CN104370985A - 一种类辣椒素类化合物及其制备方法和应用 - Google Patents
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Abstract
本发明公开了一种类辣椒素类化合物及其制备方法和应用,所述类辣椒素类化合物分子式为C27H21N2O9F3ClBrR,是以4-溴-2-(4-氯苯基)-5-三氟甲基吡咯-3腈、辣椒素酯和葡糖醛酸为原料,并将原料溶于苯类溶剂中,催化回流反应4~8h,经洗涤、干燥、蒸馏、重结晶得到。该制备方法中原料易得,成本低,收率高。本发明制备的类辣椒素类化合物用作防污剂时能够在海水环境中快速降解,对海洋生物影响小,在生物体内累积少、低毒、防污效果好、使用寿命长。
Description
技术领域
本发明涉及一种类辣椒素类化合物及其制备方法和应用。
背景技术
船舶在海洋行驶中常常遭受海藻、藤壶等海洋生物的表面附着,称为生物污损。生物污损使舰船的自重和航行阻力增加,从而增加燃油消耗,当海洋生物附着在船底时,还会使舰船表面发生一系列复杂的物理化学变化,大大加速船底钢板的腐蚀,降低舰船的使用寿命。据不完全统计,全世界仅生物污损给各种水下工程设施与舰船设备造成的经济损失每年可达数百亿美元。
为了减少污损危害,许多国家都开展了船舶防污技术的研究,并取得了一定的成果。其中,涂装防污涂料是最方便、有效、经济的方法,防污涂料是通过海洋防污剂的可控释放,与海洋污损生物发生作用,从而阻止海洋生物在物体表面附着。自20世纪70年代研制成以有机锡(TBT)为防污剂的防污涂料以来,由于它具有广谱性、防污期效长和成本低等优点,受到全世界造船和航运部门的热烈欢迎,但是到80年代初,法国首先发现该涂料释出的防污剂的毒性衰减期长,这种有毒化合物长期沉积在海泥和累积在生物中,造成严重的环境污染问题,为此引起国际上高度重视。联合国所属国际海事组织为加强海洋环境保护,通过了禁止使用TBT防污涂料的决议。而以氧化亚铜作为防污剂的防污涂料也可能存在严重的环境污染问题。另一种广泛使用的防污剂是除草剂,而研究者们日益关心它可能对水生和海洋植物的影响。各国面对这种严峻形势,纷纷开始进行长效无毒防污剂的开发研究工作。
发明内容
本发明的目的是提供一种类辣椒素类化合物及其制备方法和应用,将具有微生物趋避作用的辣椒素酯和具有杀菌作用的4-溴-2-(4-氯苯基)-5-三氟甲基吡咯-3-腈与葡糖醛酸在催化剂作用下发生接枝反应,生成类辣椒素类化合物,并将其用于制备海洋防污涂料,提高辣椒素酯和4-溴-2-(4-氯苯基)-5-三氟甲基吡咯-3-腈的协同作用,并起到一定的缓释作用,提高其作用时间,从而达到高效防污。
为了达到上述目的,本发明的技术方案如下:
一种类辣椒素类化合物,其分子式为:C27H21N2O9F3ClBrR,结构式如式I所示:
其中,R为7~10个碳原子的直链或支链的烷烃或烯烃,具体结构式如下:
一种类辣椒素类化合物的制备方法,包括如下步骤:以4-溴-2-(4-氯苯基)-5-三氟甲基吡咯-3腈、辣椒素酯和葡糖醛酸为原料,将原料溶于苯类溶剂中,催化回流反应4~8h,经洗涤、干燥、蒸馏除去苯类溶剂得到含目标化合物的粗产品,经环己烷重结晶得到目标化合物。
进一步,所述的4-溴-2-(4-氯苯基)-5-三氟甲基吡咯-3腈、辣椒素酯和葡糖醛酸三种原料反应摩尔比为1:1:2~4。
优选地,所述的苯类溶剂为甲苯、二甲苯、氯苯中的一种。
所述催化回流反应中所用催化剂为苯磺酸、对甲苯磺酸、十二烷基苯磺酸中的一种。
本发明如式I所示的类辣椒素类化合物作为防污剂用于制备海洋防污涂料中的应用。
一种海洋防污涂料,其组分包括30~80wt%树脂溶液、5~20wt%增塑剂、10~20wt%填充料和5~30wt%如式I所示的类辣椒素类化合物。
进一步地,所述的树脂溶液浓度为15~70wt%;树脂溶液中的溶剂为有机溶剂,为乙酸乙酯、乙酸丁酯、二甲苯或甲苯中的一种;树脂溶液中的树脂为丙烯酸树脂、丙烯酸锌树脂或丙烯酸铜树脂中的一种。
另,所述增塑剂为凡士林、松香、氯化石蜡、邻苯二甲酸二丁酯或邻苯二甲酸二辛酯中的一种。
另,所述填充料为氧化铁红、滑石粉、二氧化钛、二氧化硅或氧化锌中的一种。
经检测,本发明所述类辣椒素类化合物的制备方法,收率>71%,纯度>96%,包含本发明所述类辣椒素类化合物的防污涂料最佳作用时间可以达到540天以上,具有良好的防污效果。
本发明制备的类辣椒素类化合物的分子结构结合了辣椒素酯和4-溴-2-(4-氯苯基)-5-三氟甲基吡咯-3-腈,并充分考虑了合成的类辣椒素类化合物在海水环境中分解速度和分解后化合物特性的保留,(分解后的产物含有辣椒素酯和4-溴-2-(4-氯苯基)-5-三氟甲基吡咯-3-腈的有效成分,其中分解得到的辣椒素酯的有效成分可以防止藻类、贝类等海洋生物附着,具有驱避作用,分解得到的4-溴-2-(4-氯苯基)-5-三氟甲基吡咯-3-腈有效成分具有杀菌作用,可以避免海洋微生物在海装设备表面附着繁殖。
将本发明的类辣椒素类化合物应用于制备海洋防涂料。辣椒素酯由于具有一定的刺激性,直接应用于涂料中,提高了喷涂的难度,给操作工人带来一定的危险,同时辣椒素酯和4-溴-2-(4-氯苯基)-5-三氟甲基吡咯-3-腈单独应用于防污涂料中,最佳作用时间均低于360天,而采用本发明的类辣椒素类化合物,最佳作用时间可以达到540天以上。
本发明所述类辣椒素类化合物的制备方法中原料易得,收率>71%,纯度>96%,用作防污剂时,能够在环境中快速降解,对海洋生物影响小,在生物体内累积少、低毒、防污效果好、使用寿命长。
具体实施方式
下面通过具体实施例对本发明做进一步的说明,但实施例并不限制本发明的保护范围。
实施例1
类辣椒素类化合物1a(C35H37N2O9F3ClBr)的合成:
在配有温度计、搅拌器、回流冷凝管装置的500ml三口反应瓶中,加入35.0g(0.1mol)4-溴-2-(4-氯苯基)-5-三氟甲基吡咯-3腈、38.8g(0.2mol)葡糖醛酸、29.4g(0.1mol)辣椒素酯(化合物2a)、250ml甲苯,搅拌溶解后,加入17.2g(0.1mol)对甲苯磺酸,回流反应6小时,用饱和碳酸氢钠溶液洗涤至pH=7~8,静置,分液,100ml蒸馏水洗涤,静置,分液,无水硫酸钠干燥,过滤,蒸馏除去溶剂,得到类辣椒素类化合物1a粗品,将其溶于160ml环己烷中,5℃重结晶,得到59.9g白色固体粉末状类辣椒素类化合物1a,收率为74.9%,纯度96.8%(HPLC)。1a 1HNMR(DMSO/500MHz):7.42(d,1H,Ar-H),7.42(d,1H,Ar-H),7.32(d,1H,Ar-H),7.32(d,1H,Ar-H),6.91(d,1H,Ar-H),6.75(d,1H,Ar-H),6.67(s,1H,Ar-H),5.91(d,1H,CH),5.35(s,3H,CH3),4.54(m,1H,CH),4.07(m,1H,CH),3.79(s,2H,CH2),3.51(m,1H,CH),3.41(d,1H,CH),2.27(t,2H,CH2),1.71(m,2H,CH2),1.36(m,2H,CH2),1.33(m,2H,CH2),1.33(m,2H,CH2),1.33(m,2H,CH2),1.33(m,2H,CH2),0.99(t,3H,CH3)。
实施例2
类辣椒素类化合物1b(C36H37N2O9F3ClBr)的合成:
在配有温度计、搅拌器、回流冷凝管装置的500ml三口反应瓶中,加入35.0g(0.1mol)4-溴-2-(4-氯苯基)-5-三氟甲基吡咯-3腈(化合物3)、77.6g(0.4mol)葡糖醛酸(化合物4)、30.6g(0.1mol)辣椒素酯(化合物2b)、250ml二甲苯,搅拌溶解后,加入15.8g(0.1mol)苯磺酸,回流反应6小时,用饱和碳酸氢钠溶液洗涤至pH=7~8,静置,分液,100ml蒸馏水洗涤,静置,分液,无水硫酸钠干燥,过滤,蒸馏除去溶剂,得到类辣椒素类化合物1b粗品,将其溶于160ml环己烷中,5℃重结晶,得到58.1g白色固体粉末状类辣椒素类化合物1b,收率为71.5%,纯度97.5%(HPLC)。1b 1H NMR(DMSO/500MHz):7.42(d,1H,Ar-H),7.42(d,1H,Ar-H),7.32(d,1H,Ar-H),7.32(d,1H,Ar-H),6.91(d,1H,Ar-H),6.75(d,1H,Ar-H),6.67(s,1H,Ar-H),5.91(d,1H,CH),5.51(m,1H,CH=CH),5.51(m,1H,CH=CH),5.35(s,3H,CH3),4.54(m,1H,CH),4.07(m,1H,CH),3.79(s,2H,CH2),3.51(m,1H,CH),3.41(d,1H,CH),2.53(m,1H,CH),2.27(t,2H,CH2),1.71(m,2H,CH2),1.99(m,2H,CH2),1.36(m,2H,CH2),1.15(d,3H,CH3),1.15(d,3H,CH3)。
实施例3防污性能测试
将80.0g浓度为30%的丙烯酸锌树脂溶液(有机溶剂为二甲苯)、5.0g松香、10.0g二氧化钛、5g类辣椒素类化合物1a混合物在一个含有玻璃珠的油漆振荡器中振荡2.0h,然后用100目的过滤器过滤,制备得到防污涂料A1。
将50.0g浓度为50%的丙烯酸树脂溶液(有机溶剂为甲苯)、10.0g邻苯二甲酸二丁酯、10.0g二氧化硅、30g类辣椒素类化合物1a混合物在一个含有玻璃珠的油漆振荡器中振荡2.0h,然后用100目的过滤器过滤,制备得到防污涂料A2。
将30.0g浓度为80%的丙烯酸树脂溶液(有机溶剂为乙酸丁酯)、20.0g氯化石蜡、20.0g滑石粉、20.0g类辣椒素类化合物1b混合物在一个含有玻璃珠的油漆振荡器中振荡2.0h,然后用100目的过滤器过滤,制备得到防污涂料A3。
参照国家标准《防污漆样板浅海浸泡试验方法》(GB5370-2007)对上述得到的防污涂料进行防污性能测试,将防污涂料涂刷在板长为250mm,宽为150mm,厚为2mm的低碳钢试验样板上,试验样板采用带槽长方形木条两头使用螺栓固定。将该试验样板挂在上海涂料公司厦门测试场地,分别于6、12、和24个月后测定空白样板和涂刷有制得的防污涂料的样板,试验结果表明,制得的防污涂料具有良好的防污效果。结果如下表1所示:
表1
需要说明的是,以上实施例仅用以说明本发明的技术方案而非限制。尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的范围,其均应涵盖在本发明的权利要求范围中。
Claims (10)
1.一种类辣椒素类化合物,其分子式为:C27H21N2O9F3ClBrR,结构式如式I所示:
其中R为7~10个碳原子的直链或支链的烷烃或烯烃,具体结构式如下:
2.一种类辣椒素类化合物的制备方法,包括如下步骤:以4-溴-2-(4-氯苯基)-5-三氟甲基吡咯-3腈、辣椒素酯和葡糖醛酸为原料,并溶于苯类溶剂中,催化回流反应4~8h,经洗涤、干燥、蒸馏除去苯类溶剂得到含目标化合物的粗产品,经环己烷重结晶得到如式I所示的类辣椒素类化合物。
3.如权利要求2所述的制备方法,其特征在于,4-溴-2-(4-氯苯基)-5-三氟甲基吡咯-3腈、辣椒素酯和葡糖醛酸的摩尔比为1:1:2~4。
4.如权利要求2所述的制备方法,其特征在于,所述苯类溶剂为甲苯、二甲苯或氯苯中的一种。
5.如权利要求2所述的制备方法,其特征在于,所述催化回流反应中所用催化剂为苯磺酸、对甲苯磺酸或十二烷基苯磺酸中的一种。
6.如式I所示的类辣椒素类化合物作为防污剂用于制备海洋防污涂料中的应用。
7.一种海洋防污涂料,其组分包括30~80wt%树脂溶液、5~20wt%增塑剂、10~20wt%填充料和5~30wt%如式I所示的类辣椒素类化合物。
8.根据权利要求7所述的海洋防污涂料,其特征在于,所述的树脂溶液浓度为15~70wt%;溶剂为有机溶剂,为乙酸乙酯、乙酸丁酯、二甲苯或甲苯中的一种;树脂为丙烯酸树脂、丙烯酸锌树脂或丙烯酸铜树脂中的一种。
9.根据权利要求7所述的海洋防污涂料,其特征在于,所述增塑剂为凡士林、松香、氯化石蜡、邻苯二甲酸二丁酯或邻苯二甲酸二辛酯中的一种。
10.根据权利要求7所述的海洋防污涂料,其特征在于,所述填充料为氧化铁红、滑石粉、二氧化钛、二氧化硅或氧化锌中的一种。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105400270A (zh) * | 2015-12-03 | 2016-03-16 | 昆明七零五所科技发展总公司 | 驱赶海洋生物污染的油脂 |
CN112759579A (zh) * | 2019-11-04 | 2021-05-07 | 鲁南制药集团股份有限公司 | 一种抗肿瘤类药物替加氟的制备方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0312723A2 (en) * | 1987-10-23 | 1989-04-26 | American Cyanamid Company | Method of and bait compositions for controlling mollusks |
CN1111354C (zh) * | 1995-05-23 | 2003-06-18 | 美国氰胺公司 | 吡咯化合物作为防污剂的用途 |
CN1616560A (zh) * | 2004-10-12 | 2005-05-18 | 朱松年 | 环保型防污剂材料及防污油漆涂料 |
CN1849068A (zh) * | 2003-09-12 | 2006-10-18 | 阿克西迈德股份有限公司 | 辣椒素衍生物及其生产方法和应用 |
CN101420851A (zh) * | 2006-04-10 | 2009-04-29 | 詹森药业有限公司 | 4-溴-2-(4-氯苯基)-5-(三氟甲基)-1h-吡咯-3-腈和杀生化合物的组合 |
CN103288665A (zh) * | 2013-06-27 | 2013-09-11 | 上海化学试剂研究所有限公司 | 一种辣椒素的制备方法 |
CN103608411A (zh) * | 2011-06-21 | 2014-02-26 | 阿克佐诺贝尔国际涂料股份有限公司 | 生物杀伤性污垢释放涂料体系 |
CN103951576A (zh) * | 2014-05-06 | 2014-07-30 | 中国海洋大学 | 单官能度具类辣椒素功能结构的丙烯酰胺化合物及其制备方法与应用 |
-
2014
- 2014-09-30 CN CN201410522106.8A patent/CN104370985B/zh active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0312723A2 (en) * | 1987-10-23 | 1989-04-26 | American Cyanamid Company | Method of and bait compositions for controlling mollusks |
CN1111354C (zh) * | 1995-05-23 | 2003-06-18 | 美国氰胺公司 | 吡咯化合物作为防污剂的用途 |
CN1849068A (zh) * | 2003-09-12 | 2006-10-18 | 阿克西迈德股份有限公司 | 辣椒素衍生物及其生产方法和应用 |
CN1616560A (zh) * | 2004-10-12 | 2005-05-18 | 朱松年 | 环保型防污剂材料及防污油漆涂料 |
CN101420851A (zh) * | 2006-04-10 | 2009-04-29 | 詹森药业有限公司 | 4-溴-2-(4-氯苯基)-5-(三氟甲基)-1h-吡咯-3-腈和杀生化合物的组合 |
CN103608411A (zh) * | 2011-06-21 | 2014-02-26 | 阿克佐诺贝尔国际涂料股份有限公司 | 生物杀伤性污垢释放涂料体系 |
CN103288665A (zh) * | 2013-06-27 | 2013-09-11 | 上海化学试剂研究所有限公司 | 一种辣椒素的制备方法 |
CN103951576A (zh) * | 2014-05-06 | 2014-07-30 | 中国海洋大学 | 单官能度具类辣椒素功能结构的丙烯酰胺化合物及其制备方法与应用 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105400270A (zh) * | 2015-12-03 | 2016-03-16 | 昆明七零五所科技发展总公司 | 驱赶海洋生物污染的油脂 |
CN112759579A (zh) * | 2019-11-04 | 2021-05-07 | 鲁南制药集团股份有限公司 | 一种抗肿瘤类药物替加氟的制备方法 |
CN112759579B (zh) * | 2019-11-04 | 2023-12-26 | 鲁南制药集团股份有限公司 | 一种抗肿瘤类药物替加氟的制备方法 |
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