DE1244179B - Process for the preparation of polythio-amidothiolphosphoric acid esters - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C07f

German KL: 12 ο - 26/01

Number:
File number:
Registration date:
Display day:

Ν / ς

1 244 179
C34948IVb / 12o
January 26, 1965
June 13, 1967

The invention relates to a method of manufacture of polythio-arnidothiolphosphoric acid esters of the general formula

t
R ¹ P (S) _{n + 1} R

R ² NR ³

which is characterized in that one has an amidothiophosphoric acid ester the general formula

R ¹ POR ¹
R ² NR ³

with a sulfenyl halide of the general formula

R (S) _n X

at 0 to 125 ° C, preferably 20 to 100'C, optionally in the presence of an inert solvent, where in the formulas η 1 or 2, X is chlorine or bromine, R is an organic radical with 1 to 18 carbon atoms which is free from is functional groups that react with amidothiolphosphoric acid esters, R ^{1 is} an organic radical with 1 to 18 carbon atoms which is bonded to the phosphorus atom via an oxygen or sulfur atom, R and R ^{3 are} hydrogen or organic radicals and R ^{4 is} an alkyl - or aralkyl group.

The R in the sulfenyl halide can be alkyl, cycloalkyl, aryl, or heterocyclic Group having no more than 18 carbon atoms and preferably no more than 12 carbon atoms be.

Preferred sulfenyl halides are those in which the alkyl group has 1 to 6 carbon atoms, in particular has 1 to 3 carbon atoms and polyhaloalkylsulfenyl or thiosulfenyl halides, in which the halogens are chlorine or bromine. The preferred radicals are from 0 to 6 halogen atoms and zero to one carbalkoxy group as substituents. Substituents of the basic carbon chain can halogens, i. H. Fluorine, chlorine, bromine and iodine, nitro, cyano, keto or aldehyde groups and other radicals containing the C = O moiety.

Method of manufacture

of polythio-amidothiolphosphoric acid esters

Applicant:

California Research Corporation,

San Francisco, Calif. (V. St. A.)

Representative:

Dr. W. Beil, A. Hoeppener, Dr. HJ Wolff
and Dr. H. Chr. Beil, lawyers,
Frankfurt / M.- Höchst, Adelonstr. 58

Named as inventor:
Philip Stewart Magee, San Rafael, Calif .;
Larry Edward Stevick, Berkeley, Calif. (V. St. A.)

Claimed priority:
V. St. v. America January 27, 1964 (340 501)

R ¹ can be an alkyl, aryl, heterocyclic or cycloaliphatic group bonded via an oxygen or sulfur atom, each having not more than 18, especially not more than 12 carbon atoms. The remainder can contain substituents which do not react with the sulfenyl halide. Such substituents can be halogens, ether, thioether, keto or aldehyde groups and other radicals containing the C = O group, nitro groups or cyano groups.

Preferred R ¹ groups are lower saturated alkoxy or lower saturated alkyl mercapto groups with up to 6 carbon atoms.

R ² and R ³ can be the same or different. In general, R ² and R ^contain;? no more than 12 carbon atoms, especially no more than carbon atoms. R ² and R ³ can be alkyl, hydrocarbylcarbonyl groups, ie acyl, hydro

709 610/576

carbyloxycarbonyl, aryl hydrocarbon groups having no more than 10 carbon atoms, and heterocyclic groups having no more than one heteroatom, that is, oxygen or nitrogen, and no more than 10 carbon atoms. In general, R ² and R ^{3 are} saturated. Most often R ² and R ³ contain 1 to 10 carbon atoms and

1 nitrogen atom, or they are free of nitrogen or denote hydrogen. Preferably either R ² or R ^{3 represents} a hydrogen atom.

R ⁴ is an alkyl or aralkyl group with generally no more than 1.2 carbon atoms, usually no more than 6 and preferably no more than 3 carbon atoms. Examples of R ⁴ are methyl, ethyl, propyl, benzyl, / j-phenetyl or dodecyl groups. Since R ^{4 is} not contained in the end product, it only has to be substitutable by a halogen.

The reaction of sulfenic acid halides with thionocarbamic acid esters or benzenesulfonylthioureas, as they are from the USA patent specification

2,813,902 and J. Am. Chem. Soc, 82, 1960, p. 155

to 158, is known, provides no information about the course of the claimed method. the known reaction of a perchloromethylmcrcaptan with compounds that contain the thionocarbonyl group

- Οίο contain, so where the central atom is a carbon atom is, from which a double bond originates, thus does not allow any conclusion as to the mode of reaction the Amidothiopbosphorsäureester to, in which the central atom is a phosphorus atom with a is covalent bond to sulfur, d. i.e., where the heavy weight of the positive charge is at Phosphorus lies.

Those molecular regions that are responsible for the

methods according to the invention for the preparation of polythio-amidothiolphosphoric acid esters from sulfonyl halides and amidothiophosphoric acid esters are important, the following equation shows:

S.
\
- P - OR ⁴ + - S - X

- N -

- P - S - S - + R ⁴ X

- N-

R ¹ , R ² , R ³ and R behave relatively passively.

The reaction takes place by mixing the sulfenyl halide and the amidothiophosphoric acid ester at the specified temperatures, if appropriate in the presence of an inert solvent. With a few connections, a small amount of mild Friedel-Crafts catalyst may be required.

Inert hydrocarbons or halogenated hydrocarbons can be used as solvents, such as chloroform, benzene, hexane, octane, toluene, xylene, chlorobenzene or fluorobenzene. Inert esters or ethers can also be used. If the reaction increases Performed temperature, it is appropriate to use a solvent that is at the desired Temperature is boiling. The concentration of the reactants is not critical; the concentrations generally vary in the range from 0.5 up to 2 moles.

The catalysts that may be used are mild Friedel-Crafts catalysts, such as B. mercury chloride, copper (ü) chloride, antimony trichloride or zinc chloride.

example 1

Production of N-phenyl-O-ethyl-carbethoxydichloromethyldithiophosphoramidate

N-phenylamidothiophosphoric acid diethyl ester and Ethoxycarbonyldichloromethylsulfenyl chloride was dissolved in benzene and refluxed for 4 hours heated. The solvent was then distilled off. The analysis of the reaction product showed:

Analysis:

Calculated ... Cl 17.55, S 15.81, P 7.66;
found ... Cl 18.15, S 16.00, P 7.72.

Example 2

Production of N-methyl-O-ethyl-carbäthoxydichlormethyldithiophosphorainidat

N-methylaraidothiophosphoric acid diethyl ester was added dropwise to ethoxycarbonyldichloromethylsulfenyl chloride given, whereupon a violent reaction began with the formation of ethyl chloride. The flask was then heated to remove the ethyl chloride. It turned orange get oil.

Analysis:

Calculated ... Cl 20.7, S 18.7, P 9.05;
found ... Cl 21.0, S 19.25, P 9.1.5.

The table below shows a number of connections that were made after the Procedures of Examples 1 or 2 were prepared.

link 2 temperature
° C Time
hours solvent C.
calculated Ί
found S.
calculated found 1
calculated found Melting point
"C O
T
C ₂ H ₅ OP (S) ₂ CCl ₂ CCl ₂ H 30th 1 chloroform 33.2 35.5 30.0 28.7 9.68 8.95 84 to 89 N
χ / Γ ο " ^Ί
ί
CH ₃ OP (S) ₃ CCb O
ΐ
C ₂ H ₅ OP (S) ₃ CCl ₃ 25th 1 benzene 34.1 34.7 15.4 15.4 7.45 7.70 NHCH ₂ - HNC ₆ H ₅ 0
T
C ₂ H ₅ OP (S) ₂ CCL, Reflux temperature 4th chloroform 26.7 26.7 24.1 24.2 7.78 7.61 128 to 131 HNC ₆ H ₈ 0
ΐ
C ₂ H ₅ OP (S) ₂ CCI ₂ CCl ₂ H Reflux temperature 2 chloroform 29.0 28.7 17.48 17.55 8.46 8.76 101 to 103 HNC ₆ H ₅ O
ί
CH ₃ OP (S) ₃ CCl ₂ CCl ₂ H Reflux temperature 2 chloroform 34.2 33.7 15.43 15.95 7.47 7.85 104 to 105 HN-allyl 25th 2 Hexane 35.7 3.5.75 24.2 24.5 7.8 7.53

continuation

link O
T m temperature
⁰ C Time
hours 1 Va Vs solvent C.
calculated found S.
calculated found I.
calculated found Melting point
⁰ C CH ₃ OP (S) ₈ CCI ₃ HN-allyl 50 ^l k Hexane 30.5 29.2 27.6 28.1 8.9 9.4 O 4th IVa T
C ₂ H ₅ OP (S) ₃ CCb HN - CH ₃ Reflux temperature 1 benzene 31.6 31.45 28.6 28.28 9.2 8.93 O
t I.
C ₂ H ₅ OP (S) ₂ CCl ₂ CCl ₃ HN-t-butyl Reflux temperature chloroform 41.3 41.3 14.9 14.95 7.23 6.70 76 to 77 O I.
C ₂ H ₅ OP (S) ₂ CCl ₂ CCl ₂ H HN-t-butyl 50 chloroform 35.9 35.6 16.2 16.8 7.85 7.87 O
t C ₂ H ₅ OP (S) ₃ CCIs HN-t-butyl 50 chloroform 28.0 28.0 25.4 25.7 8.18 7.88 64 to 66 O
T
C ₂ H ₅ OP (S) ₂ C ₂ H ₅ HNCgH ₅ Reflux temperature Carbon tetrachloride 23.15 23.50 11.17 12.08 O
♦ ■ T
C ₂ H ₅ OP (S) ₃ CCk O
Il Reflux temperature benzene 28.0 27.35 25.3 24.8 8.15 8.77 CH ₃ OC - ΐ

continuation

link temperature Time
hours solvent <
calculated : i
found calculated 5
found I.
calculated >
found Melting point
⁰ C O
C ₂ H ₅ OP (S) ₂ CCl ₂ CCl ₂ H Reflux temperature benzene 35.7 35.10 16.15 16.95 7.8 7.65 O CH ₃ OC - NH O Reflux temperature benzene 10.48 10.42 18.88 18.85 9.13 9.10 59 to 61 C ₂ H ₅ OP (S) ₂ - \ _ \ - ^C1 t-butyl - NH 4th 0.0 0.0 16.2 16.18 7.86 7.74 228 to 236
(Decomposition) O
C ₂ H ₅ OP (S) ₂ - \ ~ \ - ^N ° 2
t-butyl - NH ^ q ₂ O Reflux temperature 5 chloroform 19.18 20.9 32.00 31.30 T
C ₂ H ₅ -OP (S) ₂ CCb O
π CH ₃ C - NH 0 to 25 2 Ether — triethylamine 34.30 33.75 23.30 22.55 O
* T
C ₂ H ₅ OP (S) ₃ CCl ₂ CCl ₂ H 0
Il 25th 1 Ether — triethylamine 29.19 30.40 26.4 27.95 Il
CH ₃ C - NH O T
C ₂ H ₅ OP (S) ₃ CCl ₃ O
Il Il
CH ₃ C- Ϊ m

The compounds prepared according to the invention can be used as pesticides, in particular as fungicides.

Claims (1)

Claim: Process for the preparation of polythio-amidothiolphosphoric acid esters the general formula RiP (S) _{n + 1} R R ² NR ³ characterized,
an amidothiophosphoric acid ester
my formula R ¹ POR ⁴
R ² NR ³ that one of the general with a sulfenyl halide of the general formula R (S) _n X at 0 to 125 ° C, preferably 20 to 100 ⁰ C, optionally in the presence of an inert solvent, where in the formulas η 1 or 2, X is chlorine or bromine, R is an organic radical with 1 to 18 carbon atoms which is free from is functional groups that react with amidothiolphosphoric acid esters, R ^{1 is} an organic radical with 1 to 18 carbon atoms that is bonded to the phosphorus atom via an oxygen or sulfur atom, R ² and R ^{3 are} hydrogen or organic radicals and R ^{4 is} an alkyl - or aralkyl group. Considered publications:
U.S. Patent No. 2,813,902;
J. Am. Chem. Soc, 82, pp. 155-158 (1960).