CN1064477A - Oxo process for organic acid with halohydrocarbon under normal pressure - Google Patents
Oxo process for organic acid with halohydrocarbon under normal pressure Download PDFInfo
- Publication number
- CN1064477A CN1064477A CN 91106046 CN91106046A CN1064477A CN 1064477 A CN1064477 A CN 1064477A CN 91106046 CN91106046 CN 91106046 CN 91106046 A CN91106046 A CN 91106046A CN 1064477 A CN1064477 A CN 1064477A
- Authority
- CN
- China
- Prior art keywords
- reaction
- normal pressure
- palladium
- catalyzer
- organic acid
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The synthetic organic acid method of halohydrocarbon carbonylation under a kind of condition of normal pressure, the macromolecule loading palladium catalyst is adopted in the used reaction of this method, for example: polyvinylpyrrolidone (PVP), polyphenylene oxide (PPO), polystyrene (PS), polysulfones (PSu) and polyacrylamide polymer loaded palladium catalysts such as (PAA), and add a certain amount of alkali metal hydroxide, be reflected to be lower than under 80 ℃ of temperature and carry out, catalyzer is not only active high, and efficient is also high.Especially for the carbonylation reaction of halogenated aryl hydrocarbon (as chlorinated benzene), use this catalyst system under normal pressure and 70 ℃ of temperature, to have high catalytic activity.
Description
The present invention belongs to the synthetic organic acid preparation method of halohydrocarbon carbonylation, and specifically normal pressure makes halohydrocarbon carry out the synthetic organic acid of carbonylation reaction in the presence of macromolecule load catalyst.
Halohydrocarbon directly carries out a kind of some effective that carbonylation reaction is important Organic Chemicals such as synthetic organic acid, ester and acid amides or product.This building-up reactions is normally carried out under the condition that catalyzer exists, except with the title complex of some Rh, Pd, Co and Ni as the catalyzer, also need add a certain amount of alkali (generally being oxyhydroxide, oxide compound or the organic acid salt and the amine etc. of some basic metal or alkaline-earth metal).The research of relevant this respect has many patent reports, may be summarized as follows substantially: (1) catalyzer is a metal-organic complex of Rh, Pd, Co or Ni, is reflected at homogeneous phase or water and organic phase and carries out in the presence of phase transfer reagent; (2) catalyst consumption is all bigger, and activity is relatively low; For example United States Patent (USP) (1976, US3,991, No. 101) is with (PPh
3)
2PdCl
2Catalysis vinylchlorid carbonylation reaction, catalyst consumption are the 1/50(mol ratios of substrate), at 95 ℃, reaction is after 7 hours down for 1.3MPa pressure, and transformation efficiency is 83%.Japanese Patent (open, 1988,126, No. 843) Pd(PPh
3)
4Catalyzer is at 2.4MPa and 80 ℃ of following catalysis 1.4-dibenzyl chlorocarbonylations, reacts that transformation efficiency is 56.1% after 24 hours, and the mol ratio of substrate and catalyzer is 50; (3) except that indivedual allyl group halohydrocarbon, the carbonylation reaction of most of halohydrocarbon all is to carry out under pressurization and higher temperature, and especially chlorobenzene generally must just can carry out carbonylation reaction under higher pressure and temperature, and activity is very low; For example European patent (1988, EP283, No. 194) makes the condition of orthodichlorobenzene carbonylation employing be: 5MPa, 210 ℃, PdCl
2Be catalyzer, react that transformation efficiency is 75% after 3 hours, it is that every mole of palladium is had to 4 moles of products that the efficient of catalyzer has only 4().United States Patent (USP) (1989, US4,845, No. 273) makes the reaction conditions that the diiodo-benzene carbonylation is adopted be: 6MPaCO, 190 ℃, RhCl
3Being catalyzer, is 88% to the productive rate of dibenzoic acid.
The objective of the invention is to make the reaction of halohydrocarbon (comprising halogenated aryl hydrocarbon) catalyzed carbonylation to carry out under normal pressure (0.1MPa or a little higher than 0.1MPa), catalyzer is not only active high, and efficient is also high.
The synthetic organic acid reaction of halohydrocarbon carbonylation of the present invention can be used reaction formula ↓ expression:
In the formula: R=alkyl, aryl, allyl group or benzyl
M=basic metal, X=Cl, Br, I
Can under normal pressure and lower temperature, carry out for making reaction 1, the present invention adopts loaded palladium catalyst, and add an amount of alkali metal hydroxide, it is characterized in that catalyzer is a soluble palladium salt, Palladous chloride for example, load on the loaded catalyst on solubility or the insoluble polymer carrier, can be represented by the formula: F-PdCl
2, wherein F is polyvinylpyrrolidone (PVP), polyacrylamide (PAA), polystyrene (PS), polyphenylene oxide (PPO) or polysulfones macromolecular compounds such as (PSu).This class loaded palladium catalyst not only has very high activity to the carbonylation reaction of allyl group halohydrocarbon, can reach 80molCO/molPd, mln, and the carbonylation reaction of various halogenated alkanes and aromatic hydrocarbons also had high activity.Particularly to the carbonylation reaction of chlorobenzene, the used catalyst body of the present invention ties up to that activity can reach 1.5molco/molPd.mln under 80 ℃ of temperature of normal pressure; In addition, the concentration of catalyst system of the present invention palladium in reaction is 4～400PPm, and the mol ratio of substrate and palladium is 1.5 * 10
2～3 * 10
4, and activity of such catalysts is stable, below by example building-up reactions provided by the invention is described further.
Example 1 in 50ml glass reaction bottle, adds 1 gram NaOH, 10ml ethanol, 1ml(12.2mmol) chlorallylene and 0.1ml PVP-PdCl
2Ethanolic soln (contains palladium 3.5 * 10
-4Mmol), homo(io)thermism is at 40 ℃, and CO pressure is 0.1MPa, reacts after 2.5 hours, and chlorallylene all transforms, and after the salt acid treatment of reaction solution footpath, the productive rate of butenoic acid is 72%.
Example 2 in the glass reaction bottle of 50ml, adds 1 gram NaOH, 50mg PPO-PdCl
2(contain palladium 7.2 * 10
-3Mmol), 10ml benzene, 10ml water and 1ml allyl bromide 98 (11.5mmol), homo(io)thermism is at 40 ℃, and CO pressure is 0.1MPa, reacts after 2.5 hours, uses hcl acidifying, and the yield of butenoic acid is 98%.
Example 3 adds 1 gram NaOH in the glass reaction bottle of 50ml, 10ml water, 0.5 gram tetramethyl ammonium chloride, 1ml(9.5mmol) bromobenzene and 1ml PVP-PdCl
2Ethanolic soln (contains palladium 3.5 * 10
-3Mmol), homo(io)thermism is at 70 ℃, and CO pressure is 0.1MPa, reacts after 23 hours, uses hcl acidifying, and benzoic productive rate is 80%.
Example 4 adds 1 gram NaOH according to example 3 described experiment condition and processes, 10ml water, 0.5 gram tetramethyl ammonium chloride, 1ml(9.85mmol) chlorobenzene and 1ml PVP-PdCl
2Ethanolic soln (contains palladium 3.5 * 10
-3Mmol), react after 22 hours, use hcl acidifying, the phenylformic acid yield is 55%.
Comparative example 1
Press example 1 described reaction conditions, just use 0.1mlPdCl
2Solution (contains palladium 3.5 * 10
-4Mmol) replace equivalent PVP-PdCl
2Catalyzer repeats example 1 reaction, and reaction solution is after the salt acid treatment, and the productive rate of butenoic acid is 5%.
Comparative example 2
Press example 4 described reaction conditionss, just use 1ml PdCl
2Solution (contains palladium 3.5 * 10
-3Mmol) replace equivalent PVP-PC
2Catalyzer repeats example 4 reactions, and reaction solution hcl acidifying, phenylcarbinol yield are 2%.
Comparative example 3
With 1mmol1,4-dibenzyl chlorine, 5ml CH
3OH, 0.02mmol Pd(PPH
3)
4Add in the autoclave with 3mmol CaO, logical CO is 2.4MPa to pressure in still, and homo(io)thermism is at 80 ℃, reacts that the yield to the diphenyl acetic acid methyl esters is 56.1% after 24 hours.
By above-mentioned example and comparative example,, under normal pressure, can make various halohydrocarbon carbonylations synthesize organic acid when adopting macromolecule loading palladium catalyst system provided by the invention.This building-up reactions does not need high-tension apparatus, and temperature of reaction is low, has reduced energy consumption, is easy to prevent the shallow leakage of CO.
Claims (2)
1, a kind of halohydrocarbon carbonylation catalyzed reaction of utilizing is synthesized the organic acid preparation method, it is characterized in that catalyzer is to adopt soluble palladium salt, for example Palladous chloride loads on the load type palladium catalyst on solubility or the insoluble polymer carrier, can be represented by the formula: F-PdCl
2, wherein F is polyvinylpyrrolidone (PVP), polyacrylamide (PAA), polystyrene (PS), polyphenylene oxide (PPO) or polysulfones macromolecular compounds such as (PSu); Reaction is that Controllable Temperature is built in carrying out below 80 ℃ at normal pressure (0.1MPa or a little higher than 0.1MPa).
2, according to the described preparation method of claim 1, the working concentration that it is characterized in that catalyzer palladium in reaction is 4～400PPm, and the mol ratio of substrate and palladium is 1.5 * 10
2～3 * 10
4
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91106046 CN1031506C (en) | 1991-03-04 | 1991-03-04 | Oxo process for organic acid with halohydrocarbon under normal pressure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91106046 CN1031506C (en) | 1991-03-04 | 1991-03-04 | Oxo process for organic acid with halohydrocarbon under normal pressure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1064477A true CN1064477A (en) | 1992-09-16 |
| CN1031506C CN1031506C (en) | 1996-04-10 |
Family
ID=4907485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91106046 Expired - Fee Related CN1031506C (en) | 1991-03-04 | 1991-03-04 | Oxo process for organic acid with halohydrocarbon under normal pressure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1031506C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368078C (en) * | 2005-06-20 | 2008-02-13 | 淮北煤炭师范学院 | Nano Pd catalyst and its preparation and application |
| CN109943004A (en) * | 2019-02-25 | 2019-06-28 | 郭迎庆 | A kind of preparation method of butadiene rubber composite material |
| CN110075917A (en) * | 2019-04-03 | 2019-08-02 | 万华化学集团股份有限公司 | A kind of loaded catalyst, Its Preparation Method And Use |
-
1991
- 1991-03-04 CN CN 91106046 patent/CN1031506C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368078C (en) * | 2005-06-20 | 2008-02-13 | 淮北煤炭师范学院 | Nano Pd catalyst and its preparation and application |
| CN109943004A (en) * | 2019-02-25 | 2019-06-28 | 郭迎庆 | A kind of preparation method of butadiene rubber composite material |
| CN110075917A (en) * | 2019-04-03 | 2019-08-02 | 万华化学集团股份有限公司 | A kind of loaded catalyst, Its Preparation Method And Use |
| CN110075917B (en) * | 2019-04-03 | 2022-02-18 | 万华化学集团股份有限公司 | Supported catalyst, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1031506C (en) | 1996-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4855635B2 (en) | Method and apparatus for sequestering entrained volatile catalyst species in a carbonylation process | |
| CN1044572C (en) | Polymeric carbonylation catalyst system | |
| Herrmann et al. | Water-soluble metal complexes and catalysts Part 6. A new, efficient water-soluble catalyst for two-phase hydroformylation of olefins | |
| EP0977628B1 (en) | Carbonylation catalyst system | |
| EP0277824B1 (en) | Process for acetic acid preparation and heterogeneous catalyst for same | |
| US4233460A (en) | Alkoxyalkanoic acid preparation | |
| CN1064477A (en) | Oxo process for organic acid with halohydrocarbon under normal pressure | |
| CN1023977C (en) | Method of preparing catalyst useful in dimerization of butadiene | |
| EP0970745B1 (en) | Catalytic system and method for coupling of aromatic compounds | |
| US4238358A (en) | Heterogeneous catalytic hydrogenation | |
| IL44084A (en) | Homogeneous catalytic reduction of 6-methylenetetracyclines | |
| US4313018A (en) | Heterogeneous catalytic hydrogenation | |
| Kudo et al. | Cobalt salts-catalyzed carbonylation of aromatic halides under photostimulation | |
| CN1033038C (en) | Preparation of polymers | |
| JPH04216824A (en) | Manufacture of polymer of carbon monoxide and at least one olefinically unsaturated compound | |
| KR20030003239A (en) | Catalytic composition for carbonylation including iridium and pyridine polymers | |
| US5169981A (en) | Synthesis of alpha-substituted alkadienes | |
| US4730080A (en) | Process for the preparation of diesters of alkanedioic acids | |
| US20090131630A1 (en) | Process For the Preparation of a Dicarboxylic Acid | |
| EP0498857B1 (en) | Process for dimerizing or codimerizing an alpha-olefin | |
| CN1035543C (en) | Water soluble catalyst loaded on high carbon aldehyde by hydrogen formylating high carbon nuber terminal olefine | |
| US5440010A (en) | Gas phase process for forming polyketones | |
| CN1274414C (en) | Catalyst for preparing 2,6-diiso proplyl aniline | |
| EP4121407B1 (en) | Catalytic process for preparing an alpha, beta-ethylenically unsaturated carboxylic acid salt | |
| CN1192821C (en) | Catalyst for preparing 2,6-diisopropyl aniline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |