JPS6114154B2 - - Google Patents
Info
- Publication number
- JPS6114154B2 JPS6114154B2 JP51011649A JP1164976A JPS6114154B2 JP S6114154 B2 JPS6114154 B2 JP S6114154B2 JP 51011649 A JP51011649 A JP 51011649A JP 1164976 A JP1164976 A JP 1164976A JP S6114154 B2 JPS6114154 B2 JP S6114154B2
- Authority
- JP
- Japan
- Prior art keywords
- copper salt
- acid
- dodecylamine
- general formula
- amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000001879 copper Chemical class 0.000 claims description 44
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 19
- 150000001412 amines Chemical class 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 claims description 3
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 claims description 3
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000005266 diarylamine group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- VFFDVELHRCMPLY-UHFFFAOYSA-N dimethyldodecyl amine Natural products CC(C)CCCCCCCCCCCN VFFDVELHRCMPLY-UHFFFAOYSA-N 0.000 claims description 2
- JMLPVHXESHXUSV-UHFFFAOYSA-N dodecane-1,1-diamine Chemical compound CCCCCCCCCCCC(N)N JMLPVHXESHXUSV-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 description 5
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- -1 copper salt compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- UIAFKZKHHVMJGS-UHFFFAOYSA-N 2,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 description 2
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 2
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 2
- XHQZJYCNDZAGLW-UHFFFAOYSA-N 3-methoxybenzoic acid Chemical compound COC1=CC=CC(C(O)=O)=C1 XHQZJYCNDZAGLW-UHFFFAOYSA-N 0.000 description 2
- AUZQQIPZESHNMG-UHFFFAOYSA-N 3-methoxysalicylic acid Chemical compound COC1=CC=CC(C(O)=O)=C1O AUZQQIPZESHNMG-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000009102 absorption Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- JMSVCTWVEWCHDZ-UHFFFAOYSA-N syringic acid Chemical compound COC1=CC(C(O)=O)=CC(OC)=C1O JMSVCTWVEWCHDZ-UHFFFAOYSA-N 0.000 description 2
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 description 1
- CXKCZFDUOYMOOP-UHFFFAOYSA-N 3,5-dichlorobenzoic acid Chemical compound OC(=O)C1=CC(Cl)=CC(Cl)=C1 CXKCZFDUOYMOOP-UHFFFAOYSA-N 0.000 description 1
- GRLQBYQELUWBIO-UHFFFAOYSA-N 4,6-dichlorobenzene-1,3-diol Chemical compound OC1=CC(O)=C(Cl)C=C1Cl GRLQBYQELUWBIO-UHFFFAOYSA-N 0.000 description 1
- 125000005274 4-hydroxybenzoic acid group Chemical group 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229940114055 beta-resorcylic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical group 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は新規なるアミン複合有機銅塩の製造法
に関するものである。
一般式
〔但し、Ｘは水素、アルキル基、アルコキシル基
またはハロゲン原子を示し、ｌは１〜３の整数、
ｍは０、１または２およびｎは１または２を示
す。〕
にて示されるヒドロオキシ化合物の銅塩は人体や
各種有用生物体に対する毒性が低く、効力持続期
間が長い有害防除作用を有する。
これらを構成する有機酸部は多塩基酸として作
用し銅塩を形成する場合、銅が２価であるから高
分子体または多分子体を形成しやすい。
本発明者等はこれ等の有機銅塩化合物について
研究したところ、
一般式
にて示されるアミンが前記一般式(A)にて示される
有機銅塩と複合して新規なるアミン複合有機銅塩
を形成せしめることが見出され、且つこの新規な
るアミン複合有機銅塩は一般式(A)にて示される有
機銅塩の保持せる有害防除作用より一層強力であ
ることが判明した。
更に詳しくは本発明は
一般式
〔但し、Ｘは水素、アルキル基、アルコキシル基
またはハロゲン原子を示し、ｌは１〜３の整数、
ｍは０、１または２およびｎは１または２を示
す。〕
にて示されるヒドロオキシ化合物の銅塩と
前記一般式(B)のアミン、具体的には、ドデシル
アミン、ジブチルアミノエタノール、ジアリール
アミン、アミノブタン、ジメチルドデシルアミ
ン、ポリエチレンイミン、ジシクロヘキシルアミ
ン、ジベンジルアミン及びジアミノドデカンの群
より選ばれアミンを水性媒質または上記アミンに
可溶性のある有機溶媒中で、０〜50℃の範囲の温
度で反応せしめることを特徴とするアミン複合有
機銅塩の製造法である。
本発明において、一般式(A)の銅塩と一般式(B)と
の反応は、一般式(A)の有機銅塩１モルに対して一
般式(B)にて示されるアミンは４乃至0.001モル
で、好ましくは0.5乃至0.05モルを０〜50℃の温
度範囲において加えることによつて実施できる。
この際一般式(A)の銅塩は水またはアルコール類、
ケトン類、エーテル類、炭化水素類、芳香族炭化
水素類等のアミンに対して可溶性のある有機溶媒
中にスラリー状として懸濁せしめておくとよい。
一般式(B)のアミンが、アミンが水溶性であれば、
一般式(A)の銅塩のスラリー状の懸濁液中に直接、
またはあらかじめ水に溶解せしめた溶液を添加
し、接触せしめて反応することが好適であり、必
要に応じてメタノール、エタノール等のアルコー
ル類や、他の有機溶剤に溶解せしめて反応するこ
ともできる。一般式(B)のアミンが、有機溶媒に対
して可溶性を示す場合には、あらかじめアミンを
その溶媒中に溶解せしめて、一般式(A)にて示され
る銅塩のスラリーと接触せしめて実施することが
できる。
かくして生成したアミン複合有機銅は過、分
離して得られる。
一般式(A)にて示される銅塩は、無水または水和
の形態をした前掲の如き、４−ヒドロオキシ安息
香酸、３−ヒドロオキシベンゼン、４−ヒドロオ
キシ−３−メトキシ安息香酸、３・５−ジヒドロ
オキシ安息香酸、１・６−ジヒドロオキシベンゼ
ン等の単純銅塩に限定せられるものではなく、更
にこれ等を主成分とする有機酸として含めば、目
的が達せられるのであつて、他の多塩基酸を一
部、これ等の二塩基酸とおきかえても差支えな
く、又、他の単官能酸、例えば安息香酸、サリチ
ル酸、ハロゲノ安息香酸、ハロゲノサリチル酸等
を一部併用して、上述の如き銅塩とする事も出来
る。又、その１例として、トリカルボン酸の如き
を少量配合の上、上述の如き銅塩としても高分子
量体形成の際の架橋剤の如き作用を果して、有用
な本発明の具体例となりうる。又、銅塩結合の一
部に、他種の金属部を部分的に含ましめてもよ
い。例えばマンガン、ニツケル、鉄等も好まし
い。
以下実施例を以つて説明する。
実施例 １
300mlフラスコに乳鉢にて粉砕した４−ヒドロ
オキシ安息香酸の銅塩20ｇ及び水100mlを加えて
撹拌しながら室温にて４−ヒドロオキシ安息香酸
の銅塩のスラリーを調製した。次に２−アミノブ
タン３ｇを、徐々に撹拌しながら滴下した。滴下
後、１時間撹拌しそして撹拌を停止してから一夜
室温に放置した。結晶は吸引過し、数回水洗
後、減圧乾燥に附した。その後これを微粉砕に附
し、そして325メツシユ以下とした。
４−ヒドロオキシ−３−メトキシ安息香酸の銅
塩20ｇとポリエチレンイミン５ｇも同様に処理し
た。
実施例 ２
300mlフラスコに乳鉢にて微粉砕した４−ヒド
ロオキシ安息香酸の銅塩20ｇ及びメタノール100
mlを加えて撹拌しながら４−ヒドロオキシ安息香
酸の銅塩を懸濁させた。次に50mlのメタノールに
４ｇのドデシルアミンを溶解した溶液を室温にて
徐々に撹拌しながら滴下した。滴下後２時間撹拌
を継続し、そして次に撹拌を停止して更に一夜放
置した。結晶は吸引過し、メタノールにて数回
洗浄後、減圧乾燥（50〜60℃／５〜10mmHg）に
附した。その後、これを微粉砕に附し、そして
325メツシユ以下とした。
実施例 ３
300mlフラスコに乳鉢にて良く、粉砕した４−
ヒドロオキシ−３−メトキシ安息香酸の銅塩20ｇ
及びシクロヘキサン100mlを加えて撹拌懸濁し
た。これに50mlのシクロヘキサンに５ｇのドデシ
ルアミンを含有する溶液を滴下して室温にて１時
間撹拌した。撹拌を停止後、室温にて一夜放置し
た。結晶は吸引過し、シクロヘキサンにて数回
洗浄後、減圧乾燥（50〜60℃／５〜10mmHg）に
附した。その後これを微粉砕に附しそして325メ
ツシユ以下とした。
４−ヒドロオキシ安息香酸の銅塩20ｇとＮ・Ｎ
−ジブチルアミノエタノール４ｇ、４−ヒドロオ
キシ安息香酸の銅塩20ｇと、ジアリールアミン３
ｇ、４−ヒドロオキシ安息香酸の銅塩20ｇと、
Ｎ・Ｎ−ジメチルドデシルアミン３ｇ、４−ヒド
ロオキシ−３−メトキシ安息香酸の銅塩20ｇとジ
シクロヘキシルアミン４ｇ、４−ヒドロオキシ−
３−メトキシ安息香酸の銅塩20ｇと、ジエタノー
ルアミン５ｇ、４−ヒドロオキシ−３−メトキシ
安息香酸の銅塩20ｇとジベンジルアミン５ｇ、４
−ヒドロオキシ−３−メトキシ安息香酸の銅塩20
ｇと１・12−ジアミノドデカン４ｇ、４−ヒドロ
オキシ−３−メトキシ安息香酸の銅塩20ｇとドデ
シルアミン６ｇ及びベンジルアミン４ｇ、３−ヒ
ドロオキシ安息香酸の銅塩20ｇとドデシルアミン
５ｇ、２−ヒドロオキシ−３・５−ジクロル安息
香酸の銅塩20ｇとドデシルアミン３ｇ、４−ヒド
ロオキシ−３・５−ジメトキシ安息香酸の銅塩20
ｇとドデシルアミン６ｇ、４−ヒドロオキシ−３
−カルボキシ安息香酸の銅塩20ｇとドデシルアミ
ン３ｇ、１・３−ジヒドロオキシ−４・６−ジク
ロルベンゼン20ｇとドデシルアミン２ｇ、３・５
−ジヒドロオキシ安息香酸の銅塩20ｇとドデシル
アミン３ｇ、１・４−ジヒドロオキシベンゼンの
銅塩20ｇとドデシルアミン４ｇ、１・３−ジヒド
ロオキシベンゼンの銅塩20ｇとドデシルアミン２
ｇ、２・４−ジヒドロオキシ安息香酸の銅塩20ｇ
とドデシルアミン１ｇ、２・６−ジヒドロオキシ
トルエンの銅塩20ｇとドデシルアミン４ｇ、も同
様に処理した。
実施例 ４
300mlフラスコに乳鉢にて良く粉砕した４−ヒ
ドロオキシ安息香酸〜テレフタル酸（重量比１：
１）のアルカリ性水溶液を硫酸銅水溶液にて複分
解して調製した銅塩20ｇ、及びｎ−ヘキサン100
mlを加えて撹拌懸濁した。次にドデシルアミン３
ｇを含有する50mlｎ−ヘキサン溶液を撹拌しなが
ら徐々に滴下した。１時間撹拌後、一夜室温に放
置した。結晶は吸引過し、ｎ−ヘキサンにて数
回洗浄後、減圧乾燥に附し、その後、これを微粉
砕に附し、そして325メツシユ以下とした。
４−ヒドロオキシ安息香酸ベンゼン−１・２・
４−トリカルボン酸〜安息香酸（重量比10：10：
１）の銅塩20ｇとドデシルアミン３ｇも同様に処
理した。
前記実施例にて示された生成物は下表の如くで
ある。
The present invention relates to a method for producing a novel amine complex organic copper salt. general formula [However, X represents hydrogen, an alkyl group, an alkoxyl group, or a halogen atom, l is an integer of 1 to 3,
m represents 0, 1 or 2, and n represents 1 or 2. ] The copper salt of the hydroxy compound shown in is low in toxicity to the human body and various useful organisms, and has a long-lasting harmful control effect. When the organic acid moiety forming these acts as a polybasic acid to form a copper salt, since copper is divalent, it tends to form a polymer or a polymolecular body. The present inventors studied these organic copper salt compounds and found that the general formula It has been found that the amine represented by formula (A) is complexed with the organic copper salt represented by the general formula (A) to form a novel amine complex organic copper salt, and this new amine complex organic copper salt is It was found that the harmful control effect maintained by the organic copper salt represented by formula (A) is even stronger. More specifically, the present invention has the general formula [However, X represents hydrogen, an alkyl group, an alkoxyl group, or a halogen atom, l is an integer of 1 to 3,
m represents 0, 1 or 2, and n represents 1 or 2. ] A copper salt of a hydroxy compound represented by the above and an amine of the general formula (B), specifically dodecylamine, dibutylaminoethanol, diarylamine, aminobutane, dimethyldodecylamine, polyethyleneimine, dicyclohexylamine, dibenzylamine and diaminododecane is reacted in an aqueous medium or an organic solvent soluble in the amine at a temperature in the range of 0 to 50°C. . In the present invention, in the reaction between the copper salt of general formula (A) and general formula (B), the amount of the amine represented by general formula (B) is 4 to 4 to 1 mole of the organic copper salt of general formula (A). This can be done by adding 0.001 mol, preferably 0.5 to 0.05 mol, in the temperature range of 0 to 50°C.
In this case, the copper salt of general formula (A) is water or alcohol,
It is preferable to suspend it in the form of a slurry in an organic solvent that is soluble in amines such as ketones, ethers, hydrocarbons, and aromatic hydrocarbons.
If the amine of general formula (B) is water-soluble,
Directly into a slurry suspension of the copper salt of general formula (A),
Alternatively, it is preferable to add a solution preliminarily dissolved in water and bring them into contact for reaction. If necessary, it is also possible to react by dissolving them in alcohols such as methanol and ethanol, or other organic solvents. When the amine of general formula (B) is soluble in an organic solvent, the amine is dissolved in the solvent in advance and brought into contact with a slurry of the copper salt represented by general formula (A). can do. The amine complex organic copper thus produced is obtained by filtration and separation. Copper salts represented by general formula (A) include 4-hydroxybenzoic acid, 3-hydroxybenzene, 4-hydroxy-3-methoxybenzoic acid, 3.5 - It is not limited to simple copper salts such as dihydroxybenzoic acid and 1,6-dihydroxybenzene, but the purpose can be achieved if these are included as main components, and other There is no problem in replacing some of the polybasic acids with these dibasic acids, or in combination with some other monofunctional acids such as benzoic acid, salicylic acid, halogenobenzoic acid, halogenosalicylic acid, etc. It can also be made into copper salts such as As an example, a small amount of tricarboxylic acid may be added to the copper salt as described above, which acts as a crosslinking agent during the formation of a polymer, and can be a useful embodiment of the present invention. Further, a part of the copper salt bond may partially contain a metal part of another type. For example, manganese, nickel, iron, etc. are also preferred. Examples will be described below. Example 1 A slurry of the copper salt of 4-hydroxybenzoic acid was prepared by adding 20 g of the copper salt of 4-hydroxybenzoic acid ground in a mortar and 100 ml of water to a 300 ml flask and stirring at room temperature. Next, 3 g of 2-aminobutane was gradually added dropwise with stirring. After the dropwise addition, the mixture was stirred for 1 hour, and after stopping stirring, the mixture was left at room temperature overnight. The crystals were filtered by suction, washed several times with water, and then dried under reduced pressure. This was then subjected to fine pulverization and reduced to less than 325 mesh. 20 g of copper salt of 4-hydroxy-3-methoxybenzoic acid and 5 g of polyethyleneimine were treated in the same manner. Example 2 20 g of copper salt of 4-hydroxybenzoic acid finely ground in a mortar and 100 g of methanol were placed in a 300 ml flask.
ml to suspend the copper salt of 4-hydroxybenzoic acid while stirring. Next, a solution of 4 g of dodecylamine dissolved in 50 ml of methanol was gradually added dropwise at room temperature with stirring. Stirring was continued for 2 hours after the addition, and then stirring was stopped and the mixture was allowed to stand overnight. The crystals were filtered by suction, washed several times with methanol, and then dried under reduced pressure (50-60°C/5-10 mmHg). Then, it is pulverized, and
325 metsushiyu or less. Example 3 In a 300 ml flask, pulverized 4-
20g copper salt of hydroxy-3-methoxybenzoic acid
Then, 100 ml of cyclohexane was added and the mixture was stirred and suspended. A solution containing 5 g of dodecylamine in 50 ml of cyclohexane was added dropwise to this, and the mixture was stirred at room temperature for 1 hour. After stopping stirring, the mixture was left at room temperature overnight. The crystals were filtered by suction, washed several times with cyclohexane, and then dried under reduced pressure (50-60°C/5-10 mmHg). This was then subjected to fine grinding and reduced to less than 325 mesh. 20g of copper salt of 4-hydroxybenzoic acid and N・N
-4 g of dibutylaminoethanol, 20 g of copper salt of 4-hydroxybenzoic acid, and 3 diarylamine
g, 20 g of copper salt of 4-hydroxybenzoic acid,
3 g of N.N-dimethyldodecylamine, 20 g of copper salt of 4-hydroxy-3-methoxybenzoic acid and 4 g of dicyclohexylamine, 4-hydroxy-
20 g of copper salt of 3-methoxybenzoic acid, 5 g of diethanolamine, 20 g of copper salt of 4-hydroxy-3-methoxybenzoic acid, 5 g of dibenzylamine, 4
-Copper salt of hydroxy-3-methoxybenzoic acid 20
g and 4 g of 1,12-diaminododecane, 20 g of copper salt of 4-hydroxy-3-methoxybenzoic acid, 6 g of dodecylamine and 4 g of benzylamine, 20 g of copper salt of 3-hydroxybenzoic acid and 5 g of dodecylamine, 2-hydroxy- 20 g of copper salt of 3,5-dichlorobenzoic acid, 3 g of dodecylamine, 20 g of copper salt of 4-hydroxy-3,5-dimethoxybenzoic acid
g and 6 g of dodecylamine, 4-hydroxy-3
-20 g of copper salt of carboxybenzoic acid and 3 g of dodecylamine, 20 g of 1,3-dihydroxy-4,6-dichlorobenzene and 2 g of dodecylamine, 3.5
-20 g of copper salt of dihydroxybenzoic acid and 3 g of dodecylamine, 20 g of copper salt of 1,4-dihydroxybenzene and 4 g of dodecylamine, 20 g of copper salt of 1,3-dihydroxybenzene and 2 g of dodecylamine
g, 20 g of copper salt of 2,4-dihydroxybenzoic acid
1 g of dodecylamine, 20 g of copper salt of 2,6-dihydroxytoluene, and 4 g of dodecylamine were treated in the same manner. Example 4 4-hydroxybenzoic acid to terephthalic acid (weight ratio 1:
20g of copper salt prepared by double decomposition of the alkaline aqueous solution of 1) with an aqueous copper sulfate solution, and 100g of n-hexane.
ml and stirred and suspended. Next, dodecylamine 3
50 ml of n-hexane solution containing g was gradually added dropwise with stirring. After stirring for 1 hour, it was left at room temperature overnight. The crystals were filtered by suction, washed several times with n-hexane, dried under reduced pressure, and then pulverized to a size of 325 mesh or less. 4-Hydroxybenzoic acid benzene-1, 2,
4-tricarboxylic acid to benzoic acid (weight ratio 10:10:
20 g of the copper salt of 1) and 3 g of dodecylamine were treated in the same manner. The products shown in the above examples are as shown in the table below.
【表】【table】
【表】【table】
【表】
本発明化合物の赤外線吸収スペクトルの試験結
果について述べると、４−ヒドロオキシ安息香酸
の銅塩・ドデシルアミン複合物は第１図の赤外線
吸収スペクトルを与え、2860、2800cm-1にドデシ
ルアミン部によるアルキル基の特性吸収及び
1605、1545、1410cm-1に４−ヒドロオキシ安息香
酸部によるカルボキシレート基の特性吸収を示
す。
以下第２図から第２４図まではそれぞれの複合
物に対応する赤外線吸収スペクトルを示す。[Table] Regarding the test results of the infrared absorption spectrum of the compound of the present invention, the copper salt of 4-hydroxybenzoic acid/dodecylamine complex gave the infrared absorption spectrum shown in Figure 1, with dodecylamine moiety at 2860 and 2800 cm -1 . Characteristic absorption of alkyl groups by
Characteristic absorptions of carboxylate groups by 4-hydroxybenzoic acid moieties are shown at 1605, 1545, and 1410 cm -1 . Below, FIGS. 2 to 24 show infrared absorption spectra corresponding to each composite.
第１図から第２４図は実施例に於いて得られた
アミン複合有機銅の赤外線吸収スペクトルを示
す。
1 to 24 show infrared absorption spectra of amine composite organic copper obtained in Examples.
Claims (1)
またはハロゲン原子を示し、ｌは１〜３の整数、
ｍは0.1または２およびｎは１または２を示す。〕 にて示されるヒドロキシ化合物の銅塩と、ドデシ
ルアミン、ジブチルアミノエタノール、ジアリー
ルアミン、アミノブタン、ジメチルドデシルアミ
ン、ポリエチレンイミン、ジシクロヘキシルアミ
ン、ジベンジルアミン及びジアミノドデカンの群
から選ばれるアミンを水性媒質または上記アミン
に可溶性のある有機溶媒中で、０〜50℃の範囲の
温度で反応せしめることを特徴とするアミン複合
有機銅塩の製造法。[Claims] 1. General formula [However, X represents hydrogen, an alkyl group, an alkoxyl group, or a halogen atom, l is an integer of 1 to 3,
m represents 0.1 or 2 and n represents 1 or 2. ] A copper salt of a hydroxy compound shown in and an amine selected from the group of dodecylamine, dibutylaminoethanol, diarylamine, aminobutane, dimethyldodecylamine, polyethyleneimine, dicyclohexylamine, dibenzylamine and diaminododecane in an aqueous medium or A method for producing an amine complex organic copper salt, which comprises reacting the above amine in an organic solvent that is soluble at a temperature in the range of 0 to 50°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1164976A JPS5295642A (en) | 1976-02-05 | 1976-02-05 | Process for preparing amineeconjugated organic copper salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1164976A JPS5295642A (en) | 1976-02-05 | 1976-02-05 | Process for preparing amineeconjugated organic copper salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5295642A JPS5295642A (en) | 1977-08-11 |
| JPS6114154B2 true JPS6114154B2 (en) | 1986-04-17 |
Family
ID=11783789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1164976A Granted JPS5295642A (en) | 1976-02-05 | 1976-02-05 | Process for preparing amineeconjugated organic copper salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5295642A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0447010Y2 (en) * | 1986-03-24 | 1992-11-06 |
-
1976
- 1976-02-05 JP JP1164976A patent/JPS5295642A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0447010Y2 (en) * | 1986-03-24 | 1992-11-06 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5295642A (en) | 1977-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3293176A (en) | Method of chelating with an ethergroup-containing sequestering agent | |
| IL207721A (en) | Semiconductor nanoparticle capping agents | |
| Murphy et al. | Syntheses of iron (III) aroyl hydrazones containing pyridoxal and salicylaldehyde. The crystal and molecular structure of two iron (III)-pyridoxal isonicotinoyl hydrazone complexes | |
| SU680651A3 (en) | Method of obtaining derivatives of n-phosphonomethylglycine | |
| JP2002524548A (en) | Method for producing carboxylic acid | |
| JPS6114154B2 (en) | ||
| Balaban et al. | Synthesis and spectral data of some new N-nitroso-N-phenylhydroxylamine (cupferron) derivatives | |
| Singh et al. | Chemical and spectroscopic studies in metal β-diketonates. II. Nitration of metal β-diketonates | |
| US4116991A (en) | Hydroxy-containing agents for chelating metal ions and a process for preparing same | |
| US3114755A (en) | Process for preparing bis-(monosubstitutedamino)-benzoquinones and monosubstitutedamino-naphthoquinones | |
| JP3572009B2 (en) | Solid organometallic compounds with small molecule trapping ability | |
| Black et al. | Metal template reactions. XIX. Macrocyclic metal complexes derived from 2, 2'-iminobisbenzaldehyde and some primary diamines with additional nitrogen donor atoms | |
| PT1325939E (en) | Process for preparing co-gels having polyazacycloalkane moieties and their use | |
| JPS5934717B2 (en) | Amin Fukugou Yuuki Sandunoseizouhouhou | |
| JPH03504134A (en) | Multi-nitrogen-containing compounds and their metal complexes that can be used to fix oxygen | |
| Prakash et al. | Ru Nanoparticle Intercalated Montmorillonite Clay Catalytic System for the Reduction of Aliphatic/Aromatic Nitro Compounds | |
| JP4796235B2 (en) | Binaphthol derivative metal salt and process for producing the same | |
| Mustyatsa et al. | Compounds of Undecahydrodecaborate Anion B10H11– | |
| TW200920696A (en) | Methods of exchanging anions of tetraalkylammonium salts | |
| SU470521A1 (en) | The method of obtaining water-soluble chelating agents | |
| JPS58179300A (en) | Fluorine-containing sulfobetain type amphoteric surfactant | |
| JP2000327628A (en) | Porous complex, its production and adsorbent | |
| AT254200B (en) | Process for the preparation of disubstituted piperazine compounds | |
| JPS595198A (en) | Agent for optical resolution and optical resolution therewith | |
| KR101922520B1 (en) | Novel absorbent and catalyst for CO2 capture and conversion |