DE1668040C3 - Process for the preparation of bromoalkyl-S-alkyl or aryHdi) thiolphosphoric acid diester or ester amide chlorides - Google Patents

Description

with aliphatic or aromatic sulfenic acid bromides of the formula

R-7 S Br

reacted, where the radicals R ₁ to R _{6 are} hydrogen atoms, alkyl, alkoxyalkyl or haloalkyl _{radicals, R 7 is} an optionally substituted alkyl, aryl or aralkyl radical, X is an oxygen or sulfur atom or an N-alkyl or - Represents arylamino group and »i has the value 0 or 1.

2. The method according to claim 1, characterized in that that the 2-chlorophospholane or -phosphorinane derivatives with the reaction products from aliphatic or aromatic disulfides or mercaptans or thiophenols and converts bromine in a "one-pot process".

In the production of O-bromoalkylthiolphosphoric acid diester chlorides however, this method would have the disadvantage that as starting materials required, in the alkyl radical brominated 0,0-dialkylphosphorous acid diester chlorides . (Dialkylchlorphosphite) are difficult to access. So they became The aforementioned 0-bromoalkyl compounds have not yet been described in the literature either.

Thiolphosphoric acid c-S-monoester amide chlorides can also be used by reaction of O-alkylphosphorous acid ester dichlorides with sulfenic acid carides according to the equation

Cl

RO-P-Cl + R'- S- N (R ¹¹ J ₂
O

► (R ") ₂ N-P-Cl + RCl

R'S

after K. A. P e t r ο v, N. K. B 1 i ζ η j i k and V. A.

J ₅ Savosknok, Z. obsc. Chim., 31, 1361 [1961]), where R and R 'are as defined above, while R "is a preferably lower alkyl radical.
In this case too, starting materials that are difficult to access are required in the preparation of thiolphosphoric ester amides with a 2- or 3-bromoalkyl group on the nitrogen.

Finally, one-step processes for the production of S, S - dithiolphosphoric acid diester - halo-

genides with two different organic residues have not yet been described in the literature at all been.

It has now been found that bromoalkyl-S-alkyl- or - aryl - (di) thiolphosphoric acid diester - or

-esteramidchloride can be obtained with very good yields and in excellent purity if one 2-chlorophospholane or -phosphorinane derivatives of the formula

45

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 to form O.S-thiolphosphoric acid diester chlorides react (cf. K. A. Petrov, G. A. Sok oil ski j and B. M. P ο 1 e e s, Z. obsc. Chim., 26, 3381 [1956], reported in Chem., Abstr., 51, 1957, 9473-9474):

(RO) ₂ P-Cl + R'-S-Cl
O

(D

fto

/ R

P-Cl

(IN THE)

C O

> RO-P-Cl + RCl

R'S

R in the above equation means an alkyl and R 'is an alkyl or aryl radical.

with aliphatic ode ¹ × aromatic Sulfensäurebromiden of formula (IV).

R -, - S-Br (IV)

implements.

In the above formulas, the symbols R _{1 to} R stand for hydrogen atoms, alkyl, alkoxyalkyl or haloalkyl radicals, R _{7 stands for} an optionally substituted alkyl, aryl or aralkyl radical, and X is an oxygen or sulfur atom or an N-alkyl or N- Arylamino group and 11 has the value 0 or 1.

The smooth and uniform course of the original Procedure is completely surprising. In no way could it be foreseen that the above- ι ο Mentioned 2-chlorophospholanes or -phosphorinanes with sulfenic acid bromides with splitting of the heterocyclic Ring and formation of 2- or 3-3romalkvl - thiolphosphoric acid esters or estcramide chlorides would react. '5

Geeen über the methods mentioned at the beginning for the preparation of thiol or dithiol phosphoric acid ester The process according to the invention is characterized by and ester amide chlorides with bromoalkyl radicals offers a number of key advantages. This includes, above all, easy access to the starting materials uniform course of the reaction, good yields and very simple method of implementation.

If, for example, 2-chloro-1,3,2-dioxanephospholane is used or -dioxaphosphorinane and methyl ι; sulfenic acid bromide as starting materials, so w.rd der The course of the implementation according to the process is illustrated by the following equation (V):

N ₁ S - dimethyl - N - (2 - bromoethyl) - thiolphosphoric acid monocstcramide chloride:

CH ₃

CH ₂ -N

P-Cl + CH ₃ -S-Br

CH ₂ -O

(VIl)

CH ₁ O

^ CH ₂ -O _x

(CH ₂ ) ,,

CH ₂ -O ⁷

3 °

35

(V)

Br-CH ₂ - (CH ₂ J _n CH ₂ -O- P-Cl CH ₃ - S

The reaction of 2-chloro-1,3,2-oxathiaphospholane proceeds in the same way with phenylsulfenic acid bromide in terms of equation (VI):

> - Cl +

CH ₂ -S

(Vl)

- Br-ClU-CH, - SP-Cl

Similarly, the reaction of 2-chloro-3-methyl-1,3,2-oxaazaphospholane with methylsulfonic acid chromide leads to> Br-CH ₂ -CH ₂ -N-P-Cl according to the following reaction scheme (VH)

CH ₃ - S

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

The symbols R ₁ to R ₍ , but in formula (III) preferably denote hydrogen atoms or optionally halogen or lower alkoxy-substituted alkyl radicals with up to 4 carbon atoms, such as the methyl, chloromethyl or methoxymethyl radical. R ₇ preferably represents a straight-chain or branched alkyl radical. or alkenyl radical having 1 to 12 carbon atoms, which can be substituted by 1 to 4 halogen atoms, a lower alkoxy, alkyl mercapto, carbonyl, carboxyl, alkoxycarbonyl, alkylcarbonyl, dialkylaminocarbonyl or nitrile group; furthermore, R ₇ preferably denotes one aryl or aralkyl, especially phenyl or

Benzyl radical.
X preferably denotes oxygen, sulfur, one

lower N-alkyl or the N-phenyl radical.

Examples of phospholane or phcsphorinane derivatives to be implemented according to the invention are im named individually:

2-chloro-l, 3,2-dioxa-, 2-chloro-4-meiliyl-l, 3,2-dioxa-, 2-chloro-4-chloromethyl-1,3,2-dioxa-, 2-chloro-4,5 - dimethyl - 1,3,2 - dioxa-, 2 - chlorine - 4 - methoxymethyl-1,3,2-dioxa-, 2-chloro-3-methyl-1,3,2-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 can be used as starting materials, for example Find use:

Alkylsulfenic acid bromides such as methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl, sec-butyl, n-amyl-, isoamyl-, tert-amyl-, n-hexyl-, 1,2,2-trimethylpropyl-, n-heptyl, n-octyl, n-dodecyl, 2-methoxyethyl, 2-ethoxy-ethyl, 2-n-butoxy-ethyl, 2 - chloroethyl, 2 - ethyl mercaptoethyl - sulfenic acid bromide.

As aromatic sulfenic acid bromides are above all

suitable:

Phenyl-, 2-, 3- and 4-chloro-, 2-, 3- and 4-bromo-, 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-, S-chloro-4-methyl-, 3-methyl-4-chloro- ₁ 2-chloro-4-tert-butyl-, 2-, 3- and 4-nitro-, 2- and 3-chloro-4-nitro-, 2,5- and SS-dichloM-nitro-, 2- and 3-methyl-4-nitro, 3-nitro-4-methyl, 4-methoxy, 2- and 3-methoxy-4-nitro, 4-cyano, 2 and 3-methyl-4-cyanophenylsulfenic acid -bromide.

Particularly suitable aralkylsulfenic acid bromides are:

Benzyl, 2-, 3- and 4-chloro, 3,4-dichloro, 2-, 3- and 4-methyl-, 2-, 3- and 4-nitro, 2,4-dinitro, 4-methoxy, 2-, 3- and 4-cyanobenzyl and phenethylsulfenic acid bromide.

The 2-chlorophospholane to be used as starting substances - or - phosphorinane derivatives have already been described in the literature; you can even on an industrial scale by known methods easily from 1,2- or 1,3-glycols or the corresponding glycols - mercaptoalkanols or -alkyl- or -arylaminoalkanols and phosphorus (HI) chloride be produced, e.g. B .:

CH ₂ -OH

(CH ₂ ). + PCI.,

CH ₂ -OH

(VIII)

(CH ₂ ) "PCI + 2 HCl

CH ₂ -O

(H = 0.1)

35

40 furan, low molecular weight aliphatic *. · Ketones and nitriles, for example acetone, methyl ethyl, methyl isopropyl and methyl isobutyl octone, aceto and Pm- ^P "Du / reaction according to the invention can be carried out within a larger temperature range which varies depending on the type of starting materials to be converted . In general carried out between -20 and +50 'C ^1, preferably be. -IO to +30 "C to carry out the inventive method per mole Sulfensäurebromid 1 mol of 2-Chlorphospholan be used or -phosphorinan.

It has proven to be useful to dilute the sulfenic acid bromide with one of the above Solvents - at the stated temperatures with stirring and possibly cooling of the reaction mixture to be added dropwise to the solution or suspension of the phospholane or phosphorinane derivative. After the addition is complete, the mixture is left to stand for about 1 to 3 hours, then the The solvent is removed and the residue is subjected to fractional distillation. The process products are mostly colorless to yellow oils, some of which under greatly reduced pressure without decomposition can be distilled. If this is not possible, the compounds obtainable according to the invention can be used "and shimmer" for the purpose of cleaning, d. H. by prolonged heating under reduced pressure remove the last volatile impurities at slightly to moderately elevated temperatures. There However, the compounds are already obtained in high purity in the reaction, their further implementation is also possible without isolation and cleaning.

The bromoalkyl-S-alkyl or -aryl- (di) thiolphosphoric acid diester not yet known from the literature and -estcramidchloridc are valuable intermediates for the production of insecticides. Fungicides and other plant protection products.

The following examples provide an overview of the claimed method:

The aliphatic ones still required as starting materials or aromatic sulfenic acid bromides can also be reacted in a known manner of the corresponding mercaptans or thiophenols with bromine or by brominating cleavage of them Disulfides, which can be prepared in situ from the mercapto compounds with sulfuryl chloride, easily accessible. According to a special embodiment, the sulfenic acid bromides are used in their production not isolated, 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. Practically all inert organic solvents can be used as such. However, chlorinated aliphatic and aromatic hydrocarbons, such as methylene chloride, have proven particularly useful. Carbon tetrachloride, dichloroethane, di-, tri- and telrachlorethylene. Chloroform, carbon tetrachloride. Gasoline, benzene, chlorobenzene, toluene and xylene: ether, e.g. B. diethyl and di-n-butyl ethers, dioxane. Tetrahydro example 1
Br-CH ₂ -CH ₂ -OO

P-Cl

CH ₁ -S

24 g of dimethyl disulfide, dissolved in 300 ml of chloroform, are added at -10 to -15 ° C. with 40 g of bromine, stir the mixture until the bromate atmosphere disappears and add the resulting solution at 10 up to 20 C to 63 g of 2-chloro-1,3,2-dioxaphospholane in 100 ml of chloroform. Then the reaction mixture Stirred for a further 30 minutes, then the solvent is evaporated off and the residue is distilled.

The yield cheating 74 g (- 5 S ¹ O of theory).

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

Analysis for CJLBrCK) ₂ PS (molecular weight 254):

Calculated ... P 12.2 "»:
found P 12.6 ",,.

Example 2
Br-CHv-CU-O O

Cl

C ₂ H ₅ S

The O - (2 - bromoethyl) - S - phenyl - thiolphosphorsäurcdicster-chloride has a refractive index of ir = 1.5905.

Analysis for C "H ₁₁ BrCIO ₂ PS (molecular weight 316):

Calculated ... Br 25.3, P 9. «%; found .... Br 25.37, P 9.54%.

A solution of 65 g of ethyl mercaptan in 200 ml of chloroform is mixed at 0 C with 68 g of sulfuryl chloride added and then 80 g of bromine were added dropwise to the reaction mixture at 0 ° to 10 ° C. Then you add the resulting solution 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 drawn off and the residue is distilled.

The yield is 238 g (= 89% of theory).

O - (2 - bromoethyl) - S - ethyl - thiolphosphoric acid diester chloride owns the Breclunmsindcx ii. " = 1.5172.

Analysis for C ₄ H ₁ ) BrCIO ₂ PS (molecular weight 268):

Calculated ... Br 29.8, S 11.95%;
found .... Br 29.91. S 11.42%.

Example 3 Example 5

Br CII, -CM, O O

Cl CM, CM, -S

Cl

48 g of bis (2-chloroethyl) disulfide. dissolved in 300 ml of chloroform, are reacted with 40 g of bromine at -IOC. The solution then becomes 63 g of 2-chloro-1,3,2-dioxaphospholane added in 100 ml of chloroform, the solvent removed after stirring for one hour and the residue "distilled".

The yield of O- (2-Bronuilhyl -) - S- (2-ehloiäthyl) - thiolphosphorus diester chloride amounts to Il7g (= 78% of theory).

Analysis for C ₁ II _n Bi-CLO ₂ PS (molecular weight 302):

Calculated ... P 10.3%:
Findings .... P 10.42%.

Example 4
Br CM ₂ CIIj-C) O

P-Cl Br-CH ₂ -CH -, - OO

P-Cl

Production takes place as in Example 4, but using 4-chlorothiophynol.

The yield of O- (2-bromoethyl) -S- (4'-chlorophenyl) - thiolphosphorsäurcdicstcr - chloride entrusts 92% of the theory.

Analysis for QH _H BrCl ₂ 0 ₂ PS (molecular weight 350):

Calculated ... S 9.2, P 8.9%; rounded .... S 9.57, P 9.29%.

Example 6

Br CH ₂ CH, OO

P Cl

CH, S

Hs is described in a manner analogous to Example 4 and above, but using benzyl mercaptan procedure.

The yield is 73% of theory. The O - (2 - bromoethyl) - S - hen / yl - thiolphosphoi, is acid diesel chloride possesses / l the refractive index n 1.5655,

Analysis for (',, M ₁₁ BrClO ₂ PS (molecular weight 130):

Calculated . .. Br 24.4. P 9.4%; found ,, .. Br 23, 'λ Ρ 10.0%.

Example 7

CH, Br- ( ¹ H ₁ -CH - OO

\ Il ρ ei

CH., - S

To a solution of 110 μ thiophenol in 200 ml
Chloroform is added dropwise at 0 C, first 68 μ of sulfuryl chloride and then 80 μ of bromine, these
Mixture is at 10 to 15 ° C to 127 g 2-chlorine line solution of 141 μ Dimethyldisiillkl in 1000

1,3,2-dioxaphospholane is added dropwise, after one hour of r, s chloroform is mixed with 240 g of bromine at -10 C Stir the solvent removed and the back and until the disappearance of the bromine atmosphere | it read "partially distilled", the yield is 279 g stirs. The mixture is then added dropwise I = 88 "/» of theory). 23 g of 2 - chloro - 4 - methyl · 1.3.2 · dioxaphosphole

in 600 ml of chloroform. Thereafter, the reaction mixture Stirred for an hour, finally the solvent is drawn off and the residue is "partially distilled".

The yield of O- [3-bromopropyl- (2)] - S-ynethylthiolphosphoric acid diester - chloride is 695 g (= 87% of theory).

Analysis for C ₄ H ₁₁ BrClO ₂ PS (molecular weight 26S):

Calculated ... Cl 13.2, P 11.6%;
found .... Cl 12.32, P 12.2%.

Example p

CH,

Br-CH ₁ -CH-O O

P-Cl

Cl-CH ₁ -CH ₁ -S

A solution of 1 mole of 2-chloroethylsulfenic acid bromide prepared as described in Example 3 in 20 (fml chloroform becomes 141 g at 10 to 15 ° C 2 - chloro - 4 - methyl - 1,3,2 - dioxaphospholane, dissolved in 400 ml of chloroform, added dropwise, then the The mixture was stirred for one hour, the solvent was stripped off and the residue was "partially distilled".

294 g (-93% of theory) of O- [3-bromopropyl are obtained - (2)] - S - (2 '- ehloräthy!) - thiolphosphoric acid diester chloride with the refractive index »ι --- 1.5260.

Analysis door C ₅ H ₁₁₁ BrCl ₂ O-PS (molecular weight 316):

Calculated ... S 10.1, P 9.8%;
found .... p 10.93. P 10.24%.

Example 9

ΠΙ.,
Br CH, CII OO

\ I

\ ι
Pc

/ Vs'

B ice ρ ic
CH,

H)

Br-CH - CH O

. I!

p_.

Cl

CH ₁ S

A solution prepared as in Example 1 of 1 mol of Melhylsulfcnsäurcbromid in 300 ml of chloroform is added dropwise at 10 to 15 C to 155 g of 2-chloro 4,5-dimethyl-1,3,2-dioxaphospholane in 300 ml of chloroform. After the reaction mixture has been stirred for one hour, the solvent is drawn off and the residue is "dissolved". In this way, 225 g (80% of theory) of O- [3-bromobutyl - (2)] - S - methylthiolphosphoric acid diester chloride with the refractive index / r '= 1.5002 are obtained.

Analysis for C ₅ H _n BrCIO ₂ PS (molecular weight 282):

Calculated ... Br 28.4. Cl 12.6%;
found .... Br 28.0. Cl 12.4%.

Example 11
.ίο Cl- CIl,

YlI O O

Br-CH, P Cl

Kine manufactured as described in example I!

. | o Solution of 1 mole of methylsulfenic acid bromide in 300 m

Chloroform is at 10 to 15 C λι 175 g of 2-chlorine

4-chloromethyl-1.3.2-diox; iphospholane in 300 ml of ChIo

ro form dripped, after cooling for one period dei

Mixture stripped off the solvent and dei

., s residue "andesiillicrt".

The yield is 264 g (S7% of theory). The refractive index of the O-1 I -chloro-3-bromo-propyl- (2) I-S-methylthiolphosphorus chloride diester chloride is η; 1.5317.

^s "Analysis for C ₄ II _n BiCl ₃ O ₁ PS (molecular weight 302);

Calculated ... Cl 23.5. Hr 26.5%:
found .... Cl 23.77, Hr 27.0%.

A solution, prepared as described in Example 4, of 1.5 mol of phenylsulfonisurcbromyl is added dropwise in K) OOmI chloroform at 5 to 15 "C at 212 g 2-chloro-4-methyl-1,3,2-dioxtiphospholane in 400 ml Chloroform. After the mixture has been stirred for one hour, the solvent is evaporated off and the residue is distilled off.

The yield of O- [3-bromopropyl- (2) | -S-phenylthiolphosphoric acid diester chloride was 465 m (= 94% of theory),

Analysis for C ₁₁ H _n BrClO ₂ PS (molecular weight 330):

Calculated,., Br 24.2, S 9.7. P 9.4%; found .... Br 24.0. S 10.12. P 9.77%.

Example 12

Ur-CH ₄ -CHj-SO

P-Cl

Cl I., - S '

A solution of 1 mole of methylsulfen sliurebiOmid in 100 ml of chloroform at 5 to KVC is added dropwise to 143 g of 2> chlorine · 1,3,2 · oxuthiaphaspholim Ir 400 ml of chloroform, after stirring for one minute

Mixture, the solvent is drawn off and the residue "andistillicrt". 200 g (= 74% of theory! Of S- (2-bromoethyl) - S'-mclhy! - dithiolphosphoric acid dicloride with a refractive index n ' = 1.6041 are obtained.

Analysis door C ₁ H ₇ BrClOPS ₂ (molecular weight 270):

Calculated ... Br 29.6, P 11.5%:
liclunden .... Br 30.0, P 12.0%.

Example 13
CH ₃

Br-CH ₁ CHv-CH-OO

P-Cl

A solution of 1 mole of methylsulfenic acid bromide in 300 ml of chloroform is added dropwise at 10 to 15 ° C. to 155 g of 2-Chloι ■ -4-methyl-1,3,2-dioxaphosphorinane. _J5 Nacli stirring the mixture is taken off the Lösungsmiltel and the residue "distilled".

The yield is 228 g (= 81% of theory); the O -1 "4 - bromobutyl - (2)] - S - methyl _{thiolphosphorus-J0}

acid diester chloride has the refractive index ii: ' = 1.5083.

Analysis for C ₅ H _n BrCIO ₂ PS (molecular weight 282):

Calculated
found .

P.
P.

1.0%;
1.50%.

example
CH,
Bi-CH ₂ -CH ₂ -N

CH ₁ S

14th

Cl

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-1,3,2-oxaazaphospholane in 200 ml of chloroform. After stirring the reaction mixture for one hour, the solvent is drawn off and the residue "andistillicrt". 88 g (= 83% of theory) of N, S-dimethyl-N are obtained - (2 - bromoethyl - thiolphosphoric acid monosteramide chloride.

Analysis for C ₄ H ₁₀ BrCINOPS (molecular weight 267):

Calculated ... N 5.2, Cl 13.3, P 11.6%;
found .... N 5.7, Cl 13.7. P 11.5%.

Claims (1)

Patent claims: I. Process for the preparation of bromoalkyl-S - alkyl - or - aryl - (di) thiolphosphoric acid diester or ester amide chlorides, d ad u r c h applicable en η ze i c h η e t that 2-chlorophospholane or phosphorinane derivatives of the formula C X