US1964696A - Complex compound of metals with aliphatic polyhydroxy-carboxylic acids and process of making the same - Google Patents
Complex compound of metals with aliphatic polyhydroxy-carboxylic acids and process of making the same Download PDFInfo
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- US1964696A US1964696A US581049A US58104931A US1964696A US 1964696 A US1964696 A US 1964696A US 581049 A US581049 A US 581049A US 58104931 A US58104931 A US 58104931A US 1964696 A US1964696 A US 1964696A
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- 150000001875 compounds Chemical class 0.000 title description 46
- 238000000034 method Methods 0.000 title description 28
- 230000008569 process Effects 0.000 title description 28
- 229910052751 metal Inorganic materials 0.000 title description 18
- 239000002184 metal Substances 0.000 title description 18
- 125000001931 aliphatic group Chemical group 0.000 title description 17
- 150000002739 metals Chemical class 0.000 title description 6
- -1 metal complex compounds Chemical class 0.000 description 93
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 62
- 239000000243 solution Substances 0.000 description 56
- 150000003839 salts Chemical class 0.000 description 55
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 51
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 43
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 38
- 125000004429 atom Chemical group 0.000 description 36
- 239000007864 aqueous solution Substances 0.000 description 31
- 229910052742 iron Inorganic materials 0.000 description 30
- 229910052787 antimony Inorganic materials 0.000 description 29
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 29
- 229910052797 bismuth Inorganic materials 0.000 description 29
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 29
- 229910052783 alkali metal Inorganic materials 0.000 description 27
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 25
- 150000001735 carboxylic acids Chemical class 0.000 description 25
- 239000000174 gluconic acid Substances 0.000 description 25
- 235000012208 gluconic acid Nutrition 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 159000000009 barium salts Chemical class 0.000 description 23
- 230000001376 precipitating effect Effects 0.000 description 23
- 239000002244 precipitate Substances 0.000 description 18
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 17
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 16
- 159000000007 calcium salts Chemical class 0.000 description 14
- 230000007935 neutral effect Effects 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000004411 aluminium Substances 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 11
- 229910052804 chromium Inorganic materials 0.000 description 11
- 239000011651 chromium Substances 0.000 description 11
- 150000002763 monocarboxylic acids Chemical class 0.000 description 11
- 150000001340 alkali metals Chemical class 0.000 description 10
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
- 150000001447 alkali salts Chemical class 0.000 description 9
- 239000007900 aqueous suspension Substances 0.000 description 9
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 8
- 229910001626 barium chloride Inorganic materials 0.000 description 8
- 229940050410 gluconate Drugs 0.000 description 8
- 150000004679 hydroxides Chemical class 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000012670 alkaline solution Substances 0.000 description 7
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 229910052788 barium Inorganic materials 0.000 description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- CZNVSLGYWMSMKE-OPDGVEILSA-K Ferric gluconate Chemical compound [Fe+3].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O CZNVSLGYWMSMKE-OPDGVEILSA-K 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001342 alkaline earth metals Chemical group 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229940032296 ferric chloride Drugs 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical class 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 2
- 239000003513 alkali Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- AQTIRDJOWSATJB-UHFFFAOYSA-K antimonic acid Chemical compound O[Sb](O)(O)=O AQTIRDJOWSATJB-UHFFFAOYSA-K 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- OGNVQLDIPUXYDH-ZPKKHLQPSA-N (2R,3R,4S)-3-(2-methylpropanoylamino)-4-(4-phenyltriazol-1-yl)-2-[(1R,2R)-1,2,3-trihydroxypropyl]-3,4-dihydro-2H-pyran-6-carboxylic acid Chemical compound CC(C)C(=O)N[C@H]1[C@H]([C@H](O)[C@H](O)CO)OC(C(O)=O)=C[C@@H]1N1N=NC(C=2C=CC=CC=2)=C1 OGNVQLDIPUXYDH-ZPKKHLQPSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical class CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 description 1
- UOQHWNPVNXSDDO-UHFFFAOYSA-N 3-bromoimidazo[1,2-a]pyridine-6-carbonitrile Chemical compound C1=CC(C#N)=CN2C(Br)=CN=C21 UOQHWNPVNXSDDO-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical class NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DSLZVSRJTYRBFB-UHFFFAOYSA-N Galactaric acid Natural products OC(=O)C(O)C(O)C(O)C(O)C(O)=O DSLZVSRJTYRBFB-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- ZUJVZHIDQJPCHU-UHFFFAOYSA-N [Ba].[Bi] Chemical compound [Ba].[Bi] ZUJVZHIDQJPCHU-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GXCZIRBNDQXAKR-OPDGVEILSA-K bis[[(2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanoyl]oxy]stibanyl (2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Sb+3].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O GXCZIRBNDQXAKR-OPDGVEILSA-K 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- RMPWRUZQAKINCP-OPDGVEILSA-K bismuth;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Bi+3].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RMPWRUZQAKINCP-OPDGVEILSA-K 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229960000359 chromic chloride Drugs 0.000 description 1
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical class CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- MKYNHKOAYQRSBD-UHFFFAOYSA-N dioxouranium;nitric acid Chemical compound O=[U]=O.O[N+]([O-])=O.O[N+]([O-])=O MKYNHKOAYQRSBD-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- DSLZVSRJTYRBFB-DUHBMQHGSA-N galactaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)C(O)=O DSLZVSRJTYRBFB-DUHBMQHGSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229940099563 lactobionic acid Drugs 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- YQDGWZZYGYKDLR-UZVLBLASSA-K sodium stibogluconate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].O1[C@H]([C@H](O)CO)[C@H](O2)[C@H](C([O-])=O)O[Sb]21([O-])O[Sb]1(O)(O[C@H]2C([O-])=O)O[C@H]([C@H](O)CO)[C@@H]2O1 YQDGWZZYGYKDLR-UZVLBLASSA-K 0.000 description 1
- 229960001567 sodium stibogluconate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
Definitions
- the present invention relates to aprocess of preparing metal complex compounds of aluminium, trivalent iron, trivalent chromium, antimony and bismuth with aliphatic polyhydroxy carboxylic acids and to the basic alkaline-earth metal salts of these complex compounds being intermediate products in the said process.
- Metal complex compounds for instance of aluminium, trivalent iron and antimony have already been prepared.
- the present invention provides a process to obtain metal complex compounds of aliphatic polyhydroxy carboxylic acids from their aqueous solutions in a pure, uniform state by Way of the basic alkaline-earth metal salts of the said metal complex compound being insoluble or sparingly soluble in water.
- complex compounds of aluminium, trivalent iron, trivalent chromium, antimony and bismuth which metals have proved equivalent in the process of our present invention, are prepared by first producing basic alkaline-earth metal salts being insoluble or sparingly soluble in water by precipitating these salts by the addition of an alkalineearth metal salt or hydroxide to an aqueous alkaline solution containing an aliphatic polyhydroxy carboxylic acid to which one of the metals above specified is linked in a complex like linkage, said aqueous alkaline solutions being prepared by the action of a salt or hydroxide of the metals specified on an alkaline solution of the aliphatic polyhydroxy carboxylic acid.
- the basic alkaline-earth metal salts of the metal complex compounds thus obtained in a uniform state are further transformed into their water-soluble alkali-, ammcniumor amine salts by double decomposition with alkali-, ammoniumor amine salts of such acids which yieldwith alkaline-earth metal ions salts insoluble or sparingly soluble in water.
- the basic alkalineearth metal salts of the metallic complex compounds may further be transformed into the corresponding water-soluble neutral alka1ine-earth metal salts by reacting thereupon with about 1 mol of the complex forming aliphatic polyhydroxy carboxylic acid.
- CeHvOvFeBa +NaI-ISO4 CsHsO7FeNa+BaSO4.
- the alkaline-earth metal cation substitutes in the insoluble alkaline-earth metal salts, which have been called basic salts, one hydrogen atom of the carboxylic group and another hydrogen atom of a hydroxyl group of the polyhydroxy carboxylic acid; however, in the alkali and alkaline-earth metal salts, which have been called neutral salts, the alkali-, alkalineearth metal cation respectively, substitute only the hydrogen atom of the carboxylic group.
- Our new process is advantageously performed by reacting upon an aqueous alkaline solution of the aliphatic polyhydroxy carboxylic acid with about 1 mol of a salt or hydroxide of aluminium, trivalent iron, trivalent chromium, antimony or bismuth and then adding about 1 mol of a salt or hydroxide of an alkaline-earth metal.
- the basic alkaline-earth metal salt of the metallic complex compound precipitated is separated from the liquid.
- alkali metal, ammonium or amine salts for the decomposition of the basic alkaline-earth metal salts of the metallic complex compound preferably the salts of the sulfuric, carbonic and oxalic acid, for example, sodium and potassium sulfate, bisulfate, carbonate, bicarbonate, oxalate or bioxalate, or the corresponding salts of ammonia, diethylamine, triethylamine, diethylaminoethanol, ethylenediamine and the like have proved suitable.
- the water-insoluble basic alkaline-earth metal salts of the metallic complex compounds may, as already mentioned, further be transformed into water-soluble products by reacting upon the said basic salts with about one equivalent of the aliphatic polyhydroxy carboxylic acid used as complex forming component in the complex compound.
- the neutral water-soluble alkaline-earth metal salt of the metallic complex compound thus produced may be separated from the solution by evaporating or precipitating by means of alcohol.
- reaction in general, performs at room temperature, however, sometimes heating is of advantage.
- the complex compounds of iron, antimony and bismuth preferably the sodium salts of such ones, as contain a polyhydroxy carboxylic acid derived from hexane as complex forming component, especially gluconic acid.
- the products obtainable in accordance with our invention may be used preferably for medicinal purposes, but they may also be employed for the general technical use.
- Example 1 To a solution of 4.2 parts of ferric-chloride (1 mol) in '70 parts of water 5 parts of gluconic acid and 42.5 parts of a 12% solution of caustic soda possibly free from carbonate (5 mols) are added. The mixture is then treated with a concentrated aqueous solution of 6.2 parts of crystallized barium chloride (1 mol),
- calcium-ferric-gluconates of another composition for instance, a salt containing upon 2 molecules of gluconic acid 1 atom of iron and 2 atoms of calcium and having accordingly the formula C12I-lmO14CazFe, and a further salt, containing upon 4 molecules of gluconic acid 3 atoms of iron and 6 atoms of calcium are obtainable.
- the described barium and calcium salts may be transformed into water-soluble compounds in the following manner:
- Basic barium-ferric-gluconate is made into an even paste with about the same quantity of water.
- the basic barium-ferric-gluconate may be transformed into a water-soluble compound by making into a paste with some water and decomposing in the same manner as indicated above with the equivalent quantity of ammonium bisulfate.
- the solution, separated 1 from the barium sulfate formed, is evaporated in vacuo.
- the ammonium-ferric-gluconate obtained in this manner is readily soluble in water with neutral reaction. It is a yellow powder containing upon 1 molecule of the acid 1 atom of iron and one ammonium group. It has the probable formula: NH4[O2CsHs(OH)2.03FB13CL, and accordingly probably the following structural formula:
- the neutral dimethylamine-ferric-glueonate is l V obtained when 8 parts of the basic barium-ferric- V barium sulfate from the filtrate, the neutral magnesium-ferric-gluconate readily soluble in water may be isolated by precipitation with alcohol. According to the analysis it is composed according to the formula: (Cel-lsovFelzMg-l-HzO.
- the basic barium-ferric gluconate may further be transformed into a water-soluble compond in the following manner:
- the mixture is kept boiling for some time and the precipitate is sucked off while hot and washed first with hot water, then with alcohol and ether.
- the air-dried compound according to the analysis corresponds to the formula
- the corre- 'sponding complex compounds with similar properties are obtained.
- Example 3.2 parts of gluconic acid,'22 parts of a 12% aqueous solution of caustic soda free from carbonate and 3.1 parts of bismuth chloride are mixed together in order to obtain an alkaline solution containing bismuth This solution is dropped into a heated and continually stirred solution of 2.4 parts of barium chloride in parts of water.
- the barium-bismuth-gluconate precipitating is separated from the liquid by suction. It is in the dry state a white powder insoluble in water. The yield amounts to 50-60%.
- Example 4 Into a boiling solution of 6 parts of gluc'onic acid in 45 parts of a 13% aqueous caustic soda solution 4.3 parts of antimony trioxide are introduced in small portions. When the antimony trioxide has been dissolved the solution is cooled and mixed with a solution of 7.2 parts of crystallized barium chloride in 25 parts of water. Thereby temporarily a precipitate appears, but afterthe addition of the wholequantity of the barium chloride the solution becomes completely clear.. On heating the solution to boiling the basic barium-antimony-gluconate separates in form of a white crystalline precipitate. It is sucked off while hot, since the pre-' cipitate dissolves again on cooling of the solution.
- the basic barium-antimony-gluconate has the formula:
- antimonic acid may be used for preparing the antimony complex compounds.
- antimonic acid is dissolved in an alkaline solution of gluconic acid and caustic soda and the solution is mixed with a barium chloride solution, a whitish powder separates, which may be isolated in the usual manner.
- Example 5 A concentrated aqueous solution of one part of gluconic acid is mixed with a solution of 1.4 parts of crystallized chromic chloride (containing crystal water) and then, while well shaking, with 8 parts of an about 13% aqueous caustic soda solution; The resulting clear green solution is diluted with some water. Thereto a solution of 1.2 parts of barium chloride in some water is added. Thereby thebasic barium-chromic-gluconate separates in form of a fine-crystalline green precipitate. After heating to boiling the precipitate is sucked off, washed with water, alcohol and acetone and driedon an unglazed'burned clay plate.
- the compound has the formula:
- Example 6 To a concentrated aqueous solution of 2 parts of gluconic acid a solution of 2.4 parts of crystallized aluminium chloride and while well shaking a solution of 2' parts of caustic soda in 15 parts of water are added. The clear solution is then mixed with a concentrated aqueous solution of 2.4 parts of crystallized barium chloride. Thereby the basic barium-aluminium-gluconate separates in form of white fine crystals. The precipitate is sucked off, washed with water, alcohol and acetone and dried on an unglazed burned clay plate.
- the new compound has the formula:
- the new compound is hygroscopic and readily soluble in Water and alcohol.
- steps which comprise precipitating from an aqueous solution of an alkali metal salt of. an aliphatic polyhydroxy carboxylic acid to which a metal of the group consisting of aluminium, trivalent iron, trivalent chromium, antimony and bismuth is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of an alkaline-earth metal compound selected from the group consisting of the water-soluble salts and the hydroxides thereof the basic alkaline-earth metal salt of the metal complex compound.
- steps which comprise precipitating from an aqueous solution of an alkali metal salt of 1 mol of a polyhydroxy carboxylic acid derived from hexane to which one gram atom of a metal selected from the group consisting of trivalent iron, antimony and bismuth is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of about 1 mol of a water-soluble alkaline-earth metal compound selected from the group consisting of the water-soluble salts and the hydroxides thereof the basic alkaline-earth metal salt of the metal complex compound.
- steps which comprise precipitating from an aqueous solution of an alkali metal salt of 1 mol of a polyhydroxy mono-carboxylic acid derived from hexane to which one gram atom of a metal selected from the group consisting of trivalent iron, trivalent antimony and bismuth is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of about 1 mol of a water-soluble calcium salt the basic calcium salt of the metal complex compound.
- the process which comprises precipitating from an aqueous solution of an alkali metal salt of an aliphatic polyhydroxy carboxylic acid to which a metal of the group consisting of aluminium, trivalent iron, trivalent chromium, antimony and bismuth is linked in complex like linkage, said solution containing an alkali metal hydroxide, by the addition of an alkaline-earth metal compound selected from the group consisting of the water-soluble salts and the hydroxides thereof the basic alkaline-earth metal salt of the metal complex compound, separating the basic salt, causing it to react in aqueous suspension with at least an equivalent of a salt selected from the group consisting of alkali metal ammonium and amine salts the anion of which salt forms with alkaline-earth metal ions salts difiicultly soluble in water and separating the insoluble precipitate formed.
- the process which comprises precipitating from an aqueous solution of an alkali metal salt of one mol of an aliphatic polyhydroxy carboxylic acid to which one gram atom of a metal selected from the group consisting of trivalent iron and antimony is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of about one mol of a water-soluble alkaline-earth metal compound selected from the group consisting of the water-soluble salts and the hydroxides thereof the basic alkaline-earth metal salt of the metal complex compound, separating the basic salt, causing it to react in aqueous suspension with at least an equivalent of a salt selected from the group consisting of alkali metal, ammonium and amine salts'the anion of which salt forms with alkaline-earth metal ions salts difiicultly soluble in water and separating the insoluble precipitate formed.
- the process which comprises precipitating from an aqueous solution of an alkali metal salt of one mol of a polyhydroxy carboxylic acid derived from hexane to which one gram atom of a metal selected from the group consisting of trivalent iron and antimony is linked in complex like linkage, said solution containing alkai metal hydroxide, by the addition of about one mol of a water-soluble alkaline-earth metal compound selected from the group consisting of the watersoluble salts and the hydroxides thereof the basic alkaline-earth metal salt of the metal complex compound, separating the basic salt, causing it to react in aqueous suspension with at least an equivalent of a salt selected from the group consisting of alkali metal, ammonium and amine salts the anion of which salt forms with alkalineearth metal ions salts dimcultly soluble in water and separating the insoluble precipitate formed.
- the process which comprises precipitating from an aqueous solution of an alkali metal salt of one mol of a polyhydroxy mono-carboxylic acid derived from hexane to which one gram atom of trivalent iron is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of about one mol of a water-soluble calcium salt the basic calcium salt of the ferric complex compound, separating the basic calcium salt, causing it to react in aqueous suspension with at least an equivalent of an alkali metal sulfate and separating the calcium sulfate formed.
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Description
Patented June 26, 1934 COMPLEX COMPOUND OF METALS WITH ALIPHATIC POLYHYDROXY-CARBOXYLIC ACIDS AND PROCESS OF MAKING THE SAME Wilhelm Traube and Fritz Kuhbier, Berlin, Germany, assignors to Winthrop Chemical Company, Inc., New York, N. Y., a corporation of New York No Drawing. Application December 14, 1931, Serial No. 581,049. In Germany March 21,
32 Claims. (Cl. 260-11) The present invention relates to aprocess of preparing metal complex compounds of aluminium, trivalent iron, trivalent chromium, antimony and bismuth with aliphatic polyhydroxy carboxylic acids and to the basic alkaline-earth metal salts of these complex compounds being intermediate products in the said process.
Metal complex compounds, for instance of aluminium, trivalent iron and antimony have already been prepared.
The present invention provides a process to obtain metal complex compounds of aliphatic polyhydroxy carboxylic acids from their aqueous solutions in a pure, uniform state by Way of the basic alkaline-earth metal salts of the said metal complex compound being insoluble or sparingly soluble in water.
In accordance with the present invention complex compounds of aluminium, trivalent iron, trivalent chromium, antimony and bismuth, which metals have proved equivalent in the process of our present invention, are prepared by first producing basic alkaline-earth metal salts being insoluble or sparingly soluble in water by precipitating these salts by the addition of an alkalineearth metal salt or hydroxide to an aqueous alkaline solution containing an aliphatic polyhydroxy carboxylic acid to which one of the metals above specified is linked in a complex like linkage, said aqueous alkaline solutions being prepared by the action of a salt or hydroxide of the metals specified on an alkaline solution of the aliphatic polyhydroxy carboxylic acid. The basic alkaline-earth metal salts of the metal complex compounds thus obtained in a uniform state are further transformed into their water-soluble alkali-, ammcniumor amine salts by double decomposition with alkali-, ammoniumor amine salts of such acids which yieldwith alkaline-earth metal ions salts insoluble or sparingly soluble in water.
It may be mentioned that the basic alkalineearth metal salts of the metallic complex compounds may further be transformed into the corresponding water-soluble neutral alka1ine-earth metal salts by reacting thereupon with about 1 mol of the complex forming aliphatic polyhydroxy carboxylic acid.
When using in our new process, for instance, an aqueous alkaline solution of ferric-gluconate,
the formation of the basic barium salt proceeds in accordance with the following probable equation:
CsI-I1207+ FeCls +BaC12 5NaOH= Csl-l'zO'zFeBa 5NaCl 5H20.
When transforming the above basic barium salt into the corresponding water-soluble sodium salt the process proceeds probably for instance according to the following equation:
CeHvOvFeBa +NaI-ISO4=CsHsO7FeNa+BaSO4.
The above formula correspond to the result of the analysis.
More graphic formulae would probably be for the basic barium salt the formula:
which may be further explained by the following structural formula:
Fe for the sodium salt-the formula:
Na [O2CeHe (OH) zOsFe] aq.,
which may be further explained by the following structural formula:
CHH.CH.CH.OHOH.OHOH.C O ONa aq.,
Fe for the neutral barium salt the formula:
which may be further explained by the following structural formula:
Ba aq.,
As is to be seen from the above formulae, we presume that the alkaline-earth metal cation substitutes in the insoluble alkaline-earth metal salts, which have been called basic salts, one hydrogen atom of the carboxylic group and another hydrogen atom of a hydroxyl group of the polyhydroxy carboxylic acid; however, in the alkali and alkaline-earth metal salts, which have been called neutral salts, the alkali-, alkalineearth metal cation respectively, substitute only the hydrogen atom of the carboxylic group.
In a similar manner as described above for the production and further transformation of the basic barium ferric-gluconate the process proceeds when using instead of gluconic acid other aliphatic polyhydroxy carboxylic acids and instead of the iron complex compound the corresponding complex compounds of aluminium, trivalent chromium, antimony and bismuth; further instead of a barium salt or barium hydroxide a calciumor strontium salt or hydroxide may be employed. As complex forming polyhydroxy carboxylic acids further may be used, for instance, glyceric-, tartaric-, arabic-, mucic-, saccharic, glucoheptonic-, mannoheptonic, lactobionicacid and the like. As is to be seen from the above formulae in our metal complex compounds about one atom of. aluminium, trivalent iron, trivalent chromium, antimony or bismuth is contained in one molecule of the complex forming hydroxy carboxylic acid and one alkali or alkaline-earth metal atom is bound chiefly by the carboxylic group. This result is in general obtained when reacting upon one mol of the polyhydroxy carboxylic acid with about one mol of a salt or hydroxide of one of the metals specified and adding about one mol of the alkaline-earth metal compound to the solution obtained in order to precipitate the insoluble basic alkaline-earth metal salt. Also in such cases where dicarboxylic acids are employed sometimes no more of the alkaline-earth metal compound is required for the precipitation of the insoluble basic salt. In general, of course, it is advantageous to use a water-soluble alkaline-earth metal salt or hydroxide when precipitating the metal complex compounds as basic alkaline-earth metal salts.
Our new process is advantageously performed by reacting upon an aqueous alkaline solution of the aliphatic polyhydroxy carboxylic acid with about 1 mol of a salt or hydroxide of aluminium, trivalent iron, trivalent chromium, antimony or bismuth and then adding about 1 mol of a salt or hydroxide of an alkaline-earth metal. The basic alkaline-earth metal salt of the metallic complex compound precipitated is separated from the liquid. In order to transform it into a water-soluble product it is decomposedin an aqueous suspension while shaking or stirring with an equivalent quantity of an alkali metal, ammonium or amine salt of an acid which forms water-insoluble salts with alkaline-earth metal ions, for example, with alkali metal ammonium or amine sulfates, bisulfates, carbonates, bicarbonates or oxalates. When the whole quantity of the alkaline-earth metal present in the mixture is transformed into the water-insoluble alkalineearth metal salt, the latter salt is separated from the mixture. From the filtrate the alkali metal, ammonium or amine salt of the metallic complex compound produced may be obtained by evaporating or by precipitating by means of alcohol.
As alkali metal, ammonium or amine salts for the decomposition of the basic alkaline-earth metal salts of the metallic complex compound preferably the salts of the sulfuric, carbonic and oxalic acid, for example, sodium and potassium sulfate, bisulfate, carbonate, bicarbonate, oxalate or bioxalate, or the corresponding salts of ammonia, diethylamine, triethylamine, diethylaminoethanol, ethylenediamine and the like have proved suitable.
The water-insoluble basic alkaline-earth metal salts of the metallic complex compounds may, as already mentioned, further be transformed into water-soluble products by reacting upon the said basic salts with about one equivalent of the aliphatic polyhydroxy carboxylic acid used as complex forming component in the complex compound. The neutral water-soluble alkaline-earth metal salt of the metallic complex compound thus produced may be separated from the solution by evaporating or precipitating by means of alcohol.
The reaction, in general, performs at room temperature, however, sometimes heating is of advantage. Of particular value we consider the production, according to our new process, of the complex compounds of iron, antimony and bismuth, preferably the sodium salts of such ones, as contain a polyhydroxy carboxylic acid derived from hexane as complex forming component, especially gluconic acid.
The products obtainable in accordance with our invention may be used preferably for medicinal purposes, but they may also be employed for the general technical use.
The following examples illustrate our invention without restricting it thereto, the parts being by weight.
Example 1.To a solution of 4.2 parts of ferric-chloride (1 mol) in '70 parts of water 5 parts of gluconic acid and 42.5 parts of a 12% solution of caustic soda possibly free from carbonate (5 mols) are added. The mixture is then treated with a concentrated aqueous solution of 6.2 parts of crystallized barium chloride (1 mol),
whereby a yellow precipitate of barium-ferricgluconate of the formula CsHqovFeBa. aq. separates.
When treating a solution of ferric chloride, gluconic acid and caustic soda prepared in accordance with the above directions with a conif.
centrated aqueous solution of 2.8 parts of calcium chloride (free from water) the basic calciumferric-gluconate of the formula CsHqO7FeCa. aq. is obtained. In order to obtain a very good yield of this salt. it is necessary to heat the solution ii-t;
the calcium salt but in suitably chosen other proportions calcium-ferric-gluconates of another composition, for instance, a salt containing upon 2 molecules of gluconic acid 1 atom of iron and 2 atoms of calcium and having accordingly the formula C12I-lmO14CazFe, and a further salt, containing upon 4 molecules of gluconic acid 3 atoms of iron and 6 atoms of calcium are obtainable.
The described barium and calcium salts may be transformed into water-soluble compounds in the following manner:
Basic barium-ferric-gluconate is made into an even paste with about the same quantity of water.
After cooling to the mixture so much of a concentrated potassium bisulfate solution is added as is required for the transformation of all barium into barium sulfate. When the decomposition is complete the mixture is centrifuged from the barium sulfate. A concentrated solution of the neutral postassium-ferric-gluconate containing upon 1 molecule of the acid 1 atom each of potassium and iron is thus obtained. The salt is separated from the solution by the addition of amine-bisulfate solution).
alcohol. It has the probable formula:
K[O2C6Hs(OH) 2.03F8] aq.,
and accordingly probably the following structural formula:
({3H2.CH.OH.OH.CH.COOK. aq.
O OH H Alternatively, the basic barium-ferric-gluconate may be transformed into a water-soluble compound by making into a paste with some water and decomposing in the same manner as indicated above with the equivalent quantity of ammonium bisulfate. The solution, separated 1 from the barium sulfate formed, is evaporated in vacuo. The ammonium-ferric-gluconate obtained in this manner is readily soluble in water with neutral reaction. It is a yellow powder containing upon 1 molecule of the acid 1 atom of iron and one ammonium group. It has the probable formula: NH4[O2CsHs(OH)2.03FB13CL, and accordingly probably the following structural formula:
CH2.OH.CH.CH.CH.C O ONH4.aq.
O O H OH The neutral dimethylamine-ferric-glueonate is l V obtained when 8 parts of the basic barium-ferric- V barium sulfate from the filtrate, the neutral magnesium-ferric-gluconate readily soluble in water may be isolated by precipitation with alcohol. According to the analysis it is composed according to the formula: (Cel-lsovFelzMg-l-HzO.
The basic barium-ferric gluconate may further be transformed into a water-soluble compond in the following manner:
Into a concentrated aqueous solution containing about -30% of gluconic acid basic bariumferric-gluconate is introduced in small portions until the acid reaction of the liquid has disappeared. The iormed salt at first readily dissolves on stirring. In order to dissolve the rest, gentle heating of the liquid is required. From the finally resulting viscous solution a precipitate of neutral barium-ierric-gluconate separates on the addition of alcohol, which readily changes to a powder on kneading. It contains upon 2 molecules of gluconic acid 1 atom each of iron and barium and corresponds to the probable formula:
Ba [C1zH19O1-1Fe] aq., and probably to the following structural formula;
omoncnon-o H.CH-OH.C oomoo (105111105. aq.
When decomposing this soluble barium salt with calcium sulfate the corresponding calcium-ferricgluconate is obtained according to the following equation:
The basic calcium-ferric-gluconate of the formula: ChzHwOnCazFe, above mentioned is transformed into a soluble compound in the following manner: 2
To a concentrated aqueous solution of 2- molecules of gluconic acid 1 molecule of the basic calcium-ferric-gluconate is added in small portions. It dissolves without leaving a residue when finely ground and gently heated. Alcohol precipitates from the solution thus obtained a light yellow salt, readily soluble in water with neutral reaction, containing upon 4 molecules of gluconic acid 2 atoms of calcium and 1 atom of iron. It has the probable formula Example 2.-1 part of mucic acid is dissolved in parts of a '7-8% aqueous solution of caustic soda and to this solution 2.6 parts of a 67% aqueous ferric chloride solution are added. When adding to the liquid a solution of 0.5 parts of barium chloride in 10 parts of water a white precipitate appears temporarily. The clear solution when heated to boiling, separates a durable whitish precipitate. The mixture is kept boiling for some time and the precipitate is sucked off while hot and washed first with hot water, then with alcohol and ether. The air-dried compound according to the analysis corresponds to the formula When using instead of mucio acid in the above example corresponding quantities of, for instance, saccharic or galaetoni'c acid, the corre- 'sponding complex compounds with similar properties are obtained.
. Example 3.2 parts of gluconic acid,'22 parts of a 12% aqueous solution of caustic soda free from carbonate and 3.1 parts of bismuth chloride are mixed together in order to obtain an alkaline solution containing bismuth This solution is dropped into a heated and continually stirred solution of 2.4 parts of barium chloride in parts of water. The barium-bismuth-gluconate precipitating is separated from the liquid by suction. It is in the dry state a white powder insoluble in water. The yield amounts to 50-60%.
From the above insoluble basic salt a watersoluble product is obtained in the following manner:
Into a concentrated aqueous solution of gluconic acid so much of the difiicultly soluble basic barium-bismuth-gluconate is introduced while gently heating as is dissolved by the solution. The solution obtained, if necessary after filtration, is poured into alcohol, whereby a soluble barium-bismuth gluconate separates, which con tains the double quantity of gluconic acid than the difiicultly soluble salt.
Example 4.-Into a boiling solution of 6 parts of gluc'onic acid in 45 parts of a 13% aqueous caustic soda solution 4.3 parts of antimony trioxide are introduced in small portions. When the antimony trioxide has been dissolved the solution is cooled and mixed with a solution of 7.2 parts of crystallized barium chloride in 25 parts of water. Thereby temporarily a precipitate appears, but afterthe addition of the wholequantity of the barium chloride the solution becomes completely clear.. On heating the solution to boiling the basic barium-antimony-gluconate separates in form of a white crystalline precipitate. It is sucked off while hot, since the pre-' cipitate dissolves again on cooling of the solution. Before separating the precipitate from the liquid, the latter is kept boiling for some time. The precipitate remaining on the filter is washed with hot water, then with alcohol and acetone and dried on an unglazed burned clay plate. According to the analysis the basic barium-antimony-gluconate has the formula:
CsHvOvSbLBa-l- 3H2O.
CizI-ImOrrSbaCzHsNz aq.
separates. It is readily soluble in water.
When using instead of ethylenediamine sulfate sodium sulfate the sodium-antimony-gluconate of the probable formula: CeHsO7SbNa-l-aq. is obtained.
In a similar manner instead of antimony trioxide, antimonic acid may be used for preparing the antimony complex compounds. When, for example, antimonic acid is dissolved in an alkaline solution of gluconic acid and caustic soda and the solution is mixed with a barium chloride solution, a whitish powder separates, which may be isolated in the usual manner.
Example 5.-A concentrated aqueous solution of one part of gluconic acid is mixed with a solution of 1.4 parts of crystallized chromic chloride (containing crystal water) and then, while well shaking, with 8 parts of an about 13% aqueous caustic soda solution; The resulting clear green solution is diluted with some water. Thereto a solution of 1.2 parts of barium chloride in some water is added. Thereby thebasic barium-chromic-gluconate separates in form of a fine-crystalline green precipitate. After heating to boiling the precipitate is sucked off, washed with water, alcohol and acetone and driedon an unglazed'burned clay plate. The compound has the formula:
In order to transform the Water-insoluble basic barium-chromic-gluconate into the water-soluble neutral barium-chromic-gluconate, 2 parts .of the former salt are dissolved in a concentrated aqueous solution of about 0.9-1.0 parts of gluconic acid while gently heating. From the clear solution obtained alcohol precipitates the neutral water-soluble barium-chromic-gluconate of the formula:
Example 6.-To a concentrated aqueous solution of 2 parts of gluconic acid a solution of 2.4 parts of crystallized aluminium chloride and while well shaking a solution of 2' parts of caustic soda in 15 parts of water are added. The clear solution is then mixed with a concentrated aqueous solution of 2.4 parts of crystallized barium chloride. Thereby the basic barium-aluminium-gluconate separates in form of white fine crystals. The precipitate is sucked off, washed with water, alcohol and acetone and dried on an unglazed burned clay plate. The new compound has the formula:
In order to transform the water-insoluble basic barium-aluminium-gluconate into a neutral water-soluble salt, 10 parts of the former salt are made into a paste with 6 parts of water. After cooling to 6 C. the paste is mixed with so much of a concentrated aqueous solution of tetraethylammonium-bisulf ate as is required for the precipitation of the barium in the form of barium sul-' fate. The filtrate from the barium sulfate is evaporated to dryness, whereby the neutral tetraethylammonium-aluminium-gluconate of the formula:
remains. The new compound is hygroscopic and readily soluble in Water and alcohol.
' While we have described our invention in great detail and with respect to preferred embodiments thereof, We do not desire to limit ourselves to such details or embodiments, since many modifications and changes may be made and the invention embodied in widely different forms without departing from the spirit or scope of the invention in its broadest aspects. Hence we desire to cover all modifications and forms within the scope or language of any one or more of the appended claims. 1
We claim:
1. In the process of preparing metal complex compounds the; steps which comprise precipitating from an aqueous solution of an alkali metal salt of. an aliphatic polyhydroxy carboxylic acid to which a metal of the group consisting of aluminium, trivalent iron, trivalent chromium, antimony and bismuth is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of an alkaline-earth metal compound selected from the group consisting of the water-soluble salts and the hydroxides thereof the basic alkaline-earth metal salt of the metal complex compound.
2. In the process of preparing metal complex compounds the steps which comprise precipitating from an aqueous solution of an alkali metal salt of a polyhydroxy carboxylic acid derived from hexane to which a metal of the group consisting of aluminium, trivalent iron, trivalent chromium, antimony and bismuth is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of an alkaline-earth metal compound selected from the group consisting of the water-soluble salts and the hydroxides thereof the basic alkaline-earth metal salt of the metal complex compound.
3. In the process of preparing complex compounds the steps which comprise precipitating from an aqueous solution of an alkali metal salt one mol of an aliphatic polyhydroxy carboxylic acid to which 1 gram atom of a metal selected from the group consisting of trivalent iron, antimony and bismuth is linked in complex like linkage, said solution containing alkali metal hydroxide by the addition of about 1 mol of a watersoluble alkaline-earth metal compound selected from the group consisting of the water-soluble salts and the hydroxides thereof the basic alkaline-earth metal salt of the metal complex compound.
4. In the process of preparing metal complex compounds the steps which comprise precipitating from an aqueous solution of an alkali metal salt of 1 mol of a polyhydroxy carboxylic acid derived from hexane to which one gram atom of a metal selected from the group consisting of trivalent iron, antimony and bismuth is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of about 1 mol of a water-soluble alkaline-earth metal compound selected from the group consisting of the water-soluble salts and the hydroxides thereof the basic alkaline-earth metal salt of the metal complex compound.
5. In the process of preparing metal complex compounds the steps which comprise precipitating from an aqueous solution of an alkali metal salt of 1 mol of a polyhydroxy mono-carboxylic acid derived from hexane to which one gram atom of a metal selected from the group consisting of trivalent iron, trivalent antimony and bismuth is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of about 1 mol of a water-soluble calcium salt the basic calcium salt of the metal complex compound.
6. In the process of preparing ferric complex compounds the steps which comprise precipitating from an aqueous solution of an alkali metal salt of one mol of gluconic acid to which one gram atom of trivalent iron is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of about 1 mol of a water-soluble calcium salt the basic calcium salt of the ferric complex compound.
7. In the process of preparing antimony complex compounds the steps which comprise precipitating from an aqueous solution of an alkali metal salt of one mol of a polyhydroxy monocarboxylic acid derived from hexane to which one gram atom of trivalent antimony is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of about one mol of a water-soluble barium salt the basic barium salt of the antimony complex compound.
8. In the process of preparing antimony complex compounds the steps which comprise precipitating from an aqueous solution of an alkali metal salt of one mol of gluconic acid to which one gram atom of trivalent antimony is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of about one mol of a Water-soluble barium salt the basic barium salt of the antimony complex compound.
9. In the process of preparing bismuth complex compounds the steps which comprise precipitating from an aqueous solution of an alkali metal salt of one mole of a polyhydroxy mono-carboxylic acid derived from hexane to which one gram atom of bismuth is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of about one mol of a water-soluble barium salt the basic barium salt of the bismuth complex compound.
10. In the process of preparing bismuth complex compounds the steps which comprise precipitating from an aqueous solution of an alkali metal salt of one mol of gluconic acid to which one gram atom of bismuth is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of about one mol of a Water-soluble barium salt the basic barium salt of the bismuth complex compound.
11. The process which comprises precipitating from an aqueous solution of an alkali metal salt of an aliphatic polyhydroxy carboxylic acid to which a metal of the group consisting of aluminium, trivalent iron, trivalent chromium, antimony and bismuth is linked in complex like linkage, said solution containing an alkali metal hydroxide, by the addition of an alkaline-earth metal compound selected from the group consisting of the water-soluble salts and the hydroxides thereof the basic alkaline-earth metal salt of the metal complex compound, separating the basic salt, causing it to react in aqueous suspension with at least an equivalent of a salt selected from the group consisting of alkali metal ammonium and amine salts the anion of which salt forms with alkaline-earth metal ions salts difiicultly soluble in water and separating the insoluble precipitate formed.
12. The process which comprises precipitating from an aqueous solution of an alkali metal salt of a polyhydroxy carboxylic acid derived from hexane to which a metal of the group consisting of aluminium, trivalent iron, trivalent chromium, antimony and bismuth is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of an alkaline-earth metal compound selected from the group consisting of the water-soluble salts and the hydroxides thereof the basic alkaline-earth metal salt of the metal complex compound, separating the basic salt, causing it to react in aqueous suspension with at least an equivalent of a salt selected from the group consisting of alkali metal, ammonium and amine salts the anion of which salt forms with alkaline-earth metal ions salts difficultly soluble in water and separating the insoluble precipitate formed.
13. The process which comprises precipitating from an aqueous solution of an alkali metal salt of one mol of an aliphatic polyhydroxy carboxylic acid to which one gram atom of a metal selected from the group consisting of trivalent iron and antimony is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of about one mol of a water-soluble alkaline-earth metal compound selected from the group consisting of the water-soluble salts and the hydroxides thereof the basic alkaline-earth metal salt of the metal complex compound, separating the basic salt, causing it to react in aqueous suspension with at least an equivalent of a salt selected from the group consisting of alkali metal, ammonium and amine salts'the anion of which salt forms with alkaline-earth metal ions salts difiicultly soluble in water and separating the insoluble precipitate formed.
14. The process which comprises precipitating from an aqueous solution of an alkali metal salt of one mol of a polyhydroxy carboxylic acid derived from hexane to which one gram atom of a metal selected from the group consisting of trivalent iron and antimony is linked in complex like linkage, said solution containing alkai metal hydroxide, by the addition of about one mol of a water-soluble alkaline-earth metal compound selected from the group consisting of the watersoluble salts and the hydroxides thereof the basic alkaline-earth metal salt of the metal complex compound, separating the basic salt, causing it to react in aqueous suspension with at least an equivalent of a salt selected from the group consisting of alkali metal, ammonium and amine salts the anion of which salt forms with alkalineearth metal ions salts dimcultly soluble in water and separating the insoluble precipitate formed.
15. The process which comprises precipitating from an aqueous solution of an alkali metal salt of one mol of a polyhydroxy mono-carboxylic acid derived from hexane to which one gram atom of trivalent iron is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of about one mol of a water-soluble calcium salt the basic calcium salt of the ferric complex compound, separating the basic calcium salt, causing it to react in aqueous suspension with at least an equivalent of an alkali metal sulfate and separating the calcium sulfate formed.
16. The process which comprises precipitating from an aqueous solution of an alkali metal saltof one mol of gluconic acid to which one gram atom of trivalent iron is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of about one mol of a water-soluble calcium salt the basic calcium salt of the ferric complex compound, separating the basic calcium salt, causing it to react in aqueous suspension with at least an equivalent of an alkali metal sulfate and separating the calcium sulfate formed.
17. The process which comprises precipitating from an aqueous solution of an alkali metal salt of one mol of a polyhydroxy mono-carboxylic acid derived from hexane to which one gram atom of trivalent antimony is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of about one mol of a water-soluble barium salt the, basic barium salt of the antimony complex compound, separating the basic barium salt, causing it to react in aqueous suspension with at least an equivalent of an alkali metal sulfate and separating the barium sulfate formed.
18. The process which comprises precipitating from an aqueous solution of an alkali metal salt one mol of gluconic acid to which one gram atom of trivalent antimony is linked in complex like linkage, said solution containing alkali metal hydroxide, by the addition of about one mol of a barium salt the basic barium salt of the antimony complex compound, separating the basic salt, causing it to react in aqueous suspension with at least an equivalent of an alkali metal sulfate and separating the barium sulfate formed.
19. A basic alkaline-earth metal salt of a metal complex compound wherein a metal of the group consisting of aluminium, trivalent iron, trivalent chromium, antimony and bismuth is linked in a complex like manner to an aliphatic polyhydroxy mono-carboxylic acid, said salt being diflicultly soluble in water.
20. A basic alkaline-earth metal salt of a metal complex compound wherein a metal of the group consisting of aluminium, trivalent iron, trivalent chromium, antimony and bismuth is linked in a complex like manner to a polyhydroxy monocarboxylic acid derived from hexane, said salt being difiicultly soluble in water. r
21. A basic alkaline-earth metal salt of a ferric complex compound wherein one atom of trivalent iron is linked in a complex like manner to one molecule of an aliphatic polyhydroxy carboxylic acid, said salt being difiicultly soluble in water.
22. A basic alkaline-earth metal salt of a ferric complex compound wherein one atom of trivalent iron is linked in a complex like manner to one molecule of a polyhydroxy carboxylic acid derived from hexane, said salt being diificultly soluble in water.
23. A basic calcium salt of a ferric complex compound wherein one atom of trivalent iron is linked in a complex like manner to one molecule of a polyhydroxy mono-carboxylic acid derived from hexane, said salt being difiicultly soluble in water.
24. The basic calcium salt of ferric gluconate wherein one atom of trivalent iron is linked in a complex like manner to one molecule of gluconic acid, said salt being diflicultly soluble in water.
25. Basic alkaline-earth metal salts of antimony complex compounds wherein one atom of antimony is linked in a complex like manner to one molecule of an aliphatic polyhydroxy monocarboxylic acid, said salts being difiicultly soluble in water.
26. Basic alkaline-earth metal salts of antimony complex compounds wherein one atom of antimony is linked in a complex like manner to a polyhydroxy carboxylic acid derived from hexane, said salts being difficultly soluble in water.
27. Basic barium salts of antimony complex compounds wherein one atom of trivalent antimony is linked in a complex like manner to one molecule of a polyhydroxy mono-carboxylic acid derived from hexane, said salts being difficultly soluble in water.
28. The basic barium salt of antimony gluconate wherein one atom of trivalent antimony is linked in a complex like manner to one molecule of gluconic acid, said salt being diflicultly soluble in water.
29. Basic alkaline earth metal salts of bismuth complex compounds wherein one atom of bismuth is linked in a complex like manner to one molecule of an aliphatic polyhydroxy carboxylic acid, said salts being difficultly soluble in water.
30. Basic alkaline-earth metal salts of bismuth complex compounds wherein one atom of bismuth is linked in a complex like manner to one molecule of a polyhydroxy carboxylic acid derived from hexane, said salts being diflicultly soluble in water.
31. Basic barium salts of bismuth complex compounds wherein one atom of bismuth is linked in a complex like manner to one molecule of a polyhydroxy mono-carboxylic acid derived from hexane, said salts being difilcultly soluble 5 in water.
32. The basic barium salt of bismuth gluconate wherein one atom of bismuth is linked in a complex like manner to one molecule of gluconic acid, said salt being difiicultly soluble in water. a
W'ILHELM TRAUBE. FRITZ KUHBIER.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1964696X | 1930-03-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1964696A true US1964696A (en) | 1934-06-26 |
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ID=7811585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US581049A Expired - Lifetime US1964696A (en) | 1930-03-21 | 1931-12-14 | Complex compound of metals with aliphatic polyhydroxy-carboxylic acids and process of making the same |
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| Country | Link |
|---|---|
| US (1) | US1964696A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2446981A (en) * | 1945-12-06 | 1948-08-10 | Vick Chemical Company | Aluminum hydroxide antacid composition |
| US2473735A (en) * | 1942-03-24 | 1949-06-21 | Burroughs Wellcome Co | Manufacture of complex organic antimony compounds |
| US2503781A (en) * | 1946-04-09 | 1950-04-11 | Reed & Carnrick | Organic iron alkali metal complexes |
| US2544667A (en) * | 1946-04-27 | 1951-03-13 | Du Pont | Werner-type chromium compounds as laminating and coating compositions |
| US2823144A (en) * | 1956-06-07 | 1958-02-11 | Du Pont | Aluminum complexes and process for preparing the same |
| US2869978A (en) * | 1955-09-26 | 1959-01-20 | Union Oil Co | Method of gas purification utilizing an amine solution and an anti-corrosion agent |
| US2904572A (en) * | 1956-11-26 | 1959-09-15 | Cfmc | New water-soluble complexes and a process for their preparation |
| US4331518A (en) * | 1981-01-09 | 1982-05-25 | Vulcan Materials Company | Bismuth composition, method of electroplating a tin-bismuth alloy and electroplating bath therefor |
| US4705876A (en) * | 1985-12-31 | 1987-11-10 | Vsesojuznoe Nauchno-Proizvodstvennoe Obiedinenie Tselljuloznobumazhnoy Promyshlennosti | Process for preparing powder-like iron-sodium tartrate complex |
| DE102005061691A1 (en) * | 2005-12-21 | 2007-06-28 | Kraft-Klaunzer, Petra, Dr. | Copper compounds and their use as fungicide, algezide and bactericide |
| US9731999B2 (en) | 2011-09-23 | 2017-08-15 | Iqbal Gill | Chemical admixtures for hydraulic cements |
-
1931
- 1931-12-14 US US581049A patent/US1964696A/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2473735A (en) * | 1942-03-24 | 1949-06-21 | Burroughs Wellcome Co | Manufacture of complex organic antimony compounds |
| US2446981A (en) * | 1945-12-06 | 1948-08-10 | Vick Chemical Company | Aluminum hydroxide antacid composition |
| US2503781A (en) * | 1946-04-09 | 1950-04-11 | Reed & Carnrick | Organic iron alkali metal complexes |
| US2544667A (en) * | 1946-04-27 | 1951-03-13 | Du Pont | Werner-type chromium compounds as laminating and coating compositions |
| US2869978A (en) * | 1955-09-26 | 1959-01-20 | Union Oil Co | Method of gas purification utilizing an amine solution and an anti-corrosion agent |
| US2823144A (en) * | 1956-06-07 | 1958-02-11 | Du Pont | Aluminum complexes and process for preparing the same |
| US2904572A (en) * | 1956-11-26 | 1959-09-15 | Cfmc | New water-soluble complexes and a process for their preparation |
| US4331518A (en) * | 1981-01-09 | 1982-05-25 | Vulcan Materials Company | Bismuth composition, method of electroplating a tin-bismuth alloy and electroplating bath therefor |
| US4705876A (en) * | 1985-12-31 | 1987-11-10 | Vsesojuznoe Nauchno-Proizvodstvennoe Obiedinenie Tselljuloznobumazhnoy Promyshlennosti | Process for preparing powder-like iron-sodium tartrate complex |
| DE102005061691A1 (en) * | 2005-12-21 | 2007-06-28 | Kraft-Klaunzer, Petra, Dr. | Copper compounds and their use as fungicide, algezide and bactericide |
| US9731999B2 (en) | 2011-09-23 | 2017-08-15 | Iqbal Gill | Chemical admixtures for hydraulic cements |
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