AU646201B2 - 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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AU646201B2
AU646201B2 AU40161/93A AU4016193A AU646201B2 AU 646201 B2 AU646201 B2 AU 646201B2 AU 40161/93 A AU40161/93 A AU 40161/93A AU 4016193 A AU4016193 A AU 4016193A AU 646201 B2 AU646201 B2 AU 646201B2
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Hiroshi Hamaguchi
Takashi Ohtani
Hideo Takaishi
Kenji Tsubata
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Nihon Nohyaku Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
    • 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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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/14—Preparation of nitro compounds by formation of nitro groups together with reactions not involving the formation of nitro groups
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/16—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same carbon atom of an acyclic carbon skeleton
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/17—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and doubly-bound oxygen atoms bound to the same acyclic carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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
    • C07C59/76—Unsaturated compounds containing keto groups
    • C07C59/84—Unsaturated compounds containing keto groups containing six membered aromatic rings
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—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
    • 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
    • C07C69/708—Ethers

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Description

646201
AUSTRALIA
PATENTS ACT 1990 COMPLETE SPECIFICATION NAME OF APPLICANT(S): Nihon Nohyaku Co., Ltd.
ADDRESS FOR SERVICE: r r DAVIES COLLISON CAVE Patent Attorneys 1 Little Collins Street, Melbourne, 3000.
INVENTION TITLE: A process for producing an aromatic compound by electrophilic reaction and aromatic compound derivatives The following statement is a full description of this invention, including the best method of performing it known to me/us:r 1 BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a process for producing an aromatic compound represented by the general formula Xl
X
2
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 R2 R2 (wherein R1 and R 2 which may be the same or different, 10 are hydrogen atoms or lower alkyl groups, Z is a cyano group, -CO-OR 3 (wherein R 3 is a hydrogen atom or a lower alkyl group) or -CO-N(R4)R5 (wherein R 4 and R 5 which may be the same or different, are hydrogen atoms or lower alkyl groups, R4 and R 5 being able to be taken together to represent an alkylene group)); and Y is a la- 1 nitro group, a halogen atom, a haloalkyl group or a group represented by the formula: 0 R 6 II I -C -C R7
R
8 (wherein R 6 R7 and RS, 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 0
RO
RO
(wherein X 1 X2 and R have the same meanings as those defined above), and aromatic derivatives thus produced.
10 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 can be selectively obtained from the compound of the general formula (II) used in the present invention.
2 1 Rec. Tray. Chim., 75, 190 (1956) discloses the following process: Cl Cl Cl A1C1 3 /ClCOCH 2 C1 Cl CH3O HO COCH 2 C1 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- Sspending to the general formula which represents the 10 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 15 present invention. The aromatic compound of the general formula 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.
3 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 is explained below in detail.
T Nitration reaction This reaction is such that an aromatic compound of the general formula 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.
**X1 X1 X2 Nitrating X 2 Q NO 2 agent RO (II) (I-1) wherein Xl, X2 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, 4 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 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 -20 0 C to 150 0 C and is preferably 0°C to 50 0
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 20 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 can be produced by 5
I
1 selective halogenation of a compound of the general formula (II) with a halogenating agent in the presence of an inert solvent.
xl X1 X2 Halogenating X2 Q Y agent RO
RO
(II) (1-2) wherein Xl, 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 dichloro- 10 methane, chloroform, carbon tetrachloride, and dichloroethane), 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 15 thereof.
As the halogenating agent, there can be used, for example, chlorine, bromine, chlorine-bromine, bromine-aluminum chloride, bromine-iron, and brominesilver sulfate.
The amount of the halogenating agent used may be properly chosen in the range of 1 mole to excess 6 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 0 C and is preferably 200C to 100 0
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.
15 Friedel-Crafts reaction This reaction is such that an aromatic compound of the general formula can be produced by reacting a compound of the general formula (II) with a SLewis acid and a compound of the general formula (III), (IV) or in the presence or absence of an inert solvent and in the presence or absence of a salt.
,X1 X1 Friedel-Crafts reaction X2 O
X
2 O R 6 0 R6 RO II II RO X3-C-C-R7 O(-C-C-R 7 2 C(X4) 4 I I (II) R8 R8 (1-3) (III) (IV) or 7 1 wherein X1, X2 and R have the same meanings as those defined above, and yl is a haloalkyl group or a group represented by the formula: 0 R6 II I
I
-C-C-R7 R8 (wherein R6, R 7 and R 8 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, tetrachloroethane, dichloroethane, etc.; aromatic hydrocarbons such as nitrobenzene, etc.; amides such as N-methyl- 15 pyrrolidone, N,N-dimethylformamide, etc.; urea derivatives such as N,N,N',N'-tetramethylurea, N,Ndimethylimidazolinone, etc.; organic bases such as pyridine, triethylamine, etc.; organosulfur compounds such as carbon disulfide, dimethyl sulfoxide, sulfolane, 20 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.
8 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 tetramethylammonium chloride), and sulfonates sodium trifluoromethanesulfonate). 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).
15 As the Lewis acid, there can be used Lewis acids such as A1C1 3 AlBr 3 AlI3, FeC13, FeBr 3 TiC1 4 SnC1 4 ZnC2l, GaC1 3 etc.
The amount of the Lewis acid used may be properly chosen in the range of 1 mole to excess moles 20 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 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 may be used both as reactant and as inert solvent. In this case, it may be used in large excess.
9 1 The reaction temperature may be chosen in the range of 0°C to 180°C and is preferably 60 0 C to 100 0
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.
As mentioned before, some of the compounds thus prepared are novel. That is, an aromatic compound represented by the general formula
X
2 O-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:
R
1 -C R2 10 1 (wherein R1 and R 2 which may be the same or different, are hydrogen at--rs or lower alkyl groups, Z is a cyano group, -CO-OR 3 (wherein R 3 is a hydrogen atom or a lower alkyl group) or -CO-N(R4)R5 (wherein R 4 and R 5 which may be the same or different, are hydrogen atoms or lower alkyl groups, R4 and R 5 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: O R6 II I C -C-R7 R8 10 (wherein R6, R 7 and Rs, which may be the same or different, are hydrogen atoms, halogen atoms or cyano groups), provided that Xl 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),
-CONR
4 R5 or cyano group when Y is chlorine atom is novel.
Among them, those whose Y is 0 R6 II I -C-C -C R 7
R
R8 11 1 wherein R6, R7 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
R
1 C -z
-C-Z
R2 wherein RI and R 2 which may be the same or different, are hydrogen atoms or lower alkyl groups, Z is -CON(R4)R5 (wherein R 4 and R5, which may be the same or 10 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-nitrophenoxy)acetamide (compound No. 1) 12 F V ci Q C1 NO 2
NCCH
2 0 H 2
II
0 1 In 8 ml of 97% sulfuric acid was dissolved 3.7 g (0.02 mole) of (2-chloro-4-fluorophenoxy)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 10 0 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 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 recrystallized from ethyl acetate to obtain 2.5 g of the desired compound as light-yellow crystals.
Physical properties: m.p. 182 182.5 0 C, yield 50.5%.
NMR [DMSO/TMS, 6 values (ppm)] 4.75 2H), 7.50 (bd, 2H, J=0.6Hz), 7.75 2H, J=7Hz), 7.97 2H, J=llHz).
13 1 Example 2 Production of (2-chloro-4-fluoro-5-nitrophenoxy)acetamide (compound No. 1) F
F
Cl Q> Cl Q N0 2
H
2
NCCH
2 O H 2
NCCH
2 0 O 0 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-nitrophenoxy)acetic acid (compound No. 2) F
F
C Q Cl Q NO 2
C
2
H
5
OCCH
2 O HOCCH 2 0 0 0 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.
14 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 (CH 2 C1 2
-CH
3 0H) to obtain 1.3 g of the desired compound asocherous crystals.
Yield: 30.2%.
NMR [DMSO/TMS, 6 values (ppm)] 4.57 2H), 7.50 (bd, 2H, J=0.6Hz), 7.75 2H, J=7Hz), 7.97 2H, J=llHz), 13.90 (bs, 1H).
Example 4 Production of (5-bromo-2-chloro-4-fluorophenoxy)acetonitrile (compound No. 3) .C C Br 0
NCCH
2 0 In 10 ml of methylene chloride was suspended 1.0 g (7.5 mmoles) of anhydrous aluminum chloride, and g (5.4 mmoles) of (2-chloro-4-fluorophenoxy)aceto- 15 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 0 C, yield 77%.
Example Production of (2-chloro-5-chloroacetyl-4fluorophenoxy)acetamide (compound No. 6) Cl Q Cl COCH 2 C1
H
2 NCCH20
H
2
NCCH
2 0 II
II
0 0 With 2.0 g (15.0 mmoles) of anhydrous aluminum chloride was mixed 0.85 g (7.5 mmoles) of chloroacetyl 16 I I 1 chloride, and the resulting mixture was heated to 80 0
C.
Then, 1.0 g (4.9 mmoles) of (2-chloro-4-fluorophenoxy)acetamide was added and the reaction was carried out at for 9 hours.
After completion of the reaction, the reaction mixture was cooled to 80 0 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 g of the desired compound.
Physical properties: m.p. 166.3°C, yield 73%.
Example 6
S
Production of (2-chloro-5-dichloroacetyl-4fluorophenoxy)acetamide (compound No. 7) F F Cl /Cl Cl 0 Cl COCH \*Cl
H
2
NCCH
2 0 H 2
NCCH
2 0 II II 0 0 O O 15 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 0
C.
Then, 1.0 g (4.9 mmoles) of (2-chloro-4-fluorophenoxy)acetamide was added and the reaction was carried out at 70 80 0 C for 8 hours.
17 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 0 C, yield 33%.
Example 7 Production of (2-chloro-5-chloroacetyl-4fluorophenoxy)acetonitrile (compound No. 1i) F F Q C1 Cl Q COCH 2 C1 0 NCCH20 NCCH20 With 2.0 g (15.0 mmoles) of anhydrous aluminum 15 chloride was mixed 0.85 g (7.5 mmoles) of chloroacetyl chloride, and the resulting mixture was heated to 60 0
C.
Then, 0.9 g (4.0 mmoles) of (2-chloro- -fluorophenoxy)acetonitrile was added and the reaction was carried'out at 70 0 C for 3 hours.
After completion of the reaction, the reaction mixture was poured into ice water and stirred for 1 18 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. 122.10C, yield 73%.
Example 8 Production of (2-chloro-5-dichloroacetyl-4fluorophenoxy)acetonitrile (compound No. 13) F F Cl C1 C) 0 Cl COCH Cl
NCCH
2 0 With 2.0 g (15.0 mmoles) of anhydrous aluminum chloride were mixed 0.93 g (6.3 mmoles) of 10 dichloroacetyl chloride and 0.9 g (4.9 mmoles) of (2chloro-4-fluorophenoxy)acetonitrile, and the reaction was carried out at 60 0 C for 2 hours.
a.
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 0 C, yield 67%.
19 1 Example 9 Production of (2-chloro-4-fluoro-5-trichloromethylphenoxy)acetonitrile (compound No. 14) F F Cl Q0 Cl Q CC13
NCCH
2 0 In 10 ml of carbon tetrachloride was suspended 1.5 g (11.2 mmoles) of anhydrous aluminum chloride, and 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.
10 After completion of the reaction, the reaction mixture was allowed to cool and ice water was added and S. 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 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 [CDC1 3 /TMS, 6 values (ppm)] 4.88 2H), 7.09 1H, J=10.4Hz), 7.79 1H, J=7.1Hz).
20 1 Example Production of (2-chloro-5-cyanoacetyl-4fluorophenoxy)acetonitrile (compound No. 17) F F Cl C1 Qo COCH 2
CN
To 4.5 g (33.6 mmols) of anhydrous aluminum chloride was added 0.57 g (7.8 mmols) of dimethylformamide (DMF), and 1.0 g (5.6 mmoles) of (2-chloro-4fluorophenoxy)acetonitrile was added to the suspension at room temperature. Then, 2.9 g (28.0 mmoles) of cyanoacetyl chloride was slowly dropped into the 10 resulting mixture. After completion of the dropping, ae the reaction was carried out at 55 0 C for 3 hours.
After completion of the reaction, the reaction mixture was analyzed by a thin layer chromatography and s a gas chromatography (area percentage: The 15 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 are listed in Table 1.
Xl X2 O
(I)
RO
21 Table 1 No I R I X1 IX2 y Physical properties *5
S
*5
H
2
NCOCH
2
HOOCCH
2
NCCH
3
H
2
NCOCH
2
H
2
NCOCH
2
H
2
NCOCH
2
H
2
NCOCH
2
H
2
NCOCH
2
NCCH
2
NCCH
2
NCCH
2
NCCH
2
NCCH
2
NCCH
2 N0 2 N02 Br
COCH
3
COCH
2 Cl
COCH
2 C1 COCHC1 2 CC13
COCH
3 COCH c1
COCH
2 C1 COCH2Br COCHC1 2 CC1 3 m.p. 182.0-182.5 0
C
6 (DMSO)=4.57 2H), 7.57 2H, J=7.OHz), 7.89 2H, J=11.OHz), 13.9 (bs, 1H).
m.p. 72.3 0
C
6 (CDC1 3 )=2.64 3H, J=3.3Hz), 4.51 2H), 5.70 (bs, 1H), 6.60 (bs, 1H), 7.28 1H, J=7.9Hz), 7.41 1H, J=5.9Hz).
m.p. 171.7 0
C
m.p. 166.3 0
C
m.p. 132.3 0
C
m.P. 214.7 0
C
6 (CDC1 3 )=2.63 3H, J=3.3Hz), 4.35 2H), 7.31 1H, J=7.6Hz), 7.54 1H, J=6.lHz).
m.p. 110.9 0
C
m.p. 122.1 0
C
6 (CDC1 3 )=4.49 2H, J=2.4Hz), 4.90 2H), 7.33 1H, J=9.9Hz), 7.60 1H, J=6.OHz).
M.p. 98.7 0
C
6 (CDC1 3 )=4.88 2H), 7.09 1H, J=1.41z), 7.79 1H, J=7.1Hz).
(to be continued) 22 Table 1 (Cont'd) No R XIX2 Y Physical properties
H
2 NCOCn' F Cl COCH 2 Cl (CDC1 3 )=1.63 3H, I J=6.6Hz), 4.65 2H,
CH
3 J=6.6Hz), 4.63 2H1, J=3Hz), 6.00 (bs, 1H1), 6.67 (bs, 1H), 7.26 (d, 1H1, J=9.9Hz), 7.45 (d, 1H1, J=5.711z).
16 NCCH F Cl COCH 2 Cl 6 (CDCl 3 )=l.67 3H1, I J=6.8Hz), 4.98 2H1, UtH 3 J=6.981z), 4.70 2H1, J=3.lHz), 6.00 (bs, 1H1), 7.30 1H1, J=lflHz), 7.59 1H, J=5.8Hz).
17 NCCH 2 F Cl COCH 2
CN
e pep.
.cpp C. PP p p.
p 1 Aromatic compound derivatives represented by the formula are important especially as intermediates in preparation of the herbicides disclosed in Japanese Patent Kokai (Laid-opei) No. 3-163063. The 5 typical herbicides which are final products can be prepared, for example, by the process as illustrated below.
23 I
I
y R1 0 y R1 X-Q O-C-R R3"O-C-0R3" x O O-C-R
R
2 Base R3"O-C-CH 2 C R 0 0 y Cyclyzation alkylation R I N
O
R-C- N0O x x Halogena- *y Q tiori y Q Hal R1 N R1 N NI
I
N R511 N OR 5 1 R-C-O R-C-O 0
R
2 R2' (wherein R, Rl, R2, X and Y are as defined above, R3" denotes a lower alkoxyl group, R 4 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.) 24

Claims (6)

1. A process for producing an aromatic compound represented by the general formula xl X2 y (1) RO [wherein Xl and X2, which may be the same or different, are halogen atoms; R is a group represented by the formula: R 1 -C z *e R2 (wherein R1 and R 2 which may be the same or different, are hydrogen atoms or lower alkyl groups, Z is a cyano group, -CO-OR 3 (wherein R3 is a hydrogen atom or a lower alkyl group) or -CO-N(R4)R5 (wherein R4 and R 5 which may be the same or different, are hydrogen atoms or lower alkyl groups, R4 and R 5 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: 0 R 6 C C -R7 R8 25 (wherein R 6 R 7 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): /X1 X2 0 (II) 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 1, wherein the electrophilic reagent is a nitrating agent.
3. The process for producing an aromatic compound according to Claim 1, wherein the electrophilic reagent is a halogenating agent.
4. The process for producing an aromatic compound according to Claim 1, wherein the electrophilic reagent is a combination of a Lewis acid and a compound represented by 0 R6 II the general formula (III): X3-C-C-R7 (III), R R8 26 0 R 6 the general formula (-C-C-R7)2 (IV) I R8 or the general formula C(X4) 4 (V) wherein R6, R 7 and RS, which may be the same or different, are hydrogen atoms, halogen atoms or cyano groups, X3 is a halogen atom, and X 4 which may be the same or different, are halogen atoms. An aromatic compound represented by the general formula 2 y (I) *oo.* X2 [wherein X1 and X2, which may be the same or different, are halogen atoms; R is a group represented by the R 1 27 grup -C-R (weenR s**yrgnatmo oe may be the same or different, are hydrogen atoms or lower alkyl groups, R 4 and R 5 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: 0 R6 II I -C-C -R 7 I R8 (wherein R 6 R 7 and R 8 which may be the same or different, are hydrogen atoms, halogen atoms or cyano groups): provided that Xl 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 X 1 is fluorine atom, X2 is chlorine atom and Z is -COOR 3 (wherein R3 is a group other than hydrogen atom), -CONR 4 R5 or cyano group when Y is chlorine atom. S
6. A compound according to claim 5 wherein said Y is O* R 0 R6
555. II I -C R 7 R8 wherein R 6 R 7 and R 8 which may be the same or different, are hydrogen atoms, halogen atoms or cyano groups. 28 7. A compound according to claim 6, wherein R of said compound is R1 -C -Z R2 wherein R 1 and R 2 which may be the same or different, are hydrogen atoms or lower alkyl groups, Z is -CON(R 4 )R 5 (wherein R4 and R5, which may be the same or different, are hydrogen atoms or lower alkyl groups, R 4 and R5 being able to be taken together to represent an alkylene group). *i I 8 p 29 30 8. Compounds of formula or methods for their manufacture, substantially as hereinbefore described with reference to the Examples. rh~ =sz-ps.c faeit'"-es, comnpositions- and mpcundTh disclose emn or referrea to or indicated in the specification an claims of this application, individually or collectiv and any and all combinations -nf nny two p mr f sa d-p or featurcc *2 *S S *45 S *S S S5 S S .5.5 0S** S DATED this TENTH day of JUNE 1993 Nihon Nohyaku Co., Ltd, by DAVIES COLLISON CAVE Patent Attorneys for the applicant(s) V ii ~VTC~ ABSTRACT OF THE DISCLOSURE There are disclosed a process for producing an aromatic compound of the formula which comprises reacting an electrophilic reagent with a,compound of the formula (II) shown below: xl xi X2 (0 Electrophilic X2 Y reagent RO RO (II) (I) S (wherein R, Xl, X2 and Y are as defined in the specification) to introduce a substituent into the aromatic ring selectively and a novel compound prepared therefrom.
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