Introduction of water -solubilizing groups into some organometallic compounds

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MIRQEJCTIOH OP ?iAIEft-SOiiJBILIZI»3 GROUPS IHTG SOME ORGAIJQMKTALLIC COMPGOiaJS

*y

R obert H a ls Leeper

A T hesis Subm itted t o th e G raduate F a c u lty f o r th e Degree o f DOCTOR OF PHILOSOPHY M ajor S u b je c tt

O rganic C hem istry

Approved*

l a Ctea^ge o f M ajor Work

$ead o / l^ajo r D epartm ent'

Dean o f G raduate C ollege Ie e a S ta te C ollege 1942

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UMI Number: DP12816

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TABUS OP CONTENTS

INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2

r4pb

3

COMPOUNDS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . G eneral D isc u ssio n o f R.Fb Compounds . . . . . . . . . . . . . . Methods o f P re p a rin g R^Pb Compounds .................. R eactio n s o f lead-aodium a llo y s w ith o rg a n ic h a lid e s R e a c tio n o f sodium* o rg a n ic h a lid e * and le a d c h lo rid e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . R ea c tio n o f m e ta lli c le a d w ith a lk y l io d id e s . . R ea c tio n o f le a d c h lo rid e w ith a n a c tiv e .............. o rg a n o m e ta llic compound O rganosinc compounds . . . . . . . . . . . . . . . . . . . . . . . O rganolithium compounds .......... Organomagneeium h a lid e s . . . . . . . . . . . . . . . . . . . . R eao tio n o f h y d ra s in e s u l f a t e and o rg an o lead h a lid e s ............ B le o tr o ly tic re d u c tio n . . . . . . . . . . . . . . . . . . . . . . . . p y r o ly s is o f a pluabonio a o id . . . . . . . . . . . . . . . . . F ree r a d ic a ls and m e ta llic le a d .................

9 10 10 10

ffiy sic a l-C h e ia lc a l D ata Table 1 . R^Fb Compounds . . . . . . . . . . . . . . . . . . . . . . . . . .

10 13

SgR’P b, RgR’gPb* R2 R*S"Pb, AND RR*S»R*“Pb COMPOUNDS . . .

15

G eneral D iscu ssio n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Methods o f P r e p a r a t i o n .......... la lo g e n o r hydrogen h a lid e cleav ag e fo llo w ed by r e a o tio n w ith an a c ti v e o rg a n o m e ta llio compound . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The r e d i s t r i b u t i o n r e a c tio n D e o arb o x y latio n o f o rg an o lead s a l t s o f o rg a n ic a c id s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Table 2 . RgS*Fb Compound* . . . . . . . . . . . . . . . . . . . . . . . . Table 3 . RgBAFb Compounds . . . . . . . . . . . . . . . . . . . . . . . . Table 4 . RaB*Snl b Compounds . . . . . . . . . . . . . . . . . . . . . . Table 5 . BR*Bn&nPb Compounds . . . . . . . . . . . . . . . . . . . . .

15 16

0$

3 3 6

€ 7 7 7 7 8

16 18 19 21 28 31 S3

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iii. Page

•mmHm

RjPbX, BgR’PbX, RR‘ RnPbX, ^ P b X g , AHD RH'PbXg COMPOUHDS . .

34

G en eral D isc u ssio n « . . . ............. . . . . . . . ............ . . . . . . . . . . . P h y sic al-C h em ic a l Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Methods o f P r e p a ra tio n R eaotion betw een h a lo g e n o r hydrogen h a lid e and a n o rg an o lead compound . . . . . . . . . . . . . . . . . . . . . . . R eaotion betw een an a c id and a n o rg an o lead com­ pound, follow ed b y u se o f a m e ta l h a lid e o r hydrogen h a lid e R eao tio n o f diasoniuia c h lo rid e s w ith le a d .......... c h lo rid e s C o n tro lle d r e a c tio n o f le a d c h lo r id e w ith a G rig n ard re a g e n t R eaotion o f R^Pb o r Rgfbg compounds w ith some in o rg a n ic h a lid e s and o rg a n ic a c id h a lid e s . . . In te rc h a n g e betw een R^Pb and RgFbXg compounds . . . . Table 6 * RjPbX Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . f a b le 7* RgR'fbX Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . f a b le 8 . RR, R"FbX Confounds . . . . . . . . . . . . . . . . . . . . . . . . . T able 9 . RgFbXg Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . T able 1 0 . RRhFbXg Compounds . . . . . . . . . . . . . . . . . . . . . . . . . .

34 35 36

Bglb COf^POUiJDS .......................................... Table 1 1. BgFb Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . RgFbg COMPOUNDS

...............

G eneral D isc u ssio n .................................. Methods o f P r e p a ra tio n .............. R ea c tio n o f an a lk y l io d id e w ith sodium -lead a llo y C o n tro lle d r e a o tio n o f le a d c h lo r id e w ith a n a c ti v e o rg a n o m e ta llic compound . . . . . . . . . . . . . . . E l e c tr o ly s is o f an RgPbQH compound . . . . . . . . . . . . . . . Chemical re d u c tio n .......... B le e tr o ly tio r e d u c tio n . . . . . . . . . . . . . . . . . . . . . . . . . . . L iquid ammonia r e a c tio n s .......... T able 1 2 . RgPbgCompounds .......................

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36 36 3? 38 40 42 43 46 48 49 51 52 54 55 55 58 58 58 59 59 59 59 61

iv .

UNCLASSIFIED ORGANOLEAD COMPOUNDS .....................

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T able 13* U n c la s s if ie d O rganolead Compound* . . . . . . . . RgFbY, (RgfbJgY, RgfbYg, AM) RR*FbYg COMPOUHDS S ab le S ab le S able S ab le

14. 1 6. 16. 17.

66

..........

66

RgFbY* Compound* ......... (% Fb)gY* Compound* ............ %FbYg* Compounds . . . . . . . . . . . . . . . . . . . . . . . . RR’FbYg Compound* . . . . . . . . . . . . . . . . . . . . . . . .

67 71 72 75

UNCLASSIFIED QRSANOI£AD SALTS

.......................

76 ...............

Table 1 8 . U n c la s s ifie d O rganolead S a l t s SHE REDISTRIBUTION REACTION

..........

77 78

PYROLYSIS OF ORGANOLEAD COMPOUHDS TO GIVE FREE RADICALS.

80

INTRODUCTION OF WATER-SOLUBI LI ZING GROUPS INTO ORGANOLEAD COMPOUNDS ............

84

ORGANOLEAD COMPOUNDS IN THE TREATMENT OF CANCER

87

Table 1 9 . O rganolead Compound* and T h e ir E f f e c t Upon Mouse Canoer T able 2 0 . T o x ic ity o f Organolead S a lt*

90 91

.................

92

.........................

95

LEAD POISONING AI© ITS TREATMENT INDUSTRIAL USES OF ORGANOLEAD COMPOUNDS ANALYSIS OF ORGANOLEAD CC&PGUNDS...............

94

BIBUQGRAfBY

96

..........

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V.

Page INTlOnJCTION EXPERIMENTAL

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Organolead R eactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The i n t e r a c t i o n o f p h e n y llith iu m , iodobeneene, and le a d o h lo rid e to produce t e t r a p h a n y l le a d .. fh e i n t e r a c t i o n o f p h e n y llith iu m , brom obensene, and le a d o h lo rid e to produoe t e tr a p h a n y l le a d .• The i n t e r a c t i o n o f p h e n y llith iu m and le a d o h lo rid e to produce te tra p h e n y 1 le a d . . . . . . . . . . . . . . . . . . . The i n t e r a c t i o n o f phenylmagnesium brom ide, iodobenxene, and le a d c h lo rid e t o produce te tra p h e n y lle a d . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . R eaotion o f h e x ap h e n y ld ile a d w ith m a le ie a n h y d rid e .......... In ch lo ro fo rm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . In m olten raaleio an h y d rid e . . . . . . . . . . . . . . . . . . . Sodium s a l t o f ck j3 - d i ( t r i p h e n y H e a d ) s u c c in ic a o ld . T rlp h en y llead -so d iu m and e th y l d,JI-dIbrojRO« e u e o ln a te . . . . . . . . . . . . . . . . . 7 . . . . . . . . . . . . . . . . . . F i r s t a tte m p t ............ Second a tte m p t . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . T rip h e n y lle a d a c id m a le ate ............ D i- tr ip h e n y lle ad m a le ate .......... A ttem pts t o induce a r e a o tio n betw een hexaphenyl­ d i le a d and v a rio u s u n s a tu r a te d o rg a n ic compounds ............ T rip h e ry 1-o-hydroxypheny 1 le a d ..................... Tripheny 1-IF-phenanthry 1 le a d ......................... !>i“9 * f)i» aaath ry ld ip h ex iy llead . . . . . . . . . . . . . . . . . . . . . A ttem pted p re p a ra tio n s o f t e t r a « 8« p h e n a n th ry lle a d . T ri p h e n y l-7 - (1 ,2 -b e n a a n th ry l)~ le a d . . . . . . . . . . . . . . . B l* 7 -{ l,2 -b e n s a n th ry l)d ip h e n y lle a d . . . . . . . . . . . . . . . R eactio n s i n liq u id ammonia betw een h ex ap h en y ld ile a d and s e v e ra l m e ta ls , d eriv & tix ed w ith b e n sy l o h lo rid e Table 1 . R eactio n s i n L iq u id Ammonia i n Ih io h 0.0025 Mole o f H exaphenyldilead was T rea te d W ith V arious M etals Follow ed b y B ensyl C h lo r id e .. R eactions i n liq u id ammonia betw een d ip h en y l le a d d ih a lid e s and s e v e r a l m etals . . . . . . . . . . . . . . . . . Table 2 . R ea c tio n s i n L iq u id Ammonia Between D ip henyllead D ih a lid e s and S e v e ra l L iq u id Ammonia S o lu b le M etals . . . . . . . . . . . . . . . . . . . . .

10? 108 108 108 109 110

110

Ill Ill 112 113 114 114 114 115 116

116 117 118 118 119 120 121 122

123 124 125

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v i.

Ssss. A ttem pts to p re p a re compounds o f th e ty p e I^ R 'F b iW H g ................. sym -'Petraoyolohexy I d i p h e n y ld ile a d . . . . . . . . . . . . sy m -T e tra p h e n y ld ie th y ld i le a d .............. A ttem pted s u lf o n a tio n o f te tra p h e n y lle a d . . . . . . . . . ........... .. A ttem pted n i t r a t i o n o f te tr a p h e n y lle a d H itr a tio n o f d ip h e n y lle a d d io h lo r id e . . . . . . . . . . . . . D i-ra -n itro p h e n y lle a d d io h lo r id e . . . . . . . . . . . . . . . . . . D i-ffi-n itro p h en y llead d i io d id e ................ T rip h e n y lle a d n i t r a t e . . . . . . . . . . . . . . . . . . . . . . . . . . . . N itr a tio n o f tr ip h e n y lle a d n i t r a t e .......... n i t r a t i o n o f tr ip h e n y lle a d o h lo rid e .............. T r ie th y lle a d c h lo rid e and diasom ethane . . . . . . . . . . . T r ie th y lle a d c h lo rid e and d ia a o e th a n e ............ A ttem pted re a c tio n s o f h a lo g e n o e s te rs and le a d powder Ethy IjVbrorao p r o p i o n a t e ............ . . . . B raaam etbyl a c e ta te . . . . . . . . . . . . . . . . . . . . . . . . . . E th y l broraoacetate . . . . . . . . . . . . . . . . . . . . . . . . . . . Orgenogeraanlum R eactio n s . . . . . . . . . . . . . . . . . . . . . . . . . . . . A c tio n o f io d in e upon te tra -n -b u ty lg e rm a n iu n . . . . . P r e p a ra tio n o f tri-n -b u ty lg e rm a n iu m io d id e th ro u g h tr i- n - b u ty lg e r m n iu m b r o m i d e ................................... T e tr a -2 - fu ry lg e ra a n iu a .......... O rganotin S e a c tio n s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . n -S u ty ltin tr iio d id e ................ Y r i- n - p r o p y ltin bromide and d iazo e th a n e . . . . . . . . . . R eactio n s o f h a lo g e n a te d compounds w ith t i n pow der E th y l bromoacetat© . . . . . . . . . . . . . . . . . . . . . . . . . . . Bromomethyl a c e ta te ............................ Phenaoyl bromide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ^-B rom oethyl a o e ta te . . . . . . . . . . . . . . . . . . . . . . . . . Bthyljrt-brom opropionate . . . . . . . . . . . . . . . . . . . . . . . D ie th y l^ b ro m o s u o c in a te . . . . . . . . . . . . . . . . . . . . . . . E th y l dTbromoraalonate ......... .. 2-B roraopyridise ................ .. l-C liloro-2-iodo eth an ® ........... .. l^ ra m ^ -e h lo re e th e a e . . . . . . . . . . . . . . . . . . . . . . . l-B rom o-3-chloropropane ..........

126 126 127 127 127 128 128 129 136 130 131 131 132 132 132 132 133 133 135 134 134 136 136 137 137 137 138 139 132 139 140 141 141 142 142 143

DISCUSSION...................... ............................................

144

SUMMARY

154

........... ....................................................................................

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ACKNOWLEDGMENT The a u th o r w ishes t o e x p re ss h is a p p r e c ia tio n t o D r. Henry Gilman f o r th e v a lu a b le guidance and c r i t i c i s m he has g iv e n th ro u g h o u t th e co u rse o f t h i s re se a rc h *

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INTRODUCTION O rganic compound* o f le a d have b een known and s tu d ie d f o r th e l a s t n in e ty year* (1 5 7 ),

In th e c o u rse o f t h i s tim e a p p ro x im a te ly 550

o rg an o lead compounds have come t o o u r a tte n tio n * e i t h e r th ro u g h l i t e r a t u r e re fe re n c e s o r b y work done i n th e s e l a b o r a t o r i e s .

E x c e lle n t rev iew s o f

o rg an o lead compounds have appeared i n th e p a s t (25 , 5 7 , 5 9 , 123* 149, 193) and i t i s n o t th e in te n tio n o f t h i s rev iew to r e p e a t u n n e c e s s a rily what has a lre a d y been d is c u s s e d in th e s e sou ro e s o f in fo rm a tio n .

R a th e r, th e

aim i s t o g a th e r a d d itio n a l f a c ts co n cern in g t h i s i n t e r e s t i n g group o f compounds by review ing th e l i t e r a t u r e u p t o th e end o f 1942.

At th e same

tim e a com plete t a b u la tio n o f th e compounds has been made, l i s t i n g what we b e lie v e t o be th e im p o rta n t r e fe re n c e s t o e ac h compound*

In n e a r ly

e v e ry c a s e , a l l known l i t e r a t u r e re fe re n c e s t o eaoh compound have b een in ­ c lu d ed in t h e t a b l e s .

I n cases where more th a n common i n t e r e s t h as produced

a la r g e number o f p u b lic a tio n s on a oompound ( e . g . , t e t r a e t h y l l e a d o r te tr a p h e n y lle a d ) , a few re fe re n c e s have been o m itte d .

This o m ission has

o c c u rre d o n ly i f i t was f e l t t h a t th e a r t i c l e d id n o t add to th e chem ical o r p h y s io lo g ic a l knowledge o f th e oompound. In t h i s review th e term o rg an o lead compound i s ta k e n t o mean o n ly th o s e compounds p o s se ss in g a c a rb o n -le a d lin k a g e .

Thus d ip h e n y lle a d d i a e e t a t e ,

(G g% )2» (0 0 C (S 5 )8# i s in c lu d e d , b u t le a d a c e t a t e , (CHjCOOjgPb, i s n o t in c lu d e d .

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R4Fb COMPOUHDS G eneral D isc u ssio n of R^Pb Compounds Compounds o f th e type R^Fb, where f o u r s i m i l a r a lk y l o r a r y l groups a re a tta c h e d t o lead* r e p r e s e n t the o l d e s t ty p e o f o rg an o lead compound known* Lowig (157) f i r s t produced a compound o f t h i s ty p e b y th e a c t i o n o f e th y l io d id e upon lead-sodium a l l o y .

He b e lie v e d t h a t he had t r i e t h y l l e a d }

how ever, G h ira (6 3 ) , i n re p e a tin g th e w ork, proved t h a t Lowig had impure te tra e th y lle a d . The t e t r a l k y 1le a d compounds a r e c o lo r le s s and li q u i d even when th e o rg a n ic group i s a f a i r l y long c h a in .

The lo w e st member o f th e s e r i e s known

to be a s o l i d i s t e t r a t e t r a d e c y 1le a d , w hich m e lts a t 3 1 ° . s t a b i l i t y i s e x h ib ite d in th e s e sy m m etrical compounds.

Remarkable They w ith s ta n d

te m p e ra tu re s up t o 1 4 0 °, a r e l i t t l e in flu e n c e d b y a i r o r m o is tu re , and a r e u n a ffe c te d b y d i l u t e a c id s o r a l k a l i e s .

T e tra e th y lle a d r e s i s t s th e a c ti o n

o f oold s u lfU rio a o id o f s p e c i f i c g r a v ity 1 .4 and t h i s f a c t i s made u se o f i n p u rify in g te c h n i c a l t e t r a e t h y l l e a d . L i t t l e d i f f i c u l t y i s ex p erien c e d i n vacuum d i s t i l l a t i o n o f the s t r a i g h t ch ain ed t e t r a a l k y l l e a d compounds. d is tille d ;

Tetraraethy1le a d te n d s t o s u p e rh e a t when

t h i s b e h a v io r i s c h a r a c t e r i s t i c o f th e u n p re d ic ta b le p r o p e r tie s

o f m ost o rg a n o m e ta llic compounds c o n ta in in g th e m ethyl g ro u p .

U nless c are

i s e x e rc is e d i n d i s t i l l i n g te tr a m e th y lle a d , th e r e is d an g er o f d eco m p o sitio n w ith e x p lo siv e v io le n c e (1 3 8 ). Secondary a lk y l groups im p a rt a low er d eg ree o f s t a b i l i t y th a n do prim ary a lk y l g ro u p s.

The d if f e r e n c e i n s t a b i l i t y betw een prim ary and is o

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oompound* i s o f th e same ty p e b u t n o t so m arked. T e tra o y o lo h e x y lle ad i s p e c u lia r among th e a l i p h a t i c le a d compounds i n t h a t i t decomposes b e fo re m e ltin g . fa c to rs .

This i s p ro b ab ly h ie to s t e r i c

As w i l l be n o te d i n th e s e c t io n on %Fbg compounds, th e s t a b l e

form seems t o be hex aey o lo h ex y ld lle& d . H alogens r e a c t w ith a l k y l B^Fb compounds t o g iv e RgPbX o r

com*

pounds, depending upon t h e te m p e ratu re and c o n c e n tra tio n s o f th e r e a c t a n t s . The t r i a l k y l l e a d h a lid e s a r e p ro b ab ly formed f i r s t i n any case b u t a r e q u ic k ly co n v erted to th e d ia lk y lle a d d ih a lid e s a t h ig h e r te m p e ra tu re s and c o n c e n tra tio n s (1 0 2 ),

Cleavage w ith bromine a t -7 0 ° y ie ld s RgFbX compounds

a n d , a t - 2 5 ° , BgfbXg compounds.

I t has been im p o ssib le t o c le a v e th r e e

a l k y l r a d ic a ls and r e t a i n a s t a b l e r e s id u e .

Ih e n more th a n two atom

e q u iv a le n ts o f h alo g en a r e u s e d , th e p ro d u c t i s alw ays le a d h a lid e and th e a l k y l h a lid e .

A method o f fo rm atio n o f RFbXg compounds i s m entioned i n a

l a t e r s e c tio n . Halogen a d d s , u s u a lly in th e gaseous form , a ls o c le a v e H^Fb compounds. These r e a c tio n s a r e d is c u s s e d i n th e s e c tio n on le a d compounds c o n ta in in g two o r more d i f f e r e n t o rg a n ic r a d i c a l s . B ln d so h ad ler (14) has shown t h a t cleav ag e of one a lk y l r a d ic a l from an BgFb compound can be accom plished b y ad d in g a liq u id anaem ia s o lu ti o n o f a m e ta l to a n e t h e r s o lu tio n o f th e o rg a n o le ad compound. RgFbM compound, n e v e r a n

The p ro d u e t i s an

oompound, and i t i s n o t i s o l a t e d b u t i s

d e r iv a tis e d b y adding a n o rg a n ic h a l i d e .

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% fb * 1ft

Jffig

BsPblbk. R ' B r , BgR'Ife f SftBr

P robably because o f s t e r i o f a c t o r s , o rth o -s u b s tit u te d R^Pb compounds u s u a lly show a h ig h e r m e ltin g p o in t th a n th e c o rresp o n d in g p a ra -s u b s t i t u t e d compound.

In some oases t h i s d if f e r e n c e i n m e ltin g p o in t amounts t o o v e r

100°, halogens produce EjPbX and RgFbXg compounds i n th e t e t r a a r y l l e a d s e r i e s j u s t a s in th e t e t r a a l k y l l s a d s e r i e s .

Here a g a in , i t i s a p p a re n t t h a t

th e more s ta b l e te tr a - v a le n c y o f le a d i s found w ith e i t h e r f o u r o rg a n ic groups or two o rg a n ic and two in o rg a n ic g ro u p s.

A d d itio n o f more th a n

two atom e q u iv a le n ts of h a lo g en produces o n ly le a d h a lid e and th e a lk y l h a lid e . The gaseous h a lo g en a c id s c le a v e t e t r a a r y l l e a d compounds a s do th e h a lo g e n s ,

t h i s ty p e o f c lea v a g e i s d is c u s s e d in g r e a te r d e t a i l in th e

s e c tio n on compounds c o n ta in in g two o r more d i f f e r e n t o rg a n ic r a d i c a l s a tta c h e d to th e same le a d atom . T e tra a ry lle a d compounds, l i k e th e t e t r a a l k y l l e a d ty p e s , have been clea v e d to RgFbM compounds by Binds s h a d i e r .

The p ro d u c t i s n e v e r i s o l a t e d

b u t i s d e r lv a tis e d by a c ti o n o f an o rg a n ic h a lid e * Makarova and Besmeyanov (153) o b ta in e d a q u a n t ita tiv e y i e l d of bensenediaxonium n i t r a t e b y th e a c ti o n o f HgOg and NO on te tr a p h e n y lle a d , Sohlenk and H o lts (191) o b ta in e d im pure ethyl*odium from th e r e a c tio n o f sodium m e ta l upon t e t r a e t h y l l e a d .

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R^Pb compounds c o n ta in in g ra d io a o tiv e le a d have b e e n p re p a re d . Tetram ethylthorlum -D and tetram eth y lrad iu m -G were re p o rte d b y A ston ( 3 , 4) and te tra e th y lra d iu m -D was re p o rte d by C a lin g a e r t, B e a tty , and Hess (2 7 ). Methods o f P rep a rin g R^Pb Compounds S ince th e sim p le t e t r a - s u b s t i t u t e d le a d compounds a r e n e a r ly alw ays th e s t a r t i n g p o in t i n th e p r e p a r a tio n o f o th e r o rg an o lead compounds* con­ s id e r a b le work has been c a r r ie d o u t i n p e r f e c tin g methods o f m an u factu re. The fo llo w in g methods have been u s e d . R eactions o f lead-sodium a llo y s w ith o rg a n ic h a lid e s As s t a t e d b e f o r e , th e f i r s t o rg an o lead compound was p re p a red b y th e r e a o tio n o f e th y l io d id e w ith lead -so d iu m a l l o y .

This method i s a l s o

u s e d in th e com m ercial p ro d u c tio n o f t e t r a e t h y l l e a d (4 7 ), i n which case e th y l c h lo r id e i s th e a l k y l h a lid e em ployed.

P o lis (182) o b ta in e d

te tr a p h e n y lle a d b y u sin g brcsnobenzene, in th e p resen ce o f e th y l a c e ta te a s p ro m o ter.

I t has b e e n sug g ested t h a t th e r e a c tio n in v o lv e s re d u c tio n

( 2 5 ) , and t h a t e th y l a c e t a t e , w a te r , e t c . promote te e r e a c ti o n by a c tin g a s so u rces o f hydrogen.

Ghina (63) found t h a t u n d er a b s o lu te ly anhydrous

c o n d itio n s no r e a c tio n o ccu rred betw een a lk y l h a lid e s and le a d - s odium a l l o y , b u t th e a d d itio n o f a l i t t l e w a te r caused a smooth r e a o tio n t o ta k e p la c e . R eactio n o f sodium, o rg a n ic h a l i d e * and le a d o h lo rid e A German p a te n t (62) m entions th e p r e p a r a tio n o f R^Pb compounds by dropping a m ix tu re o f th e o rg a n ic c h lo r id e and le a d o h lo rid e i n to lu e n e

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upon sodium in tolu en e. R ea c tio n o f m e ta llic le a d w ith a lk y l Io d id e s Cahoure (24) m entioned t h a t e th y l io d id e a tta c k e d m e ta llic le a d b u t no p ro d u c t was is o la te d *

The r e a o tio n p ro b ab ly in v o lv ed th e fo rm atio n

o f (CgHgJgPblg# a n u n s ta b le oompound*

C a lin g a e rt (25) re p o rte d t h a t

a d d itio n o f some re a g e n t t o ta k e up th e h alo g en caused th e r e a c tio n t o go i n good y ie ld *

Such a g e n ts a re powdered aluminum , z in c , o r s i l i c o n w ith

c o n c e n tra te d sodium hyd ro x id e s o l u t i o n s . Pb 4 40gHgI 4 2Zn 4 8 SaGH

> Fb(C 2 Hg)4 4 4HaI 4 2Za(0Ha)2* 4HgO

R e a c tio n o f le a d o h lo rid e w ith an a o tlv e o rg a n o m e ta llic oompound OrganozIno compounds *

T e tra e th y lle a d has b e en p re p a re d (1 9 , 55) b y

adding le a d c h lo r id e t o d ie th y lz in o . 2Zn(C2 Hg)2 4 2PbClg

► Fb(C 2 Hg)4 4 2ZnClg 4 Pb

The in fla m m a b ility o f th e o rg an o zin c compounds has g r e a tl y r e s t r i c t e d t h e i r u se i n such re a c tio n s * O rganolithium oompounda.

A u stin ( 8 ) p re p a red a number o f a r y lle a d

compounds by th e a c ti o n o f a r y llith i u m compounds upon le a d c h l o r i d e .

He

s ta t e d t h a t th e a c ti o n was s im i la r t o t h a t when organomagnesturn h a lid e s a r e used*

The s e r i e s o f r e a c tio n s is g iv en u n d e r organomagnesium h a lid e

compounds, below* R ecen tly ( t h i s t h e s i s , p . 108) improved y ie ld s were o b ta in e d in p re p a r­ ing te tr a p h e n y lle a d by adding iodobenzene t o th e r e a o tio n m ixture*

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3CgHgLi 4> FbCXg * CgH gl

*> (CgHg)4Fb 4 2L1C1 * L i I

Y ie ld s b ased upon th e o rd in a ry G rig n ard r e a c tio n (se e below ) in d ic a te d a y ie ld of* 16Q>Sj

based upon th e above e q u a tio n th e y ie ld was 80$.

■Whereas f r e e le a d i s d e p o site d i n th e o rd in a ry r e a o tio n betw een le a d o h lo rid e and an o rg a n o lith iu m oompound o r organomagnes ium h a l i d e , i t i s n o t d e p o s ite d when a n o rg a n ic io d id e i s added. Organomagnesturn h a lid e s .

The f i r s t in v e s tig a to r s t o u se th e

G rignard re a g e n t i n p re p a rin g a n o rg an o lead compound w ere P f e i f f e r and Y ru sk ie r (179) who p re p a red te tr a p h e n y lle a d .

The r e a c tio n p ro d u c t

formed from th e G rignard re a g e n t and le a d c h lo r id e m ust b e h y d ro liz e d to o b ta in th e o rg a n o le ad compound (1 1 9 ), b e fo re h y d ro ly s is is n o t known.

The e x a c t n a tu re o f th e p ro d u c t

A s e r i e s o f re a c tio n s li k e th e fo llo w ­

ing i s u s u a lly g iv e n t o shew th e method o f fo rm atio n o f le a d compoundsi 12HMgX 4

* 6 H2Fb 4 12Mg(X)Cl

6R P b

2

2R Fb„ 4 2Fb 6 2

2R P b — ►3S Pb 4 8 2 4 The v a l i d i t y o f t h i s mechanism i s u pheld by th e fo llo w in g f a c t s t ( l ) The c h a r a c t e r i s t i c brown t o red c o lo r a tio n a s s o c ia te d w ith RgPb com­ pounds i s u s u a lly n o tic e d i n th e e a r ly s ta g e s o f p re p a rin g R^Pb compound*.

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(2 )

EgPb and BgPbg compounds can be is o la te d from th e r e a c tio n m ix tu re s •

(3) The HgFb and RgPbg compounds a re c o n v erted t o th e H^Pb compounds on th e a p p lic a tio n o f h e a t , i n th e p resen ce o r absence o f G rig n ard reag en t* These r e a c tio n s may n o t r e p r e s e n t th e tr u e co u rse o f r e a c t i o n , how ever, because t h e fo llo w in g r e a o tio n has been d em o n strated : HgFb-i%fis + a - t y i g U — * RgFbLi 4 ^P b -n -C ^lig A s im ila r r e a o tio n w ith & G rig n ard re a g e n t h a s n o t b een o b serv ed , b u t compounds o f th e type RgPbMgX have b een made (6 7 ) .

The

b in a ry sy ste m , Mg 4 MgXg «=* 2MgX, r e a c ts w ith HgPbg compounds by a d d in g m agnesious h a l i d e 1 % ?b 2 4 2 [-JfeX]

a 2 RsPbMgX

The fo llo w in g r e a c tio n s co u ld th e n ta k e p la c e : RgPbMgX 2 R gPb

SgPb 4 KMgX ►R4Pb 4 Pb

A c tu a lly , Gilman and B a ilie have b een a b le t o c a r ry o u t a r e a o tio n betw een SgPbg compounds and th e b in a ry system and show t h a t R^Pb compounds, f r e e l e a d , and a G rignard re a g e n t were form ed. R eaotion o f h y d ra sIn e s u l f a t e and o rg an o lead h a lid e s H ydra*ins s u l f a t e h a s b een u sed t o c o n v e rt tr ip h e n y lle a d o h lo rid e and d ip h e n y lle a d d ic h lo r id e t o te tr a p h e n y lle a d .

&jx a lc o h o l ic m ix tu re o f

th e r e a c ta n ts was h e a te d w ith sodium c a rb o n a te (6 9 ).

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10 E l e c t r o l y t i c re d u c tio n E le c tr o ly s is o f ace to n e i n d i l u t e s u l f u r i c a c id , u sin g a le a d cath o d e (188, 2 0 2 ), y ie ld e d a red o i l t h a t seemed t o he composed m ainly o f d iis o p r o p y lle a d .

There were some in d ic a tio n s t h a t some t e tr a is o p r o p y lle a d

m ight haws b e en p r e s e n t. f ir r o ly s is o f a plumbonic a c id Leabre (152) m entioned t h a t p y ro ly s is o f bensylplum bonic a c i d , CgHgCHgPb( OK) g , y ie ld e d , among o th e r p ro d u c ts , some t e tr a b e n s y ll e a d .

Ho

f u r t h e r d e ta i ls w ere g iv e n . Free r a d ic a ls and m e ta llic le a d S e v e ra l p a te n ts have appeared i n w hich i t i s claim ed t h a t when a hydrocarbon m ix tu re such as g a s o lin e v ap o r was s u b je c te d t o th e rm a l decompo­ s i t i o n , and th e gaseous m ix tu re c o n ta in in g fr e e r a d i c a ls was b ro u g h t i n c o n ta c t w ith le a d and q u ic k ly c o o le d , a s o lu tio n o f organolead compounds r e s u l t e d (2 0 7 , 2 0 8 ),

This i s a m o d if ic a tio n o f th e P an eth te c h n iq u e

on a la r g e r s c a l e . Riys io al-C h em ical Data J o n e s , Evans, G u lw ell, and G r i f f i t h s (117) have c a r r ie d o u t some e x te n s iv e s tu d ie s upon some p h y s ic a l p r o p e r tie s o f a Ik y H e a d compounds• These a u th o rs found t h a t th e b o ilin g p o in ts a t 10 jam, o f s t r a i g h t - c h a i n le a d compounds co u ld b e c a lc u la te d b y u se o f th e fo rm u lai t,n ♦ 2 7 5 .1 , 0 .8 6 7 M1*057 10 mm.

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11, •whore M I s th e xaolooular w e ig h t.

The c a lc u la te d v a lu es a g re ed e x e e l l e n t ly

w ith e x p e rim e n ta l v a lu e s e x c e p t in th e e a se o f tetrsuae th y H e a d , I t was found t h a t , w ith in th e li m it s o f p re s s u re s u s u a lly en co u n tered i n such d i s t i l l a t i o n s , th e r e c ip r o c a l o f th e a b s o lu te b o il in g p o in t was a l i n e a r fu n c tio n o f th e lo g a rith m o f th e p r e s s u r e .

For t e t r a e t h y l l e a d ,

th e n , th e e q u a tio n t * 273,1 3 2960 /(9 .4 2 6 2 - lo g 1Q p ) g iv e s th e te m p e ra tu re ( t ) o f d i s t i l l a t i o n a t any p re s s u re ( p ) . By assum ing t h a t th e r a t i o o f th e a b s o lu te b o ilin g p o in ts o f two d i f f e r e n t a lk y lle a d compounds u n d e r one p re s s u re i s e q u al t o th e r a t i o o f th e b o ilin g p o in ts o f th e two compounds u n d e r a n o th e r p r e s s u r e , i t i s p o s s ib le t o c a lc u la te th e appro x im ate v a lu e o f th e b o ilin g p o in t o f a new compound. p o in t o f a

This method i s o f e s p e c ia l i n t e r e s t i n c a lc u la tin g th e b o i lin g n ew

mixed s tra ig h t-o h & in t e t r a a I k y l l e a d compound.

The b o ili n g

p o in t o f t h e new compound a t 10 mm. co u ld be c a lc u la te d b y th e f i r s t e q u a tio n above and th e v a lu e s a t d i f f e r e n t p re s s u re s f o r t e t r a s t h y 1le a d could be c a lc u la te d from th e second e q u a tio n ,

Thus, th e approxim ate

b o ilin g p o in t o f th e unknown a t any p re s s u re c o u ld be d eterm in ed mathemat­ ic a lly . B u ck ler and H o rrish (18) found t h a t th e v a p o r p re s s u re o f t e t r a e t h y l l e a d i n th e te m p e ra tu re range 0 t o 70° c o u ld be e x p re ss e d by t h e e q u a tio n lo g 10p * 9 .428-2938/T . The io n is a tio n p o t e n t i a l o f t e t r a e t h y l l e a d has been re p o rte d a s 1 2 ,3 v . j t h a t o f te tr a m s th y lle a d ( p r o v is io n a l) a s 11.5 v* (5 6 ),

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12 The m o le c u lar volume a t t e r o a b s o lu te h as b e e s c a lc u la te d f o r te tra ra o th y lle a d , t e t r a e t h y l l e a d , te tr a - n - p r o p y l le a d , tr ie th y 1 - n - p r o p y lle a d , d ie th y ld i-n « p r o p y lle a d , triH tt-p ro p y le th y lle a d , tr ia th y lm e th y lle a d , and tr ie th y l- s i- d ju ty lle a d (112)* X -ray measurements on te tra p h e n y lle a d g iv e th e d is ta n c e betw een le a d and earbon a s 2.39 A* (64)* t o b e 17.30»17«3G i6.454.

I t s d e n s ity i s 1*745* and a t b t e m s found The elem en ta ry c e l l has fo u r m o le c u le s.

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13, Table 1*

Compound

R^R> Compounds

M.P. o r B*P*,* °C*

R eferences

f e tr a .n - a a y l.

170/1

(117)

T o tra -d l-a m y l-

150/t>.5

(U 7 )

T e tr a - o - a n is y l-

148-149

(67)

fe tra -jj-a n is y l-

145.146

T e tra b e n s y l-

(67)

———

(6 7 , 86) (1 4 6 , 155)

Tetra-jg-brom ophenyl-

187

S e tra -J * 4 w ty l-

157/fe

T e tra c y o lo h e a y l-

deo* 160*

(6 2 , 9 7 , 136)

T etra-ja-diraethylarainophenyl-

197.108

(8 )

T etra-o«-ethoxyphenyl-

210.220

(67)

T etra-j> -eth o ay p h en y l-

110

(67)

T e tr a e th y l-

78/10

T e tra -2 - fU ry l-

52-53

T e tr a - n - h e p ty l-

(180) (117)

(117)

(4 3 , 117)

(7 , 16, 17, 19, 21, 26, 2 7 , 28, 2 9 , 34, 35, 36, 37, 47, 5 5 , 6 3 , 6 6 , 8 8 , 9 1 , 100 102, 1 1 0 , 1 14, 115, 116, 11 7 , 1 1 8 , 160, 16 2 , 165, 1 7 4 , 17 5 , 17 7 , 17 9 , 204) (85)

— —

(218)

♦ In a l l o f th e t a b l e s , th e c o n s ta n ts g iv e n a r e t o b e assumed t o be B a itin g p o in ts u n le s s a / i s g iv e n . I n t h a t e a se i t i s a b o ilin g p o in t and 1 5 0 /l0 means 1S0°C. a t 10 s o b p r e s s u r e .

.

+ In a l l o f th e t a b l e s , dee* fo llo w ed by a te m p e ra tu re i n d ic a te s t h a t decom position o c cu rs w ith o u t m e ltin g a t ct h a t te m p e ra tu re , 160 deo* means m e ltin g w ith decom po sitio n a t 160 •

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14 T able 1 (concluded)

Compound T e tra -n -h e x a d e e y lTe tr a d e o a n y l-

M.P. o r B .P .,°C * 42

R eferences

(161)

d e e . on d i e t . (106)

(1 0 0 , 106)

T e tra i s obuty1 -

-2 3

(106)

(1 0 0 , 106, 177)

T e tra is o p ro p y l-

-5 3 .5 120/ U

(107) (107)

(6 0 , 9 3 , 1 0 0 , 107)

T e tra m e th y l-

-2 7 .5 6/10

(102) (117)

(1 7 , 2 3 , 2 6 , 2 8 , 2 9 , 3 4 , 3 5 , 3 6 , 6 0 , 100, 10 2 , 11 6 , 1 17, 118, 1 3 8 , 15 1 , 170, 1 7 4 , 17 5 , 17 6 , 1 8 1 , 196) (146)

T e tra p h e n e th y lT e tra p h e n y l-

223-225

(8 )

T e tm -n -p ro p y l-

126/13

(102)

T etra«® M »tradecyl«

31

Te tra .-2 - th ie n y 1 -

162

(142)

(8 5 , 142, 144)

T e tr& -o -to ly l-

201-202

(5)

( 8 , 6 , 67)

T e tre -g -to ly l-

122-123

T *tr& -_g-tolyl-

240

Tet ra-j>~xyly 1*

250}

(7 , 8 , 26, 29, 37, 41, 45, 46, 53, 62, 66, §7, 74, 75, 76, 90, 92, 98, 1 1 6 , 11 8 , 1 2 9 , 1 31, 1 3 2 , 1 33, 134, 13 7 , 141, 1 45, 147, 15 1 , 1 5 8 , 1 7 1 , 17 9 , 1 8 2 , 1 8 7 , 1 9 2 , 194, 2 0 3 , >, 2 1 3 , 2 1 8 , 219) ( 2 9 , 1 0 0 , 1 0 2 , 177) (161)

( 6 ?) (141)

d e e . 270

( 6 , 2 6 , 29 , 6 7 , 7 4 , 14 1 , 1 8 2 , 218) (147)

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RgE’f b ,

E2R, H"Pb, AND RR*RnR’ "Fb COMPOUNDS G en eral D isc u ssio n

Unsym m etrieal o rg an o lead compounds a r e ones i n which a t l e a s t two d i f f e r e n t o rg a n ic groups a r e a tta c h e d t o le a d b y o a rb o n -le a d bonds*

On

th e b a s i s o f t h e i r s tr u c tu r e s , th e s e compounds may b e d iv id e d in to two d iff e r e n t c la s s e s .

Members o f th e f i r s t c la s s h a re o n ly o rg a n ic groups

a tta c h e d t o th e le a d atom ;

b u t members o f th e second c l a s s , n ix e d uneymmet-

r i c a l o rganolead compounds, have in o rg a n ic groups a s w e ll a s o rg a n ic groups a tta c h e d d i r e c t l y t o th e le a d atom*

U nsynm etrioal o rg an o lead compounds i n

g e n e ra l were f i r s t s tu d ie d i n d e t a i l b y O ru ttn e r and Krause (1 0 1 , 10 S, 1 0 4 ). The method o f in tro d u c in g d i f f e r e n t o rg a n ic g ro u p s, a s developed b y th e s e a u th o r s , i s d is c u s s e d under th e f i r s t method o f p re p a rin g th e s e compounds. A ll un sy rm ietrio al a Ik y H e a d compounds a r e c o lo r le s s liq u id s whose p h y s ic a lchem ical p r o p e r tie s m y be p r e d ic te d b y u s in g t h e d a ta t h a t a p p ly t o th e sim ple t e t r a a l k y l l e a d compounds. The unsyim netrioal a r y lle a d compounds a re s h i t e (o r s l i g h t l y o f f - c o l o r ) c ry s ta llin e s o lid s ,

As w ith a l l o rg an o lead compounds w ith mixed sub­

s t i t u e n t s , th e degree o f s t a b i l i t y i s low er th a n f o r th e sim p le R^Pb compounds.

The s o l u b i l i t y and r e a c tiv i ty ' o f t h e u n s y n a s tr io a l ty p e s a r e

g re a te r. Unsym m etrical a lk y 1 -a ry H e a d compounds a r e e i t h e r liq u id s o r s o l i d s .

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depending upon th e s u b s t i t u e n t s .

In g e n e r a l, th o se w ith on® a r y l group

a r e liq u id s w h ile th o se w ith two o r th r e e a r y l groups a r e s o lid s *

In

clea v a g e r e a c tio n s -Kith halog en s o r hydrogen h a lid e s th e a r y l groups a r e alw ays clea v e d f i r s t * Methods o f P r e p a ra tio n Halogen o r hydrogen h a lid e c lea v a ge f o l l owed b y r e a o tio n w ith an

• • ■ M M I I M I M M k M W W ( M m *

« M M l m l '■ m a il *■ ! * ! * > ■ »W W iM M *

a c t i v e org an o a e ta llio oompound Vihen an H^Pb compound i s cleav ed w ith a h a lo g en o r hydrogen h a l i d e , an RgPbX o r RgPbXg compound i s form sd (se e u n d er th e s e compounds f o r c o n d itio n s ) .

E ith e r o f th e s e p ro d u c ts , upon r e a c tio n w ith an a c tiv e

o rg a n o m e ta llio oompound (R’ M), i s c o n v erted t o a n unsym m etrical o rg an o lead oompound.

t h i s oompound, in t u r n , may be c lea v e d to produce f u r t h e r

d i f f e r e n t i a t i o n i n th e organolead compound*

Such a s e r i e s o f r e a c tio n s

i s p o s s ib le b ecau se o f t h e g ra d a tio n in ease o f cleavage o f d i f f e r e n t o rg a n ic g ro u p s. P r e f e r e n t i a l c le a v a g e , l a b i l i t y , o r r e l a t i v e n e g a ti v ity o f organo­ m e ta llio compounds lets occupied t h e a t t e n t i o n o f a number o f w o rk ers. E x ten siv e w ork h as been done b y H haraseh and co-w orkers (ISO , 1 21, 122} on th e l a b i l i t y o f organaraereury compounds. b e en e s ta b lis h e d i n th e t i n s e r ie s (1 6 , 22)*

Less e x te n s iv e ta b le s have By combining th e la rg e

number o f s h o r t s e r i e s a v a ila b le from o rg an o lead cleav ag e s t u d i e s , i t i s

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17. p o s s ib le t o o b ta in a r a t h e r e x te n s iv e r e l a t i v e n e g a t i v ity s e r i e s o f r a d i c a l s . Comparison o f fragm ents o f s e r i e s o b ta in e d by th e stu d y o f th e s e th r e e d i f f e r e n t m e ta ls in d ic a te s t h a t th e r e i s l i t t l e i f any d if f e r e n c e i n th e o rd e r o f c le a v a g e , p ro v id in g th e same method o f clea v a g e i s u s e d . The fo llo w in g s e r i e s g iv e some id e a o f th e o rd e r o f c le a v a g e , th e m ost e a s i l y o le av e d r a d i c a l a p p ea rin g f i r s t : -x y ly l, j» * t© ly l, p h e n y l, m e th y l, e t h y l , n*»propyl, is o b u ty l* iso sa a y l, e y clo h ex y l (1 4 5 ). 2 « f u r y l, 2 - t h i e n y l , phenyl (8 5 ) . ( a l l y l , (^■ etyvyl)* p h e n y l, S -b u te n y l (2 0 5 ). I n g e n e r a lis in g upon c lea v a g e (5 ) one n ay sa y t h a t , i n th e a ro m a tic s e r i e s , th e h e a v ie s t r a d i c a l i s c lea v e d f i r s t .

I n th e prim ary a l i p h a t i c

s e r i e s , th e l i g h t e s t in m o le c u la r w eig h t i s oleaved f i r s t .

Arom atic groups

a r e oleav ed b e fo re a l l p h a t i o g ro u p s, and a l i p h a t i c groups o th e r th a n prim ary ones a r e cleav ed b e fo re th e co rre sp o n d in g p rim ary g ro u p . r a d i c a l seems h e ld more f ir m ly th a n any o th e r .

The o y clo h ex y l

I n oases where d i f f e r e n t

r a d ic a ls have q u ite s im ila r te n d e n c ie s t o be cleav ed t h a t r a d ic a l i s u s u a lly cleav ed which i s p re s e n t i n g r e a t e s t number. Some r a th e r im p o rta n t e x c e p tio n s to th e g e n e r a liz a tio n t h a t th e h e a v ie s t a r y l r a d i c a l i s c le a v e d f i r s t a p p e a r i n an a r t i c l e b y Oilman and Tcnrae (8 5 ). The c i- f u r y l and ojO*thienyl r a d i c a l s a r e c le a v e d b e fo re th e phenyl r a d i c a l .

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18. An example o f an i n t e r e s t i n g s e r ie s o f re a c tio n s making u s e o f t h i s knowledge i s ta k e n from A u stin ( 9 ) t HC1 (CgBg)4f t> HC1

n-CgHfMgBr > (Cgi%)5P b e i 3 -------------- (CQiigJgFbCligCHgCHg

o~CH5C6H4JlgBr ►(C6Hg ) (CHsCH2CHg)H)Cl2 “ ------------------ > HC1

(CgHg )(CH5GH2GH2 )Pb(o-CHgG6H4 )2

GHjGHiCHgJgCHj OCgH^Id

*■ (CgHg ) (CHgCHgCHg) (o-CHgCgH^FbCl

| W

H5

CgH5-Pb-C 6H4OCH(CH5 5CH2 ( - to ly l, bound to one o r more m e tals in c lu d in g le a d , t i n , s i l i c o n , and m ercury (2 9 , S 3 ). D e carb o x y latio n o f o rganolead s a l t s o f o rg a a io a c id s Kocheshkov and A leksandrov (1 2 6 , 127) have re p o rte d a n i n t e r e s t i n g method o f e s ta b lis h in g a c a rb o n -le a d lin k a g e .

T h e ir method in v o lv e s

d e o a rb o x y la tio n o f a n o rg a n o le ad s a l t s (C6H5 ) sFbGl 4 KOgCCHgCOgCgHg

COg

4

► (CgHeJsJbOgCQ^OOgCgHg

(GgHg) jPbCHgCOgCgEg

In t h i s c o n n e c tio n , i t m ight b e w e ll t o m ention s e v e r a l e a r l i e r a tte m p ts t o o b ta in a c a rb o n -le a d lin k a g e b y p y ro ly s is o f a le a d s a l t . Hurd and A u stin (114) a tte m p te d t o p re p a re such a compound from le a d te tr a b e n s o a te .

This w ork was p a tte r n e d a f t e r th e known fo rm a tio n o f a

o arb o n -aero u ry bond i n th e p y ro ly s is o f m e rc u ric b e n so a te (214) t

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.

(CgHgCOOjgHg

170° /N c ^ o ► CgHgCOCM* ^ 0

W hile b e n zo le a c id was d e ta c h e d , no ev id en ce co u ld be found f o r a n o rganolead compound i n th e r e s id u e .

V igorous d eco m p o sitio n alw ays to o k

p la c e upon h e a tin g th e le a d te tr& b e n z o a te » The same a u th o rs a l s o p y ro ly zed le a d t e t r a a c e t a t e .

N early

q u a n tita tiv e y ie ld s o f le a d d ia c e t a t e w ere o b ta in e d . Towns (20S) h e a te d on a w a te r b a th th e d o u b le s a l t o f a n i l i n e w ith le a d a c e t a t e , CgHgNHg.Fb(CgHgGg)g» and re c o v e re d i t unchanged.

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21.

Tabla 2 .

Compound

RjR'Pb Compounds

M.P. o r B .P .,° C .

R eferences

T r i- o - a n is y lb e n s y l-

80-81

(67)

T ri-£ « a o isy l« 2 * fu ry 1 -

83

(86)

T ri* jo -a n isy ltri|to # a y lw stfe y l-

145-146

(10)

T rio y o lo h e x y lb e iu y l-

d o c . 128

(67)

T ri-jo -eth o x y p h en y lb en sy l-

76-77

(67)

T rie th y la lly l-

86/L0

(189)*

(1QQ, 189, 201)

T rle th y l-g -a m y l-

121/15

(104)

(2 8 , 100, 104)

T r ie t h y l- s e e - a a y l -

118/13

(100)

(100, 107)

T rie th y lb ensy 1 -

1 4 9 -1 5 0 .5 /1 3 w ith some d e e .

(99)

T rieth y l-J.-b ro a o aray l-

116*8/13 (104)

(1 0 0 , 104)

T rie th y l-js -b ro a o p h e n y l-

d eo .2 1 0 /3

(189)

T r ie th y l- 3 - b u te n y l-

7 8 /3

(87)

T rie th y l-n -b u tg rl-

108/13

f r ie t h y l - s e o - b t t t y l -

105-106/14 (84)

(8 4 , 1 0 0 , 107)

T rie th y l-te rt-b u ty l-

76/fe

(84)

T rie th y lo a rb o x y ia e th y l-

137 deo*

(201)

T rle th y l-£ -d i® e t^ ls ffiin o p h e n y l-

125/1

(201)

(84)

(8 4 , 1 00, 105)

♦This ocmpound a l s o e x i s t s a s a s o lid dim er which d e e . a t 115° (2 0 1 ).

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22 Sable 2 (c o n tin u e d )

Compound

M.P. o r B .F .,°C , i

R eferences

I r i e th y l- £ -h y d r oxyethy 1 -

100/2

frle th y lis o a n y l-

1 1 4 .6 /1 3

(101)

(2 6 , 1 00, 1 0 1 , 105)

S r ie t h y lis o b u ty l -

102/10

(84)

(8 4 , 10 0 , 10 1 , 105)

T r ie th y lis o p r o p y l-

90 /1 3

(107)

(2 5 , 1 0 0 , 107)

S r ie th y ia ie th y l-

7 0 -7 0 .5 /1 6

(101)

(2 6 , 2 8 , 2 9 , 5 4 , 36, 3 6 , 9 1 , 100, 101)

T rie tb y l^ -n a p h th y l-

176/13

(99)

T rie th y l-i> -o o tad e cy l~

73-74

(185)

T rie th y lp h e n y l-

1 3 6 /lS

(201)

(99)

? rie th y l-j> - ( N -phthalim ide ) ph en y l- lOo/O.OOOl

(9 9 , 114) (201)

T rle th y l-a r* p ro p y l-

9 9 .5 /1 6

f r ie tl iy l« £ - to 3 y l-

155.5/!l3

(99)

T r ie th y l- j> - to ly l-

154/13

(9 9 )

T ri is o a a y le th y l-

steam d i e t .

(106)

(1 0 0 , 106)

f r l is o a m y lis o b u ty l-

steam d i e t .

(106)

(100, 106)

T ri ia oam ylasthy 1 -

•team d i e t .

(106)

(1 0 0 , 106)

f r%is o a m y l-a -p ro p y l-

•team d i e t .

(106)

(1 0 0 , 106)

T ri i aobu tyl*^n*»butyl«

145-146/10

T ri ie o b u ty le th y 1 -

steam d i s t .

(106)

(1 0 0 , 106)

T ri is o b u ty lis o a s y l-

steam d l s t .

(106)

(1 0 0 , 106)

(101)

(2 9 , 1 0 0 , 1 01, 105)

(42)

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23. Table 2 (continued)

CoBpeu&d T rii* o b u ty la e th y lT ri i* o b u ty l-n « p ro p y 1-

M.P. o r B . P . , C*C.

R eferen ces

121/12 (108) w ith •lo w d e o .

(1 0 0 , 106)

•te am d i e t .

(1 0 0 , 106)

T riU o p ro p y ln ie th y l-

(106)

—eteiwe

(2 8 )

T rim e th y ib e n iy l-

1 2 4 /iS w ith d e o .

(99)

T riaetiq rl* » a-b u ty l-

6 4 .6 /1 4

(101)

(1 0 0 , 101)

T rim e tiiy l-a e o -b u ty l-

69/1$

(S I)

(31* 107)

T riia e t^ y l-te £ fe » b u ty l-

6 .7 j4 7 /L 3

(31)

(2 6 , 2 9 , 31)

T r ia e th y le th y l-

27/10

(101)

(2 6 , 2 8 , 2 9 , 3 4 , 3 6 , 3 6 , 1 0 0 , 1 0 1 , 106)

T rira eth y liso a m y l-

69-71/12

Trime l& ylisobu t y 1 -

58-59/16

(101)

(1 0 0 , 101)

T rim e th y lis o p ro p y l-

76/60

(107)

(2 6 , 2 9 , 100, 107)

T rira eth y lp h ea y l-

104/13

(99)

(2 9 , 99)

T rlm e th y l-a -p ro p y l-

48-49/16

(101)

T ri» e th y l-« o -to ly l-

117.5 -1 1 8 /1 3

(99)

T r in w th y l-jJ -to ly l-

118-119/13

(99)

T r ip h e i^ r la lly l-

76-77

T ri pheny 1-^-aalnopheny1 -

166-166

(201)

T ri phenyl-_£-am inophenyl-

166-167

(82)

(101)

»ainyl-

16-17

(9 )

T ri phony !*-anisyl-

128-129

(163)

T r i phonyl-j£«ani*y 1 -

152

(86)

T r ip h e n y l- 7 - ( l ,2 -b e n s a n th ry l ) -

204-208

(th is th e s is )

T riphony lb e n z o h y d ry l-

1 2 2 ,d e o .130

(67)

T ri phonylbentsyl-

9 3 )deo.205-210

(146)

(6 7 , 8 7 , 146)

T ri phony l-dt-^einsyld^oarbotSaa^ym ethyl-

82-84

(126)

(1 2 6 , 127)

T rip h en y l-j^b rcm o p h o n y l-

115

(189)

(7 5 , 189)

f r ip h e n y l- S ^ te ia g r i-

84-86

(87)

T ri phony l- s j- b u ty l-

47

(85)

T r i p h e n y l-s e e -b u ty l-

84,

(85)

T ri phony 1 -to r t - b u t y l -

150

(83)

friphenylearboxyphenylaao }-p h e n y l] -

——

(201)

T r ip h e n y l- l- [2-dime th y lamljao-5-(j> (9 0 s )g compound, R ea c tio n o f d la a o n iu a c h lo rid e s w ith le a d c h lo rid e s W ills r e a c tio n s o f th e ty p e t (REgCl)2 .FbC l4

►RgFbCl *

or RNgOl.PbClg

RgPbClg

a r e known (ISO# 172)# th e y ie ld s a r e o n ly a few p e r o e n t,

The g e n e ra l

p ro ced u re f o r th e s e r e a c tio n s i s t o add a powdered m e ta l such as t i n , sin e# o r copper t o a su sp e n sio n o f th e diazonium c h lo r id e - le a d c h lo rid e com plex, and th e n h e a t th e m ix tu re , S te in and I M u * (169)

t e l . t o p r . p . r . R ^ t C l , oonponnd. from t h .

diasonium c h lo r id e s and antim ony powder*

The r e a c ta n ts were suspended in

a ce to n e o r e t h y l a c e ta te and th e s o lu tio n k e p t n e u tr a l b y adding chalk* When le a d powder m s s u b s tit u te d f o r th e antimony# o n ly in o rg a n ic le a d ions w ere found i n th e p ro d u o t.

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38. In some e a r l i e r work fey S a k e lla r lo s (1 9 0 ), i t had b e e n o b serv ed t h a t h e a tin g o f (M gCl)g^FbCl^ complexes w ith o u t o a t& ly s ts gave no m a te r ia l w ith a c a rb o n -le a d b o nd.

I t m ight a ls o be m entioned t h a t t h i s same a u th o r

h y d ro ly sed th e complex (CgHgSHg.HC1)g.FbCl^ and o b ta in e d o n ly le a d c h lo rid e and OjHgHClg. C o n tro lle d r e a c tio n o f le a d o h lo rid e w ith a G rig a a rd re a g e n t Krause and S c h lo ttig (146) s t a t e d t h a t tr ip h e n y lle a d c h lo rid e was produced by adding t o phenylasagnes ium brom ide a n amount o f le a d o h lo rid e somewhat in ex cess o f t h a t u sed t o produce te tr a p h e n y lle a d .

The

tr ip h e n y lle a d c h lo r id e was n o t i s o l a t e d a s such b u t was removed by sh ak in g th e r e a c tio n p ro d u c t w ith a s o l u tio n o f a l k a l i .

The y ie l d s were none to o

good. T rip h e n y lle a d brom ide has b een found as a n o c c a s io n a l b y -p ro d u e t i n th e p re p a ra tio n o f te tr a p h e n y lle a d th ro u g h th e G rig a a rd r e a c tio n (1 9 4 ).

This

compound does n o t owe i t s fo rm atio n t o a seco n d ary r e a c ti o n betw een te tr a p h e n y lle a d and magnesium brom ide o r th e b in a r y system (Mg 4 MgErg)* inasm uch a s te tra p h e n y lle a d i s u n a ffe c te d b y th e s e su b sta n c e s u n d er t h e c o n d itio n s o f th e r e a c tio n .

The n e x t method m ig h t b e u sed i n o f f e r i n g a

c lu e t o th e fo rm a tio n o f tr ip h e n y lle a d brom ide b y assum ing a r e a c tio n betw een h e x ap h e n y ld ile a d and magnesium b rom ide. Meals (1 6 1 ), i n a stu d y o f lo n g -c h a in e d o rg a n o m e ta llie compounds, p re p a red RgPbCl compounds i n o v e r 50% y ie ld s b y r e a c tio n o f a b o u t on© mole e q u iv a le n t o f le a d c h lo r id e w ith two mole e q u iv a le n ts o f lo n g -c h a in ed

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39* alkyIm agoesiura brom ide.

A ttem pts t o form R^FbBr oompounds by s i m i l a r

re a c t! o n s u s in g le a d brom ide were u n s u c c e s s fu l. Meals (161) o bserved t h a t th e m e ltin g p o in ts o f SgPbCl oompounds re a ch a minimum somewhere betw een t r i - n - b u t y l l e a d o h lo rid e (m .p. 109-111°) and tr i- n - d o d e c y lls a d c h lo r id e (m .p. 6 4 -6 8 ° ), & re g io n i n w hich R^PbCl compounds have n o t b een in v e s t ig a te d .

I t i s in te r e s t in g t o n o te t h a t i n

th e lo n g -c h a in e d a Ik y l i e ad compounds, mixed m e ltin g p o in ts do n o t seem to have much v a lu e ,

A m ix tu re of te tr a - n - h e x a d e c y lle a d and t e t r a - n -

h e x a d e o y ltin showed no d e p re s s io n i n m a ltin g p o i n t .

A m ix tu re o f t r i - n -

dodeoyllead c h lo rid e (m .p. 64-6 5 °) and t r i - n - t e t r a d e c y l l e a d c h lo rid e (m .p. 7 4-76°) m elted a t 6 6 -6 7 °. A u stin (? ) in v e s tig a te d th e u se o f th e r e a c tio n : SgPbXg 4 Ig H g

►BgPbX 4 RHgX

i n th e s y n th e s is o f o rg an o lead compounds.

D ip h en y llead d ic h lo r id e and

diphenylm ercury h e a te d i n p y rid in e gave a 21$ y ie ld o f tr ip h e n y lle a d o h lo r id e .

The low y ie ld may have been due t o th e d i f f i c u l t y in i s o l a tin g

tr ip h e n y lle a d c h lo r id e a s th e r e was a 67$ y i e l d o f phenylm erouric o h lo r id e . When th e re a c tio n s ( o-CHjCgH^) gPbClg 4 (CgHg^Hg —

(o-CSBjCgH^CgHgjFbCl 4 CgBgBgCl

was o a r r ie d o u t in an a tte m p t t o o b ta in mixed compounds, phenylm erouric c h lo rid e m s o b ta in e d i n a 38$ y i e l d , b u t none o f th e e x p e c te d d i - o to ly lp h a n y lle a d c h lo r id e could be i s o l a t e d from th e r e a c tio n p ro d u c ts . T e tra p h e n y lle a d and d i - o - t o l y l l e a d d ih a lid e s d id n o t r e a c t when h e a te d i n benzene o r to lu e n e in an a tte m p t to form mixed ary lle& d h a l i d e s .

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R eao tio n o f S^Fb o r RflFb© oompounds w ith some in o rg a n ic h a lid e s and o rg a n ic a o id h a lid e s Browne and fieid ( i d ) in v e s tig a te d th e a o tio n o f s o w o rg a n ic a o id h& lldes and in o rg a n ic h a lid e s upon t e t r a e t h y l l e a d .

T e tra e th y lle a d r e a c te d

r e a d ily w ith a e e ty l c h lo r id e a t room te m p e ra tu re on th e a d d itio n o f s i l i c a g e l*

A m ix tu re o f e q u iv a le n t amounts o f th e two r e a c ta n ts produced

t r i e t h y l l e a d c h lo rid e *

Benzoyl o h lo rid e re a c te d a ls o )

th e only p ro d u c ts

t h a t could h e is o la te d were le a d c h lo r id e and b e n zo ic a c id . W ith phosphorus p e n ta e h lo rid e , t e t r a e t h y l l e a d i n carbon d i s u l f i d e s o lu tio n produced a th ic k sy ru p from which t r i e t h y l lead c h lo r id e was e x tr a c te d w ith petroleum e t h e r .

A sim ple s o lu tio n o f t e t r a e t h y l l e a d i n

carb o n d i s u l f i d e gave a b la c k flo c c ru le n t p r e c i p i t a t e which was in s o lu b le i n e th e r* a lc o h o l* o r p e tro le u m e th e r*

I t d id n o t m elt a t 300° b u t

b urned r e a d i l y . T e tra e th y lle a d and aluminum c h lo r id e r e a c te d i n o rg a n ic s o lv e n ts t o g iv e tri© th y H e a d c h lo rid e a s th e o n ly m a te r ia l is o la te d *

S ilic o n

t e t r a c h l o r i d e lik e w is e gave t r i e t h y l l e a d c h lo r id e , b u t tita n iu m t e t r a ­ c h lo rid e was red u ced t o tita n iu m t r i c h l o r i d e w ith th e p ro d u c tio n o f a browa* t a r r y s u b s ta n c e . Goddard and Goddard (91) observed th e a o tio n o f t h a l l i o o h lo rid e w ith s e v e r a l o rg an o lead compounds.

'E m !lie o h lo rid e and tr ie th y lm e th y lle a d

y ie ld e d t r i e t h y l l e a d c h lo rid e and th a llo u s c h lo rid e *

D ie th y Id ip h e n y lle a d

y ie ld e d d ie t h y l le a d d ic h lo r id e and d i p h en y lth a 11 ium c h lo rid e *

Di-_d-

n a p h th y ld ip h e n y lle a d y ie ld e d d ip h e n y lle a d d io h lo r id e and d i- ^ - n a p h ty lt h a l l l u a c h lo rid e *

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4 1. Goddard (39) re a c te d h e x a ^ a -x y ly ld ile a d i n benzene w ith t h a l l i o c h lo r id e i n e t h e r .

The s o lu tio n became m m end & p r e c i p i t a t e a p p e a re d .

A fte r s ta n d in g a week, c r y s t a l s o f d i-® « x y ly lle a d d io h lo r id e had form ed and th e benzene s o lu tio n c o n ta in e d th a llo u s c h lo r id e . In sum m arizing th e re a c tio n s betw een a l i p h a t i c o r a ro m a tic o rg a n o le ad compounds and t h a l l i o o h lo rid e Goddard s ta t e d th a t* 1*

S u b stan ces o f th e ty p e R^Fb g iv e r i s e t o RgPbXg and RgTlX oompounds.

2*

Substances o f tfee ty p e RgFbX and RgE’Ifc (where R* i s th e r a d i c a l w ith low er m o le c u la r w eig h t) y i e l d th a ll o u s o h lo rid e and R ^ a n d RgFbX, r e s p e c tiv e ly .

3.

S ubstances o f th e ty p e BgR'gFb produce R'gFbXg and SgTlX compounds.

4.

S ubstances o f th e ty p e RgFbXg (where X i s brom ine o r io d in e ) m erely exchange h alo g en w ith t h a l l i o o h lo r id e . C h a lle n g e r and P r itc h a r d (38) i n ta b u la tin g re a c tio n s betw een v a rio u s

o rg a n o m e ta llic compounds and some in o rg a n ic h a lid e s s ta t e d t h a t te tra p h e n y lle a d re a e te d a s follo w s* 1.

W ith bism uth trib ro m id e a t 66° d ip h e n y lle a d dibrom ide and diphenylbiam uth brom ide were form ed.

2.

W ith antim ony t r i c h l o r i d e a t 110° d ip h e n y lle a d d io h lo r id e and diphenylantiraony o h lo rid e w ere form ed.

3.

W ith a r s e n ic t r i c h l o r i d e a t 110° d ip h e n y lle a d d io h lo rid e and d ip h e n y la rs e n io o h lo rid e w ere form ed.

4.

W ith phosphorus t r i c h l o r i d e a t 134° th e r e was no a o t i o n .

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42 Gilman and B a ilie (67) found t h a t when b e n z e n e -e th e r s o lu tio n s o f a n BgFbg oorapound and raagnesium io d id e w ere allo w ed t o r e a c t , h y d ro ly s is w ith ammonium c h lo r id e gave e x c e lle n t y ie ld s o f RgPbl compound. fh e b in a ry system o f Gaaberg and Baohmann (94) m s ob serv ed b y Gilman and B a i lie t o undergo two d i f f e r e n t r e a c tio n s w ith HgPbg compounds.

Ron-

s t e r i c a l l y h in d e re d RgPbg compounds r e a c te d w ith t h e b in a ry system t o g iv e an K^Fb compound, le a d , and th e G rignard r e a g e n t.

I f , however, s t e r i c a l l y

h in d e re d BgFbg compounds w ere u s e d , t h e p ro d u c t was a n B^FhX compound. Nesmeyanov and Kooheshkov (171) in v e s tig a te d th e a c t i o n o f m e rc u ric c h lo rid e upon a number o f organoraetal 1io oompounds in o lu d in g o rg an o lead compounds. Gilman and Apperaon (66) re p o rte d upon th e r e a c tio n s betw een some o rg an o lead compounds and aluminum c h lo r i d e , bism uth t r i c h l o r i d e , anhydrous f e r r i c c h lo r id e , and o h lo r o p la tin i o a c id . In te rc h a n g e betw een S^Fb and RgFbXg oompounds A u stin ( ? ) found t h a t te tr a p h e n y lle a d and d ip h e n y lle a d d ic h lo r id e h e a te d i n b u ty l a lc o h o l gave a n 86^ y ie l d o f tr ip h e n y lle a d c h lo r id e . T e tra e th y lle a d and di® th y H e a d d io h lo r id e h e a te d i n benzene gave a 39$ y i e l d o f t r i e t h y l l e a d c h lo r id e .

As m entioned i n t h e g e n e ra l d is c u s s io n

o f o rg an o lead h a l i d e s , A u stin was u n a b le t o produce compounds o f th e SgR’PbX ty p e by t h i s r e a c t i o n .

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liable 6*

Compound

RjPbX Compound#

M,P»,°C*

R eferen ces

T r ia a y l- brom ide ( ? ) •

(124)

T riam y l- c h lo r id e ( f )

------ -

(124)

T r ia s y l- Io d id e

------

(124)

122-123

(67)

---------

(86)

f r i - j j - a a i s y l - c h lo rid e

152-153

(86)

T r ib e n s y l- brom ide

d ec.150

(146)

T r ib e n s y l- c h lo rid e

u n s ta b le

(149)

(? )

T r i - ^ a n i s y l - io d id e T ri-jg -a n is y l- bromide

T r i- n - b u ty l - bromide

(4 3 , 167)

—— *

T r i- n - b u ty l - c h lo r id e

109-111

(180)

T r l- s e p - b u ty l- c h lo rid e

dec*130

(188)

T rioycloheacyl- brom ide

d e c ,210

(136)

T ricyolohexy1 - c h lo rid e

d e c *236

(136)

T ri cyo lohexy1 - f lu o r id e

d e c .198

(140)

T rio y e lo h e x y l- io d id e

9 1 .7

T ri-n -d o d e o y l- c h lo r id e

64-65

(161)

T ri-jg -eth o x y p h en y l- io d id e

99-100

(67)

(138)

(1 7 , 4 9 , 180)

(41* 6 7 , 136* 137)

♦In th e s e ta b le s * a f means no a n a ly s is s a s r u n , o r th e a n a ly s is ana n o t to o c lo s e t o th e o r e tic a l* o r th e compound m s n e v e r is o la te d * o r i t i s u n c le a r n h e th e r th e & group I s n - , is o - * e tc *

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TabIs 6 (c o n tin u e d )

Compound

R eferences

M .P „ °C .

T r i e t h y l - bromide

103-104

(102)

(2 6 , 2 9 , 3 4 , 6 7 , 102, 156, 157, 20 0 , 202)

T r ie t h y l- c h lo rid e

brown 120

(102)

( 7 , 1 6 , 1 7 , 2 0 , 2 1 , 26, 2 7 , 2 9 , 3 4 , 6 6 , 3 0 , 84, 9 1 , 9 2 , 1 0 2 , 1 1 0 , 114, 156, 157, 166, 179, 1 9 9 , 2 0 0 , 217)

T r i e t h y l - f lu o r id e

deo.240

T r i e t h y l - io d id e

(140) /

— —

■

(2 4 , 167)

T ri-n -h e x a d e c y l- c h lo r id e

79-80

T riis o a ra y l- brom ide

132-155

T riis o a m y l- f lu o r id e

deo.251

T r iia o b u ty l- brom ide

107-108

T r iis o b u ty l- c h lo rid e

122deo.

(106)

t r i i s o b u t y l - f lu o r id e

d e c .230

(140)

T r iis o b u ty l- io d id e

u n s ta b le

(106)

T r iis o p r o p y l- bromide

—

(161) (106)

(4 1 , 1 06, 135) (140)

(106)

(4 1 , 106, 157)

(93)

-------------

(9 5 , 202)

t r i i s o p r o p y l - c h lo rid e T r iis o p r o p y l- io d id e

u n s ta b le

(202)

T r im e s ity l- io d id e

200-201

(67)

T rim e th y l- brom ide

IS Sdee,

f r lm e th y l- c h lo r id e

sublim es 187 (102)

(102)

(2 3 , 2 8 , 3 4 , 1 0 2 , 211) (1 7 , 2 5 , 2 6 , 2 9 , 3 4 , 102, 1 5 6 , 19 2 , 200)

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45. Tabla 6 (conoluded)

Cempoaad T rim e th y l- f lu o r id e

M .P .,°C .► Very v o l a t i l e

R eferences (140)

T rim e th y l- io d id e

(2 3 . 2 9 . 31)

T r i- a - o o ta d e o y l- c h lo r id e

82-83

(161)

T ri phene th y 1 - brom ide

91-92

(146)

T ri p h e n y l- brom ide

166

(98)

(4 1 , 9 8 , 137, 14 5 , 156, 200)

T rip h e n y l- c h lo r id e

206

(98)

(7 , 8 , 5 1 , 63, 5 4 , 66, 6 9 , 7 9 , 9 8 , 129, 130, 1 4 5 , 1 5 6 , 158, 1 7 1 , 172, 1 9 9 , 200)

T ri p h e n y l- f lu o r id e

deo.318

(140)

(4 1 , 137, 140)

T rip h e n y l- io d id e

142

(®e)

(5 1 , 5 3 , 6 7 , 9 8 , 141, 156, 200)

T r i- n - p r o p y l- brom ide

81-82

T r i- n - p r o p y l- c h lo rid e

IS?

T r i- n - p r o p y l- f lu o r id e

explodes a t 235

(4 1 , 137, 140)

T ri-n —b e tra d e c y l- c h lo r id e

74-75

(161)

T r i - o - t o l y l - brom ide

129-130

(5 )

( 5 , 6)

T r i - o - t o l y l - c h lo r id e

141-142

(6 )

( 6 , 66)

T ri-® -fco ly l- brom ide

146-147

(67)

T r i - g - t o l y l - c h lo r id e

140-141

(6 )

T r i-j» -to ly l~ f lu o r id e

d e c .280

(140)

T r i- j> - to ly l- io d id e

115

T r i- 2 ,5 - x y ly l - brom ide

17?

(148)

T rt-g ^ o ty ly l- c h lo r id e

167.8

(141)

(180) (180)

(141)

(1 7 , 1 0 2 , 180)

(6 7 , 141)

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Table 7 ,

HgR'PbX Compounds

Compound

S e fe re n ee s

Di-n-aBQrl8»ifayl- c h lo rid e

d e c .121

-to ly l- dibrom ide

116-11?

(5)

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B ^ F b COMPOUNDS

The s o * e a lle d d iv a le n t o rg an o lead compounds a r e c h a r a c te r is e d by t h e i r h ig h ly o o lo re d s o lu tio n s and by t h e i r g r e a t i n s t a b i l i t y .

The deep

brown t o re d s o lu tio n s t h a t dev elo p i n th e e a r ly s ta g e s o f th e r e a c tio n betw een le a d c h lo r id e and a lk y l G rignard re a g e n ts have b e e n a t t r i b u t e d t o th e fo rm a tio n o f d iv a le n t le a d compounds (1 0 2 ).

Only d ip h e n y lle a d and

d i- js - to ly lle a d have b e e n i s o l a t e d (141) i n s n a i l y ie l d s b y th e r e a c tio n o f le a d c h lo r id e and th e co rresp o n d in g G rig n ard re a g e n t*

R igorous c o n tr o l

o f th e r e a c tio n and a h ig h degree o f m a n ip u la tiv e s k i l l w ere r e q u ir e d to p re v e n t th e p ro d u c ts from decom posing.

The d ia r y H e a d compounds w ere

b lo o d -re d amorphous pow ders, q u ite u n s ta b le i n th e a i r o r l i g h t b u t in t h e i r ab sen ce th e compounds o o tid b e k e p t f o r a p e rio d o f a w eek.

Io d in e

r e a c te d w ith them r e a d ily t o form th e d ia ry H e a d d le d id e s , and a lc o h o lic s i l v e r n i t r a t e was I n s t a n t l y re d u c ed .

In bensene s o lu tio n t h e compounds

w ere found t o b e i n th e monem oleoular form . D ip h e n y lle ad , when h e a te d i n a c a p i l l a r y tu b e* decomposed around 100°, tu rn e d y ello w a t 120°* m e lted above 2 0 0 °, and tu rn e d b la c k a t 26 0 °. The o n ly o th e r known method f o r p re p a rin g d i v a le n t o rg an o lead compounds i s by e l e c t r o l y t i c re d u c tio n o f a k e to n e u s in g a le a d cathode i n a s u l f u r i c a c id b a t h ,

X afel (202) p re p a re d d iis o p ro p y lle a d i n t h i s manner b u t

i s o l a t e d h i s p ro d u c t a s th e d ih a lid e d e r i v a t i v e .

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53 C a lin g a e rt (25) a tte m p ted t o p re p a re d ia lk y l i e ad compounds from d ia Ik y H e a d d ih a lid e s by th e a c ti o n o f sodium i n l iq u id ammonia.

It

h as b e en observed i n th e s e la b o r a to r ie s t h a t th e ire was a t r a n s i t o r y brown t o re d c o lo r a tio n o f th e ammonia s o lu tio n when t h e ammonia«eoluble m e ta l was f i r s t added t o a d ia ry lle & d d ih a lid e *

T h is c o lo r a tio n q u ic k ly

d isa p p e a re d as more m etal was added and th e h e x a a ry ld ile a d was I s o la te d from th e r e a c tio n . Krause and R eissau s (141) added a benzene s o lu tio n o f io d in e t o a b lo o d re d s o lu tio n o f d ip h e n y lle a d i n bensene and observed a n immediate d isap p earan o e o f th e r e d c o lo r*

They s t a t e d t h a t d ip h e n y lle a d d ilo d id e

was formed and t h a t t h i s soon decomposed w ith fo rm a tio n o f le a d io d id e . These same a u th o rs observed th e fo llo w in g changes when d ip h e n y lle a d m s h e a te d i n a m e ltin g p o in t tu b e t

t h e sample tu rn e d p a le and decomposed

a t ab o u t 1 0 0 °, th e decom positio n p ro d u c t tu rn e d y e llo w a t 1 2 0 °, and m e lted above 2 0 0 °.

Ho b la c k c o lo r had ap p eared a t 2 6 0 °.

These o b s e rv a tio n s do

n o t len d su p p o rt t o th e s e r i e s o f e q u a tio n s g iv en t o e x p la in th e fo rm a tio n o f R^Fb compounds (s e e u n d e r R^Fb compounds) .

H exaphenyldilead was formed

from d ip h e n y lle a d by g e n tly r e f lu x in g a n e th e r-b e n se n e s o lu tio n o f d ip h e n y lle a d and phanylraagnesium b ro m id e.

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la b le XI.

Ccnpound D i-a a o -b u ty lD iia o p ro p y l-

BgPb Conpounda

Commenta no a n a l , b u t d a r iv a tla a d ---------

R sfaren ces (188) (5 0 , 9 3 , 202)

D i-5 - p a n ty l-

no a n a l, b u t d e riv & tie e d

(188)

Diphonyl -

d«o. around 100 (141)

(141* 16?)

I)i■•>J»•tolyl•

(141)

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R - F b - COMPOOTTDS

6

2

Genar&l D iscu ssio n

A g r e a t d is c re p a n c y a p p ea rs i n th e l i t e r a t u r e d e a lin g w ith th e d eg ree o f d i s s o c ia tio n o f th e S^Fbg compounds in to o rg an o lead " r a d i c a l s ’*i Hglfcg S l-Z HjHj th e w ide d iv erg en ce i n th e amount o f d is s o c ia tio n a s r e p o rte d b y v a rio u s a u th o rs may be a t t r i b u t e d t o th e d i f f e r e n t methods o f m easurem ent. M olecular w eig h t measurements b y Krause and ReXssaus (141) and P o s te r , Dix, and G ru n tf e s t (S3) in d ic a te d t h a t h ex ap h en y Id ilo ad was a p p re c ia b ly d is s o c ia te d in d i l u t e bansene s o lu t io n .

The assum ption was t h a t th e

d is s o c ia tio n p ro d u e t was tr ip h e n y lle a d .

Ydiile th e r e was a s te a d y r i s e

i n m o le c u la r w eight w ith in c re a s e i n c o n c e n tr a tio n , no mass a c ti o n c o n s ta n t c o u ld bo c a lc u la te d from th e d a ta .

As tr ip h e n y lle a d would p o sse ss an odd number o f e l e c tr o n s , Pro eke1 and Selwood (186) u n d erto o k t o d eterm in e th e degree o f d is s o c ia tio n th ro u g h m agnetic s u s c e p t i b i l i t y m easurem ents.

M agnetic measurements s e t th e u p p e r

l i m i t s o f d i s s o c ia tio n a t 0 .1 # i n th e s o l i d and 1 .4 # i n a bensene s o l u tio n w ith in th e to ra p e ra tu re range o f 30 t o 80° and th e eo&oent r a t i o n ran g e o f 0.02265 H t o 0,0154? K.

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56. Under th e s e c irc u m stan c es i t was deemed a d v is a b le t o in v e s t ig a te th e s e d iv e rg e n ce s f u r t h e r .

K rause (156) found t h a t m o le c u la r w eig h t

measurements o f h e x a c y o lo h e x y ld ile a d i n f r e e s in g benzene in d ic a te d 47^ d is s o c ia tio n .

M orris and Selwood (169) found b y m agnetic s u s c e p t i b i l i t y

measurem ents t h a t h e x a e y o lo h e x y ld ile a d was p r a c t i c a l l y co m p letely a s s o c ia te d i n benzene a t 9 0 ° .

U n fo rtu n ate ly th e d eg ree o f a c c u ra cy o f m agnetic

s u s c e p t i b i l i t y m easurem ents i s n o t of a v e ry h ig h o r d e r , b u t a d eg ree o f d is s o c ia tio n su ch a s t h a t found i n fr e e z in g benzene would have b e e n v e ry a p p a r e n t.

These l a s t a u th o rs su g g e ste d t h a t a c lu e t o th e low m oleoul& r

w eig h ts found l y K rau se, F o s te r , and o th e r s m ight p o s s ib ly be found i n th e re s e t! o n e undergone l y h e x a a ry le th a n e * .

Although no ev id en ce y e t

e x i s t s f o r com parison, I t i s n o t im probable t h a t a compound such a s h e x ap h e sy ld lle a d m ig h t slo w ly decompose t o s e v e r a l frag m en ts o f r e l a t i v e l y low m o le c u lar w e ig h t, e s p e c i a l l y a t m o d e ra tely e le v a te d te m p e ra tu re s . An e x p la n a tio n f o r th e f a c t t h a t f r e e r a d i c a l s a r e n o t found may be t h a t th e atom ic r a d iu s o f th e m etal atom i s much g r e a t e r th a n t h a t o f carb o n . The c o v a le n t r a d iu s o f le a d i s a t l e a s t tw ic e t h a t o f c a rb o n , hence th e e f f e c t o f th r e e phenyl groups i s o n ly t h a t o f p ro tu b e ra n c es on th e s u r f a c e o f th e l e a d .

W ith c a rb o n , th e a c ti o n o f th e phenyl r a d ic a ls i s more t h a t

o f a t i g h t l y f i t t i n g e n v elo p e .

As a r e s u l t , th e chance o f an e f f e c t i v e

c o l l i s i o n le a d in g to th e fo rm atio n o f a dim er i s much g r e a t e r i n th e oase o f le a d th a n i n t h e c a s e o f c arb o n r a d i c a l s . E le c tro n d i f f r a c t i o n measurem ents upon h e x am e th y ld ilea d (197) have in d ic a te d t h a t th e main bond d is ta n c e s i n th e m olecule a r e 2 .8 6 * 0 .0 5 A. f o r Pb-Fb and 2 .2 5 ^ 0 .0 6 A. f o r F b -e .

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57 A u stin (5 ) added b ro m in e, w ith s t i r r i n g , to ft c h lo ro fo rm s o lu tio n o f h e x ft-'O -to ly ld ilea d u n t i l th e brosnine c o lo r no lo n g e r d is a p p e a re d .

The

s o lu tio n m s f i l t e r e d t o remove le a d brom ide and m s th e n e v a p o ra te d , R e c r y s ta lliz a ti o n from a lc o h o l y ie ld e d d i - o - t o l y l l e a d d ib ro m id e,

When

40$ hydrobrom io a o id m s shaken w ith a ch lo ro fo rm s o lu tio n o f h e x a -o t o l y l d i l e a d , & c l e a r s o lu tio n r e s u l t e d ,

This s o lu tio n on e v a p o ra tio n

y ie ld e d a m ix tu re o f t r l * o - t o l y l l e a d brom ide and d i - o - t o l y l l e a d d ib ro m id e. Krause and R eissaus (141) observed t h a t co o led benzene s o lu tio n s o f h e x ap h e n y ld ile ad and io d in e , when m ixed, p r e c ip ita te d le a d io d id e .

If,

how ever, & benxene s o lu tio n o f h ex ap h en y ld i le a d was shaken w ith & m ix tu re o f one p a r t o f io d in e in a lc o h o l s o lu tio n and two p a r ts o f w a te r , tr ip h e n y lle a d io d id e m s produced w ith o u t decom position*

S im ila r r e s u l t s ware o b ta in e d

w ith hexa«j> *tolyldi2ead e x c e p t t h a t th e io d in a tio n p ro d u et d id n o t decompose a s r e a d i l y a s i n th e e a se o f th e phenyl compound. Gilman and B a i lie (67) found t h a t ie e c o ld ch lo ro fo rm s o lu tio n s o f io d in e and hexa i-trip h e n y llle a d s u o o in io a c id

(100, 104) (149) (106)

d e e .110

(th is th e s is )

——

D i(trim e th y l)p e n ta m e th y le n e d i-

1 66.6/L 4

T r ie th y l (pentsm®thylenem&gnes ium brom ide ) -

n o t is o la te d

(104)

fr ia e th y l (g -trie th y lp h e n y le n e e ilio o n )-

191/17

(108)

T rim eth y l ( tr im e th y lpentame th y le a e t i n ) -

1 62/17.5

(109)

Lead c a rb id e (le a d a c e ty lid e )

-------

(168)

J>*j>***Bip h e n y le n e d i [5 -a s o -2 hydroxypheny 1trip h e n y l- ] jj-F h e n y len e d i ( t r i p h e n y l- )

(109)

(1 0 0 , 109)

(201) 285-288*

(163)

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.

BgPbT, (SgPbJgY, BgPbYg, AND RR'PbY,, COMPOUNDS In th e s e compounds, i n which ? re p re s e n ts e i t h e r an o rg a n ic o r in o rg a n io s a l t r a d i c a l , th e C-Y lin k a g e i s o f a C-O, C-S , C-N, o r C -m etal ty p e . S t r i c t l y speaking th e C -halogon lin k a g e sh o u ld a ls o h e in c lu d e d i n th i s s e c t i o n , b u t t h i s ty p e m s d is c u s s e d s e p a r a te ly b ecau se o f th e la r g e nunfcer o f such compounds.

The

lin k a g e s d is c u s s e d i n t h i s s e c tio n a r e formed

e i t h e r b y a c tio n o f an a c id (16) upon a compound o f th e g e n e ra l ty p e R^Fbi (C2Hg )4Fb * CHgCOOH

» (CgH5 ) s FbOOCCH3 4- CgHg

b o ilin g

♦ »», —

—

♦ *V t

o r b y r e a c tio n o f such p ro d u c ts w ith o th e r m a te r ia ls t (Cghg )gPb°0C(2Ig f KGN

a (CgHgJgPbCN f CHgCQOK

The f i r s t r e a c tio n i s som etim es c a ta ly s e d w ith s i l i c a g e l (1 6 ).

The

second r e a c tio n i s o fte n c a r r i e d o u t w ith an o rg an o lead h a lid e * (CgHgJgFbCl * Ma.0h----- » (C^H )^*b y ie ld o f t e t r a ­ p h e n y lle ad (based upon r e a c tio n (1) o f page 144) m s o b ta in e d . R e a c tio n o f h ex ap h e n y ld ile a d w ith a a l c i e an h y d rid e I n c h lo ro fo rm .

In r e a c tio n s betw een m a le ic an h y d rid e and h ex ap h en y l-

d ile a d , s m a ll amounts o f m aleic a c id o r tr a c e s o f w a te r w ere found t o cause a f lo c c u la t e p r e c i p i t a t e .

To av o id t h i s , th® raaloic an h y d rid e m s h e a te d

in a t e s t tu b e suspended i n an o i l bath* I n a d ry tu b e was p la c e d 4 g . (0*0045 m ole) o f h e x a p h e n y ld ile a d , 0 .4 5 g . (0.0045 m ole) o f m aleic a n h y d rid e , and 100 e c . o f d ry c h lo ro fo rm .

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.

The

112. tub© m s s© alad, shaken v e il* and p la o ed i n a m m la b o ra to ry d e s k . A f te r f i f t e e n m inutes o nly a s l i g h t p r e c i p i t a t e had form ed.

Five months

l a t e r a s l i g h t l y b ro w n ish -g rey s o lid f i l l e d th e low er p a r t o f th e tube* This m a te r ia l was in s o lu b le i n a c e to n e , e th y l a lc o h o l, d io x a n e , ch lo ro fo rm , carb o n t e t r a c h l o r i d e , b e n se n e , and th e p e tro le u m e t h e r s .

I t m s s lig h tly

s o lu b le in b o ilin g w a te r and d is so lv e d i n g l a c i a l a c e t i c a c id . Any u n re a c te d M a te ria ls w ere removed b y b o i l i n g , f i r s t w ith chloroform and th e n w ith a lc o h o l.

D ig e stio n w ith a n ammonium a c e t a te s o l u ti o n

removed tr a c e s o f in o rg a n ic le a d . c o lo r .

The m a te r ia l was th e n a g re y is h -w h ite

?«hen view ed u n d er a m icro sco p e, i t was se e n t o p o ssess a c u b ic

s tru c tu re s im ila r to s a l t . had n o t m elted a t 3 3 0 °, y l le a d ) s u c c in ic a c id .

When h e a te d , i t tu rn e d brown a t 265-270° and T his p ro d u c t was b e lie v e d to b e c*,£-dl ( tr ip h e n ­

B eeause o f th e v e ry lim ite d s o l u b i l i t y o f th e

compound, i t was Im possible t o ru n a n e u t r a l e q u iv a le n t upon i t . A nal.

C alod. f o r

41*75.

In m olten m a leic a n h y d rid e .

Found:

F b , 4 1 .7 0 .

In th e course o f in v e s t ig a tin g th e

p o s s ib le s tr u c tu r e o f th e compound formed by th e lo n g -tim e i n t e r a c t i o n o f hex& phenyldilead and m aleic an h y d rid e i n c h lo ro fo rm s o l u tio n , i t was found p o s s ib le t o p re p a re t h i s p ro d u c t i n a much s h o r t e r le n g th of tim e .

A

q u a n tity of m aleic anh y d rid e was h e ate d somewhat above i t s m e ltin g p o in t (5 2 .6 ° ) b u t n o t to o c lo s e t o th e d eco m p o sitio n te m p e ratu re o f h ex ap h en y ld ile a d (1 6 0 °),

To th e m o lten s o lu tio n was slo w ly added h e x ap h en y Id ilead

i n s m a ll q u a n t i t i e s .

Too la r g e in d iv id u a l a d d itio n s caused lo c a l fo rm atio n

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115. o f a deep p u rp le o r re d c o l o r . became t h i c k .

A d d itio n s were suspended when th e m ix tu re

G entle h e a tin g was c o n tin u e d f o r f i f t e e n m in u tes and th e n

th e cru d e d ,J W d l( trip h e n y lle a d ) s u c c in ic a c id was p ro g r e s s iv e ly e x tr a c te d w ith b en sen e, a lc o h o l, w a te r , and ammonium a c e ta te s o lu ti o n .

th e p ro d u c t

from t h i s tre a tm e n t was a g re y is h -w h ite powder w hich proved t o be a s in s o l ­ u b le in s o lv e n ts a s th e p ro d u c t from th e p re v io u s r e a o tio n .

From 4*33 g . (0 .0 5

m ole) o f h ex ap h e n y ld ile a d was o b ta in e d 4 .0 g . (81^ y ie ld ) o f p ro d u c t• A nal. C alcd. f o r C^QH^O^Pbg t

Fb, 4 1 .7 5 .

Found j Fb, 4 1 .9 5 .

Sodium s a l t o f d ^ - d i ( t r i phony l l e a d ) s u c c in ic a c id S in c e , in th e above e x p erim en ts, th e h e x ap h en y ld ilead co u ld have r e a c te d w ith e i t h e r th e double bond o r th e an h y d rid e lin k a g e in m a leic a n h y d rid e , a method o f d i f f e r e n t i a t i n g betw een th e two p o s s ib le s tr u c tu r e s had t o be fo u n d .

The m a te r ia l was t o o in s o lu b le t o a tte m p t t o ru n a n e u tr a l eq u iv ­

a le n t.

An a l t e r n a t i v e pro ced u re would be t o a tte m p t to p re p a re t h e sodium

s a l t o f th e a c id form , by prolonged b o il in g o f a sodium hy d ro x id e s o lu tio n w ith th e unknown product* A q u a n tity o f th e p u r if ie d p ro d u ct o f th e r e a c tio n o f h ex ap h e n y ld ile a d w ith m olten m a le ic a n h y d rid e was re flu x o d f o r e ig h t ho u rs w ith a IQ% sodium h y d ro x id e s o l u t i o n .

Some dioxane was added t o th e re f lu x in g m ix tu re t o

p re v e n t undue foam ing.

A f te r th e e ig h t hours o f r e f lu x in g , th e m ixture

was d i l u t e d w ith w a te r and f i l t e r e d *

The s o lid t h a t s e p a ra te d was washed

r e p e a te d ly w ith w a te r u n t i l th e f i l t r a t e was a l k a l i f r e e .

I t was th e n

washed w ith a lo o h o l and a i r - d r i e d to g iv e a c r y s t a l l i n e p ro d u c t t h a t s p a rk le d i n th e s u n l i g h t .

The p ro d u ct was a s In s o lu b le a s th e s t a r t i n g

m a te ria l*

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114. A nal.

C alod. f o r C^HggO^Pbglagj

F b , 3 9 .9 8 .

Founds F b, 4 0 ,4 1 .

While th e a n a ly s is m s 0 .4 3 $ h ig h e r th a n th e a n tic ip a te d v a lu e , i t was s t i l l 1.34$ low er th a n t h e o r e t i c a l v alu e o f t h e s t a r t i n g m a t e r i a l . I t burned w ith a s tro n g sodium flam e.

Undoubedly lo n g e r r e f lu x in g o f th e

s o lu tio n would have g iv en more com plete c o n v e rsio n o f th e f r e e a o id to th e sodium s a l t . T riphenyllead~sodium and e th y l c^,^-d ib ro m o 3 u ccin ate F i r s t a tte m p t.

Three grams (0.0034 mole) o f h e x ap h e n y ld ile a d was

d is s o lv e d i n 150 o c . o f liq u id ammonia i n a 250 c c . th re e -n e c k e d roundbottom ed f la s k equipped w ith a s t i r r e r .

To t h i s s o lu tio n was added 0 .1 5 7

g . (0.0083 g . atom ) o f sodium c u t i n to s m a ll p ie c e s .

This vtas fo llo w ed

b y 1 .1 4 g . (0.0034 m ole) o f e th y l ^ ,3 -d ib ro m o s u c o in a te , added i n sm a ll q u a n titie s .

The ammonia b o ile d v ig o ro u s ly when t h i s l a s t m a te r ia l was

ad d ed . A f te r th e ammonia had b o ile d o f f th e re s id u e was e x tr a c te d s u c c e s s iv e ly w ith c h lo ro fo rm , ammonium a c e ta t e s o l u t i o n , and a lc o h o l.

There was & v e ry

s m a ll re s id u e o f s h in y c o lo r le s s p la te s t h a t m elted a t a h ig h te m p e ra tu re t o g iv e a b la c k m e lt.

They burned cm a s p a tu la w ith a s m a ll fla m e , le a v ­

ing a re s id u e o f le a d .

The sample was to o sm a ll f o r an a n a l y s i s .

Second a tte m p t.

T rip h en y l lead -so d iu m was p re p a re d b y adding 0 .262 g .

(0.0114 g . atom ) o f sodium t o 5 g . (0.0057 mole) o f h e x ap h e n y ld ile a d in 200 o o . o f l i q u i d antaonia.

When ab o u t h a l f o f th e ammonia had e v a p o ra te d ,

50 c o . o f anhydrous e th e r was added and th e n th e r e s t o f th e ammonia was

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e v a p o ra te d .

th e l a s t tr a c e s w ere removed b y immersing th e r e a c t i o n fl& ak

l a warm w a te r and r e f lu x in g th e e t h e r .

A g re e n o i l m s observed u n d e r

th e c l e a r e t h e r l a y e r . To t h i s m ix tu re was added 1.8 9 g . (0.006? m ole) o f e th y l i£,b-dibrom os u c c in a te d is s o lv e d i n 20 o e . o f anhydrous e t h e r .

The e t h e r i n th e f la s k

clo u d ed up a t once and th e g re e n o i l d is a p p e a re d w ith th e fo rm atio n o f a brown and th e n a re d s c a le upon th e s id e s o f th e f l a s k . was re flu x e d in a w a te r b a th f o r o n e -h a lf h o u r.

The r e a c tio n

I t was th e n worked up

b y f i l t e r i n g th e e th e r and e x tr a c ti n g th e re s id u e s u c c e s s iv e ly w ith chloroform * ammonium a o e ta te s o lu tio n * and a lc o h o l. t h i s tre a tm e n t was a g re y powder t h a t a n a ly s e d m

The re s id u e a f t e r low f o r le a d c o n te n t,

f o r th e compound where each brom ine was re p la c e d b y a tr ip h e n y lle a d u n i t , T rip h e n y lle a d a o ld m aleate Five grams (0.011 m ole) o f tr ip h e n y lle a d h y d ro x id e was d is s o lv e d i n 250 o o . o f b o i l i n g , a b s o lu te a lc o h o l .

To t h i s s o lu tio n was added 1 ,0 ? g«

(0.011 mole) o f m a le ic an h y d rid e and th e m ix tu re was b o ile d f o r t e n m in u te s .

The m ilky s o lu tio n was f i l t e r e d and th e f i l t r a t e was d i s t i l l e d

u n t i l a p r e c i p i t a t e s t a r t e d t o form . o ooled s o l u t i o n .

A w h ite s o l i d was f i l t e r e d from th e

This s o lid was d is s o lv e d in h o t a lc o h o l and t r e a t e d

w ith a lo o h o lie p o tassiu m hydro x id e w h ile s t i l l h o t .

A d d itio n o f a l i t t l e

w a te r and c o o lin g caused t h e potassium s a l t to p r e o i p i t a t e .

The p ro d u c t

was f i l t e r e d * re d is s o lv e d i n h o t a lc o h o l , and a c i d i f i e d t o Congo re d

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116, p a p er w ith h y d ro c h lo ric a o id .

A d d itio n o f w a ter p r e c i p i ta te d th e f r e e

a c i d , which was f i l t e r e d , washed w ith w a te r , and a i r - d r i e d .

I t m elted

a t 207° and w eighed 5 ,3 g , w hich re p re s e n ts a 90# y i e l d . A nal, C aicd. f o r CggH^gO^Pb*

Fb, 3 8 ,6 4 ,

S e u tr a l E q u iv a le n t, C alod: 5 3 6 ,

Found*

F b , 3 8 .8 0 ,

Found* 525,

She s o l u b i l i t y , a n a l y s i s , and m e ltin g p o in t o f trip h e t^ rlle a d a c id m a le ate a r e d e c id e d ly d i f f e r e n t from th e co rresp o n d in g fig u r e s f o r th e p ro d u c t from h e x ap h e n y ld ile a d and m a le ic a n h y d rid e . D i-tr ip h e n y lle a d m aleate f o a h o t s o lu tio n o f 4 ,5 5 g . (0 ,0 1 mole) o f tr i p h e n y lle a d hydroxide was added a n a lc o h o lic s o lu tio n o f 0 ,5 8 g , (0 ,0 0 5 mole) o f m a leic a o id . The s o lu tio n was d i s t i l l e d u n t i l m a te r ia l s t a r t e d t o p r e c i p i t a t e .

The

mass o f c r y s t a l s produced upon c o o lin g was f i l t e r e d and a i r - d r i e d t o g iv e 3 ,9 g , (82# y i e l d ) o f a w h ite p ro d u c t s i n t e r i n g a t 198-199°. A nal.

C alod, f o r G ^ g j ^ F b g *

P b , 4 1 ,8 4 ,

Found*

F b, 4 2 ,3 0 .

The p r o p e r tie s and a n a ly s is o f t h i s compound, lik e w is e , do n o t a g ree w ith th o s e o f th e p ro d u c t from th e re a c t!c m o f h ex ap h e n y ld ile a d and m a le ic a n h y d rid e . A ttem pts to induce a r e a c tio n betw een h e x ap h e n y ld lle a d and v a rio u s u n s a tu r a te d o rg a n ic compounds Dry benzene s o lu tio n s o f th e p ro p e r m o le c u lar p ro p o rtio n s o f h e x a p h e n y ld ile a d and is o p r e n e , p y r r o le , s ty r e n e , 1 ,4 -d ip h e n y lb u ta d ie n e -1 , 3 ,

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.

117. and fu ra n war© s e a le d and s to re d in th e d ark f o r f iv e m o n th s.

T hem m s

no r e a c tio n in any c a s e . T ripheny 1 -o-hydroxypheny1le a d Upon 0 .8 8 g» (0.126 g . atom) o f lith iu m c h ip s in 50 o o . o f anhydrous o th e r m s slo w ly dropped 5.48 g . (0 .0 4 s o lo ) o f n -b u ty l brom ide i n 25 o o . o f anhydrous e th e r*

The m ix tu re m s s t i r r e d f o r o n e - h a lf h o u r a f t e r th e

a d d itio n was com pleted and th e n th e e x c e ss lith iu m m s f i l t e r e d o u t.

In to

th e s t i r r e d s o l u t i o n o f n - b u ty l lith iu m was slo w ly dropped 2 .2 5 g . (0.013 s o l e ) o f o-brom ophenol i n 25 oo. o f e t h e r .

S t i r r i n g m s c o n tin u e d f o r

o n e - h a lf h o u r a f t e r th e a d d itio n m s com pleted. To th e o—l i t h i o lith iu m phenoxide th u s formed m s added 4 .7 4 g . (0 .0 1 s o le ) o f tr i p h e n y lle a d c h lo r id e .

A fte r 100 o o . o f b en sen e wasad d ed ,

th e m ix tu re was g e n tly r e flu x e d f o r one h o u r.

The m ixture was th e n f i l t e r e d

and th e f i l t r a t e h y d ro ly se d w ith w a te r s l i g h t l y a o id u la te d w ith h y d ro o h lo rio a c id .

The s o lv e n t la y e r was s e p a ra te d and d i s t i l l e d .

The re s id u e was

washed w ith o o ld a lc o h o l and th e n r e o r y s t a l l i s e d from t h i s s o l v e n t .

There

was o b ta in e d 0 .6 4 g . (l2/£ y i e l d ) o f t r ip h e n y l- o —h y d ro x y p h en y llead . m .p . 216-218°. A nal.

C alcd . f o r Cg^BggOfbj P h. 3 8 .9 8 .

Foundj

F b . 3 9 .2 2 ,

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.

T ripheny 1-tH fo e n a n th ry 1la ad The G rignard re a g e n t wee p re p a re d b y r e f lu x in g 3 .6 7 g . (0.0143 mole) o f 9-brcm ophenanthrene and 0 .3 5 g . (0.0145 g . atom ) o f magnesium i n & m ix tu re o f 15 c o . o f d ry benzene and 15 oe* o f anhydrous e t h e r .

■mm added 5 ,1 8 g . (0 .1 mole) o f tr i p h e a y lle a d brom ide.

To t h i s

The m ix tu re m s

r e f lu x ad f o r tw e n ty -fo u r ho u rs and th e n m s h y d ro ly sed w ith a d i l u t e h y d ro c h lo ric a o id s o lu t i o n .

The e t h e r la y e r was s e p a ra te d and e v a p o r-

a te d t o g iv e a brown o i l which slo w ly c r y s t a l l i s e d .

T his m a te r ia l was

in s o lu b le i n a lc o h o l , p e t . e t h e r (b p . 6 0 -6 8 ° ) , a c e to n e , and diox&ne. The brown o o lo r o f th e o i l was removed by d is s o lv in g th e o i l in benzene and p a ssin g th e s o lu tio n th ro u g h a column o f a c tiv a te d a lu m in a .

The

benzene was th e n d i s t i l l e d and th e r e s id u e r e c r y s t a l l i z e d from e th y l a c e ta te t o g iv e a p ro d u c t m e ltin g a t 160-171°.

There was 3.5 g . (57%

y i e l d ) o f m a te r ia l w ith a s l i g h t l y y e llo w is h o a s t . A nal.

C alcd. f o r G ^ E ^ P h *

P b , 3 3 .6 6 .

Found* P b, 3 3 .4 7 .

M -9 -p h e ra n th ry ld ip h e n y l le a d The G rignard re a g e n t was p re p a red b y r e f lu x in g f o r tw e n ty -fo u r hours a m ix tu re o f 7.34 g . (0.0236 m ole) o f 9-brom ophenanthrene and 0 .7 0 g . (0 .2 3 7 g . atom) o f magnesium i n 60 s o . o f a 1*1 b e n z e n e -e th e r m ix tu re . To t h i s was added 20 o o . o f e t h e r and 5 .2 1 g . (0 .1 m ole) o f d ip h e n y lle a d d ib ro m id e.

A fte r re flu x in g f o r tw e n ty -fo u r h o u rs , i t was h y d ro ly se d w ith

d i l u t e h y d ro c h lo ric a o id and f i l t e r e d .

The e t h e r la y e r was e v ap o rate d

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.

119. t o g iv e a c l e a r brown liq u id t h a t p r e c i p i t a t e d c o lo r le e a c r y s t a l s upon ad d in g e t h y l a c e t a t e .

The crude p ro d u c t weighed 4,8 6 g . (6 6 $ ),

R e c r y s ta llin a tio n from e th y l a c e ta te gave m a te r ia l w ith a g re y is h c a s t and m e ltin g a t 208-210°, A nal.

C alcd . f o r C4OH20Pb»

F b , 2 8 .9 5 .

Pounds

P b, 2 8 .9 3 .

Yflhen 0 .8 g* (0*0007 m ole) o f d i-9 -p h e n a n th ry ld ip h e n y lle a d was d i e s o lv e d i n 30 c o . o f b o ilin g c h lo ro fo rm and d ry hydrogen c h lo rid e b u b b led i n , a p r e c i p i t a t e form ed.

The p r e c i p i t a t e was f i l t e r e d and d rie d t o

g iv e 0.29 g . (97% y i e l d ) o f d ip h e n y lle a d d ic h lo r id e , i d e n t i f i e d b y r e flu x in g w ith phenylmagneeium brom ide and making & mixed m e ltin g p o in t d e term in atio n , w ith known te tra p h e n y 1 le a d .

The c h lo ro fo rm s o lu tio n was

e v ap o rate d t o re c o v e r th e c le a v e d p h e n an th ren e , which was i d e n t i f i e d by a mixed m eltin g p o in t d e te rm in a tio n . A ttem pted p re p a ra tio n s o f t e t r a - 9-p h e n a n th ry lle a d To th e G rignard re a g e n t p re p a re d in. 50 c o . o f b e n s e n e -e th e r from 2 .5 7 g , (0 .0 1 sto le) o f 9-brom ophenanthrene and 0 .2 5 g . (0 .0 1 g , atom ) o f magnesium was added 25 e c . o f benzene and 1 .2 g . (0.0043 m ole) o f d ry le a d c h l o r i d e .

The s o lu tio n tu rn e d orange and a f t e r a few m inutes h e a t­

ing on a h o t p l a t e i t was deep r e d .

A fte r r e f lu x in g f iv e h o u rs , th e c o lo r

had d isa p p e a re d and t h e s id e s o f th e f la s k w ere co ated w ith a s o l i d .

The

m ix tu re m s h y d ro ly z e d w ith an ammonium c h lo r id e s o l u t i o n , f i l t e r e d , and th e e t h e r la y e r e v a p o ra te d .

The re s id u e d id n o t c o n ta in le a d .

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.

In a n o th e r ru n o f th e same s i z e , th e re a o ta n tB were re flu x e d f o r one h o u r o n a steam h a th *

th e m ix tu re tu rn e d tram, b r ig h t r e d t o b la o k

and a p r e c i p i t a t e a p p ea re d on th e s id e s o f t h e f l a s k . r e a c tio n was h y drolysed w ith d i l u t e h y d ro o h lo rio a c id .

This tim e th e E v a p o ra tio n o f

th e e t h e r la y e r d id n o t g iv e any m a te r ia l c o n ta in in g lead*

One gram o f

phenanthrene was re o o v e re d . f r ip h e n y l- 7 - ( 1 .2 » b s n * a n th ry l) le a d To th e a - b u ty llith iu m s o lu tio n p re p a re d i n 30 oe* o f e t h e r b y th e r e a c tio n o f 1 .5 g . (0*011 mole) o f n -b u ty l brom ide w ith 0*17 g . (0 .0 2 5 g . atom ) o f lith iu m m e ta l was added 1 g , (0.00328 m ole) o f 7 -b ra a o -l* 2 bensanthraoen® .

The r e a c tio n m ix tu re was s t i r r e d f o r two m inutes and

th e n 1*5 g . (0*00325 m ole) o f tr i p h e n y lle a d c h lo r id e was ad d ed . m s c o n tin u e d f o r t e a m inutes b e fo re h y d ro ly zin g w ith w a te r . a n t m ix tu re was f i l t e r e d and washed w ith e t h e r . o r y s t a l l i z e d from e th y l a c e t a t e .

The r e s u l t ­

The re s id u e was r e -

The p ro d u c t m elted a t 2 0 4-205°, which

was th e same m e ltin g p o in t a s tr ip h e n y lle a d c h lo r id e . p o i n t , how ever, was d e p re s s e d .

S tirrin g

A mixed m a ltin g

There was 1 .1 3 g . o f p ro d u c t w hich was

a B& y i e l d . A nal.

C alcd . f o r CggHggPbj P b , 3 1 .1 2 .

Found t P b , 3 0 .9 0 .

When d ry hydrogen c h lo r id e was p assed in to a ch lo ro fo rm s o lu tio n c o n ta in in g 0*2 g . (0 .0003 mole) o f tr ip h e n y l- 7 « (1 ,2 -b e n z a n th r y l) le a d a w h ite p r e c i p i t a t e formed*

This p r e c i p i t a t e was f i l t e r e d and d r ie d t o

g iv e 0 .1 2 g . (92$ y i e l d ) o f d ip h e n y lle a d d ic h lo r id e .

This p ro d u c t was

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121. i d e n t i f i e d by r e f lu x in g i t w ith a phenylmagnesium brom ide s o lu tio n , h y d ro ly s in g , and w orking up in th e custom ary m a n o r .

The te tr a p h e n y lle a d

th u s o b ta in e d m s i d e n t i f i e d by a mixed m e ltin g p o in t w ith a known sample o f te tr& p h e n y lle a d .

The chloro fo rm m s e v ap o rate d from th e 1 ,2 -

bens& nthraoene formed by th e hydrogen c h lo r id e cleav ag e t o g iv e 0 .0 7 g . ( q u a n tita tiv e y i e l d ) o f 1,2 -b e n z a n th ra c e n e .

I t m s id e n tifie d by a

mixed m e ltin g p o in t w ith a known sample o f 1 .E -benzanthr& cene. D i-7 -( 1 ,2 -b e n z a n th ry l)d ip h e n y lle a d To th e n -b u ty llith iu m p re p a re d in 40 c o . o f e th e r b y th e r e a c tio n o f 3 .0 g . (0.022 mole) o f n - b u ty l brom ide w ith 0 .0 3 3 g . (0.048 g . atom) o f lith iu m m e ta l was added 2 .5 g . (0.0081 m ole) o f 7 -b ro m o -l,2 b e n sa n th ra o e n e .

The m ixture was s t i r r e d f o r two m inutes and th e n 1 .7 5 g .

(0.004 m ole) o f d ip h e n y lle a d d ic h lo r id e was ad d ed .

S t i r r i n g was con­

tin u e d f o r t e n m inutes b e fo re h y d ro ly sin g w ith w ater* The r e s u l t a n t m ix tu re was f i l t e r e d and th e s o l i d e x tr a c te d w ith b e n zen e.

When th e benzene s o lu tio n was o o n c e n tra te d and a lo o h o l ad d ed ,

sm a ll s l i g h t l y y e llo w n e e d le s formed*

These n e e d le s m elted w ith some

decom position a t 295-296° (m icro m e ltin g p o i n t ) .

There was o n ly 0*3 g .

(3 .6 $ y ie ld ) o f d i - 7 -( 1 ,2 -b e n s a n th ry 1 )d ip h e n y lle a d . A nal.

C alcd. f o r C ^ h ^ P b r

P b , 2 5 .3 9 .

Foundi P b , 2 5 .4 0 .

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.

R ea c tio n s I n liq u id ammonia betw een h e x ap h en y ld ilead and a e v e ra l m e ta ls , d e r lv a tia a d w ith b en g y l c h lo r id e The fo llo w in g i s a t y p i c a l pro ced u re i n th e r e a c tio n o f h ex ap h en y ld ile a d w ith m e ta ls in liq u id ammonia, u sin g b en g y l c h lo r id e t o d e r i v a t i s e th e p ro d u c t th u s form ed. A 250 o a . th re e -n e ck e d f l a s k was f i t t e d w ith a m ech an ical s t i r r e r and th e sid e-n eo k s w ere equipped w ith s to p p e r s .

Through one o f th e s i d e -

necks was added 2 .1 9 g . (0.0025 mole) o f h e x ap h e n y ld ile a d and 150 c o . o f li q u id ammonia. I h i l e t h i s m ixture was s t i r r e d , 0 .035 g . (0.005 g . atom ) o f lith iu m , o u t in to sm all p ie c e s , was slo w ly added.

The s o lu tio n was s t i r r e d f o r

f iv e m inutes a f t e r th e a d d itio n was com pleted and th e n 1 c o . (e x c e s s ) o f b en g y l c h lo r id e was in tro d u c e d , d ro p w ise.

E v a p o ra tio n o f th e aumonia

l e f t a re s id u e which was e x tr a c te d w ith e t h e r .

The e t h e r s o l u t io n was

e v ap o rated and th e r e s id u e washed w ith 10 c c . o f a lo o h o l.

There rem ained

1 ,9 g . (72$ y ie ld ) o f tr ip h e n y lb e n s y lle a d , m e ltin g a t 9 1 -9 2 °.

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123 Table 1 .

R eact lone i n Liquid Ammonia i n Yrfhich 0.0025 Mole o f H exaphenyldilead was T re a te d W ith V arious M etals Followed b y B enayl C h lo rid e

g . atom o f m e ta l

% T rip h e n y lb e n s y lle a d

L ithium

0.005

71 * 72

Sodium

0 .0 0 8

60 | 64

Potassium

0,008

56 j 67

Rubidium

0 .0 0 5

52

M etal

----

Cesium Calcium

0.008

79 t 81

«

0.0025

40 j 41

0 .005

67 | 74

n

0.0025

34 i 36

Barium

0 .0 0 6

56 j 61

0.0025

31 f 36

S tro n tiu m

R

R ea c tio n in l i q u id ammonia betw een 0 .1 mole o f t r i e t h y l l e a d c h lo rid e and 0 .2 g . atom o f lith iu m gave a 4Q$£ y ie ld o f tr ie th y lb e n z y lle a d when b e n sy l c h lo rid e was added. When 0 .2 g . atom o f calcium was s u b s tit u t e d f o r th e lith iu m , th e y i e l d was o n ly 15$.

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124. R eao tio n s i n liq u id ammoiiift betw een d ip h e n y lle a d d ih aiid cB and s e v e r a l ate t a l a The fo llo w in g i s a ty p io a l r e a c tio n i n l i q u i d ammonia betw een a d ip h e n y lle a d d ih a lid e and a liq u id ammonia s o lu b le m e ta l.

A c tu a lly , o n ly

d ip h e n y lle a d d ic h lo r id e and d ip h e n y lle a d d i f l u o r id e were u s e d .

Caloium,

lith iu m , and sodium w ere th e m e ta ls u s e d . To 3.99 g . (0 .0 1 m ole) o f d ip h e n y lle a d d if l u o r id e suspended i n 200 o c . o f liq u id ammonia in a th re e -n e c k e d f l a s k , was slo w ly added 0 .4 g . (0 .0 1 g . atom ) o f caloium m e ta l.

The su sp e n sio n was s t i r r e d d u rin g th e whole

p rocedure and a deep re d c o lo r a tio n was n o tic e d a b o u t eaeh p ie c e o f m e ta l.

At tim e s th e w hole su sp e n sio n to o k on a momentary red d ish -b ro w n

c o lo r.

Ih e n a b o u t h a l f th e m e ta l had b een a d d e d , th e ammonia s o lu tio n

became b lu e and s ta y e d t h a t o o lo r .

The ammonia was allow ed t o e v ap o rate

and th e w h itis h re s id u e e x tr a c te d w ith c h lo ro fo rm .

F r a c tio n a l c r y s t a l l i ­

s a t i o n o f th e chloroform s o lu tio n gave crops o f to tra p h e n y 1 le a d and h e x a p h e n y ld ile a d . The fo llo w in g Table 2 g iv e s th e d a ta on t h e v a rio u s r e a c tio n s o f t h i s ty p e t h a t have b een ru n .

The p e r c e n t y i e l d was b ased upon th e

amount o f phenyl r a d ic a ls ap p earin g i n th e r e a c ta n t and i n th e p ro d u c t.

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Table 2 .

R eactio n s i n L iquid jira o n ia Between D iphenyllead, D ih a lid e s and S e v e ra l L iq u id .taraonia S o lu b le M etals

D iphenyllead d io h lo r id e

M etal ! g . g.at«*n i

*

t 4.32

m ole 0 .0 1

(C6% )JP b g* >

*

* i L ithium t 0 .2 8 0 .0 4

tra c e

I j *

((OgHgJgPbJg g, #

1.75

60.

0 .6 0

2 7 .4

0 .6 8

2 3 .3

1

2 . IS

0.005

4 .3 2

0 .0 1

D iphenyllead d if l u o r id e

t Caloium t 0 .4 0 .0 1 t t Caloium i 0 .4 0 .0 1 t t t t

0 .2 2

10.

9

2.0 0

O.OOS

2 .0 0

0.005

5.99

0 .0 1

t Lithium * 0 .0 7 0 .0 1 t t Sodium * 0 .2 3 0.01 I t Caloium : 0 .4 0 .0 1

tra c e

0*75

52,

tra c e

0 .6 5

45.

tra c e

1 .7 0

58.

i

*

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126. A ttem pts t o p re p a re compounds o f th e ty p e R gf^FbPbl^tg ajnst-T e tra o y e lo h e x y ld tp h e n y ld i le a d .

Di eye lo h e x y ld i phenyl le a d

(p re p a re d I n QS% y i e l d from d ip h e n y lle a d d io h lo r id e and cyclohexylm agnesium brom ide) m s d is s o lv e d i n p e t . e t h e r ( b . p . , 2 8 -3 8 °) and a slew stre am o f d ry hydrogen c h lo rid e was p assed i n u n t i l a p r e c i p i t a t e no lo n g e r form ed. Too ra p id a d d itio n o f hydrogen c h lo r id e c lea v e d two phenyl r a d i c a l s .

The

p r e o l p i t a t e t h a t formed was f i l t e r e d and r e c r y s t a l l i z e d from chloroform t o y i e l d c r y s ta ls o f d io y c lo h e x y lp h e n y lle a d c h lo r id e t h a t s i n t e r e d s l i g h t l y a t 195° and s t a r t e d t o decompose a t 2 0 5 °. A nal.

C alcd. f o r C ^ H ^ F b C li

P b, 4 2 .6 3 .

Found*

P b , 4 2 .5 8 .

To a su sp e n sio n o f 9 ,7 6 g . (0 .0 2 m ole) o f d io y c lo h e x y lp h en y llea d c h lo r id e i n 350 o c . o f liq u id ammonia was slo w ly added 0 .4 6 g . (0 .2 g . atom ) o f sodium , c u t in to s m a ll p ie c e s . a deep r e d .

The liq u id ammonia became c o lo re d

The ammonia was allow ed t o e v a p o ra te and th e s o l i d re s id u e

was e x tr a c te d w ith ch lo ro fo rm to g iv e a deep re d s o l u t i o n .

Exposure

o f t h i s s o lu tio n t o s u n lig h t caused a n immediate d isap p e a ra n ce o f th e re d c o lo r and th e fo rm atio n o f a p r e c i p i t a t e .

Even e v a p o ra tio n o f th e

c h lo ro fo rm i n t h e dark d id n o t keep t h e s o lu tio n from slo w ly lo s in g i t s c o lo r .

A le a d a n a ly s is was ru n upon th e supposed s y a -t e t r a e y c l o -

hexyId i phenyId i l e a d . A nal.

C alcd . f o r C^gHgyFbt

P b , 4 6 .0 0 .

Foundi

P b , 4 1 .8 3 .

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187

s y m -Ie tra p h e n y ld ie th y ld ile a d .

An 81# y i e l d o f d ip h e n y ls th y 1le a d

e h lo r id e m s o b ta in e d by slow ly b u b b lin g d ry hydrogen c h lo r id e i n t o a s o lu tio n o f tr ip h e n y le th y lle a d i n p e t . e t h e r ( b . p . , 2 8 -3 8 °)•

She

p rs o ip it& te t h a t formed was r e e r y s t a l l i s e d from a lc o h o l t o g iv e a w h ite c r y s t a l l i n e p ro d u c t w hich s i n t e r e d a t 142° and decomposed a t 146-147°. A nal.

C alcd. f o r C-^H^gPbClt

F b , 4 8 .7 0 .

Foundi

P b , 4 8 .3 7 .

No p a r t i c u l a r c o lo r changes were n o tic e d when 4.2 5 g . (0 .0 1 m ole) o f d ip h e n y le th y lle a d c h lo rid e suspended i n 250 ec« o f liq u id ammonia was t r e a t e d w ith 0 .2 3 g . (0 .0 1 g . atom ) o f sodium .

The y e llo w is h s o lu tio n

o b ta in e d by chloroform e x tr a c ti o n o f th e re s id u e a f t e r th e ammonia had e v a p o ra te d c o u ld n o t be c o n c e n tra te d w ith o u t d eco m p o sitio n ta k in g p la c e . A ttem pted a u lfo n a tio n o f te tra p h e n y lle a d To ic e c o ld 30/. fuming s u l f u r i c a o id was slo w ly added 1 g-* (0.0019 m ole) o f f in e ly powdered te tr a p h e n y lle a d .

The m a te r ia l d is s o lv e d a t onoe.

A f te r a llo w in g t h e s o lu tio n t o come t o room te m p e ra tu re , i t was poured upon i c e .

Only in o rg a n ic le a d was o b ta in e d .

A ttem pted n i t r a t i o n o f te tra p h e n y lle a d To & s o lu tio n o f 45 o c . o f fuming n i t r i c a c id and 35 c o , o f c o n c . s u l f u r i c ao id c o o led t o -5 0 ° i n an a c e to n e -d ry ic e b a th was slo w ly added sesne powdered te tr a p h e n y lle a d .

The s o lu tio n im m ediately tu rn e d brcem and

soon became b la c k , whereupon th e a d d itio n was s to p p e d .

Upon a llo w in g th e

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13 8 .

m ix tu re t o can® t o room te m p e ra tu re , c o n s id e ra b le gas m s evolved so t h e m a te ria l m s poured upon i c e .

Some gummy m a te r ia l m s o b ta in e d to g e th e r

w ith u n re a c te d te tr a p h e n y lle a d , le a d s u l f a t e , and n itro b e n z e n e . H itr a tio n o f d ip h e n y lle a d d io h lo r id e

A

s o lu tio n o f 45 c o . o f fuming n i t r i c a c id and 35 c o . o f co n e,

s u l f u r i c a o id m e c o o le d to -5 0 ° i n an a c e to n e -d ry ic e b a t h .

Upon slo w ly

adding 10 g» (0.019 mole) o f d ip h e n y lle a d d io h lo r id e a th ic k g re y p a s te form ed.

There was a s tro n g o d o r o f c h l o r in e , in d ic a tin g rep lacem en t o f

th e c h lo r in e b y th e n i t r a t e g ro u p .

The p a s te was allo w ed t o s ta n d o v e r

n ig h t a t room te m p e ra tu re and was th e n poured upon i c e .

The s o lid t h a t

s e p a ra te d was f i l t e r e d , washed w ith w a te r , and a i r - d r i e d . An a n a ly s is in d ic a te d 33.54^ le a d . m ost l i k e l y p o s s i b i l i t i e s .

This i s low er th a n any o f th e

(ja-NOgCgH^JgFbClg c o n ta in s 39.65$ le a d f

(g-H^CgS^gFbCSOgJg has 3 6 .0 $ )

and (C6Hg)2Fb(HOs )2 , 4 2 .6 8 $ .

Di-ro- n ltro p h e n y lle a d d io h lo r id e The method o f S e tz e r , b e e p e r, and Gilman'*' was fo llo w ed f o r p re p a rin g d ip h e n y lle a d d i n i t r a t e .

This m s c o n v erted t o d i-m -n itro p h e n y lla a d

d i n i t r a t e fo llo w in g th e g e n e ra l method o f C h allen g e r and R o th s te in . ■^Setzer, Lee p e r , and G ilm an, J . Am. Cham. Soo. , 6 1 , 1609 (1 9 3 9 ). ^C h a lle n g er and l o t h s t e l n , J . Chem. S o o .. 1258 (1 9 3 4 ).

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2

They

129.

recommended u s in g a b a th te m p e ra tu re o f *10 t o *16° b u t i t was found t h a t lo w erin g i t to *50° e n ab le d f a s t e r a d d itio n o f d ip h e n y lle a d d i n i t r a t e w ith o u t danger o f d e co m p o sitio n . To about 200 c c . o f b o ilin g w a ter was added 10 g . (0.02 m ole) o f d l-m -n itro p h e n y lle a d d i n i t r a t e .

A c l e a r s o lu tio n r e s u l t e d .

added a s o lu tio n o f 2 .9 g . (0 .0 5 mole) o f sodium c h lo r id e . immediate fo rm a tio n o f a w h ite p r e c i p i t a t e . f i l t e r e d , and washed w ith a l i t t l e w a te r .

To t h i s was There was an

The m ix tu re was c o o le d , Y ie ld , 10 .1 g . (9 7 $ ).

It

was s o lu b le i n a lo o h o l and r e c r y s t a l l i z e d from e th y l a c e ta te i n sm all c o lo r le s s p l a t e s ,

Tfoen observed u n d er a m icro m e ltin g p o in t a p p a r a tu s ,

th e s e p la te s sublim ed a t 250° and decomposed a t 28 5 -2 8 8 °. A nal.

C alcd. f o r C jgH gO ^PbC lg i

Pounds

Pb, 39.33*

P b . 39.65*

N, 5 .3 6 .

N, 5 .3 5 .

Dl-m- n ltro p h e n y lle a d d iio d id e D i-m -n itro p h e n y lle a d d iio d id e was p re p a red i n 95$ y i e l d s i m i l a r l y t o th e method used f o r th e d io h lo r id e .

The d iio d id e was a b r i g h t y ello w

c r y s t a l l i n e m a te r ia l w hich decomposed around 1 3 5 °,

Like d ip h e n y lle a d

d iio d id e i t ten d ed t o decompose upon a tte m p te d r e c r y s t a l l i z a t i o n , b u t t o a l e s s e r e x te n t . A n al.

C alcd . f o r C^gHgO^NgFblgt Pb, 2 9 .3 6 .

Found}

P b, 3 0 .0 5 .

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.

T rip h e n y lle a d n i t r a t e To a s o lu tio n o f 1* g . (0.0022 m o le) o f tr ip h e n y lle a d h y d ro x id e d is s o lv e d i n 30 o o . o f h o t a le o h o l was added 0 .5 co* o f oono. n i t r i c ao id d is s o lv e d i n 10 c c . o f a le o h o l.

The s o l u t io n was b ro u g h t t o a b r i s k

b o i l on a h o t p la te and th e n allow ed to c o o l.

There was o n ly a sm a ll

amount o f a c r y s t a l l i n e p ro d u c t s o t h e s o lu tio n was e v ap o rate d t o a sm a ll volume on a steam p l a t e . a p p e a re d . d rie d . A nal.

Upon c o o lin g , sm all c o lo r le s s c r y s t a l s

These were f i l t e r e d , washed w ith a l i t t l e a lo o h o l, and a i r They s i n t e r e d w ith some decom position betw een 2 2 0-225°.

C alod. f o r C^gH^gQgNFb j

P b , 4 1 .4 0 .

Founds

i t , 4 1 .0 7 .

When cono. s u l f u r i c a o id was added t o th e sam ple fo r a n a l y s i s , i t b u r s t in to f la n e s and evolved c o n s id e ra b le s e e k s .

The low a n a ly s is may

have b een due t o v o l a t i l i s a t i o n o f some o f th e le a d . H itr a tI o n o f tr ip h e n y lle a d n i t r a t e The g e n e ra l procedure (p . 128) u se d i n th e n i t r a t i o n o f d ip h e n y lle a d d i n i t r a t e m s fo llo w e d .

Ho c o lo r developed u n t i l th e c o o lin g b a th m s

rem oved, whereupon th e s o l u t i o n slo w ly tu rn e d dark b lu e .

When poured

upon ic e th e n e x t m orning, th e c o lo r d isa p p e a re d and a g re y -w h ite c r y s t a l l i n e m ass p r e c i p i t a t e d . and a i r - d r i e d .

T his was f i l t e r e d , washed w ith w a te r ,

The d ry p ro d u c t m s e x tr a c te d w ith e th y l a c e t a t e and th e

re s id u e o f tri-m p -n itro p h e n y lle a d n i t r a t e was a n a ly se d f o r l e a d . A nal.

C alcd . f o r ^X8H12^9^4?^3S

8 2 .4 4 .

Found*

P b , 3 2 .4 5 .

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.

A fte r s ta n d in g a month i n a server c ap b o t t l e i n a d ra w er, t h e m a te r ia l had tu rn e d a d i r t y g re y . a c id .

I t p a r t l y d is s o lv e d i n g l a c i a l a c e t i c

The r e s id u e d is s o lv e d i n anmonium a c e ta te s o lu t io n and gave a

heavy p r e c i p i t a t e w ith sodium chrom ate s o l u t i o n .

This is th e u s u a l t e s t

f o r in o rg a n ic le a d . N itr a tio n o f tr ip h e n y lle a d c h lo rid e The g e n e r a l procedure (p . 128) employed i n th e n i t r a t i o n o f d ip h e n y lle a d d i n i t r a t e was fo llo w e d .

Twenty grams o f tr ip h e n y lle a d

c h lo r id e was slo w ly added t o th e n i t r a t i o n m ix tu re , w ith s t i r r i n g .

A fte r

th e f i r s t a d d i t i o n , e v o lu tio n o f gas was n o te d , and th e m ix tu re became d a rk .

At th e end o f th e r e a c tio n th e s o lu t io n was d ark brown and q u ite

v is c o u s (ISO cc* o f s o l u t i o n ) .

The m ix tu re was allo w ed to come t o

room te m p e ra tu re and s ta n d f o r two h o u rs . and th e p r e c i p i t a t e f i l t e r e d .

I t was th e n poured upon ic e

The grey-brow n p r e c i p i t a t e m is washed

w e ll w ith w a te r and d r ie d t o g iv e 28 g . (98^) o f p ro d u c t. The t h e o r e t i c a l le a d c o n te n t f o r tri- m - n itr o p h e n y lle a d n i t r a t e is

52.29-% w hile an a n a ly s is on th e above m a te r ia l in d ic a te d o n ly 21.9%. This i s f a r below t h e le a d c o n te n t f o r an y p o s s ib le n i t r a t e d le a d compound. As ev id en ced b y t h e d ark c o lo r produced d u rin g th e n i t r a t i o n , c o n s id e r­ a b le deco m p o sitio n m ust have o c c u rre d . T r ie th y lle a d c h lo rid e and d iasoraethana I n to 13.48 g . (0 .0 5 m ole) o f t r i e t h y l l e a d c h lo r id e i n 50 o e . o f d ry

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.

132. benzene was passed th e diazoraethane p re p a re d from 6 ,2 g . (0*06 s o l e ) o f n itro a o m e th y lu re a .

A f te r s ta n d in g o v e r n i g h t , m ost o f th e benzene was

e v a p o ra te d o f f and th e r e s id u a l c r y s t a l s f i l t e r e d and a i r - d r i e d .

a

le a d

a n a ly s is a g re ed w ith t h a t f o r th e s t a r t i n g m a te r ia l and n o t f o r th e expected tr ie th y l« d - c h lo r o m e th y lle a d . T r ie th y lle a d c h lo r id e and d ia z o e th a n e In a s im ila r ex perim ent i n which d ia z o e th a n e was g e n e ra te d from 5 .8 5 g . (0 .0 5 m ole) o f n itr o s o e th y lu r e a , a le a d a n a ly s is in d ic a te d t h a t th e t r i e t h y l l e a d c h lo r id e was re c o v ere d unchanged, A ttem pted re a o tio n s o f h a lo g e n o e s te rs and le a d powder E th y l e^-b ro m o p ro p lo m te .

The le a d powder u sed i n th e fo llo w in g ex p er­

im ents was o b ta in e d from th e M etals D is in te g r a tin g Company, E liz a b e th , Hew J e r s e y a s a p ro d u c t d e sig n a te d MD 105.

I t was claim ed t h a t 70$ o f

th e m a te r ia l c o n s is te d o f a powder le s s th a n f i f t e e n m icrons in d ia m e te r. A m ix tu re o f 10.35 g . (0 .0 8 g . atom ) o f le a d powder and 18 .1 g . (0 .1 m ole) o f e t h y l c^-brom opropionate was h eated t o r e f lu x f o r tw e lv e h o u rs . The h e a tin g was in te r r u p te d th r e e tim e s w h ile th e c o a tin g o f le a d on th e m i l s o f th e f la s k was sc ra p e d lo o s e .

Upon vacuum d i s t i l l a t i o n th e e s t e r

was reco v ered q u a n t i t a t i v e l y . Bromomethyl a c e t a t e .

A m ix tu re o f 6 .1 7 g . (0.025 g . atom ) o f le a d

powder and 7 .6 6 g . (0 .0 5 m ole) o f bromomethyl a c e ta te was h e ate d w ith o u t s o lv e n t on a h o t p la te f o r te n hours*

There was no r e a c ti o n .

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.

135 E th y l b ro m o a c e ta te .

A m ix tu re o f 5 .1 7 g . (0.025 g . atom ) o f le a d

powder and 8.35 g . (0.05 mole) o f e th y l b rcsnoa.oeta.te m s h e a te d w ith o u t s o lv e n t on a h o t p la te f o r e ig h t h o u rs .

There m s no r e a o tio n .

Organogermanium R eactions A ctio n o f io d in e upon te tra -n -b u ty lg e rm a n iu m Anhydrous germanium te tra b ro m id e m s p rep ared a cco rd in g t o t h e a d ir e c tio n s o f Laubengayer and B randt • The g e n e ra l method o f p re p a rin g te tra a lk y lg e n m n iu m compounds* was u sed to p re p a re te tra -n -b u ty lg e rm a n iu m . From one mole o f n - b u ty l b ro m id e, 54 g* (80^ y ie l d ) o f t e t r a - n - b u t y l germanium, b . p . 127-128°a t 4 son*, m s o b ta in e d . fo 10 g .