Fun, Foibles, and Follies In Collaborative

Research

Bruce A. HathawayACS Southern IllinoisLocal Section Meeting

February 7, 2000

Foible, According to Webster The part of a sword blade between

the middle and the point. A minor flaw or shortcoming in

personal character or behavior. An eccentric or whimsical liking or

interest in something.

Introduction

Collaborative research, to me, is where two or more individuals work together on a project. Each individual has defined responsibilities, and shares the credit, glory, honor, and (heaven-forbid) blame for the results. Ideally, the collaborators should work as equals, and have input on the planning, direction, and dissemination of the results. In this presentation, I will share some of the collaborative projects I have been involved with, including how the collaboration was initiated, the nature of the collaboration, and the good and bad points of the collaborations.

2-Aminoindanes with Steve Overmann 1984-89 Students got us together (Archie

Thurston and Rick Tolan). 6 students involved: Two went on and

obtained Ph.D.’s (Archie Thurston and Chip Wittenbrink).

I supervised preparations, Steve supervised biological evaluation.

Mike Rodgers did computer interfacing.

Synthesis of 2-Aminoindanes

R

H

O

R

H

COOH

H

COOH

HOOC

Pyridine, reflux

H2/Pd

R

COOH

RO

RO

N

OH

R

NH2H2/Pd,

HOAc, 60o

n-BuONOH2SO4 orPPA

NH2

Amphetamine

55° “Hot-Plate” Latency,5 mg/kg

0

2

4

6

8

10

12

14

Saline 2-AI Me Et iProp Bu iBu tBu

Sec.

Mouse Spontaneous Motor Activity Meter

8 Photocells

Computer

Mouse Spontaneous Motor Activity, 5 mg/kg

0

100

200

300

400

500

600

700

Saline 2AI Me Et iprop Bu ibu t-buCountsPer 30Min

2-Aminoindane Conclusions No “really good” compounds were

discovered. We couldn’t obtain external funding. No publications Steve became more interested in other

research projects. 6 presentations at MAS, other

meetings. 2 GRFC grants.

NASA-JOVE: Preparation of Non-Linear Optical (NLO) Materials 1993-8 NASA invited Southeast to participate. I had to find a NASA colleague to work

with. Spent one summer at Marshall Space Flight

Center and the Univ. Alabama - Huntsville in Huntsville, AL.

6 students involved (Jennifer Mabery, Jamie Carrigan, Angela Scates, Pat Zimmermann, Brian Taylor, Jeremy Wittenborn).

Preparations of Diacetylenes

C CR H CC R'Br+ R'CCCCR(Ph3P)2PdCl2, CuIEt3N solvent

C CR H2 Air, Cu+1

aminesolvent

RCCCCR

C CR' HBr2, NaOH orAgNO3

N-Bromosuccinimide

C CR' Br

Preparation of “DAMNA”

C CHOCH2 HBr2, NaOH

C CHOCH2 Br

CH3

F

O2N

NH

CH3

CCH

K2CO3

CH3

N

O2N

CH3

C CH

CH3

N

O2N

CH3

C CHCC CH2OHBr

(Ph3P)2PdCl2, CuIEt3N solvent

CH3

N

O2N

CH3

C C C C CH2OH

"DAMNA"

Polymerization of Diacetylenes

R C C C C R

R C C C C R

R C C C C R

R C C C C R

R C C C C R

R C C C C R

UV light

Diacetylenes Polydiacetylene

NASA-JOVE “Good News” Money for summer salary, student

workers, travel, operations. Summer JOVE meetings in Texas,

Florida, and California. Three publications and several

presentations by my students and I from the work we did.

Led to further collaboration.

NASA-JOVE “Bad News” My collaborator was only interested

in his compound, “DAMNA”, and did little with 25 we made.

He only contacted me when he wanted me to make more of his compound.

He never made me a co-author on any of his publications, nor acknowledged the work I did.

Rainer Glaser: NLO Materials 1997 - present We met at Organic Chemistry Day

at University of Missouri, when I presented a poster on NASA-JOVE research.

I prepare NLO materials, and Glaser gets X-ray structures and does theoretical calculations.

Preparations of Azines as NLO Materials

C

N

R1

N

H

P

OEt

O

OEt

G1G1

O

R1

H2NN

H

P

O

OEtOEt

1. NaH

2. G2

O

R2

G1

N

R1

G2

N

R2

Azines

Glaser Results Two publications and one

presentation. I received an ACS-PRF grant for my

part of the research. Four students have been involved

(Gary Bohnert, Scott Kirkley, Rachel Phillips, Steve Updike), one who is in the Ph.D. program at Missouri (Gary Bohnert).

Preparations of Ketenes with Jin Gong. Begun seriously in 1999 (some

informal consulting earlier). I supervise preparation of ketenes,

and Jin’s students react them with transition metal complexes.

Jin pays for one student (Andy Gilbert) whom I supervise.

Preparations of Ketenes

SnCl4,

C

C

HO

HO O

H

R C

CHO O

HR

C

C

O

R

Arylphenylketene 1. SOCl22. Et3N or heat

Preparations of Ketenes

R C

CHO O

HR

C

C

O

R

Diarylketene 1. SOCl22. Et3N or heat

C C

HO

HO O

OH

H

2H2SO4, HOAc R

R

Ketene Results Seven different ketenes have been

prepared. Some ketene complexes have

been prepared. At least one presentation will be

made this year.

Acknowledgements All of the undergraduate students

who did most of the work. Funding by NASA, ACS-PRF, GRFC,

and the Southeast Chemistry Department.

Helpful conversations with Southeast faculty, especially Bjorn Olesen.