CN110143856B - 一种桃蛀螟性信息素(z,e)-10-十六碳烯醛化合物的合成方法 - Google Patents
一种桃蛀螟性信息素(z,e)-10-十六碳烯醛化合物的合成方法 Download PDFInfo
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- CN110143856B CN110143856B CN201910504455.XA CN201910504455A CN110143856B CN 110143856 B CN110143856 B CN 110143856B CN 201910504455 A CN201910504455 A CN 201910504455A CN 110143856 B CN110143856 B CN 110143856B
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- hexadecene
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- acetal
- acid
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- 238000000034 method Methods 0.000 title claims abstract description 41
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- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract 12
- 238000006243 chemical reaction Methods 0.000 claims description 45
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 28
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
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Abstract
本发明公开一种桃蛀螟性信息素(Z,E)‑10‑十六碳烯醛化合物的合成方法,ω‑溴代癸醇与二氢吡喃在催化剂作用下,得到相应的缩醛,缩醛和亚磷酸三烷/芳基酯生成缩醛膦酸二烷/芳基酯,缩醛膦酸二烷/芳基酯在有机碱作用下与正己醛反应,水解并脱保护,生成E型为主的(Z,E)‑10‑十六碳烯‑1‑醇,E型为主的(Z,E)‑10‑十六碳烯‑1‑醇与氧化剂氧化反应得到E型为主的(Z,E)‑10‑十六碳烯醛。本发明的方法合成过程副反应少,产物纯度高。
Description
技术领域
本发明涉及一种桃蛀螟性信息素,具体为(Z,E)-10-十六碳烯化合物的化学合成方法,属于生物农药技术领域。
背景技术
桃蛀螟(Dichocrocispunctiferalis)鳞翅目草螟科蛀野螟属的一种杂食性昆虫,主要分布于我国十几个省份,北起黑龙江,南到云南,西到新疆、西藏,危害作物种类广泛,除了桃子外,还危害李、杏、梨、苹果、无花果、梅、樱桃、石榴、葡萄、山楂、柿、核桃、板栗、柑桔、荔枝、龙眼、枇杷、杧果、菠萝等水果,玉米、高粱、向日葵、大豆、棉花、扁豆、蓖麻等经济作物及松、杉、桧柏和臭椿等林木。
我国是世界第一桃生产和消费大国,2016年总产量将近1350万吨,产量占世界总量的66%左右,然而,在我国部分地区,比如江南地区,由于桃蛀螟造成的损失却极为严重,甚至有了“十桃九蛀”的说法。
此外,桃蛀螟危害玉米时,百株产卵量可以高达1729枚;危害向日葵时,早播杂交油葵受害株率可达62%,晚播杂交油葵受害株率可达90%;在华东地区,桃蛀螟还是危害板栗的主要害虫。就种植面积而言,2016年我国桃种植面积超过1000万亩;同年玉米种植面积5.57亿亩;同年向日葵种植面积1490万亩;2015年,板栗种植面积2700万亩,可见由于桃蛀螟食性很杂,其在其它作物上的危害造成的损失,可见一斑。
桃蛀螟幼虫蛀食性、发蛾期较长等特点,以及长期施用化学农药,导致抗药性增加,防效明显下降,天敌数量减少,生态环境遭到破坏。昆虫性信息素是由昆虫的某一性别的个体分泌于体外,被同种异性个体的感受器所接受,并引起异性个体产生一定的生殖行为反应(如觅偶定向、求偶交配等)的微量化学物质。昆虫性信息素是一种新型的害虫防治技术,具有专一性强,无残留,环境友好等特点,是一种农业绿色生态防控技术。
桃蛀螟性信息素具体成分为(Z,E)-10-十六碳烯化合物,其中Z式和E式异构体比例在3:7到1:9之间,诱虫效果最好的是Z:E=1:9。国内外报道合成总收率只有36%左右,产品精制工序长、成本高、杂质多,导致制剂产品药效不能尽如人意。桃蛀螟性信息素的合成方法研究开始于上世纪七十年代。有如下几种合成方法:
1、以十一碳烯酸为原料,经过过酸羟基化、甲醇酯化后高碘酸钠氧化裂解乙二醇官能团得到相应的醛酯,再和溴代三苯基己基膦盐进行wittig反应,以60%的收率得到大约1:1的E/Z混合物烯酸酯,再经酯还原得到醇,PCC氧化得到最终产物,GC纯度96.3%,总共6步反应,总收率13.25%。
此反应虽然十一碳烯酸、溴己烷原料易得,但是wittig反应需要零下40度反应,总收率低且双键顺反构型低。
2、以溴癸醇、正己醛为原料,先制备溴代正癸基三苯基膦盐,再在DMSO钠盐存在下进行wittig反应得到相应的醇,再经PCC氧化可得到最终产物,立体选择性E/Z=6.6:93.4,总收率约27%。
该路线条件相对温和,但是在形成溴代正癸基三苯基膦盐时,容易发生副反应引入溴癸醇的聚合体,从而带入wittig反应得到的烯醇中,而且wittig反应本身也会产生这种聚合体;不但如此,wittig反应后处理中需要移除副产物三苯基氧磷及其类似物,即使采用氯化锌无水乙醇中络合法移除三苯基氧磷,却依然需要额外方法移除三苯基氧磷类似物,致使后处理复杂,成本高。
此外,烯醇获得后其反式构型过低,需要额外的方法去进行异构化,而异构化收率约90%,且只能得到E:Z=76:24左右的产品,这距离最佳诱虫效果E:Z=9:1,还有一段距离。
3、江苏化工学院和昆虫激素研究所以十一烯酸为起始原料,通过溴化、消除、还原、保护、缩合、顺式加氢、反式加氢、去保护、氧化等步骤合成了E-10-十六烯醛和Z-10-十六烯醛。此方法步骤长,且未见实验数据,反应条件较高。
4、中科院动物所刘孟英、孟宪佐、阎忠诚报道了题为桃蛀螟性信息素反-10-十六烯醛及其顺式异构体的合成,涉及三条路线,其中一条路线同方法2;另外一种方法只是在方法2中使用了经二溴化物脱卤素的异构化方法;最后一种为炔化物路线。
9-溴代壬醇四氢吡喃醚及庚炔为原料制得10-十六炔醇四氢吡喃醚,经水解转变为10-十六炔醇,再以过量四氢铝锂为还原试剂将炔醇还原,经PCC氧化方法得产品。
5、1987年湖北大学化学系的陈家威采用1,10-癸二醇选择性单侧二氢吡喃醚保护、氧化成醛,再与聚合物支撑的溴化己基三苯基膦盐、氢化钠发生wittig反应,经脱保护、异构化、氧化成醛获得产品。
同年,陈家威在《有机化学》3,224-226发表了另外一种聚合物支撑的合成文献,题名《聚合物试剂的研究Ⅱ.应用聚合物试剂合成桃蛀螟性信息素—反-10-十六碳烯-1-醛》。1,10-癸二醇经单侧溴代,与聚合物支撑的三苯基磷成盐,在氢化钠和DMSO存在下完成wittig反应,异构化、氧化获得产品,以上两种方法成本高昂,树脂的再生困难,1,10-癸二醇单侧羟基保护难度大。6、十一碳烯酸为原料,经四氢铝锂还原成醇、溴加成、脱卤素成十一碳炔醇,THP保护、丁基锂作用下与溴代正戊烷偶联、脱保护、反式加氢、氧化得到(E)-10-十六碳烯醛,总收率约34%。丙炔醇和溴代正辛烷在碱金属氨基化物作用下偶联,炔键移位得到端基炔醇,随后在碱金属氨基化物存在下与正丁基溴作用偶联,镍催化加氢,氧化得到(Z)-10-十六碳烯醛,总收率约28%。
7、采用类似方法2的方法,李汉东通过Schlosser-Wittig反应替代Wittig反应,得到高反式选择性的烯醇,再经氧化得到烯醛。Schlosser-Wittig反应收率60%,E/Z=98/2,无需异构化。但是,苯基锂-溴化锂为碱(4倍当量),-70度反应,成本高,条件苛刻。
发明内容
本发明的目的是提供一种桃蛀螟性信息素(Z,E)-10-十六碳烯醛化合物的合成方法,以ω-溴代癸醇为起始原料,通过羟基保护提高原料稳定性同时,避免原料自身的聚合副反应,改进wittig反应提高收率和反应选择性,合成过程副反应少,产物纯度高。
为达上述目的,本发明采取如下技术方案:
一种桃蛀螟性信息素(Z,E)-10-十六碳烯醛化合物的合成方法,包括如下步骤:
(1)ω-溴代癸醇在催化剂作用下,和二氢吡喃作用,得到相应的缩醛;
(2)缩醛和亚磷酸三烷/芳基酯发生阿布佐夫反应,生成缩醛膦酸二烷/芳基酯;
(3)缩醛膦酸二烷/芳基酯在有机碱作用下与正己醛反应,水解并脱保护,生成E型为主的(Z,E)-10-十六碳烯-1-醇;
(4)E型为主的(Z,E)-10-十六碳烯-1-醇经过氧化剂氧化反应得到E型为主的(Z,E)-10-十六碳烯醛。
本发明的合成方法以ω-溴代癸醇为原料,在催化剂作用下与二氢吡喃反应,得到相应的缩醛,缩醛和亚磷酸三烷/芳基酯生成缩醛膦酸二烷/芳基酯,缩醛膦酸二烷/芳基酯在有机碱作用下与正己醛反应,水解并脱保护,生成E型为主的(Z,E)-10-十六碳烯-1-醇,E型为主的(Z,E)-10-十六碳烯-1-醇与氧化剂氧化反应得到E型为主的(Z,E)-10-十六碳烯醛。合成过程副反应少,产物纯度高。
本发明的ω-溴代癸醇原料经二氢吡喃醚保护后,相比ω-溴代癸醇稳定,不会在后续过程中自身发生聚合反应;并且通过Arbuzov反应取代和三苯基磷成盐的反应,通过wittig-horner取代wittig反应,具有产率高,副反应少,同时有利于产物顺反结构比例在适宜范围之内。
作为优选,本发明的合成方法包括如下步骤:
(1)ω-溴代癸醇和二氢吡喃在催化剂作用下,有机溶剂中加热回流反应,反应结束后移除催化剂,除去溶剂,得到THP保护的ω-溴代癸醇,俗称缩醛;
(2)将步骤(1)所得缩醛与亚磷酸三烷/芳基酯混合,一定温度下反应,得到THP保护的缩醛膦酸二烷/芳基酯;
(3)将步骤(2)所得THP保护的缩醛膦酸二烷/芳基酯,在无水醚类混合溶剂中,经有机碱作用与正己醛反应生成E型为主的THP保护的十六碳烯醇,水解获得E型为主的10-十六碳烯-1-醇;
(4)E型为主的(Z,E)-10-十六碳烯-1-醇,在低级卤代溶剂中,经过氧化剂氧化反应得到E型为主的(Z,E)-10-十六碳烯醛,产物中Z/E摩尔比为1:7-20,优选为1:9。
本发明的方法以ω-溴代癸醇为原料,经THP保护、Arbuzov反应、wittig-horner反应、水解反应、氧化反应制备产品,方法中使用收率低下、选择性差的三苯基磷成盐反应和wittig反应,同时避免了复杂繁琐的除去三苯基氧磷和其疑似三苯基羟基磷的程序,收率更高,工艺方案更为经济、环保。
作为优选,步骤(1)中10-溴癸醇和二氢吡喃的摩尔比为1:1-1:1.2,例如为1:1.05、1:1.1、1:1.15、1:1.2等。10-溴癸醇和二氢吡喃的上述摩尔比范围既可以使得10-溴癸醇充分转化并且仅使其中的一个溴转化为盐。
优选地,10-溴癸醇在卤代溶剂中的摩尔浓度为1.0mol/L-5.0mol/L。
优选地,常温搅拌反应的时间为1-2h,优选为2h。
作为优选,步骤(2)中溶剂为反应物自身即可,其中为了保证缩醛反应彻底性,采取亚磷酸酯过量的形式,亚磷酸酯加入量多有助于转换,但是考虑成本及原材料回收等,优选过量50%,温度升高有利于反应顺利稳定充分进行,从而使得反应收率高,但是能耗也将上升,优选惰性气体保护下,副反应少,产品纯度高。
作为优选,步骤(3)有机碱为氢化钠。
优选地,有机碱以溶液形式加入。
Wittig-horner反应采用混合溶剂,有机碱采用氢化钠,更有利于在低温均相条件下进行,有利于产物顺反结构比例在适宜范围之内。
优选地,有机碱的摩尔浓度为0.5mol/L-5.0mol/L。
优选地,有机碱溶液的溶剂为四氢呋喃和N,N-二甲基甲酰胺。
优选地,盐酸的质量浓度为5-15%,优选为10%。
优选地,THP保护的缩醛膦酸酯、有机碱、醛的摩尔比为1:1.2-2.5:1.0-1.2,例如为1:1.3:1.1、1:1.5:1.2、1:1.7:1.15、1:2:1.05等。
优选地,THP保护的缩醛膦酸酯在混合溶剂中的摩尔浓度为0.5mol/L-3.0mol/L。
优选地,加入有机碱后反应的时间为0.5h以上,优选为1-1.5h。反应优选在搅拌下进行。
优选地,加入溶剂稀释的醛后反应的时间为2h以上,优选为3h-20h。
优选地,溶剂稀释的醛所用溶剂为四氢呋喃。
醛用溶剂稀释后的摩尔浓度不特别限定,例如可为0.5-10mol/L。
反应结束,中止反应时,优选先加入低级脂肪醇,后加入稀酸的方式,破坏未能反应的氢化钠,避免反应冲料问题;优选通过滴加的方式加入醇;优选低级脂肪醇为乙醇,优选加入量为氢化钠理论上发生wittig-horner反应后过量的当量数。
优选地,分离后处理为先用苯类溶剂萃取,更优选甲苯,再用饱和氯化钠水溶液洗涤,无水硫酸钠干燥,蒸馏得到粗品,再经硅胶柱层析分离得到E型为主的(Z,E)-10-十六碳烯-1-醇。
萃取可进行多次,萃取后的有机相可合并进行下一步骤。
作为优选,步骤(3)中E型为主的(Z,E)-10-十六碳烯-1-醇在甲苯中的摩尔浓度为1.0mol/L-3.0mol/L。
优选地,苯类溶剂为苯、甲苯、二甲苯中1种或2种以上的组合。
优选地,水解为常温下水解1h-2h,优选利用酸中和过程中稍过量的酸进行中和;中和后的pH值应在小于5.0,优选控制pH值3.0-4.0。
优选地,生成的E型为主的(Z,E)-10-十六碳烯-1-醇通过减压蒸馏的方式进行浓缩。
本发明中使用的惰性气体可为本领域常用的惰性气体,如氦气、氖气、氩气、氮气中1种或几种的组合。
作为优选,步骤(4)中的反应溶剂为二氯甲烷;反应温度范围从-10℃-40℃,优选为室温;优选氧化剂为PCC;PCC在溶剂中的摩尔浓度可以为0.1mol/L-1.0mol/L,优选为0.5mol/L;反应可以在空气中进行,优选在常见的惰性气氛中进行,如氦气、氖气、氩气、氮气等,及其组合,更优选氮气。
优选地,生成的E型为主的(Z,E)-10-十六碳烯醛,后处理提纯过程中,先常压蒸馏除去溶剂二氯甲烷,然后加入低沸点的醚进行溶解,如***、丙醚、甲基叔丁基醚,乙二醇二甲醚等,优选为甲基叔丁基醚;优选加入醚的量为控制理论上产品浓度0.4-0.6mol/L;产品的醚溶液优选通过吸附和柱层析结合的方式移除可能的杂质,吸附和柱层析的材料可以为普通柱层析硅胶、硅藻土、高岭土、蒙脱石、白垩土等,吸附优选硅藻土,柱层析优选硅胶。
优选地,柱层析后的流动相经水洗移除可能的金属离子等杂质,加入水量优选为产品溶液的0.2倍体积,优选洗涤次数为3次。
优选地,洗涤后的液体经常见的中性干燥剂干燥除水,比如硫酸镁、硫酸钠等,然后过滤,水浴控温45℃以下减压浓缩。
优选地,上述浓缩液加入市面上常见的抗氧化剂后,进行保存,比如1,4-对苯二酚、维生素E、叔丁基对苯二酚、茶多酚等,加入量可以为0.01%-1.00%,优选为0.1%,优选为加入维生素E。
由以上的技术方案可知,本发明的有益效果是:
(1)原料ω-溴代癸醇经THP保护后,不会在后续过程中发生自身缩合反应,避免了中间体纯度下降和对后续反应引入过多的杂质;
(2)以阿布佐夫反应替代形成季膦盐的过程,收率和纯度更高;
(3)以wittig-horner反应取代wittig反应,有利于产物的顺反结构比例保持在适宜的范围之内,避免单独需要异构化的过程,也避免了反应结束后三苯基氧磷和类似物质难以除去的问题;
(4)wittig-horner反应后处理中,采用了低级脂肪醇和酸分步中和中止反应的方法,大大提高了安全性,避免了反应冲料问题。
附图说明
图1为本发明实施例的(Z,E)-10-十六碳烯醛合成路线。
图2为本发明实施例十六碳烯醇的液相色谱图。
具体实施方式
以下实施例用于说明本发明,但不能用来限制本发明的范围。实施例中采用的实施条件可以根据厂家的条件作进一步调整,未说明的实施条件通常为常规实验条件。
实施例
一种桃蛀螟性信息素(Z,E)-10-十六碳烯醛化合物的合成方法,包括以下操作步骤:
(1)THP保护的缩醛
500ml三口瓶中,加入黄棕色透明液体单溴代醇48.5g(0.20mol),对甲苯磺酸吡啶盐1.0g(0.02eq.),二氢吡喃25.2g(0.30mol),二氯甲烷300ml,室温搅拌1h,然后水浴40℃减压蒸馏移除溶剂和多余的二氢吡喃,加入250ml60-90的石油醚和50ml水洗涤,无水硫酸钠干燥,浓缩溶剂得到黄棕色透明液体62.3g,收率97%。
(2)阿布佐夫反应
500ml三口烧瓶中,加入亚磷酸三乙酯235g(1.50mol)、催化剂碘少量,氮气保护,油浴加热温度150℃,滴加THP保护的缩醛160.5g(0.50mol),完毕反应15h,反应期间不断蒸馏出副产的溴乙烷,反应完毕,降温至50℃,开始减压蒸馏,油浴温度逐渐升到110℃,至10Pa内温110℃蒸馏不出馏分为止,共计获得177.9g浅黄色液体,收率94%。
(3)十六碳烯醇的合成
氮气保护下,2000ml烧瓶中,加入干燥除水的N,N-二甲基甲酰胺100ml,60%的氢化钠33g(0.825mol),加入150ml除水四氢呋喃,搅拌,室温滴加上述产物的四氢呋喃溶液,其中含有除水四氢呋喃150ml,完毕,使用四氢呋喃清洗漏斗,中间释放大量氢气,释放氢气完毕,降温,在冰水浴中,内温-5-0℃,滴加正己醛65g/200mlTHF(0.65mol),滴加完毕,逐步升温到25℃左右,继续反应1h,滴加无水乙醇50ml,继续释放氢气,完毕,滴加5%的盐酸溶液直至pH为5-6,停止搅拌,分层,分液,上层为THF相,水浴45-60℃旋蒸浓缩,水相使用乙酸乙酯100ml萃取2次,分液,乙酸乙酯相并入四氢呋喃浓缩液中,得到浅黄色透明液体,水浴60℃水泵减压蒸馏完毕,使用油泵在同样温度下继续蒸馏,直至10Pa下60℃内温蒸馏不出来馏分为止,得到产品合计87g,GC含量96.5%,折百收率70%。
产品经液相色谱检测为E构型为主,E:Z=9:1。
(4)PCC氧化
在1000ml三口烧瓶中,氮气保护下,加入氯铬酸吡啶盐80.0g(0.37mol),加入二氯甲烷共计600ml搅拌溶解得到橙红色透明液体,底部有固体不溶;把87gE式构型为主的十六碳烯醇,溶解在300ml二氯甲烷中,室温滴加烯醇反应,随着滴加的进行,溶液变为黑色,滴加完毕,室温继续搅拌反应1h;然后水浴45℃常压蒸馏出二氯甲烷,完毕,加入甲基叔丁基醚600ml和200ml左右的柱层析用硅胶,搅拌30min,过滤,滤饼用甲基叔丁基醚150ml洗涤2次,合并醚相,加水150ml洗涤2次,分液,有机相液体通过柱层析进行吸附去除深色物质,加入抗氧化剂少量,氮气保护下,水浴40℃旋蒸干净,获得具有刺激性气味的淡黄绿色透明液体,共计80.0g,GC含量98%,折百收率94%。
以上所述,仅是本申请的几个实施例,并非对本申请做任何形式的限制,虽然本申请以较佳实施例揭示如上,然而并非用以限制本申请,任何熟悉本专业的技术人员,在不脱离本申请技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,均属于技术方案范围内。
Claims (7)
1.一种桃蛀螟性信息素(Z,E)-10-十六碳烯醛化合物的合成方法,其特征在于,包括以下操作步骤:
(1)ω-溴代癸醇和二氢吡喃在催化剂作用下,有机溶剂中加热回流反应,反应结束后移除催化剂,除去溶剂,得到THP保护的ω-溴代癸醇;
(2)将步骤(1)所得的ω-溴代癸醇与亚磷酸三烷基酯或亚磷酸三芳基酯混合,一定温度下反应,得到对应的四氢吡喃基保护的缩醛膦酸二烷酯或缩醛膦酸二芳基酯;
(3)将步骤(2)所得的缩醛膦酸二烷酯或缩醛膦酸二芳基酯在混合溶剂中,经有机碱作用与正己醛反应生成E型为主的THP保护的十六碳烯醇,经水解生成E型为主的(Z,E)-10-十六碳烯-1-醇;
(4)E型为主的(Z,E)-10-十六碳烯-1-醇,在低级脂肪卤代烃或低级脂肪醚类溶剂中,经过氧化剂氧化反应得到E型为主的(Z,E)-10-十六碳烯醛;
上述步骤(1)中ω-溴代癸醇和二氢吡喃的摩尔比为1:1~1:1.2;
步骤(1)中溶剂为四氢呋喃、甲基叔丁基醚,***,二氯甲烷、二氯乙烷、氯仿、乙腈、丙酮、丁酮中的任意一种;
步骤(1)中催化剂为对甲苯磺酸吡啶盐;
步骤(1)中催化剂加入量为反应体系总量的0.1%~5%。
2.根据权利要求1所述的一种桃蛀螟性信息素(Z,E)-10-十六碳烯醛化合物的合成方法,步骤(2)反应温度为100℃到回流温度,回流温度为100℃~200℃;
步骤(2)中亚磷酸三烷基酯或亚磷酸三芳基酯加入摩尔当量是ω-溴代癸醇的1.0~5.0倍;
步骤(2)反应气氛为大气普通环境或者惰性气体保护气氛。
3.根据权利要求2所述的一种桃蛀螟性信息素(Z,E)-10-十六碳烯醛化合物的合成方法,步骤(3)中的混合溶剂为无水醚类、强极性偶极溶剂、苯类溶剂中的一种或者是三者的组合;
步骤(3)中缩醛膦酸二烷酯或缩醛膦酸二芳基酯和有机碱的摩尔比例在1:1~2:1;
步骤(3)中缩醛膦酸二烷酯或缩醛膦酸二芳基酯和有机碱的反应温度在-10℃~45℃;
步骤(3)中滴加正己醛时的反应温度在-25℃~25℃;
步骤(3)中加入有机碱后反应的时间为0.5h以上;其中,稀释正乙醛所用溶剂为四氢呋喃;
步骤(3)中采用加入低级脂肪醇的方式进行反应的淬灭,加入的低级脂肪醇为甲醇、乙醇、丙醇、丁醇中的一种;
步骤(3)中反应结束后,加入酸调节pH值到5~6,所用的酸为稀释后的酸,所用的酸为盐酸、硫酸、硝酸、磷酸、甲酸、乙酸、对甲苯磺酸、甲磺酸、三氟乙酸、三氟甲磺酸中的一种;
步骤(3)中正己醛和缩醛膦酸二烷酯或缩醛膦酸二芳基酯的反应气氛为惰性气体保护。
4.根据权利要求1所述的一种桃蛀螟性信息素(Z,E)-10-十六碳烯醛化合物的合成方法,上述步骤(3)中,步骤(3)中分离后处理为先用无水乙醇淬灭反应,然后加入稀酸水溶液中和,分液,对水相使用有机溶剂萃取,再用饱和氯化钠水溶液洗涤,无水硫酸钠干燥,蒸馏得到粗品,再经硅胶柱层析分离得到E型为主的(Z,E)-10-十六碳烯-1-醇。
5.根据权利要求1所述的一种桃蛀螟性信息素(Z,E)-10-十六碳烯醛化合物的合成方法,上述步骤(3)中(Z,E)-10-十六碳烯-1-醇在混合溶剂中的摩尔浓度为0.5mol/L~3.0mol/L;混合溶剂为醚类溶剂、苯类溶剂和强极性偶极溶剂中的1种或2种以上的组合;有机碱与(Z,E)-10-十六碳烯-1-醇的摩尔比为1~3:1;有机碱为氢化钠、氢化钾中1种或2种的组合;中和水解为50℃~60℃下水解4h~20h。
6.根据权利要求1所述的一种桃蛀螟性信息素(Z,E)-10-十六碳烯醛化合物的合成方法,上述步骤(4)中,低级脂肪卤代烃为二氯甲烷、三氯甲烷、四氯甲烷、二氯乙烷、三氯乙烷、四氯乙烷中的一种,脂肪醚类溶剂为***、甲基叔丁基醚、丙醚、乙二醇二甲醚中的一种,
步骤(4)中反应温度为-15℃~65℃;
步骤(4)中氧化剂为氯铬酸吡啶盐;
步骤(4)中氧化反应气氛为惰性气体保护。
7.根据权利要求1所述的一种桃蛀螟性信息素(Z,E)-10-十六碳烯醛化合物的合成方法,步骤(4)中(Z,E)-10-十六碳烯-1-醇和氧化剂的摩尔比为1:1.0-1.5;卤代溶剂与(Z,E)-10-十六碳烯-1-醇的质量比为3-15:1;(Z,E)-10-十六碳烯-1-醇在卤代溶剂中的摩尔浓度为0.3mol/L-3.0mol/L;反应在室温下进行,反应的时间为1h-10h;(Z,E)-10-十六碳烯-1-醇在和氧化剂反应结束后,蒸馏出绝大部分卤代溶剂,然后加入醚类溶剂和助剂,常压蒸馏方式,所述醚类溶剂为甲基叔丁基醚,所述助剂为普通柱层析硅胶、硅藻土、高岭土、蒙脱石、白垩土,硅藻土加入量为(Z,E)-10-十六碳烯-1-醇质量的1-5倍。
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