Patented Nov.

28, 1933 1,936,985

UNITED STATES PATENT OFFICE

1936,985
PHOSPHOROUS AND PHOSPHORIC AC)
ESTERS
Wilhelm Lommel, Wiesdorf-on-the-Rhine, and
Rudolf Engelhardt, Leverkusen-on-the-Rhine,
Germany, assignors to I. G. Farbenindustrie
Aktiengesellschaft, Frankfort - on - the - Main,
Germany, a corporation of Germany
No Drawing. Application July 22, 1930, Serial
No. 469,925, and in Germany July 31, 1929
4 Claims. (C. 260-98)
The present invention relates to a process of chlorine or bromine. The new esters are prod
preparing esters of the phosphorous and of the ucts of oily consistency the viscosity They
of which
are
phosphoric acids containing chlorine or bromide increases with increasing C-content.
only distillable in the vacuum, the tri(dichloro
and to new products obtainable thereby.
5 According to the process of the present inven propyl) phosphate for instance boiling at a vac 55
tion phosphorous or phosphoric acid esters con uum of 2 mm at 67° C. Absolutely neutral prod
taining chlorine or bromine are obtainable by ucts are only obtainable When Water is excluded.
causing a compound of the general formula: The phosphites are slowly hydrolyzed by cold
CB
water, while the phosphates are much more
stable. . 60
10

k
> The products according to the present inven
tion may find useful application as impregnating
and Softening agents, capable of reducing the
Wherein X stands for hydrogen or an alkyl group inflammability of organic materials if incorpo
5 Which may be further substituted by a halogen rated thereWith. 65
The following examples illustrate our inven
atom having an atomic weight between 30 and tion. Without restricting it thereto:
80 to be reacted upon by a compound of the Eacample
general formula: r 1.-150 parts by weight of ethylene
Oxide are passed in a slow current with cooling
20
-Hal
2-Hal
into 140 parts by weight of phosphorus trichlo
NHal ride, which is COOled to -5 to -10° C. The reac
tion proceeds without evolution of hydrochloric
wherein Z stands for = P or =P=O and Hal for acid. Any excess of ethylene Oxide is removed
a halogen atom of the atomic weight between by gradually heating the reaction product.
25 30 and 80.
Neutral tri- (chloro ethyl) phosphite remains be 75
The reaction temperature may vary in wide hind in approximately quantitative yield. Its
limits; best results are obtained when the reac boiling point is about 50° C. at 12 mm.
tion is performed at about the boiling point of Instead of ethylene oxide propylene oxide, for
the alkylene oxide used. The starting materials example, can likewise. be employed.
30 can be employed in about stoichiometric propor The respective phosphate is obtained when 80
tions, that is to Say, for obtaining a neutral ester using phosphorus oxychloride instead of phos
about 3 mols of alkylene oxide are used for ester phorus trichloride.
Eacample 2-150 parts by weight of phosphorus
ifying One mol of phosphorus trihalogenide or
phOSphorus OXyhalogenide. In some cases the oxychloride are slowly run in with stirring at
addition of "chlorination' catalysts (see “Lassar to 100° C. into 400 parts by weight of epichlorhydrin 85
Cohn, ArbeitSmethoden fir organisch-chemische Stirring which 1% of iron filings have been added, and
is continued for half an hour. The ex
Laboratorien 1923, 5. Auflage, spezieller Teil, page CeSS of epichlorhydrin
272') Will favorably influence the reaction. is distilled off in a vacuo,
According to the process of this invention com and the liquid residue is separated by pressing
40 pounds are obtainable which correspond to the With the addition of charcoal. The filtrate is
mixed with potassium carbonate, whereby the
90
general formula,
potassium Salt of an acid ester separates. After
O
-C2H3 X-CH Y repeated pressing the neutral tri- (dichloropropyl)
/ -
phosphoric acid ester is obtained in a yield
zo-ch. X-CH2 Y amounting to 80% of the theoretical, calculated 95
O On the phosphorus oxychloride. .
YC.H. X-CH, Y On decreasing the quantity of epichlorhydrin
the proportion of acid ester increases.
wherein Z. stands for = P or = PO, X stands for Eacample 3-270 parts by weight of phosphorus
50 chlorine or bromine and Y stands for hydrogen, tribrQmide are caused to react according to the 00
 2 1,936,985
directions of Example 2 with 535 parts by weight atom having an atomic weight between 30 and 80
of epichlorhydrin, while omitting, however, the with a compound of the general formula:
addition of the iron filings. After working up 400
parts by weight of tri- (chlorobromopropyl) phos / Hal
phite are obtained. Z-Hal
NHal 80
We claim:-
1. Process which comprises reacting upon a wherein Z. stands for EP or = P=O and Hal for
compound of the general formula: a halogen of the atomic weight between 30 and
80 at about the temperature of the boiling point
of the alkylene oxide used.
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Do 3. Compounds of the general formula:
/
85

O
5 wherein X stands for hydrogen or an alkyl group 90
which may be further substituted by a halogen
atom having an atomic Weight between 30 and
80 with a compound of the general formula:
wherein Z. stands for EP or EP-O, and Y stands
20 Hal for hydrogen or a halogen of the atomic weight
z/tial between 30 and 80, said esters being oily com
NHal pounds, distillable in vacuo, hydrolizing when
boiled with Water.
Wherein Z. stands for = P or EP=O and Hall for 4. The compound of the formula:, .
25 a halogen atom of the atomic weight, between C.H. C1-CH, Ci 100
30 and 80. O
2. Process which comprises reactins is: a /
compound of the general formula: o-po-cit Cl-CH2 Cl
O
30 CH2
05
tri(dichloropropyl) phosphate, forming an oil,
X
being distillable in vacuo at 67° C. under a pres
sure of 2 mm and hydrolizing when boiled with
Water.
35 wherein X stands for hydrogen or an alkyl group WLHELMIOMMEL. 1)
which may be further substituted by a halogen RUDOLF ENGELHARDT.

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