EP1601645A1 - Verfahren zur herstellung von thioessigsäure und ihren salzen - Google Patents
Verfahren zur herstellung von thioessigsäure und ihren salzenInfo
- Publication number
- EP1601645A1 EP1601645A1 EP04716226A EP04716226A EP1601645A1 EP 1601645 A1 EP1601645 A1 EP 1601645A1 EP 04716226 A EP04716226 A EP 04716226A EP 04716226 A EP04716226 A EP 04716226A EP 1601645 A1 EP1601645 A1 EP 1601645A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkali metal
- ketene
- base
- aluminum
- hydrogen sulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 37
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 150000003839 salts Chemical class 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- -1 alkali metal cation Chemical class 0.000 claims abstract description 38
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 33
- 239000002585 base Substances 0.000 claims abstract description 30
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 claims abstract description 29
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 24
- 239000010936 titanium Substances 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 20
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 18
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 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 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 150000007942 carboxylates Chemical class 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 150000004678 hydrides Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940031826 phenolate Drugs 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- 150000003973 alkyl amines Chemical group 0.000 claims description 2
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- 150000004982 aromatic amines Chemical group 0.000 claims description 2
- 150000002357 guanidines Chemical group 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 1
- 125000002619 bicyclic group Chemical group 0.000 claims 1
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 238000005580 one pot reaction Methods 0.000 abstract description 4
- 239000004411 aluminium Substances 0.000 abstract 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- JYWKEVKEKOTYEX-UHFFFAOYSA-N 2,6-dibromo-4-chloroiminocyclohexa-2,5-dien-1-one Chemical compound ClN=C1C=C(Br)C(=O)C(Br)=C1 JYWKEVKEKOTYEX-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 2
- KVLCHQHEQROXGN-UHFFFAOYSA-N aluminium(1+) Chemical compound [Al+] KVLCHQHEQROXGN-UHFFFAOYSA-N 0.000 description 2
- 229940007076 aluminum cation Drugs 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 150000004707 phenolate Chemical class 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- DPCQJLQPDJPRCM-UHFFFAOYSA-N s-acetyl ethanethioate Chemical compound CC(=O)SC(C)=O DPCQJLQPDJPRCM-UHFFFAOYSA-N 0.000 description 2
- RBBWNXJFTBCLKT-UHFFFAOYSA-M sodium;ethanethioate Chemical compound [Na+].CC([S-])=O RBBWNXJFTBCLKT-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DUYAAUVXQSMXQP-UHFFFAOYSA-M thioacetate Chemical compound CC([S-])=O DUYAAUVXQSMXQP-UHFFFAOYSA-M 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- SSUJUUNLZQVZMO-UHFFFAOYSA-N 1,2,3,4,8,9,10,10a-octahydropyrimido[1,2-a]azepine Chemical compound C1CCC=CN2CCCNC21 SSUJUUNLZQVZMO-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- 239000005541 ACE inhibitor Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229940044094 angiotensin-converting-enzyme inhibitor Drugs 0.000 description 1
- 229960002685 biotin Drugs 0.000 description 1
- 235000020958 biotin Nutrition 0.000 description 1
- 239000011616 biotin Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- FAKRSMQSSFJEIM-RQJHMYQMSA-N captopril Chemical compound SC[C@@H](C)C(=O)N1CCC[C@H]1C(O)=O FAKRSMQSSFJEIM-RQJHMYQMSA-N 0.000 description 1
- 229960000830 captopril Drugs 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- CATWEXRJGNBIJD-UHFFFAOYSA-N n-tert-butyl-2-methylpropan-2-amine Chemical compound CC(C)(C)NC(C)(C)C CATWEXRJGNBIJD-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003515 testosterones Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/02—Monothiocarboxylic acids
- C07C327/04—Monothiocarboxylic acids having carbon atoms of thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C327/06—Monothiocarboxylic acids having carbon atoms of thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of an acyclic saturated carbon skeleton
Definitions
- the invention relates to a process for the preparation of thioacetic acid and its salts.
- Thioacetic acid and its salts are important industrial starting materials and are used, for example, for the production of D-acetylthioisobutyric acid or pharmaceutical active ingredients such as captopril (ACE inhibitor against high blood pressure, JP-A-09-295963) and for the synthesis of biotin (DE-A-2807200) , Potassium thioacetate is used, for example, in the production of testosterone derivatives (DE-A-19860917).
- Known processes for the synthesis of thioacetic acid are based, for example, on acetic anhydride, which is reacted with hydrogen sulfide (OA-A-2110) or metal hydrogen sulfide (US-A-2568020) to give the desired product.
- OA-A-2110 hydrogen sulfide
- US-A-2568020 metal hydrogen sulfide
- Another method is based on ketene, which with hydrogen sulfide in the gas phase and in the presence of a solid, aluminum-containing catalyst, at 10 to 204.4 ° C (50 to 400 ° F), preferably at 65.6 to 176.7 ° C (150 to 350 ° F) is converted to thioacetic acid or diacetyl sulfide (US-A-2639293).
- a common process for the preparation of alkali metal thiocarboxylates is based on thiocarboxylic acids, which are converted into the corresponding salts, for example by means of alkali metal hydrides (Kato, S. et al., Z Naturforsch. 1983, 38B (12), 1585-1590).
- the object of the present invention was therefore to provide a simple process for the direct production of thioacetic acid and its salts, which can also be operated in a "one-pot process", works inexpensively, uses easily accessible starting materials and provides little waste and by-products.
- this object is achieved by the method according to claim 1. It has been found that in the presence of a nitrogen base, ketene is directly substance or a dissolved alkali metal bisulfide can be implemented. Depending on requirements, the thioacetic acid or subsequent addition of ammonia, an alkali metal or alkaline earth metal, aluminum or titanium base, the corresponding salt thereof can be obtained directly in good yield and high purity by subsequent distillation. The formation of the thioacetic acid with subsequent salt formation can be particularly preferred as
- M " + is ammonium or an alkali metal, alkaline earth metal, aluminum or titanium cation selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, barium, aluminum and titanium, and wherein n is the number of positive charges of the Is cation, ketene is reacted in the presence of a nitrogen base with hydrogen sulfide or a dissolved alkahmetal hydrogen sulfide and, if appropriate, subsequently the thioacetic acid obtained is reacted with ammonia or an alkali metal, alkaline earth metal, aluminum or titanium base to give the corresponding salt.
- Alkali metal hydrogen sulfides are to be understood here and below in particular as the hydrogen sulfides of lithium, sodium and potassium.
- Alkali metal or alkaline earth metal, aluminum or titanium bases include here and below in particular hydroxides, carbonates, hydrogen carbonates, alcoholates, phenolates, Carboxylates, oxides, hydrides, sulfonates, phosphates, sulfides, sulfmates, oxalates, hexafluorophosphates and tetrafluoroborates of lithium, sodium, potassium, magnesium, calcium, barium, aluminum and titanium are to be understood.
- Alcoholates and phenolates of alkali metals, alkaline earth metals, aluminum and titanium are to be understood here and below in particular the compounds of the formula R * O _ • ⁇ M " + , where R 1 is a C 1-4 alkyl or phenyl radical and M" + Alkali metal cation, preferably Li + , Na + or K + , an alkaline earth metal cation, preferably Mg 2+ , Ca 2+ or Ba, an aluminum cation or a titanium cation, and where n is the number of positive charges of the cation.
- Carboxylates of alkali metals, alkaline earth metals, aluminum and titanium are to be understood here and below in particular to mean compounds of the formula R 2 COO ⁇ • - -M " + , where R is an optionally partially or completely halogenated C 6 alkyl or phenyl radical and M "* an alkali metal cation, preferably Li + , Na + or K +
- Alkaline earth metal cation preferably Mg 2+ , Ca 2+ or Ba 2+ , an aluminum cation or a titanium cation, and wherein n is the number of positive charges of the cation.
- nitrogen bases are to be understood in particular as meaning nitrogen-containing compounds which have a pK a of> 7, such as, for example, primary, secondary and tertiary alkylamines such as, for example, di-tert-butylamine, trimethylamine and triethylamine, primary, secondary and tertiary arylamines, cyclic amines such as piperidine, pyrrolidine or morpholine, aromatic nitrogen heterocycles such as pyridine or substituted pyridines such as 4-dimethylaminopyridine, ammonia, guanidines, bicyclic nitrogen compounds such as 1,4-diazabicyclo [2.2.2] octane
- primary, secondary and tertiary alkylamines such as, for example, di-tert-butylamine, trimethylamine and triethylamine
- primary, secondary and tertiary arylamines cyclic amines such as piperidine, pyrrolidine or morpholine
- DBU 5-diazabicyclo [4.3.0] non-5-ene
- DBU 1,8-diazabicyclo [5.4.0] undecene
- basic nitrogen-containing ion exchanger for example, under the name of Lewatit ® , Duolite ® and Dowex ® are available.
- the task of the nitrogen base is to activate the H 2 S.
- M n + is selected from the group consisting of Li + , Na + , K + , Mg 2+ , Ca 2+ and Ba 2+ .
- the reaction of ketene with hydrogen sulfide or a dissolved alkali metal hydrogen sulfide is carried out in a polar solvent.
- a C 1 - alcohol, water, diethyl ether, tetrahydrofuran, dichloromethane, pyridine, methyl pyridine or dimethyl formamide is used as the polar solvent.
- a C 1 alcohol or water is used as the polar solvent.
- 1-butanol is used as the polar solvent for the production of potassium or sodium thioacetate, in which potassium and sodium thioacetate crystallize particularly well.
- ketene in a special process variant, can be reacted in aqueous solution with an alkali metal hydrogen sulfide solution, optionally with the addition of gaseous hydrogen sulfide.
- hydrogen sulfide and ketene or alkali metal hydrogen sulfide and ketene are advantageously used in a molar ratio between 0.5: 1 and 2: 1.
- a molar hydrogen sulfide: ketene ratio or alkali metal hydrogen sulfide: ketene ratio between 0.8: 1 and 1.3: 1 is used.
- a molar hydrogen sulfide: ketene ratio or alkali metal hydrogen sulfide: ketene ratio of 1: 1 is used.
- a molar ketene: nitrogen base ratio between 1: 0.001 and 1: 0.5 is used in the process according to the invention.
- a molar ketene: nitrogen base ratio between 1: 0.001 and 1: 0.1 is used in the process according to the invention.
- the reaction of ketene with hydrogen sulfide is carried out at temperatures between +60 and -40 ° C, particularly preferably between +10 and -20 ° C.
- Alkali metal, alkaline earth metal, aluminum or titanium bases can be used in the process according to the invention for the formation of the salts of thioacetic acid.
- Preferred alkali metal or alkaline earth metal, aluminum or titanium bases are hydroxides, carbonates, bicarbonates, alcoholates, phenates, carboxylates, oxides, hydrides, sulfonates, phosphates, sulfides, sulfinates, oxalates, hexafluorophosphates or tetrafluoroborates of lithium, sodium , Potassium, magnesium, calcium, barium, aluminum or titanium are used.
- the metal thioacetate obtained can optionally be separated from the corresponding acid of the metal base used by filtration, and depending on the solubility the metal thioacetate or the corresponding acid can be dissolved.
- a hydroxide, alcoholate, phenolate or carboxylate of lithium, sodium or potassium is used for salt formation.
- the alkali metal, alkaline earth metal, aluminum or titanium base can be added as a solid or as an aqueous solution and / or suspension.
- the reaction with the alkali metal or alkaline earth metal, aluminum or titanium base can be carried out at temperatures from -20 to +100 ° C, particularly preferably at temperatures from -10 to +10 ° C.
- the salt formation can be carried out as a “one-pot process” without prior isolation of the thioacetic acid.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Paper (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04716226A EP1601645A1 (de) | 2003-03-03 | 2004-03-02 | Verfahren zur herstellung von thioessigsäure und ihren salzen |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03004654 | 2003-03-03 | ||
| EP03004654 | 2003-03-03 | ||
| EP04716226A EP1601645A1 (de) | 2003-03-03 | 2004-03-02 | Verfahren zur herstellung von thioessigsäure und ihren salzen |
| PCT/EP2004/002089 WO2004078706A1 (de) | 2003-03-03 | 2004-03-02 | Verfahren zur herstellung von thioessigsäure und ihren salzen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1601645A1 true EP1601645A1 (de) | 2005-12-07 |
Family
ID=32946842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP04716226A Withdrawn EP1601645A1 (de) | 2003-03-03 | 2004-03-02 | Verfahren zur herstellung von thioessigsäure und ihren salzen |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20080161597A1 (enExample) |
| EP (1) | EP1601645A1 (enExample) |
| JP (1) | JP2006519242A (enExample) |
| CN (1) | CN1314668C (enExample) |
| CA (1) | CA2517703A1 (enExample) |
| EA (1) | EA008941B1 (enExample) |
| WO (1) | WO2004078706A1 (enExample) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045701B (zh) * | 2006-03-27 | 2010-05-12 | 浙江医药股份有限公司新昌制药厂 | 硫代乙酸钾的制备方法 |
| CN101108818B (zh) * | 2007-08-01 | 2012-03-28 | 潍坊海顺化工有限责任公司 | 一种硫代乙酸的制备方法 |
| CN106831513A (zh) * | 2017-01-06 | 2017-06-13 | 绍兴市上虞区耕创化工技术服务部 | 硫代乙酸钾的制备方法 |
| CN111302994A (zh) * | 2020-04-14 | 2020-06-19 | 陶陈丁 | 一种硫代醋酸钾的制备新方法 |
| CN111960979A (zh) * | 2020-08-14 | 2020-11-20 | 江西天新药业股份有限公司 | 硫代乙酸钠的制备方法以及用硫代乙酸钠制备硫内酯的方法 |
| CN115215777A (zh) * | 2022-07-07 | 2022-10-21 | 武穴融泰医药科技有限公司 | 五硫化二磷与乙酸制备硫代乙酸的方法 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2639293A (en) * | 1948-12-16 | 1953-05-19 | Phillips Petroleum Co | Manufacture of thioacetic acid and diacetyl sulfide |
| SU1351923A1 (ru) * | 1986-01-06 | 1987-11-15 | Северо-Западный Заочный Политехнический Институт | Способ получени тиокислот |
| SU1594174A1 (ru) * | 1988-12-26 | 1990-09-23 | Всесоюзный научно-исследовательский и проектный институт механической обработки полезных ископаемых "Механобр" | Способ получени тиоуксусной кислоты |
| FR2769626B1 (fr) * | 1997-10-15 | 1999-12-03 | Elf Aquitaine Exploration Prod | Stabilisation de l'acide thioacetique |
-
2004
- 2004-03-02 CA CA002517703A patent/CA2517703A1/en not_active Abandoned
- 2004-03-02 JP JP2006504506A patent/JP2006519242A/ja not_active Withdrawn
- 2004-03-02 CN CNB2004800057432A patent/CN1314668C/zh not_active Expired - Fee Related
- 2004-03-02 WO PCT/EP2004/002089 patent/WO2004078706A1/de not_active Ceased
- 2004-03-02 EA EA200501361A patent/EA008941B1/ru unknown
- 2004-03-02 EP EP04716226A patent/EP1601645A1/de not_active Withdrawn
- 2004-03-02 US US10/546,651 patent/US20080161597A1/en not_active Abandoned
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2004078706A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2517703A1 (en) | 2004-09-16 |
| JP2006519242A (ja) | 2006-08-24 |
| WO2004078706A1 (de) | 2004-09-16 |
| CN1756739A (zh) | 2006-04-05 |
| CN1314668C (zh) | 2007-05-09 |
| US20080161597A1 (en) | 2008-07-03 |
| EA200501361A1 (ru) | 2006-04-28 |
| HK1086549A1 (en) | 2006-09-22 |
| EA008941B1 (ru) | 2007-10-26 |
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