US2430569A - Method of the production of neutral esters of phosphoric acid - Google Patents
Method of the production of neutral esters of phosphoric acid Download PDFInfo
- Publication number
- US2430569A US2430569A US513471A US51347143A US2430569A US 2430569 A US2430569 A US 2430569A US 513471 A US513471 A US 513471A US 51347143 A US51347143 A US 51347143A US 2430569 A US2430569 A US 2430569A
- Authority
- US
- United States
- Prior art keywords
- alkyl
- pyrophosphate
- phosphoric acid
- ethyl
- preparing
- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title description 26
- 238000000034 method Methods 0.000 title description 21
- 150000002148 esters Chemical class 0.000 title description 19
- 230000007935 neutral effect Effects 0.000 title description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 title description 4
- 238000004519 manufacturing process Methods 0.000 title description 2
- 235000011180 diphosphates Nutrition 0.000 description 16
- 150000001241 acetals Chemical class 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 235000011007 phosphoric acid Nutrition 0.000 description 12
- -1 ethyl butyral Chemical compound 0.000 description 11
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 10
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 10
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- IDCBOTIENDVCBQ-UHFFFAOYSA-N TEPP Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OCC IDCBOTIENDVCBQ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000005341 metaphosphate group Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- OJDJHGIXNZPZFD-UHFFFAOYSA-N ethyl dihydrogen diphosphate Chemical class CCO[P@](O)(=O)OP(O)(O)=O OJDJHGIXNZPZFD-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
Definitions
- One object of our invention is to provide a method of preparing phosphoric acid esters in an economical manner. This economy is realized by the use of less expensive starting material, by obtaining the product in good yield, and by recovering the product merely by vacuum distillation in a form suiiiciently pure for use commercially.
- the alkyl or aryl meta phosphate or pyrophosphate or their mixture employed as the starting materials for our process may be prepared, for instance, by reacting P205 withan ether, the latter not being present in more than a theoretical amount or by treating triethyl phosphate with P205 to convert it to the meta phosphate or pyrophosphate.
- the alkyl meta phosphate or the pyrophosphate or their mixture and the acetal are mixed together and subjected to a temperature of at least 65 C. for several hours so as to form the desired product.
- alkyl meta phosphates or pyrophosphates may be employed such as those in which the alkyl group is methyl, normal or isopropyl or normal or isobutyl.
- an aryl meta phosphate or pyrophosphate may be employed such as phenyl or cresyl meta phosphate or pyrophosphate.
- the acetal employed may be any of the com- (cl. etc-4st) pounds of this type, a simple and effective compound which may be employed being ethyl butyral.
- acetals such as ethyl propional, methyl butyral, or in fact any of the 5 acetals particularly those prepared from an aidehyde having 4 ormore carbon atoms may be employed.
- the alkyl meta phosphate or pyrophosphate employed as a starting material is preferably prepared immediately prior to use and the reaction mass containing that material is employed in the reaction.
- ethyl meta'phosphate and pyrophosphate may be prepared by reacting P205 more than theoretical amount.
- triethyl phosphate may be prepared in accordance with the method described in Hull and Snodgrass application, Serial No. 513,472, now United States Patent 2,407,279, dated Sept. 10, 1946, filed of even date and the ethyl meta phosphate may be prepared therefrom by reacting the triethyl phosphate with P205.
- the triethyl phosphate used may be prepared by reactions known in the prior art. The time employed for the reaction is not critical depending upon the vigorousness of the treatment and whether or not a catalyst is employed. Any commonly known esteriflcation catalyst may be patible with the constituents of the reaction mass.
- Some of the catalysts which may be mentioned as suitable are sulfuric acid, phosphoric acid, zinc;
- Example acid esters are obtained in a more pure state than by methods previously described in the prior art. Also, the phosphoric acid esters prepared in accordance with our procedure maybe separated from the reaction ingredients by vacuum distillation thus avoiding the necessity of expensive purifying procedures.
- the method of preparing triethyl phosphate which comprises treating tetraethylpyrophosphate with ethyl butyral.
- the method of preparing a neutral ester of orthophosphoric acid which comprises treating an ester of the group consisting of alkyl metaphosphates and alkyl pyrophosphates, the alkyl being of 1-4 carbon atoms, with an acetal of 6-8 carbon atoms at 0-200 C.
- the method of preparing a neutral ester of orthophosphoric acid which comprises treating an alkyl metaphosphate, the alkyl being of 1 to 4 carbon atoms with an acetal of 6-8 carbon atoms at 0-200 C.
- the method of preparing a neutral ester of orthophosphoric acid which comprises treating an alkyl pyrophosphate, the alkyl being of l-4 carbon atoms with an acetal of 6-8 carbon atoms at 0-200 0.
- the method of preparing a neutral ester of orthophosphoric acid which comprises treating an ester of the group consisting of ethyl metacarbon atoms at 0-200 C.
- the method of preparing a neutral ester oi? orthophosphoric acid which comprises treating an ester of the group consisting of alkyl metaphosphates and alkyl pyrophosphates, the aikyl being of 1-4 carbon atoms with ethyl butyral at 0-200 C.
- the method of preparing a neutral ester of orthophosphoric acid which comprises treating an ester of the group consisting of alkyl meta-v phosphate and alkyl pyrophosphate, the alkyl being of 1-4 carbon atoms with ethyl propional.
- the method of preparing a, neutral ester of orthophosphoric acid which comprises treating an ester of the group consisting of alkyl metaphosphate and alkyl pyrophosphate, the alkyl being of 1-4 carbon atoms with methyl butyral.
- a method of preparing a neutral ester of orthophosphoric acid which comprises treating ethyl metaphosphate with an acetal of 6-8 carbon atoms at 0-200" 0.
- a method of preparing a neutral ester of orthophosphoric acid which comprises treating tetra ethyl pyrophosphate with an acetal of 6-8 DAVID C. HUIL. ALBERT H. AGE 'IT.
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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)
Description
Patented Nov. 11, 1947 METHOD 01* T PRODUCTION F NEU- TEAL ESTERS 0F PHOSPHQRKC AEKD I David 0. Hull and Albert H. dgett; Kingsport, Tenn, assignors to Eastman Kodak Company, Rochester, N.,Y., a corporation of New Jersey Application December 8, 1943,
Serial No. 513,471
, phenols and either phosphorous pentachlori'de or P205. These various methods whichhave been suggested heretofore have involved either the use of expensive starting materials or dificulty and I expense in refining the products obtained. Also,
in many cases side reactions have occurred cutting down the yields.
One object of our invention is to provide a method of preparing phosphoric acid esters in an economical manner. This economy is realized by the use of less expensive starting material, by obtaining the product in good yield, and by recovering the product merely by vacuum distillation in a form suiiiciently pure for use commercially.
We have found that the reaction of an alkyl meta phosphate or pyrophosphate with an acetal at an elevated temperature results in neutral esters of phosphoric acid which are of value for the various uses to which such compounds are put at the present time. The reaction may either be carried out without a catalyst or may be promoted by the use of an esteriflcation catalyst if desired.
The alkyl or aryl meta phosphate or pyrophosphate or their mixture employed as the starting materials for our process may be prepared, for instance, by reacting P205 withan ether, the latter not being present in more than a theoretical amount or by treating triethyl phosphate with P205 to convert it to the meta phosphate or pyrophosphate. The alkyl meta phosphate or the pyrophosphate or their mixture and the acetal are mixed together and subjected to a temperature of at least 65 C. for several hours so as to form the desired product. Instead of ethyl meta phosphate 'or pyrophosphate, other alkyl meta phosphates or pyrophosphates may be employed such as those in which the alkyl group is methyl, normal or isopropyl or normal or isobutyl. If desired, an aryl meta phosphate or pyrophosphate may be employed such as phenyl or cresyl meta phosphate or pyrophosphate.
The acetal employed may be any of the com- (cl. etc-4st) pounds of this type, a simple and effective compound which may be employed being ethyl butyral. However, other acetals such as ethyl propional, methyl butyral, or in fact any of the 5 acetals particularly those prepared from an aidehyde having 4 ormore carbon atoms may be employed.
As the acetals are not decidedly low boiling ordinarily the reaction in accordance with our pressure and it is preferred to carry out the reaction under moderate temperature conditions. Nevertheless it is to be understood that higher temperatures are not precluded, the only criterion being that the temperature be limited so as to not generate pressure which would be destructive of equipment or materials. We have found that the reaction of the acetal and a metaphosphate or pyrophosphate takes place readily and, therefore, a, wide temperature latitude is permissible. In practical operation a temperature of 80 C. is ordinarily preferred. However, ranging from 0 0. up to 200 C. are useful in the carrying out of our process, the most suitable temperatures in this range being a matter of selection depending on the reaction materials employed, particularly the acetals chosen.
The alkyl meta phosphate or pyrophosphate employed as a starting material is preferably prepared immediately prior to use and the reaction mass containing that material is employed in the reaction. For instance, ethyl meta'phosphate and pyrophosphate may be prepared by reacting P205 more than theoretical amount. However, if desired, triethyl phosphate may be prepared in accordance with the method described in Hull and Snodgrass application, Serial No. 513,472, now United States Patent 2,407,279, dated Sept. 10, 1946, filed of even date and the ethyl meta phosphate may be prepared therefrom by reacting the triethyl phosphate with P205. If desired, the triethyl phosphate used may be prepared by reactions known in the prior art. The time employed for the reaction is not critical depending upon the vigorousness of the treatment and whether or not a catalyst is employed. Any commonly known esteriflcation catalyst may be patible with the constituents of the reaction mass.
Some of the catalysts which may be mentioned as suitable are sulfuric acid, phosphoric acid, zinc;
invention may be carried out at atmospheric temperatures and diethyl ether, the latter being present in no used to promote'the reaction providing it is comtral ester of phosphoric acid in accordance with our invention.
Example acid esters are obtained in a more pure state than by methods previously described in the prior art. Also, the phosphoric acid esters prepared in accordance with our procedure maybe separated from the reaction ingredients by vacuum distillation thus avoiding the necessity of expensive purifying procedures.
We claim: 1. The method of preparing triethyl phosphate which comprises treating ethyl metaphosphate with ethyl butyral.
2. The method of preparing triethyl phosphate which comprises treating tetraethylpyrophosphate with ethyl butyral.
3. The method of preparing a neutral ester of orthophosphoric acid which comprises treating an ester of the group consisting of alkyl metaphosphates and alkyl pyrophosphates, the alkyl being of 1-4 carbon atoms, with an acetal of 6-8 carbon atoms at 0-200 C.
4. The method of preparing a neutral ester of orthophosphoric acid which comprises treating an alkyl metaphosphate, the alkyl being of 1 to 4 carbon atoms with an acetal of 6-8 carbon atoms at 0-200 C.
5. The method of preparing a neutral ester of orthophosphoric acid which comprises treating an alkyl pyrophosphate, the alkyl being of l-4 carbon atoms with an acetal of 6-8 carbon atoms at 0-200 0.
6. The method of preparing a neutral ester of orthophosphoric acid which comprises treating an ester of the group consisting of ethyl metacarbon atoms at 0-200 C.
'4 phosphates and ethyl pyrophosphates with an acetal of 6-8 carbon atoms at 0-200 C.
7. The method of preparing a neutral ester oi? orthophosphoric acid which comprises treating an ester of the group consisting of alkyl metaphosphates and alkyl pyrophosphates, the aikyl being of 1-4 carbon atoms with ethyl butyral at 0-200 C.
8. The method of preparing a neutral ester of orthophosphoric acid which comprises treating an ester of the group consisting of alkyl meta-v phosphate and alkyl pyrophosphate, the alkyl being of 1-4 carbon atoms with ethyl propional.
9. The method of preparing a, neutral ester of orthophosphoric acid which comprises treating an ester of the group consisting of alkyl metaphosphate and alkyl pyrophosphate, the alkyl being of 1-4 carbon atoms with methyl butyral.
10. A method of preparing a neutral ester of orthophosphoric acid which comprises treating ethyl metaphosphate with an acetal of 6-8 carbon atoms at 0-200" 0.
11; A method of preparing a neutral ester of orthophosphoric acid which comprises treating tetra ethyl pyrophosphate with an acetal of 6-8 DAVID C. HUIL. ALBERT H. AGE 'IT.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS OTHER REFERENCES Chemical Abstracts, vol. 31, 1937, pp. 2166-2167 (abstract of article byWagner-Jauregg et al. in Berichte).
Feiser et al., Organic Chemistry, page 32 (1944), Heath 8: Co., publishers, Boston.
Science News Letter, March 22, 1947, page 188.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US513471A US2430569A (en) | 1943-12-08 | 1943-12-08 | Method of the production of neutral esters of phosphoric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US513471A US2430569A (en) | 1943-12-08 | 1943-12-08 | Method of the production of neutral esters of phosphoric acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2430569A true US2430569A (en) | 1947-11-11 |
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ID=24043418
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US513471A Expired - Lifetime US2430569A (en) | 1943-12-08 | 1943-12-08 | Method of the production of neutral esters of phosphoric acid |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2430569A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3205285A (en) * | 1961-01-19 | 1965-09-07 | Exxon Research Engineering Co | Sulfonation of an olefin polymer |
| DE977642C (en) * | 1949-04-13 | 1967-11-23 | Durand & Huguenin Ag | Wetting agents |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2052029A (en) * | 1935-12-31 | 1936-08-25 | Benjamin R Harris | Phosphoric acid esters |
| GB481557A (en) * | 1936-06-05 | 1938-03-07 | Ig Farbenindustrie Ag | Manufacture of isocyclic compounds |
| US2325597A (en) * | 1941-01-13 | 1943-08-03 | Standard Oil Co California | Compounded mineral oil |
-
1943
- 1943-12-08 US US513471A patent/US2430569A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2052029A (en) * | 1935-12-31 | 1936-08-25 | Benjamin R Harris | Phosphoric acid esters |
| GB481557A (en) * | 1936-06-05 | 1938-03-07 | Ig Farbenindustrie Ag | Manufacture of isocyclic compounds |
| US2325597A (en) * | 1941-01-13 | 1943-08-03 | Standard Oil Co California | Compounded mineral oil |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE977642C (en) * | 1949-04-13 | 1967-11-23 | Durand & Huguenin Ag | Wetting agents |
| US3205285A (en) * | 1961-01-19 | 1965-09-07 | Exxon Research Engineering Co | Sulfonation of an olefin polymer |
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