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The Science of the Total Environment,

6 (1976) 15-29

© Elsevier Scientific Publishing Company, Amsterdam --

Printed in Belgium

THE

O.F BROMOBIPHENYLS*

SYNTHESIS AND

GAS CHROMATOGRAPHIC PROPERTIES

G. SUNDSTROM

and O.

HUTZINGER

Laboraton" t?l Env#onntental Chemistr) ~, University oJ Amsterdam, Nieuwe Achtergracht 166. Amsterdam (The Netherlands)

S. SAFE

Department

q/Chemistry,

University oJ Guelph, Guelph, Ontario (Canada)

V. ZITKO

Environment Canada,

New Brunswick (Canada)

(Received November 24th,

Fisheries and Marine Service Biologk'al Station St. Andrews,

1975)

ABSTRACT

Bromobiphenyls constitute a group of chemicals used extensively as flame retardants in textiles, etc., the environmental fate of which is not known. For a thorough insight into the chemistry, analysis and toxicological and biological ef- fects access to pure bromobiphenyl isomers will be of great value. Literature on bromobiphenyl syntheses have therefore been compiled and, in addition, a num- ber of new compounds have been prepared and characterised. The gas chroma- tographic behaviour of bromobiphenyls is also described.

INTRODUCTION

Polybrominated biphenyls (PBB) have recently attained a certain interest by environmental chemists and biologists t-s. This interest is based on two facts: (i) the structural similarity to the classical environmental pollutant PCB (polychlo- rinated biphenyls), and (ii) the PBB's -- together with some other organic bromo compounds -- seem to be extensively used as flame retardants for polymers, tex- tiles, etc., as judged from trade literature and the numerous patents issued since 1960. No figures for the production or use of PBB's have been published but it is most likely that they will be lower than those for the PCB's. PBB's on the oth- er hand are generally more highly halogenated (five or more bromine atoms per

* Environmental Chemistry of Flame Retardants 111, for part I1

~f

ref.

10.

TABLE 1 KNOWN BROMOBIPHENYLS

Name

Structure

m.p. (°C)

 

Synthetic route

Ref

Br

2-

~~"~

b.p.

297-98 (760)

l-b

37

 

160

(11)

38

114

(1.5)

39

114

(2)

51

296-98 (760)

 

54

--

1-d

72

--

73

78.79 (0.01)

2-c

92

 

5

 

Br

3-

/'~-~

~--~

b.p.

158-167 (11)

1-C

55

 

104

(0.2)

56

177

(4)

57

299-301

2-a

76

169-173 (17)

77

--

4

101

 

5

l-a

12

4-

Br~

90.5

16

 

17

18

 

1 -b

30

1-d

71

2-a

76

 

78

79

80

81

82

 

2-c

88

 

93

 

3-c

98

4

99

 

101

 

5

 

Br

2,4-

B_,/~---~ ~

b.p.

235 (15)

1-c

50

 

174-176 (7)

64

125

(2)

2-a

63

oil

2-b

this work

 

Br

2,5-

b.p.

171 (15)

1-b

43

 

oil

2-b

this work

 

m.p. 40--42

2-c

91

 

Br

2,6

69.5-70

2-b

this work

16

TABLE 1 (continued)

Name

Structure

m.p. (°C)

Synthetic route

Ref

8r

3,4-

Br /~

~--'x,

b.p.

192-195 (5)

1-b

44

 

215 (15)

50

oil

2-b

this work

 

Br

3,5-

r~~

b.p.

208 (15)

1-c

43

 

m.p. 15

61

 

42

62

 

63

 

9~

2,2'-

~

81

1-a

24

 

1-b

40

 

41

52

 

l-c

40

3-b

95

4

58

5

 

Br

2,Y-

~

b.p.

165-168 (3)

1-c

45

 

Br

 

Br

2,4'-

(~~

 

l-b

42

 

Br

56

1-c

69

 

2-c

89

 

Br

3,3'-

1-C

59

1-e

74

 

Br

75

 

53

3-a

94

 

Br

3,4'-

b.p.

175-177 (3)

1-c

42

 

135-140 (1)

60

t38-140(0.5)

2-c

89

4,4'-

Br~Br

 

l-a

13

 

164

14

 

15

 

164

16

162

19

163-164

20

 

21

22

23

24

25

 

162-164

26

162-163

27

 

1-b

53

(continued on p. 18)

17

TABLE

Name

235

2,4,6-

2,4,4’-

2,2’,5-

2,3’,5-

2,4’S_

2’$,4-

18

1 (continued)

Slruclure

Br

Br

w

00

n1.p.

PC)

Synthetic route

ReJi

168-169

3-b

95

161-162

96

 

97

 

-

3-c

98

163

4

100

 

5

 

225-227

I-C

45 (46)

 

1-c

50

2-b

this

work

2-c

90

 

65-66

3-a

48

-

l-a

28

81

l-b

30

77-78

l-b

48

 

2-b

this

work

b.p.

213-216

(6)

l-b

48

oil

2-b

this

work

 

l-b

47

 

77-18

48

 

2-b

this

work

 

91

l-b

41

 

l-a

28

I-b

45 (46)

 

68-69

1-c

65

TABLE

1 (continued)

 

Name

Structure

 

3,3',5-

~

Br

3,4',5-

Br

 

Br

4,4',X-*

Br~Br

 
 

Br

 

Br

Br

2,3,4',5-

~~.

 

2,4,4',6-

Br~Br

 

Br

2',3,4,5-

Br

2,2',4,4'-

Br

Br

 

Br

2,2',4,5'-

~

2,3,4,4 ' ' -

8r

r

 

Br

2,2',5,5'-

~

Br

Br

m.p. (°0

Synthetic route

112-113

l-b

1-b

102-103

1-C

90

1-a

127

1-b

105-106

1-C

135

l-b

273

1-b

84-84.5

2-b

124-125

1-b

143-144

2-b

(210--211)

3-c

ReJ:

48

45 (46)

48

29

45 (46)

48

45 (46)

3O

this work

30

this work

98

(Continued on p. 20)

19

TABLE 1 (continued.)

Name

2,3',4',5-

2,2',5,6'-

3,3',4,4'-

3,3',5,5'-

Structure

,,'~--~/~-'XBr

Br

~

)-=-,

Br

~r

~

Ur

Br~Br

Br

Br

Br

2,2',6,6'-

2,2',4,5',6

Br

Br

Br

Br

penta

industrial preparation

2,2',4,4',6,6'-

Br

e-

,

,

,

3,3,4,4,5,5-

B~-=--x

---~Br

~-~Br

Br

Br

Br

Br

2,2',3,Y,5,5',6,6'- ~r

20

m.p. (°C)

Synthetic route

Ref.

113-114

2

this work

132-133

2

this work

169

l-b

49

1-c

46

 

49

67

68

188-188.5

this work

215

1-c

66

125-126

2-b

this work

1-a

36

1-b

49

248-249

this work

TABLE 1 (continued)

Name

Structure

m.p. (°C)

Synthetic route

Re/'.

octa

industrialpreparation

365-367

l-a

32

 

34

35

 

D

33

nona

industrialpreparation

--

l-a

31

deca

industrialpreparation

378-379

l-a

32

 

34

35

31

* The most likely structure is 3,4,4'-tribromobiphenyl.

molecule) than the PCB's which may result in high accumulation rates in lipids, should these compounds be released into the environment. The high bromine content will likewise probably result in a low rate of degradation via metabolism. The degradation of PBB's by UV-radiation, however, will be faster than for the PCB's--a result of the weaker C-Br bond strength--as has been shown by Zabik and Ruzo t. PBB is manufactured analogously to PCB by bromination of biphenyl with elemental bromine in the presence of a catalyst. The composition of the very complex mixtures of compounds obtained by direct chlorination of biphenyl is well known 9 today while no information for the composition of PBB preparations is to be found. Investigations in this laboratory have shown that PBB mixtures are surprisingly simple in composition, the higher brominated ones containing only few major components 10(see below). There are two main manufacturers of PBB's, Chemische Fabrik Kalk GmbH, Germany, and Michigan Chemical Co., U.S.A., which uses the trademarks Bromkal and FireMaster, respectively, on their products. The acute toxicities of PBB's are low and LDs0 values larger than 21 g/kg for a hexabromobiphenyl-preparation have been reported for rats (from Michigan Chem. Co. as cited in ref. 5). Severe poisonings of cattle, hogs, sheep and chick- ens have occurred in the U.S., when they were fed PBB's by accident) 1 The PBB's were later found also in the blood of farmers which came into contact with feed contaminated with PBB. This severe accident, which was caused by an ex-

change of bags containing magnesium oxide (manufactured by the same com- pany) for bags filled with the fire retardant, has already cost 11.5 million dollars. Investigations by Strik have shown that hexabromobiphenyi preparations, similar to the well-known environmental pollutants HCB (hexachlorobenzene) and PCB, induce hepatic porphyria in birds 2-3.5. The toxicity and some other bio-

logical effects of

bromobiphenyls have also been studied 4,6-s.

21

TABLE 2

RELATIVE RETENTION OF BROMOBIPHENYLS

Compound

TIMES AND ELECTRON-CAPTURE

4'/,,

SE-30

relative *

ret.

little

response

RESPONSES

3'/,

0~-210

relative **

ret.

lime

response

2-bromo-

0.11

0.079

D

3-bromo-

0.17

0.099

4-bromo-

0.18

0.239

m

2,4-dibromo-

0.34

0.660

0.05

0.712

2,5-dibromo-

0.32

0.831

0.03

0.818

2,6-dibromo-

0.27

0.637

0.01

0.807

3,4-dibromo-

0.51

0.458

0.08

0.634

2,2'-dibromo

0.27

0.099

0.02

0.125

4A'-dibromo-

0.55

0.567

0.08

1.21

2,4,6-tribomo-

0.63

1.06

0.05

3.26

2,2',5-tribomo-

0.64

1.24

0.08

1.98

2,3',5-tribomo-

0.90

0.441

0.13

0.585

2,4',5-tribomo-

0.94

0.628

0.13

0.996

2,2',4,5'-tetrabromo-

1.63

0.633

0.22

0.818

2,2',5,5'-tetrabomo-

1.53

0.661

0.19

0.879

2,3 ',4',5-tetrabromo-

2.50

0.577

0.40

0.717

2,2',4,4',6,6'-hexabromo-

--

--

1.13

1.26

3,Y,4,4',5,5'-hexabromo-

--

--

3.61

0.495

~' p,p'-DDE=I.O0.

~* Decachlorobiphenyl= 1.00.

With the exception of the above example no reports on the presence of bromobiphenyls in environmental samples have appeared, although a release of PBB's via sewage, household wastes etc. must be considered very likely. In analogy with the PCB research investigations on the composition of PBB preparations as well as a thorough insight into the chemistry, biological ef- fects, distribution, degradation, etc. will require the access to pure bromobiphenyls of defined structure. We have therefore compiled published data on the synthesis of pure bromobiphenyls and, in addition, synthesized some new compounds (see Table 1). The methods used for the synthesis of chlorobiphenyls of known struc- ture should generally be applicable also for the bromine analogues. Some limita- tions are the higher costs of bromine compounds as compared to the chlorine analogues and that only a few aromatic bromo compounds useful as starting ma- terial for synthesis are available commercially. It is also evident that in some reac- tions, like the Gomberg-type coupling reaction of aromatic amines with aromatic substrates via decomposition with organic nitrite esters, bromoanilines give lower

22

yields than the chloroanaiogues in couplings with, e.g., 1,4-dihalobenzenes, which may be due to a greater steric hindrance imposed by the bromine atom. The different types of reactions used for bromobiphenyl syntheses will be briefly discussed below. For a general survey of synthetic methods potentially useful for bromobiphenyls we refer to the review on the synthesis of chlorobi- phenyls, chlorobiphenylols, chlorodiphenylamines and several other biphenyl systems in ref. 9 (Ch. 3-5 and 13). Many of the reactions below will not be useful for a large-scale synthesis, but are included for completeness only.

1. FORMATION OF BROMOBIPHENYLS BY DIRECT SUBSTITUTION ON THE PREFORMED BIPHENYL SYSTEM

a. Direct bromination of biphenyl

This reaction is a useful preparative route to 4-bromo- and 4,4'-dibromo- biphenyl. The brominations may be performed in a number of different solvents or solvent systems like CS2t2-15, HNO3-HOAc-H2SO416, CC1417'Is, H~O 19'2°, HOAc 2t, H2SO2 2, ether 23, fuming H2504---CC1424and liquid SO225. Surprisingly,

one of the most successful syntheses of 4,4'-dibromobiphenyl (95 % yield) is based on the reaction of solid biphenyl with bromine vapours 26'27. Except for elemental bromine only N-bromosuccinimide seems to have been used as a bromine

catalysts, when used, are the usual ones for electrophilic aromatic

substitutions, namely, FeCI3, FeBr3, AICI3, iron or iodine. A very selective ca- talyst for monobromination of aromatics--thallium (III) acetate--was recently des- cribed by McKillop et al. TM. The use of beryllium as catalyst for the synthesis of 4,4'-dibromobiphenyl has been reported 23. No investigations on the course of the direct bromination of biphenyl have been done but this is obviously a more selective reaction than the chlorination, e.g., electrophilic chlorination of biphenyl in HOAc at 25°C gives a mixture of 2-chlorobiphenyl (53 °/6) and 4-chlorobiphenyl (47 96) (for further figures cf. ref. 8, Ch. 3). Only minute amounts of brominated byproducts such as 22'-dibromobi- phenyl (<5 %)24 and 2,4'-dibromobiphenyl (1.8 %)'~ have been detected in the synthesis of 4,4'-dibromobiphenyl. A patent describes the formation of a mixture of 3,4,4'- and 2,4,4'-tribromobiphenyl upon bromination of biphenyl, 4-bromo- or 4,4'-dibromobipheny128. The formation of a compound 4,4', X-tribromobiphenyl, m.p. 90°C, formed from bromination of biphenyl have been reported 29. This m.p. is not consistent with 2,4,4'-tribromobiphenyl (m.p. 81°C 3°) and in ref. 28 no m.p. of the 3,4,4'-tribromobiphenyl described was reported. Direct bromination of biphenyl is also the reaction used for industrial pro- duction of PBB formulations which mainly are of high chlorine content. Although some PBB's seem to be produced by brominating pure anhydrous bi- phenyl3J--analogously to the PCB production--the PBB's are often obtained in the presence of a solvent such as concentrated sulphuric acid32,33,fuming sulphur-

source ~7. The

23

ic acid 34, or even oleum 35. Pentabromobiphenyls can be obtained by bromination of biphenyl in carbon tetrachloride solution according to a patent 36. The narrow range of the melting point of industrially prepared octabromo- biphenyls, 365-367°C 32.34,35, indicate that these preparations are fairly uniform in composition, containing one major compound only. This assumption is also sup- ported by the observations above on the high selectivity of bromination.

b. Sandmeyer and related reactions

The ortho-para directing and activating influence of amino groups in elec- trophilic aromatic substitution reactions have been utilised in several syntheses of bromobiphenyls. The aminobiphenyls can be selectively brominated with a cal- culated amount of bromine in which the amino group--or groups--may be sub- stituted for another bromine atom (Sandmeyer etc) or removed via diazotation (see below). For bromobiphenyl syntheses both the usual Sandmeyer procedure-diazo- tation and treatment with copper (I) bromide 3°,37-5°,as well as the modification us- ing solid biphenyldiazoniumfluoborates with iron (III) bromide in dimethyl sulfox- ide have been used St. Schwechten used a mixture of HgNO3-KBr in a Sandmey- er-like synthesis of 2,2'-dibromobipheny152. Two of the very first syntheses of bromobiphenyls, 2-bromo- and 4,4'-di- bromobiphenyl, were performed via decomposition of "diazoperbromides ''53,~, this reaction was later thoroughly investigated by Turner et al. (ref. 30 and papers cited therein) and used for the synthesis of some useful intermediates for the further preparations of tri- and tetrabromobiphenyls3°. The nature of the interme- diate in this type of reaction, a salt between a diazonium ion and B~ ion, and the structure of the products formed, which is mainly the result of direct sub- stitution of the diazonium groups for bromine (see ref. 30), justifies this reaction to be included.

c. Removal of amino groups

After taking advantage of the directing properties of the amino group, or groups (see above), they may be removed by diazotation and treatment with e.g., ethanol or hypophosphorous acid. Also this general aromatic reaction have been utilized extensively for the synthesis of bromobiphenyls4°.42,45,.6,~-5°.55-69. We have, however, in this work successfully used the recently described deamination procedure involving diazotation with organic nitrite esters in boiling tetrahydro-

furan 7° when repeating, e.g., Roosmalen's synthetic work

on bromobiphenyls 49.

d. Replacement of other substituent groups Jbr bromine

4-Bromobiphenyl have been obtained upon replacement of the sulphonic acid group of 4-biphenylsuiphonic acid for bromine with copper (I) bromide (low yield)7~. Treatment of 2-hydroxybiphenyl with phosphorus (V) bromide in tetra- chloromethane have been reported to give 2-chlorobiphenyF2,7J.

24

e. Miscellaneous reactions

3,Y-Dibromobiphenyl have been obtained by desulphonation of Y,5-dibromo-2-bi- phenyisulphonic acid 74 or decarboxylation of 5,5'-dibromo-2,2'-biphenyldicarboxy- lic acid75.

2. FORMATION

AROMATIC

OF

BROMOB1PHENYLS

SUBSTRATES

BY PHENYLAT1ON

OF

a. Gomberg-Bachmann and related reactions

In their original paper Gomberg and Bachmann described the synthesis of

3- and 4-bromobipheny176 and this type of reaction has been repeated later in the literature for bromobiphenyl synthesis 63,77,7s. Hey et al. also described the synthe- sis of 4-bromobiphenyl by a modification of the original procedure79.

The reactions described by Bamberger in 1895-1896 between "bromodia- zobenzolkalium" and benzenes°,sl and later between N-nitroso-p-bromoacetanilide and benzene in tetrachloromethane s2 which both yielded 4-bromobiphenyl must be considered as early Gomberg-Bachmann type reactions.

b. Arylation via diazotation with organic nitrite

A very convenient one-step procedure for the synthesis of biphenyl

systems utilises the decomposition of aromatic amines by treatment with organic nitrite esters in an excess of an aromatic substrate s3,~. This one-pot reaction has been extremely useful for the synthesis of both chlorobiphenyls and methoxy- chlorobiphenyls in our laboratories s~7. We have used the reaction also for the

synthesis of- a number of bromobiphenyls

by coupling of bromoanalines with ben-

zene or 1,4-dibromobenzene, which both due to the symmetry of the molecules gives only one easily isolated product (for isolation and purification procedures, e.g., cf. ref. 85).

c. Miscellaneous homolytic arylation methods

Some bromobiphenyls have. been obtained via well-known phenylation reactions like the oxidation of phenylhydrazinesss or decomposition of diazoami- nobenzenes s9 in the presence of a suitable aromatic substrate. Homolysis of 2,4,5- tribromosulphonylchloride in benzene give 2,4,6-tribmmobiphenyl according to a patent 9° and the reaction applied to benzenesulphonylchloride in 1,4-dibromoben- zene gives 2,5-dibromobipheny191. 2-Bromobiphenyl has been synthesised by de- composition of 2-bromobenzoylperoxide92. The formation of 4-bromobiphenyl from decomposition of phenyldiazoniumchloride in the presence of 4-bromo- phenylmagnesiumbromide might also be included in this paragraph 93. It should be kept in mind that all coupling reactions under 2 (except the last mentioned, ref. 93) may give rise to isometric mixtures which may be hard to separate if the selection of starting materials is not properly made.

25

3.

OTHER ARYL CONDENSATION REACTIONS

a. Ullmann

reaction

In his classical paper Ullmann describes the.synthesis of 3,Y-dibromobi- phenyl from 3-bromoiodobenzene94. Only one other bromobiphenyl, 2,4,6-tribro- mobiphenyl, has been successfully synthesised by this method (mixed Ullmann reaction)48 and it has in some cases been reported that bromoiodobenzenes give inseparable mixtures of compounds in the Ullmann reaction (e.g., ref. 30).

b. Condensation

via organometallic intermediates

Gilman and Gaj synthesised 2,2'-dibromobiphenyl (74 % yield) by coupling

of 1,2-dibromobenzene with butyllitium in tetrahydrofuran95. Analogously 4,4'-di-

bromobiphenyl was synthesised in a 21%

tions have been used for the synthesis of 4,4'-dibromobiphenyl: decomposition of

bis-4-bromophenyl-mercury in the presence of nickel or palladium 96 and decom- position of 4-bromo-phenylmagnesiumbromide with acid (low yield) 97.

yield95. Some odd organometallic reac-

c.

Miscellaneous condensations

The

pyrolysis experiments with

bromobenzenes by Meyer and

Hofmann 98

were reported to yield a number of bromobiphenyls. The structural assignment of their compound m.p. 210-211°C to 2,2',5,5'-tetrabromobiphenyl must most li- kely be reevaluated. An independent synthesis of this compound by us showed the m.p. 143-144°C and spectral data (NMR) support the structure given. The same authors also described a dibromobiphenyl of unknown structure with m.p. 117°C formed by pyrolysis of 1,4-dibromobenzene. None of the later synthesised dibromobiphenyls shows physical data similar to their compound.

4. MISCELLANEOUS BROMOBIPHENYL SYNTHESES

Aromatisation reactions with bromine of partially hydrogenated systems

have given rise to 4.99 and 4,4'-dibromobipheny1100.

bromophenyltropylium ions have given good yields of the corresponding mono- bromobiphenyls 101. Finally, treatment of biphenylene with bromine in water re- sults in the formation of 2,2'-dibmmobipheny158

Ring-contraction reactions of

5. COMMERCIALLY AVAILABLE BROM1BIPHENYLS

The isomeric monobromobiphenyls 2,2'-dibmmo- and 4,4'-dibromobiphenyl are available commercially (e.g., Chemicals Procurement Laboratories, Inc., Fluka AG). Impure preparations of 2,2',4,4',6,6'-hexabromo- and 2,2',3,Y,5,5',6,6'-octa- bromobiphenyl is supplied by Aldrich Chemical Co., Inc.

In Table 1 only one melting point (the highest one reported) is given if the variations are not more than 2-3°C, melting points dividing more than 2-3°C

26

are listed separately. However, the m.p. given is always taken from the reference

all published boiling points are given.

on the same line. For liquid compounds

RETENTION TIMES AND ELECTRON-CAPTURE DETECTOR RESPONSE

FOR SOME BROMOBIPHENYLS

The synthesised bromobiphenyls were investigated as to their gas chroma- tographic properties using electron capture detection by the methods previously described for chlorobiphenyls~%

with a 6 ft.4 mm glass column con-

A Packard A7901 gas chromatograph

taining 4 % SE-30 on acid washed Chromosorb W, 100-120 mesh or a 2 ft.4 mm column containing 3 °/6 OV-210 on Chromosorb W, 60-80 mesh were thereby used. Column temperature was 200°C, detector (3H) 210°C and carder gas flow (nitrogen) 80 and 60 ml/min for the SE-30 and OV-120 column, respectively. Res- ponses and retention times are given in Table 2, and are calculated relative to p,p'-DDE and decachlorobiphenyl. As expected both retention times and responses increase with increasing bromine content, however, more material of high-brominated compounds has to be investigated before any conclusions can be made about the trend for bromo- biphenyls beyond tetrabromo compounds. From preliminary investigations of technical PBB mixtures it seems as if the responses increase very little or even

decrease. Decomposition of the compounds in the gas chromatograph is a possible cause for this phenomenon and will be further investigated.

ACKNOWLEDGEMENTS

This work has been supported by Environment Canada (S.S.) A travel grant from Wallenbergstiftelsens Jubileumfond to one of us (G.S.) is gratefully acknowledged.

REFERENCES

1 L. O. Ruzo and M. J. Zabik, Bull. Environ. Contam. ToxicoL, 13 (1975) 181.

2 J.

3 J.

4 J. J. T. W. A. Strik, Meded. RijksJac. Landbouwwetensch., Gent, in press.

5 J. J. T. W. A. Strik, Experimentele leverporlj,rie bij vogels, Thesis, Institute of Veterinary Pharma- cology and Toxicology, State University, Utrecht, The Netherlands, t973 (in Dutch).

6 H. C. Cecil, S. J. Harris and J. Bitman, Arch. Environ. Contam. Toxicol., 3 (1975) 183.

7 J. M. Norris, R. J. Kociba, B. A. Schwetz, J. Q. Rose, C. G. Humiston, G. L. Jewett, P. J. Gehr-

J.

J.

T.

T.

W.

W.

A. Strik and

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