US2641610A - Quaternary ammonium salts - Google Patents
Quaternary ammonium salts Download PDFInfo
- Publication number
- US2641610A US2641610A US252003A US25200351A US2641610A US 2641610 A US2641610 A US 2641610A US 252003 A US252003 A US 252003A US 25200351 A US25200351 A US 25200351A US 2641610 A US2641610 A US 2641610A
- Authority
- US
- United States
- Prior art keywords
- quaternary ammonium
- acid
- embonate
- ammonium salts
- salts
- Prior art date
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- Expired - Lifetime
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- 150000003242 quaternary ammonium salts Chemical class 0.000 title description 7
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000002253 acid Substances 0.000 description 14
- 229950005627 embonate Drugs 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- WLJNZVDCPSBLRP-UHFFFAOYSA-N pamoic acid Chemical compound C1=CC=C2C(CC=3C4=CC=CC=C4C=C(C=3O)C(=O)O)=C(O)C(C(O)=O)=CC2=C1 WLJNZVDCPSBLRP-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000000875 corresponding effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- -1 polymethylene Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000002535 acidifier Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- YGLLICRFEVEWOZ-UHFFFAOYSA-L disodium;3-carboxy-1-[(3-carboxy-2-oxidonaphthalen-1-yl)methyl]naphthalen-2-olate Chemical compound [Na+].[Na+].C1=CC=C2C(CC3=C4C=CC=CC4=CC(=C3O)C([O-])=O)=C(O)C(C([O-])=O)=CC2=C1 YGLLICRFEVEWOZ-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
- C07C65/105—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups polycyclic
- C07C65/11—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups polycyclic with carboxyl groups on a condensed ring system containing two rings
Definitions
- R represents a methyl or ethyl group and X represents the residue of an acid.
- embonic acid does not form s Clainis (cram-501) readily separable salts with quaternary ammonium derivatives such as tetraethyl ammonium or polymethylene bis-quaternary ammoniums containing less than six methylene groups it has been found that the embonates referred to above may be very simplyprepared in a pure state.
- these new embonates are obtained through the double-decomposition in aqueous solution of a corresponding bis-quaternary ammonium salt of the aforesaid type by adding to that solution 'a watersoluble embonate.
- the new embonates are very sparingly soluble in water at normal temperatures although they will form solutions of reasonable concentration at elevated temperature. It is, therefore, asimple matter to isolate the new embonates from aqueous solutions in which they are prepared. Since embonic acid itself is substantially insoluble in water even at boiling point the new embonates provide a convenient and simple route to the more soluble corresponding bis-quaternary salts uncontaminated by soluble by-products. Thus embonic acid is precipitated by acidification of a quaternary ammonium embonate leaving the quaternary ammonium salt of the acidifying agent in solution in a substantially pure state.
- the process of the presentinvention can be regardedas a step in .the production of bis-quaternary ammonium salts of the. aforesaid general formula in which X represents an anion. of an acid other than embonic acid and which are more' soluble' in waterthan the corresponding embonate.
- the new embonates will be directly isolated from aqueous solution containing oneof such salts (for example, sulphate, nitrate, halideor sulphonate) by the addition thereto of a watersoluble embonate such as sodium embonate.
- aqueous solution containing oneof such salts for example, sulphate, nitrate, halideor sulphonate
- hexamethylene diamine is to be preferred from the viewpoint of accessibility.
- this compound could be directly methylated and quaternated in a single operation using, for ex ample, dimethyl sulphate or other reactive methyl ester such as a halide but in actual practice this was hitherto'found to possess serious disadvantages arising from the formation of byproducts of the methylation reaction (viz. free acids derived from the methylating agents or correspond ing salts if acid binding agents have also been used) the separation of which from the desired quaternary ammonium salts is extremely difficult.
- bitartrates bitartrates, bisulphates and dihydrogen phosphates are now rendered readily available.
- new salts which can be conveniently prepared using the process of the present invention are adipates (neutral and acid), benzoates, carbonates, chlorides, citrates, acid maleates, methosulphates, succinates (neutral and acid), neutral sulphates and neutral tartrates.
- Example I Hexamethylene diamine (116 gms.), sodium carbonate (466 gms.), and water (800 mls.) were heated to 60 C., and dimethyl' sulphate (830 gms.) added with stirringv over 1 /2 hourskeep ing the temperature below 90 C. The reaction mixture was then stirred at 90 C. for 2 hours,
- embonic acid which is regenerated can; of course, be used for the next operation. Owing to its extreme insolubility, th loss is extremely small. 7
- Example II The embonate (588 gms.) prepared by the process of Example I was dissolved in boiling water "(4 litres); Hydrobrornic acid w./w. (325 gms.) diluted with water (2' litres) was added slowly at the boil and the precipitated embom'c acid removed by filtering hot and washing twice with hot water (1 litre). The filtrate and washings were evaporated to dryness in a steam panand the residue recrystallised from ethyl alcohol (1200 mls.) to yield the dibromide (320 gms.) corresponding to the tartrate of Example I.
- R represents a member of the class consisting of methyl and ethyl and A represents the residue of 2 :2-dihydroxy-1 l-dinaphthylmethane-3z'3-dicarboxylic acid (embcnic acid).
- Hexamethylene 1- 6 '-'bis-dimethylethylammonium embonate.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented June 9, 1953 UNITED STAT ES PATENT OFFICE 2,641,610 QUATERNARY AMMONIUM SALTS Harry James Barber, Dagenham, England, as signor to' May & .Baker Limited, Dagenham, England, a British company.
No Drawing. Application October: 18,. 1951, Se-
rial No. 252,003. In Great Britain October 27,
Where R represents a methyl or ethyl group and X represents the residue of an acid. These salts are readily soluble in water and their manufacture in the pure statewith good yield is com plicated by the difiiculty experienced in the removal ofsoluble by-products.
It is the object of the present invention to provide new intermediates from which the above bis-quaternary ammonium salts can readily be prepared in a good yield on a commercial scale.
These new intermediates are salts of the foregoing type in which the groups X are replaced by the radical of 2 Z-dihydroxy-l l-dinaphthyl-methane-3z3-dicarboxyli'c' acid (hereinafter in. this specification and in the appended claims this acid is, for convenience, called embonic acid while its salts. are hereinafter called embonates). While embonic acid does not form s Clainis (cram-501) readily separable salts with quaternary ammonium derivatives such as tetraethyl ammonium or polymethylene bis-quaternary ammoniums containing less than six methylene groups it has been found that the embonates referred to above may be very simplyprepared in a pure state.
According to the present invention, these new embonates are obtained through the double-decomposition in aqueous solution of a corresponding bis-quaternary ammonium salt of the aforesaid type by adding to that solution 'a watersoluble embonate.
The new embonates are very sparingly soluble in water at normal temperatures although they will form solutions of reasonable concentration at elevated temperature. It is, therefore, asimple matter to isolate the new embonates from aqueous solutions in which they are prepared. Since embonic acid itself is substantially insoluble in water even at boiling point the new embonates provide a convenient and simple route to the more soluble corresponding bis-quaternary salts uncontaminated by soluble by-products. Thus embonic acid is precipitated by acidification of a quaternary ammonium embonate leaving the quaternary ammonium salt of the acidifying agent in solution in a substantially pure state.
It will be appreciated that the process of the presentinvention can be regardedas a step in .the production of bis-quaternary ammonium salts of the. aforesaid general formula in which X represents an anion. of an acid other than embonic acid and which are more' soluble' in waterthan the corresponding embonate. the new embonates will be directly isolated from aqueous solution containing oneof such salts (for example, sulphate, nitrate, halideor sulphonate) by the addition thereto of a watersoluble embonate such as sodium embonate. In the case,. especially, of the quaternary ammonium saltsof the aforesaid general formula in which R. represents. methyl this fact is of considerable commercial importance as will now be explained. Of the theoretically suitable hexamethylene intermediates for the production of these particular quaternary ammonium salts, hexamethylene diamine is to be preferred from the viewpoint of accessibility. Theoretically, this compound could be directly methylated and quaternated in a single operation using, for ex ample, dimethyl sulphate or other reactive methyl ester such as a halide but in actual practice this was hitherto'found to possess serious disadvantages arising from the formation of byproducts of the methylation reaction (viz. free acids derived from the methylating agents or correspond ing salts if acid binding agents have also been used) the separation of which from the desired quaternary ammonium salts is extremely difficult. If, however, a Water-soluble embonate is added to the crude reaction mixture in which any free acid has previously been neutralised and from which suspended or precipitated solids (if any) have been removed, the embonate corresponding to the. desired salt is precipitated and thereby isolated. After recrystallisation (which may conveniently be eifected from water) the embonate can then be converted into the desired salt by treatment with an acid containing the required anion. r The process of this invention is not only applicable to the production of known quaternary am monium salts of theaforesaid general type as a means for eliminating otherwise necessary purie fication steps but also renders possible the commercial production of hitherto unknown quaternary ammonium salts of the aforesaid general type that would be difficult to produce by the application of known methods. For example the quaternary ammonium salts containing a radical derived from an acid the anion of which is neither physiologically nor pharmacologically un- Thus, in general,
desirable, for example the bitartrates, bisulphates and dihydrogen phosphates are now rendered readily available. Other examples of new salts which can be conveniently prepared using the process of the present invention are adipates (neutral and acid), benzoates, carbonates, chlorides, citrates, acid maleates, methosulphates, succinates (neutral and acid), neutral sulphates and neutral tartrates.
The process of the present invention is illustrated by the following examples:
Example I Hexamethylene diamine (116 gms.), sodium carbonate (466 gms.), and water (800 mls.) were heated to 60 C., and dimethyl' sulphate (830 gms.) added with stirringv over 1 /2 hourskeep ing the temperature below 90 C. The reaction mixture Was then stirred at 90 C. for 2 hours,
then cooled to 20 C., acetone (1200 mls.) added and the whole cooled to C.
The solid formed was removed by' filtration and washed with acetone (150 mls.). Filtrate and washin s were diluted with water to 4.1itres and heated to 60 C. under'reflux. To this was added a solution prepared from embonic acid (388 gms.), sodium'hydroxide (80" gms.) and water (5 litres), the Whole refluxed for minutes 'The filtrate and washings were evaporated in a steam pan to a thick syrup which was granulated by stirringwith ethyl alcohol (1500 mls.). The ethyl alcohol was removed by filtration and hexamethylene 1:fi-bis trimethyl-ammonium bitarrtrate (400 gms.) was obtained as the monohydrate by recrystallisation from methyl alcohol (700 mls.) I
The embonic acid which is regenerated can; of course, be used for the next operation. Owing to its extreme insolubility, th loss is extremely small. 7
Example II The embonate (588 gms.) prepared by the process of Example I was dissolved in boiling water "(4 litres); Hydrobrornic acid w./w. (325 gms.) diluted with water (2' litres) was added slowly at the boil and the precipitated embom'c acid removed by filtering hot and washing twice with hot water (1 litre). The filtrate and washings were evaporated to dryness in a steam panand the residue recrystallised from ethyl alcohol (1200 mls.) to yield the dibromide (320 gms.) corresponding to the tartrate of Example I.
/ From an, aqueous solution obtained by the quaternation with the appropriate'alkyl halide of 1 :6-bis-dimethylaminohexane there was obtained in'analoguos manner to the embonate of Example I hexamethylene-l:G-bis-dimethylethylammonium embonate which crystallised from water as a hydrate and on drying gave an amorphous yellow powder M. P. 262-265 C. (with d'ecomp.).
*I claim: I r V 1; A compound of the general formula:
where R represents a member of the class consisting of methyl and ethyl and A represents the residue of 2 :2-dihydroxy-1 l-dinaphthylmethane-3z'3-dicarboxylic acid (embcnic acid).
2. Hexamethylene- 1:6 -bis-trimethylammoni.- um embonate.
3. Hexamethylene 1-: 6 '-'bis-dimethylethylammonium embonate.
HARRY JAMES BARBER.
References Cited in the file of this patent UNITED s ATEs PATENTS Number Name, Date 2,130,947 Carothers sept. 20, 1938 2,375,853 Kirby et al May 15,1945
OTHER REFERENCES Paton et al.: Nature. vol. 162, p. 810 (1948).
Claims (1)
1. A COMPOUND OF THE GENERAL FORMULA:
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2641610X | 1950-10-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2641610A true US2641610A (en) | 1953-06-09 |
Family
ID=10912441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US252003A Expired - Lifetime US2641610A (en) | 1950-10-27 | 1951-10-18 | Quaternary ammonium salts |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2641610A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2827466A (en) * | 1953-02-17 | 1958-03-18 | May & Baker Ltd | Bis-quaternary ammonium salts of amsonic acid |
| US2920040A (en) * | 1956-12-05 | 1960-01-05 | Sun Oil Co | Process for inhibiting corrosion of ferrous metals by oil well fluid |
| US3218339A (en) * | 1959-03-24 | 1965-11-16 | Parke Davis & Co | Parasiticide |
| US3268577A (en) * | 1960-11-15 | 1966-08-23 | Edinburgh Pharmaceutical Ind L | Quaternary organic salts of omega-dialkylamino-2, 6-dimethylacetanilides |
| US3372177A (en) * | 1964-08-17 | 1968-03-05 | Bristol Myers Co | Phenyltoloxamine aluminum pamoate |
| US3956271A (en) * | 1969-01-20 | 1976-05-11 | Sandoz Ltd. | Process for the production of concentrated solutions of cationic azo dyes |
| EP0209000B1 (en) * | 1985-07-16 | 1990-08-16 | Bayer Ag | Embonates of quinoline-carboxylic acids and their derivatives |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2130947A (en) * | 1935-01-02 | 1938-09-20 | Du Pont | Diamine-dicarboxylic acid salts and process of preparing same |
| US2375853A (en) * | 1942-10-07 | 1945-05-15 | Du Pont | Diamine derivatives |
-
1951
- 1951-10-18 US US252003A patent/US2641610A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2130947A (en) * | 1935-01-02 | 1938-09-20 | Du Pont | Diamine-dicarboxylic acid salts and process of preparing same |
| US2375853A (en) * | 1942-10-07 | 1945-05-15 | Du Pont | Diamine derivatives |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2827466A (en) * | 1953-02-17 | 1958-03-18 | May & Baker Ltd | Bis-quaternary ammonium salts of amsonic acid |
| US2920040A (en) * | 1956-12-05 | 1960-01-05 | Sun Oil Co | Process for inhibiting corrosion of ferrous metals by oil well fluid |
| US3218339A (en) * | 1959-03-24 | 1965-11-16 | Parke Davis & Co | Parasiticide |
| US3268577A (en) * | 1960-11-15 | 1966-08-23 | Edinburgh Pharmaceutical Ind L | Quaternary organic salts of omega-dialkylamino-2, 6-dimethylacetanilides |
| US3372177A (en) * | 1964-08-17 | 1968-03-05 | Bristol Myers Co | Phenyltoloxamine aluminum pamoate |
| US3956271A (en) * | 1969-01-20 | 1976-05-11 | Sandoz Ltd. | Process for the production of concentrated solutions of cationic azo dyes |
| EP0209000B1 (en) * | 1985-07-16 | 1990-08-16 | Bayer Ag | Embonates of quinoline-carboxylic acids and their derivatives |
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