1106

3.6%

(34)

341222

,
,

7(1960)(120)

(3)1)

81

1)

, 51%

/eo'"

Otto,Trillat2)

Briner3)

, 4)
,

Briner5)

4t123

2324'

3e4'

5"6789

/1/2

()

1234

(mo1)00.400.801.30

.
1.5mol

,
,

KeyBand
,

Base-line

1
7.2989

10.4

vr ,5.90

10.4

9 1.3mo1

,5.90

,
1

,300cc

(O.15mol/9)

(min)(mo1)(%)%)(%)(mol)
1100.4018.063.6364-

22008036.026.57350.69

3271.0843813.286.8--

432.51.3051.50100.OO.97

539.51.58476-

,
1) (2),
, 80,537(1959)

2)
3)
4)

5)
6)

M. Otto, Ann. chim. [7] 13, 77 (1898); Trillat,

113, 823 (1901).
E. Briner, H. V. Tsharner,
H. Paillard,
Hely.
406 (1925).
,

E. Dallwigk,

79,1349(1958).

M. Ricca,

hely.

churl.

rend.
9)

chim. Acta 8,

Acta

3.6%

25,631(1922).

E. Briner,
(1958.)
,

compt.

41 , 139U

(121)

(34)1(va

,


0.97mo1,
515%

o,

(C

) B
A

,

, ,

1;9T-

A,B

,50%

,2

,
50%

(1)

(2)

KI

O-CH20-CH

KSCN

BA-

1+C()

CH=CHCH3'CHOtl

CH,CH+(2)

,4-DNP

C
2

CHOO
()()

()

,
n , ,-10 -15C
A
,B

(2)

Criegeezwitterion()
,

CH3CH+A6_A

,
,8

(3)

(3)

CHC

()
2 B
,(1)
terion(1)
terion

1 zwitterion(ll)
3,4

,(1)

zwit-

zwit..

O--CH20CH2

(3)

1.

4
4.1

,
160C
2468/0

!4

()

emp67,
3

1207,"1.57790

( )

7)

Y. R. Naves,

P. Ardizio,

Bull . soc. chi*.

France,

1057, 1053.

1108

42

81

7(1960)(122)

6)

7.2939

300cc

1820g3

(o.15mel/l),-10

-15C

5.75

3001/hr

1 10,20,27,325,

200C

mp206

207C

395 ,

2,4

,5.80

5.80

0.6959

20mo1%

)100cc

46

(100200

O.1N

0.0729

(10%)

,
,
43

3.64%

(10%)

30cm,

25cc

, ,

,5cc

2 ,0.1N

09701

3cm

100200

159100cc

,0 10C

5%

, 15%

20cc

6)

DS301

,0 10C

10.4

KeyBand

Beer
0.201

,0.1mm

0.15mo1/1

20C 0.1mm

4,7

,@15332),
,

, ,

512

KeyBand

1cc

5.80

590

,2

20C

2.59,

4.4

1mo1

8)

1.59,

,n , (7:3)

Base-line

207(

210.2)

C58.11%,H4.84%
CiHsoOs

C57.14%,H4.79%

% =100

Ah:5.90

Base-1ine

47.1

,2.5%

100mg5cc

5cc

20C

2,4

4.5

1.5mo1
8)

J. P. Wibaut,

n (4:1:2)

et al., Rec. tray. chim. 73, 1033 (1954).

Rf-0.92

(123)

mp163

1649C

(34)1109

24 P

5%

4.7.3

4.Z1

cc2%

2,4

4.Zl

mp263

264C

5cc10%

5cc

4.7.4

;4.Z14.7.3

, 200c

(4)

10cc

100mg

100mg

2 ,4
472 :

2,4

2)

1) ,
,
,
, ,

U"(51%),

2)
,

, 71.3%

, ,

, ,

, 1

(mo1)

, , ,

568.71.60.19

2"579.72.00.16

= 1"5682170.17
5"66711.10.14

5"665.51.50.13

.11iS

.2"5726230.12

1"57852.60

1.2

(3),

'1555.3__

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1)

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1.5"55621.30.30
_

81,1106(1960).

50753.2___
2)

25,63i(1922).

A78

Nippon

Kagaku

Nippon Kagaku Zasshi, 81, 1094^-1097

Colorimetric
Determination
Palladium with 2-Nitroso-1

and Photometric
-Naphthol-4-Sulfonic

Zasshi
(1960)

Titration
Acid

of

by Sumio KOMATSU and Seiji KAMIYAMA

Since
divalent
palladium
reacts
with
nphthol-4-sulfonic
acid forming
a soluble
compound,
its determination
by colorimetric

2-nitroso-lred colored
method and

photometric
tiration
has been investigated.
The molor
ratio
of palladium
to the reagent
in this compound
is 1
to 2. The procedure
for the color development
is as
follows:
Stand about ten minutes
after addition of the
reagent
solution
to the test solution
and
adjust
its
acidity to about 7 N in acetic acid in order to obtain the
maximum
color
intensity.
This
colored
solution
is
stable for long time and has the absorbance
maximum
at
532 mp, in which
the absorbance
of the reagent
can be
neglected.
The Beer's
law is followed with palladium
content
from 0.6 to 18.7 r/cc. and the results are reliable
to a relative
error of less than +1.53'. The interfering
ions
are nickel,
cobalt,
iodide, and cyanide
etc..
The platinum metals
and gold do not react with the reagent,
but
except in small amounts
they interfere
because of their
color.
This colored
compound
can be extracted
with
iso-amylalcohol
from a nitric and sulfulic
acid solution
and the suitable
acidity
for extraction
is about
2.8 N
and 6N respectively.
The end point of photometric
titration
as the intersection
of two linear
parts
in the
titration
curve
by dropping
the reagent
solution
to the
neutral
test solution
shows
good agreement
with the
stoichiometric
point.
This method
serves satisfactorily
for the determination
over the range
of 0.2--0.8 mg./
50 cc. and the average
error
of the results
is of the
order of +2%.
Faculty of Literature and Science, Toyama University, Toyama-shi,
Toyama, Japan

Nippon Kagaku Zasshi, 81, 1097^-1105

Analytical
Electrolysis.

Studies
on
11^-111.

Short-Circuit

Limited

(1960)

Potential

by Ichihiko NIWA and Soichiro MUSHA

II. Determination
of Silver by Coulometric
Method of a
Short-Circuit
Limited Potential
Electrolysis (pp.1097-1102)
A
short-circuit
limited-potential
coulometry
has
been applied to the determination
of silver.
The sample
solution
was connected
through
a diaphragm
with a
solution
of
Bi (NO3)3.
By
short-circuit
the
gold
cathode
in the former
solution
and the saturated
bismuth
amalgam
anode in the latter, Ag was deposited
on the cathode.
Elimination
of dissolved
oxygen
by
passing
purified nitrogen
permitted
silver to be reduced
with the practical
current
efficiency
of 100 per cent.
The total quantity
of electricity
required
for the com-

Vol. 81 No. 7

(1960)

circuit
limited
potenial
coulometry.
An amalgamated
copper
cathode
was immersed
in the sample
solution
of 0.01F in HNO3 and 0.1F in KNO3. A saturated
lead
amalgam
electrode
served as an anode.
By short-circuit
the two electrodes,
Bi was deposited
on the cathode.
The total quantity
of electricity
required
for the electrolysis was estimated
by a current
integrating
recorder.
Quantities
from 126 to 503 pg of Bi were determined.
The relative
error was within 3% when Pb or Cd was
present from 10 to 100 times as much as Bi.
In the
presence
of about 400 times
as much
Pb or Cd, the
relative
error increased
up to more than 5%.
Department of Applied Chemistry, College of Engineering, University
of Osaka Prefecture; Sakai-shi, Osaka, Japan

4.

Organic

Chemistry

and

Biological

Chemistry

Nippon Kagaku Zasshi, 81, 1106---1112 (1960)

Studies

on Ozonolysis.

by Motoichi INDO
III. The Ozonolysis
of lsosafrol
Part I. (pp. 1106--1109)

in Carbon

Tetrachloride.

The ozonolysis
of isosafrol
in carbon
tetrachloride
was studied.
The side-chain
double bond of isosafrol
and the carbonyl
groups of heliotropin
and acetaldehyde,
produced
by ozonolysis,
were analyzed
quantitatively
by infrared
absorption
spectroscopy.
By means
of
chromatostrip
technique,
among the ozonization
products
were detected
two peroxides.
One of these peroxides
was isolated
by column
chromatography
and identified
as isosafrol
ozonide.
IV. The Ozonolysis of Isosafrol
in Carbon Tetrachloride.
Part 2.
The Reductive
Decompositions
of the Peroxides
Obtained
by the Ozonization,
and the Effects of Pyridine
and Methanol on the Ozonolysis of Isosafrol
(pp. 1109---1112)
A study
on the reductive
decomposition
of the peroxides obtained by the ozonization
of isosafrol
in carbon
tetrachloride
was carried
out.
Nine reducing
agents
were examined.
Improved
yield
of heliotropin
was
obtained
by using ferrous
sulfate,
ferrous
ammonium
sulfate, and potassium
iodide.
The effects
of pyridine
and methanol
on the ozonolysis
were studied.
Higher
yield of heliotropin
could be attained
by adding these
agents.
Takasago Perfumery Co.; Ohta-ku, Tokyo, Japan

Nippon Kagaku Zasshi, 81, 1113^-1118

Studies on Hydroxycarboxylic
by Takeyoshi RAGA

(1960)

Acids.

plete electrolysis
was measured
either
by integrating
the area on the current-time
diagram
using planimeter,
or by a current
integrating
recorder.
Quantities
from
0.5 to 2 mg of Ag could be determined
within the relative
error of 3%.

VII. The Reactions of Potassium

r-Hydroxybutyrate
Benzyl Alcohol. Part 1 (pp. 1113---1116)

III. Determination
of Bismuth in the Presence
of Lead
and
Cadmium
by Coulometric
Methad
of
a ShortCircuit Limited Potential Electrolysis
(pp. 1102-1105)

principal
products
of the reaction,
and at 180--210C.
fi-benzyl-r-hydroxybutyric
acid was obtained.
/3-Benzylbutyrolactone
was produced
by adding
mineral
acid.
To identify jl-benzylbutyrolactone,
a-benzylbutyrolactone
was prepared.

A niinute
presence

amount

of larger

of bismuth
amounts

of

was determined

in the

Pb and Cd by a short-

The
benzyl
butyric

with

reactions
of potassium
r-hydroxybutyrate
with
alcohol were investigated.
At 230-250C.
oxydiacid and
r-benzyloxybutyric
acid
were
the