CA1053660A - Adducts of carbamoyl sulphoxides - Google Patents
Adducts of carbamoyl sulphoxidesInfo
- Publication number
- CA1053660A CA1053660A CA234,594A CA234594A CA1053660A CA 1053660 A CA1053660 A CA 1053660A CA 234594 A CA234594 A CA 234594A CA 1053660 A CA1053660 A CA 1053660A
- Authority
- CA
- Canada
- Prior art keywords
- adduct
- carbamoyl
- sulphoxide
- lower alkyl
- group
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C279/28—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to cyano groups, e.g. cyanoguanidines, dicyandiamides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
ABSTRACT
Adducts having the general formula;
Adducts having the general formula;
Description
lOS36~0 This invention relates to adducts of carbamoylsulphoxides and derivatives of urea which are stable, crystalline adducts and have interesting, long-lasting herbicidal properties.
More particularly, this invention relates to the adducts, the method of preparing them and compositions containing them.
Canadian application No. 182,865, filed on October 5, 1973, and assigned to the assignee of this application, describes carbamoyl sulphoxides having the general formula:
R
\ R2 wherein R is a phenyl or benzyl group which may be substituted with an alkyl containing 1 to 4 carbon atoms, an alkoxy containing 1 to 4 carbon atoms or a halogen atom, or R represents an alkyl radical containing 1 to 4 carbon atoms and which may be substituted with a halogen atom, Rl and R2 are the same or different and each represents a hydrogen, an alkyl containing 1 to 4 carbon atoms or a cycloalkyl containing 4 to 7 carbon atoms or Rl and R2, when taken together, represent an alkylene containing 4 to 7 carbon atoms. Such carbamoyl sulphoxides exert an interesting herbicidal action towards both monocotyledons and infesting latifoliae, while they are innocuous towards important agrarian cultures.
The above carbamoyl derivatives form adducts with ~` urea, which have the general formula:
~ O O R O
~1` 11 / 1 11 ~ R - S - C - N . 3 NH2 ~ C - NH2 (I') ;:~ R2 wherein R, Rl and R2 have the aforesaid meanings. Such adducts are described in Applicant's Canadian application No. 228,686 of June 6, 1975. They are solid and crystalline and exhibit.
, ~: .,., ,.,- , . :
: lOS3660 on infrared spectrophotometric analysis, a shifting of the - frequencies relevant to the vibrations of bonds N-H, N-C-N and S-O with respect to the corresponding ones of the urea and of the starting carbamoyl sulphoxices. On X-ray analysis, they exhibit spectral lines different from those typical of urea and of the starting carbamoyl sulphoxides if the latter are in the solid state and their centesimal composition is in accordance with the above formula (I').
It is an object of the present invention to provide a new class of crystalline adducts of carbamoyl sulphoxides and mono-substituted ureas, including phenylurea, biuret, thiourea, dicyanodiamide, dichloralurea, and the like which have good thermal stability and retain at least the herbicidal activity typical of the carbamoyl sulphoxides.
Another object of this invention is ~ provide adducts having herbicidal properties which are capable of gradually and regularly releasing the active substance, once they are applied to the soil.
A further object of the invention is to provide herbicides which are easy to formulate.
A still further object is to provide a method of preparing the adducts provided by the invention.
These objects and others are achieved by providing adducts of a carbamoyl sulphoxide having the general formula:
O O R Y
'I` 11 / 1 11 A R - S - C - N . B R3 - NH - C - NH - R4 (I) ~. ' wherein R is a lower alkyl or benzyl, Rl and R2 are the same or different and each represents a lower alkyl, Y is O, S or NH, R3 and R4 are the same or different and each represents hydrogen, lower alkyl, phenyl, benzyl, a CN group, a CHOH-CC13 group or a
More particularly, this invention relates to the adducts, the method of preparing them and compositions containing them.
Canadian application No. 182,865, filed on October 5, 1973, and assigned to the assignee of this application, describes carbamoyl sulphoxides having the general formula:
R
\ R2 wherein R is a phenyl or benzyl group which may be substituted with an alkyl containing 1 to 4 carbon atoms, an alkoxy containing 1 to 4 carbon atoms or a halogen atom, or R represents an alkyl radical containing 1 to 4 carbon atoms and which may be substituted with a halogen atom, Rl and R2 are the same or different and each represents a hydrogen, an alkyl containing 1 to 4 carbon atoms or a cycloalkyl containing 4 to 7 carbon atoms or Rl and R2, when taken together, represent an alkylene containing 4 to 7 carbon atoms. Such carbamoyl sulphoxides exert an interesting herbicidal action towards both monocotyledons and infesting latifoliae, while they are innocuous towards important agrarian cultures.
The above carbamoyl derivatives form adducts with ~` urea, which have the general formula:
~ O O R O
~1` 11 / 1 11 ~ R - S - C - N . 3 NH2 ~ C - NH2 (I') ;:~ R2 wherein R, Rl and R2 have the aforesaid meanings. Such adducts are described in Applicant's Canadian application No. 228,686 of June 6, 1975. They are solid and crystalline and exhibit.
, ~: .,., ,.,- , . :
: lOS3660 on infrared spectrophotometric analysis, a shifting of the - frequencies relevant to the vibrations of bonds N-H, N-C-N and S-O with respect to the corresponding ones of the urea and of the starting carbamoyl sulphoxices. On X-ray analysis, they exhibit spectral lines different from those typical of urea and of the starting carbamoyl sulphoxides if the latter are in the solid state and their centesimal composition is in accordance with the above formula (I').
It is an object of the present invention to provide a new class of crystalline adducts of carbamoyl sulphoxides and mono-substituted ureas, including phenylurea, biuret, thiourea, dicyanodiamide, dichloralurea, and the like which have good thermal stability and retain at least the herbicidal activity typical of the carbamoyl sulphoxides.
Another object of this invention is ~ provide adducts having herbicidal properties which are capable of gradually and regularly releasing the active substance, once they are applied to the soil.
A further object of the invention is to provide herbicides which are easy to formulate.
A still further object is to provide a method of preparing the adducts provided by the invention.
These objects and others are achieved by providing adducts of a carbamoyl sulphoxide having the general formula:
O O R Y
'I` 11 / 1 11 A R - S - C - N . B R3 - NH - C - NH - R4 (I) ~. ' wherein R is a lower alkyl or benzyl, Rl and R2 are the same or different and each represents a lower alkyl, Y is O, S or NH, R3 and R4 are the same or different and each represents hydrogen, lower alkyl, phenyl, benzyl, a CN group, a CHOH-CC13 group or a
- 2 -;
;
.. . .
- lOS3660 CY-NH2 group in which Y has the aforesaid meaning, with the proviso that R3 and R4 cannot simultaneously represent hydrogen when Y is O, and A and B are integers equal to 1, 2 or 3.
The adducts of this invention are obtained by mixing the corresponding carbamoyl sulphoxide of the general formula:
l / R 1 R - S - C - N (II) \ R2 wherein R, Rl and R2 have the meanings just indicated above, with an organic compound of the general formula:
il R3 - NH - C - NH - R4 (III) wherein R3, R4 and Y have the aforesaid meanings, in a suitable solvent and concentrating the resulting mixture. The adduct precipitates and is then collected and dried.
Suitable organic compounds of the general formula (III) are monosubstituted ureas such as, for example, phenylurea, biuret, thiourea, dicyanodiamide, dichloralurea and the like.
The following Table 1 lists examples of some adducts of carbamoyl sulphoxides and urea falling under the general formula (I'),near which the infrared frequencies characteristic of the most meaningful bonds are indicated by way of comparison with the frequencies relating to urea. The shifting of the main band due ` to bond S ,O is reported as the difference - in cm 1 _ between the frequency of the most intense band due to such grouping in the adduct and the frequency of the main band of group S ~O in the starting carbamoyl sulphoxide (~r).
:, :
.. , . - ~ - . .... ~ . : .. :
1053~60 a~
~ . , O 0~ td e) .,~ ~, . . _ .
~1) H O ~) Ot) 1~ C~
H ~ ~ ~ ~ ~`J _ ou~o~OC ~ I ~ I I I ~ I I
O ~ _ Q~~ O ~ 1 o\ h h 0 ~
,dH _ __ _ _ I ~ U~ U~
~_, a) o~ ao Il~
;
.. . .
- lOS3660 CY-NH2 group in which Y has the aforesaid meaning, with the proviso that R3 and R4 cannot simultaneously represent hydrogen when Y is O, and A and B are integers equal to 1, 2 or 3.
The adducts of this invention are obtained by mixing the corresponding carbamoyl sulphoxide of the general formula:
l / R 1 R - S - C - N (II) \ R2 wherein R, Rl and R2 have the meanings just indicated above, with an organic compound of the general formula:
il R3 - NH - C - NH - R4 (III) wherein R3, R4 and Y have the aforesaid meanings, in a suitable solvent and concentrating the resulting mixture. The adduct precipitates and is then collected and dried.
Suitable organic compounds of the general formula (III) are monosubstituted ureas such as, for example, phenylurea, biuret, thiourea, dicyanodiamide, dichloralurea and the like.
The following Table 1 lists examples of some adducts of carbamoyl sulphoxides and urea falling under the general formula (I'),near which the infrared frequencies characteristic of the most meaningful bonds are indicated by way of comparison with the frequencies relating to urea. The shifting of the main band due ` to bond S ,O is reported as the difference - in cm 1 _ between the frequency of the most intense band due to such grouping in the adduct and the frequency of the main band of group S ~O in the starting carbamoyl sulphoxide (~r).
:, :
.. , . - ~ - . .... ~ . : .. :
1053~60 a~
~ . , O 0~ td e) .,~ ~, . . _ .
~1) H O ~) Ot) 1~ C~
H ~ ~ ~ ~ ~`J _ ou~o~OC ~ I ~ I I I ~ I I
O ~ _ Q~~ O ~ 1 o\ h h 0 ~
,dH _ __ _ _ I ~ U~ U~
~_, a) o~ ao Il~
3 ~ ~ ~
a~ ~æ ~ ~ t--~ I--I ~--h F~ I ~D ~ O OD O O O O ~0 O
~ r~ u~
13 1~Z; ~ -- el--O ~ ~ t~ ~ t~
~) _ H Z
Id Z; ' --~ ~ ~ r~ D- O U~ U~ ~ ~
O c~ c~ ~ - ~--~ . _ 0h Z -.. H ~ ~ _ ~ b~ .
~ ~u a~
'.` ~ P; ~c~'~' V~ ~~
I ~H _ O O O O
:~ o~
~ d , ~0 . .. . `¢
P, ~ ~ a~--~ V~
~ C) C~ V V V o o o P:
a~ ~ D ~;
E~ .. .~ _ P . .
h ~
F~ l --- I
, o P P P P :~ P P P P .
~; ~ U~ ~O
. ~ o ao ~ u~ O
~ ~ ~ ~~ ~ ~1 H
_ .
053~
'~he adduct~ of this invention, unlike the most interest-ing terms of the carbamoyl sulphoxides series, are stable in ~torage and can be indefinitely preserved at room temperature.
~ or purpo~es of comparison with the thermal stability of the carbamoyl sulphoxides as such, Table 2 reports the per-centages o~ carbamoyl sulphoxide recovered from the corresponding adduct after residence at temperatures higher than room tempera-ture, along with the percentages of same recovered after condition-ing of carbamoyl sulphoxide as such at 50C and 100C.
; 10 ~he recovery of carbamoyl sulphoxide from the adduct at the conclusion of the conditioning period is carried out by extraction with chloroform; the dose of carbamoyl sulphoxide : in the extracts is determi-ned by chromatography on a thin layer .or by gas-chromatography according to conventional techniques.
,, ~
., :
', . .- .
,' j~ . .
I
A
...... ,.~ ~ . . . .
10536~i0 CO h h h .~ L~ O
~ ~ oV
C~ ~ ~~ ~
H ¦ ~ ---E~ V ~ ~ O ~ L~ ~ ~
h ~ ; v .
h H L~
C ~ ~ ~ _ ._ ~ ~ O ) ~ O O O O
~ ' :~ ~ o ~
~; : ~ h .
O 1~ 1~ ~
O ~ ~ ~ U~ ~ O
h ~ Oo CO ~ ~ N IS~
g & _ .
~ o ~ c~
~qN ~
. ,~, ~ ,q ~ ,1 h o ~ ~t oV ~ - F~ . -. ~ O ~ . ' o p, P P P P P
~; I~ \J
E~ O O~
H _ -A
.1 ~
:_i , .. . .
Since the adducts can be easily crystallized and the carbamoyl sulphoxide is easily recoverable from same by mild hydrolysis and/or extraction with chloroform or another proper solvent, it is evident that the adduct formation may be utilized to purify the carbamoyl sulphoxide.
It is to be pointed out that the molar ratios of the carbamoyl sulphoxide (II) to the organic compound (III) vary, in the adducts of this invention, depending upon the nature of the organic compound. It is necessary, however, to ascertain each time which is the molar ratio of each individual adduct obtained, utilizing, to this aim, fractional crystallization .~ followed by infrared spectrophotometric analysis, by elemental : , . ~ . .
,.. ..
. . ' ; ' ' lOS36~;0 analysis and, optionally, by X-ray diffractometric analysis ~ the precipitate that has formed. After having ascertained which is the molar ratio at which the desired adduct forms, the carbamoyl sul-phoxide (II) may be reacted with the stoichiometric amount of the organic compound (III) necessary to provide the desired adduct and the solvent removed by evaporation.
Most of the adducts so prepared are crystalline solids, stable at room temperature and not subject to alteration during storage. Unlike carbamoyl sulphoxide, from which they are obtained, lo some of these adducts may be subjected to even long-lasting heat treatments attemperatures around 50C without undergoing substan-tial modifications.
The shifting of the frequencies relating to the vibra-tions of bonds NH, N-C-N and S--~ O with respect to those of the corresponding starting products reveals whether the adduct has ;formed, as it will clearly appear from the following examples 5 through 9.
The herbicidal activity of the adducts provided by this invention is no lower than the activity of the corresponding car-bamoyl sulphoxide as such when the doses applied ~ the soil, cal-culated as carbamoyl sulphoxide content, are equal.
The following examples are given better to illustrate -the present industrial invention.
EXAMPLE 1 (Comparative) l / _ C3H7 Preparation of iso-C3H7-S-C-N . 3H2N-C-NH2 _ C3 7 ' (5193 - U) from carbamoyl sulphoxide and urea in a 1 : 3 molar ratio. 3 g of isopropyl-N-di-n-propylcarbamoyl sulphoxide were 30 added to 13,84 g of a methanol solution containing 2.48 g of urea.
lOS3660 By slow evaporation under vacuum at room temperature the following four precipitate fractions were successively isolated which, after drying, were weighed and subjected to elemental analysis, the re-sults thus obtained being reported in the following Table III.
TABLE III
Fraction Adduct Weight, g Elemental Analysis C % H % N % S % :~
I 1.905 38.56 8.30 24.78 8.06 II 1.658 38.63 8.23 24.75 7.94 III 0.260 39.05 8.31 24.82 7.76 IV 0.770 38.05 8.16 25.07 7.40 Theoretical Analysis : 39.08 8.32 24.54 8.02 ., ' ~11 of the four fractions thus obtained, when subjected to X-ray analysis, produced Debye-diagrams containing the same spectral lines, sharply differentiated from those typical of urea. :~
The infrared spectra of the fractions were also like one -~
another and contained the absorption bands shown in Table I. :~
` EXAMPLE 2 (Comparative~ .
, :
. Preparation of 5193 - U starting from carbamoyl sulpho-20 xide and urea in molar ratios different from 1 : 3. 0.505 g of i isopropyl-N-di-_-propylcarbamoyl sulphoxide was added to 0.760 g of ~-a methanol solution containing 0.136 g of urea (initial molar ratio of the reagents in the order indicated : 1:0.98). After , having allowed the solution to stand, a precipitate was collected that, after drying, weighed 0.202 g, and from whose elemental analysis the following results were obtained:
C % H % N % S %
39.52 8.54 24.63 7.47 The infrared spectrum and the Debye-diagram of this precipitate are _ g _ ~0~3660 like the corresponding spectra relative to the precipitates obtain-ed in Example 1.
Thoroughly similar results were obtained starting from the following starting amounts of reagents:
0.268 g of isopropyl-N-di-n-propylcarbamoyl sulphoxide;
1.921 g of a methanol solution containing 0.344 g of urea (initial molar ratio between the two reagents = 1 : 4.68).
EXAMPLE 3 (Comparative) By operating according to the method described in Example 1, the compounds reported on Table I were prepared, whose adduct nature is proved by the most meaningful I.R. frequencies reported on aforesaid table. Individual samples of these adducts resulted in a correct elemental analysis.
Similar results were obtained by employing, during pre- -paration, a urea-saturated aqueous solution.
, , : ' EXAMPLE 4 ( Comparative) ''Herbicide activity tests.
Adduct M 519 3 - U, prepared according to the method of ~,Example 1, by collecting all the fractions until thorough evapora-tion of the solvent, was divided into two equal samples.
One of these samples was further treated according to known formulation techniques, thus obtaining a cellulose powder containing the 2% of adduct (Sample 2).
~`On both the adduct (Sample 2 ), herbicidal activity tests jwere carried out in comparison with the corresponding carbamoyl sulphoxide as such.
iSample 1 was dissolved in a hydroacetone solution at .25% by volume of acetone. This solution was sprayed onto the earth contained in boxes measuring 40 x 30 x 20 cm, in whose upper ` 30 part, a 5 cm thick layer, the seeds of the following infesting .~ ~
., . , . :, .. . . , . . : . . .
,, , . . - , .
-` 1053~60 weeds had been uniformly di~tributed: -monocotyledons: Echinochloa crus galli Avena fatua ~olium sp.
Sorghum 9p.
Setaria glauca dicotyledons: Stellaria media Ipomea sp.
Vigna Sinensis Rumex Crispus Galinsoga 9p.
The 5 cm layer wherein these seeds were distributed had been laid onto a previou~ly humidified soil. Under thoroughly identical conditions, as many boxes were prepared by spraying I sample 2 (prepared in powder at the indicated titra, on a cellulose ~ support) onto the surface and, for comparative purposes, a third i ~et of as many likewise prepared boxe~, onto which a hydroacetone solution of the carbamoyl ~ulphoxide as such was sprayed.
The process was repeated on further three sets of boxes, ` 20 into which the preparations were incorporated by hoeing the first ` 5 cm of th~ upper layer.
~, ~ The doses of each preparation were selected 90 as to apply to the soil amounts equal to 0.250; 0.500; 1 and 2 kg/ha respectively, calculated a~ carbamoyl sulphoxide.
¦! A~ter a 28-day re~idenoe in a glasshouse (temperature:
15 to 22C. and regular daily irrigations), the result~ obtained are those reported in the following Table IV, using the activity ! indexes indicated hereinbelow:
0 = no activity 1; 2 = insufficie-nt activity 1 3 = high activity - ~ 4 = total activity .t ' ll . ~ : . ' . . : .
.. . . .
53~60 ~
_ _ . .. .
~: g ~)OS~Iq~O o ~ ~ ~ o _ C~l ~ o o h ~ O X~l~I o ~ ~ ~ o o c~l ~ o o 1~ ,1 ~ ~)Il~
o P~~Od I o ~ o .~ N
t ~~ qq:~;S ~ ~ ~ 't N ~ ~ d~ t ~ ~ _ __ a ~ ~ tS ~ C`J ~ t ~j ~C E~ ~ IOS ~ ~ ~ ~ ~ et el ~ --o ~lIqOI ~
- O ,, ~ ~n~ ~ t O ~ ~ ~
o~ ~OIH~ONIH~: t ~ ~ ~ ~ ~ et ~0 ~ . _ g ~9OS~ ) o ~ ~ ~ o _ ~ ~ o o ~ ~t ~' ~ ~ ~ E~ x3l~n~ 0~ O~t 0O_~
h ~ ~ ~ ~ ~ ~ c~l ~ ~ ~ _ , rpq cn Pl O ~[lii[O~[I ~ ~ ~ O - ~ ~ o _ c~
~, ~ ~ .,~ ~I~Iq: I:;l;S ~ ~ ~t ~ C~J ~ ~t ~ ~ ~ ~ e~
"! H ~ g h _ . . _ ___. .
~ Y~ S ~ ~ ~ ~ ~t ~ ~ ~ ~ ~ ~ ~ .
.. O q l o H ~~ OS ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~t ~
O ~nIIO
~n~
.' ~1 ~OqH~ lIH~ ~ ~ ~ ~ ~ ~ ~ e~
b~ _ h ~o0 ~ooo ~ooo u~ooo .1 ,D ~ C~ O O N Lr~ O O N 1~ O O
h t~ ~ s O O N O O N O O ~--N
.~ ~ IOn~l $ w~ w~
~ R~ o oo .
. . _..... .
.~" ''- 0 . ~o~ ~ o ~~ ~ I $ ~
~` ~ ~ d ' td ~ ~ 'I o . . h 0 o o ~ rl ~ ~ ~ OrO O ~1 W ~1 ~ 0q~ p O ~ h~l ~ I h ~ o ~q o ~ o ~:
h o ~ ~ o ~
. ~ ~ ~ h~l ~ -h~_ o~
p A~ .
.
. .
~` 10536ti0 ,.
EXA~IE 5 Preparation and characteristics of the adduct :
O O n-C3H7 o 3 7 N \ .C6H5NH_C_NH2 Carbamoyl sulphoxide was added to a solution of pheny-lurea in methanol. After evaporation, a number of fractions ~ere obtained, out of which only one revealed, on elemental analysis and infrared spectrophotometric analysis, to be an adduct having a molar ratio of carbamoyl sulphoxide to phenylurea of 1 : 1.
The preparation was repeated adding 0.1 mole of sulphoxide ~' in a methanol solution containing 0.1 mole of urea.
~ By evaporation of the solvent a crystalline solid was ;~; obtained, that exhibited the following characteristics :
melting point = 101 to 102C
` C % : calculated = 57.90found = 57.45 ` H % : " 8.22 ~l = 8.33 N % : " 11.82 " = 11.8Z
~, S % : " 9~02 " = 9.00 ¦~1 20 ~h~ frequencies in cm 1 of the bands of the adduct infrared spectrum as compared with those of carbamoyl sulphoxide and of phenylurea .
are reported on following Table V, . ~.
. ~
~ ~: .
,. ~;` :
;' ,' " . ': ' . ,~ . .
`3 `~
1~ .
- 1 .
~;p p~,` ` /3 :
i: . . . ` . ~ .
1053~0 ~AB~E V
. .
Zone Zone Zone ~) ~(S-~ O) ~(N_C-N) Carbamoyl sulphoxide 1028 Phenylurea ~ 3425 ~ 752 : ~dduct of example 5 3378 1063 760 . .
A sample of the adduct was kept in a closed tube (in the presence I of air) at a temperature of 54C for 14 days, At the end of this ~i time-period, it was extracted with chloroform and ~ubjected to analysis on a thin layer: it resulted that the carbamoyl sul-. phoxide which remained unchanged amounted to about 90~o of the carbamoyl sulphoxide initially present in the adduct.
,, Characteristics of the adduct:
~, ~0 Il / _-C3H7 C-0 i90 c3~7-s-c_N .2 NH
, n-C3H7 C\-O
, NH2 ,:
,~ ~ollowing the method previously described, it was ascertained that :, the aaduct obtained had the composition reported hereinbefore, Thus, a certain amount of same ~as prepared by adding 0.1 mole 9 of car-bamoyl sulphoxide to 0,2 moles of biuret in methanol, After re-moval of the solvent, the crystalline product exhibited the follow-ing elemental analysis :
P~d 1 ~1 --~5-1053~;~0 r C %: calc. = 39.51 ~ound = 39.01 H %: " = 7,34 " = 7.31 N %: " = 23.04 " = 22.94 S %: " = 7,53 " = 7.53 . ~he product thus obtained had a melting point >104C,Frequencies .
~) in cm 1 of the bands o~ the adduct I,R,-spectrum as compared with those of carbamoyl sulphoxide and of biuret are reported on ~ollowing ~able VI, ~ABIæ VI- -Zone Zone Zone ¦ Sulphox:lde l l 1064 - :Biuret 3484 763 . 3485 . 711 Adduct of example 6 3356 1058 783 . l 3175 1030 716 ~ ~hi~ adduct was 2ubjected to thermal conditioning at a temperature ~,, 20 of 54C for 14 day~, according to the modalities described in example 5. ~he result~ of the analyse~ carried out on ~uch adduct ~ -1 revealed that about 85% of the carbamoyl ~ulphoxide initially co-n-, . - tained in the adduct had remained unchanged, EXAILl?Iæ 7 :~ Characteri~tic~ of the adducts:
`~ ~ R /n 3 7 /NH2 . 2 i8o-c3H7-s-c-N .3 C\= S
~-C3H7 NH2 .
''., ~. ' : tJ
_~_ ' ~ " '' '' . ~, ~ , ', ; , ~0 5 3 ~ 0 and 1` 1l N/n-C3H7 ~NH2 iso-C3H7_S_C_.2 C\ = S
n-C3H7 2 By operating according to the method previously illustrated, the two additives having the composition reported hereinabove were i~olated and prepared. Also an adduct having a 1:2 molar ratio was isolated in an impure form.
j ~lemental analysis :
C % H % N % S %
, __ calc. found calc.found calc.found calc.found - Adduct 2 : 3 41.41 40.90 8.16 8.18 16.80 16.86 24.03 23.71 Adduct 1 : 2 ~ 39.10 39.76 7.87 8.87 18.85 18.35 25.88 24.0C
.
Preguencies~ in cm 1 of the bands of the I.R.-spectra of the adducts -and of the starting products are reported on Table VII.
~A~IE VII
.
Zone Zone Zone U (NH) V(S~ O) V (N-C_N) Carbamoyl eulphoxide . _ . - 1064 . _ ~ ou~e~ 3378 ~ ~ 730 Adduct 2 : 3 3289 1059 731 Adduct 1 : 2 3289 1059 (735) l6 _~ _ .
1053~0 The adducts co~tainin~ thiourea are not so qtable, at 54C, a~
those containing urea : in fact, after a 14-day conditioning at such temperature, abcut 12% of the initial carbamoyl sulphoxide were recovered fro~ adduct 2 : 3 and about 20% of the initial carbamoyl sulphoxide were recovered from adduct 1 : 2.
EXAr~ES 8 A~ 9 Characteri~tics of the adducts prepared from isopropyl N-di-n-prop~l carbamoyl sulphoxide and dicyanodiamide, and from isopropyl N-di-n-propyl carbamoyl sulphoxide and dichloralurea :
o e / n-C3H7 NH
i90 C3H7_$_C_N . H2N-C_NH_C=N
m.p =67-68C
. i n-C3H
~ 7 and i O O --C3H7 i90 C3H7-S-C_N' C H . Cl3C-clH-NH-c-NH-cH-ccl3 -~ 3 7 OH O OH
m.p. = 140-141C.
; Elemental analy~is :
~ . , .
. , .
C % H % ~ % S %
calc. found calc. found calc. found calc,found . _ .
Adduct with 47,49 47,05 8,30 8,34 23,08 22,07 10,56 10,36 dicyanodi-amide Adduct with 31,38 31,96 4,74 4,84 7,32 7,2~ 5,58 5,58 urea i ~
p~ '7 ,. , -.. , . , .; ..... , : . .
~ lOS36~;0 ;, Frequency ~ in cm 1 of the bands of the infrared spectra of the adducts and of the starting products is reported on following Table VIII.
T A B L E VIII
Zone Zone ¦ Zone ~Nll)~ (S--~ 0) ~(N-C-N) .
Carbamoyl sulphoxide 1064 10 Dicyanodi mide 3l;- 719 ~ ~Dichloral rea 3279 1073 (636) ;~` Adduct with dicyano- 3356 1064 750 ~ diamide 3145 1032 706 ~-: . Adduct with dichloral- 3289 1085 (837) urea 3268 1055 815 .
L ~ ~ 31B5 ~1028 606 ,; ~ . -- .
~ The herbicide activity of the adducts prepared from organic .~ .
~ compounds of the formula (III), with the doses given to the soil, . ,~, ~` calculated as carba~oyl sulphoxide content, being equal, was no ~` lower than that of the corresponding carbamoyl sulphoxide as such ~ and of the adducts prepared from carbamoyl sulphoxide and urea.
`~A - 18 - -. . . - , . . . .
lOS36~0 ~ he herbicide activity was tested on the following in-festing weeds:
monocotyledons : Echinochola crus-galli Avena fatua Lolium sp.
Sorghum sp.
Setaria glauca s dicotyledons : Stellaria media Iponea sp.
Vigna sinensis : ~
Rumex crispus ~ ~.
Galinsoga sp.
under the same conditions illustrated in example 4 above. The re-sults were substantially identical with those yielded by the ad-ducts prepared from carbamoyl sulphoxides and urea. ~
; Preferred adducts prepared by reacting a carbamoyl sul- ~:
', phoxide of the formula ~II) with an organic compound having the ~ formula CIII) have the formulae:
~ 11 ~Rl f :: ~
R-S-C-N . C6H5NH
R2 ~:
Rl C 11 :
R-S-C-N. 2 NH2- -NH-C-NH2 \R2 r ¦ /Rl /NH2 A R-S-C-N . B C = S
R2 \NH2 where A and B are integers equal to 1, 2 or 3.
Although the invention has been described in detail for the purpose of illustration, it is to be understood that such de-tail is solely for that purpose and that variations can be madetherein by those skilled in the art without departing from the ;
.
1053~0 spirit and sc~pe o~ the .invention except as it may be limited by the clsimsf .
.
.
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a~ ~æ ~ ~ t--~ I--I ~--h F~ I ~D ~ O OD O O O O ~0 O
~ r~ u~
13 1~Z; ~ -- el--O ~ ~ t~ ~ t~
~) _ H Z
Id Z; ' --~ ~ ~ r~ D- O U~ U~ ~ ~
O c~ c~ ~ - ~--~ . _ 0h Z -.. H ~ ~ _ ~ b~ .
~ ~u a~
'.` ~ P; ~c~'~' V~ ~~
I ~H _ O O O O
:~ o~
~ d , ~0 . .. . `¢
P, ~ ~ a~--~ V~
~ C) C~ V V V o o o P:
a~ ~ D ~;
E~ .. .~ _ P . .
h ~
F~ l --- I
, o P P P P :~ P P P P .
~; ~ U~ ~O
. ~ o ao ~ u~ O
~ ~ ~ ~~ ~ ~1 H
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053~
'~he adduct~ of this invention, unlike the most interest-ing terms of the carbamoyl sulphoxides series, are stable in ~torage and can be indefinitely preserved at room temperature.
~ or purpo~es of comparison with the thermal stability of the carbamoyl sulphoxides as such, Table 2 reports the per-centages o~ carbamoyl sulphoxide recovered from the corresponding adduct after residence at temperatures higher than room tempera-ture, along with the percentages of same recovered after condition-ing of carbamoyl sulphoxide as such at 50C and 100C.
; 10 ~he recovery of carbamoyl sulphoxide from the adduct at the conclusion of the conditioning period is carried out by extraction with chloroform; the dose of carbamoyl sulphoxide : in the extracts is determi-ned by chromatography on a thin layer .or by gas-chromatography according to conventional techniques.
,, ~
., :
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,' j~ . .
I
A
...... ,.~ ~ . . . .
10536~i0 CO h h h .~ L~ O
~ ~ oV
C~ ~ ~~ ~
H ¦ ~ ---E~ V ~ ~ O ~ L~ ~ ~
h ~ ; v .
h H L~
C ~ ~ ~ _ ._ ~ ~ O ) ~ O O O O
~ ' :~ ~ o ~
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O 1~ 1~ ~
O ~ ~ ~ U~ ~ O
h ~ Oo CO ~ ~ N IS~
g & _ .
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. ,~, ~ ,q ~ ,1 h o ~ ~t oV ~ - F~ . -. ~ O ~ . ' o p, P P P P P
~; I~ \J
E~ O O~
H _ -A
.1 ~
:_i , .. . .
Since the adducts can be easily crystallized and the carbamoyl sulphoxide is easily recoverable from same by mild hydrolysis and/or extraction with chloroform or another proper solvent, it is evident that the adduct formation may be utilized to purify the carbamoyl sulphoxide.
It is to be pointed out that the molar ratios of the carbamoyl sulphoxide (II) to the organic compound (III) vary, in the adducts of this invention, depending upon the nature of the organic compound. It is necessary, however, to ascertain each time which is the molar ratio of each individual adduct obtained, utilizing, to this aim, fractional crystallization .~ followed by infrared spectrophotometric analysis, by elemental : , . ~ . .
,.. ..
. . ' ; ' ' lOS36~;0 analysis and, optionally, by X-ray diffractometric analysis ~ the precipitate that has formed. After having ascertained which is the molar ratio at which the desired adduct forms, the carbamoyl sul-phoxide (II) may be reacted with the stoichiometric amount of the organic compound (III) necessary to provide the desired adduct and the solvent removed by evaporation.
Most of the adducts so prepared are crystalline solids, stable at room temperature and not subject to alteration during storage. Unlike carbamoyl sulphoxide, from which they are obtained, lo some of these adducts may be subjected to even long-lasting heat treatments attemperatures around 50C without undergoing substan-tial modifications.
The shifting of the frequencies relating to the vibra-tions of bonds NH, N-C-N and S--~ O with respect to those of the corresponding starting products reveals whether the adduct has ;formed, as it will clearly appear from the following examples 5 through 9.
The herbicidal activity of the adducts provided by this invention is no lower than the activity of the corresponding car-bamoyl sulphoxide as such when the doses applied ~ the soil, cal-culated as carbamoyl sulphoxide content, are equal.
The following examples are given better to illustrate -the present industrial invention.
EXAMPLE 1 (Comparative) l / _ C3H7 Preparation of iso-C3H7-S-C-N . 3H2N-C-NH2 _ C3 7 ' (5193 - U) from carbamoyl sulphoxide and urea in a 1 : 3 molar ratio. 3 g of isopropyl-N-di-n-propylcarbamoyl sulphoxide were 30 added to 13,84 g of a methanol solution containing 2.48 g of urea.
lOS3660 By slow evaporation under vacuum at room temperature the following four precipitate fractions were successively isolated which, after drying, were weighed and subjected to elemental analysis, the re-sults thus obtained being reported in the following Table III.
TABLE III
Fraction Adduct Weight, g Elemental Analysis C % H % N % S % :~
I 1.905 38.56 8.30 24.78 8.06 II 1.658 38.63 8.23 24.75 7.94 III 0.260 39.05 8.31 24.82 7.76 IV 0.770 38.05 8.16 25.07 7.40 Theoretical Analysis : 39.08 8.32 24.54 8.02 ., ' ~11 of the four fractions thus obtained, when subjected to X-ray analysis, produced Debye-diagrams containing the same spectral lines, sharply differentiated from those typical of urea. :~
The infrared spectra of the fractions were also like one -~
another and contained the absorption bands shown in Table I. :~
` EXAMPLE 2 (Comparative~ .
, :
. Preparation of 5193 - U starting from carbamoyl sulpho-20 xide and urea in molar ratios different from 1 : 3. 0.505 g of i isopropyl-N-di-_-propylcarbamoyl sulphoxide was added to 0.760 g of ~-a methanol solution containing 0.136 g of urea (initial molar ratio of the reagents in the order indicated : 1:0.98). After , having allowed the solution to stand, a precipitate was collected that, after drying, weighed 0.202 g, and from whose elemental analysis the following results were obtained:
C % H % N % S %
39.52 8.54 24.63 7.47 The infrared spectrum and the Debye-diagram of this precipitate are _ g _ ~0~3660 like the corresponding spectra relative to the precipitates obtain-ed in Example 1.
Thoroughly similar results were obtained starting from the following starting amounts of reagents:
0.268 g of isopropyl-N-di-n-propylcarbamoyl sulphoxide;
1.921 g of a methanol solution containing 0.344 g of urea (initial molar ratio between the two reagents = 1 : 4.68).
EXAMPLE 3 (Comparative) By operating according to the method described in Example 1, the compounds reported on Table I were prepared, whose adduct nature is proved by the most meaningful I.R. frequencies reported on aforesaid table. Individual samples of these adducts resulted in a correct elemental analysis.
Similar results were obtained by employing, during pre- -paration, a urea-saturated aqueous solution.
, , : ' EXAMPLE 4 ( Comparative) ''Herbicide activity tests.
Adduct M 519 3 - U, prepared according to the method of ~,Example 1, by collecting all the fractions until thorough evapora-tion of the solvent, was divided into two equal samples.
One of these samples was further treated according to known formulation techniques, thus obtaining a cellulose powder containing the 2% of adduct (Sample 2).
~`On both the adduct (Sample 2 ), herbicidal activity tests jwere carried out in comparison with the corresponding carbamoyl sulphoxide as such.
iSample 1 was dissolved in a hydroacetone solution at .25% by volume of acetone. This solution was sprayed onto the earth contained in boxes measuring 40 x 30 x 20 cm, in whose upper ` 30 part, a 5 cm thick layer, the seeds of the following infesting .~ ~
., . , . :, .. . . , . . : . . .
,, , . . - , .
-` 1053~60 weeds had been uniformly di~tributed: -monocotyledons: Echinochloa crus galli Avena fatua ~olium sp.
Sorghum 9p.
Setaria glauca dicotyledons: Stellaria media Ipomea sp.
Vigna Sinensis Rumex Crispus Galinsoga 9p.
The 5 cm layer wherein these seeds were distributed had been laid onto a previou~ly humidified soil. Under thoroughly identical conditions, as many boxes were prepared by spraying I sample 2 (prepared in powder at the indicated titra, on a cellulose ~ support) onto the surface and, for comparative purposes, a third i ~et of as many likewise prepared boxe~, onto which a hydroacetone solution of the carbamoyl ~ulphoxide as such was sprayed.
The process was repeated on further three sets of boxes, ` 20 into which the preparations were incorporated by hoeing the first ` 5 cm of th~ upper layer.
~, ~ The doses of each preparation were selected 90 as to apply to the soil amounts equal to 0.250; 0.500; 1 and 2 kg/ha respectively, calculated a~ carbamoyl sulphoxide.
¦! A~ter a 28-day re~idenoe in a glasshouse (temperature:
15 to 22C. and regular daily irrigations), the result~ obtained are those reported in the following Table IV, using the activity ! indexes indicated hereinbelow:
0 = no activity 1; 2 = insufficie-nt activity 1 3 = high activity - ~ 4 = total activity .t ' ll . ~ : . ' . . : .
.. . . .
53~60 ~
_ _ . .. .
~: g ~)OS~Iq~O o ~ ~ ~ o _ C~l ~ o o h ~ O X~l~I o ~ ~ ~ o o c~l ~ o o 1~ ,1 ~ ~)Il~
o P~~Od I o ~ o .~ N
t ~~ qq:~;S ~ ~ ~ 't N ~ ~ d~ t ~ ~ _ __ a ~ ~ tS ~ C`J ~ t ~j ~C E~ ~ IOS ~ ~ ~ ~ ~ et el ~ --o ~lIqOI ~
- O ,, ~ ~n~ ~ t O ~ ~ ~
o~ ~OIH~ONIH~: t ~ ~ ~ ~ ~ et ~0 ~ . _ g ~9OS~ ) o ~ ~ ~ o _ ~ ~ o o ~ ~t ~' ~ ~ ~ E~ x3l~n~ 0~ O~t 0O_~
h ~ ~ ~ ~ ~ ~ c~l ~ ~ ~ _ , rpq cn Pl O ~[lii[O~[I ~ ~ ~ O - ~ ~ o _ c~
~, ~ ~ .,~ ~I~Iq: I:;l;S ~ ~ ~t ~ C~J ~ ~t ~ ~ ~ ~ e~
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O ~nIIO
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b~ _ h ~o0 ~ooo ~ooo u~ooo .1 ,D ~ C~ O O N Lr~ O O N 1~ O O
h t~ ~ s O O N O O N O O ~--N
.~ ~ IOn~l $ w~ w~
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~` ~ ~ d ' td ~ ~ 'I o . . h 0 o o ~ rl ~ ~ ~ OrO O ~1 W ~1 ~ 0q~ p O ~ h~l ~ I h ~ o ~q o ~ o ~:
h o ~ ~ o ~
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~` 10536ti0 ,.
EXA~IE 5 Preparation and characteristics of the adduct :
O O n-C3H7 o 3 7 N \ .C6H5NH_C_NH2 Carbamoyl sulphoxide was added to a solution of pheny-lurea in methanol. After evaporation, a number of fractions ~ere obtained, out of which only one revealed, on elemental analysis and infrared spectrophotometric analysis, to be an adduct having a molar ratio of carbamoyl sulphoxide to phenylurea of 1 : 1.
The preparation was repeated adding 0.1 mole of sulphoxide ~' in a methanol solution containing 0.1 mole of urea.
~ By evaporation of the solvent a crystalline solid was ;~; obtained, that exhibited the following characteristics :
melting point = 101 to 102C
` C % : calculated = 57.90found = 57.45 ` H % : " 8.22 ~l = 8.33 N % : " 11.82 " = 11.8Z
~, S % : " 9~02 " = 9.00 ¦~1 20 ~h~ frequencies in cm 1 of the bands of the adduct infrared spectrum as compared with those of carbamoyl sulphoxide and of phenylurea .
are reported on following Table V, . ~.
. ~
~ ~: .
,. ~;` :
;' ,' " . ': ' . ,~ . .
`3 `~
1~ .
- 1 .
~;p p~,` ` /3 :
i: . . . ` . ~ .
1053~0 ~AB~E V
. .
Zone Zone Zone ~) ~(S-~ O) ~(N_C-N) Carbamoyl sulphoxide 1028 Phenylurea ~ 3425 ~ 752 : ~dduct of example 5 3378 1063 760 . .
A sample of the adduct was kept in a closed tube (in the presence I of air) at a temperature of 54C for 14 days, At the end of this ~i time-period, it was extracted with chloroform and ~ubjected to analysis on a thin layer: it resulted that the carbamoyl sul-. phoxide which remained unchanged amounted to about 90~o of the carbamoyl sulphoxide initially present in the adduct.
,, Characteristics of the adduct:
~, ~0 Il / _-C3H7 C-0 i90 c3~7-s-c_N .2 NH
, n-C3H7 C\-O
, NH2 ,:
,~ ~ollowing the method previously described, it was ascertained that :, the aaduct obtained had the composition reported hereinbefore, Thus, a certain amount of same ~as prepared by adding 0.1 mole 9 of car-bamoyl sulphoxide to 0,2 moles of biuret in methanol, After re-moval of the solvent, the crystalline product exhibited the follow-ing elemental analysis :
P~d 1 ~1 --~5-1053~;~0 r C %: calc. = 39.51 ~ound = 39.01 H %: " = 7,34 " = 7.31 N %: " = 23.04 " = 22.94 S %: " = 7,53 " = 7.53 . ~he product thus obtained had a melting point >104C,Frequencies .
~) in cm 1 of the bands o~ the adduct I,R,-spectrum as compared with those of carbamoyl sulphoxide and of biuret are reported on ~ollowing ~able VI, ~ABIæ VI- -Zone Zone Zone ¦ Sulphox:lde l l 1064 - :Biuret 3484 763 . 3485 . 711 Adduct of example 6 3356 1058 783 . l 3175 1030 716 ~ ~hi~ adduct was 2ubjected to thermal conditioning at a temperature ~,, 20 of 54C for 14 day~, according to the modalities described in example 5. ~he result~ of the analyse~ carried out on ~uch adduct ~ -1 revealed that about 85% of the carbamoyl ~ulphoxide initially co-n-, . - tained in the adduct had remained unchanged, EXAILl?Iæ 7 :~ Characteri~tic~ of the adducts:
`~ ~ R /n 3 7 /NH2 . 2 i8o-c3H7-s-c-N .3 C\= S
~-C3H7 NH2 .
''., ~. ' : tJ
_~_ ' ~ " '' '' . ~, ~ , ', ; , ~0 5 3 ~ 0 and 1` 1l N/n-C3H7 ~NH2 iso-C3H7_S_C_.2 C\ = S
n-C3H7 2 By operating according to the method previously illustrated, the two additives having the composition reported hereinabove were i~olated and prepared. Also an adduct having a 1:2 molar ratio was isolated in an impure form.
j ~lemental analysis :
C % H % N % S %
, __ calc. found calc.found calc.found calc.found - Adduct 2 : 3 41.41 40.90 8.16 8.18 16.80 16.86 24.03 23.71 Adduct 1 : 2 ~ 39.10 39.76 7.87 8.87 18.85 18.35 25.88 24.0C
.
Preguencies~ in cm 1 of the bands of the I.R.-spectra of the adducts -and of the starting products are reported on Table VII.
~A~IE VII
.
Zone Zone Zone U (NH) V(S~ O) V (N-C_N) Carbamoyl eulphoxide . _ . - 1064 . _ ~ ou~e~ 3378 ~ ~ 730 Adduct 2 : 3 3289 1059 731 Adduct 1 : 2 3289 1059 (735) l6 _~ _ .
1053~0 The adducts co~tainin~ thiourea are not so qtable, at 54C, a~
those containing urea : in fact, after a 14-day conditioning at such temperature, abcut 12% of the initial carbamoyl sulphoxide were recovered fro~ adduct 2 : 3 and about 20% of the initial carbamoyl sulphoxide were recovered from adduct 1 : 2.
EXAr~ES 8 A~ 9 Characteri~tics of the adducts prepared from isopropyl N-di-n-prop~l carbamoyl sulphoxide and dicyanodiamide, and from isopropyl N-di-n-propyl carbamoyl sulphoxide and dichloralurea :
o e / n-C3H7 NH
i90 C3H7_$_C_N . H2N-C_NH_C=N
m.p =67-68C
. i n-C3H
~ 7 and i O O --C3H7 i90 C3H7-S-C_N' C H . Cl3C-clH-NH-c-NH-cH-ccl3 -~ 3 7 OH O OH
m.p. = 140-141C.
; Elemental analy~is :
~ . , .
. , .
C % H % ~ % S %
calc. found calc. found calc. found calc,found . _ .
Adduct with 47,49 47,05 8,30 8,34 23,08 22,07 10,56 10,36 dicyanodi-amide Adduct with 31,38 31,96 4,74 4,84 7,32 7,2~ 5,58 5,58 urea i ~
p~ '7 ,. , -.. , . , .; ..... , : . .
~ lOS36~;0 ;, Frequency ~ in cm 1 of the bands of the infrared spectra of the adducts and of the starting products is reported on following Table VIII.
T A B L E VIII
Zone Zone ¦ Zone ~Nll)~ (S--~ 0) ~(N-C-N) .
Carbamoyl sulphoxide 1064 10 Dicyanodi mide 3l;- 719 ~ ~Dichloral rea 3279 1073 (636) ;~` Adduct with dicyano- 3356 1064 750 ~ diamide 3145 1032 706 ~-: . Adduct with dichloral- 3289 1085 (837) urea 3268 1055 815 .
L ~ ~ 31B5 ~1028 606 ,; ~ . -- .
~ The herbicide activity of the adducts prepared from organic .~ .
~ compounds of the formula (III), with the doses given to the soil, . ,~, ~` calculated as carba~oyl sulphoxide content, being equal, was no ~` lower than that of the corresponding carbamoyl sulphoxide as such ~ and of the adducts prepared from carbamoyl sulphoxide and urea.
`~A - 18 - -. . . - , . . . .
lOS36~0 ~ he herbicide activity was tested on the following in-festing weeds:
monocotyledons : Echinochola crus-galli Avena fatua Lolium sp.
Sorghum sp.
Setaria glauca s dicotyledons : Stellaria media Iponea sp.
Vigna sinensis : ~
Rumex crispus ~ ~.
Galinsoga sp.
under the same conditions illustrated in example 4 above. The re-sults were substantially identical with those yielded by the ad-ducts prepared from carbamoyl sulphoxides and urea. ~
; Preferred adducts prepared by reacting a carbamoyl sul- ~:
', phoxide of the formula ~II) with an organic compound having the ~ formula CIII) have the formulae:
~ 11 ~Rl f :: ~
R-S-C-N . C6H5NH
R2 ~:
Rl C 11 :
R-S-C-N. 2 NH2- -NH-C-NH2 \R2 r ¦ /Rl /NH2 A R-S-C-N . B C = S
R2 \NH2 where A and B are integers equal to 1, 2 or 3.
Although the invention has been described in detail for the purpose of illustration, it is to be understood that such de-tail is solely for that purpose and that variations can be madetherein by those skilled in the art without departing from the ;
.
1053~0 spirit and sc~pe o~ the .invention except as it may be limited by the clsimsf .
.
.
..
, .; .
~ .
~, .
dO
- . . . . . .
.
Claims (12)
1. A process for preparing an adduct having the general formula:
wherein R is a lower alkyl or benzyl, R1 and R2 are the same or different and each represents a lower alkyl, Y is O, S or NH, R3 and R4 are the same or different and each represents hydrogen, lower alkyl, phenyl, benzyl, a CN group, a CHOH-CCl3 group or a CY-NH2 group in which Y has the aforesaid meaning, with the proviso that R3 and R4 cannot simultaneously represent hydrogen when Y is O, and A and B are integers equal to 1, 2 or 3, which comprises mixing a carbamoyl sulphoxide of the general formula:
wherein R, R1 and R2 have the aforesaid meanings, with a solution of an organic compound of the general formula:
wherein R3, R4 and Y have the aforesaid meanings, in a solvent therefor and recovering the resulting crystallized product.
wherein R is a lower alkyl or benzyl, R1 and R2 are the same or different and each represents a lower alkyl, Y is O, S or NH, R3 and R4 are the same or different and each represents hydrogen, lower alkyl, phenyl, benzyl, a CN group, a CHOH-CCl3 group or a CY-NH2 group in which Y has the aforesaid meaning, with the proviso that R3 and R4 cannot simultaneously represent hydrogen when Y is O, and A and B are integers equal to 1, 2 or 3, which comprises mixing a carbamoyl sulphoxide of the general formula:
wherein R, R1 and R2 have the aforesaid meanings, with a solution of an organic compound of the general formula:
wherein R3, R4 and Y have the aforesaid meanings, in a solvent therefor and recovering the resulting crystallized product.
2. Process according to claim 1, wherein the solvent is evaporated to dryness.
3. Process according to claim 1, wherein the molar ratio of the carbamoyl sulphoxide to the organic compound is 1 : 1.
4. Process according to claim 1, wherein the molar ratio of the carbamoyl sulphoxide to the organic compound is 1 : 2.
5. Process according to claim 1, wherein the molar ratio of the carbamoyl sulphoxide to the organic compound is 2 : 3.
6. An adduct having the general formula:
wherein R is a lower alkyl or benzyl, R1 and R2 are the same or different and each represents a lower alkyl, Y is O, S or NH, R3 and R4 are the same or different and each represents hydrogen, lower alkyl, phenyl, benzyl, a CN group, a CHOH-CCl3 group or a CY-NH2 group in which Y has the aforesaid meaning, with the proviso that R3 and R4 cannot simultaneously represent hydrogen when Y is O, and A and B are integers equal to 1, 2 or 3.
wherein R is a lower alkyl or benzyl, R1 and R2 are the same or different and each represents a lower alkyl, Y is O, S or NH, R3 and R4 are the same or different and each represents hydrogen, lower alkyl, phenyl, benzyl, a CN group, a CHOH-CCl3 group or a CY-NH2 group in which Y has the aforesaid meaning, with the proviso that R3 and R4 cannot simultaneously represent hydrogen when Y is O, and A and B are integers equal to 1, 2 or 3.
7. An adduct according to claim 6, having the formula:
wherein R, R1 and R2 have the aforesaid meanings.
wherein R, R1 and R2 have the aforesaid meanings.
8. An adduct according to claim 6, having the formula:
wherein R, R1 and R2 have the aforesaid meanings.
wherein R, R1 and R2 have the aforesaid meanings.
9. An adduct according to claim 6, having the formula:
wherein R, R1, R2, A and B have the aforesaid meanings.
wherein R, R1, R2, A and B have the aforesaid meanings.
10. An adduct according to claim 6 having the formula:
wherein R, R1, R2, A and B have the aforesaid meanings.
wherein R, R1, R2, A and B have the aforesaid meanings.
11. An adduct according to claim 6, having the formula:
wherein R, R1, R2, A and B have the aforesaid meanings.
wherein R, R1, R2, A and B have the aforesaid meanings.
12. A process for inhibiting plant growth, which comprises contacting the plant with an adduct as defined in claim 6.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2686174A IT1048195B (en) | 1974-09-03 | 1974-09-03 | CARBAMOIL SULPHOXIDES ADDUCTS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1053660A true CA1053660A (en) | 1979-05-01 |
Family
ID=11220396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA234,594A Expired CA1053660A (en) | 1974-09-03 | 1975-09-02 | Adducts of carbamoyl sulphoxides |
Country Status (7)
| Country | Link |
|---|---|
| BE (1) | BE833021R (en) |
| CA (1) | CA1053660A (en) |
| DE (1) | DE2538857C2 (en) |
| FR (1) | FR2283890A2 (en) |
| GB (1) | GB1505137A (en) |
| IT (1) | IT1048195B (en) |
| NL (1) | NL7510164A (en) |
-
1974
- 1974-09-03 IT IT2686174A patent/IT1048195B/en active
-
1975
- 1975-08-28 NL NL7510164A patent/NL7510164A/en not_active Application Discontinuation
- 1975-08-29 GB GB3580575A patent/GB1505137A/en not_active Expired
- 1975-09-01 FR FR7526760A patent/FR2283890A2/en active Granted
- 1975-09-01 DE DE19752538857 patent/DE2538857C2/en not_active Expired
- 1975-09-02 CA CA234,594A patent/CA1053660A/en not_active Expired
- 1975-09-03 BE BE159702A patent/BE833021R/en active
Also Published As
| Publication number | Publication date |
|---|---|
| FR2283890B2 (en) | 1978-04-07 |
| DE2538857A1 (en) | 1976-03-11 |
| FR2283890A2 (en) | 1976-04-02 |
| IT1048195B (en) | 1980-11-20 |
| BE833021R (en) | 1976-03-03 |
| GB1505137A (en) | 1978-03-22 |
| NL7510164A (en) | 1976-03-05 |
| DE2538857C2 (en) | 1985-06-20 |
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