Title Page
 Table of Contents
 List of Tables
 List of Figures
 The interaction of two Alkyl hydrazines...
 Reactions of arylhalophosphines...
 Biographical sketch

Group Title: study of the synthesis of some aluminum and phosphorus derivatives of alkyl hydrazines
Title: A study of the synthesis of some aluminum and phosphorus derivatives of alkyl hydrazines
Full Citation
Permanent Link: http://ufdc.ufl.edu/UF00091617/00001
 Material Information
Title: A study of the synthesis of some aluminum and phosphorus derivatives of alkyl hydrazines
Physical Description: vii, 153 l. : illus. (part fold.) ; 28 cm.
Language: English
Creator: Nielsen, Robert Peter, 1937-
Publisher: s.n.
Place of Publication: Gainesville
Publication Date: 1962
Copyright Date: 1962
Subject: Hydrazines   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
Thesis: Thesis--University of Florida.
Bibliography: Bibliography: l. 149-152.
Additional Physical Form: Also available on World Wide Web
General Note: Manuscript copy.
General Note: Vita.
 Record Information
Bibliographic ID: UF00091617
Volume ID: VID00001
Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
Resource Identifier: alephbibnum - 000423905
oclc - 11025334
notis - ACH2310


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Table of Contents
    Title Page
        Page i
        Page ii
    Table of Contents
        Page iii
    List of Tables
        Page iv
        Page v
    List of Figures
        Page vi
        Page vii
    The interaction of two Alkyl hydrazines with triethylaluminum
        Page 1
        Page 2
        Page 3
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    Reactions of arylhalophosphines and derivatives of arylhalophosphines with several Alkyl hydrazines
        Page 36
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    Biographical sketch
        Page 153
        Page 154
        Page 155
Full Text







June, 1962


The author wishes to acknowledge the friendly cooperation

of his committee and the faculty of the Chemistry Department of the

University of Florida. It is considered both an honor and an oppor-

tunity to have worked under the direction of Dr. Harry II. Sisler, who,

although entrusted with the momentous task of administration of this

Department, is able to give generously of his time and abilities

to direct meaningful scientific inquiry. His friendship and wide

scope of interests have proved inspiring.

The time and effort spent by Comaander N. L. Smith (Ret.

USIR) in acquainting the author with synthetic technique and

phosphorus-nitrogen chemistry is sincerely appreciated. Besides

offering an open door and a sympathetic ear, he provided encourage-

ment when it was needed and advice when it was desired.

Thanks go also to Dr. Wallace Brey and Mr. Ken Lawson for

nuclear magnetic resonance measurements, and Mr. Howard Latz and

Mr. Leo Pijanowski for assistance in obtaining infrared spectra.

The fellow members of the Inorganic Section deserve thanks for

friendly competitive spirit and helpful discussion.

The author is indebted to the Petroleum Research Fund for a

financial grant which made this work possible.








Experimental and Results





Experimental and Results










Table Page

1 Amine Alanes 5

2 Bic-Anine Alanes 6

3 Bis-(Mixed)amine Alanes 6

4 Inner Complex Anine Alanes 6

5 Aminoalanes 7

6 Extended Network Aluminum-Nitrogen Polymers 8

7 hydrazine Alanes 8

8 Hydrazinoalanes 8

9 Hydrazinoalane-Hydrazine Adducts 9

10 Polyneric Species 9

11 Alkyl and Aryl Phosphorohydrazidates 39

12 Alkyl and Aryl Hiosphorohydrazidothiontes 40

13 Alkyl and Aryl Phosphorophenylhydraeidothioates 42

14 Phenylhydrazidoalkylphosphcnates 43

15 Bis(hydrasino)phenylphosphine Oxides 44

16 Arylpho phorodihydrazidothioates 45

17 Tris(hydrazino)phosphine Oxides and Sulfides 47

18 Arylphosphorochloridoliydrazidothioates 48

19 Alkylphosphorohydramidoic Acids 49

20 Arylphosphorommidohydrazidothioates 50

21 Amino-bis(hydrazino)phosphine Oxides 54

22 Amino-bis (hydrazino)phosphine Sulfides 55

23 Salts of Phosphorohydra=idates 56



able Page

24 Benzylidene Derivatives of Alkylphosphoro-
hydrazidates 58

25 Hydrazones of Bis(hydrazino)phcnylphosphine
Oxides-lydrazones of Bis(hydrazino)phenylphosphino
Sulfides 59

26 Principal Infrared Absorption Frequencies for
Some Phosphorus Hydr.zine Derivatives 124

27 Infrared Absorption Frecuencies and Assignments 125

28 Nuclear Ihgnetic Resonance Data Sumary 128

29 Scale of Chenical Shift Values from 1. M. R.
Data 133


Lgure Page

1 Mini-Lab Distillation Apparatus 12

2 Reaction Apparatus 13

3 Molecular Weight Apparatus (Mbdified for Atmosphere-
Sensitive Compounds) 14

4 Infrared Spectrum of 2,2-Dimethylhydrazinodiethyl-
alane (Melt) 18

5 Infrared Spectrum of 2,2-Dimethylhydrazinodiethyl-
alone (Dilute Hexane Solution) 19

6 Infrared Spectrum of Condensation Product,
(EtAlNNMe2), (Hexane Solution) 22

7 Mini-Lab Reaction Apparatus 63

8 Dry Box (Three-eighths Inch Lucite Construction) 64

9 Infrared Spectrum of 2,2-Dimethylhydrazinodiphenyl-
phosphine (Nujol Mull) 67

10 Proton Nuclear Magnetic Resonance Spectrum of 2,2-
Dinethylhydrazinodiphenylphosphine 68

11 Infrared Spectrum of 2,2-Dimethylhydrazinodiphenyl-
phosphine Oxide (Nujol Mull) 71

12 Infrared Spectrum of 2,2-Dimethylhydrazinodiphonyl-
phosphine Sulfide (Nujol Mull) 73

13 Infrared Spectrum of 2,2-Dimethylhydrazinomethyl-
diphenylphosphonium Iodide (Itujol Mull) 75

14 Infrared Spectrum of l,l-Bis(diphenylphosphino)-
2,2-dimethylhydrazine (lujol Mull) 81

15 Infrared Spectrum of the Product of the Reaction of
2,2-Dimethylhydrazinodiphenylphosphine and Carbon
Disulfide (Nujol ll) 85

16 Infrared Spectrum of Diphenylphosphine (Cell) 90


Figure Page

17 Infrared Spectrum of 1,1,2-Tris(diphcnylphosphino)-
methylhydrazine (Nujol Mull) 93

18 Infrared Spectnra of 1,2,2-Trimethylhydrazino-
diphenylphosphine Oxide (Nujol 1Mll) 96

19 Infrared Spectrum of l-Ethyl-2,2-dimnthylhydrazino-
diphenylphosphine Sulfide (Nujol I1ull) 101

20 Infrared Spectrum of 1-Ethyl-2,2-dinctlrylhydrazino-
dinhmnylphosphine Oxide (Nujol ITll) 104

21 Infrared Spectrum of 1,2-Bis(diphenylphocphino)-
hydrasine. (-ujol ll) 107

22 Infrared Spectrum of Bis(2,2-dimethylhydrazino)-
phenylphosphine (Nujol Iull) 110

23 Infrared Spectrum of Bis(2,2-dlmethylhydrazino)-
phenylphosphine Oxide (Mujol Mull) 113

24 Infrared Spectrum of Bis (2,2-dimethylhydrazino)phenyl.
phoschine Sulfide (Nujol Null) 116

25 Infrared Spectrum of Phosphoryl Tri(2,2-dinethyl-
hydrazide) (Hujol Mull) 119

26 Infrared Spectrum of Thiophocphoryl Tri(2,2-
dimethylhydrazide) (Nujol Mull) 121




The highly interesting and challenging field of organometallic

chemistry has undergone tremendous growth in recent years, and cmong

other valuable contributions to the science of chemistry there have

been discovered new modes of chemical combination, entirely new

types of chemical compounds, ne~ useful materials at lower costs than

previously-used synthetics, and new routes to known materials.

Evidence of great interest in the field of organometallics

manifests itself in the recent appearance of several te::ts devoted to

this unique combination of organic and inorganic chemistry ( 1-4 ).

One of the areas of organometallic chemistry which has in-

terested investigators for as long as metal alkyls have been known is

the preparation end study of molecular addition complexes between

the metal alkyls and various Le;is bases (electron pair donor

compounds). The metals in which most interest has been shown are

those of Group III of the Periodic System. Review articles covering

various such molecular addition complexes have appeared over the

years (5-11 ), but none of these articles is concerned exclusively

with nitrogen complexes of aluminum, although aluminun-nitrogen

complexes have been mentioned (3L.

The reason that the many nitrogen-base complexes of aluminum

alkyls and the various other alenes have not been the subject of an

extended review article is that work on this group of compounds was

begun in earnest only within the past few years. The importance of

such compounds at this point seems to lie in their intrinsic properties

as well as the fact that they are intermediates in condensation reac-

tions. The aluminum-nitrogen compounds in which this great interest

has been demonstrated may someday find application as high temperature

polymeric materials and perhaps as propulsion fuels. As intermediates

to new and exotic compounds they are virtually uncxplored.

Well-established chemical and physical evidence concerning the

nature of various alanes, and specifically the aluminum alkyls, indicate

that they act as electron pair acceptors, or Lewis acids. The acceptor

tendency is co great as to preclude their existence in the unassociated

state (1,2). This fact provides a basis for the observed reluctance

of investigators to use the GriGnard method for preparing aluminum

alkyls, since the compounds prepared can with only very great effort be

freed of the ether used in the synthesis (6. The diethyl etherate

of triethylaluminum has been studied in detail ( 13-15 ). The dimethyl

etherate of trimethylaluminum has been found to be an extremely stable

compound, so stable in fact that no dissociation data can be obtained

in the gas phase (16); ruch data have been obtained for many other

Group III addition complcxec, however.

Various methods of preparation of molecular addition complexes

of aluminum alkyls hnve been used, but the most common include direct

combination in the vapor phase (both diluted and undiluted), direct

combination in the liquid phase, and direct combination in a suitable

solvent. Some experiments have been carried out in which one (or

both) of the reactants were generated in situ.

Since this work is concerned with nitrogen derivatives of

aluminum it is appropriate to discuss those reactions and compounds

reported in the literature which include aluminum-nitrogen molecular

addition complexes and the aluminum-nitrogen covalent bond.

At this writing there have been reported in the literature

three main types of covalently bonded aluminum-nitrogen compounds:

the amine-alanes, the aninoalanes, and polymeric materials which

contain aluminum-nitrogen bonds. These three types of compounds are

intimately related and may be arranged in a reaction sequence where

the initial molecular addition complex is the parent compound in a

pyrolytic series, as in the following example: (17,18)

1. Adduct Formation of an Amine Alane.

A12(CH3)6 + 2tH3 = 21H3N:A(C}3)3

m.p. 56.70C.

2. Condensation to an Aminoalane.

H3:All(C113) = H2N-Al(CIH3)2 + CH4

m.p. 134.20C.

3. Further Condensation to Polymeric Material.

H11-Al (CH3)2 = (RUlCH3) x + CH4

not fully


4. High Temperature Pyrolysis to Extended Polymer.

y(HIQIlCH3)x = (NA1)Dy + C114

A systematic investigation of systems of this nature has

recently been carried out and the scope of the reaction has been

extended to include many aeines and several alones (1T. Exa.ples of

compounds of this type (excluding those shor above) are given in

Tables 1-10, pages 5-9.

Reactions of these compounds other than by hydrolysis and

condensation are largely unlknon, and to date there is no mention in

the literature of a useful polymer in the aluminum-nitrogen system.

Various theoretical aspects of aluminum chemistry have been demon-

strated, however, and no tendency for gi-bond formation between

aluminum and nitrogen has been found.

Logical extensions to this work with alanes seem to lie in

two directions: 1) Lewis bases can be used which contain functional

groups other than and in addition to an amino group, and 2) poly-

nuclear Lewis bases can be used.

The first of these alternatives has been explored in a very

perfunctory manner and involves the reactions of alanes with olefinic

amincs, ethers, and thioethers to give various ring compounds and

organic derivatives (19). Obvious possible uses for those reactions

and intermediates lie in the field of polymerization catalysts.

The use of polynuclear Lewis bases with alanes was, until very

recently, totally une::plored. Within the last year, however, there

have appeared two articles concerning the interactions of aluminum

alkyls with hydrazine and alkyl hydrnz-t:. (20, 2L ). It is interesting

to note that the experimental results obtained by these workers are

in most aspects in accord with the results we have recently obtained

Amine Alanes

Compound m.p. b.p. Roferencec

(CI3) 3N: AH3 760C. ---- 22-24
(CHL) 31:A1D3 77-78oC. ---- 22

(C2H5)311: A1H3 1S-190C. ---- 22
(C3117) 3N:AIH3 80-310C. ---- 22
II3CN(C21l5)2:A1H3 --. ---- 22
H12C=CCCH21 (CH3)2: AlH3 120C. ---- 22

(CH3)3N:Al(CH3)H2 -35C. 250/1 mi. 25
(CH3)3N:Al(C2H5)IH2 --. 390/1 am. 25
(CH3)3N:Al(CHI3)2H ---- 42/1 mn. 25
(CH3)311: Al(C2115)211 -280C. 63/1 n. 25
(CH3) 2H:A1 (CH3)3 510C. 1860C. 16
(CH13)3N1:Al(CH3)3 1050C. 1770C. 16

(CI13)33: Al(CHi3)2C1 124C. ---- 16
(CH3)3N:A1(C2H5)201 -50C. --- 17
H3CMI2:Al(C2H5)2C1 -11.5C. ---- 17
H3CIH2:Al(C2H5)C12 150C. --- 26

H3N:A1( /---- )326

S )3 ---- ---- 26


Bis-Amine Alanes

Compound m.p. b.p. References

[(CH3)3N]2:A1H3 950C. d. ---- 23,27,28

[ (C2H5)3N4]2:A1H3 --- ---- 28

[(C2H5)2NC1132 :AlH3 ---- ---- 28

[(C3H7)3N]2:A1H3 ---- ---- 28
[CH2=CHCH2N(CH3)212 :All3 ---- --- 28


Bis-(Mixed)amine Alanes

Compound m.p. b.p. References

(CH3)3N (C3117)3N:A1H3 ---- ---- 28

(CH3)3N(C2H5) 3:A1H3 ---- ---- 23
H3C(C2H5)2N(H3C)3N:AlH3 ---- ---- 28


Inner Complex Amine Alanes

Compound m.p. b.p. References

CH2-- CH2

(15C2)2N CI2 ---- 115-1160C./1.5 am. 19
S(04119) i-(C4H9)



Compound n.p. b.p. References

[(CI3)21-A1 (CH3) 212

C(CH3) 2N-AlH2]3


([(CH3)2C11 2N-A1H2 2.16
[CH3bH-A1 (C2') Cl]

[(C2H5)2N-Al (C2H5)21n

[(CH3)2NA1(C2H5)C i


[(CU3)21lA1C12 2.4

[ (CH3) 2 12A1H)2.

(CH13) 2ClI2HAl1H(CH3) 2}2


f[(CH3)2CH]2N} 3A1


98- 900C.



91 C.

80- 81C.

















55- 57C.

87- 89C.

58- 59C.

141-1450C./14 mm.


Extended lIctuork Aluminum-Nitrogen Polymers

Compound m.p. b.p. Rcfcrencec

[(CH3)IACl] --- ---- 17
(AlH)n above 2200C. ---- 18,30


Hydrazine Alanes

Compound m.p. b.p. References

(CH3)21-II(CH3)2:Al(CH3)3 80 -83 oC. --- 21

(CH3) 21H-1CI3: Al (CH3)3 65.5-66.00C. ---- 21



Compound n.p. b.p. References

[(CH3)2N-I1R-A1(CH3)2]2 77.0-78.50C. --- 21

[(CH3) 2I-N (CH3) -AI(CH3)212 125.0-126.50C. ---- 21
L(CH3)2Al-NH 3-I-A1 (CU3)2] shock sensitive ..-- 20


Hydrazinoalane-Hydramine Adducts

Compound m.p. b.p. References

H2-N(CH3)2: (CH3)2Al-NH-N(C13) 31.0-32.0C. --- 21


Polymnric Species

Compound n.p. b.p. References

(H3CAlItHCH3)n 200C. d. ---- 21

[A1( Ct3-UCH3)3]n --- ---- 21

independently at the University of Florida. Fortunately, there has

been no duplication of effort since our work is concerned with

triethylaluminum and the studies reported in the literature were made

with other aluminum alkyle.

E:perimental and results

The following procedure uwa found to be very satisfactory for

studying the interaction of triethylaluminum with 1,1-dimathyl-

hydrazine and nonomethylhydrazine.

IM1terinls. 1,1-Dimethylhydrazine is commercially available

and was distilled prior to using. The material used had a boiling

range of 62.2-63.00C./753 ma. Distillation anc carried out over

calcium hydride to remove any traces of water which the commercial

material may have contained. Care was taken to observe completely

anhydrous conditions during the transfer and handling of this and the

other reagents and solvents used.

Treithylaluminum was purchased in 250 graa quantities in

steel lecture bottles which were fitted with Teflon-packed needle

valves. The purity of this material was not high enough to permit use

without purification. Distillation at 56CC./0.50 mn. provided samples

which analyzed 99.6 per cent tricthylaluminun, as determined by

measuring the ethane evolved upon aqueous hydrolysis.

Analytical Reagent grade solvents were distilled over calcium

hydride prior to using and were then stored in air-tight glass con-

tainers with metal foil or polyethylene closure liners. All transfers

were performed either in a dry box or by pipette with a nitrogen flush.

High purity nitrogen was used in the dry box and wherever a

constant flush seemed necessary to avoid contact with the atmosphere.

Equipment. A dry box is essential in carrying out synthetic

work with triethyloluminum and this piece of equipment is described

in detail in Chapter II of this dissertation, under the Equipment


Distillations were carried out in 1lini-Lab Standard Taper

14/20 apparatus as shown in Figure 1. The actual reactions were

carried out in a Standard Taper 14/20 100 ml. round bottom flask

fitted with two 10 nm. diameter by 30 em. length side arms. Figure 2

illustrates this flask and the complementary equipment, which includes

a pressure-equalizing addition funnel of 50 nl. capacity and a

Precision Wet Test Meter. The Wet Test Meter'can be read directly to

the nearest 3 ml.

A freezing point depression type apparatus was used for

molecular weight determinations. Its design was modified slightly in

order to provide a constant, slou nitrogen flush so that contact of

the solution with atmospheric oxygen could be avoided, as shown in

Figure 3.

Elemental analyses were performed by Galbraith Microanalytical

Laboratories, Knoxville, Tennessee. Carbon, hydrogen, and nitrogen

were estimated by combustion methods and special precautions were

observed to maintain sample integrity before combustion.

Aluminum analyses cwre performed by the method of Schwcrzen-

bach (3) in which the aluminum-containing solution is treated with

excess disodium cthylenediaminetetraacetate and the excess titrated

with standard zinc sulfate solution to the pini: Eriochrome Blach T

end point.

The interaction of triethylaluminum with 1,1-dimethylhydrazine

In a typical experiment 8.0321 grams (0.0704 mole) triethyl-

aluminum was vacuum distilled intz a 100 ml. Standard Taper 14/20 round

bottom flask fitted with two side arms and which contained a small,

Teflon-encapsulated, magnetic stirring bar. All ground glass joints

were lubricated with Kel-F fluorocarbon grease, which was found to be

more resistant to attach by triethylaluminum than are other, more

conventional stopcock greases, including silicone grease.


Figure 1. Mini-Lab Distillation Apparatus

I'I- ~. I.--:i I I .1 1 '-r' IU S


i -

1 --

'- - r i 1

L ilI IL, .I"' I., I

S I..i. I I I i .ll' .

.'l .. l Ir I 1 ,

1 ru~c/l l oi' I. 'p.> 10 .PP.L ,tot : '0l r' .t P' 'lblur

([or ac ati, : r- itd o o,ol)

I; :1Muolcilav \VWfI,4t Apoa'.-at-.t Mofliicd br Ani o-picrci> !it' Co polv,,l

The triethylaluminum was frozen by imrersing the lower half of

the flask in a dry ice-acetone slurry. While a nitrogen flush was

maintained above and around the flask, the stoppers which capped the

side arms during distillation were removed and through one side arm

was inserted a low range (to -1000C.) pentane thermometer. The other

side arm was connected via two dry ice-acetone traps to the Wet Test


The addition funnel, containing 4.44 grams (0.0739 mole)

1,1-dimethylhydrazine, was fitted to the flask and with the lower half

of the flash at -780C. the Wet Test Meter was set to zero.

The contents of the addition funnel was added in very small

increments (one drop or less) to the frozen triethylaluminum, and

the system was warmed and melted for mixing between additions. Ethane

(identified by vapor phase chromatography) was the only gaseous product

and the evolution was slow and controllable.

Evolution of gas was evident at temperatures as low as -600C.

for the first half of the addition, but during the second half higher

temperatures (near 0C.) were needed. No liquid or solid collected in

the cold traps. The addition took four hours, after which the system

was warmed to 250C. and stirred oaernighL (12 hours) to assure complete

ethane evolution.

The observed, corrected volume of ethane was 1.596 liters;

theory calls for 1.577 liters for the reaction

A12(C2H5)6 + 2(CH13)211-12 = f(CH3 )21-I-Al(C2 5) 22 + 2C2H6

The 5 per cent excess 1,1-dimethylhydrazine was removed by

pumping briefly at 450C./0.15 rm. The resulting product was a colorless,

crystalline solid which weighed 10.11 grnmn (99.6 per cent yield,

based on triethylalurinum used) and which melted at 43-44C. (sealed

tube, uncorrected).

Hydrolysis of a 2.7071 gram sample of the product gave 0.845

liter of ethane. Calculated for [(CII3) 21nAI(C2115) 2: 0.841 liter.

[(C L H (C HO'c + 4H20 = 4C2 6 + 2(CI3)2 II3
(cu3) 2m1Ml (C215)) 2 C2116 +

+ 2A1(H20)63

analysis. Found: C, 50.05; 1, 11.61; 11, 19.70; Al, 10.57;

C2H5, 40.73. Calcd. for [(CIl3)21NAl(C2H15)2 2: C, 49.93; H, 11.38;
N, 19.43; Al, 10.71; C2H5, 40.31. lolccular weight, found: 231

(cryoscopic in benzene). Calcd. for [(C113)2RIFail(C225)2 2: 233.4.

The product is soluble in most cotton, inert solvents. The

infrared spectra obtained on a melt and 10 per cent in n-hexane show

bands in the regions expected for C-H stretch and bend, I-II, I1-N,

C-N-1I, and Hi-CH3. Figures 4 and 5 show the infrared spectra.

The observed molecular weight indicates a dineric structure.

Three possible structures, two of which are geometric isomers may

be considered.
H5C2 C215


IN (C')2

(13C)211 K -I1

ll5C2 C2H5

1. Si:: Membered Ring

H5C2 C2 H5 115C2 502

S Al U (113C) 2N Al II
'/NH/ I-1/\1

(13C)2N Al 1 (C3)2 I/ Al II(C3')2
H5C2 C2115 H5C2 C215

2. CiL-Four Mbnbered Ring 3. Trans-Four tMcabrcd Ring

The proton nuclear nagnetic resonance spectrun of 2,2-dimethyl-

hydrazinodiethylalane indicates that only one molecular species is

present and shOws the Al-C12'-C13 and N-CH3 structure peaks. Because

of the uncertainty in position associated with the 11-11 group, and in

addition some overlapping of peak areas, the data obtained were

insufficient to uuc in assigning a definite structure on the basis of

the spectrum alone. It is felt however, that if the structure involves

the four embcered ring, there night be expected two forms (cis- and

trenc-) in a mixture, and the n.n.r. spectrum would certainly indicate


Infrared data give circumstantial evidence for the six membered

ring. The position of the 1-11 stretch in 2,2-dinetyhyhydrazinodiethyl-

alone corresponds closely to that observed for tricovalcnt nitrogen

compounds which contain the IU-11 group. The four membered ring does

not contain this particular arrangement since it is the nitrogen atom

involved in the Il-II group which coordinates the aluminun atom and thus

becomes tetracovalent. Little importance can be placed upon these

observations, however, since hydrogen bonding in the solid sample would

tend to equalize the environments of the nitrogen tons in question.

2 l -1
2001 1 50( 1000 (!
1- t_ I I_


i ,! ""
i "'

Figure 4. Infrared Spectrum of 2. 2--Dimethiylhydrazinodiethlalane (Melt)


c 'I



K, \!


s1 I iI / 11 1 .'/1I L' ll [ *'l. '
IL .J- 1 r.1 V

I -

S i1'' / if ."1
-i I, ,I . ,
. I 'i f

S: ; 1 '' ; \"
- I j' I ,

i- I I I
I li I

1 i 1r, . jlll l, LI l'C ~l_, lll ,, ' ~ II I h ',(1 1 .1 ,,L,,'p 'I, 1 1 111 (1,I1,, I f , I 11 ,, .1 ,1 ',1 ''

t I ,

As a possible solution to the problem of analyzing the infrared

data, a sample of 2,2-dinethylhydrazinodiethylalane was run as a 10 per

cent solution in n-hexane, where IH bonding would be minimized. The

resulting spectrum (Figure 5) shows little, if any, shift in the N-Il

stretching frequency at approximately 3150 am.- A new peak was

observed at 1590 cm..1a which is in the region usually associated with

the N-Hl deformation frequency. This observation was not explained.

Support for the four-membercd ring structure might lie in the

observed peak at 1400 cm."- which is generally found in compounds con-

taining an cniuonitu or substituted ammonium ion. This too, however,

could be a result of hydrogen bonding in either the four or six member

ring structure. The prospects for elucidating the structure of this

dimer b infrared means appear rather bleak. Suggestions for further

voil; along these lines might include a study of frequencies associated

with various ring sizes which contain atonm of size similar to aluminum

and nitrogen, perhaps cyclic silylhydrazines.

Pyrolytic condensation of 2 2-dnoethylhydrazinodiethylalcne.

In an experiment designed to test the degree of liability of the N-H

bond in 2,2-dimethylhydrazinodiethylalano, a pyrolytic condensation

was performed.

In the first experiment in this series the sample was heated to

1950C. at which point rapid evolution of gases caused the reaction

vescal to be blown apart. The product of the reaction was n light

brown solid which was very brittle and apparently highly polymeric in

nature. analysis of this solid residue for carbon, hydrogen, and

nitrogen gave a ratio which corresponds to C1.0 3.1 1.0 which may be
1.0 3.1 1.0

formulated as N-N(CH3)2, thus indicating that even though the material

was subjected to temperatures in excess of 3500C, the dimethyl-

hydrazino group remained intact.

This material was highly opaque to infrared and had no

melting point; thus, little characterization was possible..

In a second experiment the condensation was run at 1500C. over

a five hour period. Ethane evolution was slow and easily controlled

in the temperature range 110oC. (where evolution first is observed)

to 160C. The product, in this case was a dark, viscous tar which was

easily soluble in benzene and hexanc. The material was analyzed for

active ethyl content by aqueous hydrolysis and gave the following


Found: C2H5, 25.52. Calcd. for [(CH3)21NAlC21H5y, 25.46.

It thus appears that the condensation occurs according to the reaction

nf(CH3)2NNHAl (C21 5)2 2 = 2nC2H6 + x [(CH3)2NUlA1C21q y

and the hydrolysis may be represented by the equation

[(C113)2IRNAlC215]y + 2yll0 + 4yH30+ = yC2116 y(CH3)2R1nH3

+ yAl(H20)6

Other evidence which serves to substantiate this reaction

sequence is demonstrated by the conspicuous absence of the UI-II absorp-

tion bands in the infrared spectrum (Figure 6). The presence of the

1,1-dinmthylhydraziniun ion in the hydrolyzed sample was shown by

adding aqueous sodium hydroxide until the pH was 10, and testing the

vapor above the solution for a volatile free base (1,1-dimethyl-

hydrazine) with moist red litmus, and for a reducing substance with a

0ili0 :;o1) 2(1)8 1 5n8

L f

1 1

I: I


'., ... . Ilral 'idl ci r(l'ni t ('c

HiI 9) 0k
- ___.1.




\ !\

ndensal ion T'roldui (Lt INNM (Ilexann' Solution)



drop of Ka0O4 solution on a strip of filter paper. Both tests were


A third experiment was designed to carry out the condensation

as slowly as possible at a lower temperature in order to see if ethane

could be removed without opening the ring or changing the degree of

polymerization from a dimeric species. A sample of 2,2-dimethyl-

hydrazinodicthylalane was heated at 750C./0.20 .m. for a period of

144 hours. During this time the colorless, mobile liquid gradually

became dark in color and grew increasingly viscous. 1hen 'zhn reaction

was complete, as evidenced by the disappearance of the tl-11 band in

the infrared, the material had become a dark, viscous tar.

A molecular weight determination was performed cryoscopically

in benzene. Iblecular weight found: 646. The formula weight of a

[(CH13)2RI1nAlC21 unit is 114.13, thus the polymer formed in this

experiment has an average degree of association, y = 5.66.

Possible structures for this polymer include 1) rings linked

together, 2) rings larger than six member, and 3) chains with end

groups of an undetermined nature. In any event, the polymer appears

to have the repeating unit

C2y15 (C113) 2

Al N_

The information gained in this experiment indicates that the

hydrogen atom in the U-H group in 2,2-dimethylhydrazinodiethylalane

is less labile than that in l,l-dimethylhydrazine itself (or in some

intermediate molecular addition complex formed prior to 2,2-dimethyl-


These additional data are better interpreted on the basis of a

six membered ring rather than on a four membered ring. In the four

menbered ring the aluminum atom is coordinated by the nitrogen atao

which contains the 1I-H group




The effect to be expected if the N-HI nitrogen ato m acts as a Lewis

base is labilization of the 1-II bond, which is not the experimental


Attempted de-dinerizntion of 2,2-dinethylhydrazinodiethyl-

aelne by adduct formation. A sample of 2,2-dinethylhydrazino-

dicthylalane was nixed with a twofold excess of unsynn.-dimethyl-

hydrazine and heated to 65 C. for five hours. The product of the

reaction was a light straw liquid after the cxcess unswcn.-dimethyl-

hydrazine had been removed by puapingat 250C./0.20 ra. for one hour.

The desired reaction nay be represented by the following


[(CHi3)2ml Nn(C21L)2] 2 + (CH3)2ImH2 = 2 (CII3)CIiAl (C2-5)2:(CH)21Tc12

A possible reaction that was thought unlikely would proceed via ethane


[(C:I3)2inkurl (C25)212 + 2(C03)21 I2 = 2 ((C13)2 ]2Al1C25 -:- 2C2 6

Analysis of the product of the reaction disclosed, however,

that the only process that had occurred was that or partial condensa-

tion to [(CH3)2 UA^IC2I] .

Found: N, 20.05, 20.39. Calcd. for [(CHl3)2rAl(C2 15)2 2:

19.43. Calcd. for [(C113)2 INAlC2 ] : 24.56. A change in the peak

height of the H-H band in the infrared spectrum served to confirm the

course of the reaction.

These data give an indication of the strength of the dative

Al-IH bond in the dimor and also seems to chow that l,l-dincthylhydrazine

is capable of catalyzing the pyrolytic condensation.

Attempted de-dinerizntion using phosphines. Experiments in

which tributylphosphine and triphenylphosphine were heated with 2,2-

dinethylhydrazinodiothylalane resulted in dark, uncharacterizable,

viscous liquids.

The interaction of triothylaluminum with methylhydrazine

In en experiment identical in detail with that performed in

the synthesis of 2,2-dimethylhydrazinodiethylalane, 1.569 grams

(0.0341 mole) methylhydrczine was reacted with 3.337 grams (0.0341

mole) of triethylaluminun. Very slou dropuise addition was carried

out at -730C. with waring for melting and mixing between additions.

It was immediately apparent that the reaction was very

exothermic (more so than with l,l-dimcthylhydrazine) and that a sone-

what different product nas being produced than was found uith 1,1-

dimcthylhydrazinc. The amount of othane evolved approached three times

the theoretical and the reaction product was a brorn, inhonogeneous


The total volume of ethane evolved was 2.029 liters. The

amount calculated for the reaction

A12(C215)6 + 2CH3hII i2 = 2 [2Iy(C1I3)Al(C2115)2 + 2C2 1

was 0.763 liters. For the reaction

Al2(C2Il)6 + 2CHitlTnH2 = 2[A1N(CI9)NI]

+ C2!15

however, the calculated volume of ethane was 2.203 liters. The quan-

tity observed was 37.5 per cent of that required for the elimination

of 3 moles of ethane per mole reaction unit.

The solid was collected and any excess triethylaluminum was

removed by pumping at 250C./0.20 mm. for five hours. An attempt to

prepare a Hujol mull for infrared analysis resulted in spontaneous

combustion of the solid upon contact with air. Whether this was due

to the material itself or unrcmoved triethylaluminum is not Inowm.

The infrared spectrum was obtained on a mull prepared in the

dry box and was very opaque, which is characteristic of highly

polymeric materials. A very weak N-II peak showed that the reaction

had not gone to completion.

Analysis. Found: Al, 37.15 per cent. Calcd. for CR312A1:

Al, 33.55 per cent.

The material was found to be insoluble in all the solvents

tried, and dissolved only with very great reluctance in hot 151M nitric

acid. The nitric acid solution was highly colored, but uac decolorized

with hydrogen peroxide in order for aluminum analysis to be run on the


The solid has no melting point, but chars when heated to

360 C.


Although there are not a large amount of data collected in

our study of the interactions of 1,l-dimethylhydrazine and methyl-

hydrazine with triethylaluminun, certain interesting differences were

noted in the behavior of the two different hydrazines and in the

behavior of hydrazines and amines with respect to their interactions

with aluminum alkyls. One pleasing result of this work is the syn-

thesis and characterization of the new compound, 2,2-dimothylhydra-

zinodiethylalane. Although a recent publication (2!) reports

methylaluminum derivative of hydrazines, this compound is the sole

known ethylaluminum derivative of a hydrazine.

An idea which was a motivating factor in the initial phases

of this work concerned the possibility of preparing a solid adduct

between triethylaluminum and l,l-dimethylhydrazine. Both the alane

and the hydrazine are mobile liquids and both have been used as liquid

propellants in the missile industry and in the U. S. pace effort.

For many reasons solid fuels are preferred to liquids in certain types

of applications. Thus, a solid adduct formed from the two liquids

might well be an interesting fuel.

From the preceding description of the observations made of

the interaction of triethylaluninun with 1,1-dimethylhydracine it can

be seen that no adduct was found in the temperature range studied. It

is possible, of course, that work at very low temperatures would

produce evidence indicating the formation of such an adduct, but in

any case no such compound exists above -600C. Similar results were

encountered in the reaction of triethylaluminum with monomethyl-


Of the various nitrogen donor-alane systems which are knorn,

those systems containing a hydrazine are certainly the most reactive.

Of the reported amine-alcnes, where the amine may or may not contain

the Il2 group, it may be generally caid that the adduct formed between

the amine and the lane is stable at room temperature. In the case

of hydrazine-alanes, however, none have been reported which contain

the Ni2 group except (CH3)21S11IA1(CH3)2:1NH2N(CH3)2 which is not a

simple hydrazine-alane. (21)

An approach to a clearer understanding of the nature of the

hydrazine-alanes, the hydrazinoalanos, and their condensation products

rmay lie in a stepwise consideration of the interactions involved in

the formation of these compounds.

Any acceptable mechanism must be consistent with the following

known facts: 1) the reaction was carried out in such a way as to have

an excess of triethylaluminu- present in the reaction mixture until

addition of l,l-dimethylhydrazine was essentially complete, 2) ethane

evolution occurred at -600C. during the first half of the reaction,

but was less rapid during the second half and required higher tempera-

tures, O-.Ino., 3) the product is a dimer, and 4) the N-Il group in the

product is less active than that in l,l-dinethylhydrazine.

Fetter and Bartocha (21) have recently made statements concern-

ing proposed mechanisms of interaction and the structure of hydrazino-

alanes. They believe that a plausible first stop in the interaction

of 1,1-dimethylhydrazine with an a clinun all:yl is the coordination

of the -tl end of the molecule with the AlR3 unit,

R3Al + 11-: (CI3)2 = R31:IT2y(CI3)2

rather than coordination of the -N(CII3)2 end, as shown belowr:

R3Al -- (CIL)2111R2 = R3Al:1(CHI3)2112

The reason for their choice is the fact that their preparations

of dinethylhydrazinoclanes produce as a gaseous product, R-H, rather

than R-CII3. From a consideration of the bond energies alone, N-1i

(92 kcal./mole), and N-C (66 Ical./mole), one might favor such an

interpretation. However, if there are kinetic effects which favor a

different reaction, there is no reason to dismiss coordination by the

-I (C13)2 end of 1,1-dimethylhydrazinc.

If we first accept the promise that the-1(C113)2 end of the

IH2lN(CI3)2 molecule is more basic than the -TN2 end because of the

inductive effect of the methyl groups,

1\ /

/ \

1 CH3

then in the presence of the strong Lewis acid, AlEt3, we should

expect the initial coordination as shown in equation 1 on pae 30.

In the presence of a large excess of Lewis acid, AlEt3, we

uould expect a second step (equation 2) to occur very quickly, to

form the bis- complex, Et3A1:1nT2-I(CH3)2:AlEt3.

A Proposed Ilcclhnism for the Interaction of Unsyra. -Dimethylhydrazine uith Triethylaluminum


1. :11--1i:

II C113

+ Al-Et

II C113
:H-IT:A Et3


iolccular Addition


2. EL-Al


II C113
+ :-1- l:AlEtI3 =

I1 CIl

Et 1 CII3
Et--,l :i!--:AlEt3
I i I

molecular Addition
Second FlEt3

Et II CI13

3. Et--Al:IT-- E:AlEt3
Et H C013

11\ /

/ \
4. :1-CU:


S C211I

+ Et-Al- 1- -IIAlEt3

EL 11 %

S Et-Al- II--1 :AlEt3


Ethane Elimination

Et II CH3 Et

S Et-L-----UII:l- Et
/ I \
(In3C) 21 CH3 Et



Et ,Et


(1I3C)21I 1l-Il

112H: 11(0113)2

I Et

Et Et


6. (113C)211 U-11
(I13C) 2 (C-I3)


11 Al--Et
/ "Et

Et Et


(113c),2 Il-I1

11-11 11 (13 )2

I \Et

Et Et


(I13C) 2 -11II
= C2 -+ |
H-tl '1(CIl3)2

/ \
Et Et

clization by

Second Ethane
Elimination to
Form Six Iembered
RinA Diinor

The decomposition of the bic- complex to ethane and the Alst3

adduct of the hydrasinoalane, Et2p'i HEI(CIt)2:AlEt3, would follow

according to equation 3. At this point the stoichionetry is a 2:1

ratio of lane to hydrazine, and it is at this point in the

preparation where the temperature at which ethane will evolve suddenly

change to a higher value. In fact it has been observed in the

laboratory that the remaining addition of 1,1-dimethylhydraaine may

be made quickly at -250C. and that no appreciable gas evolves until

the mixture is warmed to 00C.

In the presence of additional free l,l-dinethylhydraaine

addition would be expected according to equation 4, followed by

cyclization as shorn in equation 5, and ethane elimination to the

final cyclic six membered ring diner as in equation 6.

A suggestion for further work in this system appears quite

obvious at this point. If the mechanism proposed above is correct

there should exist the possibility of propcring Et2Al-iIKJ(CII3)2:AEt3

by the reaction of the alane with the hydrazine in a 2:1 mole ratio.

The prospects for preparing any of the other intermediates do not

appear promising, however. It is quite possible that

Etc2Al-:IE(CH13)2:AlEt3 would not be isolated as a monomer since it could

very well associate to form diners or chain polymers; these species

would probably react in much the same manner as the monomer with 1,1-

dimethylhydrazine, although less vigorously. An interesting point is

that if this material did exist as a monomer, it would indicate that

the need of aluminum for an electron pair was being satisfied by the

adjacent nitrogen atom which has on unshared pair of electrons available.

This observation would provide evidence for the existence of pi-

bonding between aluminum and nitrogen, which has boon discounted

by Laubcngayer (30).

Condensation of 2.2-dinethylhydrazinodietlivlrl.ne. Since it

has not been observed that ethane is intramolecularly eliminated, a

process which would result in the formation of [(CH3)21iIAlC2H5]2,

with a molecular weight of about 223, it appears reasonable to assume

that the mechanism of the condensation involves attack of an 1i-Hl

group on the Al(C2H5)2 group in 2,2-dimethylhydrazinodiethylalane.

This condition could only be fulfilled if the II-IH group has an

unshared pair of electrons and rc act as a Lewis base; thus it does

not appear that the four membered ring structure, page 17 can

participate in such a condensation reaction.

In the presence of excess l,1-dimethylhydrazine it was found

that the condensation proceeds at a lower temperature than is observed

when pure 2,2-dimethylhydrazinodiethylalnne is condensed by heating.

Thus it appears that the presence of N-H groups (with free electron

pairs) is necessary for the condensation reaction.

These observations leave doubt that a dineric condensation

product will be observed since intramolecular elimination of ethane

in the ring apparently does not occur, as evidenced by the observed

high molecular weight of the condensation product.

Condensation of tricthylaluninun with nethylhydrazine. The

observations made on this system tend to corroborate the mechanism

suggested for the interaction of triethylaluminum with 1,1-dimethyl-


In nmthylhydrazine we should expect, from considerations

of the inductive effect, that the most acidic 1-II bond is on the

-1112 end of the molecule and that the stronger Lewis base is the

-I (CI3) I end.

\ /
11 -N:

/ \
II Ci3

Once a ncthylhydrazine molecule donates an electron pair, however,

there is come question as to which I-II bond is most acidic.

An initial attack: of mothylhydrazine on tricthylaluminum

would produce the molecular couple Et3A1:~'1:CI3iI which could either

cliinate ethane intra- or intermolecularly. The inhomogeneity of

the product may serve to indicate that both these processes occur,

or that at any rate, molecular species are produced in various degrees

of association.

Considering the abundance of active H-II groups in the initial

adduct, it is not surprising that complete condensation to

[(11P(CIl3)1]y is the final product.

Although it is not implicit in the formulation of this

polymeric species, it is expected that aluminum achieves a covalency

of four, either by accepting a pair of electrons from a nearby nicrogcn

etona or by accepting a pair of electrons from an adjacent nitrogen

atom. The fact that the polymer appears to be a highly extended net-

rorh would lend support to the former suggestion.


The results of our study of the interactions of triethyl-

aluminun with two different allyl hydrczlnes has resulted in the

synthesis of three new species, [(CH-3)2rnIhAl(C215)2]2,

R(CH3)21INAlC21516 [AlI(CH3)IT]y, and has given various data through
observation of reactivites, stoichionetries, and reaction

conditions. Some physical characterization was possible, and all

available tools were cnployed in n attempt to elucidate the structure

of 2,2-diIethylhydrazinodiethylalacn, which is thought to have a si:-

menbered ring structure.

A mechanism for the formation of these species consistent

with the observed data is suggested and applied to both this world and

some additional work reported in the literature.

Although no evidence for pi-bonding between aluminum and

nitrogen has been found, it is certainly within the realm of possi-

bility that such bonding acy exist. Preparation of the intermediate,

Et2AlIT (CH3)2:AlEt3, in a monomeric form would lend more credence to

the possibility of aluminum forming pi-bonds with nitrogen.

Further study is indicated.




The field of phosphorus-nitrogen chemistry has been periodically

reviewed and there are two major reference texts (32,33) and an

excellent review article (34) which although not chiefly devoted to

phosphorus-nitrogen chemistry certainly provide a foundation for the

worker in this field. No up-to-date listing of phosphorus-nitrogen

compounds is available, however. Particularly lacking are reference

summaries in the area of the hydrazine derivatives of phosphines and

phosphorus acids.

A thorough compilation of all known hydrazine derivatives of

the phosphines and related compounds uas prepared in order to determine

the extent to which those materials have been studied and to what use

the information has been put. As a result of this survey it has been

found that hydrazinophosphine, I12fPlHIH2, has never been reported, nor

have any of its organic derivatives. Most of the work with hydrazino-

phosphorus compounds has been in the area of hydrazine derivatives of

the esters of phosphorus acids.

There exist, on the basis of the more common substituents for

phosphorus, a great variety of possible classes of compounds containing

the hydrazinophosphorus group, -P-N-N-, but the survey shows that world

has been done on only a few of the possible series of such compounds.

Many of the compounds reported in this dissertation are the only known

mcnbers of their series of compounds.

The general method of preparation of hydrazine derivatives of

organophosphorus compounds is analogous to the methods used for the

syntheses of aminophocphines and aninophosphorus compounds (35,36).

The hydrazine is usually dissolved in an anhydrous solvent and the

resulting solution is added to a halophosphoruc compound dissolved

in the sane solvent. Excess hydrazine can be used to absorb the

hydrogen halide produced in the reaction, or a tertiary Ecine such as

triethylanine or pyridine nay be used for this purpose.

Example (37):

0 0
i I
(PhO)2PCl + 212124 -- (Ph0)2P2mnl2 -+ (I1H5)Cl

The monohydrazinophosphorus compounds which have been reported

in the literature are listed in Tables 11-14 along with pertinent data;

bis- and tris-hydrazinophosphdrus compounds comprise Tables 15-17.

Recent work has shown that stepwice substitution of chlorine

can be obtained in some arylphosphorodichloridothioates by partial

solvolysis (38):

S S Cl
1 I/
PhO-PC12 + 22H ---- PhO-P + (iy2)Cl

The remaining chlorine is found to be less labile as a result

of the substitution of the less electronegative hydrazino group and is

thus resistant to further solvolysis. In some cases the compounds

can be water-washed without appreciable hydrolysis. Arylphosphoro-

chloridohydrazidothioates are listed in Table 10.

The second chlorine in these mlecules can be made to undergo

solvolysis at higher temperatures, and in the presence of water, form

arylphocphorohydrazidothioic acids, while in the presence of anines

the various arylphosphoroamidohydrazidothioates are formed (see

Tables 19 and 20).


Pho-P-1NTH2 +-I 2R2H ---- PhOPInilI2 -- (R2H2)C1

C1 1R2
Cl NR2

kn effect of changing the reactant ratio has been observed in

the formation (in small yield) of a cyclic compound (9):

SS Nt-- 111I S
s \/ \/
2PhOPC2 + 612H -H4 P P
2 2/ /\

+ 4(12 15)C1

m.p. 1833C.

A scheme devised by A. llichaelis is responsible for the

synthesis of amino-bis (hydrazino)phosphine oxides (40). lie found that

s idophosphonic dichlorides can be prepared by refluxing a mixture

of phosphoryl chloride and a secondary amine hydrochloride until HC1

evolution ceases:


Alkyl and Aryl Phosphorohydrazidates

Product Yield m.p. Reference

(C250)2HuNHPi n.a. 113-1140 41

(PhO)2P2IREH n.a. 1120 42

(PhCHlO)2PNHNH 95% 730 43

(CH2=CHCH20)2PI UHiPh 76% 85-870 42
(C1130)2 NINHPh 93% 132-134 42

CH130(C21I50) ~HIuPh 82% 77.5-80.50 42

n.a. not available.


Alkyl and Aryl Phosphorohydrazidothioatcs

Product Yield n.p./b.p.

(PhO)2E 2

(02HN O) (CH30) P NITH2

( / \0) (CH30)'1HuH2
(CH30 O0) (CH30) fIHnU^I2

( o ) (0c 30) PHi 1Ug1


( / -) (C130)PHNH2



(tert. -C4Hg 0) (CH30) PHrTHg

n. 630 39,44

78% no distillate 45
at 0.01 mm. IH

68% m. 103 45,4(


m. 76-77 46

n. 85-870 46

-- 46

m. 92.5-93.50




TABLE 12 Continued

Product Yield m.p./b.p. Reference

U 0) (CH3o) brNMrIi2

0) (C2H50) PFRnn12

(02N~ / O) (C2H50)P(S)IThfNH2
C1 S
(/\0) (C21,10)'q*UflH2

-- 83-88.50

b. 147-1500

M. 800

no distillate
at 0.01 mm. It

m. 117-1180

i3C) 2"'i-

Alkyl and Aryl Phosphorophenylhydrazidothioates

Product Yield n.p.

(PhO) (C1130) NHNHPh
(PhO) (C2H50) I'UHPh

(02N -0) (CH30) iMNHPh

(02o 0) (C2150) R TIIPh

010 o)(C2H5)pmnmp

(Cl 0) (C2H50)PNIUHNPh










(l13C)2N NH 1N(C313)2


146-147.5 47




Product Yield m.p. Reference

C2H50-P(CC13)NIINHPh --- 154-156.50 42

S 0- (CH2 / )NN --- 173-1740 48,49


Bis (hydrazino)phenylphosphine Oxides

Product Yield m.p. Reference

Ph (NNI)2 -- 1310 50

Ph (NINHPh) --- 1750 48


H3C (I/IH ) 2 -- 208 51


H3C (Nmi )2 --- 171o 49

A Bis(hydrazino)phenylphosphine Sulfide

Product Yield m.p. Reference

PhP (I'Mfln2)2 --- 115 50



Product Yield m.p.



Ph02 P(O-P(NiI)

/7i3 0-POII HW)2

02N1 P-0- (INHFHPh)2

S-P (m~NI2)2


C1/ \1 0-P(NIlH2)2



/C I O- P(NHNHPh)2


Cl. / 0-(NIHNHPh)2


247 95 (1030)









93.5% 152-153o

96.7% 156-1570

73% 153-1590








38, 54



TABLE 16 Continued

Product Yield M.p. Reference


(113 C) 3 / P O-(ThHi Ph)2


C / \ o- [ITnEI(c113)2] 2

92.3% 151-153o

93.5% 123-1250 38,54


Tris(hydrazino)phosphine Oxides and Sulfides

Product Yield m.p. Reference



P (tmin2)3 75% -- 43


P (NHHPh)3 --- 1960 55


1 (INH- / CH3)3 -- 1890 55



P( IHML2) 3 -unstable 44


P (HIPHh)3 -- 1540 55


P(InHH- CH3)3 -- unstable 55



Product Yield m.p. Reference

PhO-P-NEI(CH3)2 97.1% -- 38

C1 S

o$j-0-P-,NH 1(CH3)2 95.3% -- 38


Cl O-P-UIM(CH3)2 99.0% 74-750 38


Cl 0-P-I'HIT(CII3)2 84% -- 38


Cl-/ C-P-NIHN(C113)2 1007. 76-780 38

C c1

O-P-IN 79% 120-122 38



Alkylphosphorohydrazidoic Acids*

Product Yield m.p. Reference


C250-p-NI ir H CI3 -- 1950 (d.) 52




C2 50-P-NIIIHPh -- 1920 (d.) 52



C2HO5-P-Iffl-2 -- 1000 52


*See TABLE 3 for cxarples of salts of acids of this type.



Product Yield m.p. Reference



Cl- 10 0- (NHCl)1WIn2


Cl- / (C-T(HCH3)TH (CH3) 2


Ci 0- (/HCl3) MNI


90.5% 104-1050




ci-< / \oPflr

0 0
1 1
PC13 + (R2i2)Cl --- R2NPC12 -:- 21C1

The ino-bic(hydr.aino)phosphine oxide is the product

obtained upon hydrazinolysis of the nmidophosphonic dichloride:

0 0
1 1
R2NPC12 -I- 4I1 aIyPh ---'- P IIIP)2

+ (Phl1IHn13)C1

Tables 21 and 22 list the reported anino-bis(hydrazino)-

phocphine oxides and sulfides.

Mn example of another reaction which produces mixed amino-

hydrazino derivatives of arylphosphonic acid involves a transamination

reaction (56):

0 0 112
1 1/
PhP(C12)2 4 [1211 -- Ph P + ir3

llydra-inolysis of the phosphonitrilic chloride triner is also

Inorwn (57,58):

113N2 12113

(C12p1f)3 + 12112114 --- /P + 6(111"5)C1

113112 \ J / 2 3
11F2 N Il 112"3


The reactions of the hydrazine derivatives of organo-

phosphorus compounds are interesting in that they may help to

determine the structure of the compounds and in many cases lead to

entirely now classes of compounds. The reactions are frequently

troublesome and may occur as side reactions during the preparation

of the desired compound and thus lower the yield.

The P-N bond is susceptible to hydrolysis and the degree to

which this occurs depends in large part on the nature of the sub-

stituents on the phosphorus atom and whether or not the phosphorus

is in either of the o::idized states, the o::ide or the sulfide. In

some cases, especially when the compound contains an ester group, it

is not the P-NI bond .which undergoes hydrolysis initially, but the ester

group (37,43):

0 0
1 1
(PhO)2Ptn" -:- NaOIll (aq.) > N IP [OPIMo"'rI -:- PhO0


Further hydrolysis will yield a salt of the phosphorus acid

0 0
1 1


and the free acid can be obtained by metathesis:

0 0

Na2 [O2PHI2] -- 211" ------- (110)2P11lRmT2 -+ 21Na

Complete hydrolysis is obtained by prolonged boiling in

aqueous sodium hydroxide and yields free hydrazine and the phosphate


1 -
[02PmHHR] + OH -- P + 12H4

Table 23 lists some hydrolysis products obtained in this


Hydrolysis does not always occur in the manner described above,

but may immediately attack the P-H bond as in the illustration below


0 0
1 1
Ph-P(1NHNl2)2 + 2H20 > PhP(OH)2 + 212114

In this case hydrolysis occurs so readily as to preclude the

existence of the hydrazine derivative in the preccnce of water.

The former behavior is typical of esters of phosphoric acid

and the latter is generally observed for derivatives of phosphonic


Hydrolysis is a competing reaction when a hydrazine derivative

of an organophosphorus compound is treated with a chloroester,

consequently low yields are to be expected for a reaction of this

nature (50):

S 0 S 0
II 1I M IaOH _
PhP(NIRH2)2 + 2C1-C-OC2H5 22c1 PhP(NHNHCOC2H52

m.p. 1330C. (46 per cent)


Amino-bis (hydrazino)phosphino Oxides

Product Yield m.p. Reference


C2115mi-in (I-p HPh)2 1530 40

n-C3117,H- (uHPbh)2 -- 1510 40

ico-C4H9N1I- (NH cPFh)2 -- 1410 40
n-C5H11111- P (nIHHPh)2 -- 1220 40


(CH3) 2- (In-IPh)2 194-1950 40

(C2H5)2N- P (NiHHPh)2 -- 184-1850 40

(a-C3H7) 2- (NHNHPh)2 -- 1640 40

(iso-C41y)2N- (NmHPh)2 -- 1683 40

P1h(Cr1 ) (MHNHPh)2 -- 1480 40


,Amino-bis (hydrnzlno)phosphine Sulfides

Product Yield ra.p. Reference


Lco-CO9F14Th ('ITHMlPh)2 -- 1290 40


(c2145)2tN- P( NWI1h)2 -- 40

S -
(n-C3II7)2 U- p CIfV I)2 1960 40

J.N-i(uIHfImI)2 -- 1580 40


Salts of Phosphorohydrazidates

Product m.p. Reference

Na (Ph0P02N1IHI2) 37,43

Na2 (OP2O1H T12) -- 37

Na2 (OPO9INHM2) '20 43

Na (HOPO21In I2) -- 37

K(PhOPO2NHNH2) -- 43

K (IIOP2N111m2) -- 37

114 (PhOPO2NHNH2) 37

Ba (PhOP02NIIIH12)2 -- 37

Ba (OPO2NMlH) -- 37

Pb (PhOPO2IIH2)2 -- 37

Pb (OPO2TI~H2) -- 37





a (PhCH2OPO2NHNH2) -- 43

K(PhCI12GC02 TnIh2) -- 43

Hydrazone formation has been observed in compounds where the

water produced in the reaction does not appreciably hydrolyze T.:h

reactants or products ( 43 ):

0 0 0 CH3
1 II 1 /
(PhC 20)2PNHIH' + CII3CCH3 > (PhCH20)2PNIIN=C + I20


n.p. 1090C.

Other such known hydrazones are listed in Tables 24 and 25.

Both aldehydes and ketones have been used to prepare such hydrazones

and the reaction is apparently general for hydrazine derivatives which

contain the -1H2 group.

Ihcn an arylphosphorohydrazidate is treated with -nhydrous

hydrogen chloride salt formation is observed (43):

0 0
1 r 1 + -
(PhO)2 P111 + *iHC1 O)- [(FhO)2fliII3 Cl

m.p. 1500C. (dec.)

This reaction is analogous to the formation of hydrazinium salts and

the proton attack invariably occurs on the most nucleophilic nitrogen

atom (59).

Quarternization reactions using methyl iodide have been

reported, but the reactions described are not always similar to the

reaction described above with hydrogen chloride. Instead, it is found

that some nucleophilic centers will quarternize in preference to the

nitrogen atoms contained in the hydrazino group (47).


Benzylidene Derivatives of Alkylphosphorohydrazidates

Product m.p. Reference

(Clt30) 2PN(CH3)N=CHF \Cl 69-710 60


(C1130) 2-r'1I=CH 1 123-1240 60


(C2gO)) 2%TnH H 52-530 60


(C2l50)2 p(CH3)N=CH-~ CI 54-550 60


(C2o50) 2UNm=Cl/ 122-1230 60

Cl Cl


Hydrazones of Bis(hydrazino)phenylphosphine Oxides-
Hydrazones of Bis(hydrazino)phenylphosphine Sulfides

Product M.p. References

Ph-P(iHn=c (CH3)2)2 1700 58

Ph-P(lHNC(Cc13) 1)2 201 58

Ph-P (NIHI=CH<' CIl3)2 171 58

Ph- (NlH=C (CI3) 2)2 155 58

Ph-P(MIN=C(CH3) C) 2 162 58

Ph-P( 1H=C(CH2)4C12)2 1330 58

(H13C)2N- O-P-O- 1(C I32 + 2C113 -I- 2120 ----


(3C) 3N O-P-O- N (CH0)3 I22H20

I 112

m.p. 156-1538C. (dec.)

The final reaction to be mentioned here is that of conden-

sation. This type of reaction is potentially very promising as a

preparative method and occurs with the intermolecular elimination of

hydroaine at elevated temperatures (37):

0 0 0
1 1500C. 1
2(PhO)2Pnn11I2 (PhO)2PUIIIlP(OPh)2 -I- N214

m.p. 1400C.

Te product of this reaction was synthesized by another route in

order to confirm its identity (43).

With respect to the practical applications of hydrazino-

phosphorus compounds several patents have been granted uhich relate

to the use of these materials as insecticides, fungicides, ncua-

todicides, and fertilizers.

Epoerinental and Results

M ateril 1

HIdrazines. 1l1-Dimcthylhydrazine and methylhydrazine are

both commercially available. The smEples used in this work were

purified prior to use by distillation from calcium hydride. The

reagents thus purified possessed very narrow boiling ranges: 1,1-

dincthylhydrc=ine, 62.2-63.00C./753 mn., methylhydrazine, 87.3-

88.00C./761 mr. All hydrazincs were stored in air-tight glass con-

tainers in a cool, dark location.

1,1,2-Trimethhyhydrazine wns prepared from 1,l-dimethyl-

hydrazine by the method of Class, et al. ( 61 ); similarly, 1-athyl-

2,2-dimethylhydrazine was prepared as reported by Ilaces, et al. (62).

Both wore distilled from calcium hydride or lithium aluminum hydride

and boiled in the ranges 50-62 C. and 92-930C., respectively. Identity

in each case was confirmed by comparison of the infrared spectrum

with that reported in the literature (63).

Triethylanine was purchased in the highest available purity

and then refluxed over calcium hydride and distilled; the fraction

collected was in the range 08.5-89.50C./759 mm.

Phosphorus compounds were obtained commercially and in most

cases were used as received. Many oxygen- and moisture-cnsitive

phosphinos deteriorated with age once the container had been opened and

these were vacuum distilled prior to using.

Solvents. Reagent Grade solvents were used throughout. Where

drying was required the usual drying procedures were used. The dry

solvents were then distilled. Every effort was made to avoid absorption

of moisture by these solvents.

NitroFen. Nitrogen was used to provide a dry, inert atmo-

sphere wherever it was called for. Water-pumped nitrogen was purified

by passing the gas over metallic copper turnings at 400C. to remove

oxygen and then through anhydrous magnesium perchlorate to remove



In addition to the usual laboratory glassware, several pieces

designed to carry out small scale reactions in the absence of air and

moisture were used. Ace Mini-Lab apparatus (Figure 7) is an example

of such special equipment.

Transfers and handling under anhydrous conditions were

facilitated by the use of a Lucite dry box in which was maintained a

dry, nitrogen atmosphere, Figure 8. Manipulations were performed

through a pair of Neoprene gloves and every effort was made to avoid

unnecessary opening of the box. Several dishes of phosphorus (V)

oxide were placed in each stage of the box to absorb moisture.

Most elemental analyses were performed by the Galbraith Micro-

analytical Laboratories, Enosville, Tennessee. Some nitrogen

analyses, however, were performed with a Coleman nitrogen analyzer,

Model 33.

Melting points were determined in scaled capillary tubes in

a Thomas-Hoover melting point apparatus. Infrared spectra were

obtained on a Perkin-Elmer Infracord Model 137 infrared spectro-

photometer. Nuclear magnetic resonance spectra were obtained on a

Varian High-Resolution Nuclear Magnetic Resonance Spectrometer,

Model V-4300-2.

ILtrogln I;,lct


I Ih lil *'ni r L ti

l,:Un LII
1 "`1 I.

Illt I :LLi
R cl Lui. r

I .-'.ir.-' T I'.ln -l-,il, Pe ..LR v r .'pp1iatiul

Stir ,er


.\ il.l ion 'linclI

Nit roLen
Inlet Nitrogen Outlet
net I


Inner Stage Outer Stage

Figure M. Dry Pox (Three-Eighths Inch l.ucitc Construction)

Experiments with l.l-dinethylhydrazine and chlorodiphenylphosphine

2.2-Diaethylhydrazinodiphenylphosphine. 2,2-Dimethylhydrazino-

diphenylphosphine was synthesized by the hydrazinolysis of chloro-

diphenylphosphine as shown below:

Ph2PCl + 2H2N1R12 = Ph2PNIRlU2 + Pe21NHa-HC1

Similar solvolytic reactions are well known and have been used

to prepare aminophosphines and other compounds in which it was desired

to form a phosphorus-nitrogen covalent bond. However, this method had

not been used previously to synthesize hydrazinophosphines. The nature

of the reactants are such that moisture and oxygen must be avoided. It

is also desirable to use a solvent in which the desired product is

soluble, but from which the 1,1-dimethylhydrazinium salt will


Fifty-five and one tenth g. (0.25 mole) chlorodiphenylphos-

phine was dissolved in 25 ml. dry benzene and added, with stirring and

cooling, to a solution of 33 g. (0.55 mole) 1,1-dimethylhydrazine in

25 ml. benzene. The addition took four hours after which time the

mixture was allowed to slowly warm to room temperature. The mixture

was then stirred for an additional hour at room temperature to allow

the precipitated crystals of 1,l-dimethylhydrazinium chloride to

assume sufficient size for easy filtration.

Filtration yielded, after washing successively with benzene

and ether, 23.99 g. of a white, crystalline solid, m.p. 79-810C.

(literature value for 1,1-dimethylhydrazinium chloride, 81-82C.

(64)). This amount is 99.3 per cent of theory.

Evaporation of the filtrate at room temperature and reduced

pressure gave 59.97 g. of white solid, m.p. 62-660C. This solid was

dissolved in 175 ml. dry hexane at 700C. and the resulting solution

was filtered. Upon cooling the solution to room temperature,

crystals formed; these were collected and found to weigh 55.0 g.

and melted at 65-670C.

Sublimation of this product at 600C./0.20 Em. gave long,

prismatic crystals, m.p. 68.5-69.50C. The overall yield was 51.5 g.

(84.5 per cent of thcory bared on the equation presented above).

Analysis. Found: C, 68.65; H, 7.17; N, 11.29; P, 12.66.

Calcd. for C14HI172P: C, 68.03; H, 7.02; N, 11.47; P, 12.68.

The infrared spectrum (Figure 9) and nuclear magnetic resonance

spectrum (Figure 10) are consistent with the following structure:

Ph H

.P---H CH3
Ph' CH3

2,2-Dimethylhydrazinodiphenylphosphine oxide. In order to

further characterize 2,2-dimethylhydrazinodiphenylphosphine its oxide

was prepared by three alternate routes: 1) atmospheric oxidation of

the hydrazinophosphine, 2) oxidation of the hydrazinophosphine with

activated manganese dioxide, and 3) the reaction of diphenylphosphinic

chloride with l,l-dimetI1"ylhydrazine.

1. Atmospheric oxidation.


FhPNtUIHIe2 + 1/2 02 > Ph2PHItMa2


* '1,1 i1,i11 I .ii "1 **i~' '
I ~ _I __ _ __ __ __ __ _ -

, -




I L v ,. L It ., l . l l .., -. ,. ,\ I 11 1 1 i I J. 11,, II lI l,: t I i, l

Sollvent .CDC13

F'reqcuienc : 56. -I nic.

Peak Area Position

A 1U. 2 -1. ss

B 1.0 i3.l29

C G. 2 -1. 07


Figure 10. Proton Nuclear Magnetic IResonance Spectrum

of 2. -Dimethylhydlirainviuoliphcni\ ihosphine




-Cl 3

A solution of 2.94 g. (0.012 mole) 2,2-dimethylhydrazino-

diphenylphosphine in 50 ml. benzene was heated overnight while a

stream of dry air was passed over the solution. Upon complete

evaporation of the benzene there was obtained a white, crystalline

mass and a dark oil. The crystals were collected and recrystallized

from van benzeno and then sublimed at 1600C./0.32 nrm.; 0.94 g.

(30 per cent of theoretical, based on 2,2-dmethlylhydrasinodiphenyl-

phosphine) of a white, crystalline solid, m.p. 166.5-163.00C. resulted.

2. Oxidation with activated MnO2.

PhIzPrHMe2 + IMnO2 Ph2PNUHIe2 + ItO

Two and ninety-four hundredths grans (0.012 mole) 2,2-dimcthyl-

hydrazinodiphenylphosphine in 50 ml. benzene was heated at 500C. with

4.1 g. (0.72 mole) activated manganese dioxide (65) for 12 hours. The

mixture was then filtered and upon evaporation of the benzene there was

obtained a crop of white crystals. This solid was recrystallized from

benzene and then sublimed at 1600C./0.30 rn. to give 1.60 g. of a white,

crystalline solid, n.p. 166.5-163.50C. (45 per cent yield, based on


3. Reaction of diphenylphocphinic chloride with 1.1-dimethyl-


0 0
1 I
Fh2PCl + 2HI211Rie2 ----> PI-2PTIHTIaP2 + Ie2NIH2II.HCl

Twenty-three and seven tenths grams (0.10 role) diphenylphoo-

phinic chloride in 35 ml. benzene was added, vith stirring and cooling,

to a solution of 13.0 g. (0.21 mole) 1,1-discthylhydrazine in 20 ml. of

dry benzone.

When the addition was complete the mixture was heated to 70C.,

stirred for one-half hour and filtered hot. Upon cooling, the fil-

trato deposited a white, crystalline solid, m.p. 155-164C. The 1,1-

dimethylhydrazinium chloride on the filter was extracted with hot

benaene and the washings combined with the filtrate. Reduction of

the volume of the resulting solution gave additional solid.

Recrystallization of the solid from 1:3 n-hexane:benzene

solution followed by sublimation at 1400C./0.20 em. gave 21.6 g. of

product, m.p. 167.0-168.50C. (32.5 per cent yield, based on diphenyl-

phosphinic chloride).

Analysis. Found: C, 64.39; 1, 6.33; N, 10.73; P, 11.92.

Calcd. for C14H17N2PO: C, 64.60; H, 6.58; N, 10.77; P, 11.90.

The infrared spectrum of this product is identical with those

obtained from the products of atmospheric and I02 oxidation of

2,2-dimethylhydrasinodiphonylphosphine. Mixed melting point deter-

minations melted at 166-1680C.

The infrared spectrum (Figure 11) and n.m.r. spectra (both

II and31 ) are consistent with this structural formula:

Ph 0 H

Ph N


I (



-'-I [ I- '- l 1- h 11%* 1- 11 11 -| 1- I IL 1 11I'd It- ,

2,2-Diaothyvlhydracinodiphcnvlphosphine sulfide.

Ph2PHI'g2 +- 1/8 S --- Ph2PIRHMeb2

Threc and forty-seven hundredths grams (0.0142 mole) of 2,2-

dimethylhydrazinodiphenylphosphine was dissolved in 50 ml. dry benzene

and added to 0.43 g. (0.015 mole) of finely divided sulfur in a small

flask. The sulfur dissolved easily as the solution was warmed to 60 C.

The solution was heated at 60 C. for 30 minutes and then cooled to

room temperature; no solid appeared on cooling.

Upon evaporation of the solvent a whice solid, m.p. 87-96 C.,

was obtained. PRecrystallization from 1:1 bczone:i-haxane gave

3.59 g. (92 per cent of theory, based on the above reaction) of white

crystals, o.p. 95.5-97.0C.

Analysis. Found: C, y0.67; H, 6.20; N, 10.14; P, 11.21;

S, 11.60. Calcd. for C14H17N2PS: C, 60.85; H, 6.41; N, 10.26; P,

11.45; S, 11.41.

The n.n.r. and infrared (Figure 12) spectre were consistent

with the structural formula below:

Ph S CH3

Ph CH3

2,2-Dinmthylhydrazinomethyldiphenylphoshonium iodide.

Ph2 RUNnIT2 + MI --- [ IhIUe2 ]


I 1 I, II 1.1P
_ ______ L------~-L -.------

r r

I UI i\
I 'If 1 /'

I I LI I ".' I r II I -'I II I* i I11I I,

I /


One and seventy-two hundredths g. (0.00704 mole) 2,2-

dimethylhydrazinodiphenylphosphine and 1.0 g. (0.00704 mole) methyl

iodide were dissolved in 25 ml. dry ether and the solution was stirred

at 250C. overnight. At the end of this time a solid was filtered

from the solution and dried at roon temperature and reduced pressure.

The white solid weighed 2.71 g. (100 per cent yield, based on the

above equation) and melted at 156-158C. An attempt to sublime this

material resulted in thermal decomposition at 1600C. The salt is

soluble in absolute ethanol.

Analysis. Found: C, 46.85; II, 5.47; N, 7.10; P, 7.85. Calcd.

for C15H202PI: C, 46.65; H, 5.22; N, 7.25; P, 8.02.

A water-alcohol solution of this solid gives a positive iodide

ion test, and iodine is liberated by the addition of nitric acid.

The infrared spectrum (Figure 13) is consistent with the

structural formula:


Ph /CH3

The structure was further confirmed by basic aqueous hydrolysis to

l,l-dinmthylhydrazine and methyldiphenylphosphine oxide. The oxide

was identified by conversion to methyldiphenylphosphlnic hydrogen


_ _ _ _ _ :11~ 1 -_ _ 'I"

I r I

I, \
2 L .. '

y i

i1ll 1 1 L I r :' I vU ,L 1 -'-Ij ''i. 'I i ,i ii nI i 'll 'l I i n I.'i nll I4.i minL l. I l I. ( l '.lu l.

_ a

1 Ll I *

Hydrolysis of 2,2-dimethylhydrazinomethyldiphenylphosphonium



P2P C3 I + OH ------- Ph2P-O !- IN HUM2

Two grams of sodium hydroxide was added to 3 g. of 2,2-

dinethylhydrazinomethyldiphenylphosphonium iodide in 25 ml. of 1:1

ethanol:water solution and the mixture was boiled for one hour. As

the alcohol evaporated it was replaced with water. The vapor above

the solution was tested for the presence of free base (l,l-dimethyl-

hydrazine) with damp red litmus paper and for the presence of a

reducing substance with a drop of potassium permanganate solution on

a strip of filter paper. Both tests were positive.

An oil separated from the aqueous solution. The amount of oil

was too small for distillation, but an infrared spectrum consistent

with methyldiphonylphosphine oxide was obtained. The oil was treated

with a solution of sodium carbonate at 900C. for two hours and upon

evaporation of the water a white solid residue was left. This was

extracted with hot benzene and filtered. Evaporation of the filtrate

gave one gram of a white solid, m.p. 107-109C. This solid evolved

carbon dioxide upon contact with a drop of hydrochloric acid. The

literature value for the melting point of methyldiphenylphosphinic

hydrogen carbonate, is 109-1110C. (66), and it is reported to liberate

carbon dioxide upon contact with hydrochloric acid.

CH3 0 CH3
1 II I
Ph2P-0- C-O-PFh2

From the foregoing experimental evidence we can conclude that

the alkylation of 2,2-dimethylhydrazinodiphenylphosphlne with methyl

iodide produces the hydrazinophosphonium salt rather than the hydra-

zinium salt indicated below:

[Ph2P1mH1(CH3)3 1I

Attempted alkylation of 2.2-dlnrthvlhydrazinomethyldiphenyl-

phosphonium iodide with excess methyl iodide. Treatment of 2,2-

dinethylhydrazinomethyldiphenylphophohonium iodide with excess methyl

iodide in ether or toluene (heterogeneous reaction) gives quantitative

recovery of starting materials. It is clear, therefore, that, under

the conditions cited here, alkylation of 2,2-dimethylhydrazinomethyl-

diphenylphocphonium iodide does not occur.

Other hydrazinophosphonium salts. Samples of 2,2-dimethyl-

hydrazinodiphenylphosphine were treated with various organic halides

in an attempt to obtain additional information relevant to the ease of

alkylation of the phosphine.

Reaction with benyvl chloride. Four and eight hundredths

grams (0.0168 mole) 2,2-dimethylhydrazinodiphenylphosphine and 2.12

grams (0.0168 mole) benzyl chloride were dissolved in 50 ml. dry

toluene and the mixture was refluxed at 110oC. for 12 hours.

Upon cooling to room temperature two liquid layers were

observed. The toluene was removed and attempts were made to initiate

crystallization by cooling and by adding ether to the layer containing

the desired product. No crystallization occurred and the product

could not be purified by crystallization from absolute ethanol. The

clear, yellow, viscous liquid gave a positive Cl" test, however, and

although the compound iwar not obtained pure, its infrared spectrum

does indicate a salt-like structure which contains the bonds expected

for 2,2-dimethylhydrazinobenzyldiphenylphosphonium chloride


[m2 -P- IH(CH3)2]Cl

Reaction with carbon tetrachloride. Upon dissolving 2,2-

dimethylhydrazinodiphenylphosphine in reagent grade carbon tetrachloride

there forms in the yellow solution a faint precipitate which gradually

disappears upon standing. Although no compound was isolated, there is

the possibility that alkylation occurs according to the following



Ph2IPNI (CH3)2 + CC1 ----- [P2P-NIH(CH3)2] C

Reaction with phenyl iodide. One gram 2,2-dinethylhydrnzino-

diphenylphosphine was mixed with excess phenyl iodide in dry ether

and heated for one hour on the steam bath while the sample was

protected from moisture with a drying tube. Several small crystals

formed in the liquid and these were washed with ether and dried in the

air. The melting point was 162-175C., and a nitric acid solution

gave a positive I test.

No suitable method of purification was found. Sublimation

attempts resulted in thermal decomposition. The compound is thought

to be 2,2-dimethylhydrazinotriphenylphosphonium iodide,

[Ph3PNHN(CH3)2] I

Reaction with / 'dibromoethyl ether. Two and forty-three

hundredths g. (0.01 mole) 2,2-dimethylhydrazinodiphenylphosphine was

reacted with a threefold excess of /3 'dibromoethyl ether in toluene

at 600C. for 5 hours. A semi-solid which was not purified was the only

observed product.

Synthesis of 1 l-bis(diphenylphosphino)-2.2-dimethylhydrazine.

An experiment designed to test whether chlorodiphenylphosphine would

undergo hydrazinolysis by 2,2-dimethylhydrazinodiphenylphosphine

resulted in the synthesis of 1,l-bis(diphenylphosphino)-2,2-dimethyl-

hydrazine according to the following equation:

Ph2P Me
Ph2PNrMle2 + Ph2PCl + Et3N 500C.- N-N
/ \
Ph2P Me

+ zEt3I i]C1

Three and fifty-four hundredths g. (0.0161 mole) chloro-

diphenylphosphine and 3.62 g. (0.0358 mole) triethylamine were

dissolved in 50 ml. dry toluene and to this was added quickly at room

temperature a solution of 3.84 g. (0.0161 mole) 2,2-dimethylhydrazino-

phenylphosphine in 50 ml. toluene. There was no immediate evidence

of reaction.

The temperature was slowly increased and at 50 C. a solid

appeared in the solution. Above 500C. the precipitation was

copious. The mixture was stirred at 110C. for one hour and filtered;

the precipitate melted at 251-2530C. (literature value for triethyl-

amnonium chloride is 254C.). Yield: 2.12 g. (96 per cent of theory,

based on the above equation).

Evaporation of the filtrate gave 6.51 g. of a white solid,

m.p. 126-1330C. An attempt at sublimation resulted in decomposition

at 1350C. Recrystallization from dry n-heptane gave fine, white

crystals, m.p. 129.5-132.50C., in 76 per cent yield, based on the

equation above.

Analysis. Found: C, 72.65; H, 5.98; N, 6.39; P, 14.56.

Calcd. for C26 26 2P2: C, 72.88; H, 6.12; N, 6.54; P, 14.46.

The n.m.r. spectra and infrared spectrum (Figure 14) are

consistent with the proposed structure, but a small absorption peak
at 1176 cm.- in the infrared shows some oxygen (as P=O) as an im-


Chlorophosphination of triethvlemine. Since, as in the syn-

thesis described above, it has in several instances proved convenient

to use triethylamine rather than an excess of the hydrazine as a

hydrogen chloride acceptor, it was desirable to determine whether or

not chlorodiphenylphosphine reacts directly with triethylamine.

I / IV /I
I I/*I
i'l I i I
r i r i; I~

i I



I'1',ilt i I h T1,11 L .I .- I, ,lI, 111. .1 -I 1 -1 ii-( .1| lis i I I ll- I I-



_- I ~1 ~~ I 11, '.~1.. 'I'l,

I c ------- ---


I ,,iJ

I ,


In view of the fact that chloramine has been shown to react

with tertiary phosphines in accordance with the equation (67)

CINH2 + R3P [R3PNHj Cl

it might be expected that chlorophosphines such as (C615)2PC1 would

react with tertiary amines according to the following equation:

Ph2PC1 + R3N --- 3RgPFh2) C1

In an experiment designed to test whether or not chlorophos-

phination of triethylamine occurs under the conditions usually employed

in the hydrazinolysis of chlorodiphcnylphosphine 5.46 g. (0.054 mole)

triethylamine was dissolved in 50 ml. anhydrous ether and added to

11.90 g. (0.054 mole) chlorodiphenylphosphine in 50 ml. ether. An

immediate cloudiness appeared in the solution which persisted through-

out a 30 minute reflux at 40 C.

Filtration gave 0.63 g. of a white solid, m.p. 254-2550C., which

was completely water soluble. A mixed melting point determination

with an authentic sample of triethylanmonium chloride melted at 253-

2540C.; the infrared spectrum of this solid is identical with that of

tricthylamonium chloride.

Evaporation of theedher and triethlyamine from the filtrate at

reduced pressure gave a yellow viscous liquid which was distilled

at 105-1070C./0.17 rm. and shorn to be chlorodiphenylphosphine by its

infrared spectrum.

It may, therefore, be concluded that chlorophosphination of

triethylamine with chlorodiphenylphosphine does not occur under the

conditions employed here for the hydrazinolysis of chlorodiphenyl-


It should be noted that a little triethylaamonium chloride

resulted from the reaction mixture, showing that although all reagents

had been previously distilled and dried, some hydrolysis had occurred.

It was later found to be possible to avoid the formation of triethyl-

ammonium chloride upon mixing chlorodiphenylphosphine and triethyl-

amine by performing all transfers in the dry box. For the usual bulk

reaction, however, it is unnecessary to take the extra care to avoid

this small amount of hydrolysis as it lowers the yield by only a

fraction of a per cent.

Reaction of 2.2-dimethylhvdrazinodiphenylphosphine with carbon

diculfide. Five ml. reagent grade carbon disulfide was added to 1.97 g.

(0.0807 mole) 2,2-dimcthylhydrazinodiphenylphosphire in 10 ml. anhydrous

ether. A deep red color developed immediately and slowly faded to

yellow as the solution was evaporated at 400C. over a five hour period.

Upon standing overnight, large, white crystals appeared in the

solution. These were collected and washed with hexrne and melted at

140.5-141.50C. The yield was 82 per cent of theory, assuming the 2,2-

dimethylhydrazinodiphenylphphophin reacted with the carbon diculfide in

a 1:1 ratio. The analysis corresponds to (C6I15)2PtHN(CH3)2-CS2: Found:

C, 56.09; ,H 5.55; N, 8.69; P, 9.46: S, 20.17. Calcd. for C15H17N2PS2:

C, 56.23; H, 5.35; N, 8.74; P, 9.67; S, 20.01.

It was found that if the white, crystalline product of this re-

action is redissolved in carbon disulfide, the red color appears once


The literature describes the interaction of tertiary phosphines

with carbon disulfide, and there are reported compounds of the type

+ /
R3 P--C

which are red, crystalline solids (55,68 ). The structures of these

compounds have been confirmed by X-ray diffraction analysis (69 ) and

it is well-known that the compounds contain a P-C bond and no formal

P-S bonds. The red color is thought to arise as a result of the

Zwitterion-type structure.

Since a red color develops in the interaction of 2,2-dimethyl-

hydrazinodiphenylphosphine with excess carbon disulfide, it appears

that a Zwitterion complex is the initial product of the reaction:

s- s

Ph2P -NMI (CH3)2

As the reaction proceeds, however, the color fades as the

amount of carbon disulfide is decreased. The final product is a

white solid and has an infrared spectrum (Figure 15) which is complex,

but shows no absorption in the region assigned to the NI-H bond. The

N-I absorption has been shifted to a higher frequency which indicates

a change in one of the substituents on the nitrogen atom attached to

the phosphorus; the -N(CH3)2 group appears to be intact. A weak

absorption is evident in the S-H region. The monosubstituted phenyl








P'\I ii

I1 I, t r .:. II J 'ib ,I .:'I'. I '. Jnl (_h i I [. i I i .'f I i i .LI II, ,, I1 -i , ,.L I 1, I 1L I .s lil, i I I ,i .. i I
,' Ill ll' i lJ , s IJI I ,. ( ..,,r ,L ",[s, I




I --~


group peaks are unchanged and the P-phcnyl absorption has not been

shifted at all. The structure best fitting the infrared data is

drawn below:

P - N
Ph CH3

The proton nuclear magnetic resonance spectrum is in general

agreement with this structure. Four peaks are observed, none of which

is the characteristic IT-H close double which is observed in 2,2-

dimethylhydrazinodiphenylphosphine. The peaks assigned as phenyl

protons and methyl protons agree with the areas expected for the struc-

ture given above. The remaining two peaks are of unequal area and are

presumed to arise from 1) the S-H proton and 2) the proximity of the

S-11 proton to the 31P atom, which is an odd nucleon and with which H

will interact by spin-spin coupling.

The fact that a red color develops on dissolving this material

in carbon disulfide may indicate that the phosphorus atom is still

available for loose coordination in excess carbon disulfide, and gives

a molecular complex as shown below.

S S Sr
sa /s" s
C C--S

Ph2P -N

Treatment of 2,2-dimethylhydrazinodiphenylphosphine oxide with

carbon disulfide resulted in no reaction.

Pyrolytic condensation of 2,2-dimethvlhydrazinodiphenylphos-

Phine. It has been observed that when a sample of 2,2-dimethylhydra-
zinodiphenylphosphine is purified by sublimation, there sometimes is

left behind in the pot of the sublimation apparatus a yellow,

resinous material. On these occasions there is also found in the cold

trap used to protect the vacuum pump a small amount of a volatile

liquid. Infrared analysis and vapor phase chromatography data indicate

that this liquid contains dimcthylamine and 1,1-dinethylhydrazine.

Dimethylamine can be produced by a thermal decomposition

which produces the phosphonitrilic system,

xPh2PHHIR(C113)2 > (Fh2PNOx + x(CH3)2tH

and l,l-dimethylhydrazine can be one of the products when 1,1-bis-

(diphcnylphosphino)-2,2-dimethylhydrazine is also a pyrolytic

condensation product:

2Ph2 FIN (CH3)2 --- >-(Ph2F)2NN(CH3)2 + (CH3)2N1R12

It should be noted that only a small amount of this solid,

resinous material is observed after sublimation of 2,2-dimethylhydra-

zinodiphenylphosphine, but a suggestion for further work would be to

investigate these reactions on a larger scale and identify with

certainty the reaction products.

Hydrolysis of 2.2-dinethylhydrazinodiphenylphosphine. A sample

of 2,2-dimethylhydrazinodiphnylpsposphine was treated with 0.1 N IIC1

with the result that both l,l-dincthylhydrazine and diphenylphosphinic

acid (m.p. 191-1930C.) were isolated in high yield from the product

mixture. The diphenylphosphinic acid was filtered from the solution

and the 1,1-dimcthylhydrazine was distilled from the filtrate which

was made basic by the addition of NaOH solution.

Hydrolysis by atmospheric moisture was found to be a minor

problem with 2,2-dimcthylhydrazinodiphenylphosphine.

Execriments with methylhydrazine and chlorodiphcnylphosphine

Reaction of nethylhydrazine with chlorodiphcnylphosphine. Ten

and four tenths g. (0.0472 mole) chlorodiphenylphosphine was dissolved

in 35 ml. dry ether and added to 4.35 g. (0.0945 mole) methy1hydrazine

(redistilled and dried over calcium hydride) in 40 ml. dry other. The

addition took four hours and was performed with cooling and stirring

under a nitrogen atmosphere. No precipitation occurred at 00C., but

upon warming the mixture to 250C. solid appeared and the mixture was

stirred at 25C. to allow the reaction to proceed to completion.

Filtration gave 3.71 g. nethylhydrazinium chloride (theoretical

is 3.88 g., based on chlorodiphonylphosphine), and 9.57 g. of a yellow,

viscous liquid which did not contain chlorine, as evidenced by a silver

nitrate test on a small portion dissolved in dilute nitric acid. No

crystallization could be induced in the liquid and no way was found to

effect purification.

Analysis. C, 67.55; H, 6.46; N, 11.96; P, 14.34. Calcd. for

C13H1512P: C, 67.81; H, 6.57; II, 12.17; P, 13.45.

The reaction product may have either of two forms.


Ph2PMIInCII3 or Ph2N

The n.n.r. spectra indicate that a mixture of both these species is

present in the product, but the data are too complex to indicate the

relative percentages of the constituents. The infrared spectrum

contains all the expected absorption frequencies, but is of little

value in determining per cent composition.

An attempt to vacuum distill the product resulted in thermal

decomposition. A liquid fraction was collected in the range

98-99C./0.36 am.; however, the bulk of the product remained in the

distilling flask as a resinous, amber-colored solid.

Extrapolation of the boiling point at reduced pressure to the

normal boiling point of the liquid on a temperature-vapor pressure

omnograph gave ca. 175C./760 mm. (diphenylphosphine boils at 2800C.

per 760 am. (32).

Analysis. Found: C, 77.42; II, 6.22; N, 0.25; P, 15.88.

Cnlcd. for (C6U5)2PH: C, 77.41; II, 5.95; N, 0.00; P, 16.64.

The molecular weight (cryoccopically, in benzene) is 185.

Calcd. for diphonylphosphine: 186.2.

A methyl iodide derivative, prepared according to the equation

Ph2PH + 2CH3I ---- Ph2P(CH3)2]I + HI

has a n.p. 2410C.

The infrared spectrum (Figure 16) is consistent with the

structure for diphenylphosphine and contains a very prominent absorp-

tion peak at 2295 cm.-1, which is characteristic for the P-H bond.

The thermal decomposition of the product mixture apparently

is according to the following equation:

Ph2PNHNC} 13
2 ---- -- Ph2PH + condensed species



1 0(;O

7i.'ure 16. Infrared Spectllrum ol Dipheni lphosp!iinle (Cellj

10Uo 3000




An attempt was made to separate the two components from each

other by reaction with benzaldehyde, but the only isolated product

was nethylbenzylidenchydrazine, C61CI-H=N-IICH3, n.p. 178-1790C.

(literature value 1790C.). Apparently the water produced in hydrazone

formation hydrolyzed the P-i! bond in the product.

No separation las made on the residue from the thermal

decomposition and the analytical results did not agree with any

single compound. The infrared spectrum was highly opaque, which is

characteristic of polymeric materials.

Reaction of nethylhydrazinodiphenylphosphine with sulfur. The

mixture of mnthylhydrazinodiphenylphosphines produced in the reaction

of chlorodiphonylphocphine with methylhydrazine was reacted with a

mall amount of finely divided sulfur in benzene solution with the

result that hydrogen sulfide evolved and a dark gum was produced from

which no product was isolated.

Reaction of nethylhydrazinodiphenvlphosphine with carbon

disulfide. Upon dissolving the methylhydrazinodipyenylphosphine

mixture in carbon disulfide there was no immediate evidence of reaction,

however, over a 12 hour period hydrogen sulfide evolved, and upon

removal of the solvent a dark gum remained from which no pure material

was isolated.

Synthesis of .1,2-tris(diphenylphosphino)methylhydrazine.

3Ph2PCl + CH3IaIHN% 3(C21 )31 ---> (Ph2P)2 -!- 3 (C2115)3N1 C1


Eleven and ninety hundredths g. (0.054 mole) chlorodiphenylphosphino

and 7.24 g. (0.0732 mole) triethylamine were dissolved in 50 ml. dry

toluene (b.p. 109.1-109.20C.) and to this was added slowly with stirring

and cooling 0.03 g. (0.018 mole) mothylhydrazine in 35 nl. dry tolueno.

Mien the addition was complete the mixture was heated to

100oC. and stirred for one hour and filtered hot. The weight of

triethylamnoniua chloride on the filter was slightly more than

theory based on the above equation; apparently some of the toluene-

soluble product was occluded in the salt. Upon evaporation of the

solv.nt at room temperature and reduced pressure, there was produced

a yellow gun. Three hundred ml. of dry ether was added to the gun and

a white solid separated from the resulting solution. This solid was

washed with additional ether, collected, and dried under vacuum. The

amount collected was 2.55 g. (21.8 per cent yield, based on chloro-

diphenylphosphine), n.p. 1510C. dec.

Purification was effected by recrystallization from acetone in

the dry box. The resulting crystals melted at 152.3-153.00C.(dec.).

Analysis. Found: C, 74.33; II, 5.71; N, 4.75; P, 15.41. Calcd.

for C37113312P3: C, 74.24; H, 5.56; I, 4.68; P, 15.52.

The infrared spectrum (Figure 17) of this material is consis-

tent with the structure

Ph2P PPh2
2i^ all3

I I I. ilt.1


---- 1

-- -----\


I I.- , - 1 Ii 1 1 t I t I - L i j i;'i 1 1 - I z I II 10 I I 1 -11 ; 1'.1 a ..-.. .. I h 1 .I -I i I I i I I I I III .

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