JPS6056712B2 - Synthesis method of imidazole dithiocarboxylic acid carbomethoxymethyl ester compound - Google Patents
Synthesis method of imidazole dithiocarboxylic acid carbomethoxymethyl ester compoundInfo
- Publication number
- JPS6056712B2 JPS6056712B2 JP57176712A JP17671282A JPS6056712B2 JP S6056712 B2 JPS6056712 B2 JP S6056712B2 JP 57176712 A JP57176712 A JP 57176712A JP 17671282 A JP17671282 A JP 17671282A JP S6056712 B2 JPS6056712 B2 JP S6056712B2
- Authority
- JP
- Japan
- Prior art keywords
- carbomethoxymethyl
- methyl
- dithiocarboxylic acid
- absorption
- acid
- 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
- -1 imidazole dithiocarboxylic acid carbomethoxymethyl ester compound Chemical class 0.000 title claims description 56
- 238000001308 synthesis method Methods 0.000 title 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 38
- 150000003839 salts Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 239000012433 hydrogen halide Substances 0.000 claims description 8
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 8
- 238000006482 condensation reaction Methods 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 113
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 108
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 81
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 65
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 59
- 238000010521 absorption reaction Methods 0.000 description 56
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- 239000013078 crystal Substances 0.000 description 43
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- 235000019441 ethanol Nutrition 0.000 description 34
- 239000000047 product Substances 0.000 description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- WREDNSAXDZCLCP-UHFFFAOYSA-N methanedithioic acid Chemical compound SC=S WREDNSAXDZCLCP-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- 230000007935 neutral effect Effects 0.000 description 18
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 description 14
- 230000000007 visual effect Effects 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 12
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000007858 starting material Substances 0.000 description 9
- 125000002948 undecyl 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])[H] 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- CFYUKQRGWSQKNU-UHFFFAOYSA-N 1h-imidazole;methanedithioic acid Chemical compound SC=S.C1=CNC=N1 CFYUKQRGWSQKNU-UHFFFAOYSA-N 0.000 description 5
- IZYGCWIXHKMALW-UHFFFAOYSA-N 2-methyl-1h-imidazole-5-carbodithioic acid Chemical compound CC1=NC=C(C(S)=S)N1 IZYGCWIXHKMALW-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000002960 margaryl 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])[H] 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- QLTXPYPAYKMBTK-UHFFFAOYSA-N 2-ethyl-1h-imidazole-5-carbodithioic acid Chemical compound CCC1=NC=C(C(S)=S)N1 QLTXPYPAYKMBTK-UHFFFAOYSA-N 0.000 description 3
- FWWVSTJJEPANBO-UHFFFAOYSA-N 5-methyl-1h-imidazole-4-carbodithioic acid Chemical compound CC=1NC=NC=1C(S)=S FWWVSTJJEPANBO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- UNPLRYRWJLTVAE-UHFFFAOYSA-N Cloperastine hydrochloride Chemical compound Cl.C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)OCCN1CCCCC1 UNPLRYRWJLTVAE-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- YDCHPLOFQATIDS-UHFFFAOYSA-N methyl 2-bromoacetate Chemical compound COC(=O)CBr YDCHPLOFQATIDS-UHFFFAOYSA-N 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- WQKQGRXNHYXVAH-UHFFFAOYSA-N 2-ethyl-5-methyl-1h-imidazole-4-carbodithioic acid Chemical compound CCC1=NC(C(S)=S)=C(C)N1 WQKQGRXNHYXVAH-UHFFFAOYSA-N 0.000 description 2
- BPFXGDCUBZBEQF-UHFFFAOYSA-N 2-phenyl-1h-imidazole-5-carbodithioic acid Chemical compound N1C(C(=S)S)=CN=C1C1=CC=CC=C1 BPFXGDCUBZBEQF-UHFFFAOYSA-N 0.000 description 2
- PAEDOSGPFZUHAK-UHFFFAOYSA-N 5-methyl-2-undecyl-1h-imidazole-4-carbodithioic acid Chemical compound CCCCCCCCCCCC1=NC(C(S)=S)=C(C)N1 PAEDOSGPFZUHAK-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 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 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 101100184046 Schizosaccharomyces pombe (strain 972 / ATCC 24843) mid1 gene Proteins 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- LANOUGPDGLREPK-UHFFFAOYSA-N acetic acid;chloromethane Chemical compound ClC.CC(O)=O LANOUGPDGLREPK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- YDGMIJCIBXSCQR-UHFFFAOYSA-N methyl 2-iodoacetate Chemical compound COC(=O)CI YDGMIJCIBXSCQR-UHFFFAOYSA-N 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- IQZFEWXBHUWSDX-UHFFFAOYSA-N 1h-imidazole-2-carbodithioic acid Chemical compound SC(=S)C1=NC=CN1 IQZFEWXBHUWSDX-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- LSLHHVSRCDKRKB-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole-5-carbodithioic acid Chemical compound CCCCCCCCCCCCCCCCCC1=NC=C(C(S)=S)N1 LSLHHVSRCDKRKB-UHFFFAOYSA-N 0.000 description 1
- JLPZJNSJPMYRJA-UHFFFAOYSA-N 2-undecyl-1h-imidazole-5-carbodithioic acid Chemical compound CCCCCCCCCCCC1=NC=C(C(S)=S)N1 JLPZJNSJPMYRJA-UHFFFAOYSA-N 0.000 description 1
- FNKXLEZIGQBFIA-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole-4-carbodithioic acid Chemical compound SC(=S)C1=C(C)NC(C=2C=CC=CC=2)=N1 FNKXLEZIGQBFIA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002310 Isopropyl citrate Substances 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
- KSZVHVUMUSIKTC-UHFFFAOYSA-N acetic acid;propan-2-one Chemical compound CC(C)=O.CC(O)=O KSZVHVUMUSIKTC-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004309 nisin Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- QZNVHCWSDFYKTO-UHFFFAOYSA-M sodium;methanedithioate Chemical compound [Na+].[S-]C=S QZNVHCWSDFYKTO-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- UANXSGVNVXTETO-UHFFFAOYSA-N trifluoro(hydroperoxy)methane Chemical compound OOC(F)(F)F UANXSGVNVXTETO-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
【発明の詳細な説明】
本発明は、イミダゾールジチオカルボン酸カルボメトキ
シメチルエステル化合物の合成方法に関するものであり
、詳しくは構造式
Ｒ・了一下へ。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for synthesizing an imidazole dithiocarboxylic acid carbomethoxymethyl ester compound, and in detail, see the structural formula R and Ryoichi below.
〔但し、式中Ｒ、は水素原子又はメチル基、エチル基、
ウンデシル基、ヘプタデシル基及びフェニル基より成る
群より選ばれた残基、Ｒ４は水素原子又はメチル基を表
わす。[However, in the formula, R is a hydrogen atom, a methyl group, an ethyl group,
A residue selected from the group consisting of undecyl, heptadecyl and phenyl, R4 represents a hydrogen atom or a methyl group.
〕で示されるイミダゾールジチオカルボン酸化合物とモ
ノハロ酢酸メチルを縮合反応させることを特徴とする構
造式
〔但し、式中Ｒ２とＲ，は前記と同じである。[However, in the formula, R2 and R are the same as above.
〕で示されるイミダゾールジチオカルボン酸カルボメト
キシメチルエステル化合物の合成方法に係るものである
。本発明方法の出発物質であるイミダゾールジチオカル
ボン酸化合物およびそのアルカリ金属塩は、次示の反応
式で示されるように、相当する母体イミダゾールと二硫
化炭素から高収率かつ容易にえられることが、既に本発
明者等によつて見い出されている。] This relates to a method for synthesizing the imidazole dithiocarboxylic acid carbomethoxymethyl ester compound. The imidazole dithiocarboxylic acid compound and its alkali metal salt, which are the starting materials for the method of the present invention, can be easily obtained in high yield from the corresponding parent imidazole and carbon disulfide, as shown in the following reaction formula. , has already been discovered by the present inventors.
（特開昭５７−１７６９６５号公報参照）出発物質イミ
ダゾールジチオカルボン酸とモノハロ酢酸メチルを縮合
反応させると次示の反応式に従つて、先ず該ジチオカル
ボン酸カルボメトキシメチルエステルハロゲン化水素塩
が生成し、次いで該ハロゲン化水塩をハロゲン化水素受
容体と反応させると目的物カルボメトキシメチルエステ
ルがえられる。また出発物質イミダゾールジチオカルボ
ン酸とモノハロ酢酸メチルをハロゲン化水素受容体の共
存下で縮合反応させると次示の反応式に従つて目的物カ
ルボメトキシメチルエステルがえられる。(Refer to JP-A-57-176965) When the starting material imidazole dithiocarboxylic acid and methyl monohaloacetate are subjected to a condensation reaction, the dithiocarboxylic acid carbomethoxymethyl ester hydrogen halide salt is first produced according to the following reaction formula. Then, the desired product carbomethoxymethyl ester is obtained by reacting the halogenated water salt with a hydrogen halide acceptor. Further, when the starting material imidazoledithiocarboxylic acid and methyl monohaloacetate are subjected to a condensation reaction in the presence of a hydrogen halide acceptor, the desired product carbomethoxymethyl ester is obtained according to the following reaction formula.
また出発物質イミダゾールジチオカルボン酸アルカリ金
属塩とモノハロ酢酸メチルを縮合反応させると次示の反
応式に従つて目的物カルボメトキシメチルエステルが同
様にえられる。出発物質イミダゾールジチオカルボン酸
アルカリ塩は主としてナトリウム及びカリウム塩である
。Further, when the starting material, an alkali metal salt of imidazole dithiocarboxylic acid, is subjected to a condensation reaction with methyl monohaloacetate, the desired product, carbomethoxymethyl ester, can be similarly obtained according to the following reaction formula. The starting imidazoledithiocarboxylic acid alkali salts are primarily sodium and potassium salts.
イミダゾールと二硫化炭素を水酸化アルカリの存在下で
反応させてイミダゾールジチオカルボン酸を合成する際
、まず該ジチオカルボン酸アノヒカリ金属塩が生成する
ので、そのものをそのままイミダゾールジチオカルボン
酸カルボメトキシメチルエステル合成の出発物質として
使用することが出来る。酸ジチオカルボン酸は塩基性イ
オンＢ１と容易に造塩し、次示の反応式の如く、ジチオ
カルボン酸Ｂ塩を与えるので、該Ｂ塩を出発物質として
使用することも出来る。When imidazole and carbon disulfide are reacted in the presence of an alkali hydroxide to synthesize imidazole dithiocarboxylic acid, the dithiocarboxylic acid anohikari metal salt is first produced, and this is directly used to synthesize imidazole dithiocarboxylic acid carbomethoxymethyl ester. can be used as a starting material. Since the acid dithiocarboxylic acid easily forms a salt with the basic ion B1 to give the dithiocarboxylic acid B salt as shown in the following reaction formula, the B salt can also be used as a starting material.
塩基性イオンＢ１として使用されるものはＬｉｌ、Ｎａ
４、Ｋ４、Ｃａ４４、曳４１、Ｍｇ４ｌ、Ｚｎｌｌ、Ｃ
ｕｌｌ、Ｍｎｌｌ、ＣＯｌｌｌ、Ｎｉｌ４、Ｆｅ４ｌ４
、Ｈｇ４４、Ｓｎ４４、Ｐｂ４ｌ、ＮＨ４ｌ、有機アン
モニウムイオン等である。Those used as basic ions B1 are Lil, Na
4, K4, Ca44, Hiki41, Mg4l, Znll, C
ull, Mnll, COll, Nil4, Fe4l4
, Hg44, Sn44, Pb4l, NH4l, organic ammonium ions, etc.
該ジチオカルボン酸は上述の如く、各種金属イオンと容
易に造塩し各種の塩を作るが、それら金属塩を出発物質
として使用することは、ナトリウム及びカリウム塩の使
用に比し、経済上、別段得策とは考えられない。As mentioned above, the dithiocarboxylic acid easily forms various salts with various metal ions, but the use of these metal salts as starting materials is economically disadvantageous compared to the use of sodium and potassium salts. I can't think of any particular advantage.
本発明において使用されるハロゲン化水素受容体は極く
一般的な種類のものであつて、ハロゲン化水素と反応し
て中和塩を与えるものであれば、いかなるものも使用出
来る。The hydrogen halide acceptor used in the present invention is of a very general type, and any acceptor can be used as long as it reacts with hydrogen halide to give a neutralized salt.
それらは次示の如きものである。ＮＨ３、ＮＨ４ＯＨ，
．ＬｉＯＨｌＮａＯＨ．．ＫＯＨ．ｓＣａ（０Ｈ）２、
Ｂａ（０Ｈ）２、Ｍｇ（０Ｈ）２、Ｌｉ２ＣＯ３、Ｎａ
ｃＯ３、Ｋ２ＣＯ３、ＣａｃＯ３、ＢａｃＯ３、ＭｇＣ
Ｏ３、ＣＨ３ＣＯＯＮａ．．ＣＨ３ＣＯＯＫ．．Ｅｔ３
Ｎの如き第３級アミン、第４級アンモニウム水酸化物（
例えばＴｒｉｔＯｎＢｌ）等。They are as shown below. NH3, NH4OH,
．． LiOHlNaOH. ．． KOH. sCa(0H)2,
Ba(0H)2, Mg(0H)2, Li2CO3, Na
cO3, K2CO3, CacO3, BacO3, MgC
O3, CH3COONa. ．． CH3COOK. ．． Et3
Tertiary amines such as N, quaternary ammonium hydroxides (
For example, TritOnBl), etc.
本発明で使用されるモノハロ酢酸メチルは、モノクロル
酢酸メチル、モノブロム酢酸メチル及びモノヨード酢酸
メチルであるが、モノブロム酢酸メチル及びモノヨード
酢酸メチルは高価に過ぎ、モノクロル酢酸メチルに比し
実用性に乏しいと判断される。The methyl monohaloacetates used in the present invention are methyl monochloroacetate, methyl monobromoacetate, and methyl monoiodoacetate, but methyl monobromoacetate and methyl monoiodoacetate are judged to be too expensive and less practical than methyl monochloroacetate. be done.
溶剤の活性水素とモノハロ酢酸メチルとの反応を考慮す
れば、理論的には反応に使用される溶剤は活性水素を持
たないものが望ましいと考えられるが、実験結果は必ず
しもそのような予測は適中せず、水、アルコールと云つ
た溶剤も充分使用できることが判つた。Considering the reaction between active hydrogen in the solvent and methyl monohaloacetate, theoretically it would be desirable for the solvent used in the reaction to have no active hydrogen, but experimental results do not necessarily suggest that such a prediction is accurate. It has been found that solvents such as water and alcohol can also be used satisfactorily.
従つて溶剤に関する制限はそれ程大した意味を持たない
と考えられる。本発明の実施に適する代表的な溶剤は、
水、メチルアルコール、エチルアルコール、ジメチルフ
ォルムアミド、ジメチルスルフオキシド、アセトニトリ
ル、アセトン酢酸等である。本発明の反応は発熱反応で
ある。Therefore, restrictions regarding solvents are not considered to have much significance. Representative solvents suitable for the practice of this invention include:
These include water, methyl alcohol, ethyl alcohol, dimethyl formamide, dimethyl sulfoxide, acetonitrile, acetone acetic acid, and the like. The reaction of the present invention is exothermic.
従つて大量合成の場合、反応開始時には冷却が必要であ
るが、少量反応の場合は別段冷却の必要はない。ある程
度反応が進行したのちでは発熱は弱まるので加温が逆に
必要となる。これは反応時間短縮を考慮した場合の温度
調節の仕方である。反応温度は、この場合、室温ないし
約８０℃の間を維持すればよい。この場合の反応は約４
時間以内て完結する。８０℃以上の反応温度は特に必要
ではない。８０℃以下で充分である。Therefore, in the case of large-scale synthesis, cooling is required at the start of the reaction, but in the case of small-scale synthesis, no special cooling is necessary. After the reaction has progressed to a certain extent, the heat generation weakens, so heating is necessary. This is a method of temperature control when shortening the reaction time is taken into consideration. In this case, the reaction temperature may be maintained between room temperature and about 80°C. In this case, the reaction is about 4
It will be completed within hours. A reaction temperature of 80° C. or higher is not particularly required. A temperature below 80°C is sufficient.
発熱を緩漫化させるためには、モノハロ酢酸メチルを反
応系に除々に添加することが望ましい。反応時間短縮を
考慮しなければ氷冷下長時間あるいは室温長時間の反応
を行なうことも勿論できる。反応装置は攪拌機と還流冷
却機を備えていることが必要であるが、これらの反応は
常圧で進行するので別段加圧を行なう必要はない。イミ
ダゾールジチオカルボン酸あるいはそのアルカリ金属塩
、モノハロ酢酸メチルおよびハロゲン化水素受容体のモ
ル当量関係については、出発物質ジチオカルボン酸又は
その塩１モル当量に対し１モル当量若しくは１モル当量
以上のモノノ田酢酸メチル及び受容体を使用すれば良い
。In order to slow down the heat generation, it is desirable to gradually add methyl monohaloacetate to the reaction system. It is of course possible to conduct the reaction for a long time under ice cooling or at room temperature unless shortening the reaction time is taken into account. The reaction apparatus must be equipped with a stirrer and a reflux condenser, but since these reactions proceed under normal pressure, there is no need to apply additional pressure. Regarding the molar equivalent relationship of imidazole dithiocarboxylic acid or its alkali metal salt, methyl monohaloacetate, and hydrogen halide acceptor, 1 molar equivalent or more than 1 molar equivalent of monomer dithiocarboxylic acid or 1 molar equivalent of the starting material dithiocarboxylic acid or its salt should be used. Methyl acetate and an acceptor may be used.
但し甚だしく過剰のそれらを使用するのは不経済で、意
味がない。目的物の単離精製は常法に従つて行なわれる
。However, it is uneconomical and meaningless to use them in gross excess. Isolation and purification of the target product is carried out according to conventional methods.
その具体的な態様については実施例で後述する。本発明
の方法によつて得られる各種のイミダゾールジチオカル
ボン酸カルボメトキシメチルエステル化合物は農薬中間
体及び医薬中間体として有用である。次に出発物質と目
的物の性質を例示する。Specific aspects thereof will be described later in Examples. Various imidazole dithiocarboxylic acid carbomethoxymethyl ester compounds obtained by the method of the present invention are useful as agricultural chemical intermediates and pharmaceutical intermediates. Next, the properties of the starting material and the target product will be illustrated.
１ イミダゾールジチオカルボン酸ナトリウム塩〔いず
れも高融点で通常の融点測定に基づいた融点表示は困難
である。1 Imidazole dithiocarboxylic acid sodium salt [Both have high melting points and it is difficult to indicate the melting point based on normal melting point measurement.
代りにＴＷ．（シリカＧｌＥｔＯＨ）におけるＲｆを表
示する。〕イミダゾ−ルー４ージチオカルボン酸Ｎａ塩
１Ｒｆ：０．０（Ｎａに由来、Ｂ．Ｔ．Ｂ）、０．４
５〜０．６０（目視）２−メチルイミダゾールー４ージ
チオカルボン酸Ｎａ塩Ｒｆ：０．０（Ｎａに由来、Ｂ．
Ｔ．Ｂ）、０．５０〜０．６０１（目視）２−エチルイ
ミダゾールー４ージチオカルボン酸Ｎａ塩Ｒｆ：０．０
（Ｎａに由来、Ｂ．Ｔ．Ｂ）、０．６３〜０．７７（目
視） ２２
−ウンデシルイミダゾールー４ージチオカルボン酸Ｎａ
塩Ｒｆ：０．０（Ｎａに由来、Ｂ．Ｔ．Ｂ）、０．５７
〜０．７０（目視）２−ヘプタデシルイミダゾールー４
−ジチオカニルボン酸Ｎａ塩Ｒｆ：０．０（Ｎａに由来
、Ｂ．Ｔ．Ｂ）、０．６３〜０．７５（目視）２−フェ
ニルイミダゾールー４ージチオカルボン酸Ｎａ塩Ｒｆ：
０．０（Ｎａに由来、Ｂ．Ｔ．Ｂ）、０．５２〜０．６
６（目視）４−メチルイミダゾールー５ージチオカルボ
ン酸Ｎａ塩Ｒｆ：０．０（Ｎａに由来、Ｂ．Ｔ．Ｂ）、
０．４４〜０．５８．（目視）２，４−ジメチルイミダ
ゾールー５ージチオカルボン酸Ｎａ塩Ｒｆ：０．０（Ｎ
ａに由来、Ｂ．Ｔ．Ｂ）、０．５５〜０．６８（目視）
２−エチルー４−メチルイミダゾールー５ージチオカル
ボン酸Ｎａ塩Ｒｆ：０．０（Ｎａに由来、Ｂ．Ｔ．Ｂ）
、０．６０〜０．７３（目視）２−ウンデシルー４−メ
チルイミダゾールー５ージチオカルボン酸Ｎａ塩Ｒｆ：
０．０（Ｎａに由来、Ｂ．Ｔ．Ｂ）、０．７８〜０．９
０（目視）２−フェニルー４−メチルイミダゾールー５
ージチオカルボン酸Ｎａ塩Ｒｆ：０．０（Ｎａに由来、
Ｂ．Ｔ．Ｂ）、０．６２〜０．７４（目視）前記の各Ｎ
ａ塩は、いずれも９５０〜１０３０ｃｍ−１に強いνＣ
＝Ｓ吸収を示す。TW instead. (Silica GlEtOH) is displayed. ] Imidazole-4-dithiocarboxylic acid Na salt 1Rf: 0.0 (derived from Na, B.T.B), 0.4
5-0.60 (visual observation) 2-methylimidazole-4-dithiocarboxylic acid Na salt Rf: 0.0 (derived from Na, B.
T. B), 0.50-0.601 (visual observation) 2-ethylimidazole-4-dithiocarboxylic acid Na salt Rf: 0.0
(derived from Na, B.T.B), 0.63 to 0.77 (visual observation) 22
-Undecylimidazole-4-dithiocarboxylic acid Na
Salt Rf: 0.0 (derived from Na, B.T.B), 0.57
~0.70 (visual) 2-heptadecyl imidazole-4
-Dithiokanylboxylic acid Na salt Rf: 0.0 (derived from Na, B.T.B), 0.63-0.75 (visual observation) 2-phenylimidazole-4-dithiocarboxylic acid Na salt Rf:
0.0 (derived from Na, B.T.B), 0.52 to 0.6
6 (visual observation) 4-methylimidazole-5-dithiocarboxylic acid Na salt Rf: 0.0 (derived from Na, B.T.B),
0.44-0.58. (Visual observation) 2,4-dimethylimidazole-5-dithiocarboxylic acid Na salt Rf: 0.0 (N
Originated from a, B. T. B), 0.55 to 0.68 (visual observation)
2-ethyl-4-methylimidazole-5-dithiocarboxylic acid Na salt Rf: 0.0 (derived from Na, B.T.B)
, 0.60-0.73 (visual observation) 2-undecyl-4-methylimidazole-5-dithiocarboxylic acid Na salt Rf:
0.0 (derived from Na, B.T.B), 0.78-0.9
0 (visual observation) 2-phenyl-4-methylimidazole-5
-dithiocarboxylic acid Na salt Rf: 0.0 (derived from Na,
B. T. B), 0.62 to 0.74 (visual observation) each of the above N
All a salts have a strong νC between 950 and 1030 cm-1.
= indicates S absorption.
イミダゾールジチオカルボン酸 イミダゾ−ルー４ージチオカルボン酸 赤褐色結晶。Imidazole dithiocarboxylic acid imidazo-4-dithiocarboxylic acid Reddish brown crystals.
中性。Ｍ．ｐ．ｌ５７〜１５９℃。水、メタノール、ク
ロロホルム、アセトン、酢酸に難溶。ＤＭＦ．．ＤＭＳ
Ｏ．．ＮａＯＨ水溶液に易溶。ＴＬＣ（シリカＧｌＥｔ
ＯＨｌ目視）：ＲｆＯ．４５〜０．６００ν鵠′．１：
１４３８（第２吸収）、１０２５（第１吸収）。ＮＭＲ
（ＤＭＳＯ−Ｄ６）：８．８０、Ｄ，．ＩＨ；７．７８
、ｄ）ＩＨＯＭａｓｓ：ｍ／Ｅｌ４４（Ｍ＋）、１１１
（Ｍ＋−ＳＨ）、関（イミダゾール）、４４（：Ｃ＝Ｓ
）２−メチルイミダゾールー４ージチオカルボン酸：紅
褐色結晶。neutral. M. p. 157-159°C. Slightly soluble in water, methanol, chloroform, acetone, and acetic acid. DMF. ．． DMS
O. ．． Easily soluble in NaOH aqueous solution. TLC (Silica GlEt
OHL visual inspection): RfO. 45~0.600ν鵠′. 1:
1438 (second absorption), 1025 (first absorption). NMR
(DMSO-D6): 8.80, D,. IH; 7.78
, d) IHOMass: m/El44 (M+), 111
(M+-SH), Seki (imidazole), 44 (:C=S
) 2-Methylimidazole-4-dithiocarboxylic acid: reddish brown crystals.
中性。Ｍ．ｐ．ｌ８７〜１８８℃。水、メタノール、ク
ロロホルム、アセトン、酢酸、アセトニトリル及びピリ
ジンに難溶。ＤＭＦｌＤＭＳＯ及びＮａＯＨ水溶液に易
溶。neutral. M. p. 187-188°C. Slightly soluble in water, methanol, chloroform, acetone, acetic acid, acetonitrile and pyridine. DMF1 Easily soluble in DMSO and NaOH aqueous solutions.
ＴＣＬ（前出）：ＲｆＯ．５Ｏ〜０．６０（目視）。ν
Ｕ′．１：１６０７（第３吸収）、１２１０（第１吸収
）、１０４０（第２吸収）。ＮＭＲ（ＤＭＦ−Ｄ７）：
δ７．７５、Ｓ．．ＩＨ；２．６７、Ｓ）３Ｈ０Ｍａｓ
ｓ：ｍ／Ｅｌ５８（Ｍ＋）、１２５（Ｍ＋−ＳＨ）、８
１、７ｅＫ４４（：Ｃ＝Ｓ）２−エチルイミダゾールー
４ージチオカルボン酸紅褐色結晶。TCL (supra): RfO. 5O to 0.60 (visual). ν
U'. 1:1607 (third absorption), 1210 (first absorption), 1040 (second absorption). NMR (DMF-D7):
δ7.75, S. ．． IH; 2.67, S) 3H0Mas
s: m/El58 (M+), 125 (M+-SH), 8
1,7eK44(:C=S)2-ethylimidazole-4-dithiocarboxylic acid reddish brown crystals.
中性。Ｍ．ｐ．ｌ３７〜１３（１ｊＣ０水、クロロホル
ム、及び酢酸に難溶。メタノール、ＤＭＳＯ及びＮａＯ
Ｈに易溶。ＴＣＬ（前出）ＲｆＯ．６４〜０．７７。Ｖ
ｕｒ．１：１６０５（第２吸収）、１０４５（第１吸収
）。neutral. M. p. l37-13 (1jC0 Slightly soluble in water, chloroform, and acetic acid. Methanol, DMSO, and NaO
Easily soluble in H. TCL (supra) RfO. 64-0.77. V
ur. 1:1605 (second absorption), 1045 (first absorption).
ＮＭＲ（ＤＭＳＯ−Ｄ６）：δ７．７０、Ｓ．．ＩＨ；
２．８７、Ｑ，，２Ｈ；１．２屯Ｔ．．３ＨＯＭａｓｓ
：ｍ／Ｅｌ７２Ｉ！４＋）、１３９（Ｍ＋−ＳＨ）、９
６、９飄４４２−ウンデシルイミダゾールー４ージチオ
カルボン酸褐色結晶。NMR (DMSO-D6): δ7.70, S. ．． IH;
2.87, Q,, 2H; 1.2 tons T. ．． 3HOMass
:m/El72I! 4+), 139(M+-SH), 9
6,9 442-Undecylimidazole-4-dithiocarboxylic acid brown crystals.
中性。Ｍ．ｐ．ｌｌ６〜１Ｗ℃。水、クロロホルム及び
冷酢酸に難溶。メタノール、アセトン及び熱酢酸に可溶
。ＤＭＳＯｌＤＭＦ及びＮａＯＨ水溶液に易溶。ＴＬＣ
（前出）：ＲｆＯ．７Ｏ〜０．８１（目視）。neutral. M. p. ll6~1W℃. Slightly soluble in water, chloroform and cold acetic acid. Soluble in methanol, acetone and hot acetic acid. DMSO1 Easily soluble in DMF and NaOH aqueous solution. T.L.C.
(cited above): RfO. 7O to 0.81 (visual).
νＵ′．１：１６０２（第４吸収）、１２０５（第３吸
収）、１０４２（第１吸収）。ＮＭＲ（ＣＦ３ＣＯＯＨ
）：δ７．９８、Ｓ．．ＩＨ；３．１０１ｔｓ２Ｈ；１
．８８、Ｍ，．２Ｈ；１．３０、Ｍ，．ｌ６Ｈ；０．８
７、ｍ１狙。νU′. 1:1602 (4th absorption), 1205 (3rd absorption), 1042 (1st absorption). NMR(CF3COOH
): δ7.98, S. ．． IH;3.101ts2H;1
．． 88, M,. 2H; 1.30, M,. l6H; 0.8
7. Aim for m1.
ｒ！４ａｓｓ：ｍ／Ｅ２９８（Ｍつ、２６５（Ｍ＋−Ｓ
Ｈ）、２羽、２２＆４４０２−ヘプタデシルイミダゾー
ルー４ージチオカルボン酸褐色結晶。r! 4ass: m/E298 (M two, 265 (M+-S
H), 2 wings, 22 & 4402-heptadecyl imidazole-4-dithiocarboxylic acid brown crystals.
中性。Ｍ．ｐ．ｌＯ７〜１１（代）。水、クロロホルム
及び冷酢酸に難溶。ＤＭＳＯに可溶。ＴＬＣ（前出）：
ＲｆＯ．６３〜０．７５０νｖ＆τ：１６００（第１吸
収）、１５２５（第３吸収）、１０４０（第２吸収）。neutral. M. p. lO7-11 (generation). Slightly soluble in water, chloroform and cold acetic acid. Soluble in DMSO. TLC (mentioned above):
RfO. 63-0.750 νv&τ: 1600 (first absorption), 1525 (third absorption), 1040 (second absorption).
ＮＭＲ（ＤＭＳＯ−Ｄ６）：δ７．７０、Ｓ．．ＩＨ；
２．８０、ｍ１？；１．６５、Ｍ，．２Ｈ；１・２２）
ｍ〜２８Ｈ；０．８５ｓｍ．．３Ｈ０Ｍａｓｓ：ｍ／Ｅ
Ｍ＋出現せず、３４８（Ｍ＋−Ｈ２Ｓ）、３３屯３１７
、３０７、３０ｅＫ４４２−フェニルイミダゾールー４
ージチオカルボン酸褐色結晶。NMR (DMSO-D6): δ7.70, S. ．． IH;
2.80, m1? ;1.65, M,. 2H; 1・22)
m~28H; 0.85sm. ．． 3H0Mass:m/E
M+ did not appear, 348 (M+-H2S), 33 tons 317
, 307, 30eK442-phenylimidazole-4
-dithiocarboxylic acid brown crystals.
弱酸性。Ｍ．ｐ．ｌ５４〜１５ＴＣ０水、メタノール、
クロロホルム、酢酸及びアセトンに難溶。ＤＭＳＯ及び
ＮａＯＨ水溶液に易溶。ＴＬＣ（前出）：ＲｆＯ．５２
〜０．６６０νＵ′．１：１６１５（第２吸収）、１２
１５（第３吸収）、．１０４０（第１吸収）。ＮＭＲ（
ＤＭＳＯ−４）：δ＆羽、〜７．♀、ｍ１？；７．９２
、ＳｌｌＨ；７．７６〜７．３０ｓｍ，．３Ｈ０Ｍａｓ
ｓ：ｍ／Ｅ２２Ｏ（Ｍつ、１８７（Ｍ＋−ＳＨ）、１４
４Ｎ１Ｃ！Ｋ７７。Mild acidity. M. p. l54~15TC0 water, methanol,
Slightly soluble in chloroform, acetic acid and acetone. Easily soluble in DMSO and NaOH aqueous solutions. TLC (supra): RfO. 52
~0.660νU′. 1:1615 (second absorption), 12
15 (third absorption), . 1040 (first absorption). NMR (
DMSO-4): δ&wing, ~7. ♀, m1? ;7.92
, SllH; 7.76-7.30sm, . 3H0Mas
s: m/E22O (M, 187 (M+-SH), 14
4N1C! K77.
４−メチルイミダゾールー５ージチオカルボン酸紅褐色
結晶。4-Methylimidazole-5-dithiocarboxylic acid reddish brown crystals.
中性。Ｍ．ｐ．ｌ５９〜１６１℃。水、メタノール、ク
ロロホルム及び酢酸に難溶。ＤＭＳＯ及びＮａＯＨ水溶
液に易溶。ＴＬＣ（前出）：ＲｆＯ．４７〜０．６０。neutral. M. p. 159-161°C. Slightly soluble in water, methanol, chloroform and acetic acid. Easily soluble in DMSO and NaOH aqueous solutions. TLC (supra): RfO. 47-0.60.
Ｖｕｒ．１：１５９０、１４４０、１３７５、１２６５
、（第２吸収）、１１２０（第３吸収）、１０２０（第
４吸収）、９２臥８６０（第１吸収）、８０へ７２０。
ＮＭＲ（ＤＭＳＯ−Ｄ６）：δ＆６０ｓＳ１１Ｈ；２．
６２、Ｓ，．３ＨＯＭａｓｓ：ｍ／Ｅｌ５８（Ｍ＋）、
１２５（Ｍ＋−ＳＨ）、８１、７巳４４２，４−ジメチ
ルイミダゾールー５ージチオカルボン酸紅色結晶。Vur. 1:1590, 1440, 1375, 1265
, (second absorption), 1120 (third absorption), 1020 (fourth absorption), 92 860 (first absorption), 720 to 80.
NMR (DMSO-D6): δ&60sS11H;2.
62, S,. 3HOMass: m/El58 (M+),
125(M+-SH), 81,7 442,4-dimethylimidazole-5-dithiocarboxylic acid red crystals.
Ｍ．ｐ．ｌ８７〜１８９Ｃ０水、メタノール、エタノー
ル、クロロホルム及びアセトンに難溶。M. p. 187-189C0 Slightly soluble in water, methanol, ethanol, chloroform and acetone.
酢酸に可溶。ＭＥ及びＤＭＳＯに易溶。Soluble in acetic acid. Easily soluble in ME and DMSO.
ＴＬＣ（前出）：ＲｆＯ．５７〜０．７０。νＵｒ−１
：１６１５（第２吸収）、１０２５及び９９０（第１吸
収）。ＮＭＲ（ＣＦ３ＣＯＯＨ） δ２．７７、Ｓ，
．３Ｈ；２．７０Ｓ，．３Ｈ０Ｍａｓｓ：ｍ／Ｅｌ７２
（Ｍつ、１３９（Ｍ＋−ＳＨ）、９飄４２２−エチルー
４−メチルイミダゾールー５ージチオカルボン酸紅紫色
結晶。TLC (supra): RfO. 57-0.70. νUr−1
: 1615 (second absorption), 1025 and 990 (first absorption). NMR (CF3COOH) δ2.77, S,
．． 3H; 2.70S,. 3H0Mass:m/El72
(M, 139 (M+-SH), 9) 422-Ethyl-4-methylimidazole-5-dithiocarboxylic acid red-purple crystals.
中性。Ｍ．ｐ．ｌ７７〜１７ＣｆＣ０水、メタノール、
エタノール及びアセトンに難溶。酢酸に可溶。ＤＭＦ及
びＤＭＳＯに易溶。ＴＬＣ（前出）：ＲｆＯ．６Ｏ〜０
．７０。ν鴨Ｒ．ｌ：１６１５（第２吸収）、１０１３
（第１吸収）。ＮＭＲ（ＤＭＳＯ−Ｄ６）：δ２．８へ
Ｑ．．？：２．６０、Ｓ．．３Ｈ：１．２３．ｔ．．３
Ｈ０Ｍａｓｓ：ｍ／Ｅｌ８６（Ｍ＋）、１５３（Ｍ＋−
ＳＨ）、１鳳１０９０２−ウンデシルー４−メチルイミ
ダゾールー５ージチオカルボン酸赤色固体。neutral. M. p. l77~17CfC0 water, methanol,
Slightly soluble in ethanol and acetone. Soluble in acetic acid. Easily soluble in DMF and DMSO. TLC (supra): RfO. 6O~0
．． 70. νduck R. l: 1615 (second absorption), 1013
(first absorption). NMR (DMSO-D6): Q to δ2.8. ．． ? :2.60,S. ．． 3H:1.23. t. ．． 3
H0Mass: m/El86 (M+), 153 (M+-
SH), 10902-undecyl-4-methylimidazole-5-dithiocarboxylic acid red solid.
塩基性。Ｍ．ｐ．吸湿大で測定不能。水、メタノール及
びエタノールに可溶。basic. M. p. Unable to measure due to high moisture absorption. Soluble in water, methanol and ethanol.
ＴＬＣ（前出）：ＲｆＯ．７Ｏ〜０．８０。TLC (supra): RfO. 7O~0.80.
νＵ′．１：１５１２（第１吸収）、１３７８（第２吸
収）、１０００（第３吸収）。Ｍａｓｓ：ｍ／Ｅ３ｌ２
（Ｍつ、２７９（Ｍ＋−ＳＨ）、２４７（Ｍ＋−ＨＳ２
）２３６０２−フェニルー４−メチルイミダゾールー５
ージチオカルボン酸紅褐色結晶。νU′. 1:1512 (first absorption), 1378 (second absorption), 1000 (third absorption). Mass: m/E3l2
(M, 279 (M+-SH), 247 (M+-HS2
)23602-phenyl-4-methylimidazole-5
-dithiocarboxylic acid reddish brown crystals.
Ｍ．ｐ．ｌ６５〜１関℃。水、メタノール、エタノール
、アセトン、クロロホルム、ｔ−ブタノール及びベンゼ
ンに難溶。M. p. l65~1 Seki°C. Slightly soluble in water, methanol, ethanol, acetone, chloroform, t-butanol and benzene.
酢酸及びメチルセロソルブに可溶。ＤＭＦ，．ＤＭＳＯ
及びＮａＯＨ水溶液に可溶。Soluble in acetic acid and methyl cellosolve. DMF,. DMSO
and soluble in NaOH aqueous solution.
η℃（前出）・：ＲｆＯ．６５〜０．７８０νＵｒ．ｌ
：１６２５（第３吸収）、１６０３、１５４０、１４８
５，１２１５（第２吸収）、１０４０（第１吸収）。η℃ (mentioned above): RfO. 65~0.780νUr. l
:1625 (third absorption), 1603, 1540, 148
5,1215 (second absorption), 1040 (first absorption).
ＮＭＲ（ＣＦ３ＣＯＯＨ） δ８．００、〜７．５０
，．ｍ１史；２．８ｇｓＳ，．３Ｈ０Ｍａｓｓ：ｍ／Ｅ
２３４（Ｍつ、２０１（Ｍ＋−ＳＨ）、１関、１０屯７
７。NMR (CF3COOH) δ8.00, ~7.50
、． m1 history; 2.8gsS,. 3H0Mass:m/E
234 (M tsu, 201 (M+-SH), 1 Seki, 10 ton 7
7.
３目的物
イミダゾ−ルー４ージチオカルボン酸カルボメトキシメ
チルエステル構造式
物性
黄橙色結晶。3 Target Imidazole-4-dithiocarboxylic acid carbomethoxymethyl ester Structural formula Physical properties Yellow-orange crystals.
中性。Ｍ．ｐ．ｌ６７〜１６９℃（分解）（ＥｔＯＨ）
。熱メタノール、熱エタノール、熱アセトン、熱トルエ
ン、熱水、ＡｃＯＨ．．ＤＭＳＯ及びＤＭＦに可溶。冷
メタノール、冷エタノール、冷アセトン、冷トルエン、
冷水及びクロロホルムに難溶。ＴＬＣ（シリカＧ，．Ｃ
ＨＣｌ３／ＭｅＯＨ＝１０／１Ｖ０１．比、■２発色）
：ＲｆＯ．３Ｏ−０．４０。νＵ′．１：１７４０（第
１吸収、ＶＣ＝０）、１１６０（第４吸収、νＣ＝０）
、１０５０（第２吸収、νＣ＝Ｓ）。ＮＭＲ（ＤＭＳＯ
−Ｄ６）：δ７．９巳ＳｌｌＨ（２位プロトン）；７．
８３、ＳｌｌＨ（４位プロトン）４．２１、Ｓ，．２Ｈ
（カルボメトキシメチル基のメチレンプロトン）；３．
６１、Ｓ，．３Ｈ（カルボメトキシメチル基のメチルプ
ロトン）。neutral. M. p. 167-169℃ (decomposition) (EtOH)
. Hot methanol, hot ethanol, hot acetone, hot toluene, hot water, AcOH. ．． Soluble in DMSO and DMF. cold methanol, cold ethanol, cold acetone, cold toluene,
Slightly soluble in cold water and chloroform. TLC (Silica G,.C
HCl3/MeOH=10/1V01. ratio, ■ 2 colors)
:RfO. 3O-0.40. νU′. 1:1740 (first absorption, VC=0), 1160 (fourth absorption, νC=0)
, 1050 (second absorption, νC=S). NMR (DMSO
-D6): δ7.9SllH (2nd position proton); 7.
83, SllH (4th position proton) 4.21, S, . 2H
(methylene proton of carbomethoxymethyl group); 3.
61, S,. 3H (methyl proton of carbomethoxymethyl group).
Ｍａｓｓ：ｍ／Ｅ２ｌ６（Ｍ＋）、１８５（Ｍ＋−０Ｃ
Ｈ３）、１４３（Ｍ＋−ＣＨ２ＣＯＯＣＨ３）、１１１
（Ｍ＋一ＳＣＨ２ＣＯＯＣＨ３）、４４（：Ｃ＝Ｓ）。Mass: m/E2l6 (M+), 185 (M+-0C
H3), 143 (M+-CH2COOCH3), 111
(M+1SCH2COOCH3), 44 (:C=S).
２−メチルイミダゾールー４ージチオカルボン酸カルボ
メトキシメチルエステル構造式
物性
黄橙色結晶。2-Methylimidazole-4-dithiocarboxylic acid carbomethoxymethyl ester Structural formula Physical properties Yellow-orange crystals.
中性。Ｍ．ｐ．ｌ４５〜１４７℃（ＥｔＯＨ）。メタノ
ール、エタノール、アセトン、ＡＣＯＨｌクロロホルム
、熱トルエン、熱水、ＤＭＳＯ及びＤＭＦに可溶。冷ト
ルエン及び冷水に難溶。ＴＬＣ（前出）：ＲｆＯ．３５
〜０．４５ａ．νＵ′．１：１７２２（第１吸収、νＣ
＝Ｏ）、１０７５（第３吸収、νＣ＝Ｓ）。ＮＭＲ（Ｃ
Ｆ３ＣＯＯＨ）：δ７．９８、ＳｌｌＨ（４位プロトン
）；４．３７、Ｓ，．２Ｈ（カルボメトキシメチル基の
メチレンプロトン）；３．９１、Ｓｓ３Ｈ（カルボメト
キシメチル基のメチルプロトン）２．８１．．Ｓ，．３
Ｈ（２位メチルプロトン）。neutral. M. p. 145-147°C (EtOH). Soluble in methanol, ethanol, acetone, ACOHl chloroform, hot toluene, hot water, DMSO and DMF. Slightly soluble in cold toluene and cold water. TLC (supra): RfO. 35
~0.45a. νU′. 1:1722 (first absorption, νC
=O), 1075 (third absorption, νC=S). NMR(C
F3COOH): δ7.98, SllH (4-position proton); 4.37, S, . 2H (methylene proton of carbomethoxymethyl group): 3.91, Ss3H (methyl proton of carbomethoxymethyl group) 2.81. ．． S... 3
H (methyl proton at 2nd position).
Ｍａｓｓ：ｍ／Ｅ２３Ｏ（Ｍつ、１９９（Ｍ＋−０ＣＨ
３）、１５７（Ｍ＋−ＣＨ２ＣＯＯＣＨ３）、１２５（
Ｍ＋−ＳＣＨ２ＣＯＯＣＨ３）。２−エチルイミダゾー
ルー４ージチオカルボン酸カルボメトキシメチルエステ
ル構造式
物性
橙色結晶。Mass: m/E23O (M, 199 (M+-0CH
3), 157(M+-CH2COOCH3), 125(
M+-SCH2COOCH3). 2-ethylimidazole-4-dithiocarboxylic acid carbomethoxymethyl ester Structural formula Physical properties Orange crystals.
中性。Ｍ．ｐ．ｌｌ９〜１２２℃（ＥｔＯＨ）。メタノ
ール、エタノール、アセトン、酢酸、クロ５口ホルム、
トルエン、ＤＭＳＯ，．ＤＭＦ及び熱水に可溶。冷水に
難溶。ＴＬＣ（前出）：ＲｆＯ．４４〜０．５４０νＵ
′．１：１７３０（第１吸収、ＶＣ＝Ｏ）、１０５０（
νＣ＝Ｓ）。neutral. M. p. 119-122°C (EtOH). Methanol, ethanol, acetone, acetic acid, chloroform,
Toluene, DMSO, . Soluble in DMF and hot water. Slightly soluble in cold water. TLC (supra): RfO. 44~0.540νU
'． 1:1730 (first absorption, VC=O), 1050 (
νC=S).
ノＮＭＲ（ＣＤＣｌ３）：δ７．７２、ＳｌｌＨ（４位
プロトン）；４．１７、Ｓ．．２Ｈ（カルボメトキシメ
チル基のメチレンプロトン）：３．７４ｓＳ，．３Ｈ（
カルボメトキシメチル基のメチルプロトン）；２．７４
、Ｑ，．２Ｈ（２位エチル基のメチレンプロトン）；１
．２９、Ｔ．．３Ｈ（２位エチル基のメチルプロトン）
。NMR (CDCl3): δ7.72, SllH (4-position proton); 4.17, S.I. ．． 2H (methylene proton of carbomethoxymethyl group): 3.74sS,. 3H (
methyl proton of carbomethoxymethyl group); 2.74
,Q,. 2H (methylene proton of 2-position ethyl group); 1
．． 29, T. ．． 3H (methyl proton of 2-position ethyl group)
.
Ｍａｓｓ：ｍ／Ｅ２４４（Ｍつ、２１３（Ｍ＋−０ＣＨ
２）、１７１（Ｍ＋−ＣＨ２ＣＯＯＣＨ３）、１３９（
Ｍ＋一ＳＣＨ２ＣＯＯＣＨ３）、４４（：Ｃ＝Ｓ）。Mass: m/E244 (M, 213 (M+-0CH
2), 171(M+-CH2COOCH3), 139(
M+1SCH2COOCH3), 44 (:C=S).
２−ウンデシルイミダゾールー４ージチオカルボン酸カ
ルボメトキシメチルエステル構造式
物性
橙色結晶。2-Undecylimidazole-4-dithiocarboxylic acid carbomethoxymethyl ester Structural formula Physical properties Orange crystals.
中性。Ｍ．ｐ．７６〜８１℃（アセトン）。メタノール
、エタノール、アセトン、クロロホルム、酢酸、トルエ
ン、アセトニトリル、ＤＭＳＯ及びＤＭＦに可溶。水に
難溶。ＴＬＣ（前出）：ＲｆＯ．６５〜０．７５０νＵ
ｒ．ｌ：１７３７（第４吸収、νＣ＝０）、１１５７（
第５吸収、νＣ−０）１０６４（第３吸収、νＣ＝Ｓ）
。neutral. M. p. 76-81°C (acetone). Soluble in methanol, ethanol, acetone, chloroform, acetic acid, toluene, acetonitrile, DMSO and DMF. Poorly soluble in water. TLC (supra): RfO. 65~0.750νU
r. l: 1737 (4th absorption, νC = 0), 1157 (
5th absorption, νC-0) 1064 (3rd absorption, νC=S)
.
ＮＭＲ（ＣＤＣｌ３）：δ７．７３、ＳｌｌＨ（４位プ
ロトン）；４．１７、ＳＮ２Ｈ（カルボメトキシメチル
基のメチレンプロトン）；３．７３ｓＳ，．３Ｈ（カル
ボメトキシメチル基のメチルプロトン）；２．７１、Ｔ
ｌ２Ｈ（２位ウンデシル基のα−メチレンプロトン）；
１．７２、Ｍ，．２ｌ（（２位ウンデシル基のβ−メチ
レンプロトン）；１．２屯Ｍｌｌ６Ｈ（２位ウンデシル
基の中間メチレンプロトン）；０．８６、Ｍ．．３Ｈ（
２位ウンデシル基の末端メチルプロトン）。NMR (CDCl3): δ7.73, SllH (4-position proton); 4.17, SN2H (methylene proton of carbomethoxymethyl group); 3.73sS, . 3H (methyl proton of carbomethoxymethyl group); 2.71, T
l2H (α-methylene proton of undecyl group at 2-position);
1.72, M,. 2l ((β-methylene proton of undecyl group at 2-position); 1.2 tons Mll6H (intermediate methylene proton of undecyl group at 2-position); 0.86, M..3H (
terminal methyl proton of the undecyl group at the 2-position).
Ｍａｓｓ：ｍ／Ｅ３７Ｏ（Ｍつ、３３９（Ｍ＋−０ＣＨ
３）、２９７（Ｍ＋−ＣＨ２ＣＯＯＣＨ３）、２６５（
Ｍ＋一ＳＣＨ２ＣＯＯＣＨ３）、４４（：Ｃ＝Ｓ）。Mass: m/E37O (M, 339 (M+-0CH
3), 297(M+-CH2COOCH3), 265(
M+1SCH2COOCH3), 44 (:C=S).
２−ヘプタデシルイミダゾールー４ージチオカルボン酸
カルボメトキシメチルエステル構造式
橙色結晶。2-heptadecyl imidazole-4-dithiocarboxylic acid carbomethoxymethyl ester structural formula: orange crystals.
中性。Ｍ．ｐ．９ｌ〜９６Ｃ（アセトン）。メタノール
、エタノール、アセトン、クロロホルム、酢酸、トルエ
ン、ＤＭＳＯ及びＤＭＦ′に可溶。水に難溶。ＴＬＣ（
前出）：ＲｆＯ．６５〜０．７５０νｕ巳，：１７３５
（第４吸収、νＣ＝０）、１１５７（第５吸収、νＣ−
０）、１０６７（第３吸収、νＣ＝Ｓ）。ＮＭＲ（ＣＤ
Ｃｌ３）：δ７．７３、ＳｌｌＨ（４位プロトン）；４
．１＆Ｓ，．２Ｈ（カルボメトキシメチル基のメチレン
プロトン）；３．７３，Ｓ．．３Ｈ（カルボメトキシメ
チル基のメチルプロトン）；２．７１、Ｔ．．２Ｈ（２
位ヘプタデシル基のα−メチレンプロトン）；１．７へ
Ｍ，．２Ｈ（２位ヘプタデシル基のβ−メチレンプロト
ン）；１．２５ｓｍ１２８Ｈ（２位ヘプタデシル基の中
間のメチレンプロトン）０．８７、Ｍ．．３Ｈ（２位ヘ
プタデシル基の末端メチルプロトン）。neutral. M. p. 9l-96C (acetone). Soluble in methanol, ethanol, acetone, chloroform, acetic acid, toluene, DMSO and DMF'. Poorly soluble in water. TLC(
): RfO. 65~0.750νu, :1735
(4th absorption, νC=0), 1157 (5th absorption, νC-
0), 1067 (third absorption, νC=S). NMR (CD
Cl3): δ7.73, SllH (4-position proton); 4
．． 1&S,. 2H (methylene proton of carbomethoxymethyl group); 3.73, S. ．． 3H (methyl proton of carbomethoxymethyl group); 2.71, T. ．． 2H(2
α-methylene proton of heptadecyl group); M to 1.7, . 2H (β-methylene proton of heptadecyl group at 2-position); 1.25sm128H (methylene proton in the middle of heptadecyl group at 2-position) 0.87, M. ．． 3H (terminal methyl proton of heptadecyl group at 2-position).
Ｍａｓｓ：ｍ／Ｅ４５４（Ｍつ、４２３（Ｍ＋−０ＣＨ
３）、３８１（Ｍ＋−ＣＨ２ＣＯＯＣＨ３）、３４９（
Ｍ＋−ＳＣＨ２ＣＯＯＣＨ３）、４４（：Ｃ＝Ｓ）。Mass: m/E454 (M, 423 (M+-0CH
3), 381(M+-CH2COOCH3), 349(
M+-SCH2COOCH3), 44 (:C=S).
２−フェニルイミダゾールー４ージチオカルボン酸カル
ボメトキシメチルエステル構造式
物性
橙色結晶。2-Phenylimidazole-4-dithiocarboxylic acid carbomethoxymethyl ester Structural formula Physical properties Orange crystals.
中性。Ｍ．ｐ．ｌ４２〜１４４℃（ＥｔＯＨ）。メタノ
ール、エタノール、アセトン、クロロホルム、酢酸、ト
ルエン、ＤＭＳＯ及びＤＭＦ′に可溶。水に難溶。ＴＬ
Ｃ（前出）：ＲｆＯ．５７〜０．６７。ν鴨Ｒ．ｌ：１
７２０（第１吸収、νＣ＝Ｏ）、１０７２（第５吸収、
νＣ＝Ｓ）。ＮＭＲ（ＣＦ３ＣＯＯＨ） δ＆１６、Ｓ
ｌｌＨ（４位プロトン）：＆００〜７．５０、Ｍ，．５
Ｈ（２位フェニルプロトン）；４．４０、Ｓｌ２Ｈ（カ
ルボメトキシメチル基のメチレンプロトン）；３．部、
Ｓ，．３Ｈ（カルボメトキシメチル基のメチルプロトン
）。Ｍａｓｓ：ｍ／Ｅ２９２（Ｍつ、２６１（Ｍ＋−０
ＣＨ３）、２１９（Ｍ＋−ＣＨ２ＣＯＯＣＨ３）、１８
７（Ｍ＋−ＳＣＨ２ＣＯＯＣＨ３）、１０４（Ｐｈ−Ｃ
＝ＮＨ）、７７（フェニル基）、４４（：Ｃ＝Ｓ）。neutral. M. p. 142-144°C (EtOH). Soluble in methanol, ethanol, acetone, chloroform, acetic acid, toluene, DMSO and DMF'. Poorly soluble in water. T.L.
C (supra): RfO. 57-0.67. νduck R. l:1
720 (first absorption, νC=O), 1072 (fifth absorption,
νC=S). NMR (CF3COOH) δ&16,S
llH (proton at 4th position): &00~7.50, M, . 5
H (2-position phenyl proton); 4.40, Sl2H (methylene proton of carbomethoxymethyl group); 3. Department,
S... 3H (methyl proton of carbomethoxymethyl group). Mass: m/E292 (M two, 261 (M+-0
CH3), 219 (M+-CH2COOCH3), 18
7 (M+-SCH2COOCH3), 104 (Ph-C
=NH), 77 (phenyl group), 44 (:C=S).
４−メチルイミダゾールー５ージチオカルボン酸カルボ
メトキシメチルエステル構造式
物性
黄橙色結晶。4-Methylimidazole-5-dithiocarboxylic acid carbomethoxymethyl ester Structural formula Physical properties Yellow-orange crystals.
中性。Ｍ．ｐ．ｌ６Ｏ〜１６２℃（分解）（ＥｔＯＨ）
。メタノール、エタノール、アセトン、クロロホルム、
酢酸、ＤＭＳＯ、ＤＭＦｌ熱トルエン及び熱水に可溶。
冷トルエン及び冷水に難溶。ＴＬＣ（前出）：ＲｆＯ．
２５〜０．３５０νＵ′．１：１７３２（第５吸収、ν
Ｃ＝０）、１１６２（第２吸収、νＣ−０）、１０５５
（第１吸収、νＣ＝Ｓ）。ＮＭＲ（ＣＦ３ＣＯＯＨ）：
δ８．６６、ＳｌｌＨ（２位プロトン）；４．４３．Ｓ
．ｓ２Ｈ（カルボメトキシメチル基のメチレンプロトン
）；３．９２、Ｓ，．３Ｈ（カルボメトキシメチル基の
メチルプロトン）２．９へＳ．．３Ｈ（４位メチルプロ
トン）。neutral. M. p. l6O~162℃ (decomposition) (EtOH)
. methanol, ethanol, acetone, chloroform,
Soluble in acetic acid, DMSO, DMFl hot toluene and hot water.
Slightly soluble in cold toluene and cold water. TLC (supra): RfO.
25~0.350νU'. 1:1732 (5th absorption, ν
C=0), 1162 (second absorption, νC-0), 1055
(first absorption, νC=S). NMR (CF3COOH):
δ8.66, SllH (proton at 2nd position); 4.43. S
．． s2H (methylene proton of carbomethoxymethyl group); 3.92, S, . 3H (methyl proton of carbomethoxymethyl group) S. to 2.9 ．． 3H (4-position methyl proton).
Ｍａｓｓ：ｍ／Ｅ２３Ｏ（Ｍ＋）、１９９（Ｍ＋−０Ｃ
Ｈ３）、１５７（Ｍ＋−ＣＨ２ＣＯＯＣＨ３゛）、１２
５（Ｍ＋−ＳＣＨ２ＣＯＯＣＨ３）、４４（：Ｃ＝Ｓ）
。２，４−ジメチルイミダゾールー５ージチオカルボン
酸カルボメトキシメチルエステル構造式
物性
橙色結晶。Mass: m/E23O(M+), 199(M+-0C
H3), 157 (M+-CH2COOCH3゛), 12
5(M+-SCH2COOCH3), 44(:C=S)
. 2,4-dimethylimidazole-5-dithiocarboxylic acid carbomethoxymethyl ester Structural formula Physical properties Orange crystals.
中性。Ｍ．ｐ．ｌ６２〜１６４℃（ＥｔＯＨ）。メタノ
ール、エタノールアセトン、クロロホルム、酢酸、ＤＭ
ＳＯ．ＤＭＦｌ熱トルエン及び熱水に可溶。冷トルエン
及び冷水に難溶。Ｌ℃（前出）：ＲｆＯ．３７〜０．４
８０νＵｒ．ｌ：１７２０（第１吸収、νＣ＝０）、１
０５７（νＣ＝Ｓ）。neutral. M. p. 162-164°C (EtOH). Methanol, ethanolacetone, chloroform, acetic acid, DM
S.O. DMFl Soluble in hot toluene and hot water. Slightly soluble in cold toluene and cold water. L°C (mentioned above): RfO. 37-0.4
80νUr. l: 1720 (first absorption, νC=0), 1
057 (νC=S).
ＮＭＲ（ＣＦ３ＣＯＯＨ）：δ４．４０、Ｓ，．？（カ
ルボメトキシメチル基のメチレンプロトン）；３．９２
、Ｓｌ３Ｈ（カルボメトキシメチル基のメチルプロトン
）；２．８２、Ｓ，．３Ｈ（２位メチルプロトン）；２
．７眠Ｓ．．３Ｈ（４位メチルプロトン）。NMR (CF3COOH): δ4.40, S,. ? (methylene proton of carbomethoxymethyl group); 3.92
, Sl3H (methyl proton of carbomethoxymethyl group); 2.82, S, . 3H (2-position methyl proton); 2
．． 7 sleep S. ．． 3H (4-position methyl proton).
Ｍａｓｓ：ｍ／Ｅ２４４（Ｍつ、２１３（Ｍ＋−０ＣＨ
３）、１７１（Ｍ＋−ＣＨ２ＣＯＯＣＨ３）、１３９（
Ｍ＋一ＳＣＨ２ＣＯＯＣＨ３）、４４（：Ｃ＝Ｓ）２−
エチルー４−メチルイミダゾールー５ージチオカルボン
酸カルボメトキシメチルエステル構造式物性
黄橙色結晶。Mass: m/E244 (M, 213 (M+-0CH
3), 171(M+-CH2COOCH3), 139(
M+1SCH2COOCH3), 44(:C=S)2-
Ethyl-4-methylimidazole-5-dithiocarboxylic acid carbomethoxymethyl ester Structural formula Physical properties Yellow-orange crystals.
中性。Ｍ．ｐ．ｌ２２〜１２４℃（アセトン）。メタノ
ール、エタノール、アセトン、クロロホルム、四塩化炭
素、酢酸、トルエン、ＤＭＳＯ及び（ト）Ｉに可溶。水
に難溶。ＴＬＣ（前出）ＲｆＯ．５Ｏ〜０．６０。νＵ
′．１：１７３０（第１吸収、νＣ＝０）、１１６０（
第３吸収、νＣ−０）、１０４５（νＣ＝Ｓ）。neutral. M. p. 122-124°C (acetone). Soluble in methanol, ethanol, acetone, chloroform, carbon tetrachloride, acetic acid, toluene, DMSO and (t)I. Poorly soluble in water. TLC (supra) RfO. 5O~0.60. νU
'． 1:1730 (first absorption, νC=0), 1160 (
Third absorption, νC-0), 1045 (νC=S).
ＮＭＲ（ＣＤＣｌ３）：δ４．１ｅＫＳ，．２Ｈ（カル
ボメトキシメチル基のメチレンプロトン）；３．７５、
Ｓｌ３Ｈ（カルボメトキシメチル基のメチルプロトン）
；２．６７、Ｑｌ２Ｈ（２位エチル基のメチレンプロト
ン）；２．５３、Ｓ．．３Ｈ（４位メチルプロト″ン）
；１．２３ｓｔ．．３Ｈ（２位エチル基のメチルプロト
ン）。ｒ！４ａｓｓ：ｍ／Ｅ２５８（Ｍつ、２２７（Ｍ
＋−０ＣＨ３）、１８５（Ｍ ＋ＣＨ２ＣＯＯＣＨ３）
、１５３（Ｍ＋一ＳＣＨ２ＣＯＯＣＨ３）。NMR (CDCl3): δ4.1eKS,. 2H (methylene proton of carbomethoxymethyl group); 3.75,
Sl3H (methyl proton of carbomethoxymethyl group)
; 2.67, Ql2H (methylene proton of 2-position ethyl group); 2.53, S. ．． 3H (4-position methyl proton)
;1.23st. ．． 3H (methyl proton of 2-position ethyl group). r! 4ass: m/E258 (M two, 227 (M
+-0CH3), 185 (M +CH2COOCH3)
, 153 (M+1SCH2COOCH3).
２−ウンデシルー４−メチルイミダゾールー５ージチオ
カルボン酸カルボメトキシメチルエステル構造式物性
黄橙色結晶。2-Undecyl-4-methylimidazole-5-dithiocarboxylic acid carbomethoxymethyl ester Structural formula Physical properties Yellow-orange crystals.
中性。Ｍ．ｐ．７５〜７９℃（アセトン）。メタノール
、エタノール、アセトン、クロロホルム、酢酸、トルエ
ン、ＤＭＳＯ及びＤＭＦに可溶、水に難溶。ＴＬＣ（前
出）：ＲｆＯ．６５〜０．７５ａ．νＵ′．１：１７２
０（第２吸収、νＣ＝０）、１１６５（ＶＣ−０）、１
０５０（νＣ＝Ｓ）。ＮＭＲ（ＣＤＣｌ３）：δ４．１
５ｓＳ．．２Ｈ（カルボメトキシメチル基のメチレンプ
ロトン）；３．７５、Ｓｌ３Ｈ（カルボメトキシメチル
基のメチルプロトン）；２．６２、Ｔ．．２Ｈ（２位ウ
ンデシル基のαーメチレンプロトン）；２．５３、Ｓ．
．３Ｈ（４位メチルプロトン）；１．６７、Ｍ，．２Ｈ
（２位ウンデシル基のβ−メチレンプロトン）；１．２
４、．Ｍｌｌ６ｌ（（２位ウンデシル基の中間メチレン
プロトン）０．８ｅＫｍ．．３Ｈ（２位ウンデシル基の
末端メチルプロトン）。neutral. M. p. 75-79°C (acetone). Soluble in methanol, ethanol, acetone, chloroform, acetic acid, toluene, DMSO and DMF, sparingly soluble in water. TLC (supra): RfO. 65-0.75a. νU′. 1:172
0 (second absorption, νC=0), 1165 (VC-0), 1
050 (νC=S). NMR (CDCl3): δ4.1
5sS. ．． 2H (methylene proton of carbomethoxymethyl group); 3.75, Sl3H (methyl proton of carbomethoxymethyl group); 2.62, T. ．． 2H (α-methylene proton of undecyl group at 2-position); 2.53, S.
．． 3H (4-position methyl proton); 1.67, M, . 2H
(β-methylene proton of undecyl group at 2-position); 1.2
4. Mll6l ((intermediate methylene proton of undecyl group at 2-position) 0.8eKm..3H (terminal methyl proton of undecyl group at 2-position).
Ｍａｓｓ：ｍ／Ｅ３８４（Ｍつ、３５３（Ｍ＋−０ＣＨ
３）、３１１（Ｍ＋ −ＣＨ２ＣＯＯＣＨ３）、２７９
（Ｍ＋一ＳＣＨ２ＣＯＯＣＨ３）、４４（：Ｃ＝Ｓ）。Mass: m/E384 (M, 353 (M+-0CH
3), 311 (M+ -CH2COOCH3), 279
(M+1SCH2COOCH3), 44 (:C=S).
２−フェニルー４−メチルイミダゾールー５ージチオカ
ルボン酸カルボメトキシメチルエステル構造式物性
橙色結晶。2-Phenyl-4-methylimidazole-5-dithiocarboxylic acid carbomethoxymethyl ester Structural formula Physical properties Orange crystals.
中性。Ｍ．ｐ．ｌ９９〜２０１℃（ＥｔＯＨ）。メタノ
ール、エタノール、アセトン、トルエン、クロロホルム
、酢酸、ＤＭＳＯ及びＤＭＦ′に可溶。水に難溶。ＴＬ
Ｃ（前出）：ＲｆＯ．５８〜０．絽。νＵ′．１：１７
２０（第１吸収、νＣ＝０）、１１６５（第２吸収、ν
Ｃ−０）１０５１（第４吸収、ＶＣ＝Ｓ）。ＮＭＲ（Ｄ
ＭＳＯ−Ｄ６） δ＆１０〜７．３７、Ｍ．．５Ｈ（
２位フェニルプロトン）；４．１７、Ｓ，．２Ｈ（カル
ボメトキシメチル基のメチレンプロトン）；３．８、Ｓ
．．３Ｈ（カルボメトキシメチル基のメチルプロトン）
；２．槃、Ｓ，．３Ｈ（４位メチルプロトン）。Ｍａｓ
ｓ：ｍ／Ｅ３Ｏ６（Ｍつ、２７５（Ｍ＋−０ＣＨ３）、
２３３（Ｍ＋−ＣＨ２ＣＯＯＣＨ３）、２０１（Ｍ＋−
ＳＣＨ２ＣＯＯＣＨ，）、１０４（Ｐｈ−Ｃ＝ＮＨ）、
７７（フェニル基）、４４（：Ｃ＝Ｓ）。neutral. M. p. 199-201°C (EtOH). Soluble in methanol, ethanol, acetone, toluene, chloroform, acetic acid, DMSO and DMF'. Poorly soluble in water. T.L.
C (supra): RfO. 58-0. Rug. νU′. 1:17
20 (first absorption, νC=0), 1165 (second absorption, ν
C-0) 1051 (4th absorption, VC=S). NMR(D
MSO-D6) δ&10~7.37, M. ．． 5H (
2-position phenyl proton); 4.17, S, . 2H (methylene proton of carbomethoxymethyl group); 3.8, S
．． ．． 3H (methyl proton of carbomethoxymethyl group)
;2. Kana, S. 3H (4-position methyl proton). Mas
s: m/E3O6 (M, 275 (M+-0CH3),
233 (M+-CH2COOCH3), 201 (M+-
SCH2COOCH,), 104 (Ph-C=NH),
77 (phenyl group), 44 (:C=S).
実施例１
還流冷却器を備えた反応容器を電磁攪拌式熱板上に装着
し、イミダゾ−ルー４ージチオカルボン酸０．０３モル
（４．３ｇｒ）、水酸化カルシウム０．０１５モル（１
．１ｇｒ）及びメタノール２０ｍ１を仕込み、ついで攪
拌下にモノクロル酢酸メチル０．０３モル３．３ｙ）を
室温下に一気に加えたのち、系を２時間加熱還流（内温
６ｒＣ）したのち析出結晶を炉取し、粗目的物〔Ｍ．ｐ
．ｌ６４〜１６８℃；ＴＬＣ（シリカＧ１クロロホルム
／メタノールニ１０／１容量比、１２発色）ＲｆＯ．３
Ｏ〜０．４０〕を５．２ｆ（対ジチオカルボン酸収率８
０％）えた。Example 1 A reaction vessel equipped with a reflux condenser was mounted on a magnetic stirring hot plate, and 0.03 mol (4.3 gr) of imidazole-4-dithiocarboxylic acid and 0.015 mol (1 mol) of calcium hydroxide were added.
．． 1 gr) and 20 ml of methanol were added, then 0.03 mol of methyl monochloroacetate (3.3 y) was added all at once at room temperature while stirring, the system was heated under reflux for 2 hours (inner temperature 6 rC), and the precipitated crystals were collected in a furnace. and coarse target [M. p
．． 164-168°C; TLC (silica G1 chloroform/methanol 10/1 volume ratio, 12 colors) RfO. 3
O ~ 0.40] to 5.2f (yield of dithiocarboxylic acid: 8
0%) got it.
実施例２
実施例１の粗目的物の熱エタノール溶液を活性炭処理し
てえられた枦液から冷時析出する結晶を枦取し、炉取結
晶をエタノール再結し、前出の同定試料（Ｍ．ｐ．ｌ６
７〜１的℃）をえた。Example 2 The crystals precipitated when cold were collected from the solution obtained by treating the heated ethanol solution of the crude target product in Example 1 with activated carbon, and the crystals precipitated in the furnace were reconsolidated with ethanol to obtain the identified sample ( M.p.l6
7-1°C).
・実施例３２−メチルイミダゾールー４ージチオカルボ
ン酸０．０３モル（４．７ｆ）、炭酸カリウム０．０１
５モル（２．１ｆ）、水２０ｍ１及びモノクロル酢酸メ
チル０．０３モル（３．３ｆＩ）の４者より成る系を１
時間５０〜７０５℃に保つたのち結晶を沖取し、該結晶
をエタノール再結し、粗目的物〔Ｍ．ｐ．ｌ３９〜１４
２℃；ＴＬＣ（実施例１相当）ＲｆＯ．３５〜０．４５
〕を５．６ｆ（対ジチオカルボン酸収率８１％）をえた
。・Example 3 2-methylimidazole-4-dithiocarboxylic acid 0.03 mol (4.7f), potassium carbonate 0.01
A system consisting of 5 mol (2.1 f), 20 ml of water, and 0.03 mol (3.3 fI) of methyl monochloroacetate is
After keeping the temperature at 50 to 705°C for a period of time, the crystals were taken off the coast, and the crystals were reconsolidated with ethanol to obtain the crude target product [M. p. l39-14
2°C; TLC (corresponding to Example 1) RfO. 35-0.45
] was obtained (yield 81% based on dithiocarboxylic acid).
実施例４
１実施例３の粗目的物を実施例２の如く処理し、前出の
同定試料（Ｍ．Ｐ．ｌ４５〜１４ｒＣ）をえた。Example 4 1 The crude target product of Example 3 was treated as in Example 2 to obtain the identified sample (M.P.l 45-14rC).
実施例５２−メチルイミダゾールー４ージチオカルボン
酸０．０３モル（４．７ｆ）、炭酸マグネシウム１．５
ｆＩ１水・２０ｍ１及びモノブロム酢酸メチル０．０３
モル（４．６ｆ）の４者より成る系を２時間３紛５０〜
６０Ｃに保つたのち結晶を炉取し、該結晶をエタノール
再結し、粗目的物〔Ｍ．ｐ．ｌ３８〜１４７Ｃ；ＴＬＣ
（前出）ＲｆＯ．３５〜０．４５〕を５．９ｆ（対ジチ
オカルボン酸収）率８５％）をえた。Example 5 2-methylimidazole-4-dithiocarboxylic acid 0.03 mol (4.7f), magnesium carbonate 1.5
fI1 water 20ml and methyl monobromoacetate 0.03
A system consisting of 4 moles (4.6f) of 50 ~ 3 ml for 2 hours
After maintaining the temperature at 60C, the crystals were collected in a furnace, and the crystals were re-crystallized with ethanol to obtain the crude target product [M. p. l38-147C; TLC
(Supra) RfO. 35-0.45] to obtain 5.9f (yield based on dithiocarboxylic acid) of 85%).
実施例６
２−メチルイミダゾールー４ージチオカルボン酸０．０
３モル（４．７ｆ）、酢酸ナトリウム０．０３モル（２
．５ｆＩ）、酢酸２０ｍ１及びモノクロル酢酸メチル０
．０３モル（３．３ｆ）の４者より成る系を２時間６５
〜７０℃に保つたのち結晶をｐ別し、ｐ液を減圧濃縮し
、残留物を２０ｍ１の水と煮沸し、冷却後、結晶を枦取
し、該結晶をエタノール再結し粗目的物〔Ｍ．ｐ．ｌ３
５〜１４００Ｃ；ＴＬＣ（前出）ＲｆＯ．３５〜０．４
５〕を１．１′（対ジチオカルボン酸収率１６％）えた
。Example 6 2-methylimidazole-4-dithiocarboxylic acid 0.0
3 moles (4.7f), sodium acetate 0.03 moles (2
．． 5fI), 20 ml of acetic acid and 0 methyl monochloroacetate
．． A system consisting of 03 moles (3.3 f) of 4 members was heated for 2 hours65
After keeping the temperature at ~70°C, the crystals were separated, the P liquid was concentrated under reduced pressure, the residue was boiled with 20 ml of water, and after cooling, the crystals were collected, and the crystals were reconsolidated with ethanol to obtain the crude target product [ M. p. l3
5-1400C; TLC (supra) RfO. 35-0.4
5] was obtained at 1.1' (yield 16% based on dithiocarboxylic acid).
実施例７２−エチルイミダゾールー４ージチオカルボン
酸０．０３モル（５．２ｙ）、炭酸カリウム０．０１５
モル（２．１ｆ）、水２０ｍ１及びモノクロル酢酸メチ
ル０．０３モル（３．３ｆ）の４者より成る系を２時間
４０〜５０℃に保つたのち、結晶を沖取し、該結晶をエ
タノールで再結し、粗目的物〔Ｍ．ｐ．ｌｌ４〜１１９
℃；ＴＬＣ（前出）ＲｆＯ．４４〜０．５４〕を５．６
ｇ（対ジチオカルボン酸収率７６％）えた。Example 7 2-ethylimidazole-4-dithiocarboxylic acid 0.03 mol (5.2y), potassium carbonate 0.015
After keeping the system consisting of 20 ml of water and 0.03 mol (3.3 f) of methyl monochloroacetate at 40 to 50°C for 2 hours, the crystals were taken off the coast and the crystals were soaked in ethanol. Recombine and form the coarse object [M. p. ll4~119
°C; TLC (supra) RfO. 44-0.54] to 5.6
g (76% yield based on dithiocarboxylic acid).
実施例８
実施例７の粗目的物の熱エタノール溶液を活性炭処理し
てえられた炉液から冷時析出する結晶を枦取し、枦取結
晶をエタノールで２回再結し、前出の同定試料（Ｍ．ｐ
．ｌｌ９〜１２７Ｃ）をえた。Example 8 The heated ethanol solution of the crude target product of Example 7 was treated with activated carbon, and the crystals precipitated when cold were collected from the furnace liquid, and the collected crystals were reconsolidated twice with ethanol. Identification sample (M.p
．． ll9-127C) was obtained.
実施例９２−ウンデシルイミダゾールー４ージチオカル
ボン酸０．０３モル（８．９Ｖ）、水酸化ナトリウム０
．０３モル（１．２ｙ）、エタノール２０ｍ１及びモノ
クロル酢酸メチル０．０３モル（３．３ｙ）の４者より
成る系を４時間７５〜８０℃に保つたのち冷却し、系を
洒過し、枦液を減圧濃縮し、残留物のトルエン溶液を活
性白土層に通し、通過液をさらに活性炭処理したのち減
圧乾固し乾固物ををアセトン再結し、粗目的物〔Ｍ．ｐ
．６８〜７９℃；ＴＬｆ：．（前出）ＲｆＯ．６５〜０
．７＼０．７５〜０．７９（極く薄い）〕を２．３ｙ（
対ジチオカルボン酸収率２０％）えた。Example 9 0.03 mol (8.9 V) of 2-undecylimidazole-4-dithiocarboxylic acid, 0 sodium hydroxide
．． A system consisting of 03 mol (1.2y), 20 ml of ethanol, and 0.03 mol (3.3y) of methyl monochloroacetate was kept at 75-80°C for 4 hours, cooled, and filtered. The liquid was concentrated under reduced pressure, the toluene solution of the residue was passed through a layer of activated clay, and the permeate was further treated with activated carbon, dried under reduced pressure, and the dried substance was recondensed with acetone to obtain the crude target product [M. p
．． 68-79°C; TLf:. (Supra) RfO. 65-0
．． 7\0.75-0.79 (extremely thin)] to 2.3y (
A yield of 20% based on the dithiocarboxylic acid was obtained.
実施例１０
実施例９の粗目的のアセトン溶液を活性炭処理してえら
れた枦液を乾固し、乾固物をアセトン再結し、前出の同
定試料（Ｍ．Ｐ．７６〜８ｒＣ）をえた。Example 10 The crude target acetone solution of Example 9 was treated with activated carbon to dry the resulting acetone solution, and the dried product was reconsolidated with acetone to obtain the identified sample (M.P. 76-8rC). I got it.
実施例１１
２−ヘプタデシルイミダゾールー４ージチオカルボン酸
０．０１５モル（５．７ｆ）、炭酸カルシウム０．００
７５モル（イ）．７５ｙ）、Ｄｒ８′２０ｍ１及びモノ
クロル酢酸メチル０．０１５モル（１．６ｙ）の４者よ
り成る系を２時間７０〜７５℃に保つたのち、微量の結
晶を戸別し、枦液を減圧濃縮し、残留物を５０Ｔ１Ｌｔ
の熱水で洗滌したのち、５０Ｔ！Ｌｔの熱アセトンで抽
出し、抽出液を活性炭処理してえられた戸液を乾固し、
乾固物をアセトンで再結し、粗目的物〔Ｍ．ｐ．８Ｏ〜
８０℃；ＴＬＣ（前出）ＲｆＯ．５５〜０．６５（極く
薄い）、０．６５〜０．７５〕を３．８ｙ（対ジチオカ
ルボン酸収率５５％）えた。Example 11 2-heptadecyl imidazole-4-dithiocarboxylic acid 0.015 mol (5.7f), calcium carbonate 0.00
75 moles (a). After keeping a system consisting of 75y), 20ml of Dr8' and 0.015 mol (1.6y) of methyl monochloroacetate at 70 to 75°C for 2 hours, a trace amount of crystals was separated and the liquid was concentrated under reduced pressure. , the residue is 50T1Lt
After washing with hot water, 50T! Extract Lt with hot acetone, treat the extract with activated carbon, and dry the resulting liquid.
The dried product was reconsolidated with acetone to obtain the crude target product [M. p. 80～
80°C; TLC (supra) RfO. 55-0.65 (extremely thin), 0.65-0.75] was obtained in an amount of 3.8y (yield of 55% based on dithiocarboxylic acid).
実施例１２
実施例１１の粗目的物の熱アセトン溶液を活性炭処理し
てえられたｐ液を乾固し、乾固物をアセトンで２回再結
し、前出の同定試料（Ｍ．ｐ．９ｌ〜９６℃）をえた。Example 12 The p solution obtained by treating the hot acetone solution of the crude target product of Example 11 with activated carbon was dried, and the dried product was reconsolidated twice with acetone to obtain the identified sample (M.p. .9l~96°C) was obtained.
実施例１３２−フェニルイミダゾールー４ージチオカル
ボン酸０．０３モル（６．６′）、トリエチルアミン０
．０３モル（３．０ｆ）、エタノール２０７Ｆ！ｌ及び
モノクロル酢酸メチル０．０３モル（３．３ｆ）の４者
より成る系を３時間５０〜６０℃に保つたのち、内容物
を減圧濃縮し、残留物を３０ｍ１のアセトンで抽出し、
抽出液を減圧乾固し、乾固物をエタノールで再結し、粗
目的物〔Ｍ．ｐ．ｌ３４〜１４１℃；ＴＬＣ（前出）Ｒ
ｆＯ．５７〜０．６７〕を６．７ｆ（対ジチオカルボン
酸収率７６％）えた。Example 13 0.03 mol (6.6') of 2-phenylimidazole-4-dithiocarboxylic acid, 0 triethylamine
．． 03 mol (3.0f), ethanol 207F! After keeping a system consisting of 1 and 0.03 mol (3.3 f) of methyl monochloroacetate at 50 to 60°C for 3 hours, the contents were concentrated under reduced pressure, and the residue was extracted with 30 ml of acetone.
The extract was dried under reduced pressure, and the dried product was reconsolidated with ethanol to obtain the crude target product [M. p. l34-141°C; TLC (mentioned above) R
fO. 57-0.67] was obtained in an amount of 6.7f (76% yield based on dithiocarboxylic acid).
実施例１４
実施例１３の粗目的物を実施例８の如く処理し前出の同
定試料（Ｍ．ｐ．ｌ４２〜１４４℃）をえた。Example 14 The crude target product of Example 13 was treated as in Example 8 to obtain the identified sample (M.p.l. 42-144°C).
実施例１５４−メチルイミダゾールー５ージチオカルボ
ン酸０．０３モル（４．７ｙ）、２８％アンモニア水０
．０３モル（１．８ｙ）、水２０ｗＬ１及びモノクロル
酢酸メチル０．０３モル（３．３ｙ）の４者より成る系
を２時間４５〜５０℃に保つたのち、結晶を枦取し、該
結晶をエタノール再結し、粗目的物〔Ｍ．ｐ．ｌ４７〜
１５０℃；ＴｌＣ（前出）ＲｆＯ．ＯＯ〜０．１０（極
く薄い）、０．２５〜０．３５〕を５．２Ｖ（対ジチオ
カルボン酸収率７５％）えた。Example 15 4-methylimidazole-5-dithiocarboxylic acid 0.03 mol (4.7y), 28% aqueous ammonia 0
．． A system consisting of 03 mol (1.8y), 20wL1 water, and 0.03 mol (3.3y) methyl monochloroacetate was kept at 45 to 50°C for 2 hours, and then the crystals were collected. Ethanol reconsolidates to give the crude target product [M. p. l47~
150°C; TIC (supra) RfO. OO~0.10 (extremely thin), 0.25~0.35] was obtained at 5.2 V (75% yield relative to dithiocarboxylic acid).
実施例１６実施例１５の粗目的物を実施例８の如く処理
し前出の同定試料〔Ｍ．ｐ．ｌ６Ｏ〜１６２℃（分解）
〕をえた。Example 16 The crude target product of Example 15 was treated as in Example 8 and the identified sample [M. p. l6O~162℃ (decomposition)
] was obtained.
実施例１７２，４−ジメチルイミダゾールー５ージチオ
カルボン酸０．０３モル（５．２ｆ）、炭酸ナトリウム
０．０１５モル（１．６ｆ１）、アセトン２０ｍ１及び
モノクロル酢酸メチル０．０３モル（３．３ｙ）、の４
者より成る系を４時間加熱還流したのち結晶を戸取し、
該結晶を冷水２０ｍｔで洗滌し、粗目的物〔Ｍ．ｐ．ｌ
５ｌ〜１５４℃；ＴＬＣ（前出）ＲｆＯ．３７〜０．４
８〕を４．８９（対ジチオカルボン酸収率６６％）えた
。Example 17 2,4-dimethylimidazole-5-dithiocarboxylic acid 0.03 mol (5.2f), sodium carbonate 0.015 mol (1.6f1), acetone 20ml and methyl monochloroacetate 0.03 mol (3.3y), 4
After heating and refluxing the system for 4 hours, the crystals were taken out.
The crystals were washed with 20 mt of cold water to obtain the crude target product [M. p. l
5l~154°C; TLC (supra) RfO. 37-0.4
8] was obtained by 4.89 (yield based on dithiocarboxylic acid: 66%).
実施例１８
実施例１７の粗目的物を実施例８の如く処理し前出の同
定試料（Ｍ．ｐ．ｌ６２〜１６４℃）をえた。Example 18 The crude target product of Example 17 was treated as in Example 8 to obtain the identified sample (M.p.l. 62-164°C).
実施例１９２，４−ジメチルイミダゾールー５ージチオ
カルボン酸０．０３モル（５．２ｆ）、水酸化カリウム
０．０３モル（１．７ｙ）、ＤＭＳＯ２Ｏｍｌ及びモノ
クロル酢酸メチル０．０３モル（３．３′）の３者より
成る系を３時間５０〜６０℃に保つたのち冷却し、系を
枦過し、枦液を減圧濃縮し残留物を３０ｍ１の水と煮沸
したのち冷却し、水層を傾斜除去し、残留物をエタノー
ル再結し、粗目的物〔Ｍ．ｐ．ｌ４５〜１４ＣｆＣ；Ｌ
℃（前出）ＲｆＯ．３７〜０．４８〕を２．８ｙ（対ジ
チオカルボン酸収率羽％）えた。Example 19 2,4-dimethylimidazole-5-dithiocarboxylic acid 0.03 mol (5.2f), potassium hydroxide 0.03 mol (1.7y), DMSO2Oml and methyl monochloroacetate 0.03 mol (3.3') The system consisting of these three components was maintained at 50-60°C for 3 hours, then cooled, the system was filtered, the liquid was concentrated under reduced pressure, and the residue was boiled with 30 ml of water, cooled, and the aqueous layer was decanted. The residue was reconsolidated with ethanol to obtain the crude target product [M. p. l45~14CfC;L
℃ (supra) RfO. 37-0.48] was obtained by 2.8y (yield % relative to dithiocarboxylic acid).
実施例２０
２−エチルー４−メチルイミダゾールー５ージチオカル
ボン酸０．０３モル（５．６ｙ）、ＤＭＦｌ２ｍｌ及び
モノク曵レ酢酸メチル０．０３モル（３．３ｙ）の３者
より成る系を１時間４５〜５０℃ついで１時間７０〜７
５℃に保つたのち、内容物を減圧乾固し、乾固物をエタ
ノール再結してえられた結晶のアンモニア性メタノール
溶液を乾固し、乾固物を５０ｍ１の熱水で洗滌したのち
、アセトン再結して、粗目的物〔Ｍ．ｐ．ｌ２Ｏ〜１２
３結Ｃ；ＴＬＣ（前出）ＲｆＯ．５Ｏ〜０．６０〕を４
．２ｙ（対ジチオカルボン酸収率５４％）えた。Example 20 A system consisting of 0.03 mol (5.6y) of 2-ethyl-4-methylimidazole-5-dithiocarboxylic acid, 2 ml of DMF1, and 0.03 mol (3.3y) of methyl monochloride acetate was heated for 1 hour at 45 ml. ~50℃ then 70~7 for 1 hour
After keeping at 5℃, the contents were dried under reduced pressure, the ammoniacal methanol solution of crystals obtained by recrystallizing the dried substance with ethanol was dried, and the dried substance was washed with 50 ml of hot water. , acetone is reconstituted to obtain the crude target product [M. p. l2O~12
3 Conclusion C; TLC (supra) RfO. 5O~0.60] to 4
．． 2y (yield 54% based on dithiocarboxylic acid) was obtained.
実施例２１実施例２０の粗目的物をアセトンで２回再結
し、前出の同定試料（Ｍ．ｐ．ｌ２２〜１２４結Ｃ）を
えた。Example 21 The crude target product of Example 20 was reconstituted twice with acetone to obtain the identified sample (M.p.l 22-124 C).
実施例 坐２−エチルー４−メチルイミダゾールー５ー
ジチオカルボン酸ナトリウム塩０．０３モル（６．３ｆ
）工タノール２０ｍ１及びモノクロル酢酸メチル０．０
３モ！ル（３．３ｙ）の３者より成る系を３時間４５〜
５０℃に保つたのち、析出結晶を枦別し、枦液を減圧乾
固し、乾固物をエタノール再結し、粗目的物〔Ｍ．ｐ．
ｌｌ８〜１２２℃：Ｔ（１）（前出）ＲｆＯ．４２〜０
．５０（極く薄い）、０．５０〜０．６０〕を６．５ｙ
（対ジチオカルボン酸ナトリウム塩収率？％）えた。Example 0.03 mol (6.3 f
) ethanol 20ml and methyl monochloroacetate 0.0
3mo! (3.3y) for 3 hours 45~
After keeping the temperature at 50°C, the precipitated crystals were separated, the filtrate was dried to dryness under reduced pressure, and the dried product was reconsolidated with ethanol to obtain the crude target product [M. p.
ll8-122°C: T(1) (supra) RfO. 42-0
．． 50 (extremely thin), 0.50~0.60] to 6.5y
(yield of sodium dithiocarboxylic acid salt?%).
実施例３２
２−ウンデシルー４−メチルイミダゾールー５ージチオ
カルボン酸０．０２モル（６．２′）、炭酸ナトｌノウ
ム０．０１モル（１．１ｙ）、エタノール２０ｍ１及び
モノクロル酢酸メチル０．０２モル（２．２ｙ）の４者
より成る系を３時間５０〜５５℃に保つたのち冷却し、
系をｔ過し、枦液を減圧濃縮し、残留物のアセトン溶液
を活性白土層に通し、通過液をさらに活性炭処理したの
ち減圧乾固し、乾固物をアセトン再結し、粗目的物〔Ｍ
．ｐ．７Ｏ〜７７℃；ＴＬＣ（前出）ＲｆＯ．６５〜０
．７５〕を２．３ｙ（対ジチオカルボン酸収率３０％）
えた。Example 32 0.02 mol (6.2') of 2-undecyl-4-methylimidazole-5-dithiocarboxylic acid, 0.01 mol (1.1y) of sodium carbonate, 20 ml of ethanol and 0.02 mol of methyl monochloroacetate ( 2.2y) The system consisting of the four members was kept at 50 to 55°C for 3 hours and then cooled.
The system is filtered, the liquid is concentrated under reduced pressure, the acetone solution of the residue is passed through a layer of activated clay, the filtered liquid is further treated with activated carbon and then dried under reduced pressure, and the dried solid is reconsolidated with acetone to obtain the crude target product [M
．． p. 7O-77°C; TLC (supra) RfO. 65-0
．． 75] to 2.3y (30% yield relative to dithiocarboxylic acid)
I got it.
実施例２４
実施例２３の粗目的物を実施例２１の如く処理し、前出
の同定試料（Ｍ．ｐ．７５〜７（代））をえた。Example 24 The crude target product of Example 23 was treated as in Example 21 to obtain the identified sample (M.p. 75-7 (generation)).
実施例２５２−フェニルー４−メチルイミダゾールー５
ージチオカルボン酸０．０３モル（７．０ｆ）、炭酸ナ
トリウム０．０１５モル（１．６Ｖ）、アセトニトリル
２０ｍ１及びモノク曵レ酢酸メチル０．０３モル（３．
３ｆ）の４者よりなる系を４時間５５〜６ＣｆＣに保つ
たのち結晶を戸取し、該結晶を冷水３０ｍ１て洗滌し、
粗目的物〔Ｍ．ｐ．ｌ８ｌ〜１８５℃：Ｌ℃（前出）Ｒ
ｆＯ．５Ｏ〜０．５５（極く薄い）、０．５８〜０．６
８〕を５．６ｆＩ（対ジチオカルボン酸収率６１％）え
た。Example 252-phenyl-4-methylimidazole-5
0.03 mol (7.0 f) of dithiocarboxylic acid, 0.015 mol (1.6 V) of sodium carbonate, 20 ml of acetonitrile and 0.03 mol (3.0 f) of methyl monochloride acetate.
After maintaining the system consisting of the four components in 3f) at 55 to 6 CfC for 4 hours, remove the crystals, wash the crystals with 30 ml of cold water,
Coarse object [M. p. 18l~185°C: L°C (mentioned above) R
fO. 5O~0.55 (very thin), 0.58~0.6
8] was obtained in an amount of 5.6 fI (61% yield relative to dithiocarboxylic acid).
実施例２６
実施例２５の粗目的物を実施例８の如く処理し、前出の
同定試料（Ｍ．ｐ．ｌ９９〜２０１℃）をえた。Example 26 The crude target product of Example 25 was treated as in Example 8 to obtain the identified sample (M.p.I. 99-201°C).
Claims (1)
、ウンデシル基、ヘプタデシル基及びフェニル基より成
る群より選ばれた残基、Ｒ＿４は水素原子又はメチル基
を表わす。 〕で示されるイミダゾールジチオカルボン酸化合物とモ
ノハロ酢酸メチルを縮合反応させることを特徴とする。 構造式 ▲数式、化学式、表等があります▼ 〔但し、式中Ｒ＿２とＲ＿４は前記と同じである。 〕で示されるイミダゾールジチオカルボン酸カルボメト
キシメチルエステル化合物の合成方法。２ イミダゾー
ルジチオカルボン酸化合物とモノハロ酢酸メチルを縮合
反応させ、ハロゲン化水素受容体で脱ハロゲン化水素さ
せる特許請求の範囲第１に記載のイミダゾールジチオカ
ルボン酸カルボメトキシメチルエステル化合物の合成方
法。 ３ イミダゾールジチオカルボン酸化合物とモノハロ酢
酸メチルをハロゲン化水素受容体の共存下で縮合反応さ
せる特許請求の範囲１に記載のイミダゾールジチオカル
ボン酸カルボメトキシメチルエステル化合物の合成方法
。 ４ イミダゾールジチオカルボン酸化合物の塩を形成し
、これにモノハロ酢酸メチルを縮合反応させる特許請求
の範囲１に記載のイミダゾールジチオカルボン酸カルボ
メトキシメチルエステル化合物の合成方法。[Claims] 1 Structural formula ▲ Numerical formulas, chemical formulas, tables, etc. The residue R_4 represents a hydrogen atom or a methyl group. It is characterized by subjecting the imidazoledithiocarboxylic acid compound represented by ] and methyl monohaloacetate to a condensation reaction. Structural formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, in the formula, R_2 and R_4 are the same as above. ] A method for synthesizing an imidazole dithiocarboxylic acid carbomethoxymethyl ester compound. 2. The method for synthesizing an imidazoledithiocarboxylic acid carbomethoxymethyl ester compound according to claim 1, which comprises subjecting an imidazoledithiocarboxylic acid compound to a condensation reaction with methyl monohaloacetate, and dehydrohalogenating the compound using a hydrogen halide acceptor. 3. The method for synthesizing an imidazoledithiocarboxylic acid carbomethoxymethyl ester compound according to claim 1, wherein an imidazoledithiocarboxylic acid compound and methyl monohaloacetate are subjected to a condensation reaction in the presence of a hydrogen halide acceptor. 4. The method for synthesizing an imidazoledithiocarboxylic acid carbomethoxymethyl ester compound according to claim 1, which comprises forming a salt of an imidazoledithiocarboxylic acid compound and subjecting the salt to a condensation reaction with methyl monohaloacetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57176712A JPS6056712B2 (en) | 1982-10-06 | 1982-10-06 | Synthesis method of imidazole dithiocarboxylic acid carbomethoxymethyl ester compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57176712A JPS6056712B2 (en) | 1982-10-06 | 1982-10-06 | Synthesis method of imidazole dithiocarboxylic acid carbomethoxymethyl ester compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5965081A JPS5965081A (en) | 1984-04-13 |
| JPS6056712B2 true JPS6056712B2 (en) | 1985-12-11 |
Family
ID=16018435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57176712A Expired JPS6056712B2 (en) | 1982-10-06 | 1982-10-06 | Synthesis method of imidazole dithiocarboxylic acid carbomethoxymethyl ester compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6056712B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62184103A (en) * | 1986-02-03 | 1987-08-12 | カネボウ株式会社 | Extensible non-sewing clothing |
| JPH0464517U (en) * | 1990-10-12 | 1992-06-03 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60177966U (en) * | 1984-05-01 | 1985-11-26 | 小倉 熊雄 | Flat foil thread cutting and separation device with double ears |
-
1982
- 1982-10-06 JP JP57176712A patent/JPS6056712B2/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62184103A (en) * | 1986-02-03 | 1987-08-12 | カネボウ株式会社 | Extensible non-sewing clothing |
| JPH0464517U (en) * | 1990-10-12 | 1992-06-03 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5965081A (en) | 1984-04-13 |
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