CA2031444A1 - Process for the preparation of 3,4'-dichlorodiphenyl ether - Google Patents

Process for the preparation of 3,4'-dichlorodiphenyl ether

Info

Publication number
CA2031444A1
CA2031444A1 CA 2031444 CA2031444A CA2031444A1 CA 2031444 A1 CA2031444 A1 CA 2031444A1 CA 2031444 CA2031444 CA 2031444 CA 2031444 A CA2031444 A CA 2031444A CA 2031444 A1 CA2031444 A1 CA 2031444A1
Authority
CA
Canada
Prior art keywords
mol
process
reaction
carried out
chlorophenol
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.)
Abandoned
Application number
CA 2031444
Other languages
French (fr)
Inventor
Theodor Papenfuhs
Hans Schubert
Reiner Hess
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to DE19893940130 priority Critical patent/DE3940130A1/en
Priority to DEP3940130.8 priority
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of CA2031444A1 publication Critical patent/CA2031444A1/en
Application status is Abandoned legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01Preparation of ethers
    • C07C41/16Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups

Abstract

Process for the preparation of 3,4'-dichlorodiphenyl ether A process for the preparation of 3,4'-dichlorodiphenyl ether from 1,3-dichlorobenzene and 4-chlorophenol, which comprises mixing 1 mol of 4-chlorophenol with about 2 to about 6 mol of initially introduced 1,3-dichlorobenzene and about 1 to about 3 mol of potassium carbonate in about 1 to about 5 mol of a dipolar aprotic solubilizer which boils above l60°C, at temperatures of about 160°C
to about 190°C with stirring, then adding about 0.0l to about 1 mol-% of basic copper carbonate of the formula Cu(OH)2?CuCO3?0.5 H2O and heating with stirring to about 170 to about 173°C while removing the water formed by distillation, then optionally adding further 4-chloxo-phenol with the proviso that from the start the amount of 1,3-dichlorobenzene present in terms of moles is always 1 to 3 mol greater than the totally added amount of 4-chlorophenol and, if desired, additionally adding basic copper carbonate of the formula mentioned if at the start less than 0.1 mol-% had been added, additionally stirring within the last-mentioned temperature range and finally working up after allowing to cool.

Description

2 ~
HOECHST AKTIENGESELLSCHAFT HOE 89/F 383 Dr. M~/fe Description Process for the preparation of 3,4~-dichlorodiphenyl ether 3,4'-Dichloxodiphenyl ether is an important aromatic precursor and is used, inter alia, for the preparation of 3,4'-diaminodiphenyl ether, an important raw material for the synthesis of high modulus aramides, but is also used as a basic structure for the preparation of plant protec-tion agents.

~he chlorination of diphenyl ethers, which is carried out by reaction of diphenyl ether with SO2Cl2 (NL 75~4110 of 18.10.76) in the presence of sulfur-containing catalysts, does not lead to the desired product, but to 2,4'-di-chlorodiphenyl ether in addition to 4,4~-dichlorodiphenyl ether according to the equation ~QJ3c~--t ~
Cl ~ ~ Cl By skilful choice of the catalyst, it is actually pos-sible to influence the o/p ratio in the second chlorin-ation (BE 827,912r US 3,920,757, US 3,793,377; all to Dow Chemical Co.). However, it is not po sible in this way, i.e. by direct chlorination, to prepare the desired 3,4'-dichlorodiphenyl ether.

If the desired product is synthesized by diphenyl ether synthesis according to Ullmann (Houben-Weyl, Vol. VI/3, page 86), the following alternatives for the choice of starting materials results:

2~31 7~

Cl ~~ ~Cl Cl~O~

Reaction variant 1 OH ~ C1 ~
Cl ~eaction variant 2 1. Reaction of 3-chlorophenol with 1,4 dichlorobenzene 2. Reaction of 4-chlorophenol with 1,3-dichlorobenzene For reasons of the availability of the starting materials and the easier distillative separation of unreactad residues of the starting compounds from the product, the first variant i5 preferred for industrial production.

Thus, Oshino et al. (JP 62/281,837 of 7.12.1987) react sodium 4-phenolate, 1,3-dichlorobenzene and aqueous sodium hydroxide solution, remove water by distillation and stir in solution (dimethylformamide a the solvent) with the addition of copper(II) acetate dihydrate at 155-165C for 18 hours. Nothing is said about working-up:
88.8 % yields are obtained here. Even the stoichiometric ratios are not clarified.

The di~advantages of this pro~esæ sre, on ~he one hand, its long reaction period, on the other hand the U8e of the solvent dimethylformamide which proved to be not very thermally stable and was therefore largely eliminated from industrial processes for reasons of the formation of decomposition products.

In another literature reference, Rauber (US 4,766,253 of 23.8.1988) reacts R-C~H4-OX (X = 1 equivalent of alkali metal or alkaline earth metal) with an exce~s of 3-15 mol . !

of 1,3-C12-C~H4 in the presence of a copper catalyst (in this case CuO) for several hours at 120-220C (150C in the example), 0.003-3 mol of an aprotic solvent having to be present (N,N-dimethylacetamide in the example). An 80 ~ yield of 3,4'-dichlorodiphenyl ether is obtained in this case after a work-up which is not outlined in more detail.

In addition to the work-up which is not outlined in more detail and the moderate yield, this varian~ ha~ the disadvantage of using an alkali metal or alkaline earth metal phenolate, which first has ~o be prepared in a pre-inserted syn~hesis. Industrial production of 3,4' di-chlorodiphenyl ether - in moderate yield - can only be carried out poorly economically using this two-step reaction procedure.

Oshino et al. report in another publication (JP 63/41,434 of 22.2.19~8) another procedure for the preparation of 3,4'-dichlorodiphenyl ether:
sodium 4-chlorophenolate is reacted with 1,3-dichloro-benzene in liquid aliphatic glycol ethers in the presence of Cu catalysts to give the desired 3,4'-dichlorodiphenyl ether. In the example, 4-chlorophenol and 1,3-dichloro~
benzene are reacted with aqueous sodi~m hydroxide solu-tion to give sodium 4-chlorophenolate, the water of reaction formed and the water introduced with khe sodium hydroxide solution being removed by distillation (no azeotrope).

In the subsequent step, the residue (i.e. nearly all the water has been removed by distillation) is taken up using diethylene glycol diethyl ether and reacted at 155-160C
in the presence of Cu(I)Cl for 18 hours in order to obtain a yield of 87.2 %, it not being certain accoxding to the description ~ext whether this is an isolated or chromat~graphically determined yield.

In addition to the long reaction tLme, a disadvantage of - 4 ~ ~g~
this procedure i~ the use of diglycol dialkyl ethers which have a relatively low ignition point (under 200~C) over the whole range and therefore require increased safety expenditure for industrial production (equipping the production plant according to EXT4 ), which makes the plant mor~ expensive, or causes additional costs in an existing plant. Thus the economically favorable prepaxa-tion of 3,4'-dichlorodiphenyl ether i~ not possible even according to this outlined process.

Surprisingly, however, it has become possible a~ a result of a suitable procedure to achieve an economically and ecologically favorable preparation process for 3,4'-dichlorodiphenyl ether based on 4-chlorophenol and 1,3-dichlorobenzene, i.e. common, industrially ~vailable starting materials, in the presence of potassium car-bona~e as an auxiliary base, which saves the entrainment of large amounts of water-compared to the introduction of aqueous sodium hydroxide solution - and a suitable "solubilizer" in the presence of a copper compound as a catalyst.

The invention thus relates to an improved process for the preparation of 3,4'-dichlorodiphenyl ether from 1,3-dichlorobenzene and 4-chlorophenol, which comprises mixing 1 mol of 4-chlorophenol with about 2 to about 6 mol, preferably about 4 to about 5 mol, of initially introduced 1,3-dichlorobenzene and about 1 to about 3 mol, preferably about 1 to about 1.5 mol, of pota~sium carbonate in about 1 to about 5 mol, preferably about 1 to about 2 mol, of a dipolar aprotic solubilizer which boils above 160C, such as, for example, dimethylacet-amide, sulfolane, dimethyl sulfoxide, preferably N-methylpyrrolidone, at temperatures of about 160 to about 190C, preferably about 170 to about 180C, with stir-ring, then adding about 0.01 to about 1 mol-%, preferably about 0.1 to about 0.9 mol-% of basic copper carbonate of the formula Cu(OH)2.CuCO3Ø5 H2O, then heating with stirring to about 170 to about 173C while removing the water formed by distillation, th0n optionally adding further 4-chlorophenol, with the proviso that from the start ~he ~moun~ of l,3-dichlorobenzene prasent in terms of moles is always 1 to 3 mol greater than the totally added amount of 4-chlorophenol and, if desired, adding further basic copper carbonate of the formula mentioned, if at the start less than 0.1 mol-% had ~een added, additionally stirring within the last-mentioned tempera-ture range (about 170 to about 173C) and finally working up after allowing to cool.

The duration of the reaction is about 2-6 hours after removal of water from the circulation and, in the case of subsequent addition of 4-chlorophenol, additionally about 2-6 hours more, i.e. a maxLmum of about 4-10 hours.

Working-up after allowing the reaction mixture to cool is carried out by adjusting the pH to 6 to 6.5 after separa-ting off the resultant reæidue of the basic copper carbonate employed and the salts formed, which are additionally washed with 1,3-dichlorobenzene, and then working up by distillation.

The procass is expediently carried out at normal pres-sure. However, it can also be carried out at elevated pressure if it is carrieA out in the presence of a dipolar aprotic solubilizer which boils below 160C, such as, for ex~mple, dimethylformamide.

In addition, the proces~ can be carried out both batch-wise and also continuously.

In the work-up, the "low-boiling componentæ" ~NNP, 1,3-dichlorobenzene and 4-chlorophenol) are first removed via a short column (3-5 plates ? . The desired 3 t 4~-dichloro-diphenyl ether is then simply distilled over without a column, a distilled yield of above 90 % being obtained in very high purity (GC > 99 %).

2 ~

Three advantages are discernible in the process according to the invention:

1. As a result of the shor~ reaction period and the double addition of 4-chlorophenol, the ~pace-time yield is clearly above those of the known processes outlined above. The excess of 1,3-dichlorobenzene to 4-chloro-phenol necessary for the reaction has been en~ured without having to accept large losses in the space yield.

2. As a result of the outlined distillative work-up, it is possible to feed back the "low-boiling components"
removed by distillation into the subsequent reactions again. In this way, the "auxiliary solvent~ N-methyl-pyrrolidone can be circulated without urther replenish-ment.

3. As a result of the use of N-methylpyrrolidone as a dipolar aprotic "solubilizer", a temperature-stable system having a high ignition temperature and low toxic potential exists whose industrial availability is guaran-teed.

Altogether, owing to the use of a suitable "solubilizer", a suitable copper catalyst and the choice of khe proce-dure of doubling the addition of the standard component 4-chlorophenol, the process according to the invention i8 an economically and ecologically (by recycling all components which can be employed again) very favorable process having a high yield of a highly pure 3,4' di-chlorodiphenyl ether.

The example below i6 in particular intended to illustrate the industrial implementation of the proces~ according to the invention, without restricting the latter thereto~

Example 1 1740 kg of 1,3-dichlorobenzene (10 kmol), 260 kg of 2 ~ t. ~

4-chlorophenol (2.023 kmol) and 600 kg of N-methylpyrrol~
idone (231 ~ by weight, based on 4-chlorophenol employed) are introduced into a 2.5 m3 V4A apparatus fitted with a stirrer and gas inlet after evacuating and flushing twice with nitrogen. 310 kg of granulated potas~ium carbonate (2.246 kmol) and 3 kg (0.013 kmol) of basic copper carbonate are then additionally added under a weak stream of nitrogen. The contents of the container are heated to 170-173~C with stirring, water being removed from the reaction of the phenol with potassium carbonate and the decomposition of the basic copper carbonate by distil lation via a splash guard. The reaction mixture is kept at this temperature with stirring for 3 hours, before 3 kg of basic copper carbonate are first added again and 260 kg (2.023 kmol) of 4-chlorophenol are later 810wly metered in again as a liquid. The batch is again kept at 170-175C with stirring for 5 hours before it is stirred until cold to 20-25C.

The solid components of the reaction mixture (potassium chloride formed and copper oxide from the ca~aly~t) are removed via a pressure filter washed free of product using 300 kg of 1,3-dichloroben~ene. The filtrate is first adjusted to pH 6-6.5 by addition of aqueous 30 %
strength hydrochloric acid, then the water is removed by distillation via a splash guard up to a transition temperature of 170C and then introduced into a 3 m3 V4A
still for fractionation via a column containing Sulzer packing (25-27 theoretical plates).

In this, in a vacuum of initially 20 mbar, the low-boiling component~ of the reaction mixture are removed bydistillation up to a bottom temperature of 150~C at a reflux ratio of 1:3, the entire 1,3 dichlorobenzene and N-methylpyrrolidone as well as unreacted 4-chlorophenol passing over, and after GC checking of the composition of the distillate are fed back into the following batch. The bottom of this fractionation is directly removed from the V4A apparatus by distillation - without a column - via a splash guard. A yield of 880 kg (corresponding to 91 % of theory, based on ~he amount o~ 4-chlorophenol employed) of 3,4~-dichlorodiphenyl ether, which has a purity of > 99 ~ according to GC, is obtained here in the stationary state.

~ample 2 (comparison example) 1740 g (10 mol) of 1,3-dichlorobenzene, 257 g of 4-chlorophenol and 310 g o~ potassium carbonate are ini-tially introduced into a 4 1 four-necked flask fitted with a stirrer, internal thermometer and heated dropping funnel, and al80 a ~olid addition funnel, after purging with nitrogen. The mixture i8 heated to 170-175C with stirring and kept at this temperature for 10 hours before the conversion is measured by gas chromatography. A
lS conversion of the components to the desired 3,4'-di-chlorodiphenyl ether of less than S % (area % of the analysis) is obtained.

Claims (9)

1. A process for the preparation of 3,4'-dichloro-diphenyl ether from 1,3-dichlorobenzene and 4-chlorophenol, which comprises mixing 1 mol of 4-chlorophenol with about 2 to about 6 mol of ini-tially introduced 1,3-dichlorobenzene and about 1 to about 3 mol of potassium carbonate in about 1 to about 5 mol of a dipolar aprotic solubilizer which boils above 160°C, at temperatures of about 160°C to about 190°C with stirring, then adding about 0.01 to about 1 mol-% of basic copper carbonate of the formula Cu(OH)2?CuCO3?0.5 H2O and heating with stirring to about 170 to about 173°C while removing the water formed by distillation, then optionally adding further 4-chlorophenol with the proviso that from the start the amount of 1,3-dichlorobenzene present in terms of moles is always 1 to 3 mol greater than the totally added amount of 4 chloro-phenol and, if desired, additionally adding basic copper carbonate of the formula mentioned if at the start less than 0.1 mol-% had been added, addition-ally stirring within the last-mentioned temperature range and finally working up after allowing to cool.
2. The process as claimed in claim 1, wherein the reaction is carried out in the presence of about 0.1 to about 0.9 mol-% of basic copper carbonate.
3. The process as claimed in at least one of claims 1 and 2, wherein the reaction is carried out in the presence of about 1 to about 2 mol of a dipolar aprotic solubilizer which boils above 160°C.
4. The process as claimed in at least one of claims 1 to 3, wherein the reaction is carried out in methylpyrrolidone as the solubilizer.
5. The process as claimed in at least one of claims 1 to 4, wherein the reaction is carried out at temper-atures of about 170 to about 180°C.
6. The process as claimed in at least one of claims 1 to 5, wherein the reaction is carried out with about 1 to about 1.5 mol of potassium carbonate.
7. The process as claimed in at least one of claims 1 to 6, wherein the reaction is carried out at normal pressure.
8. The process as claimed in at least one of claims 1 to 6, wherein the reaction is carried out at elev-ated pressure in the presence of a dipolar aprotic solubilizer which boils below 160°C.
9. The process as claimed in at least one of claims 1 to 8, wherein the reaction is carried out batchwise or continuously.
CA 2031444 1989-12-05 1990-12-04 Process for the preparation of 3,4'-dichlorodiphenyl ether Abandoned CA2031444A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE19893940130 DE3940130A1 (en) 1989-12-05 1989-12-05 A process for the preparation of 3,4'-dichloro-diphenyl ether
DEP3940130.8 1989-12-05

Publications (1)

Publication Number Publication Date
CA2031444A1 true CA2031444A1 (en) 1991-06-06

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ID=6394811

Family Applications (1)

Application Number Title Priority Date Filing Date
CA 2031444 Abandoned CA2031444A1 (en) 1989-12-05 1990-12-04 Process for the preparation of 3,4'-dichlorodiphenyl ether

Country Status (5)

Country Link
EP (1) EP0431487B1 (en)
JP (1) JPH05345739A (en)
CA (1) CA2031444A1 (en)
DE (1) DE3940130A1 (en)
IN (1) IN171309B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6762329B2 (en) * 1997-10-06 2004-07-13 Massachusetts Institute Of Technology Diaryl ether condensation reactions

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001016068A2 (en) * 1999-08-30 2001-03-08 Mossi & Ghisolfi Overseas S.A. Disproportionation catalyst

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4766253A (en) * 1987-05-04 1988-08-23 Ciba-Geigy Corporation Process for preparing chlorinated diphenyl ethers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6762329B2 (en) * 1997-10-06 2004-07-13 Massachusetts Institute Of Technology Diaryl ether condensation reactions

Also Published As

Publication number Publication date
DE3940130A1 (en) 1991-06-06
EP0431487A1 (en) 1991-06-12
JPH05345739A (en) 1993-12-27
IN171309B (en) 1992-09-12
EP0431487B1 (en) 1994-10-26

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