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0 '.. Technical Document 1220 January 1988
Laser Dye Synthesis Group C Compounds E. J. Grubbs San Diego State University Foundation San Diego State University
soSTAES
*,
Approved for public release: distrbuton is urdkmited,
*
The views and conclusions contained in this report are those of the authors and should rnot be Interpreted as representing the official policies, either expressed or Implied. of the Naval Ocean Systems Center or the U.S. Government.
NAVAL OCEAN SYSTEMS CENTER San Diego, CaI1foni3 q2152-5000 E. G. SCHWEIZER. CAPT. Commander
R. N. HILLYER Technical Director
JTSN
ADMINISTRATIVE INFORMATION This task was performed for the U.S. Army, Army Missile Command, Redstone Arsenal, AL 35398. Work under contract N66001-85-D-0203 was done through the San Diego State Univerilty Foundation, San Diego, CA 92-182. The Contracting Officer's Technical Representative was T.G. Pavlopoulos of the Chemistry/Biochemistry Branch, Naval Ocean Systems Center, San Diego, CA
92152-5000.
Released by E. Lindner, Head Chemistry/Biochemistry Branch
Under authority of S. Yamamoto, Head Environmental Sciences Division
LH
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Army
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-ASK( NO
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RY
Redstone Arysenal, AL 35398RDAMY
Group C Compounds
Laser Dye Synthesis 2PERSONA.
AGENCY ACCESSION NC
A_-7HOR(S)
E.J. Grubbs TYPE OF ZE:ICRT
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PIELD
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TO-
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GROUP
DATE OF REPORT IYea(.A,V onen January 1988CON
S
4E
ON
SUBJECT TERMS (Conir"onrviwm fnewusaryadafyrby irinmbw
SUB-GROUJP Laser dyes
9~gABSTRAC7
Carnon
weIncessarynd ie"ybock
nmer)
This report describes progress on the syntheses of a number of new potential laser dyes. The goal is to generate new structures allowing the upscaling of flashlamp pumped dye lasers to high energies. These systems ideally should show a lower action thres.hold. operate with high efficiencies, and exhibit greater photochemical stabilities than do those presently available.
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T.G. Pavlopoulos
DD FORM 1473, 84 JAN
C] DTIC USERS
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This report describes progress on the syntheses of a number of new potential laser dyes.
The goa! is to generate new structures allowing the
upscaliing of flashlamp pumped dye lasers to high energies.
These systems
ideally should show a lower laser action threshold, operate with high efficiencies, and exhibit greater photochemical stabilities than do those presently available. P3vlopoulos has proposed (a) that the parent aromatic chromophores be 5!Pqtiruted by auxochromic grojpV
q,,o$
i
nd dlkyduiu
hydroxy, alko-, K
and (b) that improvement should result by restricting the chromophore and auxochromic group to coplanarity.
This should reduce intersystem crossing and
thus improve the quantum fluorescence yield.
The potential dye lasers
described below are designed to meet these objectives. I. The Synthesis of 1,2-bis-(9,10-dihydro-2-phenanthryl) ethene
(3).
This extended stilbene was prepared by converting dihydrophenanthrene to the
ald~'yde using dichloromethyl methyl ether and stannic chloride.
The
1 general method has been described by Rieche, Gross, and W6ft.
I)Cl 2 CqO'CH 3 ,SnCl 4 -
i
--
0 --
2)H 2 0
2
The crude aldehyde was obtained in 85%
H
yieiu uut appears to be a mixture
of the 2-carboxaldehyde (shown) and the 3-carboxaldehyde in a ratio of about 3:1.
The proton nmr spectrum of this mixture shows the expected aromatic
absorptions at 67.1-7.4 (7-proton multiplet), a four proton multiplet center at 62.86 and two aldehyde singlets at 69.86 and 610.3.
The mass spectrum was
consistent with the proposed isomeric mixture showing the molecular ion at m/e 208 and fragments corresponding to losses of the aldehydic hydrogen, the aldehyde group (M+-CHO, parent ion),
and the CH)CH 2 bridge.
The aldehyde mixture was subjected to the McMurry coupling procedure 2 as 3 modified by Geise and coworkers.
0
~~TiCl 3 /LiA.V14
\
