Arsenic

245

ARSENIC

Table of Contents I.

245‘

Introduction

II.

Reviews and Books

III.

_

246

Compounds Having a Metal -Arsenic

IV.

Bond

Compounds Having Arsenic-Nitrogen

V.

Arsines

247

Bonds

250

and Polyarsines

253

VI.

Compounds Containing

Arsenic-Oxygen

Bonds

VII.

Compounds Containing

Arsenic-Sulfur

or Arsenic-Selenium

VIII.

Compounds Containing

Arsenic-Halogen

IX.

Triorganyl

X. XI. XII. XIII.

I.

(Halogenoid)

258 Bonds

264

Bonds

266

Arsines

268

A.

Asymmetric Triorganylarsines

268

B.

Other Aspects

269

of Triorganylarsines

Arsonium Compounds, Arsenic Arsenic

and Arsanes

272

Heterocycles

Biochemical Industrial

Ylides

279

and Environmental Applications

Aspects

of Arsenic

Compounds

287

and Miscellaneous

291

Introduction

Tne purpose of this

review

is to cover

the recent

literature

which has

been published in the field of organoarsenic chemistry_ Specifically, those

x Arsenic, Annual Survey covering Vol. 138 (1977) p_ 125-156.

the year 1975 see J. Organometal. ..

Chem.,

246 publicatfons

are

included

which

87 of Chemical Abstracts. of publications

rather

to belong

bond has been

The literature

area could

selection

was intended

interests

of

reviewed future

the

of

is considerable

the

in

and this

a transition in this

review.

and biochemical increase

review.

reflects

Nevertheless,

number is expected

metal-

in volume

that only a selected

present

it probably

review.

this

when an unusual

number

Although the

in large

degree

the

the number of papers to increase

rapidly

in

years.

Foundation,

II.

included

be

review

metal coordination

undergone a great in fact,

as

in this

with the environmental

So much so.

to be critical,

authors

The authors

for

years.

number

and

function

In some cases,

such papers are. included

compounds. has also

during the past several

of transition

chemistry_

which is concerned

of organoarsenic

of papers in this

with the preparation

or a unique complex bearing

studied,

a large

in which arsines

to the field

than organoarsenic

has been synthesized,

aspects

metal complexes

years,

The bulk of these papers is not included

as they are considered

arsenic

in volumes 84, 85, 86, and

abstracted

As has been the case in recent

of transition

the donor molecules _

ligand

been

have appeared which are concerned

characterization

chemistry

have

again express

their

Houston, Texas and the National

financial

support

to the Robert A. Welch

appreciation Cancer

during the preparation

of this

Institute

qrant no. 16912

review.

Reviews and Books A 332 page report

medical

and biological

published

entitled effects

by the National

mental arsenic

has also

a review on environmental organoarsenicals

against

which is concerned

/rsmic,

primarily

with the

of the element in the environment, has been

Academy of Sciences

Cl]_

The toxicology

been reviewed by Fowler [Z]. pollution chick

by arsenic.

parasite

Chester

[3] has prepared

Japanese reviews

diseases

[4]

of environ-

and arsenic

on the use of in foods

C.51

have appeared. Duncan [6,7,8] chemistry. of WSeniC

has reported

The spectrophotometric have been reviewed

in

on recent

developments

methods for considerable

in synthetic

the determination detail

by

Russian

arsenic

of trace authors

amounts

[9]_

247

Hursthouse crystalline chemistry

[lo]

has reviewed

derivatives of organic

Russian authors

of arsenic derivatives

[ll].

arsenic

and a very extensive

compounds of arsenic

systems containing [16].

both silicon

Cl71 and on the reactions halides

III.

Compounds Having a Metal-Arsenic

of heterocycl inorganic,

[14]

ic

five-

have been discussed

in

the

of arsino-

presence

of

Bond

bonded compounds have been prepared

techniques

diorganylarsenide

[19].

The first

involves

by three

the reaction

different

between a lithium

and a boron ha1 ogen bond

. R2AsLi + ClBR; -

arsine

Mardell

on the chemistry oxides

[12]

[18].

Arsenic-boron

the second

arsine

by

arsines

appeared.

while

and arsenic

of tertiary

alkyl

synthetic

[15]

Reviews have been published

on the structural

of tertiary

The chemistry

by Gallagher

several

has been published

have also

on a number of organoarsenicals.

by German authors oximes

[13]

for

report

of group Va elements

compounds has been reviewed

membered ring

data reported

Reviews on the stereochemistry

and some coordination has reported

the structural

involves

RRAs-B% + LiCl ;

the reaction

and a boron-halogen

between a trimethylsilyl-

or trimethylstannyl-

bonded compound,

(CH~)~E-AS(CH~)~ f BrBRR’ -

(CH3)3EBr f (CH3)RAs-~RRl

E = Sn, Si; and the third

invo7ves

(cH,),A5-As(CH,),.BH,

BZs(amino)arsinoboranes ciated

and decomposes

are trimeric.

Trimeric

the thermal rearrangement -

adduct,

( Cii3)2A~H + ( CH3)2A~BH2.

are monomeric while readily.

of a borane-diarsine

(C6H,-)2BA~(CH3)2 is partially

The compounds,

and tetrameric

forms of

asso-

( CH3)2BA~(CH3)2 and ( CH3)2AsBBrCH3 (CH3)2A~BHZ were isolated.

248

Arsenic-silicon

and Heinicke

and arsenic-tin

bonded

The reactions

[ZO].

have been prepared

derivatives

involved

by Tzschach

are shown below.

RNH(CH2)2As(CsH5)SiMe3 + LiC7

RNH(CH2)2As(C6H5)Li + Me3SiCl -

2 EtNH(CH2)2As(Et)SnBu3

2 EtNH(CH2)2As(C2H5)H f (Bu3Sn)2q ---+

R

Lii!(Et)(C~2)2AsR(Li) E = Si.

Diarsines arsenic

I

Sn

Et

form adducts with two moles,of infrared

130 cm-l;

bands were assigned

Sn-As symmetric stretch,

From Mossbauer spectra

\ JRn-2

f RA-2 EnC12 --L

tin(IV)

tetrahalides

it was concluded

The tin-

Sn-As asymmetric stretch,

as follows:

280 cm-‘;

[21].

290 cm-‘.

Sn-As bending vibration,

that arsines

are weaker donors to3n(IV)

than either R- or 0- ligands. Oemuth [ZZ] and Beagley and Medwid [23] have reported

of molecules

bearing

the Si-As

is reported

at 254 cm-’

(SiH3)3As.

Electron

bond.

The As-Si fundamental stretching

studies

frequency

and at 346 cm-’

- trifluorosilyldimethylarsine in

diffraction

on the structures

in

of dimethyl(trifluorosilyl)arsine

[24]

n

show that the As-Si In C13SiAs(CH3)2,

bond distance

the fundamentals

by Demuth [25] at 324 cm-‘. configurational of strong

stability

stretching

vibration

Triorganostannylarsines within

number of studies

to transition

examples are the following. the cobalt-arsenic obtained

As-Si

has been observed

have been reported

the NMRtime scale

[26],

is 93.5O.

to possess

even in the presence

nucleophiles.

A large of arsines

is 2.334 A and the SiAsC bond angle

have been carried

metal atoms has been reported. The reaction

bonded derivative,

by the reaction

out in which the coordination A few representative

between CoMn(CO)9 and (CF3)2A~I yields

(CF3)2A~C~(C0)4.

between bis(trifluoromethyl)arsine

The same compound is and dicobaltocta-

249 carbonyl

or

from

cobal

tcarbonyl

fundamental

arsenic-carbon

cm-’

[27-J.

The

that

of a trigonal

of

Fe-As-Co plane. as

triangle The

fol

triangle

:

lows

groups

reaction

of

ment

of

An

in

the

molecule

i,

determined is

Co-As

below

of

located

-

the

CO)3

on

shape

2.24

i

iron

with

monoxide

dinuclear ligand

which

(C0)4Fe-As(CH3)2C1

(CF3)2A~

by Keller

in

and

reported

the with

and

Fe-Co

atom

and

from

734

and

infrared

The

726

data,

crystal

Vahrenkamp

[28].

The

mirror

the

reported

-

bond

lengths

2.70

i.

three

Four

around

results

formation

of

in which

the

the

of

the

cobalt. in

the

compound

is

structure

crystallographic

norbornadiene the

at

group. and

The

The

displacewhose

[2g].

bridging

equation

are

, as deduced

an axial

around

carbon

series

the the

been

located

of

shown

interesting

shown

are

moles

is

functions'as

with

(CO)4Fe-As(CH3)2-Co(

two

structure

(CF3)2A~C~(CC)4

has

= 2.33

bi3(trifluoromethyl)arsine.

vibrations

is unsymmetrical

Fe-As

carbonyl

of

bipyramid

of

and

stretching

structure

FeCo(CO)7As(CH3)2

hydride

ccmplexes been

has

prepared

[30]

dimethylarsino

according

group

to the

reaction

follows.

+ NaM(CO),,

-

CH3 (CO)4Fe-qs-M(CO)m,,

-

-co

H3c’As~cH3 (CO),Fe~fl(CO),

CH3 Examples M(CO),

of M(CO),l are

Mn(CO)g,

compounds

containing

functions

as

References p_ 293

are

Mn(C0)4,

Re(CO)g,

a bridging

As-Ni

Re(CO)4,

Fe(C0)3N0, [31],

ligand

As-V in

the

Fe(C0)2N0 and

[32]

COG. and

molecule

AS-MO

and

COG.

Related [333

Examples studies

bonds.

The

of

describe AsMe

group

250 Based

on va7ues

obtained

using

compounds

of

the

following

and

the

type

ii-acceptor

P(OR)3

> CN-

co-workers

is

describe

reductive

IV_

during

elimination

Compounds

molecu7ar and

structures the

aminoarsines

in

Adler

and

of

a suitable

reduction

process

formation

of

and

the

synthesis

[34]

Kobler

have

the

-60°.

of

the

resonance.

of

as

> AsPh3.

carbonyl

type,

Dorn

having

Mickiewicz

anions

e.g.,

of

the

type

R2AsC!-i2CH2CH2C7,

(sodium-amalgam)

describes

the

This

which

an

undergoes

molybdenum-arsenic

of

the

synthesis.

report the

rings.

properties

covers

As-N

organoarsenic

studied

+ H’~N(cH,),

exchange

methyl Be7ow

(in

bond

175 and

and

published the

papers

application

of

compounds-

fo7lowing

exchange

protons -60°

the

in

the

equation

( (CH3)3Si-N(CH3)2

reaction

attached

to

HN(CH3)2

and

using

studied

by

(C6HS>$s

Russian and

follows

+

[37].

Glith

+ LiNHR

+

LiNHR,

as

been

+

1

H NMR spectro-

prepared

H’~N(cH,)~

a solvent)

atoms

=AsN(CH~)~

is

appear

methyl

as

so

a single

protons

according

to

rapid

can the

be

that NMR resolved.

reaction

136-j.

(CH3)$iF

[(C6HS)4As]C7

C6H5NR2_

(C6HS)4AsCC1-

which

workers

(CH3)2A~-‘5bi(CH3)2

nitrogen

has

i- AsF3

between

i

perdeuteroto7uene

Dimethylaminodifluoroarsine

The

L,

and

[35]_

Above

shown

Rehder

ligands,

> PPh3

five-membered

reactivity of

(T),

Bonds

aminoarsines.

nature

(CH,),AS-~~N(CH,),

all

of

by Kober

the

> P(NR2)3

preparations

Arsenic-Nitrogen

review

discusses

scopy

with

Having

A useful

the

arrange

A> PPhF2

L is

parameters

:

the

Uhen

formed

shift

[n5-CpV(CO),L],

> PR3 % SbPh3

[33]

chemical

abi 1 i ties

[Mo(~-C~H~)(CO)~L]-_ anion

57V

from

and The

+ F2As-N(CH3)2

=N-lithium reaction

however,

[(C6H5)4As-NHR] + CsHs

compounds of

the

+

has

(C6HS)4A~+C1reaction

(C6H5)3As=NR

been with

proceeded

LiNR2 as

gave

follov~s.

251

Russian

workers

concerned

with

[38-41-J.

The

by

the

reported

asymmetric

following

employed

and

the

types

f

EtAsRCl

+ 2HNR;

- EtAsRNR;

+ R2NH;C1

c--, :y-, p-tolyl,

, 35C1 > 75 As)

[41]

and

Yambushev,

an SN2

in

which

R

\

.

for

(Me2N)3As,

have

reinvestigated

chloride

atom

'As' /\ R’

step

proposed

is

followed

H R \/ Cl.---IQs----NH2

by

4

R' final

mole

of The

shown

to

formation

reaction

interpret They

propose

attack

a five-coordinate

the

amide

a rapid

bonded in first

terms step

proton.

by

transition

state

chloride.

2

hydrogen and

the

(-As-H), onium

zris(dimethylamino)arsine

-I- 2 As[N(CH~)~]~

reaction

by the

manner

to produce

the

amide,

-+ As

and

a second

salt. and AsF3

fluorosulfonylisocyanate

and

the

[43].

3 FS02N=C=O

populations).

of As-N

the

been

R'

active

interesting

orbital

have

+NH-

-A"'\

haloarsine

between

of of

R\+/H

form

the

Me2NAsC12

NH2

the

in a most

References p_ 293

are

cl-

involves

reaction

equation

bond

+

displacement

Cl

step

HCl

the

and

the

electrophilic

H

R

The

prepared

(valence

They

mechanism.

undergoes

j.

calculations

in ether.

substitution

+ H+-Cl-

intermediate

compounds

(Me2N)2AsEt,

es ctz., [42]

arsenic

As-NH2

next

an arsenic-nitrogen

,7-anisyl

7?-,

MO

R4

proceeds

o--,

with

nucleophilic the

of

investigations

NaCl

correlated

with-hydrogen

of

with

of

Me

(14N

compounds

a series

equations:

-* REtAsNH2

data

of

compounds

+ NaNH2

obtained

the

results

REtAsCl

R' = Et,

The

the

organoarsenic

reactions

R = C6HS,

NQR

have

+ AsF3

compound

shown

in

252 The reaction

between

methyldisilanes type

the

N,N’-dilithio

and AsC13 give

shown below

[44]_

The

derivatives

five-membered

fundamental

of

1,2-
heterocyclic

derivatives

of

the

vibration,

Megii-l’tfle AsCl

I Fie,Si-P&e v(As-Cl) have

is

located

reported

-1 388 cm

at

the preparation

MepAsC(tl)H2 by the reaction of

CH2N12in the

presence

-

in these

of

a dimethylarsino-substituted

between of

Kronnles and Lorberih

compounds.

diazomethane,

dimethylaminodimethylarsine

Me3SnC1_

Mith P(Mle2)3

a l-l

and a large mixture

t~~~s-=~,ts(dimethylaalino)-phosphine(dimethylarsinoformaldazine)

The addition

of

diphenylarsine

to the

R=N double

[45]

of is

bond has been

excess

@c-

and

obtained-

repot-ted

[46].

(C6HS)2AsH -i- RN=NR - (CSH&As-N(R)-N(R)H The formation

of

amino)phosphine Some novel synthesized

react

and glycol

ring

systems

by Mannagat

with

Schnabl

dimethylaminodimethylarsine

[49]

esters in which

and

AsC13 to give

of

arsenous

arsenic

Schlingmann

the novel

type

is

by the

reaction

acid

has been

bonded

(483.

of

ring

between reported

to nitrogen

:%s(dimethyl by Kober

have been

Thus , ~is(alkylamino)disilanes system

shown

below.

Sherer

have

--ii ------ii

I

I

YnJNprepared leading

some similar to

the

arsenic-phosphorus-nitrogen

compound

prepared

by these

RR’ N-P=NR + AsCl 3 -f RR’ N-PC1 -NR-AsC12 Cl -R’ Cl

A’\ R-N ‘As/ I Cl

N-R

[47]

heterocycles

investigators

is

_

given

The reaction below.

and

253

Japanese workers

[50]

have carried

The reaction

Me2AsNR2with p-propiolactone. with +propiolactone of aminoarsine

out a kinetic

study on the reaction of

of N,N-dialkylamino-dimethylarsine The reaction

gave dimethylarsino-3-dialkylaminopropionate. in terms of an ion ic dipolar

is interpreted

intermed iate

of the

type shown below. 0 b' r-le 2As

;-

t

:

1 !

R’.~~~,________.6H2.~CH* 1: R1l.--_.i~‘._________~ I

I

R”’ Arsenic

containing

polyamines

studied

the condensation

have been prepared

by Carraher and Noon [51].

of triorganyldihaloarsines

They

with diamines.

R3AsX2 + H2N-R-NH2 - -&(R3)-R(H)-R-N(H)+ The reactions

between triphenylarsenic

or trimethylarsenic The products A plastic

dichloride

exhibited

crystalline

dichloride

(or dibromide)

weight-average

molecular

phase has been reported

bonded compound, cLo.w-&rriethylarsenimide. a large

V.

plastic

Arsines

range (T

= 346”,

P

with the same amine were studied. weights for

in the region

of lob_

the c-ayg arsenic-nitrogen

As (NEle) [52]. 4 6

This compound exhibits

Tm = 393OK).

and Polyarsines --

The interest in which arsines

in the preparation function

quence,

new arsines

workers

have prepared

and properties

as n-acceptor

and polyarsines

reaction

References p_ 293

ligands

are being

of transition

continues synthesized.

a number of such arsenic-bearing

of &s-Z-diphenylarsinovinyldiphenylphosphine following

and nitro-F-phenylenediamine

sequence

[53].

7:s carried

metal complexes

unabated_ McAuliffe

ligands.

As a conseand co-

The preparation

out according

to the

254 2 Li f AsPh3 -?!!!--L

LiPh -C ;-CuCl LiAsPh2

LiAsPh2

--

LiCl

f

LiPh

f PhH + (cH~)~c=cH~

CH=CHCl --

+ &.:-Cl

LiCl

-t LiPPh2 --

ck-Ph2AsCH=CHCl

Lithium diphenylarsenide

cf.?-Ph2AsCH=CHPPh2

_ czs-

arsine

[54].

or t~,:.:s-1.2-dichloroethylene

stereospecifically.

The reaction

and Li(PPh

2

) is

also

has also

been prepared

175-l 77O _

reaction

AsCl with

[57],

chloride,

P(OCH3)3 cave

[P(0)(CH3)(0CH3)]2

the

reacts

with

both &s-

The synthesis

by the

reaction

prepared

and tr~s-1.2-X.1

of 1,3-%s(

3’-dimethylarsino-

has been described [551.

The same study

as a bright

the same investigators

reaction

of

reported

between (C6H5)2AsCl

The reaction

one mole of the

[SS]

yellow

formation

of

solid,

prepared

C6H5AsC12 with

of m-p.

C6H5As

excess

tetraphenyldiarsine

and CH3P(OCH3)2 or by the

reaction

of

by (C6H5)2

(c~H~)~AsP(O)(CH~)OCH~. acid

is

reduced

by Zn/H2S04

to chloromethylarsine.

The ‘H NMR. mass and infrared spectra of this compound have been studied of chloromethylarsonic

acid

pentakis(chloromethyl)cyclopentaarsine thermal

The

RAsC12 (R = C6H5, Ye) with

of

I?‘XS[P(O)(OCH~)~]~.

C,ll,As(I)-As(I)CGHg

study,

by the

Chloromethylarsonic

Reduction

c-Z.?-

f56].

In a related

CH3P(OGH3)2.

C-G- or ;rc;:s-l-diphenyl-

(c-diphenylarsinophenyljdiphenylbismuthine,o-C6Hq(AsPh2)(BiPh2)

in methylene

C6H5As12 with

formed_

with

cis-1-dinethylarsino-2-diphenyl-

cfs-1,2-dichloroethylene

Abraham and Van blazer P(OMe)3

only

reacts

and ;2anp:c-(Z-chlorovinyl)diphenyl

Me2AsCCH2]3SrCH2]3SCCH2]3AsNe2

ligand,

also

Sodium dimethylarsenide

are

aromatic

to produce

(2-chlorovinyl)diphenylarsine

and yields

to yield

(dimethylarsinoethylene) propylthio)propane,

to give

stereospecific

(Z-chlorovinyl)diphenylarsine but with

The same reagent

between ck-

arsino-2-diphenylphosphinoethylene.

arsinoethylene;

+ LiCl

reacts with ::Mx;- 1.2-dichloroethy7ene

~XWS-1 ,P-Xs(diphenylarsino)ethylene excess

+ s-k;-Ph24sCH=CHCl

and oxidative

stabilities

The dynamic !H NIlR properties

by H3P02 results (PEA)

greater of

this

than

molecule

[60].

in the PCCA is

that

of other

are

interpreted

formation

[59]. of

characterized

by

cyclopolyarsines. in terms

of a

combination

of a low-energy

atom inversion process. by reaction to yield tion

Primary alkyl

with dibenzylmercury

motion and a higher

arsines

[61].

yield

e.g.,

to give

on the other

the monosubstitution

hand, affords

a mixture

react

have carried

reactions.

undergoes

product. of

out dynamic NMRstudies

The following

equilibrium

e.g.,

(CH~AS)~

with dibenzylmercury

reaction

The reaction

products

of

dimethylarsenic

is established

of

which include

(CH2C6H5)2 along with (CH3)2A~I, and (CH3)2A~CH2C6H5_ Rheingold [62,63]

arsenic

(CH3)2A~A~(CH3)2 and the substitu-

(CH3)2A~CH2C6H5_ Methyl-dichloroarsine

dibenzylmercury

energy

the pentamers,

Dial kylarsines

both the tetraalkyldiarsine,

product,

As+

pseudorotational

upon

with (CH3)2

CH3As

and co-workers condensation

combination

of

(CH~)~ASH with (IzH~)~AsX (X = halogen)_

KH312AsH i (Ctt3)pX The anticipated doublet.

(CH3)2A~A~(CH3)2 f HX

2

doublet

(CE3)2A~H

This is explained

is collapsed

(1)

to a singlet

or a very broadened

in terms of an NMR-fast hydrogen exchange

as shown

in (II). + wx

( CH3)pti For halogen

systems,

the starting for

eq.

excess

II,

*

(CH3)_pH*

K for

eq.

f

Hx

I is always less

However, for

materials_

(II) than 1.0 at 30”,

X = CN, K is >lOO for

X = CN is too slok~ to cause a collapse is present.

(CH3)2A~fi

This is explained

eq.

in doublet

i.e., I_

favoring Furthermore,

multiplicity

in terms of appreciably

when greater

bond energy of HCN. The interaction yield

of !+X with (CH3j2AsH can lead to the formation

of hydrogen was zero

15% for

X = Br,

(CH~)+H

I.

f

for

X = CN, extremely

small for

X = Cl,

of HZ_

The

but about

The formation of hydrogen is explained by erl. III-z, b.

kix P

C(CH~)~ASH-HX]

(III) C(CH,),ASH,]'X- 2 (CHJ~ASX + Hi

Eq. III-b by eq.

may be reversible_

IV was also

Referqnces p. ‘93

invoked

As-As/As-X in order

exchange

to explain

(except

for

the NMRchemical

X = CN) as shown shifts.

Equi Jibrium and thermodynamic parameters and Edris

Lewis

[64]

behavior

for

iodine

for the various

introduced electrical

by the starting properties

lithium

&tailed

trifluoropropynide.

reactions

of )Ie2AsC(P$)H with meta

Lorberth

[66] _

by the reaction

reactivities

have the general

(meta7organic)diazomethanes

are reported.

out

method_ for 7ated

[68].

The

by Gfozbach and Ke3M(F.?2As)012

and Hg[C(N2jAst~e2]2. those

Infrared,

of

the iSc;-

‘H and 13C NNR data

all-cSo-cyclonona-1.3,5,7-

Rapid migration

of

conformation

unsaturated

the

calculations Relative

the (CH3)24s around the Cg-

were

undergo

nucleophil

corresponding

exists

ic attack

[70].

The adducts

were

calcu-

several

mo?ecu?es.

altyldimethyl-

is obtained

are

formed

to yield

in 46%

yield

Several

R3As-BHg

by the

were

in an A~-~:a:
in an As-&s

by arsenides

CHBr, 532 from OrCPh=CHBr and 548 from BrCPh=CPhSr. have been characterized

for

the CNDO/2

and benzyldimethylarsine

is most stable

acetylene

using

energies

ang’les

allyldimethylarsine

benzyldimethylarsine

out

has been

dimethylphenylarsine.

dimethylpheny7arsine. that

arsines

carried

conformational

of dimethylvinylarsine,

SurprisingJy,

Thus,

of

the CCAsC and CCCAs dihedral

was concluded

Dibromoalkenes C69j.

of

spectra

It

the

row molecules.

trimethylarsine,

prepared_

of

Conformational

third

Photoe7ectron

form.

analysis

as a function

amine,

[67].

has

was irot observed.

A detailed carried

the heavy metals.

of

region.

formulas:

resemble

Boche and Heidenhain have prepared

tetraenyl-dimethylarsine perimeter

stabilities

from

are offered

data were obtained.

amides have been studied

and chemical

arose

from

between AsC13 and

where Pt = Si , Ge, Sn, Pb; Me$l’ (MepAs) CN, where M’ = Sb. Bi; The chemical

the optical

which melts at 23-2a”,

mass spectra7

The compounds prepared

photo-

Explanations

in the impurity

As[C=C-CF3],,

prepared by Lemmonand Jackson [65]

probably

compounds.

observed

crystals

energy qap determined

Impurity photoconduction

:z&-(trif‘Iuoropropynyl)arsine, been

intrinsic

The value of

:.J -55 e’l.

agreement with the thernal

studies.

impurities

of single

A17 samples exhibited

photon energies

energy gap is in exce77ent electrical-conduction

[63].

have measured the photoconductivity

of i :.;[catena-poly(methylarsenic)]. conductivity

were obtained

form.

acetylenes

from BrcH= adducts

introduction

of

B2H6 into

a benzene solution

enthalpies

of formation

thermodynamically rate

constants

of

stronger

for

of

the adducts complexes

the reactions

A number of publications

[73]

metal chelates

the benzyl

[72]

of

complexes

studies

as a useful

transform

The l3 C-NMRspectra

irradfated

torsional

single

shift

As=As double

assignments

[74]

‘J(Pt,C)

[78]

by these

constant

to arsenic

and 3J(Pt,C) of

their

has carried

labelled for

all

(C6H5)2A~-.

coup1 ing tensors,

Fourier

out a

trimethylarsine-

fundamentals

(except

was found to have the

have measured the ESR spectrum

of the radical,

-

to a trialkylarsine

on the results

isotopically

of

of palladium

It is suggested

llatari

The As-C force

Swiss workers

are the subject

of a series

constants,

have reported

complete

modes).

crystals

[80]

of

x-

Parameters measured

and the 75As quadrupol e

293

has commented on the incorrectness

bond to several

values

of vaporization

p_

ionization

tensor.

Levinson

gives

of

have been published

of the atom bound directly

Coupling

of the eight

the 8 and 75As magnetic

interaction

References

probe.

et al _ [77]

analysis

3.087 mdynfi.

include

chemical

The study includes

the internal

[Sl]

chemical

lluyts

normal coordinate

value

“C

[76].

l3 C-NMRstudy of triphenylarsine.

boranes.

studies

by chemical

in which the metal is coordinated

that the

are presented.

et al.,

the fragmentation

Mass spectral

in which arsines

have been measured by Balimann and Preqosin investigators

study of

Jones

by Kober [75].

have been reported.

and platinum

low-resolution

patterns

the mass spectral

triarylarsines.

(C6H5)3As which is produced

A number of physico-chemical investigation

fragmentation

has studied

C~FSRS(CH~)~.

has measured

with triethylarsine.

in which tle2As(CH2)12AsMe2 is the donor ligand

has been reported

serves

cation

as

form

Yang [71]

the mass spectral

Spalding

processes

The mass spectrum of

c741.

of

out a comprehensive

rearrangement

The phosphines

than do the arsines.

pathways of a number of substituted

have carried

and the

‘H and ‘T B NMRdata as well

are reported.

describe

which are undergone by arsines. fragmentation

the arsine.

of

of

organoarsenic

the vapor pressure,

triethylarsine_

compounds.

in the assignment

of an

A study by Russian workers

the heat of vaporization

and the entropy

VI- -Compounds Containing Arsenic-Oxygen Bonds The

reaction

between

BrMg(CH2),,MgBr gives

yields

where

and

reagents

for

c: i-

shown

a difunctional The

converted

this

manner

10,

co-workers

of

(s)

to [82]

Griqnard

latter,

the

on

treatment

difunctional

were

reagent, with

HCl

organoarsinic

prepared

acid

[RAS(O)(OH.$(CH~)~

12.

[83,84]

synthesis

oxide

as

is

n = 5-8,

the

(diphenyl)arsine compounds

In

and

Kauffmann as

which

oxidation_

R = octyl

and

[RAs(NEt2)]2(CIi2),_

CRAS(OH),](CH,)~

by peroxide

RAsCl(NEt2)

have

investigated

functionalized

undergoes

lithiomethylarsine Lithiomethyl-

hydrocarbons.

reactions

with

alkyl

oxides

halides

and

cat-bony1

below.

R-X ___

(C6H5)2As;O)-CH2R

!-!,O c + R-C(O)-R’

j

and

c are

reduced

CH2C(OH)RR’, the

--!=--

by LiAlH4

Addition

4.

haloalkane

(C~HS)~AS!;O)-CH~C(OH)RRI

from

to

of

d and

halogen

the

(C~H~)~AS(CH~)~CH~

KOH or with

of

C6H6SNa

2:&+

(C6H5)$0

and

Alkaline in

which

the

to

hydrolysis OH-

of

As04

_w&(dimethy?amino)arsine. Me2AsOCH2CH20H, is

9,

that shown below

to

form

[86].

and

thermal

2 and

(C6H5)2As

decomposition

gives

e.

+ BrAs(C&)2

BrCH=C(C6H5)2

( CsH5) *AsBr$HMeEt C6H5SCHMeEt,

+ BrAs(C6H5)2

fol lowed

by

treatment

wi th

(C6H,-)2As(0)CMeEtLi

resp.

reacts

(C6!ig)2AsjO)CMeEtC(C6H5)20H.

forms

loses

by

from

t:es(wrt-butyl

nucleophile

ultimate formation

to

yield of

[(R0)3As(O)(OH)]-.which

followed

ar2 20_120~~

EtCHMeOH H20

(C6H5)2AsCH2R,

Br(CH2)4-CH3

( C6H5)2AsCHMeEt gives

at-sines

haloalkene

(C6HS)2AsCH2C(OH)(C6HS)2

Bromination

the

OR-

the and

)arsenate

follows

five-coordinate adds

OH-

in

an

activated a step-wise

SN2 mechanism complex

sequence

anion, with

[85]. f, arsolanes,

reacts h,

with and

arsinous arsines,

acid i.

The

diolesters, reaction

mechanism

259

Me

X

-*.4-n
'As-0CH2CH20-As<

Y\As ,0-CH12 -_

tl

P-CH2 h

z,

x = Y = rlMep

1,

=

2

1 + Y-As, o-cti2

X-AsMe

X' 'O-CH2 \As' rile2

+ n Hb!lle

rle

Y’

n = 2, x = rMe2, Y = kle2As-OCH2CH20 II = 3, X = Y = Me2As-0CH2CH20

Kober

and

Riihl [88]

have

studied

the

exchange

reaction

between

cyclic

Typical reactions studied are shown

arsonous acid esters and various halides. belou.

RI

,0-As

0 +

)As-CH~

ASX~

-

(cH3)

X

R

0 Rco;As-X

-

+ CH3AsX2

'O-AsX2

0

H-C-0,

tr,c-0, /As-CH3 i

+ R'EC12

-

:R’ECI~

H2C-X

I

= tm3,

E-R'

I' H$-0'

H$-0

soc12,

(c~3)pcl~

H2C-X 'As-CH3 f EC13 -

H2C-S'

+ CH3AsC12

H ;_,:'"'

+ CH3AsC12

2

(E = P, As; X = 0, S)

Geber

and

anions, the

Elallon

were

able

to prepare

six-coordinate,

organooximethyl5is(o-phenylenedioxo)arsenate

i.e.,

reaction

[88]

of

diheteroorgano-IS

~5-arsols

with

alcohols

triethylamine.

CH3 o 1 0 R “A/‘R+R’OH+NEt3lO/

HNEt;

R

kO/

OR' R = C6Hq Referem&

f~. 2%

.

water-free

-7

.

in the

This

was

presence

arsenic done

of

by

blieber and GGtz [39] by :-chl oranil spi rocycl in

_

studied

Cleavage

i c As (11)

of

methyldiiodoarsines

in

The

the

In a subsequent substituents

__

related

other

they are retained

same oxidizinrJ

iodine

agent

cleaves

formation

[90]

do not

and the oxidation

of

As1 bonds

both

C14+Q$\~&

publication

than

with concurrent

shown by the equation:

manner

H3CAs12 f 2 ;oC14

of 2-iodo-1.3,2-diheteroarsolanes

As-I bond occurs

the

_

compounds

the oxidation

the

+ I2

same

undergo

authors

oxidative

by chloranil

noted

that

Instead,

cleavage.

proceeds

in

several

the

manner

shown

below.

0 Cl4 -

‘:/

H$-Ts

0

where X and Y may be methoxy, methylphenylamine. Details

on the synthesis

methods

0

chlorine,

ethoxy,

piperdine,

cf Z-iminoxy

and -cyclohexanes

involve

the reactions

and P-diethylaminoxy-1.3,2-

have been published

of 23 of these derivatives

takes place The reaction mechanism_ butyl

iodide

vie an $2

The reaction

The physical

mechanism and proceeds

kinetic

have been compiled

bromide yields

of E(As)(OR’)~

of R3As0 with 5CHCHXR” to give Additional

The

properties

are reported.

of (C6Hs)3As0 with z-butyl

arsonium bromide [92]_

[91]_

of Z-chloro-1,3,2-dioxaarsacyclopentanes

and -cycl ohexanes with oximes and diethyl hydroxyl amine.

The reaction

diethylamine.

or azacyclopentane.

dioxaarsacyclopentanes synthetic

c14

v\

R”X to give

more easily RiC=CHR” also

data on the reactions [94].

with

hydroxytriphenyl-

with X=1 than Br [93]proceeds

of arsines

In benzene-acetone

R”OAs(OR’ )2

via an S$

oxides

sol vent,

with z-

treatment

of

261 VeZC6H5AsO with tolyarsines method

HCl yields

have

involved

been the

(triphenylmethyl)

arsenite

of

most

the

alkyl-

and co-workers

and aryldi-o-

[96].

The preparative ~~,~,--

(D-CH~C~H~)~ASOC~H~~-~~~ and RHgBr.

has been

vibrational of

spectra

synthesized

in going

conformations

of

temperature

The changes

especially

stable

A number of

by the

reaction

between

=ris-

and triphenylcarbinol.

isomerism.

700 cm-l,

between [97]

and Raman) as a function rotational

by Sigauri

prepared

reaction

(diethylamino)arsine Studies

[Me2C6H5AsOH]C7 -

from

for

five

[9B]

trialkyl

give

evidence

are

most pronounced

the

liquid

various

alkyl

arsenites

to the

(infrared

characteristic

in

the

region

crystalline

substituted

of from 550-

phase.

(R0)3A~

The

compounds

are

suggested. The deshielding studies

of

about

arsenites

are

with

respect

pounds

studied.

two chair

L:Y?.;;D:~;!.

been

to

oxides

the

subject

configuration

of

of

which

differ

arsenic

only

(see

two chair

are

respect

in ‘H NMR

Cycl ic The

[loo].

conformations

atom.

which

with

[99].

analysis

arsenic

1 H NMR patterns

display

of

on the

demonstrated

esters

‘H NMR spectral in terms

substituent

conformations

has been

and orthoarsenate

explained

the

thirteen

the As-O group

of

statisfactorily

differ

of

15 arsines

have also

NFiR data

influence

Of fifteen explicable

to

which com-

in terms

the ictia2

or

below) _

X

In

the

case

of

conformational

two other equilibria

A number of

theory.

of

excitation

A number of

organoarsenic References p. 393

the

physicochemical

energy nuclear

the

situation

ring

carbon

studies

of

The experimental

[loll.

functions

about

The mass spectra

reported. ally

compounds,

As(OMe)S spectra using

more complex,

atoms

resonance

compounds

were measured

we1 1 with

a simplified

involving

as well.

bonded

and As(OEt)3

agreed

quadrupole

compounds containing

on As-0

is

values

equation

have been experiment-

calculated

as

of quasi-equilibrium

(NOR) spectra

As-O bonds have been measured.

of

75As in Zaki rov and

262 co-workers

[lo,?‘],

following

type:

observed

(RO)~ASO, RAs(O)(OR’)2,

the higher

In general,

75As IIQRmethod, have investigated

using the

the coordination

75As PIQR resonance

total

acids

electronic

the inductive

effect effect

Chatterjee

[103]

oxide

observed

dipole

acids

[113]

based

)arsine

oxide-phenol

acceptor

R3As0, R2As(O)OH,

[114].

dynamics

of

ionization

The

changes

at

980

cm-l,

an entire

Also,

The disappear-

of \J(As-O-AS) bands in the Heats of

of As-O-As bonded dimers.

in

[ill

for

and chemical

shifts

of OH protons

The phase diagrams for have been published

constants

of

effects

22 organoarsenic

from

of

arsenic

the systems

[112].

Wauchope

for H3As04, oK2 = 7.089;

(CH3)2A~(0)OH, pKl = 6.288.

and RAs(O)(OR’)~ The

aGo.

1.

(or alcohol)

R2As(0)OR’,

constants

L-1151.

oxide

strengths,

stituent

proton

= 0)

in the crystal.

and the appearance

dissociation

PK~ = 4.114;

on proton

v(As

-1 in the 600-700 cm region.

~(As03)

are coordi-

for the interaction between trichloro- and trifluoroacetic

has measured acid

CH3As(0)(W2,

entirely

to the formation

and ttis(n-octyl

triphenylarsine

oxides

Crystal

[109]_

On cooling,

moments, H-bond polarities

have been determined

hydrogen

of (R0)3AsO compounds have been carried

[110-J.

disappears

of bands replace

formation,

adduct which

of a strong

compounds in which arsine

spectra

of temperature

is attributed

structure

has been determined

the formation

U(IV) Cl081 and Co(II)

ance of u(As = 0) in the liquid crystal

the crystal

of the crystalline

indicates

for

of the vibrational

in the liquid,

new series

from

group of the phenol and the arsenyl-oxygen.

or Mg [107],

out as a function

with the

is that arising

and pentafluorophenol

2.599i

have been reported

Studies

have determined

The structure

acid.

the hydroxyl

nated to Ni(I1)

of the NQR frequencies

that the primary factor

and Sen Gupta [104,105]

The O---O distance,

structures

In the case of alkylarsonic

the correlation

forms between triphenylarsine

bond involving

were correlated

of the substituent.

of o-aminophenylarsonic

[106].

the lower is the

75As NQt?frequencies The

constants.

indicates

of the

(R0)3As and EtAs(OEt)2.

number of arsenic,

frequency.

with the sum of- the Taft induction and dialkylarsinic

R2As(O)OR’,

molecules

compounds

have been

basicities,

of the types

correlated

alkyl

chain

length

and

arsinic

acids

AH0 and ASO with increasing

The

with

on the have

for

thermo-

been

chain length

sub-

measured

for

both

263

arsenic

and arsinic

protonated

amino acids

not presently its

arsenic

spectra

dissociated

of o-[(H0)2(0)As]2C6H4

dialkylarsinic

The formation

acids

constant

are weaker than alkylarsonic

triphenylarsine interaction

separations

with alcohols

and phenols,

i.e.,

has been studied using infrared spectroscopic

acids

acid

solutions

The extraction

has also

by natural

of phenylarsonic

out in connection _

among those

the

of arsenic

been carried

The compound,

oxide

the adsorption

from acid

As expected,

The

Infrared spectroscopy

on silica-gel

arylarsonic

for which pK = 14.65 was the weakest.

niques [119].

The effect

to

[Cr(00CCH2As03)]

have been measured in dimethylformamide.

(c~H,,)~As(O)OH,

sAs=O- - *H-O-,

The

dissociatcbd

a number of alkyl-.

acid

of

acid.

of

HOOCCH2As(O) (OH)2 for which pK1 = 8.95 was the strongest

interaction

French workers

most easily

[118].

while

along with

group attached

acids

studied

is

group for which Y2 = 1.49 x 10 -4; the trivalent ion

Acid dissociation constants for

acids

[116]_

the hydroxyl

amines,

explanation

of carboxymethylarsonic

is that of

is -OOC-CH2AsOi and K3 = 1.46 x lO-‘_

and dialkylarsinic

protonated

A satisfactory

-2 for which K, = 1.39 x 10 ; the next oroton

x 1o’O.

c.p.,

have been reported

the dissociation

is that of the carboxyl

is 4.74

predicted,

The thermal stability

and infrared

most easily

from those

and carboxyl ic acids.

have investigated

proton

differ

available.

ultraviolet

[117]

acids

tin

been utilized dioxides

on the sorption

has been studied

by tris(i:-octyl)arsine

in the study of

and other of zirconium

[121].

with the investigation

tech-

minerals

[120].

and hafnium

These studies

have

of fission-product oxide

in benzene of Mo(V1)

from its aqueous acid solutions was found to be very high in the pH range 3-4

[122-j _ Overlap

integrals

have been discussed

Finally,

[123].

in contrast

in chlorosulfuric

basicities

The basic

with triphenyl acid.

( C6H5)3AsOH+ cl 24]-

Referencesp. 293

and the

strengths

stibine

triphenylarsine

of four-coordinated follow

compounds

the order:

and -bismuthine, is oxidized

arsenic

which are sol volysed

to the protonated

form,

261 VII_

Compounds Containing

Very little thio

has been

and seleno

[125]

ing

on arsenic-selenium

The reaction

of

red selenium

in

boiling

Amido>k( kiT:-butyl )arsine reacts sulfide-

by the folloGng

PhSPS f

(‘,-Bu)2AsCl

•I- Hz0

The Russian

Z-Bucl

in

24-52X

published

methylpheny7arsine

continues

sulfur)

its

which

deal

and with

When R2R’AsS with

an

BrCCl3,

Carbon

[129].

(PBuAsS)

to

first

react

time

[127].

form amidol.in(

the

latter

of

Z.Y-

converts

I are

it

to

summarized

sulfide

mechanism

X

activity

in the

sulfides

have been prepared

characterized

with

is

group

is

is

of

at-sine

and

inertgives

The

which

the

not

only

(C,H5)(C6H5)A~(S)C(0)OCH3 electron

pair

Pr,

reaction

on sulfur

and

halogen

Bu,

Ph)

is of

the 3,

conven-

papers

RR’AsSCC13

(C2H5)(C6H,)As-S-C(O)OCH

in

of

sulfides

Bu; R’ = Et,

lost

sulfides_

in the

A number arsine

Pr,

methylchloroformate

sulfide, one

between

(R = Me, Et, alkyl

field

[128].

reactions

tetrachloride

ethyl(methoxycarbonyl)phenylarsine proposed

to

not

does

the

Some reactions

ethyl[(methoxycarbonyl)thio]phenylarsine,

The

sulfur

interest-

(t-BU)~AS(S)OH

f

molecules.

yield

+

and alkylarylarsine

(arsine

reaction

-

school

aryl-

manner

undergoes

for

the

(~~I)$Ls(S)NR~

:40°

containing

solvents_

(I)_

----

been

organic

HCl in ether

al.,

(t+t_i)p(S)R

+ R2NH -

I

have

Triphenylarsine

sulfide

f RMgCl -L

tional

of

Se02 gives

[126].

elemental

Chen, et

of x-D-glucopyranose =

with

reported

Both

scheme.

+ PhSP w

A number of

with

The addition

chloro3io(?-ert-butyl)arsine

derivatives

has been

comoounds-

derivatives_

triphenylarsine

(C6H5)3AsO-Se02

Bonds

bonded

or .--- -dimethylarsino

A chlorodiorganylthioarsorane

butyl)arsine

or Arsenic-Selenium

and .:.I-dimethylarsino

compound,

elemental

reported

form :-

Z-

at C6.

addition

with

sugars

have prepared

substituted

Arsenic-Sulfur

formed ethyl-

expected

but

also

[130]. undergoes

265 electrophilic tion

attack

by the carbon atom of methyl chloroformate

of a ..z!T-’ ..,carsonium

C2HS,&_~H

compound as an intermediate, cl-

3

C6HS’ ‘S-C(O)OCH3 Isolation

-

and identification

the proposed

mechanism_

to the formation been reported

of

of the ,Tzdasiarsonium salt Treatment of arsine

the arsine

[132]

dichloride

and benzoyl

ethyl

occurred

dihalide

chloride

Hark of a similar arsine

tertiary

methyl ether,

The formation

but in a few cases

With hydrogen halides,

in support

with acetyl

of tertiary

chloromethyl

vlere studied.

generally,

is offered

leads

nature

sulfides

of

has

with

RR;AsC~2

chlorides,

chloroacetate

sulfides

[131].

in which the reactions

RRiAsS + 2 CH3C(O)Cl acetyl

with the forma-

arsine

of

the arsine sulfides

chloroacetonitrile

the tertiary

sulfide

also

arsine

dichloride

was recovered

yield

and

unchanged_

the tertiary

arsine

[133].

The reaction

of phenylpropyliodoarsine

with (-)menthol

in pyridine

gives

the menthyl phenylpropylarsinite (C3H7)(C6H5)AsI

The arsinite

+ HO(CloH19) -

adds a mole of sulfur

to form a mixture

menthyl phenylpropylarsinothioatehydrocarbons, this

the ester

[134].

synthesized

general

By fractional

can be resolved

way, a number of optically

and resolved

active

Asymmetric esters

and their properties

formula

RPhAs(S) (OR’ ) ~

tertiary

arsine of

monosubstituted discussed. References

p. 293

the

frequency

arsine

[135].

have also difference

The ultraviolet been reported between

to the benzene ring,

forms.

sulfides

In

were prepared acids

have been

The esters studied have the

of four spectra [137].

the

of c-

from

diastereoisomeric

of alkylarylthioarsinic

phenyl groups on K-band shift

GIith respect

its

tertiary

of diastereoisomers

crystal 1 ization

The ‘H NMRspectra

have been measured [136]. sulfides

into

described

sulfides

dependence

(C3"7)(C,",)AsO(CloH19)

K-band

triorganylarsine of a number of

In this

maximum of

of p-X disubstituted the As(S

study

the

di-

and

benzenes

group is a poorer

is

266 electron thermal

acceptor

than

analysis

As(O

arsine

ha1 ides

[138].

mediate

formation

sulfides_

The mechanism of catalysis

[RR+sc~H~]BF~

been

Triorganylarsine

carried

oxides

and

In this

out in dry benzene under nitrogen.

complexes

and thermal behavior

of Br2As[S2CN(Etj2]

centrosymmetrically

coupled

coordinated

centers.

arsenic

the As-Br distances

Ar2AsC1

f BrMgCzC6H5

was

between

.3,2_dithiaarsolane [142].

[143].

The crystal

Two units

are

between 5-

are 2.270 and 2.374 i and

Infrared

and Raman studies

of

out Ci44].

Arsenic-Hal oqen (Hal ogenoi d) Bonds

have been prepared with the product [145]:

C6HBCXMgBr+ C2H6 -

to yield

mass and ESR spectra,

were investigated.

have been carried

with phenylacetylene

C2H6MgBr+ C6H6CrCH-

takes place

and its

2.920 and 3.066 i.

between diarylchloroarsines

alkylhalomagnesiums

[140].

study the reaction

of VO(IV) have been prepared

The As-S bond distances

Diaryl(phenylethynyl)arsines reaction

with thiols

to dimers with two bromide bridges

are 2.404,

Compounds Containing

The ‘H llMR spectra

and Z-ethyl-l

has been determined

the fundamental Y(As=S) vibration

VIII.

formula

to form 1,2-dithio?Cc(diethylarsine)

The .formula of the compound is OV[S,As(CH,),],

structure

acid.

have been recorded

reaction

to triethylarsine

3
susceptibility

salts

the inter-

of thioarsenous

[139].

particular A

acid and 1,2-ethanedithiol

ethane which disproportionates

magnetic

esters

characterized

by alkyl

to involve

having the general

alkylthioarsonium

[141].

Differential

is catalyzed

undergo an oxidation-reduction

and the disulfide

diethylarsinic

ring.

to study the thermal rearran-qe-

to give

salts

prepared

of a number of these and other

benzene

is believed

of qrm;_Sarsonium salts

have

to the

The rearrangement

A number of alkylthioarsonium

the arsine

respect

has been used as a tool

(DTA)

ment of tertiary

with

Ar2AsCzCC6H5

in good yields

by the

formed by the reaction

of

267

Secondary

alcohol

the reaction

derivatives

of the type Ar2AsCzCCH(OH)Rwere synthesized

between Iotsich

2 C2H5MgBr

reagents

+ RCH(OH)CXH

react

and 112 addition cationic

with thiourea

of the trivalent

spectra

?.hich show the presence

1inkage

[146].

The crystal

Cl bond distance, changes

for

Ar2AsCzCH(OH)R

compounds formulated

nature

and diarylchloroarsines:

RCH(OMgBr)C-CMgBr+ 2 C2H6

_I

Ar2AsC1 + BrMgC:CCH(0MgBr)R Dimethylhaloarsines

(tu)

in aprotic

as Me2As(tu)CX-

arsenic

of

is so long

to yield

1:l

tu.

The

by the study of vibrational

but absence

of an As-X covalent

[Me2As(tu)]+Cl--tu

that the bonding

of the adducts

the decomposition

solvents

and ?le2As(tu)+X--

is evidenced

of an As-S,

structure

3.715 i,

by

reveals

the As-

Enthalpy

is ionic.

to yield

that

Me2AsX and tu (thiourea)

were measured. The vibrational out.

A

analyses

normal coordinate

been reported vibrational

Vibrational

[150].

Evidence

is presented

The radicals, e-s-r

days _

They are prepared

in

presence

khe

of

Chlorine-35

an

nuclear

spectra

or C(t4e3Si)2N]2As-

by the photolysis

of

resonance

spectroscopy

have measured the 35 Cl NOR resonances

RnAsC13_n and (R0)nA~Ci3_n.

The directions

an increase

Cl atoms and decrease

the electron

References P_ 293

density

400-600

been

the corresponding

et al..

decreases

have

the study of a number of As-Cl

is interpreted

(Cl-C4) have been -1 cm .

characterized

are very persistent,

tool

group increases,

the

t,,2

Z- 30

arsenic

chlorides

olefin.

quadrupole

in the number of

simple

of MeAs

in the region

investigative [152]

for

F has

As. --N bonds.

These radicals

electron-rich

been carried

normal coordinate

been measured for

occurs

intermolecular

Cl%].

has

has investigated

and performed

Raman and infrared

[(Me,Si)2CH]2As-

spectra

haloarsines

(CF3)2A~X, where X = I, Br, Cl,

have also

The v(As-CCN) stretch for

of

The same group [148]

spectra [149].

recorded

their

of

of CFSAsX2 molecules

alkyldichloroarsines

by

a number

analysis

by Demuth [147]spectra

analyses.

for

has been used as an

bonded compounds.

of the series

of the shifts,

Jugie

of molecules

which increase

with

as the number of alkoxy

in terms of the electronegativity on As and a back-donation

of Cl, which

of electrons

from the

_

oxygen on the alkoxy

group to the arsenic

it is indicated that AsPhCl,, bipyramidal

structures

equatorial torial with

in the solid

Lewis

all

possess

study [153]

trigonal-

with the phenyl groups occupying

structures.

X, such as BC13, SbCl5,

or

Adducts ICl have

groups of

occupy

As(V)

the expected

equa-

compounds ionic

struc-

[AsR,,Cl4_n][XCl].

tures,

The mass spectral by chemical [154]_

atoms,

fragmentation

ionization

[155].

but not

fragmentation

The formation

methyl

groups,

The He I photoelectron have been interpreted C3v/C5

patterns

have been compared

The mass spectral

investigated

for

and AsPh$lp

state

in trigonal-bipyramidal acids,

From a 35C1 n-q-r.

In Me3AsClp and tle2AsC13 the methyl

positions.

sites

AsPh,Cl,

atom.

is

of

Sb were also measured,

obtained

by electron

of methyldihaloarsines halogen

bridged

has also

dimers

which

lose

impact

been halogen

of a number of tdeAsXp and 1Sle2AsXcompounds

in terms of a “composite

Since analogues

systems.

With those

F, obtained

observed.

spectra

[156]

of AsX3, X=1, Br, Cl,

containing

a trend comparison

molecule”

the other

was made.

approach derived

group V elements,

Ionization

energies

r‘l, P, were

assigned.

IX.

Triorganyl

A_

Arsines

Asymmetric

Two closely

Triorganylarsines

related

ethyl-m-tolylarsines The procedure fractional

into

involves

the optically

describe active

as follows

for

the resolution

isomers

The alkylation

the synthesis

and it

of aminophenyl-

(o-,m-,p-aminophenyl).

of the diastereomeric

from ethanol _

has been utilized proceeds

[157,158]

the preparation

recrystallization

arsonium salts The reaction

papers

(+)-tartrates of phosphincs

of asymmetric arsines

is preferably

carried

C6H5CH2/ ‘R

f

X-

(C6H5)3P

RAs,c6H5 ‘CH6 C5H2

f

by [159].

out in an aprotic

sol vent such as dimethyl formamide. c6H5CHZ,As,C6H5

and

[(C6H5)3RCH2C6H51fX-

269

The reaction eliminated

proceeds from

tertiary

best

the

arsines

arsonium

11601

Gri gna rd reagents

when X = I.

.

utilizes

the

The pertinent

( .4rAs=O)n + nRMgX --

its

stereoisomer

6.

RArAsR’

[161].

including

MepAsC(NpjCOOEt,

In the

9.3,

6.8

38.4,

reactions

is

reaction

carboxylic

of

following

observed

through

of the

the

use of

asymmetric

react

with

and separated dextrorotatory fusion

diagrams.

.

the

between

13

prepared

in liquid

R = “Bu,

is

a number of

referred shifts

to

are

(He2As)2CN2,

Pb,

Sb,

attributed

acid metal

salts

of

by 13C NMR

revealed

the cAs-13CH3 45.7,

1,3-dipol

shift

27.2,

have

46.4

When M = As,

synthesized

[164]

MHAsR and halo-

ammonia as follows: RAs(H)-R’-COOY

NH2; n = 1-4,

+ MX

CHMe. CHEt; X = Cl, 10.

9.9,

and

effects.

been

al kylarsines,

is

ar cycl oaddi tion

Bi or Hg and L = Me. to steric

derivatives

and

are

24.7,

L,,MC(N2) R undergo

reagents,

organometallic

derivatives:

properties

just

C6H5; R’ = (CH2),,,

Y = OM, OR’,

nucleophilic

MeAs(NMe2)C(r$)COOEt,

C(N2)

type

and this

alkali

more powerful

nucleophilic

sM-

arsinocarboxylic

acids

P. 293

synthesized

configuration

arsenic

compounds

ppm, resp.;

MAs(H)R + X-R’-COOY -

References

have

to Me02CsCCCOOMewhen M = Sn,

Secondary by the

the

Compounds of

no reaction

to

of

as follows:

has been

to produce

[162,163]

Enhanced

series

and 9.7

resp.

aryloxoarsines

are

primarily

Fle2As[C(N2)COOEt]2,

(r~le2r~)2AsC(N2)COOEt. shifts.

synthesis

+ MgX2 f MgO

The absolute

designed

and co-workers

diazoalkanes

the

preferentially

Aspects of Triorganylarsines

In an investigation Lorberth

of

bromide

has been established

Other

ability

for

is

RArAsX + Mg(OH)X

R’MgX --

enantiomers

route

reactions

Benzylisopropylmethylphenylarsonium into

Another

group

nRArAsOMgX

RArAsOMgX + HX ~ PArAsOMgX f

salt.

The benzyl

Br-; M = Na, K;

Reactions

of

carboxylic to

the

these

anhydride

[165-J.

The

the

and

The The

As-Cl

arsino

its

Pizey

substitution

conversion

have

compounds As-C1

bonds

are

bonds

at

to the

prepared

formed

in

undergo

derivative-

the

The

and

by the

amide,

vinylic

studied

of

across

Kauffmann

by the

and

are

between

exceedingly

to the

reduction

of

readily

with

chlorine

can

C6H511gBr be

of

COOR’

G-styrylarsines

AsCl3

and

sensitive to

reduced

yield

by

and

1.3-diphenyl-2-azallyllithium

the

double

co-workers

phenylacetyl to

the

hydrolysis diphenyl-

LiAlH4/LiH

to

give

bond

of

The

[166].

and

H2C=CHAsPh2

diphenylvinylarsine reaction

proceeds

in

has

been

studied

the

manner

shown

+

H20 ---Ph

Ph-CH2WCH2-PhLi+

i

I

As(C6H5)2

l-

H3CCH2fiCHPh2Li~

A

H28 Ph2

0

reaction

of

a lengthening

diphenylvinylarsine of

the

H2C=CHAsPh2

E-Aminoethylarsines of

cis-

-

RLi Bu,

or and

vinyl

f

R = Et,

mixtures

l,l-diphenyl-P-

equation

--

in

conversion

a number

reaction

compounds

reaction

cycloaddition

azallyllithium

The

Y,

styrylarsine. The

by

and

include

alcohol.

Peterson

enes.

compounds

with

an al kyllithium

FL28 l

sez-Pu,

R,

= n-Bu,

R2 = -CH2CH2NH2,

[167]

results

ter-c-Bu

arms-styrylarsines

Ph,

THF

RCH2CH2AsPh2

o-aminophenylarsines

+ HCeCPh -

in

qroup

add [168].

acetylene

R&ASH

N

R, R2AsCH=CHPh Et -CH2CH2NHEt,

o-C6H4NH2

to

phenylacetylene

The

addition

to to

give

isopropenyl-

271

gives

90:: ~1~35-4.3

pyridine,

and 10% of the 4,l

R2AsCsCCH2(0H)R’ reacts

to eliminate

addition

with acetyl

product.

chloride

In the presence

of

or chlorotriethylsilane

HCl and form R2As.c~CCH2(0G)R’, where G is CH3C(q) or Et3Si,

resp.

[169]. ~i-,.s(pentafluorophenyl)arsenic yield

the adduct,

L-1703.

analogue

is oxidized

An interesting [li’l]_

Tertiary

(halogen

ligand at-sines

which contain

groups as the main or sole

The latter

involves

decomposes

then reacts

the

into

benzyl

which bears

diphenylethoxyarsine of diphenylarsinic

initial

ligand(s)

has been observed react

arsonium salt

formation

an additional

reacts acid.

the

benzyl

The reaction tertiary

of

of

the

The benzyl

halide

the quarternary

In a similar

ethyl

dihalide.

manner,

bromide and the ester

crie(o-dimethylarsinophenyl)bismuthine

results

formation

proceeds

arsine

to give

ligand-

two benzyl

of the bis(arsonium)

and the haloarsine.

with bromine to yield The reaction

and the

of

with 1.2-dihaloethane

containing

formation

(benzyl-substituted)arsine

with sodium tetrachloropalladate(I1) bismuth,

halide

compound, the

by nitroxyl.

ligands

The predicted

the benzyl

with the original

arsonium salt

free

benzyl

the quarternary product.

oxide

does not occur or to a very limited extent.

in a manner which

of

also forms an addition

involving

to

s[di(trifluoromethyl)nitroxide]

to the phosphine

shift

= I or Br) to yield

either

with bts(trifluoromethyl)nitroxyl

?&s(pentafluorophenyl)arsenicLL

Al though the antimony analogue

phosphorus

salt

reacts

in Bi-C bond cleavage,

Pd(II)

the deposition

complex of phenyldimethylarsine

[172-j. Rate and equilibrium triarylarsines

reactivity

and benzyl

and to the fact

results

in increasing

operative

have been measured for in chloroform

bromide

of the o-anisyl-

effects

torsional

reaction

that increasing

electron

electron

between

The considerably

‘JS. the phenyl compound is attributed demand (of

supply when an anchimeric

barriers

spectra

have been recorded

have been obtained.

have been shown to be configurationally 1 H NMRstudies References

[173].

the

greater

to steric

the ether

assistance

groups)

effect

is

(as is the case here)_

Raman and infrared its

constants

P- 293

were carried

out for

for

trimethylarsine

Triorganostannylarsines,

stable

within

[174]

R3SnAsPh2,

the NMRtime scale

a number of arylarsines

and

[175].

over the temperature

2'72

range -196” internal

to 20”.

rotations

were observed attached

From these data the magnetic of arsine

which could

to arsenic

arsines

are coordinated reveal

of the phenyl ring

directly

to phenyl-

Electron

to the metal [777]. of solutions

the cation,

spin resonance

of Ph3As in sulfuric In sulfuric

Ph3Ast.

acid,

radicals

propanol

has

benzoates

been

investigated

one electron

to As-C bond rupture

processes

were studied

an appreciable Dipole

experimental

and to the formation The radical

triphenylarsine,

using the vectorial

The crystal

X.

The first

esters

(from alkyl

formed during the reduction moment of As was found

to make

a number of arsines

parameters_

The

set of data that allow

method, of suitable The greater

[181,182-j.

dipole

group moments, moment of

has been attributed

to the

compound. fur tetranitride

has been

[183].

Tewari and co-workers

Ylides

continue

and Arsanes

their

activity

Z?wzs-1-aryl-Z-(3-indo7yl)ethylenes

L-1841 by the interaction olefins

in iso-

of arsino-

[180].

of benzoate

of triphenylarsine-trisul

Arsonium Compounds, Arsenic

ylides_

reduction

as a consistent

additive

in the latter

structure

solutions

process

compared to that of trimesitylarsine

CAsC bond angle

The quantum yield

to the width of the ESR lines.

bond moments and configurational

determined

anions

been measured for

have

acid at 77°K

The transfer of the second electron

moments have been discussed

calculation

greater

a three-step

by ESR and the quadrupole

contribution

moments

of Ph$s

The electrolytic

[179].

and is reversible.

substituent on the arsine) _

for

photolysis

has been found to involve

involves leads

formed by the ultraviolet

studies

Ph3As0 gives

Ph3Asr, but in methanol either Ph3Asa- or Ph3AsOR was formed. of

WlR

' 3C

+2 complexes in which triorganylfor a number of Fd

that the exposure

to 6o Co -<-rays yields

and

No relaxations

with the mobility

or of the methyl group linked

have been reported

of protons

substi tuents vrere interpreted.

be associated

studies

[178]

relaxation

have been prepared

of arsonium ylides

formed have the trcqs-geometry.

in the field

of arsonium in good yields

with indole-3-carboxaldehyde.

A new series

of arsonium ylides

The (A),

273 CHO Ph3As = CHR’ f

+ Ph3As0

R’ = nitrophenyl

or bromonaphthyl

2-naphthylmethylenetriphenylarsenane, pounds have been investigated

and their

reactions

toward carbonyl

com-

[185].

R’ Ph$s-C-H

The reaction if

of fi with an aryl

A

aldehyde

gives

R’ = H, but when R’ = Br, the product

In both cases, center

the carbonyl

of either

ylide

group of

the epoxide

is the olefin

the aldehyde

to form a cyclic

and triphenylarsine

and triphenylarsine

is attached

transitional

oxide.

by the carbanionic

intermediate

(B).

Ph,As----CHR J

I I

&-----CHAr

The intermediates In a related with anthrone yield

study

[186],

olefins,

obtained

With g-anthraldehyde,

e thy1 enes , exclusively. of arsonium betaines investigated

steric

dibenzarsolium

ring

electron-withdrawing betaine

semistabilized

and 2-chioroanthrone

exocyclic

isomers.

decompose by different

collapse

References p_ 293

Allen contrasts

effects,

via

arsonium ylides

at the reflux

the respective

products.

were found to react

temperature

almost exclusively

of benzene

to

in the form of the ZPCLZS-

Ph3As=CHAr gave the s:nails-1-aryl-2-(9-anthryl)and Jackson

11871 have discovered

that the behavior

with that of the phosphonium analogues. by enclosure

system and electronic P-fury1

paths to give

substituent

of

the arsenic

effects,

in the strained

by the presence

on the arsenic.

They

In neither

of the case was

attack of betaine oxygen at the arsonium center observed.

274 Both Z-furyl(methy7)diphenylarsoniumiodide and 5-methyl-5phenyldibenzylarsoniur iodide, on treatment with benzaldehyde and NaOEt pave the

olefin

epoxide

and

and tertiary arsine, exclusively. Gosney, Lillie and Lloyd Cl881 studied product formation, i.e., epoxide f arsine 7.~.olefin + arsine oxide as a function of the substituents on arsenic. The olefin/epoxide product ratio was found to increase as the electron donating ability of the organic substituent on arsenic increased. Triethylmethylenearsoranehas been

prepared

by

the

dehydrohalogenation

of

salts by NaNH* [189],

triethylmethylarsonium

+ - NaNH2 C(C2H5)3AQ3131Br _NaBr b (C2H5)SAs=CH2-

The same compound can also be prepared by desilylation of triethyl(trimethylsilylmethyl)arsoniumchloride &) EtSAs + C1CH2SiMe3 -

[Et$CHpSiMe3]C1‘ c

c - BuLi

(C,HS)8As=CH-Si(CH3)S -D

+CHBOH !? -(CHS)SSiOCH -+ (C2H5)3A~=CH2.

Triethyliminoarsorane(E) is formed exclusively from MeqAst salts and NaNH2,

MeqAsfBr-

NaNH2 _CHq

l

(CH&As=NH.

Triphenylmethylenearsorane forms stable silver and copper complexes, MCI Ph3As=CH2 M=Ag,Cu F CPh3AsCHZAgClln CPh3AsCHZ-Cu-CH2AsPh3]Cl The preparation of ylides of the type MeSAs=CH-GeMeS and Me3.4s=CCGe(CH3)812 has been carried out as shown by the following equations [190].

275

Me3As = CHSiMe3 -I- Me3SiOGeMe3__

2 -F -_-

Me3As = CH2 + Me3As = C[Ge( CH3)3],

Trimethylmethylene arsolane

(g)_

arsorane

From variable

been assigned in axial

positions

form azobenzene

with ethylene

temperature

reacts

structure

readily

The reaction

to give

the l,2A5compound has

with a methyl group and an oxygen

with phenyldiazonium

and tetraphenylarsonium

of a trivalent

oxide

1 H and l3 C NMRdata this

[1911_

A most interesting

bond.

reacts

a trigonal-bipyramidal

Tetraphenylarsenic

tion

Me3SiOSiMe3 f Me3As = CH - GeMe3

tetrafluoroborate

tetrafluoroborate

paper by Becker and Gutekunst

arsenic sequence

compound containing

to

[192]. [193]

a formal

claims

the prepara-

arsenic-carbon

double

is shown as follows: SiKe3

MeAs(Si@3)p

PivaloYl

chloride

/ + MeAs \ ‘C(0)

5o”,

CMe3 12 h.

y 0-SiMe3 / MeAs = C \

The evidence infrared

data.

boration. References

p. 293

is based largely This interesting

on T3C and

1

CMe3

H NMRspectral

work mer,its further

shifts

investigation

and some and corro-

2’76 The synthesis at-soniun

of

bromide

Yields

with

obtained salts

general,

quarternary when

similar

conditions,

with

with In

involving

reaction

salts

O-5 p! sodium

s_

Re(C0);

reacts

PIaOHyields order

to

an ylid

between

carbonyl

carbony?

has been

At room temperature,

dinitrodibenzyl.

the

hydroxide

at

such

Ph3As0, for

account

as

the

slowly Mn(CO)&

the is

qives

Co(CO),

arsines

yield

and

and ally1

toluene

under

and triphenyl-

p-nitrotoluene of

proposed.

Ellis

and various a phenyl

only

In

However,

70-700°.

formation

of

al lyl-

of e-nitrobenzyltriphenyl-

Ph3As,

salts

addition and

salts

of

by Samaan [195].

hydroxide

tetraphenylarsonium

much more

anions

studied

reaction

and Sharma [194].

The cleavage

tertiary

the

phenylacyltriphenyl-

by Sansal

yield

intermediate

Mith C5H5Fe(CO);

of

from 51-725.

benzyltriphenylarsonium

bromide

mechanism

vary

reaction

reported

been

allylarsonium

treated

oxide.

by the

has

reaction

by sodium

alcohol

arsonium

anilines

in this

arsonium

at-sine

Z-phenylindoles

group

give

the

last

product,

Cl961 has studied cyclopentadienylmetal gives

Less

Re2(CO)10_

V(CO)i

and 4,4’-

CSH5Fe(C0)2Ph.

nucleophilic

quaternary

arsoniun

salts. A number pared

[197].

of

optically

Trial

against

chloramines

Sarcina

arsonium

salts,

kylcarbamoylmethylarsonium

tetraiodocadmates, with

active

[R,AsCH,C(0)NH2]2Cd14 to

give

arsinimines

(5)

Zutica and StiphyZococcus

iodides

react

[198].

Phenarsazine

[199].

These

epide_tis.

N-S02C6H4-R

II

RR’ EtPhAsX

have with

been Cd12

chloride

compounds

are

preto

give

reacts active

a

277

A Japanese

patent

manufacture

of

[ZOO]

organic

describes

a number

of

transitions, of

physical

izing

relaxation

a phase

in

microscope,

absorption

bipyramidal

TCNQ anion Iida

Devreux

when the

structures

for

possess

tetragonal

arsonium

a series

They

Cl,

to

have

of

the

in

has the

been

studied

the

the

the

[2Q3]

have

properties

investigated

Using

indicatrix

subject

phase

thermodynamic

[Ph3AsCH3][TCNQ]2_

ideal

such

i zed

ionic

arsenic

structures,

the

polar-

and directions

ylides

been

carbanion

have

of ylides

in 13

Br,

the

The crystal [206]. of

C chemical

bearing

,

When X = I or

a variety

presented

to the

lead

trigonal

[R AsXfX-. 3

used

ylides.

[205]

possess

has been determined

and arsenic

on a series

molecules

C3v symmetry_

resonance has been

salts

concentrated

linked

of

has measured

X = F or

with

Nuclear magnetic of

[201,202]

and Nechtschein

dynamics

[204]

radical

and measured

structure of [(CH3)4As][( CH3)21nBr2]

study

as a catalyst

NeaAs- [TCNQ]2.

that

molecules

Ph4Asifjr-

Raman and NMR analysis of R3AsX2 molecules

Infrared, conclusion

the

diagram

exciton

Helberg

in

of

measurements.

Ph3Aslle+-TCNQ-- systems.

nuclear

of

salts

prepared

use of

isocyanates.

Tetraphenylarsonium of

the

ways

shift

by Froyen

in

the

assignments

and Morris

a ;-substituted

[207].

phenacyl

group

(I)_

?h As=CH-C” \ Ar

Chemical shifts of the ylide carbon in this group of molecules dependence resonance not rings shifts been

with term

display

those

published

compound

exhibits

References p_ 293

dual

substituent

a correlation.

to

arsenic

carbon [208]. rapid

atoms.

“F

contrast

ligand

arsenic

exchange

Swain of

interaction atom

NMR spectral with

of

shifts

A limited

and the

In

parameters

The chemical

predominating.

such

attached of

the

the

is

phosphorus

down to

and Lupton,

the

-90”.

carbonyl

between

indicated

studies

show a linear with

the

carbon

do

the

aromatic

by the

chemical

on (C6H5)2A~F3 analogue, Whether

the this

have arsenic

results

from a Berry pseudorotation energy barrier,

or an intermolecular

NMRinvestigation

the reorientation

also

[ill]

compounds including

a reference

shifts

chlorides,

AsF;.

AsRi salts,

alkylarsonium

for

deriva-

and iodides

75As NMR shifts

have

salts

shift

Al though 75As chemical widths vary greatly

shift

range exceeds

is 50 ppm.

Relative

shift

of

of -291 ppm is observed

for

shifts

solvent

are not strongly

served

600 ppm although

for

arsonium salts. to

369 ppm relative

AsHqfas the Ta2F;l

salt.

the line-

dependent,

This has been attributed

solvents.

as

to AsF6, downfield

are observed

a downfield

in different

in a number of

As0i3 and PsF6_ The latter

chemical

AsOQm3, exhibits

ion,

An uofield

and

are responsible

fluoborates

from 206 (AsMe:) to 258 ppm (AsPr3Et*)

The arsenate

It is concluded

of a number of arsenic(V)

have studied

The observed

ion.

the range for

[209]_

in poly-

[ZlO].

Balimann and Pregasin arsenic

tumbling

at high temperatures

1H MMRspectra

ethylphenylarsonium

been reported

and cation

A ‘H

motion of the methyl groups at 10~ temperatures

mechanism.

including

a lower

is not certain.

by Rager and Heiss

of the whole cation

the relaxation

atom providing

exchange process

has been reported

that the reorientational

tives

arsenic

of methyl group reorientation

AsMe

crystalline

with the larger

to ion-

pairing. He(I)

photoelectron

(CH3)3As=C[Si(CH3)3]2 electronic

structure

spectra

tion

po-int

has been obtained

to possible

of arsenic

for

The results

Ph As=CH-i-R 3

30% Jananese workers arsonium ha1 ides_

changes

.

A consistent

from semiempirical potentials

in the ylidic

model of the

NO calculations

and calculated

ylides

with the following

total

methyl anion upon substitu-

An ESCA study of the As-C ylide

triphenylarsonium

are consistent

[ZlZ].

The ionization

phosphorus.

carbonyl-stabilized

( CH3)As=CH2, (CH3) 3As=CHSi( CH3)3 and

have been studied

(CNDO, EHMO)and ‘13C data. energies

of

bond in

has been undertaken by Dale [213]. resonance

structures:

PH A:-CH-&R 3

-70%:----i Cl241 have measured the viscosities

of aqueous solutions

of

279

XI.

Arsenic

Heterocycles

Ashe and Friedman [215]

have prepared

benzene and dimethylacetylene reagents

at 80° gives

Diels-Alder

The reaction

dicarboxylate.

a good yield

adducts

between arsa-

between these

two

of arsabarrelene.

d5 X

AS

X

arsabarrelene X = C02CH3

The pyrolysis

of the adduct results

arsabenzene

(A) by loss -

methylarsabenzene

yields

in an 80% yield

of acetylene.

manner, flash

pyrolysis

piolate

and arsabenzene

benzene

in a 3:2 ratio.

adds to arsabenzene synthesis

of the Diels-Alder

with 2-

and 432 of 6In a similar

adduct formed between methylpro-

The same authors

report

and Z-carbomethoxyarsa-

[216)

that methyllithium

the 1-methyl-heterocyclohexadienide

of l,l-dimethyl-hb-phosphabenzene

ion in DMSOgives

of acetylene.

gave 3-carbomethoxyarsabenzene

to give

sequence

of methylacetylene

U~G loss

is accomplished

anion.

1 ,I-dimethyl-A5-arsabenzene

The

by quaternization

Treatment of the arsonium salt

of l-methyl-2,4-arsacyclohexadiene. dimsyl

The same reaction

47% of A vice loss

methyl-2.3-dicarbomethoxyarsabenzene

of 2.3-dicarbomethoxy-

with

[217].

A number of papers have appeared based on the work of Miirkl and co-workers. The pK of arsabenzene-4-carboxylic that of related ul traviol

et,

References p. 293

is 4.10.

compounds along with other

‘H NMR, and mass spectra

to b&(propynyl)serT;-butylphosphine derivatives

acid

physical

[218]. gives

with the isomer distribution

This value

is compared with

measurements such as

The cycl oaddi ti on of phenyl arsine

1,4-dihydro-1-phospha-4-arsabenzene shown below [219].

R ti Me3CP(C:CR)2

+ H2PPh

--

Me3CP

AsPh

4 H’

Atmospheric of

oxidation

converts

the

R

phosphorus

4-hydroxy-1.4-dihydrostannabenzene

reacts

with

AsC13

rearrangement,

to

give

has

to

been

phosphoryl.

described

an oxa-arsascyclopentene

presumably

31~

Sn(;z-bu)2

AsCl 3 3

[ZO].

which

a free-radical

The

mechanism

This

can to

synthesis compound

undergo

the

thermal

4-substituted-

arsabenzene.

HO

-

Glhen 6hydroxyarsabenzene in the

presence

of

is

anhydrous

cyclohexa-2.5diene-4-one noted.

In acid

alcohol

and rearranges

involves

the

migration proton

of

formation

Lambert

and Sun [223].

structures i.e.,

while

presence

of

group

to the

to yield form with

1:2(Br2)

A1C13 gives

of

a l-arylarsabenzene-onium

The lrl

of

Only traces

iodide

formed

of

%AsMeX+ X3, where The acetylation

product

2-arylarsabenzene

which

the

K2C03, the

an alkyl

to

position

complexes

with

the

, 1 -aryl-4-methoxy-arsacycl

the As-aryl

Halogen

treated

[221]_

sol ution

from that

R

4-al

[222].

methyl-lo-phenoxarsine 2-acetyl

l-al

kyl-l-arsa-

derivative

koxy

loses

intermediate is

followed

a mole

of

probably

in which

by the

been

studied

1OSS Of

a

by

have trigonal

“molecular

bipyramidal

complex”structure,

methylarsenane by acetyl

and 2,8-diacetyl

are

product.

have

Cl2 and Br2 complexes

the

the

solution

The rearrangement

1-methylarsenane

has the

acetone

ohexadiene

Z-position

R3AsMe represents

the

is

the P-aryl-substituted

adduct

in

group.

chloride

derivatives

in the [224].

281 oxides

Because alkyl-10-phenoxarsine

of derivatives adducts

were isolated

From chemical like

and identified

formed with mineral

Dutch workers

acids,

I&Z.,

originally

evidence proposed

hold on to water,

in the form of

a number

the anhydrous

HCl, HBr and HClO [225]. 4

have reinvestigated

and spectral

structure

obtained

[226]

tenaciously

the structure

they conclude is incorrect

of “phenarsazine.”

that the aromatic,

anthracene.

and that the compound actually

is lO,lO’-SZs(Li,lO-dihydrophenarsazinyi).

Four-membered alicyclic

tertiary

arsines

ment of 3-chl oropropyl (methyl )iodoarsine

have been prepared

homologues,

Treat-

and 3-chl oropropyl (phenyl ) iodoarsine

with sodium in tetrahydrofuran yield l-substituted arsetans. manner, five-membered

[~2i].

l-substituted

In a similar

arsolans, are prepared from

4chlorobutylorganylarsines.

R = Ph, Me

R

arsetan

A similar

arsolan

ring

system,

between the diester amine is present

of malonic

as a hydrogen

R-A,sy-

I

(COOR)2-C -As-R

diarsacycl References

p_ 293

diarsacyclobutane,

( COOR)2

I

obutane

acid

has been prepared

and alkyldichloroarsines

chloride

scavenger.

by the reaction [228].

A tertiary

282 A number

ElJermann the

of

novel

arsenic-containing

and Schoessner

synthesis

[229]

of some metal

ring

have

utilized

carbonyJ

systems

have been

organotriarsines

introduced.

of type

B in

5,JO-Dihydro-5,1Gdimethyl-

derivatives.

octafluoroarsanthrene Me

-6

has been

prepared

[230]

by the

and diiodomethylarsine. As-P-N

Bhatia

used

and Jit

acid

azarsenine

E is

by cyclization

and Tillott

J ,2-di J ft;;iotetrafl

[23J]

have

with

System

LiAlH4’to

by the

anhydrous

the

oxarsenin

dfchloride.

prepared

by arsenic(V)

reported

cl ,z] (Q-

with

closure,

have

[2,1 ,c]

an intermediate

System

ring

[232,233]

by reduction

gives &

[1,23

between

(g)

alcohol

which,

The latter, reaction aluminum

phosphazene.

of 4-chloro-1,2,3,4-

and 6-chloro-5,6-dihydrodibenz

g was synthesized

the

a mixed -C. The

of linear

preparation

uorobenzene

reported

J,3,5,2A5,6A6,4A5-triaza-arsatriphosphorine,

involves

tetrahydronaphth [c,e]

Sorverby

heterocycJe,

reaction

reaction

from J-naphthyl-acetic on treatment

on distillation,

of AsC13 with

with cyclizes

2-aminobiphenyl

AsC13 to followed

chloride.

o&~s-cJ Qej? L!

-E

283

Aminoarsines structure

of the type As4(NMe)5NR, in which R = Me and having the adamantane

have been previously

preparation

of several

such derivatives [235].

of 9-(o-chlorophenyl)-9,10-dihydro-9-arsanthracene

acids

to give

a-(J-aminophenylarsino)-carboxylic (1)

involves

the has

cycliza-

biith Ziis(isopropy1)

o-aminophenylarsines

tetrahydro-1,4-benzazarsenine-2-one

Arsatriptycene

The new synthesis

tion

As-metallated

manner

has now described

in which R # Me.

synthesized

THF.

a novel

Kober [234]

been

N-Li+in

in

described.

react

with u-halocarboxylic

acids

which cyclize

to

’

[236].

P

blhen 1,2-diiodotetrafluorobenzene

and arsenic

evacuated, sealed tube at 300” for . ptycene is obtained [237]. P-Aminoethylarsines and

ketones

to yield react

to

yield

three

3 H-1,3-azarsolidines

with 2-aminoalkylarsines

(H) [239].

R’ -G

H2NCH2CH2AsHR f R’C(OR” ) = NH.HCT-

reactions

(G) [238]

with formation

11 S

E

together

in an

dodecafluoro-13,14_diarsatri-

undergo cyclocondensation

1,3-azarsolidine-Z-thiones

References p_ 293

days,

are heated

and with carbon

Iminoester of

vJ>th aldehydes

disulfide

hydrochlorides

1,3-azarsolines

(L)

C2401.

281 In a manner similar heterocyclic pared

to

systems

in

the

manner

that

just

having shown

but using

dEscribed,

an S-As-N below

heteroatom

thiolethanolamines,

distribution

have

been

pre-

[247]:

Ph I AS

PhNHCH2CH2SH

Refl

uxing

P41.

+ PhAs(OMeI2

--

from toluene gives the heterocyclic

G-HO(0)CC6H4AsC12

of

Kober

NPh

S

System

2.

and 0

Ri.ihl

[243]

have

aminoarsines r

having

and 8-10

/

investigated

the

synthesized

membered

reactions

a number

ring

of

of

alcoholamines

macrocyclic

and

esters

thioglycols

typified

w

by j$ and

systems.

GH2CH2-o\ As-CH3

““\,,,C,d I

K

Maroni ring

and systems

co-workers of

the

[244,245.246] types

shown

0 0

have

al so prepared

8-membered

heterocyl

by E and &_

\-0

\

N: LO’

-N

As-Me

ic

The crystal

structure

with the four R axially trigonal

oriented

[247]

vJith respect

bipyramidal

considerable

positions

investigated

trimethylsilyl

arsines

the to

(methylene)arsolenes-4

directly

In E 12451,

the structure

positions.

cycloaddition

of

pentadiyn-1,4-ones-3.

can be dehydrogenated

from the reaction

of phenylarsine

pair

occupy-

M;irkl and Hauptmann

phenylarsine reaction

to give

and yields

2-methylene-

disubstituted

PJhich undergo thermal electrocyclic

arsolenes

about As is

These papers include

This

PJith diphenylketene

and N and

electron

from dynamic NMRstudies_

radical

react

which

ing benzannelated

to As.

obtained

about arsenic

the square plane of the octahedron

and N and Me apical

information

arsolene-4-o&s-3

coordination

with the t.kJooxygen atoms and the free

have

lated

shokJs octahedral

oxygen atoms forming

equatorial

ing

of -PI [244]

2,3-5:s

reactions.

to arsoles

The result-

which can be iso-

PJith S-diphenylmethylene-

pentadienes-i,4. A considerable cyclic

arsenic

Samaan [248]

number of physico-chemical

the conformation

-.azarsenanium

salts.

The proton

oxazaarsolane

is very

sensitive

VJhich deal PJith hetero-

Using ‘H and l3 C NMRspectroscopy,

compounds have appeared. has determined

studies

and configuration

of 1,4-0x-

NMRspectrum of 2-dimethyl amino-3-methyl to solvent

effects

and temperature

spectrum was carefully analyzed and at -48" in perdeuterotoluene

exists

in a preferred

conformation

the spectrum corresponds about that bond.

temperatures

explained

in terms of inversion

[250,251]

have carried

cyclic

arsenic

out proton

compounds_

5-methyl-1,3,2-oxathiarsolane 1,3,2-dioxarsol tion

presence adequately similar sis

described

analysis

for

Geometrical the ring

the molecule

on the basis

has been carried

of flexible out for

phenomenon is

five-membered

has been reported

[25].

hetero-

and Z-phenyland

were identified

angles

in solu-

were obtained.

ring-puckering. twist-envelope

ten arsolanes.

at 31”

free rotation

of 2-chloro-5-methyl-

isomers

The

Aksnes and co-workers

of several

torsional

atom tends to increase

of 1-methylarsenane

References p_ 293

analysis

atom.

[249].

and 2-chloro-5-methyl-1,3,2_dithiarsolane

values

of the sulfur

NMRanalyses

A complete

ane was performed.

and approximate

a new coalescence

by the arsenic

1,3,2-

In nitrobenzene

in the C4-C5 region.

to that of an A2X2 system which indicates

At higher

and

The

The NMRdata are conformations.

A conformation

The barrier

to ring

A analy-

reversal

2S6 is 7.8 kcal.

mol

-1

The coa?escence

_

of activation is 6.8

kcal.

mol

indicate

the cyclohexane

in Arsaspirane

mined and correlated

structures

different

I-chloro-1,3,2_dioxarsenane

VJith respect

portions

to the shape of

“Polyhedral

Stereoisometry

[253]_

arsenic

compounds have been deter-

[254].

The infrared

and Raman spectra

The frequencies

modes of P-chloro-1,3,2_dioxarsenane for

the cL,? and c.y

entitled

have been measured [255].

with those observed

and the free energy

the axial and equatorial conformation

Systems” has appeared

of ti-relve cyclic

PJith their

of 1,3,2-dioxarsenanes

for

At -140”,

A Russian publication

75As NQR frequencies

vibrational

_

is -218”

a small but uniform puckering

chair.

and Pseudorotation

temperatute

The R value of 2.7 for

are about equally populated-

of the ring

-1

VJere calculated The preferred

conformations.

is that of the chair

and normal and compared conformation

form VJith the As-Cl bond

axial _ Kober [256]

has reported

on the effect

of the gases,

FIH3, methylamine and ethylamine

isobutane, by chemical

ionization

on the mass spectral

of 2-dimethylamino-1,3,2-diox-,

Ashe, et al _ , [257]

-dithiarsolanes.

energies first

photoelectron

spectrum of arsabenzene

in the region

-oxathi-

have measured the angular

dependence of band intensities in the photoelectron

The He( II)

I+,:, N2, Hz, acetylene,

from 17 to 20 eV.

fragments and and energy

spectrum of arsabenzene.

yields

The relarive

additional intensity

ionization changes in the

three bands. compared with their relative intensities in the He(i)

provide

support

in excellent The He(I)

for

the previously

agreement with those photoelectron

proposed predicted

sequence of states. from theoretical

spectrum of the heterocyclic

t

Y-

Y

I

I

formed

spectra,

The results

are

considerations.

system shown belopr

Z-BhNB-z

Y = N-CH3; Z = CH3; X = N-As(CH& has been recorded The crystal a heteroatom

and interpreted

structures

by Kroner

a number of heterocyclic

have been reported.

et al.

[258].

molecules

in which arsenic

1 ,1,3,3,5,5-hexaphenyl-1.3-diphospha-5-

is

287 arsatriazine

is a planar,

disordered

is planar,

except

As-C bond distance

for

dnd the transannular

1,4-As---O

investigated

[262].

reduction

that when small alkyl an irreversible,

Biochemical

XII -

of

to take place

played

effects

toxic

compound_

to display References

p_ 293

step

occurs

of phenyl and phenoxyl has been

measurements that the orienta-

salts

in aqueous solution

at arsenic,

[263].

the reduction

The reduction

in two single

of lo-methyl-

electron

steps.

bond in the side

The

chain

arsine.

Aspects

of Arsenic

problems together

by trace

elements

and represents

has reviewed

of arsenic Arsenic

and crustaceans

on enzymes.

conformation

Compounds

with a growing interest

has caused a veritable in this

area.

a relatively

in

explosion

The fol 1owing review modest fraction

of all

Vfhich have appeared.

genic

attributed,

chair

and the mean

[261].

the orientation

in the number of publications

Reeves [264,265]

fish

is 3.10 i

of the arsenic-carbon

a tertiary

is by no means comprehensive publications

has the

are substituted

and Environmental

role

rinq

of phenoxarsonium

iodide

Concern about environmental the biological

of

In the 2,6-dimethyl-

atom is tetrahedral

from these

one-electron

with rupture

formation

[260].

atom in 1,3,2_dioxaarsenanes

radicals

lo-cyclohexylphenoxarsonium

and the

is

is axial.

The electrochemical

occurs

arsenic

It is concluded

of both groups

reduction

distance

moment measurements,

on the trivalent

involves

the arsenic

A_ The six-membered

substituents

shows

The structure

of 1.790 A and an As-C bond distance

the methyl groups ion,

is 1.91

Using dipole

[259].

The 5,10-dihydro-5,10-dimethyloctafluoroarsanthrene

4,4-diphenyl-1,4-oxarsenonium

tion

AsNPNPNring

and two As-M bond distances

1.91 i are reported. molecule

six-membered

(compounds).

teratoqenic

He points

concentrations

(25-80

ppm)_

at the molecular Arsenic

the noncarcinogenic

level,

The toxic

effects

to chemical

in animals.

as the carcino-

out that As203 is not a highly.

reach relatively

(compounds not defined) effects

as well

high levels

of arsenic

reactions

in shell-

poisoning

with sulfhydryl

are groups

have been shown, experimentally, Evidence which incriminates

arsenic

2ss

is based

as a carcinogen

on epidemiologic

to induce neoplasms experimentally [266]

has also

the question

arsenicals.

In their

of arsenic

carcinogenesis

the mutation

Pel ft-ene

is unsettled_

induction

particular

and cancer.

capacity

bacterial

of

He concludes

that

Japanese biorkers [267]

166 pesticides,

studies

their

includin9

mutagenicities

five

were

detected.

Several [268].

acids

and their

Aryluroniumarylarsonates

display

nigicant

arylarsonic

antifungal

ethyl aryl arsines

and

antibacterial

salts

have been shown to be phytotoxic

high fungicidal

activity

been

has

activity

or arsenite) inhibitory thioctic

effect

on internal

gluthathione

Arsenic(II1)

into the circulating absorption

increase

and reach normal levels

MAAand OMAAdo not reach maximumlevels and return

to normal levels

about 50 percent

periods

arsenic(II1)

arsenic

48 hours.

percent _

After

Guinea pig, diphetarsone

After eight

principally that already

until

for

melarsoprol route

[274]

arsenic

of it

over

concentrations

of

in the form of As(V)

acetarsol,

excretion.

[274].

In the

tryparsamide

and

On the other

the arsenic

The results

has been published

and As(II1)

of As(V) was more than 95

and arsthinol,

[275].

ingested,

is a primary detoxification

of As( III) were detected

of the pharmaceuticals

ingestion

is excreted

to toxic

80 percent

and

However,

arsenic

14 percent

20 percent

the proportion

mainly in faecal

The As(IIE)

ingestion-

Of the total

Mice exposed

only traces

(DHM).

involv-

of As(III),

about 40 hours after

The remainin

four days,

by the biliary described

each.

days,

the case of melarsonyl,

such as dimercapro

levels

20 hours after

as OMAA. MAAaccounts

water excreted

administration results

acid

about 85 hours.

in man [273].

in drinking

A strong

(in an experiment

in urinary

This shows that methylation

of time.

mechanism for

after

is excreted

and As(V) about 8 percent, longer

ten

(arsenate

[271,272].

by thiols

ingestion

(MM) and dimethylarsinic

decrease

of arsenic

blood

was exerted

4-10 hours after

causes a five-fold

As(V).methylarsonicacid levels

for

and by glucoronolactone.

in wine,

ing a human subject)

As(V)

Sig-

[270] _

from the intestine

acid,

[269].

demonstrated

Japanese workers have measured the rate of transfer

after

been possible

in animals by the use of arsenicals.

the subject

of arsenic

have surveyed

not

reviewed

has not yet

It

studies.

hand, in

is eliminated

of a study very similar

by the same authors

[276].

to

One of the important isolation

breakthroughs

and identification

lobster

[277].

Crayfish

of arsenobetaine exposed

showed a concentration

factor

involved

phase involves during

Parris

of

its

the

from the Australian

containing

56 days of

[278].

20-30

days

slow

levels

to 1.0 pg/cJ [280-J. samples collected Unwashed plant

rate

of

Arsenic

oxidation,

foliage

arsenic

did not possess containing

soluble

distribution

soil.

has important

Benson [285]

of apple

trees

arsenic

in the

studied

et

seeds. of

and found that arsenic

that it

is of minor importance

factors

other

than arsenic

unless

of

that

in distilled

[284].

Only 0.2

the

soil

growth.

inhi bition

arsenic

that are acid

or The

of sodium methanepercent out

carbon-arsenic

the concentrations for

inorganic

was exuded

arsenic

near

was

water [2831.

application

does retard

are responsible

200

was grown

in yield

decrease

foliar

months,

the effect

When rice

of the soil

Twenty percent

three

within

grown in home gardens

reveals

portions

al.

[282].

about 30 times greater

concentrations.

in wheat following by Domir,

lead smelters

samples collected

a 50 percent

for

and soil

were 200 times above “normal_”

than that which dissolves

Over a period

intact.

arsenic,

of soils

studied

was found

In soil

from garden crops

amounts in those

of arsenic

has been

References p_ 293

because

considerable

in vegetable

concentrations

concentrations

abnormal arsenic

Analysis

rather

of two secondary

plants

100 ppm of

[282] _

the

can travel

This observation

was reported

urban backgrounds_

may be found in greater

into

that

have been found to vary from about 0.4

was found to possess

However, samples of edible

application

is

of Me3As by

They conclude

trimethylarsine

contamination

in the vicinities

meters of the smelters

arsonate

phase

have measured the rate of oxidation

in Indian tobaccos

than that of “normal”

alkali

uptake

implications_

Arsenic

reported

greater

phases of uptake were noted. and a second

distances without undergoing chemical change.

in soil

rock

the next 30 days.

relatively

smelters

(whole body)

oxygen in methanol and in the gas phase.

environmental

western

monosodium methylarsonate

3.7-3.8

Two distinct

first

and Brinckman [279]

atmospheric

to waters

after

than that of the environment An initial

in arsenic speciation has been the

of of bond

residues

the the

leaf roots

remained

on the growth

However, he concluded are very high and that of growth.

Sandhu [286] reservoir

resulting

defoliaticn. sible_

a fish

locations

residues

of arsenic

from 100 stations

throughout

in a

and cotton

was found to be irrever-

and soils

to those of the surrounding [288]

contents

v!eed control

vegetation

by the Department of the Interior obtained

for

arsenic

by the fish

in animal tissues,

have been related

prepared

ki71 to excessive

from the use of arsenicals

The bioaccumulation

Arsenic

in fish

attributed

habitat

tabulates

from different [287].

arsenic

A report

concentrations

the U.S.

Air samples have been found to contain inorganic arsenic, dimethylarsine and trimethylarsine,

but no methylarsine.

to the alkylated

forms Q88]_

The bio-transformation and importance_ _%eecZis

of arsenicals

Phillips

and Taylor

from raw sewage.

of arsenite

About 20 percent

is a topic

[289]

of considerable

have isolated

L290] have reported

to oxidize

that selenite,

of .GZzzZi_:z~:es

to the toxic

arsenite

selenate

contribution

to the function

biotransformations Sco~riZario~sis aerobically

of biological

has been made by Cullen,

and tellurate

methylating et al.

[291].

of -L-methionine-methyl+

adenosylmethionine

or a related

The existence

has been clearly

Several

sulfonium

of methylated demonstrated

papers describe

has been prepared for

arsenite

by Milovanov

the removal of arsenic

The selective

adsorption

and arsenate

Arsenic

A meaning-

in arsenic

compound is involved arsenic

[293].

compounds that s-

in the biological

compounds in western

rock

[292].

carbon,

ion-exchange

from its

A Russian patent

[294]

the incidence

describes

methods a pro-

with ore beneficiation.

gel impregnated with ferric

has been described

water solutions.

and precipitation

from water in connection

on silica

does not affect

This indicates

the removal of arsenic

A review on the use of activated

cess

inhibit

The microorganisms

and arsenic

incorporate CD3 into the evolved methyl arsine(s).

lobsters

agents

cox

~_B?nicazrZis, cc~zdidir ~W-I~COZCI and CZiocZad%~~ TosezLq when grown

in the presence

methylation-

effects

to arsenate.

the conversion of arsenate to trimethylarsine by rmd7Jdn hmic~Zaful

is converter

interest

13 strains

These organisms are resistant

up to 0.01 -M and they are able

and Alexander

of the arsenic

hydroxide

of

[295-j. of white muscle disease

in ewes [296-j_

291

--Industrial

XIII.

Applications

The rate constant

and Miscellaneous

for- the reaction

estimated

to be 3 x 10 -3 M-l *ec-’

following

a single

The sensitivity

to soil

soybeans>potatoes>cottonthe increase

concentration

used,

centrations.

The arsenic

Core level

arsenic

It was concluded Auger chemical

contents

energies

energy

Fe(III)

by extracting

2-ethylhexanol

were not affected

at all

three

seldom exceeded

to adsorb

adsorbent

energies

and organic

have been

derivatives

from binding

iodide.

with lithium

associated

with extra

aqueous solutions

Arsenicals

arsenic

energy

followed

atomic

relaxation.

from

by c_tis(+butyl)phosphate

as an ion-exchanger of a Russian patent

to the epoxides

acid

groups,

in

is catalyzed

I 1 meq/g fiber, [302].

divinylbenzene-styrene

by quaternization

compounds have found use in the conversion

[303].

Arsonium copolymer

with methyl

The ion exchanger

[304]. applications.

The oxidation

by Ph3As(OH)2 [305]. of olefins

has been found to catalyze

of

Other

to the epoxides;

As, As205, AsC13, Ph3As and PhAs03Hp [306].

[(C5H5)2C1As]2PtC12-SnC12

References p_ 393

and

by Zs(E-octy7)arsinic

LIOF, has been prepared

have found a number of catalytic

they are Asp03, As(OEt)g, complex,

e.g.,

dialkylarsenide

is the subject

a number of alkenes arsenic

aqueous solutions

on a chloromethylated

The polymer functions

described

[299].

independent of coordination number, independ-

containing

heavy metals,

groups have been introduced treated

twice

MSMAlevels.

changes derived

from its

from its

con-

[301].

A polymer fiber and able

it

to

but were reduced at the highest

and L;x.! Auger transition

and are predominantly of

yields

portions

inorganic

snap beans>rice

were proportional

were unaffected

the edible

and a number of its

seasons

in chloroform has been investigated [300]. Arsenic can be seoarated

copper

just

22 and 45 kg/ha,

even at the highest

energy shifts are:

The extraction

in the order:

of snap beans and rice

of

three

of MSMA[CH3As(0)(OH)ONa] [298].

decreased

Cotton yields

that relaxation

ent of bond type

acid

used,

controls,

binding

Crops were grown for

Soybeans and potato

2C9 kg/ha.

the untreated

measured for

arsenic

in MSMAapplication. concentrations

(CH3)3A~ with CH31 in water has been

application

The yields

at the lowest

that of

[297].

soil-incorporation

of crops

of

The platinum

the homogeneous

292

carbonylation

of u-olefins

of a nickel catalyst

salt

for

the trimerization

electrochemically moted

by the

salts

function

isocyanates

use of

arsonium

reaction

by the reaction

catalyst

of olefins

the preparation

in

as catalyst

during

and a thiol

[313]_

the binding

of glass

esters

Alkoxides fibers

by the reaction

of arsenic

the manufacture

like

in peptide

synthesis

[317]

describes

are resistant

dithiarsetanes

are claimed properties

[Ph2(p-PrC6H5)2As]C104

as a plant

by-products,

to bacterial to possess [319].

useful

Arylarsonium

residues

A Russian patent

describes

the preparation

with tribromoarsine [321].

salts

l-phenyl-2,5Cotton

lO,lO’-oxyj
nematocidal

such as

to suppress

fog formation

of AlBr3-oleum

of AlC13 together

due to

in the manufacture of

of bromobiphenylenearsine

in the presence

In the presence

fungicidal,

and the like

[320].

oleum catalysts

having

Hydrazono-1.3,2-

herbicidal,

are used as antifoggants catalyst

components,

growth [3181_

emulsions

biphenyl

Com-

NH2 and OH groups

growth regulator.

among other

halide-gelatin

heating

[314].

Arsonium salts

the use of the heterocycle,

dipped in a mixture which contains.

impurities,

resins

in

and have been used

streams [315].

methyl iodide

(phenoxarsine)

silver

and thermosettinq

agents

[316].

dimethyl-4-arsacyclohexanone

and insecticidal

as a catalysl

of al kenes or al kynes with CO

Ph3AsiCH2CH202CC1-Cl- cab be used to protect

A Russian patent

gloves

of aldehydes

functioals

to complex with olefins

to separate complexable ligands from feed

and

[312].

have been used as coupling

to elastomers

pounds of the type R3AsCuX are able

structures

stabilizers

with CO and Hz over rhodium catalysts

of thiol

organic

compounds of the type R3Fl, where

function

stabilization

of

with organic halides in

cyanates

Group,

pro-

Tetraphenylarsonium

A complex which forms between PdC12 and triarylarsines in the preparation

a

The

[309]_

is most efficiently

[310].

catalysts

Organoarsenic

alkoxy or phenoxy

,

of styrene

water-soluble

systems [311].

the need for

eliminate

of

such as Bu3As produces

of a French patent

as electrolytes

transfer

The reduction

[307].

to H,C=Cf+e(CHZ)3Cl.re=CHCH2CH2C(=CH2)Ctf=

the subject

salts

and esters

of a ligand

polymerization

as inter-phase

two phase liquid aryl

acids

of isoprene

is also

initiated

by the

,

carboxylic

with Et3Al in the presence

The catalyst

CH8 [308].

R = alkyl

to

by

or SnCl4-

with SnC14 and/or

oleum,

293 the

reaction

The

reactions

presence Another

of

of

of

The subject

oieum

Co.

In

sorbent

the

and ether

[324]

as of

biphenyl with

from

publication

the

20

trioxide gives

the

waste

[325]

case,

contains

9-chlorobiphenylenearsine

one

between

[322].

100-260”

in

lo-chlorophenoxarsine just

presented

the

[323].

but

describes

the

component.

arsenic

latter

agent

parallels

another

describes

yields arsenic

a chlorinating

patent

one

Development [326-J.

as

removal of

AsCl-

diphenyl

AlC13

Soviet

addition

The

between

and

waters a patent

removal the

of

is

Pb and

issued

arsenic

arsenic

percent

by electrolytic

from

removed

has

to

coagulation

the

Gulf

gaseous

Research

density

the

and

hydrocarbon

by PbO supported

a compacted

is

streams

on Al,03.

of

-

0.084

g/cm

3

.

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