US2510740A - Tri-(cyclic-lower alkylene mercapto)-s-antimonous acids - Google Patents

Tri-(cyclic-lower alkylene mercapto)-s-antimonous acids Download PDF

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Publication number
US2510740A
US2510740A US792612A US79261247A US2510740A US 2510740 A US2510740 A US 2510740A US 792612 A US792612 A US 792612A US 79261247 A US79261247 A US 79261247A US 2510740 A US2510740 A US 2510740A
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United States
Prior art keywords
tri
antimonous
compounds
cyclic
compound
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Expired - Lifetime
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US792612A
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English (en)
Inventor
Le Roy W Clemence
Marlin T Leffler
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Abbott Laboratories
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Abbott Laboratories
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Application filed by Abbott Laboratories filed Critical Abbott Laboratories
Priority to US792612A priority Critical patent/US2510740A/en
Priority to US723907A priority patent/US2510738A/en
Priority to BE479768D priority patent/BE479768A/xx
Priority to CH276550D priority patent/CH276550A/fr
Priority to FR1018759D priority patent/FR1018759A/fr
Priority to NL138499A priority patent/NL67719C/xx
Priority to GB2173/48A priority patent/GB669304A/en
Priority to CH280921D priority patent/CH280921A/fr
Application granted granted Critical
Publication of US2510740A publication Critical patent/US2510740A/en
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Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/90—Antimony compounds
    • C07F9/902—Compounds without antimony-carbon linkages

Definitions

  • R1, R2 and R3 are organic radicals, either the same or different, each containing at least eight carbon atoms.
  • R1, R2 and R3 are hydrocarbon radicals each containing 8 to 18 carbon atoms inclusive.
  • antimoni'al compounds characterized by the above formula are active chemotherapeutic agents. They are effective, for example, in the treatment of certain tropical parasitic diseases, such as schistosomiasis.
  • the compounds of the present invention have the property of being soluble in oils, such as the fatty oils.
  • oils such as the fatty oils.
  • administration of the compounds for application as medicaments is very practical in oil mediums of this type.
  • the compounds of this invention may be resolved into three groupings.
  • the first group are the tri-(n-alkyl mercapto) S antimonous acids. These alkyl groups have from eight to eighteen carbon atoms.
  • the second grouping is the tri- (w-cyclic-alkyl-mercapto) -S-antimonous acids.
  • Group three has substituents similar to group two except that an alkyl chain and ether linkages exist in addition to the cyclic group.
  • the preparation of the compounds of the pres.- ent invention may be accomplished in several novel ways.
  • One way which has been successful is to dissolve one mole proportion of antimony trihalide in an inert solvent bywarming. This so-v lution is filtered into an equal quantity of an inert solvent miscible with the first solvent and containing three-mole proportions of the suitable R- mercaptan where the B group represents an organic radical as indicated above.
  • the resulting solution is distilled under vacuum until the solvents have been removed.
  • the residual oil is placed in a vacuum dryer over but not in contact with solid sodium hydroxide until the hydrohalic acid has been removed.
  • the general reaction of this process may be expressed as follows:
  • M is a cation selected from the group comprising hydrogen and alkali and alkaline earth metals, and a: is three divided by valence of M.
  • a: is three divided by valence of M.
  • halide as used in referring to an antimony trihalide throughout the specification cedure otherwise identical with that employing the chloride or the bromide, except that the iodide is employed, has not succeeded in causing the reaction to take place. It remains for some modified procedure to be found to cause the iodide reaction to be initiated and to proceed to completion. As compared to the trichloride and the tribromide, however, the cost would be very unfavorable due to the much higher cost of the triiodide.
  • Some of the compounds of the present invention have no exact physical constants such as melting point, boiling point, etc. Antimony analyses, however, demonstrate the compounds to be substantially pure. Most of the compounds are oils at room temperature, but those containing the higher R groups are often waxy substances either immediately after formation or upon standing. As the products are of an oily or waxy nature, solid halides may be removed by filtration and hydrohalides may be removed by volatilization.
  • the antimony trihalide with a mixture or blend of selected mercaptans or mercaptides in such a way that the resulting therapeutic product Will be an antimony compound containing substituted mercaptide groups in the approximate percentages present in the original blend but obviously may result in variable analyses for antimony.
  • Certain mercaptans are commercially in the form of mixtures having various hydrocarbon groups. For example, dodecyl mercaptan may have present decyl and tetradecyl mercaptans. Such products are suitable for use if reasonably pure and if not too much of non-mercaptans impurity is present.
  • the residual oil which smells slightly of hydrochloric acid formed during the reaction, is placed in a vacuum dryer over solid sodium hydroxide until all of the hydrochloric acid has been removed.
  • the product obtained is a clear, pale yellow oil which becomes a waxy solid on standing at room temperature.
  • the compound may be further solidified by cooling. Upon solidification it may be recrystallized from heptane giving a compound having a melting point of 38-40 C.
  • EXAMPLE IA Also, by using 10.0 gms. (0.05 mole) of the mercaptan and 6.03'gms. (0.017 mole) of antimony tribromide andproceeding as in Example I the compound tri- (n-dodecyl-mercapto) -S-antimonous acid is prepared.
  • cyclic alkyl compounds which have been prepared are those with the alkyl chain having from one to ten carbon atoms.
  • the preferred range of compounds includes those having from one to five carbon atoms because the compounds are relatively easier to prepare.
  • the cyclic group may be varied; it may be partially or totally saturated; it may be heterocyclic, also, it may be substituted.
  • the residual oil which smells slightly of hydrochloric acid formed during the reaction, is placed in a vacuum dryer over solid sodium hydroxide until all of the hydrochloric acid has been removed.
  • the product obtained is a clear, pale yellow oil which becomes a waxy solid on standing.
  • Tfi- (R -m e rcapto) -S-antimnous acids rate that the temperature remains below 0 C.
  • the mixture is next permitted to reach room temperature while being stirred. After standing' overnight it is heated to 100 C. for several hours.
  • the mixture is then cooled and poured sb-s-R, into 1,000 cc. of ice and water with agitation.
  • the heavy, oily layer is separatedand dissolved Antimony Content 3;, It; and R; Formula Theoretical Found Percent Percent n-Octyl- (11CaH11S):Sb 21. 9 20. 8 n-Decyl-. gfl-CwHflS-hSb 19. 0 l9.
  • the w-cyclic-alkyl alcohol is converted to the w-cyclic alkyl halide by means of a phosphorous halide or a hydrohalogen acid.
  • This halide is reacted with thiourea to form the w-cyclicalky1 isothiuronium halide.
  • This compound is hydrolyzed to the w-cyclic alkyl mercaptan by alkaline hydrolysis using a dilute base such as sodium hydroxide.
  • the B-(p-diisobutylphenoxyethoxy)-ethyl mercaptan used in making the last compound in the table may be prepared by the same synthesis. Namely, this involves converting the alcohol to the halide; reacting the halide with isothiourea and hydrolyzing this to the mercaptan.
  • the compounds of the invention may be prepared as described above.
  • these compounds may be prepared as follows:
  • EXAMPLE X w-TB-tetrdZy'l) butyl bromide In a manner analogous to that of Example VII but substituting w-(p-tetral'yl) butyl alcohol (prepared by hydrogenating ethyl w- (tetralyl) butyrate. This alcohol has a boiling point of 167 C. at mm. and a refractive index of 1.5391 at 25 C. as compared to the D line of sodium.) for wcyclohexylamyl alcohol; the above-mentioned compound is prepared.
  • the w-(c-tetralyl) butyl bromide obtained has a boiling point of 147-8 C. at 1 mm. pressure and a refractive index of 1.5528 at 25 C. when compared to the D line of sodium.
  • EXAMPLE XI -w-D8CdlfljlbtLtZ/Z bromide In a manner analogous to Example VII but substituting w-dec'alyl butyl alcohol (prepared by hydrogenating ethyl w-decalylbutyrate. This alcohol has a boiling point of 148-9 C. at 0.5 mm. pressure and a refractive index of 1.4919 at 25 C. when compared to the D line of sodium.) for a w-cyclohexylamyl alcohol; the above mentioned compound is obtained.
  • This w-decalylbutyl bromide has a boiling point of 121-3 C. and a refractive index of 15020 at 25 C. when-compared to the D line of'sodium.
  • Example XII the compound w-(e-tetra1yl) -butyl isothiuronium bromide (Example XII) may be converted to the above mercaptan.
  • This-compound has a boiling point of 143 C. at 0.8 mm. pressure and "has a refractive index of 1.5569 at 25 C. when compared with the D line of sodium.
  • Example XV w-Decalylbutyl mercaptan -C HaCHzCHgCHzSH Using the procedure described in Example IX, the compound w-decalylbutyl .isothiuronium bromide (Example XI-II) may be converted to the above-mentioned mercaptan.
  • This compound, w-decalylbutyl mercaptan has a boiling point of 124 C. at 0.5 mm. pressure.
  • halogen in the preparation of intermediates includes-the elements, chlorine, bromine and-iodine.
  • the compounds of the present invention may be incorporated into pharmaceutical vehicles, and since they are oil soluble, they may beeffectively administered in oil solutions.
  • the solutions may be prepared by dissolving the compounds in fatty or vegetable oils such as peanut, olive or :almond oil, 'indesired concentrations. Concentrations of about 10 per cent .havebeen found to be satisfactory.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US792612A 1947-01-27 1947-08-09 Tri-(cyclic-lower alkylene mercapto)-s-antimonous acids Expired - Lifetime US2510740A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US792612A US2510740A (en) 1947-08-09 1947-08-09 Tri-(cyclic-lower alkylene mercapto)-s-antimonous acids
US723907A US2510738A (en) 1947-08-09 1947-12-18 Oil soluble tri-(substituted-mercapto)-antimonous acids
BE479768D BE479768A (ko) 1947-08-09 1948-01-21
FR1018759D FR1018759A (fr) 1947-08-09 1948-01-22 Procédés de préparation de compositions thérapeutiques
CH276550D CH276550A (fr) 1947-08-09 1948-01-22 Procédé de préparation d'un composé stibié soluble dans les huiles.
NL138499A NL67719C (ko) 1947-08-09 1948-01-23
GB2173/48A GB669304A (en) 1947-08-09 1948-01-23 Improvements in or relating to tri-(substituted mercapto)-s-antimonious acids and intermediates therefor
CH280921D CH280921A (fr) 1947-01-27 1948-01-26 Magasin pour lames de rasoir de sûreté.

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US90847XA 1947-08-09 1947-08-09
US792612A US2510740A (en) 1947-08-09 1947-08-09 Tri-(cyclic-lower alkylene mercapto)-s-antimonous acids
US723907A US2510738A (en) 1947-08-09 1947-12-18 Oil soluble tri-(substituted-mercapto)-antimonous acids

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US723907A Expired - Lifetime US2510738A (en) 1947-01-27 1947-12-18 Oil soluble tri-(substituted-mercapto)-antimonous acids

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BE (1) BE479768A (ko)
CH (1) CH276550A (ko)
FR (1) FR1018759A (ko)
GB (1) GB669304A (ko)
NL (1) NL67719C (ko)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3530158A (en) * 1966-11-25 1970-09-22 M & T Chemicals Inc Organo antimony mercaptides and the preparation thereof
US4367304A (en) * 1979-11-08 1983-01-04 Ciba-Geigy Corporation Novel organic antimony-sulfur compounds and their use as stabilizers for chlorine-containing thermoplasts
WO2002024630A1 (en) * 2000-09-22 2002-03-28 Eli Lilly And Company Pharmaceutical compounds useful as modulators of endocannabinoid-mediated response

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2684956A (en) * 1952-02-25 1954-07-27 Metal & Thermit Corp Antimony mercaptide compounds and compositions containing same
DE1038276B (de) * 1954-03-10 1958-09-04 Metal & Thermit Corp Verfahren zur Stabilisierung chlorhaltiger Kunstharzmassen
BE566528A (ko) * 1958-04-05
US4279806A (en) * 1978-08-23 1981-07-21 Associated Lead Inc. Antimony mercaptides as processing stabilizers for vinyl halide resins
US4287118A (en) * 1978-08-23 1981-09-01 Associated Lead Inc. Antimony (V) mercaptides as processing stabilizers for vinyl halide resins and method of manufacturing same
GB2196004B (en) * 1986-09-03 1990-03-28 Sakai Chemical Industry Co Passivators used in catalytic cracking of hydrocarbons
US4830731A (en) * 1987-08-28 1989-05-16 Sakai Chemical Industry Co., Ltd. Passivators used in catalytic cracking of hydrocarbons

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1561535A (en) * 1924-12-10 1925-11-17 Farbenfab Vorm Bayer F & Co Pharmaceutical compound
US2226530A (en) * 1939-04-07 1940-12-31 Jensen Salsbery Lab Inc Sodium antimonyl-catecholthiosalicylate
US2229992A (en) * 1936-06-26 1941-01-28 Winthrop Chem Co Inc Antimony oleate

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2066742A (en) * 1929-12-12 1937-01-05 Winthrop Chem Co Inc Antimony compounds of polyhydroxy carboxylic acids and process of making them
CH169577A (de) * 1931-08-03 1934-05-31 Schering Kahlbaum Ag Verfahren zur Darstellung von 1-Antimonthioglucose.
AT149988B (de) * 1931-12-29 1937-06-25 Henkel & Cie Gmbh Verfahren zur Darstellung von höhermolekularen Äthern.
GB436742A (en) * 1934-05-09 1935-10-17 Rhone Poulenc Sa Improvements relating to the manufacture of therapeutically valuable antimony compounds
US2130321A (en) * 1934-05-14 1938-09-13 Lilly Co Eli Stabilization of sulphur-containing compounds and systems
US2137927A (en) * 1935-02-16 1938-11-22 Chem Fab Johann A Wulfing Process for obtaining metal compounds of water-soluble keratin splitting products
US2116182A (en) * 1935-03-01 1938-05-03 Ig Farbenindustrie Ag Production of mercaptans
US2180262A (en) * 1936-07-24 1939-11-14 Wuelfing J A Fa Process for preparing metal sulphhydryl compounds from keratin degradation products
US2250553A (en) * 1938-04-18 1941-07-29 Simon L Ruskin Medicinal preparation
US2402640A (en) * 1940-09-19 1946-06-25 Du Pont Chemical processes and product
US2374983A (en) * 1941-04-29 1945-05-01 Shell Dev Sulphur compounds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1561535A (en) * 1924-12-10 1925-11-17 Farbenfab Vorm Bayer F & Co Pharmaceutical compound
US2229992A (en) * 1936-06-26 1941-01-28 Winthrop Chem Co Inc Antimony oleate
US2226530A (en) * 1939-04-07 1940-12-31 Jensen Salsbery Lab Inc Sodium antimonyl-catecholthiosalicylate

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3530158A (en) * 1966-11-25 1970-09-22 M & T Chemicals Inc Organo antimony mercaptides and the preparation thereof
US4367304A (en) * 1979-11-08 1983-01-04 Ciba-Geigy Corporation Novel organic antimony-sulfur compounds and their use as stabilizers for chlorine-containing thermoplasts
WO2002024630A1 (en) * 2000-09-22 2002-03-28 Eli Lilly And Company Pharmaceutical compounds useful as modulators of endocannabinoid-mediated response

Also Published As

Publication number Publication date
FR1018759A (fr) 1953-01-30
BE479768A (ko) 1948-02-16
GB669304A (en) 1952-04-02
NL67719C (ko) 1951-04-16
US2510738A (en) 1950-06-06
CH276550A (fr) 1951-07-15

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