JPS6139932B2 - - Google Patents
Info
- Publication number
- JPS6139932B2 JPS6139932B2 JP7353978A JP7353978A JPS6139932B2 JP S6139932 B2 JPS6139932 B2 JP S6139932B2 JP 7353978 A JP7353978 A JP 7353978A JP 7353978 A JP7353978 A JP 7353978A JP S6139932 B2 JPS6139932 B2 JP S6139932B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- acid
- dioxane
- pinacolon
- trimethyl
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 239000002253 acid Substances 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 16
- ULMSSYJQRGAMHY-UHFFFAOYSA-N 4,4,5-trimethyl-1,3-dioxane Chemical compound CC1COCOC1(C)C ULMSSYJQRGAMHY-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 150000007522 mineralic acids Chemical class 0.000 claims description 13
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 27
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 239000012074 organic phase Substances 0.000 description 12
- 239000008346 aqueous phase Substances 0.000 description 11
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 8
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- -1 manganese () Chemical class 0.000 description 4
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 3
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 3
- YJRVQISHPNMAQI-UHFFFAOYSA-N 4-ethyl-4-methyl-1,3-dioxane Chemical compound CCC1(C)CCOCO1 YJRVQISHPNMAQI-UHFFFAOYSA-N 0.000 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 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical compound ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- ITZWYSUTSDPWAQ-UHFFFAOYSA-N 2,3-dimethylbutane-1,3-diol Chemical compound OCC(C)C(C)(C)O ITZWYSUTSDPWAQ-UHFFFAOYSA-N 0.000 description 1
- JOUWCKCVTDSMHF-UHFFFAOYSA-N 2-bromo-2-methylbutane Chemical compound CCC(C)(C)Br JOUWCKCVTDSMHF-UHFFFAOYSA-N 0.000 description 1
- BLGVDCMNIAOLHA-UHFFFAOYSA-N 2-bromo-3-methylbutane Chemical compound CC(C)C(C)Br BLGVDCMNIAOLHA-UHFFFAOYSA-N 0.000 description 1
- JMTRCXPSDMMAGM-UHFFFAOYSA-N 2-chloro-3-methylbutane Chemical compound CC(C)C(C)Cl JMTRCXPSDMMAGM-UHFFFAOYSA-N 0.000 description 1
- BSPCSKHALVHRSR-UHFFFAOYSA-N 2-chlorobutane Chemical compound CCC(C)Cl BSPCSKHALVHRSR-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical class CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010478 Prins reaction Methods 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000005446 dissolved organic matter Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- JNZGLUUWTFPBKG-UHFFFAOYSA-K magnesium;potassium;trichloride Chemical compound [Mg+2].[Cl-].[Cl-].[Cl-].[K+] JNZGLUUWTFPBKG-UHFFFAOYSA-K 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
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ãè¡šãDETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing pinacolon from 4,4,5-trimethyl-1,3-dioxane. The method of producing pinacolon by decomposing 4,4,5-trimethyl-1,3-dioxane, which is synthesized by the Prins reaction between 2-methylbutene-2 and formaldehyde, in the presence of a strong inorganic acid aqueous solution has been known for a long time. (for example, German patent no.
No. 714488). In addition, as an improvement to this method, by coexisting 2-methylbutene-2 in the reaction system, formaldehyde produced as a by-product in the reaction process is reactively captured, increasing the yield of pinacolon, and at the same time recovering formaldehyde and purifying pinacolon. It is disclosed in US Pat. No. 4,059,634 that this can be facilitated. On the other hand, it is well known that the concentration of the acid aqueous solution when producing pinacolon by decomposing 4,4,5-trimethyl-1,3-dioxane in the presence of an inorganic strong acid aqueous solution has a large effect on the yield of pinacolon. ing. For example, Chemical Abstract 78 71330d
(1973), the yield of pinacolon is only 2.3% when using 2.5% hydrochloric acid, and even when using 20% hydrochloric acid, the yield of pinacolon is only 34% at most. It has been reported. This means that in order to obtain pinacolon from 4,4,5-trimethyl-1,3-dioxane with a satisfactory reaction yield, it is necessary to use a strong inorganic acid aqueous solution at a high concentration of at least 20% by weight. do. However, the same report also states that 4,4,5-trimethyl-1.
It is described that the production of pinacolon by acid hydrolysis of 3-dioxane occurs via the dehydration reaction of the primary product, 2,3-dimethylbutane-1,3-diol. This suggests that since the same reaction conditions are also the conditions for the Prince reaction, there is a possibility that the intermediate of the reaction may react with the formaldehyde produced in the reaction system and change into a high-boiling point compound (Bull.Soc .Chim.France, 1964 (4)800ïœ
811), by simply hydrolyzing 4,4,5-trimethyl-1,3-dioxane with acid, pinacolon cannot be obtained with a reaction yield that is industrially satisfactory even if a highly concentrated acid aqueous solution is used. means difficult. The invention of U.S. Pat. No. 4,059,634 was made in consideration of this fact. For example, in addition to hydrochloric acid at a concentration of 36% by weight, 2-methylbutene-2 is allowed to coexist to eliminate formaldehyde produced as a by-product in the reaction system. By reacting to produce pinacolon, the pinacolon yield was increased by 4.4.5-trimethyl-1.
This shows that the yield can be improved to 69% of the theoretical yield based on 3-dioxane. However, even in this case, the pinacolone yield is only 35% of the theoretical yield when converted to a yield that takes into account formaldehyde generated from the dioxane.
When this method is carried out on an industrial scale, there are considerable disadvantages not only in terms of the chemical consumption rate but also in terms of the separation and purification of the product pinacolon and the recycling and reuse of the highly concentrated hydrochloric acid used in the reaction. As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention found that 4,4,5-trimethyl-1,3-dioxane with the general formula () (In formula (), W and Z are hydrogen atoms, and either one of X and Y is OH, Cl or Br and the other is a hydrogen atom, or the adjacent one of W, X, Y and Z When thermal decomposition is carried out in the presence of a strong inorganic acid aqueous solution in the presence or absence of butenes or their derivatives (where two that match form a single bond and the remaining two represent hydrogen atoms), a small amount is added to the reaction system. By coexisting a salt of a strong inorganic acid that is partially soluble in both, the concentration and amount of the strong inorganic acid can be reduced, and the above-mentioned problems are not only alleviated, but also the yield of pinacolon is improved; In particular, it has been found that when the compound represented by the general formula () is coexisting, the formaldehyde by-produced during the reaction can be reused efficiently, and the yield of pinacolon can be dramatically increased. It came to this. Inorganic strong acids preferably used in the present invention include sulfuric acid,
hydrochloric acid, hydrobromic acid, phosphoric acid or perchloric acid;
Two or more of them may be used in combination. According to the method of the present invention, in which a salt of a strong inorganic acid is coexisting in the reaction system, even when using any of the above-mentioned acids, the concentration and amount are much lower than those required by the conventionally known methods described above. The reaction can be carried out in a high yield with a small amount. However, the acid concentration in the aqueous phase of the reaction system should be 0.5 mol/Kg (aqueous phase) or more, and the amount of inorganic strong acid used should be 4,4,5-trimethyl-1,3
- The amount is preferably maintained at 0.1 times or more, preferably 0.3 times or more by mole relative to dioxane. In the present invention, the salt of the inorganic strong acid to be used in combination with the inorganic strong acid must be at least partially soluble in the reaction system, and preferably has a solubility in water of 35 or more at 100°C. Both neutral and acid salts can be used, such as lithium, sodium, potassium, rubidium, cesium, copper (), magnesium, calcium, strontium, barium, zinc, cadmium, aluminum, scandium, zirconium, titanium ( ), tin (), manganese (), iron, cobalt (), chlorides and bromides such as nickel, ammonium, sodium, rubidium, cesium,
Magnesium, cadmium, zinc, aluminum, cobalt (), copper (), nickel (),
Sulfates such as manganese (), perchlorates such as calcium, silver, strontium, sodium, barium, magnesium, acid salts such as sodium hydrogen sulfate, potassium hydrogen sulfate, ammonium dihydrogen phosphate, sodium dihydrogen phosphate, Further examples include complex salts such as magnesium potassium chloride and sulfate. Among these, those having high molar solubility and high stability in the aqueous phase under reaction conditions are preferred, and in consideration of this point, salts of alkali metals and alkaline earth metals are most preferred. Although the acid group of the inorganic strong acid and the acid group of the inorganic strong acid salt used in the reaction do not necessarily have to be the same, combinations that would produce a poorly soluble salt under the reaction conditions must be avoided. Furthermore, two or more salts of inorganic strong acids may be used in combination within the range that satisfies the above-mentioned solubility, but in this case as well, combinations that would produce poorly soluble salts under the reaction conditions must be avoided. The amount of the inorganic strong acid salt to be used will depend on the concentration of the inorganic strong acid used together with the inorganic strong acid salt, and will be smaller if the inorganic strong acid concentration in the aqueous phase under the reaction conditions is high, and conversely if the acid concentration is low. It is controlled so that it is large, but it is used so that it is 1/10 or more of the saturated dissolution amount in the inorganic strong acid aqueous solution under the reaction conditions. The above general formula () coexisting in the reaction system in the present invention
Specifically, the butenes represented by are 2-methylbutene-1,2-methylbutene-2,3-methylbutene-1, and the butene derivative is 2-methylbutene-1.2-methylbutene-2,3-methylbutene-1.
2-chlorobutane, 2-methyl-2-bromobutane, 2-methyl-3-chlorobutane, 2-methyl-3-bromobutane, 2-methylbutanol-2
and 3-methylbutanol-2. Among these, butenes can be easily obtained industrially, for example, by partial hydrogenation of isoprene. Further, butene derivatives can be obtained industrially, for example, by adding hydrogen chloride, hydrogen bromide or water to the above-mentioned butenes. These butenes and their derivatives do not necessarily have to be pure, and may contain, for example, isoprene, methylbutane, or inorganic or organic acids. Butenes represented by the general formula () or derivatives thereof are used together with the raw material dioxane,
And if it contains a strong inorganic acid group,
Within the above acid amount ranges, relatively smaller amounts of acid are used. In addition to water, the reaction can also be carried out in the presence of a diluent inert to the reaction, such as saturated hydrocarbons, chlorinated hydrocarbons and ketones, such as methylbutane, hexane, cyclohexane,
Butyl chloride, 1,1,1-trichloroethane,
Hydrophobic compounds such as 1,1,1,2-tetrachloroethane, carbon tetrachloride, and pinacolone can be mentioned. However, no particular benefit is provided by the use of diluents. The reaction temperature is preferably in the range of 70 to 200°C, particularly 90 to 150°C. The reaction is also carried out at a pressure above atmospheric pressure, usually between atmospheric pressure and 30 kg/cm 2 . When the reaction is carried out at a temperature higher than the boiling point of the reaction mixture, the appropriate reaction pressure is the autogenous pressure of the reaction mixture at the reaction temperature, and pressurization with nitrogen or other inert gas is not particularly necessary. The reaction method is as follows: (1) An aqueous solution containing a strong inorganic acid and a strong inorganic acid salt is kept at a predetermined temperature while stirring, and 4,4,5-trimethyl-1,3-dioxane or 4,4,5-trimethyl -1ã»
3-dioxane and the butenes represented by the above general formula () or their derivatives are reacted while continuously or intermittently added; (2) an aqueous solution containing a strong inorganic acid and a strong inorganic acid salt and 4,4,5-trimethyl; - In the method of (3) and (2), in which 1,3-dioxane is reacted by mixing and stirring at a predetermined temperature, the butenes represented by the above general formula () or its derivatives are added continuously or intermittently during the reaction. (4) an aqueous solution containing a strong inorganic acid and a strong inorganic acid salt, and 4.4.5
A method may be used in which -trimethyl-1,3-dioxane and the butenes represented by the general formula () or a derivative thereof are simultaneously mixed and stirred to react, but method (1) is generally preferred. The method of the present invention can be carried out by either a continuous method or a batch method, but since it is a heterogeneous phase reaction, the reaction must be carried out under vigorous stirring, and for the same purpose, a surfactant is present. The reaction can also be carried out below. The reaction time naturally varies depending on the amount of starting materials used, the concentration and amount of the aqueous solution of the inorganic strong acid and the salt of the inorganic strong acid, the reaction temperature, and other factors, but is usually 1 to 20 hours. Methods for obtaining pinacolon from the reaction mixture after the reaction include (a) separating the organic phase from the aqueous phase and then subjecting the organic phase to distillation as it is or after neutralizing if necessary; (b) reaction. Methods such as neutralizing the mixture and then subjecting it to distillation as it is or only the organic phase, and (c) subjecting the reaction mixture to distillation as it is, are used. If method (a) or (c) is used, it is possible to circulate all or part of the aqueous phase to the reaction system and reuse it, but from the standpoint of efficient separation and acquisition of pinacolon, (a) ) is preferred.
As the distillation method, steam distillation, normal pressure distillation, or vacuum distillation is used. The use of a salt of a strong inorganic acid in the present invention is advantageous in reducing the amount of organic matter partitioned into the aqueous phase when the reaction mixture is separated into an organic phase and an aqueous phase. Therefore, all or part of the aqueous phase separated from the organic phase can be re-supplied to the reaction system as it is or after being mixed with a dilute circulating aqueous phase, after concentrating and removing water if necessary. In addition, components with boiling points lower than pinacolone obtained when the organic phase of the reaction mixture is distilled are mainly 2-methylbutenes,
Since it is a precursor of 2,3-dimethylbutadiene and other reaction raw materials or pinacolon, it can be recycled to the reaction system as a mixture. The method of the present invention is applicable to the above-mentioned operation in which the organic phase is separated from the reaction mixture to obtain pinacolon, and at the same time, the inorganic strong acid aqueous solution is recovered, recycled, and reused. It is also advantageous because it is effective in suppressing the distribution of organic matter into the aqueous phase (reducing dissolved organic matter). Pinacolon obtained by the present invention is industrially useful as a solvent or as a synthetic intermediate for agricultural chemicals, rubber chemicals, etc. Next, the present invention will be explained in more detail with reference to Examples. Comparative Example 1 100 with stirrer, reflux condenser and thermometer
Purity 91.9 containing 7.8% 4-methyl-4-ethyl-1,3-dioxane in a ml three-necked flask.
% 4,4,5-trimethyl-1,3-dioxane and 36.5 g of hydrochloric acid with a concentration of 10% by weight.
The reaction was carried out under reflux for 3 hours while stirring. During the reaction, the reflux temperature decreased from 92.8â to 86.5â.
The temperature reached 91.5â. The reaction mixture was neutralized with calcium hydroxide while being cooled in an ice-water bath, then transferred to a separatory funnel with 50 ml of diisopropyl ether, shaken well, and then separated. Analysis of the organic phase by gas chromatography revealed that no raw material dioxane remained and the amount of pinacolon produced was 3.16 g. This is the preparation 4.4.5-trimethyl-1.
This corresponds to 34.4% of the theoretical yield based on 3-dioxane. In addition, products other than pinacolon include 3.
4-dimethyl-5,6-dihydro-2H-pyran and 2,3-dimethyl-1,3-butadiene were determined to be 8.0% and 1.7%, respectively. Example 1 The reaction and treatment analysis were carried out in exactly the same manner as in Comparative Example 1 except that 7.5 g of lithium chloride was added to the reaction system. The yield was 44.1%. 3,4-dimethyl-5,6-dihydro-2H
The amounts of -pyran and 2,3-dimethyl-1,3-butadiene produced were 1.0% and 0.2%, respectively. Example 2 Raw material dioxane with the same composition as used in Comparative Example 1 was placed in a pressure-resistant glass electromagnetic stirring reactor with an internal volume of 300 ml.
18.5g, 2-methylbutanol-213.7g, concentration
52.0 g of 10% by weight hydrochloric acid and 10.7 g of lithium chloride
was charged and kept at 100°C for 6 hours with vigorous stirring. After the reaction, the mixture was cooled in an ice-water bath, 70 ml of xylene was added, stirred again, and the organic phase was separated using a separatory funnel. The organic phase was washed once with 30 ml of a 10% sodium carbonate aqueous solution and twice with 30 ml of water, and then analyzed by gas chromatography. The yield was 112.3 mol%. Example 3 In the same apparatus as in Example 2, 52.0% hydrochloric acid with a concentration of 10% by weight was added.
g and 10.7 g of lithium chloride while stirring.
It was kept at 100â. A mixed solution of 18.5 g of raw material dioxane and 13.7 g of 2-methylbutanol-2 having the same composition as used in Example 2 was introduced into the solution using a micro-metering pump and allowed to react over a period of 4 hours. After the introduction was completed, the mixture was stirred at the same temperature for another 2 hours, and then treated and analyzed in the same manner as in Example 2. The yield of pinacolon was 146.4 mol% based on the 4,4,5-trimethyl-1,3-dioxane charged. Ta. Comparative Example 2 The reaction was carried out in exactly the same manner as in Example 2 except that 100 g of 28 wt% hydrochloric acid was used instead of 52.0 g of 10 wt% hydrochloric acid and the addition of lithium chloride was omitted. Process analysis revealed that the yield of pinacolon was The rate is 4.
The amount was 87.1 mol% based on 4,5-trimethyl-1,3-dioxane. Example 4 80.3 g (0.11 mol) of hydrochloric acid with a concentration of 5% by weight and 43.2 g of magnesium chloride were charged into the same reaction apparatus as used in Example 3, and the temperature was raised to 400° C. while stirring. Next, in this state, 4,4,5-trimethyl-1,3-dioxane (composition: 4,4,5-
Trimethyl-1,3-dioxane 98.06%, 4-
Methyl-4-ethyl-1,3-dioxane 1.55
%) 14.3g (0.11 mol) and 10.5g of 2-methylbutanol-2 using a micro metering pump.
The reaction was carried out by keeping the same conditions for an additional 2 hours. The reaction mixture was treated and analyzed in the same manner as in Example 2, and the following results were obtained. Pinacolone yield 130.1 mol% 2,3-dimethylbutadiene yield 0.9 mol% However, the charge 4,4,5-trimethyl-1,3
- Mol% based on dioxane Example 5 Concentration 10 instead of hydrochloric acid and magnesium chloride
The reaction and analysis were carried out in exactly the same manner as in Example 4, except that 108 g (0.11 mol) of sulfuric acid and 71.9 g of sodium hydrogen sulfate were used, and the following results were obtained. Pinacolone yield 102.2 mol% 2,3-dimethylbutadiene yield 5.5 mol% However, the charge 4,4,5-trimethyl-1,3
-Mole% based on dioxane Examples 6 to 14 In a pressure-resistant glass electromagnetic stirring reactor with an internal volume of 300 ml, 52.0 g of hydrochloric acid with a concentration of 10% by weight and 10.7 g of lithium chloride
g was charged and kept at 100°C while stirring. Add 4-methyl-4-ethyl-1,3-dioxane to this.
18.5 g (0.131 mol) of 4,4,5-trimethyl-1,3-dioxane with a purity of 91.9% containing 7.8%
A mixed solution of 0.156 mol of butenes or a derivative thereof represented by the general formula () shown in Table 1 was introduced over a period of 4 hours using a micro-metering pump and allowed to react. After the introduction was completed, the mixture was stirred at the same temperature for an additional 2 hours. After the reaction, the mixture was cooled in an ice-water bath, 70 ml of xylene was added, stirred again, and the organic phase was separated using a separatory funnel. The organic phase was washed once with 30 ml of a 10% aqueous sodium carbonate solution and twice with 30 ml of water, and then analyzed by gas chromatography.
Table 1 shows the yield of pinacolone produced based on the 4,4,5-trimethyl-1,3-dioxane used. ãtableã
Claims (1)
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ãããããã³é¡ãããã¯ãã®èªå°äœã®å ±åäžãŸã
ã¯äžå ±åäžã«ç¡æ©åŒ·é žæ°Žæº¶æ¶²ã®ååšäžã§å ç±å解
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ãšãç¹åŸŽãšããããã³ãã³ã®è£œé æ¹æ³ã[Claims] 1 4,4,5-trimethyl-1,3-dioxane represented by the general formula () (In formula (), W and Z are hydrogen atoms, and either one of X and Y is OH, Cl or Br and the other is a hydrogen atom, or Pinacolon is produced by thermal decomposition in the presence of a strong inorganic acid aqueous solution in the presence or absence of butenes or their derivatives (two that match form a single bond and the remaining two represent hydrogen atoms). A method for producing pinacolon, which comprises coexisting at least a partially soluble salt of an inorganic strong acid in the reaction system.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7353978A JPS54163510A (en) | 1978-06-15 | 1978-06-15 | Preparation of pinacolone |
DE19792918521 DE2918521C3 (en) | 1978-05-15 | 1979-05-08 | Process for the production of pinacolone |
NL7903751A NL185562C (en) | 1978-05-15 | 1979-05-12 | PROCESS FOR PREPARING PINACOLON. |
US06/039,300 US4224252A (en) | 1978-05-15 | 1979-05-15 | Production of pinacolone |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7353978A JPS54163510A (en) | 1978-06-15 | 1978-06-15 | Preparation of pinacolone |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS54163510A JPS54163510A (en) | 1979-12-26 |
JPS6139932B2 true JPS6139932B2 (en) | 1986-09-06 |
Family
ID=13521131
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7353978A Granted JPS54163510A (en) | 1978-05-15 | 1978-06-15 | Preparation of pinacolone |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS54163510A (en) |
-
1978
- 1978-06-15 JP JP7353978A patent/JPS54163510A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS54163510A (en) | 1979-12-26 |
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