DE1195750B - Process for the preparation of organic phosphorylimino compounds - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

Number:
File number:
Registration date:
Display day:

C07f

German class: 12 ο -26/01

1195 750
F40988IVb / 12o
October 15, 1963
July 1st, 1965

The present invention relates to a process for the preparation of organic phosphorylimino compounds the general formula

(S) (XS)
RiOvJI / SR ₃

) P —N = C (
R ₂ O / ^X S -R ₄

(S)

in which Ri and R2 represent identical or different _{alkyl, cycloalkyl, aryl or aralkyl groups, optionally substituted by halogen atoms, alkyl, alkoxy,! 5} nitro, alkylamino, acylamino, carbalkoxy groups, R3 and R4 optionally through Halogen atoms, alkyl, alkoxy, nitro, alkylamino, acylamino, carbalkoxy groups mean substituted alkyl, cycloalkyl, aryl, aralkyl or heterocyclic radicals.

The process is characterized in that (thio) -phosphoryl isocyanide dichlorides of the general formula Process for the preparation of organic
Phosphorylimino compounds

Applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:

Dr. Bertram Anders, Cologne-Stammheim;

Dr. Manfred Federmann, Wuppertal-Elberfeld;

Dr. Engelbert Kühle, Cologne-Stammheim

The reaction proceeds in the sense of the following equation:

/ Hal / OR '

R-N = C; + 2MeSP (
\ Il \

SO)

(S) (XS)

/ PN =.
(S)

/ Cl
^ Cl

R-N = C

-SP

SO)

OR

OR "

2MeHaI

/ 2

at -20 to + 10O ⁰ C with mercaptans of the general formula

R ₃ -SH and R ₄ -SH

converts, where Ri, R2, Rs and R4 the above have given meaning.

The reaction is preferred in the presence of acid-binding agents or with the appropriate Salts of the aforementioned mercaptans and carried out in the presence of inert organic solvents.

The Belgian patent 596 090 already describes a process for the preparation of phosphoric acid esters described, which is characterized in that one thiol or thionothiol phosphoric acids or their salts are reacted with isocyanide dihalides.

In the last-mentioned formers, R, R 'and R "represent optionally substituted, aliphatic or

aromatic hydrocarbon radicals, while Hai is a halogen atom and Me is an alkali metal or Represents ammonium ion.

The one known from the above-mentioned Belgian patent specification and the one according to the method The way of working therefore differ in terms of the chemical constitution of the two classes of Starting materials are crucial from each other. While namely in the case of the Belgian patent specification 596090 method disclosed alkyl or aryl isocyanide dihalides Find use as starting substances, phosphoryl isocyanide dichlorides are used in the process according to the invention. Furthermore, one goes in the first case of thiol

_s0 or thionothiol phosphoric acids or their salts, in the second case, however, from mercaptans. However, these two substance classes can be used in terms of

509 598/433

their chemical behavior and mode of reaction should not be regarded as analogous. So is z. B. known from the literature that alkyl or aryl isocyanide dihalides with dithiocarbamic or xanthogenic acids or mercaptans react to mustard oils (see "Zeitschrift für angewandte Chemie", Vol. 74 [1962], pp. 861 to 866, especially p. 864, as well as the Belgian patent 613 428).

In contrast, the phosphoryl isocyanide dihalides to be used as starting materials according to the invention react smooth with mercaptans in the sense of the claimed process. Given the state of the art, this was extraordinary A smooth and uniform course of the reaction according to the procedure is by no means to be expected.

The (thio) -phosphoryl isocyanide dichlorides required as starting materials for the process according to the invention can be prepared by the process of patent 1,173,469.

Examples of suitable phosphoryl isocyanide dichlorides are Ο, Ο-diphenyl-, O, O-di- (4) -chlorophenyl-, O-ethyl-O-phenyl-, S, S-diethyl-trithio- and Ο, Ο-dicyclohexylphosphoryl isocyanide dichloride.

Examples of suitable mercaptans or their salts, preferably alkali salts, are methyl, ethyl, Butyl, dodecyl, / ί-Ν, Ν-diethylaminoethyl, cyclohexyl, Benzyl, 2-chlorobenzyl, 3,4-dichlorobenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 4-nitrobenzyl mercaptan, Thio-, pentachlorothio- and 4-chlorothiophenol, 3-thiocresol, thionaphthol, 4-mercaptobenzoic acid ethyl ester, Thioglycolic acid ethyl ester, 2 - mercaptothiazoline, 2 - mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercapto-4,5-dimethylpyrimidine, 2-mercaptofuran.

Practically all inert organic solvents can be used as solvents or diluents Question. These preferably include chlorinated hydrocarbons, such as benzene, toluene, Xylene, chlorobenzene, chloroform, carbon tetrachloride, further ethers, e.g. B. diethyl ether and dioxane. In addition, the reaction can also be carried out in an aqueous medium.

If in the reaction according to the invention it is not the salts of the thioalcohols but the corresponding free mercaptans are used as starting materials, all common acid binders, z. B. triethylamine, dimethylcyclohexylamine or alkali hydroxides, carbonates or bicarbonates find application as acid acceptors.

The reaction is preferably carried out at temperatures between -20 and +100 ⁰ C at room temperature.

If the method according to the invention is carried out using mercaptides, then the (thio) -phosphoryl-isocyanide dichloride in question is added to the suspension of the solution added dropwise to the temperatures indicated above or the salt added in portions to the solution of the

ίο Dichlorids joined. If you use the free mercaptans, so the dichloride and mercaptan can be presented in a solvent and the Acid acceptor, e.g. B. a tertiary amine, are added dropwise to the reaction mixture ·. In general

! In my opinion, 2 moles of mercaptan are used per mole of dichloride and 2 moles of acid binder. In the production of asymmetrical dimercapto compounds 1 mol of mercaptan and 1 mol of acid acceptor are first introduced into the solution of 1 mol of (thio) -phosphoryl isocyanide dichloride.

The mixture is then left to react for a short time and then used in the same way with 1 mole of another mercaptan.

The novel phosphorus compounds which can be prepared by the process according to the invention have excellent insecticidal and fasciolicidal properties. They are particularly suitable for combating from liver fluke and ticks and are therefore used in veterinary medicine.

yj The following examples illustrate what is claimed Procedure:

example
O

(C ₂ H ₆ O) ₂ PN = C (

/ SC ₂ H ₅
^X SC ₂ H ₅

In a solution of 23.4 g of 0,0-Diäthylphosphorylisocyaniddichlorid and 12.4 g of ethylmercaptan in 150 cc of benzene at a temperature below 20 ⁰ C. 20.2 g of triethylamine dissolved in 50 cc of benzene, added dropwise. The reaction mixture is then stirred for a short time, the triethylammonium hydrochloride is filtered off and the filtrate is concentrated. The residue left behind is 28 g of 0,0-diethylphosphorylimino-SS-diethyl-dithiocarbonic acid ester, boiling point o5 147 to 149 ° C.

In an analogous manner, the following compounds are obtained in very good yields:

formula F. Physical Properties P. S. C. 11.3
10.8 H N ⁰ C Analysis (calculated / found) % % % % ° / o oil 9.1
9.8 4.1
4.54 O N = C (SC ₄ Hg) ₂ oil 5.4
4.7 (C ₂ H ₅ O) ₂ P-
O
Il N = C (SCi ₂ H ₂₅ ) S (C ₂ H ₅ O) ₂ P-

O
π > - N = C s-CH ₂ -4 y
Cl .-, S - CH ₂ - <^ J> CH ₃ j _; 2 O ³ -N = C S - / V - COC ₂ H ₅ 2 F. Physics
t
P. 6th 57.6
57.44 η
'found
H 1)"
N (C ₂ H ₅ O) ₂ P -N = C [S (CH ₂ ) 2 N (C ₂ H ₅ ) ₂ ] ₂ O ( Cl χ S - CH ₂ - / V _{- CH 3} (C ₂ H ₅ O) ₂ P - N = c (s - <^ ^ - Cl) _β ical properties
\ nalysis (t
S. 59.3
59.25 5 O
Ij (C ₂ H ₅ O) ₂ P -N = C O 'v_, Xj.2>, / ν-ί V CH ₃ O
I. oil 9.8
10.14 (C ₂ H ₅ O) ₂ P -N = C (SCH ₂ - COOC ₂ Hs) ₂
O ( Ci \ (C ₂ H ₅ O) ₂ P - N = C (s - \ J __ / ~ ^CH3 ) , (C ₂ H ₅ O) ₂ P -N = C f SCH ₂ ~ / \\
\ / / 2
O
Il, S - CH ₂ - '/' ^ / ■ ο ί ο)
Il oil 7.7
8.5 shanks
calculated
C. (C ₂ H ₅ O) ₂ P - N = C (S - CH ₂ - '(Jy- ^C1 )., I.
\ Cl ι (C ₂ H ₅ O) ₂ ] oil 7.6
7.55 O
IN oil 6.5
6.45 15.0
15.33 formula (C ₂ H ₅ O) ₂ PN = C ₀ oil 6.5
6.55 16.0
16.09 (C ₂ H ₅ O) ₂ : 15.7
15.85 O
I! oil 5.7
6.0 13.4
13.3 (C ₂ H ₅ O) ₂ P -N = C
O
H (C ₂ H ₅ O) ₂ P -N = C 118 to 120 13.4
13.65 11.7
11.2 oil 6.4
6.55 oil 6.9
6.99 85 to 88 100 to 103 oil 5.9
5.5 2.7
3.18

formula

Physical Properties

P.
% Analysis (t
S.
% jerecnnet /
C.
% geiundenj
H
% · 5.0
4.6 10.4
10.60 5.0
4.8 10.4
10.4 5.0
4.9 10.4
10.6 10.4
10.6 7.1
6.5 6.6
6.1 13.0
13.2 14.6
14.9

O
(C ₂ H ₅ O) ₂ PN = I.

Cl

S - CH ₂ - <

Il

(C ₂ H ₅ O) ₂ PN:

(C ₂ H ₅ O) ₂ PN = C

Il

(C ₂ H ₅ O) ₂ P -N = C

Cl Cl \

S - CH ₂

Cl / ₂

Cl

CI

Cl

S -CH ₂

Cl

Cl Cl J ₂

JH ₅ O) ₂ P - N = C [s - CH ₂ - CH ₂ - / \)

(C ₂ H ₅ O) ₂ P-N = C

(SC ₄ H ₉ O) ₂ P - N = C (s - CH ₂

Il

(1-C ₄ H ₆ O) ₂ P - N = C (s - CH ₂ - CH ₂ ~ \ _ /)

(DC ₄ H ₉ O) ₂ P - N = C (s - CH ₂ - \ _ y>),

Il /

(iC ₃ H ₇ ) 2P -N = C (S.

3.2 3.3

8.9 8.94

3.0

3.5

2.8

3.0

3.4

3.2 3.6

Claims (2)

Patent claims: 1. A process for the production of organic phosphorylimino compounds, characterized in that that one (thio) -phosphoryl isocyanide dichloride of the general formula (S) 0 (S)
RiO _x I
) P P-N = C Cl C1 (S) ^{in which R 1 and R 2 represent} identical or different alkyl, cycloalkyl, aryl or aralkyl groups optionally substituted by halogen atoms, alkyl, alkoxy, nitro, alkylamino, acylamino, carbalkoxy or aralkyl groups, from -20 to + 10O 0 C with mercaptans of the general formula R ₃ -SH and R ₄ -SH to phosphorylimino-dithiol carbonic acid esters of the general formula 10 (S) (XS)
RiO _x H / S - R ₃ ) P -N = Cf
R ₂ O / \ s - (S) R ₄ implements, in the Ri and R2 the above Have meaning, while R3 and Rj for optionally by halogen atoms, alkyl, alkoxy, Nitro, alkylamino, acylamino, carbalkoxy groups, substituted alkyl, cycloalkyl, Aryl, aralkyl or heterocyclic radicals. 2. The method according to claim 1, characterized in that that the reaction in the presence of acid binders or with the appropriate Mercaptides as well as in inert organic solvents or in an aqueous medium. Considered publications: Announced documents of Belgian patents Nos. 596 090, 613 428;
Angewandte Chemie, 74, 1962, pp. 861 to 866; Z. obsc. chim., 29, 1959, pp. 1815 to 1818 and 3424 to 3427.