GB2023581A - A Process for Producing p- Hydroxy Methyl Benzoic Acid Esters - Google Patents
A Process for Producing p- Hydroxy Methyl Benzoic Acid Esters Download PDFInfo
- Publication number
- GB2023581A GB2023581A GB7920221A GB7920221A GB2023581A GB 2023581 A GB2023581 A GB 2023581A GB 7920221 A GB7920221 A GB 7920221A GB 7920221 A GB7920221 A GB 7920221A GB 2023581 A GB2023581 A GB 2023581A
- Authority
- GB
- United Kingdom
- Prior art keywords
- process according
- catalyst
- acid alkyl
- carried out
- ester
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 44
- BBMFSGOFUHEVNP-UHFFFAOYSA-N 4-hydroxy-2-methylbenzoic acid Chemical class CC1=CC(O)=CC=C1C(O)=O BBMFSGOFUHEVNP-UHFFFAOYSA-N 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 11
- 150000002148 esters Chemical class 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000005749 Copper compound Substances 0.000 claims description 3
- 150000001880 copper compounds Chemical class 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluenecarboxylic acid Natural products CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 claims 1
- 239000007858 starting material Substances 0.000 abstract description 7
- 150000004702 methyl esters Chemical class 0.000 abstract description 6
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 22
- FEIOASZZURHTHB-UHFFFAOYSA-N methyl 4-formylbenzoate Chemical compound COC(=O)C1=CC=C(C=O)C=C1 FEIOASZZURHTHB-UHFFFAOYSA-N 0.000 description 11
- VBWFYEFYHJRJER-UHFFFAOYSA-N methyl 4-(hydroxymethyl)benzoate Chemical compound COC(=O)C1=CC=C(CO)C=C1 VBWFYEFYHJRJER-UHFFFAOYSA-N 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 4
- WWYFPDXEIFBNKE-UHFFFAOYSA-N 4-(hydroxymethyl)benzoic acid Chemical class OCC1=CC=C(C(O)=O)C=C1 WWYFPDXEIFBNKE-UHFFFAOYSA-N 0.000 description 3
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical class OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RHQKKJPJCHGKQO-UHFFFAOYSA-N [Cu+2].[O-][Cr]([O-])=O Chemical compound [Cu+2].[O-][Cr]([O-])=O RHQKKJPJCHGKQO-UHFFFAOYSA-N 0.000 description 2
- -1 alkyl radical Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/78—Benzoic acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
In preparative chemistry, a process for producing a p-hydroxy methyl benzoic acid alkyl ester comprises reacting terephthalaldehydic acid alkyl ester with hydrogen in the presence of a hydrogenation catalyst to form the desired ester. The ester products, particularly the methyl ester, are useful starting materials for polycondensation reactions.
Description
SPECIFICATION
A Process for Producing p-Hydroxymethyl
Benzoic Acid Esters
This invention relates to a process for
producing p-hydroxymethyl benzoic acid alkyl
esters.
It is known that p-hydroxymethyl benzoic acid
esters can be obtained by halogenating p-toluic acid, followed by hydrolysis and esterification (Z.
Zamorsky, Chem. Listy 52, 1192 (1958), or even by the electrochemical reduction of terephthalic acid dimethyl ester (German Offenlegungsschrift 2,428,878). However, in the first case several reaction steps are necessary: halogenation of the p-toluic acid or even the ptoluic acid ester (German Patent 1,001,253) gives only a relatively poor yield or, to avoid higher chlorination products, can only be carried out with low conversions. In the second case the operation of electrochemical processes generally involves technical difficulties and fairly heavy outlay on apparatus.
There is thus a need to be able to produce phydroxymethyl benzoic acid esters, particularly the methyl ester, by a simple process and as far as possible by the use of the readily available terephthalaldehydic acid esters, particularly the methyl ester, as starting material. Although it is known that benzaldehyde for example can be reduced to benzyl alcohol, it is also known that in this reaction relatively large quantities of secondary products are formed, particularly because of the reduction of the aldehyde group to the methyl group: these secondary products cannot be completely prevented even by special measures such as the addition of amines in accordance with German Offenlegungsschrift 1,568,894.
According to the present invention there is provided a process for producing a p-hydroxy methyl benzoic acid alkyl ester which comprises reacting a terephthalaldehydic acid alkyl ester with hydrogen in the presence of a hydrogenation catalyst to form the desired ester.
A particular feature of the process according to the invention has been found to be its high selectivity. Thus in accordance with the invention it has generally been found to be possible to form the target product in a high purity which generally amounts to at least 98% and usually, it has been found, to more than 99%; further, the yield of target product is generally very high. Another feature of the process according to the invention is that the p-hydroxymethyl benzoic acid alkyl esters can be produced both in batches and also continuously from the corresponding terephthalaldehydic acid alkyl esters.
Of the terephthalaldehydic acid alkyl esters used as starting material, those containing from 1 to 6 carbon atoms in the alkyl radical are preferred, those containing from 1 to 3 carbon atoms being particularly preferred. It is especially preferred to produce the methyl ester (HMBE) from terephthalaldehydic acid methyl ester (TAE), a readily available starting material.
The process according to the invention may be carried out in the absence of solvents above the melting point of the starting materials, although it is preferably carried out in the presence of solvents in which both the starting materials and the end product are sufficiently soluble. Solvents which may be used are, for example, alcohols such as lower aliphatic monohydric alcohols, preferably containing from 1 to 8 carbon atoms, for example methanol; cycloaliphatic alcohols such as cyclohexanol; polyhydric alcohols such as butane diol or glycerol; or even ethers, such as diethyl ether, dimethoxy ethane, tetrahydrofuran or dioxane, or the esters of organic carboxylic acids such as methyl acetate or ethyl acetate.
The hydrogenation catalysts employed in the process of the invention are preferably those comprising copper or copper compounds, in which other metals or metal compounds, particularly chromium oxide, may optionally be present. There may also be mentioned the noble metals of Group VIII of the Periodic System, particularly palladium and platinum. Such a
Periodic System may be found, for example, in the
Patents Classification Key.
Other catalysts may also be used, optionally as constituents of the above mentioned catalyst systems, providing that the desired hydroxymethyl group is at least predominantly formed at the position of hydrogenation. Coppercontaining catalysts, particularly copper/chromium oxide catalyst systems, are preferably used in the process because of the generally high purity of the products which they yield.
Many of the catalysts which may be used are commercially available, although they may even be separately produced before use. Where the process is carried out with noble metal catalysts, these noble metal catalysts may be used for example in finely divided metallic form or even on supports.
The catalysts are preferably used in a quantity of from 0.1 to 30% by weight, and more preferably from 2 to 20% by weight, based on the substrate, i.e. the terephthalaldehydic acid alkyl ester.
In general, the hydrogen pressure employed during the process is preferably from 2 to 400 bars and more preferably to from 10 to 250 bars, for example from 30 to 250 bars. The hydrogenation reaction temperature is preferably from 1 5 to 2000 C, more preferably from 20 to 1 500C.
Although in cases where catalysts containing copper or copper compounds, such as for example RCH copper catalyst of the VP 33/35 type (manufactured by Hoechst AG), Cu-i 106 P
Copper Chromit (manufactured by Harshaw
Chemie BC, De Meern/Holland) or C 00/13 copper chromite activated with barium (manufactured by
Degussa, Hanau, West Germany) are used, pressures and temperatures in the general ranges mentioned above may be applied, it is particularly preferred both in batch operation an in continuous operation to apply pressures in the range from
100 to 400 bars, more particularly in the range from 1 50 to 250 bars, and temperatures above
800C, more especially in the range from 100 to 1 500 C, by virtue of the higher conversions, yields
and purities which may thereby be obtained.
Where the above-mentioned catalysts are used, it
is desirable to keep to the above-mentioned pressure and temperature conditions, because where higher pressures and, more particularly, higher temperatures are applied it has been found that the yields obtained are generally reduced by the formation of impurities.
Where noble metal catalysts are used, it has
been found that the selective hydrogenation of the carbonyl group to the hydroxymethyl group
may even be carried out at room temperature and
under a slight hydrogen excess pressure of, for example, 2 to 5 bars. In order to obtain higher volume-time yields, it has been found to be of advantage and, in many cases, necessary to increase the pressure to from 10 to 400 bars.
In batch operation, pressures of from 2 to 50 bars and temperatures in the range from 1 5 to 500C have usually been sufficient. Although pressures and temperatures in the same ranges may be used for continuous operation, it is preferred to apply pressures of from 1 0O to 400 bars and, more particularly, from 100 to 250 bars and temperatures in the range from 80 to 1 500C in order to obtain high yields.
Since it is easier to maintain constant reaction parameters in continuous processes, continuous hydrogenation represents the preferred embodiment of the process according to the invention.
The solutions containing the reaction product may be worked up very simply by, where appropriate, distilling off the solvent which is used; the catalyst has to be filtered off in batch operations. After washing, for example with methanol, the catalyst may be re-used for further hydrogenation reactions.
Test runs have shown that the product may be obtained in a purity of up to 99.3% (analysis by gas chromatography). Depending on the catalyst used, the crude product is accompanied by small quantities of secondary products which can differ according to the type of catalyst used. If necessary, the crude product may be further purified by recrystallisation. After the purification step, the melting point of the product generally amounts to 51 OC (GC: > 99%). It has further been shown that for a quantitative TAE-conversion, the yield generally amounts to between 90 and 100% of the theoretical.
The p-hydroxymethyl benzoic acid esters,
particularly the methyl ester, which may be
obtained by the process according to the
invention are valuable starting materials for
polycondensation products.
The following Examples illustrate the invention.
Example 1
Into a 1 litre autoclave equipped with a lifting
magnet stirrer was introduced 122.4 g of 98.9% pure terephthalaldehydic acid methyl ester (TAE), corresponding to 0.738 mole of TAE, 500 ml of methanol and 10 g of a PD-catalyst (5% of Pd on carbon, a product of Engelhard Ind., Hannover).
After the air contained in the autoclave had been displaced by nitrogen, the vessel was placed under a hydrogen pressure of 30 bars and the temperature was increased, with stirring, to 300C. Hydrogen immediately began to be taken up. The gas pressure was maintained at 30 bars by continuously introducing hydrogen, whilst the temperature was kept at 30 to 31 0C by heating.
After 1 hour, most of the hydrogen had been taken up; the gas pressure fell by only about 1 bar over the next 30 minutes. After venting the autoclave, the catalyst was filtered off and the solvent was distilled off, leaving as residue 11 6 g of p-hydroxymethyl benzoic acid methyl ester (HMBE) which had a melting temperature of 50 to 51 0C. According to analysis by gas chromatography, the content of HMBE in the product residue was 99.3% (corresponding to 0.694 mole). Yield 94.02% of the theoretical.
Example 2
The autoclave of Example 1 was filled as described above with 196.8 g of 95.9% pure TAE (corresponding to 1.1 5 moles of TAE), 500 ml of methanol and 5 g of a Pd-catalyst (5% of Pd on carbon, a product of Degussa, Hanau, West
Germany); hydrogenation then followed at 450C under a hydrogen pressure of 30 bars. After the hydrogen had been taken up (3 hours), more hydrogen was introduced up to a pressure of 50 bars to complete the reaction. Another 3 bars of hydrogen were taken up by the mixture in the autoclave over a period of 30 minutes. Working up in the manner of Example 1 yielded 193.9 g of
HMBE melting at 48 to 49 OC. According to analysis by gas chromatography (GC), the HMBE content of the product residue was 98.7% (corresponding to 191.5 g=1.15 mole). Yield: 100%.
Example 3
The catalyst recovered by filtration from the product mixture of Example 2 was washed with methanol. While still moist, this catalyst was used to repeat the process described in Example 2.
Working up of the product mixture in the same way yielded 193.4 g of HMBE (GC purity: 98.8%).
Yield; 100%.
Example 4
A vertically arranged 0.5 litre pressure tube, filled with 0.35 litre of a Pd-catalyst (1% of Pd on Al2O3, 4x4 mm tablets, a product of Engelhard
Ind. GmbH, Hannover), was placed under a hydrogen pressure of 1 20 bars after the air had first been displaced by nitrogen. Methanol was then trickled over the catalyst (500 ml/hour), whilst the temperature of the catalyst bed was brought to 900 C. After this temperature had been reached, a solution containing 100 g of TAE per litre of methanol, was delivered to the reactor instead of the pure methanol, and the hydrogen gas was circulated by means of a gas recirculating pump, the pressure being kept constant at 120 bars.After passing through a cooling coil, the reaction product solution flowing off from the reactor was delivered into a receiver from which it was continuously removed. 48 to 50 g/hour of
HMBE were obtained from 50 g/h of TAE, corresponding to a substantially complete conversion. M.p. of product: 46---48"C; GCpurity: 90 to 93%.
Example 5
The procedure as described in Example 1 was repeated. However hydrogenation was carried out at 1 200C/250 bars in a 2 litre capacity autoclave using 50 g of copper/chromium oxide catalyst (VP 33/35, a product of Hoechst), on a mixture of 246 g of 97.3% pure TAE and 1.2 litres of methanol.
Working up in the manner of Example 1 yielded 237 g of 98.8% pure HMBE corresponding to a yield of 96.7% of the theoretical.
Example 6
Following the procedure described in Example 4, the pressure tube was filled with 360 ml of Cu 3705 E (1/6 inch) catalyst (14% by weight of Cu and 14% by weight of Cr, a product of Harshaw), then 500 ml/h of solution of 100 g of TAE in 1 litre of methanol were run through at 1000C/150 bars hydrogen pressure. The reaction product solution was continuously removed from the receiver and concentrated. 49 to 50 g/h HMBE melting at 48 to 490C were obtained (GC-purity: 98.0 to 98.6%). A substantially complete conversion was thus obtained with a very high degree of purity.
Example 7
The procedure of Example 5 was repeated, except that the methyl ester of terephthalaldehydic acid was replaced by the ethyl ester. Working up in the same way gave phydroxymethyl benzoic acid ethyl ester in a yield of 96.2%.
Example 8
The procedure of Example 6 was repeated, but using Cu-1 106 T Copper Chromit (39% by weight of CuO, 43.5% by weight of Cr203,10% by weight of BaO, a product of Harshaw) a) at 1 200C/1 80 bars and b) at 1000C/200 bars. In each case, high conversions and purities were again obtained.
As may be seen from the Examples, terephthalaldehydic acid esters may be simply reacted with hydrogen using commercial catalysts to form high yields of p-hydroxymethyi benzoic acid esters, substantially without any of the disadvantages which may attend conventional processes, such as the formation of secondary products, an additional outlay on chemicals, a reduction in reaction velocity, and difficulties both in working up and in recycling of the catalyst.
Claims (22)
1. A process for producing a p-hydroxy methyl benzoic acid alkyl ester which comprises reacting a terephthalaldehydic acid alkyl ester with hydrogen in the present of a hydrogenation catalyst to form the desired ester.
2. A process according to claim 1 wherein the alkyl radical contains from 1 to 6 carbon atoms.
3. A process according to claim 2 wherein the alkyl radical contains from 1 to 3 carbon atoms.
4. A process according to claim 3 wherein the alkyl radical is methyl.
5. A process according to any one of the preceding claims wherein the reaction is carried out at a temperature of from 15 to 2000C.
6. A process according to claim 5 wherein the reaction is carried out at a temperature of from 20 to 1500C.
7. A process according to any one of the preceding claims wherein the reaction is carried out at a pressure of from 2 to 400 bars.
8. A process according to claim 7 wherein the reaction is carried out at a pressure of from 30 to 250 bars.
9. A process according to any one of the preceding claims wherein the catalyst comprises copper or a copper compound.
10. A process according to claim 9 wherein the catalyst comprises a copper/chromium oxide mixture.
11. A process according to any one of claims 1 to 8 wherein the catalyst is a metal of Group Eight of the Periodic System (as hereinbefore defined).
12. A process according to claim 11 wherein the catalyst comprises palladium or platinum.
13. A process according to any one of the preceding claims wherein the catalyst is present in an amount of from 0.1 to 30% by weight, based on the terephthalaldehydic acid alkyl ester.
14. A process according to claim 1 3 wherein the catalyst is present in an amount of from 2 to 20% by weight based on the terephthalaldehydic acid alkyl ester.
1 5. A process according to any one of the preceding claims wherein the reaction is carried out in the presence of a solvent for the terephthalaldehydic acid alkyl ester and the phydroxyl methyl benzoic acid alkyl ester.
16. A process according to claim 1 5 wherein the solvent is an alcohol.
1 7. A process according to claim 1 6 wherein the solvent is methanol.
1 8. A process according to claim 1 5 wherein the solvent is an ether or a carboxylic acid ester.
1 9. A process according to any one of the preceding claims which is carried out continuously.
20. A process according to any one of claims 1 to 18 which is carried out in batch manner.
21. A process according to claim 1 substantially as described in any one of the
Examples.
22. p-Hydroxy methyl benzoic acid alkyl ester whenever produced by the process according to any one of the preceding claims.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2825347A DE2825347C2 (en) | 1978-06-09 | 1978-06-09 | Process for the preparation of p-hydroxymethylbenzoic acid alkyl esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2023581A true GB2023581A (en) | 1980-01-03 |
Family
ID=6041438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7920221A Withdrawn GB2023581A (en) | 1978-06-09 | 1979-06-11 | A Process for Producing p- Hydroxy Methyl Benzoic Acid Esters |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS55395A (en) |
| BE (1) | BE876860A (en) |
| DE (1) | DE2825347C2 (en) |
| FR (1) | FR2428024A1 (en) |
| GB (1) | GB2023581A (en) |
| IT (1) | IT1162323B (en) |
| NL (1) | NL7904538A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2466323A (en) * | 2008-12-22 | 2010-06-23 | Umbra Inc | Picture / photo frame with magnetic attachment means |
| CN101531593B (en) * | 2009-04-08 | 2017-12-05 | 大连九信精细化工有限公司 | The synthetic method of 4 (methylol) methyl benzoates |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3968731B2 (en) * | 1997-04-07 | 2007-08-29 | イハラケミカル工業株式会社 | Method for producing 5-methylindolines |
-
1978
- 1978-06-09 DE DE2825347A patent/DE2825347C2/en not_active Expired
-
1979
- 1979-06-05 FR FR7914344A patent/FR2428024A1/en not_active Withdrawn
- 1979-06-07 IT IT49339/79A patent/IT1162323B/en active
- 1979-06-08 JP JP7131679A patent/JPS55395A/en active Pending
- 1979-06-08 BE BE0/195641A patent/BE876860A/en unknown
- 1979-06-08 NL NL7904538A patent/NL7904538A/en not_active Application Discontinuation
- 1979-06-11 GB GB7920221A patent/GB2023581A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2466323A (en) * | 2008-12-22 | 2010-06-23 | Umbra Inc | Picture / photo frame with magnetic attachment means |
| CN101531593B (en) * | 2009-04-08 | 2017-12-05 | 大连九信精细化工有限公司 | The synthetic method of 4 (methylol) methyl benzoates |
Also Published As
| Publication number | Publication date |
|---|---|
| BE876860A (en) | 1979-10-01 |
| JPS55395A (en) | 1980-01-05 |
| DE2825347C2 (en) | 1986-07-17 |
| FR2428024A1 (en) | 1980-01-04 |
| DE2825347A1 (en) | 1979-12-13 |
| IT7949339A0 (en) | 1979-06-07 |
| IT1162323B (en) | 1987-03-25 |
| NL7904538A (en) | 1979-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100510000B1 (en) | Method for Producing 1,6-Hexanediol | |
| AU675990B2 (en) | Process for the preparation of carboxylic acids and esters thereof by oxidative cleavage of unsaturated fatty acids andesters thereof | |
| GB1565781A (en) | Process for the preparation of trimethylolalkanes | |
| KR20120004513A (en) | Method for producing 1,6-hexanediol and caprolactone | |
| US20080132742A1 (en) | Process for the preparation of a tetraalkycyclobutane-1,3-diol using a promoted-copper catalyst | |
| KR20120005018A (en) | Method for producing 1,6-hexanediol | |
| EP0069339B1 (en) | Process for producing 7-octen-1-al and derivatives thereof | |
| EP1182184B1 (en) | Process for producing tetrafluoro benzenecarbaldehydes and tetrafluoro benzenemethanols | |
| US7521583B2 (en) | Process for the preparation of tetraalkylcyclobutane-1,3-diol in the presence of a cobalt-based catalyst | |
| US4311854A (en) | Process for the production of di-n-propyl-acetic acid | |
| GB2023581A (en) | A Process for Producing p- Hydroxy Methyl Benzoic Acid Esters | |
| US5073650A (en) | Preparation of 1,4-butanediol | |
| US4647706A (en) | Process for the synthesis of 2,2,2-trifluoroethanol and 1,1,1,3,3,3-hexafluoroisopropanol | |
| EP0584408A2 (en) | Process for the preparation of gamma-butyrolactone | |
| EP0421759B1 (en) | Method for producing 1-indanone derivatives | |
| US5777170A (en) | Process for the preparation of a naphthylbutanone | |
| US6429319B1 (en) | Continuous process for the production of optically pure (S)-beta-hydroxy-gamma-butyrolactone | |
| US5072037A (en) | Process for the preparation of 2-(4-chlorophenyl)-3-methylbutyric acid | |
| KR20000052945A (en) | Manufacture of adipic acid | |
| US3914291A (en) | Process for splitting cycloaliphatic hydroperoxides | |
| IL158331A (en) | Single-step method for producing toluene derivatives | |
| JP3529876B2 (en) | 3-methyl-3-methoxybutanoic acid. | |
| JP3756537B2 (en) | Dimethyldecandial and process for producing the same | |
| JP3805435B2 (en) | Process for producing 6-methyl-3-hepten-2-one | |
| GB2086889A (en) | Process for preparing acetaldehyde |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |