JPH04297451A - Production of isothiocyanic acid ester - Google Patents
Production of isothiocyanic acid esterInfo
- Publication number
- JPH04297451A JPH04297451A JP10630991A JP10630991A JPH04297451A JP H04297451 A JPH04297451 A JP H04297451A JP 10630991 A JP10630991 A JP 10630991A JP 10630991 A JP10630991 A JP 10630991A JP H04297451 A JPH04297451 A JP H04297451A
- Authority
- JP
- Japan
- Prior art keywords
- group
- general formula
- formula
- thiocyanate
- compound
- 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.)
- Pending
Links
- -1 isothiocyanic acid ester Chemical class 0.000 title claims abstract description 31
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 229910006080 SO2X Inorganic materials 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 14
- 150000003459 sulfonic acid esters Chemical class 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 8
- 150000004714 phosphonium salts Chemical class 0.000 abstract description 4
- 150000003863 ammonium salts Chemical class 0.000 abstract description 3
- GRHBQAYDJPGGLF-UHFFFAOYSA-N isothiocyanic acid Chemical class N=C=S GRHBQAYDJPGGLF-UHFFFAOYSA-N 0.000 abstract description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 125000005842 heteroatom Chemical group 0.000 abstract 1
- 159000000000 sodium salts Chemical class 0.000 abstract 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 54
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 238000006317 isomerization reaction Methods 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 6
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012990 dithiocarbamate Substances 0.000 description 4
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000004659 dithiocarbamates Chemical class 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- MDKCFLQDBWCQCV-UHFFFAOYSA-N benzyl isothiocyanate Chemical compound S=C=NCC1=CC=CC=C1 MDKCFLQDBWCQCV-UHFFFAOYSA-N 0.000 description 2
- ABNDFSOIUFLJAH-UHFFFAOYSA-N benzyl thiocyanate Chemical compound N#CSCC1=CC=CC=C1 ABNDFSOIUFLJAH-UHFFFAOYSA-N 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 2
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- UIZVMOZAXAMASY-UHFFFAOYSA-N hex-5-en-1-ol Chemical compound OCCCCC=C UIZVMOZAXAMASY-UHFFFAOYSA-N 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KKASGUHLXWAKEZ-UHFFFAOYSA-N 1-isothiocyanatopropane Chemical compound CCCN=C=S KKASGUHLXWAKEZ-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- WRFHVMFZOJHYGN-UHFFFAOYSA-N 6-isothiocyanatohex-1-ene Chemical compound C=CCCCCN=C=S WRFHVMFZOJHYGN-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- QAADZYUXQLUXFX-UHFFFAOYSA-N N-phenylmethylthioformamide Natural products S=CNCC1=CC=CC=C1 QAADZYUXQLUXFX-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- BQWQGEBNCNNFCI-UHFFFAOYSA-N butan-2-yl methanesulfonate Chemical compound CCC(C)OS(C)(=O)=O BQWQGEBNCNNFCI-UHFFFAOYSA-N 0.000 description 1
- HMDYBNCYTSFZEL-UHFFFAOYSA-N butan-2-yl thiocyanate Chemical compound CCC(C)SC#N HMDYBNCYTSFZEL-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IAVRLKGIJBOQFZ-UHFFFAOYSA-N hex-5-enyl thiocyanate Chemical compound C=CCCCCSC#N IAVRLKGIJBOQFZ-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- JTTWNTXHFYNETH-UHFFFAOYSA-N propyl 4-methylbenzenesulfonate Chemical compound CCCOS(=O)(=O)C1=CC=C(C)C=C1 JTTWNTXHFYNETH-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VDQRHYCVPYJPHU-UHFFFAOYSA-N propyl thiocyanate Chemical compound CCCSC#N VDQRHYCVPYJPHU-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- CCIYPTIBRAUPLQ-UHFFFAOYSA-M tetrabutylphosphanium;iodide Chemical compound [I-].CCCC[P+](CCCC)(CCCC)CCCC CCIYPTIBRAUPLQ-UHFFFAOYSA-M 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- LIXPXSXEKKHIRR-UHFFFAOYSA-M tetraethylphosphanium;bromide Chemical compound [Br-].CC[P+](CC)(CC)CC LIXPXSXEKKHIRR-UHFFFAOYSA-M 0.000 description 1
- FBOJNMRAZJRCNS-UHFFFAOYSA-M tetraethylphosphanium;chloride Chemical compound [Cl-].CC[P+](CC)(CC)CC FBOJNMRAZJRCNS-UHFFFAOYSA-M 0.000 description 1
- WKSYTZHMRBAPAO-UHFFFAOYSA-M tetraethylphosphanium;iodide Chemical compound [I-].CC[P+](CC)(CC)CC WKSYTZHMRBAPAO-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- ZTXFOCMYRCGSMU-UHFFFAOYSA-M tetramethylphosphanium;bromide Chemical compound [Br-].C[P+](C)(C)C ZTXFOCMYRCGSMU-UHFFFAOYSA-M 0.000 description 1
- NJFUXFRJVIXVSG-UHFFFAOYSA-M tetramethylphosphanium;chloride Chemical compound [Cl-].C[P+](C)(C)C NJFUXFRJVIXVSG-UHFFFAOYSA-M 0.000 description 1
- TVVPMLFGPYQGTG-UHFFFAOYSA-M tetramethylphosphanium;iodide Chemical compound [I-].C[P+](C)(C)C TVVPMLFGPYQGTG-UHFFFAOYSA-M 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Landscapes
- Hydrogenated Pyridines (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、イソチオシアン酸エス
テル類の製造方法に関し、更に詳しくは、医農薬をはじ
め、各種化学品の合成原料として有用なイソチオシアン
酸エステルを簡便にしかも高収率で得る新規な製造方法
を提供するものである。[Industrial Application Field] The present invention relates to a method for producing isothiocyanate esters, and more particularly, isothiocyanate esters useful as raw materials for the synthesis of various chemical products, including medicines and agrochemicals, can be obtained easily and in high yield. This provides a new manufacturing method.
【0002】0002
【従来の技術】従来、イソチオシアン酸エステル類の合
成法に関しては、幾つか報告がある。例えば、(1)チ
オシアン酸金属塩とハロゲン化合物を用いる方法(J.
Am.Chem.Soc.59,2012(1937)
、特開平1−172371、特開平2−221255)
NaSCN(又はKSCN)+RX→RNCS+N
aX(又はKX)……………………………(式1)(2
)ジチオカルバミン酸塩を重金属塩の存在で分解する方
法(Ber.1,170(1868)、Org.Syn
th.,I,447(1941)) RNH−C(=
S)−SNa +Pb(NO3)2+NaOH→〔RS
CN〕→RNCS+PbS +2NaNO3…(式2)
(3)ジチオカルバミン酸塩とクロル蟻酸エステルを反
応させる方法(Org.Synth.,III,599
(1955)) RNH−C(=S)−SNa +C
l−C(=O)−OC2H5→RNCS+NaCl+C
2H5OH+COS ………(式3)(4)一級アミン
とチオホスゲンを反応させる方法(Acta,Chem
.Scand.,11 1298(1957)、J.A
m.Chem.Soc.54,781(1962))
R−NH2 +CSCl2 →RNCS+2HCl
………………………………………………(式4)(5)
ジチオカルバミン酸とシアナミドを反応させる方法(特
開昭56−172371)
RNH−C−(=S)−SH +NH2CN →R
NCS+(NH2)2CS………………………………(
式5)などがある。BACKGROUND OF THE INVENTION There have been several reports on methods for synthesizing isothiocyanate esters. For example, (1) a method using a metal thiocyanate and a halogen compound (J.
Am. Chem. Soc. 59, 2012 (1937)
, JP-A-1-172371, JP-A-2-221255) NaSCN (or KSCN)+RX→RNCS+N
aX (or KX)…………………………(Formula 1) (2
) Method for decomposing dithiocarbamates in the presence of heavy metal salts (Ber. 1, 170 (1868), Org. Syn
th. , I, 447 (1941)) RNH-C (=
S)-SNa +Pb(NO3)2+NaOH→[RS
CN]→RNCS+PbS+2NaNO3…(Formula 2)
(3) Method of reacting dithiocarbamate and chloroformate (Org.Synth., III, 599
(1955)) RNH-C(=S)-SNa +C
l-C(=O)-OC2H5→RNCS+NaCl+C
2H5OH+COS......(Formula 3) (4) Method of reacting primary amine and thiophosgene (Acta, Chem
.. Scand. , 11 1298 (1957), J. A
m. Chem. Soc. 54,781 (1962)) R-NH2 +CSCl2 →RNCS+2HCl
………………………………………………(Formula 4) (5)
Method of reacting dithiocarbamic acid and cyanamide (JP-A-56-172371) RNH-C-(=S)-SH +NH2CN →R
NCS+(NH2)2CS………………………………(
Equation 5) etc.
【0003】しかしながら、これらの方法において、(
1)では、チオシアン酸塩に対して非プロトン性極性溶
媒を多量に必要とし、又、チオシアン酸エステルからイ
ソチオシアン酸エステルへの異性化収率が低い等の欠点
がある。(2)では、重金属塩を使用するため、廃液か
らの金属回収や公害防止の為の確実な処理を必要とする
など経済性の面で工業的に有利ではない。(3)では、
クロル蟻酸エステルが比較的高価であること、これとの
反応で生成するCOS が有毒であり、安全上の注意が
必要であること、更に(4)では高価かつ猛毒なチオホ
スゲンを使用することなどの欠点がある。(5)では、
シアナミドが吸湿性のため取扱いが煩雑となり、又、高
品位の工業用原料として入手困難であるなど、いずれも
問題点があり、工業的に有利な方法とは言いがたい。However, in these methods, (
Method 1) requires a large amount of aprotic polar solvent relative to the thiocyanate, and has drawbacks such as a low isomerization yield from thiocyanate to isothiocyanate. In method (2), heavy metal salts are used, which requires reliable treatment for recovering metals from waste liquid and preventing pollution, which is not industrially advantageous from an economic point of view. In (3),
There are several problems, such as the fact that chloroformate is relatively expensive, the COS produced by the reaction with it is toxic and requires safety precautions, and (4) requires the use of expensive and highly toxic thiophosgene. There are drawbacks. In (5),
Since cyanamide is hygroscopic, handling is complicated, and it is difficult to obtain as a high-grade industrial raw material. All of these methods have problems, and cannot be said to be industrially advantageous.
【0004】0004
【発明が解決しようとする問題点】本発明者らは、この
ような状況に鑑み、従来技術の問題点を解決すべくイソ
チオシアン酸エステル類の製造法について鋭意研究を重
ねてきた結果、簡便かつ高収率で、しかも安全性の高い
工業的に有利なイソチオシアン酸エステル類の製造方法
を見出し、本発明を完成するに至った。[Problems to be Solved by the Invention] In view of the above circumstances, the present inventors have conducted intensive research on a method for producing isothiocyanate esters in order to solve the problems of the prior art. The present inventors have discovered an industrially advantageous method for producing isothiocyanate esters with high yield and high safety, and have completed the present invention.
【0005】[0005]
【問題点を解決するための手段】即ち、本発明は、一般
式〔1〕
R−OH 〔1〕
(式中、RはC1〜C18の範囲のアルキル基、アラル
キル基、シクロアルキル基、アルケニル基、アルキニル
基、およびヘテロ環を表わす。)で表わされるアルコー
ルを、一般式〔2〕
R’−SO2X 〔2〕
(式中、R’はアルキル基またはアリール基を表わし、
Xはハロゲン原子を表わす。)で表わされるハロゲン化
スルホニル化合物と反応させ、一般式〔3〕R−OSO
2R’ 〔3〕
(式中、R,R’は前記した基と同一である。)で表わ
されるスルホン酸エステルとした後、チオシアン酸塩と
反応させて得られる一般式〔4〕
R−SCN 〔4〕
(式中、Rは前記した基と同一である。)で表わされる
チオシアン酸エステルを異性化することを特徴とする一
般式〔5〕
R−NCS 〔5〕
(式中、Rは前記した基と同一である。)で表されるイ
ソチオシアン酸エステル類の製造方法をその要旨とする
ものである。本発明の態様を更に詳しく説明すると、イ
ソチオシアン酸エステルを得る基本の反応は、(式6)
によって表わされる。即ち、
R−OH──→R−OSO2R’
──→R−SCN ──→R−NCS (式6
) 〔1〕 〔3〕
〔4〕 〔5〕(式中、RはC1〜
C18 の範囲のアルキル基、アラルキル基、シクロア
ルキル基、アルケニル基、アルキニル基、およびヘテロ
環を表わし、R’はアルキル基またはアリール基を表わ
す。)であり、一般式〔1〕で表わされるアルコールを
出発原料とし、ハロゲン化スルホニル化合物と反応させ
、一般式〔3〕で示されるスルホン酸エステル(J.O
rg.Chem. 37 1162(1972) 、J
.Org.Chem. 35 3195(1970)
、J.Amer.Chem.Soc., 91 260
3(1969))とした後、有機溶媒中、チオシアン酸
塩と所定の温度で、所定の時間反応させて得られる一般
式〔4〕で示されるチオシアン酸エステルを触媒を用い
、溶媒の存在下または無溶媒下で、所定の条件で加熱異
性化させて一般式〔5〕で示されるイソチオシアン酸エ
ステル類を高収率で得ることができる。[Means for Solving the Problems] That is, the present invention provides a general formula [1] R-OH [1] (wherein R is an alkyl group in the range of C1 to C18, an aralkyl group, a cycloalkyl group, an alkenyl represents an alkyl group, an alkynyl group, or a heterocyclic ring.
X represents a halogen atom. ) to react with a halogenated sulfonyl compound represented by the general formula [3] R-OSO
General formula [4] R-SCN obtained by forming a sulfonic acid ester represented by 2R' [3] (in the formula, R and R' are the same as the above-mentioned groups) and then reacting it with a thiocyanate [4] General formula [5] R-NCS [5] (In the formula, R is the same as the above-mentioned group) characterized by isomerizing a thiocyanate ester represented by The gist of the present invention is a method for producing isothiocyanate esters represented by the above-mentioned groups. To explain the aspect of the present invention in more detail, the basic reaction to obtain the isothiocyanate ester is (Formula 6)
is expressed by That is, R-OH──→R-OSO2R'
──→R-SCN ──→R-NCS (Formula 6
) [1] [3]
[4] [5] (wherein, R is C1~
It represents an alkyl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, and a heterocycle in the range of C18, and R' represents an alkyl group or an aryl group. ), the alcohol represented by the general formula [1] is used as a starting material and reacted with a halogenated sulfonyl compound to form a sulfonic acid ester represented by the general formula [3] (J.O
rg. Chem. 37 1162 (1972), J.
.. Org. Chem. 35 3195 (1970)
, J. Amer. Chem. Soc. , 91 260
3 (1969)), the thiocyanate represented by the general formula [4] obtained by reacting with a thiocyanate in an organic solvent at a predetermined temperature for a predetermined time is reacted with a thiocyanate in the presence of a solvent using a catalyst. Alternatively, the isothiocyanate ester represented by the general formula [5] can be obtained in high yield by heat isomerization under predetermined conditions without a solvent.
【0006】前記一般式〔1〕、一般式〔2〕、一般式
〔3〕、一般式〔4〕、一般式〔5〕、および(式6)
で示されるRのうち、アルキル基としては、例えば、メ
チル基、エチル基、プロピル基、ブチル基、ペンチル基
、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デ
シル基、ラウリル基、ヘキサデシル基、ステアリル基な
どが挙げられ、置換アルキル基としては、例えば、2−
メトキシエチル基、クロルエチル基、ブロムエチル基、
3−トリエトキシシリルプロピル基、6−メチルチオヘ
キシル基などが挙げられる。アラルキル基としては、例
えば、ベンジル基、ベンゼン環にクロル、メトキシ基、
またはニトロ基が置換したベンジル基、フェネチル基な
どが挙げられ、シクロアルキル基としては、例えば、シ
クロブチル基、シクロペンチル基、シクロヘキシル基、
シクロヘプチル基などが挙げられる。アルケニル基とし
ては、例えば、アリル基、ブテニル基、ペンテニル基、
ヘキセニル基などが挙げられ、アルキニル基としては、
例えば、プロパルギル基、ブチニル基などが挙げられる
。ヘテロ環としては、O、SおよびN原子を含む飽和ま
たは不飽和環を挙げることができる。The above general formula [1], general formula [2], general formula [3], general formula [4], general formula [5], and (formula 6)
Among R represented by R, examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, lauryl group, hexadecyl group, Examples of substituted alkyl groups include stearyl groups, and examples of substituted alkyl groups include 2-
Methoxyethyl group, chloroethyl group, bromoethyl group,
Examples include 3-triethoxysilylpropyl group and 6-methylthiohexyl group. Examples of the aralkyl group include a benzyl group, a chloro group on a benzene ring, a methoxy group,
or a benzyl group substituted with a nitro group, a phenethyl group, etc., and examples of the cycloalkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group,
Examples include cycloheptyl group. Examples of alkenyl groups include allyl group, butenyl group, pentenyl group,
Examples of alkynyl groups include hexenyl groups,
Examples include propargyl group and butynyl group. Heterocycles may include saturated or unsaturated rings containing O, S and N atoms.
【0007】前記、一般式〔2〕および一般式〔3〕で
示されるR’のうち、アルキル基としては、例えば、メ
チル基、エチル基などが挙げられ、アリール基としては
、例えば、フェニル基、トリル基、メトキシフェニル基
、ナフチル基などが挙げられる。[0007] Among R' shown in the above general formula [2] and general formula [3], examples of the alkyl group include a methyl group and an ethyl group, and examples of the aryl group include a phenyl group. , tolyl group, methoxyphenyl group, naphthyl group, etc.
【0008】本発明で用いられるチオシアン酸塩として
は、チオシアン酸ナトリウム、チオシアン酸カリウム、
チオシアン酸アンモニウムなどが挙げられる。使用量は
、原料に対して、 1.0〜2.0 モル、望ましくは
、 1.0〜1.3 モルが適当である。所望のイソチ
オシアン酸エステルへの異性化工程には、触媒の使用が
望ましく、例えば、ヨウ化ナトリウム、ヨウ化カリウム
、ヨウ化カルシウム、臭化ナトリウムの如きハロゲン化
物、塩化カルシウム、硫酸カルシウム、塩化マグネシウ
ムの如きアルカリ金属、又は、アルカリ土類金属塩など
の無機触媒が知られている(特開昭49−88878、
特開昭61−143353 、特開平1−172371
、特開平2−221255)。本発明者らは、新たに、
この異性化触媒につき精査した結果、例えば、テトラメ
チルアンモニウムクロライド、テトラメチルアンモニウ
ムブロマイド、テトラメチルアンモニウムアイオダイド
、テトラエチルアンモニウムクロライド、テトラエチル
アンモニウムブロマイド、テトラエチルアンモニウムア
イオダイド、テトラブチルアンモニウムクロライド、テ
トラブチルアンモニウムブロマイド、テトラブチルアン
モニウムアイオダイド、ベンジルトリエチルアンモニウ
ムクロライド、ベンジルトリエチルアンモニウムブロマ
イドの如き第四級アンモニウム塩、又、テトラメチルホ
スホニウムクロライド、テトラメチルホスホニウムブロ
マイド、テトラメチルホスホニウムアイオダイド、テト
ラエチルホスホニウムクロライド、テトラエチルホスホ
ニウムニウムブロマイド、テトラエチルホスホニウムア
イオダイド、テトラブチルホスホニウムクロライド、テ
トラブチルホスホニウムブロマイド、テトラブチルホス
ホニウムアイオダイドの如きホスホニウム塩が極めてす
ぐれか反応促進効果を有することを見出した。
これらの触媒物質の使用量は、一般式〔3〕、又は、一
般式〔4〕で示される化合物に対して0.05モル以上
、望ましくは 0.1〜1.0 モルである。[0008] The thiocyanate used in the present invention includes sodium thiocyanate, potassium thiocyanate,
Examples include ammonium thiocyanate. The appropriate amount to be used is 1.0 to 2.0 mol, preferably 1.0 to 1.3 mol, based on the raw material. In the isomerization step to the desired isothiocyanate ester, it is desirable to use a catalyst, for example, halides such as sodium iodide, potassium iodide, calcium iodide, sodium bromide, calcium chloride, calcium sulfate, magnesium chloride. Inorganic catalysts such as alkali metal or alkaline earth metal salts are known (JP-A-49-88878,
JP-A-61-143353, JP-A-1-172371
, Japanese Patent Publication No. 2-221255). The present inventors newly
As a result of careful investigation of this isomerization catalyst, for example, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium bromide, Quaternary ammonium salts such as tetrabutylammonium iodide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, tetramethylphosphonium chloride, tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetraethylphosphonium chloride, tetraethylphosphonium bromide, It has been found that phosphonium salts such as tetraethylphosphonium iodide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, and tetrabutylphosphonium iodide have extremely excellent reaction-promoting effects. The amount of these catalyst substances used is 0.05 mol or more, preferably 0.1 to 1.0 mol, relative to the compound represented by general formula [3] or general formula [4].
【0009】本発明で一般式〔4〕で示されるチオシア
ン酸エステルを加熱異性化し、一般式〔5〕で示される
イソチオシアン酸エステルを得るには、無溶媒でもよく
、また溶媒を使用する場合は、一般式〔1〕、一般式〔
2〕、一般式〔3〕、および一般式〔4〕で示される化
合物を溶解し、反応させることができるものであれば良
く、例えばメタノール、エタノールの如きアルコール系
溶媒類、酢酸メチル、酢酸エチルの如きエステル類、エ
チルエーテル、テトラヒドロフラン、ジオキサンの如き
エーテル類、アセトニトリル、ジメチルホルムアミド、
ジメチルスルホキシド、ジメチルアセトアミド、N−メ
チルピロリドン、スルホラン、1,3−ジメチル−2−
イミダゾリジノンの如き非プロトン性極性溶媒などが特
に好ましい。In the present invention, the isomerization of the thiocyanate ester represented by the general formula [4] by heating to obtain the isothiocyanate ester represented by the general formula [5] may be carried out without a solvent, or if a solvent is used, , general formula [1], general formula [
2], general formula [3], and general formula [4] and can be reacted with each other, such as alcoholic solvents such as methanol and ethanol, methyl acetate, and ethyl acetate. esters such as ethyl ether, tetrahydrofuran, ethers such as dioxane, acetonitrile, dimethylformamide,
Dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, sulfolane, 1,3-dimethyl-2-
Particularly preferred are aprotic polar solvents such as imidazolidinone.
【0010】本発明の反応に有用な温度は、イソチオシ
アン酸エステルの生成率が最も良好になるように適宜選
択が可能であり、20℃〜250 ℃、好ましくは特に
50〜170 ℃が適当である。本発明方法は、下記の
(式7)によって表わされる如く、工業的に有利なイソ
チオシアン酸エステルの製造法を提供することにある。
すなわち、その第一の特徴である出発原料として一般式
〔1〕で示されるアルコールを用い、ハロゲン化スルホ
ニル化合物を反応させ、一般式〔3〕で示されるスルホ
ン酸エステルとした後、単離することなくチオシアン酸
塩と反応させ、一般式〔4〕で示されるチオシアン酸エ
ステルを高収率で得る経済性の高い方法と、第二の特徴
であるここに得られたチオシアン酸エステルを第四級ア
ンモニウム塩またはホスホニウム塩などの触媒の存在下
、非プロトン性溶媒中、異性化させ、イソチオシアン酸
エステルを簡便かつ高収率で得る経済的な方法を効果的
に連結した新規な製造方法である。
ROH +R’−SO2X →ROSO2R’
+ M+ SNC − →RSCN→RNCS
(式7) 〔1〕 〔2〕 〔3〕
〔4〕〔5〕(式中、Rお
よびR’は前記した基と同一である。Mはアルカリ金属
元素、および無置換アンモニウムを表わす。)[0010] The temperature useful for the reaction of the present invention can be appropriately selected so as to obtain the best production rate of isothiocyanate ester, and is suitably 20°C to 250°C, preferably 50°C to 170°C. . The purpose of the present invention is to provide an industrially advantageous method for producing isothiocyanate esters, as represented by the following formula (7). That is, the first characteristic is that an alcohol represented by the general formula [1] is used as a starting material, and a halogenated sulfonyl compound is reacted to form a sulfonic acid ester represented by the general formula [3], which is then isolated. A highly economical method for obtaining a thiocyanate ester represented by the general formula [4] in a high yield by reacting the thiocyanate with a thiocyanate without any This is a new production method that effectively combines an economical method of isomerizing isomerization in an aprotic solvent in the presence of a catalyst such as a grade ammonium salt or phosphonium salt to obtain isothiocyanate ester easily and in high yield. . ROH +R'-SO2X →ROSO2R'
+ M+ SNC − →RSCN→RNCS
(Formula 7) [1] [2] [3]
[4] [5] (In the formula, R and R' are the same as the groups described above. M represents an alkali metal element and unsubstituted ammonium.)
【0011】[0011]
【発明の効果】従来のイソチオシアン酸エステルの製造
法では、ジチオカルバミン酸塩とクロル蟻酸エチルとの
反応や、ジチオカルバミン酸塩を重金属塩の存在で分解
する方法が一般的であるが、前者では有毒なCOS が
発生するため一旦アルカリ液に吸収させるなど安全上、
充分な管理を必要とすること、又、後者では廃液からの
金属の回収や公害防止のための確実な処理を必要とする
ことなど製造上および経済上の問題点が存在する。又、
シアナミドを用いる方法は、シアナミドが極めて吸湿性
が高いため取扱いが厄介であり、かつ、高品位の工業用
原料として入手困難であるなど工業上、問題点が多い。
これに対し、本発明は、安価な出発原料である一般
式〔1〕で示されるアルコールを一般式〔3〕で表わさ
れる対応するスルホン酸エステルとした後、これを単離
することなく、チオシアン酸塩と反応させ、一般式〔4
〕で示されるチオシアン酸エステルを得、更に、非プロ
トン性極性溶媒中、好ましい触媒として、第四級アンモ
ニウム塩またはホスホニウム塩の存在下、異性化させ、
目的とする一般式〔5〕で示されるイソチオシアン酸エ
ステル類を簡便にかつ高収率で得る経済性の高い画期的
な製造法である。以下、本発明を更に詳しく説明するた
めに実施例を示すが、これらの実施例は本発明を限定す
るものではない。[Effect of the invention] Conventional methods for producing isothiocyanate esters generally involve the reaction of dithiocarbamates with ethyl chloroformate, or the decomposition of dithiocarbamates in the presence of heavy metal salts, but the former is toxic. Because COS is generated, for safety reasons, such as absorbing it in alkaline solution, etc.
There are manufacturing and economical problems, such as the need for sufficient management and, in the latter case, the need for reliable treatment to recover metals from waste liquid and prevent pollution. or,
The method using cyanamide has many industrial problems, such as cyanamide being extremely hygroscopic and difficult to handle, and difficult to obtain as a high-grade industrial raw material. On the other hand, the present invention converts the alcohol represented by the general formula [1], which is an inexpensive starting material, into the corresponding sulfonic acid ester represented by the general formula [3], and then converts the alcohol into a thiocyanate without isolating it. By reacting with an acid salt, the general formula [4
] is obtained, and further isomerized in an aprotic polar solvent in the presence of a quaternary ammonium salt or a phosphonium salt as a preferred catalyst,
This is an innovative and highly economical manufacturing method that allows the desired isothiocyanate ester represented by the general formula [5] to be obtained easily and in high yield. EXAMPLES Hereinafter, Examples will be shown to explain the present invention in more detail, but these Examples are not intended to limit the present invention.
【0012】0012
【実施例】〔実施例1.〕イソチオシアン酸n−プロピ
ル(化合物No.1)の合成
P−トルエンスルホン酸n−プロピルエステル75.2
g 、KSCN 42.0g、テトラエチルアンモニウ
ムブロマイド8.7gを酢酸エチル145ml 、水3
0mlに添加し、80℃で3時間撹拌した。反応終了後
、水洗し、無水硫酸マグネシウムで乾燥後、酢酸エチル
を減圧留去して得られた油状物チオシアン酸n−プロピ
ル40.6g にテトラエチルアンモニウムブロマイド
8.4gを添加し、1,3−ジメチル−2−イミダゾリ
ジノン75mlに溶解後、 140〜145 ℃で2時
間撹拌した。反応終了後、酢酸エチル250ml で抽
出し、水洗し、無水硫酸マグネシウムで乾燥値、酢酸エ
チルを減圧留去して得られた油状物を蒸留し、沸点 1
51〜152 ℃で化合物No.1 37.9g(収率
75%)を得た。[Example] [Example 1. ] Synthesis of n-propyl isothiocyanate (compound No. 1) P-toluenesulfonic acid n-propyl ester 75.2
g, KSCN 42.0 g, tetraethylammonium bromide 8.7 g, ethyl acetate 145 ml, water 3
0 ml and stirred at 80°C for 3 hours. After the reaction was completed, it was washed with water, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. To 40.6 g of n-propyl thiocyanate, 8.4 g of tetraethylammonium bromide was added to give 1,3- After dissolving in 75 ml of dimethyl-2-imidazolidinone, it was stirred at 140-145°C for 2 hours. After the reaction was completed, the mixture was extracted with 250 ml of ethyl acetate, washed with water, dried over anhydrous magnesium sulfate, and the oil obtained by distilling off the ethyl acetate under reduced pressure was distilled to a boiling point of 1.
Compound No. 51-152°C. 137.9g (yield 75%) was obtained.
【0013】〔実施例2.〕イソチオシアン酸 sec
−ブチル(化合物No.2)の合成
メタンスルホン酸 sec−ブチルエステル92.3g
、NaSCN 45.2g 、ヨウ化ナトリウム21
.0g を酢酸エチル200ml 、水35mlに添加
し、80℃で2時間撹拌した。反応終了後、水洗し、無
水硫酸マグネシウムで乾燥後、酢酸エチルを減圧留去し
て得られた油状物チオシアン酸 sec−ブチル66.
4g にテトラエチルホウホニウムブロマイド8.5g
を添加し、N−メチル2−ピロリドン110ml に溶
解後、 140〜145 ℃で3時間撹拌した。反応終
了後、酢酸エチル380ml で抽出、水洗し、無水硫
酸マグネシウムで乾燥後、酢酸エチルを減圧留去して得
られた油状物を蒸留し、沸点159〜160 ℃の化合
物No.2 57.0g(収率82%)を得た。[Example 2. ]isothiocyanic acid sec
-Synthesis of butyl (compound No. 2) Methanesulfonic acid sec-butyl ester 92.3g
, NaSCN 45.2g, sodium iodide 21
.. 0 g was added to 200 ml of ethyl acetate and 35 ml of water, and the mixture was stirred at 80°C for 2 hours. After the reaction was completed, the oil was washed with water, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain sec-butyl thiocyanate.
4g and 8.5g of tetraethyl borophonium bromide
was added, dissolved in 110 ml of N-methyl 2-pyrrolidone, and stirred at 140-145°C for 3 hours. After the reaction was completed, it was extracted with 380 ml of ethyl acetate, washed with water, dried over anhydrous magnesium sulfate, and the ethyl acetate was distilled off under reduced pressure. 257.0g (yield 82%) was obtained.
【0014】〔実施例3.〕イソチオシアン酸5−ヘキ
セニル(化合物No.6)の合成
5−ヘキセン−1−オール30.5g 、トリエチルア
ミン34.0g を酢酸エチル280ml に溶解後、
P−トルエンスルホニルクロライド56.9g を5℃
以下で添加し、20〜25℃で2時間反応した。反応終
了後、水120ml を注加後、更に、KSCN 29
g、テトラエチルアンモニウムクロライド 5.0g
を添加し、80℃で3時間撹拌した。反応終了後、酢酸
エチルで抽出、水洗し、無水硫酸マグネシウムで乾燥後
、酢酸エチルを減圧留去して得られた油状物チオシアン
酸5−ヘキセニル40.0g にテトラエチルアンモニ
ウムブロマイド 5.9g を添加し、1,3−ジメチ
ル−2−イミダゾリジノン55mlに溶解後、 140
〜145 ℃で2時間撹拌した。反応終了後、酢酸エチ
ル180ml で抽出、水洗し、無水硫酸マグネシウム
で乾燥後、酢酸エチルを減圧留去して得られた油状物を
蒸留し、沸点70〜72℃/7mmHgの化合物No.
6 33.0g(収率78%)を得た。[Example 3. ] Synthesis of 5-hexenyl isothiocyanate (compound No. 6) After dissolving 30.5 g of 5-hexen-1-ol and 34.0 g of triethylamine in 280 ml of ethyl acetate,
56.9g of P-toluenesulfonyl chloride at 5℃
It was added below and reacted at 20-25°C for 2 hours. After the reaction was completed, 120 ml of water was added, and then KSCN 29
g, tetraethylammonium chloride 5.0g
was added and stirred at 80°C for 3 hours. After the reaction was completed, the mixture was extracted with ethyl acetate, washed with water, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure.To 40.0 g of 5-hexenyl thiocyanate, an oily product was added to 5.9 g of tetraethylammonium bromide. , after dissolving in 55 ml of 1,3-dimethyl-2-imidazolidinone, 140
Stirred at ˜145° C. for 2 hours. After the reaction was completed, it was extracted with 180 ml of ethyl acetate, washed with water, dried over anhydrous magnesium sulfate, and the ethyl acetate was distilled off under reduced pressure.
6 33.0g (yield 78%) was obtained.
【0015】〔実施例4.〕イソチオシアン酸ベンジル
(化合物No.11)の合成
ベンジルアルコール43.2g をピリジン34.8g
に溶解後、メタンスルニルクロライド45.5g を
5℃以下で添加し、5〜10℃で2時間反応した。反応
終了後、酢酸エチル150ml で抽出後、水25ml
を添加し、更にNH4SCN 30g、テトラエチルア
ンモニウムブロマイド8.5gを添加し、80℃で4時
間撹拌した。反応終了後、水洗し、無水硫酸マグネシウ
ムで乾燥後、酢酸エチルを減圧留去して得られた油状物
チオシアン酸ベンジル53.7g にテトラエチルアン
モニウムブロマイド7.5gを添加し、N,N,−ジメ
チルアセトアミド75mlに溶解後、 140〜145
℃で 1.5時間撹拌した。反応終了後、酢酸エチル
250ml で抽出、水洗し無水硫酸マグネシウムで乾
燥後、酢酸エチルを減圧留去臭て得られた油状物を蒸留
し、沸点 105〜106 ℃/10mmHg の化合
物No.11 40.5g(収率68%)を得た。本発
明の方法によって合成した種々のイソチオシアン酸エス
テルを表−1に示す。[Example 4. ] Synthesis of benzyl isothiocyanate (compound No. 11) 43.2 g of benzyl alcohol was mixed with 34.8 g of pyridine.
After dissolving in the solution, 45.5 g of methanesulnyl chloride was added at 5°C or lower, and the mixture was reacted at 5 to 10°C for 2 hours. After the reaction is complete, extract with 150ml of ethyl acetate, then add 25ml of water.
was added, and further 30 g of NH4SCN and 8.5 g of tetraethylammonium bromide were added, and the mixture was stirred at 80°C for 4 hours. After the reaction was completed, it was washed with water, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. To 53.7 g of benzyl thiocyanate, 7.5 g of tetraethylammonium bromide was added, and N,N,-dimethyl After dissolving in 75ml of acetamide, 140-145
Stirred at ℃ for 1.5 hours. After the reaction was completed, it was extracted with 250 ml of ethyl acetate, washed with water, dried over anhydrous magnesium sulfate, and the ethyl acetate was distilled off under reduced pressure to distill the resulting oil. 40.5 g (yield 68%) of 11 was obtained. Table 1 shows various isothiocyanate esters synthesized by the method of the present invention.
【0016】[0016]
【表1】[Table 1]
Claims (1)
キル基、シクロアルキル基、アルケニル基、アルキニル
基、およびヘテロ環を表わす。)で表わされるアルコー
ルを、一般式〔2〕 R’−SO2X 〔2〕 (式中、R’はアルキル基またはアリール基を表わし、
Xはハロゲン原子を表わす。)で表わされるハロゲン化
スルホニル化合物と反応させ、一般式〔3〕R−OSO
2R’ 〔3〕 (式中、R,R’は前記した基と同一である。)で表わ
されるスルホン酸エステルとした後、チオシアン酸塩と
反応させて得られる一般式〔4〕 R−SCN 〔4〕 (式中、Rは前記した基と同一である。)で表わされる
チオシアン酸エステルを異性化することを特徴とする一
般式〔5〕 R−NCS 〔5〕 (式中、Rは前記した基と同一である。)で表わされる
イソチオシアン酸エステル類の製造方法。Claim 1: General formula [1] R-OH [1] (wherein R represents an alkyl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, or a heterocycle in the range of C1 to C18. ) is represented by the general formula [2] R'-SO2X [2] (wherein R' represents an alkyl group or an aryl group,
X represents a halogen atom. ) to react with a halogenated sulfonyl compound represented by the general formula [3] R-OSO
General formula [4] R-SCN obtained by forming a sulfonic acid ester represented by 2R' [3] (in the formula, R and R' are the same as the above-mentioned groups) and then reacting it with a thiocyanate [4] General formula [5] R-NCS [5] (In the formula, R is the same as the above-mentioned group) characterized by isomerizing a thiocyanate ester represented by A method for producing an isothiocyanate ester represented by the above-mentioned group.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10630991A JPH04297451A (en) | 1991-03-26 | 1991-03-26 | Production of isothiocyanic acid ester |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10630991A JPH04297451A (en) | 1991-03-26 | 1991-03-26 | Production of isothiocyanic acid ester |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04297451A true JPH04297451A (en) | 1992-10-21 |
Family
ID=14430392
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10630991A Pending JPH04297451A (en) | 1991-03-26 | 1991-03-26 | Production of isothiocyanic acid ester |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04297451A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111018759A (en) * | 2019-12-31 | 2020-04-17 | 浙江工业大学 | Method for preparing organic cyanide |
-
1991
- 1991-03-26 JP JP10630991A patent/JPH04297451A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111018759A (en) * | 2019-12-31 | 2020-04-17 | 浙江工业大学 | Method for preparing organic cyanide |
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