US3179696A - Preparation of methane phosphonyl dichloride via phosgenation - Google Patents
Preparation of methane phosphonyl dichloride via phosgenation Download PDFInfo
- Publication number
- US3179696A US3179696A US404372A US40437254A US3179696A US 3179696 A US3179696 A US 3179696A US 404372 A US404372 A US 404372A US 40437254 A US40437254 A US 40437254A US 3179696 A US3179696 A US 3179696A
- Authority
- US
- United States
- Prior art keywords
- preparation
- phosphonyl dichloride
- methane
- phosgenation
- methane phosphonyl
- 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title description 6
- 238000002360 preparation method Methods 0.000 title description 6
- 150000001875 compounds Chemical class 0.000 description 8
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- -1 alkyl radicals Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MXBDBLBKBBAYGD-UHFFFAOYSA-N P(O)(O)=O.C Chemical compound P(O)(O)=O.C MXBDBLBKBBAYGD-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- WOAFDHWYKSOANX-UHFFFAOYSA-N diisopropyl methylphosphonate Chemical compound CC(C)OP(C)(=O)OC(C)C WOAFDHWYKSOANX-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 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
- 239000012263 liquid product Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000126 substance 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/42—Halides thereof
Definitions
- our invention concerns a method in which the following reaction takes place:
- R, R and R" being alkyl radicals.
- R, R and R" are alkyl radicals, the sum of the carbon atoms in R and R preferably not exceeding 8 and the number of carbon atoms in R" preferably not exceeding 4.
- R and R can be, or example, methyl, ethyl, n-propyl, n-butyl, Z-ethylhexyl and the like and R" can be, for example, methyl, ethyl, n-propyl, i-propyl, n-bu-tyl, and isobutyl.
Landscapes
- 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
United States Patent 3,179,696 PREPARATION OF METHANE PHOSPHONYL Di- CHLORIDE VIA PHOSGENATION Bernard B. Brown, Leland J. Lutz, and Charles J. Smith, In, Grand Island, N.Y., assignors to Olin Mathieson Chemical Corporation, a corporation of Virginia No Drawing. Filed Jan. 15, 1954, er. No. 404,372 1 Claim. (Cl. 268-543) Our invention relates to a method for the preparation of certain dichloro compounds by phosgenation.
More particularly, our invention concerns a method in which the following reaction takes place:
R, R and R" being alkyl radicals.
To the best of our knowledge, the aforementioned reaction has not heretofore been carried out at least on a satisfactory basis, and the carrying out of the reaction to produce the desired compounds at a rapid rate and in good yield based upon the amounts of reactants taken is difiicult of attainment. One of these reasons is the tendency of the ester used as a starting material to chlorinate insufiiciently with the formation of monochloro compounds of the formula:
This is undesirable in that it represents reactant loss. Other reasons why it is difficult to carry out the desired reaction rapidly and in good yield are found in the tendency of the aforementioned monochloro compounds to condense with themselves and also to react with the ester starting material to form an anhydr-ide as shown in the following equation: (RO)(Cl) P(O)R"+(RO) (:RO)P(O )R"- In accordance with our present invention, we have discovered that by the use of certain critical reaction conditions, particularly relative amounts of reactants, temperature and pressure, it is possible to convert in high yield and at a rapid rate a phosphonate of the formula:
to a compound of the formula:
by reaction with phosgene, where R, R and R" are alkyl radicals. Thus, in accordance with our invention we react the phosphonate of the formula:
with from 2 to 3 molar amounts of phosgene at 100- 200" C. and at a pressure of 100-600 p.s.i.g., thereby rapidly producing a high yield of the desired product with minimum formation of by-products.
The following example illustrates the preparation of methane phosphonyl dichloride by the phosgenation of cliisopropyl methane phosphonate in accordance with the method which we have devised:
Pure diisopropyl methane phosphonate (11, of 1.4079) in the amount of one mole was reacted with 2.5 moles of liquid phosgene at a temperature of 100-120 C. and at a pressure of 350 p.s.i.g. fora period of 28 minutes. The reaction mixture was thereafter distilled at an absolute pressure of 1-2 mm. of mercury to yield a water-white liquid distillate which solidified rapidly to a colorless solid melting slightly above room temperature. The yield of the desired product, methane phosphonyl dichloride, was 48.5 percent. in two determinations, the product analyzed 52.47 and 52.67 percent hydrolyzable chlorine, the theoretical percentage for methane phosphonyl dichloride be ing 53.4 percent.
A similar experiment using the same proportions and pressure was run at a temperature of -95 C. Distillation at an absolute pressure of 12 mm. of mercury gave a colorless liquid product which on cooling precipitated only a very small amount of solid similar to that described in the preceding paragraph. Thus, the carrying out of the reaction at temperatures of 90-95 C. is undesirable.
Various modifications can be made in the specific procedures just described to provide other embodiments which fall within the broad scope of our invention. Thus, our invention is generally applicable in the preparation of compounds of the formula:
by reacting compounds of the formula:
with phosgene under the conditions specified. In the two preceding formulas, R, R and R" are alkyl radicals, the sum of the carbon atoms in R and R preferably not exceeding 8 and the number of carbon atoms in R" preferably not exceeding 4. Thus, R and R can be, or example, methyl, ethyl, n-propyl, n-butyl, Z-ethylhexyl and the like and R" can be, for example, methyl, ethyl, n-propyl, i-propyl, n-bu-tyl, and isobutyl.
We claim:
A method for the preparation of a compound of the generic formula:
which comprises reacting a compound of the formula:
(R n m 0) (R") with from 2.0 to 3.0 molar amounts of phosgene at a temperature within the range of IOU-200 C. and a pressure within the range of -600 p.s.i.g., R and R being isopropyl radicals and R" being a methyl radical.
References Cited by the Examiner UNITED STATES PATENTS 8/58 Dawson et al. 260--543 3/60 Dawson et al. 260-543
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US404372A US3179696A (en) | 1954-01-15 | 1954-01-15 | Preparation of methane phosphonyl dichloride via phosgenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US404372A US3179696A (en) | 1954-01-15 | 1954-01-15 | Preparation of methane phosphonyl dichloride via phosgenation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3179696A true US3179696A (en) | 1965-04-20 |
Family
ID=23599338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US404372A Expired - Lifetime US3179696A (en) | 1954-01-15 | 1954-01-15 | Preparation of methane phosphonyl dichloride via phosgenation |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3179696A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4849724A (en) * | 1971-10-26 | 1973-07-13 | ||
| FR2208913A1 (en) * | 1972-12-05 | 1974-06-28 | Hoechst Ag | |
| US3950413A (en) * | 1971-10-26 | 1976-04-13 | Hoechst Aktiengesellschaft | Process for the preparation of phosphonic acid dihalides |
| EP0047460A1 (en) * | 1980-09-06 | 1982-03-17 | Hoechst Aktiengesellschaft | Process for the preparation of vinyl phosphoric-acid dichloride and 2-chloroethane phosphoric-acid dichloride |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2847469A (en) * | 1955-04-26 | 1958-08-12 | Thomas P Dawson | Method of manufacture of rp(o) cl2 from rp(o)(or)2 and socl2 |
| US2929843A (en) * | 1949-09-20 | 1960-03-22 | Thomas P Dawson | Process for the manufacture of methyl dichloro phosphine oxide |
-
1954
- 1954-01-15 US US404372A patent/US3179696A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2929843A (en) * | 1949-09-20 | 1960-03-22 | Thomas P Dawson | Process for the manufacture of methyl dichloro phosphine oxide |
| US2847469A (en) * | 1955-04-26 | 1958-08-12 | Thomas P Dawson | Method of manufacture of rp(o) cl2 from rp(o)(or)2 and socl2 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4849724A (en) * | 1971-10-26 | 1973-07-13 | ||
| US3950413A (en) * | 1971-10-26 | 1976-04-13 | Hoechst Aktiengesellschaft | Process for the preparation of phosphonic acid dihalides |
| FR2208913A1 (en) * | 1972-12-05 | 1974-06-28 | Hoechst Ag | |
| EP0047460A1 (en) * | 1980-09-06 | 1982-03-17 | Hoechst Aktiengesellschaft | Process for the preparation of vinyl phosphoric-acid dichloride and 2-chloroethane phosphoric-acid dichloride |
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