GB2194239A - Process for the thiophosphorylation of alcohols or phenols - Google Patents
Process for the thiophosphorylation of alcohols or phenols Download PDFInfo
- Publication number
- GB2194239A GB2194239A GB08718040A GB8718040A GB2194239A GB 2194239 A GB2194239 A GB 2194239A GB 08718040 A GB08718040 A GB 08718040A GB 8718040 A GB8718040 A GB 8718040A GB 2194239 A GB2194239 A GB 2194239A
- Authority
- GB
- United Kingdom
- Prior art keywords
- ultrasound
- alcohol
- metal salt
- reaction
- phosphorous
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 19
- 150000001298 alcohols Chemical class 0.000 title claims description 6
- 238000006863 thiophosphorylation reaction Methods 0.000 title claims description 5
- 150000002989 phenols Chemical class 0.000 title description 2
- 238000002604 ultrasonography Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 12
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical class OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 claims description 9
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- 230000026731 phosphorylation Effects 0.000 claims description 7
- 238000006366 phosphorylation reaction Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000010687 lubricating oil Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- 239000007866 anti-wear additive Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 description 5
- -1 aromatic alcohols Chemical class 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical class CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical class CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Lubricants (AREA)
Description
SPECIFICATION
Process for the thiophosphorylation of alcohols
The present invention relates to a process for the thiophosphorylation of alcohols with phosphorous sulphide. The product of this phosphorylation is a dithiophosphoric acid derivative which is an intermediate in the preparation of additives for lubricating oils.
These additives are prepared in two steps. The first step comprises the phosphorylation of the alcohol with phosphorous sulphide and the second step comprises the treatment of the phosphorylated product with a metal oxide, hydroxide and/or salt.
The first step of this process takes place slowly. In order to obtain commercially feasible reaction rates it may be necessary to heat the reaction mixture to temperatures at which decomposition of the phosphorylation product may occur. This step is particularly slow in the case of the phosphorylation of phenol or substituted phenols, and heating is likely to cause some decomposition of the phosphorylated product.
It has now been found that satisfactory reaction rates can be obtained at low temperatures if ultrasound is applied during the phosphorylation. "Ultrasound" is the term used to designate sonic radiation with a frequency at or above that audible to the human ear, i.e. normally at least 20kHz, and usually from 20kHz to 60kHz. Accordingly, the present invention provides a process for the thiophosphorylation of alcohols which comprises contacting the alcohol with phosphorous sulphide and subjecting the reaction mixture to ultrasound.
The alcohol employed can be any primary, secondary or tertiary alcohol. Suitable alcohols include alkanols, such as the pentanols and hexanols, cycloalkanols, such as cyclohexanol, bi- or tri-cycloalkanols, aromatic alcohols, such as phenol and naphthol, arylalkyl alcohols such as benzyl alcohol, all of which may be substituted by one or more alkyl or alkoxy groups. Preferably the alcohol is selected from a C1 20 alkanol, C58 cycloalkanol optionally substituted with one or more C14 alkyl groups, phenol and C1 25-alkyl phenol. In case of alkylphenols it was found that the p-alkyl phenols were somewhat more reactive than the 0- or m-alkyl phenols.The phosphorous sulphide employed can be tetraphosphorous heptasulphide or tetraphosphorous trisulphide, but is preferably phosphorous pentasulphide.
The process according to the invention can be carried out in a diluent. However, it is preferred to work with a reaction mixture which consists essentially of phosphorous sulphide and the alcohol. The molar ratio of the two reactants may' vary within a wide range, such as from 0.1 to 10 equivalent alcohol per equivalent phosphorous sulphide; it is however preferred to employ substantially stoichoimetric quantities of the reactants. Thus, when phosphorous pentasulphide is used the molar ratio of sulphide:alcohol is suitably about 1:4.
The reaction rate is directly influenced by the intensity of the ultrasound, though the upper limit is largely conditioned by practical and economic considerations. On the one hand the sound intensity should not be so high that carrying out the process would become very expensive; high levels can also cause practical problems of cavitation. On the other hand there is little benefit if the sound intensity is so low that the reaction rate is hardly increased. Good results are normally obtained with a sound intensity from 30 to 300 W/cm2. The frequency of the ultrasound is not critical, but for practical convenience it is desirably in the range generated by readily available equipment. Good results can be obtained by using sound frequencies between 15 and 100kHz.
Ultrasound may be employed during part of the reaction only, but since the accelerated reaction rate normally occurs only during the period in which ultrasound is actually applied, it is preferred to apply ultrasound during the entire reaction time.
The reaction temperature can be selected from as low as feasible to the temperature where the phosphorylated product gets unstable. Preferably the temperature ranges from 0 to 150"C, in particular from 20 to 110 C. The reaction may be carried out at elevated pressure, though atmospheric pressure is normally more convenient.
As stated above, the phosphorylated product is an intermediate in the preparation of additives for lubricating oils. Those addivites are the metal salts of such products. Accordingly, the present invention further provides a process for the preparation of metal salts of dithiophosphoric acid derivatives which comprises the phosphorylation of an alcohol with phosphorous sulphide as described above, followed by conversion of the phosphorylated product to the metal salt by reaction with a metal oxide, hydroxide or by using a base and a metal salt. Preferred metals include group I and group II metals, such as sodium and especially zinc. These zinc salts are preferably obtained by treating the phosphorylated product with zinc oxide.
It is possible to add more than the stoichiometric amount of metal oxide or hydroxide to the phosphorylated product to create a basic metal salt prepared according to the invention. This basic salt may also be formed by the reaction of a neutral metal salt of a dithiophosphoric acid derivative with a metal oxide or hydroxide. The formation of the (basic) metal salt from the phosphorylated product and (an excess of) the metal oxide or hydroxide, can also be promoted by the use of ultrasound. This finding, combined with the teaching of the present invention enables a convenient one-step synthesis of a metal salt of dithiophosphoric acid derivative.
Accordingly, the present invention further relates to a process for the preparation of a metal salt of a dithiophosphoric acid derivative which comprises mixing an alcohol, a phosphorous sulphide and a metal oxide and/or metal hydroxide and subjecting the resulting mixture to ultrasound. The metal salt includes both neutral salts and basic salts. In this one-step process the alcohol is first phosphorylated, and subsequently the phosphorylated product reacts with the metal oxide or hydroxide.
The metal salts, in particular the zinc salts, of the dithiophosphoric acid derivatives prepared according to the invention are commercially used as anti-wear additives in lubricating oils.
The invention is illustrated in the following Examples.
Example 1
40.59 (1 lOmmole) of C1818 alkyl phenol was mixed in a vessel with 6.49 (29mmole) of phosphorous pentasulphide. The reaction mixture was kept at a temperature of 50"C and subjected to ultrasound at a frequency of 20kHz and a sound intensity of 150W/cm2. The reaction was stopped after 55 hours, and 389 of di(C16 ,8 alkylphenyl)dithio-phosphoric acid was obtained after purification of the reaction mixture by filtration (yield 72.8%).
As comparison a similar experiment carried without the application of ultrasound produced the dithiqphosphoric acid derivative in a yield of only 18.8%.
Example 2
The reaction described in Example I was repeated, but with the procedural variations described below.
In experiment 2a ultrasound was applied in a pulsed fashion: 1/3 s sound, 2/3 s no sound, yielding an ultrasound employment during 33% of the time. In experiment 2b no ultrasound was applied, but the reactor mixture was continuously stirred. Experiments 2c and 2e were carried out under the continuous impact of ultrasound whilst in experiments 2d and 2f, like in 2b, only stirring occurred. The reaction between C16 18 alkylphenol and P2S5 (in stoichiometric amounts) gave the results as indicated in the Table below.
Table 1
Exper. Ultrasound Reaction Yield No. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ dithiophosphoric Frequency Intensity Duration Temp. Time acid derivative kHz W/cm2 % react. C" h time 2a 20 150 30 38 70 15 2b - - - 38 70 2 2c 20 150 100 65 46 75 2d - - - 65 47 34 2e 20 80 100 95 1.5 87 2f - - - 95 7.5 54 From the above results it is clearly evident that the application of ultrasound provides substantially accelerated reaction rates and enhanced product yields.
Claims (8)
1. Process for the thiophosphorylation of alcohols which comprises contacting the alcohol with phosphorous sulphide and subjecting the reaction mixture to ultrasound.
2. Process according to claim 1, in which the alcohol is a C1 20 alkanol, C58 cycloalkanol, optionally substituted with one or more C14 alkyl groups, phenol, or C1 25-alkyl phenol.
3. Process according to claim 1 or 2, in which phosphorous pentasulphide is employed.
4. Process according to any one of claims 1-3, in which the frequency of the ultrasound is from 15 to 100kHz, and the ultrasound intensity is from 30 to 300W/cm2.
5. Process for the preparation of a metal salt of a dithiophosphoric acid derivative which comprises phosphorylation of an alcohol with a phosphorous sulphide according to a process as claimed in any one of claims 1-4, followed by conversion of the phosphorylated product to the metal salt by reaction with a metal oxide or hydroxide or by using a base and a metal salt.
6. Process according to claim 5, in which the phosphorylated product is converted to the zinc salt by reaction with zinc oxide.
7. Process for the preparation of a metal salt of a dithiophosphoric acid derivative which comprises mixing an alcohol, a phosphorous sulphide and a metal oxide or hydroxide, and subjecting the resulting mixture to ultrasound.
8. Use of the metal salt prepared in the process according to any one of claims 5 to 7 as anti-wear additive in a lubricating oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8718040A GB2194239B (en) | 1986-08-01 | 1987-07-30 | Process for the thiophosphorylation of alcohols or phenols |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB868618861A GB8618861D0 (en) | 1986-08-01 | 1986-08-01 | Phosphorylation of alcohols |
| GB8718040A GB2194239B (en) | 1986-08-01 | 1987-07-30 | Process for the thiophosphorylation of alcohols or phenols |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8718040D0 GB8718040D0 (en) | 1987-09-03 |
| GB2194239A true GB2194239A (en) | 1988-03-02 |
| GB2194239B GB2194239B (en) | 1990-05-23 |
Family
ID=26291114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8718040A Expired - Fee Related GB2194239B (en) | 1986-08-01 | 1987-07-30 | Process for the thiophosphorylation of alcohols or phenols |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2194239B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993006195A1 (en) * | 1991-09-19 | 1993-04-01 | Exxon Chemical Patents Inc. | Overbased metal-containing detergents |
| US5624999A (en) * | 1991-03-05 | 1997-04-29 | Exxon Chemical Patents Inc. | Manufacture of functionalized polymers |
-
1987
- 1987-07-30 GB GB8718040A patent/GB2194239B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5624999A (en) * | 1991-03-05 | 1997-04-29 | Exxon Chemical Patents Inc. | Manufacture of functionalized polymers |
| WO1993006195A1 (en) * | 1991-09-19 | 1993-04-01 | Exxon Chemical Patents Inc. | Overbased metal-containing detergents |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8718040D0 (en) | 1987-09-03 |
| GB2194239B (en) | 1990-05-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19960730 |