1, 4-Phenylenebisboronic acidyog ib qho organoboron compound, uas feem ntau yog siv los ua ligand, catalyst thiab nruab nrab hauv cov organic synthesis. Cov hauv qab no yog ob peb txoj kev siv hluavtaws:
1. Reaction synthesis ntawm catechol thiab boric acid:
Catechol thiab boric acid tsim 1,4-Phenylenebisboronic acid los ntawm kev hloov cov tshuaj tiv thaiv nyob rau hauv alkaline tej yam kev mob. Cov tshuaj tiv thaiv feem ntau yog ua tiav thaum molar piv ntawm cov tshuaj reactants yog 2: 3, thiab siv cov xwm txheej yooj yim xws li sodium hydroxide, sodium carbonate lossis triethylamine. Qhov sib npaug ntawm cov tshuaj tiv thaiv ib nrab yog raws li hauv qab no:
2C6H4(OH)2plus 3 H3BO36 NaOH → C6H4(OH)2B (OH)2C6H4plus6 ua2BO3lwm 9h2O
1,4-Phenylenebisboronic acid yog ib qho organic molecule uas muaj ob pawg boronic acid, uas tuaj yeem siv los ua cov organic molecules uas muaj benzene rings. Feem ntau, 1,4-Phenylenebisboronic acid tuaj yeem ua ke los ntawm kev ua haujlwm catechol thiab boric acid.
Cov kauj ruam tshuaj tiv thaiv:
1.1. Ua ntej, sib tov thiab do boric acid tetrahydroboron dioxide (B2O3•H2O) thiab catechol, thiab ntxiv qhov tsim nyog ntawm sodium carbonate (Na2CO3) los kho tus nqi pH ntawm cov tshuaj tiv thaiv;
1.2. Hauv qhov sib tov, ntxiv palladium chloride (PdCl2) thiab dej-soluble phosphine ligand. Feem ntau siv phosphine ligand yog triphenylphosphine (PPh3) los yog tri (p-toluenesulfonyl) phosphine (PTSA). Tom qab ntxiv cov catalysts hauv qhov sib tov, cov tshuaj tiv thaiv condensation ntawm catechol thiab boric acid tuaj yeem txhawb nqa, thiab kev ua kom lub zog ntawm cov tshuaj tiv thaiv tuaj yeem txo;
1.3. Cov tshuaj tiv thaiv sib xyaw yuav tsum tau ua ntawm qhov kub thiab txias, feem ntau ntawm 60 degree thiab 80 degree, thiab lub sijhawm tshuaj tiv thaiv yog 4 teev txog 12 teev. Cov txheej txheem tshuaj tiv thaiv qee zaum ua raws li qhov chaw tsis muaj zog;
1.4. Tom qab cov tshuaj tiv thaiv, cov tshuaj tiv thaiv cov khoom yog kho nrog dilute acid rau precipitate 1, 4-Phenylenebisboronic acid. Cov khoom siv tshuaj tiv thaiv kuj yuav tsum tau lim thiab qhuav kom tau txais cov khoom siv crystallized;
Hauv kev xaus, cov tshuaj tiv thaiv ntawm catechol thiab boric acid rau synthesize 1, 4-Phenylenebisboronic acid suav nrog ntxiv catechol thiab boric acid rau hauv cov catalyst sib tov, kho tus nqi pH thiab nqa tawm cov tshuaj tiv thaiv condensation ntawm qhov tsim nyog kub, tom qab cov tshuaj tiv thaiv yog ua tiav, dilute acid yog siv los ua haujlwm, pom thiab ziab tawm cov khoom siv crystalline.
2. Reaction synthesis ntawm aryl azobenzene thiab boronic acid:
Aryl azobenzene reacts nrog sodium nitrite los tsim aryl diazonium compound, thiab ntxiv reacts nrog boric acid nyob rau hauv alkaline tej yam kev mob kom tau 1,4-Phenylenebisboronic acid. Txoj kev siv cov alkaline nruab nrab xws li sodium carbonate, sodium hydroxide lossis triethylamine, thiab feem ntau yog ua tiav thaum molar ratio ntawm cov reactants yog 1: 2. Qhov sib npaug ntawm cov tshuaj tiv thaiv ib nrab yog raws li hauv qab no:
C6H4(N2)2plus 2 H3BO32 NaOH → C6H4(N2)B (OH)2C6H4plus 2 NaNO2plus 2 H2O
Cov theem synthesis yog raws li nram no:
Kauj Ruam 1: Synthesis ntawm Phenylazobenzene:
Phenylazobenzene tuaj yeem npaj los ntawm azo coupling cov tshuaj tiv thaiv. Ua ntej, nitrosated aniline yog npaj los ntawm dissolving aniline hauv HCl acid thiab reacting nrog sodium nitrite. Tom ntej no, cov nitrosated aniline hloov mus rau hauv nruab nrab ntawm azobenzene, thiab cov khoom Phenylazobenzene tau los ntawm kev txo cov tshuaj tiv thaiv.
Kauj Ruam 2: Cov tshuaj tiv thaiv boric acid thiab Phenylazobenzene:
Ntxiv boric acid thiab Phenylazobenzene rau hauv cov tshuaj tiv thaiv cov hlab ntsha, sib tov thiab ua kom sov maj mam mus txog 80 degree, thiab txuas ntxiv cua sov kom txog thaum cov tshuaj tiv thaiv tiav tom qab cov reactants tau ua tiav. Tom qab cov tshuaj tiv thaiv dhau lawm, 1,4-Phenylenebisboronic acid yog tau los ntawm kev txias thiab lim. Lub luag haujlwm tseem ceeb ntawm cov tshuaj tiv thaiv yog tias boric acid reacts nrog Phenylazobenzene los tsim ib qho nruab nrab, thiab tom qab ntawd qhov nruab nrab hloov mus thiab tshem tawm los tsim 1,4-Phenylenebisboronic acid.
Qhov kom zoo dua ntawm cov tshuaj tiv thaiv no yog tias cov tshuaj tiv thaiv mob me me, nws yog qhov tsim nyog rau kev sib xyaw ua ke loj, thiab nws tuaj yeem siv los tsim lwm cov organoboron tebchaw.
3. Reaction synthesis ntawm benzaldehyde thiab boric acid:
Benzaldehyde thiab boronic acid tsim 1,4-Phenylenebisboronic acid ntawm methoxylation ntev kauj ruam nyob rau hauv tej yam kev mob. Cov tshuaj tiv thaiv siv qhov nruab nrab nruab nrab xws li sodium carbonate, sodium hydroxide lossis triethylamine, thiab feem ntau yog ua tiav thaum molar ratio ntawm cov reactants yog 1: 2. Qhov sib npaug ntawm cov tshuaj tiv thaiv ib nrab yog raws li hauv qab no:
C6H5CHO + 2H3BO3 plus 2NaOH → C6H4(BOMe)2C6H4 plus 2NaHCO3 plus 3H2O
C6H4(BOMe)2C6H4 plus HCl → C6H4(OH)2B(OH)2C6H4 plus 2MeOH
Kev sim cov kauj ruam:
Kauj Ruam 1: Synthesis ntawm benzaldehyde thiab anhydrous dimethylsulfinamide complex:
Electrostatically qhuav anhydrous dimethylsulfinamide (5.97 g) tau ntxiv rau benzaldehyde (5.0 g) thiab cov catalyst sodium hydroxide (0.73 g) ntxiv. Cov tshuaj tiv thaiv yog propelled nrog nitrogen thiab rhuab mus boiling. Tom qab reacting rau 25 feeb, nws tau lim, thiab cov filtrate yog ntxuav nrog kiag li ethanol thiab ces qhuav kom tau ib tug complex ntawm benzaldehyde thiab anhydrous dimethylsulfinamide.
Kauj Ruam 2: Cov tshuaj tiv thaiv condensation ntawm hluavtaws benzaldehyde thiab boric acid:
Benzaldehyde thiab boric acid tau ntxiv rau hauv methylene chloride uas muaj me me ntawm sodium hydroxide hauv molar ratio ntawm 1: 1. Tom qab nplawm thiab sib tov nrog ib lub khob pas nrig, cua sov rau 80 degree nyob rau hauv ib tug kub kub da dej rau react rau 6 teev. Tom qab cov tshuaj tiv thaiv, ntxuav nrog dej, thiab tom qab ntawd mloog zoo rau kev daws nrog lub evaporator teb. Nyob rau tib lub sijhawm, chloroform (50 mL) tau ntxiv rau yaj cov tshuaj thiab cov tshuaj saturated sodium chloride tau ntxiv, thiab chloroform raug tshem tawm nrog lub evaporator teb. Ua li no, peb tau txais 1,4-Phenylenebisboronic acid peb xav tau.
Kauj Ruam 3: Sib cais ntawm chloroform extract:
Cov khoom tau muab rho tawm los ntawm cov tshuaj tiv thaiv nrog chloroform, tom qab ntawd lim thiab dhau los ntawm dej, thiab cov lim dej tau muab rho tawm nrog isopentane. Ob qho kev rho tawm tau muab tso ua ke thiab evaporated nyob rau hauv ib lub evaporator teb kom tau ib yam khoom.
Kauj Ruam 4: Purification thiab characterization ntawm cov khoom:
Lub resulting precipitated khoom yog ntxuav nrog methanol, soaked nyob rau hauv dej kom txog thaum pH mus txog 6-7, ces centrifuged thiab drained. Thaum kawg, cov khoom ntshiab 1,4-Phenylenebisboronic acid tau txais los ntawm cov roj distillation rotary volatile. Kev tsom xam spectrometry ntawm cov khoom los ntawm UV-Vis spectrophotometer tuaj yeem tau txais nws cov khoom siv tshuaj, xws li qhov hnyav molecular, qauv molecular, thiab lwm yam.
nyob rau hauv xaus:
Los ntawm cov kauj ruam saum toj no, peb ua tiav cov khoom sib xyaw ua ke ntawm benzaldehyde thiab boronic acid, uas yog 1, 4-Phenylenebisboronic acid. Txoj kev no yog qhov yooj yim thiab meej, yooj yim rau kev khiav lag luam, thiab cov nyhuv yog qhov zoo, thiab cov khoom huv si tuaj yeem tau txais. Nws muaj qee yam practicability thiab kev cia siab rau kev thov.
4. Reaction synthesis ntawm o-aminophenylboronic acid thiab thiosulfuric acid:
Anthranilic acid thiab thiosulfuric acid react nyob rau hauv tooj liab catalysis los tsim 1,4-Phenylenebisboronic acid. Cov tshuaj tiv thaiv feem ntau yog ua tiav thaum molar ratio ntawm reactants yog 1: 1, siv benzene ua hnyav. Qhov sib npaug ntawm cov tshuaj tiv thaiv ib nrab yog raws li hauv qab no:
C6H4(NH2)B(OH)2C6H4 plus Cu plus 1/2(S2O6)2- → C6H4(OH)2B(OH)2C6H4 plus CuSO4 plus 1/2(S2O6)2-
Cov kauj ruam yooj yim:
1. Synthesis ntawm o-diborobenzoic acid:
Ntxiv benzoic acid, boric acid thiab sulfuric acid rau hauv cov tshuaj tiv thaiv chamber, sib tov thiab do, thiab kub kom txog thaum cov tshuaj tiv thaiv tiav. Cov tshuaj tiv thaiv sib tov yog txias thiab dej ntxiv, thiab cov khoom yog natured thiab ces qhuav kom tau o-diboronic acid.
2. Taw qhia ntawm cov amino pawg:
Ntxiv o-diborobenzoic acid thiab ammonia dej rau hauv cov tshuaj tiv thaiv sib xyaw ua ke, sib tov thiab do thiab kub kom tau o-diborobenzoic acid nrog cov amino pawg.
3. Kev npaj tshuaj tiv thaiv:
Sib tov thiab do o-diborobenzwiric acid zwitterions nrog cov amino pawg thiab thiosulfuric acid, tshav kub thiab hnov mob kom tau lub hom phiaj cov khoom 1,4-Phenylenebisboronic acid o-aminophenylboronic acid thiab thiosulfuric acid.
Cov saum toj no yog cov tswv yim yooj yim thiab cov kauj ruam ntawm cov tshuaj tiv thaiv synthesis, thiab cov ntsiab lus ntawm cov kev sim tshwj xeeb thiab cov txheej txheem kev sim tuaj yeem raug xa mus rau cov ntaub ntawv cuam tshuam.
Txhawm rau ua kom tiav, muaj ntau txoj kev siv hluavtaws rau 1,4-Phenylenebisboronic acid, thiab ib txoj kev tsim nyog tuaj yeem xaiv raws li qhov xav tau sib txawv. Ntawm lawv, thawj peb txoj kev siv boric acid ua cov khoom siv raw, uas yooj yim thiab yooj yim kom tau, tab sis feem ntau yuav tsum tau siv sijhawm ntev dua thiab cov xwm txheej. Txoj kev thib plaub yuav tsum muaj tooj liab catalyst thiab siv thiosulfuric acid ua ib qho tseem ceeb raw khoom, tab sis cov tshuaj tiv thaiv yog huab cua-rhiab heev thiab yuav tsum muaj kev txawj ntse kev sim.