CS251657B1 - Preparation method of the 11a-chlorine-5-hydroxytetracyclone-6,12-hemiketale - Google Patents
Preparation method of the 11a-chlorine-5-hydroxytetracyclone-6,12-hemiketale Download PDFInfo
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- CS251657B1 CS251657B1 CS833524A CS352483A CS251657B1 CS 251657 B1 CS251657 B1 CS 251657B1 CS 833524 A CS833524 A CS 833524A CS 352483 A CS352483 A CS 352483A CS 251657 B1 CS251657 B1 CS 251657B1
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- preparation
- mol
- hydroxytetracyclone
- hemiketale
- chlorine
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- 238000002360 preparation method Methods 0.000 title claims 2
- 238000000034 method Methods 0.000 claims 4
- 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 1
- 239000004100 Oxytetracycline Substances 0.000 claims 1
- 150000001447 alkali salts Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000012320 chlorinating reagent Substances 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 159000000011 group IA salts Chemical class 0.000 claims 1
- 238000002955 isolation Methods 0.000 claims 1
- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 claims 1
- 229960000625 oxytetracycline Drugs 0.000 claims 1
- 235000019366 oxytetracycline Nutrition 0.000 claims 1
- 238000004062 sedimentation Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 101100172132 Mus musculus Eif3a gene Proteins 0.000 description 1
- 241001089215 Notomys Species 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
11
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Cnocofi nojiyqeHHH Ha-xjxop-5-rHflpoKcnTeTpaiu«cnHH-6,12-ΓβΜΗκβταπ«Cnocofi nojiyqeHHH Ha-xjxop-5-rHflpoKcnTeTpaiu «cnHH-6,12-ΓβΜΗκβταπ«
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XapaKTepHCTHKa Η3βθοτημχ TexHHnecKHX pemeHU# fljiH nojiyqeHHH I la-xjiop-5-rnflpoKCHTeTpauHKJiHH-6,12- reMHKgTanH npennoxeHo yxe He-cxojibKO cnocofioB (U.S.P. 2984 686, DE-OS 2 164 840, DD-AP 113 527). B οοοτΒβτ-ctbhh co bc6mh npejvtoxeHHbíMH cnocofíaMH 5-rHflpoKCHTeTpaiíHKjiHH xjiopHpyioT b peaK-μΗΟΗΗΟ-ίΉΗβρΤΗΟΜ, CMePlHBaFHHeMCH C BOflOň paCTBQpHT&Jie, ΠρΗΗβΜ HKO6bI MOryT npHMe-HHŤbCH cňeflywDpie xjiopHpjnoncHe BeinecTBa: xnop, aMHflw N-xjiop-HH3KoajiKanoBoň khcjio-Tbl, HMHflbl XJlOpflHKapBOHOBOň KHCJIOTM, N-HH3KOaJlKaHOHJiaHHJIHflbI, XJIÓpflHMeTHnrHflaHTO-jíh, nepxjiopnHpHflHHOBHÍi rHflpoxnopHfl h HH3inne · ajiKHJirHnoxjiopuTbi. CornacHo cnocoCyIj.S.P. 2 984 686 - xjiopHposaHHe 5-rHflpoKCHTeŤpauHKJiHHa kaK ocHOBaHHH πρπ TeMne-paTypax 0 - 50°C - nojiyxeHM Jiranb cpaBHHTejibHO HH3Kne Bbixoflbí (okojio 40% TěopHH),τβκ κβκ nacTb nponyKTa xjiopHpoBaHHH nonynaeTCH b MaJiocTa6HJibHoii κετοφορΜβ. BcooTBeTCTBHH Co cnocofíoM DE-OS 2 164 840 o6pa6oTKoň peaKiiHOHHoň cMecu τρηβτηπ-aMMHOBbíM 6y$epoM no pH 3 - 5, npeflnoHTHTeJibHO 4 - 4,5, b peeyjibTaTe xjiopHposa-hhh b npeflejiax -15 po -4®C nonynaioT JiyBunoi Bbixop sa cneT cnoHTaHHoň KpHCTanjiH-3aiJHH CTaOnjlbHOií SHOJIbHOH φθρΜΜ* B OTJIHHHe OT 3Τ0Γ0, cnoco6 COmaCHO DD-AP113 527 npeflycMaTpHBaeT xjiopupoBaHHe tipneme 6onee hh3khx TeMnepaTypax (-40°C) H o6pa6oTKy peaKiíHOHHOň cmsch 6ojiee cwibHMM τρη3τκπ3μβΗοβημ 6y<l>epoM ro pH = “ 6,5 - 7,7, b nacTHocTH 7,3 - 7,5, H ocaxpeHHe npoflyKTa peaKUHH H3 peaKiiHOHHott CMeCH B Ka^eCTBe COJTH SHOJTbHOÍÍ <J)OpMbI C MHHepajIbHOň KHCJTOTOK C BbIXOflOM οκοπο78% ΤβΟρΗΗ. JBih scex npexHHX cnocofios, Hapn^y c πρΗΜβΗβΗΗβΜ cMeniHBawiuHXCH c bojích pacTBopH-XapaKTepHCTHKa TexHHnecKHX pemeHuJqHH-6,12-ReMHKgTanH npennoxeHoYxHeH-6,12-ReMHKgTanHnHxHygOnHe-xxlHygOB (U.S.P. 2984 686, DE-OS 2 164 840, DD-AP 113 527). B οοοτΒβτ-ctbhh what bc6mh npejvtoxeHHbíMH cnocofíaMH 5 rHflpoKCHTeTpaiíHKjiHH xjiopHpyioT b Peak-μΗΟΗΗΟ-ίΉΗβρΤΗΟΜ, CMePlHBaFHHeMCH C BOflOň paCTBQpHT & Jie ΠρΗΗβΜ HKO6bI Ballad npHMe-HHŤbCH cňeflywDpie xjiopHpjnoncHe BeinecTBa: xnop, aMHflw N xjiop-HH3KoajiKanoBoň khcjio-TBL HMHflbl XJlOpflHKapBOHOBOň KHCJIOTM, N-HH3KOaJlKHOHHiHHlIHflbI, XJOpflHMeTHnrHflpoxHlHlHHHHlHHHlHnHHlpoxnopHflHHH3inne · ajKHJirHnoxjiopuTbi. CornacHo cnocoCyIj.S.P. 2,984,686 - xjiopHposaHHe 5-kak rHflpoKCHTeŤpauHKJiHHa ocHOBaHHH πρπ dark-paTypax 0-50 ° C - nojiyxeHM Jiranb cpaBHHTejibHO HH3Kne Bbixoflbí (okojio TěopHH 40%) τβκ κβκ nacTb nponyKTa xjiopHpoBaHHH nonynaeTCH b MaJiocTa6HJibHoii κετοφορΜβ. BcooTBeTCTBHH DE-OS 2 164 840 o6pa6oToPeaKiHOHHoM cMecu-aMMHOBBiM 6y $ epoM no pH 3 - 5, npeflnoHTHTeJibHO 4 - 4.5, b peeyjibTaTe xjiopHposa-hhh b npeflejiax -15 po -4®C nonynaioT JiyBunoi Bbixop sa cneT cnoHTaHHoň KpHCTanjiH-3aiJHH CTaOnjlbHOií SHOJIbHOH φθρΜΜ * B OTJIHHHe OT 3Τ0Γ0, cnoco6 Comach DD-527 AP113 npeflycMaTpHBaeT xjiopupoBaHHe Predict 6onee hh3khx TeMnepaTypax (-40 ° C) H o6pa6oTKy peaKiíHOHHOň cmsch 6ojiee cwibHMM τρη3τκπ3μβΗοβημ 6y <l> EPDM ro pH "6.5 - 7,7, b nacTHocTH 7,3 - 7,5, H ocaxpeHHe npoflyKTa peaKUHH H3 peaKiiHOHHott CMeCH B Ka ^ eCTBe COJTH SHOJTbHOIi <J) OpMbI C MHHepajIbHO KHCJTOTOK C BbIXOflOM οκοπο78% ΤβΟρΗΗ. JBih scex npexHHX cnocofios, Hapn ^ y c πρΗΜβΗβΗΗβΜ cMeniHBawiuHXCH c fight pacTBopH-
TeJiéft, ofinu®* HBJweTCH npennoHHTaeMoe b ππτβΗτΗΜΧ <t>opMynax h onHCbmaeMoe hckjtw-ΊΗΤβπΒΗο B npHMepax ocynecTBJíeHHH Htcn0Jib3OBaHne N—xjiopcyKtjHHHMHfla b Ka^ecTBe 251657 2 xnopupyrauero BewecTBa, xoth sto BeiqecTBo naneKo ne HBjínercH Han6ojiee peHTa6enb-HblM H3 Bcex ΠρηβΜΠβΜΗΧ CpeflCTB ΧΠΟρΗρΟΒΗΗΗΗ. flpyrne cpeflCTBa xnopupoBaHHH^ Ha3HBaeMMe b HBBecTHblx npennaraeMbix cnoco6ax, XOTH H MOryT RbtTb HCnOJIbaOBaHH &ΠΗ XJIOpHpOBaHBH, ΒΜβΟΤΟ N-XJTOpCyKBHHHMHfla, HOBáwT npHHHHnHajibHo Ronee ηη3κηθ βηχοημ, neM Nr-xnopcyKUHHHMHn. fljia cneijHanbHMxBejieň xnopupoBaHHH ncnonb3OBanHCb Taxxe. ywe h aMHflbí H Ν-χπορ- η N,N-nHXJiopapHji-cyjibfJiOHOBOH khcjiotm (cm. Houben, Weyl, Methoden der organischen Chemie, GeorgThieme Verlag Stuttgart, 4, Auflage Bd, V/3, S. 808 ff. u» Bd, IX S. 645). 3th coeflHHeHHH, KOTopbie, oueBHnHo, enje He HcnojibaoBajiHCb po chx nop íwh xjioph-poBaHHB 5~rnBpoKCH-TeTpanHKBHHa, mowho HcnojibaůBaTb Taxxe, κβκ h N-XJiopeyKUHH-HMHfl, ho ohh ne ofijianaioT ηηκλκημη npeHMymecTBaMH no cpaBHeHHto c nocJteflHHM.TeJiéft, ofinu® * HBJweTCH npennoHHTaeMoe b ππτβΗτΗΜΧ <t> h opMynax onHCbmaeMoe hckjtw-ΊΗΤβπΒΗο B npHMepax ocynecTBJíeHHH Htcn0Jib3OBaHne N-K ^ b xjiopcyKtjHHHMHfla ecTBe 251657 2 xnopupyrauero BewecTBa, XOTH hundred BeiqecTBo naneKo not HBjínercH Han6ojiee peHTa6enb HblM-H3 Bcex ΠρηβΜΠβΜΗΧ CpeflCTB ΧΠΟρΗρΟΒΗΗΗΗ. flpyrne cpeflCTBa xnopupoBaHHH Ha3HBaeMMe ^ b HBBecTHblx npennaraeMbix cnoco6ax, XOTH Ballad RbtTb HCnOJIbaOBaHH H & ΠΗ XJIOpHpOBaHBH, ΒΜβΟΤΟ N XJTOpCyKBHHHMHfla, HOBáwT npHHHHnHajibHo Ronee ηη3κηθ βηχοημ, NEM-xnopcyKUHHHMHn Nr. fljia cneijHanbHMxBenny xnopupoBaHHH ncnonb3OBanHCb Taxxe. ywe h aMHflbH Ν-χπορ-η N, N-NHXJiopapHi 1 -cyjibibiOHOBOH khcjiotm (cm. Houben, Weyl, Methoden der organischen Chemie, GeorgThieme Verlag Stuttgart, 4, Auflage Bd, V / 3, S. 808 ff. , IX S. 645). 3th coeflHHeHHH, KOTopbie, oueBHnHo, enje He HcnojibaoBajiHCb after CHX NOP IWH xjioph poBaHHB-5-rnBpoKCH-TeTpanHKBHHa, mowho HcnojibaůBaTb taxxi, κβκ H N-XJiopeyKUHH HMHfl, it ooh not ofijianaioT ηηκλκημη npeHMymecTBaMH well cpaBHeHHto nocJteflHHM C.
KpoMe toto, ofia cnocofia corjiacHo DE-OS 2 164 8,40 h DD-AP 113 527, ocymeCTBnae-Mbie c yBOBBtíTBopHTenbHWM bhxoaom, TpefiytoT τοηηογο cofijnoneHHH y3KHX npeflenoB3HaneHHH pH, oneBH/xHO, aaBHCHMNx ot nannoro cnocofia. OflHaxo, xaK noKaawBaeTojibiT, H3MepeHHe 3HaqenHH pH cBHaaHo co 3HauHTenbHbiMH TpyflHOCTHMH b npoH3BOflCT-BeHHoň npaxTHKe npH pacTBopax, He coflepxawux Bony hbh coflepJKamHX He3HaHHTejtbHoeKonnuecTBo BOflH, τβΜ fionee npH TeMnepaTypax tuwe -5°C.KpoMe this, ofia cnocofia corjiacHo DE-OS 2 164 8.40 h DD-AP 113 527, ocymeCTBnae-Mbie c yBOBBtTBopHTenbHWM bhxoaom, TpefiytoT cofijnoneHHH y3KHX npeflenoB3HaneHHH pH, oneBH / xHO, aaBHCHMNx ot nannoro cnocofia. OflHaxo, xaK noKaawBaeTojibiT, H3MepeHHe 3HaqenHH pH cBHaaHo what 3HauHTenbHbiMH TpyflHOCTHMH b npoH3BOflCT-BeHHoň npaxTHKe NPH pacTBopax, Ile coflepxawux Bony HBH coflepJKamHX He3HaHHTejtbHoeKonnuecTBo BOflH, τβΜ fionee NPH TeMnepaTypax tuwe -5 ° C.
Uejlb Η3θ6ρβΤβΗΗΗUejlb Η3θ6ρβΤβΗΗΗ
Uejibw npeftnaraeMoro Η3θ6ρβτβΗΗΗ ΗΒΠΗβτοπ cnocofi nonyneHMa I la-xnop-S-rHgpoKCH-TeTpanHKBHH-6,12-reMHKeTaJiH TexHojiornnecKH npocTttM cnocofioM h c Hcnojib3OpaHHeMfiojiee fleineBoro cpegcTBa xnopupoBaHHH no cpaBHeHHto c N-xnopcyKUHHHMHBOM. Πρρ#γκτ,npH 3TOM, flojmeH fíbiTb nojiyHtíH, no xpaňHeň Mepe, c T8khm jte BbtxonoM, xatc h nonyniUHM H3 H3BeCTHHX CnOCOfíOB, B 3HOJIbHOřt φΟρΜβ.Uejibw npeftnaraeMoro Η3θ6ρβτβΗΗΗ ΗΒΠΗβτοπ cnocofi nonyneHMa Ia-I-S-xnop rHgpoKCH-TeTpanHKBHH-6,12-reMHKeTaJiH TexHojiornnecKH npocTttM cnocofioM c h Hcnojib3OpaHHeMfiojiee fleineBoro cpegcTBa xnopupoBaHHH well cpaBHeHHto c N xnopcyKUHHHMHBOM. Π ρ,,,, flo flo flo flo flo flo flo flo flo flo flo flo ep ep ep ep ep ep ep ep ep ep ep ep ep ep ep ep ep ep ep ep ep ep ep ep ep ep ep,,,,,,,,....
HanoweHHe cymnocTH Η3θβρβτβΗΗΗ 3aflaua 3aKJnonajiacb b tom, hto6h HaňTH ηοβοθ, fionee nemeBoe cpencTBO xnopupoBa-hhh, κοτοροβ no3BonH.no 6bi fie3 3aTpyflHeHHň b ycTanoBKe npenenos pH c bmcokhmBbixoflOM npoBecTH xnopHpoBaHHe 5-rHflpoKCHTeTpanHKjiHHa b xenaeMbiň 11 a-xjiop-S-THflp-,OKCH-TeTpanHKJiHH-6,12-reMHKeTaJib.HanoweHHe cymnocTH Η3θβρβτβΗΗΗ 3aflaua 3aKJnonajiacb b that hto6h HaňTH ηοβοθ, fionee nemeBoe cpencTBO xnopupoBa-hhh, κοτοροβ no3BonH.no 6bi fie3 3aTpyflHeHHň b ycTanoBKe npenenos pH c bmcokhmBbixoflOM npoBecTH xnopHpoBaHHe 5 rHflpoKCHTeTpanHKjiHHa xenaeMbiň b-11 and S-xjiop THflp-, OKCH -TeTpanHKJiHH-6,12-reMHKeTaJib.
PeuiHTb 3aflany η6οβηβ;βηηο y/vuioch τβΜ, hto fiuno naň^eHo, hto menoHHbte cojih N-MOHOXJlOpapHJICyjIb<í)OHaMHBOB HBJIHWTCH OTJIHHHblMH CpeflCTBaMH ΧΠΟρΗρΟΒΗΗΗΗ 5~ΓΗβρθΚ-ch-TeTpanHKJiHHa b nonoxeHHH 11a c ofipasoBaHHeM 6,12-reMHKeTajia b οηοπβηοη φόρΜβ,ΧΟΤΗ 3TH COeBHHeHHH HapHfly G HX KOMMepBeCKHM ΠΡΗΜβΗβΗΗβΜ B KaBeCTBe fle3HH<í)HIj(H“pytomHX cpeflCTB flo chx nop HcnoJib3OBajiHCb b xanecTBe OKHCHHTeJieň, ho ne xax cpefl-cTBa xnopHpoBaHHH (Houben-Weyl, Methoden der organischen Chemie Bd, IX S. 644),yflHBJíHJio η το, hto ofipa3OBanca xejiaeMbiň προπγκτ xnopHpoBaHHH BbtcoKorO KanecTBaH C OTJIHUHHM ΒΗΧΟ^ΟΜ 6β3 yCTaHOBKH OflHOrO H3 flO CHX ΠΟρ ΠρΗ3Η3ΗΗΕ1Χ ΟΠΤΗΜβΠΒΗΗΜΗ ·npeflejioB 3HaneHHň pH (4-4,5 ηπη 7,3-7,5) po hjjh bo BpeMH peaKiwH.PeuiHTb 3aflany η6οβηβ; βηηο y / vuioch τβΜ, HTO fiuno thereto ^ EHO HTO menoHHbte cojih MOHOXJlOpapHJICyjIb N <i) OHaMHBOB HBJIHWTCH OTJIHHHblMH CpeflCTBaMH ΧΠΟρΗρΟΒΗΗΗΗ ΓΗβρθΚ-5-chloro-TeTpanHKJiHHa b nonoxeHHH 11a-c 6,12 ofipasoBaHHeM reMHKeTajia b οηοπβηοη φόρΜβ TH 3TH COeBHHeHHH HapHfly G HX KOMMepBeCKHM ΠΡΗΜβΗβΗΗβΜ B B CT 3 3 3 j j j j j j j j j j j j j j j j j ax ax ax ax ax ax ((((( 644) yflHBJíHJio η το, HTO ofipa3OBanca xejiaeMbiň προπγκτ xnopHpoBaHHH BbtcoKorO KanecTBaH C ^ OTJIHUHHM ΒΗΧΟ ΟΜ 6β3 yCTaHOBKH OflHOrO H3 FLO CHX ΠΟρ ΠρΗ3Η3ΗΗΕ1Χ ΟΠΤΗΜβΠΒΗΗΜΗ · npeflejioB 3HaneHHň pH (4-4.5 ηπη 7.3-7.5) after hjjh bo BpeMH peaKiwH.
HanpuMep, npn Hcnojib3OBaHHH tnenouHbix coneň N-xnopcynbtitoHaMHjia b ycnoBHHX yxa-áaHHbix b DD-AP 1 13 527 nonynawT 1 la-xjiop-6,12-reMHKeTanb c bmxobom πηπιβ οκοπο60%, h c BbicoKoň floneň HeKenaTenbHoň κβτοφορΜΜ, B yenOBHHX xe npH3HaHHNX Η3θ6ρβΤβΗΗβΜ OnTHManhHblMH BbIXOfl Ha 5% Bbnne, HeM cornac-ho DD-AP 113 527.HanpuMep, npn Hcnojib3OBaHHH tnenouHbix Conen N xnopcynbtitoHaMHjia ycnoBHHX YXA b-b áaHHbix DD-AP 1 13 527 1 la-nonynawT xjiop-6,12-reMHKeTanb c bmxobom πηπιβ οκοπο60% HC BbicoKoň floneň HeKenaTenbHoň κβτοφορΜΜ B yenOBHHX xe npH3HaHHNX Η3θ6ρβΤβΗΗβΜ OnTHManhHblMH BbIXOfl Ha 5% Bnnn, HeM cornac DD-AP 113 527.
HeoKHflaHHHM fiwno rnanKoe προτβκβΗΗβ peaKUHH h noTOMy, hto cšmh no ce6e cnnbHOnonnpHbie conn TpygHo pacTBópHMH b opraHHHecKHx pacTBOpax, conepjKamHX πηππ» He-3HanHTenbHoe KonimecTBO βολμ h TeMnepaTypax peaxuHH* 0co6o BMroflHHM npeflCTaBHTeneM ηηββηηηογο Knacca coeflHHeHwS ηβπηθτοη N-xnop-n-Tonyoncynb(íioHaMH,nHHň HaTpHft (τορτοΒοβ-HaasaHMe xnopaMHH T). PeaKium c bhm npo-TexaeT b oneHb μηγκηχ ycnoBHHX aa oxéHb κοροτκοβ βρθμη πηηιβ cna6o3K3OTepMH5tec“ 251657 3 κη η 6jih3Ko κ KojiHxecTBeHHoň c ποπγπβΗΗβΜ pacTBopa 11 a-xnop-5-rHnpoKCH-TeTpa-UHKJihh-6 ,12-reMHKeTajiH, IIpeHMyiuecTBO ncnonb3OBaHHH aMHflHbixt coneň Ν-χπορ-3ριπιογπ&φθΗθΒθή khcjiotw b3Toň peaKiuw npoHBHnocb h b tom, hto pacTBop ηπη cycneH3Hio 5-ΓΗηροκςΗ-τβτρβιχΗΚ-JiHHa cjieflyer oxnajtnaTb tojibko onHH pas, HanpHMep, b 6e3BonHOM aneTOHe no τβΜ-nepaTypw -1O...-4O°C, a πρκ npHfiaBneHHH cpencTBa xnopnpOBaHHH He cnenyeT najibmeqxjiaxnaTb. Πρκ 3tom TeMnepaTypa BoapacT&na no -15...+5°C. HHTepecHbíMH 6μπη pe-3yjibTarbi H3MepeHHH pH b peaKipťbHHoíi cMecH. B cnynae ncnojib3OBanMR Heo6xonnMoroΑΠΗ nOCTHXeHHH ΧΟρΟΙΠβΓΟ BMXOna KOJBfyeCTBa N-MOHOXJIOp-n-TOJTyOJlCyjlb$OHaMHnHOrOΗΗτρκΗ πορπηκβ 1,1 no 1,3 moji Ha moji S-rnnpoKCH-TeTpaUHKJiHHa nojiynHJiH 3HaqeHnepH 5,1-6,3. IIpH npennoHTHTejibKOM κοπκηβοτΒβ cpencTBa xnopHpoBaHHH b 1,2 moji no-JiyuHjiH 3HaneHHe pH, paeHoe 5,8, T.e. 3HaHeHne, κοτοροβ He naeT o»nnaeMbix pe3yjib-~T3TOB HpH paCoTe no H3B€CTHMM CnOCO6aM. HeOJKHnaHHO CbUlO, Hro 6bUI nOCTHTHyT xopo“iunň Bbixon h KanecTBO nponyKTa, HecMOTpa Ha to, hto ycTaHaBJíHBaeMoe 3HaneHHepH (5,1 ηθ 6,3) b cnocoCe, cornacno Η3θβρβτβΗΐοο, ne neacHT b oSnacTH pH HaftnenHoftxax oitTHMaJibHoň bo Bcex npenraecTBywmHX cnocoGax (pH = 3 no 5 DE-OS 2 164 840 hpH * 6,5 no 7,7 corjiacHo DD-AP 113 527).HeoKHflaHHHM fiwno rnanKoe προτβκβΗΗβ peaKUHH h noTOMy, HTO CSMA well ce6e cnnbHOnonnpHbie Conn TpygHo pacTBópHMH b opraHHHecKHx pacTBOpax, conepjKamHX πηππ »Ile-3HanHTenbHoe KonimecTBO βολμ h TeMnepaTypax peaxuHH * 0co6o BMroflHHM npeflCTaBHTeneM ηηββηηηογο Knacca coeflHHeHwS ηβπηθτοη N xnop N Tonyoncynb (íioHaMH, nHHň HaTpHft (τορτοΒοβ-HaasaHMe xnopaMHH T). PeaKium c BHM NPO-TexaeT b oneHb μηγκηχ ycnoBHHX aa oxéHb κοροτκοβ βρθμη πηηιβ cna6o3K3OTepMH5tec "251657 3 κη η 6jih3Ko κ KojiHxecTBeHHoň c ποπγπβΗΗβΜ pacTBopa 11a-xnop 5-rHnpoKCH-tet p-UHKJihh-6 12-reMHKeTajiH, IIpeHMyiuecTBO ncnonb3OBaHHH aMHflHbixt Conen Ν-χπορ-3ριπιογπ & φθΗθΒθή khcjiotw b3Toň peaKiuw npoHBHnocb HB fact HTO pacTBop ηπη cycneH3Hio 5 ΓΗηροκςΗ-τβτρβιχΗΚ-JiHHa cjieflyer oxnajtnaTb tojibko onHH passport HanpHMep b 6e3BonHOM aneTOHe no τβΜ-nepaTypw - 1O ... 4O ° C, and πρκ npHfiaBneHHH cp encTBa xnopnpOBaHHH He cnenyeT najibmeqxjiaxnaTb. Πρκ 3tom TeMnepaTypes of BoapacT & nt -15 ... + 5 ° C HHTepecHbiMH 6 μπη pe-3yjibTarbi H3MepeHHH pH b ea K o o o o M cMecH. B cnynae ncnojib3OBanMR Heo6xonnMoroΑΠΗ nOCTHXeHHH ΧΟρΟΙΠβΓΟ BMXOna KOJBfyeCTBa N-MOHOXJIOp-n-TOJTyOJlCyjlb $ OHaMHnHOrOΗΗτρκΗ πορπηκβ 1.1 no 1.3 my Ha my-nnpoKCH-TeTpaUHKJiHHa nojiynHJH3HaqeHnepH 5.1-6.3. IIpH npennoHHTBH b π η η η Β Β Β Β Β Β B B B B B B a n n n 1,2 1,2 1,2 1,2 1,2,,,,,,,, pH, paeHo pH 5.8, T.e. 3HaHeHne, κοτοροβ He naeT o »nnaeMbix pe3yjib- ~ T3TOB HpH paCoTe no H3B € CTHMM CnOCO6aM. HeOJKHnaHHO CbUlO, HRO 6bUI nOCTHTHyT xopo "iunň Bbixon KanecTBO nponyKTa H, Ha HecMOTpa it HTO ycTaHaBJíHBaeMoe 3HaneHHepH (5.1 ηθ 6.3) b cnocoCe, cornacno Η3θβρβτβΗΐοο not neacHT b oSnacTH pH HaftnenHoftxax oitTHMaJibHoň bo Bcex npenraecTBywmHX cnocoGax (pH = 3 no. 5 DE-OS 2,164,840 hpH * 6.5 and 7.7 coriHi DD-AP 113,527).
PeiuaraÍHHM npeHMymecTBOM no cpaaHeHHio c ypoBHeM τθχηηκη ηβπηθτοβ raKace το, htooTnanaeT HeoSxonHMocTb b H3MepeHHH 3HaueHHH pH.HHMM npeHMymecTBOM no cpaaHeHHio c ypoBHeM ηβπηθτοβ raKace το, htooTnanaeT HeoSxonHMocTb b H3MepeHHH 3HaueHHH pH.
UsMepenne pH πρκ TeMnepaTypax Hiáte -10°C no chx nop He ηβπηθτοη HeynoBJíeTBOpH-TejibHo peraeHHoň npoBjíeMoň H3Mepemut. H3JiHpoBanHe nponyKTa mojkho oeymecTBHTbο6ηηηημ o6pa3OM, HanpHMep, nyTeM ocaatfleHHH coJWHoft KHCJioToň b xanecTBe ranpo-XJIOpHna, ΠρΗΗβΜ H6T Heo6XOnHMOCTH paĎOTaTb B 6e3BOnHWX yCJIOBHHX. Πρκ 3T0M UaCTbηβτρηη, H3 xjiopaMHHa T, ocaxnaéTCH b KanecTBe xjiopHCToro Harpna, yjiynmaa peraa-ioiuhm o6pa3OM $HJibTpyeMOCTb nponyKTa. Πρη naJibHeftmeň o6pa6oTKe, HanpHMep, H3-BeCTHblM cnOCOfíOM nerHňPaTaiIHH C φΤΟρΗΟΤΜΜ BOnOponOM B 1 la-XJIOp-MeTanHKJlHH,xjiopHCTHft HaTpnň He MémaeT, nojiyna»T Bbixon 11 a—xjiop—MeTanHKJiHHa nopHnKa * 95%TeopHH. H3oRpeTeHne ofíbHCHaeTca Ha cnenywmHX npHMepax nonpo6Hee. IIpHMep 1 6,25 κγ (12,5 moji) rnnpoxnopHna 5-rHnpOKCH~TeTpaiiHKJiHHa pacTBopaioT hjih cyc-neHnHpywT b CMecH 5,5 ji BonH H 30 a aneTOHa, CMecb oxjiaxnaioT no TeMnepaTypbi-30 - -40°C. BbicTpo npHOaBJíjnoT (b Tenemie 1-2 MHHyT) 4,25 κγ (15 moji) xjiop-aMHHa T h nonojiHHTejibHO nepeMemHBawT b TeneHHe 5-6 MHHyT. Πρκ BO3pacTaHHHTeMnepaTypbi no -15.,.-10°C oGpasyeTCH ποητη, npospaHHbiň acejiTbiň pacTBop. npH6aB-neHHeM CMecH H3 87,5 ji aneTOHa h 2,25 ji KOHneHTpupoBaHHoň cojihhoh khcjioth,npenBapHTejibHO oxjiaxneaHoň n° 0 ” +5°C, ocaxnaioT nponyKT peaKiiHH. flonojiflHTejibHO;nepeMeiiHBaioT b TeneHHe 1 naca npH 18 - 20®C h b TeneHHe 1,5 naca npn -5 no I-10°C, φκπΒτρνιοτ, npoMMBawT aneTOHOM h cyrnať. nojiynaioT 6,9 κγ 1 la-xjiop-5-rHnpoKCHTeTpanHKJiHH-6,12-reMHKeTajib-rHnpoxjiopHn-nwrnnpaTa c conepxaHHeM NaCl οκοπο 14%, αοοτΒβτοτΒβΗΗΟ 5,93 κγ ηηοτογο nponyKTa f(83% TeopHH). 2Ό T.nn.: 212 —216 (pasn.), - 22,5°C (c = 1, MeTaHon c 1% HCl) b nepecneTe HaNaCl- h ReaBonHoe semecTBO. nponyKT He HMeeT HK nonocw Bwne 1666 cm_í , hto CBHfleTenhCTByeT 06 otcvtctbhhUsMepenne pH πρκ TeMnepaTypax Hiáte -10 ° C No chx nop He ηβπηθτοη HeynoBJíeTBOpH-TejibHo peraeHHoň npoBjíeMoň H3Mepemut. H3JiHpoBanHe nponyKTa my oeymecTBHTbο6ηηηημ o6pa3OM, HanpHMep, nyTeM ocaatfleHHH coJWHoft KHCJioToň b xanecTBe ranpo-XJIOpHna, ΠρΗΗβΜ H6T Heo6XOnHMOCTH paĎOTaTb B 6e3BOnHWX yCJIOBHHX. Πρκ 3T0M UaCTbηβτρηη, H3 xjiopaMHHa T, ocaxnaéTCH b KanecTBe xjiopHCToro Harpna, yjiynmaa peraa-ioiuhm o6pa3OM $ HJibTpyeMOCTb nponyKTa. N η H pa 6 Han Han Han Han Han Han Han n n n n n n n n n n n n n n n n n b b b b%%%%%%%% H3oRpeTeHne ofíbHCHaeTca Ha cnenywmHX npHMepax nonpo6Hee. IIpHMep 1 6.25 κγ (12.5 µm) npoxnOn 5-rHnpOKCH T T ii J a a a a ac ac ac ac ec ec ji H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H. BbicTpo npHOaBJoT (b Tenemie 1-2 MHHyT) 4.25 κγ (15 mi) xjiop-aMHHa T h nonojiHHTejibHO nepeMemHBawT b TeneHHe 5-6 MHHyT. Πρκ BO3pacTaHHHTeMnepaTypbi no -15., .- 10 ° C oGpasyeTCH ποητη, npospaHHbiň acejiTbiň pacTBop. npH6aB-neHHeM CMecH H3 87,5 it ah 2.25 it KOHneHTpupoHo cojihhoh khcjioth, npenBapHTejibho oxjiaxneaHoň n ° 0 ”+ 5 ° C, ocaxnaioT nponyKT peaKiiHH. flNiiflHTejibHO; hEnHeHeHeHtHeHeHnHn 1 npH 18 - 20 CC h b TeneHHe 1.5 npn -5n I-10 ° C, φκπΒτρνιοτ, npoMMBawT aneTOHOM h cyrnit. nojiynaioT 6,9 κ 1 la-xjiop-5-rHnpoKCHTeTpanHKJiHH-6,12-reMHKeTajib-rHnpoxjiopHn-nwrnnpaTa c conepxaHHeM NaCl to 14%, α,9οτΒβτοτΒβΗΗΟ 5,93 κη ηηοτογο nponyKTa f (83% TeopHH). 2Ό Tnn: 212-216 (pas.), - 22.5 ° C (c = 1, MeTaHon c 1% HCl) b impure HaNaCl- h ReaBonHoe semecTBO. nponyKT He HMeeT HK nonocw Bwne 1666 cm_i, hto CBHfleTenhCTByeT 06 otcvtctbhh
HexenaTenbHoft κβτοφορΜΜ. ngHMej>_2 C ΤβΜ, HTOOM nOKasaTb ΒΠΗΗΗΗβ paŠnHHHbiX KOJItmeCTB CpenCTB XnopHpoBaHHH npHMepnOBTOpHJIH C pasnHHHHMH ΚΟΠΗΗβΟΤΒΒΜΗ XJIOpaMHHa T. 251657 4 riojiyHeHbí cjienywimie pe3yjn>TaTbi:HexenaTenbHoft κβτοφορΜΜ. ngHMej> _2 C ΤβΜ, HTOOM nOKasaTb ΒΠΗΗΗΗβ paHnHHbiX KOJItmeCTB CpenCTB XnopHpoBaHHH npHMepnOBTOpHJIH C pasnHHHHMH ΚΟΠΗΗβΟΤΒΒΜΗ XJIOpaMHHa T. 251657
moji xnopAMHHa T/moji OTUmy xnopAMHHa T / my OTU
Bwxofl reMHKeTann 1 40% 1,4 ' 70% 1,6 54% ΠρΗΜβρ 3 ΠΟΒΤΟΡΚΠΗ ΠρΗΜβρ 1 , OflHaKO BM6CTO OKCHTeTpaiIHKJIHH-rHApOXJIOpH.ria HCnOJIb3y»T ORCH~TeTpaiíHKJIHH-flHrHflpaT BMeCTe CO CTeXHOMtíTpHHeCKHM KOJIHHeCTBOM COJIHHOň KHCJ10TM.nojiynawT 63,6% (.τβορΗκ) 1 la—xJiopoKCHTeTpaijHKJiHH—reMHKeTajia·Bwxofl reMHKeTann 1 1.4% 40 '70% 54% 1.6 3 ΠρΗΜβρ ΠΟΒΤΟΡΚΠΗ ΠρΗΜβρ 1 OflHaKO BM6CTO OKCHTeTpaiIHKJIHH-rHApOXJIOpH.ria HCnOJIb3y »T ~ OrChem TeTpaiíHKJIHH flHrHflpaT BMEC-CO CTeXHOMtíTpHHeCKHM KOJIHHeCTBOM COJIHHOň KHCJ10TM.nojiynawT 63.6% ( .τβορΗκ) 1 la — xJiopoKCHTeTpaijHKJiHH — reMHKeTajia ·
ΦΟΡΜΥΠΑ H30RPETEHHU 1. CnocoC πο,πγηβΗΗΒ 1 la-xjiop-5-FHflppKCHTeTpaiiHKjiHH-6,12-reMHKeTajia nyTeM ;XJlOpupOBaHHH ΟΚΟΗΤβΤρβμΗΚΠΗΗβ B CMeiDHBaiOmeMCH C BOflOň paCTBOpHTejie ΠρΗ ΤβΜΠβ*paTypax b npenejiax -40 - +5°C, H H3OJiHpoBaHHH προπγκτβ peaKtiHH nyTeM ocaamemijí,oTjiHMaraimtíicH τβΜ, ητο b KanecTSe cpencTBa xjiopHpoBaHHH Hcnojib3yioT mejionHyw COJlfeΝ-μοήοχλο papnricyjih<í>OHaMHfla. 2. Cnoco6 no nyHRTy 1, OTJiHnawnmftcH τβΜ, hto ^ejionnyio conb - Monoxjiop-apHn-cyjib$OHaMH^a Hcnojib3ywT b KOJiHnecTse 1-1,6 moji, πρβπποΗΤΗΤβπΒΗο 1,2-1,3 moji :Ha moji OKCHTeTpanHKjiHHa. 3. Cnocofí no nyHKTy 1 ,OTJinHaK>mnňcH τβΜ, πτο b KanecTBe menoMHoň cojih N-moho*xjiop-apitncyjibftoHaMH/ia Hcnojib3ywT N-MOHOxjiop-ii-Tonyojicyjib^HaMHflHbiň naTpHň. 4. Cnoco6 no nyHKTy 1, oTjnniawnmHCJi .τβΜ, πτο peaKima npoBOflHTCH np« 3HaneHHHpH ot 5 p;o 6,5, npeflnouTHTejibHO 5,5 no 6.ΦΟΡΜΥΠΑ H30RPETEHHU first CnocoC πο, πγηβΗΗΒ 1 la-xjiop 5-FHflppKCHTeTpaiiHKjiHH-6,12-reMHKeTajia rivet; XJlOpupOBaHHH ΟΚΟΗΤβΤρβμΗΚΠΗΗβ B CMeiDHBaiOmeMCH C BOflOň paCTBOpHTejie ΠρΗ ΤβΜΠβ paTypax * b npenejiax -40 - + 5 ° C, H H3OJiHpoBaHHH προπγκτβ peaKtiHH rivet ocaamemijí, oTjiHMaraimtíicH τβΜ, ητο b KanecTSe cpencTBa xjiopHpoBaHHH Hcnojib3yioT mejionHyw COJlfeΝ-μοήοχλο papnricyjih <í> OHaMHfla. 2. Cnoco6 no nyHRTy 1, OTJiHnawnmftcH τβΜ, hto ^ ejionnyio conb - Monoxjiop-apHn-cyjib $ OHaMH ^ and Hcnojib3ywT b KOJiHnecTse 1-1,6 my, πρβπποΗΤΗΤβπΒΗο 1,2-1,3 my: Ha my OKCHTeTpanHKjiHHa. 3. Cnocofíne nyHKTy 1, OTJinHaK> mnňcH τβΜ, πτο b KanecTBe menoMHoň cojih N-moho * xjiop-apitncyjibftoHaMH / i and Hcnojib3ywTN-MOHOxjiop-ii-Tonyojicyjib ^ HaMHflHbiň naTpHň. 4. Cnoco6 no nyHKTy 1, oTjnniawnmHCJi .τβΜ, πτο peaKima npoBOflHTCH np «3HaneHHHpH ot 5 p; o 6,5, npeflnouTHTejibHO 5,5 no 6.
AHHOTAUHHAHHOTAUHH
Cnocó6 nojiyneHHH 1 l{i-xnop-5-rHflOKCH-TeTpanHKJiHH-6,12-reMHKeTajni Η3θ6ρβτβΗΗβ KacaeTca cnocoĎa nojiyneHHH 1 ía-xJiop-5-rHflpoKCHTeTpauHKJiHH-6,12-reMtíKeTajiH nyTeM xjiopHpoBaHHH 5-rnflpoKCHTeTpauHKJinHa.Cnocó6 nojiyneHHH {i 1 l-5-xnop rHflOKCH-TeTpanHKJiHH-6,12-reMHKeTajni Η3θ6ρβτβΗΗβ KacaeTca cnocoĎa nojiyneHHH 1 IA-5-xJiop rHflpoKCHTeTpauHKJiHH-6,12-reMtíKeTajiH rivet xjiopHpoBaHHH 5 rnflpoKCHTeTpauHKJinHa.
UeJIbW Η3θ6ρβΤβΗΗΗ HBJIHeTCH CHOCO6 npOCTOft B ΤβΧΗΟΠΟΓΗΗβΟΚΟΜ ΟΤΗΟΙΠβΗΗΗ H HC"nojib3y»nptó 6ojiee nemeBoe cpeflCTBO χιιορκροΒβΗΗΛ no cpaBHeHmo c N-xjiopcyKijHHHMH-flOM. Bbino HaňfleHo, hto njejionHbie cojih N-MOHoxJiop-apHJicyjih<i>oHaMHflOB hbjuhotchOTJIHHHMMH CpeflCTBaMH flJIH ΧΠΟρΗρΟΒβΗΗΗ S—rHflpOXCH“ΤβΤρ,ΗΠΗΚΙΙΗΗΗ B ΠΟΙΙΟΜβΗΗΗ 11ac o6pa3OBaHHeM 6,12-reMHKeTajiH b 3HOJibHoň φσρΜβ. ÍIpH3HaHo Η3θβρβτβΗΗβΜ no pe3yjibTaTaM 3KcnepyH3H, ocymecTBJíeHHoň Betonetbomno fleJiaM Η3θ6ρβτβΗΗΑ η πβτβΗΤΟΒ TUP. 251657UeJIbW Η3θ6ρβΤβΗΗΗ HBJIHeTCH CHOCO6 npOCTOft B ΤβΧΗΟΠΟΓΗΗβΟΚΟΜ ΟΤΗΟΙΠβΗΗΗ H HC "nojib3y» nptó 6ojiee nemeBoe cpeflCTBO χιιορκροΒβΗΗΛ well cpaBHeHmo c N xjiopcyKijHHHMH-Flom. Bbino HaňfleHo, HTO njejionHbie cojih N MOHoxJiop-apHJicyjih <i> oHaMHflOB hbjuhotchOTJIHHHMMH CpeflCTBaMH flJIH ΧΠΟρΗρΟΒβΗΗΗ S rHflpOXCH " AcβΤρ, ΗΠΗΚΙΙΗΗΗ B ΠΟΙΙΟΜβΗΗΗ 11ac o6pa3OBaHHeM 6,12-reMHKeTajiH b 3HOJibHoň φσρΜβ. ÍIpH3HaHo Η3θβρβτβΗΗβΜ no pe3yjibTaTaM 3KcnepyH3H, ocymecTBJíeHHoon Betonetbomno fleJiaM Η3θ6ρβτβΗΗΑ η πβτβΗΤΟΒ TUP.
Claims (4)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD24273682A DD219021A3 (en) | 1982-08-24 | 1982-08-24 | PROCESS FOR PREPARING 11A-CHLORO-5-HYDROXY-TETRACYCLINE-6,12-HEMICETAL |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS352483A1 CS352483A1 (en) | 1985-07-16 |
| CS251657B1 true CS251657B1 (en) | 1987-07-16 |
Family
ID=5540820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS833524A CS251657B1 (en) | 1982-08-24 | 1983-05-19 | Preparation method of the 11a-chlorine-5-hydroxytetracyclone-6,12-hemiketale |
Country Status (2)
| Country | Link |
|---|---|
| CS (1) | CS251657B1 (en) |
| DD (1) | DD219021A3 (en) |
-
1982
- 1982-08-24 DD DD24273682A patent/DD219021A3/en not_active IP Right Cessation
-
1983
- 1983-05-19 CS CS833524A patent/CS251657B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS352483A1 (en) | 1985-07-16 |
| DD219021A3 (en) | 1985-02-20 |
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