Process for producing N-(halomethyl)acylamides

The disclosure herein relates to a new process for the preparation of N-(halomethyl)acylamides by reacting the corresponding N-(alkoxymethyl)acylamide with thionyl chloride or thionyl bromide in the presence of a Lewis Acid catalyst.

BACKGROUND OF THE INVENTION 
The invention herein pertains to the field of processes for the preparation 
of N-(halomethyl)acylamides particularly, 
N-(chloromethyl)-2-chloroacetamides. 
DESCRIPTION OF THE PRIOR ART 
N-(halomethyl)-2-haloacetamides generally are known in the prior art. These 
compounds are useful as herbicides themselves or as intermediates in the 
production of a wide variety of other N-methylene ether substituted 
2-haloacetamides as disclosed, e.g., in U.S. Pat. Nos. 3,442,945, 
3,630,716, 3,637,847, 3,574,746 and 3,586,496 and German Application No. 
2,648,008. Other prior art N-methylene ether substituted 2-haloacetamides 
derived from the above N-(halomethyl) intermediates include those wherein 
the halogen atom of the N-(halomethyl) radical is replaced by alkoxy, 
polyalkoxy, aryl, heterocyclyl, etc., radicals. 
The primary method disclosed in the prior art for producing 
N-(halomethyl)-2-haloacetamides involves the reaction of a primary 
aromatic amine with formaldehyde to produce the corresponding 
phenylazomethine which is then haloacetylated to obtain the desired 
N-halomethyl compound as disclosed, e.g., in said '716 and '847 patents. 
Canadian Pat. No. 779,917 discloses alternative methods for producing 
N-(chloromethyl)-2-haloacetamides. In a first embodiment, a primary or 
secondary amine is reacted with formaldehyde to obtain the corresponding 
hexahydrotriazine which is then reacted with chloroacetyl chloride to 
obtain the corresponding N-(chloromethyl)-2-chloroacetamide. In a second 
procedure, a primary amine is reacted with chloroacetyl chloride, then 
with formaldehyde to produce the corresponding 
N-methylol-2-chloroacetamide, which, in turn, is reacted with phosphorus 
pentachloride to obtain the corresponding 
N-(chloromethyl)-2-chloroacetamide. 
The above methods all possess limitations, thereby restricting access to 
these desirable intermediates. Thus, the addition of acid chlorides to 
monomeric or trimeric azomethines can be practically applied only when 
these latter materials are formed easily in high yields, necessitating 
electron-rich amines or anilines, in condensation with formaldehyde. 
Further, although the conversion of N-(hydroxymethyl)amides with 
phosphorus pentachloride, thionyl chloride or bromide or halogen acids can 
be convenient, this method is largely limited to substrates derived from 
reaction of formaldehyde with selected imides or amides wherein the 
methylol compound can be prepared; anilides and many other amides do not 
readily undergo such N-methylolation. 
In order to develop a more general procedure to prepare 
N-(halomethyl)amides, advantage was taken of recent advances in amide 
N-alkylation, particularly under phase transfer conditions. The facile 
preparation of N-(alkoxymethyl)acylamides from secondary acylamides and 
halomethyl ethers can now be easily achieved, particularly for the more 
acidic substrates such as sec-anilide and 1-enamides; these and other 
N-(alkoxymethyl)amides unexpectedly provide the substrates for the new, 
general method for N-(halomethyl)amide formation described below. 
To the knowledge of the inventor herein, it is unknown in the prior art to 
prepare N-(halomethyl) acylamides by the reaction of an N-methylene ether 
substituted-acylamide with thionyl chloride or bromide in the presence of 
a Lewis Acid catalyst as described in more detail below. 
SUMMARY OF THE INVENTION 
The invention herein relates to a process for preparing compounds of 
Formula I 
##STR1## 
which comprises reacting a compound of Formula II 
##STR2## 
with thionyl chloride or thionyl bromide in the presence of a Lewis Acid 
catalyst where in the above formulae 
X is hydrogen, halogen, a C.sub.1-6 alkyl or haloalkyl radical, a C.sub.3-7 
cycloalkyl radical, a phenyl or benzyl radical or any of said radicals 
optionally substituted with other radicals which are inert to a thionyl 
chloride, e.g., halogen, NO.sub.2, CF.sub.3, C.sub.1-6 alkyl or alkoxy, 
phenyl or benzyl, etc.; 
R is a C.sub.1-20 alkyl radical, an acyclic 1-alken-1-yl radical having up 
to 10 carbon atoms, a cycloalkyl or 1-cycloalken-1-yl radical having up to 
7 carbon atoms, a phenyl radical or said cycloalkyl, 1-cycloalken-1-yl or 
phenyl radicals substituted with one or more C.sub.1-6 alkyl, alkoxy or 
alkoxyalkyl, C.sub.2-4 alkenyl or C.sub.3-4 alkenyloxy, NO.sub.2 or 
CF.sub.3 radicals or halogen; 
R.sup.1 is a hydrocarbyl radical having up to 10 carbon atoms or such 
radical substituted with halogen or C.sub.1-8 alkoxy or alkoxyalkyl groups 
and 
R.sup.2 is a chloro or bromo atom. 
The process of this invention in preferred aspects is used to prepare 
compounds according to Formula I wherein X is chloro and R is a 
substituted phenyl radical as defined above. 
The process of this invention is suitably conducted at room temperatures, 
but in preferred embodiments at reflux temperatures and, more broadly, 
within the range of 20.degree. to 100.degree. C. 
Lewis Acids used to catalyze cleavage of the N-methylene ether group with 
thionyl chloride include sulfuric acid, hydrogen chloride, hydrofluoric 
acid, boron trifluoride, aluminum trichloride, etc. The preferred Lewis 
Acid herein is boron trifluoride etherate, BF.sub.3.O(C.sub.2 
H.sub.5).sub.2. 
The unique and unobvious character of the present invention is made 
manifest by reference to expected reactions which do not occur when 
N-(alkoxymethyl)acylamides are reacted with thionyl chloride according to 
this invention. For example, in starting N-(alkoxymethyl)-2-haloacetamides 
having alkoxy or alkoxyalkyl radicals substituted on the anilide ring, 
there are two ether linkages which could interchange with the reactant 
halide. However, according to the process of this invention, only the 
ether linkage in the N-methylene ether moiety is interchanged, leaving the 
anilide-substituted ether linkage intact. Although the reaction of 
alcohols with a thionyl halide to form alkyl halides is known, the 
reaction of such halides with ethers is not known; in fact, such reactions 
can only proceed with the use of Lewis Acids as first described herein. 
An advantageous feature of the process of this invention is that thionyl 
chloride and thionyl bromide are scavengers of water, thus preventing 
hydrolysis of the final product to secondary anilide by water formed or 
present in the reaction. 
Yet another advantage in the use of thionyl chloride or bromide herein is 
their transparency to hydrogen magnetic resonance ('Hmr) spectrometry, a 
convenient and occasionally necessary analytical technique for 
N-halomethyl amides, since gas-liquid chromatography temperatures often 
decompose this reagent type.

DETAILED DESCRIPTION OF THE INVENTION 
EXAMPLE 1 
This example illustrates an embodiment of the invention wherein the 
N-methylene ether radical of the substrate compound is cleaved by the 
catalytic action of the Lewis Acid hydrogen chloride generated in situ by 
the reaction of methanol and thionyl chloride (SOCl.sub.2). Without the 
methanol present in this embodiment, thionyl chloride, although an 
electrophilic reagent, does not effect said ether cleavage. 
Ten (10.0) g of 2',6'-diethyl-N-(methoxymethyl)-2-chloroacetanilide (common 
name "alachlor") when refluxed with 60 ml of SOCl.sub.2 for periods from 
12-24 hours gave little evidence of the formation of 
2',6'-diethyl-N-(chloromethyl)-2-chloroacetanilide ("CMA"), the desired 
product. 
The reaction mixture was cooled to room temperature and 1-2% methanol (0.3 
ml) added; the mixture was permitted to stand about 12 hours. Nmr analysis 
revealed the presence of appreciable CMA, which did not increase upon 
heating. Upon standing for about three days at room temperature complete 
conversion of the starting material to CMA occurred. 
In this embodiment, SOCl.sub.2 reacts with the alcohol, methanol, to 
produce HCl which protonates the ether oxygen, catalyzing carbonium ion 
formation, thus inducing reaction with SOCl.sub.2. Refluxing of this 
reaction mixture does not hasten the reaction, but, in fact, inhibits 
conversion of the starting material to CMA. This apparent anomaly, 
however, is explained on the basis of catalyst loss by facile HCl 
elimination by refluxing. Accordingly, in preferred embodiments, the 
process of this invention is more beneficially-conducted by using a 
non-volatile Lewis Acid catalyst which will not be eliminated during 
refluxing to enhance reaction rates, as illustrated by the use of 
BF.sub.3.etherate in the examples below. 
EXAMPLE 2 
This example illustrates the preparation of CMA from alachlor as in Example 
1 above, except a different acid catalyst system is used. 
Alachlor (10.0 g) was dissolved in 60 ml of SOCl.sub.2 containing 0.20 ml 
of BF.sub.3.O(C.sub. 2 H.sub.5).sub.2. The mixture was refluxed six (6) 
hours, at which time Nmr analysis of the solution indicated complete 
conversion of alachlor to CMA. The SOCl.sub.2 was stripped, toluene added 
and the mixture re-stripped under vacuum to give greater than 90% yield of 
CMA. 
EXAMPLE 3 
To 100 ml of SOCl.sub.2 containing 4 drops of BF.sub.3.O(C.sub. 2 
H.sub.5).sub.2 was added 5.7 g of 
2'-sec-butyl-6'-ethyl-N-(methoxymethyl)-2-chloroacetanilide and the 
mixture refluxed for one hour. The mixture was cooled to room temperature 
and the SOCl.sub.2 stripped off. The residue was taken up in CH.sub.2 
Cl.sub.2 and washed with 37% HCl, then dried over MgSO.sub.4. There was 
obtained 3.1 g (52% yield) of yellow oil, boiling at 122.degree. C. at 0.1 
mm Hg (Kugelrohr). 
______________________________________ 
Calc'd for C.sub.15 H.sub.21 Cl.sub.2 NO (%): 
Element Theory Found 
______________________________________ 
C 59.61 59.06 
H 7.00 7.04 
Cl 23.46 22.96 
______________________________________ 
The product was identified as 
2'-sec-butyl-6'-ethyl-N-(chloromethyl)-2-chloroacetanilide. 
EXAMPLE 4 
2'-(Trifluoromethyl)-6'-n-propyl-N-(methoxymethyl)-2-chloroacetanilide (6.6 
g) was dissolved in 100 ml of SOCl.sub.2 to which was added 4 drops of 
BF.sub.3.O(C.sub. 2 H.sub.5).sub.2 ; the mixture was heated to reflux and 
held at that temperature for about 18 hours. The mixture was cooled to 
room temperature. Nmr showed complete reaction. The SOCl.sub.2 was 
stripped, the residue taken up with hexane and then stripped again. Ether 
was added to the residue and washed with 10% HCl. 
After layer separation, the organic layer was dried, filtered and stripped. 
Ether and hexane were added to the residue and after cooling, 5.5 g of a 
white solid (82% yield) was obtained. The product was identified as 
2'-(trifluoromethyl)-6'-n-propyl-N-(chloromethyl)-2-chloroacetanilide. 
EXAMPLE 5 
2'-(trifluoromethyl)-6'-ethyl-N-(methoxymethyl)-2-chloroacetanilide, 14.8 
g, was dissolved in 100 ml SOCl.sub.2 and about 4 drops BF.sub.3.O(C.sub. 
2 H.sub.5).sub.2 added thereto. The temperature was raised to reflux and 
held there for about 24 hours. The SOCl.sub.2 was stripped, CH.sub.2 
Cl.sub.2 added and the mixture vacuum stripped again. Additional CH.sub.2 
Cl.sub.2 was added and the mixture washed with 37% HCl, dried 
(MgSO.sub.4), filtered and stripped. The residue was taken up in a 
hexane/ether solution and recrystallized to give 11.7 g (78% yield) of 
white solid, m.p. 46.degree.-50.degree. C. 
______________________________________ 
Anal. Cal'd for C.sub.12 H.sub.12 Cl.sub.2 F.sub.3 NO (%) 
Element Theory Found 
______________________________________ 
C 45.88 45.89 
H 3.85 3.89 
N 4.46 4.45 
______________________________________ 
The product was identified as 
2'-(trifluoromethyl)-6'-ethyl-N-(chloromethyl)-2-chloroacetanilide. 
EXAMPLE 6 
Following substantially the same procedure as described in Example 5, but 
substituting 
2'-(trifluoromethyl)-6'-methyl-N-(methoxymethyl)-2-haloacetanilide as 
starting material, there is obtained the corresponding N-chloromethyl 
compound as a yellow oil N.sub.D.sup.25 1.5076. 
______________________________________ 
Anal. Cal'd for C.sub.11 H.sub.10 Cl.sub.2 F.sub.3 NO (%) 
Element Theory Found 
______________________________________ 
C 44.02 44.82 
H 3.36 3.43 
N 4.67 4.74 
______________________________________ 
EXAMPLE 7 
Similarly prepared as above is the compound 
2'-trifluoromethyl)-N-(chloromethyl)-2-chloroacetanilide, while crystals, 
m.p. 63.degree.-65.degree. C. 
______________________________________ 
Anal. Calc'd for C.sub.10 H.sub.8 Cl.sub.2 F.sub.3 NO(%) 
Element Theory Found 
______________________________________ 
C 53.90 53.79 
H 6.33 6.36 
Cl 21.21 21.15 
N 4.19 4.15 
______________________________________ 
The advantageous feature of selectively cleaving the ether group on the 
amide nitrogen atom rather than on the anilide ring by the thionyl 
chloride with Lewis Acid catalyst is shown below in Examples 8-10. 
EXAMPLE 8 
2'-n-Butoxy-6'-ethyl-N-(methoxymethyl)-2-chloroacetanilide, 6.35 g., in 100 
ml SOCl.sub.2 containing 4 drops of BF.sub.3.O(C.sub. 2 H.sub.5).sub.2 
were refluxed for two hours. The SOCl.sub.2 was stripped, then toluene 
added and the mixture again stripped. Additional toluene was added and the 
mixture washed with 10% HCl, dried over MgSO.sub.4 and evaporated by 
Kugelrohr at 140.degree./0.1 mm Hg to give 4.6 g (72% yield) of yellow oil 
N.sup.23.2 1.5334. 
______________________________________ 
Anal. calc'd for C.sub.15 H.sub.21 Cl.sub.2 NO.sub.2 (%): 
Element Theory Found 
______________________________________ 
C 56.61 56.48 
H 6.65 6.68 
Cl 22.28 22.20 
N 4.40 4.37 
______________________________________ 
The product was identified as 
2'-n-butoxy-6'-ethyl-N-(chloromethyl)-2-chloroacetanilide. 
EXAMPLE 9 
Five (5.0) g of 2'-isobutoxy-N-(methoxymethyl)-2-chloroacetanilide and 4 
drops of BF.sub.3.O(C.sub. 2 H.sub.5).sub.2 were added to 100 ml of 
SOCl.sub.2 and the mixture heated at reflux temperature for 1.5 hours. The 
SOCl.sub.2 was stripped off and toluene added, then stripped again to 
remove all SOCl.sub.2. The residue was taken up in ether, washed with 10% 
HCl, dried and evaporated to give 5.0 g (86%) of a yellow oil, 
b.p.137.degree. C. at 0.15 mm Hg (Kugelrohr). 
______________________________________ 
Anal. Calc'd for C.sub.13 H.sub.17 Cl.sub.2 NO.sub.2 (%): 
Element Theory Found 
______________________________________ 
C 53.81 53.85 
H 5.91 5.95 
Cl 24.43 24.34 
N 4.83 4.83 
______________________________________ 
The product was identified as 
2'-isobutoxy-N-(chloromethyl)-2-chloroacetanilide. 
EXAMPLE 10 
Following substantially the same procedure as above, but substituting as 
the starting amide, 6.2 g of 
2'-(isopropoxyethoxy)-N-(methoxymethyl)-2-chloroacetanilide, and refluxing 
the mixture for 2.5 hours, there is obtained 5.3 g (84% yield) of an amber 
oil, b.p. 138.degree. C. at 0.05 mm Hg (Kugelrohr); N.sub.D.sup.23.2 
1.5311. 
______________________________________ 
Anal. Calc'd for C.sub.15 H.sub.21 Cl.sub.2 NO.sub.3 (%): 
Element Theory Found 
______________________________________ 
C 53.90 53.79 
H 6.33 6.36 
Cl 21.21 21.15 
N 4.19 4.15 
______________________________________ 
The product was identified as 
2'-(isopropoxyethoxy)-6'-methyl-N-(chloromethyl)-2-chloroacetanilide. 
The process of this invention is of wide applicability as indicated in the 
above working embodiments. Substitution of thionyl bromide for thionyl 
chloride produces the analogous N-(bromomethyl) compound. Since the 
reactive site in the halogen-ether cleavage process is at the N-methylene 
ether position, a wide variety of substituents may occupy the other 
non-acyl position in the amide. That is, in Formulae I and II herein, in 
addition to the R members exemplified above, other R members are within 
the purview of this invention. Thus, R may be hydrogen, aliphatic, 
cycloaliphatic, heterocyclic or aromatic members, including alkyl, 
alkenyl, alkynyl, cycloalkyl, alkylcycloalkyl, all preferably having up to 
6 carbon atoms, N--, O--, or S-heterocyclic radicals, which members may be 
independently substituted with non-interfering radicals, e.g., alkyl, 
halogen, nitro, CF.sub.3, alkoxy, polyalkoxy, alkoxyalkyl and the like. A 
subgenus of N-halomethyl compounds of particular interest is that wherein 
the R group is a phenyl radical substituted in one ortho position with a 
C.sub.1-4 alkyl radical and in the other ortho position with a 
trifluoromethyl, C.sub.1-4 alkyl or alkoxy or C.sub.3-4 alkenyloxy 
radical. Exemplary of such compounds are the following: 
N-(chloromethyl)-2'-methoxy-6'-methyl-2-chloroacetanilide 
N-(chloromethyl)-2'-isopropoxy-6'-methyl-2-chloroacetanilide 
N-(chloromethyl)-2'-isobutoxy-6'-methyl-2-chloroacetanilide 
N-(chloromethyl)-2'-isobutoxy-6'-ethyl-2-chloroacetanilide 
N-(chloromethyl)-2'-n-butoxy-6'-methyl-2-bromoacetanilide 
N-(chloromethyl)-2',6'-dimethyl-2-bromoacetanilide 
N-(chloromethyl)-2'-methyl-6'-ethyl-2-chloroacetanilide 
N-(chloromethyl)-2'-(trifluoromethyl)-6'-methyl-2-chloroacetanilide 
N-(chloromethyl)-2'-(trifluoromethyl)-6'-ethyl-2-chloroacetanilide 
N-(chloromethyl)-2'-(trifluoromethyl)-2-chloroacetanilide 
N-(bromomethyl)-2'-methoxy-6'-methyl-2-chloroacetanilide 
N-(bromomethyl)-2'-isopropoxy-6'-methyl-2-chloroacetanilide 
N-(bromomethyl)-2'-isobutoxy-6'-methyl-2-chloroacetanilide 
N-(bromomethyl)-2'-isobutoxy-6'-ethyl-2-chloroacetanilide 
N-(bromomethyl)-2'-n-butoxy-6'-methyl-2-bromoacetanilide 
N-(bromomethyl)-2',6'-dimethyl-2-bromoacetanilide 
N-(bromomethyl)-2'-methyl-6'-ethyl-2-chloroacetanilide 
N-(bromomethyl)-2'-(trifluoromethyl)-6'-methyl-2-chloroacetanilide 
N-(bromomethyl)-2'-(trifluoromethyl)-6'-ethyl-2-chloroacetanilide 
N-(bromomethyl)-2'-(trifluoromethyl)-2-chloroacetanilide 
Another subclass of compounds of interest is that wherein R in the above 
formulae is a C.sub.5-7 1-cycloalken-1-yl group, optionally substituted 
with one or more C.sub.1-6 alkyl groups, e.g., 
N-(chloromethyl)-N-(2,5-dimethyl-1-cyclopenten-1-yl)-2-chloroacetamide and 
N-(chloromethyl)-N-(2,6-dimethyl-1-cyclohexen-1-yl)-2-chloroacetamide. 
Yet another subclass of compounds according to Formula I herein is that 
wherein R is an acyclic 1-alken-1-yl radical having up to 10 carbon atoms 
as exemplified, e.g., by 
N-(chloromethyl)-N-[2-methyl--(1-methylethyl)-1-propenyl]-2-chloroacetamid 
e and N-(chloromethyl)-N-(1,2-dimethyl-1-propenyl)-2-chloroacetamide. 
In addition to N-(halomethyl)-2-haloacetamides, other acrylamides having 
non-halogen substituents in the 2- or .alpha.-position which may be 
prepared according to the process of this invention, include those wherein 
X in Formulae I and II above may be hydrogen, a C.sub.1-6 alkyl or 
haloalkyl radical, a C.sub.3-7 cycloalkyl radical, a phenyl or benzyl 
radical or any of said radicals optionally substituted with other radicals 
which are inert to a hydrogen halide, e.g., halogen, NO.sub.2, CF.sub.3, 
C.sub.1-6 alkyl or alkoxy, phenyl, benzyl, etc. 
As indicated above, the N-(halomethyl)acylamide compounds prepared 
according to the process of this invention are generally known compounds, 
some of which have herbicidal activity themselves. All of the N-halomethyl 
compounds disclosed above have utility as intermediate compounds 
(precursors) in the preparation of other compounds having herbicidal 
activity as disclosed, e.g., in the references cited above. Additionally, 
N-(halomethyl)-2-chloroacetamides prepared in accordance with the process 
of this invention are useful in the preparation of novel 
N-(azolylmethyl)-2-haloacetamides as set forth in this inventor's 
co-pending application Ser. No. 211609, filed Dec. 1, 1980. Examples 11-13 
below are illustrative of the preparation of said novel 2-haloacetamides. 
Example 11 
To 1.4 g (0.0059 mol) of 
N-(chloromethyl)-N-[2-methyl-1-(1-methylethyl)-propen-1-yl]-2-chloroacetam 
ide was added 0.8 g (0.012 mol) of pyrazole and the mixture heated in about 
20 ml of toluene at 80.degree.-90.degree. C. for about 6-7 hours. The 
material was decanted, washed with 10% caustic then with water, stripped 
and recrystallized from methylcyclohexane to give 1.0 (63% yield) of white 
solid, m.p. 101.0.degree.-101.5.degree. C. 
______________________________________ 
Anal. calc'd for C.sub.13 H.sub.20 ClN.sub.3 O(%): 
Element Theory Found 
______________________________________ 
C 57.88 57.41 
H 7.47 7.59 
N 15.58 16.25 
______________________________________ 
The product, structure confirmed by Nmr, was identified as 
N-[(2-methyl-1-(1-methylethyl)-1-propen-1-yl]-N-(1H-pyrazol-1-ylmethyl)-2- 
chloroacetamide. 
Example 12 
Pyrazol, 0.54 g (0.008 mol) and 0.8 g (0.0038 mol) of 
N-(chloromethyl)-N-(1,2-dimethyl-1-propen-1-yl)-2-chloroacetamide were 
mixed in toluene and heated at 90.degree. C. On work-up as described in 
Example 11, 0.6 g (62% yield) of an amber oil was obtained. 
______________________________________ 
Anal. calc'd for C.sub.11 H.sub.16 ClN.sub.3 O(%): 
Element Theory Found 
______________________________________ 
C 54.66 54.71 
H 6.67 6.80 
N 17.38 17.51 
______________________________________ 
The product, confirmed by Nmr, was identified as 
N-(1,2-dimethyl-1-propen-1-yl)-N-(1H-pyrazol-1-ylmethyl)-2-chloroacetamide 
Example 13 
To 8.9 g (0.036 mol) of 
N-(chloromethyl)-N-(2,6-dimethyl-1-cyclohexen-1-yl)-2-chloroacetamide 
dissolved in toluene was added 4.9 g (0.072 mol) of pyrazole; this mixture 
was heated to 90.degree. C. with stirring for 7 hours. The following day, 
the toluene solution was decanted, washed twice with water, then vacuum 
distilled to remove the solvent and traces of moisture. The residue was 
9.0 g of an oil which crystallized on standing. A sample of the product 
was recrystallized from a heptane/methylcyclohexane solvent to give a 
solid product, m.p. 83.degree.-84.degree. C., in 89% yield. 
______________________________________ 
Anal. calc'd for C.sub.14 H.sub.20 ClN.sub.3 O(%): 
Element Theory Found 
______________________________________ 
C 59.67 59.64 
H 7.15 7.17 
N 14.91 14.96 
______________________________________ 
The product was identified as 
N-(2,6-dimethyl-1-cyclohexen-1-yl)-N-(1H-pyrazol-1-ylmethyl)-2-chloroaceta 
mide. 
Example 14 
This example describes the use of an 
N-(halomethyl)-substituted-2-haloacetanilide to prepare other novel 
N-heteromethyl-2-haloacetanilides as disclosed and claimed in this 
inventor's co-pending application, Ser. No. 133,763, filed Mar. 25, 1980. 
N-(chloromethyl)-2'-methoxy-6'-methyl-2-chloroacetanilide 3.6 g (0.0137 
mol), in 100 ml of CH.sub.2 Cl.sub.2 were mixed with benzothiazolin-2-one, 
2.2 g (0.0145 mol) and 1.0 benzyl triethyl ammonium bromide. To this 
mixture with stirring was added 30 ml of 50% caustic; the mixture was 
allowed to react for about three hours. On work-up 5.8 g crude product was 
isolated, then recrystallized from isopropanol to a light buff-colored 
solid, m.p. 120.degree.-121.degree. C. 
______________________________________ 
Anal. calc'd for C.sub.18 H.sub.17 ClN.sub.2 O.sub.3 S(%): 
Element Theory Found 
______________________________________ 
C 57.37 56.89 
H 4.55 4.51 
N 7.43 7.34 
______________________________________ 
The product was identified as 
N-(2'-methoxy-6'-methyl)-N-[(2-oxo-3(2H)-benzothiazolyl)methyl]-2-chloroac 
etanilide. 
It will be appreciated by those skilled in the art that the process of this 
invention may be modified in non-inventive modes by those skilled in the 
art having particular reference to the nature and ratio of reactants, 
particular species within the defined genus of reactants, catalysts, 
solvents, reaction temperatures, times, pressures, etc.