PL212283B1 - Process for the preparation of fluorohalogenmethylaryl sulphides - Google Patents
Process for the preparation of fluorohalogenmethylaryl sulphidesInfo
- Publication number
- PL212283B1 PL212283B1 PL389594A PL38959409A PL212283B1 PL 212283 B1 PL212283 B1 PL 212283B1 PL 389594 A PL389594 A PL 389594A PL 38959409 A PL38959409 A PL 38959409A PL 212283 B1 PL212283 B1 PL 212283B1
- Authority
- PL
- Poland
- Prior art keywords
- sulfide
- mol
- preparation
- chlorophenyl
- hours
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 30
- 238000002360 preparation method Methods 0.000 title claims description 16
- 150000003568 thioethers Chemical class 0.000 title claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- FPGGTKZVZWFYPV-UHFFFAOYSA-N tetrabutylazanium;hydrofluoride Chemical compound F.CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- VRLDVERQJMEPIF-UHFFFAOYSA-N dbdmh Chemical compound CC1(C)N(Br)C(=O)N(Br)C1=O VRLDVERQJMEPIF-UHFFFAOYSA-N 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical group 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- -1 alkyl halogen Chemical group 0.000 description 13
- 150000003457 sulfones Chemical class 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- RTWXZOGOAQDOBE-UHFFFAOYSA-N 1-chloro-3-[3-chloro-2-(fluoromethyl)phenyl]sulfanyl-2-(fluoromethyl)benzene Chemical compound FCC1=C(Cl)C=CC=C1SC1=CC=CC(Cl)=C1CF RTWXZOGOAQDOBE-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VFQYMJYUSRAJCZ-UHFFFAOYSA-N 1-(chloromethylsulfanyl)-4-methylbenzene Chemical compound CC1=CC=C(SCCl)C=C1 VFQYMJYUSRAJCZ-UHFFFAOYSA-N 0.000 description 2
- VSQXHZCKWWCIEM-UHFFFAOYSA-N BrCC1=C(C=CC(=C1)Cl)SC1=C(C=C(C=C1)Cl)CBr Chemical compound BrCC1=C(C=CC(=C1)Cl)SC1=C(C=C(C=C1)Cl)CBr VSQXHZCKWWCIEM-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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GEOWMGXEZOADNA-UHFFFAOYSA-N 1-(chloromethylsulfanyl)-4-methoxybenzene Chemical compound COC1=CC=C(SCCl)C=C1 GEOWMGXEZOADNA-UHFFFAOYSA-N 0.000 description 1
- VVPUIKNICYCXJZ-UHFFFAOYSA-N 4-iodobutyl benzoate Chemical compound ICCCCOC(=O)C1=CC=CC=C1 VVPUIKNICYCXJZ-UHFFFAOYSA-N 0.000 description 1
- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 description 1
- 241000223600 Alternaria Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241001465180 Botrytis Species 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- HHLAOSMDXUQSJZ-UHFFFAOYSA-N ClC1=C(C(=C(C=C1)SC1=C(C(=C(C=C1)Cl)Cl)CF)CF)Cl Chemical compound ClC1=C(C(=C(C=C1)SC1=C(C(=C(C=C1)Cl)Cl)CF)CF)Cl HHLAOSMDXUQSJZ-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000223218 Fusarium Species 0.000 description 1
- 229910020261 KBF4 Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- ZDJQWFUQFDIBLS-UHFFFAOYSA-N fluoromethylsulfanylbenzene Chemical compound FCSC1=CC=CC=C1 ZDJQWFUQFDIBLS-UHFFFAOYSA-N 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Przedmiotem wynalazku jest sposób wytwarzania sulfidów dihalogenometyloarylowych zawiera1 jących w grupie halogenometylowej atom fluoru o wzorze ogólnym 1, gdzie R1 stanowi atom chloru, bromu, jodu lub fluoru, R stanowi atom wodoru chlorowiec lub alkil. Sulfidy te można utlenić w znany sposób za pomocą nadtlenku wodoru i kwasu octowego do sulfonów - związków o dużym znaczeniu praktycznym.The present invention relates to sulfides dihalogenometyloarylowych contains 1 to co- group halogenometylowej fluorine atom of formula 1 wherein R 1 is chlorine, bromine, iodine or fluorine atom, R represents a hydrogen atom or an alkyl halogen. These sulfides can be oxidized in a known manner with hydrogen peroxide and acetic acid to give sulfones - compounds of great practical importance.
Sulfony chlorowcometyloarylowe są stosowane jako substraty w wielu syntezach organicznych, przede wszystkim środków agrochemicznych oraz substancji chroniących materiały techniczne przed biodegradacją. Wykazują one wysoką aktywność fungicydową w stosunku do grzybów Alternaria, Botrytis, Fusarium i Rizoctonia, a także w stosunku do wielu innych fitopatogenów i mogą być stosowane w ochronie roślin uprawnych i przechowalnictwie płodów rolnych. Sulfony dihalogenometylofenylowe wykazują również aktywność bakteriobójczą, hamując wzrost bakterii typu Gram-dodatnie i Gram-ujemne. Przyczyną wąskiego wykorzystania tych sulfonów jest brak skutecznych metod ich otrzymywania.Halomethylaryl sulfones are used as substrates in many organic syntheses, mainly agrochemicals and substances protecting technical materials against biodegradation. They show high fungicidal activity against Alternaria, Botrytis, Fusarium and Rizoctonia fungi, as well as against many other phytopathogens, and can be used in the protection of crops and storage of crops. Dihalomethylphenyl sulfones also exhibit bactericidal activity, inhibiting the growth of gram-positive and gram-negative bacteria. The reason for the narrow use of these sulfones is the lack of effective methods of their preparation.
Interesującym sposobem syntezy sulfonów di- i trihalogenometylowoarylowych jest metoda polegająca na oksydatywnym halogenowaniu sulfidów przy użyciu chloranu (I) lub bromianu (I)., Stosując ten sposób można uzyskać sulfony z mieszanymi chlorowcami, (polskie zgłoszenie patentowe nr P-362261). Sposobu tego nie można jednak zastosować do sulfidu fluorometylofenylowego, gdyż jest on związkiem nietrwałym w środowisku wodnym. Jedynym sposobem otrzymywania sulfidów dichlorowcometylowofenylowych z różnymi atomami chlorowca, w tym zawierających atom fluoru, jest metoda polegająca na reakcji disulfidu difenylowego z odpowiednią pochodną halogenometanu (freonu) [Anil K. Saikia, Sadao Tsuboi; J. Org. Chem., 2001, 66, 645]., Jest to jednak reakcja dwuetapowa, a pierwszy etap nigdy nie przebiega selektywnie, dając najczęściej mieszaniny produktów. Ujemną stroną tego procesu jest również fakt, że stosowane freony są zagrożeniem dla środowiska naturalnego (niszczą warstwę ozonową atmosfery). Ponadto tym sposobem otrzymano jedynie sulfid chloroofluorometylofenylowy. Do tej pory nie udało się otrzymać sulfidów i sulfonów fluorobromo- i fluorojodometyloarylowych.An interesting method of synthesizing di- and trihalomethyl aryl sulfones is the oxidative halogenation of sulfides using chlorate (I) or bromate (I). Using this method, sulfones with mixed halogens can be obtained (Polish patent application No. P-362261). However, this method cannot be applied to fluoromethylphenyl sulfide as it is an unstable compound in an aqueous environment. The only way to obtain dihalomethylphenyl sulfides with various halogen atoms, including those containing a fluorine atom, is the method of reacting diphenyl disulfide with an appropriate halogenomethane (freon) derivative [Anil K. Saikia, Sadao Tsuboi; J. Org. Chem., 2001, 66, 645]. However, this is a two-stage reaction, and the first stage is never selective, usually giving mixtures of products. Another disadvantage of this process is the fact that the freons used are a threat to the natural environment (they destroy the atmosphere's ozone layer). Moreover, only chlorofluoromethylphenyl sulfide was obtained by this method. So far, it has not been possible to obtain fluorobromo- and fluoroiodomethylaryl sulfides and sulfones.
Celem wynalazku było opracowanie sposobu wytwarzania sulfidów zawierających atom fluoru, znajdujących następnie zastosowanie jako substraty do wytwarzania sulfonów.The object of the invention was to develop a process for the preparation of sulfides containing a fluorine atom, which can then be used as starting materials for the production of sulfones.
Sposób wytwarzania sulfidów fluorohalogenometyloarylowych o wzorze 1, według wynalazku 1 charakteryzuje się tym, że sulfid o wzorze 2, gdzie R stanowi atom wodoru, chlorowiec lub alkil, a R1 stanowi atom fluoru, chloru bromu lub jodu, poddaje się działaniu fluorowodoru tetrabutyloamoniowego o wzorze 3, w obecności 1,3-dibromo-5,5-dimetylohydantoiny (DBH) w rozpuszczalniku organicznym polarnym lub niepolamym.The process for the preparation of the fluorohalogenomethylaryl sulfides of the formula 1 according to the invention 1 is characterized in that the sulfide of the formula 2, wherein R is hydrogen, halogen or alkyl and R 1 is fluorine, chlorine, bromine or iodine, is treated with 3, in the presence of 1,3-dibromo-5,5-dimethylhydantoin (DBH) in a polar or non-polar organic solvent.
Korzystnie jako rozpuszczalnik organiczny stosuje się: benzen, toluen, tetrahydrofuran, chloroform, tetrachlorek węgla, chlorek metylenu, chlorek etylenu, najkorzystniej chlorek metylenu.Preferably, the organic solvent used is: benzene, toluene, tetrahydrofuran, chloroform, carbon tetrachloride, methylene chloride, ethylene chloride, most preferably methylene chloride.
Korzystnie fluorowodorek tetrabutyloamoniowy stosuje się w 10 - 20% nadmiarze molowym.Preferably, tetrabutylammonium hydrofluoride is used in a 10-20% molar excess.
Korzystnie proces prowadzi się w temp 20 - 30°C.Preferably the process is carried out at a temperature of 20-30 ° C.
Korzystnie proces prowadzi się w czasie 3 do 5 godzin.Preferably the process is carried out for 3 to 5 hours.
W sposobie według wynalazku osiąga się wydajności w granicach 65-95% w zależności od stosowanego sulfidu i warunków procesu. Zastosowanie w sposobie według wynalazku łatwego do otrzymania fluorowodorku tetrabutyloamoniowego jako czynnika fluorującego sulfidy halogenometylofenylowe w obecności 1,3-dibromo-5,5-dimetylohydantoiny (DBH) pozwala na proste i skuteczne uzyskanie sulfidów zawierających atom fluoru.In the process according to the invention, yields in the range of 65-95% are achieved, depending on the sulfide used and the process conditions. The use of tetrabutylammonium hydrofluoride as a fluorinating agent for halogenomethylphenyl sulfides in the presence of 1,3-dibromo-5,5-dimethylhydantoin (DBH) in the presence of 1,3-dibromo-5,5-dimethylhydantoin (DBH) allows a simple and effective preparation of sulfides containing a fluorine atom in the process of the invention.
Sposób według wynalazku ilustrują następujące przykłady stosowania.The process according to the invention is illustrated by the following application examples.
P r z y k ł a d 1.P r z k ł a d 1.
Otrzymywanie fluorowodoru tetrabutyloamoniowego (H-C4H9)4N+H2F3-.Preparation of tetrabutylammonium hydrogen fluoride (H-C4H9) 4N + H2F3 - .
W kolbie trójszyjnej o poj. 500 mL zaopatrzonej w termometr, mieszadło mechaniczne i chłodnicę zwrotną umieszczono 98 g (0,3 mol) bromku tetrabutyloamoniowego i 45 mL acetonitrylu. Mieszając dodano w temperaturze pokojowej 89,14 g (0,63 mol) eteratu trifluoroboru. Mieszaninę ogrzewano przez 18 godzin w temperaturze 50°C. Po ochłodzeniu rozpuszczalniki oddestylowano, a do pozostałości dodano eter etylowy, aż do wypadnięcia białego osadu. Uzyskano 94,78 g tetrafluoroboranu o temperaturze topnienia 158 - 160°C. Wydajność reakcji 95%. Uzyskaną sól rozpuszczono w 200 mL metanolu, a następnie dodano 17,83 g fluorku potasu rozpuszczonego w 60 mL wody. Odsączono powstały osad KBF4 (32,25 g) i przemyto 150 mL metanolu. Przesącz zatężono do konsystencji olejuIn a three-neck flask with a capacity of 500 mL of a thermometer, mechanical stirrer, and reflux condenser were placed in 98 g (0.3 mol) of tetrabutylammonium bromide and 45 mL of acetonitrile. 89.14 g (0.63 mol) of boron trifluorate etherate was added at room temperature while stirring. The mixture was heated for 18 hours at 50 ° C. After cooling, the solvents were distilled off and diethyl ether was added to the residue until a white solid appeared. 94.78 g of tetrafluoroborate were obtained, mp 158-160 ° C. The reaction yield is 95%. The obtained salt was dissolved in 200 mL of methanol, and then 17.83 g of potassium fluoride dissolved in 60 mL of water was added. The resulting precipitate KBF4 (32.25 g) was filtered off and washed with 150 mL of methanol. Concentrate the filtrate to an oil
PL 212 283 B1 i rozpuszczono w 500 mL chlorku etylenu, a następnie umieszczono w pojemniku polipropylenowym zaopatrzonym w mieszadło. Dodano roztwór złożony z 56 g 48% HF, 99,24 g KHF2 i 300 mL wody. Całość mieszano przez 2 godziny w temperaturze pokojowej. Z oddzielonej fazy organicznej oddestylowano rozpuszczalniki i uzyskano 86,22 g fluorowodoru tetrabutyloamoniowego (H-C4Hg)4N+H2F3- o konsystencji gęstego oleju.The mixture was dissolved in 500 mL of ethylene chloride, and then placed in a polypropylene container equipped with a stirrer. A solution of 56 g 48% HF, 99.24 g KHF2, and 300 mL of water was added. The mixture was stirred for 2 hours at room temperature. From the separated organic phase, the solvents were distilled off and 86.22 g of tetrabutylammonium hydrogen fluoride (H-C4Hg) 4N + H2F3 - with the consistency of a thick oil were obtained.
Otrzymywanie sulfidu chlorofenylo-4-chlorofluorometylowego.Preparation of chlorophenyl-4-chlorofluoromethyl sulfide.
W kolbie o pojemności 100 mL umieszczono 2 g (0,01 mol) sulfidu chlorofenylo-4-chlorometylowego, 4,34 g (0,014 mol) (n-C4H9)4N+H2F3- oraz 34 mL chlorku metylenu. Następnie dodano 4,16 g (0,014 mol) DBH. Zawartość kolby mieszano w temperaturze pokojowej przez 4 godziny, po czym dodano 60 mL heksanu i eteru w stosunku 10 : 1. Powstały osad odsączono, oddzielono górną warstwę, którą przemyto dwukrotnie nasyconym roztworem wodorowęglanu sodu i raz solanką. Po wysuszeniu nad bezwodnym siarczanem magnezu oddestylowano rozpuszczalniki, a produkt oczyszczono przez destylację pod zmniejszonym ciśnieniem. Otrzymano 1,57 g sulfidu chlorofluorometylo-4-chlorofenylowego o temp. wrzenia. 56-58°C (0,2 Tr), co stanowi 74% wydajności.2 g (0.01 mol) of chlorophenyl-4-chloromethyl sulfide, 4.34 g (0.014 mol) (n-C4H9) 4N + H2F3 - and 34 mL of methylene chloride were placed in a 100 mL flask. Then 4.16 g (0.014 mol) of DBH was added. The flask contents were stirred at room temperature for 4 hours, then 60 mL of 10: 1 hexane and ether were added. The resulting precipitate was filtered off, the upper layer was separated, washed twice with saturated sodium bicarbonate solution and once with brine. After drying over anhydrous magnesium sulfate, the solvents were distilled off, and the product was purified by distillation under reduced pressure. 1.57 g of chlorofluoromethyl-4-chlorophenyl sulfide with boiling point was obtained. 56-58 ° C (0.2 Tr), 74% efficiency.
P r z y k ł a d 2P r z k ł a d 2
Otrzymywanie sulfidu chlorofenylo-4-bromofluorometylowego.Preparation of chlorophenyl-4-bromofluoromethyl sulfide.
W kolbie o pojemności 100 mL umieszczono 5 g (0,021 mol) sulfidu bromometylo-4-chlorofenylowego, 9,12 g (0,03 mol) (H-C4H9)4N+H2F3-, 50 mL chlorku metylenu oraz 8,73 g (0,3 mol) DBH.. Zawartość mieszano przez 5 godzin w temperaturze pokojowej. Dalej postępując jak w przykładzie 1 uzyskano 3,9 g sulfidu bromofluorometylo-4-chlorofenylowego o temp wrzenia 62 - 64°C (0,2 Tr), co stanowi 86% wydajności.In a 100 mL flask were placed 5 g (0.021 mol) of bromomethyl-4-chlorophenyl sulfide, 9.12 g (0.03 mol) (H-C4H9) 4N + H2F3 - , 50 mL of methylene chloride and 8.73 g ( 0.3 mol) DBH .. The contents were stirred for 5 hours at room temperature. Further proceeding as in Example 1, 3.9 g of bromofluoromethyl-4-chlorophenyl sulfide with a boiling point of 62-64 ° C (0.2 Tr) was obtained, which is 86% yield.
P r z y k ł a d 3P r z k ł a d 3
Otrzymywanie sulfidu chlorofenylo-4-jodofluorometylowego.Preparation of chlorophenyl-4-iodofluoromethyl sulfide.
Do reakcji użyto 5 g (0,0175 mol) sulfidu jodometylo-4-chlorofenylowego, (6,93 g, 0,023 mol) (H-C4H9)4N+H2F3-, 50 mL tetrahydrofuranu oraz 6,57 g (0,023 mol) DBH. Zawartość mieszano przez 5 godzin w temp. pokojowej. Postępując dalej jak w przykładzie I uzyskano 4,26g sulfidu chlorofenylo-jodofluorometylowego o temperaturze wrzenia 88-90°C (0,2 Tr), co stanowi 80,5% wydajności.5 g (0.0175 mol) of iodomethyl-4-chlorophenyl sulfide (6.93 g, 0.023 mol) (H-C4H9) 4N + H2F3 - , 50 mL of tetrahydrofuran and 6.57 g (0.023 mol) of DBH were used for the reaction. . The contents were stirred for 5 hours at room temperature. Proceeding further as in Example 1, 4.26 g of chlorophenyl iodofluoromethyl sulfide were obtained, boiling point 88-90 ° C (0.2 Tr), which is 80.5% yield.
P r z y k ł a d 4P r z k ł a d 4
Otrzymywanie sulfidu chlorofenylo-4-difluorometylowegoPreparation of chlorophenyl-4-difluoromethyl sulfide
Do reakcji użyto 2,5 g (0,014 mol) sulfidu chlorofenylo-4-fluorometylowego, (5,43 g, 0,018 mol) (n-C4H9)4N+H2F3- 40 mL chlorku etylenu oraz 5,15 g (0,018 mol) DBH. Zawartość mieszano przez 4 godziny w temperaturze pokojowej. Postępując dalej jak w przykładzie I uzyskano 2,11 g sulfidu chlorofenylo-4-difluorometylowego o temp wrzenia 52-54°C (0,3 Tr), co stanowi 77% wydajności.2.5 g (0.014 mol) of chlorophenyl-4-fluoromethyl sulfide (5.43 g, 0.018 mol) (n-C4H9) 4N + H2F3 - 40 mL of ethylene chloride and 5.15 g (0.018 mol) of DBH were used for the reaction. . The contents were stirred for 4 hours at room temperature. By proceeding as in Example 1, 2.11 g of chlorophenyl-4-difluoromethyl sulfide with a boiling point of 52-54 ° C (0.3 Tr) were obtained, which is a 77% yield.
P r z y k ł a d 5P r z k ł a d 5
Otrzymywanie sulfidu chlorofluorometylofenylowego.Preparation of chlorofluoromethylphenyl sulfide.
W kolbie o pojemności 100 mL umieszczono 1,58 g (0,01 mol) sulfidu chlorometylofenylowego, 4,34 g (0,014 mol) (n-C4H9)4N+H2F3- oraz 34 mL chlorku metylenu. Następnie dodano 4,16 g (0,014 mol) DBH. Zawartość kolby mieszano w temperaturze pokojowej przez 5 godzin. Postępując dalej jak w przykładzie I otrzymano 1,67 g sulfidu chlorofluorometylofenylowego, co stanowi 87% wydajności.1.58 g (0.01 mol) of chloromethylphenyl sulfide, 4.34 g (0.014 mol) (n-C4H9) 4N + H2F3 - and 34 mL of methylene chloride were placed in a 100 mL flask. Then 4.16 g (0.014 mol) of DBH was added. The contents of the flask were stirred at room temperature for 5 hours. Proceeding further as in Example 1, 1.67 g of chlorofluoromethylphenyl sulfide was obtained, which is 87% yield.
P r z y k ł a d 6P r z k ł a d 6
Otrzymywanie sulfidu chlorofluorometylo-4-metylofenylowego W kolbie o pojemności 100 mL umieszczono 1,72 g (0,01 mol) sulfidu chlorometylo-4-metylofenylowego, 4,34 g (0,014 mol) (H-C4H9)4N+H2F3- oraz 34 mL benzenu. Następnie dodano 4,16 g (0,014 mol) DBH. Zawartość kolby mieszano w temperaturze pokojowej przez 4 godziny. Postępując dalej jak w przykładzie I otrzymano 1,65 g sulfidu chlorofluorometylo-4-metylofenylowego, co stanowi 86% wydajności..Preparation of chlorofluoromethyl-4-methylphenyl sulfide 1.72 g (0.01 mol) of chloromethyl-4-methylphenyl sulfide, 4.34 g (0.014 mol) (H-C4H9) 4N + H2F3 - and 34 were placed in a 100 mL flask. mL of benzene. Then 4.16 g (0.014 mol) of DBH was added. The contents of the flask were stirred at room temperature for 4 hours. Proceeding further as in Example 1, 1.65 g of chlorofluoromethyl-4-methylphenyl sulfide was obtained, which is 86% yield.
P r z y k ł a d 7P r z k ł a d 7
Otrzymywanie sulfidu chlorofluorometylo-4-metoksyfenylowego W kolbie o pojemności 100 mL umieszczono 1,88 g (0,01 mol) sulfidu chlorometylo-4-metoksyfenylowego, 4,34 g (0,014 mol) (H-C4H9)4N+H2F3- oraz 34 mL toluenu. Następnie dodano 4,16 g (0,014 mol) DBH. Zawartość kolby mieszano w temperaturze pokojowej przez 4 godziny. Postępując dalej jak w przykładzie I otrzymano 1,88 g sulfidu chlorofluorometylo-4-metoksyfenylowego, co stanowi 70% wydajności.Preparation of chlorofluoromethyl-4-methoxyphenyl sulfide 1.88 g (0.01 mol) of chloromethyl-4-methoxyphenyl sulfide, 4.34 g (0.014 mol) (H-C4H9) 4N + H2F3 - and 34 were placed in a 100 mL flask. mL of toluene. Then 4.16 g (0.014 mol) of DBH was added. The contents of the flask were stirred at room temperature for 4 hours. Proceeding further as in Example 1, 1.88 g of chlorofluoromethyl-4-methoxyphenyl sulfide were obtained, which is 70% yield.
PL 212 283 B1PL 212 283 B1
P r z y k ł a d 8P r z k ł a d 8
Otrzymywanie sulfidu chlorofluorometylo-4-metylofenylowego W kolbie o pojemności 100 mL umieszczono 1,72 g (0,01 mol) sulfidu chlorometylo-4-metylofenylowego, 4,34 g (0,014 mol) (H-C4H9)4N+H2F3- oraz 34 mL chloroformu. Następnie dodano 4,16 g (0,014 mol) DBH. Zawartość kolby mieszano w temperaturze pokojowej przez 4 godziny. Postępując dalej jak w przykładzie I otrzymano 1,58 g sulfidu chlorofluorometylo-4-metylofenylowego, co stanowi 83% wydajności.Preparation of chlorofluoromethyl-4-methylphenyl sulfide 1.72 g (0.01 mol) of chloromethyl-4-methylphenyl sulfide, 4.34 g (0.014 mol) (H-C4H9) 4N + H2F3 - and 34 were placed in a 100 mL flask. mL of chloroform. Then 4.16 g (0.014 mol) of DBH was added. The contents of the flask were stirred at room temperature for 4 hours. Proceeding further as in Example 1, 1.58 g of chlorofluoromethyl-4-methylphenyl sulfide were obtained, which is 83% yield.
P r z y k ł a d 9.P r z h o m 9.
Otrzymywanie sulfidu chlorofenylo-4-bromofluorometylowego.Preparation of chlorophenyl-4-bromofluoromethyl sulfide.
W kolbie o pojemności 100 mL umieszczono 5 g (0,021 mol) sulfidu bromometylo-4-chlorofenylowego, 9,12 g (0,03 mol) (n-C4H9)4N+H2F3-, 50 mL tetrachlorku węgla oraz 8,73 g (0,3 mol) DBH. Zawartość mieszano przez 5 godzin w temp pokojowej. Dalej postępując jak w przykładzie 1 uzyskano 3,8 g sulfidu bromofluorometylo-4-chlorofenylowego o temperaturze wrzenia 62-64°C (0,2 Tr), co stanowi 77% wydajności.In a 100 mL flask were placed 5 g (0.021 mol) of bromomethyl-4-chlorophenyl sulfide, 9.12 g (0.03 mol) (n-C4H9) 4N + H2F3 - , 50 mL of carbon tetrachloride and 8.73 g ( 0.3 mol) DBH. The contents were stirred for 5 hours at room temperature. Further, following the procedure of Example 1, 3.8 g of bromofluoromethyl-4-chlorophenyl sulfide was obtained, boiling point 62-64 ° C (0.2 Tr), which is 77% yield.
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| CN110698375A (en) * | 2018-07-10 | 2020-01-17 | 中国科学院上海有机化学研究所 | Compound containing monochlorofluoromethylthiosulfonate and preparation method and application thereof |
| CN110698375B (en) * | 2018-07-10 | 2021-09-03 | 中国科学院上海有机化学研究所 | Compound containing monochlorofluoromethylthiosulfonate and preparation method and application thereof |
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