to do: work on memo in support of motion for injunction.
draft letter re steve buchanan X
find death date for c a stewart jr for tax purposes X 4/2/1998
Clare A. Stewart, Jr.
Consultant, Wilmington, Delaware
Chloroprene (under Chlorocarbons and chlorohydrocarbons)
he belonged to zeta chi fraternatity at baker university .. just one of many things i didn't know about him.
pubs.acs.org/cgi-bin/abstract.cgi/jacsat/1962/84/i01/f-pdf/f_ja00860a033.pdf?sessid=9497 -
118 COMMUNICATIOTON TSH E EDITOR voi. a4
than a hundred times faster in nitromethane than in
tetrahydrofuran while several related Diels-Alder
reactions4 are accelerated by a factor of about two
for the same solvents. If both I and I1 were formed
from a common, rate-limiting transition state,
as would be expected for an intermediate of the
type proposed by Woodward for the Diels-Alder
reaction collapsing in either of two possible directions,
the total rate of reaction would be expected
to show only the slight solvent effect which is
generally characteristic of Diels-Alder reactions.
Since this is not the case, it is necessary to conclude
either that a change in mechanism has occurred
with a change in solvent or else that I and I1 are
formed in either solvent through separate ratelimiting
transition states, quite likely involving,
respectively, the transoid and cisoid configurations
of the diene. Attempts at thermal interconversion
as demonstrated by Woodward5 and Roberts7 in
related systems (at the suggestion of Prof. Roberts)
were thwarted by the limited thermal stability of I
under conditions such that I1 was virtually unchanged.
Decomposition appeared to be accompanied
by gas evolution and formation of conjugated
structures (strong absorption at 4.5, 6.1,
6.3 microns) and may be related to elimination
reactions previously described for tetracyanocyclobutanes.
s
Acknowledgments.-The author wishes to thank
Dr. P. D. Bartlett, in whose laboratories several
aspects of this reaction are being investigated, and
Dr. J. 11. Roberts for helpful discussions.
(7) R. P. Lutz and J. D. Roberts, J. Am. Chem. Soc., 83, 2199
(1961).
(8) J. K. Williams, D. W. Wiley, B. C. McKusick, 139th ACS
Meeting, St. Louis, Mo. (1961) abstracts p. 9-0.
CONTRIBUTIONNo . 113
ELASTOMECRH EMICALDSE PARTMENT
EXPERIMENTASLT ATION
E. I. DU PONTD E NEMOUR&S COMPANY
WILMINGTOND,E LAWARE
CLAREA . STEWARTJR, .
RECEIVEDN OVEMBE1R5 , 1961
CYCLOPROPENYL COMPLEXES OF IRON AND
COBALT
Sir :
n-Bonded metal complexes of the
Atmospheric Circulation of DDT: Clare A. Stewart, - letters to science magazine, about DDT, 1971, 72.
http://www.sciencemag.org/content/vol177/issue4050/index.dtl
COMPETING CYCLOBUTANE FORMATION AND
DIELS-ALDER REACTION
Sir:
We wish to report what appears to be the first
observed instance of competitive formation of
cyclobutane and cyclohexene adducts under mild
conditions. The only previous instances of such
competition are the condensation of tetrafluoroethylene
with cyclopentadienela and the thermal
dimerization of butadiene, Ib both of which involve
rather drastic conditions and are relatively unsuited
for the determination of differences in reac-
http://pubs.acs.org/cgi-bin/archive.cgi/jacsat/1962/84/i01/pdf/ja00860a031.pdf
1,3-pentadiene,? which will not undergo a normal
Diels-Alder reaction with maleic anhydride, reacts
overnight at room temperature with the more
potent dienophile, tetra~yanoethylenet~o form in
good yield a mixture of 3-(2-methylpropenyl) -
1,1,2,2-tetracyanocyclobutan(Ie) and 3,3-dimethyl-
4,4,5,5-tetracyanocyclohexene-1(1 1). The cyclobutane
(I) is isolated readily by ether extraction of
the crude solid reaction product from tetracyanoethylene
and excess methylpentadiene in tetra-
I I1
hydrofuran solution at room temperature,3 to give a
69% yield of insoluble white crystals, m.p. 136-
137 after recrystallization from benzene-cyclohexane
(Anal. Calcd. for C12H10N4: C, 68.5; H,
4.8; N, 26.6. Found: C, 68.8; H, 4.9; N, 26.1).
The cyclohexene adduct (11) was obtained in 11%
yield by passage of the ether extract through a short
column of alumina, evaporation, recrystallization
from benzene, cyclohexane and subsequent sublimation.
The melting point of this compound
appeared to lie in the range of 155-165", but was
obscured by sublimation and/or phase change even
in a sealed tube (Anal. Calcd. for C12H1nN4: C,
68.5; H, 4.8; N, 26.6. Found: C, 68.8; H, 5.0;
N, 26.2, by difference). Xuclear magnetic resonance
and infrared spectra are in agreement with the
assigned structures.4
In view of the possibility of these compounds
arising from a common intermediate as postulated
by Woodward5 for the Diels-Alder reaction, a brief
examination of the effect of synthesis conditions
on the ratio of products was made. The crude
product obtained in essentially quantitative yield
at 2" (2400 min. time for color fading3) contained
12y0 I1 while at 57" (35 min.) 17% I1 was observed,
as estimated by comparison of infrared spectra with
known mixtures. The differences of enthalpy and
entropy of activation are calculated to be 1.4 f
0.5 kcal. (favoring I) and 1.4 =t 1.5 cal./°C. (favoring
11), respectively. Reaction in cyclohexane
(180 min. at 65') gave a product containing more
than 30% I1 in addition to a small amount of
degradation products. Reaction in nitromethane6
gave essentially pure I in 7 minutes at room temperature.
The very small differences in activation
parameters are to be expected if the two products
are formed from a common high-energy intermediate
or transition state, but are more likely fortuitous
in view of the remarkable solvent effect.
As can be seen above, the formation of I is more
(2) G. B. Bachman and C. G. Goebel, J . Am. Chem. Soc.. 64, 787
(1942).
(3) W. J. Middleton, R. E. Heckert, G. L, Little and C. G. Krespan,
ibid., 80, 2783 (1958).
(4) Elaboration of the spectra of these and related compounds will
be reported in a forthcoming publication.
( 5 ) R. B. Woodward and T. J. Katz, Tetrahedvon, 6 , 70 (1959).
(6) D. W, Wiley, private communication, has found that the rates
for cyclobutane formation from tetracyanoethylene and electron-rich
olefins vary over a 105-0 range depending on solvent, with nitromethane
being one of the fastest and cyclohexane one of the slowest.
Competing Diradical and Eleetrocyclic Reaciions.
Difference in Activation Volumes
Sir:
Numerous examples are now known in which thermal
reaction of a diene with a dienophile reagent produces
mixtures of cyclohexenes and vinylcyclobutanes.' It
is generally accepted that the cyclohexenes result from
concerted, electrocyclic reaction allowed by orbital
(I) (a) P. D. Bartlett, Quorf. Reo., Cihcm. Soe.. 24. 473 (1910);. (b)
C. A. Stewart. Jr., 3. Amrr. Chem. Soc.. 84, 117 (1962); (e) J. C. Llttle.
ibid.. 87. 4020(1965).
(3) W. L. Dilling, Chem. Reu., 69, 845 (1969), and references cited.
(
4) C. A. Stewart, Jr.,J. Amer. Chem. Soc., 93,4815 (1971).( 5 ) Isomer 5 results from rearrangement of lb during the course
http://pubs.acs.org/cgi-bin/archive.cgi/jacsat/1972/94/i02/pdf/ja00757a055.pdf
Competing Diradical and Eleetrocyclic Reaciions.
Difference in Activation Volumes
Sir:
Numerous examples are now known in which thermal
reaction of a diene with a dienophile reagent produces
mixtures of cyclohexenes and vinylcyclobutanes.' It
is generally accepted that the cyclohexenes result from
concerted, electrocyclic reaction allowed by orbital
(I) (a) P. D. Bartlett, Quorf. Reo., Cihcm. Soe.. 24. 473 (1910);. (b)
C. A. Stewart. Jr., 3. Amrr. Chem. Soc.. 84, 117 (1962); (e) J. C. Llttle.
United States Patent 5064935
Continuous process for preparing poly(butylene terephthalate) oligomer or poly(butylene isophthalate) oligomer
US Patent Issued on November 12, 1991
Inventor(s)
Clare A. Stewart
David J. Lowe
Roy Jackson
Assignee
E. I. DuPont de Nemours and Company
Application
No. 561468 filed on 1990-08-01
Current US Class
528/272 , From di- or higher ester of a polycarboxylic acid as sole reactant, or from a polycarboxylic acid or derivative with a compound containing two or more hydroxyl groups or salts thereof 528/279 Material contains a Group IVB metal atom (Ti, Zr, Hf)
Field of Search
528/272 , From di- or higher ester of a polycarboxylic acid as sole reactant, or from a polycarboxylic acid or derivative with a compound containing two or more hydroxyl groups or salts thereof 528/279 Material contains a Group IVB metal atom (Ti, Zr, Hf)
Examiners
Primary: Harold D Anderson
Assistant: T Mosley
Attorney, Agent or Firm
Abstract Claims Description Full Text
Abstract
Economic and efficient process for preparing an oligomer of poly(butylene terephthalate) or an oligomer of poly(butylene isophthalate) from a transesterification reaction mass by using a countercurrent column reactor system wherein the transesterification reaction mass is fed into the countercurrent column reactor and continuously flows downward while simultaneously a heated inert gas stream continuously flows upward to scrub out volatiles from the transesterification reaction mass, thereby yielding from the bottom of the countercurrent column reactor an oligomer of poly(butylene terephthalate) or an oligomer of poly(butylene isophthalate) suitable for use in a polycondensation reaction. Butanediol is recycled throughout the process through an absorber column.
Dad had a patent! not surprizing really.
http://www.patentstorm.us/patents/5064935.html
Inventor Clare A. Stewart
Address: Wilmington, DE
No. of patents: 1
Last patent issue date: 1991-11-12
I like to joke that he was employed by the military industrial complex, inventing new carcinogens. Polybutalene, something to look into later.
remember some other thing...
collect rent
food to 227
get truck
charge phone
make to do list.
cle's
letter to lawyer for WRTV6.
