CN1007979B - 2, 2-dioxygen 6-methyl-3, 4-dihydro-1, 2, 3-oxathiazin-4-one and its nontoxic salt preparing method - Google Patents
2, 2-dioxygen 6-methyl-3, 4-dihydro-1, 2, 3-oxathiazin-4-one and its nontoxic salt preparing methodInfo
- Publication number
- CN1007979B CN1007979B CN85106284A CN85106284A CN1007979B CN 1007979 B CN1007979 B CN 1007979B CN 85106284 A CN85106284 A CN 85106284A CN 85106284 A CN85106284 A CN 85106284A CN 1007979 B CN1007979 B CN 1007979B
- Authority
- CN
- China
- Prior art keywords
- aceto
- alkali
- acetamide
- compound
- methyl
- 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.)
- Expired
Links
- 150000003839 salts Chemical class 0.000 title claims abstract description 17
- 231100000252 nontoxic Toxicity 0.000 title claims abstract description 10
- 230000003000 nontoxic effect Effects 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 23
- HQTYWLJBELLQCX-UHFFFAOYSA-N 6-methyloxathiazin-4-one Chemical compound CC1=CC(=O)NSO1 HQTYWLJBELLQCX-UHFFFAOYSA-N 0.000 title abstract description 3
- 229910001882 dioxygen Inorganic materials 0.000 title abstract 2
- GCPWJFKTWGFEHH-UHFFFAOYSA-N acetoacetamide Chemical compound CC(=O)CC(N)=O GCPWJFKTWGFEHH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 17
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000004408 titanium dioxide Substances 0.000 claims description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 6
- 150000003512 tertiary amines Chemical class 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 239000012442 inert solvent Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- 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 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052728 basic metal Inorganic materials 0.000 claims description 3
- 150000003818 basic metals Chemical class 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- -1 potassium salts Chemical class 0.000 abstract description 22
- XSXHWVKGUXMUQE-UHFFFAOYSA-N osmium dioxide Inorganic materials O=[Os]=O XSXHWVKGUXMUQE-UHFFFAOYSA-N 0.000 abstract 2
- 229910005143 FSO2 Inorganic materials 0.000 abstract 1
- 235000003599 food sweetener Nutrition 0.000 abstract 1
- 159000000001 potassium salts Chemical class 0.000 abstract 1
- 239000003765 sweetening agent Substances 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000002023 wood Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000005885 Buprofezin Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- PRLVTUNWOQKEAI-VKAVYKQESA-N buprofezin Chemical compound O=C1N(C(C)C)\C(=N\C(C)(C)C)SCN1C1=CC=CC=C1 PRLVTUNWOQKEAI-VKAVYKQESA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 2
- 238000003810 ethyl acetate extraction Methods 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 239000003049 inorganic solvent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- SNDGLCYYBKJSOT-UHFFFAOYSA-N 1,1,3,3-tetrabutylurea Chemical compound CCCCN(CCCC)C(=O)N(CCCC)CCCC SNDGLCYYBKJSOT-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 1
- VZAWCLCJGSBATP-UHFFFAOYSA-N 1-cycloundecyl-1,2-diazacycloundecane Chemical compound C1CCCCCCCCCC1N1NCCCCCCCCC1 VZAWCLCJGSBATP-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 1
- AXWKFRWLYPZEFQ-UHFFFAOYSA-N 3-oxobutanoyl chloride Chemical compound CC(=O)CC(Cl)=O AXWKFRWLYPZEFQ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- UGAPHEBNTGUMBB-UHFFFAOYSA-N acetic acid;ethyl acetate Chemical compound CC(O)=O.CCOC(C)=O UGAPHEBNTGUMBB-UHFFFAOYSA-N 0.000 description 1
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 239000002024 ethyl acetate extract Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- ISRXMEYARGEVIU-UHFFFAOYSA-N n-methyl-n-propan-2-ylpropan-2-amine Chemical compound CC(C)N(C)C(C)C ISRXMEYARGEVIU-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- USPTVMVRNZEXCP-UHFFFAOYSA-N sulfamoyl fluoride Chemical compound NS(F)(=O)=O USPTVMVRNZEXCP-UHFFFAOYSA-N 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 235000019605 sweet taste sensations Nutrition 0.000 description 1
- JKUYRAMKJLMYLO-UHFFFAOYSA-N tert-butyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OC(C)(C)C JKUYRAMKJLMYLO-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
2, 2-dioxygen 6-methyl-3, 4-dihydro-1, 2, 3-oxathiazin-4-one and its non-toxic salt are prepared by reacting acetoacetamide with an S-O compound of formula I in the presence of a base,
FSO2Y (I)
in the formula: y ═ F, Cl, -OSO2F or-OSO2F is preferably used as Cl. Non-toxic salts, particularly potassium salts, are valuable synthetic sweeteners.
Description
2,2-titanium dioxide 6-methyl-3,4-dihydro-1,2,3-Evil thiazine-4-ketone is the compound that belongs to following formula.
Because on the nitrogen-atoms acidic hydrogen is arranged, this compound can form salt (with alkali).Because their sweet taste is still very strong in some cases, non-toxic salt (for example sodium, potassium and calcium salt) can be used as sweeting agent in foodstuffs industry, sylvite (" A Saisuofa wood potassium ") (acesulfam k) or abbreviation " A Saisuofa wood " (acesulfam) potassium have special importance.
Many different preparations 2,2-titanium dioxide 6-methyl-3,4-dihydro-1,2, the method for 3-Evil thiazine-4-ketone and non-toxic salt thereof all is known.Referring to 1973 the 85th volumes of " applied chemistry " (Angewandte Chemie), 22 phase 965-73 pages or leaves are corresponding to 1973 the 12nd volumes of international version, 11 phase 869-76 pages or leaves.In fact all methods all are with isocyanic acid chlorine sulfonyl ester or fluorine sulfonyl ester (XSO
2NCO
1X=Cl or F) as starting raw material.Isocyanic acid chlorine sulfonyl ester or fluorine sulfonyl ester and monomethyl acetylene, acetone, etheric acid, tert-butyl acetoacetate or benzyl allyl ethers reaction (normally polystep reaction) and obtain N-chlorine sulphonyl aceto-acetamide or the cyclisation under the effect of alkali (for example potassium hydroxide methanol solution) of N-fluorine sulphonyl aceto-acetamide obtains 2,2-titanium dioxide-6-methyl-3,4-dihydro-1,2, the corresponding salt of 3-Evil thiazine-4-ketone.If necessary, can obtain free De Evil Buprofezin with general method (with acid) by salt.
The method of another Zhi Bei Evil Buprofezin intermediate N fluorine sulphonyl aceto-acetamide is the partial hydrolysate aminosulfonyl fluorine H from isocyanic acid fluorine sulfonyl ester
2NSO
2(DE-OS2 453 063) that F begins.Aminosulfonyl fluorine (H in this method
2NSO
2F, with the acetoacetyl agent diketene of equimolar amount almost when the inert organic solvents neutralization has amine to exist, reaction between in-30 to 100 ℃, reaction is carried out (with triethylamine as amine) by following equation:
N-fluorine sulphonyl aceto-acetamide
N-fluorine sulphonyl aceto-acetamide is used alkali then, and for example the methanol solution with potassium hydroxide obtains sweeting agent with the general fashion cyclisation:
The A Saisuo magic arts
Though in some cases, 2 of the productive rate that currently known methods obtains feeling quite pleased, 2-titanium dioxide 6-methyl-3,4-dihydro-1,2, (with starting raw material aminosulfonyl halogen is benchmark for 3-Evil thiazine-4-ketone and non-toxic salt thereof, almost up to theoretical amount 85%), but these methods still need to improve, especially industry law, because need to use isocyanic acid chlorine sulfonyl ester or fluorine sulfonyl ester as starting raw material, these very uneasy obtaining.In fact, preparation isocyanic acid chlorine sulfonyl ester and fluorine sulfonyl ester need considerable preventive measures and safety precautions, are quite to bother because starting raw material operates sometimes, particularly HCN and HF.Isocyanic acid chlorine sulfonyl ester and fluorine sulfonyl ester are made according to following formula.
Therefore, except other problem, also advise by aceto-acetamide with at least about the SO of two times of molar weights
3Reaction prepares 2,2-titanium dioxide 6-methyl-3,4-dihydro-1,2,3-Evil thiazine-4-ketone and non-toxic salt thereof, if suit in the inorganic or organic solvent at inert, and subsequently with alkali neutralization with the formation of acid produce 2,2-titanium dioxide 6-methyl-3,4-dihydro-1,2,3-Evil thiazine-4-ketone is (the applying for a patent 3410 440.2-HOE B4/F 065) that suits.
N-alkylsulfonyl aceto-acetamide may be earlier by-mole aceto-acetamide and-mole SO in the reaction
3Generate, and then further with-mole SO
3Cyclisation obtains 2,2-titanium dioxide 6-methyl-3, and 4-dihydro-1,2,3-Evil thiazine-4-ketone:
If want to obtain salt, can be 2,2-titanium dioxide 6-methyl-3,4-dihydro-1,2, the 3-thiazine-4-ketone potassium hydroxide that neutralizes-for example use:
So just having obtained is about 30～90% the productive rate of theoretical value of benchmark with the aceto-acetamide.
If aceto-acetamide and SULPHURYL CHLORIDE SO
2Cl
2Reaction rather than and SO
3Reaction obtains α, α-dichlorated product with regard to α-chlorination that aceto-acetamide takes place
CH
3COCCl
2CONH
2, this compound is pressed the following formula fracture with alkali:
CH
3COCCl
2CONH
2+ NaOH → CH
3COONa+Cl
2CHCONH
2Referring to JP-OS 73-39431, with reference to " U.S. chemical abstract " 1973 the 79th volumes 65827a bar digest.
Exceeding is to have found that sulfonic acid fluoride reacts in a completely different way as other special fluoro sulfonyl compounds and aceto-acetamide and alkali unexpectedly, that is generates 2,2-titanium dioxide 6-methyl-3,4-dihydro-1,2,3-Evil thiazine-4-ketone or its corresponding salt.
Therefore, the present invention relates to by aceto-acetamide and-the S-O compound begins to prepare 2,2-titanium dioxide 6-methyl-3,4-dihydro-1,2, the method for 3-Evil thiazine-4-ketone and non-toxic salt thereof, this comprises aceto-acetamide and the reaction of S-O compound when having alkali to exist with following formula I:
FSO
2Y （Ⅰ）
Y=F, Cl in the formula ,-OSO
2F or-OSO
2Cl preferentially selects F for use.Reaction be based on the reaction formula of bottom (with K
2CO
3Be alkali):
The productive rate of the method for mentioning by this method gained productive rate and top of applying for a patent is same grade, with initial aceto-acetamide be basic point be approximately theoretical value 20～90%.
Aceto-acetamide is got by for example acetoacetyl chlorine or diketene and ammonia effect, is a kind of common Industrial products.
The included compound of formula I has sulfonic acid fluoride SO
2F
2Chlorine sulfonic acid fluoride SO
2ClF, pyrosulfuryl fluorine FSO
2OSO
2F and chlorine pyrosulfuryl fluorine ClSO
2OSO
2F, the compound of preferentially selecting for use are sulfonic acid fluoride SO
2F
2
These sulfonic acid halides are made by currently known methods.SO for example
2F
2And SO
2ClF can be with SO
2Cl
2Be heated to about 60-80 ℃ with NaF and obtain ((JOrgChem) nineteen sixty the 25th is rolled up 2016 pages for CWTullock and DDCoffman, organic chemistry magazine).
In principle might provide alkali reaction material all can be used as alkali according to method of the present invention, but preferably reach the tertiary amine of 15 carbon atoms, also have oxide compound, oxyhydroxide and the acid carbonate of alkaline ion exchanger and basic metal and alkaline-earth metal in addition with sum.
The example of tertiary amine has: Trimethylamine 99, triethylamine, N-methyl Diisopropylamine, benzyldimethylamine, xylidine, N, N-lupetazin, N-ethylpiperidine, pyridine, α, β, γ-Pi Courlene, diaza-bicyclo octane, diaza-bicyclo undecane etc.
The alkaline ion exchanger that can use is commercial available product.
Be to can be used as the basic metal that example mentions and oxide compound, oxyhydroxide, carbonate and the acid carbonate of alkaline-earth metal below:
LiOH、Li
2CO
3、LiHCO
3
NaOH、Na
2CO
3、NaHCO
3
KOH、K
2CO
3、KHCO
3
CaO Ca(OH)
2, CaCO
3, Ca(HCO
3)
2Deng
Gratifying especially alkali is that sum only is the tertiary amine of 10 carbon atoms and the oxide compound and the carbonate of potassium and sodium.K
2CO
3Good especially, because of making A Saisuofa wood potassium, it obtains with a kind of much easy way.
The use of uniting of several alkali also is fine, for example earlier with a kind of tertiary amine thereupon again with a kind of alkali metal hydroxide effect.
According to method of the present invention, the S-O compound of aceto-acetamide and formula I is about 1 with mol ratio: (1-1.5) use better; For making cyclisation complete, every mole of aceto-acetamide at least will be with about 3 equivalent alkali, preferably 3-5 equivalent.So just obtained 2 of salt formula, 2-titanium dioxide 6-methyl-3,4-dihydro-1,2,3-Evil thiazine-4-ketone, available in case of necessity usual way obtains acd compound by salt, for example uses ore deposit acid (hydrochloric acid, sulfuric acid etc.), acid-salt (KHSO
4Deng) or acid ion exchangers.
According to the present invention, be reflected at or carried out when not having inert solvent and thinner, just the sort of solvent and the thinner that under reaction conditions, does not react in undesirable mode with starting raw material and final product.
The organic solvent of proton transfer or non-proton transitivity all suits, lower alcohol (methyl alcohol for example, ethanol, Virahol, the trimethyl carbinol etc.), lower aliphatic hydrochloric ether (ethylene dichloride, 1, the 2-ethylene dichloride, chloroform, tetracol phenixin, zellon etc.), fragrance hydrochloric ether (chlorobenzene, chlorotoluene etc.), ketone (acetone, methylethylketone, the ring ethyl ketone, methyl phenyl ketone etc.) aliphatic carboxylic acid fat (ethyl acetate, butylacetate, methyl propionate, diethyl malonate, Succinic acid dimethylester, the acetate methoxyethyl ester, ethylene glycol acetate, glycol diacetate, ethyl cyanoacetate etc.), aromatic carboxylates's (methyl benzoate, ethyl benzoate etc.), aliphatic amide (dimethyl formamide, N,N-DIMETHYLACETAMIDE etc.), urea derivative (tetramethyl-urea, tetrabutyl urea etc.) and aliphatics and aromatics nitrile (acetonitrile, cyanobenzene etc.).
Solvent and thinner can use separately or intermingling uses (even in scope of miscibility gap).
Use inorganic solvent also to be fine for example liquid SO
2, also used water when suitable.If but chlorinated products and pyrosulfuryl fluorine can not waters during as the compound of formula I, because they are easy to water and hydrolytic action takes place soon.Sulfonic acid fluoride is stable to water, is like this when temperature is not too high at least.
Satisfied solvent is that acetonitrile and aqueous acetone, especially water-content are the aqueous acetone of the 1-12% of weight ratio.
The amount of solvent and thinner is not very strict in principle, should determine the degree that is easy to stir at reaction mixture.The upper limit amount of solvent and thinner depends mainly on economic consideration, and rare excessively solution no longer is favourable.
Temperature of reaction also can change in quite wide scope.Reaction can approximately-70 ℃ carry out between the boiling point of solvent or thinner, this depends on the selection of alkali and solvent or thinner.Speed of response can slow down under lower temperature, and productive rate can reduce under too high temperature.Usually, general temperature range is at-70 ℃ to+100 ℃ approximately, preferably make an appointment with-10 and+60 ℃ between.
Though depress also and can react adding, best reaction pressure is normal atmosphere normally, decompression is little suitable.
React according to the present invention, say that in principle it is possible that the reactive component that enters reactor with any order or while is continuously measured.A kind of embodiment of superiority is to introduce aceto-acetamide and alkali, is dissolved in the S-O compound of a kind of inert solvent or thinner and metering-type I in the time of suitably.
Reaction mixture is checked with usual method.
The present invention has tangible economic worth, because the raw material simple reaction is carried out and high yield in some cases easily.
Now the present invention is described in detail with following embodiment.
Embodiment 1
10,1 gram (0.1 mole) aceto-acetamide and 33.0 gram (0.33 mole) triethylamines are dissolved in 100 milliliters of acetonitriles, put to the round-bottomed flask that agitator and solidified carbon dioxide condenser are housed, restrain (0.1 mole) sulfonic acid fluoride gases under-70 ℃ with 10.2 then, feed in 30 minutes.
With reaction mixture restir 3 hours subsequently, be allowed to warm to room temperature during this.It is dropped in 90 milliliters of 4NKOH methanol solutions then, suction filtration goes out reaction product.Obtain 7.2 gram (theoretical value 36%) A Saisuofa wood potassium, the infrared spectra qualification result is identical with reliable material.
Embodiment 2
As example 1, with 10.1 gram (0.1 mole) aceto-acetamides, 50.5 gram (0.5 mole) triethylamines and 100 milliliters of acetonitriles are put to one and are equipped with in the round-bottomed flask of agitator and solidified carbon dioxide water cooler.In 20 minutes, feed 15.3 gram (0.15 mole) sulfonic acid fluoride gases, reactant is warm down to room temperature in stirring.Stir after 2 hours, 230 milliliters of (0.46 mole) 2NKOH methanol solutions are splashed into, suction filtration goes out product.Obtain 9.7 gram (theoretical value 48%) A Saisuofa wood potassium.
Embodiment 3
With a cumulative volume 50 milliliters 40.4 gram (0.4 mole) triethylamine and liquid SO
2Mixture drip to 70 milliliters of liquid SO in-10 ℃
2Contain in the solution of 20.2 gram (0.2 mole) aceto-acetamides and 23.7 gram (0.2 mole) chlorine sulfonic acid fluoride.This mixture stirred 2 hours, steamed liquid SO then
2, under vacuum, handle at last.Residue drops in 400 milliliters of NaOH aqueous solution, with the concentrated hydrochloric acid acidifying, with ice-cooled, uses ethyl acetate extraction.Ethyl acetate is with gac and Na
2SO
4After the processing, the extracting solution vaporising under vacuum.Obtain 15 grams (almost be theoretical value 20%) 2,2-titanium dioxide 6-methyl-3,4-dihydro-1,2,3-Evil thiazine-4-ketone.
Embodiment 4
The water of different amounts adds in 150 milliliters of acetone.10.1 gram (0.1 mole) aceto-acetamide and 69 gram (0.5 mole) finely powdered are done K
2CO
3Add in each aqueous mixture.Feed 13.5 gram (0.15 mole) sulfonic acid fluoride gases, at room temperature carry out, the temperature of reaction mixture rises to about 40 ℃ in the venting process, restir 2 hours, and bleeding leaches product.Filter residue contains A Saisuofa wood potassium, and (silica gel, solvent system: ethyl acetate/Glacial acetic acid (5: 1) check is identical with reference sample through thin-layer chromatography.Filter residue changes in the mixture of ice and excessive hydrochloric acid, with ethyl acetate extraction.Acetic acid ethyl acetate extract is with Na
2SO
4Doing the baking back evaporates under vacuum.Obtain crystalline 2,2-titanium dioxide 6-methyl-3,4-dihydro-1,2,3-Evil thiazine-4-ketone transfers this product to A Saisuofa wood potassium with the KOH methanol solution again.The results are shown in the following table.In the table in listed last experiment, K
2CO
3Be to use with 50% the aqueous solution.
Table
The productive rate of amount of water A Saisuofa wood potassium
With acetone is the percentage ratio of the theoretical value of benchmark
The milliliter gram
Weight percentage (%) (%)
0????-????3.75????23
2????1.7????10.86????67
6????5.1????12.15????75
8????6.7????14.10????86.5
10????8.4????12.20????75
12????10.1????11.54????71
14????11.8????8.3????51
69????58????6.4????39
Claims (7)
1, a kind ofly begins to prepare 2 by aceto-acetamide and S-O compound, 2-titanium dioxide 6-methyl-3,4-dihydro-1,2, the method of 3-Evil thiazine-4-ketone and non-toxic salt thereof is characterized in that comprising that aceto-acetamide and the S-O compound with formula I react in the presence of alkali
FSO
2Y (Ⅰ)
In the formula, Y=F, Cl ,-OSO
2F or-OSO
2Cl preferentially selects F for use.
2,, it is characterized in that wherein used alkali is oxide compound, oxyhydroxide, carbonate and the acid carbonate of rudimentary tertiary amine, alkaline ion exchanger and basic metal and alkaline-earth metal according to claim 1 described method.
3,, it is characterized in that wherein used alkali is the oxyhydroxide and the carbonate of rudimentary tertiary amine and sodium and potassium, especially only uses K according to claim 1 or 2 described methods
2CO
3
4,, it is characterized in that wherein every mole of aceto-acetamide will be with about 1-1.5 mole formula I S-O compound with at least about 3 equivalent alkali, preferably 3-5 equivalent alkali according to claim 1 described method.
5, according to claim 1 described method, it is characterized in that reacting in the presence of inert solvent or thinner and carry out, preferably in acetonitrile or aqueous acetone, especially water content is about 1-12%(weight) aqueous acetone in carry out.
6,, it is characterized in that reaction is to be about in temperature between-10 ℃ to+60 ℃ to carry out according to claim 1 described method.
7, according to claim 1 described method, it is characterized in that adding earlier aceto-acetamide and alkali (can suitably be dissolved in inert solvent or the thinner), be metered into formula I S-O compound again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85106284A CN1007979B (en) | 1984-08-07 | 1985-08-20 | 2, 2-dioxygen 6-methyl-3, 4-dihydro-1, 2, 3-oxathiazin-4-one and its nontoxic salt preparing method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843429039 DE3429039A1 (en) | 1984-08-07 | 1984-08-07 | METHOD FOR PRODUCING 6-METHYL-3,4-DIHYDRO-1,2,3-OXATHIAZINE-4-ON-2,2-DIOXIDE AND ITS NON-TOXIC SALTS |
| CN85106284A CN1007979B (en) | 1984-08-07 | 1985-08-20 | 2, 2-dioxygen 6-methyl-3, 4-dihydro-1, 2, 3-oxathiazin-4-one and its nontoxic salt preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85106284A CN85106284A (en) | 1987-02-18 |
| CN1007979B true CN1007979B (en) | 1990-05-16 |
Family
ID=25741973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85106284A Expired CN1007979B (en) | 1984-08-07 | 1985-08-20 | 2, 2-dioxygen 6-methyl-3, 4-dihydro-1, 2, 3-oxathiazin-4-one and its nontoxic salt preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1007979B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11718594B2 (en) | 2016-09-21 | 2023-08-08 | Celanese International Corporation | Acesulfame potassium compositions and processes for producing same |
| US11724994B2 (en) | 2016-09-21 | 2023-08-15 | Celanese International Corporation | Acesulfame potassium compositions and processes for producing same |
| US11724993B2 (en) | 2016-09-21 | 2023-08-15 | Celanese International Corporation | Acesulfame potassium compositions and processes for producing same |
| US11731948B2 (en) | 2016-09-21 | 2023-08-22 | Celanese International Corporation | Acesulfame potassium compositions and processes for producing same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787001A (en) * | 2010-03-17 | 2010-07-28 | 广东省食品工业研究所 | Synthesis process of acesulfame potassium |
-
1985
- 1985-08-20 CN CN85106284A patent/CN1007979B/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11718594B2 (en) | 2016-09-21 | 2023-08-08 | Celanese International Corporation | Acesulfame potassium compositions and processes for producing same |
| US11724994B2 (en) | 2016-09-21 | 2023-08-15 | Celanese International Corporation | Acesulfame potassium compositions and processes for producing same |
| US11724993B2 (en) | 2016-09-21 | 2023-08-15 | Celanese International Corporation | Acesulfame potassium compositions and processes for producing same |
| US11731948B2 (en) | 2016-09-21 | 2023-08-22 | Celanese International Corporation | Acesulfame potassium compositions and processes for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN85106284A (en) | 1987-02-18 |
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