CS215132B2 - Method of making the o-halogenalkyl-2-halogenacetanlilide derivatives - Google Patents

Description

The invention relates to a process for the preparation of novel o- (haloalkyl) -2-haloacetanilide derivatives which are useful as selective herbicides and as intermediates for the production of certain o-alkoxymethyl-2-haloacetanilides which also have selective herbicidal activity.

U.S. Patent No. 4,070,389 discloses the use of certain chloroacetanilides, including certain N-substituted 2 ', 6'-haloalkyl-2-chloroacetanilides, as ¹² herbicides. However, the patent does not disclose how to prepare or use the above compounds. There are references to NSR Publication Nos. 2,212,268, 2,305,495, 2,328,340, 2,402,983,

405 183 a, 2 405 · 479. As can be seen, none of the above references disclose N-substituted 2 ', 6'-haloalkyl-2-chloroacetanilides. The only reference which marginally suggests the above compounds is NSR Laid-Open No. 2,410,547, which corresponds to British Patent No. 1,455,474.

British Patent No. 1,455,474 describes the use of N-2-methoxyethyl- or N-2-ethoxyethyl-2'-trifluoromethyl-6'-alkyl-2-chloroacetate as herbicides (an example of this type of acetanilide is U.S. Patent No. 4 152 137). British Patent No. 1,455,474 does not refer to the compounds of the present invention, i.e., ·-methyl-, N-bromoethyl, or

N- (chloromethyl) -o- (haloalkyl) -2-haloacetanilides.

With regard to the process for the preparation of the compounds according to said British patent specification, the substituents on the phenyl ring of the compounds must be introduced on the ring before the reaction on the amino group occurs. That is, the appropriately substituted aniline compounds are processed to the desired hatagenacetanilides.

The literature further describes bromination of o-methylacetanilide with N-bromosuccinimide (NBSj (EG Kleinschmidt et al. Pharmazie 24 (2), 87 (1969)), which occurs exclusively on the phenyl ring, i.e. only bromination at the ring nucleus occurs. is substituted with an alkyl group at the o-position.

Ulrich et al. J. Org. Chem. 39 (19), 2897 (1974J) disclose the preparation of N- (chloromethyl) -N-phenylcarbamoyl chloride by monochlorating N-methyl-N-phenylcarbamoyl chloride in the presence of ultraviolet light.

However, none of the above references disclose reactions that relate to the process of the invention.

However, none of these references disclose reactions relating to the process of the invention.

The subject of the invention is a method of manufacturing o215132

- haloalkyl-2-haloacetanilide derivatives of the general formula I,

O

II

wherein X is a chlorine or bromine atom,

R is hydrogen, methyl, chloromethyl or bromomethyl,

R 1 is hydrogen, chlorine, C 1-6 alkyl, chloromethyl, bromomethyl, bromoethyl or trifluoromethyl,

R2 is hydrogen, methyl, bromomethyl, bromoethyl, chloromethyl or dichloromethyl,

Y 1 is hydrogen or chlorine, or bromine methyl.

The process according to the invention is characterized in that the derivative of the general formula II,

O

H

C-CH.X

Z ΑR

N

wherein X and R are as defined above,

R "represents a hydrogen or chlorine atom, C 1-4 alkyl or trifluoromethyl,

R "‘ hydrogen, methyl, ethyl or bromoethyl,

Y‘ is hydrogen or chlorine or methyl reacts with a halogenating agent in the presence of a solvent which is inert to the halogenation under irradiation with a source of ultraviolet and / or white light.

According to the above reaction scheme, the corresponding starting material, i.e. the compound of formula II, is dissolved in a suitable volume of solvent inert to the halogenation. Examples of such suitable solvents are: carbon tetrachloride, chloroform, petroleum ether, methylene chloride and the like. The preferred solvent for use herein is carbon tetrachloride. At this point, a catalyst such as benzoyl peroxide may be added to the mixture to facilitate processing. The above catalyst may be used but is not required. To the mixture is added a stoichiometric amount of a halogenating agent selected from the group consisting of molecular chlorine, molecular bromine,

N-bromosuccinimide (NBSJ or other N-bromoquivalonts, for example N-bromo-N-methylacetamide or N-bromophthalimide. It will be appreciated that more halogenating reagent than stoichiometric equivalent may be used in this method. The reactants are usually mixed at room temperature, i.e. at about 25 ° C, and then kept at the boiling point of the reaction mixture. however, even lower temperatures are used, as illustrated in the following examples.

The resulting reaction product is separated from the reaction mixture by conventional means. For example, unreacted halogenating agent and succinimide are removed by filtration while the solvent is stripped or distilled off, preferably distilled off under vacuum at low temperature. The product is usually purified by crystallization from suitable solvents.

The starting compounds, i.e. the compounds of formula II, are known to those skilled in the art, for example from U.S. Patents 3,442,945, 3,637,847, 3,966,811, and Sharp Patent 1,445,474.

In the above-described process, chlorination or bromination of o-alkyl-2-haloacetanilides, as opposed to o-alkoxy-2-haloacetanilides, results in halogenation of the phenyl ring, i.e., halogenation of the core. When halogenation is carried out with molecular chlorine using 2 ', 6'-dimethyl-N-methyl-2-chloroacetanilide as the starting material, both methyl groups [N-methyl and ring-methyl (benzyl')] are chlorinated at comparable rates . When the o-alkyl-2-chloroacetanilides described herein are brominated, this process proceeds more slowly and more selectively than chlorination. Thus, optimal results are obtained when molecular amine (dissolved in carbon tetrachloride) is added dropwise to a solution of the amide containing about 0.1% benzoyl peroxide, heated to reflux and illuminated (UF and / or white light). Generally, when 2-halo-N-methyl-2 ', 6'-dialkylacetanilides are brominated, only carbon atoms (benzylic on the phenyl ring chain) are brominated.

The bromination of the 2-chloroacetanilides of the formula II with molecular bromine (Brz) leads, to varying degrees, to the internal exchange of halogens with the partial formation of 2-bromoacetanilides. Secondary and tertiary anilides are sensitive to these internal changes when prepared in larger quantities at higher bromine and amide concentrations. The bromine at position 2 is derived from an internal replacement of chlorine with hydrogen bromide to form hydrogen chloride. The interchange of halogens can be reduced by bubbling nitrogen, which helps to remove hydrogen bromide (HBr).

To avoid confusion of halogen atoms, but still to take advantage of bromination, N-bromosu215132 cinimld (NBS) or a similar N-briomokvivalen, such as N-bromo-N-methylacetamide or N-bromophthalimide, or benzoyl peroxide are used as reagents . Only an equimolar amount of this suitably prepared material is necessary to exclusively accumulate into the side benzyl chain, with succinimide being formed as a by-product.

Molecular bromine or NBS brominates exclusively the o-methyl group in the presence of the o-tert-butyl group. Conversely, chlorine is not so selective, partial chlorination of the tert-butyl residue occurs.

The following examples illustrate in more detail the process for preparing the compounds of the invention. Example 1

Preparation of 2 ‘, 6‘-bis (1-bromoethyl) -2-bromo-N-methylacetanilide

To 2-chloro-N-methyl-2 ', 6'-diethylac & tanilide (23.9 g, 0.1 mol) in 300 mL of carbon tetrachloride was added 0.2 benzoyl peroxide. After heating to boiling, bromine (16/0 g, 0.02 mol) in 50 ml of carbon tetrachloride was added dropwise to the reaction mixture. The mixture is irradiated with both internal (submerged) ultraviolet and external white light. The solvent was distilled off in vacuo. The crude product was dissolved in ethyl acetate. The solid product is recrystallized repeatedly from ethyl acetate. 2 ', 6'-Bis- (1-bromoethyl) -2-bromo-N-methylacetanilide, m.p. 162-164 ° C, is produced.

Analysis - calculated for ΟηΗΐβΒηΝΟ:

C 35.32, Br 54.24, N 3.17, found:

C, 35.18; Br, 54.29; N, 3.16. Example 2

Production of 2 '- (bromomethyl) -6`-tert-butyl-2-bromo-N-methylacetanilide

To 38.0 g (0.15 mol) of 2-chloro-N, 2 ' -dimethyl-6 ' -t-butylacetanilide in carbon tetrachloride was added 0.2 g of benzoyl peroxide. The mixture is heated to reflux. To the above mixture was added dropwise bromine (24.0 g, 0.15 mol) in 50 mL of carbon tetrachloride. After addition (1 1/2 hour) and further reflux (1/2 hour) the solvent was distilled off. The residue solidifies by scratching. The product is recrystallized from heptane. 2 '- (Bromomethyl) -6'-tert-butyl-2-bromo-N-methylacetanilide, m.p. 86-87 ° C, yield 65%.

Analysis calculated for CuHuiBrzNO:

C, 44.59; Br, 42.38; N, 3.71.

S found:

C, 44.62; Br, 42.27; N, 3.72%.

Example 3

Preparation of 2-chloro-N, 2 ', 6-tris (bromomethyl) acetanilide

A mixture of 2-chloro-N- (chloromethyl) -2 ', 6'-dimethylacetanilide (0.04 mol, 10 g) in 100 ml of carbon tetrachloride and 0.14 g of benzoyl peroxide was heated to reflux with internal (submerged) irradiation. To this mixture was added bromine (13 grams) in 50 ml of carbon tetrachloride. After the addition of the theoretical amount of bromine, an additional 3.0 g of bromine was added. After cooling, the solvent was removed and the resulting viscous oil was treated with ether to give a solid which was crude according to the NMR spectrum of 2-chloro-N-2 ', 6'-tris (bromomethyl jacetanilide). but treated with 200 ml of boiling methanol to give 2 ', 6'-bis (bromomethyl) -2-chloro-N- (methoxymethyl) acetanilide, m.p.

127.5-129 ° C.

Example 4

Production of 2'- (bromomethyl) -2-chloro-6'-tert-butylacetanilide

A mixture of 2'-chloro-2'-methyl-6'-tert-butylaeetanilide (5.6 g, 0.025 mol) in about 120 mL of carbon tetrachloride was heated to reflux with 0.15 g of beinzoyl peroxide. A solution of broim (4.0 ^L , 0.025 mol) in 50 mL of carbon tetrachloride is added dropwise, after addition, the reaction is complete by NMR spectrum. 1- (bromomethyl) -2-acetol-6'-tert-butylaicetanilide, melting at 142-147 ° C, yield 88%.

Analysis for C 18 H 25 BrClNO calculated:

49.00% C, 25.08% Br, 11.13% Cl;

found:

% C, 47.93;% Br, 4.50%; Example 5

Production of 2-chloro-N, 2 ‘, 6‘-tris (chloromethyl) acetic or folk

A solution of 2-chloro-N, 2 ', 6 ' -trimethylacetanilide (21.1 g, 0.1 mol) in 260 ml of carbon tetrachloride is placed together with a UF source (22A) in a 500 ml flask. With stirring, chlorine (0.1 mol, 7.0 g) was passed under the surface of the re215132 action mixture. The reaction is slightly exothermic with temperature changes ranging from 20 to 40 ° C. After addition of all of the chlorine, a substantially colorless solution is obtained. The mixture is cooled to about 5 ° C, 0.1 mol of chlorine is added, and finally a third molar equivalent of chlorine is added. The reaction mixture was allowed to stand for about 48 hours. Removal of the solvent gave a viscous oil. A portion of this oil was recrystallized from pentane / petroleum ether. Crystals of 2-chloro-N, 2 ', 6'-tris- (chloromethyl) acetanilide, mp 70-75 ° C, were prepared. This crude product is not further purified, but is treated directly with boiling methamol. 2-Chloro-N- (methylmethyl) -2 ', 6'-bis- (chloromethyl) acetainide is prepared and the compound of Example 5 can also be prepared by using 2-chloro-N- (chloromethyl) -2 ', ^6'-dimethyl! thylacetanilid.

Example 6

Preparation of 2'- (bromomethyl) ^-6'-te! tert -Butyl-2-chloro-N- (chloromethyl) acetanilide

To a solution of 17.3 g (0.06 mol) of 2-chloro-N-chloromethyl-2'- (methyl) -6'- (tert-butyl) acetanilide in 250 ml of carbon tetrachloride was added. 11.2 g (0.053 mol) of recrystallized N-bromosuccinimide (NBS) and 0.25 g of benzoyl peroxide are added. The resulting mixture was heated to reflux in a 500 ml three-necked flask under irradiation by immersion in UF light and external white light. According to NMR spectroscopy, processing is complete in about 0.5 hours. After standing at room temperature for about 48 hours, 2.2 g of product, 2'- (bromomethyl) -6 '-, tert-butyl-2-chloro-N- (chloromethyl) acetanilide, mp 124-125 ° C, were prepared ^. C. Further product was isolated by partial evaporation of the solvent (7.9 g). The product was not further purified but treated with methanol to give 2 '- (bromomethyl) -2-chloro-N- (methoxymethyl) acetanilide.

Example 7

Preparation of 2 ‘- (bro.methyl) -6‘-tert-butyl-2-chloro-N-methylcetane 11 d u

A solution of 2-chloro-6'-tert-butyl'-N, 2'-dimethylacetamilide (17.5 g, 0.069 mol) in 250 ml of tetrtachloromethane together with 0.2 g of benzioylperoxide and 13 g (0.072 mol) of recrystallized NBS is irradiated in a flask as described in Example 6. Processing is complete in about 1/2 hour. Succinimide floats on the surface of a tetraichloirmethian solution. The material was filtered. The filtrate was washed with water. The solvent was removed in vacuo. 24.9 g of residue are obtained. The residue was recrystallized from hexane. 14.8 g of product are produced, a second recrystallization from hexane gives 2 ‘- (bromomethyl) -6-tert-butyl-2-chloro-N-methyl-lacephanilide, m.p. Mp 112-114 ° C. Yield 63%.

Analysis for CuHisBrClNO calculated ·:

50.54% C, 2.4.62% Br, 10.66% Cl; found:

C 50.33%, Br 24.63, 10.61% 01. Example 8

Preparation of 2‘- (chloromethyl) -6‘-methyl-2-chloroeetanilide

2 ', 6'-Dimethyl-1,2-chloroacetanilide is chlorinated as described in Example 5. A white solid is identified which is identified as 2' - (chloromethyl) -6'-methyl-2-chloroacetanilide, 1.1. 133-134 ° C.

Analysis for C 10 H 11 Cl 2 NO calculated:

C, 50.54; Br, 24.02; Cl, 10.66; found:

C, 50.33; Br, 24.63; Cl, 10.61. Example 8

Preparation of 2‘- (chloromethyl) -6‘-ethyl-2-chloroacetanilide

2?, 6? -Dimethyl-2-chloroacetanilide was chlorinated as described in Example 5. A white solid was identified which was identified as 2? - (chloromethyl) -6-methyl-2-chloroacetanilide, m.p. 133-134 ° C.

Analysis for C10H11Cl2NO calculated:

% C, 51.74;% H, 4.77;% N / 6.03;

found:

% C, 51.69;% H, 4.66;% N, 6.03.

Example 9

Preparation of 2 ‘, 6‘-bis- (bromomethyl) -2-chloro-N- (chloromethyl) acetanilide

To a solution of 2-chloro-N- (chloromethyl) -2,6,6-dimethylacetanilide (10.0 g, 0.04 mole) in 10 mL of TeCH3 was added 0.14 g of benzoyl peroxide. The reaction mixture is heated to reflux and the flask is irradiated with internal submerged UF light and external white light. A solution of 13.0 g of molecular bromine in 50.0 ml of carbon tetrachloride was added dropwise. When the NiMR spectrum indicates that the processing is nearly complete, additional 3.0 g of bromine are added. The mixture was cooled and the solvent was distilled off in vacuo. The resulting viscous oil is treated with ether. A solid was obtained which was identified as · 2 ‘, 6'-bis- (bromomethyl) -2215132

The product is not further purified but treated with boiling methanool to produce 2 ‘, 6‘-bis- (bromomethyl, hlyl-2-N- (meithoxymethyl) acetanilide).

Example 1.0

Preparation of 2‘- (dibromomethyl) -6‘-tert-butyl-2'-chloroacetanilide

To a solution of 0.3 g of benzoyl peroxide in 300 ml of tetrachlarmethane, the compound of Example 4 (9.54 g, 0.03 mol) was added, two white lights were used to irradiate the reaction vessel, and 4.8 g of bromine were added to the irradiated reaction mixture. in 50 ml of carbon tetrachloride (dropwise) with a gentle stream of nitrogen bubbling in. After 1 1/2 hour, remove the radiation source, allow the mixture to stand and cool overnight. The precipitated solid is filtered off. 4 g po'díl second 1.4 g. the solid was recrystallized from isopropylalkobolu. Prepared 2 ^{<- (i} diibrommef hyl j-6'-tert-butyl-2-ohloraceitanilid, mp 145-147 ° C, yield 99%.

Analysis for C 13 H 16 Br 2 Cl.NO calculated:

% C, 39.28;% H, 4.06;% N, 3.52;

found:

% C, 38.99;% H, 4.10;% 3.58

Production of 2‘- (bromomethyl) -2,6‘-dichloroacetililide

To 3.00 ml of carbon tetrachloride in a 50 ml flask was added 15.0 g of 2,6'-dichloro-2'-methylacetainilide (0.068 moles and 0.5 g of benzoyl peroxide. The reaction mixture was irradiated with two external white lights. Then 10.9 grams of bromine in 50 ml of carbon tetrachloride are added dropwise, nitrogen is bubbled into the reaction dropwise, and if NMR spectroscopy shows that the work-up is incomplete, further

2.5 g of bromine. The solvent was distilled off in vacuo. The crude product is recrystallized from isopropyl alcohol and then sublimed under vacuum (at 6.7 Paj) to give 2 ‘- (bromomethyl) -2,6‘-dichloroethanilide, mp H 15-159 ° C, yield 58%.

Analysis calculated for: C 9 H 8 BrCl 2 NO:

C, 36.40; H, 2.72; N, 4.72; found:

H, 2.72; N, 4.80. Example 1.2

Preparation of 2‘- (bromoethyl) -2,3‘-dichloro-6‘-tert-butylacetanilide

Dissolve 2,3‘-dichloro-2‘-methyl-6‘-tert-butylacetanilide (15.0 g, 0.055 mol) in 600 mL of THF in a 1 L flask. The reaction mixture was irradiated with two white lights (located outside the reaction vessel). The reaction mixture is heated to (boiling point. A solution of 8.8 g of molecular bromine in 50 ml of carbon tetrachloride is added dropwise. The excess solvent is removed in vacuo. The solid product is recrystallized twice to give 2 '- (bromomethyl) -2,3. Dichloro-6'-tert-butylacetanilide, mp 182-184 ° C, yield 65%.

Analysis calculated for C CHHieBBrClkNO:

C, 44.22; H, 4.57; N, 3.97; found:

44, C9% C, 4.62% H, 3.96% N.

Example 13

Preparation of 2 ‘, 3‘-bie- (bromomethyl) -2-chloro-6‘-tert-butylacetanilide

Dissolve 15 g (0,059 mol) of 2-chloro-2 ‘, 3‘-dimethyl-6‘-tert-butylacetanilde in 600 ml of carbon tetrachloride in a 1-liter flask. The mixture is irradiated with two white light reflectors. The reaction mixture was heated to reflux, purged with nitrogen, and then 9.44 g (0.059 elemental bromine in 50 ml of carbon tetrachloride) was added dropwise, after the addition of a second molar equivalent of molecular bromine and after about 48 hours the reaction mixture was filtered. The solid was recrystallized from isopropanol to give 2 ', 3'-bis- (bromomethyl) -2-chloro-O-tert-butyiacetlanilide, mp 180-182 degrees Celsius (mp 195-197 ° C after vacuum sublimation) ).

Analysis for C 11 H 16 BrClClNO calculated:

H, 4.41; N, 3.40. found:

H, 4.37; N, 3.40.

Example 14

Production of 2‘- (bucmmethyl) -2-chloroacetanilide

Dissolve 2-chloro-2'-methylacetanilide (4.0 g, 0.02 mol) and N-bromosuccinimide (3 mL) in carbon tetrachloride (300 mL) with 0.3 g 2,2'azo-bis-2-methylprapionitrile. 9 g, 0.02 mol). The mixture is irradiated with a theatrical reflector and heated to reflux for 2 1/2 hours. After this time, the mixture was cooled to room temperature, filtered, washed with 1 X water, dried over magnesium sulfate, filtered again and the solvent was stripped off. The white solid was recrystallized from toluene. 2.2 g of product are obtained, 2 ‘- (bromomethyl) -2-chloroacetylinilide, m.p. 125-127 ° C, yield 38%.

Analysis calculated for C9H9BrClNO:

41.17% C, 3.46% H, 5.34% N; found:

H, 3.40; N, 5.30.

Example 15

Production of 2‘- (bromomethyl) -6‘- (trifluoromethyl) -2-chloroacetate

To 12.5 g (0.05 mol) of 2'-meithyl-6 '- (trifluoromethyl, thyl) -2-chloro (raceil) anilide in a one-liter flask was added 300 ml of carbon tetrachloride and 10.0 g (0.056 mol) of recrystalline N The mixture is maintained at room temperature for about 1 to 1 1/2 hours, then at 70 to 75 ° C for about 4 to 5 hours The crude product is isolated as a solid (blister) in an amount of 17.7 g. Recrystallization from isopropyl alcohol gave 9.8 g of the product, 2 '- (trimethyl) -6' - (trifluoromethyl) -2-chloroacetanilide, mp 98-101 ° C, yield 59.4 θ / ο.

Analysis for C 10 H 9 ClBrF 5 O calculated:

36.34% C, 2.44 θ / ο H, 4.24 θ / ο N; found:

C, 35.94; H, 2.27; N, 4.19.

Example 16

Preparation of 2-chloro-N-chloromethylacetanilide

200.0 ml of carbon tetrachloride solution with 0.1 mol of 2-chloro-N-methylacetanilide are placed in a suitable flask with a stirrer, a gas inlet tube, a thermometer and an internal low pressure UF light. A molar equivalent of chlorine gas was slowly introduced into the flask at room temperature. The solution is then irradiated. After a short induction period, the temperature of the solution was raised to 38 ° C due to the exothermic reaction. According to NMR spectroscopy of the tetrachloromethane solution, the treatment is complete after a 10% excess of chlorine has been introduced into the solution. Working up under vacuum removes gases and solvent. It is produced in 98% yield of 2-chloir-N- (chloro, methyl jacetanilide) which is heat-sensitive (oil) with the following NMR spectrum:

(CDCl 3), δ 3.9 (s, 2 H, C 1 H 2 CO), δ 5.55 (s, 2 H, Cl 2 CH 2, N), δ 7.6 (broad s, 5 H, ArH).

Example 17

Preparation 2 ⁱ -chliormet'hyl-6'-trifluoromethyl-2-chlorination tanilidu

In a one-liter flask equipped with a stirrer, a thermometer and a bubbling tube, 10.0 g of 2‘-methyl-6‘-trifluoromethyl-2-chloroethylenilide and 206 ml of carbon tetrachloride are added, followed by heating to 56-60 ° C. It illuminates with two external white light sources. The reaction mixture is heated to boiling, i.

to 84 ° C, and 2.7 g of molecular chlorine gas in a slow stream are added to the mixture. Then another batch of molecular chlorine is added again to achieve a total batch of added molecular chlorine of 7.0 grams. The excess solvent was removed under reduced pressure to give the crude product in a yield of 12.1 g, identified as 2‘-chloromethyl-6‘-itrifluoromethyl-2-chloroacetamilide. The solid product is recrystallized from methylcyclohexane, m.p. 95-96 ° C.

Analysis for C 10 H 15 Cl 2 F 3 NO calculated:

H, 2.82; N, 4.90. found:

42.33% C, 2.79 θ / ο H, 4.90 θ / ο N.

Example 18

Preparation of 2Umethyl-6‘-trifluoromethyl-N-chloromethyl-2-chloroacotanilide

Into a suitable flask equipped with a stirrer, a gas inlet pipe, a thermometer and an interior low pressure source · ultraviolet radiation can be 300 ml carbon tetrachloride solution containing 0.02 mol of 2'-Me: methyl-6 ^{<-trifluormiethyl-N-methyl-} 2-chloroacetates of the people. The molar equivalent of chlorine gas at room temperature is then slowly introduced into the flask. The solution is then irradiated and after a short induction period the temperature rises to ^{C &lt; 0 &gt;} C. Once the chlorination is complete, gases and solvent are distilled off from the cooled mixture. The mixture contains approximately 33% of 2'-methyl-6'-trifluoromethyl-N-chloroethyl-2-chloro-racetanilide which, after purification, forms an oil which can be distilled in a bead cooler at 115-120 ° C (6.666 Pa).

Analysis calculated for C11H10Cl2F3NO:

% C, 44.02;% H, 3.36;% N, 4.67; found ·:

44.82% C, 3.43% H, 4.74% N.

The compounds of the invention have been found to have herbicidal activity and are also useful as intermediates for the production of o215132

- (alkoxymethyl) -2-halogen, nucetanillides, which are effective herbicides. The process for producing the latter compounds is characterized in that the above-described compounds of the formula I are treated with an alcohol, preferably in the presence of heavy metal cations such as potassium, sodium, silver, lead, mercury, etc., or Other Lewis acids, such as aluminum chloride, tin (II) chloride, zinc chloride, etc. With the use of the novel compounds of formula (I), it has been found that a halogen atom of o-haloalkyl groups, especially It could also be selectively replaced with the corresponding alcohol without attacking the otherwise labile 2-acetyl halogen atom.

Although the present invention is described with respect to specific modifications, its details are not to be construed as limiting, since it is understood that various equivalents, changes, and modifications may exist without departing from the spirit and scope of the invention. It is to be understood that such equivalent arrangements are included in the present invention.

Claims (13)

SUBJECT Process for the preparation of o-haloalkyl-2-haloacetanilide derivatives of the general formula I, O in which means X is chlorine or bromine, R is hydrogen or methyl, chloromethyl or bromomethyl, R 1 is hydrogen or chlorine, or a C 1-4 alkyl, chloro-methyl, bromomethyl, bromoethyl or trifluoromethyl group, R2 is a hydrogen atom or a methyl, bromomethyl, bromoethyl, chloromethyl or dichloromethyl group and Y 1 is a hydrogen or chlorine atom or a bromomethyl group, characterized in that the derivative of the general formula II O n wherein X and R are as defined above, R "represents a hydrogen or chlorine atom, or a C 1-4 alkyl or trifluoromethyl group, R “‘ is hydrogen, or methyl, ethyl or bromomethyl; and OF THE INVENTION Y is hydrogen or chlorine, or ^one methyl group, is reacted with a halogenating agent in the, presence of a solvent which is inert to the halogenation, for • radiation source of ultraviolet and / or white light. 2. A process according to claim 1, wherein the solvent is tetrachloride of ethane. 3. A process according to claim 2 wherein the halogenating agent is a molecular chlorine. 4. A process according to claim 2, wherein the halogenating agent is molecular bromine. 5. The method of claim 2, wherein N-bromosuccinimide is used as the balogenic agent. 6. A process according to claim 1, wherein R @ 1 is chlorine or methyl tert-butyl or trifluoromethyl, and R, R @ ', X and Y &apos; 1. 7. A process according to claim 6, wherein Y is hydrogen and R, R &apos;, R &apos; and X are as defined in item 1. 8. A process according to claim 6, wherein Y is a chlorine atom and R, R &apos;, R &apos; and X are as defined in item 1. 9. A process according to claim 1, wherein the compound of formula (II) wherein R &quot; is ethyl and R, R &apos;, X and Y &apos; are as defined in item 1. 10. The process of claim 1 wherein the reaction is carried out at the boiling point of the reaction mixture. 11. A process according to claim 1, wherein R &apos; and Y &apos; are each hydrogen atoms and R, R &apos; and X are as defined in item 1. 12. A process according to claim 1, wherein R @ 1 is chlorine, Y @ 1 is hydrogen and R @ 1, R @ 1 and X are as defined in point 1. 13. The process of claim 1 wherein the compound of formula (II) wherein R &lt; 1 &gt; is trifluoroethyl, Y &apos; is hydrogen, and R, R &apos; and X are as defined in item 1. Severography, n. P., Plant 7 Most Price 2,40 Kčs