CN102712576B - 制备芳族甲酰胺的方法 - Google Patents
制备芳族甲酰胺的方法 Download PDFInfo
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- CN102712576B CN102712576B CN201080055140.9A CN201080055140A CN102712576B CN 102712576 B CN102712576 B CN 102712576B CN 201080055140 A CN201080055140 A CN 201080055140A CN 102712576 B CN102712576 B CN 102712576B
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- Prior art keywords
- manthanoate
- salt
- catalyzer
- acid
- methyl
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- -1 aromatic formamides Chemical class 0.000 title claims abstract description 49
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- 238000000034 method Methods 0.000 claims abstract description 31
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000019253 formic acid Nutrition 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 16
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical group C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
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- 125000003277 amino group Chemical group 0.000 claims description 3
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 16
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- 238000000926 separation method Methods 0.000 description 8
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- 239000000295 fuel oil Substances 0.000 description 5
- 238000004809 thin layer chromatography Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
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- RNVCVTLRINQCPJ-UHFFFAOYSA-N ortho-methyl aniline Natural products CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 4
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- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
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- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical class ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N meta-toluidine Natural products CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
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- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 1
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- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
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- WRDWWAVNELMWAM-UHFFFAOYSA-N 4-tert-butylaniline Chemical compound CC(C)(C)C1=CC=C(N)C=C1 WRDWWAVNELMWAM-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
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- 125000003342 alkenyl group Chemical group 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
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- 150000003624 transition metals Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- AWSFICBXMUKWSK-UHFFFAOYSA-N ytterbium(3+) Chemical compound [Yb+3] AWSFICBXMUKWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种制备甲酰胺的方法,其中使芳族胺与甲酸酯在催化剂的存在下转化,此方法的特征在于催化剂是磷酸或路易斯酸性金属盐。
Description
本发明涉及一种制备芳族甲酰胺的方法,其中在催化量的含磷的酸或路易斯酸性金属盐的存在下使单官能、双官能或多官能的芳族胺与甲酸酯反应,此方法即使在短的反应时间后也能获得高选择性和高收率。用此方法制得的甲酰胺可随后转化为工业上重要的异氰酸酯。
脂族胺与甲酸甲酯制备得到相应甲酰胺的热反应可以以很好的选择性和时空产率进行,而且也可在工业规模上例如用于生产N,N-二甲基甲酰胺(DMF)(Industrielle Organische Chemie,Wiley-VCH,Weinheim,2007(6),49)。相比之下,芳族胺向相应甲酰胺的类似转化反应却由于这些胺的亲核性降低而具有明显降低的效率。其中,即使经过长时间的反应,也仅获得不令人满意的转化率和收率,这阻碍了这些方法的潜在工业应用(例如DE 3832571,Journal of OrganicChemistry 1966,(31),3473-3482和Tetrahedron 2004,(60),81-92)。
为了弥补此缺陷,在过去公开了许多替代性的制备芳族甲酰胺的方法。因此,过量的甲酸与芳族胺的反应以高产率生成相应的甲酰胺(DE 138839和Bulletin ofthe Korean Chemical Society 2002,(23),149-150)。然而,在这方面,由于甲酸的腐蚀性相当大,所以设备必须由更高级并且因此更昂贵的材料制造。此外,甲酸是工业上通过甲酸甲酯的酸性水解获得的。甲酸甲酯的直接使用将因此导致更有效和更具成本效益的合成路线。
甲酸酯与例如2,2,2-三氟乙醇或五氟苯酚的反应能实现在温和条件下的高收率(Synthesis 1987,510和Organic Letters 2002,(4),111-113)。然而,这些试剂只能非常有限地用于工业应用,因为它们既昂贵也不能大量获得。
强碱如氢化钠和六甲基二硅烷锂或负载于硅胶上的三氯化磷的化学计量使用同样可实现有效的反应(Organic Letters 2009,(11),389-892,Organic Letters2007,(9),3631-3634和Tetrahedron Letters 2005,(46),7963-7966)。然而产生了大量副产物,其必须被抛弃或以高成本进行回收。
到目前为止,仅公开了少数在催化活性化合物存在下从芳族胺和甲酸烷基酯制备甲酰胺的合成方法。为此,首先已经使用酸,例如对甲苯磺酸、三氟乙酸或少量的甲酸(Organic Letters 2006,(8),1875-1878,Tetrahedron 2005,(61),7144-7152,Journal of Organic Chemistry 1966,(31),3473-3482and ChemicalPapers 1993,(47),109-113)。Daszkiewicz等(Chemical Papers 1993,(47),109-113)公开了例如通过环取代的苯胺与甲酸正丁酯在作为催化剂的三氟乙酸存在下反应制备芳族取代的N-甲酰苯胺。甲醇钠或钐茂金属的使用也同样被公开(US 2005/0027120和Journal of Organic Chemistry 1996,(61),3088-3092)。然而,在这些情况下也同样存在着以下问题:对于工业应用而言的收率太低,使用昂贵的高级烷基甲酸酯,和/或催化剂是非常昂贵的或具有腐蚀性。
本发明的目的在于开发一种可工业实施的从单官能、双官能或多官能的芳族胺制备甲酰胺的方法,其中即使当在催化剂存在下使用工业可得到的甲酸酯时也能达到高的时空产率和选择性。
惊奇地发现,由芳族胺和甲酸烷基酯在含磷的酸或路易斯酸性金属盐的存在下反应,即使在短的时间反应后也能以非常好的收率分离得到所需的甲酰胺。
本发明提供一种制备甲酰胺的方法,其中通过在催化剂的存在下使芳族胺与甲酸酯反应,其中催化剂是含磷的酸或路易斯酸性金属盐。
在本发明方法中使用的含磷的酸(=质子给体)例如是三价磷(III)酸,例如C1-C10烷基膦酸,优选C1-C4烷基膦酸,或C6-C14芳基膦酸,优选C6-C10芳基膦酸,如果合适的话负载于聚合物固相上;以及五价磷(V)酸,例如正磷酸和其高级缩合物(焦磷酸、偏磷酸或多磷酸)。在上述磷酸的情况下,一些酸官能团可以被低级C1-C4醇酯化,如甲醇、乙醇或正丁醇。这些含磷的酸可以以纯的形式或作为混合物使用。特别优选使用无水或水溶液形式的正磷酸。
在本发明方法中使用的路易斯酸性金属盐(=电子对受体)例如是过渡金属的盐,镧系元素的盐,或第二、第三或第四族金属的盐,或者无机或有机酸的盐。优选,路易斯酸性金属盐的金属是选自以下的组:锌,铅,锡,铁,铝,钛,锆,钪,钇,镧,铈或镱。上述金属盐一般是相应的氟化物、氯化物、硫酸盐、硝酸盐、磷酸盐、羧酸盐或磺酸盐。
羧酸盐通常是阴离子,由通式为R(CO2H)n的羧酸去质子化形成。R在此是指C1-C18烷基,C2-C7链烯基,优选乙烯基,C5-C8环烷基,芳族C6-C14芳基,优选苯基或萘基,或通式(I)的环烷酸基:
其中R1是氢或亚甲基环戊基,m是0或1-12的整数,n是1-4的整数。优选,n为1。
优选这样的羧酸盐,其中R是C1-C10烷基,特别是C1-C6烷基,C5-C8环烷基或上述式(I)结构的环烷酸基。尤其优选,R是甲基、乙基、丙基或环戊基。所有具体的羧酸盐可以单独使用,或作为混合物使用。
磺酸盐通常被理解为任选被取代的C1-C4烷基苯磺酸盐,特别是甲基-或乙基-苯磺酸盐,C6-C10芳基-苯磺酸盐,特别是苯基苯磺酸盐或甲苯基苯磺酸盐,或C10-C14烷基苯磺酸盐。上述烷基优选被卤素单取代或多取代,优选氟。特别优选是三氟甲烷磺酸盐。
所述的路易斯酸性金属盐也包括含结晶水的相应单-、二-或多-水合物。
特别优选的是锌、铅、镱、钪或镧的路易斯酸性金属盐,尤其是其羧酸盐、磺酸盐或硝酸盐。非常优选使用乙酸锌、乙酸锌二水合物、环烷酸锌或三氟甲烷磺酸镱。
催化剂按照摩尔比率为0.001-0.3使用,优选为0.01-0.1,在每种情况下基于氨基基团计。
甲酸酯是衍生自直链或支化的具有1-6个碳原子的脂族醇,例如甲醇、乙醇、正丙醇、正丁醇、正戊醇或正己醇;或衍生自直链或支化的1-链烯基甲酸酯,其中链烯基具有2-6个碳原子,例如甲酸乙烯基酯或甲酸异戊二烯基酯。上述甲酸酯可以单独使用或作为混合物使用。优选使用直链或支化的甲酸C1-C6烷基酯,特别优选甲酸甲酯,其也可以按工业规模获得。甲酸甲酯优选通过一氧化碳与甲醇反应制得。
所述甲酸酯按照甲酸酯与氨基的摩尔比率为1∶1至20∶1使用,优选1.5∶1至8∶1。
芳族胺与甲酸酯在催化剂存在的下反应是优选在20-160℃的反应温度下进行,特别优选60-120℃。在此温度下,芳族胺的定量转化是在0.5-5小时内获得,通常达到2小时的反应时间。压力条件的选择通常依赖于所用的甲酸酯和其沸点温度。此反应可以在自压下进行(在密闭容器中在反应温度下在反应期间产生的压力),或也可以在1-100巴的更高绝对压力或0.001-1巴的低于大气压的绝对压力下进行。溶剂可以使用甲酸酯自身或其他惰性化合物。合适的溶剂是酰胺例如N,N-二甲基甲酰胺或N,N-二甲基乙酰胺,亚砜例如二甲亚砜,具有或不具有烷基、卤素或烷氧基取代基的芳烃,例如甲苯、二甲苯异构体、均三甲苯、乙苯、氯苯、二氯或三氯苯的同分异构体,苯甲醚,单醚或聚醚,例如四氢呋喃、二烷或二甲氧基乙烷,二烷基二醇,例如二甘醇二甲醚和三甘醇二甲醚。这些溶剂可以单独使用,或作为混合物使用。
在本发明方法中,使用单官能、双官能或多官能的芳族胺。上述胺是具有通式R2(NHR3)n的伯胺或仲胺,其中R2是任选被取代的C6-C34芳基,优选C6-C20芳基,特别为C6-C14芳基,特别优选苯基或甲苯基或苯亚甲基。R3为C1-C4烷基,特别是甲基或乙基,或氢原子,以及n是1-3的整数,优选1或2,按每个芳族环计。优选,R3是氢原子。芳基的合适取代基例如是氯、氟、溴、氰基、烷基、烷氧基、烷基羰基和/或烷氧基羰基,基中烷基和烷氧基通常具有1-10个、优选1-6个、特别优选1-4个碳原子。这些基团中有代表性的是例如苯胺,邻-、间-和/或对-甲苯胺,邻-、间-和/或对-氯苯胺,邻-、间-和/或对-溴苯胺,邻-、间-和/或对-三氟甲基苯胺,2,4-、2,6-、3,4-和/或3,5-二甲基-、-二氯-苯胺、-二溴-苯胺或-二乙基苯胺,对叔丁基苯胺,二氨基甲苯(TDA),特别是2,4-和/或2,6-二氨基甲苯,二氨基二苯基甲烷(MDA),特别是2,4′-二氨基二苯基甲烷、4,4′-二氨基二苯基甲烷、2,2′-二氨基二苯基甲烷和/或高级同系物(多亚苯基多亚甲基多胺),或邻-、间-和/或对-苯二胺。优选使用苯胺,二氨基甲苯的异构体,特别是2,4-和2,6-二氨基甲苯,和/或二氨基二苯基甲烷的异构体和高级同系物。
芳族甲酰胺的分离可以使用本领域技术人员已知的多种方法进行。这例如可以是分馏。或者,反应排出物可蒸发至干,而且所得到的固体可以通过用合适的溶剂洗涤或用合适的溶剂重结晶进行纯化。此外,有价值的产物可以通过加入合适的溶剂进行沉淀,通过过滤分离以及通过洗涤或重结晶进行纯化。
在一个根据本发明制备甲酰胺方法的优选实施方案中,早在反应期间或仅仅在反应完成之后作为悬浮在过量试剂或溶剂中的固体制得有价值的产物,然后通过过滤分离。这可以在反应温度或在例如自压、大气压或加压下合适地冷却到室温下发生。在此,甲酰胺通常以适宜进一步工艺的足够纯的形式制得,但是,如果必要,也可以进一步通过用甲酸酯或其他溶剂洗涤以纯化。在从滤液分离完固体后,所述固体可以作为固体形式、作为熔体或溶解在合适的溶剂中之后分离出来,以及任选地被送至进一步的反应阶段。从滤液中,过量的试剂、可能用于反应的溶剂和催化剂,可以单独或各自独立地分离出来,且可用于进一步反应循环。任何未反应的起始原料和/或在多胺反应期间形成的反应中间体(氨基甲酰胺)的残留物也可以分离出来并返回制备流程中。该方法可以连续或间断地进行。
所得的甲酰胺,如果其衍生自芳族伯胺的话,则可制备成工业上重要的芳族异氰酸酯,例如通过氧化脱氢。
进一步通过以下实施例详述本发明,但不仅局限于此。
实施例
实施例1
10.0g(81.9mmol)的2,4-二氨基甲苯溶解于40.0g的N,N-二甲基乙酰胺和49.2g(819mmol)的甲酸甲酯中,并使之与0.47g(4.1mmol)的85%重量浓度的正磷酸水溶液混合。将混合物倒入300ml的高压釜中并在自压和90℃下搅拌4小时。冷却至室温后,得到的混合物蒸发至干。根据NMR光谱,所得到的褐色固体(17.3g)除了溶剂残留物和催化剂外,还包括摩尔比率为97∶3的双甲酰胺和区域异构的单酰胺。
实施例2
10.0g(81.9mmol)的2,4-二氨基甲苯溶解于40.0g的N,N-二甲基乙酰胺和49.2g(819mmol)的甲酸甲酯中,并使之与2.54g(4.1mmol)的三氟甲烷磺酸镱(III)混合。将混合物倒入300ml的高压釜中,并在自压和90℃下搅拌4小时。冷却至室温后,得到的混合物蒸发至干。根据NMR光谱,所得到的褐色固体(23.4g)除了溶剂残留物和催化剂外,还包括摩尔比率为94∶6的双甲酰胺和区域异构的单酰胺。
实施例3
10.0g(81.9mmol)的2,4-二氨基甲苯溶解于40.0g的N,N-二甲基乙酰胺和49.2g(819mmol)的甲酸甲酯中,并使之与0.75g(4.1mmol)的乙酸锌(II)混合。将混合物倒入300ml的高压釜中,并在自压和90℃下搅拌4小时。冷却至室温后,得到的混合物蒸发至干。根据NMR光谱,所得到的褐色固体(16.4g)除了溶剂残留物和催化剂外,还包括摩尔比率为92∶8的双甲酰胺和区域异构的单酰胺。
实施例4
10.0g(81.9mmol)的2,4-二氨基甲苯溶解于40.0g的N,N-二甲基乙酰胺和49.2g(819mmol)的甲酸甲酯中,并使之与1.55g(4.1mmol)的乙酸铅(II)混合。将混合物倒入300ml的高压釜中,并在自压和90℃下搅拌4小时。冷却至室温后,得到的混合物蒸发至干。根据NMR光谱,所得到的褐色固体(15.7g)除了溶剂残留物和催化剂外,还包括摩尔比率为73∶27的双甲酰胺和区域异构的单酰胺。
比较实施例1
10.0g(81.9mmol)的2,4-二氨基甲苯溶解于40.0g的N,N-二甲基乙酰胺和49.2g(819mmol)的甲酸甲酯中,并使之与0.40g(4.2mmol)的甲磺酸混合。将混合物倒入300ml的高压釜中,并在自压和90℃下搅拌4小时。冷却至室温后,得到的混合物蒸发至干。根据NMR光谱,所得到的棕色高粘度油(14.8g)除了溶剂残留物和催化剂外,还包括摩尔比率为10∶75∶15的双甲酰胺、区域异构的单酰胺和2,4-二氨基甲苯。
比较实施例2
10.0g(81.9mmol)的2,4-二氨基甲苯溶解于40.0g的N,N-二甲基乙酰胺和49.2g(819mmol)的甲酸甲酯中,并使之与0.42g(4.1mmol)的96%重量浓度的硫酸水溶液混合。将混合物倒入300ml的高压釜中,并在自压和90℃下搅拌4小时。冷却至室温后,得到的混合物蒸发至干。根据NMR光谱,所得到的棕色高粘度油(15.2g)除了溶剂残留物和催化剂外,还包括摩尔比率为23∶74∶3的双甲酰胺、区域异构的单酰胺和2,4-二氨基甲苯。
比较实施例3
10.0g(81.9mmol)的2,4-二氨基甲苯溶解于40.0g的N,N-二甲基乙酰胺和49.2g(819mmol)的甲酸甲酯中,并使之与0.65g(4.1mmol)的苯磺酸混合。将混合物倒入300ml的高压釜中,并在自压和90℃下搅拌4小时。冷却至室温后,得到的混合物蒸发至干。根据NMR光谱,所得到的棕色高粘度油(15.6g)除了溶剂残留物和催化剂外,还包括摩尔比率为12∶76∶12的双甲酰胺、区域异构的单酰胺和2,4-二氨基甲苯。
比较实施例4
10.0g(81.9mmol)的2,4-二氨基甲苯溶解于40.0g的N,N-二甲基乙酰胺和49.2g(819mmol)的甲酸甲酯中,并使之与1.57g(4.1mmol)的叔丁氧基锆(IV)混合。将混合物倒入300ml的高压釜中,并在自压和90℃下搅拌4小时。冷却至室温后,得到的混合物蒸发至干。根据NMR光谱,所得到的棕色高粘度油(15.4g)除了溶剂残留物和催化剂外,还包括摩尔比率为41∶58∶1的双甲酰胺、区域异构的单酰胺和2,4-二氨基甲苯。
比较实施例5
10.0g(81.9mmol)的2,4-二氨基甲苯溶解于40.0g的N,N-二甲基乙酰胺和49.2g(819mmol)的甲酸甲酯中。将混合物倒入无催化剂的300ml的高压釜中并在自压和90℃下搅拌12小时。冷却至室温后,得到的混合物蒸发至干。根据NMR光谱和薄层色谱,所得到的棕色高粘度油(15.4g)除了溶剂残留物外,无显著量的双甲酰胺,仅有区域异构的单酰胺和2,4-二氨基甲苯。
实施例5
10.0g(81.9mmol)的2,6-二氨基甲苯溶解于40.0g的N,N-二甲基乙酰胺和49.2g(819mmol)的甲酸甲酯中,并使之与0.47g(4.1mmol)的85%重量浓度的正磷酸水溶液混合。将混合物倒入300ml的高压釜中,并在自压和90℃下搅拌4小时。冷却至室温后,得到的混合物蒸发至干。根据NMR光谱,所得到的褐色固体(14.6g)除了溶剂残留物和催化剂外,还包括摩尔比率为97∶3的双甲酰胺和单酰胺。
实施例6
21.7g(178mmol)的2,4-二氨基甲苯溶解于21.7g的N,N-二甲基乙酰胺和107g(1.78mol)的甲酸甲酯中,并使之与1.02g(8.8mmol)的85%重量浓度的正磷酸水溶液混合。将混合物倒入300ml的高压釜中,并在自压和90℃下搅拌2小时。冷却至室温后,所得悬浮液用70g的甲酸甲酯稀释并过滤,基本上无色的固体用70g的甲酸甲酯洗涤并干燥。通过此方式,根据薄层色谱和NMR光谱,分离得到29.6g(94%)的纯的双甲酰胺。
实施例7
21.7g(178mmol)的2,4-二氨基甲苯溶解于128g(2.13mol)的甲酸甲酯中,并使之与1.63g(8.9mmol)的乙酸锌(II)混合。将混合物倒入300ml的高压釜中,并在自压和90℃下搅拌2小时。冷却至室温后,所得悬浮液用70g的甲酸甲酯稀释并过滤,基本上无色的固体用70g的甲酸甲酯洗涤并干燥。通过此方式,根据薄层色谱和NMR光谱,分离得到29.8g(94%)的纯的双甲酰胺。
实施例8
20.0g(164mmol)的2,6-二氨基甲苯溶解于118g(1.97mol)的甲酸甲酯中,并使之与5.01g(8.0mmol)的65%重量浓度的于矿物油中的环烷酸锌(II)(对应于浓度为10重量%的锌溶液)混合。将混合物倒入300ml的高压釜中,并在自压和90℃下搅拌2小时。冷却至室温后,所得悬浮液用70g的甲酸甲酯稀释并过滤,实质上无色的固体用70g的甲酸甲酯洗涤并干燥。通过此方式,根据薄层色谱和NMR光谱,分离得到26.7g(92%)的纯的双甲酰胺。
实施例9
21.7g(178mmol)的比率为80∶20的2,4-二氨基甲苯和2,6-二氨基甲苯溶解于128g(2.13mol)的甲酸甲酯中,并使之与1.02g(8.8mmol)的85%重量浓度的正磷酸水溶液混合。将混合物倒入300ml的高压釜中并在自压以及90℃下搅拌2小时。冷却至室温后,所得悬浮液用70g的甲酸甲酯稀释并过滤,基本上无色的固体用70g的甲酸甲酯洗涤并干燥。通过本方法,根据薄层色谱和NMR光谱,分离得到27.8g(88%)的区域异构的双甲酰胺的纯混合物。
实施例10
15.0g(161mmol)的苯胺溶解于60.0g的N,N-二甲基乙酰胺和48.5g(808mmol)甲酸甲酯中,并使之与1.07g(4.9mmol)的乙酸锌(II)二水合物混合。将混合物倒入300ml的高压釜中,并在自压和90℃下搅拌2小时。冷却至室温后,过量的甲酸甲酯和形成的甲醇被蒸馏掉。所得红棕色油状物中除了大量溶剂和催化剂外,根据NMR光谱,仅包含摩尔比率为99∶1的N-甲酰苯胺和苯胺。
实施例11
15.0g(161mmol)的苯胺溶解于60.0g的N,N-二甲基乙酰胺和48.5g(808mmol)甲酸甲酯中,并使之与0.56g(4.9mmol)的85%重量浓度的正磷酸水溶液混合。将混合物倒入300ml的高压釜中,并在自压和90℃下搅拌2小时。冷却至室温后,过量的甲酸甲酯和形成的甲醇被蒸馏掉。所得红棕色油状物中除了较大量的溶剂和催化剂外,根据NMR光谱,仅包含摩尔比率为98∶2的N-甲酰苯胺和苯胺。
这些实施例表明,根据本发明的方法能以高选择性和高时空收率获得芳族甲酰胺。这些产品以高纯度形成,意味着不需要复杂的后纯化步骤。
Claims (13)
1.一种制备甲酰胺的方法,其中使芳族胺与甲酸酯在催化剂的存在下反应,其中催化剂是含磷的酸或路易斯酸性金属盐,其中路易斯酸性金属盐的金属是选自以下的组:锌、铅和镱。
2.根据权利要求1的方法,其中含磷的酸是正磷酸,或其较高分子量的缩合物之一。
3.根据权利要求1的方法,其中路易斯酸性金属盐是锌、铅或镱的羧酸盐、磺酸盐或硝酸盐。
4.根据权利要求1的方法,其中路易斯酸性金属盐是乙酸锌、乙酸锌二水合物、环烷酸锌或三氟甲烷磺酸镱。
5.根据权利要求1的方法,其中催化剂按照摩尔比率为0.001-0.3使用,基于氨基基团计。
6.根据权利要求1的方法,其中甲酸酯是直链或支化的甲酸C1-C6烷基酯或C2-C6-1-链烯基甲酸酯。
7.根据权利要求1的方法,其中甲酸酯是甲酸甲酯。
8.根据权利要求1的方法,其中甲酸酯按照甲酸酯与氨基基团的摩尔比率为1:1至20:1使用。
9.根据权利要求1的方法,其中芳族胺是具有通式R2(NHR3)n的伯胺或仲胺,其中R2为任选被取代的C6-C34芳基,R3为C1-C4烷基或氢原子,以及n是1-3的整数,按每个芳族环计。
10.根据权利要求1的方法,其中芳族胺是伯胺。
11.根据权利要求1的方法,其中芳族胺是选自以下的组:苯胺,二氨基甲苯,二氨基二苯基甲烷,以及它们的混合物。
12.根据权利要求1的方法,其中从所述反应获得的类似悬浮物的排出物进行过滤,甲酰胺是作为固体分离出来的。
13.根据权利要求12的方法,其中存在于滤液和任何溶剂中的催化剂、过量的甲酸酯、起始原料残留物和氨基甲酰胺,各自独立或分别地在进一步的反应循环中再利用和/或再循环。
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