JPS6334864B2 - - Google Patents
Info
- Publication number
- JPS6334864B2 JPS6334864B2 JP55127182A JP12718280A JPS6334864B2 JP S6334864 B2 JPS6334864 B2 JP S6334864B2 JP 55127182 A JP55127182 A JP 55127182A JP 12718280 A JP12718280 A JP 12718280A JP S6334864 B2 JPS6334864 B2 JP S6334864B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- ether
- compound
- chloro
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 nitrodiphenyl ether compound Chemical class 0.000 claims description 34
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 10
- 238000005917 acylation reaction Methods 0.000 claims description 7
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 claims description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 16
- 239000010410 layer Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 230000002363 herbicidal effect Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000004009 herbicide Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- 230000010933 acylation Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- UNFBXLHCJMSGRQ-UHFFFAOYSA-N 2-chloro-1-[3-[2-chloro-4-(trifluoromethyl)phenoxy]-4-nitrophenoxy]-4-(trifluoromethyl)benzene Chemical compound C1=C(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)C([N+](=O)[O-])=CC=C1OC1=CC=C(C(F)(F)F)C=C1Cl UNFBXLHCJMSGRQ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 3
- 239000012346 acetyl chloride Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical compound ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- QXSZNDIIPUOQMB-UHFFFAOYSA-N 1,1,2,2-tetrabromoethane Chemical compound BrC(Br)C(Br)Br QXSZNDIIPUOQMB-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 description 1
- JVSFQJZRHXAUGT-UHFFFAOYSA-N 2,2-dimethylpropanoyl chloride Chemical compound CC(C)(C)C(Cl)=O JVSFQJZRHXAUGT-UHFFFAOYSA-N 0.000 description 1
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- XPXMKIXDFWLRAA-UHFFFAOYSA-N hydrazinide Chemical compound [NH-]N XPXMKIXDFWLRAA-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- QTBFPMKWQKYFLR-UHFFFAOYSA-N isobutyl chloride Chemical compound CC(C)CCl QTBFPMKWQKYFLR-UHFFFAOYSA-N 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Hydrogenated Pyridines (AREA)
- Pyrrole Compounds (AREA)
- Indole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
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The present invention relates to a method for producing a substituted hydrazinonitrodiphenyl ether compound, and more particularly, the present invention relates to a method for producing a substituted hydrazinonitrodiphenyl ether compound, and more specifically, the formula () (In formula (), -D is -NO 2 or
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ããSubstitution reaction of a nitrodiphenyl ether compound represented by [formula] with a hydrazine compound in the presence of a hydrophobic inert organic solvent selected from aliphatic halogenated hydrocarbons or aromatic hydrocarbons. The resulting reaction solution in which D of the compound of formula () was hydrazinated was washed with water and separated to remove the aqueous layer containing the unreacted hydrazine compound, and then the hydrophobic inert solution containing the hydrazino compound was washed with water and separated. The organic solvent layer is expressed by the formula () Formula () characterized in that a lower fatty acid chloride or lower fatty acid anhydride represented by (R represents a lower alkyl group) is subjected to an acylation reaction to acylate a hydrazino group. (R is the same as R in formula ()) The present invention relates to a method for producing a substituted hydrazinonitrodiphenyl ether compound represented by the formula (R is the same as R in formula ()). A number of diphenyl ether compounds have been considered for practical use as herbicides, but these compounds differ in their herbicidal activity due to slight differences in their chemical structure, such as the type, number, or position of substituents. It is extremely difficult to predict the herbicidal activity of these compounds based on similarities in their chemical structures, as the presence or absence of these compounds, mode of expression, selectivity, and persistence of efficacy often differ significantly. It is a well-known fact that certain types of diphenyl ether compounds have excellent herbicidal activity. For example, 2,4,6-trichlor-
4'-nitrodiphenyl ether and 2,4-dichloro-3'-methoxy-4'-nitrodiphenyl ether are widely used as herbicides for initial use in paddy fields. However, these compounds have insufficient residual efficacy and are difficult to completely control weeds if the timing of their use is missed. It has been desired to develop a herbicide for paddy fields that has safe selectivity and herbicidal activity that can control difficult-to-control perennial weeds in paddy fields. On the other hand, 2,4-dichlor-
4'-Nitrodiphenyl ether is widely used, and several other diphenyl ether compounds are known, but these compounds are
It is insufficiently effective against certain broad-leaved weeds, and it has been desired to develop a field herbicide with even higher herbicidal activity and safer selectivity than these known diphenyl ether compounds. Recently, substituted hydrazinonitrodiphenyl ether compounds, which also include the compound represented by the formula () above, have been discovered to have extremely superior herbicidal activity, high selectivity, sufficient residual efficacy, and herbicidal properties compared to known diphenyl ether compounds. It has been found that it has herbicidal activity that can control even difficult perennial weeds.
(Japanese Patent Application Laid-open No. 55-64557). It has been found that among the novel compounds provided in JP-A-55-64557, the compound represented by the formula () has particularly remarkable activity, and the method of the present invention is an improved method for producing these compounds. Kaisho
This method solves the economic disadvantages of the manufacturing method disclosed in No. 55-64557 on an industrial scale. In JP-A-55-64557, for example, 2 in the formula ()
When obtaining chloro-4-tolyluomethyl-3'-cetylhydrazino-4'-nitrodiphenyl ether, 2-chloro-4-trifluoromethyl-
3â²,4â²-dinitro diphenyl ether was dissolved in dioxane solvent and subjected to hydrazine reaction with a hydrazine compound. After the reaction was completed, the reaction solution was discharged into ice water, and the precipitated crude crystals were separated, washed with water, dried, The hydrazinide is isolated as crystals through purification. This is then subjected to an acetylation process using glacial acetic acid as a solvent to obtain the desired product. However, in the hydrazine formation process, it is inevitable that some unreacted hydrazine remains in the system, and the acyl of the next hydrazine is In the acylation step, the presence of hydrazine as an unreacted substance will hinder the acylation reaction. Therefore, in this publication, the hydrazine reaction completed liquid is discharged into ice water, and unreacted hydrazine is removed by washing with water. It is difficult to efficiently separate and recover the solvent from the hydrazino compound crystals obtained by precipitation, and moisture containing unreacted hydrazine adheres to the hydrazino compound crystals obtained by precipitation, thus requiring steps such as drying and recrystallization. Ta. The present inventors investigated the solvent for reacting a hydrazine compound with a nitrodiphenyl ether compound, and found that in a hydrophobic inert organic solvent that does not mix with water, such as 1,2-dichloroethane, which is easy to recover. A hydrazinonitrodiphenyl ether compound is produced in a very high yield, and when only the aqueous phase is separated by liquid separation and then acylated in the same solvent, the desired substituted hydrazinonitrodiphenyl ether is obtained. The inventors discovered that it was possible to synthesize such compounds, and as a result of intensive study, they completed the present invention. The substituted hydrazinonitrodiphenyl ether compound produced in the method of the present invention is represented by the formula (), specifically 2-chloro-4-
Trifluoromethyl-3'-(2-acetylhydrazino)-4'-nitrodiphenyl ether, 2-chloro-4-trifluoromethyl-3'-(2-propionylhydrazino)-4'-nitrodiphenyl Ether, 2-chloro-4-trifluoromethyl-
3'-(2-pivaloylhydrazino)-4'-nitrodiphenyl ether, 2-chloro-4-trifluoromethyl-3'-(2-isobutyroylhydrazino)-4'-nitrodiphenyl Ether, 2-chloro-4-trifluoromethyl-3'-(succinimidamino)-4'-nitrodiphenyl ether,
2-chloro-4-trifluoromethyl-3'-(glutarimidamino)-4'-nitrodiphenyl ether, 2-chloro-4-trifluoromethyl-
Examples include compounds such as 3'-(adipineimidoamino)-4'-nitrodiphenyl ether. Further, in the method of the present invention, the nitrodiphenyl ether compound of formula () which is the starting material is 2
-chloro-4-trifluoromethyl-3',4'-dinitrodiphenyl ether or 2,4-bis(2-chloro-4-trifluoromethylphenoxy)nitrobenzene, It can be obtained by nitrating the diphenyl ether compound represented by the formula with a mixed acid of nitric acid-sulfuric acid or nitrate-sulfuric acid in sulfuric acid, acetic anhydride, or 1,2-dichloroethane using a conventional method. - When dichloroethane or the like is used as a solvent, the produced nitrodiphenyl ether compound can be used as a raw material for the method of the present invention without being taken out, and the above-mentioned diphenyl ether compound can be nitrated, hydrazined, and It has the advantage that acylation can be carried out without removing intermediates. It is better to use hydrazine hydrate as the hydrazine compound used in the substitution reaction of hydrazinization in the method of the present invention, and the molar ratio is preferably 1.0 to 10 per mole of the nitrodiphenyl ether compound represented by formula (). used. If the amount used is less than this, the reaction rate will be poor and the yield will be reduced, and if it is more than this, it will be difficult to purify the product during post-treatment after the reaction. In addition, specific examples of the acylating agent used in the method of the present invention include acetic anhydride, succinic anhydride,
Examples include acid anhydrides such as glutaric anhydride, adipic anhydride, and maleic anhydride; acid halides such as acetyl chloride, propionyl chloride, pivaloyl chloride, and isobutyl chloride; and hydrazinonitrodiphenyl ethers. Preferably a molar ratio of 1.0 to 5 is used per mole of compound.
If the amount used is less than this, the reaction rate will be poor and the yield will be reduced, and if it is more than this, not only will there be a loss of the expensive acylating agent, but there will also be a loss of the product during post-treatment after the reaction. Makes refining difficult. Hydrophobic inert solvents used in the method of the present invention are specifically dichloromethane, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,
2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,
1,2-tetrachloroethane, 1,1,2,2-
Tetrachloroethane, pentachloroethane, hexachloroethane, 1,2-dichloroethylene, trichlorethylene, tetrachlorethylene, propyl chloride, isopropyl chloride, 1,2-dichloropropane, 1,2,3-triclopropane, 1-
Chlorpentane, 1,2-dibromoethane, 1,
Aliphatic halogenated hydrocarbons such as 1,2,2-tetrabromoethane, propyl bromide, isopropyl bromide, benzene, toluene, o-xylene,
Examples include aromatic hydrocarbons such as m-xylene and p-xylene, but aliphatic halogenated hydrocarbons such as 1,2-dichlorothane are particularly preferred. The amount of these solvents to be used is 1 to 50 parts by weight, preferably 2 to 20 parts by weight, per 1 part by weight of the nitrodiphenyl ether compound represented by formula (). If the amount used is larger than this, the reaction rate will be slow and industrial productivity will be low. Furthermore, if the amount used is less than this, stirring becomes difficult and partial heating of the reaction temperature tends to occur. Furthermore, in the method of the present invention, when a basic substance such as potassium carbonate, pyridine or triethylamine is present during hydrazination or acylation, the reaction proceeds smoothly. A general embodiment of the method of the invention is as follows. That is, a nitrodiphenyl ether compound represented by the formula () is dissolved or suspended in a hydrophobic inert organic solvent, and heated at -10 to 50°C, preferably 10 to 40°C.
Add the hydrazine compound at . Then, after stirring at 10°C to the boiling point, preferably for several minutes to several tens of hours, the organic layer is separated, and the organic layer is washed with water, dehydrated, dried, and heated to -10°C.
The acylating agent is added at ~°C to boiling point. Then 10âïœ
After stirring at the boiling point, preferably for several tens of minutes to several tens of hours, the mixture is cooled, washed with water, and separated. After the organic layer is dehydrated and dried, the solvent is removed under reduced pressure and dried to obtain a crude product. Generally, this level is sufficient for practical use, but if desired, the substituted hydrazinonitrodiphenyl ether compound of formula () can be purified by recrystallization activated carbon treatment or silica gel column chromatography. Obtainable. The substituted hydrazinonitrodiphenyl ether compound of formula () produced by the method of the present invention exhibits excellent herbicidal activity as a herbicide for paddy fields and fields, and has high selectivity. Next, the present invention will be specifically explained using examples. Example 1 15.9 g of 2-chloro-4-trifluoromethyl-3'-nitrodiphenyl ether was dissolved in 32 g of 1,2-dichloroethane, and 4.0 g of 98% nitric acid and 98%
A mixed acid consisting of 26.8 g of % sulfuric acid was added dropwise at 10 to 15°C for 1 hour. Then the temperature was raised to 30â, and at the same temperature
I stirred the time. After the reaction, the mixture is separated into an organic layer and a sulfuric acid layer at room temperature, and the upper layer (organic layer) is washed with water and then transferred to the next hydrazination step. On the other hand, the lower layer (sulfuric acid layer) is boiled down and reused as sulfuric acid in the next reaction. To 53.0 g of the nitrated liquid thus obtained, 7.0 g of anhydrous potassium carbonate and 1,2-dichloroethane were added.
80.2 g was added, and while stirring, 3.8 g of an 80% hydrazine hydrate aqueous solution was added dropwise at 20°C for about 10 minutes, then the temperature was raised to 80°C, and the mixture was stirred at the same temperature for 5 hours. After cooling to room temperature, 80 ml of water was added and stirred to secrete the mixture, and the aqueous layer was further extracted with 20 ml of 1,2-dichloroethane and combined with the organic layer. The obtained organic layer was dehydrated and then transferred to the next acetylation step. On the other hand, the aqueous layer was treated as wastewater after decomposing excess hydrazine with an aqueous solution of crude sodium hypochlorite. 4.08 g of acetyl chloride was added dropwise to 138 g of the hydrazinated liquid thus obtained at 20 to 25°C for 10 minutes. After raising the temperature to 40°C, the mixture was heated at 40 to 50°C for 2 hours, then further raised to 80°C, and stirred at the same temperature for 5 hours. After the reaction, it was cooled and washed with water. After adding 1 g of powdered activated carbon, stirring and filtration for 1 hour, and further dehydration, the solvent was evaporated to dryness under reduced pressure to obtain crude 2-chloro-4-trifluoromethyl-3'-acetylhydrazino.
4â²-nitrodiphenyl ether 11.0g (yield 56.4
%, vs. 2-chloro-4-trifluoromethyl-
3â²-nitrodiphenyl ether) was obtained. Recrystallize this with benzene-n-hexane
Pale yellow crystals with mp 151.5-153.5°C were obtained. This product is sold separately with 2-chloro-4-trifluoromethyl-
The results of mixing test, IR spectrum, gas chromatography, and thin layer chromatography showed that the sample was identical to the standard obtained by acetylating 3'-hydrazino-4'-nitrodiphenyl ether with acetic anhydride in glacial acetic acid. confirmed. The recovered solvent was recycled and used as a solvent for the initial nitration, and the washing solution was neutralized and then drained for treatment. Example 2 2-chloro-4-trifluoromethyl-3',
1.82g of 4â²-dinitrodiphenyl ether 1,2
-Dissolve in 25.1g of dichloroethane and stir at 20â to make 0.63% 80% hydrazine hydrate aqueous solution.
g was added dropwise. Next, after stirring at 30°C for 3 hours, 60°C for 3 hours, and 80°C for 3 hours, 20ml of water was added and stirred to separate the liquids. After the organic solvent layer was dehydrated and dried, 0.52 g of acetic anhydride was added dropwise and stirred at 58 to 60°C for 4 hours. After draining into 20ml of water, separate the liquids. The aqueous layer was further extracted with 10.0 g of 1,2-dichloroethane and combined with the previous organic solvent layer. After washing with water, dehydration, and drying, the solvent was evaporated to dryness under reduced pressure to crystallize 2-chloro-4-trifluoromethyl-3'-acetylhydrazino-4'-nitrodiphenyl ether.
1.87g was obtained. (Yield 96.0%, vs. 2-chloro-4
-trifluoromethyl-3',4'-dinitrodiphenyl ether) mp152.5-154â. In addition, instead of the solvent 1,2-dichloroethane,
Using dioxane as a solvent during the hydrazination reaction, the same amount of 2-chloro-4-trifluoromethyl-
3',4'-dinitrodiphenyl ether was subjected to a hydrazination reaction, the reaction completed liquid was discharged into ice water, this was precipitated, separated and dried, and the resulting product was acetylated in the same manner as described above to give 2-chloro- 1.54 g of crystals of 4-trifluoromelyl-3'-acetylhydrazino-4'-nitrodiphenyl ether were obtained. This is 2-chloro-4-trifluoromethyl-3â²,
Yield for 4â²-dinitrodiphenyl ether
It is 79.0%. Example 3 2.56 g of 2,4-bis(2-chloro-4-trifluoromethylphenoxy)nitrobenzene was
Dissolve in 25.1g of 2-dichloroethane and stir at 27â to prepare 80% hydrazine hydrate aqueous solution.
0.63g was added dropwise. The temperature was then raised to 80°C for 1.5 hours, and then stirred at 79-80°C for 6 hours.
0.63 g of 80% hydrazine hydrate aqueous solution was added, and the mixture was further stirred at 80°C for 50 hours. Add 20 ml of water and stir to separate the liquid. Dehydrate the organic solvent layer,
After drying, 0.52 g of acetic anhydride was added dropwise and stirred at 60°C for 6 hours. After draining into 50ml of water, separate the liquids. The aqueous layer was further extracted with 25.1 g of 1,2-dichloroethane, combined with the previous organic solvent, washed with water, dehydrated, and dried. After evaporating the solvent to dryness under reduced pressure, benzene-
Recrystallization from a mixed solvent of n-hexane (1:1) gave 1.55 g of crystals of 2-chloro-4-trifluoromethyl-3'-acetylhydrazino-4'-nitrodiphenyl ether (yield 79.6%, pair 2,4-bis(2
-chloro-4-trifluoromethylphenoxy)
Nitrobenzene) was obtained. mp152.5~153â. Example 4 2-chloro-4-trifluoromethyl-3',
1.82 g of 4'-dinitrodiphenyl ether was dissolved in 17.4 g of toluene, and 0.63 g of an 80% aqueous hydrazine hydrate solution was added dropwise while stirring at 20°C.
Then, after stirring at 30°C for 5 hours and at 60°C for 16 hours, 20ml of water was added and stirred to separate the liquids. After dehydrating and drying the toluene layer, 0.41 g of acetyl chloride was added dropwise. The mixture was stirred at 40â for 4 hours and at 80â for 5 hours.
After washing twice with 10 ml of water, it was dehydrated and dried. The solvent was evaporated to dryness under reduced pressure to obtain 1.94 g of crude product.
mp111~131â. This product was recrystallized in a mixed solvent of benzene-n-hexane (1:1) to give crystals of 2-chloro-4-trifluoromethyl-3'-acetylhydrazino-4'-nitrodiphenyl ether.
1.50 g (yield 76.7%, 2-chloro-4-trifluoromethyl-3',4'-dinitrodiphenyl ether) was obtained. mp152~153.5â. Examples 5 to 9 According to Example 2, in the acylation step of Example 2, 2-chloro-4-trifluoromethyl was used as the acylating agent shown in Table 1 instead of acetic anhydride as the acylating agent. Compounds of formula () shown in Table 1 were synthesized in exactly the same manner as in Example 2, except that 1.1 times the mole of -3',4'-dinitro diphenyl ether was used.
Claims (1)
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ãã«ç³»ååç©ã®è£œé æ¹æ³ã[Claims] 1 Formula () (In the formula (), -D represents -NO 2 or [Formula]) A nitrodiphenyl ether compound represented by The reaction solution in which D of the compound of formula () obtained by substitution reaction with a hydrazine compound in the presence of an organic solvent was hydrazinated was washed with water and separated into layers to remove the aqueous layer containing the unreacted hydrazine compound. After that, the hydrophobic inert organic solvent layer containing the hydrazino compound was added using the formula () (R represents a lower alkyl group.) A formula () characterized in that the hydrazino group is acylated by subjecting it to an acylation reaction using a lower fatty acid chloride or lower fatty acid anhydride represented by (R represents a lower alkyl group) (R is the same as R in formula ()) A method for producing a substituted hydrazinonitrodiphenyl ether compound represented by:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12718280A JPS5750950A (en) | 1980-09-16 | 1980-09-16 | Preparation of substituted hydrazinonitrodiphenyl ethereal compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12718280A JPS5750950A (en) | 1980-09-16 | 1980-09-16 | Preparation of substituted hydrazinonitrodiphenyl ethereal compound |
Publications (2)
Publication Number | Publication Date |
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JPS5750950A JPS5750950A (en) | 1982-03-25 |
JPS6334864B2 true JPS6334864B2 (en) | 1988-07-12 |
Family
ID=14953698
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JP12718280A Granted JPS5750950A (en) | 1980-09-16 | 1980-09-16 | Preparation of substituted hydrazinonitrodiphenyl ethereal compound |
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WO2019241850A1 (en) * | 2018-06-22 | 2019-12-26 | La Trobe University | Substituted sulfonyl hydrazides as inhibitors of lysine biosynthesis via the diaminopimelate pathway |
Citations (1)
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JPS5564557A (en) * | 1978-11-08 | 1980-05-15 | Mitsui Toatsu Chem Inc | Diphenyl ether compound and herbicide containing the same |
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1980
- 1980-09-16 JP JP12718280A patent/JPS5750950A/en active Granted
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Publication number | Priority date | Publication date | Assignee | Title |
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JPS5564557A (en) * | 1978-11-08 | 1980-05-15 | Mitsui Toatsu Chem Inc | Diphenyl ether compound and herbicide containing the same |
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