SI8012432A8 - Process for preparing diphenylethers - Google Patents

Description

The invention relates to a novel process for the preparation of diphenylethers of the general formula (M ⁱⁿ In

NC (I) in which n is an integer from 1 to 3, hydrogen, halogen, alkyl of 1 to 8 carbon atoms, triuoromethyl, acetyl, cyano, C 1 -C 4 -alkoxy, C 1 -C 6 alkoxy , hydrogen; alkyl, alkenyl or alkynyl having up to 18 carbon atoms; an alkyl residue of 2 to 6 carbon atoms, dry-substituted with hydroxy, C 1 -C 4 -alkoxy, phenoxy, halo genphenoxy, C 1 -C 4 -alkylphenoxy, C 1 -C 4 -alkoxy-phenoxy, nitrophenoxy, cyanophenoxy, amino or C 1 -C 6 alkylthio; optionally halogen-substituted benzyl, trifluoromethylbenzyl, -NR ^ R ^, CHR ^ -COOR ^, or

CHR ^ -CONR ^ R ^, wherein R ^, R _4, and R ^, which may be the same or different, are hydrogen or C1-6alkyl radicals, and

Χη and X ₂ , which may be the same or different, stand for hydrogen or halogen.

Values 2 and 3 have n only if R4 stands for halogen or alkyl.

By "halogen" ¹ is meant fluorine, chlorine, bromine and iodine. Fluorine, chlorine and bromine are preferred, especially fluorine and chlorine.

To the extent that R ^, R ₂ , R ^, R ^, R ^ represent or contain hydrocarbon residues, these may be branched or unbranched.

In the context of the definitions of the front standing R is preferably hydrogen, fluorine, chlorine, bromine or methyl, R ₂ for hydrogen, C ^ -C ^ alkyl, allyl, 2-hydroxy-ethyl, 4-fluoro- or 4-chlorobenzyl or dimethylamino. R < 2 > is preferably hydrogen or methyl, R < 2 > If n is 2 or 3, different residues of ILj may occur at the same time.

Compounds of general formula I have an excellent herbicidal effect.

A technical problem

The technical problem is to create a process in which diphenyl ethers of general formula I are practically isomerically pure and in good yield, with the metabolism of new starting materials that are readily available and can also be used in aqueous solutions, which is a simplified and inexpensive process.

- 3 State of the art

Some compounds of general formula I are known (German patent application P 28 51 261.1). They have excellent herbicidal effect.

To prepare the 'metabolism of phenolates by halogenation' we nitroanilinyl. Nitrnan-ί l-inj must be free of isomers and free of diamines.

As solvents, e.g. acetonitrile, dimethylformamide, dimethylsulfoxide.

N-substituted nitroanilines lead easily to side reactions and thus to reduced yields.

Description of the solution to the technical problem with examples

As we have now found, compounds of the general formula I can be obtained in very good yield and almost pure pure nitrodiphenoxybenzene of the general formula

(II) in which n, R 4, and the above meaning and R 'are optionally substituted phenyl radicals, is reacted with an amine of the general formula hnhr ₂ (III) at temperatures between about 20 ° C and 160 ° C.

The residue R 'stands generally for

however, it may also represent an otherwise substituted phenyl residue, because any substituents present, provided they are sufficiently stable under the reaction conditions, have no significant effect on the course of the reaction.

Inert organic solvents can be used as the reaction medium, e.g. dioxane, tetrahydrofuran, benzene, toluene, xylene, chlorinated hydrocarbons and dimethylsulfoxide as well as water. The choice of reaction medium is not critical, but we prefer to use a medium in which the reaction components have sufficient solubility.

Compared to the process of patent applicationP 28 p1 261.1, the advantage of the new process is that it is

- The 5 starting materials of Formula II are easier to prepare in a suitable quality than the chloronitroanilines required for the earlier process and can also be used with inexpensive solvents as a reaction medium, e.g. with water, yielding very good winnings.

The starting materials of formula XI are known in part. However, they can also be prepared in a novel way by the compound of the general formula

in which both are defined as above, e.g. 2,5,4-trichloronitrobenzene and 2,5,4-, 5-tetrachloronitrobenzene, is reacted with the corresponding phenolate of the general formula (M) \ K0Ot (VI) (Kat is 1 cation equivalent)

Preferably, alkali phenolates, in particular sodium phenolate, is used. phenol and e.g. alkali carbonate. For simple phenols, especially unsubstituted phenol, Iciko uses the appropriate phenol as the reaction. medium. Particularly advantageous is the use of dimethylsulfoxide as a solvent.

0 ';

chlorine atoms in the position of the phenoxyl ion

- 6 groups, show distinct unequal reactivity.

Therefore, it is possible to synthesize compounds with two different phenoxyl groups without further ado. To this end, we first substitute the chlorine atom closer to the nitro group under milder conditions for the desired phenoxyl residue, before replacing the chlorine atom in position 4 with the group of formula VI under more stringent conditions.

The compounds of general formula I are partially novel. Also, these new compounds exhibit excellent herbicidal efficacy and can, in addition, be used as intermediates for the preparation of new pesticide agents or novel drugs, since their functional groups allow for many changes.

For use as herbicides, compounds of formula I are recovered in a manner known per se by conventional excipients and / or carriers into conventional preparations, e.g. into emulsion concentrates or suspension powders in which the active ingredient content is between about 10 and 95 weight percent. %, which can be adjusted for application with water to the desired effect concentration. However, preparations can be made that are used undiluted, e.g. powders or granules. Here, the active substance content is between 0.2 and 20 weights. %, preferably between 0.5 and 3 weights. %.

Examples of preparations

1. Suspension powder Composition:

weight. % 2-Chloro-5 “TeHoxy-6-nitro-N- (2-aminoethyl) aniline hydrochloride by weight. % kaolin weight. % colloidal flint weight. % calcium ligninsul phonate 1 weight. % sodium tetrapropylene benzenesulfonate

2. Emulsion concentrate weight. % of the active ingredient according to the invention is a weight. % Aromatic Hydrocarbon Liquid Liquid Mixture ^- High Boiling (Shellsol A)

6.5 weight. % Tensiofix AS (emulsifier)

5.5 weight. % Tensiofix DS (emulsifier)

From the concentrates of Examples 1 and 2, spray sprays containing generally about 0.05 to 0.5 weights were prepared by mixing with water. % of the active substance.

5. Weightlifting agent. % of the active ingredient according to the invention is a weight. % talc weight. % of methylcellulose

-8 It is also possible, and in some cases useful, to use the active ingredients of the invention together with other herbicides, e.g. with triazine herbicides, such as Simazine or Atrazine in maize, with urea herbicides, such as e.g. Linuron or Monolinuron in potatoes or cereals, with dinitroaniline t

herbicides, such as Dinitramine or Trifluoralin in cereals, with diphenylethers, e.g. Irtrophenome in cereals, with carboxylic acid amides, such as Alachlorum onion.

The compounds of the invention can be used in the pre-emergent and post-emergent processes. By way of example, using the amount of 1 kg / ha of 2-chloro-3-phenoxy-6-nitro-IT- (2-aminoethyl) aniline hydrochloride in the field, with pre-emergent use, mustard, mustard, broom, chamomile, and fungus can be suppressed foxes, 'tail' in portability in potatoes and maize exceeds 3 kg / ha, in wheat and peas above 2.5 kg / ha. The use of these compounds by origin can be suppressed by 1 kg / ha, e.g. rapeseed, petiole fox tail, with a slight dose also mustard, hives and chamomile. Except in the said cultures, the compounds of the invention may be used e.g. in barley and rice.

Preparation of starting materials:

1. 2-Chloro-4-nitro-1,5-diphenoxybenzene

S

a) 114.5j of 2,3,4-trichloronitrobenzene, 400 ml of dimethylsulfoxide and 130 S of sodium phenolate stirred for 1 hour at

100 ° C. After this time, water was added to the reaction mixture and shaken with chloroform. The chloroform solution was washed with dilute sodium hydroxide solution, dried with sodium sulfate and the solvent removed. The residue was recrystallized from ethanol.

Yield: 152 g (89% of theory);

M.p .: 106 to 107 ° C.

h) 56.7 S of 2,5,4-trichloronitrobenzene (0.25 mol), g of phenol and 3 ^, 5 S of potassium carbonate (0.25 mol ')' are heated for 1 hour at 130 to 140 ° C. The reaction mixture was added to 2 n sodium hydroxide solution. The reaction product is obtained in a yield greater than 95% of theory.

M.p .: 106 to 107 ° C (from ethanol)

2. Heat 6-chloro-4-nitro-1,5-diphenoxybenzole mol of 2,4,5-trichloro-1-nitrobenzene with 2 moles of potassium phenolate in phenol at 165 ° C and isolate the reaction product.

M.p .: 95 (from ethanol).

- 10 3. 2,6-Dichloro-4-nitro-1,5 ~ chifenoxybenzene ·

26.2 g (0.1 mol) of 2,3,4,5 ~ tetrachloro-1-nitrobenzene was heated with 20.7 S phenol and 30 S potassium carbonate in 100 ml dimethyl sulfoxide for 110 h at 110 ° C. The reaction mixture is placed on water and the product is sucked off. Yield: 35.5 S (89% of theory); m.p. 152 ° C (from ice).

The same compound is obtained from 52.4 g of 2,3,4,5-tetrachloronitrobenzene, 122 g of phenol and 60 g of potassium carbonate by heating the ingredients for 1 1/2 hours at 160 ° C, stirring the hot mixture in 1.2 1 2 n The sodium hydroxide solution and the recovered product are aspirated. Recrystallization from 3QQ ml of glacial gave 70.5 S of the desired compound (95.8% of theory); m.p. 164 ° C.

4. 2-Chloro-4-nitro-5-phenoxy-1- (2,4,5-trichlorophenoxy) -benzene

28.4 g 4.5-dichloro-2-nitro-1-phenoxybenzene, 21.6 g

2,4,5-trichlorophenol, 10 ml of 10 n sodium hydroxide and 80 ml of dimethyl sulfoxide are stirred for 6 hours at 150 ° C, then allowed to stand overnight at room temperature. The reaction mixture was mixed with 600 ml of water, basified and the reaction product was taken up in chloroform. The organic phase was washed, dried and evaporated. The residue was recrystallized from 200 ml of ethanol. We get 4; With light yellow. of crystals (97 / ^J theory, mp 84 ° C.

5. 2-Chloro-4-nitro-5-phenoxy-1- (2,5-dichloro-4-bromophenoxy) benzene

Mix 28.4 g of 4,5-dichloro-2-nitro-1-phenoxybenzene, 24.2 g of 2,5-dichloro-4-bromophenol, 10 ml of 10 n sodium hydroxide and 80 ml of dimethyl sulfoxide and stir for 5 hours at 100 ° C. The reaction mixture was then stirred with 700 ml of 1 n sodium hydroxide solution, allowed to stand at room temperature overnight, decanted and the reaction product taken up in chloroform. The solution was washed, dried with sodium sulfate and evaporated. The residue was recrystallized from 200 ml of ethanol + 2 ml of dimethylformamide. Yield.'36.5 6 light yellow crystals (75% of theory); m.p. 85 ° C.

6. 2-Chloro-4-nitro-3-fluoxy-1- (2,5- dichloro-4-methylthiophenoxy) benzene

14.2 g of 2,5-chloro-6-nitro-1-phenoxybenzene, 10.2 g

2,5-Dichloro-4-methylthiophenol, 5.0 ml of 10 n sodium hydroxide and 40 ml of dimethylsulfur oxy are stirred for 5 hours at 100 ° C, allowed to stand overnight and then mixed with 400 ml of 1 n sodium hydroxide. The recovered product is recrystallized from 150 ml of ethanol. Yield: 20.5 S light yellow crystals (90 Theore.) M.p. 158 to 144 ° C.

- 12 7 · S-Chloro - N - nitro - 5 - phenoxy - 1 - C 3-6 - trichlorophenoxy) - benzene 28.4 g of 2,5 - dichloro - 6 - nitro - 1 - phenoxybenzene, 21.6 g

2,4,5-trichlorophenol, 10 ml of 10 n sodium hydroxide and 80 ml of dimethyl sulfoxide are stirred for 6 hours at 100 ° C and then mixed with 600 ml of 1 n sodium hydroxide. Suction off and recrystallize the product from 150 ml of ethanol.

Yield: 51 S (77% of theory);

Melting point: 112 ° C.

A further portion of the reaction product (about 6 g) can be obtained by evaporation of the mother liquor.

8. 2-Chloro-4-nitro-5-phenoxy-1- (4-cyanophenoxy) -benzene

14.2 g of 2,5-dichloro-6-nitro-1-phenoxybenzene, 6.5 S

Of 4-cyanophenol, 40 ml of dimethylsulfoxide and 5 ml of 10 n sodium hydroxide were stirred for 5 hours at 100 ° C. Dilute with water, shake with chloroform, dry and distill off the solvent. Purification via a silica gel column and recrystallization from ethanol yielded 11 g of colorless crystals (60.2% of theory); m.p. 140 to 142 ° C.

The following examples illustrate the process of the invention:

EXAMPLE 1

2-chloro-3-phenoxy-6-nitro-N- [1- (methylcarbamoyl) -ethyl] -aniline

NO,

MH-CH-CO-MMCH63) 3 6 2-Chloro-4-nitro-1,3-diphenoxybenzene stirred at 70 ° C for 24 hours in 200 ml of dioxane with 60 g of α-alanine-M-netilamide. The dioxane is distilled off, the residue is dissolved in ethylene chloride and the solution is shaken with dilute sodium hydroxide solution. After drying the organic phase with sodium sulfate, the solvent is distilled off. The residue was recrystallized from ethanol. Yield: 61.5 6 (87.2% of theory.)} M.p. 122 ° C.

The product is thin layer chromatographically uniform.

Analysis: C H Cl calc .: 54.62 ^, 55 10,10 found: 54.30 4,41 10.07 EXAMPLE 2 2-chloro-3-phenoxy · aniline -6-nitro-l I- [2- (2,5- dichlorophenoxy)

Proceed as in Example 1 but instead of using alanine-methylamide [2- (2,5-dichlorophenoxy) -ethyl] -anine.

- 14 Also the processing corresponds to Example 1. The reaction product is an oil which is obtained in a yield of 97% of theory. Thin layer chromatography is uniform.

Analysis: C E Cl calc .: 52.92 3.31 23,46 found: 52,8? 3.24 23,7

EXAMPLE 3

4-Chloro-3 ~ phenoxy-6-nitro-N-allylaniline

63.3 With 6-chloro-4-nitro-1,3-diphenoxybenzene was heated with excess allylamine in 120 ml of dioxane for 12 hours at 60 ° C.

After distilling off the solvent, the residue is taken up in methylene chloride, washed with dilute sodium hydroxide solution, the organic phase is dried with sodium sulfate and the solvent is distilled off. Recrystallization from toluene / bexane, optionally after further purification via a silica gel column, gave the reaction product in 51 S yield (83.6% of theory); m.p. 81 to 82 ° C.

Analysis: C il Ci calc .: 59.11 4.27 11.66 found: 58,9 ² S52 11.80

EXAMPLE 4

4-Clpr-5-lenoxy-6-nitro-N- (2-aminoethyl) -aniline hydrochloride

6.83 Dissolve 6-chloro-4-nitro-1,3-diphenoxybenzene in 15 Bil dioxane and heat with excess 1,2-diaminoethane for 12 hours at 70 ° C. Processing corresponds to example 3 «

For purification, it was recrystallized from dilute hydrochloric acid. Yield: 6.1 g (88% of theory); white crystals, m.p. 255 ° C (dec).

EXAMPLE 5

3-Phenoxy-6-nitro-R-allylaniline g 4-nitro-1,3-diphenoxybenzene was heated in 30 ml of tetrahydrofuran, and 10 ml of allylamine for 8 hours under reflux. Processing is done analogously to Example 5- The resulting product is recrystallized from ethanol. Yield: 6.1 g (69% of theory); According to the thin - layer chromatogram (this product is unique.

6? to 68 ° C.

oxhexar / toluene 1: 1; is

- 16 Analysis:

CEN calc.

found:

66.67 5.19 10.57

66.85 5.50 10.24

EXAMPLE 6

2-Chloro-5-phenoxy-6-nitroaniline

a) 68.3 S of 2-chloro-4-nitro-1,3-diphenoxybenzene was dissolved in 300 ml of toluene and 100 ml of conc. of aqueous ammonia. The pressure is then adjusted to 3 bar with gaseous ammonia. The mixture was then heated to 120 ° C for 12 hours, increasing the pressure to about 13 bar. After cooling, the organic phase is separated, shaken with dilute sodium hydroxide solution, dried and the solvent distilled off. The reaction product was obtained in almost quantitative yield (54 g). After gas chromatography, the product contains 98% of the title compound. Tal. 81 to 82 ^υ 0.

b) The adapter complies with a) but no gaseous ammonia is introduced. The reaction temperature is 15θ ° C. We process as described above. The gain is almost quantitative. After gas chromatography, the product consists of 9θ% of the title compound and about 4% of starting material.

- 17 «

EXAMPLE 7

2-chloro-3- (2,5-cyclic or 4-methylthiophenoxy) -6-tri-N-b enzylaniline

A mixture of 4.6 g of 2-chloro-4-nitro-5-phenoxy-1- (2,5-dichloro-4-methylthiophenoxy) -benzene, 3, θ S benzylamine and 10 ml of dioxane was stirred for 6 hours at 40 ° C. stand overnight at room temperature and then evaporate. It is taken up in chloroform, the solution is shaken with dilute sodium hydroxide solution and then with water, the separated organic phase is dried and evaporated. The resulting dark-brown oil was purified over a column

And with a quartz gel.

Yield: 4.2 g of an orange-colored viscous oil, which is uniformly thin layer chromatographic.

EXAMPLE 8

4-Chloro-3- (2,5 ~ chloro-4-bronf enoxy) -6-nitro-1''-T-allylaniline

4.9 g of 2-chloro-4-nitro-5-phenoxy-1- (2,5-dichloro-4-bromophenoxy) -benzene, 1.8 g of allylamine and 10 ml of dioxane are mixed. The mixture is stirred for 7 hours at 40 ° C. then for another 3 hours at 60 ° C and evaporated. The residue was taken up in chloroform, the solution was washed with acid and then made alkaline, dried and evaporated. The crude product (5.6 g) was purified over a pyrex gel column.

Yield: 3.0 S yellow, crystals (66.6 theory.); m.p. 102,5 0.

EXAMPLE 9 ^with t-Chloro-5- (2,5-dichloro-4-bromoxy) -6-nitro-R-benzylaniline

A mixture of 4.9 g of 2-chloro-4-nitro-5-phenoxy-1- (2,5 dichloro-4-bromoenoxy) -benzene, 5.0 g of benzylamine and 10 ml of dioxane was reacted according to Example 8. The crude product (6 , 2 g) is stirred hot with 50 ml of ethanol and then sucked off after cooling to room temperature. 5.2 g of dark yellow crystals, m.p. 157 ° C.

EXAMPLE 10

2-chloro-5- (2,5-dichloro-4-methylthiophenoxy) -6-nitro-N-allylaniline nh-ctu-ch = ck ₂

Mixture of 4.6 g of 2-chloro-4-nitro-5-phenoxy-1- (2,5 dichloro-4-methylthiophenoxy) -benzene, 1.8 g of allylamine and 10 ml

stand at room temperature. The mixture is evaporated, taken up in

- 19 crystals (91% of theory); m.p. 107 ° C.

EXAMPLE 11

2-Chloro-3-fluoxy-β-tri-N- (4-chlorobenzyl) aniline g 2-chloro-4-nitro-1,3-diphenoxybenzene was stirred in ml of dioxane with 6 g of 4-chlorobenzylamine for 12 hours at 80 ° C.

The mixture was then evaporated, the residue taken up in chloroform, the solution shaken with 1 n sodium hydroxide solution and dried over sodium sulfate. After the solvent was distilled off, the residue was recrystallized from ethanol. Yield: 4.7 g (82.7% of theory), m.p.

to 96 ° C.

Analogously, we get

2-chloro-3-phenoxy-6-nitro-N- (4-fluorobenzyl) -aniline; yellow crystals, yield 4.1 g (75> 4% of theory); m.p. 75 to 76 ^c C.

EXAMPLE 12

2-chloro-3-phenoxy-6-nitro-N- (5-trifluoromethylbenzyl) -aniline

3.41 g of 2-chloro-4-nitro-1,5-diphenoxybenzene are stirred in 5 Eyl dioxane with 4 g of 5-trifluoromethylbenzylamine for 12 hours at 100 ° G. - After evaporation, it is taken up in chloroform, shaken with 2 n sodium hydroxide and 2 n hydrochloric acid and the organic phase are dried over sodium sulfate. Distillation of the solvent gave the title compound as a dense liquid yellow oil (4.0 g ^ 95% of theory).

Analysis: C H N calc .: 56,8% 3,32 6.64% found: 56,5% 3.57% 6.47%

EXAMPLE 15

4-Chloro-5-phenoxy-6-nitro-H- (5-trifluoromethylbenzyl) -aniline _z Analogous to Example 12, 5.41 g of 6-chloro-4-nitro-1,5-diphenoxybenzene and 4 g of 5-trifluoromethylbenzylamine are obtained in 5 ml of dioxane (20 hours at 100 ° C) the title compound in 3 S yield (71.2% of theory), m.p. 140 to 142 ° C (from ethanol).

EXAMPLE. 14

2-chloro-5- (4 ~ cyanophenoxy) -6-nitro-R-allylaniline

A mixture of 4 g of 2-chloro-4-nitro-5-phenoxy-1- (4-cyanophenoxy) -benzene, 10 ml of dioxane and 2 g of allylamine was allowed to stand at room temperature for 50 hours. The solvent is then distilled off, the residue is taken up in chloroform, shaken with dilute sodium hydroxide, the organic phase is dried over sodium sulfate, the chloroform is distilled off and the residue is crystallized from ethanol.

Yield: 5.5 G (97.2% of theory), yellow crystals;

m.p. 85 to 87 ° C.

EXAMPLE 15

2-chloro-5-phenoxy - 6-nitro-rP, or ^1- dinethylphenylhydrazine

ci nh-n (ch,) ₉

M

O -

A mixture of 6.85 S of 2-chloro-4-nitro-1,3-diphenoxybenzene, 20 ml of dioxane and 9 g of Κ, din-dinethylhydrazine is boiled for 10 hours under Triflux. "'The solvent is distilled off, taken up in chloroform, washed with dilute sodium. brine and dried over sodium sulfate. After distillation of chloroform, dissolve the residue in diethyl ether and precipitate the hydrazine derivative i

with the introduction of hydrogen chloride. Suction off, the residue is treated with water, shaken with chloroform, the chloroform solution is dried and the solvent is distilled off.

4.5 S (73% of theory) of an orange oil was obtained.

Analysis:

calculated:

found:

54,7% 55,11%

4.55% 13.65% 4.86% 13.56%

- 22 EXAMPLE 16

2-chloro-5-phenoxy-6-nitro-ii- (6-aninohexa) x) -aniline

A mixture of 17.5 6 2-chloro-4-nitro-1,3-difenoksihenzola, ELL of dioxane and 9 6 1,6-di amino cracker ana was stirred for 4 hours at 50 'C ^O,' the solvent was distilled off and the residue was taken up in chloroform . This solution is washed with dilute sodium hydroxide and dilute hydrochloric acid, dried over sodium sulfate, distilled off with chloroform and the residue taken up in diethyl ether, precipitated with hydrogen chloride, filtered off with suction, and treated with chloroform / soda solution. The chloroform solution was separated, dried and the chloroform was distilled off. Yield: 12.5 S (69% of theory) of viscous yellow oil.

Analysis: C H N calc .: 59.3% 5.52% 11.55% found: 59,1 /, 5,3 11,72 70

The following compounds have been prepared in the following tables by the following general methods of operation:

Starting substances:

mio;

.and hydrogen

- 23 a) Volatile amine metabolism (A) is allowed to stand with 10% excess amine in dioxane for 2 to 3 days. Then it was evaporated, the residue was taken up in ether and the phenol formed was removed by shaking with 2 n sodium hydroxide solution. Shake the ether solution 2 times with water, then dry with hatrium sulfate and evaporate.

b) Metabolism with non-volatile amines (A) is heated with 100% excess ari on in dioxane for 2 to 5 hours at 80 ° C. After evaporation, the residue is taken up in ether and shaken with 2N sodium hydroxide solution. Any amine present is removed by shaking with 2 n hydrochloric acid. After washing with water, the organic phase is dried over sodium sulfate and evaporated.

TABLE I Compounds of Formula

RP value 27 ° C

Num. R ₂ Conditions Profit Acetone / heptane 1: 1 Toluene Tal. 1 CH - 2 days 100% Tal. 72 do P s.t. oil 74 ° C 2 ^C 2 ^H 5 " 5 days 85.5% 0.51 0.46 (from isopro pill alcohol - s.t. oil 5 n-CjB, - 2 hours 97.5% 0.615 0.47 80 ° C oil 4 1 ** C 6 hours 94% 0.61 0.45 80 ° C oil 5 nC ₄ H ₉ - 2 hours 92% 0.625 0.50 80 ° C oil 6 i-C ^ H ^ 5 hours 96.5 0.60 0.51 80 ° C oil 7 HO-CHp-CHp- 2 hours 94% O, 4A5 0.01 80 ° C oil 8 -CHCCpHPp 5 hours 95 / ^j 0.47 ** 80 ° C no 9 -CH ₂ -C ^ CH 5 hours 91 P 0.51 30 ° C oil S · t. = room t emperature

all = toluene / cyclohexane 1: 1

- 25 TABLE II

Compounds of Formula

RP-values 27 ° C

Num. R ₂ Conditions Profit Acetone / heptane 1: 1 Toluol Tal. 1 CH _Z - 2 2 days s.t. 64% 71 to 72 ° C (from isopro- pilalkohol) 2 CH ₂ = CH-CH ₂ - 2 days s.t. 98.5% 0.52 0.51 5 -CHCCgH ^ g 3 days s.t. 74% From 2,4-Dichloro-6- -no tr o-1,3- -dif enox. of ibenzene we get in the table

III said compounds of general formula

C.

- 26 TABLE ·! III

Num . R ₂ Amine / reaction conditions Profit Properties / floors. 1 CH _Z im ₂ CH./24 m? at s? t. in dioxane 74% theory. red crystals, m.p. 101 ° C 2 ^θ Λ ΝΗ ^^ / Ιδ hours in dimethylsulfoxide 85% of theor. light brown oil, thin film coated with graphical uniformity 3 ^{and C} 3 ^H 7 NI ^ -i-C ^ Hr? / 16 hours at s.t. in dioxane 88% theor. orange soil crystals. 83 ° C 4 nC ₄ H ₉ EH ₂ -NC ₄ H _9/2 days at rt in dioxane 92% of theor. orange oil thin layer chromatographic uniform 5 ⁿ ” ^G 12 ^E 25 KH _{2-NC 12} H _25/5 days at rt in dioxane, cleaning: chromatographic 58 theor. orange soil crystals. 43 ° C 6 ^{n C} 18 ^H 57 NH ^ n-CzjgH ^ r, / 5 days at s.t. in dioxane, purification: chronatographic 51 theor. 47 to 48 ° C 7 -CH ₂ -CH ₂ -OH kh ₂ ch ₂ ch ₂ oh / <4 days at st in dioxane 100% theor. dark oil Oh -c: i (c ₂ h ₅ ) ₂ 12i ₂ CH (C ₂ H _{5) 2/3} of days at rt in dioxane Ό i t e o r.

TABLE IV

- 2? From 1,3-Lifenoxybenzenes of the formula

in which Itj has the meaning given below, the following compounds of formula are prepared

° C

RF values 27

Num. 4 R ^ a Conditions Profit teor.J Acetone / • heptane 1: 1 Toluene 1 CH, P CH, P 2 days s.t. 96 f 0.61 0.45 2 CH, P ch ₉ = ch ^ά I CH ₂ - 8 hours _ 60 ° C 94 f 0,6p 0,515 th most common F g ₉ h _with t—. s 7, QT-t-> S.t. 35 d h H- OCH, P V Ji- P 2 days s.t. r- '> About z '/' r ~ P OCH, P ⁿ ~ ^C 4? 5 hours 80 ^c C 95 - 0.59 0, a>

Tal.

° C (with and alcohol alcohol 100 to

101 ° C in-- ¹ ω

Indication of the best known applicant for the economic exploitation of the claimed invention

Dissolve 68.5 g of 2-chloro-4-nitro-1,5-diphenoxybenzene in 500 ml of toluene and add 100 ml of conc. of aqueous ammonia. The pressure is then adjusted to 5 bar with gaseous ammonia. The mixture was then heated to 120 ° C for 12 hours, increasing the pressure to about 15 bar. After cooling, the organic phase is separated, shaken with dilute sodium hydroxide solution, dried and the solvent distilled off. The reaction product was obtained in almost quantitative yield (54 g). · After gas chromatography, the product contained 98% of the title compound. Tal. 81 to 82 ° C.

For

CELAMERCK GMBH & CO., LTD. KG i — iuslana i

Process for the preparation of diphenyl ethers 3 general formula

Claims (2)

in which n is an integer from 1 to 3 » R _{1 is} hydrogen, Cl, Br, F, alkyl of 1 to 8 carbon atoms, trifluororaethyl, acetyl, cyano, methoxy, methylthio, R _{2 is} hydrogen, alkyl of 1 to 18 carbon atoms, allyl or alkynyl of up to 3 carbon atoms; an alkyl residue of 2 to 6 carbon atoms substituted by hydroxy, -C 1 -alkoxy, phenoxy, halogenphenoxy, C ₁ -C ₂ -alkylphenoxy, C ₁ -C ₂ -alkoxy-phenoxy, nitrophenoxy, cyanophenoxy, amino or C ₁ - C ₂ ~ alkylthio; optionally halogen substituted benzyl, trifluoromethylbenzyl, NR ^ R ^, CHRg-COOR ^ or CHRg-CONR ^ Rg, wherein Rg, Rjj and Rg, which may be the same or different, are hydrogen or C1-6alkyl radicals , and X ^ and X ₂ , which may be the same or different, are hydrogen or Cl or Br, characterized in that nitrodiphenoxybenzene of the general formula (II) in which n has a group Rp R _2> X ₁ and X _{2 have the} above meaning and R 'stands in which R ^ and n have the above meaning, reacted with an amine of the general formula hnhr ₂ (III) in which R _{2 has the} above meaning, in an inert organic solvent at temperatures between about 20 ° C and 16O ° C and pressures from 3 to 13 bar. Process according to claim 1, characterized in that an inert organic solvent such as dioxane, tetrahydrofuran, toluene, or water is used as the reaction medium. For CELAMERCK GMBH & CO., LTD. KG: PATENT OFFICE LJUBLJANA 17249-111-87 / KA SUMMARY A process for the preparation of diphenyl ethers of the general formula is described wherein n, R ₂ , X ₁ and X ₂ have the meanings given in the claim. Compounds of the general formula I are obtained by nitrodiphenoxybenzene of the general formula (M 1'n in which n, R 1, R ₂ , X ₁ and X _{2 have the} above meaning and R 'stands for the optionally substituted phenyl residue, metabolised at temperatures from about 20 ° C to 160 ° C with an amine of the general formula HNHR ₂ (III). The compounds of general formula I are distinguished by their excellent herbicidal effect.