Several synthetic routes were studied for the synthesis of the compound 1, 1, 3-trimethyl-1, 3-dicyclohexyl-2 chloropropane. This halogen-labeled fluid would be of use in the study of high traction lubricants under elastohydrodynamic lubrication conditions using infrared emission spectroscopy. The synthetic routes included: dimerization of alpha-methylstyrene, methanol addition to alpha-methylstyrene, a Wittig reaction, and an organometallic approach. Because of steric hindrance and competing reactions, none of these routes were successful

Jones, W. R., Jr.

Zimmer, H.

English

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https://ntrs.nasa.gov/search.jsp?R=19790002948 2020-03-22T02:23:12+00:00Z
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William R. Jones, Jr. and Hans Zimmer
Lewis Research Center
Cleveland, Ohio
November 1978
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NASA Technical Memorandum 79024
(NASA-TM-79024) A STUDY OF VARIOUS
	 N79-11119
SYNTHETIC ROUTES TO PRODUCE A
HALOGEN-LABELED TRACTION FLUID (NASA) 10 p
HC A02/MF A01
	 CSCL 07C	 Onclas
G3/23 36991
A STUDY OF VARIOUS SYNTHETIC
ROUTES TO PRODUCE A HALOGEN-
LABELED TRACTION FLUID
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SUMMARY
Several synthetic routes were studied for the sytaliesis of 'he compound 1, 1, 3-
trimethyl-1, :1-dicyclohexyl-2-chloropmpane. This halogen-labeled fluid would be
of use in the study of high traction lubricants (i, c., 11uids which exhibit high c(-*-
efficients of friction), This compomid was tA) be used as an indicator of Iluid molec-
ular aligiinient in clastohydrodynamic contacts, Alignment would he detected uy de-
teririinin t; the direction of the carlom • -chlorine hand n ►ument using; polarized infrared
cillission spectra.
The synthetic routes investigated were:
(1) A dinivrization of a-mcthylstyrene.
(2) Copper (1) promoted addition of methanol to a-mcthylstyrene.
(3) A Wittig reaction and
(4) An organomet :tllic ;approach
Because of steric hmulrance and competing r eactions, none of Ihese synthetic routes
wt ce successful, it was concluded that this compound could not be easily synthesized
:uu, that a less complicated Halogenated structure be colisfdere(l.
INTROD'JC'l'ION
The increased interest in traction drives for power transmission is causing a
dem.uul for improved hi gh traction luhrlVat ►ts (i. C. , fluids which exhibit higii coeffi-
cients of friction (ref. 1). Present lubricants I'or these applications have been em-
pirically developed since their mech:uusm of operation is unknown (ref. 2). Ilecent
studies (refs. :3 to 5) iiiw, 1 —Nin to elucidate how these Itibric • ants function in clasto-
hydrodynamic contacts In another study (ref. G) inf cared emission spectroscopy is
being used to determine the chemical and physical states of lubricant., clastohydro-
dvnamic conditions.
It was f h that a lialogenatrd comp owed, sirfilar in structure to the traction lubri-
cants, would provide further information m the above spectroscopic study. In partic-
ul:tr, a chlorinated compound was considered because the direction of the carbon-
chlorine bond moment could be deternimcd from polarized infrared spectra 'Then,
in principle, molecular fluid alignment in an elastohydrodynanuc contact could be
determined from these measurements.
Therefore, the objective of this study was to synthesize the chlorinated conilx,un(l,
1, 1, 3-trimeth .0-1, 3-dicyclohcayl-2-chloropropane. The synthetic routes studied
were: (1) a dimerization of n- methyl. tyrene, (2) copper (1) promoted addition of meth-
anol to n— mcthylstyrene, (3) ;i Wittig reaction, arnl (4) :ui organometallic approach
I.
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RENITTS AND DISCUSSION
I'lti,lnlsetl Ilalugenated Compound
Pile proposed IlAognenatt • t1 conllxl.uul to Iv used as a indicator fluid in infrared
emission spectroscopy studies on	 contacts is shown in fi.;ure 1.
This cyclualphatic	 is structurally similar to tilt, high traction compo-
nents used in high traction luhncants. Its cht,rtlic:ll nalms • is: I, 1.:1-1 rinlethyl- 1, a-
i.l
	
dicyclohexyl	 chloropropanc.
several m e thods for synthesis were attempted, Vioures 2 and :1 sumin;irized
representative syntheses performed and the e\pectctl products.
Itimorization of a- Mothylst\ rene
'rhe dinrt,t• ization of n- nu • lhy-lsivrene (11) :nave nunu • rous products. A tllinilnul-n
of six different a- Whvlstvrent, dlnu • rs flornit,d in acid havt, been isolated ill •mail
(It :I lit lTit's :lull atl:Ilyzed by NJllt (ref, 7). The lack of specificity of this reaction and
the problems :Issot • i :it ed \vltII the ( , It ro Illatt,gla Jill it , isolation of iht , desired di lilt' r front
the Imilly other products formod led us to abandon this route (fipn. '_'(al, Il - IV).
Copper (1) Promoted Addition of Moth:idol to o- lletlivistyrene
\Then (1-- 1110hylstyrt,tlt , \\as treated with ;(rid and l'ul'l, '. phenyl- ^- methoxy
propane (111) \\ , :is loaned, lull In V01*V poor Field as determined by thin hyer (hroma
togr:Iphy (lid. ''(b), 11-111). ltoutt,s employing 	 lhcrt,fore
Judged to ht , unsatisfactory.
wittl`n 11t,at,tlon
•hilt • Wittl`n 1 •t,at,l1011 Is \el • \' llsefill fo1 • tut , s\'llthcsis of olchIls,	 Ty picAl \', all
:Ippropriately substituted ylid is reacted \\ith ;In aldt,hvde or ketone, hl this study
(fig. 2(c),	 to meth^lh^'dr, ► tro1,;11deh^'de, \"III) Ind see-
phcnethyll ripht,nylphosphoniuIll iodide t\') wert , required. To obtain (v-
phollylisobutyr"IIdt,hyde (\'111). nl:lndcbc acid (\'1) \k ;IS t st. I	 ' in '•till percent
Field; this was followed III • treatment \\ith lilt' ih)lnlagiles it) Ill iodide to gi\'c the dial
(\ • 11 in -G,, percent (ref. tit. Using formic acid as a	 nlediunl
(ref, 9) the Advilyde (\"111) was isolated in S3 l,ero • enl of theory (fi:;. 2"1 \'11 \'1111.
tier phcnethy l chloride (I\) did net react \0111 l riph. n^ ll,hosphine, even under
forcing conditions; ho\\•c\'cr, sec- pht,nt,thyI iodide t\1 1%%ltily formed tilt , dc,ircd
l
t ► I I
V	 CII.,,
+
C'113
C -= 0
I
c• I I :;	 ^
C'11 : ;C IL1113
i
t
I
w2fia mom
i
phosphoniunt Salt (V) (fig. 2(c), X- V), Treatment of the phonphonium :salt (V) with
n - hutyllithitim 91tre a I ► lood-reel color in THF. 1 ►ut addition of the aldehyde (VIII) to
the Ylid, c\en when followed Iry refluxing, ga\e :o, ineotnplete reat,tiot ► as e0der►eed
by tilt
,
 chromatographic recovery of* unreac •ted aldehyde :r ► d phosplioniunt salt. Worl.-
ttp by vaeunnt (list i11:11ion o, the ort;: ► na product.': resulted in pol
.
\ merii.ation in the
t r ot. The • outcome of titose e\perinwnts tle'nu ►nar:tte • s 111:11 steri ► • hindrance scriously
intpait • S tilt , Wittig approach to the desired olc hil.
ttrwanonml.tllie Approach
:fin org:nlomcfallte str:ttv* , (1",g. .;) „:tK developed, ;mcc • , in general, organo-
metallie, are less .ens ► IIw to steric factors. Neoph0 chloride Ah trrf. 101, pro,
pared in 7 . 1 percent yield, \cas comorted to neoph
.
0nta gilt's III III chloride and reacted
with acelol+ht,none. More Ilmn 5.1 percent of nnt •e: sled aeelol,ht'nortt , \\:Is rt eoterc tl
by vaeutlnt distillation in addition to ,e\er,tl otlwr fraction,, :Ill of \01it'h :ate ne
tive chromic anhydride :tncl curie nit rate ic -A"; for tilt' h^tlrom l Ittnelion. The lack
of,
 not • ntal 1	 ulditfon ltc ut , nt:tY perlulps lit altril ► tltc1l to , tt .'it, hindt •:tnce, Stich thal
enolization of flit ,
 Ict,tone is preferred over normal add1t jolt a• Must rated hY t,tluafion t I);
t
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m, Ige1 (111,1
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i
-----►
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^^
tll
To avoid this pruhlen ► , neoplwl lithium (Xii) (ref. 11) W:tr ► reacted wtth aeetuphenonc
, i 	(fig. :1),	 l'nfortun:ticlV, this reaction ►tti\ittrr Solidified oil ttarn ► utl; inclicatin^; pol%-
mcriiation, Agait1, no lwdroxylic products were lurttted. Allcrn:tlt-ty, Sec-
'	 phe11011 I lilhiunt (X111) was prop: ► rcd and was reaclod with , p^^^n^'lisubut^'raldch^do
(VI11)	 Tlw predon ► in:tnt prodttcl here scen ► od to he SIN rent IS 11"I"d l ►y its Char-
actcrl -, ttcally 111111 ;cnt odor. Once :tgaut, .111 undesired reaction, In this ease ch
Imitation, seemed !o he lavored mer I, 2-addilion,
II \\:ts rt • copli/ed : ►1 the outset that the !,tnthosis of the destrod Intermediate
olelln \\1 ► uld he ditlicult because of Iho obOotls Sleric factors. I•'or Ihls reason
when the Wittig ut'actio;1 failed, the organun ► t • t:tllit- route tt:IS , ►tlrSUed, Since org:1110-
ntciAltcs are III general loss Scn,tti\t • to Stcrtc laclors (fig. :3, XI - 1).
Sl'NiN1A10 , t ► t' RESUi.TS
Several : •ynlhetic routes were ShOwd fur s
.
\ 11thesis of the compound, 1, 1, : 3-
I I • , metlty1- 1,	 This compound \% . :Is to I ►c used as ::n
indicator of fluid molecular ahi^Ilr ►► t • rtt In clastollYdrud.na III it- Studios of high traction
lul,ricants using tnl raced emiSSiott Spect roscupY. The routt's Studied \tore: (1) a
dinwrization of (Y- nitth. • lslYrcne, (2) copper (1) promoted addition of n ► cthanol to
t
ct 1 ► I1 the lst^ • rene, (;3) n Wittig roactton, anti ( I) :In or^:uton ,t:tlltc :tppt o:u h.	 The
m::jor reSnits N•ere:
I. None of the sy nthetic routes tt•ere successful hoc;ulse of con,pcttn:; reactions
t or s.oric hindrance.
It was concluded that this compom ' d could not be easil.' S.nlhosimd :11111 that
a loss complicated h:1lu cnalcd St ructure he considered.
i
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:\c • KNOW I.I • M A-' Nlt•:NT
I'ho ^.\ nthcsis work described heroin tt . ,Is perlornu • d by the Depart nicnt of Chem-
istry of the i'nitorsih• of Cinc• inn:llt. Onctnn:tti, Ohio under NASA purchase ardor
C-7 . 1 . 1 . 1- 1).	 The work ttas directed hY l)t • . 11mi-, %ininter.
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ItEF I •: ItENC ES
1. Green, It. 1.. ; and I.:ulgenfeld, F. 1,.: Lubricants for Traction D ►•ives,
Mach, Ws.	 %-ol. - 16, no. 11, May 2, 197 I, pp, 108-11:1,
2. Ilaseltine, M. W. ; et al.: Design and Development of Fluiths for Traction
mi(i 1 riction 'Type Transmission s. SAE'; Paper 7!OS:17, Oct. 1971.
3. Winer, W. O,; and Sanlxwn, 1). 111.: Surface Tvmpc rat tires :nul Glassy
State L► wtstigations in THWlo kN, Part 1. NASA C11- :101:3, 1975.
•1. Rd r, S,; and Winer, W. ().: Shear Stt'cngili NIvasurcrlients of 1.ul1ricants
-it high 1 1 1-essul •(1 , AS111E? 1 1aper 78-1,UB-8, Oct. 1975,
5, M ij r, S. ; and Wint e r, W. O.: A 111leological Model for E?lasto}tydrodynan ► ie
Contacts Based 4)n Primary 1.alooralory Data. ASAIE Paper 78 - L.UB- 9,
Oct. 1975.
(i, Latter, J. L..: Sludy of' DY11milic• Emission Spe'. •tra from lubricant Films in
:u1 Elastodydrodynamic Contact using Fourier Transform Spectroscopy.
(Suntech, hic. ; NASA Conti-act NAS3-	 ) NASA Clt- 159418, 1975.
7. Svob, A. J. ; and Cernicki, 13, K, : N. 111. It, Mcntification of n- Mothylstyrent,
1)lnters. Chi mia, vol. 22, no. 11, 196S, pp. •13.1-436.
S. Tiffeneau, AI.: :md I)orloncourt, 11,	 IIYdrobonroin Trmisformatitm. I. An n.
Chi m. I'll  s., vol, 16, 1909, pp. 3:17-257.
9, Cromwell, N. H.;  and Eby, 11. 11.	 1 1 1 ,e aration and Reactions of n •
-I'hcnylisobutyraldellN,dc and ov - 1 1 henylisobuty-1c Acid. J. Am, Chem. Soc. ,
vol. 7 .1, 1952, pp. •1201-4:102.
I
	
	
Smith, W. T. , Jr. ; and Sellas, J. T.: Organic Synthe: vs. Collective Vol. 1.
N. Itabjohn, ed,, John Wiley i\ Sons, 1nc., 196:1, pp. 702-705.
11. Grovenstein, Erh ng-, Jr. ; and C lieng, S• ao- Aling.: J. Chem. Commun. , no. 2,
1970, pp. 101- 102,
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i'I I
c--c--cI	 I	 I
CN 3 N	 (113
figure I. • Proposed helalrnat.4t traction comp<,und
11, 1, 3-trimethyl-1, 3-dicyctoh*%Vl-2-chloropropanti.
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1
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kf 1
I,)lilt ^lh	 l^^t AI J'1•Y
HI I I	 Ic—C—cI	 I
CH j H	 CHI
	
U H2, catalyst	 11 H 2, catalyst
21 SOC1 2 	 11	 ` 21 SOC12
CH I OH H	 CHI OH H
I	 I	 I	 I	 I	 I
PhC—C—CPh	 PhC--C—CPh
I	 I	 I	 I	 I	 I
CH I 
1
H CH I 	 HI H	 CHI
	
PhCHCHO `
	
804
GHfIiRHf	 ^H3	 CHIN	 ^CH2	 fl	 IHI	 /CN
I
	
PhCOCHI	 +^
cucl
	
PhC` 	o.`► 	 PhC—(,H=
CHI HO	 CHI molecular	 CHI
s(eves
111 1 	 Ib1	 Ills	 u1 (IV)
OH	
1
l
Ph3PI
SOC12	
I	 Nal
	
j
	 Pt' 	 1	 n_ BuU
	
PhCHCH I r	 PhCHCHI	 ...	 PhCHCHI	 ^•+	 PhCHCHI	 iHF	
PhC•PPh3
acetone
11X1	 IXI	 Iv1	
CH3
IV1111RHF
CN I
 ON H
I	 I	 I
PhC — C — CPh
I	 I	 I
CH I H	 CHI
OH OH
LH IMgI
	
I	 HCO2H	 1 3
PhCHCO2H	
^H I0N
	
PhCHCO2CHI	 ^+	 PhCHCICHj12 	 ^► PhCCHO
	
3	 OH	
2	
OH	 CHI
Ivn
	
will	 (V1111
(c 1
1
t
i k jr
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i
J
Figure 2. - Flow chart of reactions and expected products.
(a1 Dimerltation of 2 methyl styrene.
iU Wittlq reaction.
(b1 Copper 111 promoted addition of methanol to a - methyl s(;rene.
I
1
(
1
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C
1
j J 1
{{	 t
r^
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^H2C1
I 4,504
CH3
PhCCH CIMy ►t,c/	 I 2 \nHr
CH3	 CH3	 CH)
	PhCCH2Mg( l	 lx 11
	
Ph ; CH211	 1%I11
CH 3 	 H{
0
I	 PhCCH3
CH 3 )H
	
PhCCH2
 CPh	 PhCCH3	 11CHCH3 t	 ^ Ill1
I	 1
	CHI
 CH3	 1X1111
w 1111
-H20
	
li H 3	 /Ph	
12Hb	
CH 3 H H	 Ill H2, Catalyst
IhCCH+C
	
Ph^	 Ph ^+ ► i
	
CH 3	NCH 3 	CH3 H	 3
	II 	 t ►+	 12l SOCII
C 
1111
Figure 3. - {law chart of reactions and expel led products for oryanometallie
approach.
'	 II
I	 ^	 I
I
1 I	 1
	
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i


A study of various synthetic routes to produce a halogen-labeled traction fluid

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