JP2588969B2 - Method for producing phenoxyethylaminopyrimidine derivative - Google Patents
Method for producing phenoxyethylaminopyrimidine derivativeInfo
- Publication number
- JP2588969B2 JP2588969B2 JP13920389A JP13920389A JP2588969B2 JP 2588969 B2 JP2588969 B2 JP 2588969B2 JP 13920389 A JP13920389 A JP 13920389A JP 13920389 A JP13920389 A JP 13920389A JP 2588969 B2 JP2588969 B2 JP 2588969B2
- Authority
- JP
- Japan
- Prior art keywords
- derivative
- phenoxyethylaminopyrimidine
- present
- compound
- producing
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- SHAIKASNPONUMB-UHFFFAOYSA-N N-(2-phenoxyethyl)pyrimidin-2-amine Chemical class N=1C=CC=NC=1NCCOC1=CC=CC=C1 SHAIKASNPONUMB-UHFFFAOYSA-N 0.000 title claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- -1 2,3-dimethyl-4- (2-ethoxyethyl) phenol 2,5-dimethyl-4- (2-ethoxyethyl) phenol Chemical compound 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 17
- 239000007858 starting material Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 230000000749 insecticidal Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- ZDSXISAAQRPVIX-UHFFFAOYSA-N 1$l^{2}-aziridine Chemical group C1C[N]1 ZDSXISAAQRPVIX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 230000001747 exhibiting Effects 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 230000003129 miticidal Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- BZKBCQXYZZXSCO-UHFFFAOYSA-N sodium hydride Chemical compound [H-].[Na+] BZKBCQXYZZXSCO-UHFFFAOYSA-N 0.000 description 3
- RPVZESOQOOPTGU-UHFFFAOYSA-N 4,5-dichloro-6-ethylpyrimidine Chemical compound CCC1=NC=NC(Cl)=C1Cl RPVZESOQOOPTGU-UHFFFAOYSA-N 0.000 description 2
- FCVDTAYAMCMPEY-UHFFFAOYSA-N 4-(aziridin-1-yl)pyrimidine Chemical class C1CN1C1=CC=NC=N1 FCVDTAYAMCMPEY-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000008079 hexane Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L mgso4 Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FWHAPCYJCGPVLR-UHFFFAOYSA-N 2-(2-ethoxyethyl)phenol Chemical compound CCOCCC1=CC=CC=C1O FWHAPCYJCGPVLR-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- IMLAIXAZMVDRGA-UHFFFAOYSA-N 2-phenoxyethanamine Chemical class NCCOC1=CC=CC=C1 IMLAIXAZMVDRGA-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N 289-95-2 Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- NHTURKUJYDHMIQ-UHFFFAOYSA-N 4,5-dichloropyrimidine Chemical class ClC1=CN=CN=C1Cl NHTURKUJYDHMIQ-UHFFFAOYSA-N 0.000 description 1
- IEDZVIMHFKUZCF-UHFFFAOYSA-N 4-(2-ethoxyethyl)-2,6-dimethylphenol Chemical compound CCOCCC1=CC(C)=C(O)C(C)=C1 IEDZVIMHFKUZCF-UHFFFAOYSA-N 0.000 description 1
- PVJBTJCXIGHIAO-UHFFFAOYSA-N 4-(2-ethoxyethyl)phenol Chemical compound CCOCCC1=CC=C(O)C=C1 PVJBTJCXIGHIAO-UHFFFAOYSA-N 0.000 description 1
- HZNIPSKFWIGHTG-UHFFFAOYSA-N 4-(2-methoxyethyl)-2,3-dimethylphenol Chemical compound COCCC1=CC=C(O)C(C)=C1C HZNIPSKFWIGHTG-UHFFFAOYSA-N 0.000 description 1
- OQNYOLDMUFAAEJ-UHFFFAOYSA-N 4-(2-methoxyethyl)-2-methylphenol Chemical compound COCCC1=CC=C(O)C(C)=C1 OQNYOLDMUFAAEJ-UHFFFAOYSA-N 0.000 description 1
- FAYGEALAEQKPDI-UHFFFAOYSA-N 4-(2-methoxyethyl)phenol Chemical compound COCCC1=CC=C(O)C=C1 FAYGEALAEQKPDI-UHFFFAOYSA-N 0.000 description 1
- DBPKMSBWOKAKLA-UHFFFAOYSA-N 4-chloropyrimidine Chemical class ClC1=CC=NC=N1 DBPKMSBWOKAKLA-UHFFFAOYSA-N 0.000 description 1
- GWWYNHMPBDBCJC-UHFFFAOYSA-N C(C)C1=C(C=CC(=C1)CCOC)O Chemical compound C(C)C1=C(C=CC(=C1)CCOC)O GWWYNHMPBDBCJC-UHFFFAOYSA-N 0.000 description 1
- CGMKLTBEWSMMES-UHFFFAOYSA-N CCOCCC1=CC=C(O)C(C)=C1 Chemical compound CCOCCC1=CC=C(O)C(C)=C1 CGMKLTBEWSMMES-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N Octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N Potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N Sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 230000000895 acaricidal Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atoms Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RYPWQHONZWFXBN-UHFFFAOYSA-N dichloromethyl(methylidene)-$l^{3}-chlorane Chemical compound ClC(Cl)Cl=C RYPWQHONZWFXBN-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N ethoxyethane;trifluoroborane Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N iodine atom Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- OCFVSFVLVRNXFJ-UHFFFAOYSA-N potassium hydride Inorganic materials [H-].[K+] OCFVSFVLVRNXFJ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、高い殺虫・殺ダニ活性を示すフェノキシエ
チルアミノピリミジン誘導体の製造方法に関するもので
ある。Description: TECHNICAL FIELD The present invention relates to a method for producing a phenoxyethylaminopyrimidine derivative exhibiting high insecticidal / miticidal activity.
〔従来の技術〕 多くのフェノキシエチルアミノピリミジン誘導＊が、
高い殺虫・殺ダニ活性を有することが知られている（特
開昭62−67号、特開昭59−36666号、特開昭59−36667
号）。[Prior art] Many phenoxyethylaminopyrimidine derivatives *
It is known to have high insecticidal and acaricidal activity (Japanese Patent Application Laid-Open Nos. 62-67, 59-36666, 59-36667).
issue).
フェノキシエチルアミノピリミジン誘導体の製造方法
としては、従来、次式で示されるように、４−クロロピ
リミジン誘導体とフェノキシエチルアミン誘導体とを塩
基存在下で反応させることによって得られていた。A method for producing a phenoxyethylaminopyrimidine derivative has been conventionally obtained by reacting a 4-chloropyrimidine derivative with a phenoxyethylamine derivative in the presence of a base, as shown in the following formula.
（式中、Ｒは水素原子、低級アルキル基を表し;AはCH2C
H2ORを表し;Xはハロゲン原子を表す。） この反応で用いる原料のフェノキシアルキルアミン誘
導体は、その製造方法が難しいために、フェノキシエチ
ルアミノピリミジン誘導体を工業的に製造するための原
料としては適していないという問題があった。 (Wherein, R represents a hydrogen atom or a lower alkyl group; A represents CH 2 C
X represents H 2 OR; X represents a halogen atom. The raw material phenoxyalkylamine derivative used in this reaction has a problem in that it is not suitable as a raw material for industrially producing a phenoxyethylaminopyrimidine derivative because its production method is difficult.
本発明の目的は、高い殺虫・殺ダニ活性を示すフェノ
キシエチルアミノピリミジン誘導体を簡便、かつ収率よ
く製造する方法を提供することである。An object of the present invention is to provide a method for producing a phenoxyethylaminopyrimidine derivative exhibiting high insecticidal / miticidal activity in a simple and high yield.
本発明者等は、前記の問題点を解決するために鋭意研
究した結果、４−アジリジニルピリミジン誘導体とフェ
ノール誘導体とを反応させることによって、工業的に製
造困難なフェノール誘導体のアミノエチル化を回避する
ことによって、フェノキシエチルアミノピリミジン誘導
体を工業的規模で簡便、かつ収率よく得ることができる
ことを見出し、本発明を完成させるに至った。The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by reacting a 4-aziridinylpyrimidine derivative with a phenol derivative, aminoethylation of a phenol derivative which is industrially difficult to produce is carried out. By avoiding this, they have found that a phenoxyethylaminopyrimidine derivative can be obtained easily and with good yield on an industrial scale, and have completed the present invention.
即ち、本発明は、 一般式： （式中、R1は水素原子、低級アルキル基を表し;R2は低
級アルキル基を表し;mは２〜４の整数を表し;nは１〜３
の整数を表す。） で示されるフェノール誘導体と 一般式： （式中、R1は前記と同義であり;R3は水素原子、ハロゲ
ン原子を表す。） とを反応させることを特徴とする 一般式： （式中、R1、R2、R3、ｍ、ｎは前記と同義である。） で示されるフェノキシエチルアミノピリミジン誘導体の
製造法に関するものである。That is, the present invention provides a compound represented by the general formula: (Wherein, R 1 represents a hydrogen atom or a lower alkyl group; R 2 represents a lower alkyl group; m represents an integer of 2 to 4;
Represents an integer. ) And a phenol derivative represented by the general formula: Wherein R 1 has the same meaning as described above; R 3 represents a hydrogen atom or a halogen atom. (Wherein, R 1 , R 2 , R 3 , m, and n have the same meanings as described above.) A phenoxyethylaminopyrimidine derivative represented by the following formula:
前記のR1、R2およびR3における、低級アルキル基とは
炭素数１〜５の直鎖状または分岐状のアルキル基であ
り、例えば、メチル基、エチル基、プロピル基、ブチル
基、イソブチル基、sec−ブチル基、tert−ブチル基、
ペンチル基などを挙げることができるが、好ましくは、
メチル基、エチル基であり、ｍは２であり、ｎは２であ
るのがよく、例えば、原料化合物（Ｉ−Ａ）の好ましい
例としては、 一般式： （式中、R4およびR5は水素原子、メチル基またはエチル
基を表し;R6はメチル基またはエチル基を表す。） を挙げることができ、原料化合物（II−Ａ）の好ましい
例としては、 一般式： （式中、R5は前記の同義であり;R7はメチル基またはエ
チル基を表し;Xはハロゲン原子を表す。） を挙げることができ、目的化合物（III−Ａ）の好まし
い例としては、 一般式： （式中、R4、R5、R6、R7、Ｘは前記と同義である。）を
挙げることができる。In R 1 , R 2 and R 3 , the lower alkyl group is a linear or branched alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group. Group, sec-butyl group, tert-butyl group,
Although a pentyl group and the like can be mentioned, preferably,
It is a methyl group or an ethyl group, m is 2 and n is preferably 2. For example, preferable examples of the starting compound (IA) include a compound represented by the following general formula: (Wherein, R 4 and R 5 represent a hydrogen atom, a methyl group or an ethyl group; R 6 represents a methyl group or an ethyl group). Preferred examples of the raw material compound (II-A) Is the general formula: (Wherein, R 5 has the same meaning as described above; R 7 represents a methyl group or an ethyl group; X represents a halogen atom). Preferred examples of the target compound (III-A) include , The general formula: (Wherein, R 4 , R 5 , R 6 , R 7 and X have the same meanings as described above).
そして、好ましい原料化合物（II−Ｂ）および目的化
合物（III−Ｂ）におけるＸとしては、塩素原子、臭素
原子、ヨウ素原子、フッ素原子などを挙げることができ
るが、好ましくは塩素原子であるのがよい。Examples of X in the preferred starting compound (II-B) and target compound (III-B) include a chlorine atom, a bromine atom, an iodine atom, a fluorine atom and the like, and preferably a chlorine atom. Good.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明で用いる原料化合物（Ｉ）は、特開昭63−2136
36号、特開昭63−313743号に記載の方法に準じて、４−
プロモフェノール類からグリニャール反応などによっ
て、容易にかつ収率よく得ることができる。そして、そ
のような原料化合物（Ｉ）としては、例えば、 ４−（２−エトキシエチル）フェノール、 ４−（２−メトキシエチル）フェノール、 2,3−ジメチル−４−（２−エトキシエチル）フェノー
ル、 2,5−ジメチル−４−（２−エトキシエチル）フェノー
ル、 2,6−ジメチル−４−（２−エトキシエチル）フェノー
ル、 2,3−ジメチル−４−（２−メトキシエチル）フェノー
ル、 2,5−ジメチル−４−（２−メトキシエチル）フェノー
ル、 2,6−ジメチル−４−（２−メトキシエチル）フェノー
ル、 ４−（２−エトキシエチル）−２−メチルフェノール、 ４−（２−エトキシエチル）−３−メチルフェノール、 ４−（２−メトキシエチル）−２−メチルフェノール、 ４−（２−メトキシエチル）−３−メチルフェノール、 ４−（２−エトキシエチル）−２−エチルフェノール、 ４−（２−エトキシエチル）−３−エチルフェノール、 ４−（２−メトキシエチル）−２−エチルフェノール、 ４−（２−メトキシエチル）−３−エチルフェノール、 などを挙げることができる。The starting compound (I) used in the present invention is described in JP-A-63-2136.
No. 36, 4-method according to the method described in JP-A-63-313743.
It can be obtained easily and in good yield from a bromophenol by a Grignard reaction or the like. Examples of such a raw material compound (I) include 4- (2-ethoxyethyl) phenol, 4- (2-methoxyethyl) phenol, and 2,3-dimethyl-4- (2-ethoxyethyl) phenol 2,5-dimethyl-4- (2-ethoxyethyl) phenol, 2,6-dimethyl-4- (2-ethoxyethyl) phenol, 2,3-dimethyl-4- (2-methoxyethyl) phenol, 2 , 5-dimethyl-4- (2-methoxyethyl) phenol, 2,6-dimethyl-4- (2-methoxyethyl) phenol, 4- (2-ethoxyethyl) -2-methylphenol, 4- (2- Ethoxyethyl) -3-methylphenol, 4- (2-methoxyethyl) -2-methylphenol, 4- (2-methoxyethyl) -3-methylphenol, 4- (2-ethoxy) Ethyl) -2-ethylphenol, 4- (2-ethoxyethyl) -3-ethylphenol, 4- (2-methoxyethyl) -2-ethylphenol, 4- (2-methoxyethyl) -3-ethylphenol, And the like.
本発明で用いる原料化合物（II）は、例えば、参考例
に記載の方法によって、対応する4,5−ジクロロピリミ
ジン誘導体とアジリジンとを、トリエチルアミンなどの
塩基存在下で反応させることによって容易にかつ収率よ
く得ることができる。そして、そのような原料化合物
（II）としては、例えば、 ４−（１−アジリジニル）−５−クロロ−６−エチルピ
リミジン、 ４−（１−アジリジニル）−５−クロロ−６−メチルピ
リミジン などを挙げることができる。The starting compound (II) used in the present invention can be easily and easily recovered, for example, by reacting the corresponding 4,5-dichloropyrimidine derivative with aziridine in the presence of a base such as triethylamine by the method described in Reference Example. Can be obtained efficiently. Examples of such a starting compound (II) include 4- (1-aziridinyl) -5-chloro-6-ethylpyrimidine, 4- (1-aziridinyl) -5-chloro-6-methylpyrimidine and the like. Can be mentioned.
本発明の２−置換フェノキシアミノエチルピリミジン
誘導体の製造法は、原料化合物（Ｉ）と原料化合物（I
I）（４−アジリジニルピリミジン誘導体）とを無溶媒
下または不活性な溶媒存在下で加熱反応させることによ
って行うことができるが、不活性な溶媒存在下で行うの
が好ましい。The process for producing a 2-substituted phenoxyaminoethylpyrimidine derivative of the present invention comprises the steps of starting material (I)
The reaction can be carried out by heating with I) (4-aziridinylpyrimidine derivative) in the absence of a solvent or in the presence of an inert solvent, but is preferably carried out in the presence of an inert solvent.
本発明で用いることができる不活性な溶媒としては、
例えば、塩化メチレン、クロロホルム、ジクロロエタン
などのような塩素原子を有する化合物系の溶媒、ベンゼ
ン、トルエン、キシレンなどのような芳香族炭化水素系
溶媒、ヘキサン、シクロヘキサン、オクタンなどのよう
な脂肪族炭化水素系溶媒、ジエチルエーテル、エトラヒ
ドロフラン、ジオキサンなどのようなエーテル系溶媒、
ジメチルホルムアミド、アセトニトリル、ジメチルスル
ホキシドなどのような非プロトン性溶媒などを挙げるこ
とができる。As the inert solvent that can be used in the present invention,
For example, a compound-based solvent having a chlorine atom such as methylene chloride, chloroform and dichloroethane, an aromatic hydrocarbon-based solvent such as benzene, toluene and xylene, and an aliphatic hydrocarbon such as hexane, cyclohexane and octane. Ether solvents such as system solvents, diethyl ether, etrahydrofuran, dioxane,
Aprotic solvents such as dimethylformamide, acetonitrile, dimethylsulfoxide and the like can be mentioned.
そして、この反応を促進させるためには、塩基性物質
またはルイス酸を、原料化合物（Ｉ）（置換フェノール
類）の0.05〜20モル％、好ましくは0.1〜10モル％添加
するのがよい。In order to promote this reaction, a basic substance or a Lewis acid is added in an amount of 0.05 to 20 mol%, preferably 0.1 to 10 mol%, of the starting compound (I) (substituted phenols).
本発明で用いることができる塩基性物質としては、例
えば、ナトリウムメチラート、ナトリウムエチラート、
カリウムメチラート、カリウムｔ−ブチラートなどのア
ルカリ金属アルコラート、または水素化ナトリウム、水
素化カリウムなどの金属水素化物を挙げることができ
る。Examples of the basic substance that can be used in the present invention include sodium methylate, sodium ethylate,
Examples thereof include alkali metal alcoholates such as potassium methylate and potassium t-butylate, and metal hydrides such as sodium hydride and potassium hydride.
本発明で用いることができるルイス酸としては、例え
ば、BF3エーテルコンプレックスなどを挙げることがで
きる。Examples of Lewis acids that can be used in the present invention include BF 3 ether complex.
本発明の製造法は、反応濃度が５〜100％で行うこと
ができる。The production method of the present invention can be performed at a reaction concentration of 5 to 100%.
本発明における原料化合物（Ｉ）と原料化合物（II）
とを用いる割合は、原料化合物（Ｉ）１モルに対して、
原料化合物（II）を0.5〜３モルの割合で加えることが
できるが、特に好ましくは1.0〜1.2モルがよい。Starting Compound (I) and Starting Compound (II) in the Present Invention
Is used with respect to 1 mole of the starting compound (I),
The raw material compound (II) can be added in a ratio of 0.5 to 3 mol, and particularly preferably 1.0 to 1.2 mol.
本発明における反応温度は、０〜200℃で行うことが
できるが、特に好ましくは60〜120℃で行うのがよい。The reaction temperature in the present invention may be from 0 to 200 ° C, but is particularly preferably from 60 to 120 ° C.
本発明の製造法は、前記の濃度、温度によって変化す
るが、通常0.5〜10時間で行うことができる。The production method of the present invention varies depending on the concentration and temperature, but can usually be carried out for 0.5 to 10 hours.
本発明での目的化合物（III）の単離は、反応終了
後、反応混合物から溶媒を除去することによって簡単に
粗製の目的化合物（III）得ることができ、さらに、こ
れを再結晶、クロマトグラフィーなどの通常の精製方法
によって高純度の目的化合物（III）得ることができ
る。In the present invention, the target compound (III) can be isolated by simply removing the solvent from the reaction mixture after completion of the reaction, whereby the crude target compound (III) can be easily obtained. Thus, the target compound (III) having a high purity can be obtained by a conventional purification method.
このようにして得られる目的化合物（III）として
は、例えば、 ４−［２−［2,3−ジメチル−４−（２−エトキシエチ
ル）フェノキシ］エチルアミノ］−５−クロロ−６−エ
チルピリミジン、 ４−［２−［2,3−ジメチル−４−（２−エトキシエチ
ル）フェノキシ］エチルアミノ］−５−クロロ−６−メ
チルピリミジン、 ４−［２−［２−メチル−４−（２−メトキシエチル）
フェノキシ］エチルアミノ］−５−クロロ−６−メチル
ピリミジン、 ４−［２−［2,3−ジメチル−４−（２−メトキシエチ
ル）フェノキシ］エチルアミノ］−５−クロロ−６−エ
チルピリミジン、 ４−［２−［2,3−ジメチル−４−（２−メトキシエチ
ル）フェノキシ］エチルアミノ］−５−クロロ−６−メ
チルピリミジン、 ４−［２−［２−エチル−４−（２−エトキシエチル）
フェノキシ］エチルアミノ］−５−クロロ−６−メチル
ピリミジン、 などを挙げることができる。The target compound (III) thus obtained is, for example, 4- [2- [2,3-dimethyl-4- (2-ethoxyethyl) phenoxy] ethylamino] -5-chloro-6-ethylpyrimidine 4- [2- [2,3-dimethyl-4- (2-ethoxyethyl) phenoxy] ethylamino] -5-chloro-6-methylpyrimidine, 4- [2- [2-methyl-4- (2 -Methoxyethyl)
Phenoxy] ethylamino] -5-chloro-6-methylpyrimidine, 4- [2- [2,3-dimethyl-4- (2-methoxyethyl) phenoxy] ethylamino] -5-chloro-6-ethylpyrimidine, 4- [2- [2,3-dimethyl-4- (2-methoxyethyl) phenoxy] ethylamino] -5-chloro-6-methylpyrimidine, 4- [2- [2-ethyl-4- (2- Ethoxyethyl)
Phenoxy] ethylamino] -5-chloro-6-methylpyrimidine, and the like.
以下、本発明を参考例および実施例によって示す。な
お、これらの実施例は、本発明の範囲を限定するもので
はない。Hereinafter, the present invention will be described with reference examples and examples. Note that these examples do not limit the scope of the present invention.
参考例１ 〔４−（１−アジリジニル）−５−クロロ−６−エチル
ピリミジンの製造〕 4,5−ジクロロ−６−エチルピリミジン3.4g、アジリ
ジン2.5mlおよびトリエチルアミン2.5gをトルエン10ml
に加え、25℃で20時間反応させた。Reference Example 1 [Production of 4- (1-aziridinyl) -5-chloro-6-ethylpyrimidine] 3.4 g of 4,5-dichloro-6-ethylpyrimidine, 2.5 ml of aziridine and 2.5 g of triethylamine were added to 10 ml of toluene.
And reacted at 25 ° C. for 20 hours.
反応終了後、10％炭酸水素ナトリウム水溶液15mlでそ
の反応混合物を洗浄し、残った有機層を硫酸マグネシウ
ムを用いて乾燥し、減圧下で濃縮することによって、原
料化合物（II−Ａ）である黄色オイル状の４−（１−ア
ジリジニル）−５−クロロ−６−エチルピリミジンを2.
4g（収率は70％）得ることができた。After the completion of the reaction, the reaction mixture was washed with 15% of a 10% aqueous sodium hydrogen carbonate solution, and the remaining organic layer was dried over magnesium sulfate and concentrated under reduced pressure to obtain a yellow compound (II-A). The oily 4- (1-aziridinyl) -5-chloro-6-ethylpyrimidine was converted to 2.
4 g (70% yield) could be obtained.
参考例２ 〔４−（１−アジリジニル）−５−クロロ−６−メチル
ピリミジンの製造〕 参考例１において、4,5−ジクロロ−６−エチルピリ
ミジンの代わりに4,5−ジクロロ−６−メチルピリミジ
ンを用いることによって、無色固体の原料化合物（II−
Ａ）である４−（１−アジリジニル）−５−クロロ−６
−メチルピリミジンを2.6g（収率は68％）得ることがで
きた（融点は53〜55℃）。Reference Example 2 [Production of 4- (1-aziridinyl) -5-chloro-6-methylpyrimidine] In Reference Example 1, 4,5-dichloro-6-methyl was used instead of 4,5-dichloro-6-ethylpyrimidine. By using pyrimidine, a colorless solid starting compound (II-
4- (1-aziridinyl) -5-chloro-6 which is A)
2.6 g (yield 68%) of -methylpyrimidine were obtained (melting point 53-55 ° C).
実施例１ 参考例１の原料化合物（II−Ａ）（0.70g、3.8mmol）
と原料化合物（Ｉ−Ａ）である2,3−ジメチル−４−
（２−エトキシエチル）フェノール（0.73g、3.8mmol）
とナトリウムメトキシド（0.01g、0.2mmol）とを、DMF
（ジメチルホルムアミド）8mlに入れ、80℃で３時間撹
拌した。Example 1 Starting compound (II-A) of Reference Example 1 (0.70 g, 3.8 mmol)
And 2,3-dimethyl-4- that is the starting compound (IA)
(2-ethoxyethyl) phenol (0.73 g, 3.8 mmol)
And sodium methoxide (0.01 g, 0.2 mmol) in DMF
(Dimethylformamide) was stirred in 8 ml at 80 ° C. for 3 hours.
この反応液を冷却後、減圧下で濃縮し、これをカラム
クロマトグラフィー（ワコーゲルＣ−200を使用。ヘキ
サン：酢酸エチル＝5:1で溶出。）することによって４
−［２−［2,3−ジメチル−４−（２−エトキシエチ
ル）フェノキシ］エチルアミノ］−５−クロロ−６−エ
チルピリミジンを1.1g（収率は70％。融点は70〜71
℃。）得ることができた。After cooling, the reaction mixture was concentrated under reduced pressure, and the residue was subjected to column chromatography (using Wakogel C-200, eluted with hexane: ethyl acetate = 5: 1) to obtain a solution.
1.1 g of [-[2- [2,3-dimethyl-4- (2-ethoxyethyl) phenoxy] ethylamino] -5-chloro-6-ethylpyrimidine (yield 70%, melting point 70-71)
° C. ) Was able to get.
実施例２〜６ 実施例１において、第１表に示した原料化合物（Ｉ−
Ａ）〔一般式（Ｉ−Ｂ）で表される原料〕と原料化合物
（II−Ａ）〔一般式（II−Ｂ）で表される参考例１また
は２で製造した原料〕とを用いて実施例１と同様に行う
ことによって、第２表に示した目的化合物（III−Ａ）
〔一般式（III−Ｂ）で示される化合物〕を得ることが
できた。Examples 2 to 6 In Example 1, the starting compounds (I-
A) Using [the raw material represented by the general formula (IB)] and the raw material compound (II-A) [the raw material produced in Reference Example 1 or 2 represented by the general formula (II-B)] The target compound (III-A) shown in Table 2 was prepared in the same manner as in Example 1.
[Compound represented by general formula (III-B)] was obtained.
実施例７ 実施例１において、ナトリウムメトキシドの代わりに
三フッ化ホウ素エーテルコンプレックス（0.023g、0.19
mmol）を触媒として使用した以外は、実施例１と同様に
することによって、実施例１と同一の化合物を45％の収
率で得ることができた。Example 7 In Example 1, a boron trifluoride ether complex (0.023 g, 0.19 g) was used in place of sodium methoxide.
The same compound as in Example 1 was obtained in a yield of 45% in the same manner as in Example 1 except that (mmol) was used as a catalyst.
〔発明の効果〕 本発明の製造法によれば、高い殺虫・殺ダニ活性を示
すフェノキシエチルアミノピリミジン誘導体を簡便、か
つ収率よく製造することができる。 [Effects of the Invention] According to the production method of the present invention, a phenoxyethylaminopyrimidine derivative exhibiting high insecticidal / miticidal activity can be produced simply and with high yield.
Claims (1)
級アルキル基を表し;mは２〜４の整数を表し;nは１〜３
の整数を表す。） で示されるフェノール誘導体と 一般式： （式中、R1は前記と同義であり;R3は水素原子、ハロゲ
ン原子を表す。） とを反応させることを特徴とする 一般式： （式中、R1、R2、R3、ｍ、ｎは前記と同義である。） で示されるフェノキシエチルアミノピリミジン誘導体の
製造法。(1) a general formula: (Wherein, R 1 represents a hydrogen atom or a lower alkyl group; R 2 represents a lower alkyl group; m represents an integer of 2 to 4;
Represents an integer. ) And a phenol derivative represented by the general formula: Wherein R 1 has the same meaning as described above; R 3 represents a hydrogen atom or a halogen atom. (Wherein, R 1 , R 2 , R 3 , m, and n have the same meanings as described above.) A method for producing a phenoxyethylaminopyrimidine derivative represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13920389A JP2588969B2 (en) | 1989-06-02 | 1989-06-02 | Method for producing phenoxyethylaminopyrimidine derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13920389A JP2588969B2 (en) | 1989-06-02 | 1989-06-02 | Method for producing phenoxyethylaminopyrimidine derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH035466A JPH035466A (en) | 1991-01-11 |
| JP2588969B2 true JP2588969B2 (en) | 1997-03-12 |
Family
ID=15239953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13920389A Expired - Lifetime JP2588969B2 (en) | 1989-06-02 | 1989-06-02 | Method for producing phenoxyethylaminopyrimidine derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2588969B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0453137A3 (en) * | 1990-04-14 | 1992-09-23 | Nihon Nohyaku Co., Ltd. | Aminopyrimidine derivatives, a process for production thereof, and uses thereof |
| US8601223B1 (en) | 2006-09-19 | 2013-12-03 | Nvidia Corporation | Techniques for servicing fetch requests utilizing coalesing page table entries |
| US8707011B1 (en) | 2006-10-24 | 2014-04-22 | Nvidia Corporation | Memory access techniques utilizing a set-associative translation lookaside buffer |
-
1989
- 1989-06-02 JP JP13920389A patent/JP2588969B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH035466A (en) | 1991-01-11 |
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