CN1143065A - 羟甲基环丙烷的制备方法 - Google Patents
羟甲基环丙烷的制备方法 Download PDFInfo
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- cyclopropane
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- 238000000034 method Methods 0.000 title claims description 37
- KVVDRQDTODKIJD-UHFFFAOYSA-N 2-cyclopropylacetic acid Chemical compound OC(=O)CC1CC1 KVVDRQDTODKIJD-UHFFFAOYSA-N 0.000 title claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011787 zinc oxide Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical compound OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 230000002411 adverse Effects 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- LIPBOXJCSTXWSK-UHFFFAOYSA-N cyclopropylmethanol Chemical compound C1(CC1)CO.OCC1CC1 LIPBOXJCSTXWSK-UHFFFAOYSA-N 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- ZIODMHXAGZXTJF-UHFFFAOYSA-N 2-methylpropyl cyclopropanecarboxylate Chemical compound CC(C)COC(=O)C1CC1 ZIODMHXAGZXTJF-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- -1 isopropyl ester Chemical class 0.000 description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 3
- ZMVXVXYJRSLRDH-UHFFFAOYSA-N C(CC)(=O)OCCC.C1(CC1)C(=O)O Chemical compound C(CC)(=O)OCCC.C1(CC1)C(=O)O ZMVXVXYJRSLRDH-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- PKAHQJNJPDVTDP-UHFFFAOYSA-N methyl cyclopropanecarboxylate Chemical compound COC(=O)C1CC1 PKAHQJNJPDVTDP-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- PVVDRTVFKQOPFN-UHFFFAOYSA-N C1(CC1)CO.C(=O)(O)CC1CC1 Chemical compound C1(CC1)CO.C(=O)(O)CC1CC1 PVVDRTVFKQOPFN-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- 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 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000004476 plant protection product Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic
- C07C35/04—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a three or four-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
如果使用不含铬的氧化锌催化剂,则可以通过在加压和升温的条件下将环丙烷羧酸酯催化氢化,以经济和对环境友善的方式获得羟甲基环丙烷。
Description
本发明涉及通过将环丙烷羧酸的烷基酯在包含氧化锌的无铬催化剂(chromium-free catalyst)存在下的氢化来制备羟甲基环丙烷(环丙基甲醇)的方法。
羟甲基环丙烷在药剂和植物保护剂的制备中被用作合成单元。
从US 4,720,597得知,通过环丙烷羧酸酯的催化氢化可获得羟甲基环丙烷。尽管与该专利提及的先有技术的方法相比收率大幅度提高,但必须使用Zn-Cr催化剂,该催化剂由于使用了Cr化合物而具有剧烈的毒性。
因此,有必要开发出一种由既经济又对环境友善的环丙烷羧酸酯的氢化来制备羟甲基环丙烷的方法,特别是可以不使用剧毒的Cr化合物进行制备的方法。现在我们惊讶地发现:通过使用含锌催化剂而无需使用毒性的Cr可以达到上述两个目标。
本发明涉及由环丙烷羧酸C1-C10烷基酯制备羟甲基环丙烷的方法,其特征在于用过量氢气使环丙烷羧酸酯在包含氧化锌的无铬催化剂的存在下,在50-350巴和在150-350℃下氢化。
本发明方法所用的环丙烷羧酸烷基酯是烷基基团具有1-10个碳原子的酯,例如是甲酯、乙酯、丙酯、异丙酯、丁酯、异丁酯、戊酯、己酯、辛酯或癸酯,优选所述类型的C1-C8烷基酯,特别优选所述类型的C1-C4烷基酯。
本发明方法的压力范围是50-350巴,优选180-350巴,特别优选190-300巴。
本发明方法的温度范围是150-350℃,优选250-325℃,特别优选270-325℃。
本发明的方法可以在不使用溶剂或溶剂混合物的情况下进行,但也可以使用在反应条件下稳定的溶剂或溶剂混合物,也可以使用本领域技术人员熟知的该领域使用的溶剂。因为,所述溶剂的存在会使得后处理困难,所以该反应最好在没有所述溶剂的情况下进行。
根据本发明,可以使所有蒸馏回流物(例如含有未完全氢化的环丙烷羧酸酯的的回流物)循环进入反应中。
本发明的方法可以不连续或连续地进行。实施本发明方法所需的装置是先有技术已知的并且是本领域技术人员所熟悉的。可以提及的例子有具有固定或搅拌催化剂床的两相反应器,催化剂形成固相,其它成分(离析物、产物和H2)处于气相中;和多相反应器,其中,除了固相和气相外还存在一个或多个液相,例如充气搅拌罐、鼓泡塔、液相反应器或滴流相反应器。本发明的方法以连续进行的方式特别有利。这可通过使液体原料流过在反应器中呈片状排列的催化剂方便地进行,例如按照滴流相原理进行,同时使氢气并流或逆流通过反应管。使所用的过量的氢气(过量1-500摩尔)方便地循环。本发明的方法特别优选在气相中进行。对比的氢化方法以及按照所选条件(例如温度、压力和离析物:氢气摩尔比)的实施对于本领域技术人员是已知的。
本发明方法的特征在于使用含有氧化锌的无铬催化剂。氧化锌可以通过本领域技术人员已知的任何方法和方式获得,例如通过金属锌的燃烧或通过用碱处理锌盐的水溶液获得。将如此沉淀的氧化锌干燥。氧化锌既可以以获得的形态也可以以经过一个或多个处理步骤后的形态使用。从而,优选将粉末状氧化锌用于悬浮相反应器,而将氧化锌转化为片状用于滴流相和气相反应器比较有利。在这种情况下,例如,将通过锌盐溶液的沉淀获得的湿沉淀物在捏合机中充分捏合并在造粒设备中加工成形件。将仍然湿的成形制品在300-500℃烘烤1-10小时。然而,同样也可以将氧化锌催化剂吸附在本领域技术人员公知的载体如SiO2,Al2O3,TiO2,ZrO2,MgO等上,或者借助于粘合剂(制片助剂)压制和造粒。基于所用的纯氧化锌(100%)计,ZnO在催化剂中的含量为20-100%,优选为催化剂总重量的50-100%。基于其排出物(0%)计,制片助剂(例如石墨)的用量为催化剂总重量的0-20%。
氧化锌是本发明方法的活性物质,其活性可通过与其它固体混合而获得、改变或增加。为增加该催化剂的活性,再加入其它成分可能是有利的,例如加入1-30克原子%钠、钾、镁、钙、钒、铌、钽、钼、铁、钌、钴、铑、镍、钯、铂、铼、铜或银的化合物(以作为成分的基础的金属和基于Zn的克原子量计算)。这些成分可以以本领域技术人员已知的任何方式加入,例如通过同时或分别沉淀并随后合并的方法,或者通过用溶于水或其它液体的化合物浸渍氧化锌并随后干燥的方法。
铜的添加被证明是特别适合的。
优选使用内表面积大于10平方米/克(BET),特别优选大于35平方米/克直到150平方米/克的纯氧化锌,必要时可载于载体上或用惰性材料稀释。
实施例1
使4g环丙烷羧酸甲酯和每小时80Nl的氢气通过填有40ml ZnO催化剂(片状,5×3mm)的反应管。温度为297℃,压力为300巴。
环丙烷羧酸甲酯的转化率为99%,羟甲基环丙烷的选择性为92%。实施例2
过程与实施例1的相同,但使用环丙烷羧酸乙酯。
环丙烷羧酸乙酯的转化率为99%,羟甲基环丙烷的选择性为93%。实施例3
过程与实施例1的相同,但使用环丙烷羧酸丙酯。
环丙烷羧酸丙酯的转化率为98%,羟甲基环丙烷的选择性为90%。实施例4
过程与实施例1的相同,但使用环丙烷羧酸丁酯。
环丙烷羧酸丁酯的转化率为99%,羟甲基环丙烷的选择性为89%。实施例5
过程与实施例1的相同,但使用环丙烷羧酸异丁酯。
环丙烷羧酸异丁酯的转化率为99%,羟甲基环丙烷的选择性为93%。实施例6
使5.5g环丙烷羧酸异丁酯和每小时300Nl的氢气通过填有50ml掺杂有铜的ZnO片(每升ZnO片剂含有50g氧化铜和/或氢氧化铜)的反应管。温度为207℃,压力为300巴。
环丙烷羧酸异丁酯的转化率为98%,羟甲基环丙烷的选择性为91%。
Claims (12)
1.由环丙烷羧酸C1-C10烷基酯制备羟甲基环丙烷的方法,其中用过量氢气使环丙烷羧酸酯在包含氧化锌的无铬催化剂的存在下,在50-350巴在150-350℃下氢化。
2.权利要求1的方法,其中氢化在180-350巴进行。
3.权利要求1的方法,其中氢化在250-325℃进行。
4.权利要求1的方法,其中使用环丙烷羧酸C1-C8烷基酯。
5.权利要求1的方法,其中使用环丙烷羧酸C1-C4烷基酯。
6.权利要求1的方法,其中用氧化锌作催化剂。
7.权利要求1的方法,其中氢化在气相进行,并流通过氢气。
8.权利要求1的方法,其中氢化在滴流相进行,并流通过氢气。
9.权利要求1的方法,其中氢化在气相进行,逆流通过氢气。
10.权利要求1的方法,其中氢化在滴流相进行,逆流通过氢气。
11.权利要求1的方法,其中氢化在气相进行。
12.权利要求1的方法,其中用加有铜的氧化锌作催化剂。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1995105939 DE19505939A1 (de) | 1995-02-21 | 1995-02-21 | Verfahren zur Herstellung von Hydroxymethyl-cyclopropan |
DE19505939.5 | 1995-02-21 |
Publications (2)
Publication Number | Publication Date |
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CN1143065A true CN1143065A (zh) | 1997-02-19 |
CN1063738C CN1063738C (zh) | 2001-03-28 |
Family
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Application Number | Title | Priority Date | Filing Date |
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CN96103457A Expired - Fee Related CN1063738C (zh) | 1995-02-21 | 1996-02-16 | 羟甲基环丙烷的制备方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US5728896A (zh) |
EP (1) | EP0728722B1 (zh) |
JP (1) | JPH08245448A (zh) |
KR (1) | KR960031413A (zh) |
CN (1) | CN1063738C (zh) |
DE (2) | DE19505939A1 (zh) |
ES (1) | ES2130704T3 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114702416A (zh) * | 2022-03-30 | 2022-07-05 | 法姆瑞斯医药科技(北京)有限公司 | 一种高效制备孟鲁司特钠侧链中间体的方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19611142A1 (de) * | 1996-03-21 | 1997-09-25 | Bayer Ag | Verfahren zur Herstellung von Hydroxymethylcyclopropan |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2358234A (en) * | 1932-01-02 | 1944-09-12 | Du Pont | Hydrogenation process |
DE3538132A1 (de) * | 1985-10-26 | 1987-04-30 | Huels Chemische Werke Ag | Verfahren zur herstellung von hydroxymethylcyclopropan (cyclopropylmethanol) |
EP2222988B1 (en) * | 2007-11-20 | 2016-09-14 | Flowserve Management Company | Upset resistant mechanical seal |
-
1995
- 1995-02-21 DE DE1995105939 patent/DE19505939A1/de not_active Withdrawn
-
1996
- 1996-02-08 ES ES96101799T patent/ES2130704T3/es not_active Expired - Lifetime
- 1996-02-08 DE DE59601796T patent/DE59601796D1/de not_active Expired - Fee Related
- 1996-02-08 EP EP19960101799 patent/EP0728722B1/de not_active Expired - Lifetime
- 1996-02-15 US US08/601,931 patent/US5728896A/en not_active Expired - Fee Related
- 1996-02-16 CN CN96103457A patent/CN1063738C/zh not_active Expired - Fee Related
- 1996-02-16 JP JP5261096A patent/JPH08245448A/ja active Pending
- 1996-02-17 KR KR1019960004001A patent/KR960031413A/ko active IP Right Grant
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114702416A (zh) * | 2022-03-30 | 2022-07-05 | 法姆瑞斯医药科技(北京)有限公司 | 一种高效制备孟鲁司特钠侧链中间体的方法 |
Also Published As
Publication number | Publication date |
---|---|
CN1063738C (zh) | 2001-03-28 |
DE59601796D1 (de) | 1999-06-10 |
EP0728722A3 (de) | 1997-01-08 |
JPH08245448A (ja) | 1996-09-24 |
EP0728722A2 (de) | 1996-08-28 |
KR960031413A (ko) | 1996-09-17 |
ES2130704T3 (es) | 1999-07-01 |
EP0728722B1 (de) | 1999-05-06 |
US5728896A (en) | 1998-03-17 |
DE19505939A1 (de) | 1996-08-22 |
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