CN102365393B - 生产3-叔丁基苯甲醛缩二甲醇的电化学方法 - Google Patents
生产3-叔丁基苯甲醛缩二甲醇的电化学方法 Download PDFInfo
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- 238000002848 electrochemical method Methods 0.000 title abstract description 5
- 238000000034 method Methods 0.000 claims description 47
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- -1 3-tertiary butyl benzyl compounds Chemical class 0.000 claims description 24
- 238000006198 methoxylation reaction Methods 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 23
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 15
- JZMJDSHXVKJFKW-UHFFFAOYSA-N methyl sulfate Chemical compound COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 claims description 12
- 239000008151 electrolyte solution Substances 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- LNYJYVGUHXQWLO-UHFFFAOYSA-M methyl sulfate;triethyl(methyl)azanium Chemical compound COS([O-])(=O)=O.CC[N+](C)(CC)CC LNYJYVGUHXQWLO-UHFFFAOYSA-M 0.000 claims description 9
- IGVZPDMKUBZLKT-UHFFFAOYSA-N 1-tert-butyl-3-[(3-tert-butylphenyl)methoxymethyl]benzene Chemical class CC(C)(C)C1=CC=CC(COCC=2C=C(C=CC=2)C(C)(C)C)=C1 IGVZPDMKUBZLKT-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
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- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
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- 125000004432 carbon atom Chemical group C* 0.000 claims 1
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 12
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- 239000003054 catalyst Substances 0.000 description 2
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- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- HEPHYCJJLAUKSB-UHFFFAOYSA-N 2-methyl-3-phenylpropanal Chemical compound O=CC(C)CC1=CC=CC=C1 HEPHYCJJLAUKSB-UHFFFAOYSA-N 0.000 description 1
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- 244000287680 Garcinia dulcis Species 0.000 description 1
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- 125000006177 alkyl benzyl group Chemical group 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- FIMHASWLGDDANN-UHFFFAOYSA-M methyl sulfate;tributyl(methyl)azanium Chemical compound COS([O-])(=O)=O.CCCC[N+](C)(CCCC)CCCC FIMHASWLGDDANN-UHFFFAOYSA-M 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
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- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- ZFNVDHOSLNRHNN-UHFFFAOYSA-N xi-3-(4-Isopropylphenyl)-2-methylpropanal Chemical compound O=CC(C)CC1=CC=C(C(C)C)C=C1 ZFNVDHOSLNRHNN-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/17—Unsaturated ethers containing halogen
- C07C43/174—Unsaturated ethers containing halogen containing six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/30—Compounds having groups
- C07C43/303—Compounds having groups having acetal carbon atoms bound to acyclic carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/515—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an acetalised, ketalised hemi-acetalised, or hemi-ketalised hydroxyl group
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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Abstract
本发明涉及3-叔丁基苯甲醛缩二甲醇和3-叔丁基苄基甲基醚以及一种生产3-叔丁基苯甲醛缩二甲醇的电化学方法和通过所述方法生产的中间体。
Description
本发明涉及3-叔丁基苯甲醛缩二甲醇和3-叔丁基苄基甲基醚以及一种生产3-叔丁基苯甲醛缩二甲醇的电化学方法。
已知直接通过对应甲苯的电化学甲氧基化生产取代的苯甲醛缩二甲醇。P.Loyson,S.Gouws,B.Barton,M.Ackermann,S.Afr.J.Chem 2004,57,53-56描述了这样一种方法。甲苯类的电化学侧链甲氧基化的缺点是只能以经济上令人感兴趣的收率甲氧基化被推电子基团如叔丁基、甲基或烷氧基取代的甲苯。尽管诸如乙基、异丙基或异丁基的基团同样具有推电子效果,但它们的苄基质子同样可以在电化学反应过程中在次级反应中被甲氧基替代。因此,如F.Vaudano,P.Tissot,Electrochimica Acta 2001,46,875-880所述,对异丙基苯甲烷不能平稳地甲氧基化而得到对异丙基苯甲醛缩二甲醇,因为异丙基总是也被成比例地甲氧基化。
取代的苯甲醛缩二甲醇和这些所基于的醛类是重要的中间体,例如在2-甲基-3-苯基丙醛香料如仙客来醛,(BASF SE)或银醛(silvial)的合成中。
EP 0 129 795 A2描述了一种通过电氧化相应取代的烷基甲苯而生产取代的苯甲醛缩二烷醇的方法,其中使用包含50-90重量%对应链烷醇、8.5-40重量%烷基甲苯和0.01-1.5重量%包含基团HO3S的酸的电解质。
EP 0 554 564 A1公开了一种通过在对应链烷醇存在下以及也在辅助电解质存在下电化学氧化对应的苄基醚而生产取代的苯甲醛缩醛的方法,其中该芳烃的取代基具有至少一个苄属氢原子,其中在酸性、中性或弱碱性范围电解。
EP 0 638 665 A1公开了一种通过电化学氧化相应取代的甲苯化合物而生产取代的苯甲醛缩二烷醇的方法,其中在链烷醇和辅助电解质存在下在电解槽中氧化取代的甲苯化合物并将以此方式得到的反应溶液在电解槽外部减压至比电解槽中的压力低10毫巴至10巴的压力。
本发明的目的是提供一种生产3-叔丁基苯甲醛缩二甲醇的电化学方法,其特征在于非常好的产物收率、非常好的产物选择性和高电流效率(current yield)并且同时可以容易地使用廉价的原料和试剂和/或助剂以工业规模进行。
该目的通过提供一种通过在包含甲醇、至少一种导电盐和任选一种助溶剂或两种或更多种不同助溶剂的电解溶液中电化学阳极甲氧基化式(II)的3-叔丁基甲苯和/或式(III)的3-叔丁基甲基苄基化合物和/或式(IV)的二(3-叔丁基苄基)醚而生产式(I)的3-叔丁基苯甲醛缩二甲醇的方法实现:
其中基团R为甲基或C(O)R’,其中R’为具有1-6个碳原子的直链或支化烷基,
用于实施本发明方法的原料或者为如下化合物:式(II)的3-叔丁基甲苯:
和/或式(III)的3-叔丁基甲基苄基化合物,即式(III)的3-叔丁基甲基苄基醚和/或酯:
其中基团R为甲基或C(O)R’,其中R’为具有1-6个碳原子的直链或支化烷基,
和/或式(IV)的二(3-叔丁基苄基)醚:
所述化合物原则上在每种情况下可以单独或以所述化合物中的两种或全部三种的任何混合物形式用于本发明方法中。
在本发明可以使用的式(III)化合物中,尤其优选式(IIIa)的3-叔丁基甲基苄基醚:
其中Me为甲基。在根据本发明同样可以使用的式(III)的酯的情况下,基团R’可以为具有1-6个碳原子的直链或支化烷基,优选甲基、乙基、丙基或异丙基,特别优选甲基。根据本发明同样优选的起始化合物因此为式(IIIb)的乙酸酯:
在本发明方法的优选实施方案范围内,仅将式(II)的3-叔丁基甲苯用作原料。在根据本发明的电化学阳极甲氧基化过程中,这可能首先形成所述式(III)化合物,尤其是式(IIIa)的3-叔丁基甲基苄基醚:
其中Me为甲基,随后该化合物本身在反应条件下完全反应或进一步反应而得到所需产物式(I)的3-叔丁基苯甲醛缩二甲醇。
在本发明方法范围内作为原料优选的式(II)的3-叔丁基甲苯可以通过已知方法制备,例如通过对位取代的异构体的异构化,例如如JP 2738093所述。
式(IIIa)的3-叔丁基苄基甲基醚例如可以通过叔丁基苯与甲醛缩二甲醇在沸石催化剂上的甲氧基甲基化而制备。
通常由烷基苯(甲苯、乙苯、异丁基苯、异丙基苯、叔丁基苯等)通过与甲醛缩二甲醇在沸石催化剂上反应而生产取代苄基甲基醚描述于DE199 04 900 A1中。在低转化率(<30%)下,得到良好的产物选择性;在更高转化率下,得到二芳基甲烷的反应占主导。本领域熟练技术人员已知用于生产式(II)的苄基甲基醚的其他方案是3-叔丁基苄醇的甲基化或3-叔丁基苄基卤化物与甲醇或甲醇盐在Williamson醚合成中的反应。
在本发明方法的另一实施方案中,单独或如上所述以与其他可能的式(II)和/或(III)原料的混合物形式使用式(IV)的二(3-叔丁基苄基)醚:
此时由一当量二苄基醚(IV)形成两当量式(I)的3-叔丁基苯甲醛缩二甲醇。
式(IV)的二苄基醚例如可以通过使式(V)的相应取代苄醇:
与通式(VI)的相应取代苄基卤反应而制备:
就此而言,该方法在大多数情况下在用于醇脱质子化的碱存在下进行(Fileti,Gazz.Chim.Ital.1884,14,498-501)。醚合成还可以通过两分子苄醇的酸催化缩合进行(Fileti,Gazz.Chim.Ital.1882,12,501;F.Shirini,M.A.Zolfigol,K.Mohammadi,Phosphorus,Sulfur SiliconRelat.Elem.2003,178(11),2357-2362)。该文献中存在许多该反应的其他实施例。
式(IV)的二(3-叔丁基苄基)醚还可以通过未取代的二苄基醚按照本领域熟练技术人员已知的相关方法官能化,如亲电芳族取代或Friedel-Crafts烷基化而生产。二苄基醚是尤其用作增塑剂的工业产物。
烷基苄基甲基醚作为烷基甲苯电化学甲氧基化的中间体,例如作为对叔丁基甲苯或对二甲苯甲氧基化的中间体的出现描述于P.Loyson,S.Gouws,B.Zeelie,S.Afr.J.Chem.,2002,55,125-131或P.Loyson,S.Gouws,B.Barton,M.Ackermann,S.Afr.J.Chem.,2004,57,53-56中。此时第一甲氧基的引入为速率决定步骤,其因此仅以中等收率进行。
在式(IV)的二苄基醚的电化学甲氧基化过程中,式(I)的苯甲醛缩二甲醇经由二苄基醚双甲氧基化中间体(VII)直接得到。然而,该中间体在反应条件下不稳定且与甲醇反应而释放水,得到式(I)化合物。
在本发明方法范围内,电解溶液至少包含甲醇和至少一种导电盐以及选取的式(II)、(III)和/或(IV)的原料。
可以存在于电解溶液中的导电盐通常为碱金属盐,四(C1-C6烷基)铵盐,优选三(C1-C6烷基)甲基铵盐。合适的抗衡离子是硫酸根、硫酸氢根、烷基硫酸根、芳基硫酸根、烷基磺酸根、芳基磺酸根、卤离子、磷酸根、碳酸根、烷基磷酸根、烷基碳酸根、硝酸根、醇根、四氟硼酸根或高氯酸根。
此外,衍生于上述阴离子的酸适合作为导电盐,因此例如为硫酸、磺酸以及羧酸。
此外,合适的导电盐还有离子液体。合适的离子液体描述于“IonicLiquids in Synthesis”,Peter Wasserscheid,Tom Welton编辑,Verlag WileyVCH,2003,第1-3章以及DE-A 102004011427中。
在本发明方法范围内优选的导电盐是甲基硫酸甲基三丁基铵、甲基硫酸甲基三乙基铵、甲基硫酸钠、甲烷磺酸钠和硫酸,特别优选甲烷磺酸钠、甲基硫酸甲基三丁基铵和甲基硫酸甲基三乙基铵,甚至更优选甲基硫酸甲基三丁基铵和甲基硫酸甲基三乙基铵,非常特别优选甲基硫酸甲基三丁基铵。所述导电盐,尤其是甲基硫酸甲基三丁基铵和甲基硫酸甲基三乙基铵,可以单独或以相互间的混合物形式使用。
在本发明方法的优选实施方案范围内,所用导电盐为甲基硫酸甲基三丁基铵和/或甲基硫酸甲基三乙基铵。特别优选所用导电盐为甲基硫酸甲基三丁基铵。再次优选单独或以两种不同导电盐的混合物形式使用所述导电盐,但优选单独使用。
在本发明方法的有利实施方案范围内,将导电盐在电解溶液中的浓度选择为0.1-20重量%,优选0.2-15重量%,甚至更优选0.25-10重量%,甚至更优选0.5-7.5重量%,尤其优选1-5重量%。
本发明方法的另一优选实施方案是其中电化学阳极甲氧基化在35-70℃,优选45-60℃的电解溶液温度下进行的实施方案。
此外,本发明方法的进行优选使得电化学阳极甲氧基化在500-100 000毫巴,优选1000-4000毫巴的绝对压力下进行。
任选将常规助溶剂加入电解溶液中。这些为通常在有机化学中常见的具有高氧化电势的惰性溶剂。例如可以提到碳酸二甲酯或碳酸亚丙酯。在优选实施方案范围内,本发明方法因此在碳酸二甲酯和/或碳酸亚丙酯作为助溶剂存在下进行。
原则上水也适合作为助溶剂;电解质中水的比例优选小于20重量%。
本发明方法可以在所有常规隔膜或无隔膜电解槽类型中进行。它可以非常成功地不连续或连续进行。在优选实施方案范围内,本发明方法连续进行。优选使用无隔膜流通型电解槽连续操作。
非常特别合适的是双极毛细管隙电解槽(bipolar capillary gap cell)或叠板电解槽(stacked plate cell),其中电极构造成板且呈平面相互平行地设置(Ullmann′s Encyclopedia of Industrial Chemistry,1999年电子版,第6版,VCH-Verlag Weinheim,Volume Electrochemistry,第3.5章‘特殊电解槽设计’和第5章,Organic Electrochemistry,第5.4.3.2分章‘电解槽设计’)。作为电极材料,优选贵金属如铂、混合氧化电极如RuOxTiOx(所谓的DSA电极)或含碳材料如石墨、玻璃碳或金刚石电极。非常特别优选使用石墨电极。在优选实施方案范围内,本发明方法使用叠板电解槽进行。
进行该方法的电流密度通常为1-1000mA/cm2,优选10-100mA/cm2。该方法特别优选在10-50mA/cm2的电流密度下进行。该方法通常在大气压力下进行。若该方法要在升高的温度下进行,则优选使用更高压力,以避免起始化合物和/或溶剂的沸腾。
合适的阳极材料例如为贵金属如铂或金属氧化物如钌或铬氧化物或RuOx类型、TiOx的混合氧化物和金刚石电极。优选石墨或碳电极。
合适的阴极材料例如为铁、钢、不锈钢、镍或贵金属如铂,以及石墨或碳材料,还有金刚石电极。优选石墨作为阳极和阴极的体系,以及石墨作为阳极和镍、不锈钢或钢作为阴极的体系。
反应完成之后,通过常规分离方法后处理电解质溶液。为此,通常首先蒸馏电解溶液并以不同馏分形式单独得到各化合物。进一步提纯例如通过结晶、萃取、蒸馏或层析进行。
本发明的另一方面涉及一种生产式(VIII)的3-叔丁基苯甲醛的方法:
包括根据上述方法制备式(I)的3-叔丁基苯甲醛缩二甲醇并随后水解。所述水解可以通过本领域熟练技术人员本身已知的方法进行,例如通过简单地使式(I)化合物与水或酸如稀盐酸、硫酸或乙酸接触而进行。
在另一方面,本发明涉及式(I)的3-叔丁基苯甲醛缩二甲醇:
在另一方面,本发明涉及式(IIIa)的3-叔丁基甲基苄基醚:
其中Me为甲基。
在另一方面,本发明涉及式(IV)的二(3-叔丁基苄基)醚:
最后,本发明在另一方面涉及作为中间体得到的式(VII)化合物:
其中Me为甲基。
本发明通过下列实施例更详细说明。
实施例1-5:制备式(I)的3-叔丁基苯甲醛缩二甲醇
实施例1:
为了电化学甲氧基化式(II)的3-叔丁基甲苯,将由105g式(II)化合物、1.9g作为导电盐的硫酸(96-98%)和593.1g甲醇构成的电解质在45℃和34mA/cm2的电流密度下在具有10个圆形石墨电极的无隔膜毛细管隙电解槽(A=32cm2)中电解,直到式(II)化合物的电荷量达到15F/mol。通过蒸馏后处理产生33.3g式(I)化合物和7.5g 3-叔丁基苄基甲基醚,对应于缩醛和醚的总收率为30%。
实施例2:
为了电化学甲氧基化式(II)化合物,将由140g式(II)化合物、1.9g硫酸(96-98%)、3.47g作为导电盐的甲醇钠(30%甲醇溶液)和554.6g甲醇构成的电解质在45℃和22mA/cm2的电流密度下在具有10个圆形石墨电极的无隔膜毛细管隙电解槽(A=32cm2)中电解,直到式(II)化合物的电荷量达到15F/mol。通过蒸馏后处理产生54.5g式(I)化合物和17.0g 3-叔丁基苄基甲基醚,对应于缩醛和醚的总收率为38%。
实施例3:
为了电化学甲氧基化式(II)化合物,将由105g式(II)化合物、14g作为导电盐的甲基硫酸甲基三丁基铵(MTBS,60%甲醇溶液)和581g甲醇构成的电解质在53℃和22mA/cm2的电流密度下在具有10个圆形石墨电极的无隔膜毛细管隙电解槽(A=32cm2)中电解,直到式(II)化合物的电荷量达到18F/mol。通过蒸馏后处理产生48.3g式(I)化合物和10.5g 3-叔丁基苄基甲基醚,对应于缩醛和醚的总收率为41%。
实施例4:
为了电化学甲氧基化式(II)化合物,将由14g式(II)化合物、1.4g作为导电盐的甲基硫酸甲基三乙基铵(MTES)和54.6g甲醇构成的电解质在53℃和22mA/cm2的电流密度下在无隔膜烧杯罐式电解槽(beaker potcell)(A=10cm2)中电解,直到式(II)化合物的电荷量达到14F/mol。通过蒸馏后处理产生9.99g式(I)化合物以及0.54g 3-叔丁基苄基甲基醚,对应于缩醛和醚的总收率为54%。
实施例5:
为了电化学甲氧基化式(II)化合物,将由14g式(II)化合物、0.42g作为导电盐的甲烷磺酸钠和55.6g甲醇构成的电解质在53℃和22mA/cm2的电流密度下在无隔膜烧杯罐式电解槽(A=10cm2)中电解,直到式(II)化合物的电荷量达到19F/mol。通过蒸馏后处理产生8.75g式(I)化合物以及0.42g 3-叔丁基苄基甲基醚,对应于缩醛和醚的总收率为47%。
Claims (15)
1.一种通过在包含甲醇、至少一种导电盐和任选一种助溶剂或两种或更多种不同助溶剂的电解溶液中电化学阳极甲氧基化式(II)的3-叔丁基甲苯和/或式(III)的3-叔丁基苄基化合物和/或式(IV)的二(3-叔丁基苄基)醚而生产式(I)的3-叔丁基苯甲醛缩二甲醇的方法:
其中基团R为甲基或C(O)R’,其中R’为具有1-6个碳原子的直链或支化烷基,
其中所用导电盐为甲基硫酸甲基三丁基铵、甲基硫酸甲基三乙基铵、甲基硫酸钠和/或甲烷磺酸钠。
2.根据权利要求1的方法,其中仅将式(II)的3-叔丁基甲苯用作原料。
3.根据权利要求1的方法,其中所用导电盐为甲基硫酸甲基三丁基铵和/或甲基硫酸甲基三乙基铵。
4.根据权利要求2的方法,其中所用导电盐为甲基硫酸甲基三丁基铵和/或甲基硫酸甲基三乙基铵。
5.根据权利要求1-4中任一项的方法,其中所用导电盐为甲基硫酸甲基三丁基铵。
6.根据权利要求1-4中任一项的方法,其中所用助溶剂为碳酸二甲酯和/或碳酸亚丙酯。
7.根据权利要求1-4中任一项的方法,其中将所述导电盐在所述电解溶液中的浓度选择为0.1-20重量%。
8.根据权利要求1-4中任一项的方法,其中电化学阳极甲氧基化在35-70℃的电解溶液温度下进行。
9.根据权利要求1-4中任一项的方法,其中电化学阳极甲氧基化在500-100000毫巴的绝对压力下进行。
10.根据权利要求1-4中任一项的方法,其中电化学阳极甲氧基化在10-100mA/cm2的电流密度下进行。
11.根据权利要求1-4中任一项的方法,其中电化学阳极甲氧基化使用叠板电解槽进行。
12.根据权利要求1-4中任一项的方法,其中电化学阳极甲氧基化连续进行。
13.一种生产式(VIII)的3-叔丁基苯甲醛的方法:
包括根据权利要求1-12中任一项制备式(I)的3-叔丁基苯甲醛缩二甲醇并随后水解。
14.3-叔丁基苯甲醛缩二甲醇。
15.式(IV)的二(3-叔丁基苄基)醚:
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JP2738093B2 (ja) * | 1989-12-19 | 1998-04-08 | 三菱化学株式会社 | 第3級ブチルベンズアルデヒド異性体混合物の製造方法 |
JP3159471B2 (ja) * | 1991-07-11 | 2001-04-23 | 三井化学株式会社 | サリチル酸誘導体の製造方法 |
DE19904900A1 (de) | 1998-06-26 | 1999-12-30 | Basf Ag | Verfahren zur Herstellung von Alkoxymethylaromaten |
DE102004011427A1 (de) | 2004-03-09 | 2005-09-29 | Basf Ag | Absorptionsmittel mit verbesserter Oxidationsbeständigkeit und Verfahren zum Entsäuern von Fluidströmen |
WO2009059944A1 (de) | 2007-11-06 | 2009-05-14 | Basf Se | Elektrochemisches verfahren zur herstellung von benzaldehyddimethylacetalen |
US20100256421A1 (en) * | 2009-03-23 | 2010-10-07 | O'laughlin Industries, Co. Ltd. | Propanal Production Methods |
EP2411564B1 (de) | 2009-03-27 | 2017-05-10 | Basf Se | Elektrochemisches verfahern zur herstellung von 3-tert.-butylbenzaldehyd-dimethylacetal |
-
2010
- 2010-03-22 EP EP10709552.3A patent/EP2411564B1/de not_active Not-in-force
- 2010-03-22 CN CN201080014651.6A patent/CN102365393B/zh not_active Expired - Fee Related
- 2010-03-22 MX MX2011010107A patent/MX2011010107A/es active IP Right Grant
- 2010-03-22 US US13/260,650 patent/US8629304B2/en not_active Expired - Fee Related
- 2010-03-22 ES ES10709552.3T patent/ES2637018T3/es active Active
- 2010-03-22 JP JP2012501264A patent/JP5553884B2/ja not_active Expired - Fee Related
- 2010-03-22 WO PCT/EP2010/053656 patent/WO2010108874A1/de active Application Filing
Patent Citations (4)
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US4539081A (en) * | 1983-06-22 | 1985-09-03 | Basf Aktiengesellschaft | Preparation of benzaldehyde dialkyl acetals |
US4820389A (en) * | 1987-04-24 | 1989-04-11 | Basf Aktiengesellschaft | Novel benzaldehyde dialkyl acetals and preparation and use thereof |
DE4201544A1 (de) * | 1992-01-22 | 1993-07-29 | Basf Ag | Verfahren zur herstellung von benzaldehydacetalen |
DE59400935D1 (de) * | 1993-08-14 | 1996-12-05 | Basf Ag | Verfahren zur Herstellung von Bezaldehyddialkylacetalen |
Also Published As
Publication number | Publication date |
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JP2012522125A (ja) | 2012-09-20 |
EP2411564A1 (de) | 2012-02-01 |
JP5553884B2 (ja) | 2014-07-16 |
ES2637018T3 (es) | 2017-10-10 |
MX2011010107A (es) | 2011-10-19 |
CN102365393A (zh) | 2012-02-29 |
US8629304B2 (en) | 2014-01-14 |
EP2411564B1 (de) | 2017-05-10 |
WO2010108874A1 (de) | 2010-09-30 |
US20120016162A1 (en) | 2012-01-19 |
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