Laser Dye Synthesis - Group C Compounds - DTIC

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TiCI3 /LiAlH4. 5 ... Q. Q CH3 + other products. ThF. C. Condensation-dehydrobromination of 2-bromomethylfluorene. Pinck and Hilbert5 have described theĀ ...
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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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Approved for public release; distributiorn is unlimited. 5 MONITORING ORGANIZATION REPORT NUMBERS

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NOSC TD 1220 6a. NAME OF PERFORMING ORGANIZATION San Diego State University Foundation San Diego State University 6c; ADDRESS 'ClySaMand7JPCode)

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a NAME OF MONITORING ORGANIZA7hON NvlOenSsesCne NaaIca ysesCne 7b, ADDRESS (CIv.Stale andZIPCaa

San Diego. CA 9182

San Diego, CA 92152-5000

8a. NAME OF PUNDING, SPONSORING ORGANIZATION

Army

issie

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ComandN66001-85-D-0203

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10. SOURCE OF FUNDING NUMBERS PROGRAM ELEMENT NO. PROJECT NO

-ASK( NO

N015

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

13a

13b. TIME COVERED

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FnlFROM SUPPLEME' NAP'" NOTATION

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COSATI CODES

PIELD

14,

TO-

1S.

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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TELEPHONE In#chhACade

(619) 553- 2792 83 APR EDITION MAY BE USED UNTIL EXHAUSTED ALL OTHER EDITIONS APP ORSO1rTF

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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.

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