CA1072574A

CA1072574A - Process for the preparation of phosphoric acid ester halides

Info

Publication number: CA1072574A
Application number: CA246,203A
Authority: CA
Inventors: Dieter Arlt
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1975-02-22
Filing date: 1976-02-20
Publication date: 1980-02-26
Also published as: ZA761006B; BE838737A; AU1130776A; NL7601697A; ATA122076A; JPS5910677B2; DK141936B; DK141936C; AT341543B; FR2301531B1; IL49077A0; GB1513341A; ES445370A1; DE2507779A1; IL49077A; IT1053874B; NL187355C; CH623058A5; BR7601096A; PL99859B1

Abstract

Abstract of the Disclosure A phosphoric acid esterhalide is prepared by simultaneously reacting a phosphoric acid ester of formula I

(I) wherein R is alkoxy with 1 - 8 carbon atoms optionally substituted by halogen, and R' is C1 - C8 alkoxy radical, optionally substituted by halogen, or is chlorine, bromine fluorine or C1 - C6 alkyl or phenyl, each optionally sub-stituted by halogen. and X is fluorine, chlorine or bromine, with a halogenat-ing agent and an olefin of formula II

Description

~7Z57~

The present invention relates to a new process for the preparation of phosphoric acid ester-halides and to new phosphoric acid ester-halides obtainable with the aid of this process.
It is known to prepare phosphoric acid ester-chlor-ides by selective reaction of phosphoryl chloride with alcohols (compare Houben-Weyl XII/2J page 212 (1964)). The disadvan-tage of this process is that only a limited number of alcohols, especially primary alcohols, can be used as the starting material. Thus, the preparation of substituted compounds is correspondingly restricted and in certain cases, for example . for phosphoric acid alkyl ester-halides halogenated in the 1-position in the alkyl radical, can be achieved in a controlled manner at best via a multi-stage reaction sequence.
. A new process for the preparation of phosphoric acid ester-halides has now been found which is characterised in that a phosphoric acid ester of the general formula I

:~ o R' -'. "/
X - P (I) - R
. in which the radical R represents an alkoxy radical with 1 -. 20 8 carbon atoms, which is optionally substituted by halogen, `. and R' represents a Cl-C8 alkoxy radical which is optionally substituted by halogen, or represents chlorine, bromine, fluorine or a Cl-C6 alkyl or phenyl radical, which is option-ally substituted by halogen, cmd X represents fluorine, chlorine or bromine, is reacted simultaneously with a halogenating agent and an ,' -.
_ z _ ~' ' .

~07Z~7~

olefine of the general ~ormula II

R2 ~ ~R4 (II) ", C = C
R
in which the radicals R2 and R4 are identical or different and represent hydrogen, halogen or a straight-chain or branched, optionally substituted C1-C18 alkane, Cl-C6 acyloxy or C2-C12 alkenyl radical, substituents which may be mentioned being halogen, acyloxy or alkoxy groups with 1 - 18 carbon atoms, the isocyanate group, the isocya-nide-dichloride group, the chlorocarbonyl group, the ni-trile group or -the chlorosulphone group, a carb-alkoxy group with 1-8 carbon atoms in the alcohol radical or an optionally substituted carbamino group with up to 12 carbon atoms in -the molecule, and also represent a phenyl radical which is optionally sub-stituted by halogen and/or by Cl-C4 alkyl groups and the radical R4 also represents, in addition to the . abovement~oned groups, the chlorocarbonyl or nitrile group or a carbalkoxy radical or a carbamino radical, which is optionally substituted on the nitrogen atom, with9 in each case9 up to 9 carbon atoms in the mole-cule, or represents an alkylcarbonyl, an alkylsulphonyl, . an arylcarbonyl or an arylsulphonyl group with, in each case, up to 7 carbon a-toms in the molecule or ~: 25 represents the aldehyde group and optionally the radicals R2 and R4 conJointly are, as ~ result of an additional bond between the radicals R2 and R4, a : constituent o~ a 4-membered to 12-membered, pre~erably Le A 16 296 - 3 -. . .

; ..
.,, , , ! . , . , . . ~ .

~', . ~ ' 1C~7;~57~

5 membered or 6-membered, carbocyclic or heterocyclic ring, oxygen, sulphur or ni-trogen preferably occurring as hetero-atoms, and R3 and R5 are identical or different and represent ; 5 hydrogen, halogen or a Cl-C4 alkyl radical.
Preferred phosphoric acid esters, according to the general formula I, which may be mentioned are those in which R represents a Cl C6 alkoxy radical 9 preferentially i; the methoxy and the ethoxy radical, and R' represents a Cl-C4 alkoxy radical or represents a Cl-C3 alkyl radical, chlorine, bromine, fluorine or the phenyl radical and preferentially represents the . methoxy, ethoxy, propoxy, isopropoxy, methyl or ethyl radical and X represents chlorine~
. Examples which may be mentioned are: phosphoric acid dimethyl ester-monochloride, phosphoric acid diethyl ester-: monochloride, phosphoric acid diethyl es-ter-monobromide, - phosphoric acid dimethyl ester-monofluoride, phosphoric acid dibutyl ester-monochloride, phosphoric acid monomethyl ester-dichloride9 phosphoric acid monoethyl ester-dichloride, phosphoric acid monoethyl ester-difluoride, phosphoric acid mono-(2-chloroethyl) ester-dichloride, phosphoric acid monoiso-.
propyl ester-dichloride, phosphoric acid monopropyl ester dichloride, methanephosphonic acid monomethyl ester-chloride, ~ ethanephosphonic acid monoethyl ester-chloride and phenyl-phosphonic acid monomethyl ester-chloride.
The phosphoric acid es-ters which are used for -the . process according to the invention are known and can be : 30 prepared by reacting the corresponding phosphoric acid chlo-rides such as, for example, phosphoryl chloridel with the . Le A 16 296 - 4 -. ~

';~

''' ~L~7~574 apFropriate alcohols (compare ~ouben-Weyl, Methoden der Organischen Chemie ~Methods of Organic Chemistry) Volume XII 9 : 2, page 211 (Stuttgar-t 1964)).
Preferred olefines, according to the general formula II, which may be mentioned are those in which R2 and R4 are identical or different and represent hydrogen, fluorineJ chlorine, bromine or an optionally substituted Cl-C5 acyloxy radical, a Cl-C6 alkane radical or a C2-~6 alkenyl radical, substituents of these radicals which may be mentioned being chlorine, bromine, the isocyanate group, the isocyanide-dichlo-ride group, the chlorocarbonyl group, the nitrile group or the chlorosulphonyl group, a carbalkoxy group, an acyloxy group or an alkoxy group with, in each case, 1-5, and preferentially 1-3, carbon atoms ; in the molecule, as well as a carbamino group which is ; preferably substituted on the nitrogen atom by methyl or ethyli and R2 preferentially represents fluorine, chlorine or bromine and R4 has the abovementioned scope of meanings but does not represen-t fluorine, chlorine or bromine simultaneously wi-th R2.
Further preferred olefines which may be men-tioned are those in which .: 4 R represents the chlorocarbonyl group~ the nitrile group~ a carbalkoxy group or a mono-alkylated or di-alkylated carbamino group, with 1 to 5 carbon atoms in the molecule, an alkylcarbonyl or alkyl-sulphonyl group with 1 to 4 carbon atoms in the mole-. cule and also an arylcarbonyl or arylsulphonyl group, :~ 30 which preferably contains the phenyl radical as the aryl radical, and .: . Le A 16 296 - 5 -'', ' ' . . .

~CJ7ZS'7~

preferentially the radicals R2, R3 and R5 are identical or different and represent hydrogen, chlorine, bromine or a Cl-C6 alkane radical and at least one of the radicals R29 R3 and R5 represents hydrogen.
Examples which may be mentioned of olefines which are used for the process according to the invention are: branched and unbranched alkenes, especially ethylene, propylene, but-l-. ene and but-2-ene, isobutene, hex-l-ene 9 dodec-l-ene9 tri- and tetra-propylene, tetraisobutene, oct-l-ene, octadec-l-ene, l-phenyl-3,3,4,4-tetrafluoro~cyclo-butene, cyclopentene, cyclo-hexene, cyclooctene, cyclododecene, styrene, ~-methylstyrene, ~- and ~-pinene and camphene; diolefines, especially buta-193-diene, isoprene, 293-di.methyl-buta-1,3-diene, vinylcyclo-hexene and cycloocta-1,4-diene; halogenated olefines, such as allyl chloride, methallyl chloride and vinyl chloride9 1- and

2-chloropropene9 1,4- and 3,4 dichloro-but-2-ene, vinyl bro-mide and allyl bromide, vinyl fluoride, 191-dichloroethylene9 l,l-difluoroethylene and tr:Lfluoromonochloroethylene, l-chloro-cyclohexene and 3-chloro-cyclohexene; esters, mono- and di-alkylamides, chloridesand nitriles of unsaturated carboxylic acids, especially of acrylic acid, methacrylic acid, crotonic acid, ~,~-dimethyl-acrylic acid, ~-chloroacrylic acid, ~
dichloroacrylic acid, vinylace-tic acid, undecenecarboxylic acid, oleic acid, linoleic acid, cyclohexene-l-carboxylic .~ acid and cyclohexene-3-carboxylic acid, maleic acid, itaconic acid and fumaric acid; esters and ethers of unsa-turated alcohols, especially of allyl alcohol, butene-1,4-diol and methylene-propane-1,3-diol, for example ethyl vinyl ether, butyl vinyl ether, vinyl acetate and isopropenyl acetate and 1,3-dioxolen-2-one; isocyanates and isocyanide-dichlorideswi-th Le A 16 296 - 6 -., .: .

~72~

olefinic groupings, especially allyl isocyanate and allyl isocyanide-dichloride, 4-chloro-butenyl isocyanate and 4-chlorobutenyl isocyanide-dichloride and isopropenyl iso-cyanate; ketones and sulphones with olefinic groupings, specially methyl vinyl ketone, mesityl oxide, phenylvinyl-sulphone, sulpholene and 3-methylsulpholene; and olefinic sulphonic acid derivatives, especially ~-chloro-vinyl-, allyl-and methylallyl-, vinyl- and ~ -dimethylvinyl-sulphonyl chloride.
Very particularly preferred olefines are those according to the general formula II, in which R2 and/or R3 represent fluorine, chlorine or bromine, especially fluorine or chlorine, and R also can represent hydrogen and the radicals R4 and R5 in each case represent hydrogen, a Cl-C6 alkane radical or the phenyl radical. Examples which may be mentioned are: monofluoroethylene, monochloroethylene, mono-bromoethylene, l,l-difluoroethylene, l,l-dichloroethylene, 1-fluoro-2-methylethylene, 1-fluoro-2-ethylethylene, l-fluoro-2-phenyle~hyleneJ l-chloro-prop-l-ene and 2-chloro-prop-1-ene.
The vinyl fluorides and vinylidene fluorides : which are employed for the process according to the invention are known or can be prepared according to known processes, for example by an addition reaction of one molecule of HF with .,, appropriate acetylenes or, respectively, of two molecules of l-IF
with acetylenes, subsequent chlorination and dehydrochlori-nation.
The phosphoric acid ester-halides obtainable by the process according to the invention can be represented by the .

~1~7Z57~

-~ general formula III

R~ R2 R4 O - C - C - Y (III) in which the radicals R', R2, R3, R4, R5 and X have the same meaning as ~or the starting products of the general formula I or II
respectively and Y represents chlorine or bromine, in accordance with the halogenating agent used for the process according to the invention.
Examples which may be mentioned o~ phosphoric acid ester-halides, according to the general formula III, are:

Le A 16 296 - 8 _ .. .

~L~7Z57 ~`

_. ...... _ _ . ~.

.. . _ C~ "
~ h r~

_ ~ p~ ~
.. ~ ~ V ~l U
O ~ O O O O V O ~ O

~ r~ ~I h r-l rl V ~ V ~
~....................... . ~ - . I
., ~ ~ V~

~ .

~. .

.

Le A 16 296 - 9 -:, ,: . .

~Ot7Z574 New compounds, which are obtainable with the aid of the process according to the invention and which may be mentioned are:
Compounds of the general formula III, 5 in which X represents fluorine, chlorine or bromine, Y represents chlorine or bromine, R' represents a Cl-C8 alkyl radical or phenyl radical, which are optionally substituted by halogen, and R2 and R4 are identical or di~ferent and represent hydrogen, halogen or a straight~chain or branched, optionally substituted Cl-C18 alkane, Cl-C6 acyloxy or C2~C12 alkenyl radical, substituents which may be mentioned being halogen, acyloxy or alkoxy groups with . 15 1 - 18 carbon atoms, the isocyanate group 9 the iso-: cyanide-dichloride group, the chlorocarbonyl group, the nitrile group or the chlorosulphone group, a carb-. alkoxy group with 1-8 carbon atoms in the alcoholradical or an optionally substituted carbamino group with up to 12 carbon atoms in the molecule, and also represent a phenyl radical which is optionally sub-; stituted by halogen and/or by Cl-C4 alk groups and the radical R4 also represents, in addition to the abovementioned groups, the chlorocarbonyl or nitrile group or a carbalkoxy radical or a carbamino radical, ` which is optionally substituted on the nitrogen atom, : with, in each case, up to 9 carbon atoms in the mole-cule, or represents an alkylcarbonyl~ an alkyl : sulphonyl, an arylcarbonyl or an arylsulphonyl group with, in each case, up to 7 carbon atoms in the mole-cule or represents the aldehyde group and ~pion~ly the Le A 16 296 - 10 -~7257~

radicals R2 and Rl conjointly are, as a result of an additional bond between the radicals R2 and R4, a constituent of a 4-membered to 12-membered, prefer-ably 5~membered or 6-membered, carbocyclic or hetero-cyclic ring, oxygen, sulphur or nitrogen preferably occurring as hetero-atoms, and R3 and R5 are identical or different and represent hydrogen, halogen or a Cl-C4 alkyl radical, and also compounds of the general formula III 9 in which X represents fluorine, chlorine or bromine, Y represents chlorine or bromine, R' represents a Cl-C8 alkoxy radical, which is option-ally substituted by halogen, or represents fluorine, chlorine or bromine, R2 represents fluorine, R3 represents fluorine or hydrogen and R and/or R5 represents hydrogen, Cl-C4 alkyl or phenyl.
The compounds listed in Table 1 may be mentioned by way of example:

Le A 16 296 - 11 -:

~ ~ .
., .

~7Z~7~

_ _ _ _ U~ W ~ W ~ W
. _ . .

,' - - .

~ 1~ F~ W W 1~ W P~ W P t~l P:l ~
.~ .

c*l h 1~ h h ¢- h F~ h h F~1 h P~ q F~ F~ h . ~; O O O O U~
W :C W Pq C~l r I ~1 ~1 ~ h W W c~ ~ ~D
.~ u v o v v c~ c~ o c~ ~ m o v v v o "., ~. . ~

.- ~ ,I r l h r~ I h r~ h r~l r~ ~ h ~I r-1 ~1 .~. C~ C~ q V ~ v ~ v . ~
0 r-l ~1 ~1 ~ ~1 ~1 ~-1 ~( h ~1 ~
E-l ~ v r~ , .

`'' .

' ' ;:
Le A 16 296 - 12 _ ~7Z5~4 Elementary halogen, especially chlorine or bromine, can be used as the halogenating agent for the process according to the invention. Of course, compounds which split off chlorine or bromine under the reaction conditions, for example sulphuryl chloride, can also be employed.
The reaction temperature for the reaction according to the process of the invention is not in itself critical and can vary within wide limits. In general, the reaction is carried out at between -50 and + 120C, appropriately between about -10 and +100C and preferably at -10 to +50C.
In general, the reaction is carried out under normal pressure.
~; The process according to the invention is preferably carried out in the presence of solvents or diluents. ~ol-vents and diluents which can be used are organic solvents which are inert towards the reactants, such as, for example, aliphatic and aromatic chlorinated hydrocarbons, dichloro-methane, chloroform7 chlorobenzene or dichlorobenzene but also an excess of the particular phosphoric acid ester-halide, in so far as this is liquid under the reaction conditions.
In some cases it has also proved advantageous to add ~-~ a small amount of Friedel-Crafts catalysts, especially7 for example, iron-(III) chloride, zinc chloride or aluminium chloride, to the reaction mixture.
In order to achieve good yields, the process according to the invention is appropriately carried out using equiva-lent amounts of halogena-ting agent and at least equivalent amounts of the phosphoric acid ester-halide employed as the ' starting material, these amounts being based on -the olefine.
In general, particularly good results are obtained when the phosphoric acid ester-halide employed is used in excess, for Le A 16 296 - 13 -.

.' ' ~i~7Z57~

example in a molar ratio of 1 : 1 to 5 : 1, based on olefine employed.
Using, as an example, the reaction of phosphoric acid monomethyl ester-dichloride with vinyl chloride as the olefine and chlorine as the halogenating agent, the process according to the invention can be illustrated in more detail by the equation which follows:

:` ~
/ Cl Cl - P ~ CH2=CH-Cl ~ C12 , /.Cl ) Cl - P ~ CH3Cl OCH-CH2-Cl Cl :

~hen the phosphoric acid ester used as the start-ing material contains two alkoxy groups as the substituents R
and R', the reaction according to the process of the invention can be continued stepwise, when an appropriate excess of ole-fine and halogenating agents are present, by substitution of both alkoxy groups to give two new phosphoric acid diestermono-halides, as is illustrated in more detail by the equation which follows, using, as an example, the reaction of phosphoric acid dimethyl ester-monochloride with vinyl fluoride as the olefine and chlorine as the halogenating agent:

. .

`~ zs~

Cl 11/C~3 C12 gC~2_C~TF~ Cl ll/ocrl3 OC~3 CH3Cl \ 0-CII~
~Ir~Cl '' 7ll2 Cl Cl Cl~ C}IF 11~ CIIF

~ll2¢

, . .
In this case the phosphoric acid ester-halide obtainable as the product contains, in place of the radical R', the radical R2R4 .

--O--C--C--Y

3 5 R R

In order to carry out the process according to the invention in practice it is appropriate initially to intro-duce the phosphoric acid ester-halide employed, if necessary ' in an inert solvent or diluent, and to add the halogenating ` 10 agent and the olefine simultaneously to this solution at the indicated temperatures, the internal temperature of the mix-ture being regulated by external cooling. After the reaction has subsided, the batch is stirred for a further period whilst warming (preferably at 40 to 100C) in order to carry the ` 15 reaction to completion. The reaction mix-ture is then cooled to room temperature and worked up according to customary methods, for example by ~ractlonal vacuum distillation.
The products obtainable according to the process of ; the invention are generally obtained in the form of colour-less to pale yellow coloured oils, which are insoluble in water and which generally can be distilled without decom-position under reduced pressure and can be purified in this Le A 16 296 - 15 -", ';
, ., ~(97Z57~

way. When mixtures of different isomers are obtained as the product, these can be separated by fractional distillation.
An advantage of the process according to the inven-tion is that the preparation of known phosphoric acid ester-halides is considerably simplified and numerous new compounds of this type, whlch cannot be prepared according to methods known hitherto, are accessible.
A further advantage is that the process according to the invention has universal applicability and can be car-ried out industrially in a simple manner and that the requisite starting materials are readily accessible. The high purity and good yields of the products obtainable by the process accor-ding to the invention is also advantageous.
The phosphoric acid ester-halides which can be prepared according to the process of the invention serve as intermediate products for the preparation of insecticides and flameproofing agents ~compare United States Patent Specification 2,947,773/Table 1).
Example 1 55 g of vinyl fluoride and 70 g of chlorine are simultaneously passed into 308 g of phosphonic acid dimethyl ester-monochloride ~CH30)2POCl at -5C to 0C, whilst stirring and cooling. After the reaction has taken place, the mix-ture is first degassed in vacuo at room temperature and then is subjected to fractional distillation. 143 g ~= 69% of theory) of phosphoric acid 0-methyl-0-~2-chloro-1-fluoro-ethyl) ester-monochloride of the formula Cl-PO(OCH3) tOCHF-CH2Cl) which has a boiling range b.p. 0 3:
69 - 72C, and 11 g ~= 8% of theory) of phosphoric acid di-(2-chloro-1-fluoroethyl) ester-monochloride of the formula Cl-PO(OCHF-CII2Cl)2 which has a boiling range b.p. 0 2:

':
;

~0~;~57~

85 - 90C, are obtained.

The reaction is carried out analogously to Example 1, using 600 g of (CH30)2P0cl~ 195 g of C12 and 140 g of vinyl fluoride, instead of the amounts indicated in Example 1.
In this case 307 g (52% of theory) of the compound Cl-PO(OCH3)(0CHF-CH2-Cl) and 72 g (= 21.5%) of the compound Cl-PO(OCHF-CH2Cl)2 are obtained.
Example 3 71 g of chlorine and 90 g of vinyl chloride are passed into 172 g of phosphoric acid diethyl ester-mono-chloride Cl-PO(OC2H5)2. The temperature is kep-t at about 0C by cooling. The reaction mix-ture is warmed to 50C in , order to remove ethyl chloride and is then subjected -to fractional distillation in vacuo. 105 g (= 43.5% of theory) of phosphoric acid 0-ethyl-0-(1,2-dichloroethyl) ester-mono-chloride of the formula Cl-PO(OC2H5)(0CHCl-CH2Cl), which has a boiling point b.p.o 1 : 72C, and 52 g (= 33.4% of theory) of phosphoric acid di-(1,2 dichloroethyl) ester-monochloride Cl-PO(OCHCl-CH2C1)2, which has a boiling point b.p.o 1 :
110C, are obtained.
E~ple 4 70 g of vinyl fluoride are passed into 212 g of Cl_PO(OCH3)2 a-t about 0C, whilst stirring and cooling, 117 g of bromine ~eing added dropwise at the same time. The mix-ture is then degassed under a waterpump vacuum and subjected : to fractional distillation. 120 g (- 65% of theory) of phosphoric acid 0-methyl-0-(2-bromo-1-fluoroethyl) ester-monochloride of the formula Cl-PO(OCH3)(0CHF_CH2Br), which has a boiling range b.p.o 2 : 80 - 83C, and 14 g of the compound Cl-PO(OC`HF-CH2Br)2, which has a boiling range of ` Le A 16 296 - 17 -. .
' .

. , .
. .
'.' ; .

~C17Z574 100 - 105 / 0.15 mm Hg, are obtained.

20 g of chlorine and 20 g of vinyl fluoride are passed into 20 g of phosphoric acid monopropyl ester-di~
chloride C12P0-0-nC3H7 at -10C to 0C. 20-2 g (= 85% of ; theory, based on phosphoric acid propyl ester-dichlorideemployed) of phosphoric acid (2-chloro-1-fluoroethyl) es-ter-dichloride of the formula C12P0-OCHF-CH2Cl, which has a bolling range of 46 - 48C/0.2 mm Hg 9 are obtained by fractional distillation.
_6 30 g of vinyl fluoride and 40 g of chlorine are passed into 80 g of phosphoric acid monoethyl ester-dichloride at about 0C. After working up by fractional distillation, 75 g (= 77.5% of theory, based on phosphoric acid ethyl ester-chloride employed) of the compound C12P0-0-CHF CH2Cl, which has a boiling range of 43 - 46C/0.1 mm Hg, are obtained.
Example 7 20 g of vinyl chloride and 20 g of chlorine are passed into 20 g of phosphoric acid monopropyl ester-dichloride, the reaction temperature being kept between 0C and +10C by cooling. Working up by distillation gives 16 g (= 62.5% of theory) of phosphonic acid (1,2-dichloroethyl) ester-dichloride, which has a boiling range of 56 - 60C/0.1 mm Hg.
Example 8 80 g of vinyl bromide are added dropwise to 80 g of phosphoric acid monoethyl ester-dichloride at -5C to 0C, 45 g of chlorine being passed in simultaneously and the heat of reaction being compensated by a cooling ba-th. 52 g (= 40%
of theory) of the compound CH2Cl-CH~r-0-POC12, which has a boiling range of 66 68C/0.1 mm Hg, are obtained by frac-Le A 16 296 - 18 -:'.

~ILC)7ZS~

tional distillation of the resulting product mixture.
E~ample 9 100 g of chlorine and 65 g of vinyl fluoride are simultaneously introduced into 135 g of ethane phosphonic acid ethyl ester chloride. The temperature is kept at bet-ween -10C and 0C by means of cooling. After working up by frac-tional distillation, 120 g (= 67 % of the theory) of ethane phosphonic acid (2-chloro-1-fluoroethyl ester) chloride, which has a boiling range of 65 - 67 C / 0.2 mm Hg, are obtained.
Example 10 60 g of chlorine, 39 g of vinylidene fluoride and in addition 0.5 g of FeC13 are introduced into 67 g of phosphoric acid methyl ester dichloride. The temperature is kept at 10 to 20C by means of cooling. After working up by fractional distillation in vacuo, 75 g (75 % of the theory) of phosphoric acid (2-chloro-191-difluoro-ethyl ester)-dichloride, which has a boiling range of 45 - 50c/

4 mm Hg, are obtained.

Le A 16 296 - 19 -'

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for the preparation of a phosphoric acid ester-halide of the general formula:

(III) in which R' represents a C1-C8 alkoxy radical, which is optionally substituted by halogen, or represents chlorine, bromine, fluorine or a C1-C6 alkyl or phenyl radical, either of which may optionally be substituted by halogen, R2 and R4 are identical or different and each represents hydrogen, halogen or a straight-chain or branched optionally substituted C1-C18 alkane, C1-C6 acyloxy or C2-C12 alkenyl radical, or a phenyl radical which may optionally be sub-stituted by halogen and/or by a C1-C4 alkyl group and the radical R4 may, in addition represent a chlorocarbonyl, or a nitrile group, a carbalkoxy or an optionally N-substituted carbamino radical containing in each case, up to 9 carbon atoms, an alkylcarbonyl, alkylsulphonyl, arylcarbonyl or arylsulphonyl group containing, in each case, up to 7 carbon atoms or an aldehyde group, or the radicals R2 and R4 are joined together to form a 4-membered to 12-membered, carbocyclic or heterocyclic ring, and R3 and R5 are identical or different and each represents hydrogen, halogen or a C1-C4 alkyl radical, X represents flu-orine, chlorine or bromine, and Y represents chlorine or bromine, wherein a phosphonic acid ester of the general formula:

(I) in which R represents an alkoxy radical with 1 - 8 carbon atoms, which may optionally be substituted by halogen, and R' and X are as defined above, is reacted simultaneously with a halogenating agent and an olefin of the general formula II

(II) in which the radicals R2, R3, R4 and R5 are as defined above.

2. A process according to claim 1, wherein R represents a C1-C6 alkoxy radical, R1 represents a C1-C4 alkoxy radical, a chlorine, fluorine, bromine atom, a C1-C3 alkyl radical or a phenyl radical, and X represents chlorine.

3. A process according to claim 1 or claim 2, wherein R2 or R4 re-presents a C1-C18 alkane, C1-C16 acyloxy or C2-C12 alkenyl radical substituted by a halogen atom, an acyloxy or alkoxy group containing from 1 to 18 carbon atoms, an isocyanate, isocyanide-dichloride, chlorocarbonyl, nitrile or chlorosulphone group, a carbalkoxy group containing from 1 to 8 carbon atoms or an optionally-substituted carbamino group containing up to 12 carbon atoms.

4. A process according to claim 1 or 2, wherein R2 and R4 are identical or different and represent hydrogen, fluorine, chlorine, bromine an optionally substituted C1-C5 acyloxy, C1-C6 alkane or C2-C6 alkenyl radical, the optional substituents in each case being chlorine, bromine, isocyanate, isocyanide-dichloride, chlorocarbonyl, nitrile, a carbalkoxy, acyloxy or alkoxy group containing, in each case, from 1 to 5 carbon atoms,or a carbamino group op-tionally N-substituted by a methyl or ethyl group.

5. A process according to claim 1 or 2, wherein R2 represents fluorine, chlorine or bromine and R4 is as defined in claim 4, but does not represent fluorine, chlorine or bromine.

6. A process according to claim 1 or 2, wherein R4 represents a chloro-carbonyl, nitrile, or carbalkoxy group, a mono- or di-alkylated carbamino group containing from 1 to 5 carbon atoms, or an alkylcarbonyl or alkylsul-phonyl group containing from 1 to 4 carbon atoms, and R2, R3 and R5 are iden-tical or different and each represents hydrogen, chlorine, bromine or a C1-C6 alkane radical, at least one of R2, R3 and R5 representing hydrogen.

7. A process according to claim 1 or 2, wherein R2 represents flourine, chlorine or bromine, R3 represents fluorine, chlorine, bromine or hydrogen and R4 and R5 each represent hydrogen, a C1-C6 alkane radical or phenyl.

8. A process according to claim 1 wherein the halogenating agent is elementary halogen.

9. A process according to claim 1, 2 or 8, wherein the reaction is effected at a temperature of from -50 to +120°C.

10. A process according to claim 1, 2 or 8, wherein the reaction is carried out in the presence of an organic solvent or diluent and a Friedel-Crafts catalyst.

11. A compound of the general formula (III) in which X represents fluorine, chlorine or bromine, Y represents chlorine or bromine, R1 represents a C1-C8 alkyl radical or phenyl radical, and R2, R3, R4 or R5 are as defined in claim 1.

12. A compound according to claim 11, wherein X represents fluorine, chlorine or bromine, Y represents chlorine or bromine, R1 represents a C1-C8 alkoxy radical, which is optionally substituted by halogen, or represents fluorine, chlorine or bromine, R2 represents fluorine, R3 represents fluorine or hydrogen and R4 and/or R5 represents hydrogen, C1-C4 alkyl or phenyl.