JPS5925781B2 - Method for producing N-alkylated aniline compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides N-alkylation and N, which are useful as herbicides.
The present invention relates to a new process for preparing N-dialylated 2,6-dinitroanilines.

The N-aloylated and N,N-dialylated 2,6-dinitroaniline compounds obtained by the novel method of the present invention are represented by the following formula (1).

Here, Y is C1-C4 alkyl or CF
3; Z is hydrogen, halodene, C1-C4 alkoxy or alkoxy, and a single substituted alkoxy in which the substituent is halogen or C, -C4 alkoxy; R1 is C, -C6
(straight chain or preferably branched), C4 to C6 cycloalkyl, C, to C4 monohaloalkyl, or C, to C4 monohaloalkyl, or C, to C4, and the alkoxy group is C1 to
and R2 is hydrogen or one of the groups corresponding to R1; To explain straight chain and branched alkyl substituents, methyl ethyl n-propyl isopropyl SSSS n-butyl
t-butyl, n-pentyl, n-hexyl, 2-pentyl, 3-pentyl, ? -butyl, l-ethylpropyl and the like.

Examples of cycloalkyl groups are cyclobutyl citalopentyl and cyclohexyl groups. Examples of halodane substituents are fluorine, chlorine, bromine, and iodine groups.

The preparation of compounds of formula (1) is conventionally accomplished by a nucleophilic substitution reaction between a suitably substituted 2,6 dinitro-1-halobenzene and a suitably substituted amine.

This substitution reaction is preferably carried out in an aromatic solvent at 50°C to 15°C.
This is done by heating the reactants to between 0°C. The prior art has not shown a method for preparing N-alkylated-2,6-dinitroaniline of formula (1) in high yield by nitrating N-alkylated aniline. .

The conventionally known method for preparing 2,6-dinitrotertiaryanilines in which both N substituents are haloalkyl is as follows:
Nitration with at least a 5-fold excess of nitric acid in the presence of a catalytic amount of nitrous acid or a nitrite ion generating substance, with a nitric acid concentration of 50% to 9070 at the start of the reaction and a nitric acid concentration of 50 at the end of the reaction. Use an amount that leaves %. According to this method, the nitration at the 2 and 6 positions of N-alkylated-Sec-anilines can be carried out in high yield unless the hydrogen atom remaining on the nitrogen atom is protected in advance by, for example, acetylation. I can't expect that.

The present invention provides the corresponding N-alkylated anilines, i.e. (H
) A safe and effective method for converting a compound of formula (1) into an N-alylated 2,6 dinitroaniline compound of formula (1) is established.

In formula (1), Rl, R2, Y and Z are as defined in formula (1) above, and W and are hydrogen or nitro, but W
and cannot be nitro at the same time; in the method of the present invention, the compound of formula (1) can be converted to (1) by nitrating the compound of formula (H) using the three-component nitration agent composition shown below. ) and, when R2 is hydrogen, to a mixture of N-nitroso-N-alkylated 2,6 dinitroanilines in high yields.

In the most preferred embodiment of this process, the nitration mixture is optionally further treated with a nitroso-removal agent to convert the nitroso by-product to the corresponding compound of formula ( ). The nitrating agent used in the process of the invention is represented schematically by a quadrilateral A in the accompanying drawings.

This quadrilateral is 60% nitric acid, 8% sulfuric acid, 32% water; 50%
Nitric acid, 35% sulfuric acid, 15% water; 2% nitric acid, 68% sulfuric acid,
30% water; and the composition within the region defined by the line connecting the four points corresponding to 2% nitric acid, 20% sulfuric acid, 78% water. Each of the above numbers represents a true weight percentage.
The preferred range of the three-component nitration agent is within the area of trapezoid B. And this area is 45% nitric acid, 19% sulfuric acid, 36% water; 45% nitric acid, 36% sulfuric acid, 19% water;
0% nitric acid, 52% sulfuric acid, 28% water and 20% nitric acid, 2
The area surrounded by the dots corresponds to 7% sulfuric acid, 53% water (weight percentage), and area B is within area A. (
The optimum number of moles of nitric acid per mole of the compound of formula ) varies depending on the compound to be nitrated and the composition of the nitrating agent used.

In general, 2.2 to 5.0 mol of nitric acid is used per 1 mol of N-alkylated aniline for the nitration of compounds of the formula W (where 5V is hydrogen).

Within this range, 2.5 to 3.5 moles of nitric acid are generally more preferred. When w or V is nitro, the aniline 1
Preference is given to using 1.2 to 4.0 moles of nitric acid. Furthermore, within this range, 1.5 to 2.5 moles of nitric acid are generally preferred. The molar ratio of sulfuric acid to N-arylaniline used in the nitration of the process of the invention is 1.5.
:1 to 15.0:1 is preferable, and 2.0:1 to 10.0:1 is more preferable. In terms of percentage by volume, this sulfuric acid ranges from about 30% to 70%, preferably about 35% to 65%. It has been found that the amount of water in the nitrating agent mixture in the present invention is an important factor and is related to the optimum temperature.

Reaction mixtures containing higher water generally require higher reaction temperatures. The starting moisture content in the nitration mixture should be about 15% to about 78%, based on the weight of the nitration mixture. Sufficiently high temperatures must be used to convert any N-alkylated mononitroaniline to N-γ-alkylated 2,6-dinitroaniline. Although the compound of formula () can be nitrated at a temperature in the range of 0°C to 70°C, it has been found that temperatures below about 15°C are not suitable because the completion of dinitration is hindered. Furthermore, temperatures higher than 70°C are undesirable because it is difficult to control the reaction. This reaction is exothermic and generally requires cooling to keep the temperature below an upper limit and preferably within the optimum range. The optimum temperature will vary depending on the composition of the starting N-alylated aniline and nitration agent used. Generally suitable reaction temperatures are from about 35°C to about 60°C. 0℃～7
Nitration with mixed acids can be easily controlled when operating in the range 0°C (preferably 35°C to 60°C).

It has been found that uncontrollable reactions occur unless nitration with concentrated nitric acid is carried out at a temperature below 10°C. When mixed acids are used, control is relatively simple and the cooling capacity can be much smaller. Even if excessive or insufficient cooling power occurs, nitration with mixed acids can be easily handled, but explosions are likely to occur in the case of concentrated nitric acid. Another feature of nitration using mixed acids is that the amount of nitric acid required to complete the reaction is in slight excess (0.50
to 1.

50 mol) is sufficient.

In the case of concentrated nitric acid, at least 5 to 10 moles are required. The concentrated nitric acid process has a much greater cost and potential hazard since mixed acids do not require nitric acid recovery for operational economy. According to the invention, N
- The alkylated aniline can be reacted with the nitration solution as a liquid, solid or dissolved in an inert solvent such as ethylene dichloride, chloroform, carbon tetrachloride or nitromethane.

In carrying out the present invention, it has been found that it is suitable to use N-alkylated aniline dissolved in ethylene dichloride. The a number of ethylene dichloride to 1 g IC of the compound of formula () in the solution is about 3.0:1 to about 0.5:1.
The desired ratio is 0.75:1. The mode of addition is not a limiting factor. It is also possible to add the nitrating agent to the starting compound () or optionally to the nitrating agent. The product (1) is isolated after the nitration reaction is complete. The completion point is thin layer chromatography or N, M,
R, determined by conventional methods such as spectroscopy. However, in the case of compounds of formula () where R2 is hydrogen, it is very convenient to further treat the reaction mixture from the nitration step with a denitrosating agent, preferably a mixture of concentrated hydrochloric acid and sulfamic acid. I discovered something. This treatment is particularly important as it provides a yield increase approximately equal to the subsequent N-nitroso by-product present. In the formula Rl,,W
, Y and Z are as defined above.

The molar ratio of hydrochloric acid and sulfamic acid to the number of moles of N-nitroso compound present is in all cases at least 1.
:1. Desirably, the molar ratio of hydrochloric acid to N-nitroso compound is about 5:1 to 1.5:1. Further, the molar ratio of sulfumic acid and N-nitroso compound is preferably 2:1. The temperature of the denitokaso step can range from 20°C to 100°C,
The desired temperature should be in the range of 80°C to 100°C. Although the denitrosation step can be carried out under atmospheric pressure, it is preferable to carry out it under pressure to avoid loss of hydrochloric acid. Although other denitrosating agents such as hydrochloric acid and ferrous chloride may be used in this treatment, the use of hydrochloric acid and sulfamic acid is more suitable.

The preferred method of the present invention is usually carried out in batches, but
Continuous methods are also contemplated.

Examples of compounds prepared by the method of the present invention are as follows.

N-(isopropyl)-3,4-dimethyl-2,6-dinitroaniline, N-n-propyl-3,4-dimethyl-2,6-dinitroaniline N-cyclohexyl-3,4-dimethyl-2 ,6-dinitroaniline-N-(
2-Butyl)-3,4-dimethyl-2,6-dinitroaniline N-cyclo)pentyl-3,4-dimethyl-2
, 6-dinitroaniline, N-cyclobutyl-3,4-
Dimethyl-2,6-dinitroaniline, N-(2-butyl)-3-isopropyl-4-methyl-2,6-dinitroaniline, N-(2-butyl)-4-t-butyl-2
,6-dinitroaniline, N-(2-amyl)-3-butyl-4-methyl-2,6-dinitroaniline, N
-isopropyl-3,4-diethyl-2,6-dinitroaniline N-3-nopentyl-3,4-diethyl-2,6-dinitroaniline, N-(2-butino(ha)-3-chloro-4 -Methyl-2,6-dinitro gamma niline, N-(2-butyl)-3
-methoxy-4-methyl-2,6-dinitroaniline,
N-(1-ethylpropyl)-3,4-dimethyl-2,
6-dinitroaniline.

The following derivatives of the 2,6-dinitroanilines described above may also be prepared in the manner described above by using the appropriate 3,4-disubstituted-N monosubstituted anilines. 3,4-diethyl 3-
Methyl-4-ethyl 3-ethyl-4-methyl, 3
-ethyl-4-propyl, 3,4-diisopropyl, 3
, 4-di-n-propyl, 3,4-di-n-butyl, 3
, 4-diisobutyl, 3-propyl-4-butyl, and 3-methyl-4-isopropyl derivatives.

Examples of compounds where Y is CF3 include N-n-propyl-3-methyl-2,6-dinitro-4-(trifluoromethyl)-aniline; N-Sec-butyl-3-methyl-2,6 -dinitro-4-(trifluoromethyl)-aniline; 3-methyl-2,6-dinitro-N-3-pentyl-4-(trifluoromethyl)-aniline; and 3-ethyl 2,6-dinitro-N -isopropyl-4-
(trifluoromethyl)aniline.

An example of a 2,6-dinitrotarsial aniline prepared by the method of the invention is shown below: N-methyl-N-(2
-chloroethyl)3,4-dimethyl-2,6-dinitroaniline: N,N-di(n-propyl)-α,α,α
monotrifluoro-2,6-dinitro-p-toluidine;
N-ethyl-N-butyl-α,α,α-toluidine; 2,6-dinitro-p-toluidine; N,N-di(n-
propyl)-3,4-dimethyl-2,6-dinitroaniline; N,N-dimethyl-3,4-dimethyl-2,6-
Dinitroaniline; N,N-diethyl-3,4-dimethyl-2,6-dinitroaniline; N-ethyl-N-butyl-3,4-dimethyl-2,6-dinitroaniline; N
-Methyl-N-cyclo-sil-3,4-dimethyl-2
,6-dinitroaniline; N,N-diethyl-4-chloro-3-methyl-2,6-dinitroaniline; N,N-
Dibutyl-3,4-dimethyl-2,6-dinitroaniline; N,N-di(n-propyl)-4-chloro-3-methyl-2,6-dinitroaniline; N,N-di(n-propyl) -3-chloro-4-methyl-2,6-dinitroaniline; N,N-dimethyl-3-methyl-4-chloro-2,6-dinitroaniline; N-methyl-N-ethyl-3,4-dimethyl -2,6-dinitroaniline; N,
N-dimethyl-3,4-dimethyl-α4,α4,α4-
Trifluoro-2,6-dinitroaniline; N,N-diethyl-3-chloro-4-methyl-2,6-dinitroaniline; N,N-di(n-propyl)-3,4-dimethyl-α4 , α4,α4-trifluoro-2,6-dinitroaniline; N,N-(n-propyl)-3-methoxy-4-methyl-2,6-dinitroaniline; N,N-
Diethyl-3,4-dimethyl-α4,α4,α4-tri
2,6-dinitroaniline; N,N-diethyl-3-methoxy-4-methyl-2,6-dinitroaniline; N,N-di(n-propyl)-3-ethoxyl 4-
Methyl-2,6-dinitroaniline; N,N-di(n-
N,N-bis(2-chloroethyl)-3
, 4 dimethyl-2,6-dinitroaniline; and N,
N-bis(2-chloroethyl)-4-methyl-2,6-
Dinitroaniline.

Some suitable methods of preparing suitable dinitroanilines are shown below.

A suitable method for nitrating N-(1-ethylpropyl)-3,4-dimethylaniline is that the nitrating agent contains about 35% to 53% (by weight) water and the molar ratio of nitric acid to the aniline is A molar ratio of sulfuric acid to the aniline of about 3.25:51 allows the aniline compound to react with the nitrating agent in an amount of about 2.25:1.

The reaction is carried out while maintaining the temperature of the reaction mixture at about 35°C to 70°C. The reactants are mixed for about 2 hours, and the vorticity of the reaction mixture is maintained at about 35°C to about 70°C for about 1 hour after mixing is complete. Denitrosation is then carried out by adding hydrochloric acid and sulfamic acid to the mixture at a temperature of 70°C to 100°C over a period of 1 to 6 hours.
Finally, the product N-(1-ethylpropyl)2,6-dinitro-413,4-dimethylaniline is recovered. This operation is preferably carried out in an ethylene dichloride solvent, and the solvent ratio of ethylene dichloride to 9 of N-(1-ethylpropyl)-3,4-dimethylaniline is approximately 3.0. :1.0 to 0.5:1.0, preferably about 0.75:1.0.

In a preferred process for the nitration of N-(2-butynoly-3,4-dimethylaniline), the nitrating agent is about 40% to 5%
Containing 3% (by weight) water, the reaction is carried out in an amount such that the molar ratio of nitric acid to the aniline compound is about 3.25:1 and the molar ratio of sulfuric acid to the aniline compound is about 2.25:1. However, the temperature is maintained at about 50°C to 70°C while the reactants are mixed for about 2 hours, and the reaction mixture is maintained at about 50°C to about 70°C for about 1 hour after mixing is complete.

Hydrochloric acid and sulfamic acid are then added to denitrosate the mixture at 70° C. for 1 to 6 hours.
Maintain the temperature between 100°C and 100°C. The product thus obtained N-
(2-Butyl)-2,6-dinitro-3,4-dimethylaniline is recovered. This method uses N-(2-butyl)-
The solvent ratio in terms of ml of ethylene dichloride per 19 of 3,4-dimethylaniline is from about 3.0:1.0 to about 0.5:1.0, preferably from 0.75 to 1.0. It is better to carry out in ethylene dichloride solvent, which is characterized by:

The method of the invention is further illustrated in Examples 1-38 below.

Parts and percentages in each example are by weight unless otherwise indicated. In all cases the final products were isolated by thin layer chromatography and assayed by ultraviolet absorption spectroscopy. These dinitro compounds of the invention can be prepared by nucleophilic substitution in the 1 position of 1-monosubstituted-2,6-dinitro-3,4-xylene using, for example, an amine.
It is known that it can be obtained by substituting -chloro group.

In the method of the present invention, a nitro group is introduced at the position ortho to the N-alkyl group of 3,4=xylidine.
This route has several unexpected advantages.
The first advantage is the availability of starting materials.

The final starting material in all cases is nitrated or chlorinated silane. In the case of nitration, a mixture of 3-nitro-0-xylene and 4-nitro-0-xylene is obtained; in the case of chlorination, a mixture of 3-chloro-0-xylene and 4-chloro-0-xylene is obtained. A mixture is obtained. While in the case of nitro compounds the cyclic isomers can be easily separated using conventional distillation equipment, the separation of 4-talolo-10-xylene from its disintegrating form is difficult due to the boiling point of the anomalous form. This is very difficult because they are approximate. Second method of the invention
The advantage of this is that the N-alkylamino substitution at the 4-position of the silene ring system is strongly ortho-directed with respect to the nitrolytic reaction, whereas the same substitution in 4-chloro is found to be meta-directed. That's what happened.

Along with this difficulty, the 3,4-dimethyl-2,6 produced
-Dinitrochlorobenzene forms a eutectic composition with its necrotic l-form, so that the yield by fractional crystallization of the desired compound is very low. Therefore, the present invention provides a novel method for preparing the following compound of formula (α) by reacting the compound of formula (α) with concentrated nitric acid.

In the formula, R1 is S-butyl, 1-methylbutyl and 1-
C4-C5 branched alkyl selected from the group consisting of ethylpropyl, R4 and R5 cannot be hydrogen at the same time, but are hydrogen or nitro.

When trying to obtain N-alkyl-2,6-dinitro-3,54-xylidines from non-nitrosylidines, nitration is carried out by reacting xylidine with 5 to 20 moles of nitric acid in one step. sell.

Alternatively, a two-step process in which the orthonitroxylidine is first formed and then nitrated to the 2,6-dinitro compound is also available. Nitration can be carried out in conventional equipment by reacting the novel compound with a conventional nitration reagent such as concentrated nitric acid.

Nitration in the case of one-step dinitration of non-nitrated N-γ-alkyl-3,4-xylidines or mononitration of N-alkyl-0-nitro-3,4-xylidines can be carried out if desired, such as with ethane dichloride. Preferably, this is carried out with nitric acid in a suitable solvent solution.

This reaction is usually carried out at low temperatures, such as from about -10°C to +10°C, using a large excess of nitric acid. A molar ratio of nitric acid to xylidine of about 15:1 is suitable for carrying out this reaction. When it is desired to obtain N-(alkyl)-mononitro-3,4-isosilidine, a suitable N-(alkyl)-3,4-xylidine is preferably prepared in a stoichiometric amount or slightly in the presence of concentrated sulfuric acid. Treat with excess concentrated nitric acid.

This reaction is preferably carried out in the presence of a solvent such as ethane dichloride at a temperature on the order of about 5°C to 35°C. The desired N-(alkyl)-2-nitro-3,
4-xylidine and N-6-nitro-3,
4 to yield a mixture of silysine. This mixture is separated into its respective components by column chromatography on silica using hexasan as an eluent. Such separation is not necessary if these compounds are used as intermediates to obtain 2,6-dinitrosilidine or if the heterologous mixture is used as such. N-(Al)-3,4-xylidines are prepared by preparing 4-nitro-0-xylene or 3,4-isosilidine (formula) in an atmosphere of hydrogen in the presence of a conventional hydrogenation catalyst such as palladium. Obtained by reacting with an appropriate ketone.

This reaction is as follows. In the formula, X is NH2 or NO2, the ketone is methyl ethyl ketone, methyl propyl ketone or ethyl propyl ketone, and R1 is the same as defined in the above formula.

Another way to obtain N-(alkyl)-3,4-xylidines of the formula (where X is NH2) is to prepare the compound 3,4-xylidines in the presence of an alkali metal cyanoborohydride such as NaBHCN. This method involves reacting with one of the above ketones.

If desired, water produced by the reaction is removed using a water sieve. This reaction is carried out over a wide range of temperatures, such as from about 10 DEG C. to 70 DEG C., and optionally in the presence of a solvent such as a C, to C4 lower alkyl alcohol. (
Another method of preparing compounds of formula is to treat 3,4-xylidine with one of the above ketones in the presence of molecular sieves and a solvent such as dry benzene.

This reaction results in the corresponding N-(arylidene)-3,4
-xylidine, which is reduced with gamma alkali metal borohydride or hydrogen and a hydrogenation catalyst to give the corresponding N-(alomer)-3,4-omosilidine. Since the N-alkyl group in some types of xylidine contains an asymmetric carbon, optical anomalies may exist.

In this case, the term N-alkyl silidine includes the individual enantiomers as well as mixtures thereof. Since isomer separation is an expensive and time consuming operation, it is generally preferable to use racemic compositions rather than separation.

If separation is required, the N-alkyl compound is reacted with an optically active carboxylic acid, such as L-monotartrate, and the diastereomers are then separated using separating crystals in a conventional manner. Compounds of the invention and their preparation and uses are further described in Examples 39-63 below. All parts and percentages in the examples are by weight unless otherwise indicated. Preparation of N-Alkylated Anilines A novel reductive tortuous alkylation reaction that can optionally be used to prepare certain N-alkylated anilines of the present invention will now be described.

Several methods are known for reducing aromatic amines using ketones, hydrogen gas, noble metal catalysts, and acid promoters, either directly or via oxidized precursors.

It is known, for example, to use monocarboxylic acids or halodic acids in the presence of platinum for the reductive atomization of aniline and nitrobenzene. We also perform reductive alkylation of aromatic amines and nitro compounds with hydrogen,
It is also known to carry out in the presence of acetone, methanol, platinum and phosphoric acid. Prior art methods generally use weak acids such as acetic acid or strong acids such as hydrochloric acid, which have some drawbacks.

The disadvantages are low yields, long reaction times, low conversions and undesirable by-products due to concurrent side reactions, such as reduction of aromatic rings and/or (reduction of oketones to carbinol). Therefore, overcoming some of the above-mentioned difficulties has become a major objective in the production of certain N-alkylated aromatic amines.

The starting compound N-alkylated amine of the process of the present invention has the following chemical formula (XX).

where R1 is C3-C6 cycloalkyl, C3-C8 Sec-alkyl, optionally with one substitution by one halodene or C1-C4 alkoxy;
R2 is hydrogen, halogen, C1 to C4 alkoxy, C1
-C4 alkyl and C1-C4 1-substituted alkyl in which the substituent is halodane or C1-C4 alkoxy; R3 is hydrogen, C, -C4 alkyl, C1-C4
alkyl, trifluoromethyl, methylsulfonyl or halogen. The halogen substituted moieties are fluorine, chlorine, bromine, and iodine groups. C1 to C4 alkyl substituents are methyl, ethyl n-propyl, iso-
Such as propyl, n-butyl, t-butyl, tra-butyl, and the like. Cycloalkyl includes cyclopropyl, cyclobutyl, cyclohexyl, etc. C3-C8 S
What is ec-algorithm substituent? 2-propyl 2-butyl-
3-pentyl 3-methyl-2S)-butyl 2-heptyl 2-octyl and similar SS analogs.

Mono-substituted alkyl substituents, including mono-substituted alkyl substituents, are 3-chloro-2-propyl, 4-methoxy-2,
-butyl 3-bromo-2-butyl 2-chloropropyl 2-ethoxybutyl) and the like.

Examples of compounds of formula (XX) obtained by the method of the present invention include N-2-butyl-3,4-dimethylaniline, N-3
-pentyl-3,4-dimethylaniline, N-2-propyl-3,4-dimethylaniline, N-2-butyl-3
-Methyl-4-t-butylaniline, N-3-pentyl-3-methyl-4-chloroaniline, N-3-pentyl-3-methyl-4-trifluoromethylaniline N-
)2-hexyl-3,4-dimethylaniline N-3-
pentyl 3-methoxymethyl-4-methylaniline,
N-3-pentyl-3-methoxymethyl-4-trifluoromethylaniline N-2-~butyl-4-bromo-
3-Methylaniline N-2-pentyl-4-bromo-
3-methylaniline)N-2-hexyl-4-chloro-
3-Methylaniline, N-2-pentyl-3-ethoxy-4-methylaniline, and N-2-butyl-3-(
2-chloroethino(ha)-4-butylaniline.

N-alkylated aromatic amines are prepared by reacting the corresponding aromatic amine with a suitable ketone, a noble metal catalyst, and an acid having a PKa of 0.3 to 2.0, preferably 0.5 to 1.0. It is then prepared. The PKa value is the negative value of the logarithm of the first degree of dissociation of an acid in water, with a base of 10.
The aromatic amines used as raw materials for the compounds of the method of the present invention have the following formula: r In the formula, R2 and R3 are the same as defined in the formula (XX).

Examples of these amines include 3,4-xylidine 3,
4-diethylaniline, 3,4-di-n-butylaniline 3-methyl-4-ethylaniline 3-methyl-4
-Trifluoromethylaniline 3-Methyl-4-taloloaniline 3-S)Tyl-4-bromoaniline, 3
-Chloromethyl-3-methylaniline 3-methoxymethyl-4-methylaniline, and the like.

Amines can be reacted directly with ketones or indirectly using their oxidized precursors to obtain N-alkylated aromatic amines.

Oxidized precursors of aromatic amines of formula XXI include the corresponding nitro nitroso hydrazo azo azo)1)
S-oxy, hydroxylamine, diazonium salts or Schiff base compounds.

Examples of acids used include 2-naphthalenesulfonic acid, p
-Toluenesulfonic acid/ethylbenzenesulfonic acid, trichloroacetic acid and similar.

The ketone is selected to correspond to the desired N-alkyl group. For example, if a 2-propyl substituent is desired for R, dimethyl ketone may be used. More specifically, the ketones used herein are represented by the following formulas (XXIll) and (XX). The following (XXlI) formula (
However, R1 is C3 to C7 Sec-alkyl, R2 and R3 are the same as the definitions in formula (XX)) such N-
To obtain the alkylated aromatic amine, a ketone of the following formula is used.

In the formula, R4 and R5 are C1 to C5 lower alkaline atoms, and the total number of carbon atoms in R4 and R5 does not exceed 6, so the number of carbon atoms in R1 is C8 to C7.

N-alkylated aromatic amino of the following formula (XX) (where R1 is a C3 to C4 monosubstituted alkyl, and the substituent means a halokene or a C1 to C4 alkoxy group, In order to obtain (R2 and R3 are the same as defined in formula (XX)), a ketone of the following formula is used.

In the formula, R6 and R7 are C, to C2 lower alkaline atoms, the total number of carbon atoms in R6 and R7 does not exceed 3, and R
6 or R7 has one substitution by halodene or a C1-C4 alkoxy group.

Examples of ketones used in the above method include acetone, 2-butanone, 2-pentanone, 3-pentanone, 2-pentanone,
-Hegosanone, 3-hexanone, 2-heptanone 3-
Heptanone 4-heptanoSS, 1-chloro-3-pentanone, 1-methoxy-3-pentanone, ethoxy-
2-pC]/manone methyl isobutyl ketone, and the like.

As noble metal catalysts used are those customarily used for hydrogenation reactions, namely platinum and palladium from group 8 of the periodic table.

Preferably, it is in fine powder form, absorbed or retained on a suitable substrate. Platinum and palladium are suitable catalysts. Platinum supported on carbon soil is most suitable because it is readily available commercially and because there is no conversion of the ketone to the corresponding carbinoyl, which often occurs when palladium is used. Yields of 95% or more are thereby obtained.

A typical method for carrying out the reductive alkylation described above is as follows.

A pressure reactor is charged with an aromatic amine or its oxidized precursor, a suitable ketone, an acid promoter, and a noble metal catalyst.
The reactor is then optionally evacuated to remove oxygen and then purged with purified nitrogen gas. then 10-80psi
Hydrogen gas (higher pressures can be used if desired, as permitted by the equipment) is injected and the reaction mixture is heated to react. Temperatures of 40°C to 150°C are generally suitable, with 60°C to 125°C being most suitable.

A reaction time of 10 minutes to several hours is sufficient to complete the reaction, during which time the pressure in the reactor is maintained or allowed to decrease, if necessary, by reintroducing hydrogen gas.

Thereafter, the reaction mixture is allowed to cool, the reactor is opened, and the contents are taken out. Processing of the desired product is by conventional methods. The amount of acid used in the accelerator system is 1 of the amine or its oxidized precursor.
O.O. per 00 moles. Sufficiently satisfactory results can be obtained with amounts as small as 1 mole.

The upper limit on the amount of acid is limited only by practical considerations. The optimum amount is 1 to 100 moles of amine or its oxidized precursor.
3 moles of acid range. A suitable amount of noble metal catalyst is no less than about 0.39 parts of metal (preferably platinum) per mole of oxidized precursor of amine or metal.

If the catalyst is adsorbed on a substrate, it should be adjusted so that there is at least about 0.39 metal per mole of amine or precursor, regardless of the amount of substrate. The amount of metal found in the catalyst ranges from 1% to 50% based on the weight of the support.

A suitable commercially available product containing 5% platinum on carbon is used in an amount of about 5% of the amount of amine present in the reaction mixture or resulting from the oxidized precursor. Although it can be reused in the process, it is desirable to fortify the used catalyst with sufficient fresh catalyst to keep it active.

The amount of fresh catalyst that should be calorized is 10% of the amount after normal use.
Below, a range of 2% to 5% is desirable. The catalyst can be reduced beforehand. Or the noble metal oxide can be reduced to the metal in the reaction mixture. The ketone and aromatic amine are combined in an equimolar ratio.

One mole of hydrogen is consumed in converting the amine to the corresponding N-alkylated compound. When using an oxidized precursor in place of an amine (additional hydrogen is required for reduction of the precursor), a suitable molar ratio of ketone to amine ranges from about 1.1:1 to about 1.5:1. Usually, the amount of hydrogen used is in excess of the amount needed for conversion.
A pressure of about 10 psi, more preferably a pressure of about 40-80 p.
It is desirable to use a sufficient amount to retain si.
The N-alkylated aromatic amines described herein (1) effective as herbicides and germination regulators (2)
, 6-dinitroaniline compound.

Reference Examples 2 to 12 include 4-nitro-0 1-day silane and 3,
Reductive alkylation is mentioned under the name of 4-xylidine compounds.

However, it should be understood that it is possible to replace this with any other amine or its oxidized precursor. Parts and percentages in each example are by weight unless otherwise indicated. Example 1 Nitration of N-(1-ethylpropyl)-3,4-dimethylaniline 70.5% nitric acid 145.29 (1.625
For a mixed acid solution prepared by adding 116.69 (1,125 mol) of 94.5% sulfuric acid to 58.89 mol of water,
94.6% N-(1-ethylpropyl)-3,4-dimethylaniline 101.09 (0.5 mol) to 143.5
A solution dissolved in ml of ethylene dichloride was kept at a temperature of 35° C. for 2 hours (it became stiff and thickened).

After continuing the reaction at 35°C for 1 hour, the aqueous phase was separated.

The organic phase was dissolved in 5% caustic soda solution 300 WLe and water 30
Continuous washing was performed using 0ml. The resulting organic solution was dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo at 70° C. to yield 141.59 crude products. In this product (
11179 (82.6%) of N-(1-ethylpropyl-3,4-dimethyl-2,6-dinitroaniline and 14.29 (10.0%) of N-nitrosoN-(1-
ethylpropyl)-3,4-dimethyl-2,6-dinitroaniline. The total yield of the target substance 2,6-dinitroaniline was 72.6%. Examples 2-10 Here, for N-(1-ethylpropyl)-3,4-dimethylaniline, the same molar ratios of nitric acid and sulfuric acid to starting materials as in the previous example are used, but the reaction mixtures with different amounts of water are used. Show the results.

The reaction conditions in all cases are the same as used in Example 1.

In some cases, the starting material was dissolved in the solvent L, extracted with toluene or silane, and worked up in a conventional manner.The results are shown in Table 1.Examples 11-13 N-(1 -Ethylpropyl)-3,4-dimethyl γ-niline This example shows N-(1-ethylpropyl)-3
, 4 dimethylaniline with three different water contents namely water 16.7, 21.7 and 48.

When nitrated with 7% mixed acid at 20-25℃, N-(
Yields of both N-nitroso N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitroaniline This indicates that the value decreases.

This example shows the effect of molar ratio and water content on yield and product composition. The general method used was the same as described in Example 1, with 4.869
The starting material was N-(1-ethylpropyl)-3,4-dimethylaniline dissolved in 15T11t of ethylene dichloride.

In all cases the addition time was 2 hours and the holding time was 1 hour. Examples 14-15 This example (as shown in the table) illustrates the effect of increasing temperature and water content on product composition and overall yield.

General conditions of use were as in Example 1 with exceptions as indicated. Composition (shown in terms of mol and 9). Example 16 De-nitrosation of the crude nitration product from N-(1-ethylpropino(ha)-3,4-dimethylaniline) in 3700 WLI of ethylene dichloride. 2,6-dinitro-N-(1-ethylpropyl)-3,4-dimethylaniline of 15501 and 34
To the crude nitration solution containing 2,6-dinitro-N-nitroso-N-(1-ethylpropyl)-3,4-dimethylaniline of 09, sulfamic acid of 2129 and 37.7% hydrochloric acid of 2850me were added. Ta.

The mixture was refluxed at 80°C for 6 hours, 2t of water was added thereto and the aqueous phase was separated. The aqueous phase was extracted with 500 ml of ethylene dichloride and the organic phases were combined. 3t after separating the combined organic phase
The aqueous phase was removed by washing with water, and the ethylene dichloride was removed in vacuo at 68° C. to yield product 19159. In this, 18209 of 2,6-dinitro-N-(1-ethylpropino-0-3,4-dimethylaniline and 0.1%
The following 2,6-dinitro-N-nitroso-N-(1-ethylpropyl)-3,4-dimethylaniline was contained. Example 17-24 The denitrosation of the crude nitrosation product obtained by nitration of N-(1-ethylpropyl)-3,4-dimethylOlyaniline was carried out using the general conditions described in Example 16. Examples using this method are shown in the table below.

The molar ratios in the table are moles of reagent to 1 mole of N-nitroso by-product. In most cases reactions were carried out in 5 pressure vessels. Example 25 Nitration of N-(2-butyl)-3,4-dimethylaniline 70.5% nitric acid 134,19 (1.50 mol) and 9
6.9% sulfuric acid 101.1V (1.00 mol) 87.2
A solution of 95.9% N-(2-butyl)-3,4-dimethylaniline (92,39) in ethylene dichloride (66.5a) was added to the mixed acid solution obtained by adding water (66.5a) to water at a temperature of 50°C to 5
Calorie at 5°C for 2 hours.

Further, the reaction was carried out while maintaining the temperature at 55° C. for 1 hour, and the resulting aqueous phase was separated. Add 500T of 5% caustic soda solution to the organic phase! 1e Subsequently, wash with 500 liters of water,
After drying the organic phase over anhydrous magnesium sulfate in vacuo 7
Concentration at 0°C gave 130.09 of the crude product.

In this, 1009 (yield 75.5%) of 2,6-dinitro-N-(2-butyl)-3,4-dimethylaniline and 22,09 (yield 14.9%) of 2,6- Dinitro-N-nitroso-N-(2-butyl)-3,4-dimethyl gamma niline was included. The total yield of the desired 2,6-dinitro gamma niline product was 90.4%. Example 2
6-28 N-(2-butyl)-3,4-dimethyl γ shown in Table V
Examples of the nitration of niline (1) illustrate the effect of water content in the nitration mixture on the product composition.

That is, it is shown that the use of a mixed acid with a high water content and a low molar ratio of nitric acid reduces the production rate of the by-product N-nitroso compound. In all cases the general procedure of Example 1 was carried out at 35°C.
A solution of N.59 in N-(2-butyl)-3,4-dimethylaniline was mixed with the starting material and allowed to react for 2 hours at 35 DEG C. and for an additional hour at 35 DEG C. Example 2
Examples in Tables 9 to 31 are N-(2-butyl)-3,4-
Figure 2 shows changes in total yield and product composition with changes in temperature and water content of the reaction mixture in the nitration of dimethylaniline.

According to these results, N-(2-butyl)-3,4-
The suitable temperature and water content for the nitration of dimethyl gamma niline are shown to be about 50° C. and about 40%, respectively. Example 3 Nitroso removal of nitrated crude product of 2N-(2-butyl)-3,4-dimethylaniline"15W
20.29 of 2,6-dinitro-N-(2-butyl)-3,4-dimethylaniline and 6.849 of 2,6-dinitro-N-nitroso-N in ethylene dichloride of 1e.
To a solution of the nitrated crude product 309 consisting of -(2-butyl)-3,4-dimethylaniline was added 3.949 parts of sulfamic acid and 9.849 parts of 376% hydrochloric acid.

The mixture was stirred and heated under a pressure of 8°C for 6 hours, at the end of 2 hours.
0 ml of water was added and the pH of the mixture was adjusted to 9-11 by carefully adding 50% aqueous sodium chloride solution. After phase separation, the aqueous phase was removed and the organic phase was washed with 20TIII of water and dried over anhydrous magnesium sulfate. After passing through f5, concentrate in vacuo at 70°C. The residue was 28.29, of which 2,6-dinitro-N
-(2-butyl)-3,4-dimethylaniline 24.6
9 (yield 93%), and 2,6-dinitro-N-nitroso-N-(2-butyl)-3,4-dimethylaniline 0.1% or less. Example 33 Water 1,839, 96.9% sulfuric acid 6.839 (0.067
5 mono(c) and 70.5% nitric acid 8.719(0.
A mixed acid solution was prepared by mixing 0975 mono(c).

To this solution, 5.939 (0.03 mol) of N-(2
-butyl)-3-chloro-4-methylaniline dissolved in 49 parts of ethylene dichloride was heated to 35°C to 40°C for 2 hours.
．． Addition was made over a period of 25 hours. The mixture was heated to 40°C to 45°C.
Heat to ℃ for 2.25 hours and further heat to 55℃ to 0.75
Time was hot. The mixture was diluted with ethylene dichloride, and the organic phase was washed with dilute caustic soda solution (PHlO-11), further washed with water, dried over anhydrous magnesium sulfate, and filtered through F. This was concentrated to give a 7.89 oil. When this material was analyzed by thin layer chromatography, it was found to contain one major component and three minor components. 20 oils
After dissolving me in ethylene dichloride, 13WLI of concentrated hydrochloric acid and 1V of sulfamic acid were added thereto.

After refluxing the mixture for 7 hours, a portion was analyzed by thin layer chromatography, and it was found that the three minor components mentioned above had disappeared. The mixture was cooled and the aqueous phase was discarded. The organic phase was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain an oil with a yield of 5.79. The main component in this oil was purified using liquid talomatography and examined using proton magnetic resonance spectroscopy.
It was shown to be 2,6-dinitro-3-chloro-p-toluidine. Example 34 A mixed acid solution was prepared by mixing 2.559 parts of water, 6.919 parts of 95.7% sulfuric acid, and 8.719 parts of 70.5% nitric acid.

For this solution, 6.39 N-(2
-butyl)-4-tert-butylaniline in 19 ml of ethylene dichloride was heated over a period of about 2 hours and the reaction mixture was heated to 40°C to 45°C for 1.5 hours and further to 50°C.
Stir for an hour. After adding 1.939 ml of 95.3% sulfuric acid, the mixture was stirred at 50° C. for 0.5 hour.

Testing showed that no unreacted N-2-butyl-4-t-butylaniline or its mononitroso derivative remained in the reaction mixture. The mixture was cooled, the organic phase was separated, and the The sodium chloride solution was then washed with water. To the organic phase were added 1377 Ze of concentrated hydrochloric acid and 1.09 of sulfamic acid. The mixture was refluxed for 4 hours and then cooled to remove the acid phase. After washing the organic phase with water, 14.49 when concentrated
of oil is obtained. This oil was loaded onto a silica del column and eluted with toluene. The fastest migrating components were extracted from the silica using methylene chloride. When the extract was concentrated, a yellow solid of 3.49 (more than 38% of the theoretical value) was obtained, which was N-(2-butyl)-2,6-dinitro-4-t-
It was identified as butyl gamma niline. Reference Example 1 N-Sec-butyl-2-nitro-3,4-dimethylaniline and N-? -Preparation of butyl-6-nitro-3,4-dimethylaniline N-Sec-butyl-3,4-dimethylaniline (5.3V10.03 mol) was added to 10 me
of dichloroethane and carefully treated with a mixed acid (6a0 concentrated sulfuric acid and 2.7f1 concentrated nitric acid) at 15°C to 25°C.

After the addition is complete, pour the mixture into water. The organic phase is disrupted and purified by column chromatography on silica using hexane eluent. The first eluting component is N-S
Confirmed by NMR and infrared spectroscopy as ec-butyl-2-nitro-3,4-dimethylaniline. The second eluting component was N-butyl-6-nitro-3,
Similarly with 4-dimethylaniline, N. M. R. Confirmed by spectrum. Example 35 N-(1-ethylpropyl)-2,6-dinitro-3,
Preparation of 4-dimethylaniline N in the method of Reference Example 1
−? -N- instead of butyl-3,4-dimethyl γ-niline
By using (1-ethylpropyl)-3,4-dimethylaniline, N-(1-ethylpropyl)-2-
Nitro-3,4-dimethynoleaniline is obtained.

The desired 2,6-dinitro compound can be prepared with high purity and high yield by nitrating a 2-nitro compound using the method of Example 1. Example 36 Similarly to Example 35, by replacing the starting material in the method of Reference Example 1 with N-(1-ethylpropyl)-3,4-dimethylaniline, N(1-ethylpropyl)-6- Nitro-3,4-dimethylaniline is obtained.

If this product is converted using the method of Example 1, N-(
1-ethylpropyl)-2,6-dinitro-3,4-dimethylaniline is obtained. Example 37 95.3% sulfuric acid (5.799, 0.056 mol) and 70.5% nitric acid (7,279, 0.081 mol) were dissolved in water (
1.279) to prepare a mixed acid, and while stirring, add N,N-bis-(2-
chloroethyl)-3,4-dimethylaniline (6.15
9, 0.025 mol) solution.

This addition 1 was carried out over a period of 90 minutes at a temperature of 35°C to 45°C. After the addition of caloric acid is completed, the mixture is heated further to 30℃~40℃.
After stirring at ℃ for 2 hours, the lower layer was separated and discarded. The upper layer was washed with 10 me each of dilute caustic soda and water in that order. The organic solution was dried over anhydrous magnesium merate and then chromatographed on silica gel, eluting with benzene to isolate 3.739 (44.5%) of a yellow solid. This substance is N. M. R. The spectrum shows N,N-bis-(2-chloroethyl)-2,6
-dinitro-3,4-dimethylaniline. Reference Example 2 Preparation of N-(1-ethylpropyl)-3,4-xylidine 4-nitro-0-xylene (10.09, 0.066
diethyl ketone (20 TfL1, 0.019 mol) on carbon in a Parr hydrogen addition apparatus.
? Palladium (0.59) and benzoic acid (0.59)
While shaking, the mixture was reacted with hydrogen at 3 atm.

When hydrogen consumption was completed and the suspension had passed, analysis by gas one-liquid chromatography confirmed that N-(1-ethylpropyl)-3,4-xylidine had been obtained. (Yield 83%) Reference Example 3 Preparation of N-(1-ethylpropyl)-3,4-xylidine 3,4-xylidine (1.29, 0.01 mol) and diethyl ketone (5 ml) were mixed with methanol (20 WLI). ) of sodium cyanoborohydride ( ) at room temperature.
1.19) and 3A Mole Go Yurashivu (3.09)
Stirred in the presence of.

The pH was checked every 30 minutes, and when necessary, 5 drops of acetic acid was added to maintain the pH at 6.

After 7 hours, the sieves were taken from house to house and the liquid was acidified with water (100 m diluted with hydrochloric acid).

The solution is made alkaline with solid potassium carbonate and then extracted with ethyl ether. When the ether solution was dried and then evaporated, the target substance was obtained as an oily residue in a yield of 97.570, and its purity was confirmed to be 93% by gas-one-liquid chromatography. Boiling point (80°C under 0.1 mm pressure. The analytical value is calculated as Cl8H2IN: C8l.6; Hll.l:N, 7.3; C8l.
4; H, ll. 2; N, 7.5. Reference example 4N-
Preparation of SeL-butyl-3,4-xylidine N-Sec-butyl-3,4-
- Xylidine was prepared.

The product C had a purity of 96% and a quantitative yield.
The boiling point at 0.4 mm pressure is 75°C to 77°C, and the elemental analysis results are as follows: Calculated value as Cl2H,,N: C8l.
3; HIO. 8; N7.9 Actual value: C8l. 4;HlO
．． 8; N7.9.

Reference Example 5 Preparation of N-Sec-butyl-3,4-xylidine 79.
29 (1.0 mol) of methyl ethyl ketone and 121
．． 09 (1.0 mol) of 3,4-dimethylaniline to 1
Molecule sieve (type 5A, 3009) is added to a solution of 100 ml in dry benzene; the mixture is stirred at room temperature for 1
Stir for 6 hours.

Next, the mole gouraseive is washed door to door and washed with dry benzene. The combined benzene solutions are evaporated in vacuo to yield the desired product 198V (100%). Since this product is easily hydrolyzed, it is immediately added to the hydrogenation reactor on carbon.
Reduction using a % palladium catalyst gives N-Sec-butyl-3,4-lysine. Reference Examples 6-7 Preparation of N-s-butyl-2-nitro-3,4-silidine and N-Sec-butyl-6-nitro-3,4-silidine in 10 ml of ethane dichloride. N-Flood-butyl-3,4-xylidine (5.39, 0.03 mol)
A mixed acid (6 ml of concentrated sulfuric acid and 2.79 ml of concentrated nitric acid) is carefully added to the solution at 15-25°C.

After addition I is completed, pour the mixture into water. The organic layer is separated and purified by column chromatography onto silica gel using a sunscreen eluent. Elution first component (MaN-Sec
-butyl-2-nitro-3,4 silidine is N. M. R. and could be confirmed by infrared spectroscopy. The second eluting component is N-Sec-butyl-6nitro-3
, 4 was confirmed to be silydine by NMR and infrared spectroscopy. The analysis sample of the 6 nitro compound has a melting point of 73°C to 75°C, and the elemental analysis results are C, 2Hl8N2
Calculated value of O2: C, 64.8; Hl 8.2; N,. l2
, 6 actual value; Cl64.6; Hl8.2; Nsl2.6
:. Reference Examples 8-9 Preparation of N-(1-ethylpropyl)-2-nitro-3,4-xylidine and N-(1-ethylpropyl)-6-nitro-3,4-silidine The above compounds were prepared in Reference Examples 6 and 7.
An equivalent amount of N-(1-ethylpropyl)-3,4 in place of N-Sec-butyl-3,4-xylidine in the method of
-obtained by a similar operation using xylidine.

The melting point of the 6-nitro compound recrystallized from methanol is 5
At 8°C to 60°C, the results of elemental analysis (as primary)
Calculated value of 8H2ON2O2: Cl66. l; Hl8.5
;N,ll. 9 Actual value: Cl66. l;Hl8.6;N
、． ll. 7. The 2-nitro compound obtained by chromatographic purification is oily.

The elemental analysis results are as follows. Calculated value of Cl3H2ON2O2: C, 66. l; H, 8.5; N, ll. 9 Observed values: C, 67.7; H, 8.9;
9 (0.02 mol) of N-1-(ethylpropyl)-3
, 4 1 o silydine and 5.0 me (0.08 mol) of 70
% concentrated nitric acid.

The target substance is isolated by cucamatography on silica gel in a conventional manner. Reference Examples 10-12 A test to illustrate the selective pre-emergence herbicidal activity of the compound of the present invention was conducted as follows.

Seeds of several monocotyledonous and dicotyledonous plants were potted separately and mixed with soil, and this seed-soil mixture was mixed with 200 x 2 pots.
Place it in a -7 layer on top of the approximately 1±7 soil in a trigram resin pot.

After sowing, a water-gamma setone solution is sprayed so that each needle receives a sufficient amount to provide a dose of test compound of from 0.06 to 10 pounds per acre. The treated pots are placed on a stand in the greenhouse and watered to carry out greenhouse cultivation.The test is completed 3 to 4 weeks after the treatment, and each pot is inspected and rated according to the following rating criteria.The results are shown in the table below. 4 Abnormal growth, or a certain physiological malformation,
Overall inferior to 5 *Height, size, vigor, yellowing,
Based on visual judgment of malformations and gross in vitro symptoms.

Plant abbreviation CR- Hime Lba (Digiariasanguina)
lis) PI-Ageito (Amaranihusr)
elrOfexus) LA- Lroza (ChenOpO
diumalbum)COR-Corn L(Zeam
ays) WO-Wild Karasumugi (Aveniafatu)
a) MU-mustard (BrassicaKaber) ]
RAG-Buta<sa (AjnbrOsiaarlemis
iifOlia) BA-Inubie (EchinOcOlacrusgal)
li) GRF-Enokorogusa (Setariaviri)
dis) MG-Agao (engineering IO meapurlure
a and IlOmOeahederacea)COT-
Cotton (GOssypiumhirsutum) BS-
Betabulugaris SOY - Soybean (Glyzinemax) Examples 38-42 Examples 38-42 illustrate methods for converting compounds of the present invention to 2,6-dinitroanilines.

The uses of the products thus obtained are shown in Reference Examples 13 to 21. Example 38 N-Se(,-butyl-2,6-dinitro-3,4
Preparation of N-Sec-butyl-3,4-xylidine (1.2θ6.7×10−3 mol) at 15°C.
Add to 70% nitric acid (13ml).

After 1 hour, the reaction mixture was poured into ice water and extracted with ethyl ether. The extract is dried over anhydrous magnesium sulfate and evaporated in vacuo to yield 1.55y of the desired product as a solid residue. Purification by chromatography on silica del with hexane as eluent resulted in a total weight of 1.1 V (
60%) of purified target product is obtained. Melting point 410C ~
45℃. Melting point: 43°C to 44°C when recrystallized from hexane
If you obtain an analysis sample of and analyze it, Cl2Hl7N3
O4 calculation value: C, 53.9; H, 6.4; N, l5.7
Actual wage: C, 54. O; H, 6.2; N, l5.7. Example 39 N-(1-ethylpropyl)-2,6-dinitro-3,
4. Preparation of bovine silydine The title compound was prepared by substituting an equivalent amount of N-(1-ethylpropyl)-3,4-xylidine for N-Sec-butyl-3,4-isosilidine in Example 38. can get.

The yield is 80%. When purified by recrystallization from methanol, the melting point was 56°C to 57°C, and the elemental analysis results were as follows. Cl
8H,, Calculated value of N3O4: C, 55.5; H, 6.8
;N, l4.9 Actual value: C, 55,4; H, 6.8; N
, l5. OO Example 40 N-(1-ethylpropyl)-2,6-dinitro-3,
Preparation of 4-xylidine N-(1-ethylpropyl)-2
-Nitro-3,4-xylidine (1.09, 4x10-
3 mol) of 10a of 70% nitric acid was added thereto, and the reaction mixture was treated after 90 minutes in the same manner as in Example 38 to obtain the desired dinitride compound in a crude yield of 100%.

This product was determined to have a purity of 9 by gas-liquid chromatography.
It was shown to be 7%. Example 41 N-(1-ethylpropyl)-2,6-dinitro-3,
4 Preparation of Inosilidine In place of the 2-nitro compound in the method of Example 40, an equivalent amount of N-(1-ethylpropyl)
When using -6-nitro-3,4-isosilidine, the target substance is obtained with a crude yield of 90%.

The purity of the product was 190%. Example 42 41.09 (0.214 mol) of N-3-pentyl-3
, 4-dimethylaniline and 128 ml of 1,2-dichloroethane are placed in the flask.

Stir the solution and cool it to 00-5℃, and at this temperature 135
Add 2549 (3.22 moles) of 80% nitric acid over a period of minutes. After adding H and keeping the reaction mixture at 05-5° C. for 240 minutes, pour the reaction mixture onto 2549 ice.

Add 128me0CtCH2CH2CL.

After removing the aqueous layer, the product solution was washed with 5% aqueous sodium bicarbonate and water.
The organic layer is dried over MgSO4, filtered, and the solvent is removed under reduced pressure to obtain the crude product. The purity of the crude product 5239 was tested and the yield was 89.7%. The true yield is 79
．． It is 3%. The product crystallizes during storage at room temperature. Reference Examples 13 to 21 The following tests were conducted to illustrate the selective pre-emergence herbicidal activity of the compounds of the present invention.

The various monocotyledonous and dicotyledonous plants were mixed separately with potting soil and this mixture was added to separate 2-×2-
It was placed in a one-thick layer of soil in a resin pot with a soil thickness of approximately 722 mm.

After seeding, the pots were sprayed with a chemical solution at a rate of 0.06 to 10 pounds per acre (a water-acetone solution selected to contain a sufficient amount of the test compound). The treated pots were placed on a stand in a greenhouse and irrigated in accordance with conventional greenhouse cultivation methods.The test was completed 3 to 4 weeks after the treatment, and each pot was examined according to the above evaluation criteria. The test results are shown in Table 1. As is clear from the table, the herbicidal effect of the product obtained by the method of the present invention, especially N-Sa-
Butyl-2,6-dinitro-3,4-isosilidine, N-
(1-ethylpropyl)-2,6-dinitro-3,4-
Xylidine and N-(1-methylbutyl)-2,6-
The exceptional activity of dinitro-3,4-xylidine has been demonstrated,
It can be seen that it is actually ineffective even if analogous substances are used in equivalent or (32 times the amount).Reference example 22 24.21 (0.20 mono(c) 3,4-xylidine, 38.49 (0 .44 mol) of diethyl ketone, 1.29 mol of 5% palladium on carbon and 0.909 (2 mono 0
2-naphthalenesulfonic acid was placed in an autoclave,
After sealing, it is degassed, purged with nitrogen, and hydrogen gas of 47 psi is injected.

Raise the temperature of the contents of the autoclave to 60°C.
Hold at 65°C for about 3/4 hour and then reduce to about 25°C.
The autoclave is opened and the contents are taken out and filtered to separate the catalyst. The lower layer of the bottom liquid was separated using a separation load, and the catalyst cake, filter flask, and separation load were washed with 10 ml of diethyl ketone, and the washing liquid was combined with the organic phase and evaporated.
The constant weight is 29. The obtained product was N-(3-pentyl)-3, with a purity of 97.2% and a conversion rate of 97.2%.
4-xylidine. Reference Comparative Examples 1-18 The following reference examples demonstrate the effect of acid as a promoter on the yield of N-alkylated product produced and single pass conversion.

The general procedure was the same as in Example 22, with 100 mol of 3,4
- The mole % of acid and the relative amounts of ketones and catalysts per xylidine are shown in the table. Reaction conditions, unreacted 3,4
-% of xylidine, % of 3,4-xylidine converted to target material, % of product and % of theoretical yield are also shown in the table. The starting materials in all cases are diethyl ketone and 3,4-xylidine. Generally 5% platinum on carbon was used, but in some cases the catalyst was reused and in other cases 10% platinum on carbon was used.
% platinum was used. From this result, those with a PKa value of O and those with a PKa value of 2.0 or more, such as phosphoric acid, acetic acid, and benzoic acid, have lower yields and conversion rates than those with a PKa value approximately close to aromatic sulfonic acids. Reference Examples 23 to 28 The following reference examples illustrate the fact that when the acid as the promoter is p-toluenesulfonic acid, the conversion rate and yield are always excellent when using a 10% platinum on carbon catalyst repeatedly. do.

The general procedure used was the same as in Reference Example 22, using diethyl ketone and 3,4 xyricidine as starting materials, and the reaction conditions and results are shown in Table X. Reference Examples 29-38 The following reference examples are 4-nitro-0- using diethyl ketone.
For the reductive alkylation of xylene, first 5 on carbon
An example is given using % platinum fresh catalyst and β-naphthalene sulfonic acid and then adding a small amount of fresh catalyst to the used catalyst.

This system maintains excellent conversion and yield when the catalyst is reused many times. The results are shown in Table M. Reference example
39-43 Reductive alkylation of 4-nitro-0-xylene with diethyl ketone in the presence of 2-naphthalenesulfonic acid and 5% platinum on carbon at conditions of 70-80 C and 40-50 psi Reference Example 22 The results obtained using the general method are shown in Table 1.

Reference Examples 44 to 57 Temperature versus conversion for the reductive alkylation of 4-nitro-0-xylene using diethyl ketone in the presence of 2-naphthalenesulfonic acid and 5% platinum on carbon catalyst 0.789 , the influence of pressure and promoter concentration is shown in Table 1.

Example 58 Preparation of N-3-pentyl-α,α,α-trifluoro p-toluidine 8,059 (0.05 mol) of α,α,
α-trifluoro-p-toluidine, 6.99 (0.0
8 moles) of diethyl ketone, 0.39 moles of 5% platinum on carbon, and 0.239 moles of 2-naphthalenesulfonic acid are placed in a pressure vessel.

The vessel is sealed and the reaction mixture is heated to 55 C to 60 C, then hydrogen gas is introduced to 45 to 50 psi. After the reaction is allowed to continue until the hydrogen gas is consumed, the reaction mixture is cooled to room temperature and the container is opened. The mixture is taken out from the container and after rinsing, the lower layer of lachrymal fluid is removed. Vacuum evaporation of the furnace liquid yields 1 target substance.
Obtained as 1.2 g of oil (97% of theory). Confirmation of the product was performed by proton magnetic resonance spectroscopy and elemental analysis. The nitrogen analysis value was 5.92% compared to the theoretical value of 6.06%. Reference Example 59 Preparation of N-(2-butyl)-4-t-butylaniline 1
8.0 f1 (0.1 mol) of pt-butyl-nitrobenzene, 13.69 (0.22 mol) of methyl ethyl ketone, 0.6 g of 5% platinum-containing carbon and 0.469 of 2-naphthalenesulfonic acid 1 The hydrate is placed in a 500 ml pressure reactor and sealed.

Pressurized hydrogen gas is introduced into the reactor, and the reaction is continued at 60°C to 75°C until hydrogen consumption exceeds the theoretical amount by about 6%. After completion, cool to room temperature, open the container, take out the contents, and filter through F. The lower layer of the bottom liquid is discarded and the upper layer is concentrated in vacuo to obtain 20.71 of a crude product of the target substance (yield: about 100% of the theoretical value). When the infrared absorption spectrum of the product was examined, it was found to be identical to a pure analytical sample of N-(2-butyl)-4-t-butylaniline. Reference Example 60 Preparation of N-(2-butyl)-3-chloro-p-toluidine 28.39 (0.2 mol) of 3-chloro-p-toluidine, 23.0f! (0.32 mol) of methyl ethyl ketone, 1.2 g of 5% platinum-containing carbon and 0.99 of 2
- Place naphthalene sulfonic acid in a 500 d pressure reactor and close it.

Hydrogen gas was introduced into the reactor and pressurized to approximately 51 psi, and the temperature was increased to 40°C to 65°C and held there until the pressure drop indicated the stoichiometric amount of hydrogen consumption. After cooling to room temperature, the container was opened and the contents were taken out. The lower aqueous phase was discarded and the upper layer was evaporated in vacuo to obtain a crude target substance with a yield of 100%. Infrared and N.I. compared to pure N-(2-butyl)-3-chloro-p-toluidine. M. R. Examination of the spectrum confirmed its structure and revealed that it contained less than 5% of methyl ethyl ketone and a small amount of 2-naphthalenesulfonic acid as impurities.

[Brief explanation of the drawing]

The drawing shows the composition ratios of the three components of the nitration agent based on the nitrate, monosulfuric acid, and water 3-component system. Among these, particularly suitable nitrating agents are shown below.

Claims (1)

[Claims] Primary formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ {Here, R_1 is alkyl C_1 to C_6, cycloalkyl C_4 to C_6, monohaloalkyl C_1 to C_4
or alkoxyalkyl (where the alkyl group is C_1
~C_4, and the alkoxy group is C_1 to C_4); R_2 represents one of the R_1 groups;
Y is alkyl C_1 to C_4, halogen or CF_3
;Z is hydrogen, halogen, alkyl C_1 to C_4, alkoxy C_1 to C_4, monohaloalkyl C_1 to C_
4 or monoalkoxy(C_1-C_4)alkyl (
C_1 to C_4); W and V are hydrogen or nitro (
However, W and V do not represent nitro at the same time)], 60%H_NO_3, 8%H_2SO_4, 32%
H_2O, 50%HNO_3, 35%H_2SO_4,
15%H_2O; 2%HNO_3, 68%H_2SO_
4, 30%H_2O; 2%HNO_3, 20%H_2S
O_4, 78% H_2O with a limit of 3-component nitrating agent at 0° to 70°C and further N-alkylated aniline when W and V are hydrogen.
- using 2.2 to 5.0 mol of nitric acid per mole of alkylated aniline, and from 1.2 to 1.2 per mole of N-alkylated aniline when one of W and V in the N-alkylated aniline is nitro; ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (where R_1, R_2, Y and Z are the same as already defined) of the compound characterized by using nitric acid in the range of 4.0 mol. Manufacturing method. Secondary formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ {Here, R_1 is alkyl C_1 to C_6, cycloalkyl C_4 to C_6, monohaloalkyl C_1 to C_4
or alkoxyalkyl (where the alkyl group is C_1
~C_4 and the alkoxy group is C_1 to C_4); R_2 represents hydrogen; Y is alkyl C_1 to C_4, halogen or CF_3; Z is hydrogen;
Halogen, alkyl C_1 to C_4, alkoxy C_1
~C_4, monohaloalkyl C_1-C_4 or monoalkoxy(C_1-C_4)alkyl(C_1-C_
4); W and V represent hydrogen or nitro (however, W and V do not represent nitro at the same time)} N-alkylated aniline represented by 60%
HNO_3, 8%H_2SO_4, 32%H_2O; 5
0%HNO_3, 35%H_2SO_4, 15%H_2
O; 2%HNO_3, 68%H_2SO_4, 30%H
_2O; 2%HNO_3, 20%H_2SO_4, 78
3-component nitrating agent with limits of %H_2O and 0°~
70° C. and using 2.2 to 5.0 mol of nitric acid per mole of N-alkylated aniline when W and V are hydrogen in the N-alkylated aniline; When one of W and V is nitro, N-alkylation is used to produce the by-product ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (where R_1, Y and Z are as already defined). A formula ▲ is a mathematical formula, a chemical formula, a table, etc. ▼ (where R_1, R_2, Y and Z are the same as already defined) characterized by the denitrosation of a reaction mixture containing a nitroso compound represented by Method of manufacturing the compound represented. 3. Claim 1, wherein R_1 is C_4-C_5 branched alkyl selected from the group consisting of sec-butyl and 1-ethylpropyl, R_2 is hydrogen, and Y and Z are both methyl. The method described in section. 4. The method according to claim 1, wherein the nitrating agent used in the method according to claim 1 has a composition within the following four limit points. 45%HNO_3, 19%H_2SO_4, 36%H_
2O; 45%HNO_3, 52%H_2SO_4, 28
%H_2O; 20%HNO_3, 27%H_2SO_4
, 53% H_2O5 The method of claim 1, wherein the temperature range is 35°C to 60°C. 6. The method of claim 1, wherein the N-alkylated amine is N-(1-ethylpropyl)-3,4-dimethylaniline.