CA1072098A - Pyridyl alkyl sulfonic acid betaines as electroplating additives - Google Patents
Pyridyl alkyl sulfonic acid betaines as electroplating additivesInfo
- Publication number
- CA1072098A CA1072098A CA273,773A CA273773A CA1072098A CA 1072098 A CA1072098 A CA 1072098A CA 273773 A CA273773 A CA 273773A CA 1072098 A CA1072098 A CA 1072098A
- Authority
- CA
- Canada
- Prior art keywords
- pyridyl
- betaine
- sodium
- ethanesulfonic acid
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/32—Sulfur atoms
- C07D213/34—Sulfur atoms to which a second hetero atom is attached
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
- C25D3/18—Heterocyclic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Pyridine Compounds (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
ELECTROPLATING ADDITIVES
ABSTRACT OF THE DISCLOSURE:
Novel pyridyl alkyl sulfonic acid betaines useful as additives to nickel electroplating baths.
ABSTRACT OF THE DISCLOSURE:
Novel pyridyl alkyl sulfonic acid betaines useful as additives to nickel electroplating baths.
Description
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.
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
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.
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 - ' , .
~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' ~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.
.. . , .. _ _ . _ .. _ . _ . .
. ~, . . . . .
` ' '.
. ~ . , , - :
.,~ ' ' ' ' ,~ ' ' .
.
....
,,; - :
.' ' '' " ' .
~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 . .
~, . . ..
.. . . . . .
." ~ . . . .
~ . .
.; ~ . , , .
.
' , .. . _ .. _ , ... . _ .. _ _ .. . _ . , _ . .. . .. _ . . . . ~ ...... _ _ . _ .. _ . _ . _ . _ , .
. _ . _ .. . . . ..
~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.
- , . - ~ : ~' ' ' ~
` ' ' .
.~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 - ' , .
~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' ~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.
.. . , .. _ _ . _ .. _ . _ . .
. ~, . . . . .
` ' '.
. ~ . , , - :
.,~ ' ' ' ' ,~ ' ' .
.
....
,,; - :
.' ' '' " ' .
~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 . .
~, . . ..
.. . . . . .
." ~ . . . .
~ . .
.; ~ . , , .
.
' , .. . _ .. _ , ... . _ .. _ _ .. . _ . , _ . .. . .. _ . . . . ~ ...... _ _ . _ .. _ . _ . _ . _ , .
. _ . _ .. . . . ..
~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.
- , . - ~ : ~' ' ' ~
` ' ' .
Claims (25)
WHAT IS CLAIMED IS:
1. A pyridyl alkyl sulfonic acid betaine having the formula:
in which the substituent -(CH2)nSO3? is in the 2- or 4-position of the pyridyl ring; n is the integer 1 or 2; and R is a member selected from the group consisting of methyl.
methallyl; CH2COOH; sodium 2-hydroxypropylsulfonate; sodium 2-hydroxybutylsulfonate; sodium 3-hydroxybutylsulfonate; halobenzyl wherein said halo has an atomic weight less than 80; loweralkylbenzyl wherein said loweralkyl has from 1 to 4 carbons; and benzyl substituted with the group:
wherein the substituent -(CH2)nSO3? is in the 2- or 4-position of the pyridyl ring and n is the integer 1 or 2.
in which the substituent -(CH2)nSO3? is in the 2- or 4-position of the pyridyl ring; n is the integer 1 or 2; and R is a member selected from the group consisting of methyl.
methallyl; CH2COOH; sodium 2-hydroxypropylsulfonate; sodium 2-hydroxybutylsulfonate; sodium 3-hydroxybutylsulfonate; halobenzyl wherein said halo has an atomic weight less than 80; loweralkylbenzyl wherein said loweralkyl has from 1 to 4 carbons; and benzyl substituted with the group:
wherein the substituent -(CH2)nSO3? is in the 2- or 4-position of the pyridyl ring and n is the integer 1 or 2.
2. The betaine according to claim 1 which is 2- [N-carboxymethyl-pyridyl-(2)]-ethanesulfonic acid betaine.
3. The betaine according to claim 1 which is 2-[N-carboxymethyl-pyridyl-(4)]-ethanesulfonic acid betaine.
4. The betaine according to claim 1 which is [N-carboxymethyl-pyridyl-(4)]-methanesulfonic acid betaine.
5. The betaine according to claim 1 which is 2-[N-methyl-pyridyl-(2)]-ethanesulfonic acid betaine.
6. The betaine according to claim 1 which is 2-[N-(2-methylbenzyl)-pyridyl-(2)]-ethanesulfonic acid betaine.
7. The betaine according to claim 1 which is 2-[N-(2-methylbenzyl)-pyridyl-(4)]-ethanesulfonic acid betaine.
8 . The betaine according to claim 1 which is 2-[N-(2-chlorobenzyl)-pyridyl-(2)]-ethanesulfonic acid betaine.
9 . The betaine according to claim 1 which is 2[N-(4-chlorobenzyl)-pyridyl-(2)]-ethanesulfonic acid betaine.
10 . The betaine according to claim 1 which is 2-[N-(2-chlorobenzyl)-pyridyl-(4)]-ethanesulfonic acid betaine.
11 . The betaine according to claim 1 which is 2-[N-(3-Na-sulfo-2-hydroxypropyl)-pyridyl-(2)]-ethanesulfonic acid betaine.
12. The betaine according to claim 1 which is 1,4-Bis-[2-(2-sulfoethyl)-pyridinium-(1)-methyl]-benzene.
13. The betaine according to claim 1 which is 1,2-bis-[2-(?-sulfoethyl)-pyridinium-(1)-methyl]-benzene.
14. The betaine according to claim 1 which is 1,3-bis-[2-(2-sulfoethyl)-pyridinium-(1)-methyl]-benzene.
15. The betaine according to claim 1 which is 1,4-bis-[4-(2-sulfoethyl)-pyridinium-(1)-methyl]-benzene.
16. The betaine according to claim 1 which is 2-[N-methallyl-pyridyl-(2)]-ethanesulfonic acid betaine.
17. The betaine according to claim 1 which is 2-[N-methallyl-pyridyl-(4)]-ethanesulfonic acid betaine.
18. In a bath for electro-depositing leveled and lustrous nickel and comprising an aqueous acidic solution of at least one nickel salt, the improvement wherein said bath comprises an additive having the formula:
in which the substituent -(CH2)nSO3? is in the 2- or 4-position of the pyridyl ring; n is the integer 1 or 2; and R is a member selected from the group consisting of methyl; methallyl;
CH2COOH; CH2(CH2)xCH2S03Na wherein x is the integer 1 or 2;
sodium 2-hydroxypropylsulfonate; sodium 2-hydroxybutylsulfonate;
sodium 3-hydroxybutylsulfonate; benzyl; halobenzyl wherein said halo has an atomic weight less than 80; loweralkylbenzyl wherein said loweralkyl has from 1 to 4 carbons, and benzyl substituted with the group:
in which the substituent -(CH2)nSO3? is in the 2- or 4-position of the pyridyl ring; n is the integer 1 or 2; and R is a member selected from the group consisting of methyl; methallyl;
CH2COOH; CH2(CH2)xCH2S03Na wherein x is the integer 1 or 2;
sodium 2-hydroxypropylsulfonate; sodium 2-hydroxybutylsulfonate;
sodium 3-hydroxybutylsulfonate; benzyl; halobenzyl wherein said halo has an atomic weight less than 80; loweralkylbenzyl wherein said loweralkyl has from 1 to 4 carbons, and benzyl substituted with the group:
19. The bath of claim 18 wherein the additive is 2-[N-benzylpyridyl-(2)]-ethanesulfonic acid betaine in a concentration of from 0.1 to about 0.5 gram per liter.
20. The bath of claim 18 wherein the additive is 2-[N-benzylpyridyl-(4)]-ethanesulfonic acid betaine in a concentration of from 0.1 to about 0.5 gxam per liter.
21. The bath of claim 18 wherein the additive is 1,2-bis-[2-(2-sulfoethyl)-pyridinium-(1)-methyl]-benzene in a concentration of from 0.1 to about 0.5 gram per liter.
22. A process for preparing a pyridyl alkyl sulfonic acid betaine having the formula:
in which the substituent -(CH2)nSO3? is in the 2- or 4-position of the pyridyl ring; n is the integer 1 or 2; and R is a membèr selected from the group consisting of methyl; methallyl; CH2COOH;
CH2(CH2)xCH2SO3Na wherein x is the integer 1 or 2; sodium 2-hydroxypropylsulfonate; sodium 2-hydroxybutylsulfonate; sodium 3-hydroxybutylsulfonate; benzyl; halobenzyl wherein said halo has an atomic weight l?ss than 80; loweralkylbenzyl wherein said lower alkyl has from 1 to 4 carbons; and benzyl substituted with the group .
wherein the substituent -(CH2)nSO3? is in the 2- or 4-position of the pyridyl ring and n is the integer 1 or 2, characterized by refluxing an appropriate 2- or 4- pyridyl alkyl sulfonic acid (II-a) or its alkali metal salt (II-b) wherein Z is an alkali metal; and the substituent -(CH2)nS03(H,Me) is in the 2- or 4- position of the pyridyl ring, and n is 1 or 2 with an appropriate quaternizing agent suitable for introducing the above defined R substituent on the ring nitrogen of the pyridyl function.
in which the substituent -(CH2)nSO3? is in the 2- or 4-position of the pyridyl ring; n is the integer 1 or 2; and R is a membèr selected from the group consisting of methyl; methallyl; CH2COOH;
CH2(CH2)xCH2SO3Na wherein x is the integer 1 or 2; sodium 2-hydroxypropylsulfonate; sodium 2-hydroxybutylsulfonate; sodium 3-hydroxybutylsulfonate; benzyl; halobenzyl wherein said halo has an atomic weight l?ss than 80; loweralkylbenzyl wherein said lower alkyl has from 1 to 4 carbons; and benzyl substituted with the group .
wherein the substituent -(CH2)nSO3? is in the 2- or 4-position of the pyridyl ring and n is the integer 1 or 2, characterized by refluxing an appropriate 2- or 4- pyridyl alkyl sulfonic acid (II-a) or its alkali metal salt (II-b) wherein Z is an alkali metal; and the substituent -(CH2)nS03(H,Me) is in the 2- or 4- position of the pyridyl ring, and n is 1 or 2 with an appropriate quaternizing agent suitable for introducing the above defined R substituent on the ring nitrogen of the pyridyl function.
23. The process according to claim 22 for preparing 2-[N-benzylpyridyl-(2)]-ethanesulfonic acid betaine characterized by refluxing 2-pyridyl ethane sulfonic acid sodium salt with benzyl chloride.
24. The process according to claim 22 for preparing 2-[N-benzylpyridyl-(4)]-ethanesulfonic acid betaine, characterized by refluxing 4-pyridyl ethane sulfonic acid sodium salt with benzyl chloride.
25 . The process according to claim 22 for preparing 1,2-bis-[2-(2-sulfoethyl)-pyridinium-(1)-methyl]-benzene, characterized by reacting 2-pyridyl ethane sulfonic acid sodium salt with .alpha.,.alpha.,'-dichloro-o-xylol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US66652576A | 1976-01-12 | 1976-01-12 | |
| US05/763,452 US4067785A (en) | 1976-03-12 | 1977-01-27 | Electroplating additives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1072098A true CA1072098A (en) | 1980-02-19 |
Family
ID=27099476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA273,773A Expired CA1072098A (en) | 1976-03-12 | 1977-03-11 | Pyridyl alkyl sulfonic acid betaines as electroplating additives |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS52116475A (en) |
| AT (1) | AT361266B (en) |
| BR (1) | BR7701506A (en) |
| CA (1) | CA1072098A (en) |
| CH (1) | CH630355A5 (en) |
| DE (1) | DE2710721A1 (en) |
| ES (1) | ES456723A1 (en) |
| FR (1) | FR2343729A1 (en) |
| GB (1) | GB1578168A (en) |
| IT (1) | IT1083723B (en) |
| NL (1) | NL7702673A (en) |
| SU (1) | SU791230A3 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2242200B (en) * | 1990-02-20 | 1993-11-17 | Omi International | Plating compositions and processes |
| IT1275486B (en) * | 1995-07-06 | 1997-08-07 | Giuseppe Faranda | SYNTHESIS SYSTEM FOR OBTAINING PIRIDIN PROPIL ON SULFO BETAINE, WITHOUT RISKS FOR HUMANS AND THE ENVIRONMENT |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2839456A (en) * | 1956-11-16 | 1958-06-17 | Hanson Van Winkle Munning Co | Electroplating |
| US3336324A (en) * | 1966-06-24 | 1967-08-15 | Cilag Chemie | N-allyl-pyridine-3-sulfonic acid betaine |
| DE1621157A1 (en) * | 1967-08-16 | 1971-05-19 | Riedel & Co | Acid galvanic nickel bath |
| US3821095A (en) * | 1972-09-26 | 1974-06-28 | M & T Chemicals Inc | Zinc electroplating process and electrolyte therefor |
| US3862019A (en) * | 1974-04-26 | 1975-01-21 | R O Hull & Company Inc | Composition of electroplating bath for the electrodeposition of bright nickel |
-
1977
- 1977-03-04 GB GB931877A patent/GB1578168A/en not_active Expired
- 1977-03-10 ES ES456723A patent/ES456723A1/en not_active Expired
- 1977-03-10 JP JP2554577A patent/JPS52116475A/en active Pending
- 1977-03-10 IT IT4841677A patent/IT1083723B/en active
- 1977-03-11 CA CA273,773A patent/CA1072098A/en not_active Expired
- 1977-03-11 FR FR7707349A patent/FR2343729A1/en active Granted
- 1977-03-11 SU SU772458751A patent/SU791230A3/en active
- 1977-03-11 CH CH310777A patent/CH630355A5/en not_active IP Right Cessation
- 1977-03-11 AT AT166477A patent/AT361266B/en not_active IP Right Cessation
- 1977-03-11 BR BR7701506A patent/BR7701506A/en unknown
- 1977-03-11 DE DE19772710721 patent/DE2710721A1/en not_active Withdrawn
- 1977-03-11 NL NL7702673A patent/NL7702673A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| NL7702673A (en) | 1977-09-14 |
| CH630355A5 (en) | 1982-06-15 |
| FR2343729A1 (en) | 1977-10-07 |
| JPS52116475A (en) | 1977-09-29 |
| ES456723A1 (en) | 1978-12-16 |
| BR7701506A (en) | 1977-11-29 |
| SU791230A3 (en) | 1980-12-23 |
| ATA166477A (en) | 1980-07-15 |
| GB1578168A (en) | 1980-11-05 |
| FR2343729B1 (en) | 1982-07-02 |
| IT1083723B (en) | 1985-05-25 |
| DE2710721A1 (en) | 1977-09-15 |
| AT361266B (en) | 1981-02-25 |
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