DE1938247C - Process for the preparation of 4,5-epoxypentene- (2) -al- (1) - Google Patents

Description

i S -. Vs-, mT. \ i> iveiiu ι-- ,. ; - ^ -'-; ; "■■; ■ - ■

■: _h ,., ". ₍ ,:, vks: ihcr- ... Lt N.tr.um ^ mpi-1 »^, -:".,;■;: _r ,:.,. _lc , i be. H, -oru: er ^ ", r'.e.li.,;: - ^ i ί", V-; .-. ^! Vi-V "! '"'" ¹ - ¹ " ¹ - ^l '·' ^{ni! L} '''new ei "e :; .- ■. *",'. ':: ' ■ .. '.', '-'! ■ -! '^ ■! t.i'io ·! -.! ! ·.! ..! :: um .: dam :! be-serc '·,:, .-

\ «. E- \ ic ;. der durcii lieix '!; ::! · - - ^ n I ·? ^ :: · ^: - ^Γ - ^α; - ^{l !:} ^ ', "' \, ^^ '' · '", ■'., "Chlorophyll. Ro * .- \: J; · -

-. ' ■ nv .-. Leakage; \,:, _r . _: . ; T - ^ akünisj-.en " ¹ ^" ₍ ^! ^. ', ^: ''^^"^ ,, Λ .'i'.5. (.'- retrachlor-2.-i.- ^:. - _: ...

s: - .: hLü ι: · fiejcnw.:;t :::: .- c-ier,:; ju γ er '. rag-. ·· ¹ ./.·- "; - ^;: ; '._? ■' · '■';" ^ ' _N -. ". ·.,. ,, - _o j _jr Tiinapii ^1. ! ·. :.: '-

Se! Isibi!: - at, 'rs;:. -it .:; ergesteüi -. J ^ .s :. ■ - ". "; Y ' ^c ~' - ■; '. """. _iC V; _{c: 1} w .- ^ licngaL ·! -: .'.-..-

Lcke-.::/CK; lu ;. d.:ü: 'ii :; die ι >> \ d.:i:.-r: r-, ι lively: - ■ ^x / '"'T"', -,,.,. ".'. ,, ι - .., _iX , -: ·: ■! -.--

-.- ■■■■ .-,., V, -, h-.Ii ₁₁₁ Ji ^ n ι · γ ^ .: τ -.-: e-

d:; rci: Hci '.-. n.üiriü mi; "',' _ΛΠ \.,, '„, V'.jk.-Km.1: 10; ..-. Lr

/v.c \

Λ.Μΐ: ιΐΰΜΐ κ. . t ^ ^ irt e.rc- hi.-i ^ K .i _-;! . icr 'I ..- ;: iil: - ^ e' use. Go to Γ Γ- · ί

crM.r.ini: ..:.;, .- ·; - durc, f:.:> n. ' _n :,. i, r -, - Uli-, V- - --m-. -enn a; e

Κ · ι :: κ ':.: · .Ν.Γ; ΐη .v ^'. End: -te: i Lo ^ - ^ -, n.ntel i ... ι \ ,, "- ^ n -, ■■ '· -v. C ^- ! -C'. Erv-endei inaii \ i'h; _lM ,, | ^l ^ dcr "^;." I! -Chc., Ic-er A! Koiv) ! c

d der Γ.πίη,!: ;; υ ι «· em \ eruti.rcn. ·., · <>v-Δ.'Μχ» ae- I ;, h-pentad.e ^ through, u uv, 4.5 -! - PoX ^ -PCiCr ₁ -, ') .. !! -!' 1 l) i _; -c -etc, ion-: ch iHvr a hrcitcil Kc.vicii.

kanr: ^. ,,, l · ..! ran, -k,

-.Mrd die '.v> d.ili

etua O to etua 2

bjsii.'e ι uiui contains three rc. '. k'u'nsbarenüjc l-i'nkMonen. U irrjra ;:: ci m ". ^ L> -. I

rämlic "the Carboinlgruppe. a Dopp ^ Püidanc 4- ef.v. ·. ' ■ · carried out up to about 20 C,

and, the () xir.ingri: ppc. You κι. ai: this, ί Tundc 1 s ii \ orte'lliaf ;. uie Oxidation of Cyclops ¹ .: egg

a fiif Jiemische Syn ';, cscn \ iel> e,; ig usable- in (ieger.wir: one-pole> merisatioiishemmeiule - - 'i-

/v%;s,ii-jnprodi:'-.t. 'te! - dnrcli / ufuliren. In this way you can

iici the \ request. C \ ci``pen! En-i 2i-o1- (4) - .. mi- (I i wün-Jnte - \ i :: ixvdad.uis side reactions. Die; -. ■ -, .-

«! ■ arc! -! f.irbstoiTs _L 'ii-, ibili \ iene Pl-iotiuixuijnJcruriL:' .on i "da '.,'iristei" .perature ': over 0 (nierKi'ar.;":.■■■; ■

<"v ^ lnjicrtadicii according to Newiss _L -ii information in tier ιι- · ''<. \ / u Polymers can lead to almost \ oil-:. ^

f '-. cmischen l.iierat.ir (see /. ii. Angew. Chcn-.ic. M. suppress. AU polv meiisavonshemmend-. · -iiiel

I ^ [! "^ 2] i, instead of the above- can use the usual. As is well known / ur iic ;: -:; :: g

fenaniiieii I iydroxyketo: is liberrasciienderweise from radik.ili ^ .h induced Pol> merisatioiien> .c: .. en-

4.5-1 poxy-penten- (2Kil- (I) obtained. 5 ^ deten Su '.' Punch / iigesctzt be: ·, example! · -.-. Ei.sc

The disabling failure / disintegration 1 Ivdrochi'ion. substituted phenols such as Oi-te:;. buivl-

imi -i. ^; -! iioxy-penien- (2) -al-i I ι is characterized by phenol or aromatic amines such as phen \ le: niimiii.

draws. ci ^{ \ man Cyclopentadiene by means of S;: i> iulett- Hydroquinone is advantageously used.

Oxygen at temperatures of about 5n bj _{s that} by the above-described oxidation of

5ii C in a against aktmische Str. '.! Ilen bcstan- J- Cyclopentadiene obtained 4.5 - !: poxy-pcnten- (2l-a! - (1)

lying organic solvent oxidized. Singlet '.- has / u about W to'.'5"" cis-conligination.

Satii.Ts! Iiff K.iiMi n; u'h known methods is see for most purposes is a higher one

zH "Accounts of Chern. Research.!. 104 [I ¹ XiH]) contoured purity not required. lür

be generated. With regard to the Uegnffes, singlet analytical / awaken, one can, however, use the product

Oxygen is on H on b e η -W es I. »Much Im- 6o by conventional methods, for example by gas

that of organic chemistry ". Hd. Ill, part 2. S. ⁽ ) 2 ') phase chromatography, purify in order to then cnt-

and ^l ). * (). referenced, wii the electronic Konligulialtenen to develop about 5 to 10 ° _{0 of} the trans isomer.

Describe ration of molecules in the singlet state and add pure 4,5-epoxy-cis-pentene- (2) -al- (l)

hen is there is also given how to get oxygen.

from the paramagnetic triplet state a dia- ⁶ 5 The 4,5-epoxy-cis-pentene- (2) -al- (1) can through

magnetic singlet state can be generated treatment with a basic isomerization

Line advantageous method is to use triplet means to 4,5-F.poxy-trans-penten- (2) -al- (T) isomeric

Oxygen (molecular oxygen) can either be in pure form. Suitable isomerizing agents are

i 938 247

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«'' ..! ^."Enpri'dii'kt Γι '. ¹ "/.!p'ri-iefie ( ^; .: ^ Eie. ^: ." Ir ·: ..- minute.' Zi 'Cl jrercinij '. Ha »pure 4 ^ ■! P. Ν. · -

livelier, ι! 'eniie J. ^. Mark k. '. R.n the x:,! C :: lpo \> - penler-. Z i-.ti-i '. > v. ic <die fo! ec;: üe: 'pK ;. Nika! ^. ν: ·

] · 'Ie-MIe ί-ci-pie' -ve ^; -e r.ataiw ^ eii '-, \ dr; e'e :, .μ ;. ί iye !! - vi ':: i; en .ιί: Γ: V] p. U ρ · -. 3ι. ν "f - ■ _ * - *" Kv:

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i ^ - '. ^; -! -. • ■! • i \ -.- pe, -i! .Ei! - (. '. I-ai-i ^! )>■.'.'■ η au ^' ,. : ii- C-J '''' iZii. nii. 4.15 (i !!. In :, .- .: "ii Ii.. '- ir., ..

\ criV-M / iTi ". '. Ink'/'.:·. ^. 'nel / en \>Ί' * ■. r> ei le · - !: · ¹ -!] ./ 5 .: and - · ep-i. Z.7n: i I., / ■ ·., M \ i. · '. ./ ^ / _i: iiv:

p>!;.: ieiei: St ₁ ItTe ₁ :. . ·. (;. i oUoleliner. L'nH.imkk'n. Ζ.4.; Ρ-ι - ^ ppn ;: Nia-Nen-peki:. !! ·! M ^ iek:!;.;! p: k τ,

'■' * '■■ frelhaue'i v.rö. l '<i \ e>; ern. serve, in: Ivson- 3 η <is ή. i I. \ ^ euere Spades at ^in: ~ ιΖ. ^ν ·. "· 1.: ■ ..

u..; ■ '>v>r; ei! - ^: er \ er \ ^ e-, d ar.g de- 4.5-! 0.ι \.-rvir.ei- ¹ O ι; a and Si 1 Z ..> 1. ~ IH | ; .7). (^ t \ Ζ · ^!.; ι ^<x; ~~ 1 ~ ^{':. ·:.}

iZi-.i ¹ - '1 ι.: U \ e. nel / iii ^ ünlte! in iiir d: e I! er - '. e'.ii " ¹ u 4 I (Z". (M ^{..: i} > ι 1'^; ί ί : <. nd 2 '> 1 ^; S.Zi. v.in Ϊ e \ ü! fl-ern be-innit-n pol ^ niereP. S'olle: ^1. he; J

d.rir. '-euruiide !. there ^! > in iie-ci \! 'ob. nvereii eejieiuiber Bei-piei Z

I -.irKioiren kMktm · MoloküKicIlcn en! -; ehen. do .55, ι ^ ,. Γ, ι.η *: _W! i 4.5-1 poNN-eis-penten-, Z, -.-.! - ι! -

e- eriia-uhcie · !. henii I ärhen the lelitixn four i ir-

! ~ ii'v_e :! / : raise. i in (ienii-eh '.on Hi s: 1: NK-! 1 (.'vei ^ peiuadien.

M, 1 κ .in; also there- - !. ν! pi> \\ - pe! ': li .-! i- (Zi-ai-i i I: "·: i Isdrochinor ,. Ί y Ru-e i'enya.le ^.; i' .icAenen:

iPii ll; .di ' _l i.'indcn ⁱ ..i ^! e: i > ■ , iiK'eiisiercn. uil Pj.ra.M-li. · Methanol and i .4! Ik π · Öl ui; rde in the <iv. By-piei

ner / a-leHen. the f: ^r c'ie p'iarnia.'Ciiii ~ ci i: id>: - tne 40 re ^ ehnehenen V. ei-. under \ inheriting un; j one

'..in i.rL', Lre - e -, ind. ! ine -λ pus X'er- ^ enr;.: ^ -πΊ> '.:' i ..- 'i-' Hlli-Watl-Queck-.iiberdaii'pfianipe photcn'X) .lemer '

!.he. ie-ie '::! there. ild-, 4.5-! now -ρ. ·: Ηι.π-ι Z i-.t! -:!) The Sauer-toffnaiime betrui 'ZZ 1 pr ·.' MiitiiL.

/ ■■; halogenate, e.ie hdouenietUii i'rodiiku: / u ) c ^ \ c hour '.Uu ₁ : -. ¹ a / usat / hetie Menye μή ^λ Π ί;

Ir'.druh -icren and the I i \ (. Lr'.i | \> t; npr '.. dukte im! Phos- (\ clopemadien .liee ^ even. In-ge-anit were / u-a! / -

piii'i ^ ä'.ire.ierisiite'i / u k- · d.-p-ieren. to Sel'adupy- 43 borrowed .v ^; ll; ! 5NU ¹ Il (\ e! Op; iitadier, / UüeecKr. \ Ae '

bekanipfunyt.mitte '! ler / Lislelleii. About 7 hours were IZl) I oxygen \ e: biaueh :.

!) ;! ■ - 4.si pow-ncnten-lZt-al-t 1 1 i- ^; ν.-iteriiin al- 1); i>Re.iklior.-i'enii-eli became as in the example! a ::: '-

/ wiseiieiiprodukt in the Uiech-tofT- and (.ieschni.ii.k- eearheite !. Mn ₁ received 2XIi ü a- product, i.e. :--

fabric industry \ erv.endlvir. Fs can neisp.ie ingenious ^ iiasehroni.ili ^ iraplMscher AnaKse / u 77 ",,

i.ireh reduction in pentadienal. we'ehcs a smelling;, o from 4.5-1 pii \\ - ei -, - penten- (Z) -al-l 1 I. / Ι 'ίι ¹ ",, from

step! ' is. be transferred. 4.5 - i pov - p ^ nie: - 4.5-I ^: .po \\ -; rar.s-penten- (Zl-al- (1) *. 1 r i ■ - / u Ml ¹ ,, aü-

l2) -a! -l i 1 can, for example, also / ur S \ inl'.e-e .on liiehl identified by-products of n / usarinienye-

neeatlieii- (Z.4) acid; uhyl ester. an important constellation was.

ponente ties hirnenaronia.s (see J. Kind Seienec. Z9. Example 3

yd [IVM]). to be donated. This thesis can be, _ä , _{lcrstdhini,, on 4} . _3. [. _lrans " _{n! cI1} . _(: ,. _al ., _M

by U iiliy-Reaklion \ on n-l le \ yl-tripiien> l-phos- - -

phoniumbroiiiid with 4.5-i; povv-tran: .- penten-iZ) -ai-i I) I in demisch \ <η (V. ο C \ clopent; idien. II Metha-

/ U l, 2-r ^; poxy-Lindee; idien- (j, 5). subsequent period- nn !. 250 ml P \ ridm, 2 1 Ücn / ol. i) .5 g rose llengale

acid oxydalion / 11 DcaiJicii- (2.4) -; il-t i) and O \ y- and 3 g ί lydnicliiiion was in the example 2

d: üion of the same with MnO., / u decadieno (2.4) acid 60 described by means of 25 l of oxygen

can be obtained. Irradiation with a 900 W att mercury vapor

The following examples explain the invention. phouioxygenated lamp. After the usual work-up of the reaction mixture became the crude product

Example 1 distilled. 56 g (57 °, _O ) 4,5-Hpo \\ - trans-

,, ,1 , - , · . , - ,, i, n 65 pentene- (2) -al- (l) with a purity of ^l ) 2 ° ,,.

Manufacture of 4.> hpoxy-ci.s-penten- (2) -al- 1) '. ... ',. · Ι · 1 ·. · ■.

^b 'ti ι Q _le remaining 8 ° ,, · “consisted of non-ideological

(1 (1 g (IMoI) of freshly distilled cyclopentadiene, by-products. By cias phase normnography

5 g hydroquinone. Ig Rose Bengal. 1.4 1 of benzene obtained pure 4,5-epoxy-trans-pentene- (2) -al- '!) Showed

die i.>iüendc; i p'i-.s:! · .ih-ohcn ί :: '. ". SJp. ~ 2 (::' lVrr. / ;. '.- ■■' ■ '.. -

IR-spekiP.im: 2 ~ 2O. 1: -. "> I.! '> - ii.''- ¹ I. NMR-Spckirum:'>.-;<■ -. M. ir, i. '.-2 2 CW. · - :! . 3. (P ι: H..;. · :; /. ./ - "-"

Γ) .in M.lNsCIlNpcklriini Λ..Γ:,.; Ic / ι! ■■;. ·: -In

H e · - ρ 1 CI ■ perruhr.ni: .on J.5-Ipiv> - _L '

: κ; -i «ir; i! lien. '..! v. ', rden -λ ^.

-μ i ". π ·., ;; i

-.r-ί p .'-;. -'-: 'iN-;vi; eri- (2i-.i ee \ wn "er
: ¹ I ■ _ ■ ι s ρ ι e ί ■ -

pen! ... hen ι ^: Mi-I). Ί ι: ~ Ri! -. E licnpale. 2.5! : ι · rd i \ '~''!'.'.' kciie- Metha: ". i ^: u'.irde \ '~ ei:! a:

! <·.; Ι »· '· ϋ; ΐ ..ic-tiliicrt. M.in received

! ■ e- '· ι> | s.nier ··;, - !! ' absorhierl \>. a "en. '-.uroe .π«. * · 1 i. "for: 2SiL! V: those at R;>.,; nleu \ pc! \; iur -! ei ^; iL

se seeds [nlferiHin ^ der! .nviinii-inüiel :: nle · .. '. erlem Priick -.viirvie i ^! -? r Riiok -:;, !! «.; at ^: - '<. ..! estiiiieit and creab with 35 ", '"' L: er - \ ·.! νΡοι 4.5-1 po \> - 2-peniena! with a Rciinieil-i: ' ¹ ' 2 ', .. Oie rhyme · : .mti «-«. iirde in de. '>c!'"C! i ^ ¹ . i.me I: .siihü \ on M) nil 4. ^< -rpo \\ - _i iN-pen! e; i- ij im iieiNpic! ■ pe-ichritten duieheefahr ;. Ii (2i - '! - i ^! ) And 0.! ü Triphcn> ipr ..-> ph: n in! mi nil i ^ ii-above v \ erte «.timmien mi! those de ·· He Hen / · ι '.-. was in RaunVicniiie- uh during 4S mouths.

H cis ρ ι ei 5

i berfiihrun.il \ on 4.5- | -p> i \\ - eis-pe ;;; en-i 2i- i! -i; i I ίι
J. · .- ent-preaching tnin - N, imer durch! -! -. RperiMcrune

Claims (1)

S.:i-ersi.>;· r> ei I cmnc ^r . : '. ".. re :' ·. ■: c ■■ - .: 50 C ; r. .iivn iiL-LT:. ::,!;: ■ ·, -. ■ '■ .. sirJi!. ·· lü-jM .T-.ini ^ -hcn i /' - .. ι: ^ -: - !. ■ ·! · :! > ■■ ·.;. dicr Ζ. \. crf.ihren r:: ch. \ n-pr: J ·!. d ■ · .- .: nch ■ ι ... ₍ k ι, enii-.ci r.iit an inert. Ci.:s πι. '^', '""ErVirLihic-n' in ^ cgenwar: one energy '-,'. "Ι. .. s>,;.: ii! i,; i! ors zu rv ^ ciHen. .- \ 's; nert _;