TW201725194A - Method for preparing an aromatic sulfide or salt thereof - Google Patents
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本揭露關於一種芳香硫醚或其鹽類的製備方法。 The present disclosure relates to a process for the preparation of an aromatic thioether or a salt thereof.
芳香硫醚是有機合成中的重要的反應物,例如作為製備農藥和醫藥領域化合物的重要中介反應物。烷芳香硫醚(例如大茴香硫醚)目前主要的製備方法是利用苯硫酚與氯烷(例如氯甲烷)在鹼性條件中反應取得。然而,由於苯硫酚價格較高,使得烷芳香硫醚的製備成本增加。 Aromatic thioethers are important reactants in organic synthesis, for example as important intermediate reactants for the preparation of pesticides and compounds in the pharmaceutical field. Alkyl aromatic thioethers (such as anisole thioether) are currently produced primarily by the reaction of thiophenol with chloroalkane (e.g., methyl chloride) under basic conditions. However, due to the higher price of thiophenol, the production cost of the alkane aryl sulfide is increased.
因此,業界需要一種新的方法製備芳香硫醚。 Therefore, the industry needs a new method for the preparation of aromatic thioethers.
根據本揭露實施例,本揭露提供一種芳香硫醚或其鹽類的製備方法,包含將具有式(I)所示結構的化合物在具有式(II)所示結構的化合物存在下與具有式(III)所示結構的化合物進行反應,得到具有式(IV)所示結構的化合物,
其中R1及R2係獨立為C1-6烷基、或C5-7環烷基;R3係獨立為C1-6烷基、C5-7環烷基、C1-6鹵烷基、或芳香基;R4係獨立為氫、或C1-6烷基;Y係氫、或-X-R5,其中X係-O-、-NH-、-PH-、或-S-,且R5係氫、C1-6烷基、C5-7環烷基、或芳香基;以及Z-係R3SO3 -。 Wherein R 1 and R 2 are independently C 1-6 alkyl or C 5-7 cycloalkyl; and R 3 is independently C 1-6 alkyl, C 5-7 cycloalkyl, C 1-6 halo An alkyl group, or an aryl group; R 4 is independently hydrogen or a C 1-6 alkyl group; Y is a hydrogen group, or -XR 5 , wherein X is -O-, -NH-, -PH-, or -S- And R 5 is hydrogen, C 1-6 alkyl, C 5-7 cycloalkyl, or an aromatic group; and Z - series R 3 SO 3 - .
本揭露實施例提供一種芳香硫醚或其鹽類的製備方法,藉由亞碸作為硫化劑並用磺酸酐將亞碸活化,可避免使用苯硫酚作為反應物,除了可降低芳香硫醚的製備成本,也可避免鹵副產物殘留於所得之芳香硫醚中,並具有良好的產率。 The present disclosure provides a method for preparing an aromatic thioether or a salt thereof, which can prevent the use of thiophenol as a reactant by using a hydrazine as a vulcanizing agent and a sulfonium anhydride to activate the hydrazine, in addition to reducing the preparation of the aromatic thioether. At the cost, it is also possible to prevent the halogen by-product from remaining in the obtained aromatic thioether with good yield.
根據本揭露實施例,該方法包含將具有式(I)所示結構的化合物在具有式(II)所示結構的化合物存在下與具有式(III)所示結構的化合物進行反應,得到具有式(IV)所示結構的化合物,
其中,R1及R2可獨立為C1-6烷基、或C5-7環烷基;R3係可立為C1-6烷基、C5-7環烷基、C1-6鹵烷基、或芳香基;R4係獨立為氫、或C1-6烷基;Y係氫、或-X-R5,其中X係-O-、-NH-、-PH-、或-S-,且R5係氫、C1-6烷基、C5-7環烷基、或芳香基;以及Z-係R3SO3 -。根據本揭露實施例,該具有式(I)所示結構之化合物可作為硫化試劑,並在磺酸酐存在下將其亞碸(S=O)官能基質子化為具有反應活性之氫氧化鋶(sulfonium hydroxide)官能基,與具有式(III)所示結構的芳香化合物進行親電取代反應,得到芳香硫醚鹽類。此外,所得之芳香硫醚鹽類可再利用親核試劑進行去烷基化反應,得到芳香硫醚。 Wherein R 1 and R 2 may independently be a C 1-6 alkyl group or a C 5-7 cycloalkyl group; and the R 3 system may be a C 1-6 alkyl group, a C 5-7 cycloalkyl group, or a C 1 group; 6 haloalkyl, or aryl; R 4 is independently hydrogen or C 1-6 alkyl; Y is hydrogen, or -XR 5 , wherein X is -O-, -NH-, -PH-, or - S-, and R 5 is hydrogen, C 1-6 alkyl, C 5-7 cycloalkyl, or aryl; and Z - -R 3 SO 3 - . According to an embodiment of the present disclosure, the compound having the structure of the formula (I) can be used as a sulfurizing agent, and its sulfonium (S=O) functional group is converted into a reactive cerium hydroxide in the presence of a sulfonic acid anhydride ( The sulfonium hydroxide functional group is subjected to an electrophilic substitution reaction with an aromatic compound having a structure represented by the formula (III) to obtain an aromatic thioether salt. Further, the obtained aromatic thioether salt can be subjected to a dealkylation reaction using a nucleophilic reagent to obtain an aromatic thioether.
根據本揭露實施例,該烷基可為直鏈或分支(linear or branched)鍵烷基。因此,R1及R2可獨立為甲基(methyl)、乙基(ethyl)、丙基(propyl)、異丙基(isopropyl)、正丁基(n-butyl)、叔丁基(t-butyl)、仲丁基(sec-butyl)、異丁基(isobutyl)、戊基(pentyl)、己基(hexyl)、環戊基(cyclopentyl)、環己基(cyclohexyl)、或環庚基(cycloheptyl)。此外,根據本揭露實施例,該具有式(I)所示結構的化合物可為 ,因此本揭露所述方法可製備烷甲基芳香硫醚或其鹽類,其中R2係之定義與前述相同。再者,根據本揭露實施例,該具有式(I)所示結構的化合物可例如為二甲基亞碸、二乙基亞碸、甲基乙基亞碸、甲基苯基亞碸、或二苯基亞碸。 According to an embodiment of the present disclosure, the alkyl group may be a linear or branched bond alkyl group. Therefore, R 1 and R 2 may independently be methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl (t- Butyl), sec-butyl, isobutyl, pentyl, hexyl, cyclopentyl, cyclohexyl, or cycloheptyl . Further, according to an embodiment of the present disclosure, the compound having the structure represented by the formula (I) may be Thus, the process of the present disclosure can produce an alkylmethyl aryl sulfide or a salt thereof, wherein the definition of the R 2 system is the same as described above. Furthermore, according to the disclosed embodiments, the compound having the structure of the formula (I) may, for example, be dimethyl hydrazine, diethyl hydrazine, methyl ethyl hydrazine, methyl phenyl hydrazine, or Diphenylarsinium.
根據本揭露實施例,該氟烷基係指碳上的氫全部或部份被氟全代的烷基,且可為直鏈或分支(linear or branched)鍵。舉例來說,氟甲基可為單氟甲基、二氟甲基、或全氟甲基。根據本揭露實施例,R3可獨立為甲基、乙基、丙基、異丙基、正丁基、叔丁基、 仲丁基、異丁基、戊基、己基、氟甲基、氟乙基、氟丙基、環戊基、環己基、或環庚基。根據本揭露某些實施例,該具有式(II)所示結構的化合物可為甲基磺酸酐、乙基磺酸酐、丙基磺酸酐、或三氟甲基磺酸酐、或其組合。根據本揭露實施例,該具有式(II)所示結構的化合物與該具有式(I)所示結構的化合物的莫耳比可為約1至2,例如約1.1至1.5。在此,該磺酸可提供酸性環境促進該具有式(I)所示結構的化合物與該具有式(III)所示結構的化合物進行反應。此外,根據本揭露實施例,亦可添加過量的磺酸酐同時作為反應的溶劑。 According to an embodiment of the present disclosure, the fluoroalkyl group means an alkyl group in which all or a part of hydrogen on the carbon is wholly made of fluorine, and may be a linear or branched bond. For example, the fluoromethyl group can be a monofluoromethyl group, a difluoromethyl group, or a perfluoromethyl group. According to an embodiment of the present disclosure, R 3 may independently be methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, pentyl, hexyl, fluoromethyl, fluoro. Ethyl, fluoropropyl, cyclopentyl, cyclohexyl, or cycloheptyl. According to some embodiments of the present disclosure, the compound having the structure of formula (II) may be methanesulfonic anhydride, ethylsulfonic anhydride, propylsulfonic anhydride, or trifluoromethanesulfonic anhydride, or a combination thereof. According to an embodiment of the present disclosure, the molar ratio of the compound having the structure of the formula (II) to the compound having the structure of the formula (I) may be from about 1 to 2, for example from about 1.1 to 1.5. Here, the sulfonic acid can provide an acidic environment to promote the reaction of the compound having the structure represented by the formula (I) with the compound having the structure represented by the formula (III). Further, according to the embodiments of the present disclosure, an excess of sulfonic acid anhydride may also be added as a solvent for the reaction.
根據本揭露實施例,該具有式(III)所示結構的化合物與該具有式(I)所示結構的化合物的莫耳比可為約1.2至10,例如約1.2至5。R4可獨立為氫、甲基、乙基、丙基、異丙基、正丁基、叔丁基、仲丁基、異丁基、戊基、或己基;Y可為氫、苯基、-O-R5、-NH-R5、-S-R5、或-PH-R5,且R5可為氫、甲基、乙基、丙基、異丙基、正丁基、叔丁基、仲丁基、異丁基、戊基、己基、環戊基、環己基、環庚基、或苯基。根據本揭露實施例,該具有式(III)所示結 構的化合物係,其中R4及R5的定義與前述相同。舉例來說,該具有式(III)所示結構的化合物可為苯、聯苯、二苯胺、二苯硫醚、或二苯醚。 According to an embodiment of the present disclosure, the molar ratio of the compound having the structure of the formula (III) to the compound having the structure of the formula (I) may be from about 1.2 to 10, for example from about 1.2 to 5. R 4 may independently be hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, pentyl or hexyl; Y may be hydrogen, phenyl, -OR 5 , -NH-R 5 , -SR 5 , or -PH-R 5 , and R 5 may be hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, sec. Butyl, isobutyl, pentyl, hexyl, cyclopentyl, cyclohexyl, cycloheptyl, or phenyl. According to an embodiment of the present disclosure, the compound having the structure represented by formula (III) is Wherein R 4 and R 5 have the same definitions as described above. For example, the compound having the structure represented by the formula (III) may be benzene, biphenyl, diphenylamine, diphenyl sulfide, or diphenyl ether.
根據本揭露實施例,該具有式(III)所示結構的化合物其Y與相鄰的R4與其各自鍵結的碳原子可構成一芳香基,例如苯基。舉例來說,該具有式(III)所示結構的化合物可為萘。 According to an embodiment of the present disclosure, the compound having the structure of the formula (III), wherein Y and the adjacent R 4 and their respective bonded carbon atoms may constitute an aromatic group, such as a phenyl group. For example, the compound having the structure represented by the formula (III) may be naphthalene.
根據本揭露實施例,該具有式(IV)所示結構的化合物 可為,其中R2、Y、及Z-的定義與前述相同。 According to an embodiment of the present disclosure, the compound having the structure represented by the formula (IV) may be Wherein R 2 , Y, and Z - are as defined above.
根據本揭露實施例,該芳香硫醚或其鹽類的製備方法,在獲得該具有式(IV)所示結構的化合物(芳香硫醚鹽類)後,可更包含將一親核試劑(nucleophile)與該具有式(IV)所示結構的化合物反應,得到具有式(V)所示結構的化合物(芳香硫醚)。 According to an embodiment of the present disclosure, the method for preparing the aromatic thioether or a salt thereof, after obtaining the compound having the structure of the formula (IV) (aromatic thioether salt), may further comprise a nucleophile (nucleophile) The compound having the structure represented by the formula (IV) is reacted to obtain a compound (aromatic thioether) having a structure represented by the formula (V).
其中,R2係C1-6烷基、或C5-7環烷基;R4係獨立為氫、或C1-6烷基;Y係氫、芳香基、或-X-R5,其中X係-O-、-NH-、-PH-、或-S-,或Y與相鄰的R4與其各自鍵結的碳原子構成一芳香基;以及,R5係氫、C1-6烷基、C5-7環烷基、或芳香基。 Wherein R 2 is C 1-6 alkyl or C 5-7 cycloalkyl; R 4 is independently hydrogen or C 1-6 alkyl; Y is hydrogen, aryl, or -XR 5 , wherein X a -O-, -NH-, -PH-, or -S-, or Y and an adjacent R 4 and their respective bonded carbon atoms constitute an aromatic group; and, R 5 is hydrogen, C 1-6 alkane a group, a C 5-7 cycloalkyl group, or an aromatic group.
根據本揭露實施例,具有式(V)所示結構的化合物可為,其中R2、及Y的定義與前述相同。此外,該
具有式(V)所示結構的化合物可為、
根據本揭露實施例,該親核試劑(nucleophile)可為具有取代/非取代基的吡啶或其衍生物(例如:吡啶、4-甲基吡啶)、胺類 (如:三乙胺)、鹵化鹽類(例如:氯化鉀)、醇類(例如:甲醇、乙醇)、或醯胺類(例如:二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯酮)。該親核試劑與具有式(IV)所示結構的化合物的莫耳比可為約1至10。 According to an embodiment of the present disclosure, the nucleophile may be a substituted/unsubstituted pyridine or a derivative thereof (eg, pyridine, 4-methylpyridine), an amine (eg triethylamine), halogenated salts (eg potassium chloride), alcohols (eg methanol, ethanol), or guanamines (eg dimethylformamide, dimethylacetamide, N-methylpyrrolidone). The molar ratio of the nucleophile to the compound having the structure of the formula (IV) may be from about 1 to 10.
為了讓本揭露之上述和其他目的、特徵、和優點能更明顯易懂,下文特舉數實施例及比較實施例,作詳細說明如下: The above and other objects, features and advantages of the present invention will become more apparent and understood.
實施例1: Example 1:
將13ml(141.5mmol)之苯、2ml(28.3mmol)之二甲基亞碸、與50ml之二氯甲烷加入一反應瓶中,在氮氣下降溫至-35℃。攪拌數分鐘後,加入6ml(35mmol)之三氟甲基磺酸酐。在0℃下冰浴並攪拌1小時後,有白色懸浮物產生。接著,移除冰浴並在室溫下反應約12小時後,將所得之溶液濃縮,得到化合物1,產率約為90%。上述反應之反應式如下所示:
利用核磁共振光譜分析化合物1,所得之光譜資訊如下:1H NMR(400MHz,ppm,Acetone):3.49(-CH3,6H,s),8.16-8.18(phenyl,2H,d),7.83-7.86(phenyl,1H,t),7.75-7.79(phenyl,2H,t)。 The compound 1 was analyzed by nuclear magnetic resonance spectroscopy, and the obtained spectral information was as follows: 1H NMR (400 MHz, ppm, Acetone): 3.49 (-CH 3 , 6H, s), 8.16-8.18 (phenyl, 2H, d), 7.83-7.86 ( Phenyl, 1H, t), 7.75-7.79 (phenyl, 2H, t).
接著,將6.52g(22.6mmol)之化合物1及30ml之丙酮加入一反應瓶。接著,在氮氣下緩慢加入氯化鉀(KCl)水溶液(6g之氯化鉀加入30ml之水)於反應瓶中。攪拌約1小時後,加入KOH水溶液(4g之氫氧化鉀加入10ml之水)於反應瓶中。接著,升溫至100℃至迴流,並持續攪拌20小時。接著,待冷卻後,利用50ml的水及50ml的
正己烷萃取三次,並收集有機層。接著,對有機層除水及濃縮後,得到甲基苯基硫醚,產率約為87%。上述反應之反應式如下所示:
利用核磁共振光譜分析甲基苯基硫醚,所得之光譜資訊如下:1H NMR(400MHz,ppm,CDCl3):2.52(-CH3,3H,s),7.14-7.19(phenyl,1H,t),7.31(phenyl,4H,m)。 The methyl phenyl sulfide was analyzed by nuclear magnetic resonance spectroscopy, and the obtained spectral information was as follows: 1 H NMR (400 MHz, ppm, CDCl 3 ): 2.52 (-CH 3 , 3H, s), 7.14-7.19 (phenyl, 1H, t ), 7.31 (phenyl, 4H, m).
實施例2: Example 2:
將2.4g(14mmol)之二苯醚、0.92g(12mmol)之二甲基亞碸、與15ml之二氯甲烷加入一反應瓶中,在氮氣下降溫至-35℃。攪拌數分鐘後,加入2.3ml(14mmol)之三氟甲基磺酸酐。在0℃下冰浴並攪拌1小時後,有白色懸浮物產生。接著,移除冰浴並在室溫下反應約12小時後,將所得之溶液濃縮,並用乙醚做再結晶,得到化合物2,產率約為65%。上述反應之反應式如下所示:
利用核磁共振光譜分析甲基苯基硫醚,所得之光譜資訊如下:1H NMR(400MHz,ppm,Acetone):3.50(-CH3,6H,s),8.18(phenyl,2H,d),7.52(phenyl,2H,t),7.26-7.34(phenyl,3H,m),7.18(phenyl,2H,d)。 The methyl phenyl sulfide was analyzed by nuclear magnetic resonance spectroscopy, and the obtained spectral information was as follows: 1 H NMR (400 MHz, ppm, Acetone): 3.50 (-CH 3 , 6H, s), 8.18 (phenyl, 2H, d), 7.52 (phenyl, 2H, t), 7.26-7.34 (phenyl, 3H, m), 7.18 (phenyl, 2H, d).
接著,將2.9g(7.6mmol)之化合物2及10ml之乙腈加入一反應瓶。接著,在氮氣下緩慢加入氯化鉀(KCl)水溶液(9g之氯化鉀加入20ml之水)於反應瓶中。攪拌約1小時後,加入0.22g之KOH水溶液於反應瓶中。接著,升溫至100℃至迴流,並持續攪拌17小時。接著,待冷卻後,利用50ml的水及50ml的正己烷萃取三次,並收集有機層。接著,對有機層除水及濃縮後,得到甲基(4-苯氧基)苯基硫醚(methyl(4-phenyloxy)phenyl sulfide),產率約為60%。上述反應之反應式如下所示:
用核磁共振光譜分析甲基(4-苯氧基)苯基硫醚,所得之光譜資訊如下:1H NMR(400MHz,ppm,CDCl3):2.50(-CH3,3H,s),6.97-7.03(phenyl,4H,m),7.15(phenyl,1H,t),7.32-7.42(phenyl,4H,m)。 The methyl (4-phenoxy)phenyl sulfide was analyzed by nuclear magnetic resonance spectroscopy, and the obtained spectral information was as follows: 1 H NMR (400 MHz, ppm, CDCl 3 ): 2.50 (-CH 3 , 3H, s), 6.97- 7.03 (phenyl, 4H, m), 7.15 (phenyl, 1H, t), 7.32-7.42 (phenyl, 4H, m).
雖然本揭露已以數個實施例揭露如上,然其並非用以限定本揭露,任何本技術領域中具有通常知識者,在不脫離本揭露之精神和範圍內,當可作任意之更動與潤飾,因此本揭露之保護範圍當視後附之申請專利範圍所界定者為準。 The present disclosure has been disclosed in the above several embodiments, but it is not intended to limit the disclosure, and any one skilled in the art can make any changes and refinements without departing from the spirit and scope of the disclosure. Therefore, the scope of protection of this disclosure is subject to the definition of the scope of the patent application.
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JP2017002111A JP2017160185A (en) | 2016-01-11 | 2017-01-10 | Method for preparing aromatic sulfide or salt thereof |
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TW105142423A TW201725193A (en) | 2016-01-11 | 2016-12-21 | Method for preparing a polymer |
TW105142916A TWI646129B (en) | 2016-01-11 | 2016-12-23 | Polymer |
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TW106127927A TWI646128B (en) | 2016-01-11 | 2017-08-17 | Method for preparing a polymer |
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JP6800920B2 (en) * | 2017-08-01 | 2020-12-16 | 財團法人工業技術研究院Industrial Technology Research Institute | Method for producing compound and method for producing polymer using it |
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JP3123724B2 (en) * | 1992-02-29 | 2001-01-15 | 財団法人生産開発科学研究所 | Poly (alkyl-P-thiophenoxyphenylsulfonium salt) compound |
US5618981A (en) * | 1995-05-19 | 1997-04-08 | Phillips Petroleum Company | Process for producing aromatic sulfides |
JP3160214B2 (en) * | 1996-12-27 | 2001-04-25 | 科学技術振興事業団 | Method for producing poly (arylene sulfonium salt) compound |
JP3145324B2 (en) * | 1996-12-27 | 2001-03-12 | 科学技術振興事業団 | Method for producing poly (thioarylene) compound |
JP2002265603A (en) * | 2001-03-12 | 2002-09-18 | Idemitsu Petrochem Co Ltd | Method for producing polyaryrene sulfide |
KR101183780B1 (en) * | 2006-08-24 | 2012-09-17 | 에스케이케미칼주식회사 | Manufacturing process for Polyarylene sulfide |
JP6327616B2 (en) * | 2013-09-03 | 2018-05-23 | Dic株式会社 | Resin composition containing polyarylene sulfide resin, method for producing the same, and molded article |
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JP6429096B2 (en) | 2018-11-28 |
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