Electro-Organic Chemical Preparations

A paper presented at the Sixty-ninth Gen-eral Meeting, held at Cincinnati, Ohio,April 24, 1936, Dr. R. L. Seabury pre-siding.

ELECTRO-ORGANIC CHEMICAL PREPARATIONS.'

By SHgRLOCR SWANN, JR. 2

ABSTRACT.

A review of the chemical literature has shown that electro-organicmethods compare favorably with purely chemical methods for certainsyntheses belonging to the following general classes of reactions : cou-pling, oxidation, reactions with halogens, and reductions. Electro-or-ganic methods have been used most successfully in synthesis by reduc-tion.

Since its incipiency in the early part of the nineteenth century electro-organic chemistry has been the subject of a large number of researches.It is interesting to note, however, that these researches have been putto comparatively little practical use. The number of patents in thisfield is small and electrochemical preparations are rarities in the organicchemical laboratory manuals.

A search of the literature has uncovered a great many electro-organicsyntheses which should have preparative value. There will be tabulatedin this paper only preparations which give yields equal or superior tothose obtained by purely chemical methods. The yields are stated in percent by weight of pure product. It was, unfortunately, necessary toeliminate many preparations, probably useful, because the purity of theproduct was not indicated or because the product was estimated and notrecovered.

The results of this research are classified in the tables on the follow-ing pages.

1 Published by permission of the Director of the Engineering Experiment Station, Universityof Illinois, Urbana, Illinois. Manuscript received February 14, 1936.

2 Research Assistant Professor of Chemical Engineering, University of Illinois.

287

) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 142.150.190.39Downloaded on 2014-11-19 to IP

http://ecsdl.org/site/terms_use

288 SHERLOCK SWANN, JR.

N m äi S II)N 04, 4,

ä. ä

0~)4-,

ä

d4,

ä

04,

a:

^ ^ ^00 r

0

O



U—C^—U ++N ^

^^ x x x xU—V—U ^:0 0 0 0, U

0 0 0 0 0^ Y. ^.`=1. -

-a !Nx -^-U x x xr.'0 ä^,, U_U .''_.)..._,C1:.)

«f c^^d g 4.. e^ .aivti öV ä: i ^°"

^ +j cd b U ,.+ . a) x.^. ^+

C:' q O OÄ 2S ^ ^^ ^ cö. Ar.a ^-d .

a )ify ux V. 8 a)^8A ti. a AU A Li .--6A-ö :.ö

,,- . . .. p

ELECTRO-ORGANIC CHEMICAL, PREPARATIONS. 289

7:1%,bp q C c?49-Vcdm cd cd ^

a^) p C a~) ^ u? q ^ Ü e

1... w t0.. O •y'^ ni ^ , O Ocz, x aa m cnÖ w c"n

M v) -ti v) 0N

N N i/) bM

Oöä

'C 9. ^ ^ ^

ö-2 ö c öö^ ö ö öv Ü



bU

1 dö'z4 c ä0

x ¢ Ä.k^ U'-o

Q,' Ü Ü ^ö Ü $� x

A

^ U öN

•

^'•^ N w..ea Ü d•t4 00 ö

N ^^ xL,0- x

Z• .a

iÜÜ d..N x^

fa U atu^ ä

N dT. .äXO Ô .0

▪

'U [ äU

•

7

▪

NU k f.,O o ..

Z Cd CU 2 b w

Z .T-2 ,UA>, gZZ ^(.4u ^ ^ ^Ü o.)i~

r!,

cv 0.


0

/0.05cn>

'"

i. N d A

^ E i y.14 ^ d da N .Q .~.

a ca ts. x

4.,C yj^ ^3

^ a.^^ ^ ^

44bß.

x x» » b b Ü Üü U *. 00 00Ö Ö Ö Ö Û UV U U0 0

pÜ Üxxxx x x x ö xV—^ U U LOUE^ ^—v i. ro »

^ ,;y , +000,

O0 4

6.1;

q^^.x x

,,,U Pxxxxî '_>>'^' i!>. O"

^." ÄU 0 0 0

E C^^ â

dx x^y Û UA c°^'ö A $'C7 A U—V

S^t'^^^^^

xö xU O

O—Ü G ÜÜ g »0 q ÜÜ

= äx^x O

^ ^° ^ xx0.0 E tiÛ ä ;ti ÛU

> E' w okÜU

EÖ 04, 4.,Ô00 0 övoa 0 c ^ x

Ü .-.-Ü



0^

bn45cn

G'.

Ü

ö

ELECTRO-ORGANIC CHEMICAL PREPARATIONS. 291



292 SIURI,OCK SWANN, JR.

mö

.$•+

da

co

0

'O 'C 'D 'C0 0 0 0td td cd cd

y .+ ^.. ^.,C y.,C C L C

Ü y Ü y Ü y Ü yw ^. x wx w x

^00

Ü ° Cx.`Z --U —z

I x O_°0

/U ^ ° 0

° I IX x 0 O o—o—o —Zz z i—^ —i 1^ Î0

z —u —z z—u —z bö—o I ° ^ u ^

x C ä77 ^' ^

7e4 ä.^

'E .0^

• ^ 4-




bC

bC

0 0

4-“14 •^•CC C

4-.4 C

w w^



294 SHtRIACK SWANN, JR.

w0b

b b b^ ^ ^^ ^^ ^^

. dx ;s d d ; ^ v ^^ 4-, ^ .ê 4,.J ++ 4+ +, 44^ ü a0i ü aCi v:ö .0 ü:"d.^ (s,^ W^ fsîn IL, ix.

d x

In O r ^ O

OÔ N M N1^ Ô 0, Ces O^

m Ö

i ä ä¢

^ Ü

öä




4oa+ro

.B.m7,=i+dEbbCcdNE

h b66)O a

:? O ö

w% ^ z x a)U â x ^.4

•

N O cl^ + z ^

U 4.,

'^ ^ ^� 4,O^ a;T ^ C

� x .^ •^

I.i. N 4 O.d + ^d

1.x f, UUI b ❑p o

^

jiz^

I L ^ '^'4 o ^v?..

IIO x ...,' .+ S äi°.aa1.4

\ /zö ä

W U3 CI) •^ö ä^ $^ D'o yd v^ ^v Z

7°rd 4.'v bPA N.b

.R0




wo^.^N>H

^>

^4

++'N^ CMr g

C 4)CO N $

i R4 CW Wt.4)++ 0.) 'r" .

N .G O 4) d 0w W w F a 1:4

4.,R7 y ^

I"i

-9:S. ° s. Tä ^

n O .44 os^ ä ä ^ ä ^* * * * *

.4.

x .: ^ CO 41.U xff U Ü Ü Ü Ü

°E P g P: 82 w w w w wisO 0 0 O 0 0Ü ö ö ö ö •ö

aoâ•w

^^^^

QZ x x

MM yy^^yy MMq q W W WZ x x U U U000000

- - - U U U

o 0 ö x x xU U u U U U

>, .5,7,

W W w Q d 6 1




"FtZ y b 'Ow^

^ w ^:C

^.[-^ o ^ ^ m

N ^ Ü^ ^^

)00

oCo

cd

Ü ^1 Ü Ü to^'^ O ^^ /"^^

ö ° 0 0 ^Ô

x UOx zoom x xUOx xOUx °xOUx xUOx xOUx xOUx xUOxxUOx O xOUx xUOx xOUx

xUOx U xUOx xUOx xUOx

xÖ

xÖ Ö

-------- ^./ ^_^ ^^ ^.----bdcdaai ++

o q G ÖTin o

^ ^ ^+cu .1 ^ Gui ^ 0

^ ^ 5 ô a ^

'V Ü 'U bAcdÜ Ü

O O O OÜ Ü Ü Ü O

xUOx xOUx xUOx xOUx UxOUx xOUx xOVx xOUx xUOx

xUOx zoom xOUx xUOx xOUxriy,Ox x(../oz xUOx xUOx xUOx

Ü Ü Ü Ü Üx x x x

Q^ Ü

0

ÖaÄ C7 0 ro X

Üöä



W

298 SHRRI.00K SWANN, JR.

00r.

n „ er r r r

a ä ä ä a 8.,

UU U ^ ^ C6.6. 6 =o :ti ,oZ ^ ^ 6

ti ^ ^ ti b b b 7. p-. q

p •O ^ ^ y w ^

¢ ä, ä. H a ä dö i 4. d



EI,ECTRO-ORGANIC CHEMICAL PREPARATIONS. 299

mi

2

eu

^

-oC-p ctl .7 mm ä ä^ w ^ = y

m k caC ^ ....•Ö >4 E w EE

GQ ^ ..^.. i= I-.) ;X^

^Ü^^. yâ ä

M ,K)

^ oNO ä 00

^"J%

xöZ6

ä.^ÖbE

z

ÖC.^

o6ääÄ.Q.C.

x

/

zu/\

\/• '^•N

td _a^ ^

ZZ/^

\/o—

.^,

a^.+Cl.)2

v^ö

.:x

^v^"°

x zU.A Ux o— ^—z

q zI

7,d Cd•^^.—. pk ^ C

ä^ Cdeip

\

^

>,;xCC.â7 yA2we,;(/)

x z=0^ j" I^

^ ö>C..0CL ti

68C öENw^ ä

G'^7.1a)

cn ^

°z

Ü

Z6G

..o^•

^

d

z

/

z

n

\/

^C1ö4z oÖ ^45.a

Z

%\

\/

..li.ti

4.2

LJ

o—^

dao.^

K;b....a

ö °z

c)--(-)

öq +°

Ü z^\/.

g Ö,d'''S cd^.. :^F.a+

aî o1 3

\

/^ö/\

^X^

Q CC

M (/)

x °zx j =uCZ I

x Uo

C.0.0acMO C

^ ^.- w

+ 0.



300 SH ERLOCK SWANN, JR.

Ü

0a

äÖ

Ü

•NO to)

'4......, 0

hi0

y (!)Ncd

^ Ö, '[...4 x a0 0

^ z ö14-1 x 1...

oo .1:4In ^ 0 x ;0 "5'

ö Z ^ y

^..`1

o ^N.

•^ t•,) x ^w^ ö U öb

I. C^

c.) ,..t0.•'>' ay +U Ow CO 0 ^ ^ Ü

^ 4..

x = I.^ 2 + .tiä N

v ö ö ^^ ^^ ^ z '^ ti b7N C

o x $.4 d ^ ^

^ ^ ö ^° ^ ^

^ '^ x -=.5> M ä1... (,/Ü Î ro'O ^ .Q M? .

J ^

^ Q^ .1) ^ •". ö

v 4+.w ^ U

C V •^ O • O^T ä

t^ ti 4.) u) ^ ^ o^c,3v W ^<d ^- 'ü^ ö

UA ' w a^ d.`',•Ti ^ (d C M p Ü .94

m y^ ^ ^ ä

^ WG U

w d Q ^

L ^ ä ^ ä äa ^ .; HW '0 4 : a .

00 O

a

Cn




0 0 0

^ x

(-4^ ÜU

'^ w

ä ^ ÖDUÖxxx

^00.

b ^ro 00^ -1-ö

x.U




wmomao

yC.,

°^ ti

N b aw

►ai tYiN

e'.•ò ^00do

xxa+

d Ü^

^â

•41ä

^^ d ^

,

;

a

zxzxzuz=oxÜz

g',;[q

ald,:n›,OOE

N

^

x^ ^z

IIz—o

x lu \ ^Üz

*5

II zz=o öÜ ^ äd ,^ °N N^+0 ^ ^.L±O.Gq'O

! ONN I

c•wt!!,3 a,^^

0 ö

Cz>6* xö ö zz xÜ ^_O dN O C,'N tO, :.

^0

.^ [ OO q ^^ z^ ^Z.- N i



00

000

O

EI,ECTRO-ORGANIC CH EMICAI, ;PREPARATIONS. 303

bCca.,^ 6^b ^

^ 5 ^• n1 .4tO..I--^ (!T (/)

VI^ dp

cd_,hWc7

Ü

ö

Ü 01 IIx z=z

o=zÛ x x



^b0ä


w°äoco

r.

ä n ecd 23 cdE E .x

a ^ aC.1 ä

U.. p soo. a '"0. Pi ocX c x '13 x cb cd b cd e b 21N is,t^ E ^

0

▪

^N b x N x ,^ N xw •

U

U¢ w ä

rz .C1 c.)

8ä 00

ä ^ ^ d^ ^ ä äâ, CO

z

Z x z x z zÜ U x Ü x x

x x x x x cj x U UÜ Ü Ü V U x UZ z z ö c v v U

II II II , ö ö 6 a äZ. z z ^ ,; a.> ^ ai a>Z x x ^ ^ ? ^ ^ ;Ü Ü Ü ö ö ö 0N ö ö� ^ ^ ^ ^ N ^ ^ 4d (I) N '^ .G .G N Ö ÖdN N N N ^

'5's.' ^cl.: N .5N ^

.0N N N C ^ Ö `^ '^ ^Q ''t d Ö Ö ö e A, iL

Ü Ü Z x v x Ü Üz z x U x ;,.

II II U Uz z z z z z

II II



305ELECTRO-ORGANIC CHEMICAL PREPARATIONS.

w

.C0E-b4U

m ä o ä.^°x b Ê C

> m e n,° mN a°'ix ^ öN v ^ ^ä

wo

w ^ ä ä ä

[ 4; w) o

1^^ d ^ ^ ^ ^ © ^4

Üx

v%\ z ^ =zH Z-=---Z x x z=z z=zz u x x ^ U = x ^:/\/\ ^

^

zu

z^c?ä

z 0 cl z z U U xx zz ^^ z zz x x Ü Ü Ü Ü z\//z

0

öä Ux

^\ ä

v

x U U ^ .^ ^' x x

^^

^ -9. ^^ n,\/U C

pâi 5.

3,^ ^

d+6

cx ^

E

^0

'^ a°E

4 ^ ^ ^ ^ '..6^^^^

Ö Ö N N N dl ^

.'5 N '5 ^ ^ ^..< y

''^ O5 ^

ä, E:y iS

t^,a

• C

i ^ • ctl^'^^

F. ä•:[A, cd

A'$NN ctl

°z6zx

öx j\

b474b474 U Cz d^ c_ N

.-^^

.5.,c

Uz /

.^ :4S)^^

U

x^ä6.6

^^°z^^ >,x... ^Ü

`Ôz^x&J(..)

^öz^x.0

Y.x

ö^ °'z _°.'4.‘

öx ö öZ^Ü ^ ^xzU z ZU4.6.E EE

öz^ xzv^ E

cz^ xZV^,ä

6,t' 6^ o Cz ^•E c<'rb . r




z=zZ

x—x z----z ö ^tl x x x xva co ,y,^ U U

x x Ö Ö E /

'E.. x xIz=zlI ff

a ^/\ ^/\ °' z^

°' a c u^ _ z z ö z/o ^ \/ \^ U

W \ .

473 A ^ .5.1 .t] c

E Ä O CR. 2 ^ ^ ti.^ ^ N

9 1 5 m-.,.,9^ö ^^ ^^ a'r N .-O. Ne NW ^ W diN yO+ e at

05 fd

N

•C .^ U %\ • ^ N ^^ wC a^ Ö° o ^â ^

-,-(5 ? x Ö -%. c .,. ' ' -z Nö z ;z M nB^g

C Cz \^ p o-; o" ü ü G

Nx Nx 6 Û ^MA^^V...) yU N ..^.. U Q - . L W iyC ^ Au) C v 0 ^C.' . ö

,-?1:',,i4W W ä

.t...0x "O E. ....ix

Q^ ^ ;a

¢

^^ <4.a. ^1^ .ö ^^ cNS«ä

^

öä

aÖ pMo

.b b e+ Q .^r O^ äU U Q z N

M00

^

O^




ä n ä a „a. ^ a 0 1o ^ O o %-:, he)

b ^ m b ^ ° ww.0W -o

0 ^8. 0^^. o•=^ CO ^ 3w ^ c^ w ^c^ ¢¢

ä 0, 0,

^ oo co oo co

x—x x x z—z z—z z—zz z z.—z

x x x x x xÜ Ü Ü Ü x x

x x U Ü V U x x x x U 0cc x x x x U U c..)()z z ö U ö U ä ä Ü Ü

ä ciz zx xU Üti ti

0

ä.cN N w ö ö ö^^

^ ^ .%^ .7.x

P..x

°,> *-Q, ö ^ ^ ^Z x n o ^, '4. 41.

z

^?

zxy.

zxU

zÜ

°z^

Ü Ü Ü Üo ° Ö. G.v d ai ar0

^

0

^

0

ö.4,^Ö

U

1.. 14 0 ^ ^ N:4z

a+z z ^

z dÖ a 4. 41. 4,^

° ^ 6 ^ ai;

c 8 ^ ^ ^.a):ö ° ° ok

° % % 72 J,.561

;ö :n :n :c



O O O <4,00 00 t- P

Ü

ö

• ^ ^z z z z z

"Cl

cd... ^dodo


eNa

"Cl^

N.Oj-0 vE-., ä

6,ti vÜA

0 0^ üp

Ü p0

U ^y.I mm

''ö Qc .0^ x 9 ^^

U 0Ü ap w.v

' C °^

d x w y

z 00,

^ ^x ^ ^ M•N 0 CL a a0 w v -. / W Y

sb w

^Q C

°^ ^^ ^ ^ ^•U .^. u!'fl N

^ 1 GT..a vN . ^ N .d.

cu } W 0.

N + Ü ü

^ + ^ ¢

N xx ö ^-, °°°.O^ösU ^ r.•

'8 u12' ^^

z ^`N ^ b ^ 4.N x C 6 B... 0 a^ o wy /U a,U Cy

w .0

:3

^

O ä öU N Md ri ci

N4I.~ N VO Oz ^ â

a.^.



d4io,.,^

>ä G c0 0 0^ v ää is. ii.

N^ o

äa,xabrä ^

'i7 Cca

äNx oaâ^ x

4.,ä^Ü 3

â 'iâ 4

,o, 00^ ^ ^

so^

Mn

.pO'°ä

xxZ x u° 0 ^zz z

^Ü Ü c

*c M ^c E kd ^>, 0

.0

0 ^

.[^>, '.^ öv .c ä

^W o

uxu x°UxxzO°U^^z

Ü U

' l'' - N '.xôO c? 0

^zö:E,........

• ^4,-5,-3en w •-•$ä^

u uÜ°z—Ö

z °U _ q\L„

d ^ -0ai0äa7 ^. .0 0^^^ä++5 a+ ^v' Ü O

en d • 0tt vZm

°^cn

c•^

x°(5 UzZ z xx UU x6 () a0p cCcd C 0.

^

^ ö.y, 2

° ^ zZ Z N

^Ü°z ^ö^^°O

xÜx UU

^

00xK xt'-..+ U O^ «i g^ Y äC:),--0^> a

^ E P.1 ,ö p: C

Ü^ °z_

qö^

^ I° \Ü

xU

> ox0oäa.) 0C OSd ^7+ ti.^ Cä oil.E-,^>,^^ö G.




310 SFi$RI,OCK SWANN, JR.

0

äoco

^ m ^.. d

,aä aä . i ^ x ä .Û U U ^ h U0] Pa Oa 4.4M ßa

I

a0o 0

^

OsCO n n O O

'x zzö (:)"

z z^*^

Zx z

Z •Nz z O O ^x* ö z

xzx

^,.4^ *

• 4— ^^-0

4-.•Nos

4,

415..9.,N

cl;GN

.,C0C^.

^ os

V

Ä

d-Cä x •E 1 4/2

W î1 ' ^




bit

•

L L. 44 h1 E!y. .9E .9E .9E 3E UCtd0.1 fÄ ^ n7 U w

r.. 4 .y .-.1/) N 00

x x xzz z z z(--2x

/\ /\^ /z\Üx ^Z Ü Ü Ü Ü Ü Üzz x x

\^x Ü U Ü\ /Ü Ü\ /ÜU C z xU

3, .^ x c+ô öb

O• 0.° ^ • o CN N C ...

NN ^ ti A•N •^.dyy

•

• C z :.. Q ü. ^

wx xx z8. zä,

•^ a

ö^x ° " ° *i' °a; E. a^




WirQ

^COI a F

^

C6 ©,

LCU

.0 ()^

44bC Cl

ci f.2ctsacd

acdC— ^

(i)^F'

^ w(X W

vn+

Ecn

EV)

5cn

E,

cn

^

vÜ3 N tn t-.. co

^, 141 ^,a -°

^ MCO ä ^ ä oOOo co n

.:

UZUÜx x / \ Ü xO

Üx x x x^' U Ux Ü Ü UU Ü U U Ux

ö ^ Ü Ü Ü Ü Ü Ü Ü Uä U \Ü / ä x x x eU U U ^x x x o x x x y6. U

ai x C.)° Ü Ü a'

CCCO _

L O N N Nacd+

+'0.0.) }' a) 'C ^ N N.o

Câ

wa

ö4

a0i^

EÂ Ü

;nA

;nA A A

Ü Ü U

Ü U

b471

o

x

Zc.),

U O U

/U \ v

U x O^ ^ ^ o I l o C) x ^^4 ö x

U ^ ^ x U x ^ ^^ \x/

Y.U\

U/ö ö ö ^ x

x U UO 8 x / \E)x O 'O (1)°

,4.,a)

ö•47, a) .^

CO

d a+

aia..0Ca)

aa _O ON ÖN U

Ü x c cÜ °' d

.O ^. k Op

d ^ y ^.ê A^ Oa a1 A 0.l



EI,ECTRO-ORGANIC CHEMICAL PREPARATIONS.

N Ä rVon

EE E E E E Eci) u) v) v) v) v) v)

313

,C)00

00^

r--^

ÜÜ

xxVU




'O Ir ni+

^

U >,aw

M 00CO. No N,.r 42. r

Ü

ä

ö ö`11N1,7 cd'V>, C >, G Uâ+ ^' a+ "27 C ^.ti -

ß; ! ^ Z?... ^ kN C^ M 4 C3 .$



U

OxU

Oxn

/U \xU

U — U0


-o ê ^

fd EE-1

V "itb F Ed

CA v) co)

GO

‘,0 •et, ä ^

Ü7

ö

O

O x^

U

/ \



31 6 SHERLOCK SWANN, JR.

e a^ .{ _ E.§ /^\ \ .§1 Ek\ \\ƒ ^/

\ ƒV

Qu

(/\ / e )gU^ o ^ L.) / ^(k k ^

co / 2 ^

as 9 ^ / /- a

. © =2co

."5 / / ^ \^ ^= f \ ^ ^ ^.-0 Q. § ^ u Z e \ ^ 0 /a u _ .^§ ^ /\ \ ./ b k

Ü / \\.... « \ \ \ { Q!). ^ g = •I 7 4/ } 0) \ s.-\ C %

E f6 % E § t ^ b (§/ $ ~ / s-CE

^ 2.))] -";%4 / ^ ƒ § ®

• ^ ^\

4.0' k + ^] # § / E

+ ° % r=4zE.4 ^+^ 7 ^ 3 / k C ^ ^

\ ^ ^ • ^ ^ \ ^ \ \ / COcA

\ ^ ^ j ^ % £ Il \( /

(TSö ) \ \ 7^^ k / 2 -0 m = aƒ \ \•$ ^^ § ^ G t% . \ö ^ k ^ ^ ^ d ^2.. / k V . }2 k7 ] . r. ƒ ^ /2 'A 5 2 ; o

)Q.j \ \ ^/ ^

7 -0)ƒ \Q)^ ^ 2 § ^_ \ ^/P. k • \^ s ( B} /

N .^ /k kA 2§ 4, ;^^

k }2 S




^.a) ;.a)i+ 7..d N

00 ^/)

o"'o r co °r° ° co

m0ÂO

zÖä



318 SI-MLOCB SWANN, JR.

MMooq

"qC0

^^+G8wda++4ca

:'8 ^ ^'" d

4 aü ►°'.?, p

(5 o•^ v

n Tid o co ^y

0

^1 t) ^ ^v to Ü

x cd ^

K x°o °o

.0E

V' Ü Ü '0 .5s x O

cd°2

gx Cb .5)

Ü

"'l^ ^d T b^ 011 ca

.1+ + O,,,

öO + + :o F.

ö N w ° ä+ +^^Q

^v_

IL8U ^

^, 0N ° TAV+.Na a y ^ N^lc ' d yr4..o ~ ^ ^ M4.4

y 7 0A^ Y Û aöW w .Ö

D Q0 D .p.

pa .a T 0.m^ .

^ ^toA

.^ M .^ aOi

n ti V N ^ By .^ V M ^ üA • ,cd w 1 co C rC PÖ Z bZ uO : 8 ffi

wyyGL




cn N Osä 00 ö 00

^'z•.. x4x, ö 0w0

d ^Ü —Ü\ ^

^%.. ....

E-4 U^« Û üQ Ü—Ü &s t

I^°

^ I Cv ..zq d ^. N + Q.ti

,a

+d .!E

w xx OÖ '^

^ u—() ,°',

^ x x^ ^ xU U 4'

CIN \Ü ^J / ^ ^.^

^ ...;o =.y W H ''^ 7 FN.. >W a ., x

x ^C ^ ö Ô .nrVM5 .^°,:V) 8x o,

q Ü q ^. m ti4. °^ u .wB W •^ ..0 ,d a ü= ^ 6 w

i I




w 4 L Ir lyG) N 0) 4) ^

q C//

CI, 11

q^ W W ^ W

o°0 00 ä ^ 00

tiC0

C C d >,ti C 0.^ C

.^ .^ .^ •^ 0.^ ^ ca 7,7

.E ^ w d w

^ m ^^ ^

� ^^ vx dx [x ^x 4 ä> äx "a,.....0 aV xU

°'U ?Üm N Z -5..n> az — z >,^•� äx ^x ^x ^, x A.x ^z°' ^ 7,(..).Û Û Û äU Ex

^ ö vÜ ÄÜ ÄÜ ÄÜ ÄÜ Ac?W.5 ^x Zx Zx Z4 zx zxz ö' zÜ zÜ zÜ zu zu zÜ

W

o

x xU-U

\z Ü

UÜ

zOU

U6ticb

O

Ü




v^

ßaM «, M M M M M M M o

0N a4ii G4.) VG4.1 G4.1 G4) G1 N d C

'Ö 'Ö ^d Ô 'O 'O 71 'O 71 -o yO C CG 0 0 0 0 0 C ^X x x x x x x x x x F .,

n• • i

� 00 r 00a

se) ^ ^ r

ÜCb0

63;m, z x

/\ x z xx^xo

Ü Ü ° • Z x Z z x UI I C'^ Ü N V Ü Ü Up

Ü Cx,) ö•Ü x z Ü x x x\/ ?-Z U x co w U &

Z Z U x ^öx a a cÜ ^ ^? x ° Ü ä ä c •EU

vs

•

ex x c U m m ^ ^,L.?, TO U ^ a N N N vc).^ e ^, e ; C a .a

a"iU . F. c .S .c ä p >,ä c E ca -El m 8 0 0 x^ ^ b A 6. D, a C O ^ C 4-..4a ,[ Z ^^ aCi F" H ^ 4 Ü

42-2: o z [d a a ^, i 4., 4, 4.

Ü -ö

/ \ .E

xX. x g z ^^ ^[ zzxxx° /\x x •ö ° ^ ° ö ö x Ü ÜU U bx x x x ^ ^ ö x I I\

z/ .c U x xÜ U C) x o 0 0o > Z x x ^ y C) U U

UU k U W ^ Ü C^ Z/x x^ z b ^ E p, a, v ou ^ ^ b L.),x ^ U V:ox o ^ db:b ;n be x

U ax x ^ ^ ^ ^ ^ ^ ^ 0.C`° U C 0 ^ N N v

gy x .d .ä Ä A

.^ .Ö .c cd

aci ._. b 4o, 5.c .^ 5 E c ^ L N :ti(a ,.+ ++ 0 0 .1-. ß aai'^Z N 0$..• .c ^

0 -, t' zU g^^M co U °? 8.Z (%) •ä Z p, ca d 4, i 4, 4, ti $ Z'ä




6) 6) 6) at 6) 6) 4.,6. b 1:1 'V b b 71C C C C C C C

"►r+ )'rti x X x "^

0 00 00 8 ^ ^^

^

2ä

6;[ ,;'.[ e E C^ C i, eNU 4; ^ .0>,N .0(xj 8 c ^ ^ c ^

,ä ä ^, ä °'x2 xU ^ au5 s

x ^ a ä x^ ^"

U °^ " a) p v .^ G .^Ü ^x dx ä Ä ^x dxE dx dz ä^? rx n.0 îU(/ 09z Fu .v.z ^,^ 7,x 7,x^ äx äY. -zx dz Û Û^, x" ^^ ^"« gx ax I x^ to Ü AV CaV AVdx A

Zuä x ^ (j Zx z..;x z..0Ü ZÜoi Ü z Zu Zu z c>. z 6.

t 1 1U § 2 '

Ob q 0 ^

E E Q;

rx `° ; o ^ ° N x^c; ^ 8 -2 .^ : ^ x axa^ ö ö >. > x ^ V >,Vb ^x ^x ^x xz a zE > U >,U aU ^ ^ 41Z.)) dV• .^z ^z ;z ;^ ;^ ;x

0.(/) acn ^^ ^x ^ Û

^ äx .-Ztu V^ ^ E

^ dU äU AUQU 6Ci ^x ^x Zx zx Z (xj z (xj"G+ zÜ zÜ zÜ ZÜ z ä z cL

P



323

a 2 wP P q q N

N 4) Q) _d Q)b b -15b ^f.' 6Aq/ 6 .^.X R. t+i R".^+

^

Ü^ U

^ -o x z cU 9..6- U

Ü x / \x Ü 8\ Û U x a^ g

d c^ U .^'px x ti m 2

O :c U U ;o N }Z / > \z / I "8 ›'U" xU x aCi Ü a ^^ ^ z^C. x ^ ; d^'5,'^, ,, ^ 2 7.,z^ ^^^b 0 x 4-,^ U °'xA ^^b ^ c >, 2z ^,^'p" ,^ V ^ O v MU ^0

^;v 4-' 3 ^ zx ^ ^zm--5. 5 z 0. z z(3 z6.

ELECTRO-ORGANIC CHEMICAL PREPARATIONS.



• +,

-00

U

z/\ \

8 3\/

z

00


u)1..

./.nalOA

fi0

.--.

o:..of1...=

.Wal

Cl)

0 +al 1

750)0)al 0Cl. I-•

(/) 0:1

0 +al .4

4 g0)0)al 00. I-•cn al

.w0 4;-.0 a., ,.

a. 4

00cm

(-4mee)6

1-30

-00

x x xz z z

c.4 /\ . ci\z / \ x x X ZQ 00 00 0

I I I I I Ix x =U —LI0-0z0

5

t

a

.0.6.0

4)

u

5

6.6.

ca.

.0.6.4.)

4)

Q. 0x(.1

5

6..

0.

0a.)

.4a,4)

b47,i.5 . r.t !",al al

xz

o/\o0 0

I Lx x0--0

xz

o/\00 0

I Lx xy u

xz

o/\o0 0

I Lz =(Q —L)ZC5

e-0.1—0

Cl

.)

00.)=at..ef )

.Z0

<L,

E—0

'ElCl0U)

.06..CO

(4)

ZU

e—E—0—

c.)0u)

.06..

'''4)

ao

22 •

c o

E 6"-E i;

Td.oEs o

+At S




•L7

ci)

7

^

md^ U

0 al

Ü fi

Cncc) Ü

C

Ü fi

OcoOco000

N

Uzo/\x x

z U U zx /\x L L a/ \xI I Ü —Ü U

\—/Ux x ^

U —Ux xÜ Ü

Ü

ö

.Ö

.0+XQr

b

4.,.L"a




e.ace 'v 'U 'v'F.

^°U0 al^ ^ x^ x ^

...4 ^ v d^ d^ ceai(g ä vi vi cä maä moä

.•

o_z\o

U U




'v.1) ö›. It

4.+y 5^ dö. 4

ä °v1.3 ^ ›.

x.0 ^ C w

Ü

++

m^

^0

•^

0 _a^ o

^ >,0:V

x ° ..„..4,4,) °1^^ x x

U >, ö C . ü ö.o a. ^ o •o ow U —U yp ai 0 ^ ° .0 z?"1

^ \zÜ ... .t U x ^ • t.4 U +°.

-.$Ü,O/ö ^ x U

0`' ö

v U/^ .ä ‘. „ x ^h1... w T„ z Z .^ V, x Ü Ü

ö° ä x I I ^-0, ^ ^^ ^ ^ U—U=v .... 1.2. x/

—z \xx öA I I . ^ z Uo ;a• C N 4,p j--- /

.N ^ + +°+ .,---U —Z 'd s / \ 7,Ö ^

?•1 x 0•^ x x y " _—^ //JJ yN ^ ° • N V U N V

en

s + ^ C+^ , c3' Cö ^ t ^7aa^ ^ x a ^ i ^ ^ z a.. ^;

P ,s U es)Ö ^L

^ C .N GL .a ü;X ^ U =U -5, S: + N ^ ^ ft$ N0 75W ?1 L \z U ^ •

ü ^ ^ e x

E M^ ^x o/ g + -34 0 N.4 o U—U

..01 c .^ + 0E-{

3”+ °' °4 Ü w ^ x ^ h^ ^^ ^

^'Ü /\ ä x U ^ a

ä+^ « ;, s z z p (^ U —z ° g .

I w ^ ° O I I "' ^ 4," \c,i .0

N soöp

It U—U°U ^ .^ z U ^ ^N^,0

'^ ^•o ^ ü w I I 0 ^ ^ V ^ a^?1 I.4• ü 7 ^ O s+ ^ .0 ,T,.....4ö . ^Q v ^ z—U—Z c v G' .....>,-4.. ^ x ,g Z 5 j^'

Ü ^^ U U ^ W "' M'ü^W .0 3' 4'.c q!r! ^ ^,^ ^ 0 • ^ ^

L\ x° o y ++ a +o^v 1 •C ^^ özU^^ ^ e eW^

V__Ü/ U ^ 8 p c ov^"^'m r. ^ ^

ä.

c4 ^, ^ u ,b ,^ ^ 0.x a^ .

F. 0 „ ›, ^'' ü^W ° .°, C ^ ü d

Q7 .b

cwd G V ö N a~i ".a ^ H : ^ Ûa ^

^ sa5s

d^



x


öä




Ü7O




T)b..N

oxo ^^ö Ur.. x xtl U —U^ x/ \x

d U\x x/Uoxi U —U

x \ zs / <W a 7... ^ < }

U •N U U^ o ^›, ^

o ^ x^ ^ 40-.4..\

/

^ ti b a c' - ^ ^

e^ ^

^ `^ ^"b

z ^ ^ ^^..^ qy ^ ^ o I v) e.^ x ^ka o E ^

(II ^ N

k ^ ^ .^ w +t:'^

^ 717 ^° d

xb wW.a

^ .1.,CI) ^ ^ x Ü g ^

c4-1>

� +- C ^ 4.Ü ä Ö ^

E-+ ^ + v u x ^ ° ^ ;

r4 ^ E ti^ Ü C a'^ Ü—Ü ^

?. r:4 +^+

• D

v ^ - --z eSa ^ 1 Ü / \^: aai

^

•

p / \x ° > V N V04

\U =U /U °, . W I-.^ U U ^î .ä y ?, \ a

w ^

b ^ ö-° ^ x ^� `' ^ ^y V z 0 M

▪

^:

o -ö i ^'\

y ° äN N +'• W \. C ^ ^Z > b

n M

e Cl a x / ^ t.:2'^41✓ ►y.

wV L. w • V

p N^ C]. cot^ S. .r Vj .r(^ d.:

•p Wco

.0^ ^ ed LL ^L (!^

a s0 "4. .:F‚ a ,;" g"' ° ^Ü4 "d "H a8 caö yiL.yp ^ ödU

U;°

.5

%667 4^;

r a^ â

ä ä

g ^^. ^.° yy

• ö

..5 .O U. k ,,sO O110N aC O

Ö At^.)C. q 0N ^^

Ü x ...„ z .,

s U t

Ca

es

y

^

0 Ü d Ü 0 .ti ^ xa^+

;^ m y N U >w ^� x N •N ^ =

bu ^, e ^^ö .^ rx (I ^ 5^ .,I*. 4, e s ^ ^ ^

'..gÛ a y U ^^,

ti :ti i c ►°'.•N N• to

z 0 -^ z ^ b''S :'4 x/ \x ^



\ /ÖU—z-^x

x \ /U

U =U/ \

331EI,ECTRO-ORGANIC CH E MICAI, I'REPARATION5.

"0a'O^ a î.al '0 "i., c4N 0 ›.. q.§^w ä 0ä:ww C.I) It

0äo

^.

^

0

ä ,^

d ^Fy

^

C1g y

\ \/x oy .^Ü —z^ Ü U—U/ N ä Î 1 pi^ U

Ü O x ÜÖ 0 Ü ,V•a \Ü-Z/

> < ° ^%)x ^q ^/ ^

01 ^ \ /v ô ^ ,^^?, U=U^ Q

^ öp" N ^ / \•, j ö ü e x d^ ö ö4,, ^ " ^^ ö w x ^zco >

Nö (s, 'v 0 °'^ ^ 'v ^^

Z ^ N ^ ^ U

•V) + ^ ? ,v + + ^ ,LT +

^x^Ä^ +

"8+

^^Cl^ E^ Ü ^n ä N N xw Et'+ + +

Ü

0ä

\^-z ^/U—

x/ UU—O —U O \\ / O — -

N

NNMN

^



332 SlitRI,OCK SWANN, JR.

..Cal

N

^H

-oC

01 C

Q^C^s^. cVtlwa

-oo<Cd i.p'CC,^t^. ^w4.

'D öucCd d

^ CaCiC'Cs^. û.aa

aa

^Ü3^ t â

"'^ "'4..^

\^—z/ \^ /—z ^_^/ \ / \ / \

Ü Ü ^ Ü Ü—Ü --(...) — U Z

-gä

\ //U =U \

\ / x/U =U \ Ü

\U —4..)/

/\

ö ^^^x

öTx 1 e

öTx ö^

^^ . ^ .s^^ ^ ^

N öA z ^ ^^z ^ boz+ äbx + ^ ox

y 4+ ›,-= xc,

x ^^ü ^ aab c.S 0^ cä •^c..^+ + • + CO,

/—z/U \ / x x\ z /U—z\ x U—U

x/ \

\ /Z.---Ux \ /U

---Y.x --U\ /z

U = Ü Ü U=U^^

/U\ /U=U\ / \

5.'C!!^cd O

^ Zwz vöxx N o z 0:;,-',U d.nx cä.^QÄ

vb UN ^

CC0

^ C '^. q^^ ^.ä,ä Ü




b0^

L. yd

11) cn x

ed ^.-. N

^cnÜ

ä, ^•ti N 0"•

v,^ ^ v—^

x ° x—Ü —Ü \

^z ...t

^ °x /U =U \ o

ö a• N -0

IT

h

I

° • U U

^ °^' ( ) C5. ^C d xx ^ bx x 2 ^ ..,54

^ bk. 'b C O N (s' G.0 p z+ ,b ö ^z + bz "öt x ^ A.l.,"q t ,^x kxxx x 2^ A'U öÜ `" A ÄÜ^ fb + M-

xU =U

Üb0

Z xU —U/ \

—^ —U\ / — — ——^^^

/ =U \ \—\o/

Öo zz xx ÜÜ ä

as 'dc ö^ bä NÜ 4




0

g0'd

a a^ ^ ^„ m^.r 0 ^. N •^ _.f0 y fC Y 0 "rev5i C) v

5i..o ^ vi

V)tr)

000 ros.0

-.51ox x ox

d^ Ü :'-z;C [ Üb0 •^, cgx ^ ^^^^z k ^z^^ö §z ö

bx ö Ö bx^ R.•C.) >,x 7.,(..)Cars1 ÄÜ Ä ^'4-- •

.O bU ö -oü.^ L ^öz : F ^ z%ö ^ z

8ö ;,o

^x Lx w xA Ü UÜ ^öÜ



EI,ECTRO-ORGANIC CH EMICAI, PREPARATIONS.

Ow

V)w

^ u.)M M M

C..' ..0 'V^^3

n "0 F.^^3

0 ^

td .. ,q ° .c _O.^ w öc LO ö 3

.^^

^w ^3 °caî ^3[aicn oa I. Ö .EX Ö . c x

C.)

0

p ^ O%

Ô

ä ää ^R ER

335




M0 'Li 'C TJ '0 R7 '0pa cd cd cd cd . cd cd

IrN 14 I. i..ä L.0 i+u LrV) d^ M dM a) dN a)« a)N :. i.. ... i.. ;;-. N',',^-.^

.f: ^• .:+'• ^• .f.: .'.' .L .^_' ..0'—' y+'..'^.^ ^.'.. ^. .r ^... y.i ^.'^'..

^ i^3 w3 i^3 w3 ix. 3 w 3

M d4 C\ M O

00 0 N 00 1^ NC` O C\ 00 •,t, v).-.

Ü

ö

^ x

°0ö

ÎI ai ai x0 Zz 74 ^ z u

^ x ^ ^ II _ Z:

oi^ Ü ;, ; Z,

'6 T% N N•k 5 5x o* (,9Z ^ ^ ^

p .a 'a) x0 .^ x e e

cz ^ ^z ^ z° cuk ^ ^°x v ^ II y lI a°i1°. ^ o

'L .$ W z oa z ^ p, id >.o^ ox ^ö xö

20 0 ."-z" V 0I-1 IU.. cd 41 cad . 500 0:1:00:1:0;x UU Zig zb

ca 6. oa .4. 6. -4. ä 6.5 ai $



U =U^z(.5

Ü=Ü/

Ü=Ü xÜ\ ^ZÜ

< > <U=U >


• rVI 5t "ti wEE EE E Ei:7 W W

0

>

0 O

/\/\




b bö (Ti (Ti°+J(Ti

o(Ti

(Ti+

+6^ caa ä ^ et)äe

q . aN+ ."-0 ^ .0 N..V.,..t cd cd cd cd .0..C'.

z ^z ^CX



EI,ECTRO-ORGANIC CH EMICAI, PREPARATIONS. 339

CONCLUSION.

A review of the chemical literature has shown that in many instanceselectrolytic methods compare favorably with purely chemical methodsfor organic syntheses. In general, reductions offer the greatest pos-sibility for successful application of electrolysis.

Until recently electro-organic methods of preparation were most wide-ly used in the alkaloid field. Their use in other fields has increasednoticeably during the past few years. It is to be expected that electro-organic methods will increase in popularity as investigation in electro-organic chemistry becomes more quantitative.

ACKNOWLEDGMENT.

Most of the literature references previous to 1925 were found in thebibliography of electro-organic chemistry by Knobel, Brockman and theNational Research Council.

DISCUSSION.

SHERLOCK SwANN, JR. (Communicated) : The following material should alsobe included in this paper :

In Table II Farmer and Kracovsky5 have obtained diethyl 13, (3, 13', 13'-tetramethylCH3CH3

I /adipate CIHSO0CCH2C-CCH2COOC2H6 in 5 to 8 per cent yields from the cor-

iCH3CH3

CH3

responding acid ester, C2HSO0CCH3CCOOH.

CH3In Table VIII Hockett29a has obtained 95 per cent yields of strontium xylonate

from xylose.In Table XI Hartley and Lyonssoa have obtained o, o'-azoxy bis biphenyl,

N

N/II0

in 63.8 per cent yields from o-nitrobiphenyl,NO2_ _

They have also obtained p, p'-azoxybisbiphenyl29a. J. Am. Chem. Soc., 57, 2260 (1935).50a. Proc. Indiana Acad. Sci., 44, 124 (1934).



340

DISCUSSION.

NIIN=0

in 90.8 per cent yield from p-nitrobiphenyl

N 0 2

In Table XIII the same authors have obtained an 81.6 per cent yield ofo, o'-hydrazobisbiphenyl

NHNH

from o-nitrobiphenyl,

NO2

Under Table XVII.Electrolytic Reduction of p, p '-Tetramethyldiaminobenzophenone to

p, p', p", p"'-Tetrabisdimethylaminobenzopinacol.2 p, p' ( CHs)2NCBH;COCBH,N ( CHg) y-F 2H* 2F—>

(C11 5) 2 N N(CH 3)2

_^C H 3) 2 N<--CO — CO --^^ N ^CH3)2 (Cathode

H H

Escherich and Moest 77a have carried out this reaction in 75 per centyield.

Also under Table XVII.Electrolytic Reduction of 4-Keto-3-Methyl-l-Phenyl Pyrazolone to

4-Hydroxy-3-Methyl-l-Phenyl Pyrazolone.

CH 3 II 1 0 I ZH' + ZF . CH3 II — CHOH

N Bisulfite N 2.111 Cathode)CO CH3000H

N NC6 Hs C6 H5

Fichter and de Montmollin7sa have carried out this reaction in 46 per centyield.

77a. Z. Elektrochem., 8, 849 (1902).79a. Helv., 5, 256 (1922).




In Table XXII Sakurai 95a has obtained pyrrolidine, CH.—CH,, in 28 perI ICHs CH,

VNH

CH2COcent yield by the electrolytic reduction of succinimide I >NH.

CH2COAlso under Table XXII.

Electrolytic Reduction of Theobromine to Desoxy Theobromine.

NH — CO NH — CH2CH 3 +4H++4F --- I I CH 3

CO C—N\ H2SO4 CO C—N\ (Cathode)I II CH I 11 NCH

CH 3 N—C—N! CH3N—C —N^

Tafelsoa has obtained 60 to 70 per cent yields in this reduction.Under Table XXIII Perkin and Plant 119 have obtained 9-methyl decahydro-

carbazole,CH2 CH2

CH2 C=C CH2I I I

CH2 CH CH CH2

CH 2 N CH2CH 3

in 78 per cent yield from the corresponding octahydrocarbazole,

/C\ _ Z

H2 II 11 I M2CH2 C C CMZ

CH2 /N CM

CH3z

In Table XVII.Law77a has carried out the reduction of the following aldehydes to alcohols:o-Tolualdehyde, o-CH3C.H4CHO to o-tolubenzyl alcohol, o-CH.C.H4CH2OH in

30 per cent yield;m-Tolualdehyde, m-CH3C.H4CHO to m-tolubenzyl alcohol, m-CH.C.H4CH2OH

in 70 to 75 per cent yield;p-Tolualdehyde, p-CH.C.H4CHO to p-tolubenzyl alcohol, p-CH3C.H4CHO in

41.5 per cent yield;2, 4-Xyly1 aldehyde, 2, 4(CH3),C.H.CHO to 2, 4-dimethyl benzyl alcohol,

2, 4(CH.)2C•Ha2H2OH in 70 to 75 per cent yield;Mesitylene aldehyde, 3, 5(CHa),C.HaCHO to 3, 5-dimethyl benzyl alcohol,

3, 5-(CH.),C.H.CH2OH in 70 to 75 per cent yield;Cumaldehyde, p-(CH3)2CHC.H4CHO to cumyl alcohol, (CHa)2CHC.H.CH2OH

in 65 to 75 per cent yield.95a. Bull. Chem. Soc. Japan, 10, 311 (1935).90a. Bet., 32, 3194 (1899).77a. J. Chem. Soc., 91, 748 (1907).



342

DISCUSSION.

m-Hydroxybenzaldehyde, m-HOC6H4CHO has been reduced to m-hydroxybenzylalcohol, m-HOC6H4CH2OH in 57 per cent yield by Rapson and Robinson. 77b Shima77chas carried out the reduction of salicylic aldehyde o-HOC6H4CHO to saligenin,o-HOC6H4CH2OH in 93 per cent yield and p-hydroxybenzaldehyde, p-HOC6H4CHOto p-hydroxybenzyl alcohol, p-HOC6H4CH2OH in 93 per cent yield.

Under Table XVII.Rapson and Robinson77b have carried out the reduction of m-hydroxybenzaldehyde

m-HOC6H6CHO to in, m'-dihydroxy hydrobenzoin m, m'-HOC6H4CHCHC0H4OHin 26 per cent yield. 0 0

H HUnder Table XVIII.Sakurai84a and Delfino and Somlo 84b have found that ammonium phthalate

COONH41s reduced to phthalide

COONH4

CF^

C0^0 in 96 and 90 percent yields respectively.

In Table XIX.Ingerso11S 8 has prepared ß-furylpropionic acid,

CH—CH

ICH ICCH2CH2000H

0from ß - furylacrylic acid

CH—CH

CH CCH—CHCOOH

0in 60 to 70 per cent yields.

In Table XI the preparations of 4, 4-azoxybis-m-xylene and m, m'-azoxyhis-chlorobenzene will be found described in Elbs "t7bungsspiele für die ElektrolytischeDarstellung Chemischer Preparate," 1911.

CoraN G. FINK12T: Our Society is very much indebted to Dr. Swann for thisvery valuable paper. It represents hours and hours of patient work. I knowthose of you who are interested particularly in electro-organic chemistry wel-come this summary that Dr. Swann has prepared.

ALEXANDER L,owv1° : I can second what Dr. Fink has said, except change theword "hours" to "days." This compendium has required a tremendous amountof library work and I certainly feel that Dr. Swann should be congratulated bythe Society for undertaking this work.

C. J. BROCKMAN °: I wish we could repeat all this work—I do not mean thelibrary work but the electrolytic work—and get the same yields. Dr. Swann,you have done probably more on electro-organic than I have—what is the per-centage yield you actually obtained compared with what the authors you citeclaim ?

SHERLOCK SWANN, JR.; I have had no occasion to check the work reportedin this paper. I do, however, agree with Dr. Brockman that the literature shouldbe checked. On the other hand, I have no particular reason to doubt the ac-curacy of the results reported in this paper.

77b. J. Chem. Soc., 91, 1537 (1935).

77c. Mem. Coll. Sci. Kyoto Imp. Univ., [A] 11, 407 (1928).

84a. Bull. Chem. Soc. Japan, 7, 127 (1932).

84b. Congr. intern. quim. pura aplicada, 4, 360 (1934).

127 Head, Division of Electrochemistry, Columbia University, New York City.148 Professor of Organic Chemistry, University of Pittsburgh, Pittsburgh, Pa.

12° Assoc. Prof. of Chemistry, University of Georgia, Athens, Ga.




I would like to point out that in a lot of this work only one kind or type ofcathode has been used. Now that, of course, does not mean that other cathodescannot be used. But investigations should be made with other cathodes.

COLIN G. FINK : They would be very welcome and acceptable.H. S. LuxENS 13°: In support of Dr. Swann's very excellent effort it will be

recalled that Dr. Brockman published a book on Electro-Organic Chemistrysome years ago, and I think that anyone who has dabbled in electro-organicchemistry has come to the conclusion that that book is one of the finest com-pendiums of mis-information in existence. Not that that it is any reflectionwhatsoever on Dr. Brockman. It is a result of the condition of the literature andnot a criticism of his earnest and sincere effort. Dr. Swann is undertaking astupendous task, one in which I think we all should support him. A review ofthe organic electrochemical literature is most necessary.

CHAS. D. LOWRY, JR.1" : I would like to suggest, possibly it has already oc-curred to Dr. Swann, that the editorial staff of the new journal "OrganicSyntheses" might be glad to cooperate with him.

SHERLOCK SWANN, JR.: In order to get a paper into "Organic Syntheses" itis necessary to go into infinite detail.

J. C. WARNER 132 : I wish to vouch for the yields in at least two electro-or-ganic preparations. I believe that the work on the reduction of ortho-and para-nitrophenols has been described carefully enough by Professor Brown and myselfthat any chemist could reproduce the yields we have reported. My own studentshave been able to obtain good results by following the directions given in ourpublications. The discouraging thing about electro-organic chemistry to me—and the reason I dropped the field some time ago—is that almost invariablysome other method such as vapor phase or liquid phase catalysis will produce abetter product with higher yields and at lower cost. I would like to have someof the experts in the field tell me of the progress electro-organic methods aremaking in industry.

D. B. KEYEs133 : Dr. Swann and I have noticed for years a tendency on thepart of the man working in industry, who is not at all familiar with electrolyticmethods, to steer clear of them as much as possible. Dr. Swann and I hopethis paper will stimulate an interest among the synthetic organic chemists in in-dustry. If it does that, regardless of the accuracy of the yields and conver-sions, I think it will do something that is of real value, not only to the syntheticorganic industry, but also to this Society.

130 Director of Dept. of Chemistry and Chemical Engineering, University of Pennsylvania,Philadelphia, Pa.

131 Universal Oil Products Co., Chicago, Ill.132 Assoc. Prof. of Theoretical Chemistry, Carnegie Institute of Technology, Pittsburgh, Pa.133 Dept. of Chemistry, University of Illinois, Urbana, Ill.



Documents

Electro-Organic Chemical Preparations