Method of preparing oxalic acid esters

专利摘要:
A method for the preparation of organic esters of oxalic acid by reaction of carbon monoxide under pressure with the corresponding alcohol is disclosed, the improvement consisting in the use of a quite particular catalyst system. The catalyst is a binary system in which the principal member is a palladium complex and the co-catalyst is a compound, preferably an organic compound having an acidic nature, no matter how weak.
公开号:SU831070A3
申请号:SU782603198
申请日:1978-04-07
公开日:1981-05-15
发明作者:Романо Уго；Риветти Франко
申请人:Снампрогетти С.П.А. (Фирма)；
IPC主号:

专利说明:

This invention relates to organic chemistry, specifically to an improved process for the preparation of oxalic acid esters, which are important chemical products. A method of producing oxalic acid esters is known by esterifying the acid with an appropriate alcohol fl. The closest to the proposed technical essence and the achievable results is a method of producing oxalic esters, for example dimethyl oxalate, by reacting carbon monoxide with methanol at 30-ZOO C and pressure 5-700 atm, in the presence of a catalyst metal salt platinum group and soluble salts of iron and copper, as well as in the presence of oxygen and water-withdrawing agent, such as orthoformic acid ester G23. The disadvantage of this process is the use of oxygen in it, which forms ICI carbon monoxide, in addition, carrying out the process in the presence of oxygen leads to the formation of water - an undesirable by produk ta. The purpose of the invention is to simplify the process. This goal is achieved by the method of obtaining oxalic acid esters of the general formula (where R is CH, j, C, jHj, CHjCj Hg, by reacting carbon monoxide with the corresponding alcohol at 70-120 ° C and a pressure of 20-50 atm in the presence of catalyst, which is used as a complex of divalent palladium of the formula: Pd (OOSN. ,,) 2 (PPh) or a complex of zero-valent palladium of the formula: Pd (PPh) :, or Pd (CO) (PPhg), where either 4, or the presence of a cocatalyst, which is used as hydrobromic diisopropylamine triethylamine, benzoic, ant formic acid slots succinimide, phthalimide. The use of the proposed catalyst systems allows to obtain oxalic esters without using oxygen and water formation. The catalyst system includes either a divalent complex or zero-valent palladium. The complex can be introduced into the reaction system as such, or be prepared in situ by an appropriate combination of the palladium salt and the ligand. Organic substances, for example, succinimide, benzoic acid or formic acid, hydrobromic acid, are used as the cocatalyst Diyeopropylamine or triethylamine phthalimide. Example. 79 g of methanol, 1.50 g of Pd (OOSNp,) ,, (PPhn,) and 0.50 g of succinimide are loaded into a stainless steel autoclave. The autoclave was flushed with nitrogen, filled with carbon monoxide at a pressure of 50 atm, and heated at 120 ° C for 10 hours. Analysis by gas-liquid chromatography showed the presence of dimethyl oxalate (3.2 g) and dimethyl carbonate (0.6 g) in the reaction mixture. substances are carried out by rectification. Data analysis presented in the table. Example 2: 79 g of methanol, 1.85 g of Pd (CO) (PPhrj), j and 0.50 g of succinimide are loaded into the autoclave and heated for 10 hours at a pressure of carbon monoxide of 50 atm. Analysis of the reaction mixture shows the presence of dimethyl oxalate (2.9 g) and dimethyl carbonate (0.5 g). Allocation is carried out analogously to Example 1. Example3. 79 g of ethanol, 1.85 g of Pd (CO) (PPhii,) - i, and 2.0 g of formic acid are loaded into the autoclave and heated at 70 ° C at a pressure of carbon monoxide of 20 atm. 1.3 g of diethyl oxalate and 0.2 g of diethyl carbonate are obtained. The isolation was carried out as in Example 1. Example 4, 79 g of methanol, 2.0 g of Pd (PPh, j) were charged into the autoclave; and 1, O g of hydrobromic diisopropylamine and heated at 120 ° C for 4 hours at a pressure of carbon monoxide of 50 atm. Analysis of the gas-liquid chromatography mixture after the completion showed the formation of dimethyl oxalate (1.7 g) and dimethyl carbonate (0.3 g). The allocation is carried out analogously to example 1. Example 5. 79 g of methanol, 1.50 g of Pd (COOCH), j (PPh, j), j, and 0.70 g of phthalimide are loaded into the autoclave and heated for 4 hours at 150 ° C. under a carbon monoxide pressure of 50 atm. Received 1.1 g of dimethylcarbonate. The selection is carried out analogously to example 1. Example 79 g of ethanol, 0.45 g of palladium acetate, 0.81 g of tributyl phosphine and 2.50 g of benzoic acid are loaded into the autoclave and heated for 4 hours at 100 ° C under a carbon monoxide pressure of 50 atm. 1.5 g of diethyl oxalate and 0.2 g of diethyl carbonate are obtained. The selection is carried out analogously to example 1. Example7. 1.04 g of benzyl alcohol, 1.85 g of Pd (CO) (PPh, j) 3 and 1.0 g of hydrobromic triethylamine are charged into the autoclave and heated at 120 ° C for 4 h at a carbon monoxide pressure of 50 atm, 3.5 g of dibenzyl oxalate are obtained. The separation is carried out as in Example 1. Example B. 79 g of methanol and 1.85 g of Pd (CO) (PPho) j are loaded into the autoclave and heated at 120 ° C for 10 hours at a pressure of carbon monoxide of 50 atm. Analysis by gas-liquid chromatography showed the absence of dimethyl oxalate and even dimethyl carbonate in the reaction mixture.
Dimethyl oxalate
Dimethyl oxalate
Diethyloxalate
Diethyloxalate
Diethyloxalate
Dibenzyloxalate
Dibenzyloxalate
40.7
5.1
49.4
6.85
71
5.25
80.5

权利要求:
Claims (2)
[1]
Invention Formula
The method of producing oxalic acid esters of the general formula (COORl, j, where R is SND, by reacting carbon monoxide with a corresponding alcohol at 70120 ° C and a pressure of 20-50 atm in the presence of a palladium-containing catalyst, in order to simplify the process, as a catalyst, a complex of divalent or zero valent palladium of the formula; Pd (OCOCH, j) a (PPh ,,) j or Pd (PPh3) or
Pd (CO) (PPhj), where either 4 and the process is carried out in the presence of a cocatalyst, which is hydrogen boron diisopropylamine or triethylamine or benzoic or formic acid or succinimide or phthalimide.
Sources of information taken into account in the examination 1. Buhler K., Pearson D. OrgMir
1973
nical syntheses. M., Part 11, p. 282.
[2]
2. US patent 3.393.136, cl. 204-59, published. 1968 (prototype).

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RU2659069C1|2014-06-05|2018-06-28|Шанхай Учжэн Инжиниринг Текнолоджи Ко., Лтд|Method and system of devices for producing dimethyloxalate by carbonylation of industrial synthesis gas under medium-high and high pressure and production of ethylene glycol by hydration of dimethyloxalate|

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---

US4005128A|1975-04-02|1977-01-25|Atlantic Richfield Company|Process for the preparation of oxalate esters|

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US4005129A|1975-06-04|1977-01-25|Atlantic Richfield Company|Process for the oxidative carbonylation of alcohols and method for the reoxidation of reduced copper salts produced by the oxidation carbonylation|

---

JPS5542058B2|1976-07-27|1980-10-28|US4614832A|1979-12-17|1986-09-30|Chevron Research Company|Dialkyl oxalates from carbon monoxide and an alcohol|

---

JPS6212781B2|1981-10-15|1987-03-20|Ube Industries|

---

US4523029A|1982-06-15|1985-06-11|Chevron Research Company|Oxidative carbonylation of alcohols to produce dialkyl oxalates|

---

US4454342A|1982-07-13|1984-06-12|Atlantic Richfield Company|Preparation of dialkyl oxalates using a heterogeneous Pd-V-P catalyst for the oxidative carbonylation of alcohols|

---

US4447638A|1982-08-02|1984-05-08|Atlantic Richfield Company|Preparation of dialkyl oxalates by the oxidative carbonylation of alcohols with a heterogeneous Pd-V-P-Ti containing catalyst system|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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IT22209/77A|IT1078033B|1977-04-07|1977-04-07|PROCESS FOR THE PREPARATION OF ESTERS OF OXALIC ACID|

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