DE1668040A1 - Process for the preparation of bromoalkyl-S-alkyl- or -aryl- (di) thiolphosphoric acid diester or ester amide chlorides - Google Patents

Description

FARBENFABRIKEN BAYER AG

LE VE RKU S E N - Bayeiweric P «tent-AbteUuni Hu / vR

Process for the preparation of bromoalkyl-S-alkyl- or -aryl-Cdijthiolphosphorsäurediester- or ester amide chlorides

The present invention relates to a process for the preparation of new bromoalkyl-S-alkyl- or -aryl- (di) -thiolphosphorsäuredieater- or ester amide chlorides.

It is already known that 0,0-dialkyl phosphorous diester chlorides with sulfenic acid chlorides in the sense of the following equation with elimination of alkyl chloride OjS-thiolphosphoric acid diester chlorides react (cf. N.A. Petrov, G.A. Sokolskij and B.M. Polees, Z. obW Chim.

26, 3381 ^ "1.9567:

(RO) ₀ P-Cl + R '-S-Eq ^. RO-P-Cl + RCl

R ¹ S (D

In the above equation, R denotes ^{an alkyl radical and R 1} denotes an alkyl or aryl radical.

In the production of O-bromoalkylthiolphosphoric acid diester chlorides However, this process would have the disadvantage that those required as starting materials are in the alkyl radical

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brominated 0, O-dialkyl phosphorous acid diester chlorides (Dialkylchlorphosphite) are difficult to access. This is how the aforementioned O-bromoalkyl compounds have been hitherto also not yet described in the literature.

Furthermore, thiolphosphoric acid-S-monoester-amide chlorides can be prepared by reacting O-alkyl-phosphorous acid ester dichlorides with sulfuric acid amides according to the equation

egg o

RO-t-Cl + R'-SN (R ") ₂ ->(R") ^ - P-Cl + RCl

(H)

R ¹ S

according to KAPetrov, NKBIiznjik and VASavoeknck, Zi3bsc ^/ . Chia. 21 »1361 / T961JO, where R and R ^{1 have} the meaning given above, while R ″ stands for a preferably lower alkyl radical.

In this case too, starting materials that are difficult to access in the preparation of thiolphosphoric ester amides with a 2- or 3-bromoalkyl group on the nitrogen were found are needed.

Finally, there are one-step processes for the production of S.S-Dithiolphosphorsäurediester halides with two various organic residues have not yet been described in the literature at all.

It has now been found that bromine alkyl-S-alkyl- or -aryl- (di) thiolphosphoric acid di-8ter- or ester amide chlorides can be obtained with very good yields and in excellent purity if 2-chlorophospholane or -phosphorinane derivatives of the general formula

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^ 1 b B β U 4 O

R,

⁵ ;

^R 6

(III)

with aliphatic or aromatic sulfenic acid bromides of formula (IV)

R ₇ -S-Br

(IV)
implements.

In the above formulas, the symbols R ₁ to Rg stand for hydrogen atoms, alkyl, alkoxyalkyl or haloalkyl radicals, R _{7 stands for} an optionally substituted alkyl, aryl or aralkyl radical, while X is an oxygen or sulfur atom or an N-alkyl or Represents N-arylamino group and η has the value zero or 1.

The smooth and uniform course of the invention Procedure is completely surprising. It could in no way be foreseen that the above-mentioned 2-chlorophospholanes or -phosphorinanes with sulfenic acid tetjromides with splitting of the heterocyclic ring and formation of 2- or 3-bromoalkyl-thiolphosphoric acid ester or -esteramide chlorides would react.

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Compared to the above-mentioned methods for the preparation of thiol or thiol phosphoric acid ester and ester amide chlorides with bromoalkyl radicals, the process according to the invention is distinguished by a number of essential advantages. This includes mainly light to _to än _ö friendliness of the starting materials, uniform reaction course, good yields and very simple way of performing.

For example, 2-chloro-1,3,2-dioxaphospholane is used or -dioxaphosphorinane and methylsulfenic acid bromide as Starting materials, the course of the procedural Implementation illustrated by the following formula scheme (V):

CH ₉ O ₀

/ ² Y ^υ

(V) (CHp) _x , P-Cl + CH, -S-Br> Br-CH ₉ - (CH ₉ ICH ₉ -OPC]

• (n = 0.1)

The reaction of 2-chloro-1,3-2-oxathiaphospholane proceeds in the same way with phenylsulfenic acid bromide within the meaning of Equation (VI):.

(VI) CH ₂ -Ck _p _ _{cl +} / Λ_ ₅ _ _ΒΓ ^ Br-CH ₀ -CH ₀ -SP-Cl

0 p

The reaction of 2-chloro-3-methyl-1,5,2-oxaazaphospholane is analogous with methylsulfenic acid bromide according to the following reaction scheme (VII) to N, S-dimethyl-N- (2-bromoethyl) - thiolphosphoric acid monoester amide chloride:

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ORIGINAL INSPECTED

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gh- ^ K56BÜ4Ö

'^ α _CH Q

(VII) CH ₉ N ^ V

¹ * P-Cl + CH _x -S-Br-> Br-CH ₀ -GH ₀ -NP-Cl

CH ₀ - O ^ ■ ⁵ ■ ^{ά ά} '

The starting materials for the process according to the invention 2-chloro-dioxaphospholanes or -phosphorinanes to be used and aliphatic or aromatic sulfenic acid bromides are represented by the general formulas (III) and (IV) given above clearly defined.

However, the symbols R ^ to Rg in formula (III) preferably denote hydrogen atoms or optionally halogen- or lower-alkoxy-substituted alkyl radicals having 1 to 4 carbon atoms, such as the methyl, chloromethyl or methoxymethyl radical. Ry preferably stands for a straight-chain or branched alkyl or alkenyl radical having 1 to 12 carbon atoms, which is replaced by 1 to 4 halogen atoms, a lower alkoxy, alkyl mercapto, carbonyl, carboxyl, alkoxycarbonyl, alkylcarbonyl, dialkylaminocarbonyl or nitrile group may be substituted; furthermore, R ₇ preferably denotes an aryl or aralkyl, especially phenyl, optionally substituted one or more times by lower alkyl groups, halogen atoms, metro, cyano, rhodan, lower alkoxy, alkyl mercapto, alkylsulfoxyl or alkylsulfonyl groups - respectively.

Benzyl radical.

X preferably denotes oxygen, sulfur, a lower N-alkyl or the K-phenyl radical.

As examples of phospholane or phospholane to be reacted according to the invention Phosphorinane derivatives are mentioned in detail:

2-chloro-1,3,2-dioxa, 2-chloro-4-methyl-1,3,2-dioxa, 2-chloro-4-chloromethyl-1,3,2-dioxa, 2-chloro-4,5-dimethyl-i, 3,2-dioxa-,

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2-chloro-4-methoxym6thyl-1,3,2-dioxa-, 2-chloro-3-methyl-i, 3,2-oxaaza- and 2-chloro-1,3,2-oxathiaphospholane, 2-chloro-1,3,2-dioxa-, 2-chloro-4-methyl-1,3,2-dioxa-, 2-chloro-4-propyl-5-ethyl-1,3,2-dioxa-, 2-chloro-5,5-dimethyl-1,3,2-dioxa- and 2-chloro-4-methyl-1,3,2-dioxa-phosphorinane.

Aliphatic or aromatic sulfenic acid bromides For example, the following are used as starting materials: alkylsulfenic acid bromides such as methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl, sec-butyl, n-amyl, isoamyl, tert-atnyl,

^ n-hexyl, 1,2,2-trimethylpropyl, n-heptyl, n-octyl, n-dodecyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-butoxyethyl, 2-chloroethyl, 2-ethyl mercaptoethyl sulfenic acid bromide.

The following are particularly suitable as aromatic sulfenic acid bromides: Phenyl-, 2-, 3- and 4-chloro-, 2-, 3- and 4-bromine-, 2,4-, 3,4- and 2,5-dichloro-, 2,4,5- and 2,4,6-trichloro-, 2-, 3- and 4-methyl-, 4-isopropyl-, 2-chloro-4-methyl-, 3-chloro-4-methyl-, 3-methyl-4-chloro-, 2-chloro-4-tert-butyl-, 2-, 3- and 4-nitro-, 2- and 3-chloro-4-nitro-, 2,5- and 3 , 5-dichloro-4-nitro, 2- and 3-methyl-4-nitro, 3-nitro-4-methyl, 4-methoxy, 2- and 3-methoxy

W 4-nitro-, 4-cyano-, 2- and 3-methyl-4-cyano-phenylsulfenic acid bromide. Particularly suitable aralkylsulfenic acid bromides are: Benzyl, 2-, 3- and 4-chlorine, 3,4-dichloro, 2-, 3- and 4-methyl-, 2-, 3- and 4-nitro, 2, 4-Dinitro-, 4-Methoxy-, 2-, 3- and 4-Cyanobenzyl- and Phenäthylsuli'ensaure-bromicl.

The 2-chlorophospholane or -phosphorinane derivatives to be used as starting substances have already been described in the literature; they can easily be prepared on an industrial scale by known methods from 1,2- or 1,3-glycols or the corresponding glycol-mercaptoalkanols or -alkyl or «

bBöü40

-arylaminoalkanols and phosphorus (III) chloride produced be, e.g .:

(CH ₀ )

CH ₂ -OH

+ PCI

(n- 0.1)

(CH ₀ V

PCI + 2. HCl

CH ₂ - (

D: _e aliphatic products still required as starting materials or aromatic sulfuric acid bromides are also known Way by reacting the corresponding mercaptans or thiophenols with bromine or by brominating cleavage of their disulfides, which are produced in situ from the mercapto compounds with sulfuryl chloride can be easily accessible. According to a particular embodiment, the sulfenic acid brooids are not isolated during their preparation but the reaction products of the corresponding disulfides or mercaptans or thiophenols and bromine in the "one-pot process" immediately with the relevant 2-chlorophospholanes or phosphorinanes implemented further within the meaning of the present invention. The claimed process can be carried out in the presence or absence of solvents or diluents. As such Practically all inert organic sovereigns come into consideration. However, chlorinated ones, where appropriate, have proven particularly useful aliphatic and aromatic hydrocarbons, such as methylene chloride, Carbon tetrachloride, dichloroethane, di-, tri- and tetrachlorethylene, Chloroform, carbon tetrachloride, gasoline, benzene, chlorobenzene, toluene and xylene; Ether, e.g. B. diethyl and di-n-butyl ethers, Dioxane, tetrahydrofuran, low molecular weight aliphatic ketones and Nitriles, for example acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, aceto and propionitrile.

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OFUGlNAt. , M * rcCTED

The reaction according to the invention can be carried out within a relatively wide temperature range, which varies depending on the nature of the starting materials to be converted. In general, preferably the reaction is carried zwichen -20 ° and +50 ⁰ C at -10 ° C to +30 ⁰ C. To carry out the process of the invention per mole Sulfensäurebromid 1 mol of 2-Chlorphospholan or -phosp ^ Orii-cji be used.

It has proven to be expedient to add the sulfenic acid bromide, diluted with one of the abovementioned solvents, to the solution or suspension of the phospholane or phosphorinane derivative at the specified temperatures with stirring and possibly cooling of the reaction mixture. After the addition is complete, the mixture is left to stand for about 1 to 3 hours, the solvent is then stripped off and the residue is subjected to fractional distillation. The products of the process are mostly colorless to yellow oils, some of which can be distilled under greatly reduced pressure without decomposition. If this is not possible, the compounds obtainable according to the invention can be "incipiently distilled" for the purpose of purification, ie freed from the last volatile impurities by prolonged heating under reduced pressure to slightly to moderately elevated temperatures. However, since the compounds are already obtained in high purity during the reaction, their further conversion is also possible without isolation and purification. -

The bromoalkyl-S-alk ^ l- or -aryl- (di) thiolphosphoric acid diester or ester amide chlorides are valuable intermediates for the production of insecticides

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cides, fungicides and other crop protection products.

The following examples provide an overview of the claimed methods:

Example 1t

Br-GH ₉ -CH ₉ -O. »

0 »P-Cl

24 g of dimethyl disulfide, dissolved in 300 ml of chloroform, are ^{mixed with 40 g of bromine at -10 to -15 g} C, the mixture is stirred until the bromine atmosphere disappears and the resulting solution is added to 63 g of 2- Chlorine-1,3 »2-dioxaphospholah in 100 ml of chloroform. The reaction mixture is then stirred for a further 30 minutes, then the solvent is evaporated off and the residue is distilled.

The yield is 74 g ( -58 fi of theory).

The 0- (2-bromoethyl) -S-methylthiolphosphoric acid diester chloride boils at 130 ° C / 2 torr.

Analysis: P

Calculated for C ₅ H ₇ BrClO ₂ PS (molecular weight 254): 12.2 δ

Found: $ 12.6>

Example 2: "

0, "■

Br-CH ₉ -CH-O _v "

■ .P-Cl

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A solution of 65 g of ethyl mercaptan in 200 ml of chloroform is mixed with 68 g of sulfuryl chloride at 0 ° C. and then 80 g of bromine are added dropwise to the reaction mixture at 0 ° to 10 ° C. The resulting solution is then added at 10 to 15 ° C. to 127 g of 2-chloro-1,3 »2-dioxaphospholane in 300 ml of chloroform. The mixture is stirred for a further hour, then the solvent is stripped off and the residue is distilled.
The yield is 238 g (= 89 $> of theory). The 0- (2-bromoethyl) -S-ethyl-thiolphosphoric acid diester chloride

pe

has the refractive index n ^ = 1.5172

Analysis; _{Br g}

Calculated for C ₄ H ₉ BrClO ₂ PS (molecular weight 268): 29 »8 # 11.95 Found: 29.91 # 11.42

Example 3:

0 ~ ■■■■ -. ■■. - - ■■■■

Br-CH ₀ -CH ₀ -O. "

^{2 2} P-Cl
Cl-GH ₂ -CH ₂ -S ⁷

48 g bis (2-chloroethyl) disulfide, dissolved in 300 ώΐ chloroiorm, are reacted with 40 g of bromine at -10 ° C. Then the Solution to 63 g of 2-chloro-1,3,2-dioxaphospholane in 100 ml of chloroform added, after stirring for one hour, the solvent is stripped off and the residue is "partially distilled".

The yield of 0- (2-bromoethyl -) - S- (2-chloroethyl) -thiolph08phor-. Acid diester chloride is 117 g (= Ί & $ of theory). Analysis: P

Calculated for C ₄ H ₈ BrCl ₂ O ₂ PS (molecular weight 302): 10.3 # results: 10.42 %

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O 9 8 3 0/2 0 4 5

Example 4; "'**'

O
Br-CH ₀ -CH ₀ -O "

^d ? P-Cl

First 68 g of sulfuryl chloride and then 80 g of bromine are added ^{dropwise at 0} ° C. to a solution of 11.0 g of thiophenol in 200 ml of chloroform. This mixture is added dropwise to 127 g of 2-chloro-1,3f2-dioxaphospholane at 10 to 15 ° C., after stirring for one hour, the solvent is drawn off and the residue is "distilled". The yield is 279 g (= 88 % of theory ).

The 0- (2-bromoethyl) - S-phenyl-thiolphosphoric acid diester chloride

25th
has a refractive index of n - ^ = 1.5905

Analysis; -g _r> 'ρ

Calculated for C ₈ H ₉ BrClO ₂ PS (molecular weight 316): 25.3 # 9.8% Found: ■ 25.37 % 9.54%

Example 5:

Br-CH ₀ -CH ₀ -O. "

Production takes place analogously to Example 4, but using of 4-chlorothiophenol.

The yield of 0- (2-bromoethyl) -S- (4 ^l -chlorophenyl) -thiülpLosphorsäurediester-chloride is 92% of theory.

Analysis; _{s p}

Calculated for C ₈ HgBrCl ₂ O ₂ PS (molar weight 350): 9.2 % ' 8.9 "<f<>

Found: . 9.57 % 9.29 %

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Example 6: "* ~

O Br-CH ₀ -CH ₀ -O. »

P-C1

The procedure is analogous to that described in Examples 4 and 5, but using benzyl mercaptan.

The yield beträft 73 i ° of theory.

The 0- (2-bromoethyl) -S-ienzyl-thiolphosphoric acid diester chloride

has the refractive index nip = 1.5655

Analysis: Br P

Calculated for CgH ₁₁ BrClO ₂ PS (molecular weight 330) ". ' 24.4 % $ 9.4

Found: 23.9% $ 10.0

Example 7:

CH,
■ ■ »■ ³ ■ Ö. ■

Br-CH ₉ -CH-O. "

^{d X} P-C1.

CH -S '

A solution of 141 g of dimethyl disulfide in 1000 ml of chloroform is mixed with 240 g of bromine at -10 ° C. and stirred until the bromine atmosphere disappears. The mixture is then added dropwise to 423 g of 2-chloro-4-methyl-1,3,2-dioxaphospholane in 600 ml of chloroform. The reaction mixture is then stirred for one hour, finally the solvent is stripped off and the residue is "partially distilled". The yield of 0- / ~ 3-bromopropyl (2JY ^r -S-methyl-thiolphosphorsäurediester chloride is 695 g (= 87 i "of theory) Analysis: 'P Cl

Calculated for C 1 HgBrClOgPS (molecular weight 268): 13.2 % 11.6 96 found: 12.32% 12.2 ° />

10 93 30 / 2ViS- ORIGINAL

Example 8;

GH,

■ · ³ O

Br-GH _o -CH-0 _v «■ -
^{d V} P-C1

A solution prepared as described in Example 3 of 1 mole of 2-chloroethylsulfenic acid bromide in 200 ml of chloroform is at 10 to 15 ° C to 141 g of 2-chloro-4-methyl-1,3,2 dioxaphospholane, dissolved in 400 ml of chloroform, added dropwise, then the mixture Stirred for one hour, the solvent removed and the residue "Distilled".

294 g (= 93 # of theory) of 0- £ "3-bromopropyl- (2J7"" ^s - (2'-chloroethyl) thiol-phosphoric acid diester chloride are obtained with the

27
Refractive index η - ^ = 1.5260

Analysis; . ■ _. SP

Calculated for C ₅ Hi ₀ BrCl ₂ O ₂ PS (516 molecular weight): 10.1 # 9.8 Found: 10.93 $ 10.24

Example 9t CH

«0
Br-CH ₀ -CH-O. »

A solution, prepared as described in Example 4, of 1.5 mol of phenylsulfenic acid bromide in 1000 ml of chloroform is added dropwise at 5 to 15 ° C. to 212 g of 2-chloro-4-methyl-1,3,2-dioxaphospholane in 400 ml of chloroform . After stirring the mixture for one hour, the solvent is evaporated and the residue is "partially distilled". The yield of 0- / ~ "3-bromopropyl- (2j [7-S-phenyl-thiolphosphoric acid diester chloride is 465 g (= 94 % of theory).

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Analysis: * _B ~ _p

Calculated for CQH ₁₁ BrClO ₂ PS (molecular weight 330): 24.2 # 9.7% 9.4 Found: 24.0% 10.12 % 9.77

Example 10:

Br-CH-CH-O _v »

^N P-C1

A solution of 1 mol of methylsulfene acid bromide in 300 ml of chloroform, prepared as in Example 1, is added dropwise at 10 to 15 ° C. to 155 g of 2-chloro-4,5-diethyl-1,3,2-dioxaphospholane in 300 ml of chloroform. After stirring the reaction mixture for one hour, the solvent is drawn off and the residue is "partially distilled". In this way, 225 g (= 80 $> of theory) of 0- ^ f ~ 3 ~ bromobutyl- (227 ~ S-niethylthiolphosphoric acid diester chloride with the

2 pp
Refractive index η ^ = 1.5002

^Anal .Y ^8ei Br Cl

Calculated for C ₅ H ₁₁ BrClO ₂ PS (molecular weight 282). $ 28.4> $ 12.6>

Found: 28.0 ^ 12.4 %

Example 11:

Cl-CH ₉ 0
^ CH-O · »
Br-CH ₉ '·. P-Cl
CH S

A solution prepared as described in Example 1 of 1 mole of methylsulfene bromide in 300 ml of chloroform is heated at 10 to 15 ° C to 175 g of 2-chloro-4-chloromethyl-1,3,2-dioxaphospholane in 300 ml Chloroform was added dropwise, after stirring the mixture for one hour

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The solvent is drawn off and the residue is "partially distilled". The yield is 264 g (= 87 % of theory). The refractive index of the 0 - ^ "~ 1-chloro-3-bromopropyl- (2j / -S-

22 'S methylthiolphosphoric acid diester chloride is η τ - 1.5317

Analysis; '■ Cl Br

Calculated for C ₄ H ₈ BrCl ₂ O ₂ PS (molecular weight 302); 23.5 % 26.5 # Found: 23.77 # $ 27.0

Example 12;

Br-CH ₀ -CH ₀ -S "
. - ■ ^N P-C1
CH ₅ -S "

A solution of 1 mole Methylsulfensäurebromid in 300 ml of chloroform at 5 was added dropwise to 10 ⁰ C to 143 g of 2-chloro-1,3,2-oxathiaphospholan in 400 ml of chloroform. After stirring the mixture for one hour, the solvent is drawn off and the residue is "partially distilled". 200 g (= 74 % of theory) of S- (2-bromoethyl) - S ^l methyl-dithiolphosphoric acid diester chloride with the refractive index n ² _D = 1.6041 are obtained

Analysis; Br P

Calculated for C ₅ H ₇ BrClOPS ₂ (molecular weight 270): 29.6 $> .11.5 Found: 30.0 % 12.0 ^

Example 13; CH

' ³ O
Br-CH ₀ CH ₀ -CH-O "

^{d ά} ' ^N P-C1

A solution of 1 mol. Of methylsulfenic acid bromide in 300 ml of chloroform it is added dropwise at 10 to 15 ° C. to 155 g of 2-chloro-4-methyl-13,2-dioxaphos

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phorinan. After the mixture has been stirred for one hour, the solvent is stripped off and the residue is "partially distilled". The yield is 228 g (= 81 $> of theory); dts 0-J4-J3roiabu.tyl (2) 1 -S-methylthiölphosphorsäurediester-chloride has the refractive index n ²² '^ = 1.5083

Analysis; ρ

Calculated for C ₅ H ₁₁ BrClO ₂ PS (molecular weight 282): 11.0 # Found: 11.50%

Example 14-t

CH,

Br-CH ₂ -CH ₂ -N _x ^ O CH ₃ -S ^ ^N C1

A solution of 0.4 mol of methylsulfenic acid bromide in 200 ml of chloroform is added at 10 to 15 ° C. to 56 g of 2-chloro-3-methyl-1,3- _f 2-oxaazaphospholane in 200 ml of chloroform. After stirring the reaction mixture for one hour, the solvent is stripped off and the residue is "partially distilled". 88 g (= 83 % of theory) of the N, S-dimethyl-N- (2-bromoethyl) thiolphosphoric acid monoester & mid-chlorici are obtained.

^Anal .Y ^8e: 'N Cl P.'. ,,,

Calculated for C ₄ H ₁₀ BrClNOPS (molecular weight 267): 5.2 % 13.3 96 $ 11.6

Found: 5.7 96 13 »7 # $ 11.5

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Claims (9)

16 6 B O 4 O Claims: Jl 1) Process for the production of bromoalkyl-S-alkyl or -aryl-CdiJthiolphosphorsäurediester- or -esteramidchloriden, characterized in that 2-chlorophospholane or phosphorinane derivatives of the general formula - E ₂ ' Λ, with aliphatic or aromatic sulfenic acid bromides. the general formula R-S-Br ■ ■ ■ · converts, where in the aforementioned formulas the radicals IU to Rg for hydrogen atoms, alkyl, alkoxyalkyl or haloalkyl radicals stand, R ™ is an optionally substituted alkyl, Aryl or aralkyl radical, X is an oxygen or sulfur atom or represents an N-alkyl or arylamino group and η has the value zero or 1. 2) Method according to claim 1, characterized in that one 2-chloro-1,3,2-dioxa- or -1,5,2-oxaaza- or -1,3,2-oxathiaphospholane the general formula -π- 1R Ra run R; P-Cl O' with aliphatic or aromatic sulfenic acid bromides the general formula R ₇ -S-Br reacted, where in the aforementioned formulas R-, Rp, R ₁ -, Rg, R ₇ and X have the meanings given in claim 1. 3) Process according to claim 1, characterized in that 2-chloro-1,3 »2-dioxaphosphorinanes of the general formula R, R « R, P-Eq with sulfenic acid bromides of the general formula R ₇ -S-Br converts, where in the aforementioned formulas the radicals R ^ to R _{7 have} the meanings given in claim 1 · Le A 11 081 -ie- ORSQiNAL IMSPECTED 4) Method according to claim 1 to 3, characterized in that the reactions between -20 and + 50 ° C, preferably at -10 to + 30 ° C. 5) Method according to claim 1 to 4, characterized in that one sulfenic acid bromide and 2-chlorophospholane or phosphorinane derivative used in a molar ratio of 1: 1. 6) Method according to claim 1 to 5, characterized in that the reactions are carried out in the presence of solvents or diluents performs. - 7) Method according to claim 1 to 6, characterized in that the solvent or diluent used is chlorinated aliphatic hydrocarbons, preferably dichloromethane or tetrachloromethane used. 8) Method according to claim 1 to 7, characterized in that one the 2-Ghlorphospholan- or -phophorinan-Lerivate with the Reaction products from aliphatic or aromatic lisulfides or kercaptans or thiophenols and bromine in one "One-pot process" without isolation of the corresponding sulfic acid bromides implements. \ 9) Bromoalkyl-S-alkyl- or -aryl-CdiJ-thiolphosphoric acid diester or - esteramide chlorides of the formula Br-C-t R ₂ C- ^R 4 Rc 0 t 5 H C-X-P-Eq Le A 11 081 - 19 - in which R ₁ to R ₇ , X and η have those specified in claim 1. Le A 11 081 - 20 - 109830/2045