CH676000A5 - - Google Patents

Description

CH 676 000 A5

description

The invention relates to a process for the preparation of compounds of the formula wherein

15 Ri halogen or Roi,

R2 halogen or R02,

R0i is a group of the formula -NR3R4, -OR3 or -SCH3,

R02 is a group of the formula -NR3R4, -OR3 or -SCH3,

R3 is hydrogen, optionally substituted by one or two of the following substituents: halogen, C1-4-AI-alkyl, Ci_4-alkoxy, mono- or di- (Ci_4-alkyl) -amino or -SO3M, phenyl, optionally substituted by hydroxy, cyano or Ci-4-alkoxy substituted Ci-4-alkyl, or a group of the formula

25 - [CH2-CH (R ^ J-OJjjj-Rg, -6C1_4-alkylene) -CO-N (R6) 2, -ÉCH ^ îKRg) ^

(a) (b) (c)

30 or (CH2 ^ r # (R6) 3 AÔ

(d)

R4 is hydrogen, Ci ^ alkyl, optionally phenyl monosubstituted by Ci_4 alkyl, C2-4 alkyl or a radical of the formula (a), (b), (substituted by Hy-35 hydroxy, Ci-4 alkoxy or cyano) c) or (d) or R3 and R4 together with the nitrogen to which they are bound, a saturated nitrogen-containing heterocycle,

Rs is hydrogen or methyl,

Ro is hydrogen or Ci_4-alkyl,

40 m is a number from 2 to 10,

n is a number from 1 to 4,

M is hydrogen or a colorless cation and A © is a colorless anion, which is characterized in that 45 A) is one mole of a diamino compound of the formula

50

55

H2N-n (Ô) -CH * cfH§) -NH2 (H,

with 2 moles of a compound of the formula so3m

60 (III)

Shark in which shark represents halogen, to a compound of the formula

65

2nd

CH 676 000 A5

(la)

(a) in the compound to be prepared of the formula (I) R 1 is R0i, with a compound of the formula H-R01 (IV)

15 reacts and / or (β) if R2 in the compounds to be prepared of the formula (I) means R02, with a compound of the formula

H-R02 (V)

20th

implements

or

C) if R 1 in the compound of the formula (Ia) is R01 and R 2 is R02 in the inventions of the formula (I) to be prepared, reacted with a compound of the formula (V).

25th

Ri advantageously stands for R1 ', i.e. for -NH2, -NHR3 ', -N (R4') 2, halogen, -NR7- (CH2) P-CH (R8) (CN), a nitrogen-containing saturated heterocycle which is bonded via N to the triazinyl radical (as defined above ), -OR7, phenoxy or-SCH3, wherein

R3 'optionally substituted by halogen, Ci_4-alkoxy, sulfo- and / or Ci_4-alkyl, mono- or disubstituted phenyl or optionally by hydroxy, Ci-4-alkoxy or cyano-Ci-4-alkyl, R4' Ci_4- Alkyl or C2-4-alkyl monosubstituted by Ci-4-alkoxy, cyano, carbamoyl or hydroxy, R7 is hydrogen, Ci_4-alkyl or C2-4-alkyl substituted by hydroxy or Ci-4-alkoxy,

Rs is hydrogen or methyl and 35 p is 0.1 or 2.

R-T particularly preferably denotes R1 ", i.e. -NH (R3"), -N (R4 ") 2 or a saturated nitrogen-containing heterocycle which is bonded to the triazinyl ring via N, as defined above,

wherein R3 "C1-4-alkyl, C2-4-hydroxyalkyl or phenyl monosubstituted by chlorine, methyl, methoxy or sulfo and 40 R4" Ci_4-alkyl or hydroxy monosubstituted C2-4-alkyl.

Rs advantageously means hydrogen.

The index p is preferably 1.

Preferred heterocycles in the meaning of -NR3R4 are morpholino, piperazinyl, N-methyl-pi-perazinyl, pyrrolidinyl and piperidinyl.

45 R2 preferably represents R2 ', i.e. for one of the meanings given under the definition of R1 ', independently of R-i'; R2 particularly preferably stands for R2 ", i.e. for one of the meanings of Ri", independently of R1 ".

The two symbols Ri preferably have the same meaning with one another and the two symbols R2 with one another have the same meaning.

50 The radicals R 1 and R 2 bonded to the same triazinyl radical preferably have different meanings from one another.

Ri is particularly preferably anilino and R2 is morpholino.

R3 preferably represents R3 ', in particular R3 ".

R4 preferably stands for R4 ', in particular for R4 ".

Halogen is preferably chlorine.

Suitable cations in the meaning of M are generally colorless cations, as are customary in the case of anionic optical brighteners, in particular alkali metal cations, alkaline earth metal cations and ammonium cations.

The sulfo group is preferably in the ortho position to the middle ethylenylene group. 60 The compounds of the formula (III) in which Ri is R01 can be obtained by reacting cyanuric halide with a compound of the formula (IV).

Cyanuric chloride is preferably used as the cyanuric halide.

The reaction of cyanuric halide with a compound of formula (IV) can take place in an aqueous or aqueous / organic medium (the most suitable organic solvents are methyl ethyl ketone or acetone), advantageously at temperatures in the range from -15 ° C. to + 5 ° C and

'vn I

Shark "~ Hal repositions, and

-m B) if Ri Hai in the compound of the formula (Ia) and

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CH 676 000 A5

at pH values in the range of 1-4 or still in the anhydrous organic medium (especially methyl ethyl ketone or acetone) in the same temperature range. The yield of the reaction is generally between 95-99% of theory.

The reaction (A) of a compound of the formula (II) with compounds of the formula (III) in which R 1 is halogen is advantageously carried out in aqueous or aqueous / organic medium, in particular in aqueous ketones (for example methyl ethyl ketone or acetone), chlorinated hydrocarbons in Water or aqueous Ci-4 alcohols (eg isopropanol or n-butanol) in the presence of a wetting agent (eg a sulfosuccinate), and advantageously at pH values of 1.5-6, preferably 2-5.5 and at temperatures in the range from -15 ° C to + 5 ° C, preferably -5 ° C to + 2 ° C.

The reaction of compounds of the formula (III) in which Ri is R01 with a compound of the formula (II) and the reaction of compounds of the formula (Ia) in which Ri is halogen with a compound of the formula (IV) or (V) to compounds of the formula loi .SOjM RÔ1

N

nh- <q> -ch y ~

Hal h ^ o> <ib>

respectively.

ftel nh "h (O) -ch = ch- (0) -nh— (Q) (ic)

^ 02

is advantageously carried out in the temperature range from 2-65 ° C and in the pH range from 4-8 and in an aqueous or preferably aqueous / organic medium as described above. The reaction of compounds of the formula (III), in which R 1 is R01, with a compound of the formula (II) is preferably carried out in the pH range from 5-7 and at temperatures in the range from 10-65 °, preferably 10-50 ° C ; the reaction of a compound of the formula (Ia) in which R 1 is halogen with a compound of the formula (IV) is advantageously carried out at pH values in the range from 5-7, in particular 5.5-7, and at temperatures in the range from 2 -60 ° C, preferably 10-40 ° C; the reaction of a compound of the formula (Ia) in which R 1 is halogen with compounds of the formula (V) is advantageously carried out at pH values in the range from 5-7 and at temperatures in the range from 10-50 ° C. The compounds of formula (II) are advantageously used in the form of an aqueous slurry or suspension.

The reaction of a compound of formula (Ib) with the compounds of formula (V) and the reaction of a compound of formula (Ic) with the compounds of formula (IV) is carried out in an aqueous or preferably aqueous / organic medium, in particular as described above, and advantageously at pH values in the range from 7-10, preferably 7.5-8.5, and advantageously at temperatures in the range from 40-100 ° C, preferably 50-80 ° C (optionally under reflux).

The yield of each of the above reaction stages is generally in the range of 95-99% of theory.

For the introduction of a Ci ^ alkoxy group as R0i and / or as R02, the reaction is advantageously carried out in the corresponding Ci _ * alcohol. For the reaction of cyanuric halide with the corresponding alcohol, the procedure is advantageously in the presence of sodium bicarbonate and the temperature is preferably in the range from -15 to + 5 ° C. The yield is generally 95-99% of theory.

The reaction of a compound of the formula (Ia) in which Ri is R0i with a compound of the formula H-OR3 with the exception of a Ci-4-alkanol is advantageously carried out at temperatures in the range from 60-100 ° C. and in the presence of sodium hydroxide . The yield is generally 90-95% of theory.

For the introduction of two to four phenoxy radicals into a compound of the formula (Ia) in which Ri is halogen

4th

CH 676 000 A5

10th

15

20th

means 1 mole of this compound is reacted with 2-4 moles of phenol, this reaction being advantageously carried out in an organic solvent, preferably methyl ethyl ketone or acetone, preferably in the temperature range from 50-80 ° C. In this case, both reaction sequences [the reaction of cyanuric halide with a compound of the formula (II) and the further reaction thereof with phenol] can be carried out in the same organic solvent. The yield of the entire reaction is generally in the range of 95-99% of theory.

Compounds of the formula (I) are particularly preferably prepared in which R 1 is anilino and R 2 is morpholino. These are advantageously prepared by reacting 1 mol of the compound of the formula (II) with 2 mol of cyanuric halide (preferably cyanuric chloride) and the reaction product either with 2 mol of aniline and then with 2 mol of morpholine or either with 2 mol of morpholine and then is reacted with 2 moles of aniline. The yield from this reaction sequence is generally 90-95% of theory.

According to another preferred variant, first 1 mole of cyanuric halide is reacted with one mole of aniline or morpholine and 2 moles of the reaction product are reacted with a compound of the formula (II) and the reaction product is then reacted with 2 moles of morpholine or aniline (depending on the meaning of R01) implemented.

Depending on the desired salt form, a suitable base can be used to introduce a cation M in the end product, for the alkaline setting for the respective reaction, sodium or potassium hydroxide preferably being used for this.

The invention further relates to the process for the preparation of the compounds of the formula (II), which is characterized in that an aldehyde of the formula

25th

CH0

\

(VI)

30 with a compound of the formula

35

40

(VII)

«B to a compound of the formula

45

50

implements what

Rg nitro or acetylamino,

R10 is hydrogen, cyan or a radical of the formula

(VIII)

55

60

65

-COO (C1_6-alkyl) or -P (0) - (C1_2-alkoxy) 2

and one of the two symbols Ra and Rb is hydrogen and the other is the group -SO3M, the nitro group (s) present is reduced to the amino level and, if Rg is acetylamino, the acetylamino group is hydrolyzed.

If R10 denotes a radical of the formula -P (0) - (Ci-2-alkoxy) 2, then Rb preferably denotes hydrogen.

When R10 is hydrogen, Rb is preferably the sulfo group.

The reaction of a compound of formula (VI) with a compound of formula (VII) in which R10 is -P (0) - (Ci-2-alkoxy) 2 is advantageously carried out in a polar aprotic solvent, preferably dimethylformamide, dimethyl sulfoxide or dimethylacetamide , or in a Ci-s alcohol (e.g. isopropanol or ethoxyethanol). Particularly preferred solvents are dimethyl sulfoxide and especially dimethylformamide. The reaction is advantageously carried out at pH values in the range of 8-14.

5

CH676 000A5

preferably 12-14 and at temperatures in the range of 10-100 ° C, preferably 20-40 ° C; the pH can be adjusted by adding strong alkalis (especially potassium hydroxide or sodium hydroxide). The yield is generally in the range of 50-90% of theory.

The reaction of a compound of the formula (VI) in which Ra is the sulfo group with a compound of the formula (VII) in which Rio is -CN or -COO- (Ci-6-alkyl) is advantageously carried out in an organic Solvents, especially dimethyl sulfoxide or a mixture of dimethyl sulfoxide and petroleum spirit (preferably with boiling range 100-120 ° C) preferably under strongly alkaline conditions (pH 9-12) and at temperatures in the range of 100-160 ° C. The reaction in the presence of a base, e.g. Piperidine, piperazine, sodium carbonate or morpholine. The yield is generally in the range of 40-80% of theory.

The reaction of a compound of formula (VI) with a compound of formula (VII) in which Rb is the sulfo group and Rio is -CN or -COO- (Ci_6-alkyl) is advantageously carried out in an alcohol, preferably a Ci-6 -Alkanol, e.g. Methanol or ethanol, a glycol, ethoxyethanol or methoxypropanol. If Rb is the sulfo group and Rio is hydrogen, the reaction is advantageously carried out in dimethylformamide or dimethyl sulfoxide. The pH is advantageously in the range from 10-12 and the temperature is advantageously chosen in the range from 50-150 ° C., in particular 70-120 ° C. The procedure is preferably carried out in the presence of a catalyst, e.g. in the presence of a base, primarily piperidine, piperazine, morpholine or sodium carbonate. The yield is usually 40-80% of theory.

When a compound of the formula (VI) is reacted with a compound of the formula (VII) in which Rio is -CN or -COO- (Ci_6-alkyl), an intermediate compound of the formula in which Rio '-CN or -COO- (Ci-6-alkyl) means.

The nitrile group or alkoxycarbonyl group Rio 'can be hydrolyzed to the carboxy group in a manner known per se, e.g. under acidic or alkaline conditions (for example in the presence of sodium hydroxide, potassium hydroxide or piperidine or in the presence of hydrochloric acid) and the resulting carboxy group-containing compound can then under acidic conditions at elevated temperature (advantageously at 100-200 ° C.), preferably in the presence a catalyst, primarily copper powder to be decarboxylated.

The reduction of the nitro groups in the compounds of the formula (VIII) is advantageously carried out using sodium sulfide, preferably at elevated temperature, in particular in the range from 40-40 ° C. or using iron filings in the presence of an organic acid, e.g. Acetic acid at elevated temperature, especially in the range of 80-120 ° C. The yield is generally in the range of 50-90% of theory.

If Rg is an acetylamino group, this can be hydrolyzed to the amino group, analogously as described above for the Rio 'group.

45 If in the compounds of the formula (VII) Rio denotes -P (0) - (Ci-2-alkoxy) 2, then Rb preferably denotes hydrogen; these compounds are advantageous by reacting a compound of the formula

30th

25th

(IX)

50

(x)

with a compound of the formula

55

P (C12 alkoxy) 3

(XI)

to a compound of the formula

60

65 and subsequent nitriding with fuming nitric acid.

6

CH 676 000 A5

The compounds of the formula (VI) in which Rg is -NO2 and Ra preferably denotes the sulfo group can be prepared by oxidative cleavage of compounds of the formula preferably in an alcohol-containing solvent system. The solvent system is preferably ethoxyethanol or an aqueous polyethylene glycol, the latter of which is preferred. The molecular weight of the polyethylene glycol is advantageously in the range of 300-600. The reaction is advantageously carried out in the presence of an electrolyte, preferably aqueous magnesium sulfate.

The oxidation is advantageously carried out at pH values in the range from 8-10 and at temperatures preferably in the range from 0-100 ° C., in particular 0-50 ° C. Preferred oxidizing agents are ozone, osmium tetraoxide, lead tetraacetate, sodium or potassium permanganate or a mixture of potassium periodate and potassium permanganate. If necessary, the oxidation can also be carried out electrochemically. The yield is generally 30-80 °% of theory.

For the preparation of the compounds of the formula (I), preference is given to using compounds of the formula (II) which have been prepared as described above from the compounds of the formula (VIII), in particular from the compounds of the formulas (VI) and (VII ) as described above.

The compounds of the formula (I), in particular those in which R 1 is R01 and R 2 is R02, are suitable as optical brighteners for the optical brightening of textile material and paper, in particular as an additive to detergent preparations. They can be used as described in Example 6 of U.S. Patent 3,895,009, which is incorporated herein by reference.

Depending on the process conditions, in particular pH values and any bases used, the sulfo groups -SO3M shown above can be in the free acid form or in the respective salt form.

In the following examples the percentages mean percentages by weight, the temperatures are given in degrees Celsius.

1000 g of water and 1000 g of methoxypropanol are heated to the reflux temperature and kept under reflux until a clear solution is obtained. The resulting solution is then cooled to 0 ° C. and a solution of 117 g of KMn04 and 120 g of magnesium sulfate in 2000 g of water is added at this temperature over the course of an hour. The precipitated MnÜ2 is filtered off and the filtrates are concentrated until the aldehyde of the formula a

(XIII)

example 1

A suspension of 235 g of the compound of the formula

(la)

(lb)

is crystallized out. This is then separated from the mother liquor by filtration. Example 2

791.2 g of nitrobenzyl bromide, 669 g of triethyl phosphite and 1000 g of xylene are boiled together at 130 ° C. under reflux. The resulting ethyl bromide is distilled off. 1000 g of the phosphonate of the formula are formed

5

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CH 676 000 A5

° 2N- ~ \ 0 / - ^ H2 (2a).

0

Excess triethyl phosphite and xylene are removed by heating under vacuum.

503 g of the compound of the formula (2a) and 470 g of the compound of the formula (1 b) are mixed together in 10 l of dimethylformamide which contain 100 g of potassium hydroxide. The reaction mixture is slowly warmed to 50 ° C., stirred at this temperature for 3 hours under a nitrogen atmosphere and then poured into an equal volume of water. The compound of the formula

° 2N—-, (2b)

which is in the form of precipitation is filtered off from the mother liquor.

Example 2bis

The procedure is as in Example 2, 462.4 g of benzyl chloride being used instead of 791.2 g of nitrobenzyl bromide, and the following compound being formed by reaction with the triethyl phosphite

<§> ~ ch2t (0w.2 '<2C>'

q

500 g of the phosphonate of the formula (2c) are added dropwise over a period of one hour in 1000 g of fuming nitric acid at 0 ° C. while cooling with ice. The mixture is stirred for an additional hour at 0 ° C after which it is poured onto 5000 g of ice. The organic phase is separated off and washed well with water. The resulting compound of the formula (2a) is, as described in Example 2, further reacted to the compound of the formula (2b).

Example 2nd

The procedure is as described in Example 2 or 2bis; with the difference that instead of the compound of the formula (1 b), the equivalent amount of the compound of the formula ch3-co-nh chq <2d)

\ O3Na is used, whereby the compound of formula

CHjCONH - ^ - CIKH - ^ - NO., (2e)

03Na is received.

Example 3

92 g of the moist filter cake of the compound of the formula (1b) obtained according to Example 1 (56.75% active substance content) are in a suspension of 25 g of sodium carbonate and 137 g of dimethyl sulfoxide

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CH 676 000 A5

given, the mixture is heated under vacuum and the water removed, after which the mixture is cooled to 90 ° C. Then 33.2 g of paranitrotoluene, 7.14 g of piperidine and 46.8 g of petroleum spirit 100/120 are added.

The mixture is slowly distilled azeotropically, whereby the water of reaction, dimethyl sulfoxide and some piperidine separate from the petroleum ether distillate.

After 10 hours, 3.57 g of piperidine are added and the mixture is refluxed for 20 hours. Then the reaction mixture is cooled to 70 ° C and the piperidine and petroleum spirit are distilled off under vacuum, whereby the temperature rises to about 120 ° C. The mixture is then cooled to 80 ° C and 65.6 g methoxypropanol and then 74.9 g ethyl acetate are added, causing the temperature to drop to about 50 ° C. The mixture is now heated to 60 ° C. and a solution of 58.1 g of sodium sulfide in 91.3 g of water at 60 ° C. is added dropwise over the course of 2 hours; and the temperature of the mixture is controlled so that it does not rise above 80-85 ° C. Then 83 g of a 4% sodium chloride solution are added and the reaction mixture is slowly stirred at 60 ° C. for 8 hours. The resulting product of the formula is filtered off from the mother liquor.

Example 3bis

The compound of the formula (3a) can also be prepared as follows: 92 g of the moist filter cake of the compound of the formula (1b) prepared according to Example 1 (56.4% active substance content) are added to a suspension of 25 g of sodium carbonate and 200 g of dimethylformamide and the mixture is heated under vacuum until the water is removed. Then 40 g of 4-nitrophenylacetonitrile, 7 g of piperidine and 46.8 g of petroleum spirit 100/120 are added and the mixture is distilled azeotropically for 5 hours. Piperidine and petroleum spirit are removed under vacuum distillation and then 30 g of concentrated hydrochloric acid are added to the mixture. The mixture is then refluxed for 10 hours, then cooled and neutralized with sodium hydroxide solution. The resulting nitro compound of the formula (2b) is filtered off. The reduction to the amine of formula (3a) is carried out with sodium sulfide as described in Example 3.

The procedure is as in Example 3bis, with the difference that 53 g of 4-nitrophenylacetic acid ethyl ester are used instead of 40 g of 4-nitrophenylacetonitrile.

493 g of cyanuric chloride are stirred into 3449 g of methyl ethyl ketone cooled to 0 ° C. and stirring is continued until the cyanuric chloride is completely dissolved in the methyl ethyl ketone. 1379 g of demineralized water are placed in a separate vessel and 758.8 g of the 50% moist filter cake of the compound of the formula (3a) obtained according to Example 3 are added with stirring. The resulting suspension is pumped into the cyanuric chloride solution, while the temperature is kept between 4 ° and 5 ° C. and the pH is kept between 4 and 5 by adding 138 g of sodium bicarbonate in portions. Finally, another 40 g of sodium bicarbonate are added to adjust the pH to 6.5. Then 226 g of aniline are added and by slowly adding 360 g of a 30% sodium hydroxide solution and 1000 g of water the pH is kept between 6.5 and 7 while the temperature rises. When the reaction is complete, the temperature has risen to 30 ° C while the pH is 6.5. Now 440 g of morpholine are added and the mixture is heated to 70 ° C. When the reaction is complete, 12 g of sodium hydrosulfite are added and then 3339 g of methyl ethyl ketone are distilled off from the mixture. The resulting mass is cooled to 50 ° C, filtered and washed. The resulting product corresponds to the formula

(3a)

S03 Well

Example 3ter

Example 4

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CH 676 000 A5

<2

(4a)

Example 5

Analogously to that described in Example 3, 1 mol of the compound of the formula o2n

(5a)

with 1 mole of the compound of the formula

H3C @) N0;

2nd

(5b)

S03 Well

(after the KNOEVENAGEL reaction) to the compound of the formula (2b), which is then analogously as described in Example 3, reduced with sodium sulfide to the compound of the formula (3a). The compound of the formula (5a) can be prepared by oxidation of the compound of the formula with potassium permanganate, analogously to that described in Example 1. The compound of formula (5b) can be prepared from known compounds by known methods.

142 g of cyanuric chloride are placed in 2.7 l of methyl ethyl ketone cooled to -15 ° C., then 73 g of aniline are slowly added, the temperature being kept below -3 ° C. Then 40 g of sodium bicarbonate and then 110 g of the compound of the formula (3a), which are suspended in 1000 g of water, are added. The pH is maintained at 6 by adding dilute sodium hydroxide and the temperature is slowly raised to 65 ° C.

The pH is then adjusted to 7 and the reaction mixture is diluted with 1.8 l of water. 146 g of morpholine are then added, followed by 10 g of sodium hydrosulfate and the mixture is heated to reflux temperature and 2.5 l of methyl ethyl ketone are distilled off. After cooling, the separated product is filtered off and the compound of formula (4a) is obtained in 95% yield.

Claims (6)

Claims 1. Process for the preparation of compounds of the formula or of the formula (5d) Example 6 10th 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 CH 676 000 A5 (la) where Ri is halogen or R01, Shark halogen Roi is a group of the formula -NR3R4, -OR3 or -SCH3, R3 is hydrogen, optionally substituted by one or two of the following substituents: halogen, Ci - ^ - AI-alkyl, Ci-4-alkoxy, mono- or di- (Ci_4-alkyl) -amino or -SO3M, phenyl, optionally substituted by hydroxy , Cyan or Ci-4-alkoxy substituted Ci-4-alkyl, or a group of the formula R4 is hydrogen, Ci_4-alkyl, phenyl optionally substituted by Ci-4-alkyl, C2-4-alkyl substituted by hydroxy, Ci-4-alkoxy or cyano or a radical of the formula (a), (b), (c) or (d) or R3 and R4 together with the nitrogen to which they are attached form a saturated nitrogen-containing heterocycle, R5 is hydrogen or methyl, R6 is hydrogen or Ci-4-alkyl, m is a number from 2 to 10, n is a number from 1 to 4, M is hydrogen or a colorless cation and A® is a colorless anion, characterized in that one mole of a diamino compound of the formula - {CH2-CH (R5) -0, (a) - <C1 _ ^ - alkylene> -C0-N (R6) 2, (b) ~ <CH2> irN <R6> 2 (c) or - <CH2) ir # (R6) 3 Ae (d) (ii) so3h with 2 moles of a compound of the formula R (III) Shark in which shark represents halogen, to a compound of the formula 11 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 CH 676 000 A5 (la) implements. 2. A process for the preparation of compounds of the formula (Ia) in which Ri is R01, characterized in that a compound of the formula (IA) in which Ri is Hai, prepared by the process according to Claim 1, with a compound of the formula H-R01 (IV) implements. 3. A process for the preparation of compounds of the formula wherein R02 is a group of the formula -NR3R4. -OR3 or -SCH3 and R 1, R 3, R 4 and M have the meaning given in claim 1, characterized in that a compound of the formula (Ia) prepared by the process according to claim 1 with a compound of the formula 4. A process for the preparation of compounds of the formulas (Id), which are as defined in claim 3 and in which Ri is R01, characterized in that a compound of the formula (Ia), prepared in the process according to claim 1, in which Ri is shark , with a compound of formula (IV) and a compound of formula (V). 5. A process for the preparation of the starting materials of the formula (II) for the process according to claim 1, characterized in that an aldehyde of the formula F <Id) 2nd H-R02 (V) implements. H (VI) with a compound of the formula (VII) Rb to a compound of the formula 12 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 CH 676 000 A5 R 9 ^ o2 (VIII) implements what Rg nitro or acetylamino, Rio represents hydrogen, cyano or a radical of the formula and one of the two symbols Ra and Rb represents hydrogen and the other represents the group -SO3M, reduces the nitro group (s) present to the amino level and, if Rg means acetylamino, hydrolyzes the acetylamino group . 6. Application of the method according to claim 1, to compounds of formula (II) which are prepared by the method according to claim 5. 13