JPH0442380B2 - - Google Patents
Info
- Publication number
- JPH0442380B2 JPH0442380B2 JP59266739A JP26673984A JPH0442380B2 JP H0442380 B2 JPH0442380 B2 JP H0442380B2 JP 59266739 A JP59266739 A JP 59266739A JP 26673984 A JP26673984 A JP 26673984A JP H0442380 B2 JPH0442380 B2 JP H0442380B2
- Authority
- JP
- Japan
- Prior art keywords
- butylbenzyl
- tert
- hydrogen sulfide
- mol
- reaction
- 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 - Lifetime
Links
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 16
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 16
- UIYKSYBJKIMANV-UHFFFAOYSA-N (4-tert-butylphenyl)methanethiol Chemical compound CC(C)(C)C1=CC=C(CS)C=C1 UIYKSYBJKIMANV-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003444 phase transfer catalyst Substances 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- -1 4-tert-butylbenzyl halide Chemical class 0.000 claims description 2
- 239000003021 water soluble solvent Substances 0.000 claims description 2
- 125000003352 4-tert-butyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])*)C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 239000003125 aqueous solvent Substances 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- WAXIFMGAKWIFDQ-UHFFFAOYSA-N 1-tert-butyl-4-(chloromethyl)benzene Chemical compound CC(C)(C)C1=CC=C(CCl)C=C1 WAXIFMGAKWIFDQ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 3
- IHYNKGRWCDKNEG-UHFFFAOYSA-N n-(4-bromophenyl)-2,6-dihydroxybenzamide Chemical compound OC1=CC=CC(O)=C1C(=O)NC1=CC=C(Br)C=C1 IHYNKGRWCDKNEG-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000003799 water insoluble solvent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QZNQSIHCDAGZIA-UHFFFAOYSA-N 1-(bromomethyl)-4-tert-butylbenzene Chemical compound CC(C)(C)C1=CC=C(CBr)C=C1 QZNQSIHCDAGZIA-UHFFFAOYSA-N 0.000 description 1
- OSOLHARQJQEMBZ-UHFFFAOYSA-N 1-chloropentylbenzene Chemical compound CCCCC(Cl)C1=CC=CC=C1 OSOLHARQJQEMBZ-UHFFFAOYSA-N 0.000 description 1
- VEWXSFGQEGQOAK-UHFFFAOYSA-N 1-phenylpentane-1-thiol Chemical compound CCCCC(S)C1=CC=CC=C1 VEWXSFGQEGQOAK-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は４−タ−シヤリ−ブチルベンジルメル
カプタンの新規な製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing 4-tert-butylbenzyl mercaptan.
４−タ−シヤリ−ブチルベンジルメルカプタン
は既知化合物であり、農薬特に殺虫、殺ダニ、殺
線虫及び殺菌剤の有効成分化合物の中間体として
有用である。 4-T-Butylbenzyl mercaptan is a known compound and is useful as an intermediate for the active ingredient compounds of agricultural chemicals, especially insecticides, acaricides, nematicides and fungicides.
従来、４−タ−シヤリ−ブチルベンジルメルカ
プタンの合成法としては、次の方法が知られてい
る。 Conventionally, the following method is known as a method for synthesizing 4-tert-butylbenzyl mercaptan.
(1) ４−タ−シヤリ−ブチルベンジルブロマイド
とチオ硫酸ナトリウムをエチルアルコール中還流
しＳ−（４−タ−シヤリ−ブチルベンジルチオ）
硫酸塩とし、これを50％硫酸水溶液で加熱加水分
解する方法。〔ケミカルアブストラクト79巻
104888t（1973年）参照〕上記した(1)の合成法は、
チオ硫酸ナトリウムを用い合成したＳ−（４−タ
−シヤリ−ブチルベンジルチオ）硫酸塩を硫酸で
さらに加水分解しなくてはならず、操作上複雑で
あり、且つ収率も低く、４−タ−シヤリ−ブチル
ベンジルメルカプタンを工業的に大量に製造する
方法として満足できるものとはいえない。(1) 4-tert-butylbenzyl bromide and sodium thiosulfate were refluxed in ethyl alcohol to form S-(4-tert-butylbenzylthio).
A method of heating and hydrolyzing the sulfate with a 50% sulfuric acid aqueous solution. [Chemical Abstracts Volume 79
104888 t (1973)] The synthesis method of (1) above is
S-(4-tert-butylbenzylthio) sulfate synthesized using sodium thiosulfate must be further hydrolyzed with sulfuric acid, which is operationally complex and has a low yield. - It cannot be said that this is a satisfactory method for industrially producing large amounts of butylbenzyl mercaptan.
本発明者らは、４−タ−シヤリ−ブチルベンジ
ルメルカプタンの実用上有利な合成法を種々検討
した結果、
次式（）：
〔式中、Ｘはハロゲン原子を表す。〕で表される
４−タ−シヤリ−ブチルベンジルハライドを水溶
性溶媒中、硫化水素および塩基の存在下で反応さ
せて４−タ−シヤリ−ブチルベンジルメルカプタ
ンを高収率で得る方法を見い出した。更に、この
反応をおこなう際、溶媒として、水と非水溶性溶
媒の二層系を用い、相間移動触媒を添加して反応
させることにより、高収率で目的物が得られるこ
とを見出し、本発明を完成した。 The present inventors investigated various practically advantageous synthesis methods for 4-tert-butylbenzyl mercaptan, and found that the following formula (): [In the formula, X represents a halogen atom. We have discovered a method for obtaining 4-tert-butylbenzyl mercaptan in high yield by reacting 4-tert-butylbenzyl halide represented by ] in a water-soluble solvent in the presence of hydrogen sulfide and a base. . Furthermore, we discovered that the desired product could be obtained in high yield by using a two-layer system of water and a water-insoluble solvent as the solvent and adding a phase transfer catalyst to carry out this reaction. Completed the invention.
本発明者らが検討した反応を反応式で示せば次
の通りである。 The reaction studied by the present inventors is shown in the following reaction formula.
〔反応式中、Ｘは前記と同じ意味を表す。〕
上記反応式において水溶性溶媒としては低級ア
ルコール類（例えば、メタノール、エタノール、
プロパノール、ブタノール等）およびエーテル類
（例えばテトラヒドロフラン、ジオキサン等）用
いることができる。非水溶性溶媒としては、芳香
族炭化水素類（ベンゼン、トリエン、キシレン
等）、ハロゲン化炭化水素類（塩化メチレン、１，
２−ジクロルエタン等）脂肪族炭化水素類（ｎ−
ヘキサン、ｎ−ヘブタン等）およびエチルエーテ
ルを用いることができる。塩基としては、無機塩
基（例えば、水酸化ナトリウム、水酸化カリウ
ム、炭酸ナトリウム、炭酸カリウム、水硫化ナト
リウム、水硫化カリウム、硫化ナトリウムおよび
アンモニア等）やナトリウムメトキサイドおよび
ナトリウムエトキサイド等の金属アルコキサイド
等を用いることができる。原料である（）に対
する塩基の使用量は１当量以上で良い。 [In the reaction formula, X represents the same meaning as above. ] In the above reaction formula, lower alcohols (e.g. methanol, ethanol,
(propanol, butanol, etc.) and ethers (eg, tetrahydrofuran, dioxane, etc.) can be used. Examples of water-insoluble solvents include aromatic hydrocarbons (benzene, triene, xylene, etc.), halogenated hydrocarbons (methylene chloride, 1,
2-dichloroethane, etc.) aliphatic hydrocarbons (n-
hexane, n-hebutane, etc.) and ethyl ether can be used. Examples of the base include inorganic bases (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfide, potassium bisulfide, sodium sulfide, ammonia, etc.) and metal alkoxides such as sodium methoxide and sodium ethoxide. can be used. The amount of base used relative to the raw material () may be 1 equivalent or more.
硫化水素はあらかじめ反応系内に充分吹き込ん
でおくことが望ましい。反応温度は０℃以下から
使用する溶媒の沸点までの範囲で可能であるが、
５℃から80℃位が望ましい。 It is desirable to sufficiently inject hydrogen sulfide into the reaction system in advance. The reaction temperature can range from below 0°C to the boiling point of the solvent used, but
A temperature of about 5℃ to 80℃ is desirable.
また、前記反応式で示される反応において、溶
媒として水と非水溶性溶媒の二層系を用いる場
合、相間移動触媒としては、第四級アンモニウム
塩、（例えばテトラ−ｎ−ブチルアンモニウムブ
ロマイド、テトラ−ｎ−ブチルアンモニウムハイ
ドロジエンスルフエイト、テトラメチルアンモニ
ウムクロライド、トリエチルベンジルアンモニウ
ムクロライド、トリ−ｎ−オクチルメチルアンモ
ニウムクロライド等）やホスホニウム塩（例え
ば、テトラ−ｎ−ブチルホスホニウムブロマイド
等）が使用できる。原料である（）に対する相
間移動触媒の比率は0.1モル％以上好ましくは0.5
〜10モル％に設定することが実用的に望ましい。 In addition, in the reaction represented by the above reaction formula, when a two-layer system of water and a water-insoluble solvent is used as the solvent, the phase transfer catalyst may be a quaternary ammonium salt, (for example, tetra-n-butylammonium bromide, tetra- -n-butylammonium hydrogen sulfate, tetramethylammonium chloride, triethylbenzylammonium chloride, tri-n-octylmethylammonium chloride, etc.) and phosphonium salts (for example, tetra-n-butylphosphonium bromide, etc.) can be used. The ratio of the phase transfer catalyst to the raw material () is 0.1 mol% or more, preferably 0.5
It is practically desirable to set it to ~10 mol%.
本発明方法によれば、従来法に比べて高収率で
且つ容易な操作で目的物を得ることができるとい
う利点よ有している。 The method of the present invention has the advantage that the desired product can be obtained in higher yield and with easier operation than conventional methods.
次の本発明方法について実施例を具体的に挙げ
て説明する。但し、本発明はこれらの実施例のみ
に限定されるものではない。 The following method of the present invention will be explained with specific examples. However, the present invention is not limited to these examples.
実施例 １
アンモニアガス8.5ｇ（0.5モル）を含むメタノ
ール溶液180mlに０〜５℃において硫化水素ガス
を充分吹き込んだ後、撹拌下４−タ−シヤリ−ブ
チルベンジルクロライド36.5ｇ（0.2モル）を加
え、15℃で５時間反応させた。この間硫化水素を
少しずつ吹き込み続けた。反応後、塩酸を少しず
つ加え酸性とし、減圧下反応溶液を濃縮しベンゼ
ンで抽出した。ベンゼン層を水洗し、無水硫酸ナ
トリウムで乾燥後、ベンゼンを減圧下留去するこ
とにより目的化合物４−タ−シヤリ−ブチルベン
ジルメルカプタンの無色液体35.8ｇ（純度99％）
収率98.5％沸点90〜92℃／４mmHgを得た。Example 1 After sufficiently blowing hydrogen sulfide gas into 180 ml of a methanol solution containing 8.5 g (0.5 mol) of ammonia gas at 0 to 5°C, 36.5 g (0.2 mol) of 4-tert-butylbenzyl chloride was added with stirring. , and reacted at 15°C for 5 hours. During this time, hydrogen sulfide was continuously blown in little by little. After the reaction, hydrochloric acid was added little by little to make it acidic, and the reaction solution was concentrated under reduced pressure and extracted with benzene. The benzene layer was washed with water, dried over anhydrous sodium sulfate, and the benzene was distilled off under reduced pressure to obtain 35.8 g of a colorless liquid (purity 99%) of the target compound, 4-tert-butylbenzyl mercaptan.
A yield of 98.5% and a boiling point of 90-92°C/4 mmHg were obtained.
実施例 ２
メタノール50mlにナトリウムメトキサイド1.8
ｇ（3.3×10-2モル）を加え、室温において硫化
水素ガスを充分吹き込んだ後、撹拌下４−タ−シ
ヤリ−ブチルベンジルクロライド2.0ｇ（1.1×
10-2モル）を加え35〜40℃で１時間反応させた。
この間硫化水素を少しずつ吹き込み続けた。反応
後実施例１と同様な操作をし目的化合物の無色液
体1.9ｇ（純度96％）収率92.1％を得た。Example 2 Sodium methoxide 1.8 in 50ml methanol
g (3.3×10 -2 mol), and after sufficiently blowing hydrogen sulfide gas at room temperature, 2.0 g (1.1×
10 -2 mol) and reacted at 35 to 40°C for 1 hour.
During this time, hydrogen sulfide was continuously blown in little by little. After the reaction, the same operation as in Example 1 was carried out to obtain 1.9 g (purity 96%) of the target compound as a colorless liquid with a yield of 92.1%.
実施例 ３
メタノール50mlに23％水硫化ナトリウム水溶液
5.4ｇ（2.2×10-2モル）を加え室温において硫化
水素ガスを吹き込み、撹拌下４−タ−シヤリ−ブ
チルベンジルクロライド2.0ｇ（1.1×10-2モル）
を加え25〜30℃で２時間半反応させた。この間硫
化水素を少しずつ吹き込み続けた。反応後、実施
例１と同様な操作を目的化合物の無色液体1.9ｇ
（純度97％）収率93.1％を得た。Example 3 23% aqueous sodium bisulfide solution in 50 ml of methanol
Add 5.4 g (2.2 x 10 -2 mol) of hydrogen sulfide gas at room temperature, and add 2.0 g (1.1 x 10 -2 mol) of 4-tert-butylbenzyl chloride while stirring.
was added and reacted at 25 to 30°C for 2 and a half hours. During this time, hydrogen sulfide was continuously blown in little by little. After the reaction, 1.9g of the colorless liquid of the target compound was subjected to the same operation as in Example 1.
(Purity 97%) A yield of 93.1% was obtained.
実施例 ４
エタノール50mlに20％水硫化カリウム水溶液
4.2ｇ（1.2×10-2モル）を加え、室温において硫
化水素ガスを吹き込み、撹拌下４−タ−シヤリ−
ブチルベンジルクロライド2.0ｇ（1.1×10-2モル）
を加え25〜30℃で５時間反応させた。この間硫化
水素を少しずつ吹き込み続けた。反応後実施例１
と同様な操作をし目的化合物の無色液体1.9ｇ
（純度99φ）収率95.0％を得た。Example 4 20% potassium bisulfide aqueous solution in 50 ml of ethanol
4.2 g (1.2 x 10 -2 mol) was added, hydrogen sulfide gas was blown in at room temperature, and the 4-tertiary mixture was stirred.
Butylbenzyl chloride 2.0g (1.1×10 -2 mol)
was added and reacted at 25-30°C for 5 hours. During this time, hydrogen sulfide was continuously blown in little by little. Post-reaction Example 1
Perform the same procedure as above to obtain 1.9 g of colorless liquid of the target compound.
(Purity: 99φ) A yield of 95.0% was obtained.
実施例 ５
ベンゼン50mlに23％水硫化ナトリウム水溶液
2.9ｇ（1.2×10-2モル）を加え、室温において硫
化水素ガスを吹き込み、撹拌下テトラ−ｎ−ブチ
ルアンモニウムハイドロジエンスルフエイト0.12
ｇ（3.5×10-4モル）と４−タ−シヤリ−ブチル
ベンジルクロライド2.0ｇ（1.1×10-2モル）を加
えた。65℃で２時間半反応させ、この間硫化水素
を少しずつ吹き込み続けた。反応後水を加え、塩
酸で酸性にしベンゼン層を分離し水洗した。ベン
ゼン層を無水硫酸ナトリウムで乾燥後、減圧下溶
媒を留去し目的化合物の無色液体1.9ｇ（純度95
％）収率91.2％を得た。Example 5 23% sodium bisulfide aqueous solution in 50ml of benzene
2.9 g (1.2 x 10 -2 mol) was added, hydrogen sulfide gas was blown in at room temperature, and 0.12 g of tetra-n-butylammonium hydrogen sulfate was added under stirring.
g (3.5×10 −4 mol) and 2.0 g (1.1×10 −2 mol) of 4-tert-butylbenzyl chloride were added. The reaction was carried out at 65°C for 2.5 hours, during which time hydrogen sulfide was continuously blown in little by little. After the reaction, water was added, acidified with hydrochloric acid, and the benzene layer was separated and washed with water. After drying the benzene layer over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 1.9 g of the target compound as a colorless liquid (purity 95
%) yield of 91.2% was obtained.
実施例 ６
トルエン50mlに水酸化ナトリウム1.0ｇ（2.5×
10-2モル）を水６mlに溶かしたものを加え、室温
において硫化水素ガスを充分吹き込んだ後、撹拌
下テトラ−ｎ−ブチルアンモニウムハイドロジエ
ンスルフエイト0.12ｇ（3.5×10-4モル）と４−タ
−シヤリ−ブチルベンジルクロライド2.0ｇ（1.1
×10-2モル）を加えた。60℃で２時間半反応さ
せ、この間硫化水素を少しずつ吹き込み続けた。
反応後実施例５と同様な操作をし、目的化合物の
無色液体1.9ｇ（純度94％）収率90.2％を得た。Example 6 1.0 g of sodium hydroxide in 50 ml of toluene (2.5
10 -2 mol) dissolved in 6 ml of water was added, and after sufficiently blowing in hydrogen sulfide gas at room temperature, 0.12 g (3.5 x 10 -4 mol) of tetra-n-butylammonium hydrogen sulfate was added under stirring. 4-tert-butylbenzyl chloride 2.0g (1.1
×10 -2 mol) was added. The reaction was carried out at 60°C for 2.5 hours, during which time hydrogen sulfide was continuously blown in little by little.
After the reaction, the same operation as in Example 5 was carried out to obtain 1.9 g (purity 94%) of the target compound as a colorless liquid with a yield of 90.2%.
Claims (1)
４−タ−シヤリ−ブチルベンジルハライドを水溶
性溶媒中、硫化水素および塩基の存在化で反応さ
せることを特徴とする４−タ−シヤリ−ブチルベ
ンジルメルカプタンの製造法。 ２ 次式（）： 〔式中、Ｘはハロゲン原子を表す。〕で表される
４−タ−シヤリ−ブチルベンジルを水および非水
溶性溶媒中、相間移動触媒、硫化水素および塩基
の存在下で反応させることを特徴とする４−タ−
シヤリ−ブチルベンジルメルカプタンの製造法。[Claims] Primary formula (): [In the formula, X represents a halogen atom. A method for producing 4-tert-butylbenzyl mercaptan, which comprises reacting 4-tert-butylbenzyl halide represented by the following formula in a water-soluble solvent in the presence of hydrogen sulfide and a base. Quadratic formula (): [In the formula, X represents a halogen atom. 4-tert-butylbenzyl represented by ] is reacted in water and a non-aqueous solvent in the presence of a phase transfer catalyst, hydrogen sulfide and a base.
Method for producing shary-butylbenzyl mercaptan.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59266739A JPS61145158A (en) | 1984-12-18 | 1984-12-18 | Production of 4-tertiary butylbenzyl mercaptan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59266739A JPS61145158A (en) | 1984-12-18 | 1984-12-18 | Production of 4-tertiary butylbenzyl mercaptan |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61145158A JPS61145158A (en) | 1986-07-02 |
| JPH0442380B2 true JPH0442380B2 (en) | 1992-07-13 |
Family
ID=17435025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59266739A Granted JPS61145158A (en) | 1984-12-18 | 1984-12-18 | Production of 4-tertiary butylbenzyl mercaptan |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61145158A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2630106B1 (en) * | 1988-04-14 | 1990-07-13 | Elf Aquitaine | SYNTHESIS OF BENZYLMERCAPTAN |
| JP2019178085A (en) * | 2018-03-30 | 2019-10-17 | 三井化学株式会社 | (poly)thiol compound production method |
-
1984
- 1984-12-18 JP JP59266739A patent/JPS61145158A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61145158A (en) | 1986-07-02 |
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