US2433394A - Dicyandiamide sulfonates - Google Patents
Dicyandiamide sulfonates Download PDFInfo
- Publication number
- US2433394A US2433394A US624581A US62458145A US2433394A US 2433394 A US2433394 A US 2433394A US 624581 A US624581 A US 624581A US 62458145 A US62458145 A US 62458145A US 2433394 A US2433394 A US 2433394A
- Authority
- US
- United States
- Prior art keywords
- dicyandiamide
- acid
- sulfonates
- optic
- acetic acid
- 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 - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/24—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of a carbon skeleton containing six-membered aromatic rings
Definitions
- This invention relates to the sulfonic acid salts of dicyandiamide and to methods of preparing the same.
- the sulfonate salts are prepared by reacting dicyandiamide with a sulfonic acid in a solvent for either or both of the reactants.
- Suitable solvents are ethers, esters, ketones, acids and the like. The following examples will serve to illustrate the preparation of sulfonate salts of dicyandiamide:
- the dicyandiamide is added slowly to the mechanically stirred acetic acid solution of the ptoluenesulfonic acid at 25 C.
- the product begins to crystallize from solution before the addition of the dicyandiamide is completed.
- the reaction mixture is then cooled to C.
- the colorless crystals are filtered, washed with methyl ethyl ketone containing a small amount of ptoluene sulfonic acid and dried under vacuum at 50 C.
- potentiometric titration the molecular weight was found to agree closely with the theoretical value of 256.
- Dicyandiamide p-toluenesulfonate does not have a sharp melting or decomposition point, and since analytical data checks the theoretical com position, the optical and crystallographic properties are herein presented to characterize the ptoluenesulfonate.
- the apparent optic axial angles as observed in air are estimated to be greater than 100, and the true optic axial angle estimated therefrom is greater than 54.
- the principal vibration direction of on is at an angle of 30i1' to the elongation of the crystal.
- Dicyandiamide benzylsulfonate melts at 138 C., then resolidifies.
- the optical and crystallo r phic properties are herein presented to char-l acterize this salt.
- the apparent optic axial angle as observed in air is estimated to be greater than and the true optic axial angle estimated therefrom is greater than 60.
- the optic axial plane or principal optic section is perpendicular to the crystal face presented.
- the apparent optic axial angle as observed in air is 90 and the true optic axial angle is 54.
- the optic axial plane or principal optic section is perpendicular to the plane (010).
- the sulfonate salts of dicyandiaxriide are useful as chemical. intermediatesimthe ⁇ preparation of fiameproofing compositions, chemotherapeutic agents, insecticides, synthetic "resins and for other purposes.
- a method of preparing dicyandiamide benzylsulfonate which includes the steps of reacting in acetic acid dicyandiamide with be'nzylsulfonic :acid below substantially 50 C., and recovering "the dicyandiamide benzylsulfonate.
- a method of preparing dicyandiamide ethylssulfonate which includes the steps of reacting in acetic acid dicyandiamide with ethylsulfonic sa-cidnbelowsubstantially 50 C., and recovering :the dicyandiamide ethylsulfonate therefrom.
Description
Patented Dec. 30, 1947 DICYANDIAMIDE SULFONATES Joseph H. Paden and Alexander F. MacLean, Stamford, Conn., assignors to American Cyanam d Company, New York, N. Y., a corporation of Maine No Drawing. Application October 25, 1945,
Serial No. 624,581
9 Claims.
This invention relates to the sulfonic acid salts of dicyandiamide and to methods of preparing the same.
It has been recorded in the literature that dicyandiamide, a neutral compound having a low ionization constant would not form salts with acids in aqueous solutions. In spite of this argument which refutes the formation of such salts, it has now been discovered that sulfonated salts of dicyandiamide can be prepared.
The sulfonate salts are prepared by reacting dicyandiamide with a sulfonic acid in a solvent for either or both of the reactants. Suitable solvents are ethers, esters, ketones, acids and the like. The following examples will serve to illustrate the preparation of sulfonate salts of dicyandiamide:
EXAMPLE 1 Dicyandzamide p-toluenesulfonate Reagents Molar Ratio Dicyanrliamide l. p-Toluenesulfonic acid 1.23 Acetic acid, glacial 4. 36
The dicyandiamide is added slowly to the mechanically stirred acetic acid solution of the ptoluenesulfonic acid at 25 C. The product begins to crystallize from solution before the addition of the dicyandiamide is completed. After completion of the addition of the dicyandiamide, the reaction mixture is then cooled to C. The colorless crystals are filtered, washed with methyl ethyl ketone containing a small amount of ptoluene sulfonic acid and dried under vacuum at 50 C. By means of potentiometric titration, the molecular weight was found to agree closely with the theoretical value of 256.
Dicyandiamide p-toluenesulfonate does not have a sharp melting or decomposition point, and since analytical data checks the theoretical com position, the optical and crystallographic properties are herein presented to characterize the ptoluenesulfonate. Dicyandiamide p-toluenesulfonate is a white, columnar solid with curved faces and a negative optic sign. In white light the refractive indices are as follows: e=1.54'7; p=1.582; and y=1.598. The apparent optic axial angles as observed in air are estimated to be greater than 100, and the true optic axial angle estimated therefrom is greater than 54. The principal vibration direction of on is at an angle of 30i1' to the elongation of the crystal.
EXAMPLE 2 Dicyandiamide benzy ls ulfonate Reagents 'MolarRatio Dicyandiamide. 1.00 Benzylsulfonic acid l. 16 Acetic acid, glacial 4; 00
Small portions of the benzylsulfonic acid are added to an agitated mixture of dicyandiamide and acetic acid at a temperature of substantially 40 C. The reaction mixture is stirred about one hour after the last portion of benzylsulfonic acid is added and the temperature is lowered to substantially 20 C. The solid dicyandiamide ben-, zylsulfonate is filtered, washed with methyl ethyl ketone containing 5% benzylsulfonic acid and dried under vacuum at about C. I
Dicyandiamide benzylsulfonate melts at 138 C., then resolidifies. The optical and crystallo r phic properties are herein presented to char-l acterize this salt. Dicyandimide benzylsulfonate is a white, lamellar solid with broken edges and positive optic sign. In white light the refractive indices are as follows: oz=1.4=; and 18:1.590. The apparent optic axial angle as observed in air is estimated to be greater than and the true optic axial angle estimated therefrom is greater than 60. The optic axial plane or principal optic section is perpendicular to the crystal face presented.
EXAMPLE 3 Dicyandiamide ethylsulfonate Reagents Molar Ratio Dicyandiamide l l. 00 Ethylsulfonic acid. 2. 56 Acetic acid, glacial, 31.80
55 fi=1.551; and 'y=1.569. The apparent optic axial angle as observed in air is 90 and the true optic axial angle is 54. The optic axial plane or principal optic section is perpendicular to the plane (010). The principal vibration directions are such that p is at an angle of 3i30', to 0" and 'y is parallel to fb. It"istoibe understoo'd that b= an"d' "C are the crystallographic axes.
The sulfonates described in the above e};- amples are typical of those that may be prepared by the present invention. p A
The sulfonate salts of dicyandiaxriide are useful as chemical. intermediatesimthe{preparation of fiameproofing compositions, chemotherapeutic agents, insecticides, synthetic "resins and for other purposes.
While the invention has been described' wi-th particular reference to specific embodimentsitPis to be understood that it is not to belimited thereto, but is to be construed broadly "andn' striated solely by the scope of the appended claims.
What is-claimedg;
1. sulfonic acid salt's of d jCYan'dia Iiide.
2. Dicyandiamide p-toluenesulfonate.
'Dicyandiarnide benzylsulfonate.
'4. Dicyandiamide ethylsulfonate.
. 5. A method Otpreparing SUlfQl'i3-tQSQ1tSjOfHi- "cyandiamide which includesthe steps of-reacting *dicyandiamidewitha-sulfonic acidin' a solvent for ithejicyandiamide :and asnlfionic :acid abelow .sub- :stantially;50 C. V
. a6. .Azmethod- :ofzpreparing sulforratetsaltsz Of diacyandiamide-sWhichzincludesitherstepsrof rwcting sin-. acetic aciddioyandiamide zandz'a sultonic; acid =qbelow-s substantiallyr50 =.C.,zand mecovering ;the diecyandiamidessuifonateztherefrom.
. 27.}A1methdd 16f .gureparing zdicyanfiiarnide pitoulenesulfonatemhi-ch includes -the:stepsof revact-,ing in acetic aididicyandiamide"with p tol uenesulfonic acid --b low subs'tanti-ally I50 -'C., "and recovering the dicyandiamide p-toluenesulfonate therefrom.
8. A method of preparing dicyandiamide benzylsulfonate which includes the steps of reacting in acetic acid dicyandiamide with be'nzylsulfonic :acid below substantially 50 C., and recovering "the dicyandiamide benzylsulfonate.
9. A method of preparing dicyandiamide ethylssulfonate which includes the steps of reacting in acetic acid dicyandiamide with ethylsulfonic sa-cidnbelowsubstantially 50 C., and recovering :the dicyandiamide ethylsulfonate therefrom.
JOSEPH H. PADEN. 5 ALEXANDER F. MACLEAN.
REFERENCES CITED vTheiollowing references are of record in the file of this patent:
20 UNITED STATES PATENTS IN umber Davis, Jour. Am. Chem. Soc., vol. '43; .-'2232 2233, 1921.
Davis, Jour. Am. .Chem. Soc vol. 43, n. 669. 5'40 1921.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US624581A US2433394A (en) | 1945-10-25 | 1945-10-25 | Dicyandiamide sulfonates |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US624581A US2433394A (en) | 1945-10-25 | 1945-10-25 | Dicyandiamide sulfonates |
Publications (1)
Publication Number | Publication Date |
---|---|
US2433394A true US2433394A (en) | 1947-12-30 |
Family
ID=24502536
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US624581A Expired - Lifetime US2433394A (en) | 1945-10-25 | 1945-10-25 | Dicyandiamide sulfonates |
Country Status (1)
Country | Link |
---|---|
US (1) | US2433394A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2832743A (en) * | 1949-09-29 | 1958-04-29 | Lever Brothers Ltd | Free flowing alkyl aryl sulfonate detergent compositions |
US2911438A (en) * | 1954-06-29 | 1959-11-03 | Andre Von Szombathy | Oxygen carriers and method of making them |
WO2023166367A1 (en) | 2022-03-01 | 2023-09-07 | 3M Innovative Properties Company | Epoxy resin compositions comprising dicyandiamid curing agent |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE332681C (en) * | 1917-07-28 | 1921-01-27 | Franz Hofwimmer | Process for the production of guanidine salts |
US1939365A (en) * | 1931-01-23 | 1933-12-12 | Hercules Powder Co Ltd | Paraphenylenediamine dipicrate and process of preparing same |
US2131127A (en) * | 1933-09-18 | 1938-09-27 | Us Rubber Co | Vulcanization of rubber |
US2223935A (en) * | 1939-04-01 | 1940-12-03 | American Cyanamid Co | Amidine salts of alkyl naphthalene sulphonic acids |
US2265942A (en) * | 1939-11-18 | 1941-12-09 | American Cyanamid Co | Amidine sulphamates and a process for making them |
US2323869A (en) * | 1939-11-13 | 1943-07-06 | American Cyanamid Co | Method of preparing guanyl urea formate |
US2364594A (en) * | 1943-11-10 | 1944-12-05 | American Cyanamid Co | Preparation of acid salts of guanylthiourea |
-
1945
- 1945-10-25 US US624581A patent/US2433394A/en not_active Expired - Lifetime
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE332681C (en) * | 1917-07-28 | 1921-01-27 | Franz Hofwimmer | Process for the production of guanidine salts |
US1939365A (en) * | 1931-01-23 | 1933-12-12 | Hercules Powder Co Ltd | Paraphenylenediamine dipicrate and process of preparing same |
US2131127A (en) * | 1933-09-18 | 1938-09-27 | Us Rubber Co | Vulcanization of rubber |
US2223935A (en) * | 1939-04-01 | 1940-12-03 | American Cyanamid Co | Amidine salts of alkyl naphthalene sulphonic acids |
US2323869A (en) * | 1939-11-13 | 1943-07-06 | American Cyanamid Co | Method of preparing guanyl urea formate |
US2265942A (en) * | 1939-11-18 | 1941-12-09 | American Cyanamid Co | Amidine sulphamates and a process for making them |
US2364594A (en) * | 1943-11-10 | 1944-12-05 | American Cyanamid Co | Preparation of acid salts of guanylthiourea |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2832743A (en) * | 1949-09-29 | 1958-04-29 | Lever Brothers Ltd | Free flowing alkyl aryl sulfonate detergent compositions |
US2911438A (en) * | 1954-06-29 | 1959-11-03 | Andre Von Szombathy | Oxygen carriers and method of making them |
WO2023166367A1 (en) | 2022-03-01 | 2023-09-07 | 3M Innovative Properties Company | Epoxy resin compositions comprising dicyandiamid curing agent |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Carpino | O-Acylhydroxylamines. II. O-Mesitylenesulfonyl-, Op-Toluenesulfonyl-and O-Mesitoylhydroxylamine1 | |
US2433394A (en) | Dicyandiamide sulfonates | |
US3038935A (en) | Process for the production of 3, 5, 3', 5'-tetra-substituted 4, 4'-dihydroxy-diphenylmethyl carboxylic acids | |
US2109952A (en) | Method of preparing aminosulphonic acid | |
US2512037A (en) | Dicyandiamide acid sulfate | |
US2433391A (en) | Dicyandiamide oxalates | |
Suter et al. | The Sulfonation of Isobutylene. I. 2-Methylpropene-1, 3-disulfonic Acid and Related Compounds | |
US2433393A (en) | Dicyandiamide maleate | |
US2463462A (en) | Hydroxy amides of dihydroxy | |
US2475674A (en) | Dicyandiamide hydrochloride | |
US2433392A (en) | Dicyandiamide picrate | |
US3234254A (en) | Process for preparing aromatic diisothiocyanates | |
KR900007796A (en) | Process for the preparation of substituted 1,2-naphthoquinone- (2) -diazide-4-sulfonic acid esters and their use in sensitive mixtures | |
US3341634A (en) | Process for the production of o, o-dialkyl thio-phosphoryl acetic and propionic acidmono substituted amides | |
US2892853A (en) | (alkyl and aryl sulfinyl)- and (alkyl and aryl sulfonyl)-undecanoic acids | |
US2655528A (en) | Sulfur trioxide compounds of pentaalkylguanidines | |
US3325541A (en) | Process for the manufacture of benzenesulfonyl isourea ethers | |
Yang et al. | THE FORMATION OF FURO-α, β'-DIAZOLES FROM ACYL IMIDOTHIOCARBONATES AND ACYL PSEUDOTHIOUREAS1 | |
US3679737A (en) | Production of esters of omega-hydroxyalkanesulfonic acids with alkenoic acids | |
KR810000310B1 (en) | Process for the preparation of phenol derivatives | |
US2560227A (en) | Preparation of malonaldehyde oximes | |
JPS6136750B2 (en) | ||
US2483213A (en) | Alpha naphthalene sulfonic anhydride | |
US2402511A (en) | Alpha furyl carboxylic acid sulphonates, esters, and salts thereof | |
US2333701A (en) | Acid |