A STUDY OF THE SYNTHESIS OF SOME
ALUMINUM AND PHOSPHORUS
DERIVATIVES OF ALKYL
ROBERT PETER NIELSEN
A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
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.
TABLE CF CONTENTS
LIST OF TABLES
LIST OF FIGURES
I TIE INTERACTION OF TWO ALKYL HYDRAZIMNS WITH
Experimental and Results
II REACTIONS OF ARYIJALOPHOSPFINHES AND DERIVATIVES
OP ARYLHALOPHOSPHINES WITH SEVERAL ALKYL HYDRAZIIES
Experimental and Results
LIST OF TABLES
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
LIST OF TABLES Continued
24 Benzylidene Derivatives of Alkylphosphoro-
25 Hydrazones of Bis(hydrazino)phcnylphosphine
Oxides-lydrazones of Bis(hydrazino)phenylphosphino
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.
LIST OF FIGURES
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-
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
LIST OF FIGURES Continued
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
TIE ITiE^UCTION OF TWO ALKYL )YDPRAZIIES
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
2. Condensation to an Aminoalane.
H3:All(C113) = H2N-Al(CIH3)2 + CH4
3. Further Condensation to Polymeric Material.
H11-Al (CH3)2 = (RUlCH3) x + CH4
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
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
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
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
(15C2)2N CI2 ---- 115-1160C./1.5 am. 19
Compound n.p. b.p. References
[(CI3)21-A1 (CH3) 212
([(CH3)2C11 2N-A1H2 2.16
[CH3bH-A1 (C2') Cl]
[ (CH3) 2 12A1H)2.
(CH13) 2ClI2HAl1H(CH3) 2}2
Extended lIctuork Aluminum-Nitrogen Polymers
Compound m.p. b.p. Rcfcrencec
[(CH3)IACl] --- ---- 17
(AlH)n above 2200C. ---- 18,30
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
Compound m.p. b.p. References
H2-N(CH3)2: (CH3)2Al-NH-N(C13) 31.0-32.0C. --- 21
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
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
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
'- - 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
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
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 +
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
(13C)211 K -I1
1. Si:: Membered Ring
H5C2 C2 H5 115C2 502
S Al U (113C) 2N Al II
(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 ,! ""
Figure 4. Infrared Spectrum of 2. 2--Dimethiylhydrazinodiethlalane (Melt)
s1 I iI / 11 1 .'/1I L' ll [ *'l. '
IL .J- 1 r.1 V
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
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
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
'., ... . Ilral 'idl ci r(l'ni t ('c
HiI 9) 0k
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
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,
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]
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
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,
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- l:AlEtI3 =
Et 1 CII3
I I I
I i I
Et II CII3
Et II CI13
3. Et--Al:IT-- E:AlEt3
I I I
Et H C013
Et II CLI3
I I I
+ Et-Al- 1- -IIAlEt3
Et II CIL3
EL 11 %
S Et-Al- II--1 :AlEt3
Et II CH3 Et
S Et-L-----UII:l- Et
/ I \
(In3C) 21 CH3 Et
6. (113C)211 U-11
(I13C) 2 (C-I3)
11-11 11 (13 )2
(I13C) 2 -11II
= C2 -+ |
Form Six Iembered
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.
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
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.
REACTIONS OF IAYLIHALOPHOSPHINE AND DERIVIVTVES OF
ARYLiALOPHOSPHINES WITH SEVERAL ALKYL HYDIRAZInES
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
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.
(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
S S Cl
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
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/ /\
PhO NH-NH OPh
+ 4(12 15)C1
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
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.
(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
TABLE 12 Continued
Product Yield m.p./b.p. Reference
U 0) (CH3o) brNMrIi2
0) (C2H50) PFRnn12
(02N~ / O) (C2H50)P(S)IThfNH2
at 0.01 mm. It
Alkyl and Aryl Phosphorophenylhydrazidothioates
Product Yield n.p.
(PhO) (C1130) NHNHPh
(PhO) (C2H50) I'UHPh
(02N -0) (CH30) iMNHPh
(02o 0) (C2150) R TIIPh
(Cl 0) (C2H50)PNIUHNPh
(l13C)2N NH 1N(C313)2
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.
/7i3 0-POII HW)2
02N1 P-0- (INHFHPh)2
C1/ \1 0-P(NIlH2)2
/C I O- P(NHNHPh)2
Cl. / 0-(NIHNHPh)2
247 95 (1030)
TABLE 16 Continued
Product Yield M.p. Reference
(113 C) 3 / P O-(ThHi Ph)2
C / \ o- [ITnEI(c113)2] 2
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
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
O-P-IN 79% 120-122 38
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
ci-< / \oPflr
PC13 + (R2i2)Cl --- R2NPC12 -:- 21C1
The ino-bic(hydr.aino)phosphine oxide is the product
obtained upon hydrazinolysis of the nmidophosphonic dichloride:
R2NPC12 -I- 4I1 aIyPh ---'- P IIIP)2
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
0 0 112
PhP(C12)2 4 [1211 -- Ph P + ir3
llydra-inolysis of the phosphonitrilic chloride triner is also
(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
(PhO)2Ptn" -:- NaOIll (aq.) > N IP [OPIMo"'rI -:- PhO0
Further hydrolysis will yield a salt of the phosphorus acid
and the free acid can be obtained by metathesis:
Na2 [O2PHI2] -- 211" ------- (110)2P11lRmT2 -+ 21Na
Complete hydrolysis is obtained by prolonged boiling in
aqueous sodium hydroxide and yields free hydrazine and the phosphate
[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
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
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
(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
PhCIl2OPIIRHH -- 43
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
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):
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
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
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
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
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,
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,
I Ih lil *'ni r L ti
1 "`1 I.
Illt I :LLi
R cl Lui. r
I .-'.ir.-' T I'.ln -l-,il, Pe ..LR v r .'pp1iatiul
.\ il.l ion 'linclI
Inlet Nitrogen Outlet
Inner Stage Outer Stage
Figure M. Dry Pox (Three-Eighths Inch l.ucitc Construction)
Experiments with l.l-dinethylhydrazine and chlorodiphenylphosphine
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:
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
F'reqcuienc : 56. -I nic.
Peak Area Position
A 1U. 2 -1. ss
B 1.0 i3.l29
C G. 2 -1. 07
A B C
Figure 10. Proton Nuclear Magnetic IResonance Spectrum
of 2. -Dimethylhydlirainviuoliphcni\ ihosphine
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-
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
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-
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
-'-I [ I- '- l 1- h 11%* 1- 11 11 -| 1- I IL 1 11I'd It- ,
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
Ph2 RUNnIT2 + MI --- [ IhIUe2 ]
I 1 I, II 1.1P
_ ______ L------~-L -.------
I UI i\
I 'If 1 /'
I I LI I ".' I r II I -'I II I* i I11I 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
Ph CH 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
2 L .. '
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.
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
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:
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,
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
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:
Ph2PNrMle2 + Ph2PCl + Et3N 500C.- N-N
+ 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
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
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'l I i I
r i r 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 ------- ---
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
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
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
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
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:
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
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
group peaks are unchanged and the P-phcnyl absorption has not been
shifted at all. The structure best fitting the infrared data is
P - N
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
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
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
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:
2 ---- -- Ph2PH + condensed species
7i.'ure 16. Infrared Spectllrum ol Dipheni lphosp!iinle (Cellj
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
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
NE / II
I I I. ilt.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 .