CA1098539A - Method for the preparation of esters - Google Patents
Method for the preparation of estersInfo
- Publication number
- CA1098539A CA1098539A CA269,336A CA269336A CA1098539A CA 1098539 A CA1098539 A CA 1098539A CA 269336 A CA269336 A CA 269336A CA 1098539 A CA1098539 A CA 1098539A
- Authority
- CA
- Canada
- Prior art keywords
- preparation
- reaction
- esters
- oxygen
- iodine
- 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.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Case 931 METHOD FOR THE PREPARATION OF ESTERS . -ABSTRACT OF THE DISCLOSURE . -A method is disclosed for preparing esters by react-ing an olefin with an acid in the presence of oxygen and a catalyst system, the improvement consisting in that the catalyst system is a compound of tin or cerium, used in the presence of iodine or of a iodine-yielding compound. High productivities are achieved and no pollution problems are to be solved.
Description
5~
CASE ~1 This invention relates to a method for the preparation of esters~ starting Erom c~lpounds which contain at least an e~hylenic ~nsaturation~ which are reacted with the acid concerned and with oxygen in the presence of an appropriate catalyst system.
It is known that esters can be obtained by reacting olefins with acids in the presence of o~ygen, but the catalyst systems adopted hitherto are not exempt from drawbacks.
For example9 the Belgian Patent N 803 189 relates to the use of a catalyst system formed by tellurium or selenium coupled with chlorine or bromine. Even though the results are satisfactory~
the metals mentioned above have~ however~ a rather high cost, that which has a bearing on the economy of the entire pr-ocess and are such as to introduce considerable to~icity problems~ In addition~
the reaction is limited by the fact that cer-tain conditions must scrupulously abode by~ such as temperature and pH.
The possibility is likewis0 known by employing, in -the react-ion aforementioned~ a catalyst system as Eormed by a iodide and by a transition metal selected from those having an atomic number of less than 480 ThiS catalyst system~ however~ does not permit to reach high values of hourly outp~ts~ unless the working tempe-ratures adopted are high, that which is still a serious handicap when the reaction is regarded under an industrial respect~ The present Applicants have now ascertained~ tha-t which is the subject-matter of the present invention9 that it is possible to prepare esters starting from compounds containing at least one ethylenic unsaturation, with a high output even at comparatively low values of the temperature and without rising problems as to the enciron-mental pollution~ by reacti~g the unsaturated compound with the acicl and oxygen in the presence of a catalyst system which is formecl : 2-.
..
i i3~
- by t:in or cerium in -the presence of iodine or any compound capable of setting iodine free.
~ he reaction takes place independently of the working ¢on-ditions, even :if it is preferred to work at temperatures over 80C and~ more particularly~ at temperatures in the range fro~
100C and 180C~ The pressure, in its turn, does not influence in any wise the reaction run and it will be possible to work with values of pre.ssure near the atmospherical value and~ anyhow~
always below 50 atmospheres for practical reasons.
The respective amounts oE olefins and oxygen which are caused to react can be selected within ~ide ran~es~ from an excess of the ole.Ein, to an e~cess of oxygen, It will be obviously prefer-red to work in the presence of an excess of oxygen to prevent the forma-tion of explosive mixturesq The qu~ntity of the acid~ conversely~
is not critical~ inasmuch as the acicl may also act as the reaction so:Lvent.
The reaction in fact~ can take place in -the liquid phase and the diluent can be~ as outlined above, the acid as such~ or any other inert solvent: on the other hand~ the acid can play a role in the reaction in the form of an anion oP the metal which belongs to the catalyst system~ that is~ tin or cerium. This i~
~he case of a batchwise run, since, otherwise, the reaction tak~s place in a continuous run, on account o~ the regeneration of the iodine or the metallic salt by the action bf oxygen~
All the workin~ details will become anyhow apparent from the scrutiny of the ensuing illustrative examples~ which are by no means to be construed as limltations of the invention) since the working ranges can either be ampliied or chan~ed consistently with that which has been indicated hereinaboveO
I~ L I 0~
A polytetrafluoroethylene-coated stainless steel autocla~e, e~uipped with a magnetic stirrer~ is charged with 50 grams o~
glacial acetic acid~ l millimol of SnO (135 milligrams) and 6 mil1i 53¢3 mols oP iodine (760 milli~rams)~ A mixture o-f an olefin and oxygen in the -volume ra-tio of 1 to 205 is charged under a pres-sure of 15 atmospheres. The autoclave is immersed in a thermo-static bath at 150C and stirrin~ is star-ted~ The pressure attains :25 aclnospheres and is maintained at such magnitude by allowing for -the consllmption with the introduction of olefin-oxygen mixture.
AEte'.r.6 ~ours o~ reaction~ the solution is chromatographed and p:ield and selectivity are measured. The results are reported in the follow.ing table :
Ole~in Diacetate Moniacetate Selectivity millimols millimols % ~:
.... _ ........ ____ . , E-thylene 6S 25 97 Propylene 75 . 20 98 ~utene-2 80 15 ~6 Allyl alcohol 60 15 95 Selectivity is calculated relative to the olefin which has been consllmed and on taking into account the sum of the diacetate and t}le possible monoacetates.
~XAMPLES 5 ? 8 The proce~ure is the same as for Examples 1 to 4 above~ but the temperature is 125 C4 The selectivity is thc same as for the previous case,s, whereas the conversions fall by about 20~ with respect to the previous ~alues.
EX~MPLES 9 T0 12 The procedure is the same as Eor Examples 1 to 4~ but 25 ~rams of acetic acid and 25 grams of acetic anhydride. No mono-acetat;e is formed by conversion and selectivity do not change appreciably~
EXAM_LES 13 ~0 16 The procedure is the same as for Examples 1 to 4g but 25 grams of acetic acid and 25 grams of water are used~ Conversion and selectivity do not change~ but there is a predominant formation of monoacetates, 4~ .
53~
The procedure is the same as for Examples 1 to 4 3 but the o~erall working pressure is 5 atmospheres, No substantial changes in selectivity and convarsion are experienced b . ~ .
CASE ~1 This invention relates to a method for the preparation of esters~ starting Erom c~lpounds which contain at least an e~hylenic ~nsaturation~ which are reacted with the acid concerned and with oxygen in the presence of an appropriate catalyst system.
It is known that esters can be obtained by reacting olefins with acids in the presence of o~ygen, but the catalyst systems adopted hitherto are not exempt from drawbacks.
For example9 the Belgian Patent N 803 189 relates to the use of a catalyst system formed by tellurium or selenium coupled with chlorine or bromine. Even though the results are satisfactory~
the metals mentioned above have~ however~ a rather high cost, that which has a bearing on the economy of the entire pr-ocess and are such as to introduce considerable to~icity problems~ In addition~
the reaction is limited by the fact that cer-tain conditions must scrupulously abode by~ such as temperature and pH.
The possibility is likewis0 known by employing, in -the react-ion aforementioned~ a catalyst system as Eormed by a iodide and by a transition metal selected from those having an atomic number of less than 480 ThiS catalyst system~ however~ does not permit to reach high values of hourly outp~ts~ unless the working tempe-ratures adopted are high, that which is still a serious handicap when the reaction is regarded under an industrial respect~ The present Applicants have now ascertained~ tha-t which is the subject-matter of the present invention9 that it is possible to prepare esters starting from compounds containing at least one ethylenic unsaturation, with a high output even at comparatively low values of the temperature and without rising problems as to the enciron-mental pollution~ by reacti~g the unsaturated compound with the acicl and oxygen in the presence of a catalyst system which is formecl : 2-.
..
i i3~
- by t:in or cerium in -the presence of iodine or any compound capable of setting iodine free.
~ he reaction takes place independently of the working ¢on-ditions, even :if it is preferred to work at temperatures over 80C and~ more particularly~ at temperatures in the range fro~
100C and 180C~ The pressure, in its turn, does not influence in any wise the reaction run and it will be possible to work with values of pre.ssure near the atmospherical value and~ anyhow~
always below 50 atmospheres for practical reasons.
The respective amounts oE olefins and oxygen which are caused to react can be selected within ~ide ran~es~ from an excess of the ole.Ein, to an e~cess of oxygen, It will be obviously prefer-red to work in the presence of an excess of oxygen to prevent the forma-tion of explosive mixturesq The qu~ntity of the acid~ conversely~
is not critical~ inasmuch as the acicl may also act as the reaction so:Lvent.
The reaction in fact~ can take place in -the liquid phase and the diluent can be~ as outlined above, the acid as such~ or any other inert solvent: on the other hand~ the acid can play a role in the reaction in the form of an anion oP the metal which belongs to the catalyst system~ that is~ tin or cerium. This i~
~he case of a batchwise run, since, otherwise, the reaction tak~s place in a continuous run, on account o~ the regeneration of the iodine or the metallic salt by the action bf oxygen~
All the workin~ details will become anyhow apparent from the scrutiny of the ensuing illustrative examples~ which are by no means to be construed as limltations of the invention) since the working ranges can either be ampliied or chan~ed consistently with that which has been indicated hereinaboveO
I~ L I 0~
A polytetrafluoroethylene-coated stainless steel autocla~e, e~uipped with a magnetic stirrer~ is charged with 50 grams o~
glacial acetic acid~ l millimol of SnO (135 milligrams) and 6 mil1i 53¢3 mols oP iodine (760 milli~rams)~ A mixture o-f an olefin and oxygen in the -volume ra-tio of 1 to 205 is charged under a pres-sure of 15 atmospheres. The autoclave is immersed in a thermo-static bath at 150C and stirrin~ is star-ted~ The pressure attains :25 aclnospheres and is maintained at such magnitude by allowing for -the consllmption with the introduction of olefin-oxygen mixture.
AEte'.r.6 ~ours o~ reaction~ the solution is chromatographed and p:ield and selectivity are measured. The results are reported in the follow.ing table :
Ole~in Diacetate Moniacetate Selectivity millimols millimols % ~:
.... _ ........ ____ . , E-thylene 6S 25 97 Propylene 75 . 20 98 ~utene-2 80 15 ~6 Allyl alcohol 60 15 95 Selectivity is calculated relative to the olefin which has been consllmed and on taking into account the sum of the diacetate and t}le possible monoacetates.
~XAMPLES 5 ? 8 The proce~ure is the same as for Examples 1 to 4 above~ but the temperature is 125 C4 The selectivity is thc same as for the previous case,s, whereas the conversions fall by about 20~ with respect to the previous ~alues.
EX~MPLES 9 T0 12 The procedure is the same as Eor Examples 1 to 4~ but 25 ~rams of acetic acid and 25 grams of acetic anhydride. No mono-acetat;e is formed by conversion and selectivity do not change appreciably~
EXAM_LES 13 ~0 16 The procedure is the same as for Examples 1 to 4g but 25 grams of acetic acid and 25 grams of water are used~ Conversion and selectivity do not change~ but there is a predominant formation of monoacetates, 4~ .
53~
The procedure is the same as for Examples 1 to 4 3 but the o~erall working pressure is 5 atmospheres, No substantial changes in selectivity and convarsion are experienced b . ~ .
Claims (5)
1. A method for the preparation of esters comprising the step of reacting a compound containing at least one ethylenic unsaturation with an acid and oxygen in the presence of a cata-lyst system composed by a compound of tin or cerium in the pre-sence of iodine or any compound capable of setting iodine free.
2. A method for the preparation of esters according to claim 1 characterized in that the reaction is conducted at temperatures over 80°C.
3. A method for the preparation of esters according to claim 2 characterized in that the reaction is carried out at a temperature in the range from 100°C to 180°C.
4. A method for the preparation of esters according to claims 1, 2 or 3, characterized in that the reaction is carried out under a pressure below 50 atmospheres.
5. A method for the preparation of esters according to claims 1, 2 or 3, characterized in that the reaction is carried out with an excess of oxygen.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT19095/76A IT1063233B (en) | 1976-01-09 | 1976-01-09 | PROCEDURE FOR THE PREPARATION OF ESTERS BY REACTION OF AN OLEFINE WITH AN ACID AND OXYGEN |
| IT19095A/76 | 1976-01-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1098539A true CA1098539A (en) | 1981-03-31 |
Family
ID=11154482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA269,336A Expired CA1098539A (en) | 1976-01-09 | 1977-01-07 | Method for the preparation of esters |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS5289613A (en) |
| BE (1) | BE850210A (en) |
| CA (1) | CA1098539A (en) |
| DE (1) | DE2700538C3 (en) |
| DK (1) | DK6877A (en) |
| FR (1) | FR2337708A1 (en) |
| GB (1) | GB1563519A (en) |
| IE (1) | IE44411B1 (en) |
| IT (1) | IT1063233B (en) |
| LU (1) | LU76534A1 (en) |
| NL (1) | NL7700042A (en) |
| NO (1) | NO146495C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102592936B1 (en) * | 2020-11-19 | 2023-10-23 | 주식회사 더코더 | Method of weaving fiver inserting authentication distinction code and system performing thereof |
-
1976
- 1976-01-09 IT IT19095/76A patent/IT1063233B/en active
-
1977
- 1977-01-04 IE IE25/77A patent/IE44411B1/en unknown
- 1977-01-04 NL NL7700042A patent/NL7700042A/en not_active Application Discontinuation
- 1977-01-06 NO NO770038A patent/NO146495C/en unknown
- 1977-01-06 FR FR7700264A patent/FR2337708A1/en active Granted
- 1977-01-07 CA CA269,336A patent/CA1098539A/en not_active Expired
- 1977-01-07 LU LU76534A patent/LU76534A1/xx unknown
- 1977-01-07 DK DK6877A patent/DK6877A/en not_active Application Discontinuation
- 1977-01-07 GB GB635/77A patent/GB1563519A/en not_active Expired
- 1977-01-07 BE BE173939A patent/BE850210A/en not_active IP Right Cessation
- 1977-01-07 DE DE2700538A patent/DE2700538C3/en not_active Expired
- 1977-01-10 JP JP88377A patent/JPS5289613A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| FR2337708B1 (en) | 1979-03-09 |
| FR2337708A1 (en) | 1977-08-05 |
| DK6877A (en) | 1977-07-10 |
| DE2700538C3 (en) | 1979-05-03 |
| NL7700042A (en) | 1977-07-12 |
| IE44411L (en) | 1977-07-09 |
| JPS5289613A (en) | 1977-07-27 |
| IE44411B1 (en) | 1981-11-18 |
| DE2700538A1 (en) | 1977-07-21 |
| NO770038L (en) | 1977-07-12 |
| IT1063233B (en) | 1985-02-11 |
| NO146495C (en) | 1982-10-13 |
| LU76534A1 (en) | 1977-06-17 |
| BE850210A (en) | 1977-07-07 |
| NO146495B (en) | 1982-07-05 |
| DE2700538B2 (en) | 1978-08-31 |
| GB1563519A (en) | 1980-03-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |