CN116003254A - 用于制备取代的烷基环烷酮的方法 - Google Patents
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- 238000000034 method Methods 0.000 claims abstract description 35
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 32
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 32
- 150000001336 alkenes Chemical class 0.000 claims abstract description 3
- 125000000524 functional group Chemical group 0.000 claims abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
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- 229910052760 oxygen Inorganic materials 0.000 claims description 19
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 10
- 238000010924 continuous production Methods 0.000 claims description 6
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- 238000005804 alkylation reaction Methods 0.000 claims description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 5
- -1 hydroxy, carboxy Chemical group 0.000 claims description 5
- 238000010923 batch production Methods 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 4
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 3
- 230000029936 alkylation Effects 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 229910003437 indium oxide Inorganic materials 0.000 claims description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001923 silver oxide Inorganic materials 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000005199 aryl carbonyloxy group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 230000002152 alkylating effect Effects 0.000 abstract 1
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 239000003999 initiator Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 4
- 238000010405 reoxidation reaction Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
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- 150000003254 radicals Chemical group 0.000 description 3
- 241000402754 Erythranthe moschata Species 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
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- 238000004140 cleaning Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- RMFCMEVNMFHDSL-UHFFFAOYSA-N 2-(3,4-dichlorophenyl)ethanimidamide Chemical compound NC(=N)CC1=CC=C(Cl)C(Cl)=C1 RMFCMEVNMFHDSL-UHFFFAOYSA-N 0.000 description 1
- WPUUQDHXECKYPM-UHFFFAOYSA-N 2-(3-hydroxypropyl)cyclododecan-1-one Chemical compound OCCCC1CCCCCCCCCCC1=O WPUUQDHXECKYPM-UHFFFAOYSA-N 0.000 description 1
- HFNUKGZCQLSISG-UHFFFAOYSA-N 3-(2-oxocyclododecyl)propyl acetate Chemical compound CC(=O)OCCCC1CCCCCCCCCCC1=O HFNUKGZCQLSISG-UHFFFAOYSA-N 0.000 description 1
- JSDZSLGMRRSAHD-UHFFFAOYSA-N 3-methylbutan-2-ylcyclopropane Chemical compound CC(C)C(C)C1CC1 JSDZSLGMRRSAHD-UHFFFAOYSA-N 0.000 description 1
- ZMFWTUBNIJBJDB-UHFFFAOYSA-N 6-hydroxy-2-methylquinoline-4-carboxylic acid Chemical compound C1=C(O)C=CC2=NC(C)=CC(C(O)=O)=C21 ZMFWTUBNIJBJDB-UHFFFAOYSA-N 0.000 description 1
- LYJHVEDILOKZCG-UHFFFAOYSA-N Allyl benzoate Chemical compound C=CCOC(=O)C1=CC=CC=C1 LYJHVEDILOKZCG-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001344 alkene derivatives Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000019568 aromas Nutrition 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- OTCVAHKKMMUFAY-UHFFFAOYSA-N oxosilver Chemical class [Ag]=O OTCVAHKKMMUFAY-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
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- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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- C07C67/00—Preparation of carboxylic acid esters
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- C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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Abstract
本发明涉及一种用于生产具有式(I)的取代的烷基环烷酮的方法,该方法包括将具有式(II)的环烷酮用具有式(III)的烯烃衍生物在金属氧化物存在下进行烷基化,其中n是2至20,m是0至10并且R是官能团。
Description
本申请是2016年01月13日递交的申请号为201680007124.X,发明名称为“用于制备取代的烷基环烷酮的方法”的分案申请。
技术领域
本发明涉及具有式I的取代的烷基环烷酮的制备的领域
背景技术
具有式I的取代的烷基环烷酮是重要的中间体,特别地用于合成麝香香味。麝香香味是香味的重要组分。
根据DE19853862 A1,所选择的具有式I的化合物是通过使用合适的有机自由基链引发剂将羟基烯烃或酰氧基烯烃自由基加成至环酮制备的。所使用的许多自由基链引发剂当使用时具有缺点。例如,它们必须被连续地进料到反应器中,在反应期间不可逆地消耗,并促进反应副产物特别是聚合物的形成。聚合物的形成在连续工艺中是特别不利的,因为这些连续工艺在非常长的时期内进行,使得甚至低的聚合物形成速率具有不利的影响。由于渐增的粘度或由于渐增的沉积物,反应必须不时地中断。此外,许多明确提及的自由基链引发剂具有不利的特性,如高的可燃性,形成爆炸性混合物、刺激性或有毒气体或中间体。这些特性意味着进行反应中的安全有关的支出必须是非常高的。除了所希望的取代的单烷基环烷酮之外,该反应还产生高比例的取代的二、三和四烷基环烷酮,其结果是,起始产品的消耗提高并且它们不再可以被回收。由于待在进行该工艺中使用的高温,推荐的是在高压下运行以便减少低沸点物质的损失。这要求特定的压力密封设备。
发明目的
本发明的目的是以高速率、高产率、高选择性、较低的能量消耗、较低的原料消耗以及具有较少的副产物来制备具有式I的取代的烷基环烷酮,和/或提高工艺的安全性。
发明内容
本发明涉及一种用于制备具有式I的取代的烷基环烷酮的方法
该方法包括将具有式II的环烷酮
用具有式III的烯烃衍生物
在金属氧化物存在下进行烷基化,其中n是2至20,m是0至10并且R是官能团。
具有式I的化合物可以是其中n=3至15并且m=0至5的那些。R可以是羟基、羧基、羰基氧基烷基、甲酰氧基、烷基羰基氧基、芳基羰基氧基或苄基羰基氧基烷基或者以下基团之一:
其中R’是烷基、芳基、杂芳基、烷芳基或环烷基基团。
具有式II和III的优选化合物的变量相应地类似。
出人意料地,已经发现,在进行根据本发明的方法期间,可能没有检测到具有式II的化合物的聚合物,使得该方法可以在非常长的时间段内连续且不中断地进行。在本发明的上下文中,聚合物应理解为是指具有大于或等于5的单体数的大分子。此外,形成的取代的二、三和四烷基环烷酮的比例大大减少,其结果是,反应物的消耗减少,使得可以回收和再使用更多的反应物。金属氧化物还可以在还原后被再氧化并被再使用。
具有式I的化合物是例如2-(3-羟丙基)环十二酮和2-(3-乙酰氧基丙基)环十二酮。
具有式II的化合物是例如环己酮、环辛酮、环十二酮和环十六酮。
具有式III的化合物是例如烯丙醇、乙酸烯丙酯、甲酸烯丙酯、丙酸烯丙酯、苯甲酸烯丙酯和苯乙酸烯丙酯。
根据本发明的方法可以容易地用金属氧化物进行,这些金属氧化物选自铜氧化物、铁氧化物、锰氧化物、铟氧化物、钴氧化物、银氧化物及其混合物的组。该方法可以特别容易地用选自以下项的金属氧化物进行:Ag2O、CuO、Fe2O3、Fe3O4、CuFe2O4、Co3O4、CoO、MnO2、In2O3及其混合物。
在反应条件下,氧化银如Ag2O形成银镜或非常精细分散的银颗粒,其被强烈地侵蚀到反应介质中,使得用于回收、特别是与剩余成分的分离和设备的清洗的支出增加。当使用铜氧化物、铁氧化物、锰氧化物、铟氧化物、钴氧化物及其混合物和/或CuO、Fe2O3、Fe3O4、CuFe2O4、Co3O4、CoO、MnO2、In2O3及其混合物时,这种缺点不存在,这些氧化物在该工艺中不侵蚀,或仅略微侵蚀,并且不形成金属镜。因此,用于回收和设备清洗的支出是较低的。
这些金属氧化物可优选地作为粉末或粒料使用。这些金属氧化物还可以应用于合适的无机载体材料,如氧化铝。
如果该方法在100℃至250℃的范围内、优选地在150℃至220℃的范围内并且特别优选地在160℃至190℃的范围内的温度下进行,则是有利的。该方法可以在大气压下或任选地在正压下进行。
在分批工艺中,金属氧化物的使用浓度基于具有式II的环烷酮的量可以是1-50mol%,并且优选地基于具有式II的环烷酮的量是5-25mol%。在连续工艺中,更适当的是指定空间速度(具有式II和III的化合物的连续供应的质量流与金属氧化物的质量的商)。它优选地是0.01至1/小时并且特别优选地0.02至0.5/小时。
具有式II的环烷酮与具有式III的烯烃衍生物的摩尔比可以是在1:1与10:1之间并且优选地在2:1与8:1之间。
该方法可以连续地或分批地进行。为了进行该分批方法,例如,不连续的搅拌槽反应器是合适的。适用于连续方法的是例如连续的管式反应器、搅拌槽反应器、固定床反应器或滴流床反应器。
在已经进行该方法之后,存在产物混合物,取决于应用的持续时间和工艺参数,该产物混合物是具有不同浓度的反应物和产物的混合物。可以通过合适的分离方法,特别是通过蒸馏分离该产物混合物,从而可以进一步增加所希望的α-单烷基产物的已经高的纯度,并且任选地,可以回收和再使用未反应的反应物。
所使用的金属氧化物通过该反应被还原。该还原的金属氧化物是由该金属氧化物形成的金属、较低氧化态的金属氧化物或其混合物。在该方法中,该还原的金属氧化物在固体金属氧化物的表面上形成。
本发明的另一个优点是在金属氧化物已经通过根据本发明的反应被还原之后可以再生(再氧化)它。可以通过使该还原的金属氧化物与含氧气体接触来进行再氧化。该还原的金属氧化物可以借助于加热的含氧气体流特别有效地再氧化,该气体流具有100℃至500℃的温度。该气体的氧含量可以包含在20℃和1013.25hPa下确定的基于含氧气体的总量的至少0.1vol%的氧气,以便允许该再氧化在短时间内进行。
可以将该还原的金属氧化物在与该含氧气体接触之前从该产物混合物中分离以便再氧化它。在这种程序中,该含氧气体的优选的氧含量是至少17vol%并且其温度是在150℃与500℃之间,以便使能够特别快速地再氧化。以这种方式再生的金属氧化物在根据本发明的反应中的再使用期间示出了与最初使用的金属氧化物相同的活性。例如,这种程序可以用于分批工艺中。它也适用于连续工艺,其中,例如,在该工艺开始时,存在金属氧化物的至少两个相互分开的部分。首先,该金属氧化物的部分之一进料有反应物流并移除产物流。在部分或完全还原该金属氧化物之后,将该反应物流传递到该金属氧化物的不同部分,并在其上进行反应。同时,将第一部分(现在被还原到一定程度)从该产物混合物分离并用该含氧气体流再氧化。随后,可以将该工艺切换到金属氧化物的该第一部分或另一部分,并且因此可以连续运行该工艺。
如果在该烷基化反应的过程期间将含氧气体流引入到反应器中,则可以特别有利地运行该工艺。应该使该含氧气体流与该还原的金属氧化物接触。因此,在适当连续进料反应物并去除产物混合物下,可以在非常长的时间段内不费力地连续地运行该工艺。氧化和还原工艺同时发生。在该工艺中,该含氧气体的优选的氧含量是0.1vol%至20vol%并且特别优选地3vol%至16vol%,并且因此形成来自自由基副反应的特别很少的副产物,并且使能够快速再氧化该还原的金属氧化物。在这种情况下,该含氧气体流的温度应等于或接近该反应器中的温度。
本发明还包括一种通过根据本发明的方法制备的产物。该产物可以特别地特征为以下事实:它包含非常低浓度的取代的二、三和四烷基环烷酮。
实例1:
向搅拌槽反应器填充45.5g环十二酮(CDD)和5.01g乙酸烯丙酯(AIAc)和氧化铜(CuO)(摩尔比CDD:AIAc 3:1),并且将混合物在160℃下搅拌持续24h。然后滤出氧化铜(CuO),并通过气相色谱法分析该反应混合物,并使用式S=(所形成的α-单烷基产物的量)/(所使用的CDD的量)计算该方法的选择性。该选择性是70%。
在DE 19853862的实例1(迄今为止来自现有技术的对比实例)中,选择性仅是12%。
因此,在根据本发明的方法中,相对于所使用的CDD,形成了显著更多的所希望的α-单烷基产物。
实例2:
向具有1.9cm的直径的固定床玻璃反应器填充所提供量的粒状的CuO(50.7g;17.5ml;粒径0.71-1.25mm),该反应器配备有用于液体和气体的在该反应器的顶部处的计量装置和双夹套加热器以及用于收集在该反应器出口处的产物混合物的装置。这些粒料是从粉状CuO通过压制、粉碎球粒并筛分所希望的部分获得的。在引发剂粒料的上方和下方,反应器内部的自由体积填充有惰性刚玉颗粒以使死体积最小化并固定该引发剂。允许处于比率1:7.5的环十二酮(CDD)和乙酸烯丙酯(AlAc)的混合物以2.9g/h的流速流过被加热至180℃的引发剂床。同时,使空气以2ml/min的速率穿过该反应器床。在该反应器出口处收集产物混合物,并通过气相色谱分析确定其组成。单烷基化产物的选择性是75.3%。将未反应的CDD通过蒸馏从这些产物中移除并且再循环。
Claims (10)
3.如权利要求1或2所述的方法,其中n是3至15并且m是0至5。
4.如前述权利要求中任一项所述的方法,其中该金属氧化物选自铜氧化物、铁氧化物、锰氧化物、铟氧化物、钴氧化物、银氧化物及其混合物的组。
5.如前述权利要求中任一项所述的方法,其中该金属氧化物选自CuO、Fe2O3、Fe3O4、CuFe2O4、Co3O4、CoO、MnO2、In2O3及其混合物。
6.如前述权利要求中任一项所述的方法,其中该烷基化在100℃至250℃的范围内、优选地在150℃至220℃的范围内并且特别优选地在160℃至190℃的范围内的温度下进行。
7.如前述权利要求中任一项所述的方法,其中还原的金属氧化物被含氧气体再氧化。
8.如权利要求7所述的方法,其中该含氧气体包含在20℃和1013.25hPa下确定的基于含氧气体的总体积的至少0.1vol%的氧气。
9.如权利要求7和8中任一项所述的方法,该方法包括在该烷基化反应的过程期间将含氧气体流引入到反应器中。
10.一种如前述权利要求中任一项所述的连续或分批工艺。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2136496A1 (de) * | 1971-07-21 | 1973-02-01 | Haarmann & Reimer Gmbh | Verfahren zur herstellung von oxabicycloalkenen |
US4268445A (en) * | 1979-02-19 | 1981-05-19 | Basf Aktiengesellschaft | Preparation of bicyclic enol-ethers, and novel ethers of 2-(3-hydroxyprop-l-yl)-cycloalkanones |
CN1096026A (zh) * | 1992-12-16 | 1994-12-07 | Dsm有限公司 | 环烷酮、环烷醇和氢过氧化环烷烃混合物的连续制备方法 |
US6222076B1 (en) * | 1997-12-23 | 2001-04-24 | Haarmann & Reimer Gmbh | Process for the preparation of substituted cycloketones |
CN102365256A (zh) * | 2009-01-28 | 2012-02-29 | 巴斯夫欧洲公司 | 制备纯环十二酮的方法 |
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US4387250A (en) | 1980-01-16 | 1983-06-07 | Firmenich Sa | Phosphonium salts, process for their preparation and use of same as starting materials for preparing unsaturated bicyclic compounds |
BR8506608A (pt) | 1984-04-16 | 1986-04-15 | Atlantic Richfield Co | Processo de conversao de hidrocarbonetos |
JPS6279848A (ja) * | 1985-10-01 | 1987-04-13 | Osaka Sekiyu Kagaku Kk | 炭化水素脱砒素用酸化物触媒の再活性化方法 |
DE19723949A1 (de) | 1997-06-06 | 1998-12-10 | Basf Ag | Verfahren zur Regenerierung eines Zeolith-Katalysators |
DE19853862A1 (de) | 1997-12-23 | 1999-06-24 | Haarmann & Reimer Gmbh | Verfahren zur Herstellung substituierter Cycloketone |
JP4912557B2 (ja) * | 2000-03-10 | 2012-04-11 | 株式会社ダイセル | マンガン触媒等を用いた有機化合物の製造法 |
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2136496A1 (de) * | 1971-07-21 | 1973-02-01 | Haarmann & Reimer Gmbh | Verfahren zur herstellung von oxabicycloalkenen |
US3856815A (en) * | 1971-07-21 | 1974-12-24 | Haarmann & Reimer Gmbh | Process for the production of oxa-bicyclo alkenes |
US4268445A (en) * | 1979-02-19 | 1981-05-19 | Basf Aktiengesellschaft | Preparation of bicyclic enol-ethers, and novel ethers of 2-(3-hydroxyprop-l-yl)-cycloalkanones |
CN1096026A (zh) * | 1992-12-16 | 1994-12-07 | Dsm有限公司 | 环烷酮、环烷醇和氢过氧化环烷烃混合物的连续制备方法 |
US6222076B1 (en) * | 1997-12-23 | 2001-04-24 | Haarmann & Reimer Gmbh | Process for the preparation of substituted cycloketones |
CN102365256A (zh) * | 2009-01-28 | 2012-02-29 | 巴斯夫欧洲公司 | 制备纯环十二酮的方法 |
Non-Patent Citations (1)
Title |
---|
M. HAJEK AND J. MALEK: "Radical Addition of Ketones to Alkenes Initiated by Transition Metal Oxides", SYNTHES, vol. 1976, no. 5, 31 December 1976 (1976-12-31), pages 315 - 318 * |
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