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!

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AO- 351275
SECURITY REMARKIN6 REQUIREMENTS
DOD 5200.1-R. DEC 78
REVIEW ON 28 MAy

8~

_.-•.

---.~-

-- -- -

.. .. -'

...

-

SECRET
U. S. Army
Chemical Research and Ds,elopment laborator!es
Technical Report
•

CRDtR 3213

.."
~.-

I
,

~,

Brunie E. Hackley, Jr.
(hap~elle C. Cochrane
Ethel B. Hackley

May 1964

EDGEWOOD ARSENAL, MD
Group 3
Downgraded at 12 Year Intervals;
Not Automatically Declassified.
(opy....:,;.:... of _Copies

SECRET

CR DL·P II b·4 2·S·63

Ddt:nsc D.>cum,mtation

Cent~r

AvaUabiht Z" ~OtlCC

Quahf~.:"d :-cqucstcn; n--Al" obtain copies of this report from
H,,·atlquartt-r!'. Dd,'nSl' Oo('umcntation Cl.!nter. AUn: TISIA--l.
Canlt'r(~n :Sto1l1on ••\iexandna, Vitginia.

CKDU lZ13

May 19M

SOltE CH&WlCAL. RE.~.CTI0NS Of' BZ (U)

Sret:ru.Q E. Hackley. Jr.
ChsppdJ.e C. C~hr&1'\e
Ethel & Hackley

; ...... !'P~.

!-~.~.J~

Colonel. Me
Directcr of Medu.. 4Il Ilesurch

S. D. sn..VSJt
TftCbnieal DirC4:tor

U. S. Army Ed,~ Araenal
CHEWlCAL a£SJ;A.!tCH AND OE:VJ:LOPJ.""PT LABQaAroJUltS
F.d,e.ood M.eM~. NArylarui

SKMT

(U)

This 'IIIOf'it _as ~Oftductt'd under Tuk .. .c08.0';-Ol~i1. Biochemical Action of Ch.mlu.l Aiel. {U). The e:xperunental data are com.ainet:!
m notebook. MN-14Sl.. WN-1465. )01-1-«0. MN-1400-and MN·1587. n.
work .as .lut.ed in MArch 1961 L~ completed iro Apt'll 1~6l.

~ ilu!hcra 'Wlsh to adtaCiW1edac the technical a .. b~~ ~£
David E. Il~d, CllUOTd Shlblom. M.ermeth E. Stine. a.nd
Rot>ert L. Oreef2.

.a... rt.

Tru. doc.'ment cont;uns iNormatt.nn Uf~ctml the ~tiow ~efen.e
of the United Statll!S "'l\."in the mcan!nl of the £sp1OtlSCe ~'JI". '!itle I~.
U. S. C .•• ection. 793 aa:d 194. The tl'ansmi .. icm C"l" tl1. n"'eu-tion of it~
contenh itt any m&:lnGr to ~"' un&t;tnorued per.~n ~. ~ohibitri by law.
aeptodu.t;tion of ~,t. document in _bole or p!ls-t ia prohibited
except with the pe!'nunion of tbe iuuml oUice; ru.,w.ver. DOC i, aGthQrb~
to r4tproduco th. document for U. S. ao-/eJ'runental p.up'Jaes

When thit document bu .erv~ it. ~rpou. OESTllO"! it lP;
&cccrdance .1Ut AR. laO.; DO NOT ret~n the datum.ill to U.S. A:tm.y
Chemlc:al a~ ..arch and Dey~~ lAboutoriu.

CONFID£NT'aAL
DIGES1'

tel

,nul, of the ch.1!mhtry of UZ

A runda.rn~r.tal
aSS11&t 1n prQb1=ems that m~7

v,r,s,jI

cOllduct~d 1O

:ri~~ til d~uctton. de~on"mH'Jat~on. bl0choll!mi~.u
mechanism of :>("t\on. ~nG m~taboli.m. a2 re 1eU ~'1tn t:t) .u.b~tiN· ..d pbt'nvi
I §G-I!fiS,n&tClf to 'fu:td 2. -4-oxa,c.olid1n~dioClte". (b) ni~"llel w produc;e a T.1d1eil
(Ritt~r ru.ctiO'rt1. ~ (el alkyl h.a.lldes to ,lye ~te'rn.u-y a..'<fltnOl1h - ,a.1h
Anaiy.ill of 5l. e~n be &cc:ompU.b~d by quatlerruutio\: in acetonilrilt:
lepa.r&tion of l"t!actanta. usd & • • • .,inl .pe~tral1y

SOME CHEMICAL REACTION') OF BZ {U}

IS)

(S}

INTRODUCTION
al. ill

~ cnmpaund that ha. ~fOn t~ dasai£led as an inc.,'lpac:itattng
To assat in the ev;iluation 0: the blololical propertt.cs of the
agt'!'nt. andpt'oblerns of ml'nu!acture. stor.. ge stability, detectton. dc .. 'mt.mi·
natmn. bsochrmu:>ll mechanishl of :l~ti(ln, tino mtttab;,h=tm. a tundam .... tal
.. tudv of the chemist.-'! of az has been made,

tU}
(hemic.al

IS~

,;}t~s:

ag~nt

In th,.

(,~lem~cal

structure cl BZ there Clt"e three ~rim~'1 reac:li¥e
f:') tnt" ~stn Hnkage. and tcl the qUlnuc:1idinyl

la) thr tl'tUal'\' ;:.kc~1

-0-

n)
9 j\-I
o-c-c
~tI Of!
i~Uh
~'\
{'

f

-

nitro~e'n atom, It. surv-:y of the 1ite~ature (open and claniHed) on benl-H'iie
ester! ~or.tainU'l1 a tt"rtiary nttl'olen !U the J'-pos!tion of the alcnhol
moietyl. Z. 3," shq ... s that mo~t attention ~. been c!ire<:t~d to rt:'lcttons ~! thl"
tertiary nitrolen. i. e., qU<it~rt'tu.:atiot'l and salt formAtion, ..,hd~ httle has ~~n
done or. the dlr~c:t r eacuons ot' tbf' hr"droxy' function A conSiderable errort
haSl been elCl~nd~d in th~~~ ~bt1ral0r1eS on th~ hvdrolytlc cl~a...age of Bi!.
The purpose of thl$ res .. ;ut:h Wil.!. to !tudy ru-eho:u of the teru3.ry hydroltyt
group as .. ell as reactions 'p1!clhc: fol" bt'n~,late e'lters that invr/Ol 'e a bi
functional Q'/: hl.o cente-r«i atta~]r. on th ... akoho! and ~.tf!r li:tlkagt:. 1.. additum.
stJmco prevIously unrepr>rtd q~ ~rr"'ry salts _ere pr:epart'd as model!IJ to assist
In the an:at'lSIS and tdEnt.ih~ation of BZ ...nd Its metabolic producb

n

(S)

-

PROCEDURE!" .\tiD
.....£StiLTS.

(5)
One of tbe clause mod .. of {ormation of Z. "-oxa~olidlnedlonu
results from the ,.eact;:m tR an •• hydr"llty eete:- and an i.cx:yanate to fao'm the

\

corre.porxbnl ur~lhane, which is Dub.equenUy cycli&ed by heat or aluline
t:.at~ly.t~ to the requ.:ute ()Xa&olidinetiione. S

o

n

RCH-C-OR'

!

I

o

OM

NH-R"

"-/
C

II

o
In thf' 'Fcia.l c ... e of ben&llate e.ten, the ouaohdinedioue. are
form,--d "JYlfltaneously, even at low. temFrature., 'on reacticn with .. ~ irecyanate. {, This type of two-centered attack .ou1d h- Rpecific for ben&Ual~
esters .uch as 8Z. By judicio'!•• election of the i.nc:yanatt>, the N-.ub"tl
tutt'd- 5. 5-dlphcraYl oxaaolidint'(lione (obtal:l«<l a. a .inlle proctuc:t) C(!\w:'
possibly ~ analy:ed by tluore.cent. co)orlmf'~ric:, infrared. or other physical

(5)

o

af.~l)'tical mean" that .auld proYlde an uneq'liv?Cill assay of the beNlllale to
the total exclusl0n of :)ther meubolic iralments.

1.

(U)

Glmeral Procedun for the Preparati0!L0.!
Oxaaolidinedionec From az.
_

--0

A. mmure of ) 1m (0.003 mole; of H, 0.003 mole 1)( i.ocyaNde,
and 10 ml of dry benaene WAS refia«d for I hr. The cooled baftune soObatlon
••• fdtered ~nd the Ultrate e"_p?rated to drynen under vacuum. The resl.....
c~y.taJb&cd from isopropyl alcohol afforded the ouaolicUfiedione

~

(U)

Rf'sulhl.

Th" oxa&ohdl:tecborw. prepar~ are luted Ll table 1 They all
P.Xhlbl\ ch~r&cter'~"·1C'; Jnfra .. ~ absorptlonlJ In tM relicn. of 5. s,. Cu~~thane)
and S. 11& (amid .. ,.

8

(5)

a!tter Reaction ProchKts

(S)
RaUer et al 7 report" tht' r"actlon of nitrde. with alk.. nes or
tt"rtJary alt6hol. t;-{~m Nt-alkyl .ur-ide. The pt'e.~nct- vf " tertiary
altoho! ttr~p 1ft 8Z sugie-stfll tM pouibll!' applicauon. of this reaction to BZ.
(U)

General Proced"J"e lor the Ratter Readlon.

A sglut ton of I 1m (0. 005 mo!.e. cd BZ and O. 004 moJ~ of mtr&11!'
10 mA of I!act~l Ole etsc .. ud was chlll~ In an Ice bath and 15 sr.l of concentrated SUlf\l~lC acid added ~r~).(' a\ a r;ate .\l(:h that the temt)C"at'~r~
*as m.un,~sned betwe\'en .,,0 to ~o C. Tht' re-action ms.tvre WlA. st;rr~ c.~W
fat' I h:- and at room tenlperature {or Z hr The .o)uUQn ..a. poured ontO'
cru.hed ice and nemrah.t.K with .l\tu~atH pouklt.aum carbollate ."lut!on. then
extracted wath ~hlof'ofo:rm. The t'xtract was dried over lUlhydrous potau'iWl\
c~rbonate or .odiwn .uUate line: the solvent f'emoyri- Til. reaih"
o
0..as
c ry.talhaed from ben&en~ O~ beMent' pctrch:Ym ether (bp lQ to 60 C~ to
'fIeld the de. ired producU
In

z

(5)

T~bl. /. list. the Ritter prooud. prepared Tney at. ('olorle.',
crY5faHlne .olids ,.,sth defanitt' meltlns polnb and ~how no unusual ~b&l'ac1er­
lSts~ ab.orptton. upon mfrared analy.,.

a-eN

•

cu,

TAB~..!

l.

4.0X'AZOl..!DJNEDI~N&s

~-.y=o
V/

y-a

-

-

c ... boon

.... lllnl

a-

Vos-mula

pbtnt

CH!

-

CH)O-o-

MOZ-\t>(CHJ'Z"·

~J:-

ro

o-N"N-o-

~

!

--

,.

Calcutated Found Calculated Found

°c

.r=§=

Y'.ld

-

Hydrolun

"

..

".6

14&.14,) CZ.H1S01"
Ul-a31 ClaH ...03NBr

17

76.6

I.

61. 8

1S 9
61 ..

al7-lIl CZZH,.,o]N

17, S

16.9

16.9

1 "
5.0

ellHI,o..t:

09

?l.S

73. I

4.8

CZ'"l ..OSN Z
C ZJ "1.001N Z

90

61.1-

J J

n. I)

5 ..

S 3

1"'-150 Cl~Hl;OlN

10
61

67. "
1".Z
19.1

....a

71.6

".5

5 ..

153-15. Cl-,HS,ol")

72

74.'

13

80.0_.

129

.oC,-14,
15S~&S6

,136.131 Ctt7flltP1N

-

--

(,

}~

5.0
3

~ ••
10."

.~,-7

.

.

\406
5.2

z

(U)

Rt-Iultl

Tht' OX&&ohdlOedIOMI prepue'}d ar(> tssted In t~ble
l'xhlb1\ .. haract4l!riltlt Jl'Iirared ablJor~'t)n!l in \ht' regu:ms of ')

~

They aU
(urt'thant')

and S. 7p (amide).

B

(S)

RItter Reaction Product.

Ihtter C!t al? r"!'p"rted the '~iu:bon of nstrlle» with al,,;:.nt"f or
.alkyl amldc:. The ~re'lt'nct' :,f ~ tertiary
alcohol group 1n BZ sugg\!5tr6 tht" poIslblt" apphctluon of thkS reactlon to BZ.

(5'

t~ruary aJcont\l. t;-r;;:m N
(Ul

Gen~rtI.l Proct'dure

fOF

the Ritter Reacuon.

A ~olutlon of I gm (0.003 mold of 8Z and 0.004 mole of nltnle
In 10 ml of glacJal a,-clle and was chlllt'd tn an Ice btlth and I; ml of conCl"nlTatt'd sulfuric aCid add4l!d dr~wls(> at a tate .uch that the tC' ,.;---.r~".lr ..
wa& malOt~lOed betwtoen 5° to 10 C
The reactson mixture wa~' starred cold
for' hr and at room temper-ature for l hr
The .0IuU .... " Win poured onto
crushed ice and neutrahaed wlth .. atur,:,e<! pota •• lum carbonate 501uhon. then
e"tracted w,th chloroform. The extract W~I dried over anhydrous potallium
(OI1,bonat(' or .od,um lutfatp. and th~ .olvent removed
The relS1GUe
o
0 was
(rY5talh&eo from beil&t'ne ~I' bcn&(''''' pt!tl'ol4'!um ether (bp 30 to &0 C) to
YIeld the de'lFt"d prod~tl
l

(Sl

Table' l. Issts ~h(' Rlttt'T' producUi prepared They are- colorle •• ,
crvstalhnt' lohds ""Itn dehnitt' meUmg !>OInt. and show no unu.~J cur~cter­
nBC absorption. upon mfr.ned ~naly.\s

it-eN

}J

CU)

TABLE l

RITTEIl REACTION PAODUCTS

~O

O-!"-g-OR'
I
NHR

Mellan,
Yield
polnt

R'

.\-

oc
0

II
CH -C3
0
II

CH)CHZ-C-

Ciubon:

Hydro,,,n

Formula
C~lculat.d

round C.alculat.d Found

"

"

Oulnuchdlntt 179·180

7&

C,on H Z6C )N2

Quilluc ltd'ne It''-lIS

69

C l4HZSO)NZ

Qulnuc UdinC'

1)0

I

(, 9

7 I

"7

Z

6 .,

71 0-

(,

..

0;

71

70 9

& '(

nl

71. 8 I
the" -:

73.0

;3

73 ....

71 (,

7£0 3

~

0

c;-g0
II
NHz-C-CH

'16·99

C lsH 1.80 )N Z

9.

0

~
z- -

QUlnUC

Udtne 111.- 11 :\

&1>.5 Cl .. H~70.. N3

b 7

0

CH)-~•

M.th~·1

109·1 n

oE-

(1)

t

The carbon and hydrQ.en analY.4HIl
thai re4c:tion product C=ovlate
made to {urth.r purify the .ub.t.t.nc\!.

WiU

~rom

s

9

S I
-. -I\U",npt
-'--~tJ

SECUT
,..,
..'"

C.
tCl
dif{ere~es

should

~

Ql3tern!.ry Ammonium Compov.nds.

W~n ~ tertiary base 11 quaterni&~ with an alkyllahde. the
in solubility ~f the salt-like product an<! the sta!'tmc materials

suffIcient to &How spectral determination Q{ the base. Se ....eral
phen&cyi bromide quaternarle'$ of BZ were prepared

sub.ti~uted

(C)

Gener .. l Procedure for
Salts.

Pre~ration

of QU2ternaa

A m'Xlure of I gm (0. OO~ mole) of BZ, 0.004 mole of the phenacyl
bromide. "I"!d IS ml of chlor;,fcrm W4. allowed to stiJ.nd at room temperatu!"e
{or l8 hr. The solvent was removed under 1r-acuum and the residue: W;1&
c r),s!alli&ed from ethanol-ether. acetonitrlle- t!ther. or ethanol-I, Z tiimethoxy«'thane.
l..

lasted

1h

(5)

Results.

These products, tYPlcal
table 1

high-melt~ng

crystalhnt' soHds. are

lu part of thli overall prolram, the a.uthors were interested in
preparIng the acyiate<i der:vatsves of nl.. In thla connecti~n attempts were
mac(' to ~c:etylate BZ wIth ilcetlc anhydride .and Wlt~ acetyl chloride 1,1 pyri.
dine to IU) avail. The anfrared spectrum of 8Z mdieates .tronl int~amolec:­
ular. \it' t:ntermolecular hydrolen bonelln,. which JS absent in its ~alts. The
nonreactivity oMerved wIth the us~i acetylahn, rea.ent. may be due to thi.
bondin" a . . .ell a. to .terl~ facton. Thus. treatment of the p-toluenesu1fonic acid s .. lt of 8Z with 1.0propenyl acetate ;&{forded the acetate qUIte
smoothly.

SECltET
10

CONFIDENTIAL
TABLE l

(C)

PKENACYL BROMIDE QtiA'l'£kNARY SAL1"S OF 8Z

C~rbon

Alkyl

Mli~e

p-Phenylphenuyt brOtPu:h~
p-N,trcpbeMcyl brormd~
p. BrCP.ftophenacy) ~fGmU~~
~·N& phthaevl bromld~

I

.

.

Z14-lIS'

'}l

68 b8

190-IQl

qq

~q.q

l1t\-I1S
lZO-lZ4

q()

~6.b

t)}

h 7.7

bS q
~8. }
5t. b
tl7 z;,

~en

Uyd",

Neltanl
!yleld tpennt
icakulated Fou."ld

OC

fel

Clllc;u.::.~ed

,

. Ft\Unii
~

I

S.4

S. 7

~

I)

I

".Ii
~

I

S

1

4 8
S ...

A rrn){tYfe ~f l. gm 10 003Q mule) of th~ p-tol~ene9uHom(' and "alt
0
of B7.. mp 110 1~ tSloC. lO ml of l5opropenvl acdllte and a fe_ crys,"!!> of
p.t~luenes\llfcnIC llCld -aa r~iluxed; acetone -;U dl~tilled off 510-1y oyer a
perll.M! of S hr. Th~ mixture was homoleneou. at thIS t~m('. Thoe (Oxce ••
,.opro~nyl .ac~l"'te -a. removed under ...·acuum and the refoldu1e- m~de alkahn~
_tt), ct;)id .&'ura~ed pot~,.,um carbc~t(' soluhon. Ths . . .a. extrllctecl _lth
chloroform. tined 01/4"l ""hydrou. 5OOl..1:n sulfate. ,,00 th~ 'Dlvent removed
"nder reduced preu9rl..' The re"due was rt'fluxed _lth dlethyl ether. liitered.
and t"oolt'd to rourn t~mperaturt'. :t vleldt'd 0 ~8 ~m. 44 st., of th~ act!t~t>.,.
o
0
mp IlJ to III C.
Ca£c~l.t,.d:

C, n.8; H. t> b1
Found. C. 72. 7 H. b 7

E.

(e)

~e!ctropbotome\flc

Determmatlon o! SnuU

guanh~.e!J

ot BZ

p-Br",mopbenilcyt bromldt' reach rf'adily _IU, 8l. In acnomtuie
formaDa & q~tt':-n.. ry salt. SlnCf' quaternary lJ;ut. havf' relatavely hl,h eolublHty inwate:.one may st'parate the product from r"actant. and thus tlet~rmme
the amount of tt'rtlary .mine Orlln~llU~' pft',ent. A plot of .b.of'~~cy Verttu.
concentrat:vn ~oUo." Bet'r'.
Df'tAlled p,OC't'dur ... for tht' dett'f'mlnatlon
of BZ In (a) a'Cetonltr Ie. fb) w~tu, and (c) In human ..hol~ bloed {oUow.

1._.

C'ONF1DENTlAL
Reasents: Rec ry.taJ1i~~d p-brto.nO!'h~~cyl bromidt'. spectre.grade -'l~f'~u::~!:,:~e. ·:h!"'!"J.{"':-'n. C:P. () J M t!'u(hydro~ym"'t;'rl1llminomethanc
(tris) buUer (pH 8.5). cyclohexane. ~Qd az.

tel

~lerminat1on

of

az

10

Act:fonitnle.

To O. 1 rnlof 1O-4! M .o~ution of ?-bromaphenacyl t-,romldc an
acetomtrile In a ,l•• "-atoppered botUe i. added 1 to ~O ug or l\Z dinoh'f"'
in I ml of acetonitrile. The solution IS mixed and heat~~ in <l ~CIO(' w .. ~_r
bat-~ lor 10 min
After coohng the _olutien to room temperilturt' l rol of
Q.l M Kel aM 5 ml of cyciobeXOlne are added a.nd the mixture I I mechanic~y
shaken for, min. A portion of the aq-a~ou£ phase is re<ld spectrophoto:netTieaUy at Z&5 mt! and the :adherence to Beer's lav.· demonstrated (table 4,
figure I).

ee)

TABLE ..

(U)

OETi:RMlNATICN Of" l!Z IN ACETONlTR¥

BZ
uclml

o
l.b
5.Z

0.0&6

O.ZOS

7.P.

10.4

il.O
~

Z.

I

L

O.llS
0.-150
0.597

O. 138

Averagll: of five determinatlvnl

ee)

Q!:terminatinn oC BZ in Aqueous SolutioD:!.:,

tel
To l-ml ~queous flolutiohs of BZ (S to 40 I'll an! added O.l ml
of trif! buffer (pJi 8. S) and 3 ml of chloroform. The mixture lW shaken
mech~nica.l1y for S min and the aqueous lilyt:r removed. An aliquot of the
ChlOl.,{orm la.yer is air evaporated ~nd the reSlidue di£lJolved in 1 ml of
acetonitrile. Th~ ana;lysi5 i. then made in the manner reporled above (E. 1. j
(~ble 5. Haute: Z•.

CO'AflDENTIAL
il

UNC1AS!1FJED

•

I

J'1CiUJl£ 1

DETCaMtNAnON OF Sl. iN ACETONlTJULE

CONFIDENTIAL
(U)

TABLE ;

DETERMINA nON OF 8Z IN AQU~U§ SOLUTlONS

,
I

BZ

II

ug/ml
O. ttl
1. Z5

Z.5
5.0

-

Abscrb4kncy=:

C 018

n.058
0.101

0.Z53

7.5

0. 391
0.517

IO.v
1~
~

o

5

Average of five

3.

(C)

HQ

det~rminations.

Determination of BZ in HUhl&n Wholot Blood.

(C~

To 1 ml of human "'hole blood is adt!~d a I-ml ~qu~ous solution of
BZ. The mixture is diluted to 7 mi ant! tt-.oI'01lCh1y mixed. OM mmHitc!:~ of
SOc;. znSO.. 1. added. mixed. ~nd f~Uow~d hy 1 ml of 0.3 N Ba(OH,Z' Ch}Groform (10 roll,s addled and the mixtuf'(' is sJ:allken mechanically for 10 min. It
IS then transferred \0 .. Ilass.stc;pp~red centrtfule tu~ and spn."1 at Z500 rpm
for 10 min. A -I-mt aliquot of the chloroform b.rer is air evaporated and the
analy.is performed in acetOnitrile as above (table 6. fi!:.are 3}.

TABLE

(U)

f;

DETERMINATION OF BZ IN WHOLE BLOOD

nz
lAC /ml

I 7
3.4

o
o

;. 1

C)

Obl
148

l3G
O.UO

5.9
&.8

0.317
0.388

0.418

10.l

CONfIDENTlAL
14

1.0

o,
::1.1

1l.7

Q.ft

."

c

..

J

0,

•"

II

<It

0

O.

o.

'4
FIGWl£ I.

ANALYSIS OF BZ 1M AQUEOUS SOLUnONS

o

•
i
Wkrli/lTame

•
,.,1' mWWter

10

~

11

eoh.,,_

FIGUIlE 3
ANALYstS OF BZ 1M BLOOD

14

CONFIDENTIAL
III.

(Cl

CO\~Cl..UStONS.

A rund~ment~l study of the ch~;n,stry of BZ w~s conduct~ to
problems th4t may ar he ln detectlon, decontamination. blochC!m1cal
mech~nism of action. lIrld met~bohsm.
BZ reacts with (Ol) ~ub~htut('t' phenyl
I~ocy;\n&telt to yield Z. 4-oxa... ohdine(!1ones. (~) nit riles to p,-oduce 'U'Iudes
(littler reachon). and (e) <llkyl halides to 11ve quaternary ammonunr . ~1t».
An.al),!"s of Sl. C:~n be accrimphshrd by q~tern\1~"hon In acetomtnle. .eparahon of reactant •• and auaYlnll spectrally.
>lS5lSt ~n

CONFlD£NTIAL

UNCLASSIFIED
(U)

LITERATURE CtTED

I.
Ford-MQOr~. ,,_. H .. aM lOR. H. R. Synthetic Mydriattcs.
J. Ch"!."'l. Soc. (Lonrlon) 55 (1947).
2.
St~rnbach.!... H .• ar..d l\.auer. S. Antispasmodics IiI
Esters (" B1Cyc:lk Alcohols an:! Th~lr Q'aalternat"y Salts. J. Am. Ch·r."!. Soc
~. bObS (1953).
3
Sas~. Samuel. Ma"'t~r. l:-Wlf'~ Lud~mann. Wilham D .•
Martsn. JON. J
Bratt. M"rtln. Sp-". and Mialou$hek. Ralph. PFC.
T~chn1C:al Memorandum 13-1". ColonmetTlc and Spectrophotometnc
Eshmatum of EA 2277 and Similar Compounds. Som~ Ch~mlStl"Y on the
Oecompo!lhOn of EA U71 (m June 1960 SECRET M1!1TH,fo·,·l u m
4
U. S. Arm.,' Ch~mlc.ll Resrarch and Dev~lopmEr.~
l..aboratorles. CROL SpeCial Pubhcatlon 4-28 EA 1.277 (U). A ~''::-:'I",:>ry
Report as of IS March 1qbl
March 1961
SECRET Report.

.!!.

5

C lark- LC'N1S. J. W,

Z." Oxal:oHdmedlone

Ch~m

b:; (1958)

(,
aekker. R. F .. Faber. A. C .• Tom. D. H. E .•
Verleur. H .• and Nauta. W T~_ Rec. 'ra" !:hlm ~. lid (1951).
7.

Ritter. J .. and Kahsh. J

J. Am

4(;48 (1948).

UNCLASSIFIED
19

Ch~ ..r.

Soc

70.

Revs

DiSTRIBUTION L15T :-:0. ;
No. of

I.. 8

ct - 11
ll·1~

16
37·18
19·15

3l
H
H

3;

41

-47

COPIC!':

made

ISO

M.lIl and FlIt" Record C\.·ntc.'r. CRDt. (Record C()pyl
CRDL Llbrar-y. CRDL. Bldg 3330
Blonwd:c,,) RUcdrch Lib. CRDL. Bldg 3110
Pubhcdtlons S\·ctJon. Tcc.'1nlc.,.1 R~led5es Branch. TID
DI:-ector of M(.·dlt:dl Rt:!)carch, CP..,.JL
Chid. Ph)'s~olog'f 0:"'\5100, CRDL
A\~"tTil!.an Army 5t.u{ (W). ATTN: Lt. CGI P. D. YOltE(', ZOOl
Connecticut Avenuc.'. N. W • \lw'a!fhm~ton 8. D, C.
CanadIan Lhu~on OffIcer (CBR). BUlldmg 51(11. Edgev.6Od
A:-$enal. M lryland
Chad. Bureau oS M,-,<hcUlC and Surg~r~'t Ot"partmcnt of the N·v')'.
ATTN: Code 74. Washmi:ton O. C. - l0390
ChIef. Bun'du of Nd\'al W':<!PO~5. Code CS··3. Washir.gton. O. C.
l(#380
Ch,("-f. Bureau of Na"'di W\.iJPOr.s. Code FWAM-ll. Washington,
D. C. - l0380
Cnld. Field OHv~. USA rorclgn ~t.:;:r.H and Tc;::hno!ogy C~ntcr.
BUlldml; 4585 ("~3j. £dg~wood Arsenal, M;;t yland - llOIO
Chid. Fore~lin Techno!o~)' Ol'l>HH!:)fl. ATTN TQ·EW~, Wngi-.lPan~uon AFB. OhIO - 450433
Ch,d of R~H'i'1Tch and De\'~lQpnl'n1, Department of the Army,
ATTN' Life Sc.I ... nc,-,!!- Vivl5lon. W~5hlngtor.. D. C. - l0310
Ch: cf. PrCC'\,l"nh~'e Mt"dH:mt" DIvIsion, Dlrcdorat\"' of p,.o!esSlotUll
SCl:"\'\(:c. Oii1c.e of The Surgeon Generil}, Washlr Jt<m. D. C.l03lS
ComMilndant, U S. Army CBR Weapons Oncntahon Course.
Dugw.lty Pro)vl'1g Ground, Dug~ay. Utah - &fOll
Cotnmanda.nt. U. S Army Ch~mlc~l School. ATTN: Trainmg
MedIa Op.'uum. Fort McClclhm. AlabAm;t - l£,lOS
Cc.mlntsooant. U. S. Army Commilnd • General Staff College.
AT1N: Libritr, Dl"l$~on. Fort Le.wenworth. Kanus • 66017
Co.mmandant, U. S. Army War College. ATTN: Libl"er)'.
Carlssle Batrac!(.s, P(mns~'lvania • 17013
(:c.rnm.umcr·m·Ch ... t. v S. Atlantic Fleet. Box 100. DI\'iliion 30,
ATTN: Cooe 313A, No:rfolk. Virgmia - l3511
CQmmandcr-moChlef. U. S. Pacihc F!ee~, Na..·), No. 1l8. Bo,. 11.
'0:/0 Fleet Post OffIce. San Ft"ant:i~co, Califorma - 9411S

DISTRIBUTION LIS)" NO.5 (Contd,
48
49

so
"I

5l
S3

Cornmander, Hq, RTO (RTNW). Bolling Air Force Base,
Wa5hm~ton. D. C. - lOBI
Commander (Code 88). U. S. Nit'MI Ordnance T~st St4tiar.• China
Lake. CalitoTma . 93557
Crnnmilndcr (COIle 7:;3,. U. S. Naval Ordnance Test Statltl.. ATTN'
Technlcdl Library. Chana L.tkc. Gtlifornia - 91557
Commander. U. S. NdYal Weapons l..;abordto~r. (C(,o(,
KRT).
ATTN: T('chnH: .. 1 L!brary. Dahlgren. ViTglflla
Commandln(! Gem,·r;"l. Aircraft, Flt'et Martne F->t'c~, Marine
Corp~ AI: S:.::Hon. E! Toro. Santa Anit. C"hfornia - 91709
Commar:.Jm;; Gene ral. Dt'sC'rC't T ('st CIi'nter. Fort DOllglas. Utah -

...,,,'B

84113

S4

5;
56
57

sa

60

61-cl.

63

65

66

Commanthnlt ~.·nt'ral. F i('t't Marin" Forct'. Atlantic. Norfolk.
Vlrginta - l~511
Commanding Gt-ner.), lst Marin(' Brigade. Fl~ct Mar,.iC: i·orce.
c/o FPO. San Francisco. Cahior",,, - 96601
Con..nan~hng veneral. ld Manne AIrcraft Wing. MCAS. Cherry
Point. N. C. - l85H
Commanding General. U. S. Army CombAt Developments Corr.~nd
Expenmentatlon Center, ,'\TTN; CDED-GC. Fort Ord.
C;::1:!orm .. - 93941
Commaud:ng G\·nt.. ral. U S Army MatenC'1 Comm*\nd. ATTN:
AMCAD-S. W.u:hlngton. O. C. - lOllS
Commandm~ General. U. S. Army MaterIel Command. Al'l'N:
Cheml5tr'r .. no Matt'('Iah Branth R('sf"~rch Dh·s»ion. Wafhinglon.
O. C . . lOilS
ComrT>andmg G\.'ncrai. U. S. Army Mat~r;e) Command. RelJC'arch
a:ld D('vl'lopmen-, Dlrector-OItC'. Dt'vdopment DiVision. CD Sranch
Bu)ldm$: T7. Washmgton. D. C. -lOllS
CQmmamhng Gf'lle :aJ. U. 5 Arm)' Mechcal Research. Developn-aent
Command. AT'IN. Chl(~f, Retords • Reports Bra"t:'h. Mam
Na ..·y BU1!dmg. W.uhmgton. D. C. l03lS
Con:mar.dmg Gt·neral. U. S. AMllY Mumtlon. Command. ATTN:
AMSMU-RE. Oevf'r. N~w Jersey - 07801
Cornmand:ng Gent'ul. U. S. Army M\lnit1on~ Command. ATTN:
AYSMU-RE-EP. Dover. New JC'rsey • 07501
Commanding Genenl. U. S. Arm)' Munitions Command. ATTN:
AMSMU -55·5<". Dover. Ne ... Jeuey -07801
Comrnandtrlg Gent"ral. U. S. Army N&tlck ~boratorles. ATTN:
Te~hn~t<11 J.lb~ary. N~!I(:k. Masuc.husetts - 0176l

DiSTRIBUTION LIST NO. S (Contd)
b7

68
69
70

7l-i'l
73

74-7;

16

77
78-79

80-81

83

85

81

CommOlncitng General. U. S. Anny Supply And Matntenance CommO\nd.
ATTN: AMS5M-SO-A. Wuhington. D. C. - ~0315
CommAnding Gen'ftal. U. S. Army Test .. £vOlluation CommAnd.
ATTN: AMST£-NBC. Abe:,deen Proving Ground. MarylAnd lIDOS
CommAnding Officer. 19ld Aerospilce MedIcAl Group. ATTN:
SUAM-3. Vandenberg AFB. CaliforniA
Comm~ing Ofhct't. Det4lchm~nt 4. ASD (ASOWC). Ellin Air
Force Base. Florid. - 1l,4Z
Commanding Offl\:.:r. Dugwa')' Provmg G~ound. ATTN: T~chnical
Libra ry. DU§WOl y. Utah - MOll
Cuuunanding Oificf;.'r. Plciltinny Arsenal. ATTN: SMUPA-VA6,
Dov~(. New Jen.e')· - 078Ul
Comm;lnding Officer. Technical TUinink Cente:r (TS.OF), Lo\ q'
Air Force Ba 5e. Colorado
CommAnding OOicer. USAF School of At:ros~ce Medidne (SMOTL).
ATTN: Documents Librartiln. Brooks Air Force BaBe. Texas·
7al35
Comm~ndmg (){ficer. Air Proving Ground Center (PGAPl). EC1ilt
Air Force Base. Florida -3154l
Commanding Officel'. U. S, Arm) llaillstic Rese.rch IAboratorh:es.
ATTN: AMXBR-T (Mr. William KokinakiSl}. Aberdeen Provini
Ground. Marylcand - llOOS
Commanding Officer. U. S. Army Biologli:fOl wbotatorics,
ATTN: Documents. To.'!chrnc .. l Librar)'. Fort Detrick.
Frederick. MAr")'IOlnd - lJ70l
CommOlndmg Officer. U SA CDC Artillery Agenq·. ATTN:
CAGA T -R W. Fort Sill. Oidahom" - 13,04
Commanding Oificer. U.S. Arm)' Com!>Olt De'Velopnentl. CommAnd
CBIt Agency. Fort McClellan. Alabama - 36Z05
Commanchng (){ficcr. U.S. Army Combat Developnetlt. Command
Intellilcncc Agency. Fort H:llabird. MarY!And - Z1l19
Commanding Offi(;~r. U.S. Army Com~t Developments Conun.nd
Medical Sef"\"ice -"gency, Fort S~m Houaton. Texas· 71Z3 ..
CommOlnding OOlcer. U. 5. Arm~' Limited War Laboratory. ATTN:
TechnicAl Dil'ec!or. A~rd~en Provinl Ground. Maryland
Commandin& Officer. U ~. Naval U;,it, Edlewoocl ArsenAl.
Nuyland • llOlO
Direl.:tor. Air University Library, ATTN: .~UL3T·'179. Maxwell
Air Force Ba.e. Alabam~ • 3&llZ

DISTRIBUTION 1..lST NO

90

91
98-103

104

lOS
106

10'1

S (eontd)

Oircctol". BIologIcal Scicnc('s On'iuon (COOl' 440,. Office of N~val
Resl'drch. Department of the N;wy. 17th. C:)I'IstituUon Avenue.
N. W.• Washington l5. O. C.
Director of CBR Opt-rations. 0((,('(, of thi! AUJ.t.ant Chid' t St.aU
for Force Devl'lopments. Drpt of the Army ATTN: FOIl CMSR.
Washington. o. C. - lOllO
Olrcctor 01 Engineermg • lndu§tnal St:'rVlces. ATTN: Pubhc.Jlhons
Clerk. U. S. Army Edgewood Ar.enal. EQlc"*~ Arsen~l.
Maryland - l1010
Director. U. S. Army Edgl'''''ood Arsenal. Operilhon. Re.e~rch
Group. Edgewood Artlenal. Maryland- lt010
Dlrecto:-. U. S. Naval RC'"~t'arch l~boriltory. ATTN: Army Lta,son
Ofricl'r. COOl' I07l. W.. shmgton. 0 C. l0190
DirettoI'. Waltl'r R ..·t'<f, A rm\' Institute of Rcscil rch. D,,,:,,,.,n ot
NeuropsychIatry. 'W.uhmgton. D. C. - 20011.
Director. Walter Reed Army instltute of Re.earch. W~lter R.eed
Army Medu;.JlI Center. Washinlton. O. C. - 20012
DIvision at Hc~lth Mobihution. tJ. 5. Public Health Serv;ce.
ATTN: Mr. Charlt's H. H~rp. Deputy Chief. Research Branch.
Room Il16. Tempe "R" Buddsnl. "-.shin,tOft 1.S. D. C.
Dr D. F. Downing. Dt'f~ns(' RC:h:~n.h Starr. Munition./TW.
Brsti.h Embauy. 1100 M" •• ;tc:husett. Av~nu<e. N. W. W•• hincton
8. D C.
Executive Dsrc.-c:tor. £A CBR Adv;~oq' Council. Room 1.71..
Building 5~Ol. £dg~"'ood Au('n.a!. Muyland - 1.1010
Hr..lIuquart('u. AF 1£ (MCD,. Wriaht-p.. Uerson ATB. Ohio45433
H~adqu3rters. AFMTC. Dep;.;t)" for Bi~.tl'onaut'c. (NTX),
ATTN: CQI. Wslh"m H Let-, USAF. MSC.P~tf"ick Air Force
Base. florida - 3l9lS
He~dquu~~l'S. AFSC (SCCiB). A TTK B. E. Flaherty. Lt. Col..
USAF. MC. Andrews Alr f oree Ball'. W,uhtnlton. D. C. -

l0131
108

10<)

Headquartt:rs. U. S. Army CQlnb.il Dev~lopnents Command
Cornb<lt Sl'rvice Support Group. Fort Lc!e. Virlinia - 1.3.1
Headquarteu. U. S. Army Munitions Comm~nd. Marine Corps
Reprc')cr.tativc. ATTN: AMSMU - t.M. O1wer. New Jerse~' -

07801
110

Hq. U. S. Air F~rc .... (AFMSPA-Bsonucleonics). ATTN: Spe~l.Jl!
Weapons Dderlsl' OUscer). WashIngton, D. C. - t0333

01STRlBUTION l.IST NO

90

93

96
97
911-103

104

lOS

5 (Contd)

Director. Blolog,,:al Selenet's DIVision (Cod,· 440). Ofllct' of N.\·~l
Rese.arch, Oc~rtmcnt of thc Navy, 17th. C.>n5titution "venue.
N. W.• Wa<4hinKtor. lS. D. C.
&irector of CBR OJK-rations. OfflU' of the .\uIst..nt C}1,ci '\ Stoat!
for Force l)ev('lopment•• Drpt of the Army ATTN: FOR .;MSR.
WashlnKlon. D. C. - l0310
Director 01 Er.gineersng • lndU5\fJal SerVlccf. ATTN: Pubht:.tbons
Clerk. U. S. Army EdSt'wood Arsenal. EdK~wood Arsenal.
Maryland - llOIO
Director. U. S. Army Edgt·v.ood Arsenal. Operations Research
Cruup. Edgewood Arsenal. MarYland- .uOIO
Director. U. S. Ncav..1 R ('!Ot'a ret. Laboratory, ATTN: Army uiu.on
()(fi('cr. Cod,' 1071. WashIngton. D C. lOJ90
Director. Walter Re(-d Arm.,- Institute of Res~arch. Di'·;~'''r.. of
Ncurops'Y'duatry. Washlngton. D. C, - lOOll
Director. W"ltt'r Rccd Army institute of Research. Walter Reed
Army MedIcal Ct'nt~r. W .. shin.ton. D. C. - lOO~Z
Dlvislon of HeaUh Mobih£ation. U S Pubhc Health Servu:e •
.\TTN· Mr. Charl"s H. Harp. Deputy Chit'f. Research Branch.
Room Il16. Tt'mpo "R" 8uIldlnl. Wa_hioalOO ZS. D. C.
Or D. F. Downing. Odcnsc RC$Coll ,h Stan. Mu.'"litions/TW.
8ritish Embau\·. ~ 100 Massachust'tu .\venue. N. W. W~.hinltoa
8.0 C.
Ex~o:utiye Dlr~ctor. 1:.A CDR Advi.ory Cuuocal. Room Z1l,
Building S101. £dgcwoocl Ar!~naJ. Marvland - Z1010
Hc.dquuten. AFLC (MCD). Wright-Pa.tterson AFB. Ohio-

4;433
106

107

Headquarters. Af'MTC. Deputy {or B100lstronautlcs (MTX).
ATTN: Col. Wilham H Li:t". USAF. MSC. Patrick Air Force
Base. Florida - 119l;
Headquarters, AFSC (SeCB). ATTN. 8. E. Flaherty. Lt. Col. ,
~SAF. MC. Andre"". Air Foret' B:15(" Washmllon. D. C. -

l0331
108

109

110

He~dquarters.

U. S Army Com~t Dev('lojX1lt>nts Command
Comb:At Servict' Support Croup. Fort L~e. Virlinia - 23111
Headquarters. U. S. Arm.,' Munitions Command. Marine COl ps
Representative. ATTN: .t'.MSMU - LM, Dover. New Jersey 07!Ol
Hq. U. S. Alr Force. (AFMSPA-l:honucleonics). ATTN: Special
Weapons Detcnse Officed. Washmg1on. O. C. - Z0333

.!2..ISTRIBUTION lJST NO. S (Contd)

111
112

113

11-<

Headquarteu. U. S. Joblrine Corps. ATTN: Staff MedIcal QffJt:C'r
(Code AM). Wuhinl!On. D. C. - ,(GoO
Institut~ for Cooperati,rc Research. University of Pennaylvani.i.
ATTN: Security Officer. TO: Ltbrarian. Project Summit.
}634 Walnut Street. ~~i1adelphia. Penns'Y.".ni .. - 19104
Office. Chief of Reaear..:h .... nd Development. Department 04 .fit"
Army. Room 3£ 440. ATTN; Chemic .... l-lSiololic~! Office.
Wuhinlton l5, D. C. - l0301
Olilee of the Chjd of Engineer'll. Depal·tment of the Army.
£NCiMC-£D. ATTN: Mr. Jllm .... ~. M.dcolm. W.shinaton.D. C.

l031;
115
110 • 117
118

119

lZO
III
III
III
1,,4
ll~

• 1Z6

127 -

no

131 -

1~

OOicer in Charge. NBC Defense D .. partment. U. S. :Qv.... l Schools
Comm~md. Treasure Island. San Fr~nci.co 30. Califorflia
PHS Liaison Officer. Fort Detrick. Frederick. Yaryl.arM! • !t1(l~
President. U. S. Army Airborne. Electronics. Special '''.dare
Board. Fort Brac,. North CaroHM - l8301
Pr~sident. U. S. Army Arctic Tes~ Board. APO 733. Seattle.
W.uhinlton
Rese.uch Analysis Corporation. ATTN: Library. McLean.
Virlinia - ll10l
Stanford Research lnsbtute. ATTN: Exterrai Reports. G-037
(fot' Or. Wilbur Benson). Menlo Park. California - '4015
Surleon. U. S. A. Rocky Mountain Arsenal. Denver. Colar.ado 80Z40
The RAND Corporation. noo Main Street. ATTN: Llbrary. :,anta
Monlca, California - 90406
U. S. Arm)' Sc1entific Liais"n and Advisor)' Group (1144" ATTN:
Dr. Oor. L. ben~r". rn~ Pentalon. Waohinllon, D. C. -lOliO
U. S. Army St~ndarcliution Group. UK. ATTN: CBR Representative,
Box 65. USN 100. FPO. New York. Npw York - 09599
USA CDC Liaison Offic~r. Hq. U. S. Army Munitions Command.
Dov~r. New Jersey - 07801
Defense Documrntation Center. CAmeron Station. AlexandriA.
Viramla - Z1.314

CONFIDENTIAL
ABSTRACT

SECRET

Ph"!'loluJrv DI\":51'C'n
U S Army Chl'mlCal Rt'scarc h
~nd ~"~lopment

l..aboral'.)rlt'5

(ir?up tfor DOC usc

lb

~r,".

I

£dlt'wOOO Ar!l'na1. Maryland

1

SOME CHEMICAL REACTIONS 0'- 8Z tU,

Report Tllll'

fht' •...-urk ",as !Ita rled

c ::mplt'led

5,

to

-~t~

10

March 19b1 ~nd

Apru I q6l

Hacklt'}' 8renmc E
Haddt-'l. Eth('1 n

Authors

Pubhcatlon

tn

7

;r

Ccdl?:an~. Chappelle C.

Tctal £10:0. of

~I~.

~C08

CRDLR

,01 01 {. ! 4

iH~

II

I O.

Othe'I' Rr.p?rt Nu'.

ll.

Rc:Ieasce S~at('mcnts t{or DOC use -:.niyl

~Elcmt'nt;a ry

N'.)les
Ifbr DOC use onh',

13.

Author',. Key Terms -

Uncl~ . . iHed

Only

nz
ChemIcal reactions
Detcchofl
DecontaminatIon
Blochcmunry
Metabolism
Sut-shtult!d compound.
Phenyl laocyanatcs
Chemu:al altents
Nitrile.
IncapacitatinG a;:t'"nu

Mech~niam

of ;actton
Amidea
Ritter reaction
Alkyl halides
Ammonium s.dts
Qu<&te rnl at Ion
Acetonitrile
5~ctrum

14.

DOC Descrlpton (for DOC use only)

1 ')

ld«mutu:r. - Unda"liicu ~,

16.

Body of Abat:-Act

l. of ·ox~zolidinedion~s
Biochemical actIon

(Cl The purpose of this ....vTk waS to conduct a fund;amen~ .. l study o! t~
chemUltryof BZ. to .:".i.t an problems that mey arise in detec~ion.
decontamination. biochemical mechani .. m of aaction, ;and met~boli.m.
8Z reacts ....ith (n lIubstituted phenyl u~ocyan;atea to yield.
l.4.oxazohdinedlones. (l) nitrHes to produce amide. (Ritter reaction).
and (3) alkyl haHdefi to gave quaternary ammcmh.lm salts. Analysis of BZ
c.an be accomplished b)' quaterniution an acetonitrile •• eparation uf
reactants. and a •• aYlng .pectrtlUy.

17.

Index;n. AnnotatIon
FundamentAl .tudy of the =hemistry of Bl. to "slIist in the solution
of prOblema of manuf~cture •• tor;a,c. detection. d~contami~tion. and
bivchemical mechanism of ,,"'Hop.

CONFIDENTIAL
ABSTRACT

1. Orlilnatm, Actlvaty

lao

R~pt:rt Se~urlty

PhysIology DI"'$icn
U. S. Army Chemiul Renarch
and Development Laboratories
Ed.e~·ood Arsenal. Maryland

3.

Cla.$lllcatlon

SECRET

SOME CHEMICAL REACT:ONS OF BZ (U)

Report Title

The ....-ork """. sta rted 1n
Aprtl 1q6Z.

~~rch

19b1 and

c~mpleted In

S.

Ha~kley.

AuthQr'S

Hackle~·.

6.

Publication Date

8. O!'lluutor'$ Ren!": No.

Brennie E .• Jr.
Ethel B.

Cochrane. Chappelle C.

1.

Telal No. of Pa,es

9.

Task

CR:>LR 3113

~O.

Other Report

ll.

Releaae Statements (fer DDC use c.nly)

NOli.

II. Supplementary Notes
({nr DOC use only)

CONFIDENTIAL
11.

Auttw".'s Kt.·)· Tt.·rnl$ - Undasslfu:d Only

BZ
Chl'nllc al reat. "on21
Ot.'tt.·c tlon
Dt'" ont arnln<ltlon
Bwci:cnll!lt q"
Mc(abota g.m
SubSt.llutt.'d t.umpounds
Phcn}'1 I too .. ~anatt."!>
Cht'tHIC al .\~\·nt 5
~Itnh's

Me c ham 15m of at.. tlon
Amide.
R an .... I n'acllt .
Alkyl hahd·:.
Ammonaum salts
QuaternJ zatlun
At ",·tomt nl~
Spectrum
l.. ~ -oxa 7.ohdanedJonc:.
aloc ht'mlcal action

Int. "POl" It;ttlns: .:;:·:nI5

H.

DOC Descraptors (fer DOC u!h' only'

It,

lCSenutlt.'r5 - UnclassIfied

It.,

Body of Abat. act

Onll'

(Cl The purpolh.' 01 th\!. "urk \\as to cunduct a fundamental I/.tudy uf th~
of BZ. to alUI.t to problems that llIay "nse an detection.
d"·cont,,mmallon. biochemICal mc.!cnamsnl of action. and metaboUstn.
BZ reacts with fl! 5ubst~tutcd pht.·nyl 15~)'anat('s to YIeld.
l.. ~ -0 't3"'01.dlncdlont.· •. (l) natrlle. to proauct.· amldes (Ritter reaction) •
•tnd (1) alkyl hdl.des to j.!",·t· quat('rnary i\mmomum salu Analysis of BZ
('an be accomphshl'd b)' quatcrnlZ.atlon In acetonitrile. separation of
reactanlll. and a.aa\,lnt! spectrally
du~mistq'

11

Indc"'lnS Annot:lHon
Fundamental study Q! the ,-hcmllitry of BZ to asstst 1n the solution
of problem" Qf m~nuf"cture. storage. dctc("t\on. dccont .. mmation. and
bioch~mical mechanism of h.hon

--ABSTRACT

Phva,o!OBY D'Vl$'~n
U. S. Army Chem,c.;d .R~l:I~''U< h
and Developml!nt whoI'. t"'" Ie s
Ed.ewood Arsen.-al. Ma!vla~~d

)..

Report Title

SECRET
lb.

Gr :u}! ,f<' r DOC

Uh:

r.n· )

SOME CHEM!CAL R&AC T:ONS OF SZ {U}

Tile W'7rk ...... ". I::) rled In ~rc.h 19M ~nd
c ':mplf'ted In Apr u 19E1Z.

S. Authors

H"citley. Brennlf' E .• Jr.
Ha,kley. Ethel B.

Ccchrant'. C~pptll!t C.

May IqfH

CROUl3l11

10. Other Repcl'! NCos.

11.

SUPflement.uy N-::te.
err f DDC nat! cnlv}

COHFID£NTIAL
J I.

~hor's

Key Tcr!?2 • Unclahliacd

az
ChemIcal Tede hons
Dell'chon
Dt.·collta!ll1lldlIOn
BlOehemutry
Metabolism
Substituted c"mpound,
Phen,)'l Isocyanatc.·s
Cht.'mlc "I ,"!,,"ent s
Nstral\'l\

On..!r
Mechamsm of action
AmIde.
R,tter reactIon
Alkyl h"hdca
AmnloOlum .al~,
Quate rnl zat Ion
An!tunatrll ..
Spectrurn
l. . .. -oxazohdmed.one,
Blochemlc"l ~chon

Inl' apa\ Itattr." ,'1l!"nt'

I';.

DOC Descraoton (for DOC usc cnly)

I:;

ldentiflcu - Unc:I"Silhcd Only

lb.

Body of Abst::-aet
(C) The p.1rpo5~ of thu wo rk was to conduct a fundamental study of the
chemi.!q· of BZ. to assl5t In problem, that may Olrue in detection.
d"ccntalnlnatlon. blo ... hcmu:al mechanism ol :l~\I~n. it!ld metabolism.
BZ re .. c.ts With (l! .ubshluted F;-':'-~': i'~·~'l·,_r:-- -" :":''!
I..'; -oxaz.ohdmedlon,,·IJ. (Z) nitrile. to produce amide. (RIUer reaction),
dnd 0) alkyl hahdcs to ~IVC quatern .. ,,')' •• mmonaum salts
Analysi' of BZ
c.}n be a - romphllhed by quatcrna zaUon In acetonatrlle. separation of
rc~ctanU ;l(\d .:lS5av,"~ spectrally.

I;

lndexln, Annotahon
Fundam(. ntai stad.,. of th(:' chemistry Qf BZ to a.SlSt tn the lSoJution
of problem. of manufacture. ,tor age. detection. decofttamin~tlon, ;and
biochemical m~chamsm of d-aon

CONFIDENTIAL

DEPARTMENT OF THE ARMY
US ARi\ilY RESEARCH, DEVELOPi\ilENT AND ENGINEERING COMMAND
EDGEWOOD CHEMICAL BIOLOGICAL CENTER

5183 BLACKHAWK ROAD
ABERDEEN PROVING GROUND, MD 21010-5424
REPLY TO
ATTENTION OF

2 7 ��M 2009

AMSRD-ECB-TD

MEMORANDUM FOR Army Declassification Activity, 8850 Richmond Highway, Suite 300,
IMP Building, Alexandria, VA 22309
SUBJECT: Declassification Review

1. References:
a. Executive Order 12958, Classified National Security Information, dated 17 April 1995.
b. Executive Order 13292, Classified National Security Information, dated 25 March 2003.
c.

AR 380-5,

DA Information Security Program, dated 31 October 2000.

2. In accordance with the references listed above, the purpose of tllis memorandum is to provide
the recommendation made by the Edgewood Chemical Biological Center (ECBC) Security
Classification Review Board (SCRB), regarding declassification and downgrading of the below
listed documents.
a. Isokinetic Sampling of H Aerosol, (ADA Case 080 19), (as Produced by the Comings
Candle), February 1946. Downgrade from Confidential to Unclassified/Unlimited.
b. Dugway Proving Ground Research and Development Weekly Report (Part

A),

Medical

Research Laboratory Weekly Repmi (Pmi B), Dugway Proving Ground Mobile CWS Unit
Weekly Report (Part C), (ADA Case 08024), February 1945. Distribution authorized to U.S.
Govermnent agencies and their contractors. Downgrade from SECRET to
Unclassified/Wnlimited.
c. Dugway Proving Ground Research and Development Weekl

y Report (Part A), Medical

Research Laboratory Weekly Report (Part B), Dugway Proving Ground Mobile CWS Unit
Weekly Report (Part C), (ADA Case 08023), January 1945. Downgrade from SECRET to
Unclassified/Unlimited.
d. Counter-Insurgency and Air Power: Report of a Rand Ad Hoc Group, (ADA Case 07078),
June 1962. Downgrade from SECRET to Unclassified/Unlimited.
e. The Role of Chemical and Biological Weapons in the Defense Strategy of the United
States, (ADA Case 08002), December 1964. Retain at Confidential.

c

1

_

l--1

_

.

'j

0 7 m� 2 tl-51 o 7- m- 28 31,
h 07-m- 2.:?38
o7 m. 2£?31..{ +hro�Lc,
V
_

Pnnled on

2 S .3

� Re,:ycled Paper
\;t1

....

07-m- �8-'-/2._
.

AMSRD-ECB-TD
SUBJECT: Declassification Review

f. Special Report: The Increment Flow RegulationValve, (ADA Case 08020), 3 December
1945. Distribution authorized to US Government agencies only.
g. Interim Report: Development of Decontamination Solution Unit, 3-Gallon, E8R2, (ADA
o1- �'vt ..- 2. �) �
Case 08003), 15 February 1954. Retain at Confidential.
h. Chemistry of BZ.I. Reaction of BZ with Iodine in Aqueous and Organic Solution, (ADA
Case 08007), November 1962. Downgrade from Confidential to US Government Agencies and
their contractors.
C'-;---- P!f- 2-g 7 7
i. Interim Report: Decontamination of Airplanes (F.Y. 53), (ADA Case 08006), 19
November 1953. Retain at Confidential.
·

·

·

j. Chemical Defense Experimental Establislunent Portion, (ADA Case 0801 0), 4 December
1954. This document contains Foreign Govenunent Information (British) and the decision
should be deferred to them.

k. An Evaluation of the Relative Efficacy of Five Self-Injection Ampoules, (ADA Case
08011), December 1952. This document contains Foreign Government Information

(British) and

the decision should be deferred to them.

I. Infrared Spectra and Absorption Coefficients for GA, GB, GD,VM, VX, and the G analog
(Reaction Product ofVX and Conversion Filter), (ADA Case 08000), August 1966. Retain as
US Government Agencies and their contractors.
111. Estimate of

{) ·1·- )"'/- -z_ 0

Minimal Effective Dose of BZ by the Intramuscular Route in Man, (ADA

'"2---· .:i�

Case

08004), November 1965. Downgrade from Confidential to Unclassified, US Government
agencies and their contractors.

c.' 7
•

-

/Lf

-

'?- � 3

/

n. Stability Testing of M138 BZ Bombs, (ADA Case 08008), August 1966. Downgrade from
Confidential to Unclassified, US Government agencies and their contractors. 0 1f- N ...- 2 f.· '3)
o. Some Chemical Reactions of BZ, (ADA Case 08009), May 1964. Downgrade from
Confidential to Unclassified/Unlimited.

o ?

-

J'/

-

-:;.. 9- Y r£'

3. The point of contact is Mr. Jeremy Taylor at 410-436-6810 or jeremy. taylor2@us.Cirmy.mil.