CN106883269B - 铜催化10-烷硫基-9-氧杂-10-膦杂菲-10-氧化物的制备方法 - Google Patents
铜催化10-烷硫基-9-氧杂-10-膦杂菲-10-氧化物的制备方法 Download PDFInfo
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- CN106883269B CN106883269B CN201710075387.0A CN201710075387A CN106883269B CN 106883269 B CN106883269 B CN 106883269B CN 201710075387 A CN201710075387 A CN 201710075387A CN 106883269 B CN106883269 B CN 106883269B
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- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 5
- 239000010949 copper Substances 0.000 title claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000001413 amino acids Chemical class 0.000 claims description 5
- -1 cycloalkyl sulfonic acid Chemical compound 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 3
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 3
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 5
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种铜催化10‑烷硫基‑9‑氧杂‑10‑膦杂菲‑10‑氧化物的制备方法。该方法以烷基磺酰氯和9,10‑二氢‑9‑氧杂‑10‑磷杂菲‑10‑氧化物为原料，在催化剂和配体的作用下，偶联生成相应的10‑烷硫基‑9‑氧杂‑10‑膦杂菲‑10‑氧化物。本发明反应条件温和，反应时间短。
Description
技术领域
本发明属于有机合成技术领域，涉及一种金属铜盐参与的10-烷硫基-9-氧杂-10-膦杂菲-10-氧化物的制备方法。
背景技术
众所周知，9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物及其衍生物具有优异的阻燃性能，磷系阻燃剂也一直是一个研究热点。但目前制备含硫有机磷阻燃化合物的方法较少，且多存在时间长、产率低等问题，因此，采用高效的制备方法制备含硫有机磷阻燃化合物就显得尤为重要。
发明内容
本发明的目的在于提供一种简单，高效的方法制备10-烷硫基-9-氧杂-10-膦杂菲-10-氧化物。
为实现上述之目的，本发明采用如下技术方案。
本发明提供一种铜催化10-烷硫基-9-氧杂-10-膦杂菲-10-氧化物的制备方法，具体步骤如下：将烷基磺酰氯和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物置于反应器中，在催化剂和配体的作用下，在50～100℃下的温度下反应1～10h，反应结束后浓缩、分离纯化即得相应的10-烷硫基-9-氧杂-10-膦杂菲-10-氧化物；其中：催化剂为铜盐；配体为氨基酸或者2,2-联吡啶。
本发明中，所述烷基磺酰氯为未取代或带有取代基的烷基或环烷基磺酰氯。优选的，所述取代基为卤素；所述烷基碳原子数目在1～20之间，环烷基的碳原子数在3～20之间。
本发明中，烷基磺酰氯和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物的摩尔比是1:3-1:7。
本发明中，有机溶剂为四氢呋喃；有机溶剂的用量如下：每摩尔烷基磺酰氯用1-6L有机溶剂。
本发明中，铜盐为二水合氯化铜或溴化亚铜中的一种或两种；氨基酸为L-脯氨酸。
本发明中，催化剂用量为烷基磺酰氯的物质的量(摩尔数)的5％～20％；配体的用量为烷基磺酰氯的物质的量(摩尔数)的10～40％。
本发明中，反应温度为50～70℃；反应时间为1～3h。本发明中，分离纯化时，将浓缩后的反应物以乙酸乙酯/石油醚＝2/1-1/5(V/V)为展开剂，进行柱层析分离。
本发明涉及的反应通式如下：
其中，R为未取代或者带有取代基的烷基或环烷基，所述取代基为卤素中的一种。
和现有技术相比，本发明的有益效果在于：
本发明的10-烷硫基-9-氧杂-10-膦杂菲-10-氧化物的制备方法，采用廉价的铜盐为催化剂，氨基酸或2,2-联吡啶为配体，烷基磺酰氯和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物为原料。制备过程无需氮气保护，反应条件温和，在较短时间内即可发生偶联反应制备相应的目标化合物；本发明的制备方法工艺简单，操作方便，适合推广应用；
具体实施方式
为了使本领域技术人员更好地理解本发明，以下通过实施例对本发明做进一步说明，但这些实施例并不限制本发明的范围。
实施例1
10-丁基硫基-9-氧杂-10-膦杂菲-10-氧化物的制备方法，包括下列步骤：
称取2.0mmol的9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物与0.5mmol1-丁基磺酰氯于反应瓶中，加入0.025mmol的二水合氯化铜和0.05mmol的L-脯氨酸，加入1.0mL四氢呋喃，80℃下反应3h。反应液减压浓缩，以乙酸乙酯/石油醚＝1:10-1:5(v/v)为展开剂，柱层析分离，得123mg目标化合物。
本实施例的目标产品收率为81﹪。
对目标产品进行核磁表征，如下：1H NMR(500MHz,CDCl3):δ7.91-7.86(m,1H),7.82-7.77(m,2H),7.58-7.55(m,1H),7.41-7.38(m,1H),7.28-7.24(m,1H),7.16-7.10(m,2H),2.84-2.68(m,2H),1.55-1.48(m,2H),1.26-1.19(m,2H),0.74(t,J＝7.5Hz,3H)。
实施例2
10-丁基硫基-9-氧杂-10-膦杂菲-10-氧化物的制备方法，包括下列步骤：
称取2.0mmol的9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物与0.5mmol1-丁基磺酰氯于反应瓶中，加入0.1mmol的溴化亚铜和0.2mmol的2,2-联吡啶，加入1.0mL四氢呋喃，80℃下反应1h。反应液减压浓缩，以乙酸乙酯/石油醚＝1:10-1:5(v/v)为展开剂，柱层析分离，得120mg目标化合物。
本实施例的目标产品收率为79﹪。
Claims (6)
1.一种铜催化10-烷硫基-9-氧杂-10-膦杂菲-10-氧化物的制备方法，其特征在于，具体步骤如下：将未取代或带有取代基的烷基或环烷基磺酰氯和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物置于反应器中，在催化剂和配体的作用下，在50～100℃下的温度下反应1～10h，反应结束后浓缩、分离纯化即得相应的10-烷硫基-9-氧杂-10-膦杂菲-10-氧化物；其中：催化剂为铜盐，所述铜盐为二水合氯化铜；配体为氨基酸或者2,2-联吡啶，所述氨基酸为L-脯氨酸。
2.根据权利要求1所述的制备方法，所述取代基为卤素；所述烷基碳原子数目在1～20之间，环烷基的碳原子数在3～20之间。
3.根据权利要求1所述的制备方法，其特征在于：烷基磺酰氯和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物的摩尔比是1:3-1:7。
4.根据权利要求1所述的制备方法，其特征在于：有机溶剂为四氢呋喃；有机溶剂的用量如下：每摩尔烷基磺酰氯用1-6L有机溶剂。
5.根据权利要求1所述的制备方法，其特征在于：催化剂用量为烷基磺酰氯的物质的量的5％～20％；配体的用量为烷基磺酰氯的物质的量的10～40％。
6.根据权利要求1所述的制备方法，其特征在于，反应温度为50～70℃；反应时间为1～3h。
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104292255A (zh) * | 2014-01-06 | 2015-01-21 | 郑州大学 | 一种s-芳基硫代磷酸酯的制备方法 |
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| CN104292255A (zh) * | 2014-01-06 | 2015-01-21 | 郑州大学 | 一种s-芳基硫代磷酸酯的制备方法 |
Non-Patent Citations (3)
| Title |
|---|
| Direct synthesis of thiophosphates by reaction of diphenylphosphine oxide with sulfonyl chlorides;He, Wei et al;《Tetrahedron》;20161011;第72卷;第7594-7598页 |
| Metal and base-free reductive coupling reaction of P(O)–H with aryl/alkyl sulfonyl chlorides: a novel protocol for the construction of P–S–Cbonds;Dungai Wang et al;《Org. Biomol. Chem.》;20161129;第15卷;第545-549页 |
| 铜催化芳基磺酰氯与亚磷酸酯还原偶联反应合成S_芳基硫代磷酸酯;白洁;《中国优秀硕士学位论文全文数据库》;20150215(第2期);第1-2章 |
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