulting viscous solution is refluxed fDr a further hour. Thereafter the reaction is complete, and the solution of the 2-t2-hydroxy-ethyl)a~ino-5-nitrophenyl 2-hydroxyethyl sulphone can be directly hydrogenated under the catalytic conditions. To isolate the substitution product, Z50 ml of water and 100 9 of ice are added at 95-80C. The mixture ;s after-~ards stirred for 2 hours and is brought to pH 6 ~ith 12 ml of hydrochloric acid. The product, which has come out of solution in the form of crystals, ;s filtered of~
with suction and dried. The yield of 2-thydroxyethyl)-amino-S-nitrophenyl 2-hydroxyethyl sulphone ~melting point 118OC) is 98uS 9.
Le A 22 904 ~S~44i~;
, H-NMR: ~- 1.59 (d,1H); 1.75 (dd,1~; 2.69 (t, NH); 2.97 SO2CH CH OH (d, 1H); 5.04 lt,OH); 5.13 / 2 2 (t,O~); 6.26 (m,2H1; 6.35 (m,2H);
O~N- ~ -NH-CH C~ OH 6 48 (m, 2H); 6.57 ~m, 2H).

(All the 1H-NMR data g;ven in this appl;cation were determined in d6-DMS0 as solvent, using TMS as the ;nternal standard.) S The above~ isolated aminonitrosulphone can be catalyt;cally hydrogenated as described in Example 1.
Ho~ever, as already indicated above, it is better to re-duce the reaction solution of the ethanolamine subst;tu-tion directly, i.e. without isolating the 2-t2-hyclroxy-ethyl)am;no-5-nitrophenyl 2-hydroxyethyl sulphone. This is dor,e by dilut;ng w~th 100 ml of isopropanol, addtng S g of Raney n~ckel, heating to 60C, and ~njecting about 24 lltres of hydrogen. The hydrogen pressure should be maintained within the range from 7 to 10 bar. When the rate IS of consumption gradually decreases after about 2.5 hours, the temperature can be ra;sed to 75~C. At the end of the reaction the reaction solution is diluted with 200 ml of hot ~ater at 70C and is separated hot from the cata-(yst. The resulting dark solution of 5-amino-2-~2-hydroxy-ethyl)aminophenyl 2-hydroxyethyl sulphone is directly fur-ther reacted with chloroanil ~see Example 1).
To isolate and characterise the reduction product the warm solution is concentrated to 20û ml, the concen-trated solution i~ cooled down to 20C, and the crystal-line product is filtered off with suction. Drying at 70C;n vacuo leave 84 9 of 5-amino- ~2-hydroxyethyl~aminophe-nyL 2-hydroxyethyl sulphone (of melting point 13ûC).

Le A 22 ~04 4~i , ,.

1H-NM~: ~ = 3-10 (d, 1H); 3.22 50 CH CH OH (dd,1~); 3.37 ~d,1HI;4.45 / 2 2 2 (t, NH~ 5.20 (t,OH);
H N ~ -NHCH C~ OH 5.27 (t,OH); 5.32 2 2 2 (s,NH2~; 6.40 (m, 4H):
6.65 (t,2H); 6.90 (m,2~).
The necessary intermediate 2~2-hydroxyethyl)-amino-5-n;trophenyl 2-hydroxyethyl sulphone san also be prepared as follows:
S A) A solution of ~22 g of sodium 2-chloro-5-nitroben-zenesulphinate in 300 ml of water has added to ;t 100 9 of ethanolamine, and the mixture is stirred at 110C under D~5 bar in an autoclave for 4 hours. When cold, the yel-low reaction solution is neutral;sed with hydrochloric ac;d, and 90 9 of sodium chloride are added for s~lt;ng out. The result ~s 215 9 of mo;st paste of sod~um 2-tZ-hydroxyethyl)amino-S-n;trobenzenesulphinate.
B) 122 9 of sodium 2-chloro-5~nitrobenzenesulphinate are kneaded together with 150 9 of ethanolamine, and the mixture is gradually heated to 1û0C. After 30 minu~es at 100C 500 ml of ~ater are added, ~he reaction solution is neutralised with hydrochlor;c acid, and the sodium 2-(2~hydroxyethyl)amino-5 nitrobenzenesulph;nate is isolated as above, by salt;ng out.
2n The 215 9 of mo;st sulphinate paste are dissolved in 250 ml of water and are alkyl3ted under pressure at 60C analogously to sodium 2-chloro-5-n;trobenzenesul-phinate using 120 g of ethylene oxide and about 200 9 of 25% strength sulphuric ac;d. The result ;s 121 9 of crys-talline pale yellow 2-(2-hydroxyethyl)amino-5~nitrophenyl 2-hydroxyethyl sulphone~
If the ethanolam;ne of Example 3 is replaced by different hydroxyalkylamines bf the same type~ the follow-ing nitroam;no and diamino sulphones can be prepared:

Le A 22 904 lZS~
~ 16 -Example 4: .
2-~2-hydroxyethyl)methyla~ino-S-n;trophenyl 2-hydroxy-e~hyl sulphone tpale yello~, meltin~ point 106C) S2CH2CH2H lH-NMR: ~ = 1.41 (d,lHJ 1.63 ~ (dd,lH); ~41 (d,lH);
ON2~ N-CH CH OH 5.30 ~t,OH); 5.39 CH3 It,OH); 6l20 ~t,2H);
6.37 (m, 4H); 6.70 (t,2~); 7.08 (s,CH3).
5-Amin3-2-t2-hydroxyethyl3methylaminophenyl 2-hydroxy-ethyl sulphone tcrystallising oil) NMR: 1~= 2.82 (d,lH~; 2.96 ~d, 1H); 3.21 ~dd,1H);
SO CH CB CH 4.62 ~s, NH2); 5.25 ~ 2 2 2 .(br.oad OH); 5.68 H2N- ~ N CH2CH2OH ~broad OH): 6 . 25 CH ~m,2H); 6.37 ~m,2H);
3 6.50 ~t,2H); 7.12 (t,2H); 7.42 ~s,CH3).
Example 5:
2-~3-Hydroxypropyl)amino-5-tn;trophenyl) 2-hydroxyethyl sulphone tpale yello~, melting point 65C) H-NMR: ~- 1.63 ~d,1H); 1.81 tdd, SO2CH CH OH lH~; 2.72 ~broad ~H);
/ 2 2 3.03 (d, 1H); 5.07 O2N- ~ -NH-cH2cH~cH2oH 6.25 (t,2~), 6.50 ~,6H); 8.20 ~m,2H).
5-Amino-2-t3-hydroxypropyl)aminophenyl 2-hydroxyethyl sul-phone ~crystallising oil) H-NMR: 1r= 3.12 (d,1H); 3.22 S~2cH2c~?2oH ~dd,1H); 3.38 (d,lH);
- ~ 4.65 (t,NH); S,20 H2N ~-NHcH2cH2cH2oH (broad OH); 5.31 (s, NH2); 5.50 (broad).
Le A ?2 904 lZ~ 6 ~ 17 -OH3; 6.37 (t,2H);
6.50 (t,2~) 6.68 ~m, 2H); 6.90 (m,2~); 8.40 (m,2H).
Example 6:
Z-t3'-(2"-Hydroxyethyl)methylaminopropyl~amino-5~n;trophe-nyl 2-hydroxyethyl sulphone (yellow oil) IH-NMR: 1~= I.S7 (d,1HJ; 1.82 2 ~2CH2oH (dd,lB); 2.63 (broad ~ CH NH); 3.02 (d,lH); 5.tO
2~ >-NH-CH C~ C~ N/ 3 ~broad OR); 5.67 ' (broad~ OH); 6.30 CH2 ~t,2H~; 6.50 (m,4H);
CH2 6.62 (t,2H); 7.55 (m, OH 4H); 7.Bt (s,CH3);

8.25 (m,2H).
5-Amino-2-~3'-~2"-hydroxyethyl~methylaminopropyl~amino-phenyl Z-hydroxyethyl sulphone toil) ~H-NMR: ~r~ 3.13 (d, 1H~;
3.22 (dd,1R~; 3.38 (d,1H); 4.58 ~broad 02CH2~H2Q~ NH); 4.95.6.10 ~broad, fi--~ , H3 NH2, 20H); 6.36 ~t,2H);
H2N~ )-NH-CH2CH2CH2-N 6.52 (t,2H); 6.67 (t, CH 2H); 6.92 (m, 2H);
7.51 (m,2H); 8.27 ~,CH2 (m,2H).
OH
Example 7:
1D 2-t2-Hydroxypropyl)amino-5-nitrophenyl 2~hydroxyethyL sul-phone tmelting po;nt 85C) Le A ?2 904 l~S~

~-NMR: 'r= 1.65 Id~1H):
l.B3 tdd,1H); 2.70 (t,NH); 3.02 (d, So2CE~2C~20 1B); 4.97 (t,OH);
_~ 5.12 (t,OH); 6.10 02NJ<= ~) C CH (m,lH);
OH 6.23 lt,2H~; 6.48 (t,2HI; 4.60, 4 . 80 (m, 2H);
8~80 (d~3H)o 5-Am;no-2-(Z-hydroxypropyl)a~inophenyL 2-hydroxyethyl sul-phone (crystallising oil) jH-NMR: I= 3.08 (d,lH~;
3.21 (dd,1H);
~.38 ~d,1H); q.41 S2CH2CH2H (t,NB1 7 5.21 ~ H (broa~ m, NH
H2N-~=,) CH2 C CH3 20H); 6 . 1 5 (m , OH 1H); 6.36 ~t,2~);
6.63 (t,2H); 6.90, 7. i O (m,2H); 8 .83 (d, 3~) .
SExample 8-5-Amino-2-(2-hydroxy)ethoxyphenyl 2-hydroxyethyl sulphone 136 g of sodium 2-~hydroxy~ethoxy-5-nitrobenzene-sulphinate are dissolved in 250 ml of water. The solution is brought to pH 7-R, The reaction vessel is checked for tightness and is flushed w;th nitrogen~ Meanwh;le the solution is heated up to 60C. The reaction vessel is sea~ed, and 110-120 g of ethylene oxide are passed in at constant pH 7-9 in the course of 4-5 hours. A constant pH is mainta;ned by cont;nuously adding a total of 20û
of 25X strength sulphuric acid. As soon as there is no longer any evidence of starting suLph;nate in a th;n Layer Le A 22 904 i2~l4~
. , chromatogram, the mixture is heated at 85C at pH 7 for an hour, and the apparatus is then flushed uith n;~rogen.
Gn cooling a pale yellow product crystallises out; it is filtered off ~ith surtion, is ~ashed ~ith a little ~ater, S and ;s dried.
The yield of 2-(2-hydrnxy~ethoxy-S-nitrophenyl 2-hydroxyethyl sulphone is 132 9.

1H-NMR: ~ = 1.57 (d,1H); 1.65 SO2CH2CH2OH (dd,IH); 2.32(d,1H1;
/ 5.25 (broad s,20H) .
O2N ~ CH2cH2oH 6.25 (m,4H); 6.78 ~m,4H);

117 9 of 2-(hydroxy)ethoxy-5-nitrophenyl 2-hydroxy-ethyl sulphone are dlssolved in 250 ml of methanol, 5 g of Raney n;ckel ~re added, and the mixture is heated to 60C. 34 Litres of hydrogen are then injected, and the temperature is ma;ntained at 60C unt;l the absorption has ended. ~hen cold, the solution is separated from the catalyst and can then be directly further.reacted ~;th chloroanil. To isolate and character;se the product, the solvent ;s distilled off. This leaves 102 9 of S-amino-2-t2-hydroxy)ethoxyphenyl 2-hydroxyethyl sulphone as a vi s cous oi l .
1H-NMR: ~= 2.64 ~d,1H); 2.79 (d,1H); 3.12 (dd,lH);
SO CH CH20H 4 . 3 2 ( s , NH2 ); 5 - 1 7 / 2 2 ~broad OH~; $.28 H2N-~-O-CH CH OH (broad OH); 6 . 4 4 (m , \~ 2 2 4H); 6.62 It,2~1); 7.15 (t,2H) .
Example 9:
5~Amino-2-(2-hydroxyethyl)mercaptophenyl 2-hydroxyethyl sulphone Le A 22 904 :~i25~

93 9 of 2-chloro-5-n;trophenyl 2-hydroxyethyl sul-phone are refluxed for 6 hours in 200 ml of isopropanol together ~ith 50 9 of solid sodium rarbonate and 70 9 of mercaptoethanol. The reaction mixture is separated at 50C from the precipitated salts. The solution can be directly reduced in this form. To isolate the product, the solution is e~aporated to dryness in a rotary evapor-ator, the residue is treated ~ith 300 ml of ~ater, and the crystalline sediment is filtered off ~ith suction. Drying leaves 91 9 of 2-(2-hydroxyethyl)mercapto-5-nitrophenyl 2-hydroxyethyL sulphone having a melting point of 109C.

1H-NMR: 1r= 1.43 td.1H); 1.63 (dd S2CH2CH2~ lH); 2.12 (d,1H); 4.90 ~ (t,OH); 5.19 (t,OH);
02N_ ~ S CH2CH2 6.25 (m, 6H); 6.67 ~t, . 2H).
The above reaction solution has added to lt 5 9 of Raney nickel and is reduced ~ith hydrogen as described for the correspond;ng oxygen compound ;n Example 8. 94 9 of 5-amino-2-t2-hydroxyethyl)~ercaptophenyl 2-hydroxyethyl sulphone are isolated in the form of a viscous, some~hat dark oil.
H-NMR: 1r= 2.67 (d,1H); 2.83 (d,lH); 3.25 (dd,lH~;
S02CH2cH2 q.34 (s,NR2); 5-22 ~ tbroad . s , 20H); 6.32 H N~ S-CH2CH20H (mt 4R); 6 . 50 (t , 2H);
2 ~ ~J 7.07 (t,2H).

Le A 22 904 _ _ _

Claims (10)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An amino compound of the general formula V

(V) wherein X is NR3, O or S;

R3 is H, C1-C4-alkyl, C1-C4-alkyl substituted by SO3H, OSO3H, COOH, OH or OCH3; and Y is C2-C6-alkylene, C2-C6-alkylene substituted or inter-rupted in the alkylene chain by OSO3H, O, SO2, NH, S or -NCH3.

2. An amino compound of the formula wherein X is NH, O or S.

3. The compound 5-amino-2(2-hydroxyethyl)aminophenyl 2-hydro-xyethyl sulphone of the formula

4. The compound 5-amino-2-(2-hydroxyethyl)methylaminophenyl 2-hydroxyethyl sulphone of the formula

5. The compound 5-amino-2-(3-hydroxypropyl)aminophenyl 2-hydroxyethyl sulphone of the formula

6. The compound 5-amino-2-(3'-(2"-hydroxyethyl)methylamino-propyl)aminophenyl 2-hydroxyethyl sulphone of the formula

7. The compound 5-amino-2-(2-hydroxypropyl)aminophenyl 2-hydroxyethyl sulphone of the formula

8. The compound 5-amino-2-(2-hydroxy)ethoxyphenyl 2-hydroxy-ethyl sulphone of the formula

9. The compound 5-amino-2-(2-hydroxyethyl)mercaptophenyl 2-hydroxyethyl sulphone of the formula

10. A process for preparing an amino compound of formula V as defined in claim 1, which comprises reducing the nitro group in a nitro compound of the formula wherein X and Y are as defined in claim 1, to an amino group.