US3309432A - Process for upgrading thiophosphates - Google Patents
Process for upgrading thiophosphates Download PDFInfo
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- US3309432A US3309432A US504182A US50418265A US3309432A US 3309432 A US3309432 A US 3309432A US 504182 A US504182 A US 504182A US 50418265 A US50418265 A US 50418265A US 3309432 A US3309432 A US 3309432A
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- aldehyde
- thiophosphate
- odor
- malodorous
- samples
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- 238000000034 method Methods 0.000 title claims description 25
- 230000008569 process Effects 0.000 title description 13
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 title description 7
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 claims description 25
- 150000001299 aldehydes Chemical class 0.000 claims description 22
- 239000000575 pesticide Substances 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 3
- 235000019645 odor Nutrition 0.000 description 27
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 16
- TYEYBOSBBBHJIV-UHFFFAOYSA-M 2-oxobutanoate Chemical compound CCC(=O)C([O-])=O TYEYBOSBBBHJIV-UHFFFAOYSA-M 0.000 description 13
- 239000005949 Malathion Substances 0.000 description 8
- JXSJBGJIGXNWCI-UHFFFAOYSA-N diethyl 2-[(dimethoxyphosphorothioyl)thio]succinate Chemical compound CCOC(=O)CC(SP(=S)(OC)OC)C(=O)OCC JXSJBGJIGXNWCI-UHFFFAOYSA-N 0.000 description 8
- 229960000453 malathion Drugs 0.000 description 8
- 244000290333 Vanilla fragrans Species 0.000 description 6
- 235000009499 Vanilla fragrans Nutrition 0.000 description 6
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 6
- -1 carbethoxyethyl Chemical group 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 4
- 244000144725 Amygdalus communis Species 0.000 description 3
- 235000011437 Amygdalus communis Nutrition 0.000 description 3
- 235000020224 almond Nutrition 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- KLXFSKITMRWDPM-UHFFFAOYSA-N diethyl 2-sulfanylbutanedioate Chemical compound CCOC(=O)CC(S)C(=O)OCC KLXFSKITMRWDPM-UHFFFAOYSA-N 0.000 description 3
- NAGJZTKCGNOGPW-UHFFFAOYSA-K dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [O-]P([O-])([S-])=S NAGJZTKCGNOGPW-UHFFFAOYSA-K 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 238000004332 deodorization Methods 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 238000000586 desensitisation Methods 0.000 description 2
- CBOQJANXLMLOSS-UHFFFAOYSA-N ethyl vanillin Chemical compound CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 230000000361 pesticidal effect Effects 0.000 description 2
- BULVZWIRKLYCBC-UHFFFAOYSA-N phorate Chemical compound CCOP(=S)(OCC)SCSCC BULVZWIRKLYCBC-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 244000178870 Lavandula angustifolia Species 0.000 description 1
- 235000010663 Lavandula angustifolia Nutrition 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical class OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001102 lavandula vera Substances 0.000 description 1
- 235000018219 lavender Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 1
- 229960003868 paraldehyde Drugs 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/025—Purification; Separation; Stabilisation; Desodorisation of organo-phosphorus compounds
Definitions
- the present invention relates to a novel process for upgrading pesticidal thiophosphates. More particularly, it relates to a process for upgrading malodorous pesticidal thiophosphates by substantially removing the offensive odor therefrom. Still more particularly, the invention is concerned with a method for treating thiophosphate pesticides with selective aldehydes defined with particularity hereinbelow to obtain storage-stable, odor improved thiophosphates.
- any commercially available thiophosphate pesticide can be subjected to the action of an aldehyde in which said aldehyde is at least slightly soluble in the thiophosphate and in which the formed aldehyde-mercaptan derivative is of relatively high boiling point.
- an aldehyde in which said aldehyde is at least slightly soluble in the thiophosphate and in which the formed aldehyde-mercaptan derivative is of relatively high boiling point.
- thiophosphate pesticides can be treated in accordance with theprocess of the invention.
- Illustrative of such thiophosphates are:
- Exemplary aldehydes which are characterized as being at least slightly soluble is each of the above thiophosphate pesticides illustrated above and which form mercaptanaldehyde derivatives of relatively high boiling point are: ethyl glyoxylate, acetaldehyde, paraldehyde, benzaldehyde, methylprotocatechuic aldehyde, ethylprotocatechuic aldehyde, p-tolualdehyde, salicylaldehyde, furaldehyde and a-methyl acrylicaldehyde.
- the preferred aldehydes are ethyl glyoxylate and methylprotocatechuic aldehyde, since the latter readily react without difiiculty with mercapt-ans normally present in thiophosphate pesticides. Significantly, the mercaptan content of the thiophosphate is appreciably reduced, thereby enhansing its odor characteristics.
- the process of the present invention eliminates the need for considerable specialized equipment and utilizes relatively inexpensive equipment operable over a wide temperature range.
- the aldehyde can be added prior to, during or subsequent to the preparation of the thiophosphate being treated. Deodorization is attained upon the addition of the selective aldehyde within a relatively short period of time, usually from about fifteen minutes to about three hours.
- Example 1 The reduction of methyl mercaptan in malathion by treatment with small amounts of a selective aldehyde is demonstrated by utilizing twelve individual compositions of malathion containing methyl mercaptan. To each individual composition is added from about 0.1% to about 2% by weight of diverse selective aldehydes. The product is then analyzed particularly for mercaptan retention.
- the determination of the amount of methyl mercaptan in each composition is made by heating treated samples to 56 C. for two hours and then collecting the vapors above the samples. These vapors are chromatographed at 30 C. on a six-foot column containing 10% of a mixture of cyanoethylmethyland cyanodimethyl 3 in Table I below. Untreated malathion is employed as the control.
- Example 2 The effectiveness of ethyl glyoxylate for deodorizing malathion (O,'O-dimethyl phosphorodithioate of diethyl mercaptosuccinate) is demonstrated by utilizing from to 1.5% by weight of ethyl glyoxylate.
- Determination of the amount of methyl mercaptan present in untreated malathion is accomplished by means of gas-liquid chromatography.
- the malathion samples are heated at 56 C. for two hours. Vapors above the samples are collected and chromatographed at 30 C. on a six-foot column containing 10% of a mixture of cyanoethylmethyland .cyanodimethyl silicone gum. Each determination is accomplished with a flame ionization detector.
- the amount of methyl mercaptan present in each sample is reported in Table 11 below.
- each sample is compared with each of the other (N-l) samples.
- N-l the number of permutations or combinations for N samples, two at a Preferences are scored on an arbitrary numerical scale, 12 for a higher preference, and 0 for no preference. The sign of the score depends upon whether the preference is for the first or second sample proffered.
- the preferred sample receives a positive score when it is proffered first and negative score when proifered second. In the absence of a desensitization effect and random or systematic error, the sum of the scores for both orders of presentation for each sample pair would be zero.
- a 0 score is entered for the sampled proffered first.
- a scoring box is made up with the row scores pertaining to the preference of samples proffered first and column scores pertaining to the preference of samples proffered second.
- the total score for each sample is obtained by making a sign change when adding the column scores to the row scores. After the rows and columns have been added, and allowing for the necessary sign changes, the sample with highest positive score will be the most preferred and the other samples can be ranked in descending order.
- Table III The results of the above tests are presented in Table III below.
- Example 3 Deodorization of 0,0- diethyl S- (ethylthio)methyl phosphorodithioate is demonstrated by the following procedure wherein 2.0% by weight of ethyl glyoxylate is mixed with samples of the technical grade material and with distilled technical grade material and stored at a 75 various aldehydesi The data also show that the addition of 1.5%
- a process according to claim 1 wherein the aldehyde present ranges between about 1% and about 4%, by weight.
- aldehyde is ethy-lprotocatechuic aldehyde.
- a method for the upgrading of an untreated, malodorous thiophosphate is 0,0-diethyl S-(ethylthiomethyl) odorous, mercaptan-containing thiophosphate pesticidev phosphorodithioate.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
Description
United States Patent 3,309,432 PROCESS FOR UPGRADING THIOPHOSPHATES Jackson Pollard English, Princeton, N.J., assignor to American Cyanamid Company, Stamford, Conn., a corporation of Maine No Drawing. Filed Oct. 23, 1965, Ser. No. 504,182
I 10 Claims. (Cl. 260-989) The present invention relates to a novel process for upgrading pesticidal thiophosphates. More particularly, it relates to a process for upgrading malodorous pesticidal thiophosphates by substantially removing the offensive odor therefrom. Still more particularly, the invention is concerned with a method for treating thiophosphate pesticides with selective aldehydes defined with particularity hereinbelow to obtain storage-stable, odor improved thiophosphates.
In the past, various methods for the elimination or masking of offensive OdOIS in thiophosphate pesticide have been disclosed in the literature. Unfortunately, none has been wholly successful. kor instance, it is known the useful ozonization process for successfully deodorizing malathion, that is, O,( )-dimethyl-S-(1,2-di-' carbethoxyethyl)-phosphorodithioate as succinctly described in US. Letters Patent No. 2,980,723, cannot be universally employed for the treatment of thiophosphate pesticides. Ozonization of illustrative thiophosphates, such as 0,0-dialkyl-S-(alkylthio)alkyl phosphorodithioates causes rapid degradation of such compounds. Moreover, it has been observed that certain masking agents, such as pine and lavender scents are only partially effective for stabilizing odor of particular thiophosphates. Further, they do not achieve the desired level of odor control necessary to classify a treated product as pre- -mium grade. Still others, such as spice scent, can produce an intense odor unlike that of the treated material but equally offensive. If a process whereby a storagestable, deodorized thiophosphate pesticide could be provided eliminating the difficulties of the prior such a process would satisfy a long-felt need.
It is, therefore, a principal object of the invention to eliminate rather than mask the offensive odor generally attributable to thiophosphate pesticides. It is a further object of the invention to provide a relatively simple, effective and economical method for reducing offensive odors in malodorous thiophosphate pesticides having associated therewith small amounts of at least an alkyl mercaptan. It is a still further object of the invention to provide a process for the reduction or prevention of the development of alkyl mercaptans in thiophasphate pesticides. Other objects and advantages will become apparent to one skilled in the art from a consideration of the ensuing description.
To this end, there is provided a relatively straightforward, simple and effective method for attaining a marked improvement in malodorous thiophosphate pesticides. Unexpectedly, the improvement is attained by admixing small amounts of selected aldehydes with the malodorous thiophosphate pesticides. Admixture can take place over a wide range of temperatures, usually between 0 C. and 100 C. Surprisingly, the so-treated malodorous thiophosphate is markedly improved and remains storage-stable with respect to odor over a prolonged period of time.
According to the present invention, any commercially available thiophosphate pesticide can be subjected to the action of an aldehyde in which said aldehyde is at least slightly soluble in the thiophosphate and in which the formed aldehyde-mercaptan derivative is of relatively high boiling point. In general, the addition of from about 0.5% to about 5% by weight of said selective aldepractice,
3,309,432 Patented Mar. 14, 1967 hyde to a malodorous thiophosphate is suflicient to reduce offensive odors of such thiophosphate to a commercially acceptable level. However, when utilizing an amount in excess of 5% of the aldehyde, it is found that the use of such amount is undesirable, since the cost is increased and little, if any, additional advantage either by way of increasing the level, or extending the period, of odor control is attained.
Advantageously, a large variety of thiophosphate pesticides can be treated in accordance with theprocess of the invention. Illustrative of such thiophosphates are:
and equivalents thereof.
Exemplary aldehydes which are characterized as being at least slightly soluble is each of the above thiophosphate pesticides illustrated above and which form mercaptanaldehyde derivatives of relatively high boiling point are: ethyl glyoxylate, acetaldehyde, paraldehyde, benzaldehyde, methylprotocatechuic aldehyde, ethylprotocatechuic aldehyde, p-tolualdehyde, salicylaldehyde, furaldehyde and a-methyl acrylicaldehyde. The preferred aldehydes are ethyl glyoxylate and methylprotocatechuic aldehyde, since the latter readily react without difiiculty with mercapt-ans normally present in thiophosphate pesticides. Significantly, the mercaptan content of the thiophosphate is appreciably reduced, thereby enhansing its odor characteristics.
It is an advantage that the process of the present invention eliminates the need for considerable specialized equipment and utilizes relatively inexpensive equipment operable over a wide temperature range. In general, the aldehyde can be added prior to, during or subsequent to the preparation of the thiophosphate being treated. Deodorization is attained upon the addition of the selective aldehyde within a relatively short period of time, usually from about fifteen minutes to about three hours.
The invention will be illustrated in conjunction with the following examples which are to be taken as illustrative only and not by way of limitation.
Example 1 The reduction of methyl mercaptan in malathion by treatment with small amounts of a selective aldehyde is demonstrated by utilizing twelve individual compositions of malathion containing methyl mercaptan. To each individual composition is added from about 0.1% to about 2% by weight of diverse selective aldehydes. The product is then analyzed particularly for mercaptan retention.
The determination of the amount of methyl mercaptan in each composition is made by heating treated samples to 56 C. for two hours and then collecting the vapors above the samples. These vapors are chromatographed at 30 C. on a six-foot column containing 10% of a mixture of cyanoethylmethyland cyanodimethyl 3 in Table I below. Untreated malathion is employed as the control.
Added by partitioning from saturated aqueous sodium sulfate solution. [Theoretical: 2%.]
Example 2 The effectiveness of ethyl glyoxylate for deodorizing malathion (O,'O-dimethyl phosphorodithioate of diethyl mercaptosuccinate) is demonstrated by utilizing from to 1.5% by weight of ethyl glyoxylate.
Several samples of technical grade malathion having a" rather strong offensive mercaptan odor are mixed with the treating aldehyde. Such samples are placed on a water bath maintained at 56 C. for a period of 34 days and periodically analyzed for methyl mercaptan, a particularly malodorous component.
Determination of the amount of methyl mercaptan present in untreated malathion is accomplished by means of gas-liquid chromatography. The malathion samples are heated at 56 C. for two hours. Vapors above the samples are collected and chromatographed at 30 C. on a six-foot column containing 10% of a mixture of cyanoethylmethyland .cyanodimethyl silicone gum. Each determination is accomplished with a flame ionization detector. The amount of methyl mercaptan present in each sample is reported in Table 11 below.
TABLE II 20 time, is N('N-1).
temperature held at either 34 C. or 60 C. for either 15 or 41 days. Untreated samples of each material stored under identical conditions are employed as controls. After storage for 15 or 41 days, the samples are 5 evaluated by the known Scheffes method of paired comparisons. The comparisons are randomized amongst a panel of judges with each observation or comparison of a sample pair being made by a different judge. To eliminate a possible bias due to the desensitization of the 01- factory nerves by the first sample prolfered, thereby causing a preference for the second, both orders of presentation for each sample pair are obtained for evaluation. In addition, all panels have been run in duplicate, and the degree of reproducibility has been good.
From a statistical point of view, to determine the relative preference of N samples, each sample is compared with each of the other (N-l) samples. With both orders of presentation -for each pair of samples, the number of permutations or combinations for N samples, two at a Preferences are scored on an arbitrary numerical scale, 12 for a higher preference, and 0 for no preference. The sign of the score depends upon whether the preference is for the first or second sample proffered. The preferred sample receives a positive score when it is proffered first and negative score when proifered second. In the absence of a desensitization effect and random or systematic error, the sum of the scores for both orders of presentation for each sample pair would be zero. When there is no preference for either sample, a 0 score is entered for the sampled proffered first.
A scoring box is made up with the row scores pertaining to the preference of samples proffered first and column scores pertaining to the preference of samples proffered second. The total score for each sample is obtained by making a sign change when adding the column scores to the row scores. After the rows and columns have been added, and allowing for the necessary sign changes, the sample with highest positive score will be the most preferred and the other samples can be ranked in descending order. The results of the above tests are presented in Table III below.
Untreated, Technical 0,0-Dimethyl Phosphorodithioate of DiethylMercaptosuccinate MethylMercaptan (p.p.m.) Days in 56 C. Bath Technical plus 0% ethyl glyoxylate 81 1,300 622 6, 300 Technical plus 0.5% ethyl glyoxylate. 0 0 0 2, 560 Technical plus 1.0% ethyl glyoxylate. 0 0 0 44 Technical plus 1.5% ethyl glyoxylate 0 0 1.9 0
Example 3 Deodorization of 0,0- diethyl S- (ethylthio)methyl phosphorodithioate is demonstrated by the following procedure wherein 2.0% by weight of ethyl glyoxylate is mixed with samples of the technical grade material and with distilled technical grade material and stored at a 75 various aldehydesi The data also show that the addition of 1.5%
TABLE III [Odorpreierence scores of 0,0-diethyl S-(ethylthiomethyDphos horodithioatc [Thimet] containing 2.0% ethyl glyoxylated by wei ght] O Oripr PanebScore,
ven a s Thimet Sample Temp, y m ven Technical 84 6 3 Technical plus Ethyl Glyoxylate 34 4 1 0 D stilled 34 0 7 Distilled plus Ethyl Glyoxylate 34 10 11 Example 4 In this example, the marked odor control capacity of n the treatment of phosphorodithioates is demonstrated by the following tests wherein 0,0-dimethyl phosphorodithioate of diethyl mercaptosuccinate, O,()-diethyl S-(ethylthiomethyl) phosphor-odithioate and 0,0-diethyl S-(N-methylcarbarnoylmethyl)phosphorodithioate are treated with from about 1% to about 4% by weight of a variety of aldehydes and mixtures of such al dehydes. In these tests, the technical grade phosphorodithioatesare admixed with aldehyde, permitted to stand for about 24 hours, and then sniffed to determine the level of odor control achieved by the various treatments. Untreated technical grade material is used as a control. The results of the tests appear in Table IV below.
3. A process according to claim 1 wherein the aldehyde present ranges between about 1% and about 4%, by weight.
4. A method according to claim 1 wherein the aldehyde is ethyl glyoxylate.
. 5. A method according to claim 1 wherein the aldehyde is methylprotocatechuic aldehyde.
6. A method according to claim 1 wherein the aldehyde is ethy-lprotocatechuic aldehyde.
7. A process according to claim 1 in which the malodorous thiophosphate is 0,0-dimethyl phosphorodithioate of diethyl mercaptosuccinate.
TABLE IV Sample Additive Percent Odor Control Added 0,0-dimethyl phosphorodithioate of diethyl mer- Benzaldehyde 1 Good, ahnond-like odor.
captosueeinate.
D Ethyl glyoxylate 2 Good, little or no odor.
Methylprotocatechuic aldehyde. 1 Good, slight vanilla odor. Ethylprotocatechuie aldehyde 1 Good, slight vanilla odor.
Control no additive Benzal ehyde Methylprotoeateehuie aldehyde Ethylprotocateehuie aldehyde Poor, malodorous. Good, strong almond odor.
4 Good, vanilla odor.
4 Good, vanilla odor.
2 Good, Slight vanilla odor. 2
Benzaldehyde Good, slight almond odor. Methylprotoeatech e aldehyd Good, slight almond odor. Salieylaldehyde Good, nitrobenzene-like odor. D Control, no additive Poor, malodorous. Op-diethyl S-(N-methylcarbamoylmethyDphos- Ethylprotocatechuic aldehyde 1 Good, vanilla odor.
phorodithioate.
Do Control, 110 additive Poor, malodorous.
I laim; 8. A process according to claim 1 in Which the mal- 1. A method for the upgrading of an untreated, malodorous thiophosphate is 0,0-diethyl S-(ethylthiomethyl) odorous, mercaptan-containing thiophosphate pesticidev phosphorodithioate.
9. A process according to claim 1 in which the malodorous thiophosphate is 0,0-dimethyl S-(N-methylcarbamoylmethyl) phosphorodithioate.
10. A method according to claim 1 in which the treating temperature is maintained between about 0 C. and about C.
No references cited.
CHARLES E. PARKER, Primary Examiner.
BERNARD BILLIAN, FRANK M. SIKORA,
Assistant Examiners.
Claims (1)
1. A METHOD FOR THE UPGRADING OF AN UNTREATED, MALODOROUS, MERCAPTAN-CONTAINING THIOPHOSPHATE PESTICIDE WHICH COMPRISES THE STEPS OF: TREATING SAID MALODOROUS, MERCAPTAN-CONTAINING THIOPHOSPHATE WITH BETWEEN ABOUT 0.5% AND ABOUT 5%, BY WEIGHT, OF AN ALDEHYDE, WHEREBY A HIGH BOILING MERCAPTAN-ALDEHYDE COMPOUND IS FORMED, AND, THEREAFTER, RECOVERING AN ODOR-IMPROVE, STORAGESTABLE THIOPHOSPHATE.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US504182A US3309432A (en) | 1965-10-23 | 1965-10-23 | Process for upgrading thiophosphates |
| GB41121/66A GB1152012A (en) | 1965-10-23 | 1966-09-14 | Process for Treating Malodorous Organic Thiophosphate Pesticides |
| FR79523A FR1496405A (en) | 1965-10-23 | 1966-10-11 | Process for improving the quality of thiophosphates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US504182A US3309432A (en) | 1965-10-23 | 1965-10-23 | Process for upgrading thiophosphates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3309432A true US3309432A (en) | 1967-03-14 |
Family
ID=24005192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US504182A Expired - Lifetime US3309432A (en) | 1965-10-23 | 1965-10-23 | Process for upgrading thiophosphates |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US3309432A (en) |
| FR (1) | FR1496405A (en) |
| GB (1) | GB1152012A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3714301A (en) * | 1968-12-23 | 1973-01-30 | Cheminora As | Organic thiophosphates of improved odor characteristics and process for their production |
| US3925519A (en) * | 1974-05-06 | 1975-12-09 | Mobil Oil Corp | Deodorized mercaptan-containing phosphorotrithioites and process of preparation |
| US3961043A (en) * | 1970-08-12 | 1976-06-01 | Mobil Oil Corporation | Deodorized pesticidal organothiophosphorus compounds |
| US4000271A (en) * | 1972-08-25 | 1976-12-28 | Mobil Oil Corporation | Deodorized organothiophosphorus compounds with reduced toxicity |
| US4123525A (en) * | 1973-06-15 | 1978-10-31 | Ogawa & Co., Ltd. | Sublimable insecticidal compositions containing triisopropyl- or tritertiary-butyl-s-trioxane carriers |
| US20070010496A1 (en) * | 2005-07-06 | 2007-01-11 | Daniella Gutman | Process for Preparing Malathion for Pharmaceutical Use |
| US20070065474A1 (en) * | 2004-07-12 | 2007-03-22 | Sandhya Goyal | Topical gel formulation comprising organophosphate insecticide and its preparation thereof |
| US8012498B2 (en) | 2004-07-12 | 2011-09-06 | Sandhya Goyal | Topical gel formulation comprising organophosphate insecticide and preparation thereof |
-
1965
- 1965-10-23 US US504182A patent/US3309432A/en not_active Expired - Lifetime
-
1966
- 1966-09-14 GB GB41121/66A patent/GB1152012A/en not_active Expired
- 1966-10-11 FR FR79523A patent/FR1496405A/en not_active Expired
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3714301A (en) * | 1968-12-23 | 1973-01-30 | Cheminora As | Organic thiophosphates of improved odor characteristics and process for their production |
| US3961043A (en) * | 1970-08-12 | 1976-06-01 | Mobil Oil Corporation | Deodorized pesticidal organothiophosphorus compounds |
| US4000271A (en) * | 1972-08-25 | 1976-12-28 | Mobil Oil Corporation | Deodorized organothiophosphorus compounds with reduced toxicity |
| US4123525A (en) * | 1973-06-15 | 1978-10-31 | Ogawa & Co., Ltd. | Sublimable insecticidal compositions containing triisopropyl- or tritertiary-butyl-s-trioxane carriers |
| US3925519A (en) * | 1974-05-06 | 1975-12-09 | Mobil Oil Corp | Deodorized mercaptan-containing phosphorotrithioites and process of preparation |
| US8158139B2 (en) | 2004-07-12 | 2012-04-17 | Taro Pharmaceuticals North America, Inc. | Topical gel formulation comprising organophosphate insecticide and preparation thereof |
| US20070065474A1 (en) * | 2004-07-12 | 2007-03-22 | Sandhya Goyal | Topical gel formulation comprising organophosphate insecticide and its preparation thereof |
| US8012498B2 (en) | 2004-07-12 | 2011-09-06 | Sandhya Goyal | Topical gel formulation comprising organophosphate insecticide and preparation thereof |
| US20090124823A1 (en) * | 2005-07-06 | 2009-05-14 | Taro Pharmaceuticals North America, Inc. | Process for preparing malathion for pharmaceutical use |
| US7560445B2 (en) | 2005-07-06 | 2009-07-14 | Taro Pharmaceuticals North America, Inc. | Process for preparing malathion for pharmaceutical use |
| US7977324B2 (en) | 2005-07-06 | 2011-07-12 | Taro Pharmaceuticals North America, Inc. | Process for preparing malathion for pharmaceutical use |
| US20090124822A1 (en) * | 2005-07-06 | 2009-05-14 | Taro Pharmaceuticals North America, Inc. | Process for preparing malathion for pharmaceutical use |
| US8039657B2 (en) | 2005-07-06 | 2011-10-18 | Taro Pharmaceuticals North America, Inc. | Process for preparing malathion for pharmaceutical use |
| US20070010496A1 (en) * | 2005-07-06 | 2007-01-11 | Daniella Gutman | Process for Preparing Malathion for Pharmaceutical Use |
| US8536155B2 (en) | 2005-07-06 | 2013-09-17 | Taro Pharmaceuticals North America, Inc. | Process for preparing malathion for pharmaceutical use |
| US8957238B2 (en) | 2005-07-06 | 2015-02-17 | Taro Pharmaceuticals North America, Inc. | Process for preparing malathion for pharmaceutical use |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1152012A (en) | 1969-05-14 |
| FR1496405A (en) | 1967-09-29 |
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