DE948156C - Process for the preparation of Thiolthionophosphorsaeureabkoemmlingen - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

ISSUED AUGUST 30, 195 «

GERMAN PATENT OFFICE

PATENT LETTERING

CLASS 12ο GROUP 2303 INTERNAT. CLASS C07f

D 18787 IFb112 ο

Karl A. Fischer, Hamburg-Blankenese,

Dr. Eduard Brandt, Wedel (Holst.), And Kurt Pilgram, Schneverdingen (Kr.Soltau)

have been named as inventors

Deutsche Erdöl-Aktiengesellschaft, Hamburg

Process for the preparation of thiolthionophosphoric acid derivatives

Patented in the territory of the Federal Republic of Germany from October 3, 1954 Patent application announced on Mar 8? 1966 Patent granted, since August 9, 1956

It has been found that new valuable derivatives of thiolthionophosphoric acid are obtained if Thiolthionophosphoric diesters with ethylene oxide or its substitution products to give oxy-group-containing Thiolthionophosphorsäuretriestein converts and this

R-X,

R-X '

further by treating with phosphorus pentasulfide into the corresponding thiolthionophosphoric acid derivatives convicted. The implementation takes place according to the following equations: 15

IP-SH + R ₁ -CH-CH-R ₁ =

R ₁ R ₁

- S-CH-CH-XH

R-X

RX
RX

R-X '

S = P = S

+ S +
S = P = S

SR ₁ R ₁

Il I I

P-S-CH-CH-XH P-S-CH-CH-XH

"Il I I · XVi iXi O YES. ·] YES.-! O

^R - ^X \ ll Il Il Il 1

2 ^ P-S-CH-CH-X-P-X-HC-CH-S-P

R-X

X-R

HX-HC-CH-S

HX-HC-CH-S -

X-R

SH XR ^ X-R

(2)

+ H ₂ S (3)

where: R = aliphatic, aromatic, aliphatic-aromatic or halogen-containing aliphatic or aromatic radical, R ₁ = R or H, and X = O or S.

These new thiolthionophosphoric acid derivatives

mostly represent oily, highly viscous compounds of a strongly acidic character; which enables them to form salts with alkalis, alkaline earths, heavy metals and amines. In addition, they also show the well-known reactions of the sulfhydryl group. They come together, for example, with sulfur chlorides (SO ₂ Cl ₂ , SCl ₂ , S ₂ Cl ₂ ) to form di-, tri- and tetrasulfides.

example 1

For the representation of thiolthionophosphoric acid-O, O-bis- [dibutoxythionothiolphosphoric acid-S-ethyl- (2)] - ester of the formula

SQ C

(H ₉ C ₄ O) ₂ P ^ - S • CH ₂ • CH ₂ • 0 • P - 0 - CH ₂ • CH ₂ -SP = (OC ₄ H ₉ J ₂

^X SH

one passes into thiolthionophosphoric acid O, O-dibutyl ester ethylene oxide until the reaction product reacts neutrally. The reaction is exothermic. The ester is obtained as a light, oily liquid that cannot be distilled without decomposition. Further initiation of ethylene oxide leads to higher molecular weight compounds. The analysis values found correspond the thiolthionophosphoric acid O, O-dibutyl-S-jö-oxäthylester.

Molecular weight: sulfur content: phosphorus content: theoretical: 286 22.4% 10.9%

found: 280 23.2 ° / ₀ 12.9%

The ester obtained is treated with phosphorus pentasulfide

in a molar ratio of 4: 1 at temperatures between 90 and 140 ° with stirring until the latter is completely dissolved, hydrogen sulfide ent

gives way. The result is a highly viscous, golden yellow, acidic substance whose analysis data match the theoretical Values for thiolthionophosphoric acid O, O-bis [dibutoxythionothiolphosphoric acid S-ethyl (2)] ester agree sufficiently.

Molecular weight: sulfur content: phosphorus content:

28.8% 27.O ° / o

theoretical: 665 14.0%

found: 620 i4> 7%

Equimolar amounts of this thiolthionophosphoric acid derivative were used to prepare the oleylamine salt and oleylamine added together.

Example 2

The representation of the thiolthionophosphoric acid-O, O-bis - [dibutoxythiolthionophosphoric acid - S - 3 - chloropropyl (2)] - ester the formula

(H ₉ C ₄ O) ₂ PS • CH ₂ • CH • CH ₂ Cl ClCH ₂ • CH • CH ₂ • S - P = (OC ₄ H ₉ ) ₂

- O - P - SH

took place in a manner similar to that in Example 1. Equimolar amounts of thiolthionophosphoric acid

O, O-dibutyl ester and epichlorohydrin are combined litmus no longer reddened.

added and after the reaction has subsided, heated to 100 to 140 ° until the reaction

Analysis of the oily thiolthionophosphoric acid -0,0-dibutyl-S-3-chloro-2-oxypropyl ester formed resulted in the following values:

Mol- sulfur-phosphorus-chlorine

weight: salary: salary: salary:

theoretical: 334 19.2% 9.1% 10.6%

found: 317 19.4% 10.4% 10.5%

The further implementation of this ester with phosphorus pentasulfide in a molar ratio of 4: 1 led to the thiolthionophosphoric acid-O, O-bis- [dibutoxythiolthionophosphoric acid S-3-chloropropyl- (2)] ester the one above

given formula. This substance is a highly viscous oil with a light yellow appearance.

Mol- sulfur- phosphorus- chlorine weight: content: content: content:

theoretical: 765 25.2% 12.9% 9.3%

found: 800 23.7% 10.3%. 9.1%

To convert this ester into tetrasulphide, it was converted to that in carbon disulphide at the boiling point the calculated amount of sulfuric chloride was added dropwise to dissolved ester. After the development of hydrochloric acid has ceased the solvent was distilled off. An oily tetrasulfide of the formula remained behind

(H ₉ C ₄ O) ₂ = PS-CH ₂ -CH-CH ₂ Cl S ClCH ₂ • CH • CH ₂ • S • P = (OC ₄ H ₉ ) ₂

(H ₉ C ₄ O) ₂ = PS-CH ₂ -CH-CH ₂ Cl S ClCH ₂ • CH • CH ₂ • S • P = (OC ₄ H ₉ ) _a

O O

Example 3

₃₅ The thiolthionophosphoric acid O, O-bis- [oU-p-chlorophenoxythiolthionophosphoric acid - S - α - phenylethyl - (/?)] - ester of the formula

PS-CH-CH ₂ -OPO-CH ₂ -CH-SPO

SH

was obtained by adding the equimolar amount of phenylethylene oxide to the melt of thiolthionophosphoric acid O, O-di-p-chlorophenyl ester and maintaining the temperature ^{at 100 to 140 ° for 1 to I 1 for} ₂ hours until the reaction product indicated a neutral reaction.

The thionothiolphosphoric acid O, O-di-pchlorophenyl-S-a-phenylethyl (/?) - ester obtained had the following analysis data:

Mol- sulfur- phosphorus weight: content: content:

theoretical: 471 13.6% 6.6%

Chlorine content:

15.1%

found: 465 13.9% .7.1% 14.9%

Further reaction of this ester with phosphorus pentasulfide in a molar ratio of 4: 1 gave a quantitative result Yield the thiolthionophosphoric acid-bis- [di-

phosphorus chlorine salary: salary: 9, o% . 13.7% 9.3% 13.5%

p-chlorophenyl-S-a-phenyl-ethyl- (ß)] - esters of the above Formula as an oily liquid.

Molar sulfur weight. Content:

theoretical: 1036 18.5%

found: 993 19.2%, _ ... _ _ _

The oleylamine salt of this ester was obtained by neutralization with oleylamine, including the equimolar Amount was needed.

The thiolthionophosphoric acid derivatives prepared by the process according to the invention and their Salts and sulfides are soluble in lubricating oil and greatly improve their compressive strength very low abrasion.

For example, a 3% addition of the process product of Example 1 to lubricating oil on the Wieland oil testing machine allows a load of 1050 kg / cm ² .

The shaft taper is 0.09 mm. The oleylamine salt of this ester dissolved at 3% in lubricating oil gives a compressive strength of 1750 kg / cm ² . The shaft taper is 0.11 mm.

In the case of the tetrasulfide of this ester, the compressive strength is included. 1250 kg / cm ² with a shaft taper of 0.088 mm.

If you add z. B. 3 ° / _{0 of} the symmetrical tetrasulfide of TMolthionophosphorsäure-0, O-bis- [dibutoxythiolthionophosphorsäure -S -3 -chlorpropyl- (2)] - ester added to a lubricating oil, one obtains a pressure strength of 1100 kg / cm ² (shaft taper 0.071mm).

The Oleylaminsalz of Thiolthionophosphorsäure-O, O -bis- [di-n-octyloxythiolthionophosphorsäure-S-ethyl- (2)} - ester can be, / ₀ to 3 ° dissolved in lubricating oil, a load of 1700 kg / cm ² (taper shaft 0.099 mm). The lubricating oil on which these tests are based could only be ^{loaded up to 250 kg / cm 2} and even at this load showed a shaft taper of 0.18 mm.

Claims (1)

PATENT CLAIM: Process for the production of thiolthionophosphoric acid derivatives, characterized; that one diesters of thiolthionophosphoric acids the general formula R-X. R-X IP —SH, where R is an aliphatic, aromatic, aliphatic-aromatic or a halogen-containing aliphatic or aromatic radical, and X is oxygen or sulfur, with ethylene oxide or lets its derivatives react, the resulting oxygroup-containing thiolthionophosphoric acid triesters then reacted with phosphorus pentasulphide and the acidic thiolthionophosphoric acid derivatives obtainable in this way optionally by treatment with inorganic bases or amines in their salts or by treatment with Sulfur chlorides converted into their symmetrical di-, tri or tetrasulfides. »509 696/499 2.56 (609597 8.56)