Document EMjrjqxvD0bKdmedp8x9ZbmV
3M |
bh. CCOMPPAANNYY 4
BE TIT ETE
-
E' HHEEPPTTAAFFLLUUOORROOBBUUTTYYRRIICC
E
AACCIIDD
-
y
MINNESOTA MINING & MANUFACTURING CO.
h NEW PRODUCTS DIVISION
SAINT PAUL 6, MINN.
0
EExxhhiibbiitt
1008
State of Minnesota v. 3M Co., Court File No. 27-CV-10-28862
33MM_MMNN0033110099550000
11000088..00000011
TTA ABBLLEE OOFF CCOONNTTEENNTTSS Page
Page
PPHHYYSSIICCAALL PPRROOPPEERRTTIIEESS
'
l
CCHHEEbM~IICCAALL PPRROOPPEERRTT]IES
3
DeDceacrabrobxoyxlyahttion
:
3
sans
5
3
Salts
Esters
Ll
Esters
4
Anaydride
6
Anhydride
6
Acid Halides,
6
Acid Halides
6
Amides
6
Arr~ide s
Nitrile
7
Nitrile
7
Alcohol
7
Alcohol
7
AAllddeehhyyddee
5
8
Amine
5
An~ine
8
iMvilsi~cceelillaanneeouosus,
99
APPLICATIONS
10
APPLICATIONS
lO
HANDLING
10
HANDLING
tO
TOXICITY
n
TOXICITY
Ii
APPENDIX Aln P]~NDIX
CCoorrrroossiioonn
Data
Oafa
Acid - Vapor Pressure Graph
Acid - Vapor Prcssure Graph
Acid - Viscosity=Density Graph
Acld - ViscosJty-Densily Graph
Esters - Vapor Pressure Graph
~sters - Vapor Pressure Graph
EEsstteerrss -- VViissccoossiittyy--DDeennssiittyy GGrraapphh
11000088..00000022
33MM_MMNN0033110099550011
HHEE,PPTTAAFFLLUUOORROOBBUUTTYYRRIICC AACCIIDD [Gryer,eryeoon|
IINNTTRROODDUUCCTTIIOONN.
CompanyTTshheeinCGeiennttriranalvleR Rsteeissgeeaaatrircocnhh oD Dfee|ppaIarnrtotm mroeecnnhttemoofifcM Mailinsns,neeshsoaosttaastMIM uidnJinieJnndggtaahnenddfuMMoaraninunufaaftacictotuunrriionnfgg
Company, in its investigation of Kluorochemicals, has studied the fluorination of
aiphatic acids. The physical and chemical properties of these acids have been aliphatic acids. The physical and chemical properties of these acids have been ITrhveemliatgaatseadmbeynrthiezeCdonhterrael hRaevseearrecshulDteedpaIrrtommenttheasnedvtehsetNigeawtibornosd.uctMyosLtaboofrahtiosry. investigated by the Central Research Department and the New ~roducts Laboratory.
ITUiTTnnh.eLtfeoSSosT.rdmmoaRmRattaeetathiiiiddoosNnnuaaa~tnnhhnidda~aoGassnG.rsi.b1ezeHeH,eN.n.enideSSpBtm mhrrieiieentrshtgne~eehnomhtyEfaee.vtddheBA.Ae.ii.nnrAeK RppmsaaaaueuupplrccteeihkerrcdssaaannfnbbrddyyoCwAAhDDn.ee.. mtR RRih...ceasD DHHe:iuoiwsesistSsntolosvelecledidiisnnetgaa,tinnygaaddannatddAAti..oAD Dnt.sHH.l...aGOn.AA.tMllioWbW bcrerseeietC{ccnibhhlto]ttefye,,,nnthaaitfs
NIL September. the ll~3th National 1940, Meeting o{ the Azmerican Ghe~mica[ Society at ~tlantic City,
N.
of
aftc.,omSTT pehiphinitssteemsslubyuremnrfmm ,oar~1ri9ryy4n9aii.tsoebbdeeiirnneggstppirrveeesseennFthteeudodrtfooochaauccnqqiuucaaaiilnn-tt
cchhHeeempmiaislstltsusaw wrioittbhhulttyhhriissiceexxaaacm midppll1ees
of a connpletely fluorinated reactive Fluoroche~nical. Heptafluorobutyric acid is
OThtehefrrarteamcotwivereaancdiinveonF-rleaascrtoitvheemFiicuaolratcohboemisctauldsieadreextceunrorievnetllyy aatndIeMr Iinnbvoesrtaitgoartiieosn.. ~he first new reactive Fluorochemical to be studied extensively ai 3M laboratories.
Other reactive and non-reactive Nluoroche~icals
Will be SRuepspeiairecdhonquarnetqiuteisets. of heptailuorobutyric Research quant,ties of heptafluorobutyric
acidare
acid
are available. Samples currently under investigation.
are available. San~ples
will b~ supplied on request.
Fhewse
IIwnneqquusiirtriieess
are
are
solicited
solicited
concerning
concerning
this
this
and
and
other
other
3M
3M
Fluorachemicals.
P"luorochemicals.
Please wr~te:-
bM{iinnnneessoottaa MMiiNnneiiwnnZgPraaonnddducMMeaasnnuufDfiaavccittsuuirroiinnnZg CCoo~mnppaannyy NSetw PPraodu6,ctMsinInDeivs;ostiaon
St. Paul 6~ Minnesota
11000088..00000033
33MM_MMNN0033110099550022
PHYSICAL I'ROPERTIES
PHYSICAL I~ROPERTIES
Formula Form
CF CF, GF,COOH
OF CF CF COOH
Col3orle2ss lZiquid
olorless liquid
FFoorrm muullaa WWeeiigghhtt OOddoorr
Z21144 Sharp, similar to butyric acid
5harp~ similar to butyric acid
BBooiilliinngg PPooiinntt
ve FFrreeeezziinngg PPooiinntt
DDeennssiityyty g/cg/occI1
VivisCscocnootssiiistttyoy,k!e1s
Centistokes
112Z00..00CC ((773355 rm) ram)
Rees] S150 -17.5C
1L.6o4l1
(25oC)
(z~c)
1.56z 600)
0828 R(5e0C))
0.828 00G)
IInnddexeexxooofff lRqeReteffrraaccttioionnZ? Vapor Pressure!
Va]Do r P l-e s su]-ei
w5o1.290
n25 1.290
444544D5m mmmmm aaatt 5510607.C4C
735455
735
mam mm
nnm
atat
at
120C 107.4C
lg0G
Heat
ooff
Vaporization
Vaporization
Heat
S 1!11~,220000m ccaall..//'m moollee})at bp. (cate)
52.3 cal./g
at b.p. (calc.)
Troaton Ratio
T routon Ratio
2288..55
Surface Tension
Surface Tension
E EqqCuouinivvdaaullceetnntat nce Conductance
CCoonnccmeeonnlttarrraattiioonn im(emoldairl]ation
Infinite dilution
00..000051 0.001 000O..0.0O0112O5 000x...t000g44
0.!
15.8 D Dyynneess//~ccmm
Hat 20C
pH at Z9C
313.1 23Z.3 21Z.1 111.7 is1o5 11.1
((s3o0Cc)) E Eqquuiivvaaallteenn2tt7CCCoonndduuccttaannceee ___m mhhoaosts/0g/e7qe uqCiuvivaalleennyt 33I88m33 33330761747 33355449076 "Extrapolated Value
':~Ext rapolaled Value
2tL0.. SSVeeaceriaaeppsppeeinnnddfiioxxurfftoohrr pgglrraacaepp:hh. hygroscopic
Z. Varies in fourth place; hygroscopic.
"ie 1-
11000088..00000044
33MM_MMNN0033110099550033
Sowbiliy
Solubility
Grams acid per 100grams solvent a1 20C Grams acid per 100 grams solvent at
Sectone mise _A c e to~ae Benson Ex Benzene Coon Disulfide iol. Carbon Disulfide Carbon Tetrachiorice 41.3 Carbon Tetrachloride Ener ie: E~he r Heane oy Heptane Ahn Tote N4e[hano] Ninerai 01 sel. N4ine ra] Oil Persoleum Eger fis Petroleum Ether
{b.p. 30-75C)
i]li s c.
ZZ.3 insol. 44.3 n~is c. 2.4 ~is c..
misc.
Water
misc.
Xylene
Infra-red Spectrum
In[ra-red Spectrum
N 1",90 \ N\TTVn oN
Ber o VJ
ihlhA
Ir
Po
---- |
~ I
I
3
4
Corrosion
Corrosion
i , I, I
5
G
7
I~ 8
I ~ 9
I
,
I0
we ier Wovetenglh ~n Microns
Celt Thickness 0.013mm Cell Thickness 0.013 rnm
Aluminum, brass, copper. Monel, nickel, and Aluminum, brass~ copper, Monel, nickel, and Cold rotted Sect showed Contino weight Toss cold rolled steel showed continuous weight loss henimmer sud in hemaivoroburriyc agi when inqn~ersed in heptafluorobutyric acid
throughout a 1ZO hour test period at 50~,
Stainless steel showed weight loss in 100 percent acid but was passive to 50 percent and
E eeam sohwions for the Rest 48 hour 5 percent solutions for the f[rst 48 hours rmmaraion, and showed unappreciable weight immersion, and showed unappreciable ~veight
loss in 50 percent and 5 percent concenfralions
for the uration 01 the 170 hour tot period. tot the duraiion of the IZO hour test period.
Corrosion was generally more severe in half
maton mies oar tn compietely fmmersed immersed samples than in completely i~mersed
samples. Detailed quantitative results are
vended. appended.
`ee
-Z-
11000088..00000055
33MM_MMNN0033110099550044
CCHHEEMMIICCAALL PPRROOPPEERRTTIIEESS
Decarboxyiation
De car boxy. [ation
of pyridDDieeneccaaarrnbbdooxxsyyilliaavtteiiroonnoxooiffdehheegppattvaaefflluhueooprrtooabbfuulttuyyorrriicocpaarccoiipddanooenn, hhCeeaFattii7nnHgg, iinbnottihhleiengpprraeetssee-nn1cc7eeC ttwoofoitp-Zhy11re99ixdcCCiens((es7744a11fnidrvmeamsm)ip)le..vrecreHHneeotaaxttipiidnoneggtagttsahhsveeeiuaahcmceiipddhtyaaadttfrlo22ux00oi00rd9oeCCprgoffapoovrraene4a4 'hhhCioog3uuhFrrs?y7iHiie,nnldbaaooifssleeiCaan,llgeeFdda7tHtt,-uu1bbeea7sC wwdwiiaattssihonttsehh.xeececcIsaanssseewfaiwwtviieettrhhpeatttreecnn1e5npp0teerrCpcco,eetnnattthsesssiooaudcdniii~duuhmmdyedcccraaaorrrxbbbiooodnnxeaayttlgeea~tvsseeoodlluuaatttiihooiannghuumnnyuiddceeehlrrd sssoliifmoni]wCile~laraFrr'TrHacc,tooen.na-s
ditions, In water at lSOC, the acid decarboxylated at a much slower rate.
SS~aittss
acid. AlHHleeppmtteaatffallluulooirrcoobbsuuattlyytsrriiwcchaaiccciihddhffaoovrremmbsseessanallttpssrewwpiiattrhhettdhheearceeaassceeryeesxxtppaleelccittneeedd eooxffceaapsstttrrtoohenngg alsTcoeeilaadudd.bisslaaAilllttt;;liemsbbeooatttnahhdlllliiimttcehhliistuuaimmlntgsaannpwddohiillneectaahsddohfssaaavltlettysspbiaecaarerleen mvpveeertrreayyplalhhriyyceggdrrsooaaslsrctceosoppciirccy..staTTlhlhieenettaaebbxllceeepggtiivveerissle
solubilities and melting points of typical rnetallic salts.
MELTING POINT AND SOLUBILITY OF METALLIC SALTS
MELTING POINT AND SOLUBILITY OF" METALLIC SALTS
SSooddiiuumm
LithiH HueemppttaafflluuCooarrloocbbuiututyymrraattee Lead
Lithium
Calcium
Lead
Silver
Silver
Melting Point, C
Melting Point, G
224400+255
21052
210--+2
5>335500
1304. 1304
130d.
130d.
Solubility 3/100 g Solvent
Solubility g/t00 g Solvent
SSoollvAvecennetttone
127 234
AEBBtceehennetrzzoeennneee
0001..2317]
0Z01..321.l42
MMEPeetetththehraraonnlooellum Ether 0011..220388
101i2.!Z40.4 2
WPae(t(tb0er..rpo..l33e00u--m7755EtCch))er
0.0
297
0.0
103
Water
297
403
202.00199
7I755.33 111044177
0111..52Zi8
5053..617i8 s55i690e..]s59
o01.5o08
e03.6o08
005.9d0.9
113300
4a993 a4Zz.zZ
iTTshheesoSSl-u-bbbleeennzzoyynlllttyhhiitooouurtrohoenniieuxumtmensstaallottf oo0ff.4hheegpprttaaafmlfulpouerororb1ou0bt0yurrtgiiyccraaamccsiidd wm maeteleltrtss ataatt201188C33.--44G C,,
and
and
is soluble only to the extent of 0.4 gram per 100 grams water at Z0G.
been fouFFnoodrruiisddceeinnuttlii.ffiiccTaahtteiiootnnhppruuerreppmoossoeessst,, pXXr--orrmaaiyyneaannntaallDyyessiibssyooeff-ttShhece hmmreeeattrraallXllii-ccrassyaalltltsisnehhsaass (beCeangf)ouanrdeusteafbuull.ateTdhefotrhtrheeesemossatmperosmalitnsent Debye-Scherrer X-ray ]ines
(Cu i4) are tabulated for these same salts.
DDEEBBYYEE--SSCCHHEERRRREERR XX--RRAAYY LLIINNEESS OOFF MMEETTAALLLLIICC SSAALLTTSS
Sodium
Sodium
LithHH ieuepmpttaaffi]uuCooraroolbbcuuthtyymrraattee Lead
Lithium
Calcium
1 ,ead
Silver
S~lver
IIdnintsteterarpnpclleaannaainrr AAdinnsggtssattnrrceoommissn
155...201343
a44.66844
553...33867
4t.e2r4 e
4e.l1es8
73.2817
'1.64~',~
2.64
7.21
"Frobably Kg
amor- 4I1Z23..333 paphhmooouurss- 44.2294
6.29
re -311000088..00000066
33MM_MMNN0033110099550055
~sters
and charA2acnniuuemmrbibveeerrd.ooff Rtteyypptiioccraasll oeefssttpeerrrissmaoorffyhheeappnttdaaffslleuucooorrnoobdbuuattryyyrriiacclcaaocchiioddlshhaahvvaeevebbeebeeennhpprrbeerppaaasrreedd aJnadrecdhabryacdtireercitzeeds.terEisftiecratsioonf wpirtihrnaarmyinaenrdasleaccoinddaCraytalaylscto.holFsarhaevxeambpeleen,perteh-yl
pared by direct esterification with a mineral acid catalyst. For example, ethyl
hheeppttaafflluuoorroobbuuttyyrraattee wwaass oobbttaaiinneedd iinn 8833 ppeerrcceenntt yyiieelldd ((ccrruuddee))..
3F7CO0H + Cys0H HEIICL1 , Cyri000C,Hs
of
the
a
C 3F7COOH + C2HsOH
c1MiMadtetwihiy!tl hhhaeenppttsaaxfltfuelosursoaborfuotbmyeurrtaatthtyeeanw woaalss
> C3FTCOOCzH5
ioonbbttthaaeiinnpeerddesiinnen88c99eppoeefrrccseeunlntfturyyiiiceelldad bbcyy
reaction reaction
of the acid ,Fy. co0H with an excess | Cityon 12504bc yr coocH, of n~ethanol in the presence of sulfuric acid.
C3F7COOH i CH3OH HiSO4>c3F7COOCH3
pTTrhhaeesueenssctteeerrow wfaaassn percent presence of an
aaellxsscooesffosorrm lmoeeoddceffrrotonhm~anhhheewppsttaamfflolutuoeorsro)obbuoufttyysrralam bmaiirddieec
exces~ (~nore than two moles) of sulfuric
aaanncddidm~enttehhtheaannyoiolelldiinn acid; the yield
wttahhsee
was
5Z percent. Gr co. n, + cron1F5205,0, xcooch,
ester waUUssseeprooeffpttCahhr3eeeFdaTannCihhOnyydNgdroHriiod2ddee+yooiCfefflfHeed3rrOss4sHttihhneegHuugassnSuuOaaellx4c)pperrCsees3ppFaaor7rfaCatatOiinvvO heeyCdaaH rddi3vvdaean,nttaawggheie..ch TTwhhaeesnnr--eoorccttyyll
eCostveerrawblaes splroenpgarweidthinthgeoaocdidyiefoldrmuesdi.ng an excess of anhydride, which was re-
coverable along with the acid formed.
(4F460),0 + CH, JOH C,,COOtiC +C3 4COOH
fivorobuTthyreatte-.buty] ester was prepared from t-butyl chloride and silver (C3F7CO)zO + CsHI7OH >C3FTCOOC8HI7 + C3F7COOH The t-butyl ester was prepared from t-butyl chloride and silver
hepta-
hepta-
fluorobutyrate.
4F,000Mg + C,1,G1--C 4CO0C,t,
DtDuuere ttooo ttnhhee
rieacti. vity of the G3F7COOAg
reactivity of the
ester, this preparation had to + C4H9GI --->C3F7COOC4H9
ester, this preparation had to
bebe
accomplished accomplished
under under
anhydrous conditions.
catalyseTTdhheeaddppiootlliyyommneerorfiizzhaaebbplleetaeefsslttueeror,,rovvibinnuyrytlilychhaeecppittdaafffllouuooarrcoobebusuttyeyrnracat.tee,,
was
was
obtained
obtained
bbyy
tthhee
catalyzed addition of heptafluorobutyric acid to acetylene.
,F,CO0H + CH = CH-->C,,COOCH = CH,
C3F7COOH + CH _= CH >C3F7COOCH = CHZ
butyric Tahcek:table gives physical propertics of typical esters of hepiafluora- EEtthhyyl]iiddeennee hheeppttaaff]luuoorroobbuuttyyrraattee,, CGHHy3;CCHH((OOOOCCCC33FFT;))Z,,, Wwaass aallssoo oobbttaaiinneedd iinn tthhiiss
mann e r.
The table gives physical properties of typical esters of heptaf]uorobutyric acid.
Can
-4-
11000088..00000077
33MM_MMNN0033110099550066
ESTERS OF HEPTAFLUOROBUTYRIC ACID ESTERS OF HE, PTAFLU OROBUTYRI@ ACID
ar. 2 a B,P,, C
2O
n
D
Meth) Hepeatior-o Bee 20 Lass Methyl Heptafluoro -
butyrate 1
san epratvaro- os mw on 130s Ethyl HeptafluoroJia butyrate z
Topropy] Bepatioro- 106 (Tamm 1310 Lz Isopropyl Hepta fluoro-
butyrate a
Bar Hpativoro- 2 mm dae) Law n-Butyl Heptafluoro-
bulyrate
Bagh Bepatuoro- ie nes ass s-Butyl tteptafluoro-
butyrate
[Ey Ho om Lis Lams t-Butyl Hepta[]uoroaye butyrate 4
dra Jer Las 4- Hydroxybutyl raion fi Heptafluo robutyrat e
Ving isn LE Laos Vinyl Heptafluoro-
bul y r at e
cotati "sem es siz 2-Hydroxyethyl roby i nn--OOccttyyH lleHHpeetappfttlaaufiollruuooobrruoo--tyrate
79 (737 rnm)
95 (744 rnm)
l 0(~ (7 :~9 me)
132 (740 me)
ll6 (41 me)
116 (740 m~n)
141.6-142 (74Z me)
79 (748 rnm) 44 (B.5 n~n~) 110088 {(2277 mm)
1.293
1.303Z
1 .3t0 1.3249(25
1.3212(25
i 318 1 3579 1 3086 1 33Z5
1.1 3538528(z2(5z5%)
483
394
324
298
2.84 278
1.405 1.54Z
11..118855
n-DodebcuytlyraH[oeptafluoro-
n- Dodecyl ] [eptafluoro-
115588 ((Z233 mmem)) 11 .3802(25) IL120
nn--HHeexxabauddteeyccryyallteHHeeppttaaffllnnoorroo.-
reas butyrate aeOctpir oh Hepativoro- n-Octad~cyl Heptafluoro-
butyrate
Loner 1 ,3-Bibbsuu(rthyyerrpootxxayyf))lu--oroEine Z-ethylhexane
135 (mm) 220088 ((331i mmem))
! 85 (4 me) 114455 ((3355 nm~mm))
140200259) 11.~39955o0((~2.~5%)
1.40z0(z5
11..33448888((Z255))
1I .007744 Lt 441133
I. mma.pp..-8866CC
Lal pom a9 4 0c pour point -99 i 3C Her ag n:.p.-84C to -90(] Lhe m.p.-92C
A quatitaive study of the rates of bydrolysic of n-butyl, s-buyl, and A qualitative study of the rates of hydrolysis of n-butyl, s-butyl~ and
t-butyl heptafluorobufyrates in heterogeneous systen2s has shown that all three
EE Se Thm ra ons esters are relatively susceptible to attack by' 0.0~5 N sodium hydroxide soluim B00 ee 0.03 byron Rid 1 prin and secon tion at 2.06. Ill water and ir] 0.[]3~ hydrochloric a-~id, the primary and seconery waters ydrotyond Slows: hc terns corer dsdiysed move rapidly dary esters hydrolyzed slowly; the tertiary ester hydrolyzed more rapidly frxcfupisig than the otker two.
It~ hon]oge]H>ous solution wii}~ at(creme as <i co-solvent, all three esters
deat nT he En a Th ea ie hydrolymed very rapidly in lhe presence of dilute alkali, the tertiary ester Cintaineais.onnhtahee absenScoemeosf aaliaThyro aly siswaofchilwtohreetpreancieerallwyatme rate being cons{derably slower 1ban the others~ which were practically in-
stantaneous. In the absence of alkah, hydrolysis of all three esters was slower in hon~ogencous syste~]s.
- 5-
11000088..00000088
33MM_MMNN0033110099550077
epcoon E15, cococ, Anbyaside
A acnthioyndroiHfdHeeeappnttaefaxlfcuueosroosrbouobftyuprrtHiiyoccsPaannRhhOyyrddorrwiiSddeepewwmaaossxhpptrrseeppoaamrreetdhde iiAnnc9i955d
percent
percent
yield
yield
by
by
the
the
action of an excess of 26,00on 08 phosphorous p2eFn92t9o55xi5de (Gx G0),0 on the acid.
TaThh.ee ccoommppoouunndd
was
was
alsgo
also
prepared from the acid chioride and G31,'7COOH -~eflux> (C3F7CO)20
prepared from the acid chloride and
the
the
sodium
sodium
salt. The physical properties of heptafluozobutyic anfydride ars as
eee follows: bp. 01-107.55C (130 The physical properties
follows:, b.p, 107-107,50C (730
mam) pe otek 19; of heptafluorobutyric
ram); m.p. -45_t lC;
WE 1-565: 44 anhydride are as
ngD~ 1.Z85; dZ40
1.665 g/cc.
Acid Hatides
A PhcoidspHhoaH Htlieodenppesttsaapffleulmouarotorhbiouobtryuiertyyby!el
ccihmhlleoortriirddaeex hhtuahssanbbee3ee0nn psseyyrnnctethhnaetssiiszzieeetddd:ffrroomm
the
the
acid
acid
and
and
phosphorous pentachloride in better than 90 percent yield.
PC15
G 3FTCOOH
> C3FTCOC 1
The acid bromide resulted (rom the action of bromine ard phosphorous on The acid bronaide resulted fron~ the action of brot~aine and phosphorous on Friasrobytic ack: The acid fodkie wa formed from the acid chioiie heptafluorobutyric acid. The acid iodide was for:ned from the acid chloride i Sali edide, The ccd Suoride was SsoTeted from he soaction of the and calclmn iodide. The acid fluoride was isolated from the reaction of the 3 hiaride ana siiver fluaride acid chloride and silver fluoride.
Physical propesties of the four acid halides are tabulated: Physical properties of the four acid halides are tabulated: HEPTAFLUOROBUTYRYL HALIDES HEPTAFLUOROBUTYRYL HALIDES
Hopaworomyryt Heptafluorobutyryl Frente Fluoride Chorin Chloride [i Bromide tae Iodide
Br. 2 B.P., G
|75me(74t1 mon) IB 7-7.5 55 Timm ase 38-9 Sh Taemm kel 52-4 Te Momma 75-6
(741 (740 (748 (736
rn~n) rnm) ram) ram)
n~DO
1.288 1.3Z61 1.3562
" a1531.55 Los 1.735 202.00
Amides
wAim thideeistHthteeeprptttaahffeliuuaoocrirodobtuhnattylyircdaaem,miioddmeehyhhaaarssidbbeee,eennoFpprreeeoprpeaarrr.eedd
by
by
acylation
acylation
of
of
ammenta
ammonia
with either the acid halide, anhydride, or ester.
G3F400C1 + NH, ---- GFCONE,
(G635F7T,G6O0C)1,0+ +NHN3 it>GGyF3F,T--CCoON--NH,2
C3F4G00CH; (C3F7CO)20 + +NHNb3iy -->> CF CONF, C3FTCONtI2
C3FTGOOCH3 + NH3
>- C3FTCONH2
- -611000088..00000099
33MM_MMNN0033110099550088
straighT~i[hohereassayyrnndtthhfeeasssiihasiooonff
Nesunstined
N-substituTed
amides
amides
has
has
been
been
accomplished
accomplished
in
in
straightforward fashion.
4F COC +(Ct) NH = C3F7CONIC, Hg),
Th oteCBiFstTsCOpChylsi+ca(lCcBoHnss)tzanNtHs o>f Ch3eFpr7aCtOiNso(rCo~bHutsy)aZmid and some
The <able lists physical constants of heptaf]uorobutyramide and some
of its derivatives. HHEEPPTTAAIF'L~ULOUROROOBBUUTTYYRRAAMMIIDDEESS
Heptaftuorobutyromide Heptafluorobutyramid< NN-Dicthylheptainorouty amide N,N-D{ethylheptafluorobuiyramide [II-- Heptafluorobutyranilide p-Bromowpsafivorabuty canilide p- Bromoh{~ptafluorobuty ranilide N-Octadeeylheptafiuorobutyramide N-Oc~ad0cylheptafluorobutyramide Heptatiworobatyric acid hydrazide Heptaf[uorobutyric acid hydrazide
10sM MP.D,. %CC 105 525.03 9 ~.5-93 105.4-106 105.4- 106 67.567.5 7676
BBP,P,., GC
sustimes s ublime s 161 (730.5 ram) 161 (734,5 ram)
Nitrite
Nitrile
HHeepptta~fflluuoorroobbuuttyyrroonniittrriillee ((bb,.pp.. --11 ttoo ++55%CC)) hhaass bbeeeenn pprreeppaarreedd bbyT
dehydration of the Ammde dehydration of the an]Jde. F505 . CC33FF7TCCOONNHHz, 2~7- 055 5> CG3rFo7CnN
Ateatat Alcohol The alcotol. 1,1-dikydroheptacorobstyl alcohol, has been formed by The alcohol, l,l-dihydrohcptafluorobutyl alcohol, has been fornned by
eduction of heptafluoroburtiyc ac of rs dersuarives, Hydrogenosliys of reduction of hept~fluorobutyric acid or its derivatives. Hydrog(~nolysis of eth! heptalivorabuattye aver cores Shrine alot and Leduc of he methyl heptafluorobutyrafe over copper chro~nite catalyst and reduction of the Free ici or acid chlorbae with 1hHum alumi hydride have been weed 10 free acid or acid chloride with lithium aluminum hydride have been used to Prcpace tha wicotul, Cyrrc00cH; ~My Corpo prepare the alcohol.
c rpcoon HAL, ponon
cyrqcoct HLLiiAAaInMHg4 Ccon
C3F7GOCI
> G3F7GH2OH
fTT0hh'iiassn aaalllcckooyhhloollBaiidss ecc.oommppaarrcaaabbnlleebettoostaaceppihheeinncoodll uiinnnd~aeccriiddciiottnyyd..itIIitfoan~lsissooverrneedssiifssottrssaccoopnnhvveeenrr]ssiioonn
to an &Ikyl halide, l[ can be esterified under conditions used for a phenol,
ae -7-
11000088..00001100
33MM_MMNN0033110099550099
G3F,CH,OH + CHy-CHCOCI ----> CF,CH,00CCH-CH,
C3FTCHzOH
4F4CH,OH
++ (CCHHzC--OC)H0COCI---CC2soH2sN0N>5
C3F7CHzOOCCH=CHZ
GF CH,00CCH;
C31~7CHzOH (CH3CO) 2
> C3F7CHzOOCCH3
Properties of the alcohol and some of ts derivatives are reported.
Properties of the alcohol and some of its derivatives are reported.
HHEEPPTTAAFFLLUUOORROOBBUUTTYYLL AALLCCOOHHOOLL
8p.-. % o
220ga29
]1,,I1--DDiihfyyddrroohheeppttaatfiluAuolorcraoobhbuoutltyyll
B.P., C
95 (10mm)
nZ0D
1.2948
dZ40
L601
AAAAclccecerttolaahattoteele
4911350055
(75{] mr:q)
((03m5mmm)) (735 m~na)
1111.33.23219t00140904
LL11..ii642d03os15
NNo-g4he--pNNtaaeppfhhittvhhoyyrllo--b1u1,tL~ yl-l-dAudicrinrehyytyldhdarartnooe--
43 (40 mm)
1.3299
mp. 17-8C
1.420
heptafluo r obutylurethan
m.p. 77-8G
Aldehyde
Aldehyde
co-produH Hceetppttwaaifftllhuuootrrhooebbuautltycyorrahaolldldeehbhyyyddreeedhhuaacsstibboeeneennofpphrreeeppptaaarrfeeldduoirinnob44u00typpreeirrccceeannctitdyyiwieeilltddh
as
as
a
l"lciiAotthm-hipiuirnum oemd"ua)acllutaum lmwsiioinntuhurmemtshuehhlyytaddslrcriiioddnhee,ot.hl eRbRyleeoddrruuemccdtatuitiocointnoinooonfof fohhefseppohttmeaaeipflltuauaofollrdrueooohbbyruuodtteyby.urrataym mriiicddeeac((issdeeeewuuitnnhddeerr
"Amine") also cyrqcoon HLiAaLm , crcho results in the forfnation of so,he aldehyde.
C3F7COOH LiAIH4> C3F7CHO
wTTehhliilss aaasllddaeehhdyyiddaeecetrraeetsseee.mmbbIllt eeisss sccehhnllsooirrtaaillvieinntttohhaaatilkaiittliff.oorrPmmosslyaamessrttaaibbzllaeetissooonlliioddchhcyyuddrrrsaattreeeaaadssily
Awalteatlrrelrooaoo(smmseaettedeuimm~npptdeecerrertaaattt"uuerMr.eei..sIicTeiTshhleelseabbnneeseihholaaivvu)viis.eoorrtoiinnalttkehh~eeli.GOrrPiiogglnnyaamrreddrirfzeaaactctitioiononnociisscuddreesssccrrreiiabbdeeiddly
later (see under "Miscellaneous").
given
beTTlhhoeew:pphhyyssiiccaall
properties
properties
of
of
the
the
aldehyde,
aldehyde~
hydrate,
hydrate,
and
and
diacetate
diacetate
are
are
given below:
HHEEPPTTAAFFLLUUOORROOBBUUTTYYRRAALLDDEEHHYYDDEE
Heptafluorobuty aldehyde
He p[afluor obuty ra ldehyde
Hydrate
Hydrate
Diacetate
Diacetate
BB.PP.., CC 28
28
935
93.5
164(743 men)
164(743 ram)
Mm.Pe.,.%G 661
nD
12730 1[(.24B7E3c]0)
Las 1.3378 [E32 (Z0C)
<7 Lsos
1.505
Las 1.431
Amine
Amin e
pared fAAroffmllhuueooprrtiiannfaatlteeuddoraaommbiiunnteey,,Fo1lr,,i1tlr--iddliiehhyyaddnrrdoohhheeeppptttaaafflilluuuooorrrooubbhuuuttsyyyilraaammmiiinndeee,, hbhyaassthbbeeeeernnepprree--
dpuacrteidvefraoctmiohnepotfaflliutohrioubmutaylruomniitnruimlehyadnrdidheeptafluorobutyra~nide by the re-
ductive action o[ lithicumyamleunminum EhLydiRraidtMe. cor onpnn,
C 3FTCN _
LiA1H! >
~
C3FTCHzNHz
Gyrpconn, LAL Grom,
G 3F7CONH2 LiA 1 H4 b C3. F7GHzNH)~
--88--
0100088..00001111
33MM_MMNN0033110099551100
AmAammtiieddreeiarrleeddbuueccittniigoonnreggcaaovvveeer3aed6600asppeearrcccieednn[tanyydiieeallldddeoofhfyaadmmriionln.ee,,
most
most
of
of
the
the
remaining
remaining
material being recovered as acid and aldehydrol,
ttjoo oaarroommaaAAttssiicciisstthhttahaheenn
1cc0aassaeeliwwpiihtatthhitcthheehyaaallrccaoochhooallr,,bottnhheeanaaammliiognnsee. bbee1aarr1ss5
to aliphatic hydrocarbon analogs. It is
aa a
a
ccrlleoolssaeetrriverrleeysseewmmebballkaannccee
relatively weak
base.
With
With
phosgene,
phosgene,
1,1-dibydroheptafluorobuty! oct l,l-dihydroheptafluorobutyl
isocyanate
isocyanate
was
was
ffoorrmmeedd.
cyFpciyny $C2O9CI022, rcnpnco
C3F7CH2NHz
> C3F7CII2NCO
The isocyanate reacted typically with active hydrogen compounds.
wTahteerisoacyD Dyisiaataznezoaomtttieiazziaartteliiaooocwnntetoodeffmtttphyheeperiac~atammulilirnyneeewhhhiaytyshddrraboocecctehihnvileooarrcihicddyoeedmrpiionlngieoasnhddeicidcco.hhmlloopSrrouooubcensttdehhqysy.luleeenttthheerrre.--
cwtaiteorn swyistthem hydartiolodwictaecmidpegraavtuere|,1h-adsinbyedernohaecgctoam l polirsahbeudi.y]Siuobdsiedqe.uent re-
action with hydriodic acid gave l,l-dihydroheptafluorobutyl iodide.
sven. Physical propestics of the amine and some of its derivatives are Physical properties of the an~ine and some o~ its derivatives are
given.
Br. wrltc 2S HEPTAFLUOROBUTYLAMING
H~2P TA FLUOROBUT YLAMINE
1,1 Dihyaroheptafiorobutyl- 1 ,l-Dihydroheptafluorobutyl_ ie 98 (743 mm) Les Laos Amine Hydrochloride sublimes 130-5 ttydrochloride Adi Sulfate 105204. Acid Sulfate fsocyanate 91 (137mm) S78 L352 siz Isocyanate
Bis(1.1-dibydrobeptatiuoros Bis ( 1,1 -dihyd r ohe ptafl uo r oats oaren 118.9 butyl) -urea
B.P ~ C
M.P., C
20
nD
68 (743 turn) sublimes
91 (737 turn)
130-5 105-20d. -78
1.g98 1.3152
118-9
d2~
1.493 1.512
Miscellaneous Reactions
Miscellaneou~ Reactions
A a 0s Grignaze Grignard
chhoyynddtrrooylliyyecMM lsideiys.etthhttyhyh)eelrrmm eeaaw wgganansseessooiibbuuatmamiinnfieeooddddiid22de-e-hhaaeeddppddtteeaaddfflluttuoooarnmro~eoptperthrohyoyplplyylhhl-e-e2p-p-tppiaarrffoollppuuaaoornnroooollblautiintyyrr17aa55tte--e,71,77aannppddeeroors-nn
cenfi yield.
jc000Lon, S CHiMA a M ocI cu)L on
G3FTCOOCH3 CH3Mgl) C3F7C(CH3)20H
nTpTe2hhl~eeee1ccn.aatr3rr2bb7yiie9inn;eoollldd2h40afass1.tt4hh1ee5.ffooDlDlleelohowywidinrn~aogtppihhoyynsssiiccSgaaallnv_ep~NrF2ro-hphpeeeerprptttaiiaeefhssl::ouoobbrt..opprp..rao11p00ym55l--ps66ropiCpeenn((n7ee4499i1nxmmng5m~~2));
percent yield.-
cy in ) oonn2% HH2eSsOs4 cuceennjecrry
Typ olctin hs the follCow3iFn7gCp(ChyHs3ic)2aOl Hproperties:> bp. 53.6C (133 CH2:C(CIt3)C3F7 mim)
T~_~ol. ehn hasJhe /ollo~ving physical properties: b.p. 53.6C (733 rnm);
nD 1.300Z; dZ~ 1.30~.
-?-
11000088..00001122
33MM_MMNN0033110099551111
magnesiRuymssuufbbojdjieedccett,iinn|gg-hhheeeppptttaaaffllluuuooorrraoobpburutotypyryraialeldtdheeihhnyyoddlee
wttooastthhoeebtaaaccittniieoodnn
of
of
methyl
methyl
r~agnesium iodide, l-hyepFtiafcluHoOropCCroHHp3MyMlgzetItha>noClFwaCsH(obCtaEinJeOd.H
Malonic Ester C3FTCHO
~ C3FTCH(CH3)OH
Dfalonic Ester
the
expeHHceetppettdaatfpilrvuooodrruoocbbtuu.ttyyrryyll
chloride
chloride
condensed
condensed
with
with
diethyl
dieihyl
malonate
rnalonate
to
to
give
give
the expected product.
,F,COCH + CH,{COOC,H,},-->C ,,COCH(COOCHy), C3FTCOCI + CHz(COOC2Hs)Z > C(b3p~.7C1O22CHC,(C2O2OmCm2mH) s)
(b.p. 1ZZC, ZZ mr'n)
AAPiPiLI I,CICAATTIIOONNSS
today. ItKtinniootwwannntaaippcppillpiiacctaaettdiiootnnhssatffootrrhitsthhiaisscieednntwtiiirrleelllyyinnndeewwanaacciiinddcraaerraeesioonbbgvvinioouuumssbllyyeruunnoaafvvasaiiell~satbbllee
ftaaoo5sdsaaatyi.ccmhhueeIlmtmaiiticcseaaallanptpiiilnncitticeeparratmmtieeeodddniiaattttheeaest..titnhTTgihhseebyacddoiaatdtthaaewripplsrrl.eessfeeiAnnnsdtteeaadddndhhiietenirrcoeerneaaaalrrseeitnyrrgpeeeppnsoourromttfbeeecddhreiinnmofiaacnnuasleeeffsffoorrtt
ttFroeeacacshcttntiiiimocouannllssatbaauerrleelaeptiipiddnleesinn.ctiaiitffiiioeendd
by IM, testing
by 3M,
they will be reported in the literature and in by others. As additional types of chemical
they will be reporied in ihe'lilerature and in
technical bulletins.
thereforOOeff ipptaasrrthtiiiccguuhllpaaerrnciitnntrteearrteeissntig aaprroeewettrhh:ee tllhooeww pssouusrrsffiaabcicleeitttyeennossfiiooinnntoorffodttuhhceeiaanccgiiddt,,heaannhddydzotp5p1hhheootrbbheiiefccocrhhoeeempppitttoaasuffnllhuduioo,grrhoocpppoerrunoopeppltyyerl]datggwirrinootguuhpppiotiiswnnettnooro;noo-rrtogghxaaeinndiipicoczsismminoobgllieelaccinuutdllyeenossof:;n-iaaonnntxddriodttdihhuzeecaibssnlttgerrootAnnhnggetaaahrccyieidddriiott-yy
of the compound, coupled with its non-oxidizing and non-oxidizable nature.
water.
TTShhineececcootmmhemmooacnnidssaaillsttssstoorffonhhgee,ppttsaaaffllltuusoorrooofbbsuutttryyrariinccg
aabccaiisddesaarraeereuunnhuuyssduuraaolllllyyyzessdoolluuvbballreey
in
in
wliatttleer. . TShiinscemathye baeciodf iisntselrreosntg,fosamlettsalolfursgtircoanlg bcahseemsisatrs.e hydrolyzed very
little. This may be of interest to metallurgical chemists.
HANDLING
HANDLING
cautionsHHeespphttoaaufflllduuoobrreoobbouubttsyyerrriivccedaa.cciiddCoiirssraaosvvieevrreyynesssttsrrootnnogg taahcceiidds,,kiaannnddisaalldllucnnootrrommahaillghpprraeec--id
ZsSctatoruruteelinndoggnttshhimaasmnnheddoduidldaedethhebyyleddyrroaabbttesiiennfrgglvoeaacocdtdt.iieoodnn.C.woirtIIrhnnoswcciaaatvsseeeern,eooffsfsoaalcctlccooiiwddteeehdnnett,,bsykeeinxsxpppiuoosnssgeediddunegaarrtwoeeiaahtssihgoohfffivattechhieepdebbroo-ddyy
Csceehnnottulssdooiddmiimuuemmdibbiaicctaaerrlbbyoonnbaaetteeflssoooollduuettdiioownnitoohrr wddaiitlleuurttee
ammenia. fol!owed by
ammonia.
sponging
with
five
per-
mCmlaaoddseeuriiennHHseeggppllsttaausaascssffhllbbuuaoooostlrrttoocllbboeeuurssttkyy,ssrreeiiraaccullbeeaabddcceiirwwdd,iittiihbhssappkvveooeelllrriyyytyssett,hhyyyyrraggeenrrnnodoeesscpcoccoopaalpippyicssec.t.chcooynnlSSttoaaaarnmiie~pnnpliialennerggessaaahhliilTTppeenamff~telletnoonatnntcssklleiiaadnnrreeeerr..
bbfCyyelnottdshhiueerteaaosccii"ddes..ruechcLLtooawws
surface tension makes cork, rubber~ bake]ite~
surface tension makes
tight senting difficuir, ns ~nd polyethylene are all
tight sealing difficult, a~
the acid attacked
the acid
tends to "creep".
S10.
- 10-
11000088..00001133
33MM_MMNN0033110099551122
TTOOXXIICCIITTYY acid areTThhseteilpplhhbyyessiiinoogllooiggniivcceaaslltiaagnnaddtettdoo.xxiiccDooullcooggiipccramellcappurrtooippoeenrrttsiiheeossuloodff b1he~eepeptxtaeaffrllcuuioosrroeobdbuutitnyyrriiitccs aHcainddlairneg astnidllusbee.ing investigaled. Due l~recaution should be exercised in its
handling and use.
and giveTTshheeadcceqooummapptooeuunnwddarppnooissnssgeessofssee(ssheaannpraoeddsooerrncsseiinmoaifilla1arrs tt1ooaptthohaart.t ooff bbuuttyyrriicc aacciidd,,
and gives adequate warning of the presence of its vapor.
aPalnniddcdaaxrreeeTTgbbhaheeerelldiiedidovanavtegteaaddthccttoeooonnbabtteceaaciinccnueoeordrdarrrcehheyceectrrto,e.efiinntH Hhoaaeowrsrweeeeevdvbbeaeaartrss,a,eeddnnaooroonnww (ahattrehhrrereuaasnbnbeteetsyysottfi1saastvvhaeeaeixxisllppeaarrbbpeellrsseeossdeeiiunddncfftoooosrrrr:m miiaam mttiie-oonn
piied regarding the accuracy of these data or the use og these products.
9-26-49
9-26-49
Sn.
-ii-
0100088..00001144
33MM_MMNN0033110099551133
agg
ol 3
zsl
&
%
8g:f
35gfs=
EH
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EH
ggff
agll 43
EH
87 3z
9%
82
Jx
S~u~m. 28 Bs | Sb
IEE I
==
-.000
0
0
20 ~ $5c;m' 38 c; c;
0T;otsop |o o8 & 2 I8E
ol TT rae
%,'y,
LI
:
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mleg8:8 2W 5 zFE aZ
%, op |,
SdTTEF Isds 8 3 0% 2
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"2,RYFLso 3 38
8ggoE R5mb.-
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cqO 0
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co
Teles 533 2g 3 233
0
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,-~
0
foe | oo
a 2 AR
"op |E TS ve
Rg = $23
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EER fi SEER
JE HEE
G8 re Cs
Za e =
i $[33]
i$3| i3:s 3a iH:ytosn2iZ3
a| 2T5 2S5S2%
8g%e iGfg
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|i 2f d5.|
3% 2
5% I%
535, 522
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11000088..00001155
33MM_MMNON0033110099551144
750)
750
700
700
eso
650
560O00 550
550
500
5OO
450 oof +
400
s35sOo &
soof-
300
250)
25O
200
20O
150!
150
ioof-
IO0
550O
VAPOR PoFRESSURE
HEPTAFLUOROBUTYRIC AGID
HWEMiPinNmTneeAeswFsooLtPtUoarOoMMdRiuiOncniBtnisgUnT8gD~YivMMRiIafsCgo.nGCAooC.ID
/ /
St New paul, Mimesato Products. Division
/
/
/
/
E
_
Temperature <c
Temperature ~C
EC 82549 JE,C. 8-25"-49
e076 w0 sw Wo Wo mo wo 60
70
80
90
I00
I10
120
150
11000088..00001166
33MM_MMNN0033110099551155
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Jaiouuss iano 130 sold 5480
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HHEEPPTTAAFFLLEUUSOOTRREOORBSBUUTTOYYFRRIICC AACCIIDD
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//
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St. Paul ~ es Minnesota
Teml~erat ure C.
J~C
0I
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11000088..00001188
33MM_MMNN0033110099551177
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11000088..00001199
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33MM_MMNN0033110099551199
