Canadian Patents Database / Patent 1160073 Summary

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(12) Patent: (11) CA 1160073
(21) Application Number: 144471
(54) English Title: BETA-SUBSTITUTED ETHANESULPHINIC ACIDS AND OXYGEN OR SULPHUR ESTERS THEREOF AS PLANT GROWTH REGULATORS
(54) French Title: ACIDES ETHANE-SULFINIQUES SUBSTITUES EN BETA, ET LEURS ESTERS D'OXYGENE OU DE SOUFRE, UTILES COMME REGULATEURS DE LA CROISSANCE DES PLANTES
(52) Canadian Patent Classification (CPC):
  • 260/541
  • 71/7
  • 71/8.65
  • 260/465.8
(51) International Patent Classification (IPC):
  • A01N 41/00 (2006.01)
  • C07C 313/00 (2006.01)
  • C07C 313/06 (2006.01)
  • C07C 313/12 (2006.01)
  • C07C 323/49 (2006.01)
  • C07D 307/42 (2006.01)
(72) Inventors :
  • KOLLMEYER, WILLY D. (United States of America)
  • PILGRAM, KURT H. G. (United States of America)
  • JACKSON, EARL K. (United States of America)
(73) Owners :
  • SHELL CANADA LIMITED (Canada)
(71) Applicants :
(74) Agent: SMART & BIGGAR
(74) Associate agent:
(45) Issued: 1984-01-10
(22) Filed Date: 1972-06-12
(30) Availability of licence: N/A
(30) Language of filing: English

(30) Application Priority Data:
Application No. Country/Territory Date
162-710 United States of America 1971-07-14
162,709 United States of America 1971-07-14

English Abstract




A B S T R A C T
Beta-substituted ethanesulphinic acids and oxygen
or sulphur esters thereof, and beta-substituted ethane-
sulphinamides possessing the essential. Structural moiety
-CH2-CH2-?-
are described, together with a method of regulating and/or
modifying the growth of plants by applying these compounds
to the plant locus and plant growth regulant formulations
containing these compounds.


Note: Claims are shown in the official language in which they were submitted.


- 59 -

C L A I M S
1. A plant growth regulant composition comprising a
compound of the formula
X-CH2CH2-?-A I
wherein X represents chlorine, bromine, iodine, hydroxy,
alkoxy of up to 3 carbon atoms, aryloxy of up to 10 carbon
atoms, alkylthio of up to 3 carbon atoms, aralkoxy of up
to 10 carbon atoms, acyloxy of up to 4 carbon atoms, alkyl-
sulphonyloxy wherein the alkyl group contains up to 3
carbon atoms, arylsulphonyloxy, nitro, monoalkylamino or
dialkylamino wherein each alkyl group contains up to 6
carbon atoms, or A'R' wherein A' is oxygen and R1 is
2-(dimethylcarbamoyl)-1-methylvinyl, 2-(methylcarbamoyl)-
1-methylvinyl or 2-(methoxycarbonyl)-1-methylvinyl; and
either A represents the group -Y-R wherein
Y is oxygen or sulphur with the proviso that when Y is
oxygen R is alkyl of up to 20 carbon atoms, aryl of up
to 10 carbon atoms, aralkyl of up to 10 carbon atoms,
alkenyl of up to 8 carbon atoms, alkynyl of up to 4
carbon atoms, 2-(dimethylcarbamoyl)-1-methylvinyl, 2-
methylcarbamoyl)-1-methylvinyl, 2-(methoxycarbonyl)-
1-methylvinyl or ZR2 wherein Z is alkylene of up to 4
carbon atoms and R2 is alkylthio of up to 3 carbon atoms,
alkoxy of up to 4 carbon atoms, aralkoxy of up to 10
carbon atoms, hydroxy, or a beta substituted ethane-
sulphinyloxy moiety wherein the beta substituent is
identical to the beta substituent represented by X in



- 60 -

formula I above; and when Y is sulphur R is alkyl of up
to 8 carbon atoms optionally substituted with chlorine
or bromine, or aralkyl wherein the alkyl group contains
up to 4 carbon atoms; and R may also represent hydrogen,
if Y is oxygen and X is any of the moieties represented
by X above except A'R';
or A represents the group Image wherein R3 and R4 may be
the same or different and each represents hydrogen, alkyl
of up to 20 carbon atoms or aralkyl of up to 10 carbon
atoms; either or both of R3 and R4 may be R5Y' wherein R5
is alkylene of up to 4 carbon atoms and Y' is hydroxy or
betahaloethanesulphinyloxy wherein the beta halogen
substituent is chlorine, bromine or iodine with the
proviso that when Y' is hydroxy X represents any of the
moieties described for X above except A'R' and when Y'
is a betahaloethanesulphinyloxy X is chlorine, bromine
or iodine; if R3 is hydrogen R4 may also represent aryl
of up to 10 carbon atoms, alkenyl of up to 8 carbon atoms,
cycloalkyl of up to 8 carbon atoms, R5Y2 wherein R5 is as
described above and Y2 is alkylthio of up to 3 carbon atoms,
alkoxy of up to 4 carbon atoms, when R3 is hydrogen R4 may
also represent a substituted phenyl of the formula
Image wherein Z' is alkyl of up to 3 carbon atoms,
alkylthio of up to 3 carbon atoms, alkoxy of up to 3 carbon
atoms, alkyl sulphonyl of up to 3 carbon atoms, chlorine,
bromine, nitro or trifluoromethyl, and if R3 is hydrogen,
alkyl or aryl R4 may also represent hydroxy or alkoxy of
up to 4 carbon atoms;
together with an adjuvant therefor.


- 61 -
2. A composition according to claim 1, wherein X
represents chlorine bromine or alkoxy of up to 3 carbon
atoms; and A represents the group -O-R wherein R is hydrogen,
alkyl of up to 20 carbon atoms, aryl of up to 10 carbon
atoms, alkenyl of up to 8 carbon atoms, alkynyl of up to
4 carbon atoms or ZR2 wherein Z is alkylene of up to 4
carbon atoms and R2 is alkylthio of up to 3 carbon atoms,
or alkoxy of up to 4 carbon atoms, or hydroxy; and is X is
chlorine R2 may also represent a beta-chloroethane-
sulphinyloxy moiety.
3, A composition according to claim 1, wherein X
represents alkoxy of up to 3 carbon atoms, aralkoxy of up
to 10 carbon atoms or acyloxy of up to 4 carbon atoms; and
A represents the group -O-R wherein R is hydrogen.
4. A composition according to claim 1, wherein X
represents chlorine, aralkoxy of up to 10 carbon atoms or
alkoxy of up to 3 carbon atoms; and A represents the group
-O-R wherein R is alkyl of up to 20 carbon atoms, aralkyl
of up to 10 carbon atoms, or alkenyl of up to 8 carbon
atoms.
5. A composition according to claim 2, wherein X
represents chlorine and A represents the group -O-R wherein
R is alkyl of up to 20 carbon atoms or alkenyl of up to 8
carbon atoms.
6. A composition according to claim 1, wherein X
represents chlorine or bromine and A represents the group
-S-R wherein R is betachloroethyl, betabromoethyl, alkyl
of up to 5 carbon atoms or benzyl.



- 62 -

7. A composition according to claim 1, wherein A
represents the group Image wherein R4 represents hydrogen,
aryl of up to 10 carbon atoms, alkyl of up to 20 carbon
atoms, aralkyl of up to 10 carbon atoms, alkenyl of up to
8 carbon atoms, cycloalkyl of up to 8 carbon atoms, alkoxy
of up to 4 carbon atoms or R5Y' wherein R5 is alkylene of
up to 4 carbon atoms and Y' is hydroxy or alkylthio of up
to 3 carbon atoms; R4 may also represent a substituted
phenyl of the formula Image wherein Z' is alkyl of up to
3 carbon atoms, alkylthio of up to 3 carbon atoms, alkoxy
of up to 3 carbon atoms, alkylsulphonyl of up to 3 carbon
atoms, chlorine, bromine, nitro or trifluoromethyl; and X
is chlorine, bromine, iodine or alkylsulphonyloxy wherein
the alkyl group contains up to 3 carbon atoms with the
proviso that when X is alkylsulphonyloxy, R4 is hydrogen,
alkyl of up to 6 carbon atoms or aryl of up to 10 carbon
atoms.
8. A composition according to claim 7, wherein X is
chlorine, bromine or iodine.
9. A composition according to claim 8, wherein X is
chlorine and R4 is hydrogen, alkyl of up to 8 carbon atoms,
cycloalkyl of up to 6 carbon atoms, alkenyl of up to 5
carbon atoms, unsubstituted phenyl, phenyl substituted
with chlorine, bromine or trifluoromethyl, or aralkyl of
up to 8 carbon atoms.


10. A composition according to claim 9, wherein R4 is unsubstituted
phenyl.
11. A composition according to claim 9, wherein R4 is hydrogen.
12. A method for regulating plant growth which comprises applying to
the locus to be treated, an effective amount of a composition as defined
in claim 1.

63

Note: Descriptions are shown in the official language in which they were submitted.

~0073
-- 2

The invention relates to plant growth regula~
compounds, compositions compri3ing such compounds and a
method of regulating plant growth.
It has now been discovered that certain eth~ne-
su~nic aclds and oxygen or ~ulphur e3ters thereof, andcertain ethanesulphinamides~ can be lemployed to re~ulate
and/or modi~y the growth of plants. Depending on variable~
such as the species o~ plant treatedl plant makurity at
time of treatment, the quantity and concentration of growth
regulant u~ed, the speci~ic compound used, and the formu-
lation employed, theæe compounds when applied to the plant
locus exhibit a wide variety of us~ful plant ~rowth regu-
lating properties. Some of the plant growth regulant ef~ects
which have been observed include the promotion of early
and more uniform fruit ripening and/or ab~cis~ion~ acce-
leration of l~af absci~slong promotion of flowering,
stimulation o~ sprouting of tubers, stlmu~tion o~ seed
germination, destruction of apical dominance in tubers
caus~ng lateral buds to sprout, increased formatlon of
root initials on tomato stems, the cau~ation of tomato
leaf epinasty and dwarfing of plants. It wlll be recognized
that biological response such as that realized from the
process of the invention~ when utilized as a cultural
practice in the ag~cultural industry, can provi~e a valuable
means of increasing crop productivity while at the
same time reducing the laboX and expense necessary to
produce the crops.
Accordingly the invention prouides a plant
growth regulant compo~tion comprising a compound of the


~,~

07 3
~ 5~.
formula `
X-CH2CH2-S-A
wherein X repre~ents chlorine9 bromine, lodine~ hydroxy,
alkoxy of up to 3 carbon atoms, ary loxy of up to 10
carbon atoms,alkylthio o~ up to 3 carbon atom~, aralkoxy
of up to 10 carbon atomsD acyloxy a,~ up to 4 c~rbon
atoms~ alk~lsulphonylo~y wherei~ the alkyl group contain~
up to 3 carbon atoms, arylsulphonyl.oxy, nitro9 mo~o~lkyl-
amino or dialkyls,mino wherein each ~lkyl group contains
up to 6 carbon alioms, or A'R' wherein A' 1~ oxy~en ~nd
R ' is 2 -(dlm~thylc~rbamoyl) -l~meth~rlvin~rl, 2 -(m~thylcarba-

moyl)-l-methylvinyl or 2-~methoxycarbonyl)-1-methylvinyl;
and either A repre3ents the group -Y-R wherein
Y i~ oxygen or eulphur with the provi~o that
when Y is oxygen R is alkyl of up to 20 carbon
atoms, aryl of up to 10 carbon atoms, aralkyl
of up to 10 carbon atoms, alkenyl of up to 8
carbon atoms5 alkynyl of up to 4 carbon atoms,
2-(dimethylcarbamoyl)-1-methylvinyl, 2-(methyl-

carbamoyl)-l-meth~lvinyl~ 2-(methoxycarbonyl)-
l-methylvinyl or Z~ wherein Z ls alkylene of up
to 4 carbon atoms and R2 iæ alkylthio ~E up 3
carbon atoms, alkoxy of up to 4 carbon atoms~
aralkoxy of up to 10 car~on atomsS hydroxy~ or
a beta substituted ethanesulphinyloxy moiety
wherei-n the beta substituent is identical to
the beta substituent represented by X in formula
I above; and when Y is sulphur R is alkyl of
up to 8 carbon atoms optionally substituted with
chlorine or bromine, or aralkyl whereln the

V73

alkyl group contains up to 4 carbon at~ms; and
R may also represent hydrogen~ if Y is oxygen
and X is any of the moleties represented by X
above except A'R'3
or A represent~ the group - N\ 4 wherein
R3 and R4 may be the same or dif~erent and each
represents hydrogen, alkyl o~ up to 20 carbon
atoms or aralkyl o~ up to ~.0 carbon atoms3 either
or both of R3 and R4 may be R5Y' wherein R5 is
alkylene oi up to 4 carbon atoms and Y' is hydroxy
or betahaloethanesulphlnyloxy wherein the beta
halogen substituent; is chlorine, bromine or
iodine with the proviso that when Y' is hydroxy
X represents any o~ the mo~ties described for X
above except A'RI and ~hen Y' ls a be~haloethane-
sulph~nyloxy X is chlorine~ bromine or lodine; if
R3 is hydrogen R4 may also represent aryl o~ up to
10 carbon a~s, alkenyl of up to 8 carbon atoms,
cycloalkyl o~ up to 8 carbon atoms, R5Y~ wherein
R5 is as described above and y2 is alkylthlo of
up to 3 carbon atoms3 alkoxy of up to 4 carbon
atoms; when R3 is hydrogen R4 may also represent
a substituted phenyl of the ~orm~ ~ Z

wherein Z' is alkyl o~ up to 3 carbon atoms,
alkylthio of up to 3 carbon atoms, alkoxy o~ up
to 3 carbon atoms, alkylsulphonyl of up to 3
carbon atoms, chlorine, bromine, nitro or tri-
fluoromethyl; and if R3 i~ hydrogen, alkyl or

O~3
-- 5 --

aryl R4 may also repres~ t hydroxy or alkoxy
o~ up to 4 carbon atoms9
together ~ith an ad~uvant therefor.
When A represents the gro~ ~ Y ~ R the active compounds
are represented by the formula

CH2CH2 ~ Y R II
wherein X~ Y and R are as de~ined above.
E~emplary species o~ this class o~ the invention
include:
2-(ben~yloxy)ethyl 2-chloroethane6ulphinate,
hexyl 2-iodoethanesulphinate,
S-isopropyl 2-bromoethanethiosulphinate,
allyl 2-hydroxyethanesulphinate,
2-propoxyethanesulphinic acidg
methyl 2-(2-~hthoxy)ethanesulphinab~
octyl 2 (ethylthio)ethanesulphinateJ
S-methyl 2-(methylthio)ethanethiosulphinate,
S-benzyl 2-(benzyloxy)ethanethiosulphinate9
2-~propionyloxy)cthanesulphinic acid,
2-(ethylthio)ethyl 2-acetoxyethanesulphinate9
2-(ethylsulphonyl)ethanesulphinic acid3
propargyl 2-mesylethanesulphinate9
ethyl 2-(pheny]sulphonyloxy)ethanesulphinate,
hexyl 2-nitroethanesul~lnate9
2-(butylamino)ethanesulphinic acld
propyl 2-(dipropylamino)ethanesulphinate,
2-(diethylamino)ethanesulphinic acid3
ethyl 2-(2-(methylcarbamoyl)-l-methylvinyl)ethane-

~60073

.
sulphinate, and
ethyl 2-(2-(methoxycarbonyl)-l-methylvinyl)ethane~
sulphinate.
Of the generic class of compounds wherein A represents
the group 0 - R, certain species are preferred~ i.e.
~hose compounds wherein X represents chlorine~ bromine
or alkoxy o~ up to 3 carbon atoms and R is hydrogen,
alkyl of up to 20 carbon atoms, aryl of up to 10 carbon
atoms, alkenyl o~ up to 8 carbon atoms, alkynyl of up
to 4 carbon atoms or Z~ ~hereln Z is alkylene o~ up to
4 carbon atoms and R2 is alkylthio o~ up to 3 carbon atoms,
or alkoxy o~ up to 4 carbon atoms, or hydroxy; and if X
is chlorine R may also repre~ent a beta-chloroethane-
sulphinyloxy moiety.
Exemplary species of this class of the invention
include:
2-methoxyethyl 2-chloroethanesulphinate,
propyl ~ bromoethanesulphinate,
2-bromoethanesulphinic acid,
phenyl 2-bromoethanesulphinate~
naphthyl 2-chloroethanesulphinate~
2-(ethylthio)ethyl 2-bromoethanesulphinate5
2-methoxypropyl 2-bromoethanesulphinate,
2-butoxypropyl 2-chloroethanesulphinate and
propynyl 2-bromoethanesulphinate
0~ this preferred class of compounds certain
species are especially effective in regulating the growth
of plants~ thus compounds ~hereln X is chlorine, and R

o~
- 7

is alkyl of up to 20 carbon atoms or alkenyl of up to
8 carbon atoms make up another preferred aspect of the
invention.
Specific examples o~ this preferred subclass
include:
methyl 2~chloroethanesulphinate,
am~l 2-chloroethanesulphinate3
3-buten~l 2-chloroethanesulphinate,
heptyl 2-chloroethanesulphinate,
decyl 2-chloroethanesulph~nat~ and
3-pentenyl 2-chloroethanesulphinate,
Other pre~erred compounds in the class o~ com-
pounds having -the formula I ~herein A represents the
group Y-R~ are those compounds w~ rein X represents
~koxy of up to 3 carbon atoms9 aralkoxy o~ up to 10
carbon atoms or acyloxy of up to 4 c~rbon atoms; and A
represents the group O - R wherein R is hydrogen; or
those wherein X represents chlorine~ aralkoxy o~ up to
10 carbon atoms or alkoxy of up to 3 carbon atoms, and
~0 A represents the group - O - R wherein R is alkyl of up
to 20 carbon atoms, aralkyl of up to 10 carbon atoms,
or alkenyl of up to 8 carbon atoms~ or those wherein X
represents chlorine or bromine and A represents the group
-S - R wherein R is beta-chloroethyl, betabromoethyl,
alkyl of up to 5 carbon atoms or benzyl.
/R3
When A represents the group - N \ ~ the active
compounds are represented by the ~ormula

73
. ~ W


X - CH~CH2 - S - ~ IXI

wherein X, R3 and R4 are as defined above.
Ex~mplary species o~ thls class of the inventlon
include:
~-bromo~N-t3-hydroxypropyl)ethanesulphlnamide~
2-h~droxy-N-octylethanesulphin~nide~
N-benzyl-2-eth.oxyethanesulphin~nlde~
2-phenoxyethanesulphinamlde~
N-allyl~-(ben~ylox~)ethanesulphinamide,
2-(isoprop~lthio)ethapesulphinanilide~
2-acetoxy-N-hydroxyethanesulphinamide~
2-mesyl-N-(2- ~thylthio)et~yl)ethanesulphinamideg
2-(phenylsulphonyloxy)ethanesulphinamide,
2-nitroethanesulphinanilide,
N-methoxy-2-(dimethylamino)ethanesulphinanilide,
2-(2-(dimethylcarbamoyl)-l-methylvinyl)ethanesulphin-
4-toluidideg
N-(3~butenyl)2-methox~ethanesulphinamide,
2-chloro-N-hydroxyethanesulphinamide and
2-(butylamino)-N-(cyclohe~yl)ethanesulphinamlde.
Of the generic class o~ compounds havlng ~qrmula
I wherein A represents the group / R3
N

certain species are pre~erred i.e~ those compounds
wherein A represents the group / R
\ H


.~ ,. . .


wherein R4 represents hydrogen, aryl of up to 10 carbon
atoms, alkyl o~ up to 20 carbon atoms~ aralkyl of up
to 10 carbon atoms, alkenyl o~ up to 8 carbon atoms~ cyclo-
alkyl o~ up to 8 carbon atoms, alkoxy of up to 4 carbon
atoms or R5Ys wherein R5 i~ alkylene of up to 4 carbon
atoms and Y' is hydroxy or alkylthio of up to 3 carbon
akom8; R4 may also represent a substituted phenyl o~ the
formula Z'
~'
wherein Z' i~ alkyl of up to 3 carbon a~oms~ alkylkhio of
up to ~ carbon atoms~ alkoxy o~ up to 3 carbon atomæ~
alkylsulphonyl of up to 3 carbon atoms, chlorine, bromine,
nitro or tri~luoromethyl; and X is chlorine, bromine3 iodine
or alkylsulphonylox~ wherein the alkyl gr~oup contains up to
3 carbon atoms with the proviso that when X is alkylsul-
phonyloxy~ R4 is hy~rogen, alkyl of up to 6 carbon atoms
or aryl o~ up to 10 carbon a~oms.
Exemplary species o~ this class of the invention
include:
2-bromo-N-~3-hydroxypropyl)ethanesulphinamide
2-bromo-N-octylekhanesulphinamide
2-bromo~N-benzylethanesulphinamide
2-chloro-N-heptylethanesulphinamide
2-bromo-alpha, alpha, alpha-tri~luoroethanesulphin-
3-toluidide
2-(e~hylsulphonyloxy)ethanesulphinamide
2-chloro-2~-(methylthio)ethanesulphinanilide

~6~0~3
- 10 - :

2-chloro 3'-(ethylsulphon~l)ethanesulphinanllide
2-chloro-2~-bromoethanesulphlnanilide
2-bromowN-methoxyethanesulphinami.de
2~bromo-N-(3-butenyl)ethanesulphinamide
2-chloro-N propoxyethanesulphinamide
2-bromo~2'~chloroethanesulphinani.lide
The highest plant growth ~egulatory actlvit~
appears to be assoclated with those compounds of thi,s
class ~herein ~ is chlorine~ bromine or lodine. Pre~erred
specie~ o~ ~his subclas,s include compounds whereln X is
chlorine and R4 is hydrogen, alkyl o~ up to 8 carbon
atoms, cycloalkyl of up to 6 carbon atoms9 alkenyl of up
to 5 carbon atomsy aralkyl of up to 8 carbon atoms, unsub-
stituted phenyl~ or phenyl substituted with chlorine,
bromine or trifluoromethyl.
Speci~c examples o~ this pre~erred subclass
include:
2-chloroethanesulphinamide
2-chloro-N-heptylethanesulphinamide
N amyl~2-chloroethanesulphinamide
N-(2-butenyl)-2~chloroethanesulphinamide
N-phenyl-2wchloroethanesulphinamide
N-(2-pentenyl)-2-chlorcethanesulphinamide
2-chloroethanesulphin-4~oluidide
N-phenethyl-2-chloroethanesulphinamideO
Many of the active compounds mentloned here-
before, in particular all the compounds having the
above formula T ~herein A is the group



/
\ R4




have not prevlously been known ln the art. Accordlnglv
the invention also provides novel c:ompounds de~ined by
the ~ormula ~
X - CH2CH2 - ~ - A I / R3
wherein A represents the group - N \ wherein

R~ and R4 may be the same or different and each represents
hydrogenj alkyl of up to 20 carbon atoms or aralkyl of
up to 10 carbon atoms; elther or both o~ R3 and R4 may
be R5YI wherein R5 is alkylene of up to 4 carbon atoms
and Y' ls hydroxy or betahaloethanesulphinyloxy wherein
the beta halogen substitutent is chlorine, bromlne or
iodine with the proviso that when yl is hydroxy X re-
presents any o~ the moietles described for X above
except A'R~ and when Y' ls a betahaloethanesulphinyloxy
X is.chlôrine, br-omine or iodine; if R3 is hydrogen R4
may also represent aryl o~ up to 10 carbon atoms3 alkenyl
o~ up to 8 carbon atoms3 cycloalkyl of up to 8 carbon
atoms, R5Y~ wherein R5 is as described above and y2 is
alkylthio of up to 3 carbon atoms, alkoxy of up to 4
carbon ~oms; when R3 is hydrogen R may also represent
a sub~tituted phenyl of the formula ~ ~ Z


wherein Z' is alkyl o~ up to 3 carbon atoms, alkylthio of
up to ~ carbon atoms9 alkoxy o~ up to 3 carbon atoms,
alkylsulphonyl of up to 3 carbon atoms, chlorine~ bromine~

~ 12 ~ B0073

nitro or trifluoromethyl; and if R3 is hydrogen,
alkyl or aryl R may also represent hydroxy or alkoxy
o~ up to 4 carbon atoms and X represents chlorine,
bromine, iodineg hydroxy3 alko~y of up to ~ carbon
atoms~ aryloxy o~ up to 10 carbon a.toms, alkylthlo of
up to 3 carbon atoms, aralkoxy o~ up to 10 carbon atoms~
acyloxy of up to 4 carbon atoms, alkylsulphonyloxy
wherein the alkyl group contains up to 3 carbon atoms9
arylsulphonyloxy, nitro, monoalkylamino or dialkylamino
wherein each alkyl group contains up to 6 carbon atoms,
or A~R~ wherein Al is oxygen and Rl ls 2-(dimethylcarbamoyl)-
l-methylvinyl, 2~(methylcarbamogl)-l-methylvlnyl or 2-
(methoxycarbonyl)-l-methylvinyl3
or A represents the group - Y - ~ whereln ~ is oxygen
and R ls hydrogen; and X represents bromine~hydroxy,
alkoxy o~ up to 3 carbon atoms, alkylthio of up to 3
carbon atoms, acyloxy o~ up to 4 carbon atoms9 aryloxy o~
up to 10 carbon atoms9 alkylsulphonyloxy whereln the alkyl
group contains up to 3 carbon atoms9 arylsulphonyloxy,
aralkoxy of up to 10 carbon atoms, nitro~ mono- or di-
alkylamino wherein each alkyl group conta~ns up ~o 6
carbon atoms, or A represents the group - ~ - R wherein
Y is oxygen and R is alkyl o~ ~rom 6 to 20 carbon atoms9
aralkyl o~ up to 10 carbon atoms, alkynyl of up to 4
carbon atoms, alkenyl o~ up to 8 carbon atoms9 aryl of
up to-10 carbon atoms, 2-(dimethylcarbamoyl)-l-methyl-
vinyl~ 2-(methylcarbamoyl)-l-methylvinyl~ 2-(methoxycar-
bonyl)~l-methylvinyl, or zR2 wherein Z is alkylene o~
up to 4 carbon atoms and R2 is alkylthio o~ up to 3

0073

carbon atoms, alkoxy o~ up to 4 carbon atoms, aralkoxy
of up to 10 carbon atom~, hydroxy or a beta ~ubstituted
ethanesulphinyloxy moiety wherein the beta substitutent
is identical to the beta substituent represented by X
in formula I above; and X represents chlorine~ bromine
or iodine;
or A represents the group - Y - R wherein Y is oxygen and
R is alkyl o~ up to 20`carbon atoms, aralkyl of up to 10
carbon atoms, alkenyl o~ up to 8 carbon atoms, aryl of up
to 10 carbon atoms, alkynyi o~ up to 4 carbon atoms, 2-
(dimeth~lcarbamoyl)-l-methylvinyl~ 2-(methylcarbamoyl)-
l-methylvlnyl, 2-(methoxycarbonyl)-1-methylvinyl or
zR2 wherein Z i~ alkylene o~ up to 4 carbon atoms and R2
is alkylthio of up to 3 carbon atoms, alkoxy of up to 4
carbon atoms, hydroxy or a beta substituted ethanesulphino
moiety wherein the beta sub~tituent is ldentical to the
beta substituent represented by X ~n ~ormula I above; and
X represents hydroxy~ alkoxy of up to ~ carbon atoms,
aryloxy of up to 10 carbon at.oms9 aralkoxy of up to 10
carbon atoms, alkylthio of up to ~ carbon atoms, acyloxy
o~ up to 4 carbon atoms9 alkylsulphonyloxy, wherein the
alkyl group contains up ~ 3Ic~rbon atoms, arylsulphonyl-
oxy, nitro, mono- or dialkylamino wherein each alkyl
group contains up to 6 carbon atoms or AIR~ wherein A~ is
oxygen and Rl is 2-(dimeth~lcarbamoyl)-l-mëthylvinyl,
2-(methylcarbamoyl)-l-methylvinyl, or 2~(methoxycar-
bonyl) 1-methylvi:nyl;
or A represents the group - Y ~ R wherein Y is sulphur
and R is alkyl of up to 8 carbon atoms optlonally sub

6~0~3

stltu~ed with chlorine or bromine or aralkyl wherein
the alkyl group contalns up to 4 carbon atomsg and X is
chlorlne, bromine, hydroxy, alkoxy of up to 3 carbon atoms~
aryloxy of up to 10 carbon atomsJ alkylthio of up to ~
carbon atoms, aralkoxy o~ up to 10 carbon atoms~ a~yloxy
of up to 4 carbon atoms, alkylsulphonyloxy wherein the
alkyl group contains up to 3 carbon atoms, arylsulphonyloxy,
nitro or mono- or dialkylamino wherein each alkyl group
contains up to 6 carbon atomsO
The novel compounds having the above formula I
~herein A is the group - Y - R can be d~ided in following
classes:
I. Sulphinic Acids
Compounds wherel~ X is bromine 9 hydroxy, alkoxy of
up to 3 carbon atoms~ alkylthio of up to 3 carbon
atoms, acyloxy of up to 4 carbon atoms, aryloxy o~ up
to 10 carbon atoms~ alkylsulphonyloxy wherein the alkyl
group contalns up to ~ carbon atomsg arylsulphonyloxy,
aralkoxy o~ up to 10 carbon atoms, nltro, mono- or
dialkylamino wherein each alkyl group contains up to
6 carbon atoms, Y ls oxygen3 and R is hydrogen~
II. Sulphinate Esters
Co~pounds wherein X is chlorine~ bromine, or iodine;
Y is oxygen and R is alk~l of from 6 to 20 carbon atoms,
aralkyl of up to 10 carbon atoms9 alkynyl of up to 4
carbon atoms9 alkenyl of up to 8 carbon atoms, aryl
of up to 10 carbon atoms~ 2-(dimethylcarbamoyl)~l-
methylvinyl, 2--(methylcarbamoyl)-l-methylvinylJ 2-

15 i ~ ~0~73

(methoxycarbonyl)-l-methylvinyl, or zR2 whereln
Z is alkylene o~ up to 4 carbon atoms an~ R2 is
alkylthio of up to ~ carbon atomsJ alkoxy of up to
4 carbon atoms, aralkoxy of up to 10 carbon atoms,
hydroxy or a beta-substituted ethanesulphinyloxy
moiety wherein the beta substituent is identical to
the beta substituent represented by X in formula Io
Compounds wherein X is hydroxy, a:lkoxy of up ~o
carbon atoms~ ar~lko~y of up to 10 carbon atoms 9
aralkoxy of up to 10 carbon atoms, alkylthio of up to
3 carbon atoms, acyloxy of up to 4 carbon atoms,
alkylsulphonyloxy, wherein the alkyl group contains
up to 3 carbon atoms, arylsulphonyloxy, nitro9 mono-
or dialkylamino wherein each alkyl group contains
up to 6 carbon atoms or AtR' ~hereln At i9 oxygen
and R' is 2-(dimethylcarbamôyl)-l-methylvinylg 2-
(methylcarbamoyl)-l-methylvinyl, or 2-(methoxy-
carbonyl) l-methylvinyl; Y is oxygen; and R is alkyl
of up to 20 carbon atomsg aralkyl o~ up to 10 carbon
atoms9 alkenyl of up to 8 carbon atoms, a~yl of up
to 10 carbon atoms, alkynyl of up to 4 carbon atoms,
2-(dimethylcarbamoyl)-1-methylvinyl, 2-(methyl-
carbamoyl)-l-methylvin~l~ 2-(methoxycarbon~
methylvinyl or ZR whereln Z is al~ene of up to 3
carbon atoms and R is alkylthio of up to 3 carbon
atoms~ alkoxy of up to 4 carbon atoms9 aralkoxy of
up to 10 carbon atoms or a beta substituted ethane-
sulphino moiety wherein the beta substituent is
identical to the beta substituent represented by
X in formula I.

6 ~6~3

III. Thiosulphinate Esters
Compounds wherein X i~ chlorine, bromine, hydroxy~
alkoxy o~ up to 3 carbon atoms, arylox~ o~ up to 10
carbon atoms, alkylthio of up to 3 carbon atoms, aral-
koxy o~ up to 10 carbon atoms, acyloxy o~ up to 4
carbon atoms,:alkylsulphonyloxy ~herein the alkyl group
contains up to 3 carbon atoms, arylsulphon~loxy,~nitro
or mono- or dialkylamino wherein each alkyl group
contains up to 6 carbon atoms, Y i8 ~ulphur; and R ls
alkyl of up to 8 carbon atoms optionally substituted wlth
chlorine or bromine or aralk~l wherein the alkyl group
contains up to 4 carbon atoms~
Specific examples o~ these novel compounds
include:
2-~sopropoxyethanesulphinic acidg
2-formylethanesulphinic acid,
2-phenoxyethanesulphinlc acid,
2-(methylthio)ethane~ulplhinic acid~
2-(ben~yloxy)ethanesulphinic acid,
2-(mes~loxy)ethane~ulphinlc acid,
2-(tosyloxy)ethanesulphlnic acld3
octyl 2-bromoethanesulphinate,
allyl 2-isdoethanesulphinate,
3-(propylthio~propyl 2-hydroxyethanesulphinate~
2-(dimethylcaxbamoyl~ methylylnyl 2-phenoxy-
ethanesulphinate,
2-(2-acetoxyethanesulphinyloxy)ethyl 2-acetoxy-
ethanesulphinate,

Q~3
7 ~
methyl 2-nitroethanesulphinate~
S-(s-butyl) 2-methoxyethanethiosulphinate,
S-(3-pentyl) 2-phenoxyethanethlosulphinate and
S-benzyl 2-acetoxyethanethlosulphinate.
0~ this generlc class of novel compounds useful
in the method o~ this lnventlon, certain species in each
of ~he acid a~d ester subclasses are espec~ally e~fective
in regulating the growth of plants. Preferred in this
respect are compounds o~ the ~ormula I wherein X represents
bromlne, chlorine or alkoxy of up to ~ carbon atoms and A
represents ~he group - O - R wherein R is alkyl Or from 6
to 20 carbon atoms9 alkynyl of up to 4 carbon atoms, alkenyl
of up to 8 carbon atomsg aryl o~ up to 10 carbon atoms,
or ZR wherein Z is alkylene of up to 4 carbon atom~ and
R ls alkylthio of up to ~ carbon atoms or alkoxy of up
to 4 carbon atoms, or hydroxy, and i~ X is chlorine R
also may represent a beta-chloroethanesulphlnyloxy moiety
Excellent compounds are those of formula I in ~hich X i8
bromine and A represent~ - OH.
~0 Speci~ic examples of novel compounds in the
sulphinic acid subclass lnclude:
2-methoxyethanesulphinic acid,
2-ethoxyethanesulphinic acid,
2-(butyryloxy)ethanesulphinic acid,
2-acetoxyethanesulphinlc acid,
2-(benæyloxy)ethanesulphinic acid and
2-~furfuryloxy)ethanesulphinic acid.
Speci~ic examples of novel compounds in the
sulphinate ester subclass include:

- 18 .~ l~R~

phenethyl 2-chloroethanesulphinate~
methyl 2-(benzyloxy)ethanesulphinate,
allyl 2-(phenethyloxy)ethanesulphinate,
benzyl 2-(benzyloxy)ethanesulphinate,
am~l 2-chloroethanesulphinate,
3-butenyl 2-chloroethanesulphinateg
allyl 2-methoxyethanesulphinate,
decyl 2-ethoxyethane~ulphinate,
benzyl ~-propoxyeth~sulphinate and
3-pentenyl 2 isopropoxyethanesulphinate~
Speci~ic example~ o~ novel compounds in the
thiosulphinate ester subclass include:
S.(2-chloroethyl) 2-chloroethane~hiosulphinateg
S-isopropyl 2-chlo~oethanethiosulphinate,
S-benzyl 2-chloroethanethiosulphinate,
S-(~-bromoethyl) 2-bromoethane~hiosulphinate and
S-ben3yl 2-bromoeth~thiosulphinate.
The compounds of the invention may be applied
to seeds prior to planting or to soil surrounding ~e
plants, or to plants, pre-emergence, or at harvest to
modi~y and/or regulate the grow.~h of the plant, or
optionally may be applied to stimulate, regulate and/or
modify ripening of the harvested portion, ~or applicationJ
compounds of the invention, being either solid or liquid
at ambient temperatures, ma~ be formulated using con-
ventlonal techniques and employing adjuvants and/or
modifiers which are known in the agricultural chemical
art to provide compo~itions ln the ~orm o~ wettable
powders, dusts, jgranules~ pellets~ solutions, emulsi~iable

~o~
- 19 -

concentrates, emul~lons and pastes.
Preferred for use on maturing plants or harvested
crops are those formulations which furnish the active
ingredient to the plant locus in liquid or paste form.
These preferred ~ormulations would include wettable
powders, solutions, emulsiflable concentrates, emulslons and
pastes. Wettable powders are water-dlspersible compositbns
containing the active ingredient in proportions ranging
from 10 to 90~ of ~ total composition, a~d an inert solid
carrier such as one of the natural clays or a synthetic
mineral ~iller derived fro~ silica and sllicate. Optionally,
such wettable powder may also contain 3-10~ of a dispersing
agent and where necessary 0-10% o~ stabilizer(s) and/or
other addltl~es ~uch as penetrants or stickers. The term
~solu~ion" includes both aqueous and non-aqueous solutions
o~ the compounds o~ the invention. Certain of the compounds
of the invention are soluble in aqueous media and can be
formulated and applied in aqueous solution at concentrations
up to 10%o Other compounds o~ the invention are less or
sparingly soluble ln water and e~hibit proportionally
higher solubility in ~on-aqueous solution and may be
fo~mulated and applied at concentrations of up to 50~. The
emulsifiable concentrates contemplated for use in the
method of the invention usuall~ contain, in addition to
the solvent and, when necessary, co-solventg 10-50
w/v active ingredient, 2-20 w/v emulsi~iers and 0-2G~
appropriate additives such as stabilizersg penetrants
and corrosion inhibitors. Pastes are compounded so as
to obtaln a stable ~lowable product and usually contain

i'3
- 20 -

10-60~o active ingredient, 2-20~ of appropriate additives,
and as carrier, water or an organic liquid in which the
plant growth regulator is substantially insoluble.
For season long treatment, i~e,, application at
time of plantlng or application to plants in early stages
of growth, or for other specializecl applicationsJ solid
~ormulationsof the compounds o~ the~ invention may be
desired. Suitable solid formulation~ would include dust~,
granules and pellets, Dusts usually have a composition
similar to that of a wetta~le powder but without a dis-
persant, and normally contain 1/2 to 10% of plant growth
regulatorO Dust may also be ~ormulated as concentrates
which are then usually diluted further with solid carrier
in suitable blending equipment prlor to use in the field~
Granules and pellets are usually prepared to have a size
between 10 and 100 BS mesh, and may be manufactured by
agglomeration compaction or impregnation techniques.
Generally9 granules willcontain 1/2-25% of plant growth
regulator plus additives such as stabilizers, slow-release
modifiers, binding agents, etc. ~xcept where indicated other-
wise, all percentages given in this and the preceding
paragraph are percentage~ by weight.
To achie~e the plant growth regulating and
modifylng effects hereinbefore described, formulations
of the compounds of the invention may be applied directly
to the plant fruit or as foliar-soil treatments, seed
treatments, foliar treatments or soil treatments, The
rate of application will be dependent on the type of
appllcation technique utilized as well aR other factors

~t~O~Ci~'
- 21 -

such as the particular active agent usedJ the particular
fo~mulation employed, the partlcular species of plants
involved~ the matur~ty stage of the plant, the types of
effect desired and the local conditions; for example~
temperature, humidityJ soil moisture, chemical make-up
of the soll and the like. In general, ~or plants in
agronomic environment, rates from 0.05 to ~0 pounds per
acre can be used to stimulate and/or modlfy plant growth.
However, the preferred rates for most uses range between
0.1 and 5.0 pounds per acre. For application to the plant
fruit or harvested crop, the rate of appllcation may range
between l and ~0,000 ppm (parts per million based on to~al
~ruit weight) with rates of from 100 to 4,000 ppm belng
preferred.
The compounds of the invention as described~v
formula I, above, wherein A is the group - Y - R may be
prepared by the following synthesis techniques.
I. Sulphinic Acids
The beta-substitu~ed ethane sulphinic aclds wherein
the beta substltuent, X, is halogen (chlorine, bromine
or iodlne)~ alkylsulphon~loxyJ arylsulphonyloxy, nitro~
alkoxyJ acyloxy~ aryloxy or aralkoxy may be prepared by
the reaction of a beta-substituted ethanesulphinyl chloride
of the formula I~

X-CH2CH2S-Cl I~
wherein X may be any o~ the moieties described above
in this paragraph, with water. This reaction is suitably
carried out in an inert organic solvent such as ether and

-- - 22 ~ 0073

the by-product hydrogen chlorideg which i~ generated
in the reaction, is e~ectively removed by sparging
the reaction m1xture wlth nitrogen during the
reaction period.
The beta-~ubstituted ethanesulphinic acids whereln
the beta carbon of the ethane m~ety is bonded to a
nitrogen or sulphur, i.e. 9 Whereirl X iS mono- or
dialkylaminol or alkylthlo group n~y be prepared b~
reactlons analogous to the ring opening of eth~lene
episulphone with barium hydroxide reported in G. Hesse
et al`, Chem. Ber., 90, 2106 (1957). With thi~ ~ynthesis
technique 2-(mono- or dialkylamino)ethanesulphinic acids
can be prepared by reacting a primary or secondary amine
with ethylene episulphone, whereas if ethanesulph~nic
acids substituted in the 2 position with alkylthlo
moieties are desired then an alk~l mercaptan and
ethylene epi~ulphone would be the appropriate reactants.
The~e reactions are suitably carried out in an lnert
solvent such as ether~
2-Hydroxyethanesulphinic acid, the sulphinic
acid whereln X is hydroxyJ may be prepared from the
barium salt o~ 2-hydroxy-ethanesulphinic acid by
acidification and removal o~ the barium ion through
treatment with an acid ion exchange resin such as
Amberlite IRC-50 AR or Dowex-50~ or with sulphuric
acid. The ~ree acid ls then isolated from the re~ulting
aqueous solution by lyophilization. The barium salt
o~ 2-hydro~yethanesulphlnic acid is a known compound
and may be prepared according to the technique

- 23 ~ 3

described in G. Hesse et al C em. Ber., 90, 2106(1968).
II. Sulphinate Esters
Many of the beta~substituted ethanesulphlnate
esters described above, specl~ically those whereln X
ls halogen (chlorlne~ bromlne or lodine)~ alkoxy,
acyloxy, aryloxy, aralkoxy, arylsulphonyloxy, alkyl-
sulphonyloxy or nitro and whereln R is alkyl~ alkenyl,
alkynyl~ alkylthloalkyl, alkoxya:LkylJ aralkoxyalk~l or
halogenated alkyl, ma~ be prepared by the reaction of
a beta-substituted ethanesulphinyl chloride o~ the
for~ula V with a hydroxy compound o~ formula VI as
illustrated by equation I, below

X-CH2CH2 -Cl ~ R0~ `~ X-cH2cH2~-oR Equation I
V VI
wherein X and ~ respectively~ are limited to those
specific moieties described above in this paragraph.
This reaction is suitably carried out in an inert
solvent ~uch as ether and at reaction temperatures less
than ambient. Due to the highly reactive nature o~ the
sulphinyl chloride, the reaction is preferably carried
out under an inert (nitrogen) atmosphere.
Beta-substituted ethanesulphinate esters wherein
X is as described above in this paragraph and R is aral-
kyl or aryl may be prepared by the reaction o~ a metal
salt such as sodium~ potassium, or thallium of a hydroxy
compound of formula VII with a beta-substituted
ethanesulphinyl chloride as illu~rated by equation II
below, Th~ reaction is suitably performed in an inert

~ ~ ~ 2~ 6~7~

solvent such as ether or benzene under an inert
atmosphere.
O O
r
X CH2CH2S-Cl ~ ROM > X-CH2CH2SOR ~ MCl
VII Equation II
The beta-substituted ethanesulphinate esters
wherein the ester mo~ety is vinyloxy in character~
i.e., ~herein R i5 2-(mono~ or d~ethylcarbamoyl)-l~
methylvlnyl or 2-(methoxycarbonyl) l-meth~lvinyl wherein
the beta substituentJ X, i5 as described for the esters
prepared according to equatlon X above, may be prepared
by the reaction o~ a metal salt o~ the approprlate
acetoacetic amlde or ester such as the thallium or
sllver salt (formula VIII), with a beta-substituted
ethanesulphinyl chloride of formula V above. This
reaction is illustrated by equation III below

Z-~-CH=8~CH~ + X-CH2CH2-~-Cl --~ X-CH2CH ~ -~-Z
VIII V CH3
Equation III
wherein Z is methoxy, monomethylamino or dimethylamino
and M is a metal ion, e.g., thallium or sllver. This
reaction is suitably carried out ln an!inert solvent
such as tetrahydro~uran, in whlch the by-product
metal salt of the reaction is sparingly soluble,
thereby ~acilltating ready recovery o~ the metal
for reuse in the synthesis scheme.
The beta-substitutcd ethanesulphinates wherein
the beta substituent is a vinyloxy type moiety~ i.eO

- - 25 ~'~'16~

whereln X is A~R~, A~ being oxygen and R~ being 2-
(mono- or dlmethylcarbamo~ methylvinyl or 2-(methoxy-
carbonyl)-l-methylvinyl, may be prepared by the reaction
of a 2-chloroethanesulphinate ester, with a metal salt
of an acetoacetic amide or ester as described by ~ormula
VIII above This reaction is suitably carried out ~n an
inert solvent such as ether or tetrahydro~uran.
The 2-chloroethanesulphinates prepared accordlng
to equations I~ II and III above, can also serve as
starting materials for the synthesis of khe 2-hydroxy-
ethanesulphinates of this invention~ Under this synthesis
technique the 2-hydroxyethanesulphinates are prepared
by reacting their 2-chloro analogs with silver hydroxideu
The reaction is suitably carried out ln ether with the
silver hydroxide being generated in situ b~ the action
of moist ether on silver oxide~
The beta~substituted ethanesulphinates wherein
X is alkylthioJ monoalkylam~no or dialkylamino may be
prepared from the 2-chloroethanesulphinates by a two-
step synthesls technique. In the initial stepJ a 2-
chloroethanesulphlnate prepared according to equations
I, II or III above is dehydrochlorinated by the acklon
of an organic base catalyst such as triethylamine to
yield an ethenesulphinate. This reaction is suitably
carr ed ou~ in an inert organic solvent such as ben-
zene with sufficient base being charged to the reaction
to accept the by-product hydrogen chloride which is
generatedO In the second reaction step9 the ethene-
sulphinate intermediate is reacted ~ith an alkyl
mercaptan or a mono or dialkylamine to yield the

~0~73
- 26 -

desired beta-substituted ethanesulphinate. This
reaction is suitably carrled out in an inert organic
solventg preferably the same solvent as is utilized
for the dehydrochlorination reaction~
III. Thiosulphinate Esters
The beta-substituted ethanethiosulphinates whereln X
is halogen (chlorine, bromine or iodine~ alkoxy, ar~loxy,
aralkyloxy3 acylox~, arylsulphonyloxy~ alkylsulphon~oxy
or nitro and wherein R is an alkyl or ~ralkyl may be
prepared by a 4 step synthesis scheme, utllizing as a
starting material a bis(beta substituted eth~l)disulphide
of formula IX~
(XCH2CH2S- ) 2 IX
wher.ein X is llmited to those moieties descrlbed
above in this paragraph. The disulphides of fo~ ula IX
are identical to the bis (beta-substituted ethyl)
disulphides which are utilized to prepared the bis
substituted ethanesulphinyl chlorides ln the sulphinate
preparation described abo~e~ In ~he initial reaction
of the 4-step sequence, the bis(beta-substltuted ethyl)
disulphide of formula IX is reacted with molecular
chlorine in a halogenated alkane solvent such as chloro-
form to ~ield a beta substituted ethanesulphenyl chloride
of formula X.
XCH2CH2-S-Cl X
In the second reaction, a beta-substikuted ethane-
sulphenyl chloride of formula X is reacted with phthal-
imide to yield an N-(beta substituted ethylthio)phthali-
mide of formula XI,

~`i8~0~3
- 27 -



~ N-SCH2CH2-X XI

This reaction is suitably carriecl out in an inert
solvent such as ~imethyl~ormamide~ This N-substituted
phthalimide lntermediate is then reacted with a mercaptan
of formula XII~
R-SH XII
wherein R is alkyl or aralkyl3 to yield a disulphide
of formula XIII.
X-CH2CH2S-S-R XIII
This reaction~ whlch proceeds according to the gene~al
method described by K.S. ~oustany and AoB~ Sullivan,
Tetrahedron Letters, ~547 (i970)~ ls suitably carried
out in an inert organic sol~ent such as benæe~e. In the
final reaction of the 4-step sequence a disulphide o~
formula XII is reacted with metachloroperbenzoic acid
to yield the corresponding beta substituted ethanethio-
sulphinate. This rèaction, which utilizes the general
technique described by A. Schoberl and A~ Wagner,
Methoden der Or~a~ischen Chemie, _, 691(1955) J iS
suitably carried out in a chlorinated alkane solvent
such as chloroform~
The beta substituted ethanethlosulphi~te wherein
the beta substituent ~ ls mono- or dialkylamino or
alkylthio may be prepared by a 4-step synthesis tech-
nique ~ which is somewhat analogous to the technlque

~ ~6~V~73
28 _

prevlously described for the other beta substituted
ethane thiosulphinates~ In this synthesis scheme~ a
bis dlsulphide o~ formula XIV
R-S-S~R XIV
wherein R is alkyl or aralkyl is reacted with mole-
cular chlorine in a halogenated alkane solvent such
as chloroform to yield an alkyl or aralkyl sulphenyl
chloride of formula XV.
RSCl XV
This ~ulphenyl chloride intermediate 1~ then reacted
wlth phthalimide ~o yield an ~-substituted phthallmide
of formula XVI.

~ ~ N-SR XVI

This reaction ls suitably carried out ln an inert
solvent such as dimethyl formamide. In the third reaction
o~ the sequence the N-substituted phthalimlde inter-
mediate is reacted wlth a beta substltuted eth~l
mercaptan of formula XVII~
X-CH2CH2-SH XYII
wherein X is mono- or dlalkylamino or ethylthio to
yield a dlsulphide of formula XVIII,
X-CE2CH2SSR XVIII
Thls reaction is su~ably carried out in an inert
aromatic solvent such as benæene. In the ~inal reaction
of the sequence a disulphide o~ formula XVIII is reacted
with meta-chloroperbenzoic acid to yield the desired

`` - 29 ~ 073

thiosulphinate ester~ This flnal reactlon is sultably
carried out in a halogenated alkane solvent such as
chloroform.
The beta substituted ethanesulphinamides (i,e.
those compounds having formula I wherein A is the group
- N
\ X4




wherein the amide nitrogen is unsubstituted and the beta
substituent, ~ is halogen (chlorine, bromine or iodine~,
alkoxy, acyloxyg aryloxy3 aralkoxy, alkylsulphonyl~xyJ
arylsulphonyloxy or nitro m2y be prepared by the reaction
of a beta substituted ethanesulphinyl chloride of formula
XIX 0
X-CH2CH2~S-Cl XIX
wherein X is limited to those moieties described above
in th~s paragraph, with anhydrous ammonia. The reaction is
suitably carried out under an inert atmosphere such as
nitrogen and in a water-free solvent su~h as anhydrous
ether. It has been ~ound convenient to add the sulphinyl
chloride dropwise/ to a solution o~ ammonia ln anhydrous
ether, maintaining the solution at -10 to -40C during the
addition period.-Under this procedure the reaction is
normally complete in the time required for addition o~ the
sulphinyl chloride reactant plus the time required to
warm the reaction mass to ambient temperatures by natural
convection.
In an analogous manner, the N~monosubstituted
and N,~disubstituted ethanesulphinamides o~ formula I

~6~

wherein X is any of the substituents descrlbed in the
paragraph above, excepting those compounds wherein the
amide nitrogen is substltuted ~ith a betahaloethanesul-
phinyloxyalkyl group9 may be prepared by the reactlon
of a sulphlnyl chloride descrlbe~ by f~ormula XIX above
with a primary or secondar~ amine of formula XX
/ R3
H-N XX
\ R4
wherein R3 and R4 represent any of the moieties described
for R3 and R4 in formula I above except betahaloethanesulphi-
nyloxyalkyl, This reaction is run analogously to the
unsubstituted ~mide preparation described above utilizing
the same reaction techniques and parameters~
The beta substituted ethanesulphinamides wherein
the beta substituent is a viny~oxy type moiet~, i.eO,
wherein X is AlR' J A~ being oxygen and R9 being 2-(methyl-
carbamoyl)-l-methylvinyl~ 2-(dimethylcarbamoyl)-l-methyl-
vinylJ 2 (methoxyc~rbonyl3-1-methylvln~l may be prepared
by the reaction of the appropriate 2 chloroethanesulphina~
mide, prepared according to the reactions described above,
with a metal salt o~ the appropriate acetoaceticamide
or ester, e.g.~ thallium or silver salt as descrlbed by
formula XXI O OM
Z-C-CH=~-CH~ XXI
wherein Z is methoxy~ m~me~hylamino or dimethyl~mino
and M is a metal ion, eOg., thallium or silver, This
reaction is suitabl~ carried out in an inert or~anic
solvent such as ether or tetrahydro~uran.

- 3~ 0 ~)7 3

The 2-haloethane~ulphinamides prepared according
to the! techniqu~ described above~ can also serve as starting
ma~erials ~or the synthesis of ~he 2-hydroxyethanesul-
phinamides of this invention. Under this synthesis tech-
nique the 2-hydroxyethanesulphinamide6 are prepared by
reacting thelr 2-halo analogs wlth silver hydroxide~
The reaction is suitably carried out ln ether with the
silver h~droxide belng generated in situ by the action of
moist ether on silver oxide.
The beta substituted ethanesulphinamides wherein
X is alkylthiog monoal'~ylamino or dl~lky~amino may be
prepared from the 2-chloroethanesulphinamides b~ a two
step synthesis technlque~ In the initial step, a 2-
chloroethane~ulphinamide prepared accordlng to the tech-
niques described above ls dehydrochlorinated by the action
of an organlc base catalyst such as trlethylamlne to yleld
an ethenesulphinamide. This reactlon is suitably car~ied
out in an inert organic solvent such as benzene with
su~ficient base being charged to the reaction to accept
the by-product hydrogen chlor;ide which is generated~ In
the second reaction step, the ethenesulphinamlde inter-
mediate is reac~ed with an alkyl mercaptan or a mono- or
dialkylamine to yield the desired beta substituted
ethanesulphinamide. This reactlon is suitably carried
out in an inert organic solvent~ pre~erably the s~me
solvent as is utilized ~or the dehydrochlorination reaction.
The be!ta halosubstituted ethanesulphinamldes
wherein the amide nitrogen is substituted with a beta-
haloethanesulphinyloxyallcyl moiety may be prepared

:1 ~60~73
- 32 -

by the reaction o~ a betahaloethanesulphinamlde where~n
the amide nitrogen is substltuted with hydrq~yalk~l, with
a betahaloethanesulphinyl chloride of formula XIX abovea
This reaction is suitably carried out under an lnert
atmosphere such as nitrogen and in a water-~ree solvent
such as anhydrou.~ ether~
The following examples are illustratlve o~ methods
o~ preparing the compounds of this ~nvention and their
use in regulating plant growthD In these examples, parts
1~ by weight (w) and parts ~y volume (v) b~ar the same
relation as the kl~logram to the litre and all temperatures
are in degrees centrigrade, In all cases, the compound
~tructures were confirmed by infra-red spectrag nuclear
magnetic resonance, ~pectra and elem~ntal analyse~D

~6~ 3


Example I 2~hloroethanesu~

Cl-CH2CH2-S-OH
Bis(2-chloroethyl)~disulphide was oxidatively
chlorinated according to the general method di~clo~ed in
I.B. Douglass and R.V, Norton,
~ 2104 (1968) as ~ollow~: Bis(2-chloroethyl)disulphide
(38.o w) was charged into a reaction ~e8se~ containln~
glacial acetic acid (24.0 w) and the mixtur~ was cooled to
10. Chlorine gas wa~ introduced to the cooled ~olution at
a rat~ such that the reaction mixture wa~ maint~lned at
. abou~ 10. The chlorin2 ~dd~tion was continucd until the
deep orange c~ur o~ the reaction mi~ture disappeared. The
solution wa then di~tilled at reduced pr~sure to yield a
clear liquid, 2-chloroethanesulphinyl chloride (50.4 w),
boiling point 81-82 un~er reduced pre~sure (12 torr)~
Water (3.6 w) was added in one portion to a
solution o~ 2~1oroethanesulphinyl chloride (29.4 w) in
ether (250 v). ~he reactlon mixture was held for one hour
at ambient temperatures during which time a vigorous
stream of nltrogen was bubble~ through the mixture. Upon
completion of the hol~ period~ the r~actlon sol~tion was
concentrated by distillation in a vacuum to g~ve a
colourless liquid (26,4 w). Further purification of this
llquid by molecular distillation at 75 and 1 x 10 4 torr
provided a colourless viscous o11, 2-chloroethanesulphinic
acid (140 5 w).

1 lB0073
- ~4 -
Example ~I t2-E~hyl)hex~2-chloroe~ e~}e~
o




S )C H
Cl-CH2C~ -O-CH2c~(c2~5 4 9
A stirred portion o~ 2-ch.loroethanesulphinyl
chloride (16.2 w) prepared a~ in Example I~ cooled to -15
to -30C, wa9 trea~e~ dropwise with 2-ethylhexanvl (1~.0 w)
under a nitrogen atmosphere~ Upon completlon of the addi~
tion the ~xternal cooling was removed and the reaction
mixture w~s allowed to ~tand for 16 hou~ at ambi~nt
temperature. Distillation through a 20 cm Vi~re~x column
afforded a clear whit~ liquld, (2-ethyl)hexyl 2-chloro-
ethanesulphinate (1~.7 w) bolllng at 110 to 112 under
reduced pre~æure (0.3 torr).
EXa~Pl2 III Butyl 2-chloroethanesulphi~ate

Cl-C~2CH2S-OC4Hg
2-Chloroethanesulphinyl chlorid~ ~1602 w), prepared
as in Exampl~ I was dis~olved in dry ether (130 v) and the
solution was coole~ to -15~ Normal butanol wa~ added drop-
wlse unqer a nitroeen atmosphere to the cooled solution,
Upon completlon of tho addition period the reaction mLxture
wa5 allowed to warm to ~mbient temperature~ and the solvent
was remov~d by distillation in a vacuum to yield a colour-
less lLquid, butyl 2-chloroethanesulphinate (180 5 w).
Example IV 2-(Chloroethanesulphin~lox~)eth~l 2-chloro-
ethanesulphinate
O
1` 1 .
Cl-C~2CH2-S-OC~ CH2~0-$-CH2CH2-Cl

1 lB0073
- - ~5 -
Ethylene glycol (602) was added dropwi~e under a
nltrogen atmosphere~ to a stirred solution of 2-chloroethane-
sulphinyl chloride (14.7 w), prepare~ as in :ESxample I~ in
dry ether (40 v). During khe add$tio~ ~eriod the ~emp~rature
o~ the reaction wa~ con~rolled a~ -20 b~ extern~l cooling.
Upon completion of the addition, the r~action mixtur~ was
warmed to ambie~t temperature and the sol~e~t was remo~od
by d1stillation in ~ vacuum. Examina~ion o~ the ~ due by
gas-liquid chromatography rev~aled more than on~ ma~or
component. The res~due wa~ ~hen redissolv~d in dry ether
(200 v) and further treated with 2-chloroethanesulphinyl
chloride (1407 w) as above. Using the same procedure as
above an oily re~idue wa~ obtained which a~ter purification
in a wiped film molecular still yielded as colourless
liquid 2-(chloroethanesulphinyloxy)ethyl 2-chloroethane-
sulphinat~ (8.5 w) boiling at 110~ under.reduced
pressur~ (1 x 10-4 torr~.
Example V 2-~Ethylthio)ethyl 2-chloroethanesulphinate
o
Cl-CH2CH2-S-OCH2CH2-SCH2CH2
A solution of ethyl 2-hydroxyeth~l sulphlde (10.6 w)
in dry ether (50 v) was slowly added to 2-chloroethane-
sulphinyl chloride (14.7 w) in d~y ether (200 v) maintained
at about -10 under a nitrogen atmosphere. Upon warming ~o
ambient tempera~ure, the reaction mixture was evaporated
under reduced pressure. The resldual oil was passed through
a wiped film molecular still to yield 2-(ethylthio)ethyl
2-chloroethanesulphlnate (15.4 w) bolling at 95-100 under
reduced pre~sure (1 x 10-4 torr~.

0~7
- ~6 -

Example VI Ph~n~l ? chloroethanesulphinate
o




Cl CH2C~I2 S o~3

A suspension o~ thallium(I) phenoxide (28.6 w) in
dry ether (100 v) w~s rapidly treated with 2-chloroeth~ne-
sulpinyl chlorideg prepared as in Example I. The slurry was
Yi~orouSly stirred ~or 1 hour at ambi~nt t~mperatur~ with
exclu~ion o~ moisturoO Removal o~ thallium(I) chloride b~
~iltration and evaporation o~ the ethereal ~iltrate
solution gave an oil. Thc oil was then ~ub~eeted to molecular
distillation in a wiped film ~pparatus at 70-75 (1 x 10-4
torr) to give phenyl 2 chloroethanesulphlnate (122 w) as a
mobile liquid~
Example VII
Following procedures similar to those given in
previou~ ex~mpleæt the ~ollowing other specie~ of the
compound~ o~ the invention were prepare
Table,I

X-CH2CH2S-Y-R
Melting point3 G or
X Y R Boiling_~oint,C(torr~
Cl -CH3 74 - 76 (4,0)
Cl 0 CH2CH3 62 - 64 (0.75)
Cl 0 -CH(CH~)2 64 - 67 (0.15)
Cl -CH2(CH2)~CH3 55 - 60 (1 x 10 4)
Cl -CH2(CH2)6CH3 116 -117 (0.25)
. .

- ~ 16~Ci73
- ` - 37 -

Table I f ~nt ' d~
M~lting point,C or
X Y R Bollin~Ro~ C ~ tor~r
Cl O C~2 (CH2 )10CH3 not determin~d
Cl O CH2 (CH2 ~14CH~ 27 - 29
Cl O CH2(CH2)18CH3 48 - 49
Cl O -C~I2~) not dekermined
Cl O -CH2CH=CH2 70 - 75 (1 x 10 4)
Cl -CH2C--CH 80 - 85 ~1 x 10 4)
Cl -CH2cH20(~H2)3c~:3 73 w 75 (1 x 10 4)
Cl O -CH~CH~OH not determined
Br O -CH~ 58 - 50 (0.~0~
Br O -C~2(cH2)4e~ 85 - 90 (1 x 10 4)
-OC~3 0 -C~I3 44 (0015)
O,
-OCCH3 -CH3 not determined

E ample VIII 2-Chloroetpanesulphinamide

: ~ / H
Cl-CH2C~ S-N \

Bls(2-chloroethyl)disulphide was oxlda~i~ely
chlorinated accordin~s to the general method disclosed in
I~Ba Douglas~ and R.V. Norton, Joumal o~ Or~nic Chemistry,
~ 2104 (1968) as follows: bis~?-chloroethyl)disulphide
(38..0 w) was charged into a reaction vessel containing
glacial acetic acid (24.0 w) and the mixture was cooled
to 10. Chlorine ga~ was introduc~d to the cooled solution
at a rate such that the reackion mixture wa~ maintain~d
at about 10. The chlorine addition was continued until

1 1 600~3
- 38 -

the deep orange colour o~ the reaction mixture di~appeared.
The solution W~9 then distilled at reduced pres~ure to
yield a clear liquid, 2-chloroethanesulphinyl chloride
(50.4 w) boiling point 82-84 under reduced pressure (12
torr).
2-Chloroeth~n~sulphinyl chloriae (22 w) was added
dropwise to a stirred solukion o~ anhydrou~ ammonla (5.1 w)
in dry ether (150 v) which was mainta~ned at -40 under a
nitrogen atmosphere. ~he mixture was warmed to ambient
tem;perature and filteredO The filtrate was ~hen evaporated
to dryness by distillation in ~ vacuwn. The r~ldue obtained
from evaporation of the filtrate and the ~ilter cak~ were
both extracted with dry acetone. me extracts were combined
and the solvent was removed by ~is~ tion in a vacuum.
Recry3tallization of the re~idue ~rom dry acetone yielded a
white solid~ 2~chloroe~han~sulphinamide t7.2 w) melting at
78-80,
Example IX 2-Chloroethane~ulphlnanilide
o




Cl-CH2C~2S N ~

2-Chloroethanesulphinyl chloride -(29~4 w) prepared
as in Example I was added dropwise to a ~tirred solution of
fresh~y distilled aniline (~7.2 w) in dry ether (400 v)~ The
addition wa~ carried out under a nitrogen atmosphere and
the reaction mixture was maintained at -10 to 0. Upon com-
plekion of the addikion khe reaction mixture was warmed to
ambient ~emperature and ~iltered. Evaporation of the filkrate

- 39

by distillation in a vacuum gava a white solid whlch was
recrystallized from toluene-hexane to yield 2-chloroethane-
sulphinanilide (21.0 w) melting at 78-80.
Example X N-benz~1-2-chl~e~hhaDD ylehLy~

Cl-CH2-CH2-~-N \ ~

2-Chloroethaneaulphinyl chloride (7.4 w ) prepared
as in E~ample I was added dropwise to a ~olution of benzyl-
amine (10.7 w) in dry ether (130 v). The addition was
carried out under a nitrogen atmosphere and the reaction
mixture was maintain~d ~t -10 to 0. Upon completion of the
addition the reaction mixture was warmed to amblent tem-
peratures and ~iltered. Evaporation of the ~iltrate by
distillation in a vacu~un gave a solid residue which was
recrystallized ~rom toluene-hexan~ to yield N-benz~1-2-
chloroethanesulphinamide (6.o w) melting at 54-55.
E~E~ 2-Chloro-N-(2-hydrox~et~l)athanesulphinam~de

Cl-cH2c~I2-s-N-c~2cH2OH

A stirred solution of 2-aminoethanol (12.2 w~ in dry
ether (~00 v) was cooled to -5 and treated dropwise with 2-
chloroethanesulphinyl chloride (14.7 g), prepared as in
Example 1, under a nitrogen atmosphere. A~ter warmlng to
ambient temperature9 the reaction mixture was filtared and
the filtrate wa~ concentrated by distillation in a vacuum.
Tha residue was puri~ied through a wiped film molecular

~ 1 65~V~3
- 40 -

still to yield 2-chloro-N-(2-hydroxyethyl)ethane~ulphinamide
(1.9 w) boiling at 160 under reduced pre~sure (1 x 10 4
torr)0
Example XII
sulphlnamide
/ ~
Cl-CH2CH2- -N \
~H2(~H2SCH2CK2

2-Chloroeth~ne~ulphinyl chloride (3~7 w), prepared
as in Example I, ln dry ethèr t50 v) wa~ added with ~tirring
to fre~hly diætllled 2-aminoethylethylsulphlde (5.3 w) in
dry ether (100 v) urder a nikrogen atmosphere. The reaction
ma~s was held at -35 during the addition period. Upon com-
pletion o~ thi~ a~dition t~e reaction mixture was warmed to
ambient temp~ratures and ~iltered. m e sol~ent was removed
from the filtrate by distillatlon under high vacuum at
ambient temperatures to ~leld 2-chloro~N-(2-ethylthioethyl)-
ethanesulphinamide (4.0 w).
Example XIII 2-tMet~l ulphinylox~etn~ :ul~hlo _ite
Bi~(2-hydrox~ethyl)di~ulphide was prepared by adding
dropwise 30% hydrogen peroxide (50~ w) over 2 hours to 2-
mercaptoethanol (624 w) maintained ak 55-60. Upon cooling,
the reaction mixture w~s stirred ~or about 16 hour~ at
ambient temperature~. The crude product (577 w) was i~olated
by removing water at 100 and 20 torr,
Crude bi.s(2-hydroxyethyl)di~ulphide (30,8 w)
prepared as aboveg and triethylamine (40.~ w) were dissolved
in meth~lene chloride (400 v). Methanê~ulphonyl chloride
,. .

a ~6~07~

(45.8 w) in methylene chloride (60 v) wa~l then added dropwi~e
under an inert atmo~phere. The exothermic reackion wa~
moderated by external cooling and the reaction mix~ure was
main~ained at 20-25 The reaction mixture, a~ker ~tanding
at ambient tem~erature -~or about 48 hour~ wa~ filteredO The
methylene chloride ~lltrate solution wa~ washed with water~
dried over magnes~um sulphate, and evaporated at reduce~
pressure to provide bis(2 (methy~sulphonylo~y)ethyl)disulphlde
(39.0 w) as an ~ilo
me crude bi~(2-~(methyl3ulphdnyloxy)ethyl)disulphide
oil, as prepared ~bove9 was oxidatively chlorinated accord-
ing to khe general mekhod disclosed in I~Bo Douglass and
RoV~ Nortong Journal of Organic Chemistry~ 3~, 2104 (1968)
using the experimental procedure disclosed in Example I above
except the product was not distilled~ but rather the volatile
impuritieq were removed by evaporation under reduced pressure
at ambient temperatures to yield 2-(methylsulphonyloxy)ethane-
sulphinyl chloride as an oilO
A stirred solution o~ anhydr~ ammonia (1~7 w) in
methylene chloride (200 v) at -20 wa~ treated dropwise with
2-(methyl~ulphonyloxy)ethanesulphinyl chloriqe (lOo~ w) 9
prepared as above~ under a nitro~en atmosphere. After warming
to room t~mperature, the reaction mixture was evaporated in
a vacuumO The residue wa~ex~raeted with dry aeetone. Conc~n-
tration of the acetone extract gave an amber oil which
cr~stallized upon standing~ Recrystallization from methylene
chloride-pe~roleum ether gave a light tan solid, 2-(mekhyl-
sulphonyloxy)ethanesulphinamide (200 W) melting at 64-65~

73
- 1~2 -

Example X.IV
Following procedure~ simil~r to those given in
examples on preparat~on kechniques described earli~r~ the
following other species of the compounds o~ the inventlon
were prepared.
Table II
1~ ~ Rl
X CE2CH2S N \ 2

1 2 Melting point~ C or
X R R Boilin~ point
Cl X C~ 85(2 x 10 4)
Cl H C2H5 95-100(1 x 10 4)
Cl H CH(CH~)2 90-100(1 x 10 4)
Cl H -C~CH3)~ 67-~9
Cl ( 3)~ 2 5) 50(1 x 10 4)
Cl H -cH2(cH2)2cH~ 100(1 x 10 4)
Cl H -CH2(CH2)4CH3 100(1 x 10 4)
Cl H -cH2(cH2)6cH~ 100(2 x 10 4)

Cl ~ ~ 100(2 x 10-4)

Cl H ~ 72 75

Cl Cl ~ 63-65

Cl H ~ Cl 7o 72

Cl H ~ Cl 113-114

Cl ~ ~ CF3 80-85

Cl H ~ CH3 91-92.5

~ 3
- - 4~ -

Table II (cont'd)
Melting point, C or
X Rl R2
Cl H~ ~OCH~ 95-96

Cl H-CH2(CH2)10CH3 85-100 ~dec)
Cl H-CH3(CH2)15CH3 90-105 (dec)
Cl H-C~2CH=CH2 85-95(1 x 10 4)

Cl

Cl -CH~- ~ 25

Cl ~2 ~ not determined

Br H ~ 92~94

Br HCH2(cH2)4cH~ 25
Cl H-OCX~ 85 90(1 x 10 ~)

CH3S-O- H - ~ 82~84
O

Example XVFruit abscission
,, ~
Wash~ton Navel oranges were harvested in a manner
such that the ~ruit was still a~tached to 4 inches of stem
having two (2) clu~ters o~ leaves. The pull force required
to cause absclssion o~ the fruit from the cut stems was
14-16 pounds. ~le harvested or~nges were then ~egregated
into groups o~ ~ive (5) oranges each (stems and leaves
still attached) and ~he ségregate~ groups were sprayed to
dripping wlth several concentrations of methyl 2-chloro-


~ 160~7
41~

ethanesulphinate and 2-chloroethanesulphinanilid0 in aqueous
solution. A water treatment was used as a control~ Some
oranges began to drop o~ the stems two days a~ter treakmsnt
with the higher concentrations of the active compound while
the fruit in the control groups remained attached to the
stems. The rates o~ application a~ well as t~e observations
of the frui~ abscission occurring seven day~ after treatment
for both the treatmen~ groups an~l the control group are
recorded in Table III belowO
Table_III
Mumber
Spra~ of oranges
concentration separated
Treatment _ from stems
water - 2
methyl 2-chloroethanesulphinate 4000 5
methyl 2-chloroethanesulphi~ate 2000 5
methyl 2-chloroethane~ulphinate 1000 3
2-chloroethanesulphinanilide 4000 4
2-chloroekhanesulphinanilide 2000 5
2-chloroethanesulphinanilide lOQ0
Example XVI _ F~
Green field picked tomatoes were randomized and
segregated into a treatment group and a con~rol groupO The
tomatoes ill the treatment group were painted wlth a 1000
ppm aqueous solution of methyl 2-chloroethanesulphinate
containing 0~2~ tronic as a surfactant. ~he tomakoes in
the control group were painted in the same manner with the
base solutionO Eighteen days after treatment all the
tomatoes in the treatment group were fully red whereas

~ 16~0 l~3
- 45 -

with the control group only two o~ the tcmato~s had begun
turning red twenty days after treatment.
Example XVII Stimulation o~ seed germination
Under normal condition~ experience has shown that
only 40~ o~ the cocklebur seeds will germinate. Fifty
cocklebur seeds were soaked ~or one hour in either water
or methyl 2-chloroe~hanesulphinate! at 1000 ppm w/w waker.
All seeds were planted and allowecl to germinate over a ten
day period. Treatment with methyl 2-chloroethanesulphinate
increased seed germination by 25~ over the controls.
Exam~le XVIII Stimulation of tuber sproutin~
Twenty-four yel~ow nutsedge tubers were soaked in
a 100 ppm aqueous solution of methyl 2-chloroethane-
sulphinate ~or ten minutes~ blotted dry and sealed in a
bottle. A like number of tubers were sQaked in water and
sealed according to the s~me procedure. Six days after
treatment all (100%) of the troated tubers had sprouted
whereas only 81% o~ the control tubers had sprouked. Also,
the number of shoots formed per tuber increased from 1.3
~or khe control group to 1.6 for the treatment groupO
Treatment with methyl 2-chloroethanesulphinate~ there~oreJ
stimulated sprouting and destroyed the normal dominance o~
the apical bud thus allowing lateral buds to sprouk.
Example XIX Leaf abscission
Individual branches of Washington Navel orange
trees were treated with aqueous solutions of several of
the compounds o~ the invention~ Each o~ the compounds
tested was made up as a 2000 ppm solution in water

46 ~60~)73

! containing 0~2~ Tronic as surfactant. A total o~ 100 ml o~
each of the re~ulting solution~ was applied as a foliar
spray ~o a single branch of ~ashington Nave~ orange tree~.
Seven days aff,er treatment some of the leaves on the
treated branches bec~me stif~, although still green9 and
began to ~all ~rom the trees. Ob~srvations o~ khe defolia-
tion caused by each chemical six wee~s a~ter t*eatment are
recorded in the ~ollowing table. ]3valuation of de~oliation
was based on ~our classifications: 1 to 10~3 11 ko 30~ 31
to 60~ and 61 to 100~ absci~sion of the leaves originally
presentO
Table IV
Compound tested Percent abscission
_ _ .
Control O to 2
N-methyl-2-chloroethanesulphinamide31 to 60
N-ethyl-2-chlOroethane~ulphinamide61 to 100
N-isopropyl-2-chloroethanesulphinamide 61 to 100
N-tert-butyl-2-chloroethanesulphinamide 11 to 30
N-sec-butyl-2-chloroethanesulphinamide 11 to 30
N-butyl-2-chloroethanesulphinamide .61 to 100
N-hexyl-2-chloroethanesulphin~mide61 to 100
N-octyl-2-chloroethane~ulphinamide61 to 100
N-benzyl-2-chloroethanesulphinamide31 to 60
N-cyclohexyl-2-chloroethanesulphinamide 61 to 100
25 N-2-chloroethanesulphinanilide 11 ~o ~0
2~21-dichloroethanesulphinanilide 1 to 10
2~3'-dichloroethanesulphinanilide11 to 30
2,4'-dichloroethanesulphinamide 1 to 10
2-chloro-a,~,~tri~luoroethanesulphin-
3-toluide 1 to 10

1~7 1 160()73
.

Table I~ (cont'd)
,Compound tested ~ ~c~n~
2-chloroethanesulphinamide ~1 to 60
methyl 2-chloroethanesulphinate 1 ko 10
5 ethyl 2-chloroethanesulphinate 1 to 10
i~opropyl 2-chloroethan~ulphinat~ 1 to 10
hexyl 2-chloroethanesulph~nate 11 to 30
octyl 2-chloroethanesulphinate 1 to 10
Exampla XX Frui-t ripening
Picked, green untreatad bananaæ wer~ separated and
randomly grouped for treatmentO The treatment consisted o~
spraying each of th~ di~feren~ treatm~nt groups, one un-
treated group being retained as a controlg with a 1000 ppm
aqueous solution of one of the following compounds o~ the
invention: 2-chloroethanesulphinanilide, 292'~dichloro-
ethanesulphinanilide, 2-chloroethanesulphinamide and N~
hexyl-2-chloroethanesulphinamide. In all cases the treated
bananas turned completely yellow kwoto five days before
the untreated bananas.
E~ Stimulation of tuber s~routip~
Twe~ty-four yellow nutsedge tubers were soaked in
a 100 ppm aqueous solution of 2-chloroethanes~hinanilide
~or ten minutes, blotted dry and sealed ~n a bo~tle. A
like number of tubers were soaked in water an~ sealed
according to the same procedureO Three days after treatment
all (100%) o~ the,treatied tubers had sproutied whereas only
78% of the control tubers had sprouted, A190~ the number of
shoots formed per tuber increased from 1.~ for the control
gr~up to 105 ~or the treatment group.

I l~V~3
- 4~ -

Example_XXII Fruit ripenin~
Mature green cherry tomatoes were harvested from
plants grown in a greenhou~e. The fruit was randomized into
treatment groups and a control group and the tr~atment
groups were sprayed with 20 ml of a 100 ppm aqueous solution
of several of the compounds of the invention. The tomatoes
in each group were rated periodically by visual observation
for ripene~sO The results four days after treatment are
recorded in Ta~le V.
T2ble~V
Nu~ber o~ fruit
Treatment Green Coloured R~
Control ~4 0 4
2-chloroethanesulphinanilide 18 7 12
N-hexyl-2-chloroethanesulphinamide 17 14 7
2-chloroethanesulphinamide 7 2~ 5
2,2'-dichloroe~hanesulphinan~ide 18 11 5
Example XXIII Frui~
Mature tomato plants, variety UF 145-21-~9 in a
~ .
4xlO foot plot were sprayed to run off with an aqueous
solution containing9as an ac-tive ingredient, 1000 ppm of
2-chloroethanesulphinanilide and,as adjuvants~ 1% acetone~
0 2~ tronic and 10~ proW lene glycol. For control purposes
another plot of like size in the same field was sprayed to
run off with the spra~ ~olution not containing the active
ingredientO Some damage to the foliage occurred with both
the control spr~y and the treatment spray. Thirteen day~
after treatment the tomatoes wereharvested from the

1 16~3
~ l~g _

sprayed plots as well as -from an unspra~ed plot maintained
for additional control purposes. Immediat~y after picking,
the tomatoes from each plot were sorted into green, pink
and red fruit. The observations as to the percent by weight
of ripe ~red) fruit in the plots are recorded in ~able VI
belowO
Table 'VI
Treatmenk ~ Red fruit
--- in_plots
Control 40O0
Unsprayed control 39,5 - 0,5
2-chloroethanesulphinanilide 66.8 ~2608
Example XXIV Fruit r~penin~
A second experiment was conducted to evaluate th~
efficacy of the compounds of the invention ln ripening
green harvested tomatoes. In this experiment green mature
toma~oes were picked from plants grown ~n a greenhouse
and randomly segregated into groups o~ 10 each ~or treat-
mentO The tr~tment chemicals were made up in water/acetone
solutions at a concentration of 1000 ppm alld each group of
tomatoe~ was soaked for one hour in one of the solutions
containing a treatment chemical or in the base solution
without chemical. F,ach tomato in each group was e~aluated
daily by the following colour rating~ green (0 point~,
breaker (1 point)9 1/2 orahge ~2 points)9 full orange (3
points), and red rlpe (4 points)~ When all tomatoes in a
group are fully ripe the score will be l~o points thus
equalling 100~, The dail~ percent ripeness is recorded
below for each treatment (Table VII).

~ ~V1~3
- 50 -

Tab1e VII
Percent ripeness - days after treatment
Treatment 1 2 _~ 4 ~ 6 7 8 11 14 18
Control 0 0 3 5 8 15 28 43 58 85 93
2-chloro-
ethane-
sulphinamide1020 35 50 73 88 93 93 93 98 100
N-methyl-N-
phenyl-2-
chloroethane-
sulphinamlde 815 33 45 60 8b 90 95 100100 100
2-chloro-
ethanesu~n-
3-toluide 818 30 53 65 78 80 85 95100 100
N-ockyl-2-
chloroethane-
~ulphin~mide 813 35 58 7~ 83 95 95 100100 100
N-allyl-2-
chloroethane-
sulphinamide 5 5 25 33 4~ 73 78 80 85 98 100
4'-methoxy-
2-chloro-
ethane-
sulphinanilide 5 10 18 28 43 50 58 68 80 90 100
N-cyclohe~yl-
2-chloro-
ethane-
sulphinamide 510 20 43 60 83 93 93 9~ 98 100
2-chloro-
ethanesul-
phinanilide 3 5 15 25 43 50 60 75 93100 100
2-ehloro,
a, a, a -tri-
fluoroeth~ne-
sulphin-3-
toluide 5 8 18 ~0 43 55 58 68 90 gO 98
2,~'-dichloro-
ethane-
sulphinanilide 3 5 13 18 25 30 4 55 78 93 100
N-hexyl-2-
chloroethane-
sulphinamide 315 28 45 70 85 90 95 100100 100

~ ~60~7~
- - 51 -

Table VII (cont'd)
Percent ripeness - days after tr~atment
Treatment 1 2 ~ 4 _~ 6 _1 8 1114 18
N-benzyl-2-
chloroethane-
sulphinamide 310 15 33 5370 7883 93100 100
N-i~opropyl-
2-chloro-
eth~ne-
sulphin~mide 3 5 10 23 2543 5055 6373 85
N-hexa~ecyl-
2-chloro-
ethane-
sulphin~mide 3 3 10 18 2835 5568 8398 100
N-(.2-ethyl-
thioethyl)-2-
chloroethane-
sulphinamide 3 3 8 15 2345 5575 90100 100
N-(2-hydroxy-
ethyl)-2-
chloroethane-
sulphinamide 0 3 13 18 3353 6875 90100 100
N-butyl-2-
chloroethane-
sulphinamide 0 3 8 18 2035 4058 8085 98
N-butyl-2-
chloroethane-
sulphinamide 0 3 8 18 2035 4058 8085 98
N-ethyl-2-
chloroethane-
sulphinamlde 0 0 5 10 1535 4853 7898 100
N-hex~1-2-
bromoethane-
sulphinamide 3 8 23 33 6883 83. 83 8598 ~00
2-bromoethane-
sulphinamide 3 3 10 18 2538 455~ 6085 100

0~73
- - 52 -

Tabl~ VII (cont'd)
Percent ripeness - days after treatment
Treatment 1 2 ~5 4 5 6 7 8 9 1014 18
Control 3 3 8 18 28 38 63 68 80 9398
2-chloro-
ethane-
sulphinic
acid 1315 70 48 55 68 75 78 85 9095
ethyl 2-
ch loroe t}~ne-
sulphinate 1010 ~50 38 45 53 58 73 83 8393
2-propynyl
2-chloro-
ethane-
sulphinate 825 45 55 60 68 78 80 83 9098
isopropyl 2-
chloroethane-
sulphinate 810 28 38 53 60 65 68 73 7595
allyl 2-
chloroethane-
sulphinate 811 22 28 42 58 67 72 80 8695
octyl 2-
chloroethane-
sulphinate 8 8 15 25 35 ~8 55 58 65 8398
2-butoxyethyl
2-chloro-
e thane-
sulph~nate 611 19 36 56 64 75 78 80 92100
2-(c~loro-
ethane-
sulphinyloxy)-
ethyl 2-
chloroethane-
sulphinate 510 25 43 48 65 75 75 80 85100
butyl 2-
chloroethane-
sulphinate 515 23 40 58 70 78 78 80 8395
hexyl 2-
chloroethane-
sulphinate 5 8 33 43 55 63 78 85 93 93100
2-ethyl hexyl
2-chloroethane-
sulphinate 5 5 18 23 33 55 68 70 78 8898

~ ~6~73
- 5~ -

Table VII (cont'd)
Percent ripeness - days after treatment
Treatment 1 2 ~ 4 5 6 7 8 9 1014 18
~ _ _ _ _
2-(ethylthio)-
ethyl 2-chloro-
ethane-
sulphinate 5 5 10 18~5 4~5 58 6365 7090
methyl 2-
chloroethane-
sulphlnate ~ 5 10 18~3 38 48 5063 7088
hexadecyl 2-
chloroethane-
sulphinate :S ~ 8 1315 3~i 55 6378 80 9
dodec~l 2-
chloroethane-
sulphinate 0 3 11 2025 45 61 6770 7597
eicosyl 2-
chloroethane-
sulphinate ~i 8 20 30~i3 50 58 7080 85g~ -
Example XXV Fruit ripenin~
This test was conducted to e~raluate the efficacy of
the compounds o~ the invention as ripening agents for mature
fruit prior to harvest, i.e., fruit still attached to the
growing plant. Individual clu~ters of mature green cherry
tomatoes grown in a greenhouse were treated with the com-
pounds of the invention whlls still on the vine. ~or treat-
ment the test compounds were made up in an acetone/water
solution at a concentration of 1000 ppm and each test solu-
tion was applled thoroughly to a dif~erent set of ~ clustersof tomatoes9 each cluster having 4 to 6 mature tomatoes. One
set of tomatoes was ~reated with the base solution ~or
control purposesO The re~ults are listed in Table VIII
belowO

~ ~6~07
- 54 -

Table ~III
Percent red tomatoes -
days a~ter treatment
Treatment 5 81~ 16 19
Control O 05 15 30
2-chloroethanesulphinanlllde 42 5~ 71 89 100
N-allyl-2-chlQroethanesulphinanilide 21 30 36 50 64
2 chloroethanesulphinamide 33 46 54 74 74
N-b nzyl~2-chloroethane- 8 32 44 60 76

N-hexyl-2-chloroethane- 27 36 50 59

2,2~-dichloroethanesulphinamlde 0 0 6 ~ 78

sulphinate 6 17 39 56 73
allyl 2-chloroethanesulphinate 0 0 41 47 82
cetyl 2-chloroethane~ulphinate 0 0 14 43 64
methyl 2-chloroethanesulphinate 0 0 15 34 54
lauryl 2-chloroethanesulphinate 0 0 10 27 58
eicosyl 2-chloroethanesulph~nate 0 0 11 22 58
Example XXVI Frult ripenin~
Picked3 green vntreated bananas were separated and
randomly grouped for treatment~ The treatment consisted o~
spraying each of the dif~erent treatment gr~up~, one un-
treated group being retained as a control, with a 1000 ppm
aqueous solutlon of one of the ~ollowing compounds of the
invention: meth~l 2-chloroethanesulphlnate and hexy~ 2-
chloroethanesulphinate. In all case~ the treated bananas
turned completely yellow two to five days before the un-
treated banana~.

0~3
- 55 -

Example XXVII Stimulation o~ s~ed gerrnination
Under normal growing conclitionsJ experience has shown
that only 40~ of the cocklebur seeds will germinate. Fifty
cocklebur seeds were soaked for one hour in either a water/
acetone mixture or a water/acetone mixture containlng N-2-
chloroethanesulphinanilide at 1000 ppm w/w. All eeds were
planted ~nd allowed to germinate over a two week period.
Treatment with the compound of the invention incre~ed seed
germination over the control by 25%.
Exam~le XXVIII Leaf e~inasty
Leaf epinasty ls a hormonal response whlch occurs in
plants wherein the upper side of the lea~ stalk grows more
rapidly than the lower side causing the leaf to bend down-
ward. To evaluate ~or leaf epinasty response six week old
tomato plants were randomized and segregated into groups of
three plants each and each group was sprayed wikh a di~erent
compound of the invention at a concentration of 2000 ppm in
aqueous solution containing 0.2% tronic surfactantO One un-
sprayed group was retained for control. The observations o~
the leaf epinasty which had occurred thirteen da~s after
treatment are recorded in Table IX belowO Evaluakion of the
degree of leaf epinasty is based on four classifications.
no epinastyJ indicating normal horizontal leaf growth;
complete epinasty (90 degrees)g indicating that the leaves
grew vertically downward around the stem and, 30 or 60
degrees epinastyl indicating intermediate downward growth
of leavesO

1 1 6~073
56



Tab~le IX
C~O .~h~ D~_H_ ~1~'.
Control No~e
N-methyl-2-chloroethanesulphinamide 60
N-isopropyl-2-chloroethanesulphirlamide 60
N-tert-butyl-2-chloroethanesulphinamide60
N-sec-butyl-2-chloroethaneæulphinamide 60
N-butyl-2-chloroethanesulphinamide 30
N-hexyl-2-chloroethanesulphinamicleComplete
N-octyl-2-chloroethanesulphinamicleCompleke
~-2-chloroethanesulphin~nilide 60
2,2'-dichloroethanesulphinanilideComplete
2,3~-dichloroethanesulphinanilideComplete
2,4'-dlchloroethanesulphinamide 60
2-chloro-~,aga-trifuloroethanesulphin-
3-toluide 60
2-chloroethanesulphinamide Complete
ethyl 2-chloroethanesulphinate ~0
isopropyl 2-chloroethanesulph~nate 60
hexyl 2-chloroethanesulphinate Complete
octyl 2-chloroethanesulphinate Complete
cetyl 2-chloroethanesulphinate ~0
methyl 2-chloroethanesulphinate 30
lauryl 2-chloroethanesulphinate Complete
allyl 2-chloroethaneæulphinate ~0
methyl 2-bromoethanesulphinate 60

073
- 57
Exam~ Leaf epinast~
A second leaf epinasty test was performed on tomato
plants, In this test each compo~ld evalua~ed was applied as
a foliar spray to 3 different tomato plants. Two plants
were 37 days old and the third plant was 23 da~s old. The
older plants were 14 in.~hes high with 10 leaves and the
younger plants were lO lnches high with 8 lea~es. Two ages
o~ plant~ w~re included becau~e the older plants usually
are more sensitive and give a mo:re rapld hormonal epinasty
10 responseO All test compounds were dissolved in ~cetone and
diluted to 2500 ppm with water containing 0O4% surfactant
(Wilsco Foam~pray)0 A lO ml volume of each compound so
diluted was applied as a foliar spray to 3 tomato plantsO
The treated plants were evaluated ~or epinasty (bending of
leave~ downward toward ~he ba e of the steam) 20 hours
after treatmentq The te~t was again evaluated for epinasty
as well as phytotoxici~y ~our days a~ter ~reatment, to
determine i~ the epinasty effects had dissipated. The
result~ of the test including identification of compounds
tested are recorded in Table X belowq me table heading
~ aves normal after four days" designates visual observa-
tion of whether any effects of eplnasty remained 4 days
after treatmentO

~ 7
- ~ 58 ~

Table X
Percent of Leaves Showing
Epinasty Response
Leave3
Inter- normal
No Slight mediate Complete a~ter Phyto-
Treatment r~spon~e respons response res~_nse 4 da~s t~s~
Control 100 0 0 0 Yes ~Jone
2-chloro-
eth~ne-
sulphin-
~de 17 8 75 No Moder-a)
ate
2-chloro-N-
methoxy-
ethane-
sulphin~mide 0 50 14 36 Yes None
2-(methyl
sulphonyloxy)-
ethane-
sulphinamide O 19 15 66 Yes None
2-(methyl-
sulphonyloxy)-
etha~e-
sulphinani-
llde 0 24 12 64 No None
phenyl 2-
chloroethane-
sulphinate 0 59 8 33 Yes None
~) Moderate phytotoxiclty indicates some yellowing
o~ the leaves had occurred~

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Title Date
Forecasted Issue Date 1984-01-10
(22) Filed 1972-06-12
(45) Issued 1984-01-10
Expired 2001-01-10

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Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $0.00 1972-06-12
Current owners on record shown in alphabetical order.
Current Owners on Record
SHELL CANADA LIMITED
Past owners on record shown in alphabetical order.
Past Owners on Record
None
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.

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Abstract 1993-11-18 1 13
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Description 1993-11-18 57 2,234