JP5708023B2 - α,β,β−トリフルオロスチレン類の工業的な製造方法 - Google Patents
α,β,β−トリフルオロスチレン類の工業的な製造方法 Download PDFInfo
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- JP5708023B2 JP5708023B2 JP2011038298A JP2011038298A JP5708023B2 JP 5708023 B2 JP5708023 B2 JP 5708023B2 JP 2011038298 A JP2011038298 A JP 2011038298A JP 2011038298 A JP2011038298 A JP 2011038298A JP 5708023 B2 JP5708023 B2 JP 5708023B2
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- trifluorostyrenes
- trimethylsilyl
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- 238000000034 method Methods 0.000 title description 29
- 238000009776 industrial production Methods 0.000 title description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 26
- 229910052783 alkali metal Inorganic materials 0.000 claims description 25
- 150000001340 alkali metals Chemical class 0.000 claims description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- XGIUDIMNNMKGDE-UHFFFAOYSA-N bis(trimethylsilyl)azanide Chemical compound C[Si](C)(C)[N-][Si](C)(C)C XGIUDIMNNMKGDE-UHFFFAOYSA-N 0.000 claims description 21
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- 150000007530 organic bases Chemical class 0.000 claims description 16
- 239000007810 chemical reaction solvent Substances 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Chemical group 0.000 claims description 2
- 239000011591 potassium Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 14
- 239000012264 purified product Substances 0.000 description 14
- 238000005796 dehydrofluorination reaction Methods 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 10
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 9
- 239000012043 crude product Substances 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
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- 238000000746 purification Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000004508 fractional distillation Methods 0.000 description 7
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 6
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 125000002252 acyl group Chemical group 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- -1 amino, hydroxyl Chemical group 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- CTIKAHQFRQTTAY-UHFFFAOYSA-N fluoro(trimethyl)silane Chemical compound C[Si](C)(C)F CTIKAHQFRQTTAY-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 5
- 238000012805 post-processing Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 3
- SUTQSIHGGHVXFK-UHFFFAOYSA-N 1,2,2-trifluoroethenylbenzene Chemical compound FC(F)=C(F)C1=CC=CC=C1 SUTQSIHGGHVXFK-UHFFFAOYSA-N 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-Me3C6H3 Natural products CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 3
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006471 dimerization reaction Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 125000001041 indolyl group Chemical group 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 125000000168 pyrrolyl group Chemical group 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 125000004438 haloalkoxy group Chemical group 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 125000005493 quinolyl group Chemical group 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005935 Sulfuryl fluoride Substances 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000006015 bromomethoxy group Chemical group 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000004651 chloromethoxy group Chemical group ClCO* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000004785 fluoromethoxy group Chemical group [H]C([H])(F)O* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010888 waste organic solvent Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
で示されるアルカリ金属ビス(トリメチルシリル)アミドと反応させる工程Aと、引き続いて行う、目的物のα,β,β−トリフルオロスチレン類と副生物のビス(トリメチルシリル)アミンとを含む混合物をフッ化水素、または、有機塩基とフッ化水素とからなる塩もしくは錯体と反応させる工程Bを含む、α,β,β−トリフルオロスチレン類の製造方法。
前記式[1]で示されるα,β,β−トリフルオロスチレン類のArがフェニル基または置換フェニル基であり、前記式[3]で示されるアルカリ金属ビス(トリメチルシリル)アミドのMがリチウムである、発明1に記載の方法。
前記有機塩基がトリn−ブチルアミンである、発明1または2に記載の方法。
初めに、工程Aの脱フッ化水素工程について具体的に説明する。
次に、工程Bの後処理工程について具体的に説明する。
実施例により本発明の実施の形態を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。実施例2および3の原料基質として用いたα−アリール−α,β,β,β−テトラフルオロエタン類は、参考例1を参考にして同様に製造した。
ビス(トリメチルシリル)アミン38.7g(240mmol、1.20eq)のテトラヒドロフラン溶液(溶媒使用量50.0mL、0.208L/mol)に、n−ブチルリチウムのn−ヘキサン溶液145mL(1.65M、240mmol、1.20eq)を氷冷下で滴下し、室温で30分間攪拌することにより、下記式:
反応終了液(均一溶液)に、トリn−ブチルアミン・三フッ化水素63.8g(260mmol、1.30eq)を氷冷下で滴下し、同温度で1時間攪拌し、さらに室温で1時間30分攪拌した(懸濁溶液)。反応終了液のガスクロマトグラフィー分析より、ビス(トリメチルシリル)アミンは全く検出されなかった。反応終了液を濾過し、残渣を少量のn−ヘキサンで洗浄し、濾洗液を直接、蒸留回収(留出温度27℃/減圧度13〜0.90kPa)することにより、下記式:
反応終了液(均一溶液)に、トリn−ブチルアミン・三フッ化水素69.9g(285mmol、1.43eq)を氷冷下で滴下し、室温で45分間攪拌した(懸濁溶液)。反応終了液のガスクロマトグラフィー分析より、ビス(トリメチルシリル)アミンは全く検出されなかった。反応終了液を濾過し、残渣を少量のn−ヘキサンで洗浄し、濾洗液を直接、蒸留回収(留出温度45〜97℃/減圧度30〜2.5kPa)することにより、下記式:
ビス(トリメチルシリル)アミン11.3g(70.0mmol、1.20eq)のテトラヒドロフラン溶液(溶媒使用量30.0mL、0.429L/mol)に、n−ブチルリチウムのn−ヘキサン溶液42.4mL(1.65M、70.0mmol、1.20eq)を氷冷下で滴下し、室温で45分間攪拌することにより、下記式:
反応終了液(均一溶液)に、トリエチルアミン・三フッ化水素13.1g(81.3mmol、1.39eq)を氷冷下で滴下し、室温で1時間15分攪拌した(懸濁溶液)。反応終了液のガスクロマトグラフィー分析より、ビス(トリメチルシリル)アミンは全く検出されなかった。反応終了液を濾過し、残渣を少量のn−ヘキサンで洗浄することにより、下記式:
Claims (2)
- 一般式[1]:
で示されるα,β,β−トリフルオロスチレン類の製造において、
一般式[2]:
で示されるα−アリール−α,β,β,β−テトラフルオロエタン類を、n−ヘキサン、n−ヘプタン、トルエン、キシレン、ジエチルエーテル、1,2−ジメトキシエタン、1,4−ジオキサン、テトラヒドロフラン、2−メチルテトラヒドロフラン、tert−ブチルメチルエーテル、ジイソプロピルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジn−ブチルエーテルおよびアニソールからなる群より選ばれる少なくとも1種の反応溶媒の存在下、一般式[3]:
で示されるアルカリ金属ビス(トリメチルシリル)アミドと反応させる工程Aと、引き続いて行う、目的物のα,β,β−トリフルオロスチレン類と副生物のビス(トリメチルシリル)アミンとを含む混合物、
を含む該工程の反応終了液を、直接、フッ化水素、または、「トリエチルアミン、及びトリn−ブチルアミンから選ばれる有機塩基とフッ化水素とからなる塩もしくは錯体」と反応させる工程Bを含む、α,β,β−トリフルオロスチレン類の製造方法。 - 一般式[1]:
で示されるα,β,β−トリフルオロスチレン類の製造において、
一般式[2]:
で示されるα−アリール−α,β,β,β−テトラフルオロエタン類を、n−ヘキサン、n−ヘプタン、ジエチルエーテル、1,2−ジメトキシエタン、1,4−ジオキサン、テトラヒドロフラン、2−メチルテトラヒドロフラン、tert−ブチルメチルエーテル、ジイソプロピルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジn−ブチルエーテルおよびアニソールからなる群より選ばれる少なくとも1種の反応溶媒の存在下、一般式[3]:
で示されるアルカリ金属ビス(トリメチルシリル)アミドと反応させる工程Aと、引き続いて行う、目的物のα,β,β−トリフルオロスチレン類と副生物のビス(トリメチルシリル)アミンとを含む混合物、
を含む該工程の反応終了液を、直接、フッ化水素、または、「トリエチルアミン、及びトリn−ブチルアミンから選ばれる有機塩基とフッ化水素とからなる塩もしくは錯体」と反応させる工程Bを含む、α,β,β−トリフルオロスチレン類の製造方法。
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