CN1013887B - 氨基甲酸酯类的制备方法 - Google Patents
氨基甲酸酯类的制备方法Info
- Publication number
- CN1013887B CN1013887B CN86105208A CN86105208A CN1013887B CN 1013887 B CN1013887 B CN 1013887B CN 86105208 A CN86105208 A CN 86105208A CN 86105208 A CN86105208 A CN 86105208A CN 1013887 B CN1013887 B CN 1013887B
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- alkyl
- methane amide
- alcohol
- preparation
- halogenide
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- 238000002360 preparation method Methods 0.000 title claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title description 3
- 229940112021 centrally acting muscle relaxants carbamic acid ester Drugs 0.000 title description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- -1 ion halide Chemical class 0.000 abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract 1
- 125000002877 alkyl aryl group Chemical group 0.000 abstract 1
- FATAVLOOLIRUNA-UHFFFAOYSA-N formylmethyl Chemical group [CH2]C=O FATAVLOOLIRUNA-UHFFFAOYSA-N 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 229920002635 polyurethane Polymers 0.000 abstract 1
- 239000004814 polyurethane Substances 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical class COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 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
- 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
氨基甲酸酯类(I)是在一种醇R2OH和一种离子型的卤化物存在下通过电化学氯化甲酰氨(II)制得，式中R1是氢，烷基、环烷基、或芳烷基，R2是烷基。
R1NHCOOR2 (I) R1NHCHO (II)
Description
本发明涉及一种新的制备氨基甲酸酯类的方法。
就一般所知，氨基甲酸酯类是通过碳酰氯和醇反应生成氯甲酸酯然后再氨解制得。在工业操作中处理高度毒性和腐蚀性的原料和中间产物是很费事的。另外，生产过程产生HCl和含卤素的废盐，在工业上除去它们的费用是昂贵的。（参看Ullmann，Enzyklopadie der techn.Chemmie，9，118及以下等页。）
另一方法不用碳酰氯，而用尿素和醇类反应。但这方法的缺点是反应温度高，反应时间长，以及处理固体方面技术上的困难。（参看例如，Houben-Weyl，Methoden d.org.Chemie，8，111及以下等页。）
本发明的目的是提供一种在技术上简单和经济，而又不会污染环境的制备氨基甲酸酯类的方法。
为达到此目的，在通式为R2OH的醇和离子型卤化物存在下将具有通式为（Ⅱ）的甲酰胺
进行电化学氧化，就可很有利地制得具有通式为（Ⅰ）的氨基甲酸酯类。
其中R1是氢，烷基，环烷基，或芳烷基，R2是低分子量的烷基。
此方法的成功使人感到意外，因为长期来认为在可导电性的盐类如四氟硼酸四烷基铵的存在下在醇中甲酰胺的电化反应总是生成烷氧基甲酰胺的。（参看，例如，L.Eberson and K.Nyberg，Tetrahedron32
（1976），2185-2206），反应式如下：
本发明的反应式如下：
具有通式（Ⅱ）的原料中，R1是氢，烷基，环烷基或芳烷基。
优先选用的烷基是有1-12个碳原子的烷基，尤其是1-8、最好是1-4个碳原子的烷基，如甲基，乙基，正-丙基和异丙基，正丁基以及叔丁基。
优先选用的环烷基是有3-8个碳原子的环烷基，特别是5-6个碳原子的环烷基。R1可以是有7-12个碳原子的芳烷基，特别是7或8个碳原子的芳烷基，如苯甲基和苯乙基。
所述基团可以带有取代基，这些取代基在反应条件下应是惰性的如C1-C4烷基，或C1-C4烷氧基，囟素或腈。
反应可用下述甲酰胺类进行，例如：甲基甲酰胺，乙基甲酰胺，正丙基甲酰胺和异丙基甲酰胺，正-丁基甲酰胺，正-辛基甲酰胺，环己基甲 酰胺，环戊基甲酰胺，苄基甲酰胺，和未被取代的甲酰胺。
具有通式为R2OH的醇类中，R2是低分子量烷基，特别是有1-5个碳原子的烷基，最好是甲基或乙基。可用的醇如正丙醇和异丙醇，正-丁醇，正-丙醇，特别是甲醇和乙醇。
合适的离子型卤化物是氢碘、氢溴酸及氢氯酸的盐类。氢溴酸盐如碱金属和碱土金属的溴化物和季铵盐，特别是溴化四烷基铵尤佳。本发
明对阳离子是无所谓的，因此可以用其他金属离子的卤化物，但用便宜的卤化物为好，例如包括钠，钾，钙和铵的溴化物，和溴化二甲基铵，溴化三甲基铵，溴化四甲基铵和溴化四乙基铵。
本发明的方法并不要求特别的电解池，但在一个不分隔的连续流动的电解池中进行为好。阳极可由任何一般的阳极物质组成，但它们在电解条件下应是稳定的，如贵金属，金或铂，或金属氧化物如Ni OX。较好的阳极材料是石墨，阴极可由下述金属构成，如铅，铁，钢，镍或贵金属如铂，较好的阴极材料也是石墨。
电解质组合物的选择范围较宽，如可由下列物质组成：
10-80%（重量）的R1NHCHO
10-80%（重量）的R2OH
以及0.1-10%（重量）的卤化物。
如必要可在电解质中加进溶剂比如为了改善甲酰胺或卤化物的溶解度，这些溶剂的实例为腈类如乙腈，碳酸脂类如碳酸二甲脂，和醚类如四氢呋喃。根据本发明的方法，电流密度并不是一个限制因素，如1-25A/dm2，较好是3-12A/dm2。若电解在大气压下进行，温度最好选择在最少低于电解质沸点5-10℃以下。若使用甲醇或乙醇，电解最好在20-30℃下进行。我们意外地发现，根据本发明的方法在不必降底收率的情况下仍可获得甲酰胺的高转化率，根据本发明的方法目前的产量亦特别地高。例如当电解只有2-2.5F/mole甲酰胺时，甲酰胺可达到完全转化。
电解产物可以用一般方法处理，特别有利是用蒸馏处理。过量的烷基醇或所用的助溶剂首先蒸馏出来，卤化物用一般的方法除去，如过滤或提取，氨基甲酸酯类可通过蒸馏或重结晶来提纯。烷基醇，任何未转化的甲酰胺，助溶剂及卤化物可便利地循环返回电解。本发明的方法可间歇或连续进行。
根据本发明方法制取的氨基甲酸酯类是有着多种用途的合成异氰酸酯的中间体，谷物保护剂和助剂，比如织物整理助剂。
实例
电氧化是在20-25℃下在以石墨为阴极及阳极的不分隔的电解池中进行。在电解过程中含有溴化钠作为导电的盐的电解质通过热交换器以200升/小时的速度泵进电解池，表1表明电解质的组成。
电解完后在大气压下蒸馏除去醇，直至瓶底温度达到120-130℃，然后在5-40毫巴的压力下蒸馏提纯剩余物。未被取代的氨基甲酸甲酯（实例7）产品是通过在乙酸乙酯里重结晶来提纯。在实例8和实例9中，除去醇后的残余物可在80°-100℃下热滤以除去Na Br，随后氨基甲酸乙酯在20-30℃下以光谱（1H-NMR）纯的形式从滤液中结晶而出。所得氨基甲酸酯收率为原料（Ⅱ）的57-88%，转化率100%。
表1概述3实例1至9
Claims (4)
1、一种制备具有通式(Ⅰ)的氨基甲酸酯类的方法，
式中R1是氢，烷基，环烷基，或芳烷基，R2是低分子量的烷基，该方法包括在一种具有通式为R2OH的醇和一种离子型卤化物存在下将具有通式(Ⅱ)的甲酰氨
进行电化学氧化。
2、根据权利要求1的方法，其中所用的卤化物是一种氢溴酸盐。
3、根据权利要求1的方法，用石墨阳极进行电解。
4、根据权利要求1的方法，其中所用的醇是甲醇或乙醇。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19853529531 DE3529531A1 (de) | 1985-08-17 | 1985-08-17 | Verfahren zur herstellung von carbamidsaeureestern |
| DEP3529531.7 | 1985-08-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86105208A CN86105208A (zh) | 1987-02-18 |
| CN1013887B true CN1013887B (zh) | 1991-09-11 |
Family
ID=6278769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86105208A Expired CN1013887B (zh) | 1985-08-17 | 1986-08-13 | 氨基甲酸酯类的制备方法 |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US4661217A (zh) |
| EP (1) | EP0212512B1 (zh) |
| JP (1) | JPH076075B2 (zh) |
| CN (1) | CN1013887B (zh) |
| AU (1) | AU587849B2 (zh) |
| CA (1) | CA1275066A (zh) |
| DE (2) | DE3529531A1 (zh) |
| DK (1) | DK388786A (zh) |
| FI (1) | FI86715C (zh) |
| HU (1) | HU199109B (zh) |
| IL (1) | IL79645A (zh) |
| NO (1) | NO163965C (zh) |
| ZA (1) | ZA866150B (zh) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3606478A1 (de) * | 1986-02-28 | 1987-09-03 | Basf Ag | Verfahren zur herstellung von biscarbamaten und neue biscarbamate |
| DE3730777A1 (de) * | 1987-09-12 | 1989-03-23 | Basf Ag | Verfahren zur herstellung von imidazolidinonen und oxazolidinonen |
| US5214169A (en) * | 1988-04-25 | 1993-05-25 | Merrell Dow Pharmaceuticals Inc. | N-(2,3-epoxycyclopentyl) carbamate derivatives |
| JP3168031B2 (ja) * | 1990-11-16 | 2001-05-21 | トヨタ自動車株式会社 | 耐熱性ヘラパタイト及びその製造方法 |
| CN107964668B (zh) * | 2016-10-19 | 2019-08-16 | 中国科学院上海有机化学研究所 | 化合物中C(sp3)-H键转化为C(sp3)-O键方法及制备得到的化合物 |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1078154A (en) * | 1965-02-19 | 1967-08-02 | Ici Ltd | Electro-chemical process |
| US3459643A (en) * | 1967-02-03 | 1969-08-05 | Sprague Electric Co | Alkoxylation of n-methyl-n-hydrocarbylamides |
| US3464960A (en) * | 1967-12-15 | 1969-09-02 | Us Army | Mixture for rapid polymerization |
| DE2336976A1 (de) * | 1973-07-20 | 1975-02-13 | Hoechst Ag | Verfahren zur herstellung von n-(alphaalkoxyaethyl)-carbonsaeureamiden |
| NL7600544A (nl) * | 1975-01-25 | 1976-07-27 | Hoechst Ag | Werkwijze voor de bereiding van n-(gamma-alkoxy- ethyl)-carbonzuuramiden. |
| US4138408A (en) * | 1975-12-20 | 1979-02-06 | Hoechst Aktiengesellschaft | ω-Alkoxy derivatives of lactams and process for their manufacture |
| DE2655741A1 (de) * | 1976-12-09 | 1978-06-15 | Hoechst Ag | Verfahren zur herstellung von carbamidsaeureestern hoehersiedender alkohole |
| DE2919756A1 (de) * | 1979-05-16 | 1980-11-27 | Hoechst Ag | Verfahren zur herstellung von n- alpha -alkoxyethyl-carbonsaeureamiden |
| US4430262A (en) * | 1981-06-05 | 1984-02-07 | Shell Oil Company | Preparation of isocyanates and/or derivatives thereof |
| DE3233309A1 (de) * | 1982-09-08 | 1984-03-08 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von n-substituierten carbamaten |
| DE3380065D1 (en) * | 1982-10-19 | 1989-07-20 | Mitsubishi Rayon Co | Novel polymer composition |
| US4457813A (en) * | 1983-03-04 | 1984-07-03 | Monsanto Company | Electrolysis cells and electrolytic processes |
| DE3435388A1 (de) * | 1984-09-27 | 1986-04-03 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von aromatischen carbonsaeureestern |
| US4588482A (en) * | 1985-06-10 | 1986-05-13 | Basf Aktiengesellschaft | Preparation of phthalaldehyde acetals |
-
1985
- 1985-08-17 DE DE19853529531 patent/DE3529531A1/de not_active Withdrawn
-
1986
- 1986-08-06 IL IL79645A patent/IL79645A/xx not_active IP Right Cessation
- 1986-08-08 CA CA000515607A patent/CA1275066A/en not_active Expired - Lifetime
- 1986-08-08 FI FI863246A patent/FI86715C/fi not_active IP Right Cessation
- 1986-08-09 DE DE8686111022T patent/DE3661202D1/de not_active Expired
- 1986-08-09 EP EP86111022A patent/EP0212512B1/de not_active Expired
- 1986-08-11 US US06/895,173 patent/US4661217A/en not_active Expired - Lifetime
- 1986-08-13 JP JP61188798A patent/JPH076075B2/ja not_active Expired - Lifetime
- 1986-08-13 CN CN86105208A patent/CN1013887B/zh not_active Expired
- 1986-08-15 ZA ZA866150A patent/ZA866150B/xx unknown
- 1986-08-15 DK DK388786A patent/DK388786A/da not_active Application Discontinuation
- 1986-08-15 HU HU863599A patent/HU199109B/hu not_active IP Right Cessation
- 1986-08-15 NO NO863297A patent/NO163965C/no unknown
- 1986-08-15 AU AU61507/86A patent/AU587849B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| NO863297D0 (no) | 1986-08-15 |
| EP0212512B1 (de) | 1988-11-17 |
| IL79645A0 (en) | 1986-11-30 |
| FI86715C (fi) | 1992-10-12 |
| DE3529531A1 (de) | 1987-02-26 |
| AU587849B2 (en) | 1989-08-31 |
| FI86715B (fi) | 1992-06-30 |
| JPS6240389A (ja) | 1987-02-21 |
| CA1275066A (en) | 1990-10-09 |
| DE3661202D1 (en) | 1988-12-22 |
| CN86105208A (zh) | 1987-02-18 |
| EP0212512A1 (de) | 1987-03-04 |
| DK388786A (da) | 1987-02-18 |
| AU6150786A (en) | 1987-02-19 |
| NO863297L (no) | 1987-02-18 |
| HU199109B (en) | 1990-01-29 |
| FI863246A (fi) | 1987-02-18 |
| FI863246A0 (fi) | 1986-08-08 |
| JPH076075B2 (ja) | 1995-01-25 |
| HUT43032A (en) | 1987-09-28 |
| NO163965C (no) | 1990-08-15 |
| DK388786D0 (da) | 1986-08-15 |
| ZA866150B (en) | 1987-04-29 |
| US4661217A (en) | 1987-04-28 |
| IL79645A (en) | 1990-07-12 |
| NO163965B (no) | 1990-05-07 |
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