Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
Pyridyl sulfoni~ acids or pyridyl alkyl sulfonic acids
as additiYes to nic~el plating baths have been reported~ In .
U.S. Pat. No. 2,839,456, 4-pyridyl ethane sul~onic acid, i~
combina~io~ with other additives, is descsibed as a brightener~
Though 2- and 4-pyridine ethane sulfonic acids do improvè ~he
lucter o~ deposi~ed nickel layers, they have no in~luence on
their leveling. In ~.S. Pat. No. 3,444,056, certain quaternary
compounds o pyridine-3-sulfoni~ acid ar~ mentioned.as levelers
~f and brighteners. The N-methyl-pyridine-3-sul~onic acid betaine
1.
`~ '~
.. ..... . ... .
:
,, , , , , ,, , . ... ...... ,. .... ~ ,.,.,! . .. . - ~ .... , .. , ,,.,, . !
1072~9~3 CC-179
and N-allyl-pyridine~3~sul~onic acid betaine mentioned in this
patent are, however~ not fully satisfa~tory. It appears that
nickel deposits turn lusterless and britt}e with a too low
ampere hour load per liter o~ nickel bath. This behavior
of the bath cannot be prevented by any of the regeneration
method~i employed in electroplating. The ins~ant compounds
of this invention are agents which produce a highly leveled
nickel daposit of excellent ductility in a far more constant
bath.
DESCRIPTION O:i? THE PREF:~RRED EMBODIMENTS-
This invention relates to a novel class of pyridyl alkyl
sulfonic acid betaines represented by t~e following formula:
--(CH2 ) nS3~)
R
in which the substituent (cH2)~so3~3 is in the 2- or 4-
position of the pyridyl ring; n is the in~eger 1 or 2; and
R is a member selected from the group consisting of methyl;
methallyl; C~2COOH; CH2(CH2)xCH2SO3Na wherein x is the integer
.
1 or 2; sodi~m 2-hydroxypropylsulfonate; sodium 2-hydroxybutyl-
:~ sulfonate; 30dium 3-hydroxybutylsul~onate; ben~yl; halobenzyl;
loweralkylbenzyl; and benzyl substituted with the group:
-CH2~ (CH2 ) nS03
wherein the substituent `-~CH2)nSo3~3 i~ in the 2- or 4-position
of the pyridyl riAg and n is the integer 1 or 2.
-- 2 --
0 7 Z ~ 9 8 CC-179
~ or purpose~ of nomenclature r the aorementioned groups:
sodium 2-hydroxypropylsulfonate; sodium 2-hydroxybutylsulfonate
and sodium 3-hydroxybutylsulfonate may also be denoted as 3-Na-
sulfo-2-hydroxypropyl, 4-Na-sulfo-2-hydroxybutyl and 4-Na-sulfo-
3-hydroxybutyl, respec~ively. Similarly, th~ aoreme~ioned group:
C~2(C~2~xCH2SO3Na may be denoted a 3-~a~Rulopropyl when x - 1,
and 4-Na sulfobutyl when x = 2.
A~ used herein, the term "loweralkyl" refers to an alipha-
tic hydrocarbon with 1 to 4 carbons; and the term "haloi~ include~
bromo and ~luoro, with chloro preferred, that is, those halogens
with atomic weight less than 80.
.
The subject pyridyl alkyl sulfonic acid betaines ~I)
. are conveniently prepared by ~uaternization of an appropriate
2- or 4-pyridyl alkyl sulfonic acid tTI-a) or its alkali metal
salt, preferably the sodium salt (II-b):
.~C~2~nS3E ~(CE2)~S032~a
~ a) . (II-b)
.
-~ wherein the sub~tituent -~C~2)nSO3tH,Na) i~ in the 2- or 4-
position.of the pyxidyl rlng and n i~ 1 or 2. Quaternization is
accompli~hed by u~ing~an appropria~e guaternizing agent suitable
for introducing the aforementioned R-~ubstituent on the ring
nitrogen o~ the pyridyl function, such as, for example, dimethyl
~ulfate, methallyl ~hloride, soaium ~hloroacetate, propansultone,
. . . . . .
: butansulto~e, an appropriate benzyl halide, an appropropriately
substituted haloloweralkyl, a~d the l~ke agents, as ~ore fully
, :
-
:, .
~7~g~ CC-179
described and exempli~ied hereina~ter. The compounds of formulas
~ a) and (II-b) are obtained from known procedures in the art,
for example, by reaction between 2- or 4-vinylpyridine and
sodium bisul~ite according to ~. Am. Chem. Soc., 69, 2465 (1947)
for the preparati~n of ~he ethyl sulfonic acid~ or by reaetion
betwe~n appropriate haloalkyl pyridines and sodium sulfite.
To prepare the fonmula (I) compounds with R equal to methyl,
the precursor (II-a) or (II-b) is reacted with dimethyl sulfate
a~ the quat~rnizing agent, generally utilizing a sligh~t stoichio-
metric excess of the latter. Elevated temperatures may be em-
ployed to enhance the rate of reaction. Since dimethyl sulfate
is a liquid at ambient temperatures, the use of an additional
organic solvent for the quaternization reaction is normally un-
necessary. The reaction may be illustrated as follows:
.
)nS 3 2 n 3
~ a) ~e
To prepare the formula (I) compounds with R equ~l to
CH2C00~, approximately equimolar amounts of the precursor (II-b)
and haloacetic acid in ~he ~o~m of an alkali metal ~alt, for
example, sodium (III) in an aqueous solvent are reacted, pre-
~erably under reflux conditions. The reaction mixture containing
the thus-formed alkali metal salt is then cooled and treated with
a suitable mineral acid, e.g., hydrochloric acid, to convert the
salt (IV~ to i~s corresponding acid form (V). The foregoing
- ' ,
- 4 -
.
~C-179
.
~872C~9~3
react on may be illustrate~ as follows:
~C~2) S03~a ,HO~
Cl-C~2COONa -
b) (III)
2)nS3 ~ ~C1;2)nS~)3
CH2COONa , CH2COOH~
:
- (IV) . (V~
The compounds of ormula (I) wherein R is benzyl, halo-
benzyl or loweralkylbenzyl are prepared in similar fa~hion. The
precursor (II-b) is reacted wi~h an appropriate benzyl halide
(VI~, e.g., benzyl chloride, halobenzyl chloride or loweralkyl-
benzyl chloride, in water, preferably under reflux conditions.
After cooling and treatment with mineral acid, the desired N-
` , benzyl sub~tituted product (VII) is obtained.
; (II-b) + Cl-CH2 ~ ~ ~ 2 n 3
¦ ~ ~ R'
CH2
~VI) (VII)
- R' Y~ hal~t loweralkyl
The compounds of formula (I~ wherein R is methylallyl may
be ~imilarly qua~ernized, as described abo~e for R equal to a
benzyl function, except tha~ ~ethallyl chIoride is used as the
quaternizing agent.
_ 5 _
~s
~ ~ 7 ~ ~ g 8 ~C-179
The compounds of formula (I~ wherein R is CH2(CH2)xSO3Na
may be prepared by quatérnization of the precursor (II-b) With
propansultone or butansultone, respectively tVIII~, in an a~ueous
solvent. Elevated temperatures may be employed to enhance the
~ 5 rate of reaction. Treatment of the reaction mixture with mineral
acid, preferably after volume concentration, is employed to coun-
teract the sodium ion content followed by conventional treatmen~
with sui~able bases yielding sodium anion, e~g., sodium methylate
in methanol to yield the desired sodium alkylsulfonate derivative
(IX). In like manner, ~he compounds of formula (I) wherein R is
- sodium 2-hydroxypropylsulfonate, sodium 2-hydroxybutylsulfonate
or sodium 3-hydroxybutylsulfonate are obtained by quaternizing
b) with an appropriate halo-hydr~xyalkyl sulfonic acid in
sodium salt form, as illustrated below by sodium 2 hydroxypropyl-
sulfonate (X).
.. . . . .
2~X 1~ )!3 ~1 + ~C'32)n~(~3
' ` 2 ~ , I
. (X = 1,2~ ' ~ CH2 ~c~2~X~32SO31~a
(VIII) . (IX)
,
i : ~H ~C~Hrl Nal ~ ~,tC~2)nS03
-C~ c~2-so3~a
1 - ' ' ' , ' I~3 .
C~ H-CH2-SO .Ja
OE~
:; ' ' ~)
'` '
_ 5
~ 9~ CC-~7~
.: .
. .
. - .. . ~ . .
.
: ;.... To prepare the.compounds of formula (I) wherein R is
benzyl substituted with tbe group..
~2) n~3/~
. C~2~_~
.. . . ... . . ..
~ dichloroxylol (o-, m- or p~ormj is r~acted with at least
7 . ' , two stoichiometrie e~uivalents o~ the precursor (II-b) in an
5 . aqu~ous so}vent. .EleYa~ed temperature~ are advantageously em-
ployed to e~hance the rate o~ r~action. Upon completion o~ the
reaction and subsequent cooling of the reaction mixture, followed
by ~reatment with mineral acid, ~he desired products are obtained
-through conven~ionai recovery techniques. The foregoing guater-
1~ nization can be illustrated with a,a' dichloro-~-xylol as ~ollows:
. ~ , . . . . . . . .
' ' , .
.. . 2 (II-b) + C~C~2 ~ ~
. . . . . ..... .
.. . . . , . ~ .
-
..
.' " " , " '~ ' ' ' . ' , ., ' " '- " ' ' .
.. . . .
.. - ( ~ 'nS3 - . (CH2)nS03
.- , .',. . '' ~ ;,
;. ' . ' ~ . .
.
.
., . , ~ .
.'.
- - , .
` ~
. CC-179
1(~72098
The subject compounds of formula (I) produc~ a highly
le~eled ~ickel depoait of excellent ductility when used as
a~ditives ~or th~ electro-deposition o nickel coatings in
convelltional galvanic n,icksl bathsl These c.ompounds ara
S suitable f~r use in g l~an,ic nickel baths ~ither alone or -
~~n combination with other lus~er-promoting or leveling addi~
tives. For example, an optinum lust~r is obtained in c~mbina-
. tion with ~uch generally known brighteners as saccharin, diaryl-
: sulfonLmides, naphthalene trisulfonic acids or ~ulfonates, a~e-
~ylenic compounds such 2S, or example, propargyl alcohol, and ~he
like. The latter is especially use~ul in enhancing the leveling
; effect of the subject compoul~ds. Fuxthermore, the subject com-
. . pounds may be used in conjunction with convention21 wetting agents
s~ch as, for example, sodi~m lauxyl sulfate or with other
ionized or.-non-ionized..a~ents tha~ decrease surface tension.
.: ... .. . ~ . . . . .
The galvanic baths may also contain conventiQnal bufferLng
. agents~ such as, for exa~lple,-boric acia, tartrates,.etc~
. .. . .; . ....... _ . . . - - ,
The galvanic bath comprises an acidic solution of a nickel
salt generally one selected from the group conslsting o~ nick~l
sul~ate, nickel sul~zmater nicXel ~luoborate, nickeL cb~oride,
nicXel a~ te and ~he like. Mixtures o~ such salts are also
~ . . . .
;. suitable~ Typical of the nickei gal~anic baths in which ~he
~ 7
.: . . . . . ..
.
.
- ' - ' ': , , ;
,
~7~0~8 - ~C-179 . -
.
subject compounds (I) may be employed are those shown in U.S.
Pa~. No. 3,444,056. ~he subject compounds m~y be ~dvantag~ous
- ly used in concentrations rangin~ from ab~ut 0.05 ~ram.per ~iter (g/l) ~o
about 2.0 g/l of bath, althcu~h ~rom about 0.1 to ~x~t 0.5 g/l is pre-
S ~erred~ Other preferred par~meters are a bath temperature of
about 59~60C, a p~ oX about.3~5-5.0 with about ~.5 most pre-
ferred, and a cu~renk density ranging from ab~ut 1 to abou~
10 amp/dm~.. Th~ bath may b~ mechanically or air stirred. I~
the latter, the use o~ a non-foamy wetting agent is reco~mended.
.
. . In view of the ~oregoing, the present invention provides
an improvement i~ galvanic baths for electro-depositing leveled
~- and lustrous nickel comprising an aqueous aci~i~ solution of at
least oae nicke~ salt. The.improvement in such bath~ comprise.
a pyridyl ~lkyl sulfonic acid betaine o~ formùla (I) in a con-
'~ centration of about 0~05 2~0 grams per liter and, preferabiy; .
about 0.1-0. 5 grams per liter O Th'e pxe~erred additives of
. ormul2L (i) are those wherein R i~ either benzyl or benzyl sub-
stituted wit~ the pre~ous1y described group: -CEI2~_
20 ~ncluding but no~ limited to 2-[N-berizylpyridyl-t2) 3-ethane ~ul
iEor~ic ac~d betaine and 1,2-bis-~2-(2-sul~oethyl)-pyridiniu~
~ethyl]-benzene.
, ... . . . .. _ . . .. .
The ~ol}owi~g exa~ple~ are intended to illustrate, but
not to limit, the scope of the present invention.
. ' ' ' ' ~.
~, . . .
- :- 7~ - "
~7Z~3~9~ C-179
. EXAMPLE I .
~N C~2CH2 SO3
~ ~ . "
~2-COOH
. . . ' ' , ' ' .
'""` ,.' ' '. : ' ' ' , . '
, .. , . . , --, ., ,,, . , , . , ,. , , , .. ._ .. .... . .
A. 2- EW-carbo y~hyl -pyridy~=~) ] -ethanesul~onic acid
betaine: .
' ~ . . . ' ,
. 23 . 3 Grams (0 . 2 mol) o chloroacetic .acid sodium sait, 41. 8 g
. ~ (0.2 mol) o4 2-pyridyl ethane sulfonic acid sodium salt and
5 . ~0 g of water are refluxed for ~ive. hollrs~ ~ollowing cooling
do~ to 20 C~ the reaction mixture is treated with 250 g of
. ~ ., . ~
- concentrated hydrochloric acid~. The crystallized sodium chloride
i5 ~iltered of by suction and ihe solutio~ is concentrated to
dryness under Yacuum. The residue is mixed wi~h 350 ml o~ methanol.
~The pro~uct~ 27.5 g o~ 2~ carboxymethyl-pyr~dyl-(2)1-ethane
~ul~onic acld betaine, which crystallizes at room temperature i~
~ilte~ed off by suction a~d vacuum dried at 110C; decomposition
- , pOiSI~- 2i~oc. . ~
- .
,. , - : . .
~ ' ,'
.
:' ' - , .' ~,, ,
. - ' , . , ~. .
, . : ,
107Z09~3 CC-17 9
.
.' ''
B. 2- ~N-carboxsn~et~yl-p~id~l- (4~ ~ -ethane sulfoni~ acid
betai~e is ob~ained i~ the same way, by emplo~ing a~ -
--
e~ivalent quantity each o 4-pyridyl ethane sulfonic
acid sodium salt and ~hloroacetic acid sodium salt as
5 . . reactants; ,deaomposition point: 234C .
~' ' ` - , .
. ' . .
C [N-carboxymethy~-pyridyl-~4)]-metha~esul~onic acid
e~aine is obtained in the same way, by employing
an e~uivalen~ quantity each of 4-pyridyl methane
sulfonic acid sodium salt and chloroacetic acid so-
diu~ salt as reactants; decomposition point: 290 C.
.
,, . ' ' :
, ' , ` .
,
- ' ~ ' ' .
., ' ~
' ' ' ' ' ' " ~
:
.
: - _ 9 _
,. .
.
' - ' . , _
. .
.... .
; .
~72098 CC~179;
EXAMPLE II
~C!12C~z-503a
~q ~7 , '
A. 2-rN-methYl-PYrid~l-(2~]-ethane sulfoniG acid betaine:
- ~
55 Gram-~ (0.29 mol) of 2-pyridyl ~thane sulfonic acid
and 40.7 g (0.32 mol) of dimethyl suiake are heated
to 150-155~Co Two hours later the reaction mixture is
allowed to cool down to 20~ and a mix~ure of 40 ml of
ethanol and 40 ml of isopropanol are added. .Af.ter stand-
i~g fox 24 hours, the precipitated crude product is ~il
tered of by suction. After do~le recrystallization
from methanol, the white crystals are vacuum dried at
~0C. The final yi~ld is 16.8 g of 2-[N-m~thyl-pyridyl-
(2)1-ethane ~ulfonic acid betaine; ~ecompQsition point:
209C,
-
.
B. 2wt~meth~ ~ridyl-(4)]-ethane sulfonic acid beta ne
i~ p~epared in the s~me manner from equivalent amounts
1~ , of 4-pyridyl e~ha~e sulfo~ic acid and dLme~hyl sulf ate .
.: .
' ' ' . .
.
, CC-179
. ~720g8' .,~
EXAMP~E III
.. . .
'
C~2C~2 ~O
~) I /=\j ' '.
~2 ~\ /~
~ , .
. , rH3
A.
' .
- betaine.
~ ~ .
41.8 Grams ~0.2 mol) of 2-pyridyl ethane sul~onic acid
sodium salt, 28.1 g tO.2 mol) of o-methylbenzyl chloride
. and 20 g of water are refluxed for 5 hours. The reaction
, .
m~x~ure is then allowed to cool down to 2pC and 250 g of
concentrated hydrochloric acid are ~dded. The precipitated
sodium chloride is filtered Q~f by suction and the filtrate
coDcentrated to dryness under vacuum. The residue i5 mixed
with 200 ml of e~hanol and the precipitated whi~e crystal
mass i-~ ~iltered.o~f by suctlon and vacuum dried at llOC
to yield 32 g of 2-[W-t2-methylbenzyl)-pyridyl-~2)]-ethane
sul~onic acid betaineJ decomposition point: 223C.
. .
betain~ is obtained in the same wayt by usi~g an 2quiva-
le~t quantity ~ach of 4-~yridyl ethane sulfonic acid
,~ , , .
sodium salt an~ o-m~thylbenzylc~loride as reactants; de
composition ~oint: 241C.
- ,
~ . ,
~ . ~ ; ' -
.
., : . ~ -
.. . . .
11C~72~9~ -
CC-17g
..
, ' ' ' .
~XAMP~E rv
Lc~2s~3~)
W
C~
.~ ' . ' ' .
.
1~.3 Grams (0.1 mol) of 2-pyridyl methansulfonic acid
sodium salt, 12.7 g (0.1 mol) o~ be~z~lchloride and 13 g
of water are refluxed for 2 hours at 100~10~C. The
5 reaction mixture is allowed to cool down to 20C and
.
100 ml of concentrated h~drochloric acid are added. The
pr~cipitated sodiu~ chloride is filtered off and the
solution ~oncentrated to dryness, The residue is mixed
with 100 ml o~ etha~ol. Th~ p~ecipitated white crystals
are filtexed off and vacuum dried at 110C to yield 13.7 g
o~ ~N-benzyi-pyridyl~ methane sulfonic acid betaine;
decomposition point: 230C.
' ' , .
. .
...
: . - 12 - ~
""' ' ' ' . ' .
,. . .
.~.~. ,
... ..
' ' ' ,' ~1~ ''
- ~XfiMPLE V
,
~ ~y ~ollowing the procedure of Examples III and rv,
: . . accep~ that equivalent quantities of appropriate reac~ants
are employed, the ~ollowing respective products are ob~ained~
'
. ~-[N-~enzylpyridyl-(2)l-ethane sulfonic acid betaineî
decomposition point: 198~.
. , .
2-[N-benzyIpyridyl-(4)-ethane sul~oniG acid betaine;
, decomposition point: 234C~ .
.
- 2-lN-(2-chloroben~yl)-pyridyl-t2)]-et~ane ~ulfonic acid
- betaine; decom~osition poin~: 238C.
. . . . .. .
.2-tN-t4-chlorobe~zyl)-pyridyl-~2)~-ethane sulfo~ic acid
beta.ine; decomposition point~ 201C~.
,
. 2-lN-~2-chlorobenzyl)-pyridyl-(4)]-ethane sulonic acid
e~aine; decomposit~on point~. 23~C.
_ ; . .. .. . .. .. .. . .. . . .... _ ,.. ,_ _ _ , , _ ,_, _ , .. .. .. .....
~ . . . . .
.. . .. . .
' ' ' '' . ' " ', ~ ' ' . ' ' '
.'': . . ' , . " , .
,', ' ~ ~ , ' :
.. . . .
,.~ . . .
:: . . .
- 13 - .
;'~' ' . ' ' . , , , _
: .. . . .
- ,
' ' . ', ' ' ' ., .
:. . - . .
~7Z~3 C~-l?~
~ EXAMPLE VI
.' ~ ` .
~ ~ C~ CH -SO ~3
, . . ~1 - .
CH2C~CH2-S03P7a
A~
betaine:
'
41~8 Grams ~0.2 mol) o~ 2-~yridyl ethan~ sulfonic acid
` sodium salt, 30.5 g (0.25 mol) of propansultone, 200 g of
methanol a~d lS g of water are heated to 6 sQc for 7 hours.
, The reaction mixture is then concentrated under vacuum and
the residue is mix~d with 200 ml of concentrated hydrochloric
acid . The precipitated sodium chloride is ~f iltered of f and
~ the mother liquor co~centrated to ~ryness. The Qily residue
- la ~ ~ dissolved in ~ao ml of methanol and allowed to stand for
2 days.. Some ~-pyridyl ethane sulonic acid, which preci-
pitates within thi~ time~ is filtered off and the filtrate
is neutralized with 30% ~odium methylate solution (in methanol).
A white salt precipitates which is filtered of and ~acuum
dried at 110 C to yield 1~ g of 2~[N-(3-Na-sulfopropyl)-
pyridyl ~2~ thane sulfon~c acid b~taine.,_decomposition
p~in~: 228C_
'~ ' ` ~ ' " ' ' '
~ , ~ : . .
1 . ' .
..
;~ ' '
.
~-179
07~~
.
B. The procedure o~ Example VI~A is repeatea except that
an equivalent amount o~ buta~sultone is substituted for
. -~he propansultone used therein to yield the corresponding
:~ product, 2~ (4-Na-sulfobutyl)-pyridyl-(2)~-ethane sul-
.. : . . ~ .
5fonic acid betaine.
': ' ',
, , . . . . . . . . ........ ., . . ..... .. . ~. .. .. .... ... ... . . .. . .. . .
; C- By following the procedure of Example VI-A, except
khat equivalent~amounts of appropriate starting
. materials are employed as reactants, there are ob-
't~ined as respsctive products: .
10t~-(3-Na su1fopropyl)-pyridyl-(4)]-methane-
; ~ulfonic acid betaine; and
., .
. .
. 2-tM-t4-Na~sulfobutyl)-pyridyl-(~)]-ethane sulfonic
! ~
. acid betaine.
.. . , .. _ _ . _ .. _ . _ . .
. ~, . . . . .
` ' '.
. ~ . ,
- 15 -
, - :
.,~ ' ' ' '
,~ ' '
.
.
....
,,; - :
.' ' '' " ' .
~L(il7Z6~9~3 - C~-l79
. EXAMPLE VXI
.
~3~C}~2C112503~
CX~-CHtOH)-C~2-S~3Na
. .
~ic ~d ~e~ e:
20.9 Gram3 (0.1 mol) o~ 2-pyridyl ethane sul~o~ic acid
sodium salt, 19.7 g (0.1 mol) of 3-chloro-2-hydroxy-
propyl sulfonic acid-(l)-sodium salt and 20 ml of water
are heated at 95 C for 6 hours. ~he reaction mixture
~ i9 then concentrated under vacuum and the residue is .
; mixed with 100 ml o~ concentrated hydrochloric acid.
~he insoluble sodium chloride is filtered of~ and the
mother liquor concentrated to dryness. The oily residue
is aissolved in 100 ml o~ methanol and allowed to stand
for 2 days~ Some 2-pyridyl ethane ~ulfonic acid, which
precipitates within this time r is ~iltered o~f a~d the
~iltxate as neutralized with 30~ sodium methylate solu-
tio~ ethanol). The precipitate white salt is ~
'l .
,'' tered of and vacuum dried at ~10 C to yield 11 g of 2 tn-
t3-Na sulfo-2-hydroxypropyl)-pyriayl-(2)~-ethane sulfonic
a~id betaine; decompo~ition point: 183C.
. .. .
.. . .
" , ' ' . .
: ' , . .
~ 7Z098 C~-~?gi
' '
13. ~h~ proceduxe of Example ~ A is i~ollowed, ex-
cept ~ha~ equivalent amounts of appropriate
- ~ starting materials are ~mployed a~ reactants,
to yield ~he f~llowing :respective ~?roduc~s:
.
2~ (4-Na-~uL~o-2-hydroxybutyl) -pyridyl-(2) ]-
ethane sulonic acid betaine;
,
~- ~N- ( 4-Na-sulfo-3 -hydroxy3: u~yl ) -pyridyl- ~ 4 ~ ] -
ethane. sulfonic acld betaine; a~d.
,;' , . .
tN- (3-Na-sulfo-2-hydroxypropyl) -pyridyl- ( 4 ) ] -
methane suli~onic acid betaine.
: ' ' ' . '.
, - . .
' , , . ' . .
... . .
, . . . . .
j . . .
':1 . .
~, . . ..
.. . . . . .
." ~ . . . .
~ . .
.; ~ . ,
17-
, .
.
'
,
.. . _ .. _ , ... . _ .. _ _ .. . _ . , _ . .. . .. _ . . . . ~ ...... _ _ . _ .. _ . _ . _ . _ , .
. _ . _ .. . . . ..
~7~g8 ~C-}7g
. . . EXAMPLE VIII
,.
CH2CH2s03Q C~I2C~2S03
~ 2 ~ CE2-N ~
.
.
.. .
A~ 1,4-Bis-~2~(2-sul~oeth~ pyridinium~ methyl _ enzene: .
.
~2.8 ~xams (0.3 mol~ o~ ~-pyridyl ethane sulfonic acid
sodiu~ salt, 17.5 g (0.1 mol~ of a,a'-dichloro-~-xylol
, and 50 g of water are heated to 100-105 C for 4 hours.
; 5 ~he reaction mixture is then cooled and 200 g o co~-
. ` . .
centrated hy.drochlo~ic ~cid are added. The precipitated
sodium chloride is iltered off and, the filtrate con-
centrated u~der va~uum to dry~essO 200 Ml o~ methanol
are added to the ~esidue~ ~he precipi~ated impure cry- . .
~tals are filtered off, dissolved in 120 ml of water at
20C, and again precipitated by adding 480 ~1 of ethanol.
~h~ white crystal mass is. ~iltere~ of~ a~d vaouum dried
at 110C ~o yield 26 g o~ 1,4-bis~E2-(2-sulfoethyl)-pyri-
di~ium-~l)-methyl]-benzene; decomposition point:~ 350 C
'
~.. . . .
~ ~ .
.. ~ .
~ . . . .
,
., . ~, .
,
.
~07Z~ -179
. In the same manner, except that equi~alent amounts of
appropriat~ reackants are employed, there are ob~ain~d
as respective products:
. . 1,2-pis-~2-~2-sulfoethyl)-pyridinium~ methyll-benzene;
S decomposition point: 248C.
' , ~ ' .
,3-bis-~2 ~2-sulfoethyl)-pyxidinium (l)-methyl]-benzene;
O
decomposition point: 251 C.
1,4-bis-~4-(2-sulfoethyl)-pyridinium-~ methyll-benzene;
decomposition point: 258C. ~ .
1, . . .
~; . . . .
.,, - :
.. . .
,
.,
; ' ' ' '. . . . . ... . . .
. . ' ~ ' : " ' ' . '
.. . . .
:, . . . . . .
.
,
: . . CC-179
1al7Z~9~ -
EXAMPLE n~
The f~llow~ng illustrate typical galvanic nic~el
baths in which the subject compounds of formula. (I~ may be
employed. It is understood that the h~rei~nentioned su}~ject
comp~unds are not listed ~or the purpose o~ limiti~g the
scop~ of the in~ention thereto but to ~xemplify the useful-
ness of all compounds wi~hin ormula (I).
.
; Nickel sulfate .,7H2O , . . . ~ . O . . . g/l . . O 310
Nick~l chloride 6H2O O O . . . . . . . . g/1 . . 50
Boric ~cid . . . . . . . . . . . . . , . . g/l . . . 40
Lauryl sulfate . . . . . . . . . . . . . . g/l . . . 0.2
Saccharin . O . . . r ~ g/l ~ ~ ~ 2 ~ O
Z-~N-benzyl~yridyl-(2~-ethanesulfonic . ....... . -
acid be~aine . . . . . .~ O . . . . . . g/l . 0.3
pH . . . . . . . O . . . . . ~ . . . . . . . , 4.6
~; ~5 Tempe~ature . . . . . . . . . . . . . . . ~ C 50 60
Current density . . , . ~ . . . . . . . . . amp/~m2 . . 1-7
:. , ' .
, ... . . .
Nickel sulfate ~ 7~2 ~ ~ . ~ ~ ~ ~ ~ . . g/l . . 310
Nickel chloride ~ 6~20 . . . ~ g/l . . . 50
;.... .. .
Boric Acid . ~ . ~ ~ . . . ~ . . . . . ,. ~ g/l . . . 4 0
.; . , . ~ . .
~aur~l sulfate . . . . ~ . ~ . . u . . . . g~l . O . 0.2
~1. Saccharin sodium . O ~ . . . ` . g~l . . . 1.0
:~ 1,3,6-naphthale~e trisulfonic acid sodium
salt .~ . , . g/l . . . 1.0
2-[~-benzylpyridyl-(4~-ethanesul~onic
acid betaine . . . . . . . . . . . . . g/l . . . 0.3
pH . . . . . . . ~ . . . . . . . . O . . . . . . . . . 4.~
- Temp~rature . . . . . . . . . . . . ~ . . . C . . 50-60
.Curxe~t de~sity . . ~ ~ . . . , . . amp~dm2 1 7
-- 20 -- .. ..
16~7Z{~!~8 cc-l79
c
Nickel sulfate . 7H2O . . . . . . . . . . . . g/l . . . 280
Nickel chloxide . 6H2O . . . . . . . . . O . g/l . . . 40
Boric Acid . . . . . . . . . . . . . . . . . 5/1 ~ ~ . 40
Lauryl sulfate . . . . . . . . . . . . . . . g/l . ~ . 0.2
Dibenzylsulfonimide . . . . . . ~ . . . . . . g/l . . . 8.0
Propargyl alcohol . . . r ~ o ~ g~ O ~ 04
1,2-bis-t2-(2-sulfoethyl)-pyridinium(l)~
methyI]-benzene . . . . . . . . . . . . ~ g/l . . . O.lS
p~ . . . . . . . . . . . . . . 4.6
Temper~ture . . . . . . . . . . . . . . . . . C . . . 50-60
Current density . . . . . . . . . . . . . . . amp/dm2 . 1-7
-
EXAMPLE X
,: , .
A. The procedure of Example III-A i3 ~ollowed except that
18 g (~0 . 2 mole) of methallyl chloride is substituted for the
o-methylbenzyl chloride used therein to yield, as the final
product, 2-rN-(2-methylpropen-2-yl~-pyridyl-(2)]-ethane sulfonic
i. 15 acid betaine, al~o known as 2-[N-methallyl-pyxidyl-~2)1-ethane
i, sulfonic acid betaine, decomposition point: lg6C.
: . B. 2~ 2-methylpropen-2-yl)-pyridyl-(4)]-ethane sulfonic
: acid.betaine, also known as 2OtN-methallyl-pyridyl-~4)]-ethane
8ulfonic acid betaine, decomposition point: 208C, is obtained
.; . .
ZO in similar fashion by using a~ equivalent quanti~y each of 4-
pyridyl ethane sulfonic acid sodium calt and methallyl chloride
as reactants.
- , . - ~ : ~' '
- 21 -
' ~
` ' ' .
