Wiggerink, Gerrit Lucas

University of Groningen

   University of GroningenVorming van spiranen bij de bereiding van thioacetalen en hun röntgenografisch onderzoekWiggerink, Gerrit LucasIMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite fromit. Please check the document version below.Document VersionPublisher's PDF, also known as Version of recordPublication date:1940Link to publication in University of Groningen/UMCG research databaseCitation for published version (APA):Wiggerink, G. L. (1940). Vorming van spiranen bij de bereiding van thioacetalen en hun röntgenografischonderzoek. Groningen: Noordhoff Uitgevers.CopyrightOther than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of theauthor(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).Take-down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediatelyand investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons thenumber of authors shown on this cover page is limited to 10 maximum.Download date: 12-11-2019IIIIIIIIIIIIITIIII crystalline structure ofI the aid of the ,,retigrapI - -_- the retigraph was given. XII .  SUMMARY.|  ^rt .  . ,LrrYrYrf l . f \  r  .  this instrument one canI _ lattice of a crystal in itI Tne condensation of l,3-dichloroacetone with monothioglycol reflections becomes easlI Save rise to the formation of a spirocyclic compound of formula II (scheme p. 87). Its structure was proved by the reaction of monothio- graphed on the film' a 1I slycol sodium NascHr. cHroH with dichloroacetone. 'ru- In the case of four s;I \rhen a compound can give a thioacetale as well as an ordinary ffitJlit|ïïiïtïI acetale, the former will result. In our case the sulphur atoms are considerations.I fi:ïffS,L:,9-ïïi,'#?:lJ:ïï; ;:'[i:ï,ff.iï:: :ïï"lilï rhe spirane 2 forms,rI The behaviour of dithioglycol and monothioglycol t wards 1,3- lï:"ilr:,ï.3'ïï*:Trt,|I ff11ï::ï:"ïïiË:ï'#ï:ïi"f,'lïï,Sï,:ï,':ï'.,lï,ili'ïï1,ï lffil:lï",,ïï,iïX'I ethylidene-1,3-dichloroacetone, is formed. The activity of a SH layer line around the cI group is sufficient to react with the chlorine atoms of dichloro-I acetone, whire a oH group is not enough reactive. uru- twins coincide' and noI when continuing our experiments we observed that the 2,6- -'ï?Ïïd"rïïXï:r:ÏJ:I dibromocyclohexanone gave rise to spiranes, in the same way asA n l,3-dichloroacetone did. In the case of two 1,3-dimercaptanes,E-x "piranes with two rings of seven atoms were formed.TffiWhilst dichloroacetone possesses twice the group -CO . CH2CI,I chloroacetyl chloride contains one such group besides a very reactiveI chlorine atom. Only with dithioglycol it forms a spirane.The interaction of phosgene with glycol and the thioglycols leadsI to a carbonate and thiocarbonates.One aromatic dithiol, o.dimercaptobenzene, was involved in theI research; with l,3-dichloroacetone no definite product was formed,I while chloroacetyl chloride gave rise to a spirane. The condensationsI of dithioglycol with chloroacetyl chloride and phosgene succeededI at room temperature I o.dimercaptobenzene only reacts in boilingI dioxane or in a closed tube at 160". The cause of this differenceI ls not the greater distance of the sulphur atoms in the aromaticI compound, but their immobility.In the second part of this thesis a description is given of theII(.one with monothioglycolic compound of formula Ig the reaction of monothio-:hloroacetone..ale as well as an ordinaryme the sulphur atoms areerefore we must concludeloss ofl hydrogen chloride.rnothioglycol towards 1,3-not lead to a spirane. Infl and an orclinary acetale,l. The activity ofl a SHhlorine atoms of dichloro-gh reactive.e observed that the 2,6-anes, in the same way aslf two 1,3-dimercaptanes,s were formed.: the group -CO . CH2CI,'oup besides a very reactivet forms a spirane.rl and the thioglycols leadslzene, was involved in thefinite product was formed,spirane. The condensationsle and phosgene succeeded:ene only reacts in boilinghe cause of this differencerur atoms in the aromaticlescription is given of theB9crystalline structure of some of our spiranes, as determined withthe aid of the "retigraph" and a Sauter goniometer. The theory ofthe retigraph was given besides the method of working with it. Withthis instrument one can photograph a lattice-plane of the reciprocallattice of a crystal in its real form. 'I 'herefore the indication of thereflections becomes easy and, because a whole layer line is photo-graphed on the film, a good survey of these reflections is obtained.In  the  case o f  four  sp i ranes  (scheme p .  87 :  1 ,2 ,3 ,4 )  the  spacegroup was determined. Only the spirane I proved to possess thetwofold axis we should attribute to it on account of stereochemicalconsiderations.The spirane 2 forms twins along the plane (100). Vhen the crystalis turned around the c-axis, a "retigram" of an odd layer line showsthe lattice planes of the reciprocal lattice of each twin; the netIines of one twin, parallel to the b axis, just lie between those ofthe other, so that it seems as if only one lattice is present. An evenlayer line around the c axis being photographed, the lattices of thetwins coincide, and no sign of the twinning is seen. The crystallo-graphic constants thus answer to the relation c/a : 4 cos p.Finally the crystals of some of the other spiranes were described.à,Ft ,f'aiI[-'i";Èí,I.L,lf 'í,:;LEE.

Vorming van spiranen bij de bereiding van thioacetalen en hun röntgenografisch onderzoek

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Vorming van spiranen bij de bereiding van thioacetalen en hun röntgenografisch onderzoek

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