Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
` . 1047S06
~ he present invention relates to sulphur-containing lubricating oil
additives.
According to the present invention there is provided an oil-soluble
compound having the formula:
S A
A - R - S - ~ _ oRl or~R2~
I n
(I) Rl - C- S
wherein in Formula (I) R is a sulfur-bridged hydrocarbon ring derived from
1,3,5-cycloheptatriene or 1,5~9-cyclododecatriene, said sulfur-bridge being
a single sulfur bridge between two non-ad~acent carbon atcms of said ring
forming a bicyclo compound and wherein in Formula (II) R2 is a polymer com-
prising the residue of a plurality of n hydrocarbon rings which are derivedfrom 1,3,5-cycloheptatriene, cyclooctatetrene, 1,3-cyclooct~ene, 1,5-cyclo-
octadiene, 3-alkoxy derivatives thereof and 1,5,9-cyclododecatriene, said n hy-
drocarbon rings being connected through a sulfur bridge, n being the degree of
polymerisation such that said compound is oil-soluble, R is the same or dif-
ferent and is an alkyl, aIkenyl or aralkyl grouP and A is a nucleophyllic group
selected from
r s
- LS_C_OR1~ , -CN,-NCS,-XH~-XR3,
X X 3 X oR3
-X-~_R3,_X_c_N / R and -X-P /
\ R3 \ oR3
wherein Rl is as above, X is oxygen or sulfur and R3 is alkyl, aryl, aIkaryl
or aralkyl.
The sulphur bridging in R and R is conveniently achieved by re-
acting with sulphur dichloride or other sulphur chloride compound to yield
either monomeric or polymeric derivatives. The sulphur bridges may be oxidised
to carry one or two oxygens.
The group A preferably has the formula:-
iO4'~506
(S - C~ oR13
wherein Rl is as defined above and wherein the two grouPs Rl may be the same
or different.
The invention also includes a lubricating oil composition which com-
prises a n~jor amount of a lubricating oil and a minor amount of compound as
defined above. Such compositions m~y be employed directly as lubricants and
the novel compoundsof the present invention are preferably present in an a-
mount from 0.01 to 10% by weight, more particularly ~rom 0.5 to 3% by weight,
although in a few cases, e.g. 2,6 bis(methoxythiocarbonylthio)-9-thiabicyclo
~3,3,1~ nonane, oil solubility may be somewhat li~ited. Thus the number of
carbon atoms in the, or each, group Rl, and the, or each, group R3 if present,
should be sufficiently high to render the compounds oil soluble. On the other
hand it is desirable that the number of carbon atoms in the grouPs Rl and R3
should not be too high since it is believed that the sulphur in the molecule
is the active component, and with high molecular weight large amounts of the
compounds would have to be used to give equivalent sulphur contents. Partl-
cularly preferred additives in this respect are compounds in which A is a
group of the formula:-
~ - C~ - OR~
and in which one group R is an ethyl or propyl grouP and the other grouP is
a methyl, ethyl or propyl grouP-
However, the term lubricating oil composition also embraces the ma-
terials known in the art as oil concentrates and additive packages, i.e. con-
centrated solutions in lubricating oil, optionally together with one or more
conventional additives intended to be diluted with further
,
1047S06
quantities of oil to form the final lubricant. In this case
"
the novel compounds of the present invention m~y be present
in a wide range of proportions e.g. 10% to 90%. In gener~l
such concentrated solutions will normally contain from 20%
to 50% by weight of the novel compounds of the present
invention. The lubricating oil used in the lubricants,
or the concentrates or packages, may be any of the well
known oils of appropr ate viscosity characteristics and
may include synthetic oils.
The ~ulphur-bridged compounds may be prepared by reacting
sulphur dichloride with the unsaturated ring compound preferably
in an inert solvent at a temperature betwe-en -20 and 100C to
give a dichloro derivative. Details of the preparations of
these compounds are given in J. Org. Chem. 33, p. 2627 (196&);
~15 J Org. ~h~m. 31, p. 1679 and 1669 (1966).
:. The compounds of the present invention may then be
prqpared by reàcting the metal, preferably sodium, or
e~pecially potassium, salt of an alkyl, alkenyl or
aralkyl xanthate with the d chloro sulphur-bridged
compound, in the ratio of two moles of xanthate to one mole
of dichloro sulphur-bridged compound when compounds of the
formula:- R10 - C = S
` R r- s c - ORl~ or ~R ~n
R10 - C = S
are oDt~ined wherein R, R , R and n have the same significance
as above.
When the xanthate and the dicnloro sulphur-brid~ed
- compound are reacted in a mole ratio of 1:1. one c~lorine
remains unreacted. This chlorine atom is then reacted with
me~al derivatives of the nucleophilic group A.
The invention therefore includes as ir.termediates
10~7506
compounds having the formulae Cl - R - S - ~ - ORl and
...... ..... ....... ...... rCl21
1 1 ~herein R, Rl and ~ X2~ ~have
R 0 - C = S n
the same significance as above.
Alternatively, the derivative of the nucleophilic
group A may be reacted with the dichloro sulphur-bridged
compound which may then be reacted with the xanthate.
In some cases, the compounds of the invention may
possess residual reactive ethylenically unsaturated double
bonds which may be reacted with compounds reactive therewith.
0 Such compounds reacting with residual unsaturation include
sùlphur~ phosphorus pentasulphide, mercaptans, phenols,
~ thiocyana~e anions, thiophenols and carboxylic acids. Specific
: examples of such compounds are mercaptans and carboxylic acids
con~aining from 1 to 16 carbon atomR; phenol (unsubstituted)
and thiophenol (unsubstituted). The~foregoing compounds may be
- reacted with the residual unsàturation at a temperature of
from 50 to 200C and in the case of sulphur, thiocyanates and
phosphorus pentasulphide no catalyst is required; In the
` case of the other compounds, however, it may be desiràble to
use a catalyst known to promote their reaction with ethylen-
- ically unsaturated double bonds, such as mineral acids or
Lewis acid catalysts such as boron trifluoride or the etherate
- or phenolate complex thereof.
It will be understood that the lubricating compositions
of the present invention may also contain, if desired,
conventional lubricant additives such as ancillary antioxidants
and antiwear additives (preferably ashless)~ corrosion
inh~ibitors, dispersants, particularly dispersants of the
succinimide type, detergents, thickeners, pour-point
~047S06
depressants and viscosity index improvers. Numerous examples
of such conventional additives are described in U.K. Patent
Specification No 1,205,177 and the various document3 referred
to therein.
There now follows by way of example a description
of the preparation of typica~ compounds in accordance with
the present invention:
Example 1
Preparation of Intermediate A
2,6 dichloro-9-thiabicyclo ~3;3~ nonane
Methylene chloride (1,250 ml~ wa~s stirred at a temperature
between 0 and -5C in a glass vessel fitted with nitrogen inlet
and dropping funnels. 1,5 cyclo-octadiene (1080 g, 10 mcles)
and sulphur dichloride (103 g; 10 moles)'were added from the
15. dropping f~nnel~ at equivalent ~ates over 5~ hours whilst
',",' maintaining the cooling bath at'-25 to -30C. When the
ad,ditio,n was complete the mixture was allowed to warm to room
- t~mperature overnight and then'heate~ to 46 to 47C for two
hours.
- The product was,precipitated~on cooling to below
room temperature, filtered off and dried at 50C in vacuum
' ' oven to yield 1511 g (72%) of a product containing 31.9% Cl
(calc. 33.7) and 16.4% S (calc. 15.1). The melting point,
after recrystallisation, 92.5 - 93.5C, and infrared analysis
, confirmed that the product was 2,6 dichloro-9-thiabicyclo
t3,3,1~ nonane.
Preparation of 2,6-bis(butoxythiocarbonylthio)
, -9-thiabicyclo ~,3,1~ nonane
Commerc-al grade potassium hydroxide (66g; 1 mole) of
85% purity was dissolved in n-butanol (300g) by heating
ra~idly to about 75C, then cooled rapidly to about 3~C
in a water bath. Carbon d~sulphide (76g; 1.0 moles) wa~ ~ddeQ
~047S06
dropwise over about 50 minutes and the temperature maintained
below 40C by a water bath because of the gentle exotherm,
during which time a bright yellow precipitate was formed. When
. the addition was completed the temperature of the solution
of potassium xanthate thus formed was heated to 50C and a
solution of Intermediate A (105.5g; 0.5 moles) in toluene
t400 ml) warmed to about 60C was added.
The mixture increased in viscosity and turned brown and
was refluxed (about 91C) for 4 hours and then cooled to room
temperature. After washing three times with 150 ml of water
: . -....... an~ a.further.bhree.time with lO~.~ml o~ ~aterj-the mixture.was:
dried over magnesium sulphate, filtered and stripped on a
rotary evaporator to 100C/20 torr. The residue was filtered
through`glass-fibre paper on.a hea.ted funnel to yield a
viscous li~ht brown liquid which solidified to a light yellow
: solid on standing.
181g ~83%) of the protuct containing 35.8% S (calc. 36.6)
....... and 0.36% Cl was obtained, infrared ~nalysis confirming the
structure . '
7\ 11
S ~ S C - O.- CH2CH2CH2Ch3
CH3~.CH2~CH2~CH2~~C-S ~
. .
Exam~les 2 to 20
. Further compounds in accordance with the present
invention were prepared in a ~ubstantially similar manner to
that of Example 1, the details of the preparations and amounts
25 used being summarised in Table 1.
.Intermediate B was prepared in a similar manner to
Int-ermediate A, except that the starting materials used were
.cy~loaodecatriene (410g; 5 moles) sulphur dichloride (103g;
1.0 moles) ana 2.5 litres of metnylene dichloride, -xce~s
iO47506
cyclododecatriene then being stripped off and the resulting
material recrystallised from petroleum ether (b.pt. 62-68C).
Intermediate Bl was prepared in similar manner to
. intermediate B, except that 6 moles cyclododecatriene and
1.2 moles sulphur dichloride were used.
Intermediate Al was prepared in a similar manner to
Intermediate A, except that 1620g 1,5-cyclooctadiene and
1545g sulphur-dichloride were aaded over about 6~ hours to
1800 ml methylene chloride at 0C to -5C.
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104'~S06
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1047506
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1f 47S06
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104'~S06
xample_21
Preparation of Inte.mediate
2,6 - dichloro - 9 - thiabicyclo (3,3,1) nonane
Sulphur dichloride (1030g. 10 m.) and 1,5-cyclooctadiene
(1080g. 10 m.) were added simultaneously, at equal molar rates,
to methylene dichloride (1250 ml.) maintained at 0 to -5C.
over a period of 4~ hours. The resulting mixture was allowed
to wàrm to room temperature overnight, then heated to 45C. for
2 hours, cooled to room temperature and refrigerated to yield
1670.6g. (79.3%) of solid product which was filtered off and
dried in a vacuum oven at 50C.
Analysis of product:- %S 14.86 (calc. 15.1)
%Cl.31.7 (calc. 33.7)
Preparation of 2,6-bis (methoxy/ethoxythiocarbonyl-
. .
~hio)-9-thiabicyclo (3,3,1) nonane
~otassium hydroxide (72.2g. 1;1 m. of 85~ purity) was
.. . .
added to a mixture of alcohols (ethanol 177g + methanol 123g.)
and heated until dissolved. The re~ùlting mixture was cooled
,.,, ~
to about 45~C and carbon disulphide (84g. 1.1 m.) aaded while
maintaining the reaction temperature at about 40C., where-
after a solution of the intermediate prepared above (105.5~
0.5m. dissolved in 400 ml. toluene) was added over a period of
40 minutes during which the temperature was maintained in the
range 40-50C. A yellow precipitate formed. m e reaction
mixture was refluxed ~72C.) for 4 hours, then washed with
water after addition of toluene to ensure phase separation
and the organic layer separated. The organic layer
was filtered, dried over anhydrous magnesium sulphate
o~rernight, refiltered, stripped to 100C./20 torr and the
residue refiltered to yield 106g. (57.6%) of the product
as~a viscous red iiquid.
..
. . I 1~.
104'7S06
Analysis of product:- 44.7%S ~calc. 43.5~)
0.65%Cl. (calc. 0)
Example 22
2,6 -bis (~ethoxy/n - butoxythiocarbonylthio)-9-thiabicyclo
(3,3,1) nonane
The intermediate was prepared in similar manner to
Example 21 from 940 ml. methylene dichloride, 774g. ~7.5 m.)
sulphur dichloride and 810g. (7.5 m.j 1,5-cyclooctadiene
Analysis 16 ~ 4%S ( calc. 15.1)
33.5%Cl. (calc. ~3.7)
The product was prepared in similar manner to Example 21
from 36.1g. 85% purity potassium hydroxide, a mixture of
61.6g. methanol and 142.5g. n-butanoi, 42g. (0.55 m.) carbon
disulph1de and 52.7g. (0.25 m. ) of inter~ediate dissolved in
- 200 ml. to`luene; and the yield was 59.7g.
Analysis of product;- 39.2%S (calc. 40.4~)
0.6%Cl. (calc. 0)
Example 23
The same product as in Example 22 was prepared in similar
.
manner except in that the mixture ~of alcohols consisted of 31.4
methanol and 212g. n-butanol; and the yield was 80.lg.
Analysis of product:- 39.4%S ; (calc. 38.3%)
0 . 33%Cl . ( calc. 0)
Example 24
2 - allyloxythiocarbonylthio 6 - isopropyloxythiocarbonylthio
- _ - 9 - thiabicyclo (3,3,1) nonane
The product was prepared in similar manner to Example 21
from potassium hydroxide (72. 5g. 1.1 m. 85% purity), a mixture
of allyl alcohol (145g. 2.5 m.) isopropyl alcohol (150g.
2.5 m.), carbon disulphide (~3.6g. 1.1 m.) and 2,6-dichlorv-
9-~hiabicyclo (3,3,1) nonane (105. 5g. 0. 5 m.) in 400 ml.
toluene; and the yield was 150g . ( 7 ~ . 5% ) .
104'75~)6
Analysis of product:- 37.5%S ~calc. 39.2)
0.35%Cl. (calc. 0.00)
Example 25
2,6 bis (methoxy/ethoxythiocarbonylthio) - 9 - thiabicyclo
(3 3 1) nonane
-
(a) Potassium hydroxide (36.1g. 0.55 m. 85% purity)
was dissolved in ethanol (150 ml. 740P) by heating to 50C.
for 10 minutes. The solution was cooled to 40C. and carbon
disulphide (41.8g. 0.55 m.) added over 20 minutes, toluene
(50 ml.) being added to maintain stirring. A solution of 2,6-
dichloro - 9 - thiabicyclo (3,3,1) nonane ~105.5g. 0.5 m.) in
toluene (400 ml.) was added over 40 minutes with cooling. The
temperature was allowed to rise under~the exotherm until a
steady temperature was reached and the mixture then heated to
" . . .
70C. for 4 hours. The product was allowed to cool and was
filtered, two phases being present. After drying over magnesiur.
sulphate and filtration ~ne solvent was stripped off to yield
p~oduct (a~. ~
(b) Potassium hydroxide (36.lg. 1.1 m. 85% purity)
w-as dissolved in methanol (150 ml.) in a fresh glass vessel.
Carbon disulphide (41.8g. 0.55 m.) was added over ~ hour with
stirring. Product (a) dissolved in toluene (40û ml.) was
added over 3/4 hour and the mixture heated for 4 hours at
64C. After cooling the product was washed with three portions
of water, toluene being ad~ed to aid separation. After
drying over magnesium sulphate, filtering and stripping 150g.
(81.5%) of the above named product, a viscous orange liquid,
was obtained.
Analysis of product:- 35.6%S (calc. 43.5%)
0.75%Cl. ~calc. O.OOi~)
. .
~047506
Three further examples (Examples 26 to 28) were carr ed
out in substantially the same manner as in Example 25, details
only of the reactants and product analyse~ therefore being
specified in each case.
Example 26
2,6 bis (methoxy/butoxythiocarbonylthio) - 9 - thia-
bicyclo (3,3,1) nonane
(a) KOH (72.2g. 1.1 m. 85% purity), n-butanol (400 ml.),
CS2 (83.6g. 1.1 m.) 2,6 dichloro-9-thiabicyclo (3,3,1) nonane
(211g. 1 m.) and toluene (800 ml.).
(b) KOH (72.2g. 1.1 m. 85% purity), methanol (300 ml.),
CS2 (83.6g. 1.1 m.) and toluene (600 ml.). Reaction product of
(a) added to (b). Yield of final product was 332.8g. (8470).
Analysis of product (orange liquid);-
31.7%S (calc. 40.4)
~ . 0:~5%~1. (calc. 0.00)
,
~ Example 27
2,6 bis(ethoxy/butoxythiocarbonylthio) - 9 - thiabicyclo
(3,3;1) nonane
(a) KOH (18g. 0.275 m. 85% purity) n-butanol (100 ml.)
CS2 (21g. 0.275 m.) 2, 6 dichloro- 9 thia bicyclo (3~3,1) nonane
;.
(52.8g. 0.25 m.) toluene (200 ml.).
(b) KOH tl8g. 0.275 m. 85% purity) ethanol (lOO ml.)
~ CS2 (21g. 0.275 m.) toluene (200 ml.) Reaction product of (a)
25 - added to reaction product of (b). Yield of final product
was 72.6g. ~71%).
Analysis of product:- 31.4%S ~calc. 39%)
0.5%Cl. (calc. 0.00)
Example 28
2 - allyloxythiocarbonylthlo - 6 - isopropoxythiocarbonylthio
_ - 9 - thiabicyclo (3,3~1) nonane
(a) KOH (32.9g. 0.5 m. 85% purity), iso propyl alcohol
1047506
(200 ml.) CS2 (38g. 0.5 m.) 2,6 - dichloro - 9 - thia bicyclo
(3,3,1) nonane (105.5g. 0.5 m.) toluene (400 ml.)
(b) KOH (39.5g. 0.6 m. 85% purity) allyl alcohol
(150 ml.) CS2 (45.6g. 0.6 m.). Reaction product of (a)
added to reaction product (b). Yield of final product was
176.4g. (86. 5% ) ~
Analysis of product:- 34.02%S (calc. 39. 2/o )
0.41%Cl. (calc. 0.00%)
Example 29
2-Dodecylthio-6-isopropoxythiocarbonylthio-9-thiabicyclo
(3,3,1) nonane
n-Dodecylmercaptan (50.5g. O. 25 m.) was dissolved
by stirring in toluene (200 ml.j and then sodiun, metal (5.8g.
0.25 m. 3 added over 20 minutes at 100'C. After heating for
2 hours at~ 110C. a white suspe~sion was obtained which was
' added to a solution o~ 2,6-dlchloro-9-thia bicyclo (3,3,1)
nonane (211g.-- 0.25 m.) in 'toluene (200 ml.) over 5 minutes
- 'and subsequently heated to 100C. foF 3 hours, cooled and
filtered through glass-fibre filter and added to a solution
, . . , ..... j .
of potassium isopropyl'xanthate ir~ isopropyl alcohol.
The latter was prepared by dissolving potassium hydroxide
(20g. 0.3 m. 85% purity) in isopropyl alcohol and adding carbon
disulphide (22.8g. 0.3 m.) thereto whilst maintaining the
-~- temperature at 38-40 C. The mixture was heated at 80C. for
3 hours, cooled, washed with water and dried over magnesium
sulphate to yield 101.4g. (85.2%) of the desired product.-
Analysis of product:- 26.1%S (calc. 26.9%)
O.68%Cl. ~calc. 0.00,0)
Examples 30 to 37
Further compounds in accor~ance with the present
in~vention were prepared in a substantially similar manner
to that of Example 29, details of the reactants and product
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1047506
analyses being summarised in Table 2 in which, for convenience,
2,6-dichloro-9-thiabicyclo (3,3,1) nonane has been abbreviated
to 2,6 DTN.
Example 38
2 (octanoxythiocarbonylthio) - 9 - cyano - 13 - thia-
bicyclo (8,2,1) tridec - 5 - ene
(a) Sodium cyanide (12,3g. 0.25 m.), ethanol (300 ml.
740P) and 2,9-dichloro - 13 - thia bicyclo (8,2,1) tridec-5-ene
(66.3g. 0.25 m.) were mixed and the exothermic reaction allowed
to proceed (35C.) for one hour then heated for 3 hours ~t
75C. After cooling water (600 ml.) was added to precipitate
a product which was filtered off and dissolved in toluene.
(b) Potassium hydroxide (19.8g. 0.3 m. 85% purlty) was
dissolved in n-octanol (200 ml.) by heating to 70C. for ~ hour.
After cooling to below 40~. .carbon disulphide (22.8g. 0.~ m.)
was added ovér 20 minutes, a yellow precipitate being formed.
me toluene solution from (a) was added over 1 hour and the
mixture heated to 9PC. for 3~ hours. On cooling the solution
was washed three times with water (400 m:L. each)`, toluene
.. ....
(400 ml.) being added to aid phase separation. The toluene
solution was dried over magnesium sulphate and strip~ed on
a rotary evaporator and then stripped under high vacuum from
70C. @ 0.1 Tprr to 120C. @ 0.2 Torr. The residue was a
viscous brown liquid which appeared- to be the desired product.
Analysis of product:- 13.8%S ~calc. 22.6%)
0.94%Cl. ~calc. 0.00%)
3.05%~ (calc. 3.29h)
Example 39
2 ethylhexyl xanthate of a polymer of 2,9-dichloro -
3o 1 3 -thiabicyclo (8,~,1) tridec - 5 - ene
Cis, trans, trans-cyclododeca - 1,5,9 - triene (324g.2m.)
10475U6
and sulphur dichloride (206g. 2 m.) were added simultaneously
from two dropping funnels into stirred dichloromethane (1000 ml.)
maintained at a temperature of O to -5C. Dy an acetone/dry ice
bath at a rate of 2 vols to 1 vol respectively. The mixture
was allowed to warm to room temperature over the weekend~
After heating to reflux (45C.) for 4 hours it was cooled in
a refrigerator in order to attempt recrystallisation. Since
no crystals were formed the solvent was removed on a rotary
evaporator. On stirring with 62-68C. special boiling
petroleum ether, 2,9-dichloro-13-thiabicyclo (8,2,1) -tridec-5-ene
(DCTT) was dissolved leaving a light brown solid polymer also
insoluble in toluene which was found to contain 12.7%S (calc.
12.07%) and 23.8%Cl. (Calc. 26.8%) which-figures correspond to
a polymer of DCTT.
... ..
Potassium hydroxide (49.4g. 0.75 m. 85% purity) was
.. . . . . . . .
dissolved in 2 ethyl hexanol (500 ml.) by heating to 90C. for
~ hour, c~oled to below 40C. and carbon disulphide (57g.
- 0.75 m.) added over 25 minutes, toluene (100 ml.) being added
to maintain fIuidity. DCTT polymer (66.3g. 0.25 m.) in 2-
ethyl nexanol (500 ml.) was ad~ed over 45 minutes. The solution
was heated at 80-85C. for 4 hours, cooled, diluted with~
toluene (600 ml.), washed four times with water (400 mls. each)
dried over magnesium sulphate and filtered. After removing the
solvent on a rotary evaporator the product was stripped
25- under high vacuum to a base température of 80C. @ 0.1 Torr.
The product was found to contain 15.8%S (calc. 26.5%) and
1.06%Cl. (calc. 0.00%).
Example 40
Example 39 was repeated except that the reactants
were added to the dichloromethane at a temperature of
20-30~ and then heated to 45C for 3 hours. The mixture
was then extracted with hot petroleum ether (b.pt. 62-68C)
~047506
leaving a solid polymer found to contain 12.06%S and 28%Cl.
Thereafter a ~ubsequent reaction was carried out as described
in Example 39 to yielu 80g. of product.
Analysis of product:- 25.1%S (calc 26.5%)
1.7i~Cl. (calc. 0.00%)
Example 41
2,9-bis(crotyloxythiocarbonylthio)-13-thiabicyclo (8,2,1)
tridec-5-ene
Example 19 was repeated except in that
Intermediate B (66.3g. 0.25 m.) wa~ used in place of
Intermediate Al. Yield of product was 112g, (91.4%).
Analysis of product;- 30.5%S (calc. 32.7%)
1.27~Cl. (calc. O.00Z)
Example 42
2,6-bis(isopropoxythiocarbonylthio)-8-thiabicyclo (3,2,1)
. . ....... .. .. .
~ -oct-3-ene
., ~ .
1?3,5-Cycloheptatriene (184g, 2.0 m.) and sulphur
dichloride (206g. 2.0 m.) each dissolved in 250 ml. methylene
dichloride were added simultanëous~t equimolar rates to
. ~ ..;
500 ml. methylene dichloride at -20C over 5 hours. The
mixture was allowed to warm to room temperature overnight
and the solvent stripped off on a rotary evaporator. The
product was then distilled out of the residue ~rom the rotary
.. . . .
evaporator.
` The intermediate prepared as in the preceding
paragraph (114g. 0.58 m.) dissolved in 200 ml. toluene was
added to 1.3 m. of potassium isopropyl xanthate and the
mixture heated for 5 hours at 80 C. Further toluene
was then added and the resulting solution washed with water
and dried over MgS04. The toluene was then stripped off
on a ~otary evaporator to yield 146.4g. (64.1%) of a
black liquid.
~047506
Analysis of product:- 38%S (calc. 40.6%)
2.34%Cl. (calc. 0.00%)
Tests A to R'
Certain of the compounds described in the foregoing
Examples were dissolved in lubricating oil (1% solutions) and
tested in the extended Petter Wl test.
The tests were carried out for ~6 hours, using a Petter
Wl Laboratory engine built and run according to the standard
IP 176/69 procedure, except in that a sample of' the oil was
not taken after 16 hours. The blends under test contained
an ashless dispersant, an antiDxidant, a surfactant and a
corrosion inhibitor.
The criterion ta~en was t~ ~ earing weight loss
which was of the same order or lower,than the bearing weight
"-'15 lo~s for zinc dialkyl di,thioph~;$'p ~ e.'
,:" ~ Examples 1 and 2 gave blackened bearings but when
the blénd was retested with 0.0~% of benzotriazole the bearings
had a normal colour.
, The products of Exa'~ples 4 and 5 gave particularly low
20 'bearing weight losses and gooà colour~bearings in the absence
of benzotriazole.
The product of Example 3 was only soluble to the extent
o~ 0.25S in mineral oil. .,
- '' The results of these tests are given in Table 3. It
can be seen that the results compare favourably with a blend
containing a zinc dialkyl dithiophosphate and other ash
containing additives.
, In addition Copper Strip tests were carried out in
accordance with IP Test Method 154/69 except in that the tests
were carried out at 120C using the test additive dissolved in
500 Solvent Neutral mineral oil in an amount suf~icient to give
a product sulphur level of 0.15% by weight. In this way was
25.
1047SO~i
,, tested each of the products of Examples 1, 2, 4, 5, 7-13, 16,
19, 25, 28-36 and 39-41 all of which gave results of la or lb.
Furthermore, the novel additives of the present
invention were also found to have useful load carrying properties.
`, .. . : , .
..
. ..
. .
- . . .
, .. . ... ..
.
.... .
.
~04~7S06
" TABLE ~
_ ._
TE~T BLEND CONTAINING BEARING WEIGHT COLOUR
1% of EXAMPLE No. LOSS (mg.)
1 22 BLACK
8 , 2, 30 BLACK.
4 STRAW.
_
D 5 7 STRAW.
_ 7 17 STRAW.
_ .
F 12 8.1 BROWN TO DARK
. PATCHES.
G 13 16 LIGHT STRAW.
` DARK STRAW PATCHES.
14 14 STRAW. DARK STRAW
- PATCHES.
_ .
I 15 14 LIGHT STRAW,
. PEACOCK COLOURS.
.
J- 16 53.3 DARK BROWN - BLACK
LACQUER.
_
K 17 22 - BROWN-PEACOCK.
L 28 (1.5%) 19 BROWN TRACES BLACK.
~ M ' 32 17 STRAW-PEACOCK.
N , 33 ~ 12;- BROWN TRABLACSKOF
_. ~ ., I
O 34 .1~. STRAW-PEACOCK
- p 35 12 STRAW-TRACES LACQUER. ¦
: 36 , 8 STRAW-PEACOCK.
_ 39 '20 LIGHT STRAW-COPPER/
R ; PEACOCK PATCHES.
... . . . ~ ~
., .
. ~. .
;.
.
. . ' ' , , - .
. .
,
27.
