NL8001736A - ORTHO-HALOGENALKYL-2-HALOGENENACETANILIDE DERIVATIVES AND METHOD FOR THE PREPARATION THEREOF. - Google Patents

Description

Ortho-haloalkyl-2-haloacetanilide derivatives and process for their preparation.

The invention relates to new ortho- (haloalkyl) -2-haloacetanilide derivatives and to a process for their preparation. The new compounds are useful as intermediates in the preparation of certain ortho (alkoxy-5 methyl) -2-haloacetanilide derivatives, which exhibit selective herbicidal activity.

U.S. Pat. No. 4,070,389 generally describes the herbicide use of certain chloroacetanilides, including certain N-substituted 2'6 '- (ha-10-logenealkyl) -2-chloroacetanilides. However, U.S. Pat. No. 4,070,389 does not disclose the preparation or use of the above compounds, but refers to certain German Offenlegungsschrift, namely German Offenlegungsschrift 2,212,268, 2,305,495, 2,328,340, 2,402 for the preparation and use thereof. 983, 2,405,183, and 2,405,479. None of the above references discloses N-substituted 2'6T- (halo-alkyl-O-2-chloroacetanilides. The only literature vaguely suggesting these compounds is German Offenlegungs 2,405,479, which corresponds to British Patent 20 1,455,474.

British Patent 1,455,474 generally describes the herbicide use of N- (2-methoxyethyl) - or N- (2-ethoxyethyl) -2, - (trifluoromethyl) -6, -alkyl-2-chloroacetanilides ( this type of acetanilide has also been described in, for example, U.S. Patent 4,152,137). In the

British patent 1,455,474 does not mention the 800 1 7 3 «t -, νί 2 compounds of the type according to the present invention, i.e. N-methyl-, N- (bromomethyl) or N- (chloromethyl) -ortho (haloalkyl) -2-haloacetanilides.

With regard to the process for preparing the compounds of the above-mentioned British Patent, it is noted that the phenyl ring substituents of the compounds mentioned in this British Patent must be introduced into the ring before the reactions to the amino group are carried out. That is, suitably substituted aniline materials are reacted to obtain the desired haloacetal anilides. In said British patent specification the new process according to the present invention, i.e. the selective halogenation of ortho-ring substituents and / or the N-alkyl substituent group of 2-haloacetanilides, is not disclosed.

The known literature describes the bromination of ortho-methylacetanilide using N-bromo-succinimide (NBS) (E.G. Kleinschmidt, et al. Pharmazie, 2A (2), 87-94 (1969)). However, in contrast to the new method of the present invention, the bromination according to the above literature occurs completely on the phenyl ring, ie only one core bromination is observed when the ring is substituted by ortho-alkyl.

Ulrich et al., J. Organ. Chem. 39 (19), 2897-2899 (1974), describes the preparation of N- (chloromethyl) -N-phenyl-25 carbamoyl chloride by monochlorination of N-methyl-N-phenylcarbamoyl chloride in the presence of ultraviolet light.

The present invention relates to certain ortho (haloalkyl) -2-haloacetanilides, which are intermediates in the preparation of certain substituted ortho-30 (alkoxymethyl) -2-haloacetanilide derivatives, which are useful as herbicides.

The compounds of the invention have the general formula 1, wherein n is 0 or 1, where, when n is 1, X represents chlorine, bromine or iodine, R represents hydrogen, methyl, chloromethyl or bromomethyl, R 1 represents hydrogen, halogen, methyl, tert-butyl, trifluoromethyl or 800 1 7 36 3 7. - 9 χ2 τ Λ -CR „1 * χι R2 represents chlorine, bromine or a straight alkyl group with 1-4 carbon atoms, Yj and Y2 independently represent hydrogen, halogen, methyl, tert-butyl, trifluoromethyl or h“ C -R9 1 * X1 10 Xj and X2 independently represent hydrogen, chlorine or bromine, where when R2 represents a straight alkyl group with 1-4 carbon atoms, only one of the groups Xj and X2 may represent hydrogen, chlorine or bromine, and wherein R2 * Xj and X2 cannot simultaneously represent chlorine or bromine, and where n is 0, 15 represents chloromethyl, Rj represents hydrogen, trifluoromethyl or halogen, Yj and Y2 independently represent hydrogen or halogen and R2 represents hydrogen. The compounds of the above general formula I, wherein η is 1, are new.

The term "straight alkyl-20 group of 1-4 carbon atoms" as used herein refers to methyl, ethyl, n-propyl and n-butyl.

The term "halogen" refers to chlorine, bromine, fluorine and iodine. Chlorine and bromine are preferred for use in the present invention.

The compounds according to the invention are prepared according to the new method, the reaction scheme of which is shown on the formula sheet.

In the compounds of the formula I, η, X, R, Rj, R2, Xj, X2, Yj and Y2 have the above indicated meanings.

In the compounds of the formula II, the symbols have the following meanings: when η is 1, R, X, Yj and Y2 have the meanings indicated above, R "represents hydrogen, halogen, 35 t-butyl, trifluoromethyl or 800 1 7 36 t ΐ 4 Η -C-R '' f Η and represents RT '' for hydrogen or a straight alkyl group with 1-4 carbon atoms.

When n is 0, R represents methyl, R "represents hydrogen, trifluoromethyl or halogen, Yj and Y2 independently represent hydrogen or halogen, and R1 * 1 represents hydrogen.

According to the reaction scheme shown, the suitable starting material, ie a compound of the formula II, is dissolved in a suitable volume of a solvent which is inert in the halogenation. Examples of suitable solvents are carbon tetrachloride, chloroform, petroleum ether, methylene chloride and the like. Carbon tetrachloride is preferably used in the process according to the invention. At this stage, a catalyst, for example benzoyl peroxide, can be added to the mixture to facilitate the reaction. However, the use of this catalyst is not necessary for carrying out the process. To this mixture is added a stoichiometrically equivalent amount of a halogenating agent selected from molecular chlorine, molecular bromine, N-bromosuccinimide (NBS) or other N-bromine equivalents, such as N-bromo-N-methyl acetamide or N-bromophthalimide. It will be appreciated that greater than stoichiometrically equivalent amounts of halogenating agent may be used in the practice of the method of the invention, yielding the same results. The resulting mixture is exposed to external and / or internal ultraviolet and / or white light and the reaction is allowed to proceed. The reactants are usually mixed at room temperature, i.e., about 25 ° C, and then kept at or near the reflux temperature. However, lower temperatures can be used as illustrated in the examples below.

The separation of the resulting reaction product from the reaction mixture is easy using 800 1 7 36

t 'J

5 usual means are accomplished. For example, unreacted halogenating agent and succinimide can be removed by filtration, while the solvent can be removed by stripping or distillation, preferably by vacuum distillation at low temperature. The product is usually purified by crystallization from suitable solvents.

The starting materials, that is to say the compounds of the formula II, are known, for example from US patents 3,442,945, 3,637,847 and 3,966,811 and British patent 1,455,474.

In the above-described process, the chlorination or bromination of ortho-alkyl-2-haloacetanilides, unlike ortho-alkoxy-2-haloacetanilides, does not result in the halogenation of the phenyl ring, ie a core halogenation. When halogenation is performed with molecular chlorine using 2'6'-dimethyl-N-methyl-2-chloroacetanilide as a starting material, both the N-methyl and the ring (benzyl) methyl groups are chlorinated at similar rates. When the ortho-alkyl-2-chloroacet-20 anilides described here are exposed to a bromination, the process is slower and more selective than the chlorination. Thus, to obtain optimal results, molecular bromine (dissolved in CCl 4) is added dropwise to a refluxed and exposed (ultraviolet and / or white light) solution of amide containing about 0.1% benzoyl peroxide. Generally, when 2-halogen-N-methyl-2'-6'-dialkyl acetanilides are brominated using B 1, only the phenyl ring (benzyl) side chain carbon atoms are brominated.

Molecular bromine (Br 2) bromination of 2-chloroacetanilides of the type represented by formula 2 gives rise to varying degrees of halo exchange with partial wring of 2-bromoacetanilides. Secondary and tertiary anilides are subject to this exchange when prepared in large amounts at higher bromine and amide concentrations. The bromine, present in the 2-position, comes from the exchange of chlorine with HBr under 8001736 f? 6 formation of HCl. Halogen exchange can be minimized by nitrogen purging to promote hydrogen bromide (HBr) removal.

In order to avoid a halogen exchange and still obtain the advantages of the bromination, the reagent preferably uses recrystallized N-bromosuccinimide (NBS) or an analogous N-bromine equivalent, for example N-bromo-N- methyl acetamide or N-bromophthalimide, optionally adding benzoyl peroxide. Purely equimolar amounts of this suitably manageable material are necessary to obtain an exclusive side-chain benzyl bromination to form succinimide as a by-product.

Molecular bromine or NBS bromine an ortho-methyl group only in the presence of an ortho t-butyl-15 group. On the other hand, chlorine is not so selective and some chlorination of the t-butyl portion occurs.

The invention is further illustrated but not limited by the following examples.

Example I

Preparation of 2'5'-bis (1-bromoethyl) -2-bromo-N-methylacetanilide.

2-Chloro-N-methyl-2 ', 6'-diethylacetanilide (23.9 g, 0.1 mol) was placed in 300 ml of carbon tetrachloride with 0.2 g of benzoyl peroxide. After refluxing, 16.0 g of bromine (0.2 mol) in 50 ml of CCl 2 were added dropwise to the mixture, which was then exposed to both internal UV and external white light. The solvent was removed in vacuo and the crude product was dissolved in ethyl acetate. The solid product was recrystallized several times from ethyl acetate to give 2, 6, 6 bis (1-bromoethyl) -2-bromo-N-30 methyl acetanilide; mp. 162-164 ° C.

Anal.

Calculated for C, -Η ,, Br_N0: C 35.32, Br 54.24, N 3.17%

Ulo J

Found: C 35.18, Br 54.29, N 3.16%.

Example II

Preparation of 2 - (bromomethyl) -6, -t-butyl-2-bromo-N-methyl acetyl anilide.

8001736 t "yr 7

To 38.0 g (0.15 mol) 2-chloro-N.2'-dimethyl-ö'-t-butylacetanilide (38 g, 0.15 mol) dissolved in CCl2 0.2 g benzoyl peroxide was added and the mixture was heated to reflux. Bromine (24.0 g, 0.15 mol) in 50 ml CCl 4 was added dropwise to the above mixture and after addition (1.5 hours) and further refluxing (0.5 hours) was added. stripped the material to remove solvent. The residue solidified on scratching. The product was recrystallized from heptane and identified as 2- (bromomethyl) -6,1-butyl-2-bromo-N-methyl acetanilide; mp. 86-87 ° C; yield 65%.

Anal.

Calculated for C ^ Hj ^ B ^ NO: C 44.59, Br 42.38, N 3.71%

Found: C 44.62, Br 42.27, N 3.72%.

Example III

Preparation of 2-chloro-N.2, .6, Tris (bromomethyl) acetanilide.

2-Chloro-N- (chloromethyl) -2'6T-dimethyl-acetanilide (0.04 mol, 10 g) was charged in 100 ml of CCl 4 containing 0.14 g of benzoyl peroxide, and the mixture was heated to reflux exposure with internal 0.2 amp TJV and 150 watt external-20 white light. To this mixture were added 13 g of bromine, present in 50 ml of CCl 4, and after the theoretical amount of bromine was added, 3.0 g of bromine were added. The mixture was cooled, the solvent was removed and the resulting viscous oil was triturated with ether to give a solid, which, according to nmr, consisted of crude 2-chloro-N.2'.6'-tris (bromomethyl) acetanilide . The crude product was not further purified, but then treated with 200 ml of boiling methanol to give 2'6.6-bis (broramethyl) -2-chloro-N- (methoxy-methyl) acetanilide; mp. 127.5-129 ° C.

Example IV

Preparation of 2f- (bromomethyl) -2-chloro-6'-t-butylacetanilide.

2-Chloro-2, -methyl-6'-t-butylacetanilide, (5.6 g, 0.025 mol) was charged in about 120 ml of CCl with 0.15 g of benzoyl peroxide and heated to reflux. Bromine (4.0 g, 0.025 mol) in 50 ml CCl 4 was added dropwise. After the addition, the reaction was completed by nmr. After removal of the solvent in vacuo, 7.0 g of a white solid were recovered.

After recrystallization from isopropanol several times, the product, 2, - (bromomethyl) -2-chloro-6, -t-butyl acetanilide, melted at 142-147 ° C; yield 88%.

5 Anal.

Calculated for C 11 H 21 BrCl NO: G 49.00, Br 25.08, Cl 11.13%

Found: G 47.93, Br 24.50, Cl 10.83%.

Example V

Preparation of 2-chloro-N.2 * .6'-tris (chloromethyl) acetanilide.

10 2-chloro-N.2'''-trimethylacetanilide (21.1 g, 0.1 mol) was charged in 200 ml CCl 2 and an internal 0.2 amp UV source was ignited within the 500 ml flask ; chlorine (0.1 mol, 7.0 g) was added below the surface with stirring. The reaction was mildly exothermic and the temperature rose from 20 to 40 ° C. After all the chlorine had been added, a substantially colorless solution was obtained. The mixture was cooled to about 5 ° C and an additional 0.1 mole of chlorine was added. Finally, a third molar equivalent of chlorine was added to the mixture. They left the material for about 48 hours. Then the solvent was removed to obtain a viscous oil. Portions of this oil were recrystallized from pentane ether to yield crystals identified as 2-chloro-N.2'6f-tris (chloromethyl) acetanilide; mp. 70-75 ° C.

The crude product was not further purified but directly treated with boiling methanol to give 2-chloro-N- (methoxymethyl) -2,6'-bis (chloromethyl) acetanilide. The compound of Example V can also be prepared using 2-chloro-N- (chloromethyl) -2'6'-dimethylacetanilide as a starting material.

Example VI

Preparation of 2t- (bromomethyl) -6, -t-butyl-2-chloro-N- (chloromethyl) -acetanilide.

To 17.3 g (0.06 mol) of 2-chloro-N-chloromethyl-2 '- (methyl) -6' - (t-butyl) -acetanilide dissolved in 250 ml of 35 CCl 4 were added 11 2 g (0.063 mol) of recrystallized N-bromosuccinimide (NBS) and 0.25 g of benzoyl peroxide. The resulting mixture was heated to reflux and the 500 ml three-necked flask was exposed with a low amperage submersible UV source and with external white light. According to nmr, the reaction was almost complete in about 0.5 hour. After standing at room temperature for about 48 hours, 2.2 g of the product, 2'- (bromomethyl) -6'-t-butyl-2-chloro-N- (chloromethyl) acetanilide, was isolated; mp. 124-125 ° C. A further amount (7.9 g) was recovered by partial evaporation of the solvent. The product was not further purified but reacted with methanol to give 2 - (bromomethyl) -2-chloro-N- (methoxy-methyl) acetanilide.

Example VII

Preparation of 2 - (bromomethyl) -6, -t-butyl-2-chloro-N-methyl acetyl anilide.

2-Chloro-6, -t-butyl-N.2, -dimethylacetanilide (17.5 g, 0.069 mol) was dissolved in 250 ml CCl 2 with 0.2 g benzoyl peroxide and 13 g (0.072 mol) recrystallized NBS using an exposure and flask size as described in Example VI. The reaction was completed in about 0.5 hour, with suecinimide floating on top of the CCl 2 solution. The material was filtered off and the filtrate washed with water and then treated in vacuo to remove solvent to yield 24.9 g of residue. The residue was recrystallized from hexane to obtain 14.8 g of product; a second recrystallization from hexane gave 2 '- (bromomethyl) -6'-t-butyl-2-chloro-N-methyl acetanilide; mp. 112-114 C; yield 63%.

Anal.

Calculated for C, HiriBr Cl NO: C 50.54, Br 24.02, Cl 10.66% 14 19 "

Found: C 50.33, Br 24.63, Cl 10.61%.

30 Example VIII

Preparation of 2 - (chloromethyl) -6t-methyl-2-chloroacetanilide.

2'.6'-dimethyl-2-chloroacetanilide was chlorinated according to the procedure described in Example V, whereby a white solid, identified as 2 '- (chloromethyl) -6'-35 methyl-2-chloroacetanilide, m.p. 133-134 ° C was obtained.

80 0 1 7 36 10

i V

Anal.

Calculated for CjqHjjCI2 O: C 51.74, H 4.77, N 6.03%

Found: C 51.69, H 4.66, N 6.03%.

Example IX

5 Preparation of 2 ', 6'-bis (bromomethyl) -2-chloro-N- (chloromethyl) acetanilide.

2-chloro-N- (chloromethyl) -2'6'-dimethyl-acetanilide (10.0 g, 0.04 mol) was dissolved in 100 ml CCl 2 with 0.14 g benzoyl peroxide. The material was refluxed and the flask was exposed with a low amperage submersible UV source and with external white light. To the mixture were added dropwise 13.0 g of molecular bromine contained in 50.0 ml of CCl 4. After the reaction was almost complete according to nmr, 3.0 g of bromine was added. The mixture was cooled and the solvent removed in vacuo. The resulting viscous oil was triturated with ether to give a solid, which was identified as 2 ', 6'-bis (bromomethyl) -2-chloro-N- (chloromethyl) acetanilide). The product was not further purified, but was treated with boiling methanol to give 2, 6,6'-bis (bromomethyl) -2-chloro-N- (methoxymethyl) acetanilide.

Example X.

Preparation of 2 '- (dibromomethyl) -6, -t-butyl-2-chloroacetanilide.

The compound of Example IV (9.54 g, 0.03 mol) was added to 300 ml of CCl2 containing 0.3 g of benzoyl-25 peroxide. Two white lights were used to irradiate the reaction vessel. Then, 4.8 g of bromine in 50 ml of CCl 2 were added dropwise to the irradiated mixture while maintaining a calm nitrogen gas purge in the reaction medium. The illumination source was removed after about 1.5 hours and the mixture was then allowed to stand and cool overnight. The solid egg protein was filtered off to obtain a first yield of 10.4 g and a second yield of 1.4 g. The solid material was recrystallized from isopropanol to give 2 '- (dibromomethyl) -6'-t-butyl-2-chloroacetanilide; mp = 145-147 ° C; Yield 99%.

8001736

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11

Anal.

Calculated for C HjgBi ^ Cl NO: C 39.28, H 4.06, N 3.52%

Found: C 38.99, H 4.10, N 3.58%.

Example XI

5. Preparation of 2 - (bromomethyl) -2.6, - dichloroacetanilide.

15.0 g of 2.6, -dichloro-2, -methyl acetanilide (0.068 mol) and 0.5 g of benzoyl peroxide were added to 300 ml of CCl in a 500 ml flask. The reaction vessel was illuminated with two external white lights. The reaction mixture was heated to reflux and then 10.9 g of bromine (Br 2) in 50 ml CCl 2 were added dropwise with nitrogen purge. A further 2.5 g of Br2 was added after nmr showed that the reaction was nearly complete. The solvent was removed in vacuo and the crude solid was recrystallized from isopropanol and then sublimed in vacuo (0.05mm) to give 2 - (bromomethyl) -2,6f-dichloroacetanilide; mp. 155-159 ° C; yield 58%.

Anal.

Calculated for C 8 H 8 BrCl 3 NO: C 36.40, H 2.72, N 4.72%. Found: C 36.18, H 2.72, N 4.80%.

Example XII

Preparation of 2- (bromomethyl) -2,3, -dichloro-6, -t-butylacet anilide.

In a 1 liter flask, 2,3'-dichloro-25, 2-methyl-6'-t-butylacetanilide (15.0 g, 0.055 mol) was dissolved in 600 ml CCl 2. The exposure was accomplished with two external white lights. The reaction mixture was heated to reflux and then 8.8 g of molecular bromine in 50 ml of CCl 2 was added dropwise. The excess solvent was removed in vacuo and the solid product was recrystallized twice, yielding 2 - (bromomethyl) -2,3, -dichloro-6'-t-butylacetanilide; mp. 182-184 ° C; yield 65%.

Anal.

Calcd for C 12 H 9 BrCl 3 O: C 44.22, H 4.57, N 3.97%. Found: C 44.09, H 4.62, N 3.96%.

8001736 12 I £ 1

Example XIII

Preparation of 2 '.3t-bis (bromomethyl) -2-chloro-6, -t-butyl acetyl anilide.

In a 1 liter flask, 15 g of 5 (0.059 mol) 2-chloro-2'S'-dimethyl-ö'-t-butylacetanilide were dissolved in 600 ml CCl 2. The exposure was performed with two white spotlights. The reaction mixture was heated to reflux and purged with nitrogen, then 9.44 g (0.059 mol) of elemental bromine in 5Q ml of CCl 2 was added dropwise. After a second molar equivalent of molecular bromine was added and after about 48 hours, the reaction mixture was filtered off and the solid recrystallized from isopropanol to give 2,3-bis- (bromomethyl) -2-chloro-6'-t- butyl acetanilide; mp. 180-182 ° C (vacuum sublimation, mp 195-197 ° C).

15 Anal.

Calculated for Cj ^ HjgB ^ Cl NO: C 40.85, H 4.41, N 3.40%

Found: C 40.60, H 4.37, N 3.40%.

Example XIV

Preparation of 2 - (bromomethyl) -2-chloroacetanilide.

2-chloro-2'-methylacetanilide (4.0 g, 0.02 mol) and N-bromosuccinimide (3.9 g, 0.02 mol) were dissolved in 300 ml CCl 2 with 0.3 g 2.2. azobis / 2-methylpropionitrile /. The mixture was illuminated with a spotlight and refluxed for 2.5 hours. The mixture was then allowed to cool to room temperature, after which it was filtered off, washed once with water, dried over MgSO4, filtered again and stripped to give a white solid. The solid was recrystallized from toluene to give 2.2 g of product, 2 '- (bromomethyl) -2-chloroacetanilide; mp. 125-127 ° C, yield 38%.

Anal.

Calculated for CgHgBrCl NO: C 41.17, H 3.46, N 5.34%

Found: C 41.35, H 3.40, N 5.30%.

Example XV

Preparation of 2> - (bromomethyl) -6, - (trifluoromethyl) -2-chloroacetanilide.

8001736 13 1 £

To 12.5 g (0.05 mol) of 2'-methyl-6 '- (trifluoromethyl) -2-chloroacetanilide were added 300 ml of carbon tetrachloride and 10.0 g (0.056 mol) of recrystallized NBS in a 1 liter flask. The mixture was kept at room temperature for about 1-1.5 hours and then at 70-75 ° C for about 4-5 hours. The crude product was isolated as a solid ("vessicant"); 17.7 g; recrystallization from isopropanol gave 9.8 g of product, 2 - (bromomethyl) -6, - (trifluoromethyl) -2-chloroacetanilide; mp. 98-101 ° G; yield 59.4%.

10 Anal.

Calculated for C. ~ HoClBrF ~ 0: C 36.34, H 2.44, N 4.24%

IU o J

Found: C 35.94, H 2.27, N 4.19%.

Example XVI

Preparation of 2-chloro-N-chloromethyl acetanilide.

To a suitable flask, equipped with a stirrer, gas supply tube, thermometer and internal, low-pressure UV light, were added 200 ml of a CCl 2 solution containing 0.1 mol 2-chloro-N-methyl acetanilide. A molar equivalent of gaseous chlorine was slowly added to the flask at room temperature.

The solution was then exposed and after a short induction period, the temperature of the solution rose to 38 ° C due to the exothermic chlorination reaction. It appears from nmr of the CCl 2 solution that the reaction was completed after an excess of 10% chlorine was added. After a treatment in vacuo to remove gases and solvent, 2-chloro-N- (chloromethyl) -acetanilide was obtained in 98% yield as a heat sensitive oil, showing the following nmr values: (CDCl3 ), & 3.9 (s, 2H, C1CH25), δ 5.55 (s, 2H, C1CH2N), δ 7.6 (broad s, 5H, ArH).

The compounds of the invention have been found to have a herbicidal activity and are also useful as intermediates in the preparation of certain ortho- (alkoxymethyl) -2-haloacetanilides which are effective herbicides. The method of obtaining the latter compounds comprises the reaction of the above-described compounds of the formula I with an alcohol, preferably in the presence of 800 1 7 36 s * 14 metal cations, for example potassium, sodium, silver, lead, mercury, etc., or other Lewis acids, for example, AlCl 2, SnCl 2, ZnCl 2, etc. When using the new compounds of the formula I, it was found that the halogen on the ortho-haloalkyl groups, in particular halomethyl, attached to the ring (benzyl) portion of the 2-haloacetanilide molecule of formula 1, could be selectively replaced by a suitable alcohol without disturbing the otherwise labile 2-acetyl halogen.

10 8001736

Claims (42)

1. Compounds of general formula 3, wherein X represents chlorine, bromine or iodine, R represents hydrogen, methyl, chloromethyl or bromomethyl, R 1 represents hydrogen, halo-5-methyl, tert-butyl, trifluoromethyl or-2 -C- r2 X1 R2 represents hydrogen, chlorine, bromine or a straight alkyl group with 10 1 ~ 4 carbon atoms, Yj and Y2 independently represent hydrogen, halogen, methyl, tert-butyl, trifluoromethyl or? 2 -c-r2 X1 Xj and X2 independently represent hydrogen, chlorine or bromine, where, when R2 is a straight alkyl group of 1-4 carbon atoms, only one of the groups Xj and X2 can represent hydrogen, chlorine or bromine, and where R2, Xj and X2 cannot can simultaneously represent chlorine or bromine. Compounds according to claim 1, characterized in that R2 is chlorine or bromine. Compounds according to claim 2, characterized in that X} is chlorine or bromine and hydrogen. 4. Compounds according to claim 3, characterized in that Yj and Y2 represent hydrogen. Compounds according to claim 4, characterized in that R 1 is hydrogen, methyl, chloromethyl, bromomethyl, tert-butyl or trifluoromethyl. 6. Compounds according to claim 5, characterized in that R 1 is trifluoromethyl. Compounds according to claim 5, characterized in that R 1 is chloromethyl or bromomethyl. Compounds according to claim 5, characterized in that R 1 is methyl or tert-butyl. Compounds according to claim 5, characterized in that R is methyl, chloromethyl or bromomethyl. 8001736 4 * Compounds according to claim 1, characterized in that Yj represents hydrogen and Y2 chlorine, bromine or methyl. Compounds according to claim 1, characterized in that bromine, X 1 and X 2 represent hydrogen and R 1 t-butyl 5- Compounds according to claim 1, characterized in that R represents hydrogen, Rj trifluoromethyl, Yj, Y2, Xj and X2 hydrogen and R2 chlorine or bromine. 13. 2 '- (bromomethyl) -2-chloro-6' - (tri-10 fluoromethyl) acetanilide. 14. 2-chloro-2 '- (chloromethyl) -61- (trifluoromethyl) acetanilide. 15. 2'- (bromomethyl) -2-chloro-6'-methyl-acetanilide. 16. 16-Chloro-2- (chloromethyl) -6, -methyl-acetanilide. 17. 2-chloro-2 '- (dichloromethyl) -6' - (trifluoromethyl) acetanilide. 18. A process for preparing compounds of the general formula 1, wherein n is 0 or 1, wherein, when n is 1, X represents chlorine, bromine or iodine, R represents hydrogen, methyl, chloromethyl or bromomethyl, Rj represents hydrogen, halogen, methyl, tert-butyl, trifluoromethyl or? 2 -C-R2, R2 represents hydrogen, chlorine, bromine or a straight alkyl group with 1 to 4 carbon atoms, Yj and Y2 independently represent hydrogen, halogen, methyl, tert-butyl, trifluoromethyl or 30 X2 X 'X' Xj and X2 independently represent hydrogen, chlorine or bromine, where when R2 is a straight alkyl group with 1 to 4 carbon atoms, only one of the groups Xj and X2 can represent hydrogen, chlorine or bromine, and where R2, Xj and X2 are not simultaneously 8001736 ^ % 3 may represent chlorine or bromine, and, when n is 0, R represents chloromethyl, Rj represents hydrogen, trifluoromethyl or halogen, Yj and independently represents hydrogen or halogen and R2 represents hydrogen, characterized in that a compound 5 having the formula 2, wherein n is 0 or 1, and, when η is 1, R, X, Yj and Y2 have the meanings indicated above, R "represents hydrogen, halogen, methyl, tert-butyl, trifluoromethyl or H -CR" ", 10 H R '' 'represents hydrogen or a straight allyl group with 1-4 carbon atoms, and, when n is 0, R represents methyl, R "represents hydrogen, trifluoromethyl or halogen, Yj and Y2 independently represent hydrogen or halogen and R represents hydrogen, reacting with a halogenating agent in the presence of a solvent, which is inert to the halogenation, and in the presence of an irradiation from an ultraviolet and / or white light source. 19. A method according to claim 18, characterized in that the solvent is carbon tetrachloride. 20. A method according to claim 19, characterized in that the halogenating agent is molecular chlorine. A method according to claim 19, characterized in that the halogenating agent is molecular bromine. Process according to claim 19, characterized in that the halogenating agent is N-bromosuccinimide. A method according to claim 18, characterized in that in the compound of formula 2 η is 1. 24. Process according to claim 23, characterized in that in the compound of formula 2 R "represents hydrogen, halogen, methyl, tert-butyl, trifluoromethyl or H -C-R'1 'H 35 and wherein RrT' represents hydrogen. 25. A process according to claim 24, characterized in that the compound of formula II represents R "in the compound of formula II" represents methyl, chlorine, t-butyl or trifluoromethyl. 26. Process according to claim 25, characterized in that in the compound of formula 2 R "is methyl. 27. A process according to claim 25, characterized in that in the compound of formula 2 R "is trifluoromethyl. 28. Process according to claim 25, characterized in that in the compound of formula 2 R "is tert-butyl. 29. Process according to claim 25, characterized in that in the compound of the formula, 2 Yj and Y2 represent hydrogen. 30. Process according to claim 25, characterized in that in the compound of formula II Yj represents hydrogen and Y2 chlorine. 31. Process according to claim 19, characterized in that in the compound of formula II R "is a straight alkyl group with 1-4 carbon atoms. 32. A process according to claim 31, characterized in that in the compound of the formula II, R, n is ethyl. A method according to claim 18, characterized in that the reaction temperature is or is near the reflux temperature. 34. Process according to claim 18, characterized in that in the compound of the formula 2 n is 0. 35. A process according to claim 34, characterized in that in the compound of formula II R ", Yj and Y2 represent hydrogen. 36. Process according to claim 34, characterized in that in the compound of formula 2 R "represents chlorine or bromine, 30 and Yj and Y2 represent hydrogen. 37. A process according to claim 34, characterized in that in the compound of formula 2 K "represents trifluoromethyl and Yj and Y2 hydrogen. 38. Process according to claim 18, characterized in that the compound of the formula 1 is 2, - (bromomethyl) -2-chloro-6 '- (trifluoromethyl) acetanilide. 8001736 t u 39. Process according to claim 18, characterized in that the compound of the formula I is 2-chloro-2 - (chloromethyl-b'-trifluoromethyl-acetanilide). 40. Process according to claim 18, characterized in that the compound of the formula 1 is 2, - (bromomethyl) -2-chloro-6'-methylacetanilide. 41. Process according to claim 18, characterized in that the compound of the formula 1 is 2-chloro-2f- (chloromethyl-1'-methylacetanilide). 42. A process according to claim 18, characterized in that the compound of the formula 1 is 2-chloro-2 '- (dichloromethyl-i-itrifluoromethylacetanilide). 43. Process according to claim 18, characterized in that the compound of formula I is 2-chloro-N- (chloromethyl) acetanilide. 44. Compounds and methods as described in the description and / or examples. r ƒ / "8001736 i / XT ς -, *, 22 AUG i960 Φ Τ .- .. 1,. »1 ^ 1» ίϊ: · * «. Improvement of errata in the specification associated with patent application No. 80.01736 Ned. proposed by applicant dd. 2 2 PLEASE. 1980 ____________________________________; __ On pages 3, 4, 15, 16 and 17 of the description, please make the following changes: Page 3, line 13: delete "hydrogen"; page 3, line 14 after "n is 0," supplement with X represents chlorine, bromine or iodine, ". page 4, line 6 after" n 0 is "supplement with" represents X represents chlorine, bromine or iodine, ". page 15, lines 9 and 17 delete" hydrogen ", page 16, lines 27 'and 35 delete" hydrogen, "page 17, line 1, after" n is 0, "add" X represents chlorine , bromine or iodine, "page 17, line 7, delete" methyl "page 17, line 12, after" n is 0, "complete with. "X represents chlorine, bromine or iodine," page 17, lines 29 to line 35 (claim 24) change to: "24. Process according to claim 23, characterized in that in the compound of formula 2 R" represents hydrogen, halogen, methyl, tert-butyl or trifluoromethyl. "dG / JvdB 8001736