US2009295A - Oleaginous solutions of organic salts of bismuth - Google Patents
Oleaginous solutions of organic salts of bismuth Download PDFInfo
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- US2009295A US2009295A US624148A US62414832A US2009295A US 2009295 A US2009295 A US 2009295A US 624148 A US624148 A US 624148A US 62414832 A US62414832 A US 62414832A US 2009295 A US2009295 A US 2009295A
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- Prior art keywords
- bismuth
- grammes
- solution
- acid
- salts
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- Expired - Lifetime
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- 229910052797 bismuth Inorganic materials 0.000 title description 31
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical class [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title description 30
- 150000003839 salts Chemical class 0.000 title description 10
- 239000000243 solution Substances 0.000 description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 14
- 150000001621 bismuth Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 235000011187 glycerol Nutrition 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 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 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- -1 aliphatic alcohols Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 235000008390 olive oil Nutrition 0.000 description 4
- 239000004006 olive oil Substances 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 150000001622 bismuth compounds Chemical class 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000005609 naphthenate group Chemical group 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical group [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- LBVKKIZHXBASRJ-UHFFFAOYSA-K di(hexadecanoyloxy)bismuthanyl hexadecanoate Chemical compound [Bi+3].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O LBVKKIZHXBASRJ-UHFFFAOYSA-K 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- XXRLJXZVZZXDPP-UHFFFAOYSA-N ethyl 2-chloro-2-phenylacetate Chemical compound CCOC(=O)C(Cl)C1=CC=CC=C1 XXRLJXZVZZXDPP-UHFFFAOYSA-N 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 1
- 238000010255 intramuscular injection Methods 0.000 description 1
- 239000007927 intramuscular injection Substances 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- GXKIIWJLNFCAOA-UHFFFAOYSA-N o-butyl dodecanethioate Chemical compound CCCCCCCCCCCC(=S)OCCCC GXKIIWJLNFCAOA-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000012053 oil suspension Substances 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- WBHHMMIMDMUBKC-QJWNTBNXSA-M ricinoleate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O WBHHMMIMDMUBKC-QJWNTBNXSA-M 0.000 description 1
- 229940066675 ricinoleate Drugs 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000011287 therapeutic dose Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/0012—Galenical forms characterised by the site of application
- A61K9/0019—Injectable compositions; Intramuscular, intravenous, arterial, subcutaneous administration; Compositions to be administered through the skin in an invasive manner
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/44—Oils, fats or waxes according to two or more groups of A61K47/02-A61K47/42; Natural or modified natural oils, fats or waxes, e.g. castor oil, polyethoxylated castor oil, montan wax, lignite, shellac, rosin, beeswax or lanolin
Definitions
- the present invention relates to the production of new bismuth compounds and their oleaginous solutions for therapeutic use.
- the compounds of bismuth soluble in vegetable and animal oils which have been proposed up to now still have various drawbacks.
- the naphthenates are unstable in presence of water and their oily solutions are very rapidly gelatinized in contact with it. (Lebeau et Courtois, Trait de Pharmacie Chimique, vol. 2, page 482.)
- the camphorcarbonates are unstable when heated and readily lose carbon dioxide on sterilization.
- R represents a normal saturated alkyl group
- R. represents an organic radicle containing fewer carbon atoms than R
- X represents one of the first two elements 5 of the 6th group of the periodic system (the oxygen-sulphur group).
- This invention is new, as it was so far known only (Picon, J. de Pharmacie et de Chimie, 8th series, vol. 10, page 45 that the neutral or basic bismuth salts of higher fatty acids or higher fatty oxyacids (octylate, palmitate, ricinole-ate) are extremely sparingly soluble or even insoluble in oils; one can therefore employ them in therapeutic doses only in the form of oil suspensions as, for example, in the case of the oleate (Hoflmann Laroche & 00., British Patent 206,- 487, Manufacture of emulsions of bismuth salts).
- solubility of the salts increases however, as we have found in a given series with the number of carbon atoms.
- the oily solutions of these salts have a very great stability and can be heated for a certain time at 120 C., without any decomposition; they can be-kept for a very long time without undergoing any change.
- the great stability, even at elevated temperatures, of the salts of bismuth with alkyl, aryl or aralkyl-thio-acids and the total absence of any reaction between the sulphur and the bismuth although, as is well-known, they have a very great amnity for one another.
- the sodium. salt of the particular acid is caused to react with bismuth nitrate dissolved in a mixture of water and glycerine. If only one or two molecules of the sodium salt are used for one molecule of bismuth nitrate, one or two molecules of soda are added in such a way that there are always three atoms of sodium for one atom of bismuth.
- the alkyl (aryl or aralkyl) oxy (or thio) acids are prepared by saponification of the corresponding esters.
- the latter can be easily obtained by the action of sodium derivatives of alcohols (or phenols) or of the alkyl (aryl or aralkyl) mercaptides of sodium on the zit-halogenated acids.
- Example 1.62.4 grammes of oz-DhBIIYlOXY- caproic acid are dissolved in a mixture of 300 cc. of normal soda and 450 grammes of glycerine; to this solution is added a solution of 48.5 grammes of bismuth nitrate in 50 cc. of water and '70 grammes of glycerine.
- the bismuth salt which separates is extracted by benzenes; then by the addition of olive oil and distillation of the benzene there is obtained an oily solution of the a-phenyloxycaporate of bismuth which is stable even at C.
- oily solutions can be obtained in the same way of the basic bismuth phenyloxycaproates (containing two or one molecules of the acid for one atom of bismuth) which are as stable as the preceding bismuth phenyloxycaproate.
- the a-phenyloxycaproic acid can be obtained by saponification of ethyl-a-phenyloxycaproate.
- This ester can be prepared by the action of sodium phenate on .ethyl-a-bromocaproate in a manner analogous to that which is employed for ethyl-aphenyloxybutyrate (Luchmann, Berichte, vol. 29, page 1421) It distils at C., under a pressure of 7 mm.
- Example 2.86.4 grammes of a-blltYlthiOlflllIiC acid (prepared by the .saponification of ethyl-@- butylthiolaurate) are dissolved in a mixture of 300 cc. of normal soda and 450 grammes of glycerine; to this solution is added a solution of 48.5 grammes of bismuth nitrate in 50 cc. of water and 70 grammes of glycerine. After extraction of the bismuth salt which is formed by benzene and the addition of olive oil, the benzene is distilled off and an oily solution is thus obtained of bismuth a-butylthiolaurate which is stable even at 120 C.
- I oily solution
- oily solutions of basic bismuth m-butylthiolaurate containing two or one molecules of the acid for one atom of bismuth.
- These oily solutions can be very concentrated and can contain more than 20 grammes of bismuth per 100 cc. of solution; they are as stable as the preceding ones.
- the ethyl m-butylthiolaurate can be prepared in very good yields by the action of sodium butylmercaptide on ethyl a-bromolaurate in alcoholic solution. It distils at C., under a pressure of 5 mm.
- Example 3.--62.4 grammes of a-butyloxyphenylacetic acid (prepared by the saponification of ethyl a-butyloxyphenyl acetate) are dissolved in a mixture of 300 cc. of normal soda and 450 grammes of glycerine; to this solution is added a solution of 48.5 grammes of bismuth nitrate in 50 cc. of water and 70 grammes of glycerine.
- Ethyl a-butyloxyphenyl acetate can be prepared in good yields by the action of sodium butylate on ethyl phenylchloracetate. It distils at 169 C., under a pressure of 15 mm.
- an oily solution containing up to 20% of bismuth, stable at a temperature of 120 0., and not depositing any solid or liquid at ordinary temperatures, having as solute a salt of bismuth containing at least one acid radicle of the formula H OinHzr--OOzH C4H9-S 3.
- an oily solution containing from 5 to 20% of bismuth in the form of mono-a-butyl-thiolaurate of bismuth, having the formula 4.
- an oily solution containing from 5 to 20% of bismuth in the form of di-a-butyl-thiolaurate of bismuth,
Description
Patented July 23, 1935 PATENT OFFICE OLEAGINOUS SOLUTIONS OF ORGANIC SALTS OF BISMUTH Paul Emile Charles Goissedet and Robert Ludovic Despois, Choisy-Le-Roi, France, assignors to Societe Des Usines Chimiques Rhone-Poulenc,
Paris, France No Drawing. Application July 22, 1932, Serial No. 624,148. In Great Britain May 2, 1932 5 Claims.
The present invention relates to the production of new bismuth compounds and their oleaginous solutions for therapeutic use.
The importance of bismuth derivatives in the treatment of specific diseases has long been known.
It is also known (New and Non-Official Remedies, 1929, pages 92-94) that bismuth compounds cannot be used for intravenous'injection on account of the great toxicity of this metal when rapidly introduced into the blood stream. The usual method of treatment has for a long time been by intramuscular injection of a colloidal suspension of metallic bismuth or of one of its salts. The usual vehicle for such injections is a vegetable oil, preferably olive oil. This mode of injection has, however, frequently been objected to as liable to cause the deposition of bismuth or of its insoluble salts which are only resorbed with difficulty and for this reason give rise to irregular action.
Attempts to improve the technique of bismuth treatment have been directed to two points:
1. To obtain a compound of bismuth readily soluble in oils which can be as readily resorbed as the oil itself. Examples of such compounds are the naphthenate of bismuth (German Patent 441,871 of Merck) and the camphorcarbonate of bismuth (French Patent 657,694 of M. L. Picon).
2. To obtain a, bismuth compound which should be soluble in water, stable, and non-acidic, such as the substance known as Thiobismol (New and Non-Official Remedies, 1931).
The compounds of bismuth soluble in vegetable and animal oils which have been proposed up to now still have various drawbacks. The naphthenates are unstable in presence of water and their oily solutions are very rapidly gelatinized in contact with it. (Lebeau et Courtois, Trait de Pharmacie Chimique, vol. 2, page 482.) The camphorcarbonates are unstable when heated and readily lose carbon dioxide on sterilization.
According to the present invention we have found that stable solutions of bismuth salts in vegetable or animal oils containing up to 20% of bismuth may be prepared from bismuth salts containing at least one acid radicle of the general formula.
These oily solutions are stable even at a temperature of 120 0., and can be painlessly injected into the muscles and are rapidly resorbed.
In the above formula R represents a normal saturated alkyl group, R. represents an organic radicle containing fewer carbon atoms than R, and X represents one of the first two elements 5 of the 6th group of the periodic system (the oxygen-sulphur group).
In practice the a-halogenated fatty acids used as starting materials are prepared from the readily obtainable fatty acids. 10
In the same way-R is derived from readily obtainable alcohols and thiols. such as the normal primary aliphatic alcohols from CzHsOI-I to C1oH21OH and also the alcohols from phenylethylalcohol to hydrocinnamic alcohol and the corre- '15 sponding thiols. 1
There is no reason to believe that less applicable results would be obtained with products obtained when R and R are more complex, but for practical consideration it is not necessary to consider such compounds.
This invention is new, as it was so far known only (Picon, J. de Pharmacie et de Chimie, 8th series, vol. 10, page 45 that the neutral or basic bismuth salts of higher fatty acids or higher fatty oxyacids (octylate, palmitate, ricinole-ate) are extremely sparingly soluble or even insoluble in oils; one can therefore employ them in therapeutic doses only in the form of oil suspensions as, for example, in the case of the oleate (Hoflmann Laroche & 00., British Patent 206,- 487, Manufacture of emulsions of bismuth salts).
The solubility of the salts increases however, as we have found in a given series with the number of carbon atoms. One could not anticipate, for example, that the basic butyl-oxy-la-urate or the basic butyl thio-laurate of bismuth which contain only one acid radical containing 16 atoms of carbon to one atom of bismuth would have a solubility in oil so great that it is possible to prepare oily solutions of these salts containing more than 200 grammes of bismuth for one litre of the solution, and this in face of the well known fact that the basic bismuth palmitate 4r is insoluble in oils (Picon, Loo. cit.).
The oily solutions of these salts have a very great stability and can be heated for a certain time at 120 C., without any decomposition; they can be-kept for a very long time without undergoing any change. Especially, it is noteworthy to observe the great stability, even at elevated temperatures, of the salts of bismuth with alkyl, aryl or aralkyl-thio-acids and the total absence of any reaction between the sulphur and the bismuth although, as is well-known, they have a very great amnity for one another.
According to the present invention, the sodium. salt of the particular acid is caused to react with bismuth nitrate dissolved in a mixture of water and glycerine. If only one or two molecules of the sodium salt are used for one molecule of bismuth nitrate, one or two molecules of soda are added in such a way that there are always three atoms of sodium for one atom of bismuth.
The alkyl (aryl or aralkyl) oxy (or thio) acids are prepared by saponification of the corresponding esters. The latter can be easily obtained by the action of sodium derivatives of alcohols (or phenols) or of the alkyl (aryl or aralkyl) mercaptides of sodium on the zit-halogenated acids.
The following examples serve to show how the invention can be carried out in practice, but it is understood that the invention is not limited to these examples:
Example 1.62.4 grammes of oz-DhBIIYlOXY- caproic acid are dissolved in a mixture of 300 cc. of normal soda and 450 grammes of glycerine; to this solution is added a solution of 48.5 grammes of bismuth nitrate in 50 cc. of water and '70 grammes of glycerine. The bismuth salt which separates is extracted by benzenes; then by the addition of olive oil and distillation of the benzene there is obtained an oily solution of the a-phenyloxycaporate of bismuth which is stable even at C.
By replacing the 62.4 grammes of aphenyloxycaproic acid in this example by 41.6 grammes or 20.8 grammes of the same acid, oily solutions can be obtained in the same way of the basic bismuth phenyloxycaproates (containing two or one molecules of the acid for one atom of bismuth) which are as stable as the preceding bismuth phenyloxycaproate.
The a-phenyloxycaproic acid can be obtained by saponification of ethyl-a-phenyloxycaproate. This ester can be prepared by the action of sodium phenate on .ethyl-a-bromocaproate in a manner analogous to that which is employed for ethyl-aphenyloxybutyrate (Luchmann, Berichte, vol. 29, page 1421) It distils at C., under a pressure of 7 mm.
Example 2.86.4 grammes of a-blltYlthiOlflllIiC acid (prepared by the .saponification of ethyl-@- butylthiolaurate) are dissolved in a mixture of 300 cc. of normal soda and 450 grammes of glycerine; to this solution is added a solution of 48.5 grammes of bismuth nitrate in 50 cc. of water and 70 grammes of glycerine. After extraction of the bismuth salt which is formed by benzene and the addition of olive oil, the benzene is distilled off and an oily solution is thus obtained of bismuth a-butylthiolaurate which is stable even at 120 C. I
By employing only 57.6 grammes or 28.8 grammes of a-butylthiolauric acid in place of the 86.4 grammes, one can in the same fashion prepare oily solutions of basic bismuth m-butylthiolaurate (containing two or one molecules of the acid for one atom of bismuth). These oily solutions can be very concentrated and can contain more than 20 grammes of bismuth per 100 cc. of solution; they are as stable as the preceding ones. The ethyl m-butylthiolaurate can be prepared in very good yields by the action of sodium butylmercaptide on ethyl a-bromolaurate in alcoholic solution. It distils at C., under a pressure of 5 mm.
Example 3.--62.4 grammes of a-butyloxyphenylacetic acid (prepared by the saponification of ethyl a-butyloxyphenyl acetate) are dissolved in a mixture of 300 cc. of normal soda and 450 grammes of glycerine; to this solution is added a solution of 48.5 grammes of bismuth nitrate in 50 cc. of water and 70 grammes of glycerine. To the benzene solution of the bismuth salt which is obtained by extraction with benzene, olive oil is added; after distillation of the benzene there remains a stable oily solution of the bismuth salt.
Ethyl a-butyloxyphenyl acetate can be prepared in good yields by the action of sodium butylate on ethyl phenylchloracetate. It distils at 169 C., under a pressure of 15 mm.
What we claim and desire to secure by Letters Patent is:--
1. As a new composition of matter, an oily solution, containing up to 20% of bismuth, stable at a temperature of 120 0., and not depositing any solid or liquid at ordinary temperatures, having as solute a salt of bismuth containing at least one acid radicle of the formula H OinHzr--OOzH C4H9-S 3. As a new composition of matter/an oily solution containing from 5 to 20% of bismuth in the form of mono-a-butyl-thiolaurate of bismuth, having the formula 4. As a new composition of matter, an oily solution containing from 5 to 20% of bismuth in the form of di-a-butyl-thiolaurate of bismuth,
having the formula 5. As a new composition of matter, an oily solution containing from 5 to 20% of bismuth in the form of tri-a-butyl-thiolaurate of bismuth, having the formula PAUL EIWILE CHARLES GOISSEDET. ROBERT LUDOVIC DESPOIS.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2009295X | 1932-05-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2009295A true US2009295A (en) | 1935-07-23 |
Family
ID=10895935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US624148A Expired - Lifetime US2009295A (en) | 1932-05-02 | 1932-07-22 | Oleaginous solutions of organic salts of bismuth |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2009295A (en) |
-
1932
- 1932-07-22 US US624148A patent/US2009295A/en not_active Expired - Lifetime
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