Dr. John J. Eisch Distinguished Professor, Organic Chemistry

Chemical and Personal Rearrangements

at the occasion of his Retirement Symposium October 28-29, 2011

In honor of

By Csaba A. Kovacs

10-28-2011

B.D.E. (Before Dr. Eisch)

1956-1957 For summers technician for Professor Bryce Maxwell

Princeton University’s Polymer Laboratory

1958 Thiokol

1960-1966 US Army’s Chemical Unit

1961-1966 Research Laboratories of the National Drug Company

1963-1966 Graduate Student with Professor Robert Koob, MS program

A.D.E. (After Dr. Eisch)

1966-1970 Graduate Student with Dr. John J. Eisch, Ph. D. Program

1970-1972 Research Fellow for Dr. John J. Eisch

1972-1974 Research Fellow at Wright Patterson Air Force Base

Polymer Laboratories

1974-1999 Senior Staff of Eastman Kodak’s Research Laboratories

2005-2010 Research Director of the Tianjin Zhaoyang Nanotechnology

Company’s Research and Development Laboratories

10-28-2011

B.D.E. (Before Dr. Eisch)

1956-1957 Summers technician for Professor Bryce Maxwell

Princeton University’s Polymer Laboratory Professor Maxwell was the inventor of the mechanical spectrometer to test

polymers for the loss modulus. Karl Rehn prepared poly propylene for the first time in March 1954. I was testing it in 1956. Polypropylene is in now a 65 billion/year commercial product.

1958, Thiokol Poly Urethane Foams

1960-66 US Army’s Chemical Unit Smoke Generator Operator

One 50 gallon drum of fog oil can cover 60 square miles (97 km) of land in 15 minutes.

1961- 66 Research Laboratories of the National Drug Company Pharmaceutical Chemist

In the 60-s, there was no modeling software to design active compounds. The shotgun approach

was used. A basic new core structure was selected or designed and different known active

groups were attached to it. (This always involved an extensive synthetic effort.) Then the

compounds were screened for biological activity.

1963-66 St Joseph University’s MS program with Dr. Robert Koob,

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1.75 2.27 3.93

Solvent Dipole Moment Effect on the o/p Ratio in the

Fries Rearrangement

Solvents:

o-Dichlorobenzene

Chlorobenzene

Nitrobenzene

Dipole Moment

O/P

Ratio

10-28-2011

The Start of my A.D.E. Period at

The Catholic University of America

One of Professor Eisch’s interest was to study the mechanism of

1,2 Anionic Rearrangements

10-28-2011

Found:

2-Pyridyl >Phenyl >4-Pyridyl

Migration Tendency

1,2 Rearrangement in the Reaction of Lithium with

2,2-Di phenyl-2-(2 or 4-pyridyl)ethyl Chloride

- Anticipated:

2-Pyridyl >4-Pyridy l>Phenyl CH3I

10-28-2011

Nitrogen Analog of the Wittig Rearrangement

10-28-2011

Wright-Patterson Air Force Base –

Materials Laboratory

Polymer Division

My original research proposal was to prepare spiro-silane polymers.

For polymer formation very efficient reactions were needed.(> 90%)

A large number of reactions were investigated. Two are illustrated below.

1.

2.

Boeing B-52 Stratofortress

10-28-2011

Inter Layer Development for Polycarbonate and Glass

Requirements: 1. Good optical properties. 90% transmittance, <1% haze, U.V. stability, refractive index close to glass.

2. Good adhesion to glass and polycarbonate

3. High tensile and tear strength

4. Retain physical and mechanical properties at high temperature

(350-450º F)

Modification of Polymers

ACS Symposium Series

121, 31, p457-468

10-28-2011

Eastman Kodak Company

1974-1999

1. Sensitizing Dye

2. Photographic Chemistry

3. Mass Memory (Optical Disks)

4. Inkjet

Research Laboratories

My first assignment at Eastman Kodak Company was to

determine the reason for an imaging dye fade on long term

storage in in a product. The dye of interest was a carbocyanine

dye with a structure shown below.

US Patent 3,619,194

10-28-2011

Dye Decomposition Product

Solvent, 80ºC

Proposed Mechanism for the Decomposition Rearrangement

10-28-2011

Exposed Silver Salt + Developer Oxidized Developer

Oxidized Developer + Coupler Dye

Dye Formation in Color Photography

10-28-2011

Blocked Leuco Dyes

Ag Agº +

US Patent 4,423,126 10-28-2011

Dye Based 14 inch Optical Disk

The Recording Layer

IR dye (λmax = 780nm)

with a mixture of inert

organic molecules forming

an amorphous glass on the

disk with spin coating.

10-28-2011

The Recording Layer

IR dye (λmax = 780nm) mixture forming an

amorphous glass on the disk using spin

coating.

Writable CD

10-28-2011

Specifications of DVDs and CDs

DVD CD

Spectra of DVD and CD Dyes

10-28-2011

The Inkjet years.

Designing Ink Jet Inks is a Hard Process Things that have to be considered and controlled :

Print Quality, Print Speed, Reliability, Media Flexibility, Durability, Cost and Safety.

In order to be able to get excellent prints, all parts of the system have to work together.

These are: the printer, the driver,the ink, and the receiver.

Material Selection Ink Properties Jetability Ink Media Interactions

Ink Base

water

wax

polymer

monomer

solvent

resin

Colorant

dyes

pigments

Dispersants

Humectants

Penetrants

Surfactant

Biocide

Plasticizer

Buffer

Anti-foamer

Anti-bleeding agent

Anti-cockle agent

Chelating agent

Toxicity

Chemical Hazard

Fire Hazard

Dye solubility

Pigment content

Particle size

Stability

Color

Purity all materials

Viscosity

Surface tension

pH

Melting point

Specific heat

Specific gravity

Conductivity

Sound velocity

Bubble nucleation

Kogation

Crusting properties

Drop formation

Drop volume

Drop shape

Drop velocity

Drop frequency

Drop placement

Drop satellites

Nozzle clogging

Due to:

ink drying

contamination

Ink-Print head

compatibility:

Corrosion

precipitation

softening

swelling

Air bubble

Nozzle wetting

Nozzle crusting

Color quality

Dot size

Dot shape

Optical density

Banding

Dry time

Gloss uniformity

Feathering

Spreading

Bleeding

Coalescence

Water fastness

Smear fastness

Rub resistance

Scuff resistance

Fold resistance

Light and dark fastness

Curl

Cockle

10-28-2011

•Synonym: Astra Blue Base 6 GLL, Basic Blue 140

•Empirical Formula: C47H52CuN14O6S3

•Molecular Weight: 1068.75

•CAS Number: 82864-57-1

Stable Dye Based Inks

10-28-2011

Eastman Kodak Employment Chart in Rochester

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Employees

10-28-2011

What are Kodak’s problems?

Poor market intelligence

Limited understanding of the digital world

Comparing everything to film

No holding power

R&D Organization

Dr. Csaba A. Kovacs

Director & Chief Scientist

Product R&D Dept. Dr. Csaba A. Kovacs

Department Head

Analytical & System

Evaluation Dept. Dr. Csaba A. Kovacs

Department Head

Ink Technology Dev. Lab.

Wang, Wenjie

Lab Manager

Nanoparticle

Dispersion Lab.

for Ink

Shi,

Jinyong

Group Leader

Zhang,

Junling

Technologist

Wang,

Liyuan

Technician

Bio-

Nanoparticle

Dispersion

Lab.

Liu,

Xiaojie

Group Leader

Wang,

Nan

Technologist

Piezo Group

Liu,

Xiaobo

Group Leader

Deng,

Yingchun

Technician

Thermal Group

Du,

Wenfei

Group Leader

Chen,

Yang

Technologist

Advanced

Analytical Lab.

Vacant

Lab Manager

Zhong.

Liurong

Technician

Zhang,

Zhifang

Technician

Competitive

Analysis &

Control

Testing Group

Kang,

Suxia

Engineer

Northern

Light

Liu,

Xiaojie

Project

Manager

Special

Projects

Wen,

Pei

Engineer

Printing

System

Liu,

Hongfang

Engineer

New Technology &

Applications Group Dr. Csaba A. Kovacs

Chief Scientist

Tianjin Zhaoyang Nanotechnology Company

10-28-2011

Professor Eisch’s had a major influence on my life. His drive to develop an understanding for the nature of things and to have fun doing it was infectious.

It was a joy to bring an interesting observation or a new idea to Dr. Eisch. His brain started to race and hundreds of other ideas related to the problem popped into his head. He always respectfully listened to your ideas and logically evaluated them. I had many discussions with Professor Eisch mainly in front of the lab’s blackboard.

I never enjoyed chemistry as much as during my time with Dr. Eisch. The academic freedom, the ability to do new things and get exited about discoveries was never greater then during this period of my life. I still remember this time as the most fun part of my life.

For this I thank Professor Eisch profoundly.

10-28-2011

END