US2070634A - Xanthic formates - Google Patents
Xanthic formates Download PDFInfo
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- US2070634A US2070634A US29923A US2992335A US2070634A US 2070634 A US2070634 A US 2070634A US 29923 A US29923 A US 29923A US 2992335 A US2992335 A US 2992335A US 2070634 A US2070634 A US 2070634A
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- US
- United States
- Prior art keywords
- xanthic
- formic acid
- dodecyl
- ester
- aliphatic
- 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.)
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- 150000004675 formic acid derivatives Chemical class 0.000 title 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 100
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 50
- 235000019253 formic acid Nutrition 0.000 description 50
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 37
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 150000002148 esters Chemical class 0.000 description 31
- -1 ROCSS-COOH Chemical compound 0.000 description 29
- 125000001931 aliphatic group Chemical group 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 15
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 11
- 150000001298 alcohols Chemical class 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 235000019864 coconut oil Nutrition 0.000 description 6
- 239000003240 coconut oil Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical class CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 5
- 239000008396 flotation agent Substances 0.000 description 5
- IQICNHWUOUBTNT-UHFFFAOYSA-M potassium;dodecoxymethanedithioate Chemical compound [K+].CCCCCCCCCCCCOC([S-])=S IQICNHWUOUBTNT-UHFFFAOYSA-M 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 239000012991 xanthate Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000003931 anilides Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- GDNCXORZAMVMIW-UHFFFAOYSA-N dodecane Chemical group [CH2]CCCCCCCCCCC GDNCXORZAMVMIW-UHFFFAOYSA-N 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- AFPOMDNRTZLRMD-UHFFFAOYSA-N dodecyl carbonochloridate Chemical compound CCCCCCCCCCCCOC(Cl)=O AFPOMDNRTZLRMD-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- CYDNZXGVSMCFFA-UHFFFAOYSA-M pyridin-1-ium-1-carbaldehyde;chloride Chemical compound [Cl-].O=C[N+]1=CC=CC=C1 CYDNZXGVSMCFFA-UHFFFAOYSA-M 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 240000008299 Pinus lambertiana Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-M carbonochloridate Chemical compound [O-]C(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-M 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940096386 coconut alcohol Drugs 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- VUXSSBDWTGVNIW-UHFFFAOYSA-N dodecylazanide Chemical compound CCCCCCCCCCCC[NH-] VUXSSBDWTGVNIW-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- ILRSCQWREDREME-UHFFFAOYSA-N lauric acid amide propyl betaine Natural products CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
- Y10S516/06—Protein or carboxylic compound containing
Definitions
- This invention relates to new compositions of matter, and more particularly to high molecular weight polysulfur compounds, and still more particularly to xanthic formic esters and their 5 ammonolytic derivatives.
- the object of this invention is to prepare high molecular weight water insoluble derivatives of xanthic formic acid.
- a further object is to prepare these compounds for use as insecticides, flotation agents, and rubber accelerators.
- a still further object is to prepare the esters and esteramides of xanthic formic acid, saidcompounds containing at least one long-chain radical.
- Water-insoluble'derivatives of carbon bisulflde are prepared by the introduction of long aliphatic chains into the compounds.
- Particularly a suitable are those compounds made from octyl and higher alcohols, especially those obtainable from the catalytic hydrogenation of the carboxyl group in coconut oils.
- the applicant's invention involves the derivatives of xanthic formic acid
- xanthic formic acid is a dibasic acid and this 35 invention relates to the mono esters of xanthic formic acid, such as ROCSS-COOH, in which R is an aliphatic hydrocarbon radical of at least eight carbon atoms; to the diesters of xanthic formic acid, such as ROCSS-COOR', in
- R andR" are aliphatic hydrocarbon radicals and at least one of the radicals contains at least eight carbon atoms
- xanthic esters of xanthic formic acid such as ROCSSCOSSCOR' 5 in which fR" and R' are aliphatic hydrocarbon radicals and at least one of the radicals contains at least eight carbon atoms
- ammonolytic derivatives otherwise known as amide esters such as 5o ROCSSCONR'R" in which R is an aliphatic hydrocarbon radical
- -R" is a hydrogen or an aliphatic hydrocarbon radical
- R" is hydrogen, an aliphatic hydrocarbon radical, or an aryl group, and at least 55 oneof the aliphatic hydrocarbon radicals contains at least eight carbon atoms.
- the method of preparation of the various com- 6 pounds is relatively simple. It involves the reaction of carbon bisulfide on an alcohol in the presence of a caustic alkali and then condensing the intermediate xanthate salt with phosgene or a phosgene derivative, such as an alkyl chloro- 10 carbonate or an amide chlorocarbonate.
- phosgene or a phosgene derivative such as an alkyl chloro- 10 carbonate or an amide chlorocarbonate.
- an alkyl ester of an allphatic xanthic formic acid to react an alkali aliphatic xanthate with an alml chlorocarbonate; for example, potassium dodecyl xanthate with dodecyl chlorocarbonate yields the dodecyl ester of dodecyl xanthic formic acid.
- Example 1 toluene solution was washed thoroughly with water and the toluene evaporated on a steam bath.
- the product was a yellow liquid which an- The oil was insoluble lyaed 22.5% sulfur, calculated 23.3% sulfur.
- Example trample 4 Anilide of dodecyl xanthic formic acid was preparedby the following process: Aniline was added to a cold toluene solution of dodecyl xanthic formic acid chloride. Aniline hydrochloride precipitated at onceand was filtered off.
- the water insoluble anilide of dodecyl xanthic formic acid may be isolated by evaporating the toluene at reduced pressure.
- Dodecyl ester of dodecyl xanthic formic acid was prepared by the following process: Dodecyl chlorocarbonate was dissolved in cold ethyl alcohol and mixed immediately with a cold ethyl alcohol solution of potassium dodecyl xanthate.
- the white precipitate was soluble in water.
- the product was an alcohol solution of the dodecyl ester of dodecyl xanthic formic acid.
- Example 6 I 'Dodecyl xanthic formyl pyridinium chloride was prepared by the following process: Pyridine -was added to a cold toluene solution of dodecyl xanthic formic acid chloride. The solution became slightly clou y but no precipitate formed. The product was Ta toluene solution of dodecyl xanthic formyl pyridinium chloride.
- Dodecyl xanthic ester of dodecyl xanthic formic Q acid may be used in the following manner as a xanthate resulted flotationagent.
- a Denver Sub-A flotation cell of 1000 g. capacity was charged with 800 g. of a copper sulfide ore, .08 g. pine oil, 1.2 g. sodium carbonate and .05 g. of the dodecyl xanthic ester of dodecyl xanthic formic acid.
- An analysis for copper in the heads indicated a 74% recovery in the concentrate.
- potassium ethyl V in a 32% recovery of copper in the concentrate.
- an ester of a xanthic formic acid it is meant to include: (,a.) the mono esters of xanthic formic acid, such as octyl xanthic formic acid, CaHnOCSSCOOH, and its hoinologues; '(b) the diesters 'of xanthic formic acid, such as the 75.
- esters and ester amides formic acid and its homecoconut alcohols obtainable from the catalytic hydrogenation of the carbon] group in coconut oil, coconut oil acids oil, or mixtures of these alcohols are particularly suitable.
- the naphthenyl alcohols obtainable by the carbomlic hydrogenation of naphthenic acids may be employed. 7
- NR"R"', or R'OCSS where R' is an aliphatic hydrocarbon group, "R” is hydrogen or an allphatic hydrocarbon group, and R' is hydrogen, an aliphatic hydrocarbon group or an aryl group, and where at least one of the aliphatic hydrocarbon groups contains at least eight carbon atoms.
- These compounds include the methyl ester of octyl xanthic formic acid CsHnOCBSCCCCHr; octyl ester of methyl xanthic formic acid, HsOCSSCOOCsHn: dodecyl xanthic formic acid chloride, CisHasOCBSCOCl; dodecyl xanthic formic acid.
- CzoHuOCSSCONHCsEl dodecyl xanthic ester of 9,10-octadecenyl xanthic formic acid CmHasOCSSCOSSCOCmHaa. mixed coconut alcohol esters of mixed alkyl (as present in coconut alcohols) xanthic formic acid; tetradecyl xanthic ester of naphthenyl xanthic formic acid.
- the compounds falling within the scope of my invention may be used as insecticides, flotation agents and rubber accelerators; for example, the dodecyl xanthic ester of dodecyl xanthic formic acid is a very good parasitlcide, a good flotation agent, and a rubber accelerator, and may be used as a dispersing agent for carbon black in rubber.
- An aliphatic ester of a xanthic formic acid said ester containing at least one aliphatic hydrocarbon radical having at least eight carbon atoms.
- An aliphatic ester of a xanthic formic acid said ester containing at least one alkyl radical obtainable from the alcohols obtained by the carboxyl hydrogenation of coconut oil.
- An aliphatic ester of a xanthic formic acid said ester containing at least one dodecyl radical.
- An ester of xanthic formic acid with an aliphatic alcohol said ester containing at least one aliphatic hydrocarbon radical having at least said ester containing at least one alkyl radical obtainable from the alcohols obtained by the carboxyl hydrogenation or coconut oil.
- ester containing 'at least one dodecyl radical.
- An amide ester of a xanthic formic acid said ester containing at least one aliphatic hydrocarbon radical having at least eight carbon atoms.
- An amide ester of a xanthic i'ormic acid said ester containing at least one alkyl radical obtainable from the alcohols obtained by the carboxyl hydrogenation of coconut oil.
- An amide ester of a xanthic formic acid said ester containing at least one dodecyl radical.
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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)
Description
Patented Feb. 16, 1937 i UNITED STATES xan'rmo roaus'rss James H. Wcrnts, Wilmington, DeL, assignor to E. I. du Pont de Nemours a Company, Wilmington, not, a corporation of Delaware No Drawing. Application July 5. 1835, Serial 14' Claims.
This invention relates to new compositions of matter, and more particularly to high molecular weight polysulfur compounds, and still more particularly to xanthic formic esters and their 5 ammonolytic derivatives.
Lower aliphatic xanthates, their esters and anhydrldes have been prepared and these have been proposed for insecticides, flotation agents, and rubber accelerators. However, they have the disadvantage of having an undesirable odor,
a high volatility, and poor stability in water.
The object of this invention is to prepare high molecular weight water insoluble derivatives of xanthic formic acid. A further object is to prepare these compounds for use as insecticides, flotation agents, and rubber accelerators. A still further object is to prepare the esters and esteramides of xanthic formic acid, saidcompounds containing at least one long-chain radical.
These objects are accomplished by the following invention.
Water-insoluble'derivatives of carbon bisulflde are prepared by the introduction of long aliphatic chains into the compounds. Particularly a suitable are those compounds made from octyl and higher alcohols, especially those obtainable from the catalytic hydrogenation of the carboxyl group in coconut oils.
Chemically speaking, the applicant's invention involves the derivatives of xanthic formic acid,
5 nog-s coon. xanthic formic acid is a dibasic acid and this 35 invention relates to the mono esters of xanthic formic acid, such as ROCSS-COOH, in which R is an aliphatic hydrocarbon radical of at least eight carbon atoms; to the diesters of xanthic formic acid, such as ROCSS-COOR', in
which R andR" are aliphatic hydrocarbon radicals and at least one of the radicals contains at least eight carbon atoms; to the xanthic esters of xanthic formic acid, such as ROCSSCOSSCOR' 5 in which fR" and R' are aliphatic hydrocarbon radicals and at least one of the radicals contains at least eight carbon atoms; and to the ammonolytic derivatives, otherwise known as amide esters such as 5o ROCSSCONR'R" in which R is an aliphatic hydrocarbon radical,
-R" is a hydrogen or an aliphatic hydrocarbon radical, and, R" is hydrogen, an aliphatic hydrocarbon radical, or an aryl group, and at least 55 oneof the aliphatic hydrocarbon radicals contains at least eight carbon atoms.
while various related groupings come within the scope of this invention, all of the compounds obtained have common physical properties;
so namely, high boiling, low melting, low in odor,
organic soluble, and water insoluble. The compounds having. an aliphatichydrocarbon group containing eight or more carbon atoms are markedlv superior in these characteristics.
The method of preparation of the various com- 6 pounds is relatively simple. It involves the reaction of carbon bisulfide on an alcohol in the presence of a caustic alkali and then condensing the intermediate xanthate salt with phosgene or a phosgene derivative, such as an alkyl chloro- 10 carbonate or an amide chlorocarbonate. The various methods of forming these compounds may be outlined as follows:
(1) To makean aliphatic xanthic formic acid chloride, react an alkali aliphatic xanthate with 15 phosgene; for example, potassium dodecyl xanthate will react with phosgene to form dodecyl xanthic formic acid chloride.
(2) To make a xanthic ester of an aliphatic xanthic formic acid, react an aliphatic xanthic formic acid chloride with analkali xanthate; for example, potassium dodecyl xanthate will react with dodecyl xanthic formic acid chloride to yield the dodecyl xanthic ester of dodecyl xanthic formic acid.
(3) To make an alkyl ester of an aliphatic xanthic formic acid, react dodecyl xanthic formic acid chloride with an aliphatic alcohol; for example, dodecyl xanthic formic acid chloride will react with ethyl alcohol to form the ethyl ester of dodecyl xanthic formic acid. It is preferred, however, in making an alkyl ester of an allphatic xanthic formic acid to react an alkali aliphatic xanthate with an alml chlorocarbonate; for example, potassium dodecyl xanthate with dodecyl chlorocarbonate yields the dodecyl ester of dodecyl xanthic formic acid.
(4) To make an amide of an aliphatic xanthic formic acid, react an aliphatic xanthic formic acid chloride with an amine; for example, dodecyl xanthic formic acid chloride reacts with aniline to yield the anilide of dodecyl xanthic formic acid.
, This invention will be more readily understood by reference to the following. examples, but it is not intended that these examples should limit the scope of the invention:
Example 1 toluene solution was washed thoroughly with water and the toluene evaporated on a steam bath. The product was a yellow liquid which an- The oil was insoluble lyaed 22.5% sulfur, calculated 23.3% sulfur.
in water but soluble in benzene, kerosene, and toluene.
'E:rample2" Dodecyl xanthic formic acid chloride was pre alcohol, other,
, pared by the following process: so parts by weight of a solution of potassium dodecyl xanthate in toluene wasmixed with 4 parts by weight of a solution of phosgene in toluene. The solution became warm and a solid separated. The solution was filtered and blown with air for an hour to remove hydrogen chloride. The product was a toluene solution of dodecyl xanthic formic acid chloride. The chloride may. be isolated by evaporating the toluene and by treatment with water may be converted to dodecyl xanthic formic acid.
- Example trample 4 Anilide of dodecyl xanthic formic acid was preparedby the following process: Aniline was added to a cold toluene solution of dodecyl xanthic formic acid chloride. Aniline hydrochloride precipitated at onceand was filtered off.
The water insoluble anilide of dodecyl xanthic formic acid may be isolated by evaporating the toluene at reduced pressure.
trample 5 Dodecyl ester of dodecyl xanthic formic acid 'was prepared by the following process: Dodecyl chlorocarbonate was dissolved in cold ethyl alcohol and mixed immediately with a cold ethyl alcohol solution of potassium dodecyl xanthate.
A, white precipitate which formed at once was filtered oil. The white precipitate was soluble in water. ,The product was an alcohol solution of the dodecyl ester of dodecyl xanthic formic acid.
Example 6 I 'Dodecyl xanthic formyl pyridinium chloride was prepared by the following process: Pyridine -was added to a cold toluene solution of dodecyl xanthic formic acid chloride. The solution became slightly clou y but no precipitate formed. The product was Ta toluene solution of dodecyl xanthic formyl pyridinium chloride.
Dodecyl xanthic ester of dodecyl xanthic formic Q acid may be used in the following manner as a xanthate resulted flotationagent.
A Denver Sub-A flotation cell of 1000 g. capacity was charged with 800 g. of a copper sulfide ore, .08 g. pine oil, 1.2 g. sodium carbonate and .05 g. of the dodecyl xanthic ester of dodecyl xanthic formic acid. An analysis for copper in the heads indicated a 74% recovery in the concentrate. Under similar conditions potassium ethyl V in a 32% recovery of copper in the concentrate.
By an ester of a xanthic formic acid it is meant to include: (,a.) the mono esters of xanthic formic acid, such as octyl xanthic formic acid, CaHnOCSSCOOH, and its hoinologues; '(b) the diesters 'of xanthic formic acid, such as the 75.
octyl ester of methyl xanthic formic acid,
esters and ester amides formic acid and its homecoconut alcohols" obtainable from the catalytic hydrogenation of the carbon] group in coconut oil, coconut oil acids oil, or mixtures of these alcohols are particularly suitable. In place of the coconut alcohols the naphthenyl alcohols obtainable by the carbomlic hydrogenation of naphthenic acids may be employed. 7
Compounds of the formula ROCBSCOX, where, "R" is an aliphatic hydrocarbon group "x" may be either OH, OR, halogen,
or palm kernel and where NR"R"', or R'OCSS, where R' is an aliphatic hydrocarbon group, "R" is hydrogen or an allphatic hydrocarbon group, and R' is hydrogen, an aliphatic hydrocarbon group or an aryl group, and where at least one of the aliphatic hydrocarbon groups contains at least eight carbon atoms. are the compounds that are included within the scope of this invention. These compounds include the methyl ester of octyl xanthic formic acid CsHnOCBSCCCCHr; octyl ester of methyl xanthic formic acid, HsOCSSCOOCsHn: dodecyl xanthic formic acid chloride, CisHasOCBSCOCl; dodecyl xanthic formic acid. CmHasOCSBCOOH; cetyl xanthic ester of cetyl xanthic formic acid, (CuHaaOCSB) 2C0; tetradecyl xanthic ester of octyl xanthlc formic acid, CsHuOCSSCOSSCOCuHzo; amide of decyl xanthic formic acid, CxoHsrOCSSCONHz; N-methyl N-ethyl amide of dodecyl xanthic formic acid, Ci2HzsOCSSCONCHa(C2Hs); N-dodecyl amide of methyl xanthic formic acid,
CHaOCSSCONI-ICnHm; anilide of eicosyl xanthic formic acid,
CzoHuOCSSCONHCsEl dodecyl xanthic ester of 9,10-octadecenyl xanthic formic acid, CmHasOCSSCOSSCOCmHaa. mixed coconut alcohol esters of mixed alkyl (as present in coconut alcohols) xanthic formic acid; tetradecyl xanthic ester of naphthenyl xanthic formic acid.
The compounds falling within the scope of my invention may be used as insecticides, flotation agents and rubber accelerators; for example, the dodecyl xanthic ester of dodecyl xanthic formic acid is a very good parasitlcide, a good flotation agent, and a rubber accelerator, and may be used as a dispersing agent for carbon black in rubber.
As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that I do not limit myself to the specific embodiments thereof except asdefined in the appended patent claims.
I claim:
1. An aliphatic ester of a xanthic formic acid, said ester containing at least one aliphatic hydrocarbon radical having at least eight carbon atoms.
2. An aliphatic ester of a xanthic formic acid, said ester containing at least one alkyl radical obtainable from the alcohols obtained by the carboxyl hydrogenation of coconut oil.
3. An aliphatic ester of a xanthic formic acid, said ester containing at least one dodecyl radical.
7 atoms. 7 n j 8. An xanthic ester oi a xanthic formic acid.
4. An ester of xanthic formic acid with an aliphatic alcohol, said ester containing at least one aliphatic hydrocarbon radical having at least said ester containing at least one alkyl radical obtainable from the alcohols obtained by the carboxyl hydrogenation or coconut oil.
9. A xanthic ester of a xanthic formic acid,
said ester containing 'at least one dodecyl radical.
10. An amide ester of a xanthic formic acid, said ester containing at least one aliphatic hydrocarbon radical having at least eight carbon atoms.
11. An amide ester of a xanthic i'ormic acid, said ester containing at least one alkyl radical obtainable from the alcohols obtained by the carboxyl hydrogenation of coconut oil.
12. An amide ester of a xanthic formic acid, said ester containing at least one dodecyl radical.
18; A dodecyl xanthlc ester oi dodecyl xanthic 15 formic acid. 14. A dibutyl amide ester of dodecyl xanthic formic acid.
JAMES H. mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US29923A US2070634A (en) | 1935-07-05 | 1935-07-05 | Xanthic formates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US29923A US2070634A (en) | 1935-07-05 | 1935-07-05 | Xanthic formates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2070634A true US2070634A (en) | 1937-02-16 |
Family
ID=21851585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US29923A Expired - Lifetime US2070634A (en) | 1935-07-05 | 1935-07-05 | Xanthic formates |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2070634A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2602814A (en) * | 1946-06-26 | 1952-07-08 | Minerec Corp | Dicarbonyl compounds |
| US2608573A (en) * | 1948-06-02 | 1952-08-26 | Minerec Corp | Xanthogen compounds |
| US2608572A (en) * | 1948-06-02 | 1952-08-26 | Minerec Corp | Xanthogen formates |
| US2628971A (en) * | 1947-06-25 | 1953-02-17 | American Cyanamid Co | Esters of alkylxanthic formic acid |
| US2628717A (en) * | 1947-06-25 | 1953-02-17 | American Cyanamid Co | Flotation of ores |
| US2903348A (en) * | 1955-12-09 | 1959-09-08 | Exxon Research Engineering Co | Defoliating cotton with isooctyl xanthoacetic acid |
| US3329266A (en) * | 1964-04-17 | 1967-07-04 | Kennecott Copper Corp | Flotation process involving depression of sulfide minerals previously activated |
| US3788467A (en) * | 1972-04-27 | 1974-01-29 | American Cyanamid Co | Flotation process for recovering molybdenum |
| US4136020A (en) * | 1976-11-11 | 1979-01-23 | Minerec Corporation | Flotation reagent and process |
| WO1987003221A1 (en) * | 1985-11-29 | 1987-06-04 | The Dow Chemical Company | Novel collectors for froth flotation of minerals |
| US4684459A (en) * | 1985-11-29 | 1987-08-04 | The Dow Chemical Company | Collector compositions for the froth flotation of mineral values |
| US4789392A (en) * | 1984-09-13 | 1988-12-06 | The Dow Chemical Company | Froth flotation method |
| CN113480459A (en) * | 2021-07-01 | 2021-10-08 | 云南铜业股份有限公司 | Preparation method of xanthate alkyl hydroximate |
-
1935
- 1935-07-05 US US29923A patent/US2070634A/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2602814A (en) * | 1946-06-26 | 1952-07-08 | Minerec Corp | Dicarbonyl compounds |
| US2628971A (en) * | 1947-06-25 | 1953-02-17 | American Cyanamid Co | Esters of alkylxanthic formic acid |
| US2628717A (en) * | 1947-06-25 | 1953-02-17 | American Cyanamid Co | Flotation of ores |
| US2608573A (en) * | 1948-06-02 | 1952-08-26 | Minerec Corp | Xanthogen compounds |
| US2608572A (en) * | 1948-06-02 | 1952-08-26 | Minerec Corp | Xanthogen formates |
| US2903348A (en) * | 1955-12-09 | 1959-09-08 | Exxon Research Engineering Co | Defoliating cotton with isooctyl xanthoacetic acid |
| US3329266A (en) * | 1964-04-17 | 1967-07-04 | Kennecott Copper Corp | Flotation process involving depression of sulfide minerals previously activated |
| US3788467A (en) * | 1972-04-27 | 1974-01-29 | American Cyanamid Co | Flotation process for recovering molybdenum |
| US4136020A (en) * | 1976-11-11 | 1979-01-23 | Minerec Corporation | Flotation reagent and process |
| US4789392A (en) * | 1984-09-13 | 1988-12-06 | The Dow Chemical Company | Froth flotation method |
| WO1987003221A1 (en) * | 1985-11-29 | 1987-06-04 | The Dow Chemical Company | Novel collectors for froth flotation of minerals |
| US4684459A (en) * | 1985-11-29 | 1987-08-04 | The Dow Chemical Company | Collector compositions for the froth flotation of mineral values |
| CN113480459A (en) * | 2021-07-01 | 2021-10-08 | 云南铜业股份有限公司 | Preparation method of xanthate alkyl hydroximate |
| CN113480459B (en) * | 2021-07-01 | 2023-03-14 | 云南铜业股份有限公司 | Preparation method of xanthate alkyl hydroximate |
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