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Cycloaddition reactions of the anhydro-4-hydroxythiazolium hydroxide system with dimethyl maleate and dimethyl fumarate
CYCLOADDITION REACTIONS OF THE ANHYDRO4HYDROXYTHIAOLIUh4 HYDROXIDE SYSTEM WlTH DMEI’HYL MALEATE AND DIMETHYL FUMARATE X-RAY DETERMINATION OF THE EXO !$I’RUClWRE OF THE CYCLOADDUCTS A. ROW&T.M. BAUDY and A. FQUCAUD Glopp&~dCChiCS!IWEh.
Equgc Anoch au C.N.R.S..U&vmiGde Rams. B.P.25 A. 35042m cc&x, Fnoa and
CHy&oxy thhzdtr Ir have been &own to undergo lady cyclo&ihm wit!ldhl&ytm&8temd dimctbytf&mtcvhtbcan?loioIlic~fonnl1b. to give the CiJ cydoaddum 2&maad2c,u’a.hby&o - 4 - bydroxythhhl by&oxide ryltull3 rcactl lbitbthl%samcd&hp&aubut~y~rircto butonecycbaddutinerbasc.4or5”~~ l).Tbc cot&in~ammtJ,,,,,,s&wsuarmbi(uocrrlytb~tk cunpmds4radsafcctcydoddpdr. Howeva. it ia morcdiuhlttoknowtknktivccxmf&mhoftk cubam 4 aml II. It has bcca pcmkted that tbc diumlceiocbl!hal¶hiftbctwceatk~fnw ru,toadowuductotbcdcshi&&~eudtbc rutedetw&Asaamacqucncc,tbccbmicalslifts ab8crvdfllrtbeH4aDd~~havebcul~ idWithpoloscillCX0COtl&WbiDtbCyckddpct
ofdimcthytumkewitbtbcmcsoionicthimk3.(X-H. R=Pb)whikrrmctm5)vuas+ncdtotbecy& u&&t af dimcthyKumamewith 3 (X-H, R-Pb). Howcvcr,wehavcnotiaxltbatthedihencein&mialrhiftbe!w!eom&MdaopotoasImykvery salanorevcnnia:forinstMcctbcruDtcbearialshift hbeenobwvcdfort&protonH,exoinhmdH, aldoillt).~ Tab& 1. cy-
IO*tOUWtiOtllCWtiVCCOl@K8thS~
arboaa4Mdsoftbc cyck&ms,mhve~n anXnydilhhmatudyofcoa1pouad4(X=CI,R= Ph). 7%~ W(3) and W(6) bond kagttn of I.833 and 1.63SA~CiphlUIdcmetpWito~SC(Sp~boad Tbc COWC(6) bomd angle (80.87 is cxm&hly slmlkrtbmtkmmnvallJeol9o*rforvuioussma&acdhetaacyckat&et&iuoksystan,.Thiris duetotbcsbainint&brid&f& same facta may kw the C(4)C(S)boadwimedilmceia I.mAaadthcC(6~N bomd (1.469A) wilkb ia s&i&x&y b than tbc man v&s of I.411b’ However, tbc C(4w(S) bond mayatwbcsmtchedbytbeutcr+sterrcpukhu bothaterpouprm&mtcdiutbcsmcdira%ion.Thc rho&m&d inhmokmhf distmcu q41 . .:qsl) and qa) . . qs2). wticb are 3.301and 3.2531 rcspc&cly. wicatet&ttbl!u*of8toalsarciucbsccoatrt. X-Ray discmsritm Tbemokcuhrmuctmt andatoalkbclillgscbuncarc pacatedurrtaeoscopicviewinF~I.Tbcuaitcell prclrinObgivcainFi2Asuveydtbcbondkngtha
ffom3amddLetlytmh8tcahofbyifmua&
w
No. d
iulmm
IhX-Cl 3. X-H;R-Pb 3, X-Cl;R-Pb 3, X-Cl;R-CHIPI ILX-Cl 3. X-H;R-Pi
2 I I I 2 I
3, X-Q;R-CH#b X-CI;R-Pb
:
&60%;2ba% 4 (CWH, -) 4cQCHl ato) ~(WHJ-)
k60%;31&% h
396
lb
A 4w.B lIO) tTh0 rulauing
01
Rg.lbuwd)
aoda@essbowninTabk5cmfmsttwmdecuQr stIwurc.ThecTyti,mrtmrconrittrofdhaete ubokuhfunitatiw~uy~iatamakcuLu &tur#.~itirthc6rst ntNctmdthirtypcd czmpoud(6ofuuweknow),thet!utcfnd~ 8nda@u&csaotahowumlslmif~. Tk plane thopsb the ataam S, C(3) md C(6) at&es ~*Ofl24.~WiththCbC4tptrnstb@tbcrlomc N, C(2). C(3) and C(6) md M a& of 122J’ with the bat phat W tbc umu C(3). C(J), C(5) ad C(6). wtnyl r&n C(11) . . . C(l6) axI C(61) . . . C(66) are
mean c-c-c ppdes UC mom Md Izo.o(4Y. The QIfiaths from tk best pbc in tk C(31) . . . cw phcllyl riug UC -0.020, o.an. 0.012 -0.019. o.al6 lad O.Ol3A fcspahdy. mcm bond distaDLxaId lode ir 13&X10) A and 12O.O(16Y.A sulmuyofbutphnud ciihdrd~~givcainTlble6to~tbc dtbeahcuk. com$ktccorlf~
sltnctwrof rhtothercycbaddnctr 4 ald 5 4xal,obmmdfortbe~paund4m=CI,R-W) afevaysimartotbmcobacmdfactheotber ccaw?udIWhTti7.hrtkX-rayrbudytm
eaMubodtbecu,poritioodthctwoettcrgroupain tkcaqmDd4(X=Cl,R=Pb)itrstmsr#rolmbkto
C42
Tdr12.Cryuddstn
F.W.Wn.997 b- lO.l2& c - mol(3) A B - lOl.6tl v,=2429 x ’
# = 2S.IJ cm-’ @R-U5
Tabk4.Cdadudfmaiad~(xlU’)?ab~ maml
@2) H(Cl9 WCII) HeI9 H(C16) Ha21
-‘m -1632 -m3 2 ml
ti(c33j
HIC3S1
HiC%j HOI HV32) H'(C4)
Cl &) o(41) W2) WI) iFsn all) C(l2) CO3) COI) co9 CO6) E$ cm
H(CS2) H’(CS2) H’(CS2)
-7190
H&366)
-en
- i9l\iii)
!Jm lcJy1)
mn an
44mn
cm
ciwi
6178i6j
co
S3S8t6)
61Qy6)
C(4)
C141) ccn, US) WI) cm C(6) C161)
4m
Et wS3
$5:) sstpiri %77s(l) 3s23m 33w4) lW4) I I3tM6)
CM) COB
SW
3lzzrS) 3#g(6).
siE!i/
2’73%) -7520 - Io(s(b)
-z
HKm WCW WC60 HOW
IL3 -13 -2116 -231s -3SI 5173 s#4 1979 1496
z (US 362.5 489 - 131s -1830 -SW
n&9
2 3463 2BS3 lSS4
z 4307 26S3
2078
Ii73 1493 13M 16sS 2031 w 4428 4218
E IiS2 1783 94 -‘g -113 -6.5s 1862 1101 _;
m
3sm
A.llmmlad
110.7(S)
12I.yn lnYn
l.rrXn
1.d
1.49SllI
Lmilb) l.slYlO) lszOm
C(6KUWSI) C(SKf6b-N
l39ylO~ l.3wlSI lrnlr) lsml6) l.%l(l3) lM(ll)
I.7*6) IJwlO) lW lrnl2) 1.X7(12) la(lO, I.3930
lar.Ur) I l3.7(sj I lS.9(s) loaYr) IauO Il7.4(9 l@WI l1lwl I wn lO3JUl 113.7(s) I 13.43) l@wl I l7.7(sj lll.9(9 lor.l(4l Ima 113m llP.ao II930 1103e) 128.7(1~ II920 120.70) Izayr) Il9.7(6) I Iam 12146) 118.X6) 121.1(6) l lam 12.0.4s) la(s) ll93m l lW6) 119m 11946) I 19.7(6) laayr) l2o.l~ IaOxr) II9.m UQl(6) 1m.w Izays) lOW6) l2%1(6) IlWs) Izaws) l99[6l 123m I lays)
dkaceporiarplbmmdoDfutaa a2sr -‘. No matam& vdabm d wUFJ-IFJ-n IFJ A
a
-(A) ii P2
P3
PI
Ps
m
P7
P8
E
Eo, (36) &I cm
0.0 FIti -0.013 0.013 -o.Oul ma3
us) u-3 C(I) US) C(6) C(r)
-9.26sx-I.w2ytls.27z-ao947
-6.7oOxt7.1myt11.142=u81
-:Z _;g O&B -0.001
cc411 @41) w2) cm cw Wl) Wl WI) cm C(13) WI) C(l3I W6) C(31) CM) co31 fB-34) cm cm C(61) U62) cm m4I cwl C(66)
Iii 34.3
&mfiDototboplu3t
:iE -0.W 0.019 -aO@ - 0.006 O.OW 0.003 -0.m -0.004 0.m -0.007 -0mO O+OUl 0.012 -0.019 0.W 0.013 -0.012 0.006
Il.&x-1.492y+26222-3.459
-8214x-4.311yt14.642=-0.331
-E -o.wz 0.010
P2
P3
P4
672 73.1 60.4 66.7
z 619
433
iii:
43.2 23.2
43.4 m4 64.8
Ps
P6
PI
83.3 66.4 73.4
364 IdJ
2&o
3s30
A..dal Trbb7.IRmdNMRtpctndthec~4~S
ce
wccw
x
R
H
Ph
PC0
SltraddH,
&%n,
1767;17Sl; I721
Cl
w
1767;17W;1719
Cl
CH,Pb
1764;17% VW7
Ii
n
1740;I718
a
n
1741;1716
:-:: 3:3a 3.4 3.M 3.46 3.47 3.70
4.29w2) -
3.66
b
Cl
CHsPh
1741;I700
Cl
CH,Pb
1743;1709
X
R
H Cl Cl
Ptl w PbCH,
:I Cl Cl
E CH,Pb CHQb
3.3s 3.m
4.29nH (I - MHZ) 3.nw) 4.M(dMl) J - ISHt
Yku I20 m I37 50 m m
ii E 80 89
q.p.
216t 2?0 2So lS2.t la4 l2S 178
JH&,
4.42*n
9.s
4.40an
IO
3.ww 4.4swNl) 4.2&w) JJl(dKI) 4.waKl) l.nfdNl) 4.20c2H
I3 4.5 4.5 4.5 5
3.8&w 4.6wMl,
uusspatnw’ fouml dc. 473_l2!a!l 507.lBo713 521.1lm342
473.1299 so7.cnos s21.1054
slv.090713 S21.lo6362 521.106342
nG9Os S2l.los4 s21.1054
tLitr 21>216m :lit!. ISI-ISF
‘Y. kmy. A Robat ml A. Foaaml, whrsb 261(1976). ‘hRdxttM.FanymdA.ikmcm&rcmbdnmmtn Irn (197s). ‘K.T.P~J.~~~~~H~,J.O~~.C~.~)).M~~ (1974). ‘M. B&y, Tbkc & 3bc Cyck. barn (1916). ‘w.Cv.Bwlo4&G.~A.~A Bu&k Acu Crya&833,116 (1977). ‘J. 1. H. McDwdl. lbU B32.5 (1976). ‘A. Ku& A. Rwc. 1. Dsrcrh. A. N&ukhzmJ.Am.ckm sot. 95.4244 (1973). ~.~.Y.W.W~~.L~,O.OaariaradJ.P.
&a (lQl4). ‘D. T. Omer md 1. B. b&n, Acta Cry& Au. 32l (I%& %.p.srnrtE.RRvibmadW.T.Sbsot~I.C6o1~ PLY&a 3i7i w6n “D. T. Cmaa. D. Libmm~. JW S3. I@91WW. ‘5. Y. !kwut, 0. KIpp, H. A~Do& C. H. kkbum & S. II WI. Univ. of w Compu Sci TaA R9. TR-I92 (Ipny
Equgc Anoch au C.N.R.S..U&vmiGde Rams. B.P.25 A. 35042m cc&x, Fnoa and
CHy&oxy thhzdtr Ir have been &own to undergo lady cyclo&ihm wit!ldhl&ytm&8temd dimctbytf&mtcvhtbcan?loioIlic~fonnl1b. to give the CiJ cydoaddum 2&maad2c,u’a.hby&o - 4 - bydroxythhhl by&oxide ryltull3 rcactl lbitbthl%samcd&hp&aubut~y~rircto butonecycbaddutinerbasc.4or5”~~ l).Tbc cot&in~ammtJ,,,,,,s&wsuarmbi(uocrrlytb~tk cunpmds4radsafcctcydoddpdr. Howeva. it ia morcdiuhlttoknowtknktivccxmf&mhoftk cubam 4 aml II. It has bcca pcmkted that tbc diumlceiocbl!hal¶hiftbctwceatk~fnw ru,toadowuductotbcdcshi&&~eudtbc rutedetw&Asaamacqucncc,tbccbmicalslifts ab8crvdfllrtbeH4aDd~~havebcul~ idWithpoloscillCX0COtl&WbiDtbCyckddpct
ofdimcthytumkewitbtbcmcsoionicthimk3.(X-H. R=Pb)whikrrmctm5)vuas+ncdtotbecy& u&&t af dimcthyKumamewith 3 (X-H, R-Pb). Howcvcr,wehavcnotiaxltbatthedihencein&mialrhiftbe!w!eom&MdaopotoasImykvery salanorevcnnia:forinstMcctbcruDtcbearialshift hbeenobwvcdfort&protonH,exoinhmdH, aldoillt).~ Tab& 1. cy-
IO*tOUWtiOtllCWtiVCCOl@K8thS~
arboaa4Mdsoftbc cyck&ms,mhve~n anXnydilhhmatudyofcoa1pouad4(X=CI,R= Ph). 7%~ W(3) and W(6) bond kagttn of I.833 and 1.63SA~CiphlUIdcmetpWito~SC(Sp~boad Tbc COWC(6) bomd angle (80.87 is cxm&hly slmlkrtbmtkmmnvallJeol9o*rforvuioussma&acdhetaacyckat&et&iuoksystan,.Thiris duetotbcsbainint&brid&f& same facta may kw the C(4)C(S)boadwimedilmceia I.mAaadthcC(6~N bomd (1.469A) wilkb ia s&i&x&y b than tbc man v&s of I.411b’ However, tbc C(4w(S) bond mayatwbcsmtchedbytbeutcr+sterrcpukhu bothaterpouprm&mtcdiutbcsmcdira%ion.Thc rho&m&d inhmokmhf distmcu q41 . .:qsl) and qa) . . qs2). wticb are 3.301and 3.2531 rcspc&cly. wicatet&ttbl!u*of8toalsarciucbsccoatrt. X-Ray discmsritm Tbemokcuhrmuctmt andatoalkbclillgscbuncarc pacatedurrtaeoscopicviewinF~I.Tbcuaitcell prclrinObgivcainFi2Asuveydtbcbondkngtha
ffom3amddLetlytmh8tcahofbyifmua&
w
No. d
iulmm
IhX-Cl 3. X-H;R-Pb 3, X-Cl;R-Pb 3, X-Cl;R-CHIPI ILX-Cl 3. X-H;R-Pi
2 I I I 2 I
3, X-Q;R-CH#b X-CI;R-Pb
:
&60%;2ba% 4 (CWH, -) 4cQCHl ato) ~(WHJ-)
k60%;31&% h
396
lb
A 4w.B lIO) tTh0 rulauing
01
Rg.lbuwd)
aoda@essbowninTabk5cmfmsttwmdecuQr stIwurc.ThecTyti,mrtmrconrittrofdhaete ubokuhfunitatiw~uy~iatamakcuLu &tur#.~itirthc6rst ntNctmdthirtypcd czmpoud(6ofuuweknow),thet!utcfnd~ 8nda@u&csaotahowumlslmif~. Tk plane thopsb the ataam S, C(3) md C(6) at&es ~*Ofl24.~WiththCbC4tptrnstb@tbcrlomc N, C(2). C(3) and C(6) md M a& of 122J’ with the bat phat W tbc umu C(3). C(J), C(5) ad C(6). wtnyl r&n C(11) . . . C(l6) axI C(61) . . . C(66) are
mean c-c-c ppdes UC mom Md Izo.o(4Y. The QIfiaths from tk best pbc in tk C(31) . . . cw phcllyl riug UC -0.020, o.an. 0.012 -0.019. o.al6 lad O.Ol3A fcspahdy. mcm bond distaDLxaId lode ir 13&X10) A and 12O.O(16Y.A sulmuyofbutphnud ciihdrd~~givcainTlble6to~tbc dtbeahcuk. com$ktccorlf~
sltnctwrof rhtothercycbaddnctr 4 ald 5 4xal,obmmdfortbe~paund4m=CI,R-W) afevaysimartotbmcobacmdfactheotber ccaw?udIWhTti7.hrtkX-rayrbudytm
eaMubodtbecu,poritioodthctwoettcrgroupain tkcaqmDd4(X=Cl,R=Pb)itrstmsr#rolmbkto
C42
Tdr12.Cryuddstn
F.W.Wn.997 b- lO.l2& c - mol(3) A B - lOl.6tl v,=2429 x ’
# = 2S.IJ cm-’ @R-U5
Tabk4.Cdadudfmaiad~(xlU’)?ab~ maml
@2) H(Cl9 WCII) HeI9 H(C16) Ha21
-‘m -1632 -m3 2 ml
ti(c33j
HIC3S1
HiC%j HOI HV32) H'(C4)
Cl &) o(41) W2) WI) iFsn all) C(l2) CO3) COI) co9 CO6) E$ cm
H(CS2) H’(CS2) H’(CS2)
-7190
H&366)
-en
- i9l\iii)
!Jm lcJy1)
mn an
44mn
cm
ciwi
6178i6j
co
S3S8t6)
61Qy6)
C(4)
C141) ccn, US) WI) cm C(6) C161)
4m
Et wS3
$5:) sstpiri %77s(l) 3s23m 33w4) lW4) I I3tM6)
CM) COB
SW
3lzzrS) 3#g(6).
siE!i/
2’73%) -7520 - Io(s(b)
-z
HKm WCW WC60 HOW
IL3 -13 -2116 -231s -3SI 5173 s#4 1979 1496
z (US 362.5 489 - 131s -1830 -SW
n&9
2 3463 2BS3 lSS4
z 4307 26S3
2078
Ii73 1493 13M 16sS 2031 w 4428 4218
E IiS2 1783 94 -‘g -113 -6.5s 1862 1101 _;
m
3sm
A.llmmlad
110.7(S)
12I.yn lnYn
l.rrXn
1.d
1.49SllI
Lmilb) l.slYlO) lszOm
C(6KUWSI) C(SKf6b-N
l39ylO~ l.3wlSI lrnlr) lsml6) l.%l(l3) lM(ll)
I.7*6) IJwlO) lW lrnl2) 1.X7(12) la(lO, I.3930
lar.Ur) I l3.7(sj I lS.9(s) loaYr) IauO Il7.4(9 l@WI l1lwl I wn lO3JUl 113.7(s) I 13.43) l@wl I l7.7(sj lll.9(9 lor.l(4l Ima 113m llP.ao II930 1103e) 128.7(1~ II920 120.70) Izayr) Il9.7(6) I Iam 12146) 118.X6) 121.1(6) l lam 12.0.4s) la(s) ll93m l lW6) 119m 11946) I 19.7(6) laayr) l2o.l~ IaOxr) II9.m UQl(6) 1m.w Izays) lOW6) l2%1(6) IlWs) Izaws) l99[6l 123m I lays)
dkaceporiarplbmmdoDfutaa a2sr -‘. No matam& vdabm d wUFJ-IFJ-n IFJ A
a
-(A) ii P2
P3
PI
Ps
m
P7
P8
E
Eo, (36) &I cm
0.0 FIti -0.013 0.013 -o.Oul ma3
us) u-3 C(I) US) C(6) C(r)
-9.26sx-I.w2ytls.27z-ao947
-6.7oOxt7.1myt11.142=u81
-:Z _;g O&B -0.001
cc411 @41) w2) cm cw Wl) Wl WI) cm C(13) WI) C(l3I W6) C(31) CM) co31 fB-34) cm cm C(61) U62) cm m4I cwl C(66)
Iii 34.3
&mfiDototboplu3t
:iE -0.W 0.019 -aO@ - 0.006 O.OW 0.003 -0.m -0.004 0.m -0.007 -0mO O+OUl 0.012 -0.019 0.W 0.013 -0.012 0.006
Il.&x-1.492y+26222-3.459
-8214x-4.311yt14.642=-0.331
-E -o.wz 0.010
P2
P3
P4
672 73.1 60.4 66.7
z 619
433
iii:
43.2 23.2
43.4 m4 64.8
Ps
P6
PI
83.3 66.4 73.4
364 IdJ
2&o
3s30
A..dal Trbb7.IRmdNMRtpctndthec~4~S
ce
wccw
x
R
H
Ph
PC0
SltraddH,
&%n,
1767;17Sl; I721
Cl
w
1767;17W;1719
Cl
CH,Pb
1764;17% VW7
Ii
n
1740;I718
a
n
1741;1716
:-:: 3:3a 3.4 3.M 3.46 3.47 3.70
4.29w2) -
3.66
b
Cl
CHsPh
1741;I700
Cl
CH,Pb
1743;1709
X
R
H Cl Cl
Ptl w PbCH,
:I Cl Cl
E CH,Pb CHQb
3.3s 3.m
4.29nH (I - MHZ) 3.nw) 4.M(dMl) J - ISHt
Yku I20 m I37 50 m m
ii E 80 89
q.p.
216t 2?0 2So lS2.t la4 l2S 178
JH&,
4.42*n
9.s
4.40an
IO
3.ww 4.4swNl) 4.2&w) JJl(dKI) 4.waKl) l.nfdNl) 4.20c2H
I3 4.5 4.5 4.5 5
3.8&w 4.6wMl,
uusspatnw’ fouml dc. 473_l2!a!l 507.lBo713 521.1lm342
473.1299 so7.cnos s21.1054
slv.090713 S21.lo6362 521.106342
nG9Os S2l.los4 s21.1054
tLitr 21>216m :lit!. ISI-ISF
‘Y. kmy. A Robat ml A. Foaaml, whrsb 261(1976). ‘hRdxttM.FanymdA.ikmcm&rcmbdnmmtn Irn (197s). ‘K.T.P~J.~~~~~H~,J.O~~.C~.~)).M~~ (1974). ‘M. B&y, Tbkc & 3bc Cyck. barn (1916). ‘w.Cv.Bwlo4&G.~A.~A Bu&k Acu Crya&833,116 (1977). ‘J. 1. H. McDwdl. lbU B32.5 (1976). ‘A. Ku& A. Rwc. 1. Dsrcrh. A. N&ukhzmJ.Am.ckm sot. 95.4244 (1973). ~.~.Y.W.W~~.L~,O.OaariaradJ.P.
&a (lQl4). ‘D. T. Omer md 1. B. b&n, Acta Cry& Au. 32l (I%& %.p.srnrtE.RRvibmadW.T.Sbsot~I.C6o1~ PLY&a 3i7i w6n “D. T. Cmaa. D. Libmm~. JW S3. I@91WW. ‘5. Y. !kwut, 0. KIpp, H. A~Do& C. H. kkbum & S. II WI. Univ. of w Compu Sci TaA R9. TR-I92 (Ipny