JPH0528214B2 - - Google Patents
Info
- Publication number
- JPH0528214B2 JPH0528214B2 JP13709384A JP13709384A JPH0528214B2 JP H0528214 B2 JPH0528214 B2 JP H0528214B2 JP 13709384 A JP13709384 A JP 13709384A JP 13709384 A JP13709384 A JP 13709384A JP H0528214 B2 JPH0528214 B2 JP H0528214B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- general formula
- phenoxybenzyl
- atoms
- atom
- 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 - Lifetime
Links
- -1 3-phenoxybenzyl esters Chemical class 0.000 claims description 31
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- RPTKMZRQBREOMV-UHFFFAOYSA-N propoxymethylbenzene Chemical class CCCOCC1=CC=CC=C1 RPTKMZRQBREOMV-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000002917 insecticide Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 230000000749 insecticidal effect Effects 0.000 description 4
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 4
- KGANAERDZBAECK-UHFFFAOYSA-N (3-phenoxyphenyl)methanol Chemical compound OCC1=CC=CC(OC=2C=CC=CC=2)=C1 KGANAERDZBAECK-UHFFFAOYSA-N 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 241000607479 Yersinia pestis Species 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 238000010813 internal standard method Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- FISWUVUAFGHPHT-UHFFFAOYSA-N 2-chloro-4-(1-chloro-2-methylpropan-2-yl)-1-ethoxybenzene Chemical compound CCOC1=CC=C(C(C)(C)CCl)C=C1Cl FISWUVUAFGHPHT-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000000895 acaricidal effect Effects 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 2
- 244000144972 livestock Species 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002728 pyrethroid Substances 0.000 description 2
- XPHQNMNGUGOWGU-UHFFFAOYSA-N (3-phenoxyphenyl)methyl acetate Chemical compound CC(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 XPHQNMNGUGOWGU-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- YJUUZFWMKJBVFJ-UHFFFAOYSA-N 1,3-dimethylimidazolidin-4-one Chemical compound CN1CN(C)C(=O)C1 YJUUZFWMKJBVFJ-UHFFFAOYSA-N 0.000 description 1
- UDONPJKEOAWFGI-UHFFFAOYSA-N 1-methyl-3-phenoxybenzene Chemical class CC1=CC=CC(OC=2C=CC=CC=2)=C1 UDONPJKEOAWFGI-UHFFFAOYSA-N 0.000 description 1
- LEMRHTTWKDVQEI-UHFFFAOYSA-N 2-(3-phenoxyphenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(OC=2C=CC=CC=2)=C1 LEMRHTTWKDVQEI-UHFFFAOYSA-N 0.000 description 1
- PLGYQISBTYZBSZ-UHFFFAOYSA-N 2-chloro-1-ethoxy-4-[2-methyl-1-[(3-phenoxyphenyl)methoxy]propan-2-yl]benzene Chemical compound C1=C(Cl)C(OCC)=CC=C1C(C)(C)COCC1=CC=CC(OC=2C=CC=CC=2)=C1 PLGYQISBTYZBSZ-UHFFFAOYSA-N 0.000 description 1
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 1
- 208000035473 Communicable disease Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- KSCFJBIXMNOVSH-UHFFFAOYSA-N dyphylline Chemical group O=C1N(C)C(=O)N(C)C2=C1N(CC(O)CO)C=N2 KSCFJBIXMNOVSH-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003992 organochlorine insecticide Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はベンジルプロピルエーテル類の製造方
法に関し、詳しくは殺虫活性が極めて高く、しか
も低魚毒性殺虫剤として有用な化合物一般式
（Ｉ）
〔式中、R1，R2は水素原子、塩素原子、また
は臭素原子であり、少なくとも一つは塩素原子、
または臭素原子である。またＲは低級アルキル基
であり、R3，R4は水素原子またはフツ素原子で
ある。〕で示されるベンジルプロピルエーテル誘
導体を製造するに際し、一般式（）
〔式、（）中、Ｒ，R1，R2は前記一般式
（Ｉ）と同じ意味を表わし、Ｘはハロゲン原子を
示す。〕で示されるネオフイルハライド類と、
一般式（）
〔式（）中、R3およびR4は前記一般式（Ｉ）
と同じ意味を表わし、R5は水素原子、または低
級アルキル基を示す。〕
で示される３−フエノキシベンジルエステル類と
を、非プロトン性極性溶媒中、塩基の存在下で、
反応させることを特徴とするベンジルプロピルエ
ーテル誘導体の製造方法に係わる。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing benzylpropyl ethers, and more specifically, the present invention relates to a method for producing benzylpropyl ethers, and more specifically, a compound of the general formula (I) which has extremely high insecticidal activity and is useful as an insecticide with low fish toxicity. [In the formula, R 1 and R 2 are hydrogen atoms, chlorine atoms, or bromine atoms, and at least one is a chlorine atom,
Or a bromine atom. Further, R is a lower alkyl group, and R 3 and R 4 are hydrogen atoms or fluorine atoms. ] When producing the benzylpropyl ether derivative represented by the general formula () [In the formula (), R, R 1 and R 2 have the same meanings as in the above general formula (I), and X represents a halogen atom. ] and the general formula () [In formula (), R 3 and R 4 are the above general formula (I)
and R 5 represents a hydrogen atom or a lower alkyl group. ] 3-phenoxybenzyl esters shown in an aprotic polar solvent in the presence of a base,
The present invention relates to a method for producing a benzylpropyl ether derivative, which is characterized by a reaction.
殺虫剤が農業生産向上に果たした役割は極めて
高く、有機合成農薬の登場は人類の食糧事情を一
変させ、また虫により媒介される伝染病を予防す
るなど防疫の面でも多大の恩恵をもたらした。
Pesticides have played an extremely important role in improving agricultural production, and the appearance of synthetic organic pesticides has completely changed the food situation for humankind, and has also brought great benefits in terms of epidemic prevention, such as preventing infectious diseases transmitted by insects. .
しかしながら、有機塩素系殺虫剤DDTやBHC
は使用後長く環境中に残留してしまうなどの点で
その使用量が制限されており、またこれらに代わ
つて登場した有機リン系殺虫剤やカーバメート系
殺虫剤が広範囲に使用されているが、種々の害虫
がこれらの殺虫剤に対する抵抗性が生じてきてい
る。 However, organochlorine insecticides DDT and BHC
The amount of pesticides used is limited because they remain in the environment for a long time after use, and organophosphorus insecticides and carbamate pesticides that have replaced them are widely used. Various pests have developed resistance to these insecticides.
近年、こうした背景の中で合成ピレスロイド系
殺虫剤がその優れた殺虫力とともに有機リンある
いはカーバメート剤抵抗性の害虫に対して卓効を
示し、人畜に対して比較的低毒性である点で脚光
をあびてきた。しかし、この合成ピレスロイド系
殺虫剤の欠点は極めて魚毒性が高く、その使用範
囲が限定されることである。そしてまた、従来開
発されてきた殺虫剤に比べ高価なことである。 In recent years, against this background, synthetic pyrethroid insecticides have been attracting attention because of their excellent insecticidal power, their outstanding effectiveness against pests resistant to organic phosphorus or carbamate agents, and their relatively low toxicity to humans and livestock. I came flying. However, the disadvantage of this synthetic pyrethroid insecticide is that it is highly toxic to fish, which limits its range of use. Furthermore, they are more expensive than conventionally developed insecticides.
最近、前記一般式（Ｉ）で示されるベンジルプ
ロピルエーテル誘導体が極めて高い殺虫、殺ダニ
活性を有し、速効性および残効性において優れ、
人畜に対してはもちろん、魚類に対しても毒性が
低いことが見出され、害虫防除剤として提供され
ている（特開昭56−154427，57−64632，57−
72928，58−32840）。 Recently, benzylpropyl ether derivatives represented by the general formula (I) have extremely high insecticidal and acaricidal activity, and are excellent in immediate effect and residual effect.
It has been found to have low toxicity not only to humans and livestock, but also to fish, and has been provided as a pest control agent (Japanese Patent Application Laid-Open No. 154427, 1983, 57-64632, 57-
72928, 58-32840).
上記公報には式（Ｉ）化合物の製造方法も記載
され、下記反応式（Ｉ）で示されるネオフイルア
ルコール類と３−フエノキシベンジルハライド類
を反応させ目的物を得る方法と、反応式２で示さ
れるネオフイルハライド類と３−フエノキシベン
ジルアルコール類を反応させ目的物を得る方法が
開示されている。しかしながら、反応式１で示さ
れる方法では、ネオフイルアルコール類の製造が
煩雑で工場的には実施不可能であり、反応式２で
示される方法では、３−フエノキシベンジルアル
コール類が高価である。 The above publication also describes a method for producing the compound of formula (I), including a method for producing the desired product by reacting neophyl alcohols and 3-phenoxybenzyl halides represented by the following reaction formula (I), and A method is disclosed in which a desired product is obtained by reacting a neophyl halide represented by 2 with 3-phenoxybenzyl alcohol. However, in the method shown in Reaction Formula 1, the production of neophyl alcohols is complicated and cannot be carried out in a factory, and in the method shown in Reaction Formula 2, 3-phenoxybenzyl alcohol is expensive. be.
〔式中、R6およびR7は同一または異なる水素
原子、ハロゲン原子、シアノ基、ニトロ基、また
は置換されていてもよい低級アルキル基、アルケ
ニル基、低級アルコキシ基、アシルオキシ基、低
級アルキルチオ基、低級アシル基、アルコキシカ
ルボニル基を表し、R3及びR4は水素原子、ハロ
ゲン原子、低級アルキル基または低級アルコキシ
基を表し、ｍおよびｎはそれぞれ０〜４の整数で
ｍ＋ｎは０〜４を表し、Ｘ，Ｙはハロゲンを示
す。〕
また本発明者らは、上記公報に開示された式
（）化合物の中で、式（）中のR6，R7のいず
れかが４位の低級アルコキシ基である化合物、即
ち、４位を低級アルコキシ基で置換されたネオフ
イル基を有する３−フエノキシベンジルエーテル
系化合物が、これらの化合物の中では特に殺虫効
果が大きいことを見出し、その製造法として式
（）
〔式（）中、Y1，Y2は水素原子、塩素原子
または臭素原子であり、Y1，Y2の少なくとも一
つは塩素原子、または臭素原子である。Ｒは低級
アルキル基であり、Ｘハロゲン原子である。〕
で示される４−アルコキシネオフイルハライド類
と、式（）
〔式（）中、X1，X2は水素原子またはフツ
素原子である。〕
で示される３−フエノキシベンジルアルコール類
とを、縮合反応させて、式（）
〔式（）中、Y1，Y2は水素原子、塩素原子、
または臭素原子であり、Y1，Y2の少なくとも一
つは塩素原子、または臭素原子である。またＲは
低級アルキル基であり、X1，X2は水素原子また
はフツ素原子である。〕
で示される３−フエノキシベンジル２−（４−ア
ルコキシハロゲノフエニル）−２−メチルプロピ
ルエーテル類の製造方法を先に出願した（特開昭
59−88440）。 [In the formula, R 6 and R 7 are the same or different hydrogen atoms, halogen atoms, cyano groups, nitro groups, or optionally substituted lower alkyl groups, alkenyl groups, lower alkoxy groups, acyloxy groups, lower alkylthio groups, Represents a lower acyl group or alkoxycarbonyl group, R 3 and R 4 represent a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, m and n each represent an integer of 0 to 4, and m + n represents 0 to 4. , X, and Y represent halogen. ] Furthermore, among the compounds of formula () disclosed in the above publication, the present inventors discovered a compound in which either R 6 or R 7 in formula () is a lower alkoxy group at the 4-position, i.e., a lower alkoxy group at the 4-position. It was discovered that a 3-phenoxybenzyl ether compound having a neophyl group substituted with a lower alkoxy group has a particularly large insecticidal effect among these compounds, and as a method for producing it, the formula () [In formula (), Y 1 and Y 2 are a hydrogen atom, a chlorine atom, or a bromine atom, and at least one of Y 1 and Y 2 is a chlorine atom or a bromine atom. R is a lower alkyl group, and X is a halogen atom. ] 4-alkoxyneophyl halides represented by the formula () [In formula (), X 1 and X 2 are hydrogen atoms or fluorine atoms. ] 3-phenoxybenzyl alcohols represented by the formula () are subjected to a condensation reaction. [In formula (), Y 1 and Y 2 are hydrogen atoms, chlorine atoms,
or a bromine atom, and at least one of Y 1 and Y 2 is a chlorine atom or a bromine atom. Further, R is a lower alkyl group, and X 1 and X 2 are hydrogen atoms or fluorine atoms. ] We have previously applied for a method for producing 3-phenoxybenzyl 2-(4-alkoxyhalogenophenyl)-2-methylpropyl ethers (Japanese Patent Application Laid-Open No.
59−88440).
しかしながら、前記反応式２で示される方法で
縮合反応を実施した場合、３−フエノキシベンジ
ルアルコール類は縮合反応時の加熱により比較的
容易に酸化されやすいので、ネオフイルハライド
類と３−フエノキシベンジルアルコール類との縮
合収率も満足できるものでなく、特に式（）で
示されるベンジルプロピルエーテル誘導体の製造
方法としては、必ずしも有利な工業的製法とはい
えなかつた。 However, when the condensation reaction is carried out by the method shown in Reaction Formula 2 above, 3-phenoxybenzyl alcohols are relatively easily oxidized by heating during the condensation reaction, so neophyl halides and 3-phenol The condensation yield with enoxybenzyl alcohols was also unsatisfactory, and it could not necessarily be said to be an advantageous industrial production method, especially as a method for producing the benzylpropyl ether derivative represented by the formula ().
本発明者らは、一般式（Ｉ）で示されるベンジ
ルプロピルエーテル誘導体の合成法について種々
検討した結果、一般式（）で示されるネオフイ
ルハライド類と、一般式（）で示される３−フ
エノキシベンジルエステル類とを非プロトン性極
性溶媒中、塩基の存在下で反応させると一般式
（Ｉ）で示されるベンジルプロピルエーテル誘導
体が良好な収率で得られることを見出し、本発明
を完成した。
As a result of various studies on the synthesis method of the benzylpropyl ether derivative represented by the general formula (I), the present inventors discovered that the neophilic halides represented by the general formula () and the 3-fluoryl halides represented by the general formula () It was discovered that a benzylpropyl ether derivative represented by general formula (I) can be obtained in good yield by reacting enoxybenzyl esters in an aprotic polar solvent in the presence of a base, and the present invention was completed. did.
即ち、本発明は、一般式（Ｉ）
〔式中、R1，R2は水素原子、塩素原子、また
は臭素原子であり、少なくとも一つは塩素原子、
または臭素原子である。またＲは低級アルキル基
であり、R3，R4は水素原子またはフツ素原子で
ある。〕で示されるベンジルプロピルエーテル誘
導体を製造するに際し、一般式（）
〔式（）中、Ｒ，R1，R2は前記一般式（Ｉ）
と同じ意味を表わし、Ｘはハロゲン原子を示す。〕
で示されるネオフイルハライド類と、
一般式（）
〔式（）中、R3およびR4は前記一般式（Ｉ）
と同じ意味を表わし、R5は水素原子、または低
級アルキル基を示す。〕
で示される３−フエノキシベンジルエステル類と
を、非プロトン性極性溶媒中、塩基の存在下、反
応させることを特徴とするベンジルプロピルエー
テル誘導体の製造方法である。 That is, the present invention provides general formula (I) [In the formula, R 1 and R 2 are hydrogen atoms, chlorine atoms, or bromine atoms, and at least one is a chlorine atom,
Or a bromine atom. Further, R is a lower alkyl group, and R 3 and R 4 are hydrogen atoms or fluorine atoms. ] When producing the benzylpropyl ether derivative represented by the general formula () [In formula (), R, R 1 and R 2 are the above general formula (I)
, and X represents a halogen atom. ]
Neophyl halides shown by and the general formula () [In formula (), R 3 and R 4 are the above general formula (I)
and R 5 represents a hydrogen atom or a lower alkyl group. ] This is a method for producing a benzylpropyl ether derivative, which is characterized by reacting 3-phenoxybenzyl esters represented by the following in an aprotic polar solvent in the presence of a base.
本発明方法によつて製造できるベンジルプロピ
ルエーテル誘導体は、一般式（Ｉ）
で示される化合物であり、具体的にはＲはメチ
ル、エチル、プロピル等の低級アルキル基であ
り、R1およびR2は水素原子、フツ素原子、塩素
原子、臭素原子、R3およびR4は水素原子、フツ
素原子などがあげられる。 The benzylpropyl ether derivative that can be produced by the method of the present invention has the general formula (I) Specifically, R is a lower alkyl group such as methyl, ethyl, propyl, etc., R 1 and R 2 are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, R 3 and R 4 examples include hydrogen atoms and fluorine atoms.
また、本発明方法において原料として用いられ
る３−フエノキシベンジルエステル類、一般式
（）
〔式（）中、R3，R4およびR5は前記と同じ〕
は、３−フエノキシトルエン類をハロゲン化して
得られる３−フエノキシベンジルハライド類と相
応するカルボン酸のアルカリ金属塩から公知の方
法で製造できる。また合成ピレスロイドのアルコ
ール成分として公知である３−フエノキシベンジ
ルアルコール類を公知の方法でエステル化するこ
とによつても得られる。 In addition, 3-phenoxybenzyl esters used as raw materials in the method of the present invention, general formula () [In formula (), R 3 , R 4 and R 5 are the same as above]
can be produced by a known method from 3-phenoxybenzyl halides obtained by halogenating 3-phenoxytoluenes and alkali metal salts of the corresponding carboxylic acids. It can also be obtained by esterifying 3-phenoxybenzyl alcohols, which are known as alcohol components of synthetic pyrethroids, by a known method.
本発明方法においてネオフイルハライド類と、
３−フエノキシベンジルエステル類との使用割合
は、３−フエノキシベンジルエステル類１モルに
対してネオフイルハライド類を0.1〜５モル比、
好ましくは0.4〜２モル比の使用が適当であり、
使用割合がこの範囲をはずれた場合、反応が遅く
なり、また副生物の生成も多くなり収率が低下す
る。 In the method of the present invention, neophyl halides,
The ratio of 3-phenoxybenzyl esters used is 0.1 to 5 molar ratio of neophyl halides to 1 mol of 3-phenoxybenzyl esters,
Preferably, it is appropriate to use a molar ratio of 0.4 to 2,
If the ratio used is outside this range, the reaction will be slow and more by-products will be produced, resulting in a lower yield.
本発明方法において使用される非プロトン性極
性溶媒としては、ジメチルスルホキシド、スルホ
ラン、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジ
メチルホルムアミド、１，３−ジメチル−４−イ
ミダゾリジノン、テトラメチル尿素、Ｎ，Ｎ−ジ
メチルアセトアミド、ヘキサメチルホスホリルト
リアミドなどがあげらえれ、使用量としては、−
フエノキシベンジルエステル類１部に対して0.5
〜50部、好ましくは２〜20部が適当である。使用
量がこれより少ない場合には反応が非常に遅くな
り、また、これより多い場合には反応も遅く生産
性が低い。 Aprotic polar solvents used in the method of the present invention include dimethyl sulfoxide, sulfolane, N-methyl-2-pyrrolidone, N,N-dimethylformamide, 1,3-dimethyl-4-imidazolidinone, and tetramethylurea. , N,N-dimethylacetamide, hexamethylphosphoryltriamide, etc., and the amount used is -
0.5 per part of phenoxybenzyl esters
~50 parts, preferably 2 to 20 parts is suitable. If the amount used is less than this, the reaction will be very slow, and if it is more than this, the reaction will be slow and productivity will be low.
また、本発明方法において使用される塩基とし
ては具体的には、水酸化ナトリウム、水酸化カリ
ウム、水酸化リチウムなどの水酸化アルカリ金
属、水酸化カルシウム、水酸化マグネシウムなど
の水酸化アルカリ土類金属、水素化ナトリウムな
どの水素化アルカリ金属、ナトリウムメチラー
ト、カリウムエチラート、カリウム−ｔ−ブトキ
シドなどのアルカリ金属アルコラート、酸化ナト
リウムなどのアルカリ金属酸化物、炭酸カリウ
ム、炭酸ナトリウムなどのアルカリ金属炭酸塩、
ナトリウムアミド、トリエチルアミン、ピリジン
があげられ、使用量は３−フエノキシベンジルエ
ステル類に対して1.0〜10モル、好ましくは２〜
６モルが適当である。使用量がこれより少ない場
合には反応率が低い、また多い場合には副生物の
生成が多くなり収率が低下する。 In addition, the bases used in the method of the present invention include, specifically, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, and alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide. , alkali metal hydrides such as sodium hydride, alkali metal alcoholates such as sodium methylate, potassium ethylate, potassium t-butoxide, alkali metal oxides such as sodium oxide, alkali metal carbonates such as potassium carbonate and sodium carbonate. ,
Examples include sodium amide, triethylamine, and pyridine, and the amount used is 1.0 to 10 mol, preferably 2 to 10 mol, based on the 3-phenoxybenzyl ester.
6 moles is suitable. If the amount used is less than this, the reaction rate will be low, and if it is more than this, more by-products will be produced and the yield will be lowered.
塩基として水酸化ナトリウムもしくは水酸化カ
リウムを使用する場合、通常の粒状もしくはフレ
ーク状の製品が使用できるが、場合によつては微
粉状にしたものを使用すると反応が速くなり収率
が向上する。 When sodium hydroxide or potassium hydroxide is used as the base, the usual granular or flake products can be used, but in some cases, finely divided products can be used to speed up the reaction and improve yields.
なお、本反応において系中の水分は反応開始時
で溶媒に対して10％以下、好ましくは３％以下が
適当である。 In this reaction, the water content in the system is suitably 10% or less, preferably 3% or less based on the solvent at the start of the reaction.
本発明の一般的な実施態様は次の通りである。 A general embodiment of the invention is as follows.
ネオフイルハライド類、３−フエノキシベンジ
ルエステル類、塩基及び非プロトン性極性溶媒を
反応器に入れ、50℃ないし沸点、好ましくは80℃
ないし沸点（ただし、沸点が200℃をこえる場合
は80〜200℃）に加熱、同温度で0.5〜50時間、好
ましくは３〜30時間かきまぜる。室温まで冷却し
た後、不溶の無機塩を濾別し、濾液から減圧蒸留
によつて溶媒を追い出し、残渣を水洗、脱水して
目的のベンジルプロピルエーテル誘導体を得る。
このものは、そのまま殺虫、殺ダニ剤として使用
可能であるが、場合によつてはさらに減圧蒸留、
再結晶もしくはカラムクロマトグラフイーにより
精製することも可能である。 Neophyll halides, 3-phenoxybenzyl esters, a base, and an aprotic polar solvent are placed in a reactor and heated to a temperature ranging from 50°C to the boiling point, preferably 80°C.
or boiling point (80 to 200°C if the boiling point exceeds 200°C), and stir at the same temperature for 0.5 to 50 hours, preferably 3 to 30 hours. After cooling to room temperature, insoluble inorganic salts are filtered off, the solvent is removed from the filtrate by distillation under reduced pressure, and the residue is washed with water and dehydrated to obtain the desired benzylpropyl ether derivative.
This product can be used as an insecticide or acaricide as it is, but in some cases it may be further processed by vacuum distillation or
It is also possible to purify by recrystallization or column chromatography.
なお、本反応は通常、空気雰囲気で行われる
が、場合によつては系内を窒素などの不活性ガス
で置換した後実施すると、副生物の生成が抑えら
れて収率が向上する。 This reaction is usually carried out in an air atmosphere, but in some cases, if the reaction is carried out after replacing the system with an inert gas such as nitrogen, the production of by-products can be suppressed and the yield can be improved.
また、ネオフイルハライド類、３−フエノキシ
ベンジルエステル類および塩基の添加順序は任意
でよく、場合によつては一度に装入せずに分割装
入することも可能である。 Further, the order of adding the neophyl halides, 3-phenoxybenzyl esters, and the base may be arbitrary, and in some cases, it is also possible to charge them in portions instead of charging them all at once.
以下、本発明の詳細を実施例によつて説明す
る。
Hereinafter, the details of the present invention will be explained with reference to Examples.
実施例 １
攪拌棒、温度計および冷却器をつけた反応器内
に２−メチル−２−（３−クロル−４−エトキシ
フエニル）プロピルクロリド6.2g、３−フエノキ
シベンジルアセテート7.3g、フレーク状の水酸化
ナトリウム6.0gおび１，３−ジメチル−２−イミ
ダゾリジノン30mlを装入し、窒素気流下にかきま
ぜながら140℃まで加熱し同温で15時間かきまぜ
た。Example 1 In a reactor equipped with a stirring bar, a thermometer and a condenser, 6.2 g of 2-methyl-2-(3-chloro-4-ethoxyphenyl)propyl chloride, 7.3 g of 3-phenoxybenzyl acetate, 6.0 g of flaky sodium hydroxide and 30 ml of 1,3-dimethyl-2-imidazolidinone were charged, heated to 140°C while stirring under a nitrogen stream, and stirred at the same temperature for 15 hours.
反応混合物を室温まで冷却後、水200ml中に排
出し、農塩酸を用いて弱酸性とした。沈降したオ
イル層をベンゼン50mlを用い３回抽出し、合わせ
たベンゼン層を充分水洗いした後、無水芒硝で乾
燥、引き続き溶媒を減圧下に留去し粗製物12.5g
を得た。このものは、ガスクロマトフラフイーの
内部標準法による分析の結果、３−フエノキシベ
ンジル２−（３−クロル−４−エトキシフエニル）
−２−メチルプロピルエーテルを53.4％含んでい
た。 After cooling the reaction mixture to room temperature, it was poured into 200 ml of water and made weakly acidic using agricultural hydrochloric acid. The precipitated oil layer was extracted three times using 50 ml of benzene, and the combined benzene layer was thoroughly washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 12.5 g of a crude product.
I got it. As a result of analysis using the internal standard method of gas chromatography, this product was found to be 3-phenoxybenzyl 2-(3-chloro-4-ethoxyphenyl).
It contained 53.4% -2-methylpropyl ether.
目的物の収率65.0％〔対２−メチル−２−（３
−クロル−４−エトキシフエニル）プロピルクロ
リド〕であつた。 Yield of target product: 65.0% [vs. 2-methyl-2-(3
-chloro-4-ethoxyphenyl)propyl chloride].
このものをシリカゲルカラムクロマトグラフフ
イーで分離精製し、融点42.5℃の３−フエノキシ
ベンジル２−（３−クロル−４−エトキシフエニ
ル）２−メチルプロピルエーテルの純品を得た。 This product was separated and purified by silica gel column chromatography to obtain pure 3-phenoxybenzyl 2-(3-chloro-4-ethoxyphenyl) 2-methylpropyl ether with a melting point of 42.5°C.
・元素分析結果 C2H27ClO3
Ｃ Ｈ Cl
計算値 73.07 6.62 8.63
実測値 72.89 6.75 8.72
・NMRスペクトル δCDCl3：
1.28（S.6H），1.4（ｔ，3H），3.35（S.3H），4.0
（q.2H），4.39（S.2H），6.68〜7.32（m.12H）ppm
比較例 １
攪拌棒、温度計、および冷却器をつけた反応器
内に２−メチル−２−（３−クロル−４−エトキ
シフエニル）プロピルクロリド6.2g、３−フエノ
キシベンジルアルコール6.0g、フレーク状の水酸
化ナトリウム6.0gおよび１，３−ジメチル−２−
イミダゾリジノン30mlを装入し、窒素気流下にか
きまぜながら140℃まで加熱し同温で15時間かき
まぜた。・Elemental analysis results C 2 H 27 ClO 3 C H Cl Calculated value 73.07 6.62 8.63 Actual value 72.89 6.75 8.72 ・NMR spectrum δCDCl 3 : 1.28 (S.6H), 1.4 (t, 3H), 3.35 (S.3H), 4.0
(q.2H), 4.39 (S.2H), 6.68-7.32 (m.12H) ppm Comparative Example 1 2-Methyl-2-(3- 6.2 g of chloro-4-ethoxyphenyl)propyl chloride, 6.0 g of 3-phenoxybenzyl alcohol, 6.0 g of flaked sodium hydroxide and 1,3-dimethyl-2-
30 ml of imidazolidinone was charged, heated to 140°C while stirring under a nitrogen stream, and stirred at the same temperature for 15 hours.
反応混合物を室温まで冷却後、水200mlに排出
し、濃塩酸を用いて弱酸製とした。沈降したオイ
ル層をベンゼン50mlを用い３回抽出し、合わせた
ベンゼン層を充分水洗いした後、無水芒硝で乾
燥、引き続き溶媒を減圧下に留去し粗製物12.2g
を得た。このものはガスクロマトグラフイーの内
部標準法による分析の結果、３−フエノキシベン
ジル２−（３−クロル−４−エトキシフエニル）−
２−メチルプロピルエーテルを42.3％含んでい
た。 After cooling the reaction mixture to room temperature, it was poured into 200 ml of water and made into a weak acid using concentrated hydrochloric acid. The precipitated oil layer was extracted three times using 50 ml of benzene, and the combined benzene layer was thoroughly washed with water, dried over anhydrous sodium sulfate, and the solvent was then distilled off under reduced pressure to obtain 12.2 g of a crude product.
I got it. As a result of analysis using the internal standard method of gas chromatography, it was found that 3-phenoxybenzyl 2-(3-chloro-4-ethoxyphenyl)-
It contained 42.3% 2-methylpropyl ether.
目的物の収率50.2％〔対２−メチル−２−（３
−クロル−４−エトキシフエニル）プロピルクロ
リド〕であつた。 Yield of target product: 50.2% [vs. 2-methyl-2-(3
-chloro-4-ethoxyphenyl)propyl chloride].
このものをシリカゲルカラムクロマトグラフイ
ーで分離精製し、実施例１と同様の融点42.5℃の
３−フエノキシベンジル２−（３−クロル−４−
エトキシフエニル）−２−メチルプロピルエーテ
ルの純品を得た。 This product was separated and purified by silica gel column chromatography, and 3-phenoxybenzyl 2-(3-chloro-4-
A pure product of ethoxyphenyl)-2-methylpropyl ether was obtained.
実施例 ２
攪拌棒、温度計、および冷却器をつけた反応器
内に２−メチル−２−（３−クロル−４−エトキ
シフエニル）プロピルクロリド6.2g、３−フエノ
キシベンジルフオルメート6.9g、フレーク状の水
酸化ナトリウム6.0gおよび１，３−ジメチル−２
−イミダゾリジノン30mlを装入し、窒素気流下に
かきまぜながら140℃まで加熱し同温で15時間か
きまぜた。Example 2 6.2 g of 2-methyl-2-(3-chloro-4-ethoxyphenyl)propyl chloride, 3-phenoxybenzylformate in a reactor equipped with a stir bar, thermometer, and condenser. 6.9g, flaked sodium hydroxide 6.0g and 1,3-dimethyl-2
- 30 ml of imidazolidinone was charged, heated to 140°C while stirring under a nitrogen stream, and stirred at the same temperature for 15 hours.
反応混合物を室温まで冷却後、水200ml中に排
出し、濃塩酸を用いて弱酸性とした。沈降したオ
イル槽をベンゼン50mlを用い３回抽出し、合わせ
たベンゼン層を充分水洗した後、無水芒硝で乾
燥、引き続き溶媒を減圧下に留去し粗製物12.0g
を得た。このものはガスクロマトグラフイーの内
部標準法による分析の結果、３−フエノキシベン
ジル２−（30クロル−４−エトキシフエニル）−２
−メチルプロピルエーテルを50.2％含んでいた。 After cooling the reaction mixture to room temperature, it was poured into 200 ml of water and made weakly acidic using concentrated hydrochloric acid. The precipitated oil bath was extracted three times using 50 ml of benzene, and the combined benzene layer was thoroughly washed with water, dried over anhydrous sodium sulfate, and the solvent was then distilled off under reduced pressure to obtain 12.0 g of a crude product.
I got it. As a result of analysis using the internal standard method of gas chromatography, it was found that 3-phenoxybenzyl 2-(30chloro-4-ethoxyphenyl)-2
- Contained 50.2% methyl propyl ether.
目的物の収率58.6％〔対２−メチル−２−（３
−クロル−４−エトキシフエニル）プロピルクロ
リド〕であつた。このものをシリカゲルカラムク
ロマトグラフイーで分離精製し、融点42.8℃の３
−フエノキシベンジル２−（３−クロル−４−エ
トキシフエニル）−２−メチルプロピルエールの
純品を得た。 Yield of target product: 58.6% [vs. 2-methyl-2-(3
-chloro-4-ethoxyphenyl)propyl chloride]. This product was separated and purified using silica gel column chromatography, and the melting point was 42.8°C.
A pure product of -phenoxybenzyl 2-(3-chloro-4-ethoxyphenyl)-2-methylpropylele was obtained.
Claims (1)
は臭素原子であり、少なくとも一つは塩素原子、
または臭素原子である。またＲは低級アルキル基
であり、R3，R4は水素原子またはフツ素原子で
ある。〕で示されるベンジルプロピルエーテル誘
導体を製造するに際し、 一般式（） 〔式、（）中、Ｒ，R1，R2は前記一般式
（Ｉ）と同じ意味を表わし、Ｘはハロゲン原子を
示す。〕で示されるネオフイルハライド類と、 一般式（） 〔式（）中、R3およびR4は前記一般式（Ｉ）
と同じ意味を表わし、R5は水素原子、または低
級アルキル基を示す。〕 で示される３−フエノキシベンジルエステル類と
を、非プロトン性極性溶媒中、塩基の存在下、反
応させることを特徴とするベンジルプロピルエー
テル誘導体の製造方法。[Claims] 1 General formula (I) [In the formula, R 1 and R 2 are hydrogen atoms, chlorine atoms, or bromine atoms, and at least one is a chlorine atom,
Or a bromine atom. Further, R is a lower alkyl group, and R 3 and R 4 are hydrogen atoms or fluorine atoms. ] When producing the benzylpropyl ether derivative represented by the general formula () [In the formula (), R, R 1 and R 2 have the same meanings as in the above general formula (I), and X represents a halogen atom. ] and the general formula () [In formula (), R 3 and R 4 are the above general formula (I)
and R 5 represents a hydrogen atom or a lower alkyl group. ] A method for producing a benzylpropyl ether derivative, which comprises reacting 3-phenoxybenzyl esters represented by the following in an aprotic polar solvent in the presence of a base.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13709384A JPS6117524A (en) | 1984-07-04 | 1984-07-04 | Production of benzyl propyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13709384A JPS6117524A (en) | 1984-07-04 | 1984-07-04 | Production of benzyl propyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6117524A JPS6117524A (en) | 1986-01-25 |
| JPH0528214B2 true JPH0528214B2 (en) | 1993-04-23 |
Family
ID=15190711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13709384A Granted JPS6117524A (en) | 1984-07-04 | 1984-07-04 | Production of benzyl propyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6117524A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4310970A1 (en) | 2022-07-15 | 2024-01-24 | Prime Planet Energy & Solutions, Inc. | Lithium ion battery processing method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0551945U (en) * | 1991-12-12 | 1993-07-09 | 株式会社新潟鉄工所 | Cooking pots |
| FR2764888B1 (en) * | 1997-06-24 | 2000-05-05 | Rhodia Chimie Sa | ETHERIFICATION REACTION OF AN AMINOPHENOL USING A PHASE TRANSFER SYSTEM |
-
1984
- 1984-07-04 JP JP13709384A patent/JPS6117524A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4310970A1 (en) | 2022-07-15 | 2024-01-24 | Prime Planet Energy & Solutions, Inc. | Lithium ion battery processing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6117524A (en) | 1986-01-25 |
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