CN1056833C - 杂环化合物的亚磺酰化方法 - Google Patents
杂环化合物的亚磺酰化方法 Download PDFInfo
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- CN1056833C CN1056833C CN95100789A CN95100789A CN1056833C CN 1056833 C CN1056833 C CN 1056833C CN 95100789 A CN95100789 A CN 95100789A CN 95100789 A CN95100789 A CN 95100789A CN 1056833 C CN1056833 C CN 1056833C
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- 238000000034 method Methods 0.000 title claims abstract description 31
- 150000002391 heterocyclic compounds Chemical class 0.000 title abstract description 13
- 150000001875 compounds Chemical class 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 125000005843 halogen group Chemical group 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- -1 Amino Chemical group 0.000 claims description 14
- 125000001188 haloalkyl group Chemical group 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000000623 heterocyclic group Chemical group 0.000 claims description 11
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 7
- 150000003217 pyrazoles Chemical group 0.000 claims description 6
- HGAMRMFMRCGNAR-UHFFFAOYSA-N 4-sulfinylpyrazole Chemical class O=S=C1C=NN=C1 HGAMRMFMRCGNAR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- DDKMFOUTRRODRE-UHFFFAOYSA-N chloromethanone Chemical compound Cl[C]=O DDKMFOUTRRODRE-UHFFFAOYSA-N 0.000 claims description 2
- 238000005991 sulfenylation reaction Methods 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims 5
- 150000001412 amines Chemical group 0.000 claims 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 2
- 229950004288 tosilate Drugs 0.000 claims 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 claims 1
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 claims 1
- PIZNQHDTOZMVBH-UHFFFAOYSA-N thionylimide Chemical compound N=S=O PIZNQHDTOZMVBH-UHFFFAOYSA-N 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 230000006103 sulfonylation Effects 0.000 description 8
- 238000005694 sulfonylation reaction Methods 0.000 description 8
- 239000000376 reactant Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- ZOCSXAVNDGMNBV-UHFFFAOYSA-N 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile Chemical compound NC1=C(S(=O)C(F)(F)F)C(C#N)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl ZOCSXAVNDGMNBV-UHFFFAOYSA-N 0.000 description 5
- QPZYPAMYHBOUTC-UHFFFAOYSA-N 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]pyrazole-3-carbonitrile Chemical compound NC1=CC(C#N)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl QPZYPAMYHBOUTC-UHFFFAOYSA-N 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- GWBNYWVYPASUBM-UHFFFAOYSA-N trifluoromethanesulfinyl chloride Chemical compound FC(F)(F)S(Cl)=O GWBNYWVYPASUBM-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- YBDZTDSNQMIWOG-UHFFFAOYSA-N 3-sulfinylpyrazole Chemical compound O=S=C1C=CN=N1 YBDZTDSNQMIWOG-UHFFFAOYSA-N 0.000 description 3
- PTNHUPJANGKQAM-UHFFFAOYSA-N 4-methylbenzenesulfonic acid;n-methylmethanamine Chemical compound CNC.CC1=CC=C(S(O)(=O)=O)C=C1 PTNHUPJANGKQAM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000003851 azoles Chemical class 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 150000003233 pyrroles Chemical group 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- PAPNRQCYSFBWDI-UHFFFAOYSA-N 2,5-Dimethyl-1H-pyrrole Chemical group CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 229910006124 SOCl2 Inorganic materials 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000003854 isothiazoles Chemical class 0.000 description 2
- 150000002545 isoxazoles Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002916 oxazoles Chemical class 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 125000003226 pyrazolyl group Chemical group 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 150000003557 thiazoles Chemical class 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QULMJNOWBLIQHN-UHFFFAOYSA-N 1,1,1-trifluoro-n,n-dimethylmethanesulfinamide Chemical compound CN(C)S(=O)C(F)(F)F QULMJNOWBLIQHN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DYYLCPSSSFWEEA-UHFFFAOYSA-N 4-methylbenzenesulfinyl chloride Chemical compound CC1=CC=C(S(Cl)=O)C=C1 DYYLCPSSSFWEEA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- YAMQOOCGNXAQGW-UHFFFAOYSA-M magnesium;methylbenzene;bromide Chemical compound [Mg+2].[Br-].CC1=CC=CC=[C-]1 YAMQOOCGNXAQGW-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002734 organomagnesium group Chemical group 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- KAVUKAXLXGRUCD-UHFFFAOYSA-M sodium trifluoromethanesulfinate Chemical compound [Na+].[O-]S(=O)C(F)(F)F KAVUKAXLXGRUCD-UHFFFAOYSA-M 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 125000006296 sulfonyl amino group Chemical group [H]N(*)S(*)(=O)=O 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
- C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/88—Nitrogen atoms, e.g. allantoin
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/38—Nitrogen atoms
- C07D231/40—Acylated on said nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyrrole Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Cephalosporin Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Coloring (AREA)
Abstract
一种使用BSOX直接将杂环化合物亚磺酰化的方法。
Description
本发明涉及新颖的杂环化合物的亚磺酰化方法。
杂环化合物的亚磺酰化，即引入RSO-基团，系通过由式RSX(R和X的定义见后述)表示的化合物与杂环化合物中将被取代的碳上的氢原子反应而进行。因此，上述反应生成硫基杂环化合物，后者必须经过氧化才生成所需的亚磺酰基化合物。然而，业已发现，该氧化步骤常常不易进行。而且发现有些由式RSX表示的化合物毒性很大，例如化合物CF3SCl即是如此，因而使操作变得复杂。另一个常规的方法系通过使用化合物RX，将一中间体二硫化物的S-S键断裂，生成烃硫基化合物，然后进一步氧化成亚磺酰基化合物。该方法避免了化合物RSX的使用，但未能免去其后的氧化步骤。
因此，本发明的目的在于克服上述二个缺点(氧化困难和反应物有毒性)，提出一种不降低反应的总收率，而且能减少反应步骤的使用RSOX直接与杂环化合物反应而进行亚磺酰化的方法。业已发现一种方法，它能全部或部分地满足反应的容易性、得率和安全性等方面的要求，这一方法便是本发明的主题。
欧洲专利申请EP0,295,117、0,460,940和0,484,165列举了一些制造亚磺酰化的杂环化合物的方法，可归纳为以下二种类型：
第一种系首先制造烃硫基化合物，然后将其氧化，制得所需的化合物。烃硫基化合物由反应剂RSX与杂环化合物有关位置上的氢原子直接发生烃硫基化反应，或由有机镁试剂或化合物R1I或R1Br(R1为烷基或卤代烷基)与氰硫基杂环反应，或由二硫化物在化合物R1I的存在下还原而制得。欧洲申请EP-A-0,295,117描述了这些不同方法(参见11-12页上的方法b、d1、d2和d3)。欧洲专利EP B1 374,061描述了使用二硫化物的另一种方法。
第二种系亚磺酰基化合物与特定化合物反应，使该反应的产物能通过环化而生成亚磺酰基杂环化合物。关于这些方法的详细说明，仍可参阅欧洲申请EP-A-0,295,117(参见11页上的方法a和c)。
另外，在芳香系和非杂环系方面，已有关于芳族(苯环)直接亚磺酰化的报道。例如，Bull.Chem.Soc.Jpn.46，(1973)3615描述了在催化剂AlCl3的存在下使用对甲基苯亚磺酰氯进行甲氧基苯的亚磺酰化反应。Zh.Org.Khim.，17(9)(1981)1800描述了该类型的另一个反应。在该反应中，格氏试剂即溴化甲苯基镁和萘基亚磺酰氯一起使用。
本发明系一种新颖的杂环化合物的亚磺酰化方法，它包括：化学式RSOX表示的衍生物与杂环化合物Het的反应，
其中，式RSOX中的R表示C1-C4的有一或多个相同或不同的卤原子取代的直链或支链烷基，X表示卤原子、羟基或它们的盐中的一个、二烷基氨基NR2R3，R2和R3表示C1-C4的烷基、卤代烷基，或芳氧基，其芳基部分以可任意地有一或多个卤原子或C1-C4的烷基、卤代烷基取代基的苯基为优选；
杂环化合物Het选自吡咯类、吡唑类、咪型类、噁唑类、异噁唑类、噻唑类、异噻唑类或三唑类，所有这些杂环Het上可任意地有选自下述原子或基团的一或多个取代基：卤素、无取代基的或有一或二个C1-C4烷基取代基的氨基、氰基、芳基、有一或多个卤原子和/或一或多个烷基、卤代烷基或SF5取代基的芳基，但Het为吡咯时，R不可以是正丁基，Het为2，5-二甲基吡咯时，R不可以是甲基。
在一较优选的方法中，所用杂环Het选自吡咯类、吡唑类和咪唑类，并可在约等摩尔量的对甲苯磺酸的存在下加入化合物C以使反应完全，所述化合物C选自以二甲胺、吡啶、三甲胺、二乙胺或异丙胺为优选的伯、仲或叔胺的甲苯磺酸盐、盐酸盐和甲磺酸盐，或气态氯化氢。
选自光气(COCl2)、氯甲酸酯、PCl5或SOCl2的反应剂可被任选地用于上述反应的履行。
选择有氨基取代的杂环较为有利。此氨基可与RSOX反应生成亚磺酰胺化合物，继而重排，生成在带有氨基的碳原子的一个邻位碳上有亚磺酰基的杂环化合物。
在本发明的一个具体实施例中，使用了化合物CF3SOX，其中，X为氯原子。业已知道，这里，化合物CF3SOCl的毒性小于先前使用的化合物CF3SCl，这成为本发明的优点之一。而且，如前已指出的那样，还免去了随后的氧化步骤。再有，CF3SCl在室温下是气态化合物，而CF3SOCl是液体，因而操作更方便。
在本发明的另一个具体实施例中，使用了化合物CF3SOX，其中，X为N(CH3)2或N(C2H5)2。
在本发明的还有一个具体实施例中，使用了化合物CF3SOX，其中，X为羟基OH或ONa基团，这里，反应在光气(COCl2)或SOCl2的存在下进行。
当杂环Het为下式A或B的化合物时，本发明的方法和其较佳实施例尤其合适：
其中，R1表示卤原子(以氟原子为佳)或烷基、卤代烷基(以CF3或SF5为佳)。
本发明还涉及下式所示的4-亚磺酰基吡唑的制造，
其中，R表示有一个或多个相同或不同的卤原子取代基的C1-C4直链或支链烷基，R1表示卤原子(以氟原子为优选)、烷基或卤代烷基(以CF3或SF5为优选)。该法由下式所示化合物开始，与化学式RSOX所示的反应剂反应而制得，式RSOX中，R表示有一个或多个相同或不同的卤原子取代的C1-C4直链或支链烷基，X表示卤原子、羟基或它们的盐中的一个、二烷基氨基NR2R3(R2和R3表示C1-C4的烷基或卤代烷基)、或芳氧基(芳基部分以苯基为优选，可任意地有一个或多个卤原子或C1-C4烷基或卤代烷基取代基)。进行反应时，相对于上述4-H吡唑化合物，在反应液中加入摩尔过量的反应剂RSOX。过量程度在10-50％，以20-30％为优选。
为使上述反应完全，在反应系中加入化合物C较为有利，所述化合物C选自任何伯、仲或叔胺(以二甲胺、吡啶、三甲胺或二乙胺、异丙胺为优选)的甲苯磺酸盐、盐酸盐或甲磺酸盐。它在有约等摩尔量的对甲苯磺酸存在下时可任选地使用。化合物C也可以是气态氯化氢，化合物C与杂环化合物的摩尔比以0.5-2为有利，以1-2为优选。此外，反应系数在有机溶剂中进行，所述溶剂选自甲苯、1，2-二氯乙烷和二氯甲烷。反应温度为0-100℃，以3-60℃为优选，30-55℃更佳。
可在上述反应中使用的反应剂选自光气(COCl2)、氯甲酸酯、PCl5或SOCl2。
上述吡唑的亚磺酰化尤其适用于制备下式所示的4-亚磺酰基吡唑：
人们可以按照上述方法及其实施例，或是将CF3SOCl、CF3SON(CH3)2或CF3SON(C2H5)2，或是将CF3SOOH、CF3SOONa与光气或SOCl2、ClCO2C2H5，与下列结构式所示的4-H吡唑化合物之一反应，以制取4-亚磺酰基吡唑。
本发明还涉及式RSONH-Het1所示的亚磺酰胺化合物中间体，其中，Het1-NH2为选自吡咯类、吡唑类、咪唑类、噁唑类、异噁唑类、噻唑类、异噻唑类和三唑类的有氨基取代基的杂环，所有这些杂环Het1-NH2可任意地被一个或多个原子或基团所取代，所述原子或取代基团选自卤素、无取代的或有1或2个C1-C4烷基、氰基、芳基、一或多个卤原子和/或一或多个烷基、卤代烷基或SF5取代的芳基。
下列RSONH-Het1化合物更有利地成了本发明的一部分：其中，Het1-NH2为可任意地有一或多个原子或取代基团的、有氨基取代基的吡唑杂环，所述一或多个原子或基团选自卤原子、无取代的或有一或二个C1-C4烷基取代基的氨基、氰基、芳基、有一或多个卤原子和/或一或多个烷基、卤代烷基或SF5基的芳基，而亚磺酰氨基位于该杂环的5位。
本发明对于下列化合物甚至更为有利：5-(N-三氟甲基亚磺酰基)氨基-3-氰基-1-〔2，6-二氯-4-CF3-苯基〕-4-H-吡唑和5-(N-三氟甲基亚磺酰基)氨基-3-氰基-1-〔2，6-二氯-4-SF5-苯基〕-4-H-吡唑。
下面结合实施例，对本发明进行说明，但本发明并不受限于下述实施例。实施例1
用CF3SOCl进行的亚磺酰化：5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-4-三氟甲基亚磺酰基吡唑的合成
将8.06g(25mmol)的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑和8.15g(38mmol)的二甲胺对甲苯磺酸盐悬浮于50ml的甲苯中。往该反应混合物中迅速加入三氟甲基亚磺酰氯(5g，32mmol)。加热反应物至50℃。在该温度反应8小时后，用氩气流冲洗反应物。然后将反应物冷却至20℃。往反应物中加入20ml水，滤取沉淀，用水、甲苯洗涤沉淀物。将所得产物在真空下加热干燥，得5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-4-三氟甲基亚磺酰基吡唑9.77g，得率88％，纯度＞95％(由HPLC测定)。
所得化合物的物理和光谱特性如下：
熔点：196-198℃
NMR分析
1H-NMR(CDCl3，TMS)：5.1ppm(S，2H)，7.8ppm(S，2H)
13C-NMR(丙酮-d6，TMS)：
苯基：C1：135.4ppm，C2：137.5ppm，C3：127.6ppm，C4：135.5ppm，
C(CF3)：123ppm
吡唑基：C3：126.7ppm，C4：94.6ppm，C5：152.3ppm，
C(CN)：111.7ppm，C(CF3)：126.3ppm
质谱分析(EIMS)；M+＝436(35Cl)。实施例2
用CF3SOCl进行的亚磺酰化：5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-4-三氟甲基亚磺酰基吡唑的合成
将0.81g(2.5mmol)的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑和0.29g(2.5mmol)的干燥盐酸吡啶溶解于5ml的1，2-二氯乙烷中。往该反应混合物中加入三氟甲基亚磺酰氯(0.5g，3.2mmol)。然后，将该反应混合物于50℃加热10小时。其后，按与实施例1同样的方法进行处理。被鉴定为产物5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-4-三氟甲基亚磺酰基吡唑的得率为74％。实施例3
用CF3SONMe2进行的亚磺酰化：5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-4-三氟甲基亚磺酰基吡唑的合成
将0.81g(2.5mmol)的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑和0.55g(2.5mmol)的干燥对甲苯磺酸悬浮于5ml的甲苯中。加入N，N-二甲基三氟甲基亚磺酰胺(0.53g，3.2mmol)，再加HCl(2.5mmol)在甲苯中的溶液。将该反应物于50℃加热8小时。其后的处理与实施例1相同。被鉴定为产物5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-4-三氟甲基亚磺酰基吡唑的得率为72％，实施例4
5-(N-三氟甲基亚磺酰基)氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑的合成
包括在本发明范围内的亚磺酰氨基吡唑可按下述方法制备、分离
将3.23g(10mmol)的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑和3.25g(15mmol)的二甲胺对甲苯磺酸盐悬浮于20ml的甲苯中。将温度调至50℃。迅速加入三氟甲基亚磺酰氯(2g，13mmol)。再加入二甲胺(5mmol)在甲苯中的溶液。于5℃搅拌反应物30分钟。然后加入50ml的甲基叔丁基醚。滤去生成的沉淀，冲洗。回收滤液，用2×10ml的冰水洗涤。浓缩有机层。所得残余物用甲苯结晶。得5-(N-三氟甲基亚磺酰基)氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑1.75g。
所得化合物的物理和光谱特性如下。
熔点：123-124℃
1H-NMR(丙酮-d6，HMDS)：7.06ppm(S，1H)，8.06ppm(S，2H)
13C-NMR(丙酮-d6，TMS)：
苯基：C1：136.2ppm，C2：137ppm，C3：127.4ppm，C4：135.2ppm，
C(CF3)：123.3ppm
吡唑基：C3：128.5ppm，C4：105.7ppm，C5：140.7ppm，
C(CN)：113.5ppm，C(CF3)：124.5ppm实施例5
通过将实施例4的亚磺酰基吡唑重排而进行的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-4-三氟甲基亚磺酰基吡唑的合成
将0.109g(0.25mmol)的实施例4的亚磺酰基吡唑和0.075g(0.33mmol)的二甲胺对甲苯磺酸盐悬浮于甲苯中。加入盐酸(0.25mmol)在甲苯中的溶液。于50℃加热反应混合物10小时。被鉴定为产物5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-4-三氟甲基亚磺酰基吡唑的得率为80％。实施例6
使用CF3SOONa进行的亚磺酰化：5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-4-三氟甲基亚磺酰基吡唑的合成
将0.81g(2.5mmol)的5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)吡唑、0.815g(3.8mmol)的二甲胺对甲苯磺酸盐和0.51g(3.25mmol)的三氟甲基亚磺酸钠悬浮于5ml的甲苯中。将该混合物冷却至5℃，加入SOCl2，然后于室温下搅拌约1小时。再将反应混合物于50℃加热8小时。其后的处理与实施例1相同。
被鉴定为产物5-氨基-3-氰基-1-(2，6-二氯-4-三氟甲基苯基)-4-三氟甲基亚磺酰基吡唑的得率为66％。
Claims (18)
1.一种杂环化合物的亚磺酰化方法，其特征在于，将化学式RSOX表示的衍生物与杂环化合物Het反应，
其中，式RSOX中的R表示C1-C4的有一或多个相同或不同的卤素原子取代的直链或支链烷基，X表示羟基或其钠盐；
杂环化合物Het选自吡唑类、咪唑类，所有这些杂环Het上可任意地有选自下述原子或基团的一或多个取代基：卤素、无取代基的或有一或二个C1-C4烷基取代的氨基、氰基、芳基、有一或多个卤原子和/或一或多个烷基、卤代烷基或五氟硫基取代基的芳基；
使用一种选自胺的对甲苯磺酸盐、盐酸盐和甲磺酸盐，或盐酸的化合物以完成反应。
2.根据权利要求1所述的方法，其特征在于，反应在对甲苯磺酸的存在下进行。
3.根据权利要求1所述的方法，其特征在于，所述胺选自二甲胺、吡啶、三甲胺、二乙胺或异丙胺。
4.根据权利要求1所述的方法，其特征在于，使用选自光气、氯甲酸酯、PCl5或SOCl2的反应剂以完成反应。
5.根据权利要求1所述的方法，其特征在于，杂环有氨基取代基，后者与RSOX反应生成亚磺酰胺化合物，再经过重排，生成在带有氨基的碳原子的邻位碳原子上有亚磺酰基RSO的杂环化合物。
6.根据权利要求1或4或5所述的方法，其特征在于，R为三氟甲基。
7.根据权利要求1所述的方法，其特征在于，杂环Het为下式A或B表示的化合物，
其中，R1表示卤原子、烷基、卤代烷基或五氟硫基。
8.根据权利要求7所述的方法，其特征在于，所述卤原子是氟原子，所述卤代烷基是三氟甲基。
9.根据权利要求1所述的的方法，其特征在于，将下式表示的化合物与式RSOX表示的反应剂反应，
得到下式表示的4-亚磺酰基吡唑，
其中，R和X的定义同上，R1表示卤素原子、烷基、卤代烷基或五氟硫基。
10.根据权利要求9所述的方法，其特征在于，所述卤原子是氟原子，所述卤代烷基是三氟甲基。
11.根据权利要求9所述的方法，其特征在于，在对甲苯磺酸存在下，使用一种选自胺的对甲苯磺酸盐、盐酸盐和甲磺酸盐，或盐酸的化合物以完成反应。
12.根据权利要求11所述的方法，其特征在于，所述胺选自二甲胺、吡啶、三甲胺、二乙胺或异丙胺。
13.根据权利要求9所述的方法，其特征在于，使用选自光气、氯甲酸酯、PCl5或SOCl2的反应剂以完成反应。
14.根据权利要求9所述的方法，其特征在于，使用CF3SOOH或CF3SOONa及光气或SOCl2或ClCO2C2H5与下式所示的4-H-吡唑之一进行反应，得到下式表示的4-亚磺酰基吡唑。
15.式RSOHN-Het1表示的亚磺酰胺中间体，其特征在于，Het1-NH2为在权利要求1中的定义范围内的有氨基取代基的杂环化合物。
16.根据权利要求15所述的中间体，其特征在于，Het1-NH2为任意地可有一或多个原子或取代基团的、有氨基取代基的吡唑杂环，所述一或多个原子或基团选自卤原子、无取代的或有一或二个C1-C4烷基取代基的氨基、氰基、芳基、有一或多个卤原子和/或一或多个烷基、卤代烷基或五氟硫基取代基的芳基，而亚磺酰氨基位于该杂环的5位。
17.根据权利要求16所述的中间体，其特征在于，所述化合物为5-(N-三氟甲基亚磺酰基)氨基-3-氰基-1-[2，6-二氯-4-三氟甲基-苯基]-4-H-吡唑。
18.根据权利要求16所述的化合物，其特征在于，所述化合物为5-(N-三氟甲基亚磺酰基)氨基-3-氰基-1-[2，6-二氯-4-五氟硫基-苯基]-4-H-吡唑。
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| CN1160349C (zh) | 1999-06-29 | 2004-08-04 | 日本农药株式会社 | 吡唑衍生物及其制备方法,以及含有该衍生物作为有效成分的有害生物防治剂 |
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