simmons-smith pratikriya

simmons-smith pratikriya ack carbonic cheletropic pratikriya haye jisamen ack organosinc carbenoid shamil hotaa haye joe ack alkien (yaa alkine) key saath pratikriya karke ack cyclopropen banaata haye. iska naam haward ensign simmons, junier key naam parr rakhaa gayaa haye. aur ronald dee. smith. yeh ack mithileen mukt mool madhyavarti kaa upayog kartaa haye joe ack saath alkien key donon carbons koo diyaa jaataa haye, isaliye dohare bandhan kaa vinyas utpaad mein sanrakshit haye aur pratikriya vishisht haye.
udaaharan.
iss prakaar, cyclohexin, diodomethane, aur ack jastaa-tamba jodaa (iodomethyllsinc iodide, iodide key roop mein) norkaren (saikil [4.1] hepten) kii upaj detaa haye.
cyclopropanation key anya tarikon kii tulanaa mein simmons-smith pratikriya koo aam taur parr pasand kiya jaataa haye, halanki diodomethane kii uchch laagat key kaaran yeh mahanga hoe sakata haye. saste vikalpon seey judey sanshodhan vikasit kiye gaye hain, jaise kii dibromomethane yaa diazomethane aur jink iodide. diethylsinc key liye jastaa-tambe key jode kaa adaan-pradaan karate hue, furukawa sanshodhan kaa upayog karke pranali kii pratikriyashilta koo bhee badhaaya jaa sakata haye.
simmons-smith pratikriya aam taur parr steric prabhaavon key adheen hoti haye, aur iss prakaar cyclopropanation aamtaur parr cumm baadhit chehare parr hotaa haye. haalaanki, jaba ack hydroxy pratisthaapan dohare bandhan key nikatata mein substrate mein maujood hotaa haye, tou jastaa hydroxy pratisthaapan key saath nirdeshank kartaa haye, joe hydroxyl samooh koo cyclopropanation "sis" kaa nirdeshan kartaa haye (joe dohare bandhan key steric roop seey sabse sulabh chehare key cyclopropanation key anuroop naheen hoe sakata haye): iss pratikriya kaa ack samvaadaatmak 3 dee model chematube 3 dee parr dekhaa jaa sakata haye.
asmamit simmons-smith pratikriya.
halanki diazo yaugikon parr adharit asmamit cyclopropanation vidhiyaan (dekhein bisoxazolin ligand) 1966 seey maujood hain, asmamit simmons-smith pratikriya 1992 mein diethylosinc, diodomethane aur dichloromethane mein ack kieral dysulphonamide key saath sinamil alcohol kii pratikriya key saath pesh kii gaee theeh
hydroxyl samooh jastaa key liye ack lunger key roop mein seva karane kii ack poorv shart haye. isi tarah kii pratikriya kaa ack samvaadaatmak 3dee model yahaan dekhaa jaa sakata haye (jaava aavashyak). iss pratikriya key ack anya sanskaran mein ligand selen parr adharit haye aur levis acid dibble jodaa jaataa haih
daira aur seemaaen.
achiral alkien.
simmons-smith pratikriya kaa upayog binaa kissy jatilata key saral alkien koo cyclopropanet karane key liye kiya jaa sakata haye. 1, 2-dichloroethane mein haalaanki aur ch2i2 kaa upayog karate hue, gair-karyatmak akiral alkien sabse achche cyclopropanated hain, joe furukawa sanshodhan (neeche dekhein) key saath hain. electron daan karane vaale samoohon dwara sakriya alkien kaa cyclopropanation teji seey aur aasaani seey aage badhata haye. udaaharan key liye, trimythylacyloxy-pratisthaapit olephine jaise inol eather kaa upayog aksar uchch upaj praapt karane key kaaran kiya jaataa haye.
halides kii electron-nikasi prakriti key bavjood, kaee vinail halides bhee aasaani seey cyclopropanated hotey hain, jisase floro-, bromo-aur iodo-pratisthaapit cyclopropen praapt hotey hain.
aine"-pratisthaapit alkien key cyclopropanation koo ack pratispardhi maarg key roop mein "aine"-alkilation dwara jatil banaa diyaa jaataa haye. nitrogen mein ack surakshaatmak samooh jodkar ise darkinar kiya jaa sakata haye, haalaanki electron-nikasi samoohon key judane seey alkien kii nucleophilicity cumm hoe jaati haye, jisase upaj cumm hoe jaati haye. inn mamalon mein ch2i2 key sthaan parr chfi2 jaise atyadhik electrophilic abhikarmakon kaa upayog upaj badhaane key liye dikhaaya gayaa haye.
polyn.
olephine parr ack nirdeshit samooh kii upasthiti key binaa, bahut cumm chemosalactivity dekhi jaati haye. haalaanki, ack alkien joe kissy bhee anya kii tulanaa mein kaafee adhik nucleophilic haye, atyadhik pasand kiya jaayega. udaaharan key liye, inol eather parr cyclopropanation atyadhik chayanaatmak roop seey hotaa haye.
karyatmak samooh sangatata.
simmons-smith pratikriya kaa ack mahatvapurna pahalu joe isake vyaapak upayog mein yogdan detaa haye, vaha haye kaee karyatmak samoohon kii upasthiti mein upayog kii jaane kii isaki kshamata. anya key beach, heloclesinc-madhyasth pratikriya alkine, alcohol, eather, aldehyde, keaton, carboxylic acid aur vyutpann, carbonate, sulphone, sulphonate, sylane aur stannon key saath sangat haye. haalaanki, kuchh dushprabhaav aamtaur parr dekhe jaate hain.
adhikansh dushprabhaav upotpaad, zni2 kii levis-amlata key kaaran hotey hain. acid-samvedansheel utpaadon kaa utpaadan karane vaali pratikriyaon mein, atirikt et2zn koo zni2 koo hataane key liye jodaa jaa sakata haye joe cumm amleeya etzni banaata haye. pratikriya koo pyridine key saath bhee bujhaa diyaa jaa sakata haye, joe joe aur atirikt abhikarmakon koo hataa dega.
jink carbenoids kii electrophilicity key kaaran simmons-smith pratikriya mein bhee heteroatum kaa methylation dekhaa jaataa haye. udaaharan key liye, lambe samay taka pratikriya key liye atirikt abhikarmak kaa upayog lagbhag hamesha alcohol key methylation kii or leey jaataa haye. isake alawa, haalaanki aur ch2i2 sulfur yelides utpann karane key liye elilic theoether key saath pratikriya karate hain, joe baad mein 2,3-sigmetropic punarvyavastha seey gujar sakate hain, aur ack hii anu mein ack alkien koo cyclopropanet naheen karenge jaba taka kii atirikt simmons-smith abhikarmak kaa upayog naheen kiya jaataa haye.
sanshodhan.
jabaki simmons-smith pratikriya kii aksar isake mool roop mein charcha kii jaati haye, jastaa utprerak aur atirikt carbon donon mein kaee sanshodhan prastaavit kiye gaye hain.
furukawa sanshodhan.
furukawa sanshodhan mein jastaa-tamba jode koo dialkill jastaa key saath badalana shamil haye, jisamen seey sabse sakriya haalaanki paaya gayaa thaa. vinayal eather jaise cashionic roop seey polymerised olephine koo unake sambandhit cyclopropen mein badalane key tareeke key roop mein 1968 mein sanshodhan kaa prastaav rakhaa gayaa thaa. yeh carbohydrate key cyclopropanation key liye vishesh roop seey upayogi paaya gayaa haye, joe anya tarikon kii tulanaa mein kaheen adhik prajanan yogya haye. aparivartit pratikriya kii tarah, furukawa-sanshodhit pratikriya roodhivaadi hoti haye, aur aksar aparivartit pratikriya kii tulanaa mein bahut tej hoti haye. haalaanki, haalaanki abhikarmak pyrophoric haye, aur iss tarah ise savdhani seey sambhala jaanaa chaahiye.
sigaret sanshodhan.
sigaret sanshodhan aam taur parr simmons-smith pratikriya mein paae jaane vaale ch2i2 koo aeye maarg mein phenyldiazomethane jaise arildiazo yaugikon key saath badal detaa haye. jastaa halloid kii stoichiometric matra key saath upchaar karane parr, oopar charcha kiye gaye carbenoid key samaan ack organosinc yaugik kaa utpaadan hotaa haye. yeh lagbhag sabhi alkien aur alkine key saath pratikriya curr sakata haye, jisamen styrene aur alcohol shamil hain. yeh vishesh roop seey upayogi haye, kyonki aparivartit simmons-smith koo alcohol koo deprotonate karane key liye jaanaa jaataa haye. durbhagya seey, jaisa kii maarg bee mein dikhaaya gayaa haye kii madhyavarti bhee praarambhik diazo yaugik key saath pratikriya curr sakata haye, jisase "sis"-yaa "trance"-1,2-diaphenalethane milata haye. isake atirikt, madhyavarti iodophenylmethane kaa utpaadan karane key liye alcohol key saath pratikriya curr sakata haye, joe aage rockf kaa utpaadan karane key liye ack aiss. aine. 2 pratikriya seey gujar sakata haye, jaisa kii maarg see mein hotaa haye.
gair-jastaa abhikarmak.
halanki aamtaur parr upayog naheen kiya jaataa haye, simmons-smith abhikarmak joe jastaa key samaan pratikriyaasheel guna pradarshit karate hain, unhein ch2ix kii upasthiti mein aluminium aur samariyam yaugikon seey taiyar kiya gayaa haye. inn abhikarmakon key upayog key saath, elilic alcohol aur alag-alag olephine koo ack-dusare kii upasthiti mein chayanaatmak roop seey cyclopropanet kiya jaa sakata haye. thuff mein iodo-yaa chloro-methylasamerium iodide, sambhavatah hydroxyl samooh mein chillation dwara nirdeshit, elilic alcohol koo chayanaatmak roop seey cyclopropanet karane key liye ack utkrisht abhikarmak haye. isake vipareet, ch2cl2 mein dialkill (iodomethyl) aluminium abhikarmakon kaa upayog chuninda roop seey prithak olephine koo cyclopropanet karega. inn abhikarmakon kii vishishtata cyclopropen koo polly-asantript pranaliyon mein rakhane kii anumati detee haye joe jastaa-adharit abhikarmak poori tarah seey aur anirdisht roop seey cyclopropenet karenge. udaaharan key liye, "i" -bu3al 6 sthiti mein cyclopropanial koo giraniel mein badal dega, jabaki sm/hg, 2 sthiti mein cyclopropenet karega, jaisa kii neeche dikhaaya gayaa haye. haalaanki, donon pratikriyaon key liye praarambhik dhaatu yaugik kii lagbhag stoichiometric matra kii aavashyakta hoti haye, aur atyadhik vishaakt aich. jee. see. ell. 2 key saath aiss. aim./aich. jee. koo sakriya kiya jaanaa chaahiye.
sanshleshan mein upayog karein.
simmons-smith pratikriya key adhikansh aadhunik anuprayog furukawa sanshodhan kaa upayog karate hain. vishesh roop seey praasangik aur vishvasaniya anuprayog neeche soochibaddh hain.
γ-keto ester banaane key liye sammilit karein.
ack furukawa-sanshodhit simmons-smith utpann cyclopropen madhyavarti β-keto ester seey γ-keto ester key sanshleshan mein banata haye. simmons-smith abhikarmak pahale carbonyl samooh seey aur baad mein chhadm-anol key α-carbon seey judataa haye joe pahali pratikriya banati haye. yeh doosara abhikarmak cyclopropyl madhyavarti banaata haye joe teji seey utpaad mein toot jaataa haye.
alenamides seey emido-spiro [2.2] penten kaa gathan.
ack furukawa-sanshodhit simmons-smith pratikriya cyclopropenet ack alenamide mein donon dohare bandhanon koo emido-spiro [2.2] cyclopentance banaane key liye banaata haye, jisamen dou cyclopropyl rings hotey hain joe ack carbon koo saajha karate hain. monocyclopropanation kaa utpaad bhee banata haye.
praakritik utpaad sanshleshan.
praakritik utpaadon key sanshleshan mein cyclopropanation pratikriyaon kii sameeksha kii gaee haye. β-lactamase avarodhak silastatin praakritik utpaadon key sanshleshan mein simmons-smith pratikriyashilta kaa ack nirdeshaatmak udaaharan pradaan kartaa haye. praarambhik samagri parr ack elil pratisthaapan simmons-smith cyclopropanated haye, aur carboxylic acid koo baad mein ozonolysis key madhyam seey poorvavarti banaane key liye sanrakshit kiya jaataa haye.
davaaon kaa sanshleshan.
simmons-smith pratikriya kaa upayog gsk1360707f aur ropanicant key sanshleshan mein kiya jaataa haye.

