Organic synthesis by means of noble metal compound XXIV. Palladium-catalyzed carbonylation of propargyl alcohols and propargyl chloride

Tetrahedron Letters No.16, pP, 1801-18044,1966. Porguon Printed in Great Britain.

Press Ltd.

ORGANIC SYNTHESES BY MZANS OP NOBLE METALCOMPOC8D XXIV.

PALLADIDM~ATALYZ~

CA8808YLATION OF PROPARGYL AIOOXOLS

AND PROPA8GYLCRLOIUDl+

Jiro Tsuji and Tatsuo Yogi Basic YbrsearchLaboratories, Toya 8ayon Capany,

Ltd.

Kamakura,Japan (Received 22 Feb-y

1966)

We have reported that palladium is a versatile catalyst for ths carbonylation of various acetylenic compourkls,e.g., acetylens to form muconyl chloride,2 diphenylacetylene to form (L,fdiphany1-r-cmtontone,3

aId

acatylenic mono- and dieaters to form several polycarboxylates.' The characteristic of these palladium-catalysed carbonylations is an extensive dicarbonylation, rather than oonocarbonylatlon. Theso results are quite different from the reactions catalyzed by Iron, nickel and cobalt carbonylr. Uo now studied the carbonylation of propargyl alcohols and chloride, and again reactiona specific to palladium catalysis were observed;

the results are presented In

this communication. The carbonylation of propargyl alcohol was carried out in methanol contain-

ing hydrogen chloride in the prerence of a catalytic amount of palladium on carbon at 100" under a pressure of carbon'monoxide(lOO kg/c.m2). The main product was methyl itaconate(yield 631, one experiment), accompanied by methyl aconitate(yield 16)

and methyl 2-(methoxymethyl)acrylats(in a amnll

amount).

The ratio among these products is quite variable depending on the reaction conditions.

1801

No.16

1802

CH~-oxI3 C~-ctI2OA + co + CH30HF

CH2=C:dO$H3

+ CA2=C:-CO$H3 ’

I bH240.#H3

To our knowledge, thin ie the firetexampleof formationof itaconatefrom propargylalcohol. The additionof 3 melee of carbonmonoxideto fom aconitatoie a new reaction. When the ructlon wae carriedout in benzene, only reeinouerterial wae formed. Subetituted proprgyl alooholrreactedeiailarly.Tt~e the carbonylation of 2-methyl-3-butyn-2-01 in methanolcontaininghydrogenchloridegave methyl L-methoxy-L-methyl-2-pentenoate(1, traneform),methylteraoonate(II), methyl (l-methoxy-l-methylethyl)maleate(I~I) 4 methyltere+ate(IV).When a conoentrationof hydrogenchloridein the mediumuse low, I was the main product; at a higherconcentration, II and IV wre obtainedeelactively. I / CH CR3

+

I 3

CH34=CC02CH3

in CH308

RECC-OH + CO

CHZCO2CH3

I cH3 II

I in benzene

CH3

I

CH3-C%-CO, H3CO CH-CO.$H3 CH240No

I;

kH3 III

IV

When the reactionwas carriedout in benzenein the presenceof palladium chloride,teraconicanhydride

wee obtainedselectively in I.21yield.

No.16

1803

Propargylchlorido umo carbonylmted lnmthnolintbm

prornco of l

catalyticmmountof pnllmdiumohloridounder l pmuuro of carbonm-0 (lookg/afl2).The reactionproeeedodmt room taperaturomm3 tba produatr were methylj-chloro-3-butenomto(in l amll msount)4

-

wthyl itmcoruto(yiold

66%, one experiment).Again the yloldrof tbow prcductmumrm quit@ruirblo dspandingon the reactionoonditionr mId llumyml oonmidotrblm UoulTtof resinousmaterialwmn formed. Cl CHsCH2C1

+ co

l

CA30Hr

ce2s-Capo2Ca~

+ ca,=C--c+C~3

I CR2”0$31J The formationof itmconlcacid lnd 2,3-butmdienlc mold by nickelcmrbonylcatalyzedcarbonylation of proprgyl cNoride br ken reportedby Chluroli et ml.5 Romsnthmlot al. reportodtht proprgyl ohloridoromctmwith nickel carbonylto fom ethyl2,3+utadianomto ud ethyl3-cNoro-3-butenomtm.6 The amme author8obtainedethyl2-(hydroxywthyl)aaryl~te mnd 4-hydroxycrotonato from the nickelcmrbonyl-catalywd cmrbonylmtion of rubatituted propargyl alcohol. ’ In addition,the nickelcmrbnnyl-cmtmlysod carbonylation of substitutedproprgyl alcokolswms etadiedby Jonom et ml.*; alloniceaterrvom obtainedby monocarbonylation. Sincethe above-mentioned cmrbonylation can bm cmrrimdout under rmthr mild condltionr by a rimpleprocedure, and the cmtalymtir rmy to Urn,

it

can be said tht this methodia quiteusefulfor tb rynthenemof mlkylidonmsuccinatea.

RBfsrmMs

1.

Part XXIII.J. Tmuji,H. Takah8hf and U. Ibrikmwa,Bow in press.

W

germhi,

1804

No.16

2. J. Tmji, H. Morlkawaand 1. Iwamoto,J. Amer.Chom. Sot,,&, 2095(196&). 3. J. Tsujiand T. Nogi,J. Amer.Chem. Sot,, in press. 4. J. Taujiand T. Nogi, in preparation. 5. G. P. Chluroll,Chim. Ind.(Milan), a, 513(1959). 6. R. Id.Rosenthaland L. A. Schwrtrman,J. Org. Chem,,&

836(1959).

7. R. Y. Rorentid, L. A. Schvartzman, N. P. Cmco and R. Proper,J. Orb m,

1, 28X(1%3).

8. E. R. H. Joner,G. Ii.Whithamand M. C. Whiting,J. Chem. Sot,,f,628(1957).