CN1192013C - 松香胺防污剂 - Google Patents
松香胺防污剂 Download PDFInfo
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- CN1192013C CN1192013C CNB008051399A CN00805139A CN1192013C CN 1192013 C CN1192013 C CN 1192013C CN B008051399 A CNB008051399 A CN B008051399A CN 00805139 A CN00805139 A CN 00805139A CN 1192013 C CN1192013 C CN 1192013C
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- alkyl
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- 239000002519 antifouling agent Substances 0.000 title claims abstract description 10
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- 150000002576 ketones Chemical class 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 239000003750 molluscacide Substances 0.000 description 1
- 230000002013 molluscicidal effect Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- RJMUSRYZPJIFPJ-UHFFFAOYSA-N niclosamide Chemical compound OC1=CC=C(Cl)C=C1C(=O)NC1=CC=C([N+]([O-])=O)C=C1Cl RJMUSRYZPJIFPJ-UHFFFAOYSA-N 0.000 description 1
- 229960001920 niclosamide Drugs 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
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- 150000003457 sulfones Chemical class 0.000 description 1
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- 239000004308 thiabendazole Substances 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
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- BAKXBZPQTXCKRR-UHFFFAOYSA-N thiodicarb Chemical compound CSC(C)=NOC(=O)NSNC(=O)ON=C(C)SC BAKXBZPQTXCKRR-UHFFFAOYSA-N 0.000 description 1
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- 231100000167 toxic agent Toxicity 0.000 description 1
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- WVZPYZMQQDNINJ-UHFFFAOYSA-N tributyl(butylstannyloxy)stannane Chemical compound CCCC[SnH](CCCC)O[SnH](CCCC)CCCC WVZPYZMQQDNINJ-UHFFFAOYSA-N 0.000 description 1
- YDUBPEZBWPRJJL-UHFFFAOYSA-M tributyl-(4-chloro-2-phenylphenoxy)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)OC1=CC=C(Cl)C=C1C1=CC=CC=C1 YDUBPEZBWPRJJL-UHFFFAOYSA-M 0.000 description 1
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 1
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- AMHNZOICSMBGDH-UHFFFAOYSA-L zineb Chemical compound [Zn+2].[S-]C(=S)NCCNC([S-])=S AMHNZOICSMBGDH-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/16—Isothiocyanates
- C07C331/18—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms
- C07C331/22—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
- C07C331/24—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms of an unsaturated carbon skeleton the carbon skeleton containing six-membered aromatic rings
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/46—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=C=S groups
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
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- C07C265/06—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
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- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
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Abstract
本发明涉及防止水生物粘附于长时间浸没在水中的物质表面的新化合物和已知化合物和方法。更具体地说，本发明涉及应用新的异腈、甲酰胺、异氰酸酯和异硫氰酸酯防污剂来保护浸没物的表面。
Description
发明领域
本发明涉及防止水生物粘附于长时间浸没在水中的物质表面的新化合物和已知化合物和方法。更具体地说，本发明涉及应用新的异腈、甲酰胺、异氰酸酯和异硫氰酸酯防污剂来保护浸没物的表面。
发明背景
污染性生物在水下结构表面反复生长对海水或淡水作业来说是一个危险并花费昂贵的问题，其中所述水下结构包括船舶、码头、桥基、桩结构、鱼网、热交换器、水坝、管道结构、进料滤网和冷却塔等。如藤壶、斑马壳菜类(zebra mussels)、藻类、硅藻、水螅虫、苔藓虫类生物、海鞘类、管虫和亚洲蛤等污染性生物的存在能够以多种方式引起经济损失：例如，其粘附于船体时降低燃料效能并由于需要清洁船体而造成营利性航行时间的损失。类似地，这些机体粘附于冷却水设备将降低传热性，从而最后降低或阻滞设备的冷却功率，同时也提高了成本。
已经有许多种用于控制淡水或海水中污染性生物的试剂被用来防止这些生物的粘附和过度生长。控制污染性生物存在或粘附的常规方法为：用一种含有毒性化合物例如三正丁基锡或铜化合物的混合物的组合物涂覆或渗透该水下结构。涂料形式的抗污染试剂可以含有高达60％重量的活性成分，其可以用于涂覆表面例如船壳。所述涂料能够通过在水下持续释放抗污染试剂而防止污染性生物的生长和粘附。许多现有的防污剂存在的缺点在于：它们持续存留于环境中，常常具有急性毒性，在水性环境中降解慢，因此对生态环境有害。有害的防污剂最终会形成生物聚集，进入到食物链，因此对海洋生物和人构成威胁。
例如，已经被公认：广泛用作防污剂的重金属化合物特别是有机锡化合物会在贝壳类生物中聚集。
本发明的目的是提供一种对生态环境无害的用于抵抗或控制海水和淡水污染性生物的方法。
本发明另一目的是提供一种保护水中结构物免受海水或淡水污染性生物污染的有效方法。
本发明还有一个目的是提供抗污染组合物，其含有作为活性剂的某些松香化合物衍生物。
发明概述
本发明提供防止海水或淡水污染性生物居留于物质表面的新化合物和已知化合物及方法，该方法包括：使防污有效量的至少一种式I1-I13化合物接触所述生物或其所处位置。
式I1-I13
其中，
R1代表NR2R3，其中
R2代表氢原子、C1-C8烷基，和
R3代表C＝OR4，其中
R4代表氢原子或基团OR5或NHR5之一，其中
R5为C1-C8烷基或芳基，各自任选地被卤素取代；或
R1代表N＝CR6R7，其中
R6代表氢原子、C1-C6烷基或芳基，和
R7代表C1-C6烷基或芳基，各自任选地被卤素取代；或
R1代表异腈、异氰酸酯、异硫氰酸酯或胍基基团；和
n代表0或1。
在本申请说明书和权利要求书中，所述术语定义如下：
卤素指Cl，Br，I或F；
烷基指具有1-8个碳原子、优选1-4个碳原子的直链或支链烷基；芳基指芳族单环或多环烃基，其优选的例子如：萘基、蒽基、菲基，特别优选苯基。
定义如下的式I1-I13化合物是优选的化合物，其中
R1代表NR2R3，其中
R2代表氢原子或C1-C4烷基，和
R3代表C＝OR4，其中
R4代表氢原子或基团OR5或NHR5之一，其中
R5为C1-C4烷基或芳基，各自任选地被卤素取代；或
R1代表N＝CR6R7，其中
R6代表氢原子、甲基或任选被卤素取代的芳基，和
R7代表C1-C4烷基或任选被卤素取代的芳基；或
R1代表异腈、异氰酸酯、异硫氰酸酯或胍基。
特别优选的化合物是定义如下的式I1-式I3化合物，其中：
R1代表NR2R3，其中
R2代表氢原子，和
R3代表C＝OR4，其中
R4代表氢原子。
特别优选的化合物还可以是定义如下的式I1-式I3化合物，其中
R1代表NR2R3，其中
R2代表氢原子，和
R3代表C＝OR4，其中
R4代表OR5或NHR5，其中
R5代表甲基、乙基、正或异丙基或正，仲，异或叔丁基、或任选被卤素取代的苯基。
特别优选的化合物还可以是定义如下的式I1-式I3化合物，其中
R1代表N＝CR6R7，其中
R6代表甲基、乙基、正或异丙基、正，仲，异或叔丁基、或优选氢原子，或和
R7代表甲基、乙基、正或异丙基、正，仲，异或叔丁基、或苯基。
特别优选的化合物还可以是定义如下的式I1-式I3化合物，其中
R1代表异腈、异氰酸酯、异硫氰酸酯或胍基。
优选的化合物是n代表1的化合物。
优选的化合物是式I8化合物。
上述化合物可以按照应用于松香部分的有机化学标准方法制备得到。由妥尔油、树胶或木材得到的起始原料松香类物质可以经市售得到；例如松香胺以Hercules Amine D得到。Gang-Fung Chen在Progress in Organic Coatings 20，1992，139-167中对松香酸的不同异构体及其制备方法作了综述。下列内容概述了不同松香胺衍生物的一般合成方案。为了简化，以n＝1的子结构I8概述此合成路线。这些反应程序容易应用于其它纯异构体和松香氧化/还原产物，也容易应用于这些化合物的混合物。
方案1
在惰性溶剂中，应用碱作为HCl受体，用氯甲酸酯酰化松香胺，可以制备得到式I8化合物(参见：Houben-Weyl第8卷，1952年，第137-140页；ibid.，Vol 11/2，1958年，第27-37页)。
方案2
在惰性溶剂(苯、甲苯和烃类等)中，松香胺与异氰酸酯反应合成得到式III的脲类；参见：Houben Weyl，Vol.E4，1983，352-357，或者松香异氰酸酯(见下面)和脂族胺或芳族胺反应也可以得到所述产物。
方案3
通过松香胺和醛或酮的缩合反应得到松香胺席夫碱(Houben-Weyl，卷11/2，1958年，74-85)。
松香异氰化物的合成已经被公开于现有技术中(T.Ohsawa等，四面体通讯(Tetrahedron，Lett.，)1989年，第845-846页)。
松香异硫氰酸酯(CAS-Nr.：115 269-93-7)可以从松香胺与硫光气(参见光气的类似系列：Ozaki，Chem Rev.72，457-460)或者与硫光气取代物即硫代羰基-二咪唑反应得到(参见实施例3)。
松香异氰酸酯的制备已经记载于现有技术中(E.Corey等，四面体通讯(Tetrahedron Lett.)1981，299-302)。
对于n＝0的式I混合物，所需的起始原料Dehydroabietan-1-基-胺可以按照Stockel等，加拿大化学杂志。1963，834-846的方法得到。
Dehydroabietan-1-基异氰酸酯的合成记载于Chem.Pharm.Bull.1985，1472-1487中。
可以按照类似于记载松香胺的方法合成所有其它衍生物(式I，n＝0)。
优选实施方案的详细描述
可以通过本发明方法对抗或控制的污染性生物可以是粘附于那些浸入水中或与水持续接触的结构的内外表面的任何海水或淡水生物。举例性生物包括：
藻类，包括phyla Chlorophyta、Pharophyta和Rhodophyta类的成员；
被囊动物，包括海鞘纲生物成员例如Cionaintestinalis、Diplosoma listerianium和Botryllus sclosseri，和水螅纲生物成员例如Clava squamata、贝螅属echinata、薮枝息属Geniculata和Tubularia larynx；
双壳类动物包括壳菜紫贻贝、Cassostrea virginica、可食牡蛎属、牡蛎属chilensia、Lasaea rubra，以及饰贝科(或斑马壳菜)和Corbuculidae科(或Asiatic clams)的成员，苔藓虫类包括Electrapilosa、帐苔虫属reticulatum、苔藓虫属neritina和Bowerbankiagracilis；
多毛纲虫类包括Hydroides norvegica、Pomatocerostriqueter、Mercierella enigmata和螺旋虫属spp.；
海绵门动物和蔓足亚纲(腾壶类)生物例如腾壶属amphitrite、茗荷属anatifera、腾壶属Balanus、腾壶属balanoides、腾壶属hameri、腾壶属creatus、腾壶属improvisus、腾壶属galeatus、腾壶属eburneus、扁腾壶属modestus、腾壶属tulipiformis和腾壶属perforatus。
腾壶属生物是水中结构的频繁的污染性生物。本发明所特别涉及的污染性生物包括：藤壶、斑马壳菜类、藻类、硅藻、水螅虫、苔藓虫类生物、海鞘类、管虫和亚洲蛤，另外还有粘细菌(bacterialslime)。
可用本发明方法保护的水中结构可以是任何浸入或部分浸入的、移动的或固定的结构，例如鱼网、舟、船、桩结构、冷却塔、管道、竖管、热交换器、水坝或进料滤网等。
在实际的应用中，可通过下列途径把式I1-I13化合物与污染性生物接触：
·用防污有效量的所述松香胺衍生物对所要保护的水中结构进行涂覆，这样防污化合物从要保护的表面区域立即释放至水环境中，
·把防污有效量的松香胺衍生物加入到形成水中结构的材料中，水中结构再释放出所述化合物，
·把防污有效量的所述化合物直接释放于包围所要保护结构的水环境中，
·或者任何使松香胺接触污染性生物的其它方法。
在本发明方法中，松香胺衍生物的用量也可以变化，其所依据的因素为：所用的具体化合物、所需控制的污染性生物的类型、周围水环境的污染压力程度、水温和接触方式等。
这些松香胺衍生物可以作为单个活性化合物应用，也可以与防污领域中常用的活性化合物联合应用。其中所述常用的化合物优选为重金属例如铜，或重金属化合物例如双(三烷基锡)硫化物、三正丁基月桂酸盐、三正丁基氯化物、氧化铜(I)、氯化三乙基锡、三正丁基(2-苯基-4-氯苯氧基)锡、氧化三丁基锡、二硫化钼、氧化锑、聚钛酸丁酯、苯基-(双吡啶)-氯化铋、三正丁基锡氟化物、亚乙基双二硫代氨基甲酸锰、二甲基二硫代氨基甲酸锌、亚乙基双二硫代氨基甲酸锌、2-吡啶硫醇-1-氧化物的锌盐或铜盐、亚乙基双二硫代氨基甲酸双二甲基二硫代氨基甲酰基锌、氧化锌、亚乙基-双-二硫代氨基甲酸酮(I)、硫氰酸铜、环烷酸铜和三丁基锡卤化物。
通过把这些活性化合物组合，松香胺衍生物的作用范围可以进一步增大或者可以达到特殊的效果。在许多情况中具有协同作用。如果活性化合物以某种重量比组合，则协同作用本身明显增加。然而，在活性化合物的组合中，活性化合物的重量比可以在相对宽的范围内变化。
松香胺衍生物的优选组合伴侣为：杀藻剂例如敌草隆、二氯芬、环草索、薯瘟锡或quinoclamine；杀软体动物剂例如薯瘟锡、聚乙醛、灭虫威、氯硝柳胺、硫双卡和trimethacarb；杀真菌剂例如抑菌灵、tolylfluanid、戊酸碘炔丙基酯、fluorfolpet和吡咯类化合物例如propiconazole、metonazole、cyproconazole、tebuconazole；还有常规的防污活性化合物例如2-(N，N-二甲硫基-氨基甲酰基硫基)-5-硝基噻唑基、四丁基二锡氧烷、2-叔丁氨基-4-环丙基氨基-6-甲硫基-1，3，5-三唑、4，5-二氯-2-正辛基-4-异噻唑啉-3-酮、2，4，5，6-四氯间苯二腈、二硫化四甲基秋兰姆、2，4，6-三氯-苯基马来酰亚胺、2，3，5，6-四氯-4-(甲基磺酰基)吡啶、二碘甲基-paratryl砜、噻苯达唑、四苯硼酸吡啶盐以及2-吡啶硫醇-1-氧化物的铜盐和钠盐。
优选地，所述防污组合物含有0.5-60％重量、更优选1-25％重量的松香胺衍生物。
本发明的组合物含有可用于水的惰性载体和防污有效量的式I松香胺衍生物。当用于结构表面时，优选的本发明组合物含有成膜组份例如树脂聚合物溶液。举例性的聚合物树脂包括不饱和的聚酯树脂，其由下列物质形成：a)不饱和酸或酸酐例如马来酸酐、富马酸和亚甲基丁二酸等；(b)饱和酸或酸酐例如邻苯二甲酸酐、间苯二甲酸酐、对苯二甲酸酐、四氢邻苯二甲酸酐、四卤邻苯二甲酸酸酐、己二酸和subacic酸等；(c)二元醇，例如乙二醇等；(d)乙烯基单体例如苯乙烯、乙烯基甲苯、氯苯乙烯、溴苯乙烯、丙烯酸酯类例如甲基丙烯酸甲酯、二-甲基丙烯酸乙二醇酯等。其它合适的树脂包括基于乙烯基酯、乙酸乙烯基酯和乙烯基氯的树脂、弹性体成分、硫化橡胶、松香、树脂酸金属盐和基于尿烷的树脂。
对防污剂中常用组份的进一步描述参见Ungerer，Chem.Ind.1985，37，730-732和Williams，
Antifouling Marine Coatings，Noyes， Park Ridge，1973。
实施例1
N-甲酰基松香胺(1)
起始原料松香胺(Hercules Amine D)是从改性松香得到的伯胺混合物。其被描述为脱氢枞胺技术级别，在下列合成中不需再进行纯化而直接应用该物质。
在室温和持续搅拌下，把5摩尔甲酸乙酯加入到松香胺的乙酸乙酯溶液中。室温下反应16小时后，蒸干溶剂，残余物经硅胶短柱过滤，得到致密树脂形式的N-甲酰基松香胺(产率：86％)。
表征：visqueous油；1H-NMR，δ(ppm)：7.94-8.23(1H)；7.15(1H)；6.99(1H)；6.89(1H)；5.46(1H)；2.76-3.27(5H)；1.22(6H)；1.21(3H)；0.95(3H)。
实施例2
松香异氰化物(2)
在0℃和干燥的氮气保护下，在搅拌下，依次把二异丙基胺(2.7摩尔)和三氯氧化磷(1.1摩尔)滴入到N-甲酰基松香胺的二氯甲烷溶液中。在0℃下反应1小时后，加入20％的碳酸钠溶液，让反应混合物达到室温反应1小时。加入20％的碳酸钠和水，用二氯甲烷提取水相，然后用硅胶柱过滤残余物，得到无色油状的松香异氰化物(产率：85％)。
表征：visqueous油；1H-NMR，δ(ppm)：7.16(1H)；7.00(1H)；6.88(1H)；2.76-3.34(5H)；1.22(6H)；1.21(3H)；0.98(3H)。
实施例3
松香异硫氰酸酯(3)
在0℃和干燥的氮气保护下，在搅拌下，把硫代羰基二咪唑(1.5摩尔)的二氯甲烷溶液加入到松香胺的二氯甲烷溶液中。完全加入后，使反应混合物在45℃下反应16小时。蒸发溶剂，然后用硅胶柱过滤固定残余物，得到油状的松香异硫氰酸酯(产率：87％)。
表征：visqueous油；1H-NMR，δ(ppm)：7.16(1H)；6.99(1H)；6.89(1H)；3.37(2H)；2.90(2H)；2.82(1H)；1.22(6H)；1.21(3H)；0.96(3H)。
测试化合物的海水防污活性评价
确定实验室饲养的腾壶属Balanus amphitrite介虫幼虫的居留率用于测试候选防污化合物的活性。
居留分析
以四组重复样品在无菌聚苯乙烯多孔培养板中进行测试。在含有2ml测试溶液(参见下面)、溶剂对照物或阳性对照物(二氯正辛基异噻唑啉酮)的盘中注射25-40个介虫幼虫。
把所述盘在27±2℃的温度下培养24小时。然后筛选介虫用于毒性信号。把幼虫分成三类：A)活的并且有活力的；B)活的但无活力的；C)死的。通过滴入20％甲醛终止测试，计算出居留的和未居留的介虫数目。
居留情况评价如下：1)不居留的：即不粘附的自由游泳的介虫；2)居留的介虫；粘附但不变质的介虫；3)腾壶：粘附的不成熟腾壶。
第2类和第3类被认为属于居留的范围。把测试溶液中的居留百分比与对照组比较。应用Spearman-Krber方法计算50小时后中效浓度(EC-50)值。
所有应用的海水为天然来源海水，将其通过0.2微米网。通过把一定量测试物质溶解于合适溶剂中制备测试化合物原液，然后加入海水。
所用原液用于制备不同稀释浓度的海水溶液。对照物由海水制成，如果合适，可以由海水和溶剂的混合物制成。对照物的溶剂浓度等同于测试溶液的最高浓度。作为内标(阳性对照)，在每个测试中包括0-5ppm浓度的二氯正辛基异噻唑啉酮。
测试结果
化合物 停留抑制的EC50(单位：ppm)
1 2.6
2 0.12
参考值* 0.37
*≡4，5-二氯-正辛基异噻唑啉酮
Claims (8)
1.式I化合物
其中：
R1代表NR2R3，其中
R2代表氢原子、C1-C8烷基，和
R3代表C＝OR4，其中
R4代表氢原子或基团OR5或NHR5之一，其中
R5为C1-C8烷基，各自未被取代或被卤素取代；或
R1代表异腈、异氰酸酯、异硫氰酸酯或胍基基团；和
n代表0或1，
以下化合物除外
2.权利要求1的式I化合物，其中：
R1代表NR2R3，其中
R2代表氢原子或C1-C4烷基，和
R3代表C＝OR4，其中
R4代表氢原子或基团OR5或NHR5之一，其中
R5为C1-C4烷基，各自来被取代或被卤素取代；或
R1代表异腈、异氰酸酯、异硫氰酸酯或胍基部分。
3.权利要求1的式I化合物，其中：
R1代表NR2R3，其中
R2代表氢原子，和
R3代表C＝OR4，其中
R4代表氢原子。
4.控制或抵抗海水或淡水污染性生物的方法，其包括：使所述生物或其所在部位接触防污有效量的一种或多种的式I化合物
其中：
R1代表NR2R3，其中
R2代表氢原子、C1-C8烷基，和
R3代表C＝OR4，其中
R4代表氢原子或基团OR5或NHR5之一，
其中
R5为C1-C8烷基，各自未被取代或被卤素取代；或
R1代表异腈、异氰酸酯、异硫氰酸酯或胍基基团；和
n代表0或1。
5.含有防污有效量的一种或多种权利要求4所定义的式I化合物和可在水中应用的惰性载体的试剂。
6.将式I化合物
其中：
R1代表NR2R3，其中
R2代表氢原子、C1-C8烷基，和
R3代表C＝OR4，其中
R4代表氢原子或基团OR5或NHR5之一，
其中
R5为C1-C8烷基，各自未被取代或被卤素取代；或
R1代表异腈、异氰酸酯、异硫氰酸酯或胍基基团；和
n代表0或1，
用于控制和对抗海水和/或淡水污染性生物的用途。
7.含有防污有效量的一种或多种式I化合物
其中：
R1代表NR2R3，其中
R2代表氢原子、C1-C8烷基，和
R3代表C＝OR4，其中
R4代表氢原子或基团OR5或NHR5之一，
其中
R5为C1-C8烷基，各自未被取代或被卤素取代；或
R1代表异腈、异氰酸酯、异硫氰酸酯或胍基基团；和
n代表0或1，
和可在水中应用的惰性载体的试剂用于控制和对抗海水和/或淡水污染性生物的用途。
8.制备防污剂的方法，其特征在于：把权利要求4所定义的式I化合物与可在水中应用的惰性载体混合。
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| US5116407A (en) * | 1988-10-13 | 1992-05-26 | Courtaulds Coatings Limited | Antifouling coatings |
| US5236493A (en) * | 1988-10-13 | 1993-08-17 | Courtaulds Coatings (Holdings) Limited | Antifouling coating |
| GB9008053D0 (en) * | 1990-04-10 | 1990-06-06 | Courtaulds Coatings Ltd | Coating compositions |
| US5134184A (en) * | 1990-08-27 | 1992-07-28 | The Goodyear Tire & Rubber Company | Rosin monomaleimides |
| KR19990081985A (ko) * | 1996-01-26 | 1999-11-15 | 가마쿠라 아키오 | 트리페닐보란-로진 아민 부가 화합물 및 이의 용도 |
-
1999
- 1999-03-16 EP EP99105349A patent/EP1036786A1/en not_active Withdrawn
-
2000
- 2000-03-10 US US09/936,124 patent/US6972111B1/en not_active Expired - Fee Related
- 2000-03-10 CN CNB008051399A patent/CN1192013C/zh not_active Expired - Fee Related
- 2000-03-10 JP JP2000605548A patent/JP2002539184A/ja active Pending
- 2000-03-10 AU AU32881/00A patent/AU771014B2/en not_active Ceased
- 2000-03-10 WO PCT/EP2000/002118 patent/WO2000055117A1/en not_active Application Discontinuation
- 2000-03-10 KR KR1020017011754A patent/KR20020003549A/ko not_active Application Discontinuation
- 2000-03-10 MX MXPA01009319A patent/MXPA01009319A/es not_active Application Discontinuation
- 2000-03-10 DK DK00910806T patent/DK1163210T3/da active
- 2000-03-10 NZ NZ514174A patent/NZ514174A/en unknown
- 2000-03-10 PT PT00910806T patent/PT1163210E/pt unknown
- 2000-03-10 DE DE60008078T patent/DE60008078T2/de not_active Expired - Fee Related
- 2000-03-10 AT AT00910806T patent/ATE258915T1/de not_active IP Right Cessation
- 2000-03-10 CA CA002367343A patent/CA2367343A1/en not_active Abandoned
- 2000-03-10 ES ES00910806T patent/ES2215617T3/es not_active Expired - Lifetime
- 2000-03-10 EP EP00910806A patent/EP1163210B1/en not_active Expired - Lifetime
-
2001
- 2001-08-21 ZA ZA200106885A patent/ZA200106885B/xx unknown
-
2002
- 2002-09-27 HK HK02107162.5A patent/HK1045499B/zh not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP1163210B1 (en) | 2004-02-04 |
| ATE258915T1 (de) | 2004-02-15 |
| DK1163210T3 (da) | 2004-06-07 |
| HK1045499B (zh) | 2005-08-19 |
| KR20020003549A (ko) | 2002-01-12 |
| EP1163210A1 (en) | 2001-12-19 |
| DE60008078T2 (de) | 2004-09-23 |
| AU771014B2 (en) | 2004-03-11 |
| EP1036786A1 (en) | 2000-09-20 |
| PT1163210E (pt) | 2004-05-31 |
| DE60008078D1 (de) | 2004-03-11 |
| JP2002539184A (ja) | 2002-11-19 |
| AU3288100A (en) | 2000-10-04 |
| MXPA01009319A (es) | 2004-04-23 |
| ES2215617T3 (es) | 2004-10-16 |
| HK1045499A1 (en) | 2002-11-29 |
| WO2000055117A1 (en) | 2000-09-21 |
| US6972111B1 (en) | 2005-12-06 |
| NZ514174A (en) | 2003-04-29 |
| ZA200106885B (en) | 2002-08-21 |
| CA2367343A1 (en) | 2000-09-21 |
| CN1344246A (zh) | 2002-04-10 |
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