EP0164705A2 - Procédé de production de phtalaldéhydacétals - Google Patents
Procédé de production de phtalaldéhydacétals Download PDFInfo
- Publication number
- EP0164705A2 EP0164705A2 EP85107063A EP85107063A EP0164705A2 EP 0164705 A2 EP0164705 A2 EP 0164705A2 EP 85107063 A EP85107063 A EP 85107063A EP 85107063 A EP85107063 A EP 85107063A EP 0164705 A2 EP0164705 A2 EP 0164705A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- bis
- benzene
- electrolysis
- alkanol
- methoxymethyl
- 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
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title description 3
- -1 phthalaldehyde acetal Chemical class 0.000 claims abstract description 22
- 238000009835 boiling Methods 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- 238000005868 electrolysis reaction Methods 0.000 claims description 21
- 239000003792 electrolyte Substances 0.000 claims description 17
- 125000004849 alkoxymethyl group Chemical group 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 abstract description 13
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- DAJPMKAQEUGECW-UHFFFAOYSA-N 1,4-bis(methoxymethyl)benzene Chemical compound COCC1=CC=C(COC)C=C1 DAJPMKAQEUGECW-UHFFFAOYSA-N 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910002804 graphite Inorganic materials 0.000 description 12
- 239000010439 graphite Substances 0.000 description 12
- VRKVWGGGHMMERE-UHFFFAOYSA-N 1,2-bis(methoxymethyl)benzene Chemical compound COCC1=CC=CC=C1COC VRKVWGGGHMMERE-UHFFFAOYSA-N 0.000 description 6
- SWKVSFPUHCMFJY-UHFFFAOYSA-N 6-methyl-2-oxo-5-pyridin-4-yl-1h-pyridine-3-carboxamide Chemical compound N1C(=O)C(C(N)=O)=CC(C=2C=CN=CC=2)=C1C SWKVSFPUHCMFJY-UHFFFAOYSA-N 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229940054441 o-phthalaldehyde Drugs 0.000 description 3
- 150000003738 xylenes Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical class O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 2
- ABHHITAVUODQNA-UHFFFAOYSA-M potassium;benzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC=CC=C1 ABHHITAVUODQNA-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FMGGHNGKHRCJLL-UHFFFAOYSA-N 1,2-bis(chloromethyl)benzene Chemical class ClCC1=CC=CC=C1CCl FMGGHNGKHRCJLL-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
Definitions
- This invention relates to a new electrochemical process for the production of phthalaldehyde acetals.
- Phthalaldehyde acetals can be e.g. by reacting phthalaldehydes with o-esters (J. Chem. Soc. Perkin II, 1975, 1656).
- the phthalaldehydes required as starting materials are e.g. according to the sommelet process from bis (chloromethyl) benzenes and hexamethylenetetramine. This e.g. in J. Chem. Soc.
- the process described in 1950, 2141 to 2145 provides only moderate yields and is not very environmentally friendly.
- a process for the preparation of phthalaldehyde acetals is known from DE-OS 31 08 790, in which ⁇ , ⁇ , ⁇ , ⁇ '-tetrahalo-xylenes are reacted with alkali metal alcoholates.
- a disadvantage of this synthesis is the poor accessibility of the tetrahalogen xylenes, which arise in the halogenation of xylenes only in poor selectivities in a mixture with xylenes of different degrees of halogenation.
- phthalaldehyde acetals of the general formula I in which R is an alkyl radical having 1 to 4 carbon atoms can advantageously be prepared by alkoxymethylbenzenes of the general formula electrochemically oxidized in the presence of an alkanol of the formula ROH, where R has the meaning given above. It is particularly surprising that the oxidation state of the dialdehydes can be selectively achieved by the process of the invention.
- Alkoxyme t hylbenzole of the formula may be mentioned are called II: 1,2-, 1,3- or 1,4-bis (methoxymethyl) benzene, 1,2-, 1,3- or l, 4-bis ( ethoximethyl) benzene, 1,2-, 1,3- or 1,4-bis (propoximethyl) benzene, 1,2-, 1,3- or 1,4-bis (isopropoximethyl) benzene and 1,2-, 1,3- or 1,4-bis (tert-butox-methyl) benzene.
- Alcohols of the formula ROH are, for example, methanol, ethanol, propanol and butanol. Hee / GS
- the electrochemical oxidation according to the invention can be carried out in technically customary electrolysis cells. Undivided flow cells are particularly suitable.
- a solution of the bis- (alkoxymethyl) benzene of the formula II in the alkanol is expediently used as the electrolyte, which solution may contain an auxiliary electrolyte to improve the conductivity.
- Suitable auxiliary electrolytes are, for example, bases such as alkali alcoholates, neutral salts such as fluorides, tetrafluoroborates, sulfonates and sulfates and acids such as alkyl sulfonic acids, alkanesulfonic acids and sulfuric acid.
- Neutral auxiliary electrolytes such as KF and KSO 3 C 6 H 5 or acidic auxiliary electrolytes such as H 2 SO 4 , CH 3 SO 3 H or C 6 H 5 SO 3 H are preferably used.
- Precious metals metal oxides such as Ru0 2 and Pb0 2 or graphite are used as anodes in the electrolysis according to the invention.
- the preferred anode material is graphite.
- suitable cathode materials are steel, iron, nickel, lead or graphite.
- the current densities are 0.1 to 20 A / dm, current densities between 2 and 8 A / dm are preferred.
- the temperatures are expediently at least 5 ° C. below the boiling point of the alkanol used, provided the electrolysis is carried out without pressure. For example, electrolysis is carried out at -5 to 55 ° C, preferably 10 to 50 ° C.
- the electrolysis is carried out with 4 to 12 F / mol of bis (alkoxymethyl) benzene. It is preferably electrolyzed with 7 to 10 F / mol of bis (alkoxymethyl) benzene, so that the bis (alkoxymethyl) benzene is largely reacted.
- the electrolysis can be carried out batchwise or continuously.
- the electrolysis discharges are preferably worked up by distillation. Unreacted alkanol can be returned to the electrolysis without purification. Electrode inactivations or electrode corrosion are not observed even when the electrolyte is reused many times.
- the phthalaldehyde acetals obtainable by the process of the invention are intermediates e.g. for the production of dyes and optical brighteners and also for the synthesis of special polymers.
- the electrolyte was pumped through the cell at a flow rate of 200 l / h via a heat exchanger. After the electrolysis had ended, the electrolysis discharge was neutralized with sodium methylate. Then methanol was distilled off at normal pressure and 65 to 75 ° C. and the precipitated salt was separated off at 60 to 70 ° C. using a pressure filter. The residue was pure distilled at 100 to 120 ° C and 3 mbar. This gave 3.5 g of 1,4-bis (methoxymethyl) benzene and 222.2 g of terephthalaldialdehyde tetramethyl acetal.
- the electrolyte was pumped through the cell at a flow rate of 200 l / h via a heat exchanger.
- the electrolysis discharge was like described in Example 1, but worked up without the addition of sodium methylate. Working up gave 0.4 g of 1,4-bis (methoxymethyl) benzene and 158.2 g of terephthalaldehyde tetramethyl acetal. From this, a conversion of 1,4-bis (methoxymethyl) benzene of 99.7%, a yield of terephthalaldehyde tetramethyl acetal of 80.1% and a selectivity for terephthalaldehyde tetramethyl acetal of 80.4% are calculated.
- the recovered methanol and potassium benzene sulfonate could be used again for electrolysis.
- the electrolyte was pumped through the cell at a flow rate of 200 l / h via a heat exchanger.
- methanol was distilled off from the electrolysis discharge at atmospheric pressure and 65 to 80.degree.
- the precipitated potassium benzene sulfonate was separated off using a pressure filter and the filtrate was fractionally distilled at 100 to 120 ° C. and 5 mbar. This gave 3.8 g of 1,2-bis (methoxymethyl) benzene and 230.3 g of o-phthalaldehyde tetramethyl acetal.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3421976 | 1984-06-14 | ||
| DE19843421976 DE3421976A1 (de) | 1984-06-14 | 1984-06-14 | Verfahren zur herstellung von phthalaldehydacetalen |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0164705A2 true EP0164705A2 (fr) | 1985-12-18 |
| EP0164705A3 EP0164705A3 (en) | 1986-04-23 |
| EP0164705B1 EP0164705B1 (fr) | 1987-09-02 |
Family
ID=6238274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85107063A Expired EP0164705B1 (fr) | 1984-06-14 | 1985-06-07 | Procédé de production de phtalaldéhydacétals |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0164705B1 (fr) |
| JP (1) | JPH0647746B2 (fr) |
| DE (2) | DE3421976A1 (fr) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0522312A1 (fr) * | 1991-07-05 | 1993-01-13 | BASF Aktiengesellschaft | Tétraalcoylacétals de o-phthaldialdéhyde, leur préparation et leur utilisation comme agent de dépôt |
| EP0554564A1 (fr) * | 1992-01-22 | 1993-08-11 | BASF Aktiengesellschaft | Procédé de préparation de benzaldéhydeacetals |
| EP0621352A2 (fr) * | 1993-03-19 | 1994-10-26 | BASF Aktiengesellschaft | Procédé de préparation de tétraalkylacétals de téréphtalaldéhyde |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3913166A1 (de) * | 1989-04-21 | 1990-10-25 | Basf Ag | Verfahren zur herstellung von benzaldehyddialkylacetalen und neue benzaldehyddialkylacetale und benzylester |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0012240A2 (fr) * | 1978-11-30 | 1980-06-25 | Bayer Ag | Procédé de préparation de dialcoylacétals de benzaldéhyde éventuellement substitués |
| EP0054698A1 (fr) * | 1980-12-24 | 1982-06-30 | Hoechst Aktiengesellschaft | 4,4'-Diphényléther-dialdéhyde-bis-diméthylacétale et une méthode pour sa préparation |
| DE3108790A1 (de) * | 1981-03-07 | 1982-09-16 | Dynamit Nobel Ag, 5210 Troisdorf | Verfahren zur herstellung von bis(dialkoximethyl)benzolen |
-
1984
- 1984-06-14 DE DE19843421976 patent/DE3421976A1/de not_active Withdrawn
-
1985
- 1985-06-07 DE DE8585107063T patent/DE3560532D1/de not_active Expired
- 1985-06-07 EP EP85107063A patent/EP0164705B1/fr not_active Expired
- 1985-06-14 JP JP60128382A patent/JPH0647746B2/ja not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0012240A2 (fr) * | 1978-11-30 | 1980-06-25 | Bayer Ag | Procédé de préparation de dialcoylacétals de benzaldéhyde éventuellement substitués |
| EP0054698A1 (fr) * | 1980-12-24 | 1982-06-30 | Hoechst Aktiengesellschaft | 4,4'-Diphényléther-dialdéhyde-bis-diméthylacétale et une méthode pour sa préparation |
| DE3108790A1 (de) * | 1981-03-07 | 1982-09-16 | Dynamit Nobel Ag, 5210 Troisdorf | Verfahren zur herstellung von bis(dialkoximethyl)benzolen |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0522312A1 (fr) * | 1991-07-05 | 1993-01-13 | BASF Aktiengesellschaft | Tétraalcoylacétals de o-phthaldialdéhyde, leur préparation et leur utilisation comme agent de dépôt |
| EP0554564A1 (fr) * | 1992-01-22 | 1993-08-11 | BASF Aktiengesellschaft | Procédé de préparation de benzaldéhydeacetals |
| EP0621352A2 (fr) * | 1993-03-19 | 1994-10-26 | BASF Aktiengesellschaft | Procédé de préparation de tétraalkylacétals de téréphtalaldéhyde |
| EP0621352A3 (fr) * | 1993-03-19 | 1994-12-07 | Basf Ag | Procédé de préparation de tétraalkylacétals de téréphtalaldéhyde. |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0164705B1 (fr) | 1987-09-02 |
| JPS6112886A (ja) | 1986-01-21 |
| DE3560532D1 (en) | 1987-10-08 |
| DE3421976A1 (de) | 1985-12-19 |
| JPH0647746B2 (ja) | 1994-06-22 |
| EP0164705A3 (en) | 1986-04-23 |
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