GB2073197A - Selective Production of Phenylene Diacetate - Google Patents
Selective Production of Phenylene Diacetate Download PDFInfo
- Publication number
- GB2073197A GB2073197A GB8110491A GB8110491A GB2073197A GB 2073197 A GB2073197 A GB 2073197A GB 8110491 A GB8110491 A GB 8110491A GB 8110491 A GB8110491 A GB 8110491A GB 2073197 A GB2073197 A GB 2073197A
- Authority
- GB
- United Kingdom
- Prior art keywords
- palladium
- phenyl acetate
- phenylene diacetate
- acetate
- acetoxylation
- 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
- FBSAITBEAPNWJG-UHFFFAOYSA-N (2-acetyloxyphenyl) acetate Chemical compound CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 title abstract description 15
- 238000004519 manufacturing process Methods 0.000 title description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 39
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 37
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 30
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229940049953 phenylacetate Drugs 0.000 claims abstract description 20
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006137 acetoxylation reaction Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 18
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- -1 alkali metal carboxylate Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- QUMXDOLUJCHOAY-UHFFFAOYSA-N 1-Phenylethyl acetate Chemical compound CC(=O)OC(C)C1=CC=CC=C1 QUMXDOLUJCHOAY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XRYSDRCNTMEYFH-UHFFFAOYSA-N [acetyloxy(phenyl)methyl] acetate Chemical compound CC(=O)OC(OC(C)=O)C1=CC=CC=C1 XRYSDRCNTMEYFH-UHFFFAOYSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011874 heated mixture Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940115425 methylbenzyl acetate Drugs 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- 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
- C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Phenyl acetate is converted to phenylene diacetate by a palladium catalyst in the presence of an acetoxylation amount of oxygen, acetic acid and acetic anhydride at elevated temperatures and pressures. The predominant product is the para- isomer. Phenylene diacetate may be of use as a solvent.
Description
SPECIFICATION
Selective Production of Phenylene Diacetate
This invention relates to a process for the preparation of phenylene diacetate. More particularly, the invention relates to the conversion of phenyl acetate to phenylene diacetate by a palladium catalyst in the presence of oxygen, acetic anhydride and acetic acid at elevated temperatures and pressures.
Still more particularly, the invention relates to a method of preparing para-phenylene diacetate as a major product. Phenylene diacetate may be used as a solvent. The preparation of the phenyl acetate starting material is disclosed in U.S. Patent No. 4,156,783.
The acetoxylation of chlorobenzene by Pd(OAc)2 in acetic acid with an oxygen atmosphere and with or without the presence of NO2, and with meta-selectivity, is reported inActa Chemica
Scandinavica B28 (1974) 771776, L. Eberson eft at "Ac" as used herein refers to the group
The latter publication also discloses the stoichiometric acetoxylation of phenyl acetate by 2,2'-Bipy
Pd(OAc)(NO3) in acetic acid at 11 50C and in an oxygen atmosphere, with meta-diacetoxybenzene (meta-phenylene diacetate) being the major product (60%) after a reaction period of 2 hours.The aforementioned reference, pages 597-602, states that a heterogeneous gas phase acetoxylation of a monofunctional benzene derivative that takes place in acetic acid in the presence of oxygen shows a reversal of the normal substituent effect, i.e., ortho-, para-directing substituents give predominantly meta-acetoxylation and meta-directing ones give ortho-, para-acetoxylation.
The formation of methylbenzylacetate via the homogeneous reaction between palladium (II) acetate and para-xylene in acetic acid in the presence of oxygen has been studied and reported in articles in Acta Chemica Scandinavica 27 (1973), L. Eberson et at., pages 1162-1174, 1249- 1254, 1255-1267. The acetoxylation of phenyl acetate by potassium peroxydisulfate with Pd(ll) as a catalyst in the presence of acetic acid to form 25% ortho-, 42% meta- and 33% para-isomers of
phenylene diacetate is disclosed in Acta Chemica Scandinavica B30 (1976) pages 361-364, Eberson et al.
The use of palladium (II) (together with other components such as oxidants or cooxidants) to catalyse aromatic acetoxylation is reported in the literature as examplified by U.S. Patent No.
3,772,383; Tetrahedron Letters No. 58, pp. 6123-6126, 1 968, C. H. Bushweller; J. Org. Chem., Vol.
36, No. 14, 1971, P. M. Henry; and J. S. C. Chem. Com. 1974, pages 885-886, L. Eberson eft at The acetoxylation of benzene to phenyl acetate using oxygen, palladium on silica or alumina in the presence of acetic acid is reported in ErdoiUndKoh,e, 23, 79, 1970.
According to the Journal of Organic Chemistry, Vol. 33, November 11, 1968, D. R. Bryant et at., the acetoxylation of toluene in the presence of oxygen, palladium acetate and an alkali metal carboxylate at elevated temperatures results in benzyl acetate and, at higher temperatures, in conversation to benzylidene diacetate.
However, none of the previously mentioned references discloses or suggests the conversion of phenyl acetate to phenylene diacetate via the applicants' method. Further, contrary to the previously discussed reference (Acta Chemica Scandinavica B-28, pages 597-602 and pages 771-776), the applicants' method yields predominantly the para-phenylene diacetate isomer.
As aforestated, the process of this invention comprises reacting phenyl acetate in the presence of acetic anhydride, acetic acid, an acetoxylation amount of oxygen and a palladium catalyst at an elevated temperature and pressure to yield phenylene diacetate in accordance with the following reaction:
Para-phenylene diacetate is the predominant product followed by the ortho- and meta-isomers.
The word "acetoxylation" as used in this specification refers to the additon of an acetoxy group,
to the organiv compound being processed.
The process of this invention is convenisady cardsd out at an acetoxylation temperature which favours the formation of phenylene diacetate. Elevated temperatures of from 1 000C to 3000C are preferred, and more preferably from 150 C to 250 C The reaction is in a liquid phase. Aiso, an acetoxylation pressure is used. Reaction pressures of up to 1 500 psig are preferred. The period for the reaction varies considerably, depending in part on the operating conditions, including for example, the
relative concentrations of materials, the tempperatures and the pressures employed. The process can also be carried out in a continuous system.
The phenyl acetate should desirably be reacted in .;r presence of acetic acid and acetic anhydride. The acetic anhydride should desirably ne present in the amount of from 0.1 to 3 times by weight the amount of phenyl acetate used, with 0.3 to .5 times being preferred. The molar ratio of palladium catalyst to phenyl acetate smployed should be in the range of from 0.0001 to 1, with 0.001 to 0.5 being preferred.
Oxygen is used in the applicants' acetoxylation method. The amount of oxygen is an acetoxylation amount, that is, an amount which favours tho formati-, o-F the phenylene diacetates, desirably the
para-isomer, in the presence of a palladium catalyst, acetic acid and acetic anhydride. Generally, the oxygen used can be contained in an inert gas which as nitrogen and, in such a mixture, can be at a low concentration. For example, as reported in the Example, a gas mixture containing 4% O2 and 96% N2 was effectively used.
The palladium catalyst is desirably palladium or ait alumina. Other palladium catalysts, e.g., palladium acetate and palladium on other supports, e.g., carbon and silica, which would result in an
effective reaction mixture, can be used.
Generaily, the applicants' method results in converting phenyl acetate substantially entirely to phenylene diacetate, with the para-isomer the predominant isomer. While a product other than
phenylene diacetate may be produced, the amount wi; be minor, if not merely a trace. The selectivity as to para-phenylene diacetate is also substantial, fsr example, in the run in the Example, it was 82%.
The following example is provided to illustrate the invention described herein.
Example
The following reaction was run in a stirred stainless steel autoclave using 5% palladium on alumina (2.35 mmoles) as the catalyst, acetic anhydre {510 mmoles), phenyl acetate (950 mmoles) and acetic acid (4200 mmoles). The autoclave was lea ted to 2000C under nitrogen (800 psig). Then, an acetoxylation gas, 4% O2 and 96% N2, was passed through the heated mixture for 2.5 hours at a rate of 2 liters per minute (800 psig). At the and of the run, the autoclave was cooled to room temperature and the products were analysed 4 gas chromatography, Total product yield was 800% based on Pd.By gas chromaiograph, three products were detected: ortho-phenylene diacetate, 14% selectivity, meta-phenylene diacetate, 4% selectivity; and para-phenylene diacetate, 82% selectivity.
Just a trace of any acetylation product was found. The phenylene diacetates can be recovered and separated by known methods such as diatillation and/or crystallisation. Selectivity as used herein is defined as the mole percent of one isomer relative to ail products formed.
The foregoing yields indicate that the para-isomer is the major diacetate product while the orthoisomer is a minor diacetate product. The meta-isomer is present in a nominal amount. These amounts can be modified by changes in operating conditions; however, generally, the para-isomer is favoured
and can be the predominant isomer.
Use of other palladium catalyst, e.g., palladium acetata, and use of other operating conditions
resulted in analogous yields and selectivities.
Claims (8)
1. A process for the acetoxylation of @ .renyl acetate comprisinli: reacting phenyl acetate with an acetoxylation amount of oxygen at elevated temperatures and
pressures in the presence of acetic acid, acetic a anhydride and a palladium catalyst.
2. A process according to claim 1, wherein para-phenylene diacetate is the3 major product.
3. A process according to claims 1 or, wherein the temperature is in the range of from 100 C to 300 C
4. A process according to any one of claims 1 to 3, herein the molar ratio of catalyst to phenyl acetate is in the range of from 0.0001:1 to ' :1.
5. A process according to any one of claims -, to -'4 wherein the acetic anhydride is present in the range of from 0.1 to 3 times ty weight of the phenyl acetate.
6. A process according to any one of claims 1 to 5, wherein the palladium catalyst is selected from palladium on alumina, palladium acetate, palladium on silica, palladium acetate on silica and palladium on carbon.
7. A process for the preparation of para-phenylene diacetate comprising:
reacting phenyl acetate with an acetoxylating amount of oxygen in the presence of acetic anhydride, palladium on alumina catalyst, and acetic acid, and at a temperature in the range of from 1 000C to 300"C and-an elevated pressure, and wherein the acetic anhydride is present in the range of from 0.1 to 3 times the weight of the phenyl acetate, and the molar ratio of catalyst to phenyl acetate is in the range of from 0.0001:1 to 1 :1.
8. A process for the acitoxylation of phenyl acetate substantially as herein described with reference to the specific Example.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13770780A | 1980-04-07 | 1980-04-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2073197A true GB2073197A (en) | 1981-10-14 |
| GB2073197B GB2073197B (en) | 1984-10-24 |
Family
ID=22478714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8110491A Expired GB2073197B (en) | 1980-04-07 | 1981-04-03 | Selective production of phenylene diacetate |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5936972B2 (en) |
| BE (1) | BE888319A (en) |
| CA (1) | CA1175058A (en) |
| FR (1) | FR2479811A1 (en) |
| GB (1) | GB2073197B (en) |
| IT (1) | IT1195771B (en) |
| NL (1) | NL8101686A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0185522A2 (en) * | 1984-12-14 | 1986-06-25 | The Clorox Company | Phenylene mixed diester peracid precursors |
| US4689427A (en) * | 1984-11-21 | 1987-08-25 | Hoffmann-La Roche Inc. | Hydroquinone derivatives useful in the production of vitamin E |
| US4814110A (en) * | 1984-12-14 | 1989-03-21 | The Clorox Company | Method for esterifying dihydroxybenzenes |
| US4985458A (en) * | 1986-09-26 | 1991-01-15 | Mitsui Toatsu Chemicals, Incorporated | Catechol diacetate derivatives for inducing the production of nerve growth factor to treat degenerative diseases in the central nervous system |
-
1981
- 1981-03-24 CA CA000373714A patent/CA1175058A/en not_active Expired
- 1981-03-26 IT IT20748/81A patent/IT1195771B/en active
- 1981-04-03 GB GB8110491A patent/GB2073197B/en not_active Expired
- 1981-04-06 NL NL8101686A patent/NL8101686A/en not_active Application Discontinuation
- 1981-04-07 FR FR8106922A patent/FR2479811A1/en active Granted
- 1981-04-07 BE BE0/204405A patent/BE888319A/en not_active IP Right Cessation
- 1981-04-07 JP JP56051300A patent/JPS5936972B2/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4689427A (en) * | 1984-11-21 | 1987-08-25 | Hoffmann-La Roche Inc. | Hydroquinone derivatives useful in the production of vitamin E |
| EP0185522A2 (en) * | 1984-12-14 | 1986-06-25 | The Clorox Company | Phenylene mixed diester peracid precursors |
| EP0185522A3 (en) * | 1984-12-14 | 1987-07-01 | The Clorox Company | Phenylene mono- and diester peracid percursors |
| US4814110A (en) * | 1984-12-14 | 1989-03-21 | The Clorox Company | Method for esterifying dihydroxybenzenes |
| US4985458A (en) * | 1986-09-26 | 1991-01-15 | Mitsui Toatsu Chemicals, Incorporated | Catechol diacetate derivatives for inducing the production of nerve growth factor to treat degenerative diseases in the central nervous system |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1175058A (en) | 1984-09-25 |
| FR2479811B1 (en) | 1984-05-04 |
| IT8120748A0 (en) | 1981-03-26 |
| IT1195771B (en) | 1988-10-27 |
| GB2073197B (en) | 1984-10-24 |
| FR2479811A1 (en) | 1981-10-09 |
| JPS5936972B2 (en) | 1984-09-06 |
| JPS56156234A (en) | 1981-12-02 |
| BE888319A (en) | 1981-10-07 |
| NL8101686A (en) | 1981-11-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |