KR950011360B1 - Method of preparating triarylphosphate - Google Patents
Method of preparating triarylphosphate Download PDFInfo
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- KR950011360B1 KR950011360B1 KR1019920026026A KR920026026A KR950011360B1 KR 950011360 B1 KR950011360 B1 KR 950011360B1 KR 1019920026026 A KR1019920026026 A KR 1019920026026A KR 920026026 A KR920026026 A KR 920026026A KR 950011360 B1 KR950011360 B1 KR 950011360B1
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- triaryl phosphite
- phosphite
- xylene
- yield
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- 238000000034 method Methods 0.000 title abstract description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008096 xylene Substances 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- LIGHQFMXKLNVMQ-UHFFFAOYSA-N [Cl].[Cl].[Cl].[P] Chemical compound [Cl].[Cl].[Cl].[P] LIGHQFMXKLNVMQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- -1 hydroxy group compound Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- PYFJQRSJTZCTPX-UHFFFAOYSA-N tris(2,3-ditert-butylphenyl) phosphite Chemical compound CC(C)(C)C1=CC=CC(OP(OC=2C(=C(C=CC=2)C(C)(C)C)C(C)(C)C)OC=2C(=C(C=CC=2)C(C)(C)C)C(C)(C)C)=C1C(C)(C)C PYFJQRSJTZCTPX-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
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
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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)
Abstract
Description
본 발명은 용매로 특정한 복합용매를 사용함으로서 삼할로겐화인화합물과 히드록시가 치환된 방향족 화합물로부터 산화방지제인 트리아릴포스파이트를 고수율로 제조하는 방법에 관한 것이다.The present invention relates to a method of producing triaryl phosphite, an antioxidant, from a phosphorus trihalide compound and a hydroxy substituted aromatic compound in a high yield by using a specific complex solvent as a solvent.
일반적으로 트리아릴포스파이트는 삼할로겐화인과 히드록시 치환방향족 화합물과 반응시켜 제조하게 되며, 특히 아릴기를 치환시킨 히드록시기 화합물을 반응시키는 경우에는 반응성이 낮으므로 130℃의 고온에서 반응시키지 않으면 안된다.In general, triaryl phosphite is prepared by reacting a phosphorus trihalide with a hydroxy substituted aromatic compound. In particular, when the aryl group-substituted hydroxy group compound is reacted, the triaryl phosphite must be reacted at a high temperature of 130 ° C.
그러나 고온에서 장시간 반응시켜도 완전한 반응이 이루어지기는 불충분하며, 반응결과 모노-, 디- 및 트리-아릴포스파이트 등의 혼합물이 얻어진다.However, even after prolonged reaction at high temperature, a complete reaction is insufficient. As a result, a mixture of mono-, di- and tri-aryl phosphites is obtained.
종래 트리아릴포스파이트를 제조하는 방법으로는 일본 공개특허 소 54-30140호를 들 수 있는데, 이 방법에서는 삼할로겐화인과 ROH(식중 R은 아릴기, 알킬기, 사이크로알킬기, 아릴 또는 알킬기의 1종 또는 2종 이상의 기로 치환시킨 아릴기를 의미)로 표현되는 히드록시 치환방향족 화합물을 0,005~5몰%의 아민, 암모늄염, 카르복시산 등의 촉매하에서, 크실렌이 단독용매를 사용하여 트리아릴포스파이트를 제조하는 방법을 제시하고 있다.A conventional method for preparing triaryl phosphite is Japanese Patent Application Laid-Open No. 54-30140, in which phosphorus trihalide and ROH (wherein R is an aryl group, an alkyl group, a cycloalkyl group, an aryl or an alkyl group) Xylene is a triaryl phosphite using a single solvent of 0,005 to 5 mol% of a hydroxy substituted aromatic compound represented by an aryl group substituted with a species or two or more groups) under a catalyst such as amine, ammonium salt, or carboxylic acid. How to do it.
따라서 수율을 높이기 위하여 촉매로서 피리딘과 같은 질소화합물을 사용한 예가 소련 특허 제488821호에 있으나, 어느 정도의 반응성은 증가하지만 역시 크게 효과가 있는 것은 아니었으며, 특히 치환된 아릴을 사용하면 디-혹은 트리아릴포스파이트의 혼합물이 얻어지므로 역시 트리아릴포스파이트가 낮은 수율로 얻어지게 되며, 염의 침전으로 교반이 어려워진다.Thus, there is an example of using a nitrogen compound such as pyridine as a catalyst to increase the yield in US Pat. No. 488821, but the degree of reactivity is increased but also not very effective, especially when substituted aryl is used to di- or tree Since a mixture of arylphosphites is obtained, triaryl phosphites are also obtained in low yields, and the precipitation of salts makes stirring difficult.
그러나 이 방법으로 제조한 트리아릴포스파이트는 수율이 60% 정도로 매우 저조하였다.However, the triaryl phosphite prepared by this method was very low yield of about 60%.
따라서 본 발명의 목적은 삼할로겐화인과 히드록시 치환방향족화합물로부터 보다 낮은 반응온도에서 고수율로 트리아릴포스파이트를 제조하는 방법을 제공하고자 하는 것이다.It is therefore an object of the present invention to provide a process for the production of triaryl phosphites in high yield at lower reaction temperatures from phosphorus trihalide and hydroxy substituted aromatic compounds.
즉, 본 발명은 삼할로겐화인과 히드록시 치환방향족화합물을 테트라메틸헥사메틸렌디아민과 방향족화합물의 복합용매하에서 50~90℃로 반응시켜 다음 구조식(I)로 표시되는 트리아릴포스파이트를 제조하는 방법이다.That is, the present invention is a method for producing a triaryl phosphite represented by the following structural formula (I) by reacting a phosphorus trihalide hydroxy substituted aromatic compound at 50 ~ 90 ℃ in a complex solvent of tetramethylhexamethylenediamine and an aromatic compound to be.
[-R-O-]3, P……………………………………………………(I)[-RO-] 3 , P... … … … … … … … … … … … … … … … … … … … (I)
(여기서, R은 아릴기, 직쇄 가지를 갖는 알킬기, 1종 혹은 2종의 치환기를 갖는 방향족화합물을 나타낸다.)(Wherein R represents an aryl group, an alkyl group having a linear branch, and an aromatic compound having one or two substituents.)
본 발명에서 사용하는 복합용매 성분중 테트라메틸헥사메틸렌디아민(TMHD)은 촉매겸 반응용매로 사용되어 반응속도를 증가시켜 주며, 방향족 용매를 동시에 사용하므로 상승효과(SYNERGY EFFECT)에 의해 50~90℃의 낮은 온도하에서 반응속도가 상승할 뿐 아니라 부생성물이 거의 없는 80~95% 수율의 순수한 트리아릴포스파이트가 제조된다.Tetramethylhexamethylenediamine (TMHD) in the composite solvent component used in the present invention is used as a catalyst and a reaction solvent to increase the reaction rate, 50-90 ℃ by the synergistic effect (SYNERGY EFFECT) by using an aromatic solvent at the same time Under the low temperature of, the reaction rate is increased, and pure triaryl phosphite is produced in 80-95% yield with little byproduct.
본 발명에서는 방향족화합물로는 벤젠, 톨루엔, 크실렌, 에틸벤젠, 메톡시벤젠 등을 사용할 수 있다.In the present invention, as the aromatic compound, benzene, toluene, xylene, ethylbenzene, methoxybenzene and the like can be used.
용매인 테트라메틸헥사메틸렌디아민과 방향족화합물의 사용비는 무게비로 2 : 1이며, 이 수치보다 방향족화합물을 더 사용하면 반응 부생성물이 제조되어 수율이 떨어지게 되며, 테트라메틸헥사메틸렌디아민을 더 사용하게 되면 염의 침전이 생성되어 교반이 어려원진다.The use ratio of tetramethylhexamethylenediamine, which is a solvent, and an aromatic compound is 2: 1 by weight, and when the aromatic compound is used more than this value, the reaction by-products are produced, and the yield is decreased, and the use of tetramethylhexamethylenediamine is more preferable. Precipitation of salts is then generated, making stirring difficult.
본 발명에 의해 제조된 트리아릴포스파이트는 우수한 산화방지효과가 있으므로 열가소성 고분자의 자외선 안정제로 널리 사용된다.The triaryl phosphite prepared by the present invention has excellent anti-oxidation effect and thus is widely used as an ultraviolet light stabilizer of thermoplastic polymers.
이하, 본 발명을 실시예에 의거 더욱 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
단, 본 발명이 실시예로 국한되는 것은 아니다.However, the present invention is not limited to the examples.
[실시예 1]Example 1
온도계, 교반기 및 질소주입기가 장치된 500ml 4구 플라스크에 톨루엔 30g, TMHD 15g을 투입한 후 185.7g의 2, 4-디-t-부틸페놀(2, 4-Di-t-butyphenol, 24 DTBP)을 투입하였다.Into a 500 ml four-necked flask equipped with a thermometer, agitator and nitrogen injector, 30 g of toluene and 15 g of TMHD were added, followed by 185.7 g of 2, 4-di-t-butyphenol (24 DTBP). Was added.
30℃에서 삼염소화인 41.2g을 적하하면서 첨가한 후 50℃로 승온하여 1시간 반응시키고, 다시 80℃로 승온한 후 1시간동안 교반하면서 반응시켰다. 이후 2시간 동안 질소로 버블링(bubbling)한 후 반응을 완결시키고, 진공으로 복합용매를 증류하여 회수하였다.41.2 g of phosphorus trichlorine was added dropwise at 30 ° C., and then heated to 50 ° C. for 1 hour, and then heated to 80 ° C., followed by stirring for 1 hour. After bubbling with nitrogen for 2 hours, the reaction was completed, and the complex solvent was recovered by distillation under vacuum.
반응물에 이소프로필알코올(IPA) 150g을 투입하고, 20℃로 냉각시켜 재결정시킨 후 여과, 건조하여 수율 95%의 트리스(디-t-부틸페닐)포스파이트 백색입자를 얻었다.150 g of isopropyl alcohol (IPA) was added to the reaction mixture, cooled to 20 ° C., recrystallized, filtered, and dried to obtain tris (di-t-butylphenyl) phosphite white particles having a yield of 95%.
[비교예 1]Comparative Example 1
크실렌과 TMHD의 용매비가 2 : 0.5 인 것을 제외하고는, 실시예 1과 동일하게 반응시켰다. 결과로 수율 80%의 트리아릴포스파이트 백색입자를 얻었다.The reaction was carried out in the same manner as in Example 1 except that the solvent ratio of xylene and TMHD was 2: 0.5. As a result, triaryl phosphite white particles having a yield of 80% were obtained.
[비교예 2]Comparative Example 2
크실렌과 TMHD의 용매비가 2 : 0.1 인 것을 제외하고는 실시예 1과 동일하게 반응시켰다. 결과로 수율 64%의 트리아릴포스파이트 백색입자를 얻었다.The reaction was carried out in the same manner as in Example 1 except that the solvent ratio of xylene and TMHD was 2: 0.1. As a result, triaryl phosphite white particles having a yield of 64% were obtained.
[비교예 3]Comparative Example 3
크실렌과 TMHD의 용매비가 2 : 4 인 것을 제외하고는 실시예 1과 동일하게 반응시켰다. 결과로 수율 23%의 트리아릴포스파이트 백색입자를 얻었다.The reaction was carried out in the same manner as in Example 1 except that the solvent ratio of xylene and TMHD was 2: 4. As a result, triaryl phosphite white particles having a yield of 23% were obtained.
[비교예 4][Comparative Example 4]
반응온도가 45℃인 것을 제외하고는 실시예 1과 동일하게 반응시켰다. 결과로 수율 56%의 트리아필포스파이트 백색입자를 얻었다.The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 45 ° C. As a result, triafil phosphite white particles having a yield of 56% were obtained.
[비교예 5][Comparative Example 5]
반응온도가 130℃인 것을 제외하고는 실시예 1과 동일하게 반응시켰다. 결과로 수율 54%의 트리아필포스파이트 백색입자를 얻었다.The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 130 ° C. As a result, triafil phosphite white particles having a yield of 54% were obtained.
[비교예 6]Comparative Example 6
용매로서 크실렌/TMHD 대신에 크실렌/A, N-디메틸아닐린을 사용한 것을 제외하고는 실시예 1과 동일하게 반응시켰다. 결과로 수율 90%의 트리아릴포스파이트 백색입자를 얻었다.The reaction was carried out in the same manner as in Example 1 except that xylene / A and N-dimethylaniline were used instead of xylene / TMHD as a solvent. As a result, triaryl phosphite white particles having a yield of 90% were obtained.
[비교예 7]Comparative Example 7
용매로서 크실렌/TMHD 대신에 크실렌/피리딘을 사용한 것을 제외하고는 실시예 1과 동일하게 반응시켰다. 결과로 수율 90%의 트리아릴포스파이트 백색입자를 얻었다.The reaction was carried out in the same manner as in Example 1, except that xylene / pyridine was used instead of xylene / TMHD as a solvent. As a result, triaryl phosphite white particles having a yield of 90% were obtained.
이상에서는 실시예 및 비교예의 반응조건 및 수율을 표1에 나타내었다.In the above, the reaction conditions and yields of Examples and Comparative Examples are shown in Table 1.
[표 1]TABLE 1
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019920026026A KR950011360B1 (en) | 1992-12-29 | 1992-12-29 | Method of preparating triarylphosphate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019920026026A KR950011360B1 (en) | 1992-12-29 | 1992-12-29 | Method of preparating triarylphosphate |
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| Publication Number | Publication Date |
|---|---|
| KR940014419A KR940014419A (en) | 1994-07-18 |
| KR950011360B1 true KR950011360B1 (en) | 1995-10-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019920026026A KR950011360B1 (en) | 1992-12-29 | 1992-12-29 | Method of preparating triarylphosphate |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR950011360B1 (en) |
-
1992
- 1992-12-29 KR KR1019920026026A patent/KR950011360B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR940014419A (en) | 1994-07-18 |
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