CN1062523A - 制备二醚的方法 - Google Patents
制备二醚的方法 Download PDFInfo
- Publication number
- CN1062523A CN1062523A CN91108297A CN91108297A CN1062523A CN 1062523 A CN1062523 A CN 1062523A CN 91108297 A CN91108297 A CN 91108297A CN 91108297 A CN91108297 A CN 91108297A CN 1062523 A CN1062523 A CN 1062523A
- Authority
- CN
- China
- Prior art keywords
- diether
- following formula
- catalyzer
- glycol
- aldehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000007069 methylation reaction Methods 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- 239000003456 ion exchange resin Substances 0.000 claims description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 claims description 3
- -1 isobutyl- Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 125000003710 aryl alkyl group Chemical group 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 125000000753 cycloalkyl group Chemical group 0.000 abstract 1
- 150000002009 diols Chemical class 0.000 abstract 1
- 230000001035 methylating effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 150000001299 aldehydes Chemical class 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229920001429 chelating resin Polymers 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005705 Cannizzaro reaction Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- UIOXNNAWANDJCZ-UHFFFAOYSA-N 1,1-dimethoxypropane Chemical compound CCC(OC)OC UIOXNNAWANDJCZ-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
-
- 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
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
-
- 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
- C07C43/04—Saturated ethers
- C07C43/10—Saturated ethers of polyhydroxy compounds
-
- 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
- C07C43/04—Saturated ethers
- C07C43/115—Saturated ethers containing carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
-
- C—CHEMISTRY; METALLURGY
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Dental Preparations (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
制造下式(I)表示的二醚，该式为
其中R为烷基、环烷基、芳基或芳烷基，该方法
是通过由醛醇缩合反应形成下式(II)的不饱和醛：
Description
本发明涉及下式的二醚的制备，该式为：
其中R为线型或支链C1～18烷基、C3～18环烷基、C6～18芳基或C7～18芳烷基;优选的R为异丙基。
根据公布的欧洲专利申请EP-A-361493（相应的美国申请号413409）中的方法，已经知道如何制备式（Ⅰ）的二醚。
然而，由于种种理由，上述方法远不足以适合工业应用。
例如，上述专利申请描述生产2-异戊基-2-异丙基-1，3-二甲氧基丙烷要用四个步骤，总产率为12%，而且最后的二醇甲基化反应还要使用极昂贵的试剂。
相反，用本发明的方法，使用不太贵的试剂以简单的工艺就可得到很高产率的式（Ⅰ）二醚。
本发明的方法包括以下步骤：
a）通过醛醇缩合反应形成不饱和醛（Ⅱ），其中R如同以上规定;
b）将所说的醛还原为饱和化合物（Ⅲ），其中R如同以上规定;
c）通过与甲醛的交叉的坎尼扎罗反应将（Ⅲ）转化为二醇（Ⅳ），其中R如同以上规定;
d）将二醇（Ⅳ）用CH3Cl进行甲基化反应生成二醚（Ⅰ）。该反应在二甲基亚砜（DMSO）的存在下能方便地进行。
在制备过程中出现的各反应如下面所示：
醛醇缩合反应最好在有离子交换树脂（带有强碱性功能，例如氢氧化季铵）存在下进行。这种树脂的实例是Amberlite IRA 910（由Rohm & Haas生产）。也可以使用以氯化季铵与等当量的NaOH相混合形式的树脂。
在上述条件下进行操作就可减少缩聚物的生成。事实上，如例2和例3所示，若使用NaOH的话，即使以很低的转化率进行操作，在所得的醛（Ⅱ）中不希望有的缩聚物之百分含量分别为25.7%和23.5%，而相比之下例1为5.8%（其中所用树脂为OH形式），而例4为8.7%（其中所用树脂为Cl-+NaOH形式）。
树脂可以反复再循环而不明显地丧失活性。
用在碳载体上的钯催化剂将醛（Ⅱ）选择性地还原为有实用价值量的产品（Ⅲ）。通过加入少量碱性碳酸氢盐的水溶液，就可在使用相同量催化剂的前提下显著地减少还原时间。如例5和例6所示，在加入NaHCO3的饱和水溶液之后，还原时间由80小时减为1小时。
在二醇（Ⅳ）的甲基化作用中，所得的醚（Ⅰ）不会与二甲基亚砜混在一起：这样溶剂的分离和回收就被简化了。
本发明方法的优选实施方案是以下述方式进行的：
a）在一种具有碱性官能度（OH-形式）的离子交换树脂存在下，或在作为替换物的具有相同量NaOH的氯化季铵形式的树脂存在下，将异戊醛加热至温度在70～120℃之间，并连续地除掉所形成的水。通过分馏从生成的反应混合物中分离出醛（Ⅱ）。
b）（Ⅱ）的氢化是在一种溶剂的存在下于室温和压力为1～10大气压、优选为2～3大气压下进行的，进行氢化时还存在钯基催化剂和少量的碱性碳酸氢盐的水溶液（1～10%重量的饱和溶液）。
本方法中适用的溶剂是醇类，例如CH3OH、乙醇、异丙醇和丁醇。优选使用甲醇和乙醇。
（Ⅱ）在溶剂中的浓度可在10～50%内变化，优选为15～20%。
适用的催化剂是细粉状钯，它可随意地被载于惰性介质例如二氧化硅、氧化铝、碳和硫酸钡上。每公斤（Ⅱ）的催化用量为0.2～3克钯。氢化速率（在相同压力和温度条件下）与所用催化剂的量成正比。（Ⅱ）的醇溶液在经过滤除去催化剂后，即可直接用于下一步骤而不必进一步提纯。
c）将（Ⅲ）的醇溶液与CH2O水溶液在无机碱存在下一起加热并回流直到完成反应时为止。通过蒸馏回收醇并将二醇（Ⅳ）从水相中分离出（在水相中它几乎是不溶解的）、脱水，然后将其用于下一步骤而不必进一步纯化。适用于反应的碱是NaOH、KOH、Na2CO3和K2CO3。所加入的CH2O与醛（Ⅲ）的摩尔比至少为2∶1，优选的为3∶1。
d）未提纯的二醇（Ⅳ）溶解在DMSO中，并在NaOH存在下和大气压力及30～40℃温度下用CH3Cl进行甲基化。最好使用细粉状NaOH，因为它可使反应加快。
二醚（Ⅰ）在DMSO中不溶，在把盐过滤后，因此很容易将其从溶剂中分离和精馏。在脱水（例如加入甲苯以及甲苯/H2O混合物的共沸精馏）后，可将DMSO再循环。
以下所给出的实施例仅仅是为了说明本发明，而不是对本发明作出限制。
例1
制备2-异丙基-5-甲基-2-己烯醛〔Ⅱ，R＝（CH3）2CH〕
将2070克的异戊醛和260cc的OH-形式的Amberlite IRA 910树脂（由Rohm & Haas生产）（它是由通过用NaOH洗涤Cl-形式直至洗液中不见Cl-，然后用水洗涤至中性而制备的）回流加热。
用玛尔古逊（Marcusson）蒸馏器连续除去生成的水。3小时后大约收集260cc水，蒸馏器中的温度从起始的79℃升到115℃。通过过滤分离出树脂，并在真空下分馏反应产物。得到以下产物：444克可以再循环的异戊醛，50克中间馏分，1300克基本上为（Ⅱ）组成的馏分（沸点85～90℃/20mmHg），以及75克不能蒸馏的缩聚物残渣。
（Ⅱ）的气相色谱滴定率为97%（顺式与反式异构体的比率约为20∶80）。
高沸点副产品的量相当于所得的醛（Ⅱ）的5.8%。
例2
使用例1的方法和各种成分，除了使用20.7克NaOH溶于250cc水中以代替使用树脂外。分馏后得到1233克的醛（Ⅱ）和317克残渣。残渣相对于产物（Ⅱ）的百分比为25.7%。
例3
使用例2的方法和各成分，除了使用11.3克NaOH溶于350cc水外。将反应混合物维持回流5小时（蒸馏器的最高温度为85℃）。在真空下分离并蒸馏有机相。得到980克轻馏分产物（主要由异戊醛组成），811克的（Ⅱ）和191克残渣。残渣相当于所要产物（Ⅱ）的23.5%。
例4
将1400克异戊醛和150cc Cl-形式的湿Amberlite IRA 910树脂，以及溶于100cc水中的5克NaOH一起加热。它们以回流形式被加热，用玛尔古逊装置蒸馏出反应过程中所形成的水。3小时后内部温度达到90℃。加入另外的溶于30cc水中的3克NaOH，并继续再蒸馏5小时直到温度达到120℃。随后将反应物冷却至80℃并用200cc水稀释。对水相和树脂进行分离，蒸馏反应粗产物。
结果得到110克基本由异戊醛组成的轻馏分产物，1025克醛（Ⅱ）和90克残渣。残渣相当于所想望得到的产物（Ⅱ）的8.7%。
例5
制备2-异丙基-5-甲基己醛〔Ⅲ，R＝（CH3）2CH-〕。
在装有搅拌器的双颈玻璃烧瓶中装入10克溶于70cc乙醇的例1的醛、1cc饱和的NaHCO3水溶液和0.25克的碳载体上的10%钯。向装置通入氮气，再通入氢气，装置被连接到带刻度的充满氢气的滴定管。在常温和常压下对混合物进行搅拌。
氢的吸收在60分钟后在达到化学计算值时停止。
例6
重复例5，但不添加NaHCO3溶液。仅在80小时后完成吸收作用。
例7
在20升高压釜中，在25克的碳载体上的10%钯的存在下，将1300克醛〔Ⅱ，R＝（CH3）2CH〕在7升乙醇中的溶液和80cc的饱和NaHCO3溶液进行氢化。
在起始的H2压力为3大气压时进行操作，一俟其压力降至1.5大气压立即使其恢复到起始压力。1小时后完成吸收作用。将催化剂过滤并将乙醇溶液用于下次反应。用气相色谱法计算的醛〔Ⅱ，R＝（CH3）2CH〕的含量为97%。
例8
制备2-异丙基-2-（3-甲基丁基）-1，3-二羟基丙烷〔Ⅳ，R＝（CH3）2CH〕。
将例7的醛溶液与690克K2CO3在1700cc水中的溶液以及2200cc CH2O（含水40%）回流加热7小时。通过使蒸发器中的温度达到97～98℃而蒸出乙醇。分离出有机相并用热水洗涤直到使其呈中性为止，使用甲苯通过共沸蒸馏而使油相脱水。
在真空下将甲苯蒸发后，得到1455克无色油〔Ⅳ，R＝（CH3）2CH〕。
此产物无须进一步纯化即可用于下一步反应中。
例9
制备2-异丙基-2-（3-甲基丁基）-1，3-二甲氧基丙烷〔Ⅰ，R＝（CH3）2CH〕。
在烧瓶中将例8所得的二醇溶于3.5升二甲基亚砜之中，烧瓶装有气泡阀以释放气体、机械叶片搅拌器、温度计和进气管。在搅拌的同时加入460克细粉状NaOH，并用外部浴器冷却使温度保持30℃。将CH3Cl加到充分搅拌好的物质中，同时使温度保持在30～35℃之间，调节加入量使CH3Cl不从卸料阀泄出。2.5小时后加入290克另外的细粉状NaOH，而在5小时后再加入另外415克所说的NaOH。在约8小时后CH3Cl的吸收停止。CH3Cl的总用量为925克。10小时后生成的反应混合物的气相色谱对照物显示存在有98.8%的二醚〔Ⅰ，R＝（CH3）2CH〕和仅仅为0.1%的单醚。过滤反应物并用正己烷洗涤盐。将上部相与DMSO分开，加入来自洗涤液的正己烷，用水重复洗涤，并用无水Na2SO4脱水。在除去正己烷后，由蒸馏得到沸点为105～106℃/15mmHg的（Ⅰ）的单一馏分1335克。由气相色谱测定的二醚含量为99.5%。还原、坎尼扎罗反应和甲基化反应这三步的产率为77.7%。
在用甲苯共沸脱水后，DMSO可被再循环使用。
例10～12
按表1所示的原料分别按例1、7、8和9所述的相同工艺进行缩合、加氢、坎尼扎罗缩合和醚化反应。
Claims (4)
1、一种制备下式二醚的方法，该式为：
其中R为C1～13烷基、C3～18环烷基、C6～18芳基或C7～13芳烷基，该方法包括以下步骤：
a)通过醛醇缩合反应形成下式的不饱和醛，该式为：
其中R如以上规定，
b)将所说的不饱和醛还原为下式的饱和化合物
其中R如以上规定，
c)将所说的饱和化合物转变为下式的二醇
其中R如以上规定
d)将所说的二醇甲基化成为相应的二醚。
2、如权利要求1的方法，其中R选自异丙基、乙基、丁基、异丁基、环己基、环戊基。
3、如权利要求1的方法，其中醛醇缩合反应是在具有碱性官能的离子交换树脂、或以氯化季铵形式的树脂存在下进行的，不饱和醛的还原反应是用氢进行的，使用作为催化剂的是载于惰性介质上的钯，催化剂悬浮在醇溶液中，该溶液含有少量碳酸氢盐的碱性水溶液，二醇的甲基化反应是在有二甲基亚砜存在下进行的。
4、如权利要求2的方法，其中在权利要求1的方法中，其中醛醇缩合反应是在具有碱性官能的离子交换树脂、或以氯化季铵形式的树脂存在下进行的，不饱和醛的还原反应是用氢进行的，使用作为催化剂的是载于惰性介质上的钯，催化剂悬浮在醇溶液中，该溶液含有少量碳酸氢盐的碱性水溶液，二醇的甲基化反应是在二甲基亚砜存在下进行的。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT02211990A IT1243924B (it) | 1990-11-20 | 1990-11-20 | Procedimento per la preparazione di dieteri |
| IT22119A/90 | 1990-11-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1062523A true CN1062523A (zh) | 1992-07-08 |
| CN1036846C CN1036846C (zh) | 1997-12-31 |
Family
ID=11191777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91108297A Expired - Fee Related CN1036846C (zh) | 1990-11-20 | 1991-11-20 | 制备二醚的方法 |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US5371299A (zh) |
| EP (1) | EP0487035B1 (zh) |
| JP (1) | JP2977353B2 (zh) |
| KR (1) | KR100191179B1 (zh) |
| CN (1) | CN1036846C (zh) |
| AU (1) | AU8799491A (zh) |
| BR (1) | BR9105048A (zh) |
| CA (1) | CA2055721A1 (zh) |
| DE (1) | DE69119552T2 (zh) |
| FI (1) | FI102270B (zh) |
| IL (1) | IL100074A0 (zh) |
| IT (1) | IT1243924B (zh) |
| MX (1) | MX9102147A (zh) |
| NO (1) | NO176515C (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432439A (zh) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | 一种二醚型给电子体的制备方法 |
| CN102531861A (zh) * | 2012-01-05 | 2012-07-04 | 淮海工学院 | 5-乙基-2-壬酮的制备新方法 |
| US9376513B2 (en) | 2011-01-19 | 2016-06-28 | China Petroleum & Chemical Corporation | Solid catalyst component and catalyst for olefin polymerization |
| CN116323535A (zh) * | 2020-10-13 | 2023-06-23 | Sabic环球技术有限责任公司 | 制备2-异戊基-2-异丙基-1,3-二甲氧基丙烷的方法 |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU1757100A (en) * | 1994-03-18 | 2000-05-11 | Toshikazu Nakamura | Drug for relieving side effects caused by immunosuppressants |
| IT1274250B (it) * | 1995-02-21 | 1997-07-15 | Himont Inc | Dieteri utilizzabili nella preparazione di catalizzatori ziegler-natta |
| US7049377B1 (en) | 1995-02-21 | 2006-05-23 | Basell Poliolefine Italia S.R.L. | 1,3-diethers and components and catalysts for the polymerization of olefins, containing said diethers |
| CN1266167C (zh) * | 2001-06-13 | 2006-07-26 | 巴塞尔聚烯烃意大利有限公司 | 用于烯烃共聚合的组分与催化剂 |
| CN102105503B (zh) | 2008-07-23 | 2014-03-19 | 巴斯夫欧洲公司 | 2-异丙基-2-烷基-1,3-丙二醇用于制备聚合物的用途 |
| CN103328431B (zh) * | 2011-01-19 | 2015-05-06 | 帝斯曼知识产权资产管理有限公司 | 通过催化碳碳双键加氢制备4-乙酰氧基-2-甲基丁醛的方法 |
| US9284392B2 (en) | 2013-03-15 | 2016-03-15 | Basf Corporation | Mixed internal donor structures for 1-olefin polymerization catalysts |
| CN114276221A (zh) * | 2021-12-29 | 2022-04-05 | 山东研峰新材料科技有限公司 | 一种烷基取代的二醚型给电子体的制备方法 |
| CN114768799B (zh) * | 2022-05-19 | 2022-11-29 | 研峰科技(北京)有限公司 | 一种选择性催化氢化负载型金属催化剂及其制备方法和应用 |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2413803A (en) | 1945-06-22 | 1947-01-07 | Us Ind Chemicals Inc | 2-ethyl-2-butyl propanediol-1,3 |
| FR1044689A (fr) * | 1951-05-03 | 1953-11-19 | Hoechst Ag | Procédé de préparation de 2-éthylhexanal-(1) ou de 2-éthylhexanol-(1) et produits obtenus par ce procédé |
| US3742068A (en) * | 1970-04-17 | 1973-06-26 | G Moersch | Ethers of 2,2,9,9-tetramethyl-1,10-decanediol |
| CA1005821A (en) * | 1971-02-01 | 1977-02-22 | Clive A. Henrick | 2,4-diolefinic compounds and the control of insects |
| US3752843A (en) * | 1971-10-08 | 1973-08-14 | Zoecon Corp | Aliphatic di olefinic nitriles |
| AT354187B (de) * | 1976-11-22 | 1979-12-27 | Hoffmann La Roche | Fungizides mittel |
| DE2855506C3 (de) * | 1978-12-22 | 1981-04-30 | Ruhrchemie Ag, 4200 Oberhausen | Verfahren zur Herstellung von Methyl-nonyl-acetaldehyd |
| DE2933919C2 (de) * | 1979-08-22 | 1988-12-22 | Ruhrchemie Ag, 4200 Oberhausen | Verfahren zur Herstellung von 2-Methyl-2-sek.-butyl-1,3-propandiol |
| US4435586A (en) * | 1982-04-28 | 1984-03-06 | Kruse Walter M | Etherification process for hexitols and anhydrohexitols |
| IT1227260B (it) * | 1988-09-30 | 1991-03-28 | Himont Inc | Dieteri utilizzabili nella preparazione di catalizzatori ziegler-natta |
-
1990
- 1990-11-20 IT IT02211990A patent/IT1243924B/it active IP Right Grant
-
1991
- 1991-11-18 IL IL100074A patent/IL100074A0/xx unknown
- 1991-11-18 NO NO914504A patent/NO176515C/no not_active IP Right Cessation
- 1991-11-18 CA CA002055721A patent/CA2055721A1/en not_active Abandoned
- 1991-11-19 AU AU87994/91A patent/AU8799491A/en not_active Abandoned
- 1991-11-19 DE DE69119552T patent/DE69119552T2/de not_active Expired - Fee Related
- 1991-11-19 MX MX9102147A patent/MX9102147A/es unknown
- 1991-11-19 EP EP91119740A patent/EP0487035B1/en not_active Expired - Lifetime
- 1991-11-19 FI FI915460A patent/FI102270B/fi active
- 1991-11-20 KR KR1019910020743A patent/KR100191179B1/ko not_active Expired - Fee Related
- 1991-11-20 BR BR919105048A patent/BR9105048A/pt not_active IP Right Cessation
- 1991-11-20 CN CN91108297A patent/CN1036846C/zh not_active Expired - Fee Related
- 1991-11-20 JP JP3331185A patent/JP2977353B2/ja not_active Expired - Fee Related
-
1993
- 1993-02-09 US US08/015,330 patent/US5371299A/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432439A (zh) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | 一种二醚型给电子体的制备方法 |
| US9376513B2 (en) | 2011-01-19 | 2016-06-28 | China Petroleum & Chemical Corporation | Solid catalyst component and catalyst for olefin polymerization |
| CN102531861A (zh) * | 2012-01-05 | 2012-07-04 | 淮海工学院 | 5-乙基-2-壬酮的制备新方法 |
| CN116323535A (zh) * | 2020-10-13 | 2023-06-23 | Sabic环球技术有限责任公司 | 制备2-异戊基-2-异丙基-1,3-二甲氧基丙烷的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0487035A3 (en) | 1992-11-25 |
| BR9105048A (pt) | 1992-06-23 |
| IT9022119A1 (it) | 1992-05-20 |
| MX9102147A (es) | 1992-07-08 |
| NO176515C (no) | 1995-04-19 |
| JPH0625050A (ja) | 1994-02-01 |
| KR100191179B1 (ko) | 1999-06-15 |
| IT9022119A0 (it) | 1990-11-20 |
| IT1243924B (it) | 1994-06-28 |
| AU8799491A (en) | 1992-05-21 |
| US5371299A (en) | 1994-12-06 |
| EP0487035B1 (en) | 1996-05-15 |
| JP2977353B2 (ja) | 1999-11-15 |
| IL100074A0 (en) | 1992-08-18 |
| FI102270B1 (fi) | 1998-11-13 |
| KR920009756A (ko) | 1992-06-25 |
| DE69119552T2 (de) | 1996-12-05 |
| NO176515B (no) | 1995-01-09 |
| DE69119552D1 (de) | 1996-06-20 |
| EP0487035A2 (en) | 1992-05-27 |
| CN1036846C (zh) | 1997-12-31 |
| FI915460A0 (fi) | 1991-11-19 |
| FI915460L (fi) | 1992-05-21 |
| NO914504L (no) | 1992-05-21 |
| FI102270B (fi) | 1998-11-13 |
| CA2055721A1 (en) | 1992-05-21 |
| NO914504D0 (no) | 1991-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1036846C (zh) | 制备二醚的方法 | |
| CN101747144A (zh) | 制备多羟甲基化合物的方法 | |
| CN104292085A (zh) | 一种制备聚甲醛二甲醚的装置及方法 | |
| CN101747143A (zh) | 制备多羟甲基化合物的方法 | |
| CN1671640A (zh) | 在制备多元醇中通过裂解含缩醛的副产物提高收率的方法 | |
| CN1095827C (zh) | (甲基)丙烯酸与链烷醇的酯化方法 | |
| CN100553779C (zh) | 一种不饱和醛氢转移还原制备不饱和醇反应中醇铝催化剂的回收方法 | |
| CN1095826C (zh) | (甲基)丙烯酸与链烷醇的酯化方法 | |
| CN109096065B (zh) | 聚甲醛二甲基醚的提纯方法 | |
| CN1211332C (zh) | 多元醇合成中形成的高沸点副产物的分解 | |
| CN1087013C (zh) | (甲基)丙烯酸与一种链烷醇的酯化方法 | |
| CN1239444C (zh) | 异烯烃的生产工艺 | |
| WO2005075392A2 (en) | Production process of 3-alkoxy-1-propanols, and 3-alkoxy-1-propanols obtained by the production process | |
| CN109096063B (zh) | 提纯聚甲醛二甲基醚的方法 | |
| CN115806535B (zh) | 一种5-羟甲基糠醛的制备方法 | |
| CN101092360A (zh) | 一种以萘磺酸甲缩醛催化合成柠檬酸三丁酯的方法 | |
| CN1370138A (zh) | 氟化羟基化合物的纯化方法 | |
| CN1202060C (zh) | 一种醚类产品的生产方法 | |
| EP0170205A2 (en) | Process for production of dihydromyrcenol and dihydromyrcenyl acetate | |
| CN114380664A (zh) | 一种碱金属多元醇盐及其制备方法 | |
| CN114181054A (zh) | 一种3,5-二叔丁基-4-羟基苄基甲基醚的合成方法 | |
| CN118047663B (zh) | 一种乙基己基甘油的合成工艺 | |
| CN1346820A (zh) | 2,6－二甲苯酚的制备方法 | |
| CA2466295C (en) | Method for removing acetals containing formaldehyde from polyvalent alcohols by means of tempering | |
| JP3987250B2 (ja) | エーテルの製造法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 19971231 Termination date: 20091221 |