of the · twentieth national organic chemistry symposium of the american chemical society auspices...
TRANSCRIPT
![Page 1: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/1.jpg)
TWENTIETH NATIONAL ORGANIC
CHEMISTRY SYMPOSIUM
of the
AMERICAN CHEMICAL SOCIETY
AUSPICES OF TIlE DIVISION OF ORGANIC CHEMISTRY
THE UNIVERSITY OF VERMONT
and the
WESTERN VERMONT SECTION OF THE ACS
*
June 18-22, 1967
Burlington, Vermont
![Page 2: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/2.jpg)
TWENTIETH NATIONAL ORGANIC
CHEMISTRY SYMPOSIUM
of the
AMERICAN CHEMICAL SOCIETY
![Page 3: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/3.jpg)
a'lf Speakers at the Twentieth National Organic Symposium
A" <" ,V C'r<i> '
F. A. L. Anet o. L. Chapman G. L. Closs
G. S. Hammond H. O. House R. Pettit
R. B. Woodward P. R. Schleyer H. E. Simmons
![Page 4: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/4.jpg)
PROGRAM SUNDAY, JUNE 18
Registration: Patrick Gymnasium, 2:00-11 :00 P.M.
MONDAY, JUNE 19
Registration and Meetings: Patrick Gymnasium 9:00 A.M. Welcome. CLINTON D. COOK, Vice
President, University of Vermont Response. GILBERT STORK, Chair
man, Division of Organic Chemistry, ACS
9:30 A.M. PAUL von R. SCHLEYER, "Structure and Reactivity in Carbonium Ion Reactions"
11:00 A.M. R. PETTIT, "The Chemistry of Cyclobutadiene-lron Carbonyl Complexes"
8:00 P.M. "Chemical Approaches to Enzyme Mechanisms"
WILLIAM P. JENCKS, "AcetoacetylCoA: Succinate Coenzyme A Transferase" E. T. KAISER, "Enzyme Chemistry of Highly Reactive Cyclic Esters"
TUESDAY, JUNE 20
9:00 A.M. HOWARD E. SIMMONS, "Macrobicyclic Amines"
10:30 A.M. G. L. CLOSS, "Mechanisms of Carbenoid Reactions"
8:00 P.M. JOHN D. ROBERTS, Roger Adams Award Address, "Some Problems Relating to the Calculation of Steric Effects in Simple Molecules"
9:30 P.M. Social Hour
![Page 5: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/5.jpg)
WEDNESDAY, JUNE 21
9:00 A.M. F. A. L. ANET, "Conformational and Valency Isomerism in Eight-Membered Rings"
10:30 A.M. HERBERT O. HOUSE, "A Study of Some Reactions of Organomagnesium Compounds"
8:00 P.M. R. B. WOODWARD, "Recent Advances in the Chemistry of Natural Products"
THURSDAY, JUNE 22
9:00 A.M. O. L. CHAPMAN, "Photocycloaddition Processes"
10:30 A.M. GEORGE S. HAMMOND, "The Life and Times of an Excited Molecule"
![Page 6: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/6.jpg)
THE ROGER ADAMS AWARD IN ORGANIC CHEMISTRY
The Roger Adams Award in Organic Chemistry has been established with joint sponsorship by the American Chemical Society, Organic Reactions, Inc. and Organic Synthesis, Inc. The award is made biennially to an individual, without regard to nationality, for outstanding contributions to research in organic chemistry. The award consists of a medal and an honorarium of ten thousand dollars. The presentation of the award is made at the biennial National Organic Chemistry Symposium of the Division of Organic Chemistry of the American Chemical Society: and the recipient delivers a lecture as part of the program of the Symposium.
The award recognizes the distinguished career of Roger Adams. 'He has played a vital role in each of the three organizations sponsoring the award, having been both Chairman of the Board of Directors and President of the American Chemical Society and a co-founder of both Organic Syntheses and Organic Reactions.
The recipient of the award this year is John D. Roberts of the California Institute of Technology. His award address is entitled "Some Problems Relating to the Calculation of Steric Effects in Simple Molecules."
J. D. Roberts
![Page 7: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/7.jpg)
VERMONT COMMITTEES
Executive ............... W. N. White, Chairman A. P. Krapcho, M. E. Kuehne
Registration ........... W. N. White, A. P. Krapcho Housing ....................... J. H. Waters Auditorium .......... G. C. Crooks, T. B. Flanagan Transportation .......... C. A. Wulff, M. E. Kuehne Recreation and Entertainment. . . .. R. C. Woodworth,
D. C. Gregg, M. H. Gianni Chairman of the
Western Vermont Section W. N. White
Division of Organic Chemistry
The plans and program of the Twentieth National Organic Chemistry Symposium have been developed by the members of the Executive Committee of the Division of Organic Chemistry who have served during the past two years.
1965-1966
Chairman H. O. House
Chairman-Elect Gilbert Stork
Secretary Norman A. LeBel
National Symposium Officer F. G. Bordwell
Executive Committee
Ronald Breslow Andrew Streitwieser Cheves Walling Harry H. Wasserman
1966-1967
Gilbert Stork
Harry H. Wasserman
Norman A. LeBel
F. G. Bordwell
Ronald Breslow Ernest L. Eliel William D. Emmons Andrew Streitwieser
![Page 8: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/8.jpg)
STRUCTURE AND REACTIVITY IN CARBONIUM ION REACTIONS
Paul von R. Schleyer
7
![Page 9: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/9.jpg)
THE CYCLOPROPYL CATION-OLD PROBLEM!
OH NO) HONO ( Kischner -1905 V--NH2 --+ teo) P L'ipp, et at -1932
1 ~ Corey, Atkinson-
~ H+ or (with D) 1964 V-0H OH-"'C2H5CHO
POSSIBLE ACETOLYSIS MECHANISMS
[:>-OTS HOAc
1 COl)
cer Slow (a) (b) teet
[>+ Fast (a)
Roberts, Chambers (1951) chose (a)
CYCLOPROPYL ACETOLYSIS RATE OTs OTs A-W (:r110'
rel. rates 10-5 1
Slow rate - stepwise mechanism?
8
![Page 10: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/10.jpg)
THE CHEMISTRY OF CYCLOBUTADIENE-IRON CARBONYL COMPLEXES
R. Pettit
![Page 11: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/11.jpg)
0-0
+4-
*
"""n.TT~A. (0' prj
'8Ut~"''''' (I"~)
OB~ 1(,,, ~
'II.
d~('H.I.
:«~.).
24
[(r
II> ~
(\
----+ 12D'
o
1(." III ~() .. "
aN~~,).
o
![Page 12: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/12.jpg)
MACROBICYCLIC AMINES
Howard E. Simmons
37
![Page 13: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/13.jpg)
eOCl I
(CH2)x-2 I eOel
+ HIGH DILUTION . BENZENE,25'
THF,65'
YIELDS: SO-75%
DIL~TION: 0.02M
YIELDS: 85-95%
+
.-678910126 Y - 6 8 '9 10 12 10
Method of Stetter
eOCl I
{?H2)Z-2 +
COCl
z -
OVERALL YIELD M.P.
(NH\
HIGH DILUTION
{C~NH)H2)Y • {c.H.).N,
BENZENE,25'
(1\ LiAlH4
{CQ~H2)Y THF,65'
6 9 10 12 6 6 7 9 10 12 8 6 7 8 9 10 12 8 10
0 20 75 SO 75 20 40 60 35 120 32 114 125 45 <rJ'
SHAPE n • r C(a) a n
38
(:r\ {CH~t~}Vy
({\ {CH\]~2)Y
8 8 10
70 55'
( (
S;;
![Page 14: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/14.jpg)
MECHANISMS OF CARBENOID REACTIONS
G. L. Closs
. ,
57
![Page 15: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/15.jpg)
y Tr
S
Du
L--______ ~::, Sw
CONTINUOUS FLOW EXPERIMENT
k CH30H CSH5-CHB~22 + CH3Li - CSH5-jCHLiBr T CSH5-CH2Br+ CH30Li
k2
58
![Page 16: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/16.jpg)
SOME PROBLEMS RELATING TO THE CALCULATION OF STERIC EFFECTS
IN SIMPLE MOLECULES
John D. Roberts
63
![Page 17: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/17.jpg)
1,6 -Pichloro -I, 5 - cydoodadiene
~? 7Cl~Cl
C\ ~ ~ Ij'~ ~ ~ h CI~~CI
CI
chair skew boat
.fA = 2.60 P, indi"aks boat-\i"e form
(Roberts J 1.350)
/angte strain
C1~ = ~t5 = rt;' Cl CI ~Cl
A~ r ~ Cl CI
cross-ring non-bonded repulsions
~,-d6 ~-OO-c, CI
64
A/ 9 local 3-14-kcal
![Page 18: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/18.jpg)
CONFORMATIONAL AND VALENCY ISOMERISM IN EIGHT-MEMBERED RINGS
F. A. L. Anet
87
![Page 19: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/19.jpg)
For (.'{!u.ll r>OpLilal i()n~: k A = kB
Specrra
T
II.J2
V2
VB
For more complex ~y~tem~ see:
~: ~. J~~::!r Adv~~~a~afu.\:~~:n~1(.'18~ (f~6~~)~6S);
Tc .4F" (keal/mole) at Tc e- VA - VB = 20 eps vA - v B= 1,000eps
0 13.9 11.8 -90 9.2 7.8
-120 7.7 6.5 -140 6.6 5.6 -160 5.6 4.7 -180 4.6 3.8
88
![Page 20: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/20.jpg)
A STUDY OF SOME REACTIONS OF ORGANOMAGNESIUM COMPOUNDS
Herbert o. House
105
![Page 21: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/21.jpg)
ETHER SOLUTIONS OF ORGANOMAGNESIUM REAGENTS
REAGENT NMR (cps above TMS)
Br-CH 2CH 2-Br- MgBr2
CH 38r- CH 3MgBr 92.5 cps (J13
C_
H,107CPS)
CH,I- CH,Mgl 92 cps
(CH,),Hg - (CH,),Mg 83-90 cps (J13
C•H
IOS.Scps)
(0.H.03M. 3310 -54')·
CH 3Br- CHaLi 111-114 cps
(Juc.H97CPS)
CH,CH,Br - CH,CH,MgBr 41 cps
(CH,CH,),Hg - (CH,CH,),Mg 37-42.5 cps (3510-34')
'M. B. Smilh and W. E. Becker.~,~, 3027 (1966).
bA. D. Vreugdenhil and C. Blomberg, Reo. Trav. Chim., ~Z, 453 (1963).
'L. M. Seitz and T. L. Brown. J. Am. Chem. Soc •• ii. 4140 (1966); K. C. Williams and T. L. Brown, lfuQ., as. 4134 (1966).
·E .. C. Ashby and M. B.' Smith. J. Am. Chem. Soc •• §§. 4363 (1964).
APPARENT DEGREE OF ASSOCIATION
1.09-1.62 (0_002-0.l3!!)'··
1.20-1.28 (O.l3M)
4.0'
1.04-1.96 (O.OOH.S!!)·····
1.00-l.lS (0.002-0.3M)···
EFFECT OF MANGANESE ON THE NMR SIGNAL OF
METHYLMAGNESIUM DERIVATIVES
Mg
(ordinary)
, {90 cps (w/1.34-4O cps) + CH3Br- Br-Mg-CH 3 at 30°
Et20 98 cps (w/2-Z cps) at -540
(excess) (peaksharpenejlbytheadditionof excess magnesium)
Mg
(triply sublimed)
-to CHaBr _ Br-Mg-CH! Et,O
(excess)
97 cps (w/2·1.5 cps) at 30'
CH,-Mg-Br + Mn~_ Br-Mg-CH, 90 cps (w/2-24 cps) at 30'
(from triply sublimed Mgl
(g. 0.01 mole %)
POSSIBLE INTERPRETATION
2Mno + 2CH3Br--=--(C~~Mn + MnBr~
Mnl 2 + 2CH3MgBr-(CHalzMn + 2 MgBrl
(CH,~Mn + CH,MgBr ~(CH3),Mne ~gBr (CH:S)2Mn + ",go ~ (CHa)2Mg + Mn°
106
![Page 22: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/22.jpg)
RECENT ADVANCES IN THE CHEMISTRY OF NATURAL PRODUCTS
R. B. Woodward
119
![Page 23: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/23.jpg)
Me
C'~2 Me Me H "CH2 I I CH2 CH2 I I
H~CO CONH2
ISOPROPANOL I
PHOSPHATE I
RIBOSE I
DIMETHYLBENZI MI DAZOLE - COBA~ T
ROMe
"",I Me ~ A
NH Me
120
C~~2 Me I ~H2
XCO
~Me
MeO ~ -9 A Me
N •
,H OR
OMe
![Page 24: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/24.jpg)
PHOTOCYCLOADDITION PROCESSES
O. L. Chapman
127
![Page 25: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/25.jpg)
.,,*--+-
n -;r--
.".~
tT --t+-
52
... '" ! . '" c: Ow;
" ! u .:
---- cr* -cr*
.".* -+-".* • hI! hll .,,~.,,* n_.".f1
II n -+--" ---#-- 'II' -ff--".
4T2 _~~~~~;:V~«"rvV\"trvV\rv"V'~:c/ Vibrational ,_ -~ cascade
.;---TI
50---
128
![Page 26: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/26.jpg)
THE LIFE AND TIMES OF AN EXCITED MOLECULE
George S. Hammond
141
![Page 27: of the · twentieth national organic chemistry symposium of the american chemical society auspices of tile division of organic chemistry the university of vermont](https://reader031.vdocuments.us/reader031/viewer/2022022718/5c42786e93f3c338c32b0333/html5/thumbnails/27.jpg)
'1
A Mechanism for Photosensitized Reactions I
ISO hv I Is
~ Sn ~ . I
IS lAo kst 1 lA 1. + ) So + 1
IS k is )
'3S1 1
3S + lAo k tt .~
3A + ISO 1 1
lA 1 or
3A 1 ) Chemical Reaction
s ~ . S*(1)
8*(1) k
--4.L. 8
S*(1) -.!L s + hv
S*(I) kl S*(3) -
S*(3) ~ s
S*(3) + D k z
n*(3) + S -n*(3)
k3 D
D*(J) + n ~ - Dz
142