GB2182041A - Esters of diethylene glycol - Google Patents
Esters of diethylene glycol Download PDFInfo
- Publication number
- GB2182041A GB2182041A GB08625481A GB8625481A GB2182041A GB 2182041 A GB2182041 A GB 2182041A GB 08625481 A GB08625481 A GB 08625481A GB 8625481 A GB8625481 A GB 8625481A GB 2182041 A GB2182041 A GB 2182041A
- Authority
- GB
- United Kingdom
- Prior art keywords
- acid
- ester
- ethyl ester
- process according
- amino
- 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
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 title claims description 42
- 150000002148 esters Chemical class 0.000 title claims description 17
- 239000002253 acid Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- -1 2,6-dichloro-3-methylphenyl Chemical group 0.000 claims description 15
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 125000004494 ethyl ester group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229960003424 phenylacetic acid Drugs 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 239000003937 drug carrier Substances 0.000 claims description 2
- 239000008194 pharmaceutical composition Substances 0.000 claims description 2
- 239000000546 pharmaceutical excipient Substances 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- DNUPYEDSAQDUSO-UHFFFAOYSA-N diethylene glycol monobenzoate Natural products OCCOCCOC(=O)C1=CC=CC=C1 DNUPYEDSAQDUSO-UHFFFAOYSA-N 0.000 claims 2
- LPEPZBJOKDYZAD-UHFFFAOYSA-N flufenamic acid Chemical compound OC(=O)C1=CC=CC=C1NC1=CC=CC(C(F)(F)F)=C1 LPEPZBJOKDYZAD-UHFFFAOYSA-N 0.000 claims 2
- XXXFZKQPYACQLD-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl acetate Chemical compound CC(=O)OCCOCCO XXXFZKQPYACQLD-UHFFFAOYSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229940126062 Compound A Drugs 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical group FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/21—Esters, e.g. nitroglycerine, selenocyanates
- A61K31/215—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids
Landscapes
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
A L Y 1 1 GB2182041A 1
SPECIFICATION
Preparation of esters of diethylene glycol This invention relates to a process for the preparation of esters of diethylene glycol, particularly 5 monoesters. The invention also relates to esters prepared by the process.
Thus, according to one aspect the invention provides a process for the preparation of an ester of diethylene glycol wherein diethylene glycol is reacted with an acid of general formula 1 (CH 2) n CO 2 H R 3 NH - 1 2 I (wherein n is 0 or 1; R' is Cl, H or CH,; R2 is H, CF,, or CH,; and R3 is Cl or H) or a salt thereof.
The preparation of esters in accordance with the invention may be effected in a single step and it is not necessary to protect one of the hydroxyl groups of the diethylene glycol.
The process is conveniently effected with an excess of diethylene glycol compared to the quantity of acid of formula 1 or salt thereof. The reaction is advantageously effected in the presence of thionyl chloride, which is preferably present in a stoichiometric amount, or slight excess, compared to the quantity of acid of formula 1 or salt thereof.
As indicated above the process may be effected using a salt of the acid of formula 1, preferably an alkali metal salt such as, for example, a sodium or potassium salt.
The process according to the invention is conveniently effected at a temperature of from room temperature up to the temperature of a steam bath, the temperature generally being related to the time required to complete the reaction.
Examples of acids of formula 1 which may be employed in the process include:- 2-[(2,6-dichlorophenyi)amino]benzene acetic acid (i.e. n=1, RI=R3=Cl, and R2=1-1); 2-[(3-trifluoromethylphenyl)aminolbenzoic acid (i.e. n=O, RI=W=H, and R2=CIF3); 2-[(2,6-dichloro-3-methylphenyl)aminolbenzoic acid (i.e. n=O, Rl+R3=Cl, and R2=CH3); and 2-[(2,3-dimethylphenyi)aminolbenzoic acid (i.e. n=O, RI=R2=CH3, and R3=1- 1).
The esters prepared according to the invention are novel compounds and are included within the scope of the invention.
Examples of esters according to the invention include:2-[(2,6-dichlorophenyi)aminolbenzene acetic acid 2-(2-hydroxyethoxy) ethyl ester (Compound A); 2-[(3-trifluoromethylphenyi)aminolbenzoic acid 2-(2-hydroxyethoxy) ethyl ester; 2-[(2,6-dichloro-3methylphenyl)aminolbenzoic acid 2-(2-hydoxyethoxy)ethyl ester; and 2-[(2, 3-dimethylphenyl)aminolbenzoic acid 2-(2-hydroxyethoxy)-ethyl ester.
Compound A is a particularly preferred compound according to the invention. It has been found to exhibit pharmacological activity, particularly an anti- inflammatory activity. Thus, in a further aspect the invention provides pharmaceutical compositions comprising Compound A to gether with a pharmaceutical carrier or excipient.
In the process of the invention, the crude products from the reaction of diethylene glycol with 50 the acid of formula 1, optionally in the presence of thionyl chloride, may be isolated by adding water/diethyl ether as they are readily soluble in the organic solvent. They may be purified by passing through a column of silica gel, and then show only one spot in thin layer chromato graphy (60 F251 silica gel plates; mobile phase-chloroform; detection under a 254 nm light).
They also show only one peak in high pressure liquid chromatography. On the other hand 'H-NMR spectra are as expected for these compounds. All of them show the ester group band in their IR spectra.
The following non-limiting Examples serve to illustrate the invention:
Example 1-Preparation of 2-[(2,6-dichforophenyl)aminolbenzene acetic acid 2-(2-hydroxyethoxy)- 60 ethyl ester To a mixture of 180 mi of dry diethylene glycol and 4 m] thionyl chloride are added 15 g of sodium 2-[(2,6-dichlorophenyi)aminolbenzene acetate. After stirring at room temperature, 200 mi water and 250 mi diethyl ether are added, the aqueous layer is removed and the organic layer is successively washed with water, aqueous sodium hydroxide and water again. The ether solution 65 1 2 GB2182041A 2 is dried with anhydrous sodium sulfate and the solvent is removed by distillation. The oily residue is purified by passing through a chromatography column of silica gel and eluting with chloroform. On removal of the solvent, 16.5 9 (86%) of slightly yellow oil are obtained. v (ester)= 1720 cm-1.
Example 2-Preparation of 2-[(3-trifluoromethylphenyl)aminol-benzoic acid 2-(2-hydroxyethoxy)ethyl ester To 80 litres dry diethylene glycol, 3 litres thionyl chloride and 10 kg of 2-[(3-trifluoromethylphenyi)amino]benzoic acid are added. The mixture is heated on a steam bath for 6 hours. The resultant dark green solution is cooled and water/diethyl ether is added, the product being worked up in a similar way to that described in Example 1. After purification of the product, 7.8 kg (59%) of a light yellow oily product are obtained. v (ester)= 1683 cm-1.
Claims (14)
1. A process for the preparation of an ester of diethylene glycol wherein diethylene glycol is 15 reacted with an acid of general formula 1 (CH 2)J2 H R3 NH R1 R 2 1 (wherein n is 0 or 1; R' is Cl, H or CH3; R 2 is 1-1, CF, or CH3; and R 3 is Cl or 1-1) or a salt thereof.
2. A process according to claim 1 wherein the reaction is carried out in the presence of thionyl chloride.
3. A process according to either of claims 1 and 2 wherein the reaction is carried out at a temperature of from room temperature to steam bath temperature.
4. A process according to any one of the preceding claims wherein the salt of the acid of formula 1 is a sodium or potassium salt.
5. A process according to any one of the preceding claims wherein the acid of formula 1 is selected from 2-[(2,6-dichlorophenyi)aminolbenzene acetic acid, 2-[(3- trifluoromethylphenyl)amino]- benzoic acid, 2-[(2,6-dichloro-3-methylphenyl)aminol-benzoic acid, and 2[(2,3-dimethylphenyi)ami- 35 no]benzoic acid.
6. A process according to any one of the preceding claims, wherein the ester prepared is selected from 2-[(2,6-dichlorophenyi)amino]benzene acetic acid 2-(2- hydroxyethoxy)ethyl ester, 2 [(3-trifluoromethylphenyi)amino]benzoic acid 2-(2-hyd roxyethoxy) ethyl ester, 2-[(2,6-dichloro-3-me thylphenyi)amino]benzoic acid 2-(2-hydroxyethoxy)ethyl ester, and 2-[(2,3- dimethylphenyl)aminolbenzoic acid 2-(2-hydroxyethoxy)ethyl ester.
7. A process according to claim 1 substantially as herein described.
8. A process for the preparation of an ester of diethylene glycol substantially as herein described in either of the Examples.
9. An ester prepared by a process according to any one of the preceding claims.
10. An ester of diethylene glycol with an acid of formula 1 as defined in claim 1.
11. An ester selected from 2-[(2,6-dichlorophenyi)amino]benzene acetic acid 2-(2-hydroxy ethoxy)ethyl ester, 2-[(3-trifluoromethylphenyl)amino]benzoic acid 2-(2- hydoxyethoxy)ethyl ester, 2-[(2,6-dichloro-3-methylphenyi)-aminolbenzoic acid 2-(2-hyd roxyethoxy) ethyl ester, and 2-[(2,3- dimethylphenyi)aminolbenzoic acid 2-(2-hyd roxyethoxy) ethyl ester.
12. 2,6-Dichlorophenyi)aminolbenzene acetic acid 2-(2-hydroxyethoxy)ethyl ester.
13. A pharmaceutical composition comprising the ester according to claim 12 in association with a pharmaceutical carrier or excipient.
14. Each and every novel compound, process, composition and method substantially as herein disclosed.
Printed for Her Majesty's Stationery Office by Burgess & Son (Abingdon) Lid, Dd 899 1685, 1987. Published at The Patent Office, 25 Southampton Buildings, London, WC2A 1 AY, from which copies may be obtained.
4 A lt,
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES548226A ES8605220A1 (en) | 1985-10-25 | 1985-10-25 | Esters of diethylene glycol |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8625481D0 GB8625481D0 (en) | 1986-11-26 |
| GB2182041A true GB2182041A (en) | 1987-05-07 |
| GB2182041B GB2182041B (en) | 1989-09-20 |
Family
ID=8490031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8625481A Expired GB2182041B (en) | 1985-10-25 | 1986-10-24 | Preparation of esters of diethylene glycol |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS62106064A (en) |
| BE (1) | BE905666A (en) |
| CH (1) | CH676238A5 (en) |
| DE (1) | DE3636125A1 (en) |
| ES (1) | ES8605220A1 (en) |
| FR (1) | FR2589151B1 (en) |
| GB (1) | GB2182041B (en) |
| IT (1) | IT1197255B (en) |
| PT (1) | PT81505B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9217066B2 (en) | 2008-03-31 | 2015-12-22 | Ford Global Technologies, Llc | Structural polymer insert and method of making the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3811118C1 (en) * | 1988-03-31 | 1989-10-12 | Merckle Gmbh, 7902 Blaubeuren, De |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1285400A (en) * | 1969-08-01 | 1972-08-16 | Tropon G M B H | Esters of substituted anthranilic acid |
| EP0024282A1 (en) * | 1979-06-30 | 1981-03-04 | Dr. Karl Thomae GmbH | Benzoyl derivatives, their preparation and their use as medicines |
| EP0132690A1 (en) * | 1983-07-21 | 1985-02-13 | Troponwerke GmbH & Co. KG | Thermoplastics containing antiphlogistics |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2735569A1 (en) * | 1977-08-06 | 1979-02-15 | Troponwerke Gmbh & Co Kg | Antiinflammatory and antirheumatic agent prodn. - esp. N-tri:fluoro:methyl-phenyl-anthranilic acid hydroxy-ethoxy-ethyl ester |
| DE2834168C2 (en) * | 1978-08-04 | 1984-02-09 | Troponwerke GmbH & Co KG, 5000 Köln | Process for the preparation of 2- (2-hydroxyethoxy) ethyl-N - (α, α, α-trifluoro-m-tolyl) anthranilate |
| DE2834167C2 (en) * | 1978-08-04 | 1984-01-26 | Troponwerke GmbH & Co KG, 5000 Köln | Process for the preparation of 2- (2-hydroxyethoxy) ethyl-N - (α, α, α-trifluoro-m-tolyl) anthranilate |
| DE2834169C2 (en) * | 1978-08-04 | 1984-02-09 | Troponwerke GmbH & Co KG, 5000 Köln | Process for the preparation of 2- (2-hydroxyethoxy) ethyl-N- (alpha, alpha, alpha -trifluoro-m-tolyl) anthranilate |
| IL67445A (en) * | 1982-12-09 | 1985-11-29 | Teva Pharma | Ethoxycarbonyloxy ethyl esters of non-steroidal anti-inflammatory carboxylic acids |
| US4694105A (en) * | 1983-12-20 | 1987-09-15 | Ciba-Geigy Corporation | Herbicidal alkoxyamino- and polyalkoxyaminodiphenyl ethers |
| DE3407507A1 (en) * | 1984-03-01 | 1985-09-05 | A. Nattermann & Cie GmbH, 5000 Köln | Novel o-(2,6-dichloroanilino)phenylacetic acid esters, process for their preparation, and pharmaceutical preparations containing them |
-
1985
- 1985-10-25 ES ES548226A patent/ES8605220A1/en not_active Expired
- 1985-11-15 PT PT81505A patent/PT81505B/en not_active IP Right Cessation
-
1986
- 1986-09-19 IT IT21774/86A patent/IT1197255B/en active
- 1986-10-22 CH CH3810/86A patent/CH676238A5/de not_active IP Right Cessation
- 1986-10-23 DE DE19863636125 patent/DE3636125A1/en not_active Ceased
- 1986-10-24 JP JP61252159A patent/JPS62106064A/en active Pending
- 1986-10-24 GB GB8625481A patent/GB2182041B/en not_active Expired
- 1986-10-27 BE BE0/217337A patent/BE905666A/en not_active IP Right Cessation
- 1986-10-27 FR FR868614922A patent/FR2589151B1/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1285400A (en) * | 1969-08-01 | 1972-08-16 | Tropon G M B H | Esters of substituted anthranilic acid |
| EP0024282A1 (en) * | 1979-06-30 | 1981-03-04 | Dr. Karl Thomae GmbH | Benzoyl derivatives, their preparation and their use as medicines |
| EP0132690A1 (en) * | 1983-07-21 | 1985-02-13 | Troponwerke GmbH & Co. KG | Thermoplastics containing antiphlogistics |
Non-Patent Citations (3)
| Title |
|---|
| CHEMICAL ABSTRACTS 104(13)109251Z AND ES 527,939 * |
| CHEMICAL ABSTRACTS 104(21)186145V AND ES 534,122 * |
| DICTIONARY OF ORGANIC COMPOUNDS (CHAPMAN AND HALL)FIFTH EDITION (VOLUME 3)- PAGE 2575 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9217066B2 (en) | 2008-03-31 | 2015-12-22 | Ford Global Technologies, Llc | Structural polymer insert and method of making the same |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8625481D0 (en) | 1986-11-26 |
| FR2589151B1 (en) | 1990-05-18 |
| IT8621774A0 (en) | 1986-09-19 |
| PT81505B (en) | 1987-11-11 |
| ES548226A0 (en) | 1986-03-16 |
| IT8621774A1 (en) | 1988-03-19 |
| CH676238A5 (en) | 1990-12-28 |
| FR2589151A1 (en) | 1987-04-30 |
| BE905666A (en) | 1987-02-16 |
| GB2182041B (en) | 1989-09-20 |
| ES8605220A1 (en) | 1986-03-16 |
| PT81505A (en) | 1985-12-01 |
| JPS62106064A (en) | 1987-05-16 |
| DE3636125A1 (en) | 1987-04-30 |
| IT1197255B (en) | 1988-11-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19951024 |