CN117050037A - 丙烯酰胺型化合物的制备方法 - Google Patents
丙烯酰胺型化合物的制备方法 Download PDFInfo
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- CN117050037A CN117050037A CN202210478999.5A CN202210478999A CN117050037A CN 117050037 A CN117050037 A CN 117050037A CN 202210478999 A CN202210478999 A CN 202210478999A CN 117050037 A CN117050037 A CN 117050037A
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
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- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims 1
- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 claims 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims 1
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- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims 1
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- 239000000463 material Substances 0.000 abstract description 4
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
- C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
本发明涉及新材料精细化学品领域,特别涉及一类丙烯酰胺型化合物的温和高效且经济性制备新工艺技术。该技术包含以下步骤:在适当的溶剂中,将结构式A所示的取代丙酰胺原料和试剂B所示的磺酸酯类化合物在适当的反应条件下作用,同时制备一系列结构式C和/或D所示的目标产物;使用的催化剂以及试剂均廉价易得,反应选择性以及收率较高,目标产物分离简便,相比现有技术,本发明所述合成路线具有较大的市场竞争力。
Description
【技术领域】本发明涉及新材料精细化学品领域,特别涉及一类单或多官能团丙烯酰胺型化合物的温和高效且经济性联合生产新工艺技术,丙烯酰胺则是重要的含烯不饱和型可辐射聚合单体化合物。本申请披露的工艺以其化学反应技术的新颖性,成本经济竞争力以及环境友好性与文献已知工艺路线相比具有显著的优势。
【背景技术】丙烯酰胺类化合物是重要的含烯不饱和可聚合型的有机化学品:如丙烯酰吗啉(ACMO):是可用于纤维、絮凝剂、油田用聚合物、UV树脂反应稀释剂的化合物;N,N-二乙基丙烯酰胺:可用于生产水溶性聚合物,该类聚合物可作为水处理阻垢分散剂,也可用作耐温抗盐的钻井液降滤失剂、油井水泥降滤失剂和耐温抗盐的聚合物驱油剂,也可用作纤维材料的改性,日用化学品、涂料、印刷和照相、医药卫生材料等方面;N-苯基丙烯酰胺在农业方面有着广泛的应用等等。丙烯酰胺类化合物其优越的性能使其在医药新材料等多领域都有着广泛的应用前景。而丙烯酰胺类聚合物被称为“百业助剂”,作为一种重要的水溶性聚合物,丙烯酰胺类聚合物的应用领域涉及我国各行各业,例如,其在采油,矿业,食品,农业,纺织,建材以及水处理等许多领域都有着十分广泛的应用。
文献已披露的丙烯酰胺类化合物合成技术相当有限,例如日本专利JP09-279395,JP49-66625,JP05-163279,国际专利WO2015/146876,中国申请CN103992294;以及论文Tetrahedron Lett. 2003, 44, 7485,山东化工,2015, 44, 33,应用化工,2015,44,1257,和Can. J. Chem. 1976, 266)。这些方法或者使用高温裂解等苛刻和危险工艺,或者工艺条件效率低下成本高昂。目前业界只有日本兴人化学(Konjin Chem)公司使用高温真空裂解工艺实现了单官能度丙烯酰胺的工业化生产。
由上当前的技术状况总结可知,条件间单温和,高效安全,环保节能,和低成本经济竞争力等要素,是业界从业研发和工程技术人员孜孜不倦持续追求的目标,提供一种生产效率高、产品质量高、劳动强度低且对环境友好的丙烯酰胺类化合物的制备方法,仍是本领域技术人员急需解决的技术问题。
【发明内容】本项申请现已意外地发现,经由下面方程式(I)描述的反应技术,自结构式A所示的取代丙酰胺原料出发和试剂B磺酸内脂类化合物在适当的反应条件Conditions下作用,即可制备一系列结构式C和/或D所示的目标产物。
在上述方程式(I)中,R1和R2分别独立的是氢,含有1-24个碳原子(以下标记为C1-C24)的直链或支链的烷基基团,该基团可以为1-6个非连续的氧原子,氮原子,硫原子,氟原子,硅原子,羰基,羟基,胺基,羧基,双键,三键,硅氧基,或C6-C24芳环取代;或者,R1和R2分别独立的是C6-C24芳基,该芳基可以含有0-4个C1-C24烷基,OC1-C24烷氧基,SC1-C24烷硫基,NHC1-C24烷胺基,N(C1-C24)2烷胺基,或卤素取代基;R1和R2之间也可以形成一个C3-C12环结构,该环结构可以为1-4个非连续的氧原子,氮原子,硫原子,双键,或羰基间断。
R3或R4的定义彼此独立地与R1或R2相同;R5是可以是氢或甲基。
R7是含有1-24个饱和或不饱和的碳原子(以下标记为C1-C24)的直链或支链基团。
如上式(I)所示,上述反应的结果除了产物外,无副产物产生,而且采用“一锅煮”的制备方法,展现了新工艺技术无与伦比的简单性,高效性,温和性,具有突出的环境友好型和经济竞争力。
本工艺制备目标产物的方法,具体包括以下步骤:
(1)将化合物A加入溶剂中,加热至熔融状态;
(2)将阻聚剂加入化合物中,并升高温度至回流;
(3)将化合物B缓慢滴加进化合物A中,回流反应一段时间,即可得目标产物。
一个示例性的合成是制备代表性化合物丙烯酰吗啉(ACMO)。自文献已知的方法(日本专利JP09-279395或JP2006182676)可方便制备的化合物A 3-吗啉基丙酰吗啉和B 1,3-丙磺酸内脂在合适的条件Conditions下直接作用,即可生成目标产物,如下所示:
另一个示例性的合成是由单独制备或者原位制备的3-二乙胺基丙酰二乙胺和1,3-丙磺酸内脂在合适的Conditions下作用,制备N,N-二乙基丙烯酰胺(DEAA),如下所示:
Conditions是指有机碱,无机碱,催化剂或促进剂,阻聚剂,热,微波,超声波,真空或压力,溶剂等条件中的任意一种,或是上述任意两种或两种以上因素的联合使用,并无特别限定。有机碱是脂肪或芳香叔胺型化合物;无机碱是碱金属,碱土金属,或过渡金属的氢氧化物,氧化物,碳酸盐,或磺酸盐;催化剂或促进剂是指路易斯酸性或碱性化合物,如三氯化铝,二氯化锌,二氯化镁等。
反应中优选地使用到阻聚剂,常用的阻聚剂是苯酚,苯酚类衍生物;醌类阻聚剂;芳胺类阻聚剂;或CuCl,吩噻嗪,亚磷酸酯,亚磷酸三哌啶氮氧自由基酯,N,N-二烷基二硫代氨基甲酸铜,或上述阻聚剂的混合体系;阻聚剂的用量按照原料的摩尔百分比计为0.01-5%,优选的是0.01-3%。
热是指反应体系在加热条件下进行,反应温度是-25-400摄氏度,优选的是0-200摄氏度,更优选的是10-150摄氏度。微波或超声波是指使用微波或超声波发生器辐射反应体系。反应压力可以是0.001-50个大气压,优选的是0.001-20个大气压,更优选的是0.001-10个大气压。
溶剂可以是芳香性或脂肪性烃,卤代芳香性或脂肪性烃,直链或支链的脂肪烃,(亚)砜,酰胺,醚,酯,酮,腈,羧酸,水,胺,离子液,超临界二氧化碳(Supercritical CO2),或各类酯,醇,醚,腈,酮,酰胺,砜,碳酸酯,或水,或新兴的“离子液(Ionic Liquids)型”所谓绿色溶剂;或上述任意二者或二者以上的混合溶剂体系。该反应也可以仅选用少量甚至不选用任何常规的“溶剂”,而采用原料固相加热和/或研磨,和/或超声波和/或微波辐照促进的方式进行。
可以经由本申请披露技术制备的丙烯酰吗啉类化合物的示例性而非限定性化合物例如如下结构:
上面所描述的丙烯酰胺型化合物是重要的含烯不饱和辐射聚合单体材料。
在实施例中我们将进一步说明。
【具体实施方式】下面结合具体实施例进一步说明本发明要旨:
实施例一:
在氮气保护下,将22.83克3-吗啉基丙酰吗啉,0.23克阻聚剂ZJ-705 和110毫升二甲苯加入反应瓶中,升温到140 ℃,用滴液漏斗缓慢滴加12.22克1,3-丙磺酸内脂,继续搅拌反应,回流5小时后脱除溶剂,反应体系减压浓缩后得到12.15克丙烯酰吗啉纯品(86.05%收率)。
实施例二:
在氮气保护下,将22.83克3-吗啉基丙酰吗啉,0.23克阻聚剂ZJ-705 和110毫升二甲苯加入反应瓶中,升温到140 ℃,用滴液漏斗缓慢滴加13.62克1,4-丁磺酸内脂,继续搅拌反应,回流5小时后脱除溶剂,反应体系减压浓缩后得到12.52克丙烯酰吗啉纯品(88.36%收率)。
实施例三:
在氮气保护下,将22.83克3-吗啉基丙酰吗啉,0.23克阻聚剂ZJ-705 和110毫升甲苯加入反应瓶中,升温到140 ℃,用滴液漏斗缓慢滴加12.01克1-丙烯基-1,3-磺酸内脂,继续搅拌反应,回流5小时后脱除溶剂,反应体系减压浓缩后得到11.98克丙烯酰吗啉纯品(84.84%收率)。
实施例四:
在氮气保护下,将20.04克3-二乙胺基丙酰二乙胺,0.2克阻聚剂ZJ-705和100毫升二甲苯加入反应瓶中,升温到140 ℃,用滴液漏斗缓慢滴加12.22克1,3-丙磺酸内脂,继续搅拌反应,回流5小时后脱除溶剂,反应体系减压浓缩后得到10.67克丙烯酰二乙胺纯品(83.90%收率)。
实施例五:
在氮气保护下,将20.04克3-二乙胺基丙酰二乙胺,0.2克阻聚剂ZJ-705和80毫升二甲苯加入反应瓶中,升温到140 ℃,用滴液漏斗缓慢滴加12.02克1-丙烯基-1,3-磺酸内脂,继续搅拌反应,回流5小时后脱除溶剂,反应体系减压浓缩后得到10.91克丙烯酰二乙胺纯品(85.77%收率)。
实施例六:
在氮气保护下,将24.04克N,N'-二(苯基)丙二酰胺,0.24克阻聚剂ZJ-705和120毫升二甲苯加入反应瓶中,升温到140 ℃,用滴液漏斗缓慢滴加12.22克1,3-丙磺酸内脂,继续搅拌反应,回流5小时后脱除溶剂,反应体系减压浓缩后得到13.14克N-苯基丙烯酰胺纯品(89.27%收率)。
实施例七:
在氮气保护下,将24.04克N,N'-二(苯基)丙二酰胺,0.24克阻聚剂ZJ-705和120毫升二甲苯加入反应瓶中,升温到140 ℃,用滴液漏斗缓慢滴加13.62克1,4-丁磺酸内脂,继续搅拌反应,回流5小时后脱除溶剂,反应体系减压浓缩后得到13.61克N-苯基丙烯酰胺纯品(92.45%收率)。
实施例八:
在氮气保护下,将21.43克预先制备的3-N,N-二乙胺基丙酰吗啉,0.21克阻聚剂ZJ-705和100毫升二甲苯加入反应瓶中,升温到140 ℃,用滴液漏斗缓慢滴加12.22克1,3-丙磺酸内脂,继续搅拌反应,回流5小时后脱除溶剂,反应体系减压浓缩后得到10.75克丙烯酰吗啉纯品(76.13%收率)。
实施例九:
在氮气保护下,将21.44克预先制备的3-N,N-二乙胺基丙酰吗啉,0.21克阻聚剂ZJ-705和100毫升二甲苯加入反应瓶中,升温到140 ℃,用滴液漏斗缓慢滴加12.02克1-丙烯基-1,3-磺酸内脂,继续搅拌反应,回流5小时后脱除溶剂,反应体系减压浓缩后得到11.01克丙烯酰吗啉纯品(77.98%收率)。
实施例十:以丙烯酸酯为原料“一锅煮”法合成
在氩气保护下,室温下于烧瓶中加入92.5克吗啉和0.22克阻聚剂BHT,于1小时内缓慢滴加37克丙烯酸甲酯,加毕再补加18.5克吗啉,体系于55 ℃保温反应2小时。在该温度下于1小时内缓慢滴加7.8克的30%的甲醇钠和40克甲醇的混合液,加完升温至75 ℃保温反应约5小时,反应完后缓慢滴加2.3克浓硫酸,常压蒸馏回收甲醇,减压蒸馏回收吗啉,得到的93.4克3-吗啉基丙酰吗啉中间体。直接加入0.94克阻聚剂ZJ-705和400毫升二甲苯加入反应瓶中,升温到140 ℃,用滴液漏斗缓慢滴加49.97克1,3-丙磺酸内脂,继续搅拌反应,回流过夜后脱除溶剂,反应体系减压浓缩后得到51.78克丙烯酰吗啉纯品(89.66%收率)。
需要强调的是,上述实施例仅仅为示例性而非限定性说明,基于本项申请披露,任何从业技术人员所通常可能采用的反应条件或参数等调整或变动均不会偏离本发明的要旨,本专利的保护范围应以相关的权利书记载条目为准。
Claims (10)
1.方程式(I)描述的反应工艺技术,结构式A所示的取代丙酰胺原料和试剂B所示的磺酸酯类化合物在适当的反应条件Conditions下作用,同时制备一系列结构式C和/或D所示的目标产物;
在上述方程式(I)中,R1和R2分别独立的是氢,含有1-24个碳原子(以下标记为C1-C24)的直链或支链的烷基基团,该基团可以为1-6个非连续的氧原子,氮原子,硫原子,氟原子,硅原子,羰基,羟基,胺基,羧基,双键,三键,硅氧基,或C6-C24芳环取代;或者,R1和R2分别独立的是C6-C24芳基,该芳基可以含有0-4个C1-C24烷基,OC1-C24烷氧基,SC1-C24烷硫基,NHC1-C24烷胺基,N(C1-C24)2烷胺基,或卤素取代基;R1和R2之间也可以形成一个C3-C12环结构,该环结构可以为1-4个非连续的氧原子,氮原子,硫原子,双键,或羰基间断;
R3或R4的定义彼此独立地与R1或R2相同;R5是可以是氢或甲基;
R7是含有1-24个饱和或不饱和的碳原子(以下标记为C1-C24)的直链或支链基团;
Conditions是指有机碱,无机碱,催化剂或促进剂,阻聚剂,热,微波,超声波,真空或压力,溶剂等条件中的任意一种,或是上述任意两种或两种以上因素的联合使用。
2.方程式(II)所描述的反应工艺技术,由相应的原材料E和G依次与F在适当的反应条件Conditions作用下制备一系列结构式A;A再与B磺酸内脂类化合物在适当的反应条件Conditions作用下制备目标产物;
在上述反应式II和I中,各基团,物质,和Conditions的定义与权利要求(1)中相应项相同,R6和R1的定义相同。
3.根据权利要求(1-2)描述的工艺方法,有机碱是脂肪或芳香叔胺型化合物;无机碱是碱金属,碱土金属,或过渡金属的氢氧化物,氧化物,碳酸盐,或磺酸盐;催化剂或促进剂是指路易斯酸性或碱性化合物,如三氯化铝,二氯化锌,二氯化镁等。
4.根据权利要求(1-2)描述的工艺方法,阻聚剂是苯酚,苯酚类衍生物(如对苯二酚,邻苯二酚,间苯二酚,对甲基苯酚,对叔丁基邻苯二酚,2,6-二叔丁基对甲基苯酚,4,4'-二经基联苯和双酚A等);醌类阻聚剂(如对苯醌);芳胺类阻聚剂(如对甲苯胺、二苯胺、联苯胺、对苯二胺、N-亚硝基二苯胺等);或CuCl,吩噻嗪,亚磷酸酯,亚磷酸三哌啶氮氧自由基酯,N,N-二烷基二硫代氨基甲酸铜,或上述阻聚剂的混合体系;阻聚剂的用量按照原料的摩尔百分比计为0.01-5%,优选的是0.01-3%。
5.根据权利要求(1-2)描述的工艺方法,反应温度是-25-400摄氏度,优选的是0-200摄氏度,更优选的是10-150摄氏度;微波或超声波是指使用微波或超声波发生器辐射反应体系。
6.根据权利要求(1-2)描述的工艺方法,反应压力可以是0.001-50个大气压,优选的是0.001-20个大气压,更优选的是0.001-10个大气压。
7.根据权利要求(1-2)描述的工艺方法,溶剂可以是芳香性或脂肪性烃,卤代芳香性或脂肪性烃,直链或支链的脂肪烃,(亚)砜,酰胺,醚,酯,酮,腈,羧酸,水,胺,离子液,超临界二氧化碳(Supercritical CO2),或各类酯,醇,醚,腈,酮,酰胺,砜,碳酸酯,或水,或新兴的“离子液(Ionic Liquids)型”所谓绿色溶剂;或上述任意二者或二者以上的混合溶剂体系;该反应也可以仅选用少量甚至不选用任何常规的“溶剂”,而采用原料固相加热和/或研磨,和/或超声波和/或微波辐照促进的方式进行。
8.根据权利要求(1-2)描述的工艺方法,披露技术制备的(甲基)丙烯酰胺类化合物或其混合物的示例性而非限定性化合物是如下结构:
。
9.结构式A所示的取代丙酰胺原料通常是已知的化合物,可以直接商业采购和/或经由文献已知方法自相应的胺和丙烯酸(酯)直接缩合制备(Tetrahedron Lett. 2008, 49,5147或(日本专利JP09-279395或JP2006182676),结构式B则为磺酸内脂类化合物。
10.根据权利要求(1),执行通式(I)的八种优选方式是下列反应:
在上述反应式中,各基团和Conditions的定义与权利要求(1)中相应项相同。
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