CN109232645A - 一种草铵膦中间体的制备方法 - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- IAJOBQBIJHVGMQ-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid Chemical compound CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-UHFFFAOYSA-N 0.000 title abstract 3
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- NSWQJASYEPJGJA-UHFFFAOYSA-N CCOP(C)(O)OCC.CNC(S)=N Chemical compound CCOP(C)(O)OCC.CNC(S)=N NSWQJASYEPJGJA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- ZBMRKNMTMPPMMK-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid;azane Chemical compound [NH4+].CP(O)(=O)CCC(N)C([O-])=O ZBMRKNMTMPPMMK-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 11
- 150000001241 acetals Chemical class 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 229960004756 ethanol Drugs 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- -1 methyl phosphorous Chemical compound 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 9
- AVXBTEZHGRNURI-UHFFFAOYSA-N CN=C(N)S.CN=C(N)S.COP(O)O Chemical compound CN=C(N)S.CN=C(N)S.COP(O)O AVXBTEZHGRNURI-UHFFFAOYSA-N 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims 2
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 abstract description 8
- 238000010606 normalization Methods 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- HOMDJHGZAAKUQV-UHFFFAOYSA-N 1-(propoxymethoxy)propane Chemical compound CCCOCOCCC HOMDJHGZAAKUQV-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 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
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3211—Esters of acyclic saturated acids which can have further substituents on alkyl
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3264—Esters with hydroxyalkyl compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明公开了一种草铵膦中间体的制备方法,在杂双金属分子筛型催化剂CuZr/ZSM‑5存在下,将丙烯醛滴加到甲基亚磷酸二乙酯和无水乙醇的混合溶液中进行反应,反应结束后减压浓缩,得到草铵膦中间体3‑(甲基乙氧基)膦酰基丙缩醛二乙醇。本发明方法工艺简单,易操作,反应条件温和,收率高,原子经济性高,催化剂易回收利用,工业化前景好。
Description
技术领域
本发明涉及草铵膦中间体的制备方法,具体涉及草铵膦中间体3-(甲基乙氧基)膦酰基丙缩醛二乙醇的制备方法。
背景技术
3-(甲基乙氧基)膦酰基丙缩醛二乙醇(结构如式Ⅰ所示)——缩醛是灭生性除草剂草铵膦的一个中间体,特别是通过Strecker路线来合成草铵膦的一个重要中间体。
专利US6359162B1采用甲基亚磷酸二乙酯、丙烯醛、乙醇和乙酸酐为原料来制备缩醛,反应的选择性较差,缩醛收率不高,乙酸酐参与反应,增加了原材料成本,且伴有乙酸乙酯副产生成,需进一步处理。
发明内容
本发明的目的是针对现有制备方法3-(甲基乙氧基)膦酰基丙缩醛二乙醇收率较低、原子经济性较差的情况,提供一种草铵膦中间体3-(甲基乙氧基)膦酰基丙缩醛二乙醇的制备方法,该方法工艺简单,成本低,反应条件温和,收率高,原子经济性好。
本发明的技术方案如下:
一种草铵膦中间体的制备方法,该方法以甲基亚磷酸二乙酯、丙烯醛和乙醇为原料,在催化剂CuZr/ZSM-5作用下反应得到3-(甲基乙氧基)膦酰基丙缩醛二乙醇。
本发明所述的草铵膦中间体的制备方法,包括:甲基亚磷酸二乙酯、无水乙醇和催化剂CuZr/ZSM-5混合,冷却,在氮气保护下,滴加丙烯醛,滴加完毕,控温反应,反应结束后减压蒸馏除去溶剂,得到草铵膦中间体3-(甲基乙氧基)膦酰基丙缩醛二乙醇。
所述的减压蒸馏的压力为-0.098MPa。
所述的甲基亚磷酸二乙酯、丙烯醛和无水乙醇的摩尔比为1:1~1.1:4~10,优选为1:1~1.1:8~10。
所述的催化剂CuZr/ZSM-5的用量为甲基亚磷酸二乙酯重量的0.5~4wt%。所述的催化剂CuZr/ZSM-5中铜的负载量为3~5%,锆的负载量为1~3%。
所述的催化剂CuZr/ZSM-5由以下制备方法制得:Na-ZSM-5沸石分子筛与铜盐溶液进行离子交换,获得Cu-ZSM-5前驱体;Cu-ZSM-5前驱体采用硝酸锆溶液浸渍24~48h,120~130℃干燥16~24h,500~550℃焙烧4~6h,制得杂双金属分子筛型CuZr/ZSM-5催化剂。其中,所述的铜盐溶液为质量分数10%硫酸铜或硝酸铜溶液;硝酸锆溶液的质量分数为10%。
甲基亚磷酸二乙酯、无水乙醇和杂双金属分子筛型催化剂CuZr/ZSM-5混合后冷却至-10~40℃,优选冷却至0~10℃。
滴加丙烯醛过程中放热明显,因此控制滴加温度为-10~40℃,优选为0~20℃。
滴加完毕后,所述的反应温度为-10~50℃,优选为25~50℃;反应时间为0.5~6h,优选为1~4h。
作为本发明的进一步技术方案,经减压蒸馏收集到的乙醇则可直接套用在下批投料中。
和现有技术相比,本发明的有益效果:
本发明杂双金属催化剂易回收利用,用于催化该Michael加成反应过程,缩短了反应时间,较大地提高了缩醛的反应收率。
本发明方法工艺简单,成本低,反应条件温和,收率高,绿色环保,原子经济性高等优点。
具体实施方式
结合具体实施例对本发明的技术方案做进一步详细说明。这些实施例仅是为了说明本发明,本发明不受以下实施例的限制。凡根据本发明所做出的等效变化或修饰,都应涵盖在本发明的保护范围之内。如无特别说明的实施条件通常为常规实验中的条件。
实施例1
将136g甲基亚磷酸二乙酯、460g无水乙醇和1.0g杂双金属分子筛型催化剂CuZr/ZSM-5(Cu的负载量3.5%,Zr的负载量2.2%)投入反应容器中混合,冷却至10℃;通入氮气保护,缓慢滴加56g丙烯醛到混合溶液中,控制滴加温度在15~20℃,滴加完毕,控制温度为25~30℃,反应4h,反应结束后减压蒸馏浓缩,蒸出乙醇,得缩醛226g,归一化含量为97%,收率为92%。
实施例2
将136g甲基亚磷酸二乙酯、460g无水乙醇和2.5g杂双金属分子筛型催化剂CuZr/ZSM-5(同实施例1)投入反应容器中混合,冷却至10℃;通入氮气保护,缓慢滴加58g丙烯醛到混合溶液中,滴加温度控制在15~20℃,滴加完毕,控制温度为25~30℃,反应3h,反应结束后减压蒸馏浓缩,得缩醛233g,归一化含量为98%,收率为96%。
实施例3
将136g甲基亚磷酸二乙酯、460g无水乙醇和4.0g杂双金属分子筛型催化剂CuZr/ZSM-5(同实施例1)投入反应容器中混合,冷却至10℃;通入氮气保护,缓慢滴加58g丙烯醛到混合溶液中,滴加温度控制在15~20℃,滴加完毕,控制温度为25~30℃,反应1h,反应结束后减压蒸馏浓缩,得缩醛231g,归一化含量为97%,收率为94%。
实施例4
将136g甲基亚磷酸二乙酯、368g无水乙醇和2.5g杂双金属分子筛型催化剂CuZr/ZSM-5(同实施例1)投入反应容器中混合,冷却至10℃,通入氮气保护,缓慢滴加58g丙烯醛到混合溶液中,滴加温度控制在15~20℃,滴加完毕,控制温度为25~30℃,反应1h,反应结束后减压蒸馏浓缩,得缩醛230g,归一化含量为96%,收率为93%。
实施例5
将136g甲基亚磷酸二乙酯、368g无水乙醇和2.5g杂双金属分子筛型催化剂CuZr/ZSM-5(同实施例1)投入反应容器中混合,冷却至10℃,通入氮气保护,缓慢滴加58g丙烯醛到混合溶液中,滴加温度控制在15~20℃,滴加完毕,控制温度为35~40℃,反应3h,反应结束后减压蒸馏浓缩,得缩醛230g,归一化含量为97%,收率为94%。
实施例6
将136g甲基亚磷酸二乙酯、276g无水乙醇和2.5g杂双金属分子筛型催化剂CuZr/ZSM-5(同实施例1)投入反应容器中混合,冷却至10℃;通入氮气保护,缓慢滴加58g丙烯醛到混合溶液中,滴加温度控制在15~20℃,滴加完毕,控制温度为35~40℃,反应3h,反应结束后减压蒸馏浓缩,得缩醛215g,归一化含量为94%,收率为85%。
实施例7
将136g甲基亚磷酸二乙酯、368g无水乙醇和2.5g杂双金属分子筛型催化剂CuZr/ZSM-5(同实施例1)投入反应容器中混合,冷却至10℃;通入氮气保护,缓慢滴加58g丙烯醛到混合溶液中,滴加温度控制在15~20℃,滴加完毕,控制温度为15~20℃,反应3h,反应结束后减压蒸馏浓缩,得缩醛217g,归一化含量为95%,收率为87%。
Claims (10)
1.一种草铵膦中间体的制备方法,其特征在于该方法以甲基亚磷酸二乙酯、丙烯醛和乙醇为原料,在催化剂CuZr/ZSM-5作用下反应得到3-(甲基乙氧基)膦酰基丙缩醛二乙醇。
2.根据权利要求1所述的草铵膦中间体缩醛的合成方法,其特征在于包括:将甲基亚磷酸二乙酯、无水乙醇和催化剂CuZr/ZSM-5混合,冷却,在氮气保护下,滴加丙烯醛,滴加完毕后控温反应,反应结束后除去溶剂,得到草铵膦中间体3-(甲基乙氧基)膦酰基丙缩醛二乙醇。
3.根据权利要求1或2所述的草铵膦中间体的合成方法,其特征在于所述的甲基亚磷酸二乙酯、丙烯醛和乙醇的摩尔比为1:1~1.1:4~10。
4.根据权利要求1或2所述的草铵膦中间体的合成方法,其特征在于所述的甲基亚磷酸二乙酯、丙烯醛和乙醇的摩尔比为1:1~1.1:8~10。
5.根据权利要求1或2所述的草铵膦中间体的合成方法,其特征在于所述的催化剂CuZr/ZSM-5中铜的负载量为3~5%,锆的负载量为1~3%。
6.根据权利要求1或2所述的草铵膦中间体的合成方法,其特征在于催化剂的用量为甲基亚磷酸二乙酯重量的0.5~4wt%。
7.根据权利要求1或2所述的草铵膦中间体的合成方法,其特征在于催化剂CuZr/ZSM-5由以下制备方法制得:Na-ZSM-5沸石分子筛与铜盐溶液进行离子交换,获得Cu-ZSM-5前驱体;Cu-ZSM-5前驱体用硝酸锆溶液浸渍24~48h,随后120~130℃干燥16~24h,500~550℃焙烧4~6h,制得CuZr/ZSM-5催化剂。
8.根据权利要求2所述的草铵膦中间体的合成方法,其特征在于控制丙烯醛滴加温度为-10~40℃,优选为0~20℃。
9.根据权利要求1或2所述的草铵膦中间体的合成方法,其特征在于滴加完毕后的反应温度为-10~50℃,优选为25~50℃。
10.根据权利要求1或2所述的草铵膦中间体的合成方法,其特征在于滴加完毕后的反应时间为0.5~6h,优选为1~4h。
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