Solid anti-friction devices – materials therefor – lubricant or se – Lubricants or separants for moving solid surfaces and... – Heterocyclic ring compound; a heterocyclic ring is one...
Reexamination Certificate
2000-09-15
2002-03-26
Johnson, Jerry D. (Department: 1764)
Solid anti-friction devices, materials therefor, lubricant or se
Lubricants or separants for moving solid surfaces and...
Heterocyclic ring compound; a heterocyclic ring is one...
C508S274000, C508S275000, C548S142000, C548S169000, C548S170000, C548S171000
Reexamination Certificate
active
06362138
ABSTRACT:
The present invention relates to compounds of formulae I and II, which are suitable as ash-free antiwear additives and antioxidants, to lubricant compositions comprising compounds of formulae I and II as well as to their use.
For operating combustion engines, it is necessary to use lubricants having a low metal content and, therefore, a low ash content and, in view of exhaust gas catalyst compatibility, also a low phosphorus content. This invention therefore has for its object to provide metal-free and phosphorus-free additives or additive combinations which approach the good antioxidative and wear protection of the zinc dialkyldithiophosphates used to date.
U.S. Pat. No. 3,591,475 describes the preparation of asymmetrical dithioethers of the general formula
by addition of a mercaptan R′SH to an allyl sulfide (RS—CH
2
CH═CH
2
). The definitions of R and R′ include numerous substituents of different structures. There is no description given of a dithioether containing a heterocyclic radical as a defined single compound. Benzothiazolyl is only mentioned as an example in the sense of an enumeration. The use of the compounds described in U.S. Pat. No. 3,591,475 is also disclosed unspecifically. Their suitability as agrochemicals having antiparasitic properties is mentioned there. In addition, these compounds are said to be suitable as stabilisers for polyolefins and also as additives for lubricants.
The preparation of benzothiazolyl dithioethers of formula
with herbicidal activity is described on page 1847 of the English translation of
Syntheses on the Basis of
2-
benzothiazolylvinyl Sulfide, Zhurnal Organicheskoi Khimii, Vol.
2,
No.
10, pp. 1883-1891, October 1966.
U.S. Pat. No. 5,258,258 describes processing solutions for the development of lithographic printing plates, which comprise thiadiazolyl dithioethers of formula
U.S. Pat. No. 5,051,198 describes reaction products which are obtainable by reacting mercaptans with &bgr;-thiodialkanols. These reaction products can be used as antioxidants.
This invention relates to compounds of formulae I and II described hereinafter, which are suitable as improved ash- and phosphorus-free antiwear additives and which additionally have an antioxidative effect:
wherein
R
1
is hydrogen or C
1
-C
20
alkyl;
R
2
is a substituent from the group consisting of C
1
-C
20
alkyl, C
5
-C
12
cycloalkyl, C
7
-C
12
bicycloalkyl, phenyl, C
7
-C
18
alkylphenyl, naphthyl and C
7
-C
9
phenylalkyl, which substituent may be substituted by one or more than one substituent from the group consisting of amino, carboxy and hydroxy and/or may be interrupted by one or more than one bivalent radical from the group consisting of —O—, —NR
6
—, —C(═O)—O—, —O—C(═O)—, —C(═O)—NR
6
— and —NR
6
—C(═O)—;
R
3
and R
4
are hydrogen or have the meanings of R
2
, with the proviso that R
2
is C
4
-C
20
alkyl if
R
3
and R
4
are hydrogen;
R
5
is hydrogen or groups of the partial formula
wherein R
2
, R
3
and R
4
have the cited meanings or have the meaning of R
2
;
and R
6
is hydrogen or C
1
-C
4
alkyl.
The compounds of formulae I and II are particularly suitable as multifunctional antiwear additives with additional antioxidative effect for lubricants, gear oils, hydraulic and metal working fluids as well as for greases. They are substantially ash- and phosphorus-free.
The definitions and terms used within the scope of the description of this invention preferably have the following meanings:
Examples of C
1
-C
20
alkyl are methyl, ethyl, n- or isopropyl or n-, sec- or tert-butyl and also straight-chain or branched pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl, typically isooctyl or tert-nonyl. Examples of C
5
-C
12
cycloalkyl are cyclopentyl or cyclohexyl. Examples of C
7
-C
12
bicycloalkyl are e.g. bornyl or norbornyl. Examples of C
7
-C
18
alkylphenyl are phenyl which is substituted by mono-, di- or trimethyl. Examples of C
7
-C
9
phenylalkyl are e.g. benzyl or 2-phenylethyl.
In another of its aspects, this invention also relates to compounds of formulae I and II including all cases of isomerism, for example bond isomers or stereoisomers, resulting from the presence of a chiral centre. These cases of isomerism encompass optically pure enantiomers, diastereomers as well as racemic mixtures.
Preferred compounds are those of formulae I and II described above, wherein R
1
is hydrogen; R
2
is a substituent from the group consisting of C
1
-C
20
alkyl, phenyl, C
7
-C
18
-alkylphenyl and C
7
-C
9
phenylalkyl, which substituent may be substituted by one or more than one substituent from the group consisting of amino, carboxy and hydroxy and/or may be interrupted by one or more than one bivalent radical from the group consisting of —O—, —NR
6
—, —C(═O)—O—, —O—C(═O)—, —C(═O)—NR
6
— and —NR
6
—C(═O)—;
R
3
and R
4
are hydrogen or have the meaning of R
2
, with the proviso that R
2
is C
4
-C
20
alkyl if
R
3
and R
4
are hydrogen;
R
5
has the meanings of R
2
or is groups of the partial formulae (A) and (B), wherein R
2
, R
3
and R
4
have the cited meanings; and R
6
is hydrogen or alkyl.
Particularly preferred compounds are those of formulae I and II, wherein
R
1
is hydrogen; R
2
is a substituent from the group consisting of C
1
-C
20
alkyl, phenyl, C
7
-C
18
-alkylphenyl and C
7
-C
9
phenylalkyl, which substituent may be interrupted by one or more than one bivalent radical from the group consisting of —O—, —C(═O)—O— and —O—C(═O)—;
R
3
and R
4
are hydrogen or have the meanings of R
2
, with the proviso that R
2
is C
4
-C
20
alkyl if R
3
and R
4
are hydrogen;
R
5
has the meanings of R
2
or is groups of the partial formulae (A) and (B), wherein R
2
, R
3
and R
4
have the cited meanings.
Very particularly preferred objects of this invention are compounds of formulae I and II,
wherein R
1
is hydrogen; R
2
is C
1
-C
20
alkyl which may be interrupted by a bivalent radical from the group consisting of —O—, —C(═O)—O— and —O—C(═O)—;
R
3
and R
4
are hydrogen or have the meanings of R
2
, with the proviso that R
2
is C
4-C
20
alkyl if
R
3
and R
4
are hydrogen;
R
5
has the meanings of R
2
or is groups of the partial formulae (A) and (B), wherein R
2
, R
3
and R
4
have the cited meanings.
Particularly preferred compounds are those of formula
wherein R
2
is C
4
-C
18
alkoxycarbonylmethyl, R
3
is C
4
-C
18
alkoxycarbonylmethylthiomethyl and R
4
is hydrogen; or
R
2
is C
5
-C
12
alkyl, R
3
is C
5
-C
12
alkylthiomethyl and R
4
is hydrogen; or
R
2
is C
4
-C
18
alkoxycarbonylmethyl, R
3
is hydrogen and R
4
is C
4
-C
18
alkoxycarbonylmethylthiomethyl; or
R
2
is C
5
-C
12
alkyl, R
3
is hydrogen and R
4
is C
5
-C
12
alkylthiomethyl, and compounds of formula:
wherein R
2
and R
2
′ are C
4
-C
18
alkoxycarbonylmethyl, R
3
and R
3
′ are C
4
-C
18
alkoxycarbonylmethylthiomethyl, and R
4
and R
4
′ are hydrogen; or
R
2
and R
2
′ are C
5
-C
12
alkyl, R
3
and R
3
′ are C
5
-C
12
alkylthiomethyl and R
4
and R
4
′ are hydrogen; or
R
2
and R
2
′ are C
4
-C
18
alkoxycarbonylmethyl, R
3
and R
3
′ hydrogen and R
4
and R
4
′ are C
4
-C
18
alkoxycarbonylmethylthiomethyl; or
R
2
and R
2
′ are C
5
-C
12
alkyl, R
3
and R
3
′ are hydrogen and R
4
and R
4
′ are C
5
-C
12
alkylthiomethyl.
Especially preferred are compounds of formula I′,
wherein R
2
is isooctyloxycarbonylmethyl, R
3
is isooctyloxycarbonylmethylthiomethyl and R
4
is hydrogen; or
R
2
is tert-nonyl, R
3
is tert-nonylthiomethyl and R
4
is hydrogen; or
R
2
is isooctyloxycarbonylmethyl, R
3
is hydrogen and R
4
is isooctyloxycarbonylmethylthiomethyl; or
R
2
is tert-nonyl, R
3
is hydrogen and R
4
is tert-nonylthiomethyl, and also compounds of formula II′,
wherein R
2
and R
2
′ are isooctyloxycarbonylmethyl, R
3
and R
3
′ are isooctyloxycarbonylmethylthiomethyl and R
4
and R
4
′ are hydrogen; or
R
2
and R
2
′ are tert-nonyl, R
3
and R
3
′ are tert-nonylthiomethyl and R
4
and R
4
′
Camenzind Hugo
Dratva Alfred
Evans Samuel
Hänggi Peter
Ciba Specialty Chemicals Corporation
Johnson Jerry D.
Mansfield Kevin T.
LandOfFree
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