GB2108106A - Novel macrocyclic compounds and salts thereof useful for dissolving barium sulphate scale - Google Patents
Novel macrocyclic compounds and salts thereof useful for dissolving barium sulphate scale Download PDFInfo
- Publication number
- GB2108106A GB2108106A GB08220996A GB8220996A GB2108106A GB 2108106 A GB2108106 A GB 2108106A GB 08220996 A GB08220996 A GB 08220996A GB 8220996 A GB8220996 A GB 8220996A GB 2108106 A GB2108106 A GB 2108106A
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- radical
- carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
- C09K8/78—Eroding chemicals, e.g. acids combined with additives added for specific purposes for preventing sealing
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Polyethers (AREA)
Abstract
Novel macrocyclic compounds of the general formula: <IMAGE> wherein each A<1> which may be the same or different represents a hydrocarbon radical having up to 12 carbon atoms and each D which may be the same or different represents an oxygen or a sulphur atom or a group N-R<2>, R<2> representing a hydrogen atom or a hydrocarbon radical having up to 12 carbon atoms, a hydrocarbon sulphonyl radical having up to 12 carbon atoms, an alkoxycarbonyl alkoxycarbonylmethylene radical having up to 4 carbon atoms, or a carboxymethylene radical, at least two of the said D members representing an oxygen or a sulphur atom or a group N-R<2>, and each R<1> which may be the same or different represents a hydrogen atom or an alkyl group having up to 6 carbon atoms or a carboxy group and m and n are integers from 0 to 5 inclusive, the macrocyclic compound according to the general formula I being compatible with a barium ion, and salts thereof with the exception of 1,10-di(carboxymethyl)- 1,10-diaza-4,7,13,16-tetra- oxacyclooctadecane and salts thereof are prepared by reacting a macrocyclic compound of the formula <IMAGE> with an alpha-halocarboxylic acid in the presence of a base. The novel compounds may be used for cleaning a well in accordance with U.K. Patent No. 2024822.
Description
SPECIFICATION
Macrocyclic polyethers and their preparation
The invention relates to macrocyclic polyethers which can be used, for example, in a process for cleaning a well penetrating an underground formation and/or cleaning formation parts in the vicinity of the said well, and to the preparation of such polyethers.
Such a cleaning process wherein the well and/or the formation parts in the vicinity of the well are contacted with an aqueous composition suitable for dissolving barium sulphate scale forms the subject of parent U.K. Patent Application No. 7922993.
The present invention provides macrocyclic polyethers of the general formula:
wherein each Al which may be the same or different represents a hydrocarbon radical having up to 1 2 carbon atoms and each D which may be the same or different represents an oxygen or a sulphur atom or a hydrocarbon radical having up to 12 carbon atoms or a group N-R2, R2 representing a hydrogen atom or a hydrocarbon radical having up to 12 carbon atoms, a hydrocarbonsulphonyl radical having up to 12 carbon atoms, an alkoxycarbonyl or alkoxycarbonyl-methylene radical having up to 4 carbon, atoms or a carboxymethylene radical, at least two of the said D members representing an oxygen or a sulphur atom or a group N-R2, and each R1 which may be the same or different represents a hydrogen atom or an alkyl group having up to 6 carbon atom or a carbòxy group and m and n are integers from 0 to 5 inclusive, the macrocyclic polyether according to the general formula I being compatible with a barium ion, as hereinafter defined, and salts thereof -- with the exception of 1,1 O-di(carboxymethyl)- 1,1 0-diaza-4,7,1 3,1 6-tetraoxa-cyclooctadecane and salts thereof.
The expression "the macrocyclic polyether of the general formula I being compatible with a barium ion" is used to denote that the macrocyclic polyether of the general formula I is capable of accommodating a barium ion in the intra-molecular cavity of the polyether molecule. The expression "salt of a macrocyclic polyether of the general formula I" is used to denote a carboxylate salt of this macrocyclic polyether.
Preferred compounds according to formula I are those wherein A' represents a hydrocarbon radical having in the range of from 2 to 8 carbon atoms, or a 1 2-phenylene radical; D represents an oxygen atom or a group N-R2 wherein R2 represents an alkyl group of up to 8 carbon atoms, a hydrocarbonsulphonyl radical of up to 8 carbon atoms or an alkoxycarbonyl radical of up to 4 carbon atoms; at least 4 of said D members representing an oxygen atom: and each R1 represents a hydrogen atom or an alkyl group having up to 4 carbon atoms or a carboxy atom and m and n are in the range of from 1 to 3.
More preferred compounds according to formula I are those wherein A1 represents a ethylene, diethylene, triethylene on terra ethylene radical, particularly an ethylene radical; D represents an oxygen atom or a group N-R2 wherein R2 represents an alkyl group of up to 4 carbon atoms, particularly a methyl group a hydrocarbonsulphonyl radical of up to 4 carbon atoms or a methoxy- or ethoxycarbonyl radical; at least 4 of the said D members representing an oxygen atom, and each R1 represents a hydrogen atom or a methyl, ethyl or carboxy group and m and n are 1 or 2.
The salts of the macrocyclic polyethers according to the general formula I may be prepared in a manner known per se by reacting the corresponding macrocyclic polyether of the general formula:
with a salt of an alpha-halocarboxylic acid, such as 2-chioroacetic acid, 2-bromoacetic acid, 2-chloro
or 2-bromobutyric acid, in the presence of a base. Examples of suitable salts of, for instance, 2
chloroacetic acid and 2-bromoacetic acid are alkali metal salts. Suitable bases comprise alkali metal
hydroxides, for example lithium hydroxide and potassium hydroxide. It is also possible to react a macrocyclic polyether according to the general formula II with an alpha-halocarboxylic acid in the
presence of a base, and preferably in the presence of an excess of a suitable base.Acidification of an
aqueous solution of the salts of the macrocyclic polyethers according to the general formula I yields the macrocyclic polyethers according to the general formula I. Further acidification gives quaternary ammonium salts of the macrocyclic polyethers of formula I, which inner salts are also considered to be within the scope of the present invention.In the event that at least one of the groups R' represents a carboxy group, it was found convenient to use a halmaionic ester which after subsequent hydrolysis gives the macrocyclic polyether according to the general formula
Example I
The compound 1,1 0-di(alpha-ethylcarboxymethyl)-1 , 1 0-diaza-4,7, 13,1 6- tetraoxacyclooctadecane was prepared in situ, i.e. in the presence of barium sulphate (3 moles per litre) by reacting 1,10-diaza-4,7,13,1 6-tetraoxacyclooctadecane (0.1 M) and 2-chlorobutyric acid (0.2 M) and lithium hydroxide (0.8 M) at 700C. The compound was characterised by 'H and 13C nuclear magnetic resonance technique in D20.
The following signais were assigned:
'H NMR (H20 as ppm): -1.2 (m, 1 6H; 1,2); -1.8 (t, 2H, 3); -2.1 (t, 8H, 4); -3.2 (m, 4H, 5); -4.0 (t, 6H, 6) ppm.
13C NMR (external reference):
183.4 (7); 73.2(1,2,3); 54.4 (4); 23.4 (5); 14.6 (6) ppm.
The compound was formed in about 14% yield.
Example II
The novel compound bis(dicarboxymethyl)-1 ,10-diaza-4,7,13,1 6-tetraoxacyclooctadecane was prepared by reacting dimethylbromomalonate (1.61 g, 7.2 mmol) with 1,10-diaza-4,7,13,16tetraoxacyclooctadecane (1 g, 3.8 mmol) in dry benzene (26 ml) under reflux for 6 hours. After cooling the reaction mixture was filtered and the filtrate evaporated and purified by column chromatography (A1203, CH2CI2 as eluent) yielding the tetramethyl ester of compound C (23%, 0.45 g).
The tetramethyl ester (0.35 g, 0.67 mmol) was dissolved in tetrahydrofurane (30 ml) to which lithium hydroxide (67.5 mg, 4 equivalents on ester) and water (2 ml) were added. After 5 days stirring at ambient temperature, the percipitate formed was isolated (0.21 g) as the tetralithium salt of the compound (about 65%).
Upon acidification (excess HCI) and treatment with acetone/ethanol to remove LiCI, the desired compound was obtained as a hygroscopic HCI salt.
Analysis: for C,8H52CI4N2020 (compound C 4HCl. .8H20) Calculated: C: 28.6%; H: 6.9%; CI: 18.8%; N: 3.7%
Found: C: 24.6%; H: 5.4%; Cl: 20%; N: 3.5%.
P.M.R. -- data were in accordance with the expected structure.
Claims (7)
1. A macrocyclic polyether of the general formula:
wherein each Al which may be the same or different represents a hydrocarbon radical having up to 12 carbon atoms and each D which may be the same or different represents an oxygen or a sulphur atom or a group N-R2 R2 representing a hydrogen atom or a hydrocarbon radical having up to 12 carbon atoms, a hydrocarbon sulphonyl radical having up to 12 carbon atoms, an alkoxycarbonyl alkoxycarbonylmethylene radical having up to 4 carbon atoms or a carboxymethylene radical, at least two of the said D members representing an oxygen or a sulphur atom or a group N-R2, and each R which may be the same or different represents a hydrogen atom or an alkyl group having up to 6 carbon atoms or a carboxy group and m and n are integers from 0 to 5 inclusive, the macrocyclic polyether according to the general formula I being compatible with a barium ion, as hereinbefore defined and salts thereof -- with the exception of 1,1 0-di(carboxymethyl)-1 ,1 0-diaza-4,7,1 3,1 6- tetraoxacyclooctadecane and salts thereof.
2. A compound as claimed in claim 1 , in which A1 represents an ethylene, diethylene, triethylene or tetraethylene radical, particularly an ethylene radical; D represents an oxygen atom or a group N-R2, wherein R2 represents an alkyl group of up to 4 carbon atoms, particularly a methyl group, a hydrocarbon sulphonyl radical of up to 4 carbon atoms or a methoxy- or ethoxycarbonyl radical; at least 4 of the said D members representing an oxygen atom and each R1 represents a hydrogen atom or a methyl, ethyl or carboxy group and m and n are 1 or 2.
3. 1,1 0-di(alpha-ethylcarboxymethyl)-1 1 0-diaza-4,7,1 3,1 6-tetraoxacyclooctadecane.
4. Bis(dicarboxymethyl)- 1,10-diaza-4,7,13,1 6-tetraoxacyclooctadecane.
5. Process for the preparation of macrocyclic polyethers according to the general formula I or salts thereof as claimed in any one of claims 1-4, which comprises reacting a macrocyclic polyether according to formula II as defined in the foregoing description, an alpha-halocarboxylic acid and a base or an excess of a base.
6. Process as claimed in claim 5, in which 1,1 0-diaza-4,7,1 3,1 6-tetraoxacyclooctadecane is reacted with a 2-halocarboxylic acid and sodium hydroxide or lithium hydroxide, preferably an excess of sodium hydroxide or lithium hydroxide at a temperature up to 800C.
7. Process as claimed in claims 5 or 6, in which the reaction is carried out in the presence of solid barium sulphate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7828757 | 1978-07-04 | ||
| GB7922993A GB2024822B (en) | 1978-07-04 | 1979-07-02 | Macrocyclic polyethers and the use of salts thereof for dissolving barium sulphate scale |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2108106A true GB2108106A (en) | 1983-05-11 |
| GB2108106B GB2108106B (en) | 1983-09-01 |
Family
ID=26268113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08220996A Expired GB2108106B (en) | 1978-07-04 | 1979-07-02 | Novel macrocyclic compounds and salts thereof useful for dissolving barium sulphate scale |
Country Status (2)
| Country | Link |
|---|---|
| GB (1) | GB2108106B (en) |
| SG (1) | SG65184G (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0232751A1 (en) * | 1986-01-23 | 1987-08-19 | E.R. Squibb & Sons, Inc. | 1-substituted-4,7,10-triscarboxymethyl-1,4,7,10-tetraazacyclododecane and analogs |
| EP0292689A2 (en) * | 1987-04-24 | 1988-11-30 | Bracco International B.V. | Substituted 1,4,7-triscarboxymethyl-1,4,7,10-tetraazacyclo-dodecane and analogs |
| EP0358418A1 (en) * | 1988-09-05 | 1990-03-14 | Sankyo Company Limited | Cyclic peptide, its preparation and its use in the treatment of cardiovascular disorders |
| US5674470A (en) * | 1986-01-23 | 1997-10-07 | Bracco Diagnostics Inc. | Method for imaging mammalian tissue using 1-substituted- 4,7,10-tricarboxymethyl-1,4,7,10-tetraazacyclododecane and analogs |
-
1979
- 1979-07-02 GB GB08220996A patent/GB2108106B/en not_active Expired
-
1984
- 1984-09-11 SG SG65184A patent/SG65184G/en unknown
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0232751A1 (en) * | 1986-01-23 | 1987-08-19 | E.R. Squibb & Sons, Inc. | 1-substituted-4,7,10-triscarboxymethyl-1,4,7,10-tetraazacyclododecane and analogs |
| US5674470A (en) * | 1986-01-23 | 1997-10-07 | Bracco Diagnostics Inc. | Method for imaging mammalian tissue using 1-substituted- 4,7,10-tricarboxymethyl-1,4,7,10-tetraazacyclododecane and analogs |
| US5846519A (en) * | 1986-01-23 | 1998-12-08 | Bracco Diagnostics Inc. | Method for imaging mammalian tissue using 1-substituted-1,4,7-tricarboxymethyl-1,4,7,10-tetraazacyclododecane and analogs |
| US6143274A (en) * | 1986-01-23 | 2000-11-07 | Tweedle; Michael F. | Method for imaging and radiopharmaceutical therapy using 1-substituted-4,7,10-tricarboxymethyl-1,4,7,10-tetraazacyclododecane and analogs |
| EP0292689A2 (en) * | 1987-04-24 | 1988-11-30 | Bracco International B.V. | Substituted 1,4,7-triscarboxymethyl-1,4,7,10-tetraazacyclo-dodecane and analogs |
| EP0292689A3 (en) * | 1987-04-24 | 1991-07-31 | Bracco International B.V. | Substituted 1,4,7-triscarboxymethyl-1,4,7,10-tetraazacyclo-dodecane and analogs |
| EP0358418A1 (en) * | 1988-09-05 | 1990-03-14 | Sankyo Company Limited | Cyclic peptide, its preparation and its use in the treatment of cardiovascular disorders |
| US5112807A (en) * | 1988-09-05 | 1992-05-12 | Sankyo Company, Limited | Compound "leualacin", its preparation and its use in the treatment of cardiovascular disorders |
Also Published As
| Publication number | Publication date |
|---|---|
| SG65184G (en) | 1985-03-29 |
| GB2108106B (en) | 1983-09-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |