JPH0561264B2 - - Google Patents
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- Publication number
- JPH0561264B2 JPH0561264B2 JP2118457A JP11845790A JPH0561264B2 JP H0561264 B2 JPH0561264 B2 JP H0561264B2 JP 2118457 A JP2118457 A JP 2118457A JP 11845790 A JP11845790 A JP 11845790A JP H0561264 B2 JPH0561264 B2 JP H0561264B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- reaction
- tms
- nmr
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- Prior art date
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- -1 N,N-disubstituted thiocarbamoyl group Chemical group 0.000 claims description 17
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical class [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 claims description 16
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003435 aroyl group Chemical group 0.000 claims description 2
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 150000001408 amides Chemical class 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 6
- 229910000104 sodium hydride Inorganic materials 0.000 description 6
- 239000012312 sodium hydride Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MNNJLAZJQBWSST-UHFFFAOYSA-N 1,4,2-dithiazole Chemical class C1SC=NS1 MNNJLAZJQBWSST-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UHBGYFCCKRAEHA-UHFFFAOYSA-N P-toluamide Chemical compound CC1=CC=C(C(N)=O)C=C1 UHBGYFCCKRAEHA-UHFFFAOYSA-N 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000002019 disulfides Chemical class 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012053 oil suspension Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XIPFMBOWZXULIA-UHFFFAOYSA-N pivalamide Chemical compound CC(C)(C)C(N)=O XIPFMBOWZXULIA-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IHLZYEAUHIUQFD-UHFFFAOYSA-N (thiophene-2-carbonylamino) n,n-diethylcarbamodithioate Chemical compound CCN(CC)C(=S)SNC(=O)C1=CC=CS1 IHLZYEAUHIUQFD-UHFFFAOYSA-N 0.000 description 1
- TUMNHQRORINJKE-UHFFFAOYSA-N 1,1-diethylurea Chemical compound CCN(CC)C(N)=O TUMNHQRORINJKE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- BLNVISNJTIRAHF-UHFFFAOYSA-N 4-chlorobenzamide Chemical compound NC(=O)C1=CC=C(Cl)C=C1 BLNVISNJTIRAHF-UHFFFAOYSA-N 0.000 description 1
- 125000000242 4-chlorobenzoyl group Chemical group ClC1=CC=C(C(=O)*)C=C1 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- HAXFWIACAGNFHA-UHFFFAOYSA-N aldrithiol Chemical compound C=1C=CC=NC=1SSC1=CC=CC=N1 HAXFWIACAGNFHA-UHFFFAOYSA-N 0.000 description 1
- KYYBWOQFPMAZAU-UHFFFAOYSA-N amino morpholine-4-carbodithioate Chemical compound NSC(=S)N1CCOCC1 KYYBWOQFPMAZAU-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HXLVCCRPDYIRRX-UHFFFAOYSA-N iodoamine Chemical compound IN HXLVCCRPDYIRRX-UHFFFAOYSA-N 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KKVYOWPPMNSLCP-UHFFFAOYSA-N morpholine-4-carbothioylsulfanyl morpholine-4-carbodithioate Chemical compound C1COCCN1C(=S)SSC(=S)N1CCOCC1 KKVYOWPPMNSLCP-UHFFFAOYSA-N 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- OVPLZYJGTGDFNB-UHFFFAOYSA-N propan-2-yl carbamate Chemical compound CC(C)OC(N)=O OVPLZYJGTGDFNB-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- YYWLHHUMIIIZDH-UHFFFAOYSA-N s-benzoylsulfanyl benzenecarbothioate Chemical compound C=1C=CC=CC=1C(=O)SSC(=O)C1=CC=CC=C1 YYWLHHUMIIIZDH-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- DENPQNAWGQXKCU-UHFFFAOYSA-N thiophene-2-carboxamide Chemical compound NC(=O)C1=CC=CS1 DENPQNAWGQXKCU-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Landscapes
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Pyridine Compounds (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はスルフエンアミド誘導体を製造する方
法に関し、本方法によれば、アミド型化合物を水
素化ナトリウムで処理した後、ジスルフイド体と
反応させることにより、簡便、迅速かつ好収率で
スルフエンアミド誘導体を製造する方法に関する
ものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a sulfenamide derivative, and according to this method, an amide type compound is treated with sodium hydride and then reacted with a disulfide derivative. The present invention relates to a method for producing sulfenamide derivatives simply, rapidly, and in good yields.
従来、一般式(3)で表わされるスルフエンアミド
誘導体の製造方法としては、対応するＮ−無置換
スルフエンアミドのアロイル化あるいはアシル化
反応を用いるものと（特公昭62−41712号、特願
昭63−219738号）、Ｎ−ヨードアミドとジチオカ
ルバミン酸塩との反応を利用するものがあつた
（特願平２−32214号）。
Conventionally, methods for producing the sulfenamide derivative represented by the general formula (3) include methods using aroylation or acylation reactions of the corresponding N-unsubstituted sulfenamide (Japanese Patent Publication No. 41712/1983, Japanese Patent Application No. 219738/1982). There was a method utilizing the reaction between N-iodoamide and dithiocarbamate (Japanese Patent Application No. 2-32214).
しかしながら、前者については、原料のＮ−無
置換スルフエンアミドが不安定であり、生成物の
スルフエンアミド誘導体（一般式(3)）中の置換基
R1が、アシル化及びアロイル化反応によつて、
その種類が限定されていた。また後者について
は、原料のジチオカルバミン酸塩が反応条件下で
容易に酸化され、かなりの量のテトラアルキルチ
ウムジスルフイドが副生する欠点を有していた。 However, regarding the former, the raw material N-unsubstituted sulfenamide is unstable, and the substituents in the product sulfenamide derivative (general formula (3))
R 1 is, by acylation and aroylation reaction,
The types were limited. The latter method also has the disadvantage that the raw material dithiocarbamate is easily oxidized under the reaction conditions, resulting in a considerable amount of tetraalkyltium disulfide being produced as a by-product.
本発明は、アミド型化合物を水素化ナトリウム
で処理した後、ジスルフイド体と反応させること
により、簡便、迅速かつ好収率で多種多様なスル
フエンアミド誘導体を製造する方法を提供するこ
とを目的とする。
An object of the present invention is to provide a method for producing a wide variety of sulfenamide derivatives simply, rapidly, and in good yields by treating an amide type compound with sodium hydride and then reacting it with a disulfide compound.
本発明は、一般式
（式中、R1は水素、不活性な置換基を有しても
よいアリール基、複素環基、アルキル基、ジアル
キルアミノ基、アルコキシ基を示す。）で表され
るアミド型化合物を水素化ナトリウムで処理した
後、一般式
R2SSR2 ……(2)
（式中R2はＮ，Ｎ−ジ置換チオカルバモイル基、
アロイル基、不活性な置換基を有していてもよい
アリール基、複素環基を示す。）で表されるジス
ルフイド体と反応させることを特徴とする
一般式
（式中、R1、R2は前記と同じ意味をもつ。）で表
されるスルフエンアミド誘導体の製造方法であ
る。
The present invention is based on the general formula (In the formula, R 1 represents hydrogen, an aryl group that may have an inert substituent, a heterocyclic group, an alkyl group, a dialkylamino group, or an alkoxy group.) After treatment with sodium, the general formula R 2 SSR 2 ...(2) (wherein R 2 is an N,N-disubstituted thiocarbamoyl group,
Indicates an aroyl group, an aryl group which may have an inert substituent, and a heterocyclic group. ) General formula characterized by reacting with a disulfide represented by This is a method for producing a sulfenamide derivative represented by the formula (wherein R 1 and R 2 have the same meanings as above).
本発明の方法に従えば、比較的穏和な条件下で
迅速かつ好収率でスルフエンアミド誘導体が得ら
れる。用いる原料及び反応試剤はいずれも安価で
取扱が容易であり、後処理では抽出法により無機
系成分を効果的に取り除くことができる。また、
一般式(1)で表されるアミド型化合物を適当に選ぶ
ことにより、スルフエンアミド誘導体に多様な置
換基R1を導入することができる。 According to the method of the present invention, sulfenamide derivatives can be obtained quickly and in good yields under relatively mild conditions. The raw materials and reaction reagents used are both inexpensive and easy to handle, and inorganic components can be effectively removed by extraction in post-treatment. Also,
By appropriately selecting the amide type compound represented by the general formula (1), various substituents R 1 can be introduced into the sulfenamide derivative.
本発明の方法によつて生成するスルフエンアミ
ド誘導体、及びそれらを脱水環化することにより
得られる１，４，２−ジチアゾリウム塩は、どち
らもハロゲン化銀写真用カブリ抑制効果を有す
る。（特願昭63−53073号、特願平１−94149号）
また、１，４，２−ジチアゾリウム塩は各種の含
Ｓ，Ｎ複素環化合物の中間体原料であり、有機合
成上、有用な化合物である。 Both the sulfenamide derivatives produced by the method of the present invention and the 1,4,2-dithiazolium salts obtained by cyclodehydrating them have fog suppressing effects for silver halide photography. (Patent Application No. 1983-53073, Patent Application No. 1-94149)
Furthermore, 1,4,2-dithiazolium salt is an intermediate raw material for various S,N-containing heterocyclic compounds, and is a useful compound in organic synthesis.
本発明に用いられる一般式(1)及び(3)中の置換基
R1としては、水素、フエニル基、ｐ−アニシル
基、ｐ−トリル基、ｐ−クロロフエニル基、２−
チエニル基、３−ピリジル基、２−フリル基、ｔ
−ブチル基、ｎ−ベチル基、メチル基、ジメチル
アミノ基、ジエチルアミノ基、ジイソプロピルア
ミノ基、メトキシ基、エトキシ基、イソプロポキ
シ基等が挙げられる。一般式(2)及び(3)中の置換基
R2としては、ジメチルチオカルバモイル基、ジ
エチルチオカルバモイル基、ジイソプロピルチオ
カルバモイル基、モルホリン−Ｎ−チオカルボニ
ル基、ピペリジン−Ｎ−チオカルボニル基、ベン
ゾイル基、フエニル基、２−ニトロフエニル基、
４−ピリジル基、２−ピリジル基、ベンゾチアジ
ル基等が挙げられる。 Substituents in general formulas (1) and (3) used in the present invention
R 1 is hydrogen, phenyl group, p-anisyl group, p-tolyl group, p-chlorophenyl group, 2-
thienyl group, 3-pyridyl group, 2-furyl group, t
-butyl group, n-betyl group, methyl group, dimethylamino group, diethylamino group, diisopropylamino group, methoxy group, ethoxy group, isopropoxy group and the like. Substituents in general formulas (2) and (3)
R 2 is a dimethylthiocarbamoyl group, a diethylthiocarbamoyl group, a diisopropylthiocarbamoyl group, a morpholine-N-thiocarbonyl group, a piperidine-N-thiocarbonyl group, a benzoyl group, a phenyl group, a 2-nitrophenyl group,
Examples include 4-pyridyl group, 2-pyridyl group, and benzothiazyl group.
溶媒としては、無水のエーテル系がよく、例え
ばテトラヒドロフラン、ジオキサン等が適してい
る。また、水素化ナトリウムは無水物、或はオイ
ルサスペンシヨン（50〜60％）のいずれを用いる
こともできる。 As the solvent, anhydrous ethers are preferred, such as tetrahydrofuran, dioxane, and the like. Moreover, sodium hydride can be either anhydrous or oil suspension (50 to 60%).
本反応はまず、一般式(1)で表されるアミド型化
合物を適当な溶媒に溶解し、２倍当量の水素化ナ
トリウムを加え室温で撹拌する。水素ガスの発生
が止まつた後、一般式(2)で表されるジスルフイド
体をアミド型化合物に対して当量加え、約１〜２
時間撹拌する。反応温度は通常室温で行われる
が、必要に応じて加熱し反応を促進することもで
きる。反応終了後の後処理は、まず水にあけ塩化
メチレンで抽出し、カラムクロマトグラフイーお
よび再結晶法により分離精製を行うことができ
る。 In this reaction, first, the amide type compound represented by the general formula (1) is dissolved in a suitable solvent, and two equivalents of sodium hydride are added thereto and the mixture is stirred at room temperature. After the generation of hydrogen gas has stopped, an equivalent amount of the disulfide represented by the general formula (2) is added to the amide type compound, and about 1 to 2
Stir for an hour. The reaction temperature is usually room temperature, but the reaction can be accelerated if necessary by heating. For post-treatment after completion of the reaction, first, the mixture is poured into water, extracted with methylene chloride, and separated and purified by column chromatography and recrystallization.
本発明の方法における反応機構は下記の様に表
現できる。 The reaction mechanism in the method of the present invention can be expressed as follows.
得られたスルフエンアミド誘導体の構造確認
は、既知化合物については標品との比較により行
い、新規化合物については赤外吸収スペクトル、
核磁気共鳴スペクトル、質量分析、元素分析を用
いて行つた。 Structural confirmation of the obtained sulfenamide derivatives is performed by comparing known compounds with standard products, and for new compounds by infrared absorption spectra,
This was done using nuclear magnetic resonance spectroscopy, mass spectrometry, and elemental analysis.
本発明によれば、市販品として豊富な種類を持
つアミド型化合物と一般的合成法が確立している
ジスルフイド体から容易にスルフエンアミド誘導
体が製造できる。使用する試剤も非常に安価な水
素化ナトリウムであり、後処理も効果的に行え
る。
According to the present invention, sulfenamide derivatives can be easily produced from amide type compounds, which are available in a wide variety of commercially available products, and disulfide compounds, for which general synthesis methods have been established. The reagent used is sodium hydride, which is very inexpensive, and post-treatment can be carried out effectively.
本反応で得られるスルフエンアミド誘導体はハ
ロゲン化銀写真用カブリ抑制効果を有し、また各
種の複素環化合物の中間体原料である１，４，２
−ジチアゾリウム塩の前駆体に相当する。 The sulfenamide derivative obtained by this reaction has a fog suppressing effect for silver halide photography, and is also an intermediate raw material for various heterocyclic compounds.
-corresponds to a precursor of dithiazolium salts.
反応はアミド型化合物に限定せず一級アミン或
は二級アミンにも適用可能であり、スルフエンア
ミドの一般的合成法として発展性を持つている。 The reaction is not limited to amide-type compounds, but can also be applied to primary amines or secondary amines, and has the potential to be developed as a general method for synthesizing sulfenamides.
次に本発明を実施例に基づきさらに詳細に説明
する。
Next, the present invention will be explained in more detail based on examples.
実施例 １
２−チオフエンカルボキシアミド127mg（１ｍ
mol）を無水テトラヒドロフラン４mlｌに溶解
し、水素化ナトリウム（60％オイルサスペンシヨ
ン）80mg（２ｍmol）を加え、水素ガスの発生が
止まつた後、さらに５分間撹拌する。テトラエチ
ルチウラムジスルフイド296mg（１ｍmol）を加
え、２時間撹拌する。水にあけ塩化メチレンで抽
出する。溶媒を留去した後、シリカゲルカラムク
ロマトグラフイーで処理し、ベンゼンより再結晶
すると、融点116〜117℃の白色結晶としてＮ−
（２−テノイル）−Ｓ−ジエチルチオカルバモイル
スルフエンアミド223mg（収率81％）が得られる。Example 1 2-thiophenecarboxamide 127 mg (1 m
mol) in 4 ml of anhydrous tetrahydrofuran, add 80 mg (2 mmol) of sodium hydride (60% oil suspension), and stir for an additional 5 minutes after the generation of hydrogen gas has stopped. Add 296 mg (1 mmol) of tetraethylthiuram disulfide and stir for 2 hours. Pour into water and extract with methylene chloride. After distilling off the solvent, it was treated with silica gel column chromatography and recrystallized from benzene to give N-
223 mg (yield 81%) of (2-thenoyl)-S-diethylthiocarbamoylsulfenamide is obtained.
1H−NMR（CDCl3、TMS）δ＝3.30（6H、ｔ、
Ｊ＝7.5Hz）、3.5−4.2（4H、br.）、7.05−7.2（1H、
ｍ）、7.55−7.65（1H、ｍ）、7.8−7.9（1H、ｍ）
13C−NMR（CDCl3、TMS）δ＝12（br.）、46
（br.）、50（br.）、127.83、130.57、131.68、
137.50、162.91、195.93
MS（ｍ／ｚ）274（M+）、116（Et2CS+）
IR（KBr、cm-1）3268（NH）、1658（Ｃ＝０）
元素分析（％）
測定値 Ｃ；43.72、Ｈ；10.12、Ｎ；10.12、
Ｓ；34.72
珪酸値 Ｃ；43.77、Ｈ；5.14、Ｎ；10.21、
Ｓ；35.05
実施例 ２
ｐ−トリルアミド135mg（１ｍmol）を用い、
実施例１と同様に反応及び後処理を行うと、白色
結晶Ｎ−トルオイル−Ｓ−ジエチルチオカルバモ
イルスルフエンアミド183mg（65％）が得られる。 1 H-NMR (CDCl 3 , TMS) δ = 3.30 (6H, t,
J = 7.5Hz), 3.5-4.2 (4H, br.), 7.05-7.2 (1H,
m), 7.55-7.65 (1H, m), 7.8-7.9 (1H, m) 13 C-NMR (CDCl 3 , TMS) δ = 12 (br.), 46
(br.), 50 (br.), 127.83, 130.57, 131.68,
137.50, 162.91, 195.93 MS (m/z) 274 (M + ), 116 (Et 2 CS + ) IR (KBr, cm -1 ) 3268 (NH), 1658 (C=0) Elemental analysis (%) Measured value C; 43.72, H; 10.12, N; 10.12, S; 34.72 Silicic acid value C; 43.77, H; 5.14, N; 10.21, S; 35.05 Example 2 Using 135 mg (1 mmol) of p-tolylamide,
The reaction and work-up were carried out in the same manner as in Example 1 to obtain 183 mg (65%) of white crystalline N-toluoyl-S-diethylthiocarbamoylsulfenamide.
標品（Bull.Chem.Soc.Jpn.、59、2017（1986））
との比較により同定した。 Standard specimen (Bull.Chem.Soc.Jpn., 59, 2017 (1986))
Identified by comparison with
実施例 ３
カルバミン酸イソプロピル103mg（１ｍmol）
を用い、実施例１と同様に反応及び後処理を行う
と、白色結晶Ｎ−イソプロポキシカルボニル−Ｓ
−ジエチルチオカルバモイルスルフエンアミド
150mg（60％）が得られる。Example 3 Isopropyl carbamate 103 mg (1 mmol)
When the reaction and post-treatment were carried out in the same manner as in Example 1, white crystals N-isopropoxycarbonyl-S
-diethylthiocarbamoylsulfenamide
150mg (60%) is obtained.
1H−NMR（CDCl3、TMS）δ＝2.28（6H、ｄ、
Ｊ＝7.5Hz）、3.30（6H、ｔ、Ｊ＝7.5Hz）、3.4−4.2
（4H、br.）、5.00（1H、ｍ）、6.37（br.s）
13H−NMR（CDCl3、TMS）δ＝12（br.）、
21.57、46（br.）、50（br.）、70.41、156.09、197.07
実施例 ４
ホルムアミド225mg（５ｍmol）を用い、実施
例１と同様に反応及び後処理を行うと、オイル状
のＮ−ホルミル−Ｓ−ジエチルチオカルバモイル
スルフエンアミド320mg（33％）が得られる。 1 H-NMR (CDCl 3 , TMS) δ = 2.28 (6H, d,
J=7.5Hz), 3.30 (6H, t, J=7.5Hz), 3.4−4.2
(4H, br.), 5.00 (1H, m), 6.37 (br.s) 13 H-NMR (CDCl 3 , TMS) δ = 12 (br.),
21.57, 46 (br.), 50 (br.), 70.41, 156.09, 197.07 Example 4 Using 225 mg (5 mmol) of formamide and performing the reaction and post-treatment in the same manner as in Example 1, oily N-formyl 320 mg (33%) of -S-diethylthiocarbamoylsulfenamide are obtained.
1H−NMR（CDCl3、TMS）δ＝3.30（6H、ｔ、
Ｊ＝7.5Hz）、3.4−4.2（4H、br.）、7.6−8.7（2H、
br.）
13H−NMR（CDCl3、TMS）δ＝11.6（br.）、
12.8（br.）、46.1（br.）、50.6（br.）、171.1（br.
）、
196.8（br.）
実施例 ５
ビバリン酸アミド101mg（１ｍmol）、ビス（モ
ルホリン−Ｎ−チオカルボニル）ジスルフイド
（１ｍmol）を用い、実施例１と同様に反応及び
後処理を行うと、白色結晶Ｎ−ピバロイル−Ｓ−
（モルホリン−Ｎ−チオカルボニル）スルフエン
アミド176mg（67％）が得られる。 1 H-NMR (CDCl 3 , TMS) δ = 3.30 (6H, t,
J = 7.5Hz), 3.4-4.2 (4H, br.), 7.6-8.7 (2H,
br.) 13 H-NMR (CDCl 3 , TMS) δ = 11.6 (br.),
12.8 (br.), 46.1 (br.), 50.6 (br.), 171.1 (br.
),
196.8 (br.) Example 5 Using 101 mg (1 mmol) of bivalic acid amide and bis(morpholine-N-thiocarbonyl) disulfide (1 mmol), the reaction and post-treatment were carried out in the same manner as in Example 1, resulting in white crystals N- Pivaloyl-S-
176 mg (67%) of (morpholine-N-thiocarbonyl)sulfenamide are obtained.
1H−NMR（CDCl3、TMS）δ＝1.33（9H、
ｓ）、3.7−3.9（4H、ｍ）、3.9−4.1（4H、ｍ）、
7.05（br.s）
13H−NMR（CDCl3、TMS）δ＝27.68、
40.25、50.84、66.12、179.62、198.03
実施例 ６
Ｎ、Ｎ−ジエチル尿素1.1ｇ（10ｍmol）、テト
ラメチルチウラムジスルフイド（10ｍmol）を用
い、実施例１と同様に反応及び後処理を行うと、
白色結晶Ｎ−ジエチルカルバモイル−Ｓ−ジメチ
ルチオカルバモイルスルフエンアミド1.87ｇ（80
％）が得られる。 1 H-NMR (CDCl 3 , TMS) δ = 1.33 (9H,
s), 3.7-3.9 (4H, m), 3.9-4.1 (4H, m),
7.05 (br.s) 13 H-NMR (CDCl 3 , TMS) δ = 27.68,
40.25, 50.84, 66.12, 179.62, 198.03 Example 6 Using 1.1 g (10 mmol) of N,N-diethylurea and tetramethylthiuram disulfide (10 mmol), the reaction and post-treatment were carried out in the same manner as in Example 1.
White crystalline N-diethylcarbamoyl-S-dimethylthiocarbamoylsulfenamide 1.87g (80
%) is obtained.
1H−NMR（CDCl3、TMS）δ＝3.23（6H、ｔ、
Ｊ＝7.5Hz）、3.44（4H、ｑ、Ｊ＝7.5Hz）、3.1−3.8
（6H、br.）、6.26（br.s）
13H−NMR（CDCl3、TMS）δ＝13.34、40
（br.）、41.92、45（br.）、155.54、200.13
実施例 ７
ピバリン酸アミド101mg（１ｍmol）、ジベンゾ
イルジスルフイド（１ｍmol）を用い、実施例１
と同様に反応及び後処理を行うと、白色結晶Ｎ−
ピバロイル−Ｓ−ベンゾイルスルフエンアミド34
mg（14％）が得られる。 1 H-NMR (CDCl 3 , TMS) δ = 3.23 (6H, t,
J=7.5Hz), 3.44 (4H, q, J=7.5Hz), 3.1−3.8
(6H, br.), 6.26 (br.s) 13 H−NMR (CDCl 3 , TMS) δ = 13.34, 40
(br.), 41.92, 45 (br.), 155.54, 200.13 Example 7 Using 101 mg (1 mmol) of pivalic acid amide and dibenzoyl disulfide (1 mmol), Example 1
When the reaction and post-treatment are carried out in the same manner as above, white crystals N-
Pivaloyl-S-benzoylsulfenamide 34
mg (14%) is obtained.
1H−NMR（CDCl3、TMS）δ＝1.33（9H、
ｓ）、6.87（br.s）、7.4−7.65（3H、ｍ）、7.8−7.95
（2H、ｍ）
13H−NMR（CDCl3、TMS）δ＝27.74、
40.25、126.93、128.94、134.08、134.43、179.62、
190.86
実施例 ８
ピバリン酸アミド101mg（１ｍmol）、４、4′−
ジチオジピリジン（１ｍmol）を用い、実施例１
と同様に反応及び後処理を行うと、白色結晶Ｎ−
ピバロイル−Ｓ−（４−ピリジル）スルフエンア
ミド179mg（85％）が得られる。 1 H-NMR (CDCl 3 , TMS) δ = 1.33 (9H,
s), 6.87 (br.s), 7.4-7.65 (3H, m), 7.8-7.95
(2H, m) 13 H-NMR (CDCl 3 , TMS) δ = 27.74,
40.25, 126.93, 128.94, 134.08, 134.43, 179.62,
190.86 Example 8 Pivalic acid amide 101 mg (1 mmol), 4,4'-
Example 1 using dithiodipyridine (1 mmol)
When the reaction and post-treatment are carried out in the same manner as above, white crystals N-
179 mg (85%) of pivaloyl-S-(4-pyridyl)sulfenamide are obtained.
1H−NMR（CDCl3、TMS）δ＝1.25（9H、
ｓ）、6.9−7.0（2H、ｍ）、8.3−8.4（2H、ｍ）、
9.22（br.s）
13H−NMR（CDCl3、TMS）δ＝27.12、
39.64、116.32、148.42、151.81、180.41
実施例 ９
ｐ−クロロベンズアミド312mg（２ｍmol）、ジ
フエニルジスルフイド（２ｍmol）を用い、実施
例１と同様に反応及び後処理を行うと、白色結晶
Ｎ−（ｐ−クロロベンゾイル）−Ｓ−フエニルスル
フイド161mg（31％）が得られる。 1 H-NMR (CDCl 3 , TMS) δ = 1.25 (9H,
s), 6.9-7.0 (2H, m), 8.3-8.4 (2H, m),
9.22 (br.s) 13 H-NMR (CDCl 3 , TMS) δ = 27.12,
39.64, 116.32, 148.42, 151.81, 180.41 Example 9 Using 312 mg (2 mmol) of p-chlorobenzamide and diphenyl disulfide (2 mmol), the reaction and post-treatment were carried out in the same manner as in Example 1, resulting in white crystals N- 161 mg (31%) of (p-chlorobenzoyl)-S-phenyl sulfide are obtained.
1H−NMR（CDCl3、TMS）δ＝7.2−7.4（5H、
ｍ）、7.39（2H、ｄ、Ｊ＝8.1Hz）、7.80（2H、ｄ、
Ｊ＝8.1Hz）
13H−NMR（CDCl3、TMS）δ＝126.09、
127.28、129.10、129.15（sh.）、134.64、138.36、
138.88、168.18 1H -NMR ( CDCl3 , TMS) δ = 7.2-7.4 (5H,
m), 7.39 (2H, d, J=8.1Hz), 7.80 (2H, d,
J=8.1Hz) 13H -NMR ( CDCl3 , TMS) δ=126.09,
127.28, 129.10, 129.15 (sh.), 134.64, 138.36,
138.88, 168.18
Claims (1)
よいアリール基、複素環基、アルキル基、ジアル
キルアミノ基、アルコキシ基を示す。）で表され
るアミド型化合物を水素化ナトリウムで処理した
後、一般式 R2SSR2 ……(2) （式中R2は、Ｎ，Ｎ−ジ置換チオカルバモイル
基、アロイル基、不活性な置換基を有していても
よいアリール基、複素環基を示す。）で表される
ジスルフイド体と反応させることを特徴とする 一般式 （式中、R1、R2は前記と同じ意味をもつ。）で表
されるスルフエンアミド誘導体の製造方法。[Claims] 1. General formula (In the formula, R 1 represents hydrogen, an aryl group that may have an inert substituent, a heterocyclic group, an alkyl group, a dialkylamino group, or an alkoxy group.) After treatment with sodium, the general formula R 2 SSR 2 ...(2) (wherein R 2 is an N,N-disubstituted thiocarbamoyl group, an aroyl group, an aryl group which may have an inert substituent) A general formula characterized by reacting with a disulfide represented by A method for producing a sulfenamide derivative represented by the formula (wherein R 1 and R 2 have the same meanings as above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2118457A JPH0413658A (en) | 1990-05-08 | 1990-05-08 | Production of sulfenamide derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2118457A JPH0413658A (en) | 1990-05-08 | 1990-05-08 | Production of sulfenamide derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0413658A JPH0413658A (en) | 1992-01-17 |
| JPH0561264B2 true JPH0561264B2 (en) | 1993-09-06 |
Family
ID=14737125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2118457A Granted JPH0413658A (en) | 1990-05-08 | 1990-05-08 | Production of sulfenamide derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0413658A (en) |
-
1990
- 1990-05-08 JP JP2118457A patent/JPH0413658A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0413658A (en) | 1992-01-17 |
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