DE1670991C3 - Process for the preparation of benzo- [a] phenazine di-N-oxides - Google Patents

Description

SO, N or CO N

sees where

is a hydrogen atom or a lower alkyl radical,

Y represents a hydrogen atom or a

lower alkyl radical, which is optionally replaced by a heterocyclic 5- to 7-membered ring is substituted, or a cycloalkyl radical with 5 to 8 ring members, one optionally substituted 1 to 3 times by a lower alkyl or alkoxy group or a halogen atom Represents phenyl radical or a 5- to 7-membered heterocycle and

X and Y together can themselves be part of such a heterocycle,

and the leftovers

R1 to Rh stand for hydrogen atoms, furthermore at most 3 of the named subsituents Ri to Rk. which are identical or different can, for a halogen atom, a cycloalkyl, nitro, alkoxy or sulfonic acid Carboxy, carboalkoxy or an optionally substituted straight-chain or branched one, saturated or unsaturated Alkyl group

or for the groups

CO N

CO Ii,

Il

SO ₂ R ₄ , or

SO,
CO

R ₁ , stand

whereby

X and Y have the meaning mentioned above, and

Ri for a hydrogen atom or a lower one

Alkyl group or an optionally substituted phenyl radical,

characterized in that one Benzofuroxan of the general formula

(lh

in the

Ri and Ridic have the meaning given above, with at least the equimolarcn amount of a / x- or ^ -naphthol of the general formula II

Oll

(III)

κ ,,

R,

κ,

in the

R1 to Rn have the meaning given above

to have,

in the presence of a diluent in the temperature range from about 0 "to about 100" C in the presence of a base or a basic reacting one Salts .: converts and, if necessary, after the reaction has ended, by adding an acid neutralized.

2. The method according to claim 1, characterized in that that the naphthols are used in the form of their alkali metal naphtholates, optionally in solution.

SO, N

There has been a process for the preparation of the benzo- [a] -phenazine-di-N-oxides mentioned in claim 1 above found, which is characterized in that a benzofuroxan of the general formula (II) is used the substituents mentioned in the claim above

16 7099

interpretations with at least the equimolar amount a «- or ^ -naphthol of the general formula (III) with the substituent meanings mentioned in claim I above in the presence of a diluent Reacts in the temperature range or a basic salt and optionally after completion Reaction neutralized by adding an acid.

The alkyl radicals Ri or R2 are those with up to 6 Carbon atoms, preferably 1-4 carbon atoms, to be understood which have up to 2 double bonds or may contain a triple bond. Cycloalkyl radicals are those with 5 to 8, preferably 5 to 7 Ring links. Lower alkyl radicals X and Y which may be mentioned are those with up to 4 carbon atoms, in which the radical Y can be substituted by a heterocyclic 5- to 7-membered ring containing up to 4 nitrogen atoms, or, in addition to nitrogen, can also contain oxygen or sulfur as a further heteroatom. As halogen fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, are suitable.

Benzofuroxanes used for the starting compounds are mentioned by way of example:

Benzofuroxan, 5-methyl-, 5-ethyl-, 5-propyl-, 5-butyl-, 5-methoxy, 5-ethoxy, 5-propoxy, 5-butoxy, 5-carboxy, 5-carbomcihoxy, 5-carboethoxy, 5-carbo-propoxy, 5-carboxy-buioxy, 5-carbobenzoxy, 5-sulfonamido, 5-sulfonanilido,> sulfonic (4-methylanilido), 5-sulfone- (4-methoxy-anilido) -, 5-sulfone- (2-pyridyl-amido) -, 5-sulfon- (2-pyrimidinyl-amido) -, 5-carbamido-, 5-carbanilido-, 5-carbo- (2-pyridyl-amido) -, 5-Carbo- (2-pyrimidinyl-amido) -benzo-furoxane.

The alkyl radicals Ui to Rn are those with up to 12 To understand carbon atoms which contain up to 2 double bonds or one triple bond can and by halogen, preferential ·. ' ^ ise fluorine, chlorine, Bromine, hydroxy, carboxy, alkoxy (1-4 carbon atoms), phenyl, the radicals

CO N

ink-r CO R ₁ ,

8- (2-chlorobenzoylarnino) -naphihol- (2),
8- {2,4-dichlorobenzoylamino) naphtho! - (2),
* -Bromo-8-acetylamino-naphthol- (2),
* -Heptylnaphthol- (2).

For example, the alkali metal alcoholates of lower alcohols (up to 4 carbon atoms), in particular KOCH ₁ , NaOCHj, KOC ₃ H ₅ , NaOC ₂ H ₅ and KOC ₄ Hq and NaOC ₄ H, can be used as bases. In addition, the hydroxides of the alkali and alkaline earth metals are preferably used, such as. B. NaOH, KOH, Ca (OH) ₂ . Likewise, the carbonates and cyanides of the alkali metals such as Na ₂ COj, K ₂ CO ₁ , NaCN, KCN and amines of the general formula can be used for the process according to the invention

R ₁₁ ,

Above mentioned meaning .substituiert can be. The optionally substituted phenyl base Rm can carry the following substituents 1 to 3 times: halogen, preferably fluorine, chlorine or bromine, lower alkyl (1-4 carbon atoms), SO, H, nitro and lower alkoxy.

Examples of naphthols used for the process according to the invention are:

NO

Il

R,

be used,

where Ri », Rm and Ri? for the same or different Radicals such as hydrogen, alkyl (preferably 1 - 12 carbon atoms), aralkyl (aryl, preferably phenyl, aliphatic chain preferably 1–4 carbon atoms) stand, where Rio and Ru are also part of a 5- or 6-membered ring system, which optionally as further heteroatoms also oxygen, May contain nitrogen or sulfur. The following should be mentioned here: ammonia, dimethylamine, Trimethylamine, butylamine, cyclohexylamine, dicyclohexylamine, benzylamine, piperidine and morpholine.

In general, the bases are used in at least 0.5 molar amounts, based on the naphthol used, applied. But you can also both in stoichiometric amount and in excess are used, the reaction time being considerable if an excess amount of base is used is reduced.

The reaction is carried out in diluents such as water, alcohols (preferably 1-5 carbon atoms), Acetonitrile, dimethylformamide, dioxane, tetrahydrofuran or their mixtures with water, in benzene or carbon tetrachloride in the temperature range from about 0 ° to about 100 ° C., preferably from about 10 ° to about 50 ° C, in particular about 20 'to about 30 ° C, performed.

The method of the invention is illustrated by the following implementation:

OH

Naphthol ^ I), () ,, Il NmOII •; ιι, ο I ,, The reaction will be wi 1 O 4-methoxy-naphthol- (l), N Put 1 mole of ben Naphthol- (l) -sulfonic acid- (4), ί O N Naphthol ^ I) -disulfonic acid- (4.8), N Naphthol- (2) -sulfonic acid- (4), · 'N Naphthol- (2) -sulfonic acid- (6), 6-nitronaphthol- (2) -sulfonic acid- (4). O 3 = Hydroxy-naphtho-acid- (2) -sulphonic acid- (5), 8-amino-naphthol- (2) -sulfonic acid- (b), efol Naphthol (2) disulfonic acid, zofu 2-hydroxy-naphthoic acid- (3), 2-hydroxy-naphthoic acid- (6), 3-amino-naphthol- (2), 8-methylsulfonamido-naphthol- (2), 8-acetylamino-naphthol- (2),

11.0

naphthalene in a thinner! (preferably water) and drips or passes 0.5 to 20 mol of base a. The suspension of benzofuroxan and partially dissolved naphthol turns into exothermic Reaction into the corresponding benzophenazine di-N-oxides. Of course, the naphthols in the form of their Alkalinaphtholate gegenbenenfails used in solution without further addition of a base will.

Hus carries benzofuroxan or the hydroxynaphthalene acidic groups, the corresponding alkali salts are obtained, which by acidification are converted into the free compounds can be transferred.

The products that can be prepared according to the invention are with Except for the benzophynazine di-N-oxide new. They represent valuable intermediates for dyes and Plant protection products and can also be used directly in plant protection as fungicides.

(0.1 mol) and stir for 7 hours. During this time the temperature rises to 28 ° C and from the yellow Suspension creates an orange pulp. After suctioning off, 24 g (91.6% of theory) are obtained Benzophenazine di-N-oxide as orange-yellow crystals, the decompose after dissolving from dimethylformamide at 191-C.

Analysis for CihHInN ₃ O ₂ (mol. Wt. 262):

Calculated: C 73.3, H 3.8, N 10.7;
Found: C73.0, H 3.9, N 10.7.

Example Ib
O

Example la
O

N · ■ '■ _'
^; , _ ■ 'N ^
O

13.6 g (0.1 mol) of finely powdered benzofuroxan and 14.4 g (0.1 mol) of naphthol- (2) are in 200 ml of water suspended. 40 g of 10% strength sodium hydroxide solution are added dropwise to this

13.6 g (0.1 mol) of finely powdered benzofuroxan and 14.4 g (0.1 mol) of naphthol- (2) are in 200 ml of water suspended. 50 g of 40% strength sodium hydroxide solution (5 mol) are added dropwise and the mixture is stirred for 1 hour. By the occasional Cooling with ice keeps the temperature below 30 ° C. After suctioning off, 25 g (95.5% of Theory) Benzophenazone di-N-oxide with a decomposition point of 173 ° C. After dissolving from dimethylformamide the substance decomposes at 191 "C.

Analogously to 1 a, the following were prepared:

I .ti Iv

\ ιι ·> Ιχ-ιιΐι ·

CH ₁ O

193 I ¹ MC 72 ",,

DM Ι

«Jcln

N
O

166 167 C

6N.9 ""

DM Ι

.N,

184 ISS c

92.5 ",,

I) MI-

ΙιιιΊ'-ol / uiii:

O C CH,

HN ο

N N O

Cl

O C

HN O

N N O

Cl

OC HN

9 p

C) C "ΠΙ,

HN O

hu Ix:

uc lh

nniniicrol

ininucuclb

Red

/ ei sei / 11111 - "'PlIn kl Ausheule

232 C

C '

C.

C "

95.6 ". ',,

94 ""

95.7%

DMI-

I) MI

DMI

DMI '

-Br

Orange red

192 C

55.3%

DMF

9 el 2 1 _r 6th 70 99 1 10 : l 4 B e. is ρ i O, " B e i s ρ i e , Nu : ' ' IY SO
O , ··· ■ * N

, N SO,

19, ¹ J g (0.1 MoI) Sulfonamidobenzofuroxan and 14.4 g (0.1 MoI) naphthol (2) are suspended in 200 ml of water. 80 g of 10% sodium hydroxide solution (0.2 mol) are added dropwise to this. A dark solution is created in an exothermic reaction. After 4 hours it is filtered and the filtrate is acidified with 10% hydrochloric acid. 32 g (93.8% of theory) of yellow crystals are obtained which, after dissolving from DMF, melt at 250 ° C. with decomposition.

Analysis for C ,,, H _n N, OS (mol. Wt. 341):

Ber: Γ 56.5; H 3.2, N 12.3;
Found: C 56.4, H 3.5, N 12.6.

Example 3
O

-N
O

SO, N; i

13.6 g (0.1 mol) of benzofuroxan and 25 g (0.1 mol) of naphthol (2) sulfonic acid (4) Na salt are in 200 ml Suspended in water. 40 g of 10% sodium hydroxide solution (0.1 mol) are added dropwise to this. After 8 hours it is suctioned off and 27 g (65.8% of theory) of orange-red crystals are obtained, which are recrystallized from water can.

Analysis for C ₁₆ HqN ₂ NaO ₁ S 2 H ₂ O (mol. Wt. 4IO):

Calculated: C 46.9, H 3.17, N 6.8;
Found: C 47.1, H 3.5, N 7.0.

The same compound arises from naphthol (I) sulfonic acid (4) Na salt and benzofuroxan in a yield of 50% of theory.

Analogously from naphthol- (2) -disulfonic acid- (3,6) -Na ₂ salt and benzofuroxan:

C) COOH

I 3.6 g (0.1 mol) ben / ofuroxan and 26.8 g (0.1 mol) 3-Hydroxy-naphthoic acid- (2) -sulfonic acid- (5) are suspended in 200 ml of water. 120 g are added dropwise 10% sodium hydroxide solution (0.3 mol) and stir for 18 hours at room temperature. After suctioning off, 16 g are obtained (39.2% of theory) orange-red crystals that can be dissolved from water.

Calculated: C 50.0, H 2.2, N 6.1;
Found: C 49.7, H 3.3, N 6.1.

SO ₁ H

Example 5
H ₂ N

O '

N
N
O

13.6 g (0.1 mol) of benzofuroxan and 23.9 g (0.1 mol) of 8-aminonaphthol- (2) -sulfonic acid- (6) are in 200 ml Suspended in water. 80 g of 10% strength sodium hydroxide solution (0.2 mol) are added dropwise and the mixture is stirred for 4 hours. After this Suction gives 31 g of red-violet crystals, which turn yellow when stirred in dilute hydrochloric acid Convert crystals.

Analysis for C ₁ H ,, N ₍ O> S (Mol.8Gew. 357):

Calculated: C 53.7, H 3.0, N 11.8;
Found: C 53.6, H 3.4, N 12.0,

Example 6

Nile SO, ClI,
O

SC), N; i

• Ν

■ Ν '

O SO ₃ Na

orange-yellow crystals redissolved from water, yield 40% of theory.

Analysis for C ₁₆ H ₈ N ₂ Na ₂ O ₈ (mol. Wt. 402):

Calc .: C 47.7, H 1.90, N 63;
Found: C 47.1. H 2.4, N 7.3.

13.6 g (0.1 mol) of benzofuroxan and 23.7 g (0.1 mol) of e-methanesulfonylamino ^ -hydroxynaphthalene are suspended in 200 ml of water. 40 g of 10% strength sodium hydroxide solution (0.1 mol) are added dropwise and the mixture is stirred for 4 hours at room temperature. After suctioning off, 18 g (50.7% of theory) of red-brown crystals are obtained which, after being redissolved from acetonitrile / DMF 2: 1, ^{melt at 196 °} C. with decomposition.

Analysis for Ci ₇ Hi ₃ N ₃ O ₄ S

Ben: N 11.8
Found: N 11.9

(Mol.wt. 355):

Example 7
O

NH,

13.6 g (0.1 mol) benzofuroxan and 15.9 g (0.1 mol) 3-Amino-2hydroxy-naphthalene are suspended in 200 ml of what scr. 40 g of 10% strength are added dropwise to this Sodium hydroxide solution (0.1 mol) and stir for 5 hours at room temperature. A black-violet appears Suspension. After suctioning off, 20 g (72.3% of theory) of black-violet crystals are obtained redissolving from dimethylformamide at 184 "C Melt decomposition.

Analysis for CIf ₁

Calc .: C 69.3.
Found: C 68.3,

(Molar weight 277)

H 3.9, N 15.1;
H 4.2, N 14.9

Example 8
O

N ■

O C (X) H

13.6 g (0.1 mol) of benzofuroxan and 19 g (0.1 mol) of 2-hydroxynaphthalene-carboxylic acid (3) are in 200 ml

Suspended in water. 80 g of 10% strength sodium hydroxide solution (0.2 mol) are added dropwise and the mixture is stirred for 3 hours Room temperature, the precipitate obtained after suctioning off is stirred in dilute hydrochloric acid and 12 g of yellow crystals are obtained which, after dissolving from dimethyl sulfoxide at 212 ° C., decompose melt. When acidifying with 10% hydrochloric acid, 1 g is still obtained from the filirate. Total yield 75.2% of theory.

Analysis of HIrCi ₇ HmN ₂ O ₄ (molar weight 306):

Calc .: C 66.6, H 3.2. N 9.1;
Found: C 66.4, H 3.6. N 9.1.

Example 9

NO.

SO ₁ Na

13.6 g (0.1 mol) benzofuroxan and 29 g (0.1 mol) 6-Nitronaphthol- (2) -sulfonic acid- (4) -Na salt are used in Suspended 300 ml of water. 40 g of 10% strength sodium hydroxide solution are added dropwise and the mixture is stirred for 8 hours at room temperature. After suction, 13 g (31.2% of theory) of yellow crystals are obtained, which dissolve after IJm decompose from water at 208 ° C.

Analysis for CH ₈ N ₁ NaO: ■ H _: O (mol. Wt. 417):

Ber .: C 46.6. H 2.4. N 10.1;
Found: C 46.6. H 2.5. N 10.3.

Claims (1)

Patent claims: 1. Process for the preparation of benzo- [a] -phenazine-di-N-oxides of the general formula (I) O R, in which one of the radicals Ri or R2 is a hydrogen atom and the other for a hydrogen or haloalom or for one optionally unsaturated, straight-chain or branched alkyl group, a cycloalkyl, alkoxy, carboxy, carbobenzoxy or sulfonic acid group, a carboalkoxy group with 2 to 5 carbon atoms or the groups