CA2098239C - A process for producing an aromatic compound by electrophilic reaction and aromatic compound derivatives - Google Patents
A process for producing an aromatic compound by electrophilic reaction and aromatic compound derivativesInfo
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- CA2098239C CA2098239C CA 2098239 CA2098239A CA2098239C CA 2098239 C CA2098239 C CA 2098239C CA 2098239 CA2098239 CA 2098239 CA 2098239 A CA2098239 A CA 2098239A CA 2098239 C CA2098239 C CA 2098239C
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- C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
- C07C205/37—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
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- C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C235/18—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the singly-bound oxygen atoms further bound to a carbon atom of a six-membered aromatic ring, e.g. phenoxyacetamides
- C07C235/20—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the singly-bound oxygen atoms further bound to a carbon atom of a six-membered aromatic ring, e.g. phenoxyacetamides having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
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- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
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- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
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Abstract
There are disclosed a process for producing an aromatic compound of the formula (I) which comprises reacting an electrophilic reagent with a compound of the formula (II) shown below:
[wherein X1 and X2, which may be the same or different, are each a halogen atom; R is a group represented by the formula:
(wherein R1 and R2, which may be the same or different, are each a hydrogen atom or a C1-C6 alkyl group, Z is a cyano group, -CO-OR3 (wherein R3 is a hydrogen atom or a C1-C6 alkyl group) or -CO-NR4R5 (wherein R4 and R5, which may be the same or different, are each a hydrogen atom or a C1-C6 alkyl group)); and Y is a nitro group, a halogen atom, a C1-C6 haloalkyl group or a group represented by the formula:
(wherein R6, R7 and R8, which may be the same or different, are each a hydrogen atom, a halogen atom or a cyano group)]
to introduce a substituent into the aromatic ring selectively and a novel compound prepared therefrom.
[wherein X1 and X2, which may be the same or different, are each a halogen atom; R is a group represented by the formula:
(wherein R1 and R2, which may be the same or different, are each a hydrogen atom or a C1-C6 alkyl group, Z is a cyano group, -CO-OR3 (wherein R3 is a hydrogen atom or a C1-C6 alkyl group) or -CO-NR4R5 (wherein R4 and R5, which may be the same or different, are each a hydrogen atom or a C1-C6 alkyl group)); and Y is a nitro group, a halogen atom, a C1-C6 haloalkyl group or a group represented by the formula:
(wherein R6, R7 and R8, which may be the same or different, are each a hydrogen atom, a halogen atom or a cyano group)]
to introduce a substituent into the aromatic ring selectively and a novel compound prepared therefrom.
Description
_...
Field of the Invention The present invention relates to a process for producing an aromatic compound represented by the general formula (I):
X2 O Y (I) RO
[wherein X1 and X2, which may be the same or different, are halogen atoms; R is a group represented by the formula -C-Z
(wherein Rl and R2, which may be the same or different, are hydrogen atoms or lower alkyl groups, Z is a cyano group, -CO-OR3 (wherein R3 is a hydrogen atom or a lower alkyl group) or -CO-N(R4)R5 (wherein R4 and R5, which may be the same or different, are hydrogen atoms or lower alkyl groups, R4 and R5 being able to be taken together to represent an alkylene group)); and Y is a 1 nitro group, a halogen atom, a haloalkyl group or a group represented by the formula:
-C -C R~
-(wherein R6, R~ and R8, which may be the same or different, are hydrogen atoms, halogen atoms or cyano groups)) which comprises reacting an electrophilic reagent with a compound represented by the general formula (II):
X2 O (II) RO
(wherein X1, X2 and R have the same meanings as those defined above), and aromatic derivatives thus produced.
Related Art Electrophilic substitution reaction on a benzene ring has been known since early times, but there has not been known any process by which a 1,2,4,5-substituted benzene derivative of the general formula (I) can be selectively obtained from the compound of the general formula (II) used in the present invention.
Field of the Invention The present invention relates to a process for producing an aromatic compound represented by the general formula (I):
X2 O Y (I) RO
[wherein X1 and X2, which may be the same or different, are halogen atoms; R is a group represented by the formula -C-Z
(wherein Rl and R2, which may be the same or different, are hydrogen atoms or lower alkyl groups, Z is a cyano group, -CO-OR3 (wherein R3 is a hydrogen atom or a lower alkyl group) or -CO-N(R4)R5 (wherein R4 and R5, which may be the same or different, are hydrogen atoms or lower alkyl groups, R4 and R5 being able to be taken together to represent an alkylene group)); and Y is a 1 nitro group, a halogen atom, a haloalkyl group or a group represented by the formula:
-C -C R~
-(wherein R6, R~ and R8, which may be the same or different, are hydrogen atoms, halogen atoms or cyano groups)) which comprises reacting an electrophilic reagent with a compound represented by the general formula (II):
X2 O (II) RO
(wherein X1, X2 and R have the same meanings as those defined above), and aromatic derivatives thus produced.
Related Art Electrophilic substitution reaction on a benzene ring has been known since early times, but there has not been known any process by which a 1,2,4,5-substituted benzene derivative of the general formula (I) can be selectively obtained from the compound of the general formula (II) used in the present invention.
~~98~~~
Rec. Trav. Chim., 75, 190 (1956) discloses the following process:
When the above process is employed, a substituent cannot be introduced at the desired position of substitution and moreover the methoxy group is converted to a hydroxyl group. Thus, there cannot be obtained a compound formed by selective introduction of a substituent into the position of substitution corre-sponding to the general formula (I) which represents the compound obtained in the present invention.
SUMMARY OF THE INVENTION
The present inventors earnestly investigated a method for introducing a substituent into an aromatic ring selectively, and have consequently accomplished the present invention. The aromatic compound of the general formula (I) obtained by the production process of the present invention is useful as an intermediate of medicines, pesticides, chemicals, etc, and some of them are novel.
Rec. Trav. Chim., 75, 190 (1956) discloses the following process:
When the above process is employed, a substituent cannot be introduced at the desired position of substitution and moreover the methoxy group is converted to a hydroxyl group. Thus, there cannot be obtained a compound formed by selective introduction of a substituent into the position of substitution corre-sponding to the general formula (I) which represents the compound obtained in the present invention.
SUMMARY OF THE INVENTION
The present inventors earnestly investigated a method for introducing a substituent into an aromatic ring selectively, and have consequently accomplished the present invention. The aromatic compound of the general formula (I) obtained by the production process of the present invention is useful as an intermediate of medicines, pesticides, chemicals, etc, and some of them are novel.
1 The term "lower" alkyl group or the like in the present specification denotes a group having one to six carbon atoms.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present inventive process for producing an aromatic compound of the general formula (I) is explained below in detail.
Nitration reaction This reaction is such that an aromatic compound of the general formula (I-I) can be produced by selective nitration of a compound of the general formula (II) with a nitrating agent in the presence of an inert solvent.
Xi Xi X2 ~ Nitrating X2 O NOZ
agent (II) (I-1) wherein Xl, XZ and R have the same meanings as those defined above.
As the inert solvent usable in this reaction, any solvent can be used so long as it does not inhibit the progress of the reaction greatly. There can be exemplified nitric acid, sulfuric acid, acetic acid, ~,~~~3~
1 trifluoroacetic acid, and trifluoromethanesulfonic acid.
These inert solvents may be used singly or as a mixture thereof .
As the nitrating agents, there can be used, for example, nitric acid, nitric acid-sulfuric acid, fuming nitric acid, fuming nitric acid-sulfuric acid, nitric acid-acetic acid, nitric acid-acetic anhydride, nitric acid-trifluoroacetic acid, and nitric acid-trifluoromethanesulfonic acid.
The amount of the nitrating agent used may be properly chosen in the range of 1 mole to excess moles per mole of the compound of the general formula (II).
The reaction temperature may be chosen in the range of -20°C to 150°C and is preferably 0°C to 50°C.
Although the reaction time is varied depending on the reaction temperature, the degree of reaction, etc., it may be chosen in the range of several minutes to 100 hours.
After completion of the reaction, the desired compound is isolated from the reaction mixture containing the compound by a conventional method such as solvent extraction, and if necessary, purified by recrystallization, etc., whereby the desired compound can be produced.
~ Halogenation reaction This reaction is such that an aromatic compound of the general formula (I-2) can be produced by ~~98~~9 1 selective halogenation of a compound of the general formula (II) with a halogenating agent in the presence of an inert solvent.
X2 O Halogenating X2 O y1 agent RO RO
(II) (I-2) wherein X1, X2 and R have the same meanings as those defined above, and Yl is a halogen atom.
As the inert solvent usable in this reaction, any solvent may be used so long as it does not inhibit the progress of the reaction greatly. There can be exemplified halogenated hydrocarbons (e. g. dichloro-methane, chloroform, carbon tetrachloride, and dichloro-ethane), sulfuric acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, dimethylformamide, 1,3-dimethyl-2-imidazolidinone, and sulfolane. These inert solvents may be used singly or as a mixture thereof.
As the halogenating agent, there can be used, for example, chlorine, bromine, chlorine-bromine, bromine-aluminum chloride, bromine-iron, and bromine-silver sulfate.
The amount of the halogenating agent used may be properly chosen in the range of 1 mole to excess ~~9~~3~
1 moles per mole of the compound of the general formula (II).
The reaction temperature may be chosen in the range of 0°C to 150°C and is preferably 20°C to 100°C.
Although the reaction time is varied depending on the reaction temperature, the degree of reaction, etc., it may be chosen in the range of several minutes to 100 hours.
After completion of the reaction, the desired compound is isolated from the reaction mixture contain-ing the compound by a conventional method such as solvent extraction, and if necessary, purified by recrystallization, etc., whereby the desired compound can be produced.
~3 Friedel-Crafts reaction This reaction is such that an aromatic compound of the general formula (I-3) can be produced by reacting a compound of the general formula (II) with a Lewis acid and a compound of the general formula (III), (IV) or (V) in the presence or absence of an inert solvent and in the presence or absence of a salt.
Friedel-Crafts reaction RO II ~ II I RO
X3-C-C-R~ O(-C-C-R~)2 C(X4)q I
(II) R8 R8 (V) (I-3) (III) (IV) or ",.
1 wherein Xl, X2 and R have the same meanings as those defined above, and Y1 is a haloalkyl group or a group represented by the formula:
-C-C-R~
(wherein R6, R~ and R8, which may be the same or different, are hydrogen atoms, halogen atoms or cyano groups), X3 is a halogen atom, and X4's, which may be the same or different, are halogen atoms.
This reaction proceeds in the presence or absence of an inert solvent. As the inert solvent, there can be used, for example, nitroalkanes such as nitromethane, etc.; halogenated hydrocarbons such as dichloromethane, carbon tetrachloride, tetrachloro-ethane, dichloroethane, etc.; aromatic hydrocarbons such as nitrobenzene, etc.; amides such as N-methyl-pyrrolidone, N,N-dimethylformamide, etc.; urea derivatives such as N,N,N',N'-tetramethylurea, N,N-dimethylimidazolinone, etc.; organic bases such as pyridine, triethylamine, etc.; organosulfur compounds such as carbon disulfide, dimethyl sulfoxide, sulfolane, etc.; alcohols such as ethanol, ethylene glycol, etc.;
nitriles such as acetonitrile, benzonitrile, etc.; and organophosphorus compounds such as phosphorus oxychloride, hexamethylphosphoramide, etc. These inert solvents may be used singly or as a mixture thereof.
_ g _ 2.p9~~~
1 Although not critical, the amount of the inert solvent used is preferably 0.5 to 10 moles per mole of the compound of the general formula (II).
As the salt usable in the present invention, there can be exemplified sodium chloride, potassium chloride, calcium chloride, magnesium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide, ammonium salts (e. g. tetramethylammonium chloride), and sulfonates (e. g. sodium trifluoromethane-sulfonate). These salts may be used singly or as a mixture thereof.
The amount of the salt used may be properly chosen in the range of 0.5 to 10 moles per mole of the compound of the general formula (II).
As the Lewis acid, there can be used Lewis acids such as A1C13, AlHrg, AlIg, FeCl3, FeHr3, TiCl4, SnCl4, ZnCl2, GaCl3, etc.
The amount of the Lewis acid used may be properly chosen in the range of 1 mole to excess moles per mole of the compound of the general formula (II) and is preferably 3 to 8 moles per mole of this compound.
The amount of the compound of the general formula (III), (IV) or (V) used may be properly chosen in the range of 0.5 to 2 moles per mole of the compound of the general formula (II).
The compound of the general formula (V) may be used both as reactant and as inert solvent. In this case, it may be used in large excess.
,..
1 The reaction temperature may be chosen in the range of 0°C to 180°C and is preferably 60°C to 100°C.
Although the reaction time is varied depending on the reaction temperature, the degree of reaction, etc., it may be chosen in the range of several minutes to 100 hours.
After completion of the reaction, the desired compound is isolated from the reaction mixture contain-ing the compound by a conventional method such as solvent extraction, and if necessary, purified by recrystallization, etc., whereby the desired compound can be produced.
As mentioned before. some of the compounds thus prepared are novel. That is, an aromatic compound represented by the general formula (I):
X2 ~ Y (I) RO
[wherein Xl and X2, which may be the same or different, are halogen atoms; R is a group represented by the formula -C-Z
(wherein R1 and R2, which may be the same or different, are hydrogen atoms or lower alkyl groups, Z is a cyano group, -CO-ORS (wherein R3 is a hydrogen atom or a lower alkyl group) or -CO-NR4R5 (wherein R4 and R5, which may be the same or different, are hydrogen atoms or lower alkyl groups, R4 and R5 being able to be taken together to represent an alkylene group)); and Y is a nitro group, a halogen atom, a haloalkyl group or a group represented by the formula:
-C-C-R~
Rg (wherein R6, R7 and R8, which may be the same or different, are hydrogen atoms, halogen atoms or cyano groups), provided [1] that X1 is fluorine atom, X2 is chlorine atom and Z is cyano group or -CONR4R5, when Y is nitro group, [2]
that X1 is fluorine atom, X2 is chlorine atom and Z is cyano group, when Y is fluorine atom) [3] that X1 is fluorine atom, X2 is chlorine atom and Z is -COORS (wherein R3 is other than a hydrogen atom), -CONR4R5 or cyano group, when Y is chlorine atom and [4] that Z is a cyano group, -COORS (wherein R3 is other than a hydrogen atom) or -CONR4R5, when Y is an iodine atom] is novel.
Among them, those whose Y is -C-C-R' Rg - lla -'~Q~~~3 1 wherein R6, R~ and R8, which may be the same or different, are hydrogen atoms, halogen atoms or cyano groups are useful as an intermediate for producing the herbicides disclosed in Japanese Patent Kokai (Laid-Open) No. 3-163063 (JP-A-3-163063).
Especially, compounds whose R is -C-Z
wherein R1 and R2, which may be the same or different, are hydrogen atoms or lower alkyl groups, Z is -CON(R4)R5 (wherein R4 and R5, which may be the same or different, are hydrogen atoms or lower alkyl groups, R4 and R5 being able to be taken together to represent an alkylene group) is quite useful as an intermediate for said herbicides.
EXAMPLES
Typical examples of the present invention are given below but they should not be construed as limiting the scope of the invention.
Example 1 Production of (2-chloro-4-fluoro-5-nitro-phenoxy)acetamide (compound No. 1) ,.
F F
1 In 8 ml of 97% sulfuric acid was dissolved 3.7 g (0.02 mole) of (2-chloro-4-fluorophenoxy)aceto-nitrile, and a mixed acid of 2.5 ml of 60 - 62% nitric acid and 5.8 ml of 97% sulfuric acid was added to the resulting solution with stirring at 10°C or lower, after which the reaction was carried out at room temperature for 1.5 hours.
After completion of the reaction, the reaction solution was poured into ice water and the crystals 1~ precipitated were collected by filtration, washed with water and then dried to obtain 3.4 g of the desired compound as yellow crude crystals (yield: 68%).
The crude crystals obtained were recrystal-lined from ethyl acetate to obtain 2.5 g of the desired compound as light-yellow crystals.
Physical properties: m.p. 182 - 182.5°C, yield 50.5%.
NMR [DMSO/TMS, d values (ppm)]
4.75 (s, 2H), 7.50 (bd, 2H, J=0.6Hz), 7.75 (d, 2H, J=7Hz), 7.97 (d, 2H, J=llHz).
1 Example 2 Production of (2-chloro-4-fluoro-5-nitro-phenoxy)acetamide (compound No. 1) F F
Reaction was carried out for 5 hours in the same manner as in Example 1, except that 4.1 g (0.02 mole) of (2-chloro-4-fluorophenoxy)acetamide was used in place of (2-chloro-4-fluorophenoxy)acetonitrile, to obtain 3.6 g of the desired compound.
Yield: 72.4.
Example 3 Production of (2-chloro-4-fluoro-5-nitro-phenoxy)acetic acid (compound No. 2) F F
In the same manner as in Example 1, 4.6 g (0.02 mole) of ethyl (2-chloro-4-fluorophenoxy)acetate 14 was reacted, followed by overnight standing at room temperature.
,~~~g~3g 1 After completion of the reaction, the reaction solution containing the desired product was poured into ice water, and the desired product was extracted with ethyl acetate.
The extracted solution was washed with water and dried over magnesium sulfate, after which the solvent was distilled off under reduced pressure. The resulting residue was purified by a silica gel column chromatography (CHZC12-CHgOH) to obtain 1.3 g of the l0 desired compound asocherous crystals.
Yield: 30.2$.
NMR [DMSO/TMS, d values (ppm)]
4.57 (s, 2H), 7.50 (bd, 2H, J=0.6Hz), 7.75 (d, 2H, J=7Hz), 7.97 (d, 2H, J=llHz), 13.90 (bs, 1H).
Example 4 Production of (5-bromo-2-chloro-4-fluoro-phenoxy)acetonitrile (compound No. 3) F F
C1 O C1 O Br In 10 ml of methylene chloride was suspended 1.0 g (7.5 mmoles) of anhydrous aluminum chloride, and 1.0 g (5.4 mmoles) of (2-chloro-4-fluorophenoxy)aceto-.. ~~39~~~~
1 nitrile was added to the suspension, after which 0.95 g (5.9 mmoles) of bromine was added dropwise with refluxing. After completion of the dropwise addition, the reaction was carried out with refluxing for 2 hours.
After completion of the reaction, the reaction mixture was allowed to cool and then poured into ice water, and the desired compound was extracted with ether.
The extracted solution was washed successively with water, a 10% aqueous sodium thiosulfate solution and a saturated aqueous sodium chloride solution, and dried over magnesium sulfate. Then, the solvent was distilled off under reduced pressure and the resulting residue was recrystallized from n-hexane to obtain 1.1 g of the desired compound.
Physical properties: m.p. 72.3°C, yield 77%.
Example 5 Production of (2-chloro-5-chloroacetyl-4-fluorophenoxy)acetamide (compound No. 6) F F
H2NCCH20 HyNCCH20 O O
With 2.0 g (15.0 mmoles) of anhydrous aluminum chloride was mixed 0.85 g (7.5 mmoles) of chloroacetyl z 1 chloride, and the resulting mixture was heated to 80°C.
Then, 1.0 g (4.9 mmoles) of (2-chloro-4-fluorophenoxy)-acetamide was added and the reaction was carried out at 90°C for 9 hours.
After completion of the reaction, the reaction mixture was cooled to 80°C and 5 ml of acetic acid was added. The mixture thus obtained was poured into ice water, and the crystals precipitated were collected by filtration and recrystallized from ethanol to obtain 1.0 g of the desired compound.
Physical properties: m.p. 166.3°C, yield 73%.
Example 6 Production of (2-chloro-5-dichloroacetyl-4-fluorophenoxy)acetamide (compound No. 7) F F
'C 1 C1 O .---~ C1 O COC/H
O O
With 2.0 g (15.0 mmoles) of anhydrous aluminum chloride was mixed 0.93 g (6.3 mmoles) of dichloroacetyl chloride, and the resulting mixture was heated to 50°C.
Then, 1.0 g (4.9 mmoles) of (2-chloro-4-fluorophenoxy)-acetamide was added and the reaction was carried out at 7p - g0°C for 8 hours.
1 After completion of the reaction, the reaction mixture was allowed to cool and ice water was added and then stirred for 2 hours. The desired compound was extracted with ethyl acetate and the extracted solution was washed with water and dried over magnesium sulfate.
Then, the ethyl acetate was distilled off under reduced pressure, and the resulting residue was purified by a silica gel column chromatography to obtain 0.5 g of the desired compound.
Physical properties: m.p. 132.3°C, yield 33%.
Example 7 Production of (2-chloro-5-chloroacetyl-4-fluorophenoxy)acetonitrile (compound No. 11) F F
With 2.0 g (15.0 mmoles) of anhydrous aluminum chloride was mixed 0.85 g (7.5 mmoles) of chloroacetyl chloride, and the resulting mixture was heated to 60°C.
Then, 0.9 g (4.0 mmoles) of (2-chloro-4-fluorophenoxy)-acetonitrile was added and the reaction was carried out at 70°C for 3 hours.
After completion of the reaction, the reaction mixture was poured into ice water and stirred for 1 .. ..
1 hour. The crystals precipitated were collected by filtration and recrystallized from ethanol to obtain 0.93 g of the desired compound.
Physical properties: m.p. 122.1°C, yield 73%.
Example 8 Production of (2-chloro-5-dichloroacetyl-4-fluorophenoxy)acetonitrile (compound No. 13) C1 O ~. Cl O LOCH
'C 1 With 2.0 g (15.0 mmoles) of anhydrous aluminum chloride were mixed 0.93 g (6.3 mmoles) of dichloroacetyl chloride and 0.9 g (4.9 mmoles) of (2-chloro-4-fluorophenoxy)acetonitrile, and the reaction was carried out at 60°C for 2 hours.
After completion of the reaction, the reaction mixture was allowed to cool and 5 ml of nitromethane was added) The resulting mixture was poured into ice water, after which the desired compound was extracted with ethyl acetate and the extracted solution was washed with water and dried over magnesium sulfate. Then, the solvent was distilled off under reduced pressure, and the resulting residue was purified by a silica gel column chromatography to obtain 0.97 g of the desired compound.
Physical properties: m.p. 98.7°C, yield 67%.
1 Example 9 Production of (2-chloro-4-fluoro-5-trichloro-methylphenoxy)acetonitrile (compound No. 14) F F
In 10 ml of carbon tetrachloride was suspended 1.5 g (11.2 mmoles) of anhydrous aluminum chloride, and 1.0 g (5.4 mmoles) of (2-chloro-4-fluorophenoxy)aceto-nitrile was added dropwise. After completion of the addition, the reaction was carried out at 60°C for 1 hour.
After completion of the reaction, the reaction mixture was allowed to cool and ice water was added and then stirred for 1 hour. The desired compound was extracted with ethyl acetate and the extracted solution was washed with water and dried over magnesium sulfate.
Then, the solvent was distilled off under reduced pressure, and the resulting residue was purified by a silica gel column chromatography to obtain 1.2 g of the desired compound as an oil.
Physical properties: oil, yield 72~.
NMR [CDC13/TMS, d values (ppm)]
4.88 (s, 2H), 7.09 (d, 1H, J=10.4Hz), 7.79 (d, 1H, J=7.lHz).
1 Example 10 Production of (2-chloro-5-cyanoacetyl-4-fluorophenoxy)acetonitrile (compound No. 17) F F
To 4.5 g (33.6 mmols) of anhydrous aluminum chloride was added 0.57 g (7.8 mmols) of dimethyl-formamide (DMF), and 1.0 g (5.6 mmoles) of (2-chloro-4-fluorophenoxy)acetonitrile was added to the suspension at room temperature. Then, 2.9 g (28.0 mmoles) of cyanoacetyl chloride was slowly dropped into the resulting mixture. After completion of the dropping, the reaction was carried out at 55°C for 3 hours.
After completion of the reaction, the reaction mixture was analyzed by a thin layer chromatography and a gas chromatography (area percentage: 7.0%). The analysis results obtained were in agreement with those obtained for a standard substance, whereby the production of the desired compound was confirmed.
Compounds of the general formula (I) are listed in Table 1.
X2 ~ Y ( RO
Table 1 No R X1 X2 Y Physical properties 1 H2NCOCH2 F C1 N02 m.p. 182.0-182.5C
2 HOOCCH2 F C1 N02 d (DMSO)=4.57 (s, 2H), 7.57 (d, 2H, J=7.OEz), 7.89 (d, 2H, J=1l.OHz), 13.9 (bs, lE).
3 NCCH F C1 Br m.p. 72.3C
4 HZNCOCH2 F Cl COCH3 d (CDC13)=2.64 (d, 3H, J=3.3Hz), 4.51 (s, 2H), 5.70 (bs, 1H), 6.60 (bs, 1H), 7.28 (d, 1H, J=7.9Hz), 7.4. (d, 1H, J=5.9Hz).
H2NCOCH2 C1 C1 COCH2C1 m.p. 171.7C
6 HZNCOCfi2 r~ Ci COCH2C1 m.p. 166.3C
7 H2NCOCH2 F C1 COCHC12 m.p. 132.3C
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present inventive process for producing an aromatic compound of the general formula (I) is explained below in detail.
Nitration reaction This reaction is such that an aromatic compound of the general formula (I-I) can be produced by selective nitration of a compound of the general formula (II) with a nitrating agent in the presence of an inert solvent.
Xi Xi X2 ~ Nitrating X2 O NOZ
agent (II) (I-1) wherein Xl, XZ and R have the same meanings as those defined above.
As the inert solvent usable in this reaction, any solvent can be used so long as it does not inhibit the progress of the reaction greatly. There can be exemplified nitric acid, sulfuric acid, acetic acid, ~,~~~3~
1 trifluoroacetic acid, and trifluoromethanesulfonic acid.
These inert solvents may be used singly or as a mixture thereof .
As the nitrating agents, there can be used, for example, nitric acid, nitric acid-sulfuric acid, fuming nitric acid, fuming nitric acid-sulfuric acid, nitric acid-acetic acid, nitric acid-acetic anhydride, nitric acid-trifluoroacetic acid, and nitric acid-trifluoromethanesulfonic acid.
The amount of the nitrating agent used may be properly chosen in the range of 1 mole to excess moles per mole of the compound of the general formula (II).
The reaction temperature may be chosen in the range of -20°C to 150°C and is preferably 0°C to 50°C.
Although the reaction time is varied depending on the reaction temperature, the degree of reaction, etc., it may be chosen in the range of several minutes to 100 hours.
After completion of the reaction, the desired compound is isolated from the reaction mixture containing the compound by a conventional method such as solvent extraction, and if necessary, purified by recrystallization, etc., whereby the desired compound can be produced.
~ Halogenation reaction This reaction is such that an aromatic compound of the general formula (I-2) can be produced by ~~98~~9 1 selective halogenation of a compound of the general formula (II) with a halogenating agent in the presence of an inert solvent.
X2 O Halogenating X2 O y1 agent RO RO
(II) (I-2) wherein X1, X2 and R have the same meanings as those defined above, and Yl is a halogen atom.
As the inert solvent usable in this reaction, any solvent may be used so long as it does not inhibit the progress of the reaction greatly. There can be exemplified halogenated hydrocarbons (e. g. dichloro-methane, chloroform, carbon tetrachloride, and dichloro-ethane), sulfuric acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, dimethylformamide, 1,3-dimethyl-2-imidazolidinone, and sulfolane. These inert solvents may be used singly or as a mixture thereof.
As the halogenating agent, there can be used, for example, chlorine, bromine, chlorine-bromine, bromine-aluminum chloride, bromine-iron, and bromine-silver sulfate.
The amount of the halogenating agent used may be properly chosen in the range of 1 mole to excess ~~9~~3~
1 moles per mole of the compound of the general formula (II).
The reaction temperature may be chosen in the range of 0°C to 150°C and is preferably 20°C to 100°C.
Although the reaction time is varied depending on the reaction temperature, the degree of reaction, etc., it may be chosen in the range of several minutes to 100 hours.
After completion of the reaction, the desired compound is isolated from the reaction mixture contain-ing the compound by a conventional method such as solvent extraction, and if necessary, purified by recrystallization, etc., whereby the desired compound can be produced.
~3 Friedel-Crafts reaction This reaction is such that an aromatic compound of the general formula (I-3) can be produced by reacting a compound of the general formula (II) with a Lewis acid and a compound of the general formula (III), (IV) or (V) in the presence or absence of an inert solvent and in the presence or absence of a salt.
Friedel-Crafts reaction RO II ~ II I RO
X3-C-C-R~ O(-C-C-R~)2 C(X4)q I
(II) R8 R8 (V) (I-3) (III) (IV) or ",.
1 wherein Xl, X2 and R have the same meanings as those defined above, and Y1 is a haloalkyl group or a group represented by the formula:
-C-C-R~
(wherein R6, R~ and R8, which may be the same or different, are hydrogen atoms, halogen atoms or cyano groups), X3 is a halogen atom, and X4's, which may be the same or different, are halogen atoms.
This reaction proceeds in the presence or absence of an inert solvent. As the inert solvent, there can be used, for example, nitroalkanes such as nitromethane, etc.; halogenated hydrocarbons such as dichloromethane, carbon tetrachloride, tetrachloro-ethane, dichloroethane, etc.; aromatic hydrocarbons such as nitrobenzene, etc.; amides such as N-methyl-pyrrolidone, N,N-dimethylformamide, etc.; urea derivatives such as N,N,N',N'-tetramethylurea, N,N-dimethylimidazolinone, etc.; organic bases such as pyridine, triethylamine, etc.; organosulfur compounds such as carbon disulfide, dimethyl sulfoxide, sulfolane, etc.; alcohols such as ethanol, ethylene glycol, etc.;
nitriles such as acetonitrile, benzonitrile, etc.; and organophosphorus compounds such as phosphorus oxychloride, hexamethylphosphoramide, etc. These inert solvents may be used singly or as a mixture thereof.
_ g _ 2.p9~~~
1 Although not critical, the amount of the inert solvent used is preferably 0.5 to 10 moles per mole of the compound of the general formula (II).
As the salt usable in the present invention, there can be exemplified sodium chloride, potassium chloride, calcium chloride, magnesium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide, ammonium salts (e. g. tetramethylammonium chloride), and sulfonates (e. g. sodium trifluoromethane-sulfonate). These salts may be used singly or as a mixture thereof.
The amount of the salt used may be properly chosen in the range of 0.5 to 10 moles per mole of the compound of the general formula (II).
As the Lewis acid, there can be used Lewis acids such as A1C13, AlHrg, AlIg, FeCl3, FeHr3, TiCl4, SnCl4, ZnCl2, GaCl3, etc.
The amount of the Lewis acid used may be properly chosen in the range of 1 mole to excess moles per mole of the compound of the general formula (II) and is preferably 3 to 8 moles per mole of this compound.
The amount of the compound of the general formula (III), (IV) or (V) used may be properly chosen in the range of 0.5 to 2 moles per mole of the compound of the general formula (II).
The compound of the general formula (V) may be used both as reactant and as inert solvent. In this case, it may be used in large excess.
,..
1 The reaction temperature may be chosen in the range of 0°C to 180°C and is preferably 60°C to 100°C.
Although the reaction time is varied depending on the reaction temperature, the degree of reaction, etc., it may be chosen in the range of several minutes to 100 hours.
After completion of the reaction, the desired compound is isolated from the reaction mixture contain-ing the compound by a conventional method such as solvent extraction, and if necessary, purified by recrystallization, etc., whereby the desired compound can be produced.
As mentioned before. some of the compounds thus prepared are novel. That is, an aromatic compound represented by the general formula (I):
X2 ~ Y (I) RO
[wherein Xl and X2, which may be the same or different, are halogen atoms; R is a group represented by the formula -C-Z
(wherein R1 and R2, which may be the same or different, are hydrogen atoms or lower alkyl groups, Z is a cyano group, -CO-ORS (wherein R3 is a hydrogen atom or a lower alkyl group) or -CO-NR4R5 (wherein R4 and R5, which may be the same or different, are hydrogen atoms or lower alkyl groups, R4 and R5 being able to be taken together to represent an alkylene group)); and Y is a nitro group, a halogen atom, a haloalkyl group or a group represented by the formula:
-C-C-R~
Rg (wherein R6, R7 and R8, which may be the same or different, are hydrogen atoms, halogen atoms or cyano groups), provided [1] that X1 is fluorine atom, X2 is chlorine atom and Z is cyano group or -CONR4R5, when Y is nitro group, [2]
that X1 is fluorine atom, X2 is chlorine atom and Z is cyano group, when Y is fluorine atom) [3] that X1 is fluorine atom, X2 is chlorine atom and Z is -COORS (wherein R3 is other than a hydrogen atom), -CONR4R5 or cyano group, when Y is chlorine atom and [4] that Z is a cyano group, -COORS (wherein R3 is other than a hydrogen atom) or -CONR4R5, when Y is an iodine atom] is novel.
Among them, those whose Y is -C-C-R' Rg - lla -'~Q~~~3 1 wherein R6, R~ and R8, which may be the same or different, are hydrogen atoms, halogen atoms or cyano groups are useful as an intermediate for producing the herbicides disclosed in Japanese Patent Kokai (Laid-Open) No. 3-163063 (JP-A-3-163063).
Especially, compounds whose R is -C-Z
wherein R1 and R2, which may be the same or different, are hydrogen atoms or lower alkyl groups, Z is -CON(R4)R5 (wherein R4 and R5, which may be the same or different, are hydrogen atoms or lower alkyl groups, R4 and R5 being able to be taken together to represent an alkylene group) is quite useful as an intermediate for said herbicides.
EXAMPLES
Typical examples of the present invention are given below but they should not be construed as limiting the scope of the invention.
Example 1 Production of (2-chloro-4-fluoro-5-nitro-phenoxy)acetamide (compound No. 1) ,.
F F
1 In 8 ml of 97% sulfuric acid was dissolved 3.7 g (0.02 mole) of (2-chloro-4-fluorophenoxy)aceto-nitrile, and a mixed acid of 2.5 ml of 60 - 62% nitric acid and 5.8 ml of 97% sulfuric acid was added to the resulting solution with stirring at 10°C or lower, after which the reaction was carried out at room temperature for 1.5 hours.
After completion of the reaction, the reaction solution was poured into ice water and the crystals 1~ precipitated were collected by filtration, washed with water and then dried to obtain 3.4 g of the desired compound as yellow crude crystals (yield: 68%).
The crude crystals obtained were recrystal-lined from ethyl acetate to obtain 2.5 g of the desired compound as light-yellow crystals.
Physical properties: m.p. 182 - 182.5°C, yield 50.5%.
NMR [DMSO/TMS, d values (ppm)]
4.75 (s, 2H), 7.50 (bd, 2H, J=0.6Hz), 7.75 (d, 2H, J=7Hz), 7.97 (d, 2H, J=llHz).
1 Example 2 Production of (2-chloro-4-fluoro-5-nitro-phenoxy)acetamide (compound No. 1) F F
Reaction was carried out for 5 hours in the same manner as in Example 1, except that 4.1 g (0.02 mole) of (2-chloro-4-fluorophenoxy)acetamide was used in place of (2-chloro-4-fluorophenoxy)acetonitrile, to obtain 3.6 g of the desired compound.
Yield: 72.4.
Example 3 Production of (2-chloro-4-fluoro-5-nitro-phenoxy)acetic acid (compound No. 2) F F
In the same manner as in Example 1, 4.6 g (0.02 mole) of ethyl (2-chloro-4-fluorophenoxy)acetate 14 was reacted, followed by overnight standing at room temperature.
,~~~g~3g 1 After completion of the reaction, the reaction solution containing the desired product was poured into ice water, and the desired product was extracted with ethyl acetate.
The extracted solution was washed with water and dried over magnesium sulfate, after which the solvent was distilled off under reduced pressure. The resulting residue was purified by a silica gel column chromatography (CHZC12-CHgOH) to obtain 1.3 g of the l0 desired compound asocherous crystals.
Yield: 30.2$.
NMR [DMSO/TMS, d values (ppm)]
4.57 (s, 2H), 7.50 (bd, 2H, J=0.6Hz), 7.75 (d, 2H, J=7Hz), 7.97 (d, 2H, J=llHz), 13.90 (bs, 1H).
Example 4 Production of (5-bromo-2-chloro-4-fluoro-phenoxy)acetonitrile (compound No. 3) F F
C1 O C1 O Br In 10 ml of methylene chloride was suspended 1.0 g (7.5 mmoles) of anhydrous aluminum chloride, and 1.0 g (5.4 mmoles) of (2-chloro-4-fluorophenoxy)aceto-.. ~~39~~~~
1 nitrile was added to the suspension, after which 0.95 g (5.9 mmoles) of bromine was added dropwise with refluxing. After completion of the dropwise addition, the reaction was carried out with refluxing for 2 hours.
After completion of the reaction, the reaction mixture was allowed to cool and then poured into ice water, and the desired compound was extracted with ether.
The extracted solution was washed successively with water, a 10% aqueous sodium thiosulfate solution and a saturated aqueous sodium chloride solution, and dried over magnesium sulfate. Then, the solvent was distilled off under reduced pressure and the resulting residue was recrystallized from n-hexane to obtain 1.1 g of the desired compound.
Physical properties: m.p. 72.3°C, yield 77%.
Example 5 Production of (2-chloro-5-chloroacetyl-4-fluorophenoxy)acetamide (compound No. 6) F F
H2NCCH20 HyNCCH20 O O
With 2.0 g (15.0 mmoles) of anhydrous aluminum chloride was mixed 0.85 g (7.5 mmoles) of chloroacetyl z 1 chloride, and the resulting mixture was heated to 80°C.
Then, 1.0 g (4.9 mmoles) of (2-chloro-4-fluorophenoxy)-acetamide was added and the reaction was carried out at 90°C for 9 hours.
After completion of the reaction, the reaction mixture was cooled to 80°C and 5 ml of acetic acid was added. The mixture thus obtained was poured into ice water, and the crystals precipitated were collected by filtration and recrystallized from ethanol to obtain 1.0 g of the desired compound.
Physical properties: m.p. 166.3°C, yield 73%.
Example 6 Production of (2-chloro-5-dichloroacetyl-4-fluorophenoxy)acetamide (compound No. 7) F F
'C 1 C1 O .---~ C1 O COC/H
O O
With 2.0 g (15.0 mmoles) of anhydrous aluminum chloride was mixed 0.93 g (6.3 mmoles) of dichloroacetyl chloride, and the resulting mixture was heated to 50°C.
Then, 1.0 g (4.9 mmoles) of (2-chloro-4-fluorophenoxy)-acetamide was added and the reaction was carried out at 7p - g0°C for 8 hours.
1 After completion of the reaction, the reaction mixture was allowed to cool and ice water was added and then stirred for 2 hours. The desired compound was extracted with ethyl acetate and the extracted solution was washed with water and dried over magnesium sulfate.
Then, the ethyl acetate was distilled off under reduced pressure, and the resulting residue was purified by a silica gel column chromatography to obtain 0.5 g of the desired compound.
Physical properties: m.p. 132.3°C, yield 33%.
Example 7 Production of (2-chloro-5-chloroacetyl-4-fluorophenoxy)acetonitrile (compound No. 11) F F
With 2.0 g (15.0 mmoles) of anhydrous aluminum chloride was mixed 0.85 g (7.5 mmoles) of chloroacetyl chloride, and the resulting mixture was heated to 60°C.
Then, 0.9 g (4.0 mmoles) of (2-chloro-4-fluorophenoxy)-acetonitrile was added and the reaction was carried out at 70°C for 3 hours.
After completion of the reaction, the reaction mixture was poured into ice water and stirred for 1 .. ..
1 hour. The crystals precipitated were collected by filtration and recrystallized from ethanol to obtain 0.93 g of the desired compound.
Physical properties: m.p. 122.1°C, yield 73%.
Example 8 Production of (2-chloro-5-dichloroacetyl-4-fluorophenoxy)acetonitrile (compound No. 13) C1 O ~. Cl O LOCH
'C 1 With 2.0 g (15.0 mmoles) of anhydrous aluminum chloride were mixed 0.93 g (6.3 mmoles) of dichloroacetyl chloride and 0.9 g (4.9 mmoles) of (2-chloro-4-fluorophenoxy)acetonitrile, and the reaction was carried out at 60°C for 2 hours.
After completion of the reaction, the reaction mixture was allowed to cool and 5 ml of nitromethane was added) The resulting mixture was poured into ice water, after which the desired compound was extracted with ethyl acetate and the extracted solution was washed with water and dried over magnesium sulfate. Then, the solvent was distilled off under reduced pressure, and the resulting residue was purified by a silica gel column chromatography to obtain 0.97 g of the desired compound.
Physical properties: m.p. 98.7°C, yield 67%.
1 Example 9 Production of (2-chloro-4-fluoro-5-trichloro-methylphenoxy)acetonitrile (compound No. 14) F F
In 10 ml of carbon tetrachloride was suspended 1.5 g (11.2 mmoles) of anhydrous aluminum chloride, and 1.0 g (5.4 mmoles) of (2-chloro-4-fluorophenoxy)aceto-nitrile was added dropwise. After completion of the addition, the reaction was carried out at 60°C for 1 hour.
After completion of the reaction, the reaction mixture was allowed to cool and ice water was added and then stirred for 1 hour. The desired compound was extracted with ethyl acetate and the extracted solution was washed with water and dried over magnesium sulfate.
Then, the solvent was distilled off under reduced pressure, and the resulting residue was purified by a silica gel column chromatography to obtain 1.2 g of the desired compound as an oil.
Physical properties: oil, yield 72~.
NMR [CDC13/TMS, d values (ppm)]
4.88 (s, 2H), 7.09 (d, 1H, J=10.4Hz), 7.79 (d, 1H, J=7.lHz).
1 Example 10 Production of (2-chloro-5-cyanoacetyl-4-fluorophenoxy)acetonitrile (compound No. 17) F F
To 4.5 g (33.6 mmols) of anhydrous aluminum chloride was added 0.57 g (7.8 mmols) of dimethyl-formamide (DMF), and 1.0 g (5.6 mmoles) of (2-chloro-4-fluorophenoxy)acetonitrile was added to the suspension at room temperature. Then, 2.9 g (28.0 mmoles) of cyanoacetyl chloride was slowly dropped into the resulting mixture. After completion of the dropping, the reaction was carried out at 55°C for 3 hours.
After completion of the reaction, the reaction mixture was analyzed by a thin layer chromatography and a gas chromatography (area percentage: 7.0%). The analysis results obtained were in agreement with those obtained for a standard substance, whereby the production of the desired compound was confirmed.
Compounds of the general formula (I) are listed in Table 1.
X2 ~ Y ( RO
Table 1 No R X1 X2 Y Physical properties 1 H2NCOCH2 F C1 N02 m.p. 182.0-182.5C
2 HOOCCH2 F C1 N02 d (DMSO)=4.57 (s, 2H), 7.57 (d, 2H, J=7.OEz), 7.89 (d, 2H, J=1l.OHz), 13.9 (bs, lE).
3 NCCH F C1 Br m.p. 72.3C
4 HZNCOCH2 F Cl COCH3 d (CDC13)=2.64 (d, 3H, J=3.3Hz), 4.51 (s, 2H), 5.70 (bs, 1H), 6.60 (bs, 1H), 7.28 (d, 1H, J=7.9Hz), 7.4. (d, 1H, J=5.9Hz).
H2NCOCH2 C1 C1 COCH2C1 m.p. 171.7C
6 HZNCOCfi2 r~ Ci COCH2C1 m.p. 166.3C
7 H2NCOCH2 F C1 COCHC12 m.p. 132.3C
8 H2NCOCH2 F C1 CC13 m.p. 214.7C
9 NCCH2 F C1 COCH3 d (CDC13)=2.63 (d, 3H, J=3.3Hz), 4.35 (s, 2H), 7.31 (d, 1H, J=7.6Hz), 7.54 (d, 13, J=6.lHz).
i0 NCCH2 C. C1 COCH2C1 m.p. 110.9C
11 NCCHZ r~ C1 COCfi2C1 m.p. 122.1C
12 NCCH2 F C1 COCH2Br d (CDC13)=4.49 (d, 2fi, J=2.4Hz), 4.90 (s, 2H), 7.33 (d, 1H, J=9.9Hz), 7.60 (d, 1H, J=6.OHz).
13 NCCH2 F C1 COC3C12 m.p. 98.7C
14 NCCH2 F C1 CC13 d (CDC13)=4.88 (s, 2H), 7.09 (d, 13, J=10.4Hz), 7.79 (d, lE, J=7.lHz).
(to be continued) ~~9~~~9 Table 1 (Cont'd) No R X1 XZ Y Physical properties 15 H2NCOCH F C1 COCH2C1 8 (CDC13)=1.63 (d, 3H, J=6.6Hz), 4.65 (q, 2H, CH3 J=6.6Hz), 4.63 (d, 2H, J=3Hz), 6.00 (bs, 1H), 6.67 (bs, 1H), 7.26 (d, 1H, J=9.9Hz), 7.45 (d, 1H, J=5.7Hz).
16 NCCH F C1 COCHZC1 8 (CDC13)=1.67 (d, 3H, J=6.8Hz), 4.98 (q, 2H, CH3 J=6.98Hz), 4.70 (d, 2H, J=3.lHz), 6.00 (bs, 1H), 7.30 (d, 1H, J=lOHz), 7.59 (d, 1H, J=5.8Hz).
Aromatic compound derivatives represented by the formula (I') are important especially as inter-mediates in preparation of the herbicides disclosed in Japanese Patent Kokai (Laid-open) No. 3-163063. The typical herbicides which are final products can be prepared, for example, by the process as illustrated below.
.. ~~9~~~9 Y R1 0 y Rl I ~~ I
X - O O-C-R R3"O-C-OR3" X O 0-C-R
Base CH3C R2 R3"0-C-CH2C R2 (I) Cyclyzation X ~ alkylation Rl N
I
R-C-O ~ OH
R2 R4 n Halogena-y tion y Hal R1 R~
I 5" I ORSn R. ~ -0 al R- ~ -0 al R4 n R4 n 1 (wherein R, R1, R2, X and Y are as defined above, R3"
denotes a lower alkoxyl group, R4" denotes a lower alkyl group or a lower haloalkyl group, R5" denotes a lower alkyl group or a lower haloalkyl group and Hal denotes a halogen atom.)
i0 NCCH2 C. C1 COCH2C1 m.p. 110.9C
11 NCCHZ r~ C1 COCfi2C1 m.p. 122.1C
12 NCCH2 F C1 COCH2Br d (CDC13)=4.49 (d, 2fi, J=2.4Hz), 4.90 (s, 2H), 7.33 (d, 1H, J=9.9Hz), 7.60 (d, 1H, J=6.OHz).
13 NCCH2 F C1 COC3C12 m.p. 98.7C
14 NCCH2 F C1 CC13 d (CDC13)=4.88 (s, 2H), 7.09 (d, 13, J=10.4Hz), 7.79 (d, lE, J=7.lHz).
(to be continued) ~~9~~~9 Table 1 (Cont'd) No R X1 XZ Y Physical properties 15 H2NCOCH F C1 COCH2C1 8 (CDC13)=1.63 (d, 3H, J=6.6Hz), 4.65 (q, 2H, CH3 J=6.6Hz), 4.63 (d, 2H, J=3Hz), 6.00 (bs, 1H), 6.67 (bs, 1H), 7.26 (d, 1H, J=9.9Hz), 7.45 (d, 1H, J=5.7Hz).
16 NCCH F C1 COCHZC1 8 (CDC13)=1.67 (d, 3H, J=6.8Hz), 4.98 (q, 2H, CH3 J=6.98Hz), 4.70 (d, 2H, J=3.lHz), 6.00 (bs, 1H), 7.30 (d, 1H, J=lOHz), 7.59 (d, 1H, J=5.8Hz).
Aromatic compound derivatives represented by the formula (I') are important especially as inter-mediates in preparation of the herbicides disclosed in Japanese Patent Kokai (Laid-open) No. 3-163063. The typical herbicides which are final products can be prepared, for example, by the process as illustrated below.
.. ~~9~~~9 Y R1 0 y Rl I ~~ I
X - O O-C-R R3"O-C-OR3" X O 0-C-R
Base CH3C R2 R3"0-C-CH2C R2 (I) Cyclyzation X ~ alkylation Rl N
I
R-C-O ~ OH
R2 R4 n Halogena-y tion y Hal R1 R~
I 5" I ORSn R. ~ -0 al R- ~ -0 al R4 n R4 n 1 (wherein R, R1, R2, X and Y are as defined above, R3"
denotes a lower alkoxyl group, R4" denotes a lower alkyl group or a lower haloalkyl group, R5" denotes a lower alkyl group or a lower haloalkyl group and Hal denotes a halogen atom.)
Claims (13)
1. A process for producing an aromatic compound represented by the general formula:
[wherein X1 and X2, which may be the same or different, are each a halogen atom; R is a group represented by the formula:
(wherein R1 and R2, which may be the same or different, are each a hydrogen atom or a C1-C6 alkyl group, Z is a cyano group, -CO-OR3 (wherein R3 is a hydrogen atom or a C1-C6 alkyl group) or -CO-NR4R5 (wherein R4 and R5, which may be the same or different, are each a hydrogen atom or a C1-C6 alkyl group)); and Y is a nitro group, a halogen atom, a C1-C6 haloalkyl group or a group represented by the formula:
(wherein R6, R7 and R8, which may be the same or different, are each a hydrogen atom, a halogen atom or a cyano group)], which comprises:
reacting a compound represented by the general formula:
(wherein X1, X2 and R have the same meanings as given above) with:
(1) a nitrating agent in the presence of an inert solvent, to obtain a compound of the formula (I) in which Y
is a nitro group;
(2) a halogenating agent in the presence of an inert solvent, to obtain a compound of the formula (I) in which Y is a halogen atom, (3) a compound of the formula:
(wherein R6, R7 and R8 have the same meanings as given above;
X3 is a halogen atom, and four of X4, which may be the same or different, are each a halogen atom) and a Lewis acid in the presence or absence of an inert solvent and in the presence or absence of a salt, to obtain a compound of the formula (I) in which Y is a haloalkyl group or a group represented by the formula (wherein R6, R7 and R8 have the same meanings as given above).
[wherein X1 and X2, which may be the same or different, are each a halogen atom; R is a group represented by the formula:
(wherein R1 and R2, which may be the same or different, are each a hydrogen atom or a C1-C6 alkyl group, Z is a cyano group, -CO-OR3 (wherein R3 is a hydrogen atom or a C1-C6 alkyl group) or -CO-NR4R5 (wherein R4 and R5, which may be the same or different, are each a hydrogen atom or a C1-C6 alkyl group)); and Y is a nitro group, a halogen atom, a C1-C6 haloalkyl group or a group represented by the formula:
(wherein R6, R7 and R8, which may be the same or different, are each a hydrogen atom, a halogen atom or a cyano group)], which comprises:
reacting a compound represented by the general formula:
(wherein X1, X2 and R have the same meanings as given above) with:
(1) a nitrating agent in the presence of an inert solvent, to obtain a compound of the formula (I) in which Y
is a nitro group;
(2) a halogenating agent in the presence of an inert solvent, to obtain a compound of the formula (I) in which Y is a halogen atom, (3) a compound of the formula:
(wherein R6, R7 and R8 have the same meanings as given above;
X3 is a halogen atom, and four of X4, which may be the same or different, are each a halogen atom) and a Lewis acid in the presence or absence of an inert solvent and in the presence or absence of a salt, to obtain a compound of the formula (I) in which Y is a haloalkyl group or a group represented by the formula (wherein R6, R7 and R8 have the same meanings as given above).
2. The process according to Claim 1, wherein the reaction variant (1) is selected, to produce a compound of the formula (I) in which Y is a nitro group.
3. The process according to Claim 1, wherein the reaction variant (2) is selected, to produce a compound of the formula (I) in which Y is a halogen atom.
4. The process for producing an aromatic compound according to Claim 1, wherein the reaction variant (3) is selected, to produce a compound of the formula (I) in which Y
is a group of the formula:
in which R6, R7 and R8 are as defined in claim 1.
is a group of the formula:
in which R6, R7 and R8 are as defined in claim 1.
5. An aromatic compound represented by the general formula:
[wherein:
X1 and X2, which may be the same or different, are each a halogen atom;
R is a group represented by the formula:
(wherein R1 and R2, which may be the same or different, are each a hydrogen atom or a C1-C6 alkyl group, Z is a cyano group, -CO-OR3 (wherein R3 is a hydrogen atom or a Cl-C6 alkyl group) or -CO-NR4R5 (wherein R4 and R5, which may be the same or different, are each a hydrogen atom or a C1-C6 alkyl group)); and Y is a nitro group, a halogen atom, a C1-C6 haloalkyl group or a group represented by the formula (wherein R6, R7 and R8, which may be the same or different, are each a hydrogen atom, a halogen atom or a cyano group) provided [1] that X1 is a fluorine atom, X2 is a chlorine atom and Z is a cyano group or -CONR4R5, when Y is a nit ro group, [2] that X1 is a fluorine atom, X2 is a chlorine atom and Z is a cyano group, when Y is a fluorine atom) [3] that X1 is a fluorine atom, X2 is a chlorine atom and Z is -COOR3 (wherein R3 is other than a hydrogen atom), -CONR4R5 or a cyano group, when Y is a chlorine atom, and [4] Z is a cyano group, -COORS (wherein R3 is other than a hydrogen atom) or -CONR4R5, when Y is an iodine atom].
[wherein:
X1 and X2, which may be the same or different, are each a halogen atom;
R is a group represented by the formula:
(wherein R1 and R2, which may be the same or different, are each a hydrogen atom or a C1-C6 alkyl group, Z is a cyano group, -CO-OR3 (wherein R3 is a hydrogen atom or a Cl-C6 alkyl group) or -CO-NR4R5 (wherein R4 and R5, which may be the same or different, are each a hydrogen atom or a C1-C6 alkyl group)); and Y is a nitro group, a halogen atom, a C1-C6 haloalkyl group or a group represented by the formula (wherein R6, R7 and R8, which may be the same or different, are each a hydrogen atom, a halogen atom or a cyano group) provided [1] that X1 is a fluorine atom, X2 is a chlorine atom and Z is a cyano group or -CONR4R5, when Y is a nit ro group, [2] that X1 is a fluorine atom, X2 is a chlorine atom and Z is a cyano group, when Y is a fluorine atom) [3] that X1 is a fluorine atom, X2 is a chlorine atom and Z is -COOR3 (wherein R3 is other than a hydrogen atom), -CONR4R5 or a cyano group, when Y is a chlorine atom, and [4] Z is a cyano group, -COORS (wherein R3 is other than a hydrogen atom) or -CONR4R5, when Y is an iodine atom].
6. A compound according to claim 5 wherein Y is wherein R6, R7 and R8, which may be the same or different, are each a hydrogen atom, a halogen atom or a cyano group.
7. A compound according to claim 6, wherein R is wherein R1 and R2, which may be the same or different, are each a hydrogen atom or a C1-C6 alkyl group, Z is -CON(R4)R5 (wherein R4 and R5, which may be the same or different, are each a hydrogen atom or a C1-C6 alkyl group).
8. The process according to claim 2, wherein the reaction is conducted using fuming nitric acid or nitric acid in an amount of at least one mole per mole of the compound of the formula (II) as the nitrating agent and sulfuric acid, acetic acid, trifluoroacetic acid or trifluoromethanesulfonic acid as the solvent at a temperature of -20°C to 150°C.
9. The process according to claim 3, wherein the reaction is conducted using chlorine, bromine, chlorine-bromine, bromine-aluminum chloride, bromine-iron or bromine-silver sulfate in an amount of at least one mole per mole of the compound of the formula (II) as the halogenating agent at a temperature of 0°C to 150°C.
10. The process according to claim 4, wherein the reaction is conducted using at least one mole of the Lewis acid and 0.5 to 2 moles of the compound of the formula (III), (IV) or (V), each per mole of the compound of the formula (II) at a temperature of 0°C to 180°C.
11. The process according to claim 10, wherein the compound of the formula (III) or (IV) is employed to obtain a compound of the formula (I) in which Y is a group of the formula:
12. The process according to claim 10, wherein carbon tetrachloride as the compound of the formula (V) is employed to obtain a compound of the formula (I) in which Y is trichloromethyl.
13. The compound according to claim 5, wherein X1 is a fluorine or chlorine atom;
X2 is a chlorine atom;
R is H2NCOCH2-, HOOCCH2- or NCCH2-; and Y is N02, Br, -COCH3, -COCH2C1, -COCHC12, -CC13 or -COCH2Br provided that X1 is a fluorine atom and R is H2NCOCH2- or NCCH2-, when Y is N02.
X2 is a chlorine atom;
R is H2NCOCH2-, HOOCCH2- or NCCH2-; and Y is N02, Br, -COCH3, -COCH2C1, -COCHC12, -CC13 or -COCH2Br provided that X1 is a fluorine atom and R is H2NCOCH2- or NCCH2-, when Y is N02.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18185792 | 1992-06-16 | ||
| JP04-181857 | 1992-06-16 | ||
| JP28959692 | 1992-10-03 | ||
| JP04-289596 | 1992-10-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2098239A1 CA2098239A1 (en) | 1993-12-17 |
| CA2098239C true CA2098239C (en) | 1999-11-02 |
Family
ID=26500860
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2098239 Expired - Fee Related CA2098239C (en) | 1992-06-16 | 1993-06-11 | A process for producing an aromatic compound by electrophilic reaction and aromatic compound derivatives |
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| Country | Link |
|---|---|
| KR (1) | KR0163206B1 (en) |
| CN (1) | CN1041085C (en) |
| AU (1) | AU646201B2 (en) |
| CA (1) | CA2098239C (en) |
| CH (1) | CH685200A5 (en) |
| DE (1) | DE4319820A1 (en) |
| ES (1) | ES2103163B1 (en) |
| FR (1) | FR2692258B1 (en) |
| GB (1) | GB2268175B (en) |
| IT (1) | IT1260853B (en) |
| TW (1) | TW287152B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201017242A (en) | 2008-10-30 | 2010-05-01 | Coretronic Corp | Light guide plate and backlight module |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4326882A (en) * | 1978-08-28 | 1982-04-27 | Ppg Industries, Inc. | Trichlorophenoxy alkanoic acid free of chlorinated dibenzo-p-dioxins |
| AU550845B2 (en) * | 1981-03-30 | 1986-04-10 | Sumitomo Chemical Company, Limited | Tetrahydrophthalimides and their starting compounds |
-
1993
- 1993-06-04 GB GB9311623A patent/GB2268175B/en not_active Expired - Fee Related
- 1993-06-08 ES ES9301253A patent/ES2103163B1/en not_active Expired - Fee Related
- 1993-06-09 CH CH1726/93A patent/CH685200A5/en not_active IP Right Cessation
- 1993-06-10 AU AU40161/93A patent/AU646201B2/en not_active Ceased
- 1993-06-11 CA CA 2098239 patent/CA2098239C/en not_active Expired - Fee Related
- 1993-06-14 TW TW82104718A patent/TW287152B/zh active
- 1993-06-15 KR KR1019930010915A patent/KR0163206B1/en not_active IP Right Cessation
- 1993-06-15 FR FR9307180A patent/FR2692258B1/en not_active Expired - Fee Related
- 1993-06-15 DE DE19934319820 patent/DE4319820A1/en not_active Ceased
- 1993-06-15 IT IT93TO433 patent/IT1260853B/en active IP Right Grant
- 1993-06-16 CN CN93106974A patent/CN1041085C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2098239A1 (en) | 1993-12-17 |
| GB9311623D0 (en) | 1993-07-21 |
| DE4319820A1 (en) | 1994-02-24 |
| CH685200A5 (en) | 1995-04-28 |
| ITTO930433A1 (en) | 1994-12-15 |
| CN1041085C (en) | 1998-12-09 |
| AU646201B2 (en) | 1994-02-10 |
| GB2268175B (en) | 1995-10-04 |
| TW287152B (en) | 1996-10-01 |
| FR2692258A1 (en) | 1993-12-17 |
| KR940005542A (en) | 1994-03-21 |
| KR0163206B1 (en) | 1999-01-15 |
| IT1260853B (en) | 1996-04-23 |
| GB2268175A (en) | 1994-01-05 |
| ES2103163B1 (en) | 1998-04-01 |
| CN1085545A (en) | 1994-04-20 |
| AU4016193A (en) | 1993-12-23 |
| ES2103163A1 (en) | 1997-08-16 |
| ITTO930433A0 (en) | 1993-06-15 |
| FR2692258B1 (en) | 1995-06-16 |
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