SU137511A1 - The method of obtaining complex alpha-alkenyl esters - Google Patents
The method of obtaining complex alpha-alkenyl estersInfo
- Publication number
- SU137511A1 SU137511A1 SU663724A SU663724A SU137511A1 SU 137511 A1 SU137511 A1 SU 137511A1 SU 663724 A SU663724 A SU 663724A SU 663724 A SU663724 A SU 663724A SU 137511 A1 SU137511 A1 SU 137511A1
- Authority
- SU
- USSR - Soviet Union
- Prior art keywords
- alkenyl esters
- obtaining complex
- complex alpha
- solution
- benzoquinone
- Prior art date
Links
Description
Известен способ получени а-алкениловых эфиров карбоновых кислот , основанный на нревращении специально синтезируемых ацетиленовых углеводородов.A method of producing a-alkenyl esters of carboxylic acids is known, based on the conversion of specially synthesized acetylene hydrocarbons.
С целью расширени сырьевой базы предлагаетс способ получени указанных эфиров путем взаимодействи олефинов с насыщенными карбоновыми кислотами в присутствии хлористого паллади , веществ снособных окисл ть металлический палладий (п-бензохинон или хлорна медь) и анионов соответствующей кислоты, вносимых в раствор в виде соли. Реакцию ведут в среде безводной карбоновой кислоты. Оптимальна температура реакции определ етс свойствами примен емых олифина и кислоты и может измен тьс в интервале от О до 250°.In order to expand the raw material base, a method is proposed for preparing these esters by reacting olefins with saturated carboxylic acids in the presence of palladium chloride, substances capable of oxidizing metallic palladium (p-benzoquinone or chlorine copper) and anions of the corresponding acid introduced into the solution in the form of a salt. The reaction is carried out in an anhydrous carboxylic acid medium. The optimum reaction temperature is determined by the properties of the applied olifina and acid and can vary in the range from 0 to 250 °.
Пример 1. Раствор 0,178 г (0,001 мол ) безводного хлористого паллади , 8,2 г (0,1 мол ) безводного ацетата натри и 27 г (0,25 мол п-бензохинона в 125 мл лед ной уксусной кислоты насыщают при встр хивании сухим этиленом. После поглощени 2100 мл этилена (0,0885 мол ) раствор отфильтровывают и из фильтрата путем двукратной перегонки с последующим разделением на ректификационной колонке (33 т. т.) выдел ют фракцию с т. кип. 72-86°. Затем эту фракцию промывают водой, сущат сульфатом натри и перегон ют.Example 1. A solution of 0.178 g (0.001 mol) of anhydrous palladium chloride, 8.2 g (0.1 mol) of anhydrous sodium acetate, and 27 g (0.25 mol of p-benzoquinone in 125 ml of glacial acetic acid are saturated with shaking with a dry ethylene. After the absorption of 2100 ml of ethylene (0.0885 mol), the solution is filtered and a fraction with b.p. 72-86 ° is separated from the filtrate by double distillation followed by separation on a distillation column (33 tons), then washed with water, dissolved with sodium sulfate and distilled.
Получают 3,27 г продукта с т. кии. 72,5-72,9° при 758 ш., df -Obtain 3.27 g of the product with so on. 72.5-72.9 ° at 758 w., Df -
0,9341 и пп 1,3959. 0,9341 and PP 1,3959.
ИК-спектр идентичен со спектром винилацетата.The IR spectrum is identical to that of vinyl acetate.
Пример 2. К раствору 0,178 г безводного хлористого иаллади и 4,9 г безводного ацетата кали в 50 мл лед ной уксусной кислоты добавл ют 27 г ц-бензохинона и 8,2 г циклогексена и встр хивают реакционную смесь в течение 168 час. Затем раствор отфильтровывают, выливают в 500 мл охлажденного до 0° 10%-ного водного раствора гидроокиси кали и экстрагируют эфиром. Эфирный экстракт сущат сульфатом натри , отгон ют эфир и перегон ют остаток. Получают 5,6 г циклогексе 79- 18Г при 754 мм и HD 1,4721. Йодное числоиилацетата с т. кипExample 2. To a solution of 0.178 g of anhydrous alladium chloride and 4.9 g of anhydrous potassium acetate in 50 ml of glacial acetic acid, 27 g of c-benzoquinone and 8.2 g of cyclohexene are added and the reaction mixture is shaken for 168 hours. Then the solution is filtered, poured into 500 ml of a 10% strength aqueous solution of potassium hydroxide cooled to 0 ° and extracted with ether. The ether extract is sodium sulfate, the ether is distilled off and the residue is distilled. 5.6 g of cyclohexe 79-18G at 754 mm and HD 1.4721 are obtained. Iodine number of acetate with m. Kip
№ 137511№ 137511
79. При омылении полученного вещества получен циклогексанон идентифицированный в виде гидразона и 2,4-динитрофепилгидразона.79. During the saponification of the substance obtained, cyclohexanone was identified as a hydrazone and 2,4-dinitrophenylhydrazone.
Аналогичным способом с применением в качестве окислителей п-бензохинона или хлорной меди получены изопропенилацетат, винилпронионат , винилизобутират, октенил-2-а11,етат и винилканронат.In a similar way, using p-benzoquinone or chlorine copper as oxidizing agents, isopropenyl acetate, vinyl propionate, vinyl isobutyrate, octenyl-2-a11, etat and vinyl canronate were obtained.
Предмет изобретени Subject invention
Способ получени сложных а-алкениловых эфиров, отличающийс тем, что в качестве исходных берут олефины и жирные кислоты , причем реакцию провод т в среде карбоновой кислоты прп температуре О-250° в присутствии анионов соответствующей кислоты, вносимых в раствор в виде солей хлористого паллади (катализатор) и п-бензохинона или хлорной меди (окислитель дл металлического паллади ).A method for producing α-alkenyl esters, characterized in that olefins and fatty acids are taken as starting materials, the reaction being carried out in a carboxylic acid medium at a temperature of about 250 ° in the presence of anions of the corresponding acid introduced into the solution in the form of palladium chloride salts ( catalyst) and p-benzoquinone or chlorine copper (oxidizer for metallic palladium).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU663724A SU137511A1 (en) | 1960-04-19 | 1960-04-19 | The method of obtaining complex alpha-alkenyl esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU663724A SU137511A1 (en) | 1960-04-19 | 1960-04-19 | The method of obtaining complex alpha-alkenyl esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SU137511A1 true SU137511A1 (en) | 1960-11-30 |
Family
ID=48293716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SU663724A SU137511A1 (en) | 1960-04-19 | 1960-04-19 | The method of obtaining complex alpha-alkenyl esters |
Country Status (1)
| Country | Link |
|---|---|
| SU (1) | SU137511A1 (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3221045A (en) * | 1962-03-26 | 1965-11-30 | Union Carbide Corp | Preparation of olefinic esters |
| US3227747A (en) * | 1962-05-02 | 1966-01-04 | Nat Distillers Chem Corp | Liquid phase process for the preparation of unsaturated esters by the oxidation of olefins with a group viii noble metal catalyst in the presence of an organic copper salt and a nitrile |
| US3238247A (en) * | 1963-05-15 | 1966-03-01 | Union Carbide Corp | Preparation of unsaturated acetates by the oxidation of olefins with a palladium salt in the presence of excess cupric acetate in halide free medium |
| US3253020A (en) * | 1962-07-23 | 1966-05-24 | Union Oil Co | Ester production using noble metalbromine compound catalysts |
| US3260739A (en) * | 1961-12-26 | 1966-07-12 | Union Oil Co | Production of vinyl acetate by oxidation of ethylene with a palladous salt-containing catalyst and catalyst regeneration with oxygen and a nitrite or nitrogen oxide |
| US3262969A (en) * | 1962-02-22 | 1966-07-26 | Ici Ltd | Production of mono- and di-esters of glycols by oxidation of olefins with a palladous salt in presence of a carboxylic acid, a redox system, an alkali metal halide, carboxylate ions and molecular oxygen |
| US3274238A (en) * | 1962-07-26 | 1966-09-20 | Consortium Elektrochem Ind | Production of unsaturated esters by oxidation of olefins |
| US3275680A (en) * | 1962-02-03 | 1966-09-27 | Bayer Ag | Production of organic acetates in presence of a noble metal catalyst and oxygen |
| US3277159A (en) * | 1963-06-18 | 1966-10-04 | Union Oil Company Of America | Process for the production of unsaturated esters and acetals from olefins |
| US3277158A (en) * | 1963-06-11 | 1966-10-04 | Union Oil Co | Production of vinyl acetate from ethylene |
| US3278590A (en) * | 1962-07-31 | 1966-10-11 | Ici Ltd | Process for preparing unsaturated esters by oxidation of olefins in an aromatic amide solvent |
| US3281457A (en) * | 1962-08-06 | 1966-10-25 | Rhone Poulenc Sa | Process for the production of vinyl esters by the oxidation of ethylene |
| US3290362A (en) * | 1963-08-05 | 1966-12-06 | Union Oil Co | Process for preparing esters and acetals by the oxidation of olefins |
| US3300528A (en) * | 1962-10-11 | 1967-01-24 | Asahi Chemical Ind | Vapor phase process for preparing vinyl acetate by the oxidation of ethylene with a group viii noble metal plus copper or iron |
| DE1244160B (en) * | 1962-07-06 | 1967-07-13 | Ici Ltd | Process for the preparation of unsaturated esters of monocarboxylic acids |
| US3479392A (en) * | 1960-12-23 | 1969-11-18 | Grace W R & Co | Production of unsaturated ethers and esters |
| US4057575A (en) * | 1967-09-25 | 1977-11-08 | Union Oil Company Of California | Process for the preparation of unsaturated esters |
-
1960
- 1960-04-19 SU SU663724A patent/SU137511A1/en active
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3479392A (en) * | 1960-12-23 | 1969-11-18 | Grace W R & Co | Production of unsaturated ethers and esters |
| US3260739A (en) * | 1961-12-26 | 1966-07-12 | Union Oil Co | Production of vinyl acetate by oxidation of ethylene with a palladous salt-containing catalyst and catalyst regeneration with oxygen and a nitrite or nitrogen oxide |
| US3275680A (en) * | 1962-02-03 | 1966-09-27 | Bayer Ag | Production of organic acetates in presence of a noble metal catalyst and oxygen |
| US3262969A (en) * | 1962-02-22 | 1966-07-26 | Ici Ltd | Production of mono- and di-esters of glycols by oxidation of olefins with a palladous salt in presence of a carboxylic acid, a redox system, an alkali metal halide, carboxylate ions and molecular oxygen |
| US3221045A (en) * | 1962-03-26 | 1965-11-30 | Union Carbide Corp | Preparation of olefinic esters |
| US3227747A (en) * | 1962-05-02 | 1966-01-04 | Nat Distillers Chem Corp | Liquid phase process for the preparation of unsaturated esters by the oxidation of olefins with a group viii noble metal catalyst in the presence of an organic copper salt and a nitrile |
| DE1244160B (en) * | 1962-07-06 | 1967-07-13 | Ici Ltd | Process for the preparation of unsaturated esters of monocarboxylic acids |
| US3253020A (en) * | 1962-07-23 | 1966-05-24 | Union Oil Co | Ester production using noble metalbromine compound catalysts |
| US3274238A (en) * | 1962-07-26 | 1966-09-20 | Consortium Elektrochem Ind | Production of unsaturated esters by oxidation of olefins |
| US3278590A (en) * | 1962-07-31 | 1966-10-11 | Ici Ltd | Process for preparing unsaturated esters by oxidation of olefins in an aromatic amide solvent |
| US3281457A (en) * | 1962-08-06 | 1966-10-25 | Rhone Poulenc Sa | Process for the production of vinyl esters by the oxidation of ethylene |
| US3300528A (en) * | 1962-10-11 | 1967-01-24 | Asahi Chemical Ind | Vapor phase process for preparing vinyl acetate by the oxidation of ethylene with a group viii noble metal plus copper or iron |
| US3238247A (en) * | 1963-05-15 | 1966-03-01 | Union Carbide Corp | Preparation of unsaturated acetates by the oxidation of olefins with a palladium salt in the presence of excess cupric acetate in halide free medium |
| US3277158A (en) * | 1963-06-11 | 1966-10-04 | Union Oil Co | Production of vinyl acetate from ethylene |
| US3277159A (en) * | 1963-06-18 | 1966-10-04 | Union Oil Company Of America | Process for the production of unsaturated esters and acetals from olefins |
| US3288845A (en) * | 1963-06-18 | 1966-11-29 | Union Oil Co | Method of preparing unsaturated esters by oxidation of olefins |
| US3290362A (en) * | 1963-08-05 | 1966-12-06 | Union Oil Co | Process for preparing esters and acetals by the oxidation of olefins |
| US4057575A (en) * | 1967-09-25 | 1977-11-08 | Union Oil Company Of California | Process for the preparation of unsaturated esters |
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