Dicyclohexylchlorophosphine(DCP link:https://www.bloomtechz.com/synthetic-chemical/organic-intermediates/dicyclohexylchlorophosphine-cas-16523-54-9.html) yog ib qho organophosphorus compound nrog ntau yam kev siv. Daim ntawv no yuav qhia txog ntau yam kev sib txuas ntawm DCP los ntawm cov yam ntxwv ntawm cov tshuaj tiv thaiv epoxidation, cov tshuaj tiv thaiv alkylation, cov tshuaj tiv thaiv dehydrochlorination, cov tshuaj tiv thaiv pyrophosphorylation thiab lwm yam.
1. Epoxidation tshuaj tiv thaiv txoj kev:
Epoxidation cov tshuaj tiv thaiv yog ib txoj hauv kev zoo tshaj plaws rau kev npaj DCP. Ua ntej, ethylene oxide yog reacted nrog triacone kom tau ib qho khoom epoxidized. Tom qab ntawd, cov khoom epoxidized tau alkylated nrog tricyclohexyl ketone kom tau DCP. Qhov kom zoo dua ntawm txoj kev no yog tias cov tshuaj tiv thaiv kab mob tuaj yeem tswj tau kom tau txais cov khoom lag luam siab ntshiab DCP.
Kev sim cov kauj ruam:
1.1. Epoxidation tshuaj tiv thaiv:
Muab 100 mL ntawm anhydrous aluminium chloride rau hauv cov dej khov dej npaj, thiab ntxiv 2.30 g ntawm tricerone nrog ib qho kev nplawm. Do ntawm 5-10 degree rau 15 feeb, ces ntxiv 2.03 g ntawm ethylene oxide, thiab do cov tshuaj tiv thaiv ntawm 0-5 degree rau 2 teev. Tom qab cov tshuaj tiv thaiv, 50 mL dej tau ntxiv los kho cov pH rau 7-8, thiab cov supernatant tau tso rau ntawm chav tsev kub thaum hmo ntuj. Tom qab cov precipitate accumulated, nws tau sau los ntawm centrifugation, ntxuav ib zaug, thiab ces qhuav nyob rau hauv ib tug desiccator kom tau ib tug dawb khoom khoom nyob rau hauv lub nqus tsev vacuum.
1.2. Kev kho ammonia:
Sib tov 1 g ntawm cov khoom dawb uas tau txais saum toj no nrog 5 mL ntawm titanium tetrachloride tov thiab do nyob rau hauv chav tsev kub, ntxiv 0.5 mL ntawm ammonia dej kom txog rau thaum cov tshuaj tiv thaiv tig tsaus liab, thiab mus txuas ntxiv stirring ntawm chav tsev kub rau 2. teev. Tom qab ntawd nws tau ntxuav ob zaug nrog dej thiab qhuav hauv ib lub desiccator kom tau cov khoom xim av luster nyob rau hauv lub tshuab nqus tsev.
1.3. Alkylation tshuaj tiv thaiv:
Cov khoom uas muaj xim av luster tau los saum toj no yog tov nrog 20 mL ntawm tricyclohexylmethanol, thiab nplawm nyob rau hauv chav tsev kub, 50 mg ntawm sulfuric acid catalyst ntxiv, thiab stirring cov tshuaj tiv thaiv txuas ntxiv rau 2 teev. Tom qab cov tshuaj tiv thaiv, ntxiv ib qho dej kom tsim nyog rau dilution, kho pH rau 7-8 nrog sodium hydroxide, thiab tom qab ntawd rho tawm nrog n-butanol rau 3 zaug. Cov theem ntawm cov organic tau sau, qhuav dhau anhydrous sodium chloride, thiab cov kuab tshuaj raug tshem tawm kom tau cov khoom ua kua xim av.
1.4. Crystallization sib cais:
Cov khoom ua kua yog muab tso rau ntawm qhov kub thiab txias (0} degree) thaum hmo ntuj, thiab cov khoom siv dawb crystallizes nyob rau hauv cov xwm txheej no. Cov muaju tau ntxuav ib zaug ntawm lub lim, qhuav hauv lub tshuab desiccator, thiab lub hom phiaj khoom DCP tau txais nyob rau hauv lub tshuab nqus tsev.
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Cov tshuaj tiv thaiv mechanism ntawm DCP npaj los ntawm epoxidation cov tshuaj tiv thaiv yog raws li nram no:
Ua ntej, cov tshuaj tiv thaiv epoxidation ntawm ethylene oxide nrog triacone tsim cov khoom epoxidized. Tom qab ntawd, nyob rau hauv qhov kev txiav txim ntawm titanium tetrachloride tov thiab ammonia, cov khoom epoxidized yog lub cev qhuav dej thiab chlorinated. Thaum kawg, cov khoom tau raug alkylated nrog cawv kom tau cov khoom lag luam DCP.
Hauv kev xaus, txoj kev tshuaj tiv thaiv epoxidation yog ib txoj hauv kev zoo thiab yooj yim rau kev npaj DCP. Txawm li cas los xij, hauv kev sim ua haujlwm, yuav tsum tau them nyiaj rau cov kev ua haujlwm tshwj xeeb, kom tsis txhob muaj cov pa roj carbon monoxide thiab khaus khaus, thiab ua kom muaj kev nyab xeeb thaum lub sijhawm sim.
2. Alkylation tshuaj tiv thaiv txoj kev:
Alkylation cov tshuaj tiv thaiv kuj yog ib txoj hauv kev tseem ceeb rau kev npaj DCP. Txoj kev no feem ntau siv phosphorus tetrachloride thiab tricyclohexylmethanol ua raw cov ntaub ntawv, nyob rau hauv tricyclohexylmethanol yog ntxiv ntau tshaj. Nyob rau hauv cov tshuaj tiv thaiv, phosphorus tetrachloride thawj reacts nrog tricyclohexylmethanol, thiab ces reacts nrog tricyclohexylmethanol nyob rau hauv lub xub ntiag ntawm ib tug nruab nrab ntawm tricyclohexylmethyl phosphite thaum kawg tau ib tug DCP khoom.
Kev sim cov kauj ruam:
2.1. Kev sib xyaw ntawm cov tshuaj alkylating tus neeg sawv cev thiab cov tshuaj reactant:
Dissolve 30 g ntawm tricyclohexyl phosphoric acid hydrogen oxide nyob rau hauv 100 mL ntawm ether, ntxiv 20 mL ntawm ethylene oxide, thiab muab tso rau hauv chav tsev kub rau 12 teev kom hnov mob. Ntawm no, cov khoom yog dimethyl tricyclohexyl epoxyphosphate.
Ntxiv cov hmoov lead tetrachloride aqueous tov maj mam rau tricyclohexyl epoxy dimethyl phosphate, neutralize rau pH =5, tom qab ntawd ntxiv chloroform, thiab cov reactants tuaj yeem sib cais maj mam nrog kev pab ntawm qhuav sodium chloride. Cov theem ntawm cov organic yog sau, ntxuav ib zaug thiab distilled kom tau ib tug dawb pob tshab kua khoom.
2.2. Kev kho ammonia:
Cov khoom ua kua dawb pob tshab uas tau txais saum toj no yog tov nrog 10 mL ntawm ammonia dej, nplawm hauv chav sov, thiab ua rau 2 teev. Tom qab cov tshuaj tiv thaiv, nws tau ntxuav ob zaug nrog dej thiab qhuav los ntawm centrifugation kom tau ib yam khoom nrog lub teeb daj luster.
2.3. Alkaline hydrolysis cov tshuaj tiv thaiv:
Sib tov cov khoom uas tau hais los saum toj no nrog lub teeb daj daj nrog 50 mL ntawm n-hexane, ntxiv 10 mL ntawm 2.5mol / L sodium hydroxide tov, thiab hnov mob ntawm 65 degrees Celsius rau 1 teev. Tom qab cov tshuaj tiv thaiv, faib cov khoom mus rau hauv cov organic theem thiab aqueous theem.
2.4. Sedimentation thiab filtration:
Cov txheej txheem organic tau sau tseg thiab cov khoom dawb tau ua los ntawm kev pab los ntawm cov khoom siv desiccant, tom qab ntawd lim thiab ntxuav ib zaug kom tau txais cov khoom siv hmoov dawb.
2.5. Rov qab los ntawm distillation:
Cov khoom siv hmoov dawb tau txais los saum toj no yog muab tso rau hauv lub tshuab distillation rau distillation, thiab cov khoom lag luam phiaj DCP tau rov qab los. Nco ntsoov tias thaum lub sij hawm distillation, qhov kub thiab txias yuav tsum tau tswj thiab lub siab txo kom tau high-purity DCP cov khoom.
Cov tshuaj tiv thaiv mechanism ntawm kev sib txuas ntawm DCP los ntawm alkylation cov tshuaj tiv thaiv yog raws li nram no:
Ua ntej, tus neeg sawv cev alkylating ethylene oxide tau txais lub nplhaib qhib cov tshuaj tiv thaiv nrog tricyclohexyl oxidized photohydrogen phosphate los tsim cov khoom epoxidized tricyclohexyl dimethyl epoxyphosphate. Tom qab ntawd, qhov sib ntxiv ntawm cov dej ammonia yuav txo cov reactant los tsim tricyclohexyl epoxy phosphate diacetate.
Thaum kawg, los ntawm alkaline hydrolysis cov tshuaj tiv thaiv ntawm sodium hydroxide, tricyclohexyl epoxy phosphate diacetate thiab n-hexane tau txais cawv alkylation cov tshuaj tiv thaiv los tsim cov khoom lag luam DCP. Cov tshuaj tiv thaiv mechanism yog qhov tseeb, cov txheej txheem tshuaj tiv thaiv yog qhov yooj yim thiab yooj yim, thiab tsim nyog rau cov kev xav tau ntawm ntau lub chaw soj nstuam thiab kev tsim khoom lag luam.
Hauv kev xaus, txoj kev tshuaj tiv thaiv alkylation yog ib txoj hauv kev zoo thiab yooj yim rau kev npaj DCP. Thaum lub sijhawm ua haujlwm sim, yuav tsum tau them nyiaj rau cov kev ua haujlwm tshwj xeeb, kom tsis txhob muaj cov pa roj carbon monoxide thiab khaus khaus, thiab ua kom muaj kev nyab xeeb thaum lub sijhawm sim.
3. Dehydrochlorination tshuaj tiv thaiv txoj kev:
Txoj kev dehydrochlorination cov tshuaj tiv thaiv kuj yog ib txoj hauv kev tseem ceeb rau kev npaj DCP. Txoj kev siv tricyclohexyl ketone ua cov khoom siv raw thiab siv phosphorus trichloride ua tus neeg sawv cev dehydrogenating los ua cov tshuaj tiv thaiv. Hauv cov tshuaj tiv thaiv, tricyclohexyl ketone thiab phosphorus trichloride tau txais cov tshuaj tiv thaiv dehydrochlorination los tsim cov tricyclohexyl methyl phosphite intermediate, thiab tom qab ntawd hnov mob nrog ntau tshaj tricyclohexyl methanol los tsim cov khoom DCP.
Kev sim cov kauj ruam:
(1) Pretreatment Dicyclohexylchlorophosphine
Muab Dicyclohexylchlorophosphine tso rau hauv lub desiccator thiab qhuav ntawm 80 degree kom txog thaum qhov hnyav tas li.
(2) Dissolving Dicyclohexylchlorophosphine:
Muab cov Dicyclohexylchlorophosphine pretreated rau hauv carbon tetrachloride, thiab sib nqus sib nqus kom txog thaum yaj tag.
(3) Ntxiv trichloroacetic acid:
Ntxiv trichloroacetic acid rau cov tshuaj saum toj no ntawm molar piv ntawm 1: 2, thiab do cov tshuaj tiv thaiv nyob rau hauv magnetic quab yuam rau 1 h.
(4) Ntxiv ferrous chloride:
Ntxiv ferrous chloride rau cov tshuaj tiv thaiv saum toj no sib xyaw ntawm molar piv ntawm 1: 1.2.
(5) Ntxiv propanol:
Propanol tau ntxiv dropwise rau saum toj no cov tshuaj tiv thaiv sib tov nyob rau hauv ib tug npaum li ntawm 50 feem pua ntawm trichloroacetic acid.
(6) Cov lus teb rau 24 teev:
Nyob rau hauv ib qho chaw nitrogen, cov tshuaj tiv thaiv sib tov tau tso cai rau do hauv chav sov li 24 teev.
(7) Kev kho nag lossis daus:
Cov tshuaj tiv thaiv sib xyaw yog centrifuged nyob rau hauv ib lub centrifuge, thiab cov supernatant thiab precipitate tau sau. Lub supernatant tau muab tso rov qab rau hauv tus thawj beaker, precipitate yog ntxuav nrog kiag li ethanol, thiab centrifuged dua kom tau cov khoom ntawm DCP.
(8) Kev kho kom qhuav:
Muab cov khoom uas tau txais saum toj no rau hauv qhov cub thiab qhuav ntawm 60 degree kom txog thaum nws nce mus txog qhov hnyav tas li.
Lub dehydrochlorination cov tshuaj tiv thaiv mechanism ntawm Dicyclohexylchlorophosphine yog raws li nram no:
Ua ntej, Dicyclohexylchlorophosphine thiab trichloroacetic acid hnov mob hauv carbon tetrachloride los tsim Dicyclohexylphosphoryl choroformate thiab chloride ions.
Tom qab ntawd, nyob rau hauv cov xwm txheej ntawm kev ntxiv ferrous chloride, Dicyclohexylphosphoryl chloride thiab FeCl2 yog tsim.
Tom qab ntawd, nyob rau hauv cov xwm txheej ntawm kev ntxiv propanol, Dicyclohexylphosphoryl chloride thiab propanol react los tsim Dicyclohexylphosphine oxide thiab HCl.
Thaum kawg, hnov mob hauv qhov chaw qhuav nitrogen rau 24 teev los tsim Dicyclohexylchlorophosphine.
Hauv kev xaus, cov tshuaj tiv thaiv dehydrochlorination yog ib txoj hauv kev zoo thiab yooj yim rau kev npaj ntawm Dicyclohexylchlorophosphine. Thaum lub sijhawm ua haujlwm sim, yuav tsum tau them nyiaj rau cov kev ua haujlwm tshwj xeeb, kom tsis txhob muaj cov pa roj carbon monoxide thiab khaus khaus, thiab ua kom muaj kev nyab xeeb thaum lub sijhawm sim.
4. Pyrophosphorylation tshuaj tiv thaiv txoj kev:
Txoj kev pyrophosphorylation cov tshuaj tiv thaiv kuj yog ib txoj hauv kev tseem ceeb rau kev npaj DCP. Cov txheej txheem siv alkyl phosphorus trioxide ua raw khoom, reacts nws nrog tricyclohexylmethanol, thiab tom qab ntawd ua cov kauj ruam xws li cua sov thiab lub cev qhuav dej kom thaum kawg tau DCP.
Kev sim txheej txheem
(1) Pretreatment ntawm Dicyclohexylamine:
Muab Dicyclohexylamine tso rau hauv lub desiccator thiab qhuav ntawm 80 degree kom qhov hnyav tas li.
(2) Npaj cov tshuaj tiv thaiv sib tov:
Lub pretreated Dicyclohexylamine tau ntxiv rau qhuav DMF, thiab nplawm nyob rau hauv magnetic quab yuam kom tag nrho yaj nws, ces TEP tau ntxiv, thiab cov tshuaj tiv thaiv yog txuas ntxiv mus do hauv magnetic quab yuam rau 1 h.
(3) Phosgene kho:
Siv phosgene los ua kom tsis muaj HCl tsim nyob rau hauv cov kauj ruam dhau los thiab hloov mus rau hauv Dicyclohexylchlorophosphine oxide. Cov txheej txheem tshuaj tiv thaiv yuav tsum tau nqa tawm ntawm qhov kub thiab txias kom tsis txhob muaj cov pa phem. Phosgene Ntxiv cov sib tov saum toj no ntawm molar piv ntawm 1: 2, thiab lub sijhawm tshuaj tiv thaiv yog li 30min.
(4) Kev kho nag lossis daus:
Muab cov tshuaj tiv thaiv sib xyaw rau hauv benzene lossis carbon tetrachloride, tshem tawm thiab tshem tawm cov hygroscopic tus neeg saib xyuas, tom qab ntawd lim kom tau cov precipitate, thiab muab tso rau hauv qhov cub kom qhuav kom qhov hnyav tas li.
Lub pyrophosphate cov tshuaj tiv thaiv mechanism ntawm Dicyclohexylchlorophosphine yog raws li nram no:
Ua ntej, triethyl pyrophosphate thiab Dicyclohexylamine react hauv DMF los tsim Dicyclohexylchlorophosphine oxide thiab triethanol hydroxide.
Tom ntej no, siv phosgene los nruab nrab HCl nyob rau hauv cov sib tov saum toj no thiab hloov mus rau hauv Dicyclohexylchlorophosphine oxide.
Thaum kawg, Dicyclohexylchlorophosphine tau txais los ntawm cov kuab tshuaj rho tawm thiab kev kho nag lossis daus.
Hauv kev xaus, txoj kev tshuaj tiv thaiv pyrophosphorylation yog ib txoj hauv kev zoo thiab yooj yim rau kev npaj ntawm Dicyclohexylchlorophosphine. Thaum lub sijhawm ua haujlwm sim, yuav tsum tau them nyiaj rau cov kev ua haujlwm tshwj xeeb, kom tsis txhob muaj cov pa phem thiab cov kua dej, thiab ua kom muaj kev nyab xeeb thaum lub sijhawm sim. Nyob rau tib lub sijhawm, nws yog ib qho tsim nyog yuav tsum tau them sai sai rau qhov molar piv ntawm cov reactants thiab kev txawj ntse ntawm cov tshuaj tiv thaiv kab mob hauv qhov kev sim los xyuas kom meej qhov purity ntawm cov tshuaj tiv thaiv cov khoom.
Plaub qhov kev tawm tsam saum toj no yog txhua txoj hauv kev zoo rau kev npaj DCP, nrog rau lawv tus kheej qhov zoo thiab qhov tsis zoo. Piv txwv li, cov khoom DCP npaj los ntawm epoxidation txoj kev muaj siab purity thiab siab yield, tab sis nws yuav tsum tau siv high-zoo raw khoom thiab catalysts; thaum txoj kev pyrophosphorylation cov tshuaj tiv thaiv yuav tsum muaj qhov kub thiab txias thiab lub sij hawm tswj, txwv tsis pub nws yog qhov nyuaj kom tau txais cov khoom lag luam siab.
Hauv luv luv, cov txheej txheem saum toj no muaj lawv tus kheej cov yam ntxwv, thiab ib txoj hauv kev tsim nyog tuaj yeem xaiv rau kev npaj raws li qhov xav tau tiag tiag. Txawm li cas los xij, hauv kev siv cov tswv yim, nws tseem yuav tsum tau ua tib zoo saib xyuas kev ua haujlwm nyab xeeb thiab ua raws li cov kev cai thiab cov qauv tsim los xyuas kom muaj kev nyab xeeb thiab ruaj khov ntawm cov txheej txheem tsim khoom.