PROJECT 325B MONTHLY SUMMARY REPORT PERIOD: APRIL 1, 1972 TO APRIL 30, 1972

• Document Type: CREST
• Collection: NGA Records (Formerly NIMA)
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80T01137A000100010010-8
• Release Decision: RIPPUB
• Original Classification: S
• Document Page Count: 56
• Document Creation Date: December 28, 2016
• Document Release Date: March 18, 2010
• Sequence Number: 10
• Content Type: REPORT

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PERIOD: April 1, 1972 to April 30, 1972
Submitted By:
Project 3Fa-nager
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PROJECT 325B
SUMMARY REPORT
PERIOD: April 1, 1972 to April 30, 1972
Project Manager
Copy 0 of 7
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1.0 CHEMICAL R and D .
Page
1.1 Leuco Dye Program . . . . . . . . . . . 1
1.1.1 D260 . . . . . . . . . . . . . . . 1
1.1.1.1 D260 Impurity Studies . . 1
1:1.1.2 Anthrone Route to D260
and Analogs . . . . . . . 2
1.1.1.2.1 Carbinol Resynthesis. . 2
1.1.1.2.2 Anthrone Synthesis
and Purification . . . 2
1.1.1.2.3 Attempted Brominations
of D263 . . . . . . . . 3
1.1.1.2.4 Attempted Oxidations
of Carbinol . . . . . . 4
1.1.1.3.1 Aging of Coating Solu-
tions for Formula 5 and
5/D7 . . . . . . . . . 4
C
1.1.2 Other Leuco Dyes . . . . . . . . . 5
1.2 CBr4 6
1.3 N-Oxide Program.m . . . . . . . . . . . . . 7
1.4 Binder Studies . . . . . . . . . . . . 7
1.4.1 Purification and Deoxygenation . . 7
1.4.2 Effects of Molecular Weight . . .
1.5 Environmental Studies . . . . . . . . . . 9
1.5.1 Controlled Air Studies . . . . . 9
1.5.2 Materials' Purifications . . . . . 9
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TABLE OF CONTENTS (continued)
Section Page
1.6 Other Film Systems . . . . . . . . . . . . 10
1.6.1 Formula 5/DPA . . . . . . . . . . . 10
1.8 Dye Identification . . . . . . . . . . . 12
2.0 ENGINEERING 23
3.0 PERKIN ELMER INTERFACE, QC/QA . . . . . . . 28
3.1 Supply of Film and Equipment . . . . . 28
3.1.1 Delivery pf 325B Film . . . 28
3.1.2 Delivery of Solvent Rinse . . . . . 28
3.1.3 Delivery of Red Lite Dev. Units . . 28
3.2 Cross Calibrations . . . . . . . . . . . . 28
3.3 Evaluation of Production, Shipping and
Contamination . . . . . . . . . . . . . . . 29
3.4 Monitoring of Results and Anticipation
of Subsequent Plans . . . . . . . . . . . . 29
3.7 QC/QA . . . . . . . . . . . . . . . . . . . 32
PLANS FOR REPORTING PERIOD . . . . . . . . . . . . . 38
FINANCIAL . . . . . . . . 38
Figures - 1.0 Chemistry
1 Formula 5/DPA Printouts . . . . . . . . . : . . 20
2 Formula 5/DPA Development . . . . . . . . . . . 21
3 Formula 5/D7 Developments . . . . . . . . . . . 22
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TABLE OF CONTENTS (continued)
Figure - 2.0 Engineering Page
4 Red Lite and DPO Decay Curve, AEI vs. Time . . 25
5 Decay Curve for Optical Developed Samples and
Samples Stored in CBr4 Vapors . . . . . . . . 26
6 Decay Curve for Optical Developed Samples,
Samples Stored in CBr4 Vapors, and Samples
Treated in Benzene Vapors . ... . . . . . . . 27
3.0 Perkin Elmer Interface, QC/QA
7 Printout vs. Red Lite Developed atand
P.E. . 35
8 Cabinet Filtration Units Control Chart . . . 36
9 Contaminants Pick Up by Room Air Filtration
Unit . . . . . . . . . . . . . . . . . . 37
Tables - 1.0 Chemistry
1 Aging of Formula 5 Coating Solution . . . . . 13
2 Aging Study of Standard 5/D7 Coating Solution. 14
3 Aging of Formula 5 Coating Solution (D7 Added
Just Prior to Coating) . . . . . . . . . . . . 15
4 Aging Study of 5/D7 Coating Solution Minus
D260 . . . . . . . . . . . . . . . . . . . . 16
5 Printout Exposure Comparison of LMG and
Analogs to LCV . . . . ... . . . . . . . 17
6 Structures of LMG and Analogs for Table 5 . . 18
7 Viscosity Measurements of Pressure Chemical's
Polystyrenes . . . . . . . . . . . . . . . . . 19
- 3.0 Perkin Elmer Interface, QC/QA
8 Comparison of ~ Controls and P.E.'s
Results . . . . . . . . . . . . . . . . . . . 34
Project Tracking Graphs
Project 325B Total Cost . . . . . . . . 40
Project.325B Direct Labor . . . . . . . ... . 41
Project 325B Manhours . . . . . . . . . . . . 42
Project 325B Material Only . . . . . . . . . 43
APPENDIX . . . . . . . . . . . . . . . . . . . . . . 44
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Project work has continued at a high level during the
month of April and in most task areas follows the original
plan of work and time schedules.
CHEMICAL R and D
Improvements continue to be made in yields of photograde
D259, a precursor of D260, has been positively identi-
fied as an impurity in D260.
Purifications and preliminary film evaluations have been
completed for a,series of Leuco Malachite Green (LMG) analogs.
In all cases the photosensitivities are vastly inferior to
D260 and LCV.
An apparently pronounced synergism between D260 and CBr4
has been identified. As -a result of improved D260 purity
previously labeled "bad" CBr4 is now found to give very good
5/D7 films.
Binder purification studies have continued, but have
been delayed due to mechanical difficulties.
Work has begun to study the effects of polystyrene molecular
weight.
A purified air chamber has now been used successfully
to produce good quality films.
A color interaction has been observed between benzene and
D7. The purity of benzene is now suspect and is being investigated.
Work on the 5/DPA was begun. Preliminary results appear
superior to those last obtained in late 1970. This system has
been found' to markedly differentiate samples of D26"0 which give
comparable and hence indistinguishable films with 5/D7.
Preliminary work began on the Dye Identification program.
This work was hindered as a result of two man weeks lost due to
illnesses.
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1.0 CHEMICAL R AND D
1.1 Leuco Dye Program
1.1.1 D260
A dramatic improvement in yield of photograde D260 has
now been realized by using dry column chromatography. The
yield has been raised to 84% from the 48-61% yields realized
by the trituration and recrystallization procedures described
last month.
Some one dozen small scale purification procedures were
also investigated this month. Details of these studies will
not be elaborated, but it is noted that differently prepared
samples of D260 are found to give essentially indistinguishable
results with 5/D7 but give quite dramatic differences with
5/DPA (see Section 1.6.1). These different samples are
indistinguishable by TLC except that small and different
amounts of D259 and anthrone are present as impurities. Addi-
tion of D295 and/or anthrone to either sample failed to alter
its behavior significantly. It is therefore concluded that
the differences noted by the DPA system must be due to an
undetected impurity. Mass spectral studies as well as repeats
of the purification procedures are underway to detect the
impurity(s). It is suspected that the impurity may be D260-
hydroperoxide or similarly related peroxides. Since the
hydroperoxide and other related peaks have been seen in mass
spectra of D260 samples, it is hoped that direct and careful
comparison of these different D260 samples will aid in
clarifying this suspicion.
1.1.1.1 D260 Impurity Studies
Work continues to identify gross and trace impurities in
crude and purified D260. Although D260 does not fluoresce
under long UV light, it was discovered that D259 does fluoresce
and is present-as a significant impurity in crude D260.
Virtually all D259 is removed from crude D260 by ethyl ether
trituration or by column chromatographic purification.
Decomposition of hydroperoxide of D260 has~been postulated
as one source of anthrone and concurrently, 4DMAP. Prolonged
irradiation of a benzene solution of D260 with an intense UV
source rapidly increased the amount of anthrone present.
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Irradiation in excess or in small amounts of air did not
qualitatively change the rates of decomposition of two dif-
ferent samples. Since anthrone is detected by UV on TLC
at a much lower level (10 ppb) than 4DMAP is detected by
visual spray (0.01%), irradiation was continued for a prolonged
period. At the end of 10 to 12 hours, a spot corresponding
in Rf value and color to 4DMAP was detected in this irradiated
sample. Since the presence of microgram quantities of 4DMAP
in the film system has been shown to be deleterious, the
visualization by TLC of even 10 ppb of anthrone may signal
that enough 4DMAP is concurrently present to be damaging.
Anthrone itself has been shown not to be damaging up to
the milligram level.
Work continues in an attempt to demonstrate a one-to-one
relationship of anthrone to 4DMAP. It will be remembered
that such a relationship provides convincing evidence for the
presence of D260 -hydroperoxide.
Purified D260 (2 g) was stirred with NaBH4 in methanol
in an attempt to eliminate anthrone. A TLC indicated anthrone
was still present.
1.1.1.2 Anthrone Route to D260 and Analogs
1.1.1.2.1 Carbinol Resynthesis
In a repeat of the first oxidation in March, another
10 g of D263 was oxidized to carbinol by the Aaron and Barker
procedure, using lead dioxide paste. The yield was doubled,
now closely approximating the literature report.
1.1.1.2.2 Anthrone Synthesis and Purification
The carbinol formed above was dismuted according to
Aaron and Barker to give 6.45 g of crude anthrone. Work
throughout the month on the column purification of the
anthrone hammered home the true meaning of "dismutation" as
used by Aaron and Barker. Carbinol does disproportionate
between D263 and anthrone. The many samples that were being
chromatographed this month all contained D263, carbinol and
anthrone. Highly colored impurities are left behind by
column chromatography, but a good separation of anthrone from
carbinol may require chromatography with automatic sample
collection on a tall, thin column. D263 is the most mobile
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component, fairly well separated from anthrone and carbinol.
The latter two move quite slower and are difficult to separate.
Recrystallized anthrone has been obtained, mp 210-211?
(Aaron and Barker mp 207-208?), as pale chalky-green crystals.
This procedure has been abandoned, at least temporarily,
to provide time to explore more attractive possibilities to
the anthrone.
.1.1.1.2.3 Attempted Brominations of D263
Two attempts were made to brominate D263 with N-bromo-
succinimide. The objective was to form mono- or dibrominated
derivatives of D263 which should yield carbinol or anthrone,
respectively:
CH3 CH3
(CH3)2N ^\/~ N(CH3) 2 (CH3)2N
D263
or
4f
(CH3)
H3C CH3
H3C CH3 H
OH )
HOH
carbinol
N(CH3) 2
H3C\CCH3
N(CH3)2 (CH3)2-r..> cd ?r 4 U) 0
O O a)
0
W Cq E?+ U F U
r-1 N
r-I N M d+ tf)
tf~ to t1~ U) U) tf)
N N N N N N
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