JPH03135965A - Aminopyrimidine derivative, its production and use thereof - Google Patents
Aminopyrimidine derivative, its production and use thereofInfo
- Publication number
- JPH03135965A JPH03135965A JP27427389A JP27427389A JPH03135965A JP H03135965 A JPH03135965 A JP H03135965A JP 27427389 A JP27427389 A JP 27427389A JP 27427389 A JP27427389 A JP 27427389A JP H03135965 A JPH03135965 A JP H03135965A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- alkyl group
- lower alkyl
- general formula
- represented
- 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.)
- Pending
Links
- 150000005005 aminopyrimidines Chemical class 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- 230000003373 anti-fouling effect Effects 0.000 claims abstract description 10
- 125000005843 halogen group Chemical group 0.000 claims abstract description 7
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 150000005694 halopyrimidines Chemical class 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000002519 antifouling agent Substances 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 241000238586 Cirripedia Species 0.000 abstract 1
- 241000206607 Porphyra umbilicalis Species 0.000 abstract 1
- 241000196251 Ulva arasakii Species 0.000 abstract 1
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000012442 inert solvent Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography 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
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 241000238426 Anostraca Species 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000012230 colorless oil Substances 0.000 description 3
- -1 ethyl acetate Chemical compound 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- 241001474374 Blennius Species 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 2
- MCUIEDCAVHLHPG-UHFFFAOYSA-L bis(tributylstannyl) benzene-1,2-dicarboxylate Chemical compound CCCC[Sn](CCCC)(CCCC)OC(=O)C1=CC=CC=C1C(=O)O[Sn](CCCC)(CCCC)CCCC MCUIEDCAVHLHPG-UHFFFAOYSA-L 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- ZOKXUAHZSKEQSS-UHFFFAOYSA-N tribufos Chemical compound CCCCSP(=O)(SCCCC)SCCCC ZOKXUAHZSKEQSS-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- JVVRJMXHNUAPHW-UHFFFAOYSA-N 1h-pyrazol-5-amine Chemical class NC=1C=CNN=1 JVVRJMXHNUAPHW-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- VCPXZIUQCXEVCU-UHFFFAOYSA-N 4-ethylpyrimidine Chemical compound CCC1=CC=NC=N1 VCPXZIUQCXEVCU-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 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
- WKSAUQYGYAYLPV-UHFFFAOYSA-N pyrimethamine Chemical compound CCC1=NC(N)=NC(N)=C1C1=CC=C(Cl)C=C1 WKSAUQYGYAYLPV-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は一般式 （１）
（式中、Ｒ１は水素原子又は低級アルキル基を示し、Ｒ
２は低級アルキル基を示し、Ｒ３は炭素原子数６〜１６
のアルキル基又はアルケニル基を示し、Ｘはハロゲン原
子を示す、）
で表されるアミノピリミジン誘導体及びその製造方法並
びに該誘導体を有効成分とする防汚剤に関するものであ
る。Detailed Description of the Invention The present invention is based on the general formula (1) (wherein, R1 represents a hydrogen atom or a lower alkyl group, and R
2 represents a lower alkyl group, and R3 has 6 to 16 carbon atoms.
represents an alkyl group or an alkenyl group, X represents a halogen atom), a method for producing the same, and an antifouling agent containing the derivative as an active ingredient.
従来、魚網、船底、海中構築物に付着する海棲生物を防
除するために使用されるトリブチル錫オキサイド（ＴＢ
ＴＯ）、 トリブチル錫フクレート（ＴＢＴＰ）等の
有機錫剤が多く使用されてきたが、近年、これらの薬剤
の毒性、魚体への蓄積、環境汚染等の問題が提起され、
一部使用が制限されるようになり、これらの薬剤以外に
有効な薬剤が少ない現状では、毒性が少なく、且つ海棲
生物に防除効果を有する新規な薬剤の創出が課題となっ
ている。Tributyltin oxide (TB) has traditionally been used to control marine organisms that adhere to fishing nets, ship bottoms, and underwater structures.
Organotin agents such as TO) and tributyltin fucrate (TBTP) have been widely used, but in recent years, problems such as the toxicity of these agents, accumulation in fish bodies, and environmental pollution have been raised.
In the current situation where the use of some drugs has become restricted and there are few effective drugs other than these drugs, the challenge is to create new drugs that are less toxic and have a control effect on marine organisms.
本発明者等は上記課題を解決すべく鋭意研究を重ねた結
果、−殺人 （Ｉ）で表されるアミノピリミジン誘導体
が文献未記載の新規化合物であり、且つノリ、アオサ、
フジッボ、セルプラ等の海棲生物に対して優れた防汚効
果を有することを見出し本発明を完成させたものである
。As a result of intensive research to solve the above problems, the present inventors found that the aminopyrimidine derivative represented by -murder (I) is a new compound that has not been described in the literature, and that
The present invention was completed based on the discovery that it has an excellent antifouling effect on marine organisms such as Fujibbo and Serpura.
アミノピリミジン類としては、例えばＣｈｅｍ。Examples of aminopyrimidines include Chem.
Ｐｈａｒｍ、Ｂ、ｕｌｌ、１９７８，２６（７１，２２
８６−２２８７，、Ｊ、Ａ、Ｃ，Ｓ８２、３９７１−３
９７４（１９６０）、 Ｐｈａｒｍａｚｉｅ １９６８
，２３（Ｉｌ１６１４−６１８．特開昭５７−１２６４
８１号公報、特開昭５７−１７６９６７号公報に類似の
アミノピリミジンが記載されているが、本発明のアミノ
ピリミジン誘導体及びその防汚活性については全く記載
されていない。Pharm, B. ull, 1978, 26 (71, 22
86-2287, J, A, C, S82, 3971-3
974 (1960), Pharmazie 1968
, 23 (Il1614-618. JP-A-57-1264
Although similar aminopyrimidines are described in JP-A-81 and JP-A-57-176967, there is no mention of the aminopyrimidine derivative of the present invention and its antifouling activity.
本発明の一般式 （Ｉ）で表されるアミノピリミジン誘
導体は、例えば下記に図示する方法により製造すること
ができる。The aminopyrimidine derivative represented by general formula (I) of the present invention can be produced, for example, by the method illustrated below.
［１１） ［Ｉ）（
式中、Ｒ１は水素原子又は低級アルキル基を示し、Ｒ２
は低級アルキル基を示し、Ｒ３は炭素原子数６〜１６の
アルキル基又はアルケニル基を示し、Ｘ及びＹは同−又
は異なっても良いハロゲン原子を示す、）
即ち、−６式 ＋ＩＩ）で表されるハロビリミジン類と
一般式 （Ｉｌｌ で表されるアミン類とを不活性溶媒
の存在下又は不存在下及び塩基の存在下に反応させるこ
とにより、−４９式 （１）で表されるアミノピリミジ
ン誘導体を製造することができる。[11) [I)(
In the formula, R1 represents a hydrogen atom or a lower alkyl group, and R2
represents a lower alkyl group, R3 represents an alkyl group or alkenyl group having 6 to 16 carbon atoms, and X and Y represent a halogen atom which may be the same or different. By reacting the halobyrimidines represented by the general formula (Ill) with the amines represented by the general formula (Ill) in the presence or absence of an inert solvent and the presence of a base, aminopyrimidines represented by the -49 formula (1) can be obtained. Derivatives can be produced.
本反応で使用できる不活性溶媒としては、本反応の進行
を著しく阻害しないものであれば良く、例えばメタノー
ル、エタノール、プロパツール、エチレングリコール等
のアルコール類、塩化メチレン、クロロホルム、四塩化
炭素、クロロベンゼン、ジクロロベンゼン等のハロゲン
化炭化水素類、ベンゼン、トルエン、キシレン、メチル
ナフタレン等の芳香族炭化水素類、酢酸エチル等のエス
テル類、メチルセロソルブ、ジエチルエーテル、エチレ
ングリコールジメチルエーテル等の鎖状エーテル類、ジ
オキサン、テトラハイドロフラン等の環状エーテル類、
アセトニトリル、ベンゾニトリル等のニトリル類、アセ
トン、メチルエチルケトン等のケトン類、Ｎ、Ｎ−ジメ
チルホルムアミド、Ｎ、Ｎ−ジメチルアセトアミド、ジ
メチルスルホキシド、水等を例示することができるが、
本発明はこれらの不活性溶媒に限定されるものではない
。Inert solvents that can be used in this reaction may be those that do not significantly inhibit the progress of this reaction, such as methanol, ethanol, propatool, alcohols such as ethylene glycol, methylene chloride, chloroform, carbon tetrachloride, and chlorobenzene. , halogenated hydrocarbons such as dichlorobenzene, aromatic hydrocarbons such as benzene, toluene, xylene, methylnaphthalene, esters such as ethyl acetate, chain ethers such as methyl cellosolve, diethyl ether, ethylene glycol dimethyl ether, Cyclic ethers such as dioxane and tetrahydrofuran,
Examples include nitriles such as acetonitrile and benzonitrile, ketones such as acetone and methyl ethyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and water.
The invention is not limited to these inert solvents.
これらの不活性溶媒は単独で使用しても良く、混合して
使用することもできる。These inert solvents may be used alone or in combination.
本発明で使用できる塩基としては無機塩基又は有機塩基
を使用することができ、無機塩基としては１例えば炭酸
ナトリウム、炭酸カリウム、水酸化ナトリウム、水酸化
カリウム等の無機塩基類、有機塩基としては、例えばト
リエチルアミン、ピリジン、Ｎ、Ｎ−ジメチルアニリン
、Ｎ、Ｎ−ジメチルアミノピリジン、１．８−ジアザビ
シクロ［５，４，０］−７−ウンデセン（ＤＢＵＩ等の
有機塩基類を例示することができる。The base that can be used in the present invention can be an inorganic base or an organic base. Examples of the inorganic base include inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide; Examples include organic bases such as triethylamine, pyridine, N,N-dimethylaniline, N,N-dimethylaminopyridine, and 1,8-diazabicyclo[5,4,0]-7-undecene (DBUI).
塩基の使用量は一般式 （ＩＩ）で表されるハロビリミ
ジン類に対して１／２モル乃至過剰モルの範囲から選択
すれば良く、好ましくは過剰モル使用するのが良い。The amount of the base to be used may be selected from the range of 1/2 mole to excess mole relative to the halobyrimidine represented by the general formula (II), preferably in excess mole.
又、不活性溶媒として水に不溶の有機溶媒及び水を組み
合わせて使用する場合、塩基としてトリメチルベンジル
アンモニウムハライド、トリエチルベンジルアンモニウ
ムハライド等の相間移動触媒を使用することもできる。Furthermore, when a water-insoluble organic solvent and water are used in combination as the inert solvent, a phase transfer catalyst such as trimethylbenzylammonium halide or triethylbenzylammonium halide can also be used as the base.
本反応は等モル反応であるので一般式 （Ｉｌｌで表さ
れるハロビリミジン類に対して一般式（ＩＩＩ）で表さ
れるアミン類を等モル使用すれば良いが、アミン類を過
剰に使用することもできる。Since this reaction is an equimolar reaction, it is sufficient to use equimolar amounts of the amines represented by the general formula (III) to the halobyrimidines represented by the general formula You can also do it.
又、塩基にかえて一般式 ［＋１１１で表されるアミン
類を過剰に使用することにより、塩基としての働きをさ
せることができる。Furthermore, by using an excess of amines represented by the general formula [+111] in place of the base, it can function as a base.
本反応の反応温度は室温乃至使用する不活性溶媒の沸点
域から選択すれば良く、好ましくは加熱下に行うのが良
い。The reaction temperature for this reaction may be selected from room temperature to the boiling point range of the inert solvent used, and preferably it is carried out under heating.
反応時間は、反応温度、反応量等により一定しないが、
数分乃至４８時間の範囲から選択すれば良い。The reaction time is not constant depending on the reaction temperature, reaction amount, etc.
It may be selected from a range of several minutes to 48 hours.
反応終了後、目的物を含む反応液から常法により単離し
、必要に応じて再結晶法、カラムクロマトグラフィー法
等により精製し、−６式（Ｉ）で表されるアミノピリミ
ジン誘導体を製造することができる。After the reaction is completed, it is isolated from the reaction solution containing the target product by a conventional method, and if necessary, purified by recrystallization, column chromatography, etc. to produce an aminopyrimidine derivative represented by -6 formula (I). be able to.
本発明の一般式 （ｒ）で表されるアミノピラゾール誘
導体の代表例を第１表に挙げるが、本発明はこれらに限
定されるものではない。Representative examples of the aminopyrazole derivatives represented by the general formula (r) of the present invention are listed in Table 1, but the present invention is not limited thereto.
−殺人（Ｉ）
１
本発明の一般式 ＋１＋で表されるアミノピリミジン誘
導体を製造するための原料化合物である一般式 （１■
）で表されるへロビリミジン誘導体は文献（Ｊ、 Ｍｅ
ｄ、 Ｃｈｅｎ＋６，１９６８（１１１，６０ｇ、特開
昭５７−１２６４８１号公報、特開昭６２−６７号）等
によって知られた公知の方法により製造することができ
る。- Murder (I) 1 General formula of the present invention General formula (1■
) is described in the literature (J, Me
d, Chen+6, 1968 (111,60 g, JP-A-57-126481, JP-A-62-67).
以下に本発明の代表的な製造例を示すが、本発明はこれ
らに限定されるものではない。Typical production examples of the present invention are shown below, but the present invention is not limited thereto.
製造例１．５−クロロー６−ゾシルアミノー４−エチル
ビリミジンの製造（化合物
Ｎｏ、 ｌ ）
（０，００２２モル）をトルエン２０ｍＪ２に溶解し、
撹拌還流下に３時間反応を行った。Production Example 1. Production of 5-chloro-6-zosylamino-4-ethylpyrimidine (compound No. 1) (0,0022 mol) was dissolved in 20 mJ2 of toluene,
The reaction was carried out for 3 hours under stirring and reflux.
反応終了後、反応液を冷水中に注ぎ、分離する有機相を
分液し、水洗し、無水硫酸マグネシウムで乾燥し、減圧
下に溶媒を留去し、得られた油状物をカラムクロマトグ
ラフィー（酢酸エチル二〇−ヘキサン＝１：３）により
精製して無色の油状物として目的物を０．３８ ｇ得た
。After the reaction is complete, the reaction solution is poured into cold water, the organic phase is separated, washed with water, dried over anhydrous magnesium sulfate, the solvent is distilled off under reduced pressure, and the resulting oil is subjected to column chromatography ( Purification was performed using ethyl acetate (20-hexane = 1:3) to obtain 0.38 g of the desired product as a colorless oil.
物性 ｎＤ １．５３２２（２０，６℃） 収率 ８３
．４％製造例２．４−ｎ−ブチルアミノ−５−クロロ−
４−エチルピリミジンの製造（化
合物ＮＱ、６）
５．６−ジクロロ−４−二チルアミノビリミ ５．
６−ジクロロ−４−エチルアミノピリミジン０．３５ｇ
（０，００２モル）及びｎ−へキシルアミ ジン０
．３５ｇ （０，００２モル）をエタノール２０ｍβに
ン［０，００２モル）及びトリエチルアミン０．２２
ｇ 溶解し、これにｎ−ブチルアミン（０，００４
モル）を加え、攪拌還流下に３時間反応を行った０反応
終了後、反応液を冷水中に注ぎ、分離する目的物をジエ
チルエーテルで抽出し、抽出液を水洗、無水硫酸マグネ
シウムで乾燥し、減圧下に溶媒を留去し、得られた油状
物をカラムクロマトグラフィー（酢酸エチル：ｎ−ヘキ
サン＝ｌ：３）により精製し、無色の油状物として目的
物を０．３５ｇ得た。Physical properties nD 1.5322 (20.6°C) Yield 83
．． 4% Production Example 2.4-n-butylamino-5-chloro-
Production of 4-ethylpyrimidine (compound NQ, 6) 5.6-dichloro-4-dithylaminopyrimidine 5.
6-dichloro-4-ethylaminopyrimidine 0.35g
(0,002 mol) and n-hexylamidine 0
．． 35 g (0,002 mol) of ethanol 20mβ [0,002 mol) and triethylamine 0.22
g of n-butylamine (0,004
After the reaction was completed, the reaction solution was poured into cold water, the target product to be separated was extracted with diethyl ether, the extract was washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting oil was purified by column chromatography (ethyl acetate:n-hexane=l:3) to obtain 0.35 g of the desired product as a colorless oil.
物性 ｎＤ １．５３６Ｏｆ２１．３℃） 収率 ８１
．９％製造例３，５−クロロー６−ゾシルアミノー４−
エチルピリミジンの製造（化
合物Ｎｏ、 １０ ）
５．６−ジクロロ−４−エチルアミノピリミジン０．３
５ｇ （０，００２モル）及びｎ−デシルアミン（０，
００２モル）をＮ、Ｎ−ジメチルホルムアミド２０ｍ１
２に溶解し、無水炭酸カリウム０．２１ｇ （０，００
１５モル）を加え、 １１０℃で３時間撹拌し、反応
を行った０反応終了後、反応液を冷水中に注ぎ、分離す
る目的物をジエチルエーテルで抽出し、抽出液を水洗、
無水硫酸マグネシウムで乾燥し、減圧下に溶媒を留去し
、得られた油状物をカラムクロマトグラフィー（酢酸エ
チル：ｎ−ヘキサン＝１：５）により精製し、無色の油
状物として目的物を０．４４ｇ得た。Physical properties nD 1.536Of21.3℃) Yield 81
．． 9% Production Example 3,5-chloro-6-zosylamino-4-
Production of ethylpyrimidine (compound No. 10) 5.6-dichloro-4-ethylaminopyrimidine 0.3
5g (0,002 mol) and n-decylamine (0,002 mol)
002 mol) in 20 ml of N,N-dimethylformamide
2, anhydrous potassium carbonate 0.21g (0,00
After the completion of the reaction, the reaction solution was poured into cold water, the target product to be separated was extracted with diethyl ether, the extract was washed with water,
After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting oil was purified by column chromatography (ethyl acetate: n-hexane = 1:5) to obtain the desired product as a colorless oil. .44g was obtained.
物性 ｎＤ １．５１３３（２０，７℃） 収率 ７３
．９％本発明のアミノピリミジン誘導体を有効成分とす
る防汚組成物は、ア才す、ノリ、フジッボ、セルプラ等
の藻類、貝類が漁網、船底、海洋構築物、海水導入管、
湖水、河水に接する物体等に付着するのを防止する効果
を有する。Physical properties nD 1.5133 (20.7°C) Yield 73
．． 9% The antifouling composition containing the aminopyrimidine derivative of the present invention as an active ingredient is suitable for use in fishing nets, ship bottoms, marine structures, seawater inlet pipes, algae such as seaweed, seaweed, Fujibbo, and Serupura, and shellfish.
It has the effect of preventing it from adhering to objects that come into contact with lake water or river water.
本発明の防汚組成物を使用する場合は、例えば本発明の
有効成分であるアミノピリミジン誘導体を単独若しくは
他の防汚剤とともにアクリル樹脂、酢酸ビニル樹脂、塩
化ゴム等の合成樹脂及び溶剤と混合して塗料等として、
目的とする漁網、船底、海洋構築物、海水導入管、湖水
、河水に接する物体等に塗布、乾燥させるか、本発明組
成物を予めセメント等に添加し、該セメントを使用して
海洋構築物を建設するか、既に建設された海洋構築物の
表面に塗布することもできる。When using the antifouling composition of the present invention, for example, the aminopyrimidine derivative, which is the active ingredient of the present invention, may be mixed alone or together with other antifouling agents with a synthetic resin such as acrylic resin, vinyl acetate resin, or chlorinated rubber, and a solvent. and as paint etc.
The composition of the present invention can be applied to target fishing nets, ship bottoms, marine structures, seawater introduction pipes, objects in contact with lake water, river water, etc. and dried, or the composition of the present invention can be added to cement, etc. in advance, and the cement can be used to construct marine structures. Alternatively, it can be applied to the surface of already constructed marine structures.
本発明の防汚組成物は、有効成分としてアミノピリミジ
ン誘導体を組成物１００重量部中２０〜８０重量部の範
囲で含有することができる。The antifouling composition of the present invention can contain an aminopyrimidine derivative as an active ingredient in a range of 20 to 80 parts by weight per 100 parts by weight of the composition.
又、本発明のアミノピリミジン誘導体は防汚活性を有す
る他に、殺虫、殺ダニ、殺菌活性をも有する化合物であ
る。Furthermore, the aminopyrimidine derivative of the present invention is a compound that not only has antifouling activity but also has insecticidal, acaricidal, and bactericidal activity.
以下に本発明の代表的な実施例及び試験例を示す、尚、
実施例中、部とあるのは重量部を示す。Typical examples and test examples of the present invention are shown below.
In the examples, parts indicate parts by weight.
実施例１゜ 松脂 ５０部 インプロパツール ５部 キシレン ２５部 ウレタン樹脂系塗料 ２０部 以上を均一に混合し基剤とする。Example 1゜ Pine resin 50 parts Improper Tools Part 5 Xylene 25 parts Urethane resin paint 20 parts Mix the above ingredients uniformly to form a base.
本発明化合物 ０．１〜１０部基剤
９０〜９９．９部以上を均一に混
合し溶解して、塗布剤とする。Compound of the present invention 0.1 to 10 parts base
90 to 99.9 parts or more are uniformly mixed and dissolved to form a coating agent.
本発明化合物 ０．１−１０部松脂
２５．０部塩化ゴム
ｌ０１０部塩化パラフィン ３
．０部弁柄 ２１．４〜１１．
５部タルク １４．０部ディス
パロン＃４３００ １．５部イソプロパツー
ル ５．０部キシレン
２０．０部以上を均一に混合して塗布剤とする。Compound of the present invention 0.1-10 parts pine resin
25.0 parts chlorinated rubber
10 parts Chlorinated paraffin 3
．． Part 0 valve pattern 21.4-11.
5 parts talc 14.0 parts Disparon #4300 1.5 parts isopropanol 5.0 parts xylene
A coating agent is prepared by uniformly mixing 20.0 parts or more.
試験例１．ブラインシュリンプに対する殺生物試験。Test example 1. Biocidal test against brine shrimp.
直径６ｃｍのベトリ皿にブラインシュリンプ（Ａｒｔｅ
ｍｉａ ５ａｌｉｎａ） 卿化幼生１００頭の入った
人工海水１０ｍ Ｇを入れ、これに本発明の防汚組成物
の薬液を所定濃度となるように処理した。これを２５±
２℃の恒温室に静置条件下で置き、薬液処理２４時間後
に幼生の生死数を調査し、死亡率を算出した。Brine shrimp (Arte
10 m G of artificial seawater containing 100 larvae (Mia 5alina) was added, and treated with the chemical solution of the antifouling composition of the present invention to a predetermined concentration. This is 25±
The larvae were placed in a constant temperature room at 2°C under static conditions, and 24 hours after the chemical solution treatment, the number of living and dead larvae was investigated, and the mortality rate was calculated.
結果を第２表に示す。The results are shown in Table 2.
第２表
尚、対照薬剤としてはトリブチル錫フタレート（ＴＢＴ
Ｐ）を使用した。Table 2 shows that the control drug is tributyltin phthalate (TBT).
P) was used.
以上の試験結果により、本発明の一般式（Ｉ）で表され
るアミノピリミジン誘導体はブラインシュリンプに対し
て、対照薬剤のＴＢＴＰに比して低薬量で防汚効果を示
すことは明らかである。From the above test results, it is clear that the aminopyrimidine derivative represented by the general formula (I) of the present invention exhibits an antifouling effect on brine shrimp at a lower dose than the control drug TBTP. .
Claims (3)
Ｒ＾２は低級アルキル基を示し、Ｒ＾３は炭素原子数６
〜１６のアルキル基又はアルケニル基を示し、Ｘはハロ
ゲン原子を示す。） で表されるアミノピリミジン誘導体。(1) General formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, R^1 represents a hydrogen atom or a lower alkyl group,
R^2 represents a lower alkyl group, and R^3 has 6 carbon atoms.
~16 alkyl group or alkenyl group, and X represents a halogen atom. ) Aminopyrimidine derivatives represented by
Ｒ＾２は低級アルキル基を示し、Ｘ及びＹは同一又は異
なっても良いハロゲン原子を示す。） で表されるハロピリミジン類と一般式（III）Ｒ＾３・
ＮＨ＿２（III） （式中、Ｒ＾３は炭素原子数６〜１６のアルキル基又は
アルケニル基を示す）で表されるアミン類と反応させる
ことを特徴とする一般式 （ I ） ▲数式、化学式、表等があります▼（ I ） （式中、Ｒ＾１、Ｒ＾２、Ｒ＾３及びＸは前記に同じ。 ）で表されるアミノピリミジン誘導体の製造方法。(2) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^1 represents a hydrogen atom or a lower alkyl group,
R^2 represents a lower alkyl group, and X and Y represent a halogen atom which may be the same or different. ) and halopyrimidines represented by the general formula (III) R^3.
General formula (I) characterized by reacting with an amine represented by NH_2(III) (in the formula, R^3 represents an alkyl group or alkenyl group having 6 to 16 carbon atoms) ▲Mathematical formula, chemical formula , tables, etc. ▼(I) A method for producing an aminopyrimidine derivative represented by the formula (wherein R^1, R^2, R^3 and X are the same as above).
Ｒ＾２は低級アルキル基を示し、Ｒ＾３は炭素原子数６
〜１６のアルキル基又はアルケニル基を示し、Ｘはハロ
ゲン原子を示す。） で表されるアミノピリミジン誘導体を有効成分として含
有することを特徴とする防汚組成物。(3) General formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, R^1 represents a hydrogen atom or a lower alkyl group,
R^2 represents a lower alkyl group, and R^3 has 6 carbon atoms.
~16 alkyl group or alkenyl group, and X represents a halogen atom. ) An antifouling composition characterized by containing an aminopyrimidine derivative represented by the following as an active ingredient.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27427389A JPH03135965A (en) | 1989-10-21 | 1989-10-21 | Aminopyrimidine derivative, its production and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27427389A JPH03135965A (en) | 1989-10-21 | 1989-10-21 | Aminopyrimidine derivative, its production and use thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03135965A true JPH03135965A (en) | 1991-06-10 |
Family
ID=17539362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27427389A Pending JPH03135965A (en) | 1989-10-21 | 1989-10-21 | Aminopyrimidine derivative, its production and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03135965A (en) |
-
1989
- 1989-10-21 JP JP27427389A patent/JPH03135965A/en active Pending
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