GB2268175A - 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 derivatives Download PDF

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GB2268175A
GB2268175A GB9311623A GB9311623A GB2268175A GB 2268175 A GB2268175 A GB 2268175A GB 9311623 A GB9311623 A GB 9311623A GB 9311623 A GB9311623 A GB 9311623A GB 2268175 A GB2268175 A GB 2268175A
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lower alkyl
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Takashi Ohtani
Hideo Takaishi
Kenji Tsubata
Hiroshi Hamaguchi
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Nihon Nohyaku Co Ltd
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    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
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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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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
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    • C07C255/00—Carboxylic acid nitriles
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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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    • C07C59/40—Unsaturated compounds
    • C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
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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: <IMAGE> (wherein R, X<1>, X<2> and Y are as defined in the specification) to introduce a substituent into the aromatic ring selectively and novel compounds prepared therefrom.

Description

2268175 A PROCESS FOR PRODUCING AN AROMATIC COMPOUND BY -ELECTROPHILIC
REACTION AND AROMATIC COMPOUND DERIVATIVES
1 BACKGROUND OF THE INVENTION Field of the Invention
The present invention relates to a process for producing an aromatic compound represented by the 5 general formula (I):
xl X2 0 Y (I) -0 RO [wherein X1 and-X2, which may be the same or different, are halogen atoms; R is a group represented by the formula:
R1 1 c - z 1 R2 (wherein R1 and R2, which may be the same or different, are hydrogen atoms or lower alkyl groupst 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 groupst 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:- 0 R6 11 1 C - C -R7 R8 (wherein R6, R7 and R87 which may be the same or different, are hydrogen atomst halogen atoms or cyano groups)] which comprises reacting an electrophilic reagent with a compound represented by the general formula (II):
xl X20 -0 RO (wherein Xl, 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, 2,4,5substituted benzene derivative of the general formula (1) can be selectively obtained from the compound of the general formula (II) used in the present invention.
1 Rec. Trav. Chim., 75, 190 (1956) discloses the following process:
cl cl c 0 A1C13/C1COCE2C1 C 0 1-0 1---0 CH30 HOCOCE2C1 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 corresponding to the general formula (1) 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. chemicalsr etc. and some of them are novel. 1 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 (1) is explained below in detail.
(D 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.
xl xl X2 0 Nitrating X2 0 N02 -0 agent -9 RO CH30 (11) wherein Xl, X2 and R have the same meanings as those 15 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 acidy acetic acid.
1 trifluoroacetic acid, and trifluoromethanesulfonic acid. These inert solvents may be used singly or as a mixture thereof.
As the nitrating agentsy 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 acidacetic anhydride, nitric acid-trifluoroacetic acid, and nitric acidtrifluoromethanesulfonic 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 -200C to 1500C and is preferably OOC to 500C.
Although the reaction time is varied depending on the reaction temperaturer 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.
(0 Halogenation reaction This reaction is such that an aromatic compound of the general formula (1- 2) can be produced by 1 selective halogenation of a compound of the general formula (I1) with a halogenating agent in the presence of an inert solvent.
xl xl X2 0 Halogenating X2 0 Y1 -0 agent -9 RO RO (11) (1-2) wherein Xl. X2 and R have the same meanings as those 5 defined above, and Y1 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, chloroformy carbon tetrach lotide. and dichloroethane)y sulfuric acid, acetic acidy 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 agenty there can be used, for exampler chlorine, brominer chlorine-bromine.
bromine-aluminum chlorider 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 1 moles per mole of the compound of the general formula (II). The reaction temperature may be chosen in the range of OOC to 1500C and is preferably 200C to 1000C. 5 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 recrystallizationt etc., whereby the desired compound can be produced.
Priedel-Crafts reaction This reaction is such that an aromatic compound of the general formula (1- 3) can be produced by reacting a compound of the general formula (I1) 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.
xl xl Priedel-Crafts reaction 3h.
X2 0 X2 0Y1 -0 0 R6 0 R6 -9 RO 11 1 11 1 RO X3-C-C-R7 0(-C-C-R7)2 C(X4)4 1 1 RB R8 (V) (1-3) (III) (IV) or 1 wherein X1r X2 and R have the same meanings as those defined above, and Y1 is a haloalkyl group or a group represented by the formula:
0 R6 -C-C-R7 1 R8 (wherein R6, R7 and R8y which may be the same or different, are hydrogen atoms, halogen atoms or cyano groups). X3 is a halogen atom, and X41Sy 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 usedr for exampley nitroalkanes such as nitromethane, etc.; halogenated hydrocarbons such as dichloromethane, carbon tetrachloride, tetrachloroethane, dichloroethaner etc.; aromatic hydrocarbons such as nitrobenzener etc.; amides such as N-methylpyrrolidone, NyN-dimethylformamide, etc.; urea derivatives such as N,NtNI, NI-tetramethylurear NpNdimethylimidazolinone, etc.; organic bases such as pyridine. triethylamine, etc.; organosulfur compounds such as carbon disulfider dimethyl sulfoxide, sulfolane, etc.; alcohols such as ethanol, ethylene glycolp etc.; nitriles such as acetonitrile, benzonitrile, etc.; and organophosphorus compounds such as phosphorus oxychloride, hexamethylphosphoramidep etc. These inert solvents may be used singly or as a mixture thereof.
9 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 chlorider magnesium chloride, lithium chloride, sodium bromider potassium bromider 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 acidy there can be used Lewis acids such as A1C13r A1Br3, A113r PeC13, FeBr3, TiC14, SnC14, ZnC12, GaC13, 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 (I1) and is preferably 3 to 8 moles per mole of this compound.
The amount of the compound of the general formula (III)r (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 (11).
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 OOC to 1800C and is preferably 600C to 1000C.
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. p whereby the desired compound can be produced.
As mentioned before, some of the compounds thus prepared are novel. That ist an aromatic compound represented by the general formula (I):
xl X2 0 Y (I) -0:
RO [wherein X1 and X2, which may be the same or different, are halogen atoms; R is a group represented by the formula:
R1 1 R2 1 (wherein R1 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 -M-N(R4)RS (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 groupy a halogen atomr a haloalkyl group or a group represented by the formula:
0 R6 11 1 C - C -R7 1 R8 (wherein R6, R7 and RO, which may be the same or different. are hydrogen atomst halogen atoms or cyano groups), provided that X1 is fluorine atom, X2 is chlorine atom and Z is cyano group or -CONR4RS when Y is nitro groupt that X2 is fluorine atomr X2 is chlorine atom and z is cyano group when Y is fluorine atom, and that X' is fluorine atom. X2 is chlorine atom and Z is -COOR3 (wherein R3 is a group other than hydrogen atom), -CONR4RS or cyano group when Y is chlorine atom is novel.
Among them, those whose Y is 0 R6 11 1 C - C -R7 1 RB - 12 1 wherein R6F R7 and R8r 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 R1 1 c - z 1 R2 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 differentr 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 is 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) 13 F c 0 cl 0 N02 NCCE20 E2NCCE20 In 8 ml of 97% sulfuric acid was dissolved 3.7 (0.02 mole) of (2-chloro-4fluorophenoxy)acetonitrile, 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 100C 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 precipitated were collected by filtrationy washed with water and then dried to obtain 3.4 9.of the desired compound as yellow crude crystals (yield: 68%).
The crude crystals obtained were recrystallized from ethyl acetate to obtain 2.5 9 of the desired compound as light-yellow crystals.
Physical properties: m.p. 182 - 182.50C, yield 50.5%.
NMR [DMSO/TMSt 6 values (ppm)] 4.75 (sr 2E), 7.50 (bdr 2Hp J=0.6Bz), 7.75 (dr 2E, J=7Hz). 7.97 (dr 2E. J=11Hz).
1 Example 2
Production of (2-chloro-4-fluoro-5-nitro- phenoxy)acetamide (compound No. 1) F F C1-0 cl N02 0 0 E2NCCE20 E2NCCE20 11 11 0 0 Reaction was carried out for 5 hours in the same manner as in Example ly 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-nitrophenoxy)acetic acid (compound No. 2) F c 0 cl 0 N02 1-0 -9 C2BSOCCE20 HOCCE20 11 11 0 0 In the same manner as in Example 1, 4.6 9 (0.02 mole) of ethyl (2-chloro-4-fluorophenoxy)acetate 14 was reacted, followed by overnight standing at room temperature.
- is - 1 After completion of the reactiony 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 (CH2C12-CE3OE) to obtain 1.3 9 of the desired compound asocherous crystals.
Yield: 30.2%.
NMR [DMSO/TMS, 6 values (ppm)] 4.57 (s, 2H), 7.50 (bd, 2E, J=MHz), 7.75 (d, 2R, J=7Hz), 7.97 (dr 2H, J=11Hz).
13.90 (bs,. 1E).
Example 4
Production of (5-bromo-2-chloro-4-fluorophenoxy)acetonitrile (compound No. 3) F F c 0 cl 0 Br NCCE20 NCCE20 In 10 mI, 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- 1 nitrile was added to the suspensionr after which 0.95 (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. 5 After completion of the reactiont 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 lo with water, a 10% aqueous sodium thiosulfate solution and a saturated aqueous sodium chloride solution, and dried over magnesium sulfate. Thenj the solvent was distilled off under reduced pressure and the resulting residue was recrystallized from n-hexane to obtain 1.1 of the desired compound.
Physical properties: m.p. 72.30C, yield 77%.
Example 5
Production of (2-chloro-5-chloroacetyl-4fluorophenoxy)acetamide (compound No. 6) p F- c 0 cl 0 COCE2C1 E2NCCE20 E2NCCE20 0 0 With 2.0 9 (15.0 mmoles) of anhydrous aluminum chloride was mixed 0.85 g (7.5 mmoles) of chloroacetyl 1 chloride, and the resulting mixture was heated to 800C.
Thent 1.0 9 (4.9 mmoles) of (2-chloro-4-fluorophenoxy) acetamide was added and the reaction was carried out at 900C for 9 hours.
After completion of the reaction. the reaction mixture was cooled to 800C 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 9 of the desired compound.
Physical properties: m.p. 166.30C, yield 73%.
Example 6 Production of (2-chloro-5-dichloroacetyl4fluorophenoxy)acetamide (compound No. 7) F F 1 c 0 cl 0 i COCE \Cl E2NCCE20 E2NCCE20 11 11 0 0 With 2.0 g (15.0 mmoles) of anhydrous aluminum chloride was mixed 0.93 9 (6.3 mmoles) of dichloroacetyl chloride, and the resulting mixture was heated to 500C. Then. 1.0 g (4.9 mmoles) of (2chloro-4-fluorophenoxy)acetamide was added and the reaction was carried out at 20 70 - 80C 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. 132.30C. yield 33%.
Example 7
Production of (2-chloro-5-chloroacetyl-4fluorophenoxy)acetonitrile (compound No. 11) F cl -Oi COCE2C1 c 0 0 NCCE20 NCCE20 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 600C.
Thenr 0.9 g (4.0 mmoles) of (2-chloro-4-fluorophenoxy) acetonitil'le was added and the reaction was carried"out at 700C for 3 hours.
After completion of the reaction, the reaction mixture was poured into ice water and stirred for 1 - 19 t- 1 hour. The crystals precipitated were collected by filtration and recrystallized from ethanol to obtain 0.93 9 of the desired compound.
Physical properties: m.p. 122.10C, yield 73%.
Example 8 Production of (2-chloro-5-dichloroacetyl4fluorophenoxy)acetonitrile (compound No. 13) F F / cl c 0 Cl 0 COCE 1-0 /@ \Cl NCCE20 NCCE20 With 2.0 g (15.0 mmoles) of anhydrous aluminum chloride were mixed 0.9i g (6.3 mmoles) of dichloroacetyl chloride and 0.9 g (4.9 mmoles) of (2chloro-4- fluorophenoxy)acetonitriler and the reaction was carried out at 600C 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 pressurey 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. 98.76C, yield 67%.
1 Example 9 Production of (2-chloro-4-fluoro-5trichloromethylphenoxy)acetonitrile (compound No. 14) F F c 0 31 cl - 0 NCCE2 NCCE20 In 10 ml of carbon tetrachloride was suspended 5 1._5 g (11.2 mmoles) of anhydrous aluminum chloride, and 1.0 g (5.4 mmoles) of (2-chloro-4- fluorophenoxy)acetonitrile was added dropwise. After completion of the addition, the reaction was carried out at 600C for 1 hour.
After completion of the reactionj 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. 15 Theny the solvent was distilled off under reduced pressurey 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, 6 values (ppm)] 4.88 (st 2H)r 7.09 (d, 1E, J=10.4Bz), 7.79 (d, 1R, J=7.1Bz).
- 21 1 Example 10 Production of (2-chloro-5-cyanoacetyl4fluorophenoxy)acetonitrile (compound No. 17) F c 0 cl - 0 COCE2M NCCE20 NCCE20 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 9 (5.6 mmoles) of (2-chloro-4 fluorophenoxy)acetonitrile was added to the suspension at room temperature. Thent 2.9 9 (28.0 mmoles) of cyanoacetyl chloride was slowly dropped into the resulting mixture. After completion of the droppingy the reaction was carried out at 550C 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.
xl X2 0 Y RO Table 1
No R X1 X2 y Physical properties 1 E2NCOCH2 F Cl N02 m.p. 182.0-182.50C 2 BOOCCE2 F Cl N02 6 (DMSO)=4.57 (s, 2H), 7.57 (di 2EF J=MHz).
7.89 (d, 2E, J=11.Oaz), 13.9 (bsp 1H).
3 NCCE3 F Cl Br m.p. 72.30C 4 E2NCOCE2 F Cl COCE3 6 (CDC13)=2.64 (dr 3EY J=3.3Hz), 4.51 (s, 2E), 5.70 (bs. 1H). 6.60 (bsy 1H), 7.28 (d, lK, J=7.9Bz), 7.41 (dr 1Ey J=5.9Hz).
E2NCOCK2 Cl Cl COCE2C1 m.p. 171.70C 6 E2NCOCE2 F Cl COCE2C1 m.p. 166.30C 7 E2NCOCE2 F Cl COCEC12 m.p. 132.30C 8 E2NCOCK2 F Cl CC13 m.p. 214.70C 9 NCCE2 F Cl COCH3 6 (CDC13)=2.63 (d, 3E, J=3.3Hz)r 4.35 (sy 2E), 7.31 (d, 1E, J=MHz), 7.54 (dr lK, J=6.1Hz).
NCCE2 Cl Cl COCE2,Cl M.P. 110.90C 11 NCCE2 F Cl COCE2C1 m.p. 122.10C 12 NCCH2 F Cl COCE2Br 6 (CDC13)=4.49 (d, 2E, J=2.4Hz), 4.90 (s, 2E), 7.33 (d, 1R, J=9.9Hz), 7.60 (d, 1R, J=6.0Hz).
13 NCCE2 F Cl COCEC12 m.p. 98.70C 14 NCCE2 F Cl CC13 6 (CDC13)=4.88 (s, 2H), 7.09 (d, 1R, J=10.4Bz), 7.79 (d, 1E, J=701Hz).
(to be continued) Table 1 (Contld) No R X1 X2 Y Physical properties E2NCOCE F Cl COCH2C1 6 (CDC13)=1.63 (do, 3Hr 1 J=6.6Bz)r 4.65 (qy 2EF CE3 J=6.6Bz)r 4.63 (dr 2El J=Hz). 6.00 (bst 1H)y 6.67 (bs, 1H)r 7.26 (dr 1R, J=MHz), 7.45 (d, 1Hr J=MHz).
16 NCCE F Cl COCE2C1 6 (CDC13)=1.67 (dr 3R, 1 J=6.8Hz). 4.98 (q, 2E, Uk13 J=6.98Hz)p 4.70 (dr 2E, J=3.1Hz)r 6.00 (bs, 1H), 7.30 (d, 1R, J=10Bz)r 7.59 (d, 1R, J=5.8HZ).
17 NCCE2 F Cl COCE2M Aromatic compound derivatives represented by 'the formula (V) are important especially as intermediates 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.
- 24 y R1 0 y R1 1 11 1 X 0 O-C-R RPO-C-ORP X 0 O-C-R 1 Base 1 CH3C R2 RPO-C-CH2C R2 11 11 11 0 0 0 y Cyclyzation. X 0 alkylation-- R1 N R-C-0 N OH 1 1 R2 R.1 X X Halogena Y 0 tion y 0 Hal R1 N R1 N L who n 1% hm N RS N ORSW R-C-0 1 R-C-0 1 1 R40 1 kt- R2 R2 (wherein R, R1r R2r X and Y are as defined above. RP denotes a lower alkoxyl group, RC denotes a lower alkyl group or a lower haloalkyl groupt R5w denotes a lower alkyl group or a lower haloalkyl group and Hal denotes a halogen atom.)

Claims (7)

WHAT IS CLAIMED IS:
1. A process for producing an aromatic compound represented by the general formula (I):
xl X2 0 Y RO [wherein X1 and X2, which may be the same or different, are halogen atoms; R is a group represented by the formula:
R1 1 c - z 1 R2 (wherein R1 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 RS, 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 groupy a halogen atomr a haloalkyl group or a group represented by the formula:
0 R6 11 1 C - C -R7 1 ' R8 - 26 (wherein R6, R7 and R8r which may be the same or different, are hydrogen atomst halogen atoms or cyano groups)] which comprises reacting an electrophilic reagent with a compound represented by the general formula (II):
xl X2 0 __0 RO (wherein Xl, X2 and R have the same meanings as those defined above).
2. The process for producing an aromatic compound according to Claim lr wherein the electrophilic reagent is a nitrating agent.
3. The process for producing an aromatic compound according to Claim ly wherein the electrophilic reagent is a halogenating agent.
4. The process for producing an aromatic compound according to Claim lr wherein the electrophilic reagent is a combination of a Lewis acid and a compound represented by 0 R6 11 1 the general formula (III): X3-C-C-R7 (Ili)r 1 RB - 27 0 R6 11 1 the general formula (IV): 0(-C-C-RI,)2 (IV)f 1 R8 or the general formula (V): C(X4)4 (V) wherein R6, R7 and R8. which may be the same or differentr are hydrogen atoms, halogen atoms or cyano groups, X3 is a halogen atomr and XVS, which may be the same or different, are halogen atoms.
5. An aromatic compound represented by the general formula (I):
xl X2 0 Y -0 RO [wherein X1 and X2P which may be the same or different. are halogen atoms; R is a group represented by the formula:
R1 1 - c - z 1 R2 (wherein R1 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 -M-N(R4)RS (wherein R4 and RS, which - 28 may be the same or different, are hydrogen atoms or lower alkyl groups, R4 and RS being able to be taken together to represent an alkylene group)); and Y is a nitro group, a halogen atomp a haloalkyl group or a group represented by the formula:
0 R6 11 1 -C - C -R7 1 R8 (wherein R6. R7 and R8r which may be the same or differenty are hydrogen atomst halogen atoms or cyano groups): provided that X1 is fluorine atom, X2 is chlorine atom and Z is cyano group or -CONR4R5 when Y is nitro group. that X2 is fluorine atom, X2 is chlorine atom and Z is cyano group when Y is fluorine atom, and that X1 is fluorine atom, X2 is chlorine atom and Z is -COOR3 (wherein R3 is a group other than hydrogen atom), - CONR4R5 or cyano group when Y is chlorine atom.
6. A compound according to claim 5 wherein said Y is 0 R6 11 1 - C - C -R7 1 R8 wherein R6, R7 and RB, which may be the same or differenty are hydrogen atomsf halogen atoms or cyano groups.
7. A compound according to claim 6y wherein R of said compound is R1 1 R2 wherein R1 and R2, which may be the same or different, are hydrogen atoms or lower alkyl groupst Z is -CON(R4)R5 (wherein R4 and RS, which may be the same or different, are hydrogen atbms or lower alkyl groupst R4 and R5 being able to be taken together to represent an alkylene group).
GB9311623A 1992-06-16 1993-06-04 A process for producing an aromatic compound by electrophilic reaction and aromatic compound derivatives Expired - Fee Related GB2268175B (en)

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