前苏联专利SU1068032A3 Process for preparing derivatives of phenoxycarboxylic acid

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专利摘要:
A phenoxycarboxylic acid derivative having the formula <IMAGE> (III) wherein R represents <IMAGE> and X1 represents a hydrogen atom, a halogen atom, a lower alkyl group, trifluoromethyl group, nitro group or cyano group and X2 represents a hydrogen atom, a halogen atom, a lower alkyl group, nitro group or cyano group, R' represents <IMAGE> <IMAGE> and R1 and R2 are the same and different and respectively represent hydrogen atom or a lower alkyl group, is produced by reacting a phenol compound having the formula <IMAGE> (I) with a halogen compound having X-R' wherein X represents a halogen atom in the presence of a base. The reaction is carried out in the presence of a quarternary ammonium salt or a quaternary phosphonium salt in a nonpolar solvent.
公开号:SU1068032A3
申请号:SU792836785
申请日:1979-10-31
公开日:1984-01-15
发明作者:Коике Ватаро；Сасуга Тадаси；Язава Тихиро
申请人:Ихара Кемикал Индастри Ко.Лтд (Фирма)；
IPC主号:

专利说明:

The invention relates to an organic Hamit, specifically to an improved method for the preparation of phenoxycarboxylic acid derivatives used in agriculture. A known method for the preparation of phenoxycarboxylic acid derivatives involves the interaction of p-dioxybenzene monoester with a halogen-containing compound in a solvent in the presence of bases, promoting the release of hydrogen halide, for example alkaline earth or alkali metal carbonates and C3. The closest to the proposed technical essence and the achieved result is a method of obtaining phenoxycarboxylic acid derivatives by reacting a phenolic derivative of the total |) Ormuli X - hydrogen, halogen, lower alkyl group, trifluoromethyl; a group, a nitrog group or cyano groups; 2 is a hydrogen, halogen, lower alkyl group or a nitro group, with a halogen-containing compound of the general formula RX where dHdHzuHgdooBa -bNooov: Rt-C} HdH dHCiOORz - (BI.BI where R and R are hydrogen or a lower akyl group, X is a halogen atom in a solvent containing a keto group, for example, in acetone, butanol or methyl ethyl ketone in the presence of a base that promotes separation of hydrogen halide, for example NaOH or NOjCOj, at 50-80 ° C. Target product yield 80-90% Cz. However, using this method is not high enough yield of the target product. The purpose of the invention is higher and the yield of the desired product. The aim is achieved in that according to the method for producing phenoxycarboxylic acid derivatives of the general formula C), consisting of X with sye about the interaction of the phenolic long total Foomula - hydrogen, halogen, lower alkyl group, trifluoromethyl group (Nitro group or cyano group ; hydrogen, halogen, a lower alkyl group or a nitro group, a logic-containing compound of the formula where -dHriOORi -dH (iH2 (lHzdOOR2 -dHciH 6H (iooR2 - (iH2d (JH (iooK2 KjLffU RI where (and RH are identical or different) and the numbers of the numbers and JR (jH (iooK2 KjL ffU RI where where and RH have the same or the same numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers and the numbers have lower alkyl oh group taken in a 1: 1 molar ratio of 1, 5 with a phenolic derivative of the formula (P | in the presence of a quaternary ammonium orphosphonium salt, taken in a molar ratio of 0.0050.05 with a phenolic derivative of the formula (0), and also in the presence of a base, as used with K2CO2 or NygSO3, or NaHCO, taken in a molar ratio of 0 , 5-1.5 with a phenolic derivative of formula 15), in a medium of a non-polar solvent and water at a ratio of 1: 1 at 50-80 ° C. The yield of the target product 87-98%. Distinctive features of the proposed method are carrying out the process at a molar ratio. phenol derivative of the formula (and with a halogen-containing compound of formula (I Il) 1: 1-1.5 in the presence of a quaternary ammonium or phosphonium salt, taken in a molar ratio of 0.005-0.05 with a phenolic derivative of the formula Uj), and also in the presence of the base, in the capacity of which either NoijCp ,, or HANSO, is used, taken in a molar ratio of 0.5-1.5 with the phenolic derivative of formula (b), in a medium of non-polar solvent and water at a ratio of 1: 1. Quaternary with ammonium or phosphonium salts use compounds of the following groups: benzyl trialkylammonium, benziltrialkilfosfonievye, tetraalkylammonium, or trifenilalkilammonievye trifenilalkilfosfonievye salt.
Example 1. 100 ml of chlorobenzene and 100 ml of water are loaded into the reactor and 95.3 g (O, 375 mol) of 4- (4-trifluoromethylphenoxy) phenol, 85.4 g (0.412 mol) of ethyl ether 4- bromo-2-pentenoic acid, 39, O g (0.281 mol) of potassium carbonate and 1.1 g (0.00375 mol) of tributyl ethyl ammonium bromide. The reaction mixture is heated to 80 ° C under reflux with stirring for b h, after which the The aqueous phase is washed, and the organic phase is washed with 5% hydrochloric acid solution and water, after which the 4-bromo-2-pentoic acid ethyl ester is distilled off and low boiling point products at 100 ° C under reduced pressure (0.020.05 mm Hg), thus obtaining 137.0 g of ethyl ester .- (4-trifluoromethylphenoxy) phenoxy -2-pentenoic acid. Output 96.0% (basic content product 97.1%).
Example 2. In the reactor, 100 ml of chlorobenzene and 100 ml of water are charged and 95.3 g (0, mol) of 4- (4-trifluoromethylphenoxy) phenol, 73.7 g (0.412 mol / 4-bromo) are added. 2-pentenoate, 78.0 g (0.56 mol) of potassium carbonate, and 1.1 g (0.00375 mol of tributylethylammonium bromide a. The reaction mixture is heated with stirring and refluxing for 6 h, then it is cooled to at room temperature and concentrated hydrochloric acid is added with stirring until the reaction mixture is acidic. The aqueous phase is separated, the organic phase is washed with water, after which chlorobenzene is distilled off at 100 ° C under reduced pressure (0.02-0.05 mm Hg), resulting in (4-trifluoromethylphenoxy phenoxy -2-pentenonic acid. Yield 91.2% (content of the desired product 96, 5%.) Original .products, .. Phenolic derivative Halogen-containing 3 4 5 6
Comparative experience 1.
In accordance with the method described in Example 1, except that tributylethylammonium bromide was not added to the reaction mixture, the reaction mixture was heated at reflux with stirring for 6 hours, then cooled to room temperature and 15.0 g was added {0.375 mol sodium hydroxide. After that, the reaction mixture is stirred for another 30 minutes and treated with it, resulting in 44.5 g of ethyl 4-C4- (4-trifluoromethylphenoxy) phenoxy -2-pentenoic acid. Yield 31.2%.
Comparative experience 2.
100 ml of ethanol is charged to the reactor and 95.3 g (0.375 mol) of 4- (4-trifluoromethylphenoxyJphenol), 85.4 g (0.412 mol) of 4-bromo-2-pentenoic acid ethyl ester and 39.0 g (0.281 mol) are added. potassium carbonate. The reaction mixture is stirred at reflux for 6 hours, ethanol is distilled off, 100 ml of chlorobenzene and 100 ml of water are added, and the reaction mixture is then stirred at room temperature for an additional 30 minutes. The aqueous phase is separated The organic phase is washed with a 5% solution of hydrochloric acid and water, after which it is distilled off under reduced pressure. pressure chlorobenzene, ethyl 4-bromo-2-pentenoic acid and -nizkokip boiling point byproducts, in such a way to give 10.47 g of ethyl (4-trifluoromethylphenoxy) fekoksi 1 |. -2-pentenoic acid 73.5% yield.
Examples 3-37. According to the method described in Example 1, but using the phenolic derivatives and halogen-containing compounds listed in Table 1, instead of 4- (4-trifluoromethylphenoxy) phenol and
Ethyl 4-bromo-2-pentenoic acid is carried out by appropriate reactions. The results are presented in table. 2. T pl 4- (4-Trifluoromethylphenoxy) -4-bromo-2-pente-phenolic acid ethyl ester - -4-bromo-2-pentenoic acid - -2-bromo-propionic acid - -4-ethyl ethyl ester of a new compound acids Original products Phenolic production Halogenated 94- (3-Trifluoromethylphene si) -phenol 104- (2-chloro-4-trifluoromethylphenoxy) -phenol 114- (2-Nitro-4-trifluoromethylphenoxy-phenol 124 (2-Bromo-4- trifluorometh phenoxy) -phenol 13I 4-phenoxyphenol 144- (2-chlorophenoxy) -phenol 154- (4-cyanophenoxy) pheno 164- (2,4-dichlorophenoxy-phenol 174- 12-nitro-4-chloropheno-si) -phenol 184 - (, 2-Chloro-4-nitrophene -phenol 194- (2-Nitro-4-chlorophenok si) -phenol 204- (4-Nitro. Phenoxy) phenol 21 4- (4-Bromophenoxy) pheno 4- (3,5-Dichloropyridyl-, -2-hydroxy) -phenol 4- (3,5-dichloropyridyl-. -2-hydroxy) phenol. 4- (5-nitropyridyl-2-hydroxy) -phenol 264-phenoxyphenol 274- (4-chlorophenoxy) -pheno
The continuation of the table.1. Compound 4-6hc-2-heptenoic acid ethyl ester 4-bromo-2-pentenoic acid ester 4-bromo-2-pentenoic acid ethyl ester 4-chloro-2-pentenoic acid 4-bromo-2-pentenoic acid ethyl ester 4 -Bromo-2-pentenoic acid 4-bromo-2-pentenoic acid butyl ester 4-bromo-2-pentenoic acid ethyl ester 2-chloropropionic acid ethyl ester 2-bromo-propionic acid isopropyl ester 2-bromoacetic acid ethyl ester 4 bromo-2-butenoic acid 2-bromoic acid ethyl ester. 4-bromo-2-pentenoic acid ester propyl 2-bromopropionic acid ethyl ester 4-bromo-2-pentenoic acid butyl ester 2-bromopropionic acid ethyl ester 4-bromo-2-pentenoic acid ethyl ester Methyl yfir 4-5lor-3- methyl 2-butenoic acid Iopropyl ester of 4-bromo-3-methyl-2-butenoic acid
Continued table. one
4 - (. 5-Methyl-2-isog1ropyl-phenoxy) -phenol
4- (3-Methylphenoxy) -phenol
4- (4-Chloro-3-methylfenk si) -phenol
4-U-Trifluoromethylphenoxy) -phenol
4- (2-Bromo-4-trifluoromethylphenoxy) -phenol
4- (5-bromopyridyl-2-hydroxy) -phenol
4- (3,5-Dibromopyridyl-, -2-hydroxy) -phenol
4- (3,5-Dichloropyr-2-oxy bphenol
4- - (5-Chloropyridium p-2-hydroxy) -,
4- (3,5-Diyodpiridi 4 l-2-oxy) -phenol
4-J4- {4-trifluoromethylphenoxy) fe ethyl ester hydroxy -2-pentenoic acid
4- 4- (4-Trifluoromethylphenoxy | phenoxy -2-pentenoic acid 1.5119
2-f4-U-trifluoromethylphenoxy.T.p.136 phenoxy 1-propanoic acid 138 C
Ethyl ester of (4-trifluoromethylphenoxy) -valeric acid 1.5080
Ethyl ester (.4-trifluoromethylphenoxy phenoxy-valeric acid 1,5103
Octyl ester (4-triftorg ethylphenoxy) phenoxy -2-pentanoic acid 1.5045
2-Chloropropionic acid
2-bromopropionic acid isobutyl ester
2-Bromopropionic acid ethyl ester
2-Chloroacetic acid
2-Bromopropionic acid
Methyl ester of 2-chloroacetic acid
Methyl ester of 2-bromopropionic acid
2-Bromopropionic acid ethyl ester
table 2
96.0
1.5195 91.2 90.5
94.5 95.0 96.5
1068032 °
:::::::::: L :::::::::::::::::: I: L; ::::: I; Z:
Ethyl ester (3-trifluoromethylphenoxy) -phenoxy -2-pentanoic acid 1,5155 96,0
(2-Chloro-4 trifluoromethylphenoxy) phenoxy3-2-pentenova mp 88.8 acid89 ° C 87.3
Ethyl ester (2-nitro-4-trifluoromethylphenoxy) phenoxy -2-pentenoic acid 1.5343 95.6
Ethyl ester (2-bromo 4-trifluoromethylphenoxy) phenoxy -2-pentenoic acid 1.5341. 96.0
4- (4-phenoxyphenoxy / 2-pente-T. PL. Isoat114 with 94.7
4- 4- (2-chlorophenoxy) phenoxy3-2-pentene butyl ester
Acid1.5547 95.1
Ethyl ether (4-cyanophenoxy) phenoxy -2-pentene
acids1.5625 93.7
Ethyl (2, 4-dichlorophenoxy)
phenoxy-propanoic acid 1.5601, 90.0
Isopropyl ester of 2- (4-nitro-4-chlorophenoxy) phenoxy-propanoic acid 1,5605 97.1
2-4-12-chloro-4-nitrophenoxy) phenoxy-acetic acid ethyl ester of mp.92 acid; 95 ° C 97.0
Ethyl ester 4 4- (2-nitro-4-chlorophenoxy | phenoxy -2-butenoic acid 1,5790 97.5
2-C2- (4-nitrophenoxy) phenoxy-butyl ethyl ester
acid. 1.5701 94.3
Isopropyl ester (4-bromophenoxyphenoxy) j-2-pentenoic acid 1,5724 95,0
Ethyl ester (3,5-dichloropyridyl-2-hydroxy) phenoxy propionic acid 1,5603 90,2
(3-, 5-Dichloropyridyl-2-hydroxy) phenoxy -2-pentenoic acid butyl ether 1.5565 92.7
Ethyl ester (5-nitropyridyl-2-hydroxy) phenoxy-propionic acid 1.55.57 91.3
Ethyl ester .4-C4 - (, 5-nitropyridyl-2-ox. And) phenoxy -2-pentenoic acid 1.5684 89.2
Continuation of table 2
Methyl ether. 4- (4-phenoxyphenoxy) -3-methyl-2-butene With a m.p.
4-C4- (4-chlorophenoxy-phenoxy-3-methyl-2-T. 49.4-butenoic acid isopropyl ester; 50 ° C
(.5-methyl-2-isopropylphenoxy) phenoxy-2-propionic acid-T.pl.91loty92 ° C
2- (4-3-methylphenoxy) phenoxy - mp. 78.7-propionic acid
(4-chloro-3-methylphenoxy): mp.12830 phenoxy-propionic acid 129 ° С
31 Ieobutyl ether (4-trifluorome. Methylphenoxy phenoxy} -T.p.55-propionic acid57 ° C
32 2- 4- {2-bromo-4-trifluoromethylphenoxy-phenoxy-1-propionic acid ethyl ester
(5-Bromopyridyl) 2-shri gT.pl. 130phenoxy 3 acetic acid132 С
2- (4-3,5-Dibromopyridyl-2-hydroxy) phenoxy} -propionic acid m.p.66 acid .70 ° С
Methyl ether (3,5-dichloropyridyl-2-hydroxy) phenoxy -: acc-So pl. 52 acetic acid54 0
Methyl ester of 2- (4-5-chloropyridyl-2-hydroxy) phenoxy-propio-T.pl.88nova acid. EOS
Ethyl ester, 5-dihydridyl-i-okc / phenoxy-T.PL.85 propionic acid87 6
Examples 38-48. In sorting with the method described in Example 1, but with the replacement of tributylethylammonium bromide with other quaternary ammonium salts or phosphonium salts listed in Table 3, semi-benzyltrimethylammonium chloride 93.5 95.8
39Benzyltriethyl1mmonium bromide 95., 2 96.6
40Benzyltrioctylammonium chloride 94.1 95.6
91.0
98.0
91.1
92.5
90.5
90,8
91.1
1.5541
93.1
90.3
93.7
92.0
90.0
ethyl ester (4-trifluoromethylphenoxy phenoxy -2-pentenoic acid).
The results are shown in table 3.
Table 3
MFA, 94.7 95.4.
48 Butyltriphenylphosphonium bromide. 94.3 95.3 Examples 49-56. In accordance with the method described in Example 1, but with the replacement of chlorobenzene with other non-polar solvents, in Table 4, ethyl is obtained.
Example 57. In accordance with the method described in Example 1, except that instead of 85.4 g (0.412 mol of 4-bromo-2-pentenoic acid ethyl ester, 67.0 (0.412 mol) of 4-chloro ethyl ester is used -2-pentenoic acid. Ethyl ester (4-trifluoromethylphenoxy phenoxy j-2-pentenoic acid is obtained. Yield 83.4% (content of the desired product 85.7%)
Examples 58-62, 100 ml of chlorobenzene and 100 ml of water are placed in the reactor and then 95.3 g are added.
Continued table. 3
Oh, mole) 4-. (4 trifluoromethylfansge: Si7-phenol, 85.4 g (0.412 mol / 4-bromo-2-pentanoic acid ethyl ester, 39.0 g (0.281 mol of potassium carbonate and the amount determined for each experiment (indicated in Table 5 / 6porvmcToro tributylethylammonium. The mixture is heated under reflux
with stirring for 6 hours, so that the reaction would pass. The aqueous phase is removed, the organic phase is washed with 5% hydrochloric acid and water, and then distilled off at 100 ° C and a reduced pressure of 0.02-0.05 mmHg. -chloro-benzene, 4-bromo-2-pentenether (4-trifluoromethylphenoxy) phenoxy -2-pentenoic acid ethyl ester. The results are shown in Table. 4, Table4
New acid and low-boiling by-products and get ethyl ester (4-trifluoromethylphenoxy) phen, oxy. j Amount of methyl ethylbutyrammonium, g
Molar ratio based on 4- (4-trifluoromethylphenoxy) -phenol
Product - ethyl ester (4.-triftrrmethylphenoxy) phenoxy -2-pentenoic acid
136.0 136.5
g 96.5 97.0 95.4 95.8
Examples 63-66. 100 ml of chlorobenzene and 100 ml of water are placed in the reactor, and then 95.3 g (.0.375 mol) of 4- (4-trifluoromethylphenoxy phenol, 85.4 g (0.412 mol of ethyl 4-bromo-2-pentenoic acid) are added. , 39.0 g of 10.281 mol / potassium carbonate and 1.1 g (0.00375 mol) of tributylethylammonium bromide The mixture is heated with stirring at a specific temperature for each experiment for a certain time
Product - ethyl ester 4-14- (4-trifluoromethylphenoxy) phenoxy -2-pentenoic acid
Quantity, g
. Purity,%
Output, %
-2-pentenoic acid. Outputs and quality indicators of the product are given in table.5. Table 5
3.3
4.4
5.5
0.04
0.03
0.05
137.0
136.5 96.7
96.9 96.0
95,8
(indicated in Table 6) for the reaction to take place. The aqueous phase is removed, the organic phase is washed with 5% hydrochloric acid and water, and then distilled off, under reduced pressure (0.02 g-0.05 mm Hg) chlorobenzene, 4-bromo-2-ethyl ester -pentenoic acid, low boiling point npQucts and get 4-f4- (4-trifluoromethylphenoxy-phenoxy-2-pentenoic acid ethyl ester). The outputs and 40 indicators of the quality of the product are given in Table 6.
Table 6
136.0
136.6 96.8
96.0 95.4
95,8
Examples 67 and 68, 100 ml of chlorobenzene and 100 | ears of Veda are placed in the reactor, and then 95.3 g (0.375 mol / 4- {4-trifluoromethylphenoxy) phenol, 85.4 g (0.412 mol) of ethyl ether 4 bromine are added. 2-pentenoic acid, a certain amount of or MaHCOj (indicated in tab. Bj and 1.1 g (0.00375 mol) of tributylethylamle-1-methyl bromide. The mixture is heated under reflux for 6 h. To remove the reaction. The aqueous phase is removed , the organic phase is washed with 5% hydrochloric acid and water, and then distilled off at 1QO ° C under reduced pressure (0.02-0.05 mm Hg from chlorobenzene ethyl 4-bromo-2-pentenoic ester and low boiling point by-products are used to obtain ethyl ester (4-trifluoromethylphenoxy J-phenoxy -2 pentenoic acid. The yields and purity of the product are given in Table 7.
Table 7
Thus, using the proposed method, high-purity phenoxycarboxylic acid derivatives can be obtained in high yields,

权利要求:
Claims (1)
[1]
METHOD FOR PRODUCING Phenoxycarboxylic Acid Derivatives of the General Formula
VO where R
X _l is hydrogen, halogen, lower, alkyl group, trifluoro-) methyl group, nitro group or cyano group;
- hydrogen, halogen, lower alkyl group or nitro group, ’with a halogen-containing compound of the general formula (III)
XR 'where X is halogen, in a solvent in the presence of a base at 50-80 ° C, characterized in that, in order to increase the yield of the target product, the process is carried out at a molar ratio of the phenolic derivative of the formula (β) and the halogen-containing compound of the formula (ijj ) - 1: 1-1.5 in the presence of a quaternary ammonium or phosphonium salt, taken in a molar ratio of 0.005-0.05 with phenolic, arbitrary formula (|]), as well as in the presence of a base, in which K ^ COj is used or NcijCOj, or Hc0 Mey _3, taken in the molar ratio to the phenol derivative f rmuly (17) of 0.5-1.5, among non-polar solvent and water at a ratio of 1: 1.

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同族专利:

公开号 | 公开日

HU182584B|1984-02-28|

DE2942989A1|1980-05-14|

JPS5562043A|1980-05-10|

NL7907749A|1980-05-06|

AU5162979A|1980-05-08|

FR2440352B1|1984-08-10|

IT7926964D0|1979-10-31|

US4254262A|1981-03-03|

FR2440352A1|1980-05-30|

BR7907070A|1980-07-15|

OA06369A|1981-08-31|

GB2035317A|1980-06-18|

IL58492D0|1980-01-31|

AU531187B2|1983-08-11|

ES485593A1|1980-07-01|

IN151554B|1983-05-21|

IT1124869B|1986-05-14|

GB2035317B|1983-01-12|

引用文献:

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

US3972887A|1972-12-11|1976-08-03|The Dow Chemical Company|Process for preparing phosphorothioates and phenylphosponothioates|

DE2342118C2|1973-08-21|1982-09-23|Merck Patent Gmbh, 6100 Darmstadt|Phenoxypropionic acid derivatives, processes for their preparation and pharmaceutical preparations containing these compounds|

JPS52131542A|1976-04-28|1977-11-04|Ishihara Sangyo Kaisha Ltd|Phenoxypropionic acid derivatives and herbicides containing them|EP0058173B1|1980-08-26|1984-12-05|Ici Australia Limited|Process for the synthesis of aryloxy derivatives|

DE3236730A1|1982-10-04|1984-04-05|Hoechst Ag, 6230 Frankfurt|METHOD FOR PRODUCING BENZOXAZOLYL AND BENZTHIAZOLYLOXYPHENOXYPROPION ACID DERIVATIVES|

US4608081A|1984-06-22|1986-08-26|Kanesho Company Limited|Herbicidal 2-[4--phenoxy]-alkanoic acid amides|

US4661617A|1985-04-19|1987-04-28|Sandoz Ltd.|Novel compositions|

ES2052556T3|1986-04-17|1994-07-16|Zeneca Ltd|FUNGICIDES.|

US4701531A|1986-12-01|1987-10-20|The Dow Chemical Company|Catalyzed alkylation of halopyridinates in the absence of added organic solvents|

EP0287959B1|1987-04-21|1993-04-28|BASF Aktiengesellschaft|P-phenoxy--phenoxymethyl substituted five membered heteroaromatics|

IT1265087B1|1993-05-20|1996-10-30|Recordati Chem Pharm|GEMFIBROZIL PREPARATION PROCESS|

法律状态:

优先权:

申请号 | 申请日 | 专利标题

JP13506078A|JPS5562043A|1978-11-01|1978-11-01|Preparation of phenoxycarboxylic acid derivative|

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