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Патент USA US3100779

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United States Patent*() "ice i
3,lll0,774
Patented Aug. 13, 1963
all‘
2
methylene and pentamethylene, the nitrogen rings, the
\
3,100,774
. hydrogen atoms on said rings may be substituted by an
“
PHOSPHORUS BGRON COMPOUNDS
Theodor. Reetz, Webster Groves, Mm, assignor to Mon
santo Chemical Company, St. Louis, Mo.,. a corporation
of Delaware
.
‘
p‘ ‘
,
alkyl radical, preferably having‘ from 1 to 4 carbon
atoms, and by the halogens.
r _
‘
centlyreported by Kodama.
No Drawing. ‘ Filed July 29, 1,959,‘ Ser; No.‘ 830,197‘
“
‘
‘ Phosphorous triamide bor-ane, 'H3BP(NH2)3, was-re
i
However, the compounds of'this invention are phos
pho‘rous triamide boranes having a hydrocarbon radical
20 Claims. ‘ (Cl. 260-223)
This inventionrelates to a new class of phosphorus
substituted for at least one hydrogen on each nitro
boron compounds and ‘to the methodlot preparing‘ the
10 gen atom and display a markedly superior stability. ' Of
same. .lMoore particularly, it is concerned with new com; '
the known‘ compounds containing the RH, group, perhaps
pounds which may be designated as hydrocarbon sub
the most stable ‘are the trialkylamine boranes of which
trimethylamine borane is a noteworthy example. it has
stituted phosphorous triamide boranes. .
My ‘copending application Serial No. 807,327, ?led
been determined that the borine containing compounds
April 20, 1959, now abandoned, describesrnovel phos 15 disclosed herein are considerably more stable as evidenced
by the following experiments. ‘
i
r
\
phorus boron compounds of the general formula
H3BP(»OR)3. The presentinvention, while containing
the borine group, deals with‘ compounds wherein nitro
When trimethylamine borane is mixed in a closed sys
tem with he‘xamethyl phosphorous triamide in equimolar
gen is present rather than oxygen.
amounts at room temperature, the conversion is in excess
These latter com
pounds ‘lare hydrocarbon substituted phosphorous tri 20 of 80% according to the following equation:
amides. The borine group is apparently coordinatively
‘ bound to the trivalent phosphorus? atom which supplies
the necessary electrons for the bond.
‘
Itris therefore an object‘ofr this invention to provide
new nitrogen "containing ‘phosphorus boron ‘compounds.
25
It‘ is‘ a further object to provide‘phosphorus boron com
pounds which exhibit av surprising‘ degree of stability.
Still ‘a further object is to provide a method for the prep
aration of these novel nitrogen ‘containing phosphorus
boron compounds. These ‘and other objects, advantages
and features of the invention will become apparent upon
consideration. of the following description thereof.
When trimethylamine borane is treated with concen
two
tratedhours
hydrochloricilacid
about 90%" of the
‘andproduct
methanol
is decomposed.
(1:1),
In
the case of hexamethyl phosphorous triamide lborane,
only about 18% decomposition occurs under the same
conditions. The following test is also illustrative ‘of the
greater stability of these phosphorus boron compounds in
comparison with trimethylamine borane. N,N’,N"-(tet
ramethylene) phosphorous triamide borane can be, precip
itated from a solution thereof in concentrated, hydro
‘ The structural 1formula of the new compounds of this
chloric acid, by dilution with water and recovered un
35 changed. Under the same conditions,‘ trimethylamine
biorane is ‘completely decomposed with strong evolution of
m ‘11X’ '
hydrogen. I ~
H ‘
In accordance with this invention the new compounds
invention is:
_
‘
i
‘
'
“
r
‘\Xu
r
‘
l
‘
,
{are prepared from phosphorous triarnides of the‘ formula
where X. X’ and X5.’ are ‘like? or unlike amine radicals
selected‘ from the group consisting of
.
_
R‘
.
40
r
‘
i
j
p
.
‘
‘
,/X
‘ P<X?
. , i-
X",
where hasthe, meaning’ disclosed above with a com
pound or‘ the class which‘ is capable‘ of‘releasing borine.
Compounds of this class include the trialkylamine boranes
suchas trimethylamine borane, triethylarnineaborane ‘and
‘the like; 'boron hydrides such as diborane; andrthe me
tallic borohydrides such as the alkali metal borohydrides,
eg sodium‘, potassium, etc. borohydride, when employed
in the presence‘ of such promoters as (a). carbonyl con
. /‘CHg
M.
cal-on:
’
taining compounds, (b) organic ‘acids, andr(c) inorganic
p
acids.‘ Suitable carbonyl containing‘ compounds include
.
wherein R and ‘R’ are ‘like or unlikelorgani‘c radicals or
carbon dioxide, ketones such as dimethyl ketone, diethyl
I hydrogen provided that no‘, more than one hydrogen be 55 ketone. and the ‘like, aldehydes such as acetaldehyde, ‘iso
bonded to anyone nitrogen atom.‘ ‘Illustrative,.but not
limitative, ‘of the organic radicals ‘represented by'R and
R’ are the alkyl radicals, such asmethyl, ethyLpropyl,
butyraldehyde and the like, and esters such as ethyl ace’
\ ' tate, methyl propionate‘ and the like.
isopropyl, butyl, hexyl, ~octyl, dodecyl, .?-chloroethyl', 2
methylpentyl, 2-ethylhexyl,‘ etc.; unsaturated aliphatic ra
dicals ‘such as propenyl, butenyl,,etc.; arylrradicals such
the like are also suitable.
asfphenyl, napthyl, etc; substituted aryl‘ radicals such as ‘
chlorophenyl, 2,4»dibrom'o‘phenyl, ethylphenyl, etc.; aral
kyl radicals,‘ such as benzyl, phenylethyl; etc;; alicyclic
radicals suchlas cyclohexyl, cyclopentyl, etca; and‘hetro'Z
cyclic ‘radicalswsuch. as furyl, furfuryl, thienyl,‘ etc. A
Illustrative of the reactions
which take place are the following: .
‘ HCOONa+H3BP[N(CH3)2]3
‘
compounds wherein R and R’ are selected from the group
‘
NaBHr+P[Means-F0054 ‘
. (CO2)
65
preferred embodiment of, this inventioni‘consists'f of those 1 r (Ketonel
‘i
"
on, ‘ 1T
NaBH4+ 1>‘[N<o:u,);]3+
‘
j
consisting of‘hydrogen andralkyl radicals containing from
i l to 12 {carbons provided‘ that no more thanrone hy
‘Inorganic-‘acids .
such as hydrochloric, hydrobromic and hydro?uoric‘ and
organic acidsrsuchras formic, acetic, butyric, v-aleric and
0:0 —-—>
CH:
‘ .
7
70
CH3
‘
drogen atom be‘bonded. to. any onevnitrogen atom.
ninrrmonmls +
It should. also be notedqthat in the case?ofntheitetra
‘
H
G
,
\
C—-O‘Na
i
a
3,100,774 ..
(Organic acid)
,
3
.
NaBH4+P [N (CH3 ) 2] 3
(Inorganic acid)
a ?ask at —40° C. in about 45 minutes. Then the reac
tion mixture was heated gradually to about 58° C.
Nitrogen was then passed slowly through the contents of
NaBH4+P[N(OHa)2]3
+HCI—>H3BP[N(CH3)2]3+NaCl+H2
the ?ask.
>
The diborane evolved was introduced into another ?ask
which contained a solution of 35 grams of'hexamethyl
phosphorous triamide in 50 ml. of tetrahydrofuran. Vigor
ous stirring and cooling at about —20° was maintained.
After all of the diborane was introduced, the reaction mix
ture was heated to room temperature, and then most of
The temperatures at which the phosphorous triamides
are reacted with the borine releasing compounds will
vary. depending upon the nature of the latter. With the
trialkylamine boranes, temperatures from 20° to 120° C.. .
may be employed, ‘the preferredrange-being from 70°‘
to 100° C.‘ (In the case of diborane lower temperatures ’
the solvent was stripped o?‘by distillation. . Then a su?i
ranging from —30° to 60° C. are more desirable. When
metallic lborohydrides are employed temperatures may
‘cient amountof dilute hydrochloric acid ‘was added to’
example, ethyl ether, dioxane', tetrahydrofuran ‘and the
and dried on air. Therevwas obtained 31.6 grams (897%.
dissolve the remaining solvent and the excess ‘hexam'ethyl ' ,vary from —'40° to 100° C., and usually the reaction is
‘phosphorous triamide. The oil which separated crystal
carried out in‘ the presence of other as a solvent, as, for 15 lized on standing. The crystalline product was ?ltered
'
like.
of theory) of hexamethyl phosphorous triamide borane;
1
The invention will be more fully understood by refer
ence to the ‘following examples which provide an indica
M.P. 32.5 ‘’ C.
‘
-
EXAMPLE IV
tion of suitable reactants, solvents, and the proportions 20
Hexamethyl Phosphorous Triamide Borane
of each as well as temperatures to be used in preparing
the novel nitrogen containing phosphorus boron com
pounds. These examples, however, are given for the
'
HsBP[N(CHa)2]s
'
Carbon dioxide was gradually introduced at 25° C. into
purpose of illustration only, and are not to be construed - a stirred mixture of 17.9 grams of hexamethyl phosphor
as limiting the scope of the present invention in any way. 25 ous triamide, 3.78 grams of sodium borohydride and 50 7
‘
ml. of tetrahydrofur'an until the reaction was completed
EXAMPLE I
~ and no further earbondioxide was absorbed. The reac
Hexamethyl Phosphorous Triamide Borane
'
HsBP[N(CHa)2]s
, tion product was treated with sufficient dilute hydrogen
. chloride to precipitate an oily product and dissolve the
I‘
_ A mixture of 3.64 grams of trimethylamine borane 30‘ excess hexamethyl phosphorous triamide as wellas the
solvent. The oily product was taken'up with hexane and
?ltered from a small amount of yellow insoluble solid
and 8.20 ‘grams of hexamethyl phosphorous triamide was
heated “with stirring up to 90° C., maintained, at that
temperature for about 20. minutes, and then raised to . present therein. The ?ltrate was ‘evaporated, andthe
residue was dissolved in dioxane. The addition of water
110° (C. and held there :for a short time. At 70~80° C.
a moderate, and at 90° C. a strong, evolution of trimeth 35 to this solution caused an oil to precipitate which became
trimethylamine was condensed in a trap. The reaction
crystalline'upon standing. The‘crystalline product was
?ltered and dried. A yield of 11.5 grams (65% of theory)
product, 9.2 grams, was distilled at 6l—63° C./0.5 mm.
of hexamethyl phosphorous triamide rborane was obtained.
ylamine was observed._ 2.6 grams (88% of theory).of
The distillate was ‘dissolved in dioxane. Addition of
water to the dioxane solution caused an oily product to 40,
EXAMPLE V '
separate. This oily product became crystalline on stand
ing for a short time.
p
7
‘
It was then dried and distilled.
g _Diborane
.
was generated
HaBP[-N(CgH5)2]s
from the reaction‘of
: ,
'15 .5 grams
One fraction, B.P. 49~—50° C./0.1 mm. was taken. It
‘was identi?ed as hexamethyl phosphorous triamide bor
ane; M.P. 32.5° C.
>
Hexaethyl Phosphorous Triamide Borane ‘
.
,
V
45
/
. g .
EXAMPLE. II
of boron ?uoride etherate,‘ 3.4 grams of sodium borohy~
dride and .70 m1. of tetrahydrofuran (see Example III).
The diborane thus generated was introduced into a ?ask
_
and reacted with 24.7 grams of hexaethyl phosphorous
triamide dissolved in 50 ml. of'tetrahydrofuran. Through
‘
,
H§BP[N(CHa)§]s_
V
out the reaction, vigorous stirring and‘a. temperature of
»A solution of 14.56 ‘grams of trimethylaminefborane 50 about 10° C. were maintained. The ?ask was then shak
g Hexamethyl. Phosphorous Tridmide Borane
and 35.8 grams of hexamethyl phosphorous triarnide in
en with dilute hydrochloric acid to destroy and dissolve
50 ml. of dioxane was gradually heated to about 112° C.
any unreacted hexaethyl phosphorous triamide. An oil
' within about 90 minutes. A rather rapid evolution. of .
trimethylamirre was observed at 85—90° C. Nitrogen
was. passed'slowly through the contents of the reaction
' vessel at the‘ end of the reaction. 11.0 gramsl(93% of
theory) ofgtrimethylamine was collected in a trap. The
precipitated which was Washed with water and dried in a
vacuumv (5 mm. of Hg) at-60-70" C. A yield of 22.5
5,5, grams
(86% of theory) of, hexaethyl phosphorous atri
amide borane was obtained.
_
w
‘
reaction product was ?ltered and dilute hydrochloric acid
._
‘added to the ?ltrate to remove the excess hexamethyl
Hexa-‘n-Butyl Phosphorous lTriar'r‘ziale Bordne ‘ ~
‘ phosphorous’niamide'and to dissolve‘ the dioxane'. An 60
'oil precipitated and became crystalline on standing. The
crystallineproduct was separated by ?ltration, washed
withwater and dried. There was obtained 30.5 grams
(86% of theory) of hexamethyl phosphorous‘ triamide
borane; M.P.
>
'
a
j,
.
'
,
.
.
EXAMPLE nt
.
EXAMPLE v1 '
‘
mBrwmn-mmnn.
.
$7
Diborane was generated‘from? theireaction of 18.6
grams'of boron ?uoride‘etherate, 4.1 grams of sodiuni' '
borohydn'deand 70 ml. of tetrahydrofuran (see Example
III). The diborane' so generated was introduced‘ into "a
.65 ?ask
containing 41.5 grams of hexa-n-butyl phosphorous
.
7
triamide and 30
of tetrahydrofuran. The reaction
mixture wasstirred vigorously, and .a temperature of
Hexamethyl Phosphorous Triamide Borane
25-30.° C. .Was maintained. The mixture was then'itr'eated - i
70 with su?icient dilute hydrochloric‘ acidto ‘dissolve Ethe
Diborane was ‘generated as follows according to
solvent and destroy anyfexcess of'hexa-n7butyl:phosphor= Y t
Schlesinger’s method (JACS 75, 1953, pp. 202-207). ’ ous triamide.
oily product separated and was washed _'
29.75 grams ofuboron ?uoride etherate diluted with 30
with dilute solution of sodium sulfate.) Saidjproductwas
_
'
rrsnrrmcnmn
.
_
i
ml. of ether were added to a stirred mixture of 5.7 grams
then separated from the (solution and subjected toi'vacu-i
"of sodium .borohydride and 80 ml. of tetrahydrofur'an in 75 um
(4 mm.- of Hg) at about 80°C; There was obtained
3,100,774.
39.5 grams (92% of theory) of hexa-n-butyl phosphor
ous triamide borane.
‘
.
‘onehour. ».:When 'the‘evolution of hydrogen ceased, 12‘
grams of hexamethyl phosphorous tria-midelwas added.
'
The reaction mixture was slowly heated to room tempera
ture and maintained at that point for about 2 hours. *It
was then heated for one additional hour at about 45° C.
The reaction mixture was 'then treated with su?icient
EXAMPLE VII
N,N’,N”-(Tetramerhylene) Phosphorous '
‘
Triamz'de Borane
dilute hydrochloric acid to‘ hydrolyze‘ the excess of hexa
methyl‘phosphorous triamide and dissolve the solvent.
,Hexanewas then added and the resulting mixture shaken.
A small amount of a yellow precipitate was formed which
was insoluble in hexane and was removed by ?ltration.
A mixture of 5.3 grams of N,N',N"-(tetram‘ethylene) ,
The ?ltrate was evaporated, and the residue crystallized.
phosphorous tria-mide, 1.46 grams of trimethylamine bor
There was obtained 5.6 grams (63% of theory) of hexa
ane and 2 m1. of dioxane'w'as ‘gradually heated to about
methyl phosphorous triamide borane.
130° C. Trimethylamine was evolved at 60-70° C. The
In addition to the boranes prepared in the preceding
mixture was then treated with su?icient 0.5 n hydrochloric 15
acicLto dissolve therexcess of N,N',Nf’-(tetramethylene)
phosphorous triarnide. ‘A white crystalline precipitate
examples, the following boranes are further. illustrative
“appeared and ‘was dissolved in concentrated hydrochloric
acid and precipitated by the addition of water. The latter
Hexapropenyl phosphorous triamide borane
N,N',N”-(trimethyl) phosphorous triamide borane
Hexa-B-chloroethyl phosphorous triamide borane
of compounds coming within the scope of this invention:
precipitate was then ?ltered, washed with water, and dried 20
in vacuum. A yield of 4.8 grams (94% of theory) of
Hexabenzyl phosphorous‘triamide borane
N,N’,N"-(tetramethylene) phosphorous triarnide borane
‘was obtained; M.P. 59° C.
.
EXAMPLE VIII
Héxomethyl Phosphorous Tridmz‘de Borane
25
'
Hexacyclohexyl phosphorous ‘triamide borane
N,-N',N”-i(tridodecyl) phosphorous triamide borane
Hexaphenyl phosphorous triamideborane
Tris (N-phenyl, N-methyl) phosphorous triamide borane
Tris (N-benzyl, N-ethyl) phosphorous triamide borane
N,N’,N"-(triphenyl) phosphorous triamide borane
Tris (N-octyl, N-ethyl) phosphorous triamide borane
Tris (N-tolyl, N-methyl) phosphorous triamide borane
HsBP[N(CHs)2]s
A solution of 3 grams‘ oflwater and 12 grams of acetone
was added portionwise. to a mixture of 1.9 grams of
sodium-borohydride,;9. grams of hexamethyl phosphorous
The novel boranes of this invention display considerable
‘utility and are of particular value as gasoline additives for
tri‘a‘r‘nide and 27“ ml.‘ ‘of tetrahydrofuran‘wi'th vigorous
stirring at about 27° C. over a period of three hours.
the prevention of ipreignition. By way of example, tri
The mixture was then heated at about 55° C. for 30
cresyl phosphate, a well-known pre-ignition suppressant,
minutes, after which 25 ml‘. of water was added drop
has been found to be only 60% as effective as certain of
wise at 40° C. The resulting reaction mixture was ren .35 the compounds of this invention with regard to pre
dered acidic with dilute hydrochloric acid and stirred until
ignition prevention. In addition, the new compounds of '
the unreacted hexamethyl phosphorous triamide was de
stroyed. An oil precipitated and became crystalline on
cooling. The white crystalline product was ?ltered,
the invention-?nd utility- as anti-oxidants and’ as polym
erizationcatalysts.
washed with water and dried on air. There was obtained
the‘ reaction product of bis(4-‘liydroxyphenyl) -2,2-propane
4.7 grams (53% of theory) of hexamethyl phosphorous
triamide borane‘.
‘
i
“ _
.
‘BXAMPLEIX
Hexamethyl Phosphorous Triamide Borane
They are also useful. as. blowing
“agents in‘epoxy resins representative of which would be
While the invention has been speci?cally described
with regard to several embodiments, it is not thereby
45 limited, and it is to be understood the Variations and modi
?cations thereof obvious to those skilled in the art may be
3"‘ ‘grams ‘of acetic‘ acid 1"dissoliied‘ in ‘10ml. of‘ ‘tetra
hydrofuran was added dropwise to a mixture of l.9~‘grams
of sodium borohydride and 25 ml. of tetrahydrofuran at
-2.0 to —30° C. with vigorous stirring over a' period 5.0
of 45 minutes. When the“ evolution of hydrogen ceased,
12 {grams 0t hexamethyl phosphorous tr-iamide was added
to‘i‘the- ‘reactiontnixture at ab'out‘tl‘r> C‘. This reaction
mixture was then stirred at room temperature torfabout
‘T35 hburSl‘ahdlatTabout. 60-?‘ C. for an additional‘ hour.‘ 55
made without departing from the spirit or scope of this
invention.
‘
What is claimed is:
of two layers which were separated. The hexane layer
.:wasusevapor_ated,r_leaving‘an oily residue. which was ‘then
'
‘
l. Hexamethyl phosphorous triamide borane.
2. Hexaethyl phosphorous triamide borane..‘
3. Hexa-n-butyl phosphorous triamide borane.
4. N,N’,N" - (tetramethylene) phosphorous triamide
borane.
‘
"
5. The process of preparing a compound of the formula
Dilute hydrochloric acid was then added to render. the
mixture acidic. The resulting mixture was then shaken
with hexane and ?ltered from. the small amount of a
yellow precipitate which‘formed. The ?ltrate consisted
‘
-.
X
,.
H313 P1X’
\X”
where X, X’ and X"‘each represent a member of the
group‘ consisting of
‘
“
treated with a small amount of water’. ‘ The oil became
crystalline on standing, and the crystalline product was
recovered by ?ltration, washed with water‘ and dried on
air. ‘ There was obtained 4.1- grams (46% of theory) of3 65
r
hexamethyl PhOSPhOI'OHSltl'l?IIlldG borane.
X
Hexamethyl Phosphorous ‘Triamide Borane
HsBP [N (CH3) 2] a
A solution of 1.82 grams of hydrogen chlorideidis
solved in 10 ml. of tetrahydrofuran was added to a mix
omeonz '
on,
ture of 1.9 grams of; sodium borohydride and 25 m1. of
OKs-Cg:
tetrahydro?uran at ‘about 760/“ C. within a period of‘.
wherein R and R’ each represent alkyl of from 1 to v12
3,100,774:
'8
vcarbon atoms, which compizises reacting a corrip'oundv of
where X, X’ and X” each represent, a- member of. the
the formula
group consisting of
'
'
'
,‘ r ,
'
'
.
X
P4X
\X”
"where X, X’ ‘and X” have the same meaning as above
with a borine group releasing compound selected from
C Hz-C Hi
the group consisting of rtria‘lkylamine ‘boranes, boron hy
' drides ‘and metal borohydr-ides. 7
10
'
6. The process of preparing ‘a compound of the formula
\QH:—(J112 _
and
,
CHi-CHI
H313 P4X’
.
I
" -.
\X,!
CH1
15
,
1
where ‘X, X’ and X" each represent a member of the
‘
CH'kCé,
,
_
.
wherein R and R’ each‘ represent jalkYl of'from -1 to'IZ
carbon 1atoms, which comprises reacting ‘ascompound of
group consisting of
the
‘formula
"
‘
'
.
'
'
/
25
where X, X’ and X” have ‘the samemeaning as’ above with
trimethyl-amine borane.
9. The process of preparing a compound of the formula
X
Ha B P4X’
\X”
30
where X, X’ and X” each represent a member of the group
‘ wherein R and R’ each represent alkyl of from 1 to 12
consisting of
'
carbon atoms, which comprises'reacting a compound of
the formula
'
I
'
35
/
P-X’
>7
.
I
-
V
CHI-CH1
XII
--N
~
where X, ,X’and X” have the same meaning ‘as above
with a trialkylamine borane.
.
.
i
-, >
\CHPCHI
V40
and
7. The process of preparing a com" ound of the form ‘ a
,
»
r
I
r
/"
.t/X
115B P—-X’
I
"
\X"
45
.
where X, X’ "and X" each represent a member of the
group consisting of
.
.'
’
r
55 ~
~
,
_
.
-;
/GH2—CEI
*N\' /CH2
i 1
,r
1
'
~
.
‘
~
.
,
I
-
where X, X’ and X” each
group consisting of
represent valmeniber ‘of the.
»
’
where X, X’ and X” have the same meaning as above
" with a boron hydride.
~
I
?zBPéx’ 1;‘
5'
XII
*
X
a
»
,
60
wherein R and R’ each represent alkyl of from 1 to .12
carbon atoms, which comprises reacting a compound of
I
I
10.‘ The process of preparing a compound oftthe
formula.
.
,
where X, X’ and X” have the same meaning as above
0112-0115
the formula
>
P—X’
with vdiborane.
CHr-CH:
OH:
. i/x
\
-
.
wherein R and R’ each represent alkyll of from l’to [12
carbon atoms, which comprises reacting a compound of
50
1 GHQ-CH2 I
‘I:
xCHz-C?g
the formula
3
,
‘CHE-CH1
\C Hie-CE:
I
if 8. The process of preparing a compound of the formula
vand
210155-052
-—N\'
I
I
- on:
GHQ-0g’
I
'
3,100,774
.
10
.
with ‘sodium borohydride and hydrochloric'acid in the
wherein R and" R’ each represent alkyl of from 1 to '12
carbon atoms, which comprises reacting a compound of
presence of an inert solvent.
‘ ‘
r
’
‘
13. Hexabenzyl phosphorous triamide boran .
the formula
14. Hexaphenyl phosphorous triamide borane.
15. Tris(N~pl1enyl, N-methyl) phosphorous triamide
m:
borane.
‘
_‘
16. ‘ Hex'acyclohexyl phosphorous triamide ‘borane.
‘ 17 i A compound‘ of the “ formula
"where XQX’ ‘and X” have thesame‘ meaning as above
‘
with sodium borohydride ‘and carbon dioxide in the pres 10
ence of an inert solvent.
11. The process of preparing a compound of the
formula
where-R and R’ are each‘ alkyl of from 1 to 12 carbon
15
atoms.
‘
‘
18. N,N’,N"-(pentamethy1ene) phosphorous triamfide
borane.
19. A compound of the formula
where X, X’ and X" each, represent a member of the
group consisting of
/X
HzBP<X’XII
where X, X’ and X” each ‘represent a member of the
25 group consisting‘of
/R
R!
CHz-C‘Ha
CH2——CH2
wherein‘R ‘and R’ each represent alkyl of from 1 to 112
carbon atoms, which comprises reacting a compound of
and
/
' the formula
CHz-OH:
\
—--N\OHa-QH:/CH:
40 wherein R and R’ are each selected from the group con
sisting of hydrogen, alkyl and mono and dihaloailkyl of
t where X, X’ and X” have the same meaning as above
from 1 to 12 carbon atoms, cycloalkyl and mono and
dihalocycloalkyl of from 5 to 6 carbon atoms, mono
cyclic aromatic hydrocarbon of up to 8 carbon atoms
with sodium boro'hydri-de and acetic acid in the presence
of an inert solvent.
\
12. The process of preparing a compound of the for 45 and mono and dihalomonocyclic aromatic hydrocarbon
of up to 8 carbon atoms, benzyl and mono and diahalo
mula
‘benzyl and naphthyl and mono and dihalonaphthyl, the
.
/X
halogen atoms of said mono and dihalo groups being se
lected from the group consisting of chlorine and bromine,
H315 P<X’
XII
50 provided that at least one of R and R’ must be. other than
hydrogen.
where X, X’ and X” each represent a member of the
7
20. The process of preparing a compound of the for
group consisting of
mula,
55
CH2—CH2
where X, X’ and X” each represent a member of the
——N
\CHreCH:
60 group consisting of
and
0112-0112
/
\GH2
\CHPCQ2
65
wherein Rand R’ each represent alkyl of from 1 to 12
‘carbon atoms, which comprises reacting a ‘compound of
the formula
70
where X, X’ and X" have the same meaning as ‘above 75 ,wherein R and R’ each represent alkyl of from 1 to 12
3,100,774
11v
12'
carbon ‘ atoms, 1 which ‘ comprises‘ reacting a compound
acids‘, hydrohalic acids‘and saturated carboxylic acids of
of the formula,
1 to>5 carbon atoms.
v
,
‘
;
I
-
.
X
'
‘
’ Pgx'
X”' >
5
.
Where X, X’ and ,X" have the same meamng as above,
with a metal borohydride and. a promoter selected from
V
' '
References Cited in the ?le of this patent
Bergmann: The Chemistry of Acetylene and Related
C
d ,
YZEPEJSMS)
page
_ v
‘
80,
.
l
'
r
h-ltérsclenge
Publ?18.hers , Inc .,
. Y
.
N
6w
_
[the class consisting of carbon dioxide, dialkyl ketones,
Kadama' ‘ - merfcanchémwal soclety’ 'Absst‘raqt» of
alkyl 'aldehydes, alkyl esters of saturated carboxyl-ic 10 Papers’ 135t11m¢¢t1ngmage§3M (1959)'
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