CN105693771A - 含嘧啶环的膦酸酯类化合物及其制备方法和用途 - Google Patents
含嘧啶环的膦酸酯类化合物及其制备方法和用途 Download PDFInfo
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 15
- 239000000460 chlorine Substances 0.000 claims abstract description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 125000002541 furyl group Chemical group 0.000 claims abstract description 5
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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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6509—Six-membered rings
- C07F9/6512—Six-membered rings having the nitrogen atoms in positions 1 and 3
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing heterocyclic radicals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus as a ring member
-
- 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
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Biochemistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
本发明提供了一种含嘧啶环的膦酸酯类化合物及其制备方法和用途,该化合物为式I所示化合物或其对映异构体、非对映异构体、外消旋体、药学上可接受的盐、结晶水合物或溶剂合物。X为O或S;R1为甲基、任选取代的苯基或呋喃基;R2为 或R3为氯或。该类化合物能够用于除草。
Description
技术领域
本发明涉及农药领域,具体的,本发明涉及含嘧啶环的膦酸酯类化合物及其制备方法和应用,更具体的,本发明涉及式Ι所示化合物以及衍生物及其制备方法、农药组合物、式Ι所示化合物在制备除草剂的用途。
背景技术
含嘧啶类的除草剂种类较多,主要包括嘧啶羧酸类,嘧啶磺酰脲类以及三唑并嘧啶类。嘧啶羧酸类除草剂是从磺酰脲类化合物的结构改造而来的,主要是通过抑制植物的支链氨基酸的生物合成而达到除草目的,属于乙酰乳酸合成酶(ALS)抑制剂。
然而,在有限的耕地面积上得到满足大量人口所需的粮食就必须用到农药,如何创制出高活性、高选择性、低毒、无公害、环境友好和结构新颖的新农药,是当前科学家研究关注的焦点。
发明内容
本发明旨在解决现有技术中存在的技术问题之一,为此,本发明的一个目的在于提供了一种能够用于制备除草剂的化合物。
在本发明的第一方面,提供了一种含嘧啶环的膦酸酯类化合物化合物。根据本发明的实施例,该化合物为式I所示化合物或式I所示化合物的对映异构体、非对映异构体、外消旋体、药学上可接受的盐、结晶水合物或溶剂合物,
其中,
X为O或S;
R1为甲基、任选取代的苯基或呋喃基;
R2为
R3为氯或
发明人惊奇地发现,根据本发明实施例的化合物具有好的除草活性。
根据本发明的实施例,上述化合物还可以具有下列附加技术特征:
根据本发明的一个实施例中,R1为甲基、苯基、至少一个卤素取代的苯基、至少一个甲基取代的苯基、至少一个甲氧基取代的苯基、至少一个硝基取代的苯基或呋喃基,任选地,所述卤素为氟、氯、溴。
根据本发明的一个实施例中,R1为甲基、苯基、4-甲氧基苯基、4-甲基苯基、4-硝基苯基、3-氯苯基、4-氯苯基、2,4-二氯苯基、2-溴苯基、4-溴苯基、4-氟苯基或2-呋喃基。
根据本发明的一个实施例中,化合物为下列化合物或者所述下列化合物的对映异构体、非对映异构体、外消旋体、药学上可接受的盐、结晶水合物或溶剂合物:
在本发明的第二方面,本发明提供了一种制备前面所述化合物的方法,根据本发明的实施例,该方法包括:
使式A所示化合物与式B所示化合物进行接触,以便获得式I所示化合物;
其中X、R1、R2、R3是如前面所描述的。
根据本发明的实施例,所述接触是使式A所示化合物、式B所示化合物以及DMAP溶解在二氯甲烷里,冷却至0摄氏度滴加DCC,在室温搅拌10个小时进行的。
根据本发明的实施例,所述式A所示化合物与所述式B所示化合物、DCC、DMAP的摩尔比为1:1:1:0.01~0.02。
根据本发明的实施例,进一步包括:
通过柱层析,分离所述式I所示化合物,其中,所述柱层析采用石油醚与乙酸乙酯的混合物作为分离相,并且石油醚与乙酸乙酯的体积比为1:2。
由此,根据本发明的实施例,本发明提出了一条合成路线,可以用于制备式I所示化合物
以1-(2-氯-6-((4,6-二甲氧嘧啶-2-基)巯基)苯甲酰氧基)-2,4-二氯苯基膦酸二甲酯I-1为例。向100mL圆底烧瓶中加入2-氯-6-(4,6-二甲氧基嘧啶-2-硫基)苯甲酸(A)0.98g(3mmol)、1-羟基-2,4-二氯苯基膦酸酯0.85g(3mmol)、30mL处理CH2Cl2和催化量的DMAP(4-二甲氨基吡啶),搅拌溶解,冰浴条件下滴加溶于10mL处理CH2Cl2中的DCC(二环己基碳二酰亚胺)0.62g(3mmol),滴加完毕后撤去冰浴,室温搅拌过夜,TLC监测反应结束。过滤,除去不溶于CH2Cl2的DCU,滤液脱溶后再用少量的CH3COCH3溶解,过滤,如此反复三次,所得粗品经硅胶柱层析得纯品淡黄色油状物,洗脱剂CH3COCH3:石油醚=2:1(v/v),收率43%。
本发明的第三方面,本发明提供了一种除草剂,其包括前面所描述的化合物。
在本发明的第四方面,本发明提供了前面所述的化合物或的药物组合物在除杂草中的用途,所述杂草为稗草(Echinochloacrusgalli)、马唐(Digitariaadscendens)、狗尾草(Setariafaberii)、苘麻(Abutilontheophrasti)、反枝苋(Amaranthusretroflexus)或者芥菜(Brassicajuncea)。
本发明的附加方面和优点将在下面的描述中部分给出,部分将从下面的描述中变得明显,或通过本发明的实践了解到。
具体实施方式
下面详细描述本发明的实施例。下面描述的实施例是示例性的,仅用于解释本发明,而不能理解为对本发明的限制。
实施例1
化合物I-1
(2,4-dichlorophenyl)(dimethoxyphosphoryl)methyl2-chloro-6-((4,6-dimethoxypyrimidin-2-yl)thio)benzoate
的制备
向100mL圆底烧瓶中加入2-氯-6-(4,6-二甲氧基嘧啶-2-硫基)苯甲酸(A)0.98g(3mmol)、1-羟基-2,4-二氯苯基膦酸酯0.85g(3mmol)、30mL处理CH2Cl2和0.03mmol的DMAP(4-二甲氨基吡啶),搅拌溶解,冰浴条件下滴加溶于10mL处理CH2Cl2中的DCC(二环己基碳二酰亚胺)0.62g(3mmol),滴加完毕后撤去冰浴,室温搅拌过夜,TLC监测反应结束。过滤,除去不溶于CH2Cl2的DCU,滤液脱溶后再用少量的CH3COCH3溶解,过滤,如此反复三次,所得粗品经硅胶柱层析得纯品淡黄色油状物,洗脱剂CH3COCH3:石油醚=2:1(v/v),收率43%。Yellowoil;Yield63%;nD 201.5697;1HNMR(400MHz,CDCl3,TMS)δ(ppm):3.53~3.72(m,12H,4×(OCH3)),5.64(s,1H,pyridineH),6.70(d,1H,J=13.6Hz,P-CH),7.04~7.53(m,6H,Ar-H);13CNMR(100MHz,CDCl3)δ(ppm):53.64,53.84;65.87,67.58,86.31,126.99,128.67,129.12,130.27,130.47,130.84,134.02,135.10,135.98,137.86,163.74,168.65,170.55;31PNMR(160MHz,CDCl3):17.53;IR(KBr)ν(cm-1):3324,2954,2853,1748(C=O),1713,1626,1582,1549,1475,1462,1435,1391,1376,1192(P=O),1166,1047(C-O-C),916,823,761(Ar);EI-MS(EI)m/z(%):594(M+,1),311(12),309(27),282(15),281(100);ElementalAnal.CalcdforC22H20Cl3N2O7PS(594):C,44.50;H,3.39;N,4.72.Found:C,44.16;H,3.70;N,5.05.
以下化合物按照化合物1-1的方法制备,其结构鉴定数据如下:
I-2
(dimethoxyphosphoryl)(4-methoxyphenyl)methyl2-chloro-6-((4,6-dimethoxypyrimidin-2-yl)thio)benzoate
Yellowsoild;Yield18%;m.p.65~66℃;1HNMR(400MHz,CDCl3,TMS)δ(ppm):3.66~3.72(m,12H,4×(OCH3)),3.89(s,3H,Ar-OCH 3 ),5.72(s,1H,pyridineH),6.33(d,1H,J=13.6Hz,P-CH),7.27~7.63(m,7H,Ar-H);13CNMR(100MHz,CDCl3)δ(ppm):53.72,53.90,63.39,71.09,86.42,128.54,128.88,129.54,129.60,129.88,130.12,130.41,130.49,130.75,130.97,135.81,136.14,138.31,168.83,170.72;31PNMR(160MHz,CDCl3):18.17;IR(KBr)ν(cm-1):3326,2931,2853,1744,1712(C=O),1626,1581,1550,1461,1391,1376,1192(P=O),1166,1048(C-O-C),914,757(Ar);EI-MS(EI)m/z(%):311(19),310(10),309(50),283(36),282(18),281(100),224(6),143(7),139(10),109(3),93(11);ElementalAnal.CalcdforC23H24ClN2O8PS(555):C,49.78;H,4.36;N,5.05.Found:C,50.14;H,4.52;N,5.30.
I-3
(2-bromophenyl)(dimethoxyphosphoryl)methyl2-chloro-6-((4,6-dimethoxypyrimidin-2-yl)thio)benzoate
Yellowoil;Yield18%;nD 201.5690;1HNMR(400MHz,CDCl3,TMS)δ(ppm):3.59~3.85(m,12H,4×(OCH3)),5.69(s,1H,pyridineH),6.83(d,1H,J=13.6Hz,P-CH),6.82~7.59(m,7H,Ar-H);13CNMR(100MHz,CDCl3)δ(ppm):53.96,69.13,70.87,86.50,127.29,129.03,130.17,130.38,130.45,131.16,132.27,132.77,134.62,135.49,136.10,158.69,163.82,168.95,170.74;31PNMR(160MHz,CDCl3):17.21;IR(KBr)ν(cm-1):3327,3068,2995,2934,2853,1758(C=O),1627,1579,1548,1476,1462,1391,1376,1191(P=O),1167,1039(C-O-C),918,737(Ar).
I-4
(dimethoxyphosphoryl)(4-fluorophenyl)methyl2-chloro-6-((4,6-dimethoxypyrimidin-2-yl)thio)benzoate
Yellowsoild;Yield28%;m.p.108~109℃;1HNMR(400MHz,CDCl3,TMS)δ(ppm):3.64~3.74(m,12H,4×(OCH3)),5.71(s,1H,pyridineH),6.34(d,1H,J=15Hz,P-CH),6.96~7.60(m,7H,Ar-H);13CNMR(100MHz,CDCl3)δ(ppm):53.69,53.83,69.23,70.93,86.31,115.19,115.41,127.94,128.68,130.19,130.26,130.36,130.46,130.84,136.06,138.24,161.29,164.04,164.13,168.77,170.60;31PNMR(160MHz,CDCl3):17.62;IR(KBr)ν(cm-1):3329,2992,2955,2931,2854,1738(C=O),1626,1583,1551,1510,1462,1390,1376,1192(P=O),1167,1048(C-O-C),915,819,785(Ar);EI-MS(EI)m/z(%):542(M+,1),311(19),310(10),309(52),283(38),282(17),281(100);ElementalAnal.CalcdforC22H21ClFN2O7PS(543):C,48.67;H,3.90;N,5.16.Found:C,48.70;H,3.99;N,4.79.
I-5
(dimethoxyphosphoryl)(phenyl)methyl2-chloro-6-((4,6-dimethoxypyrimidin-2-yl)thio)benzoate
Yellowoil;Yield30%;nD 20=1.5704;1HNMR(400MHz,CDCl3,TMS)δ(ppm):3.63~3.76(m,12H,4×(OCH3)),5.71(s,1H,pyridineH),6.38(d,1H,J=13.2Hz,P-CH),7.29~7.61(m,8H,Ar-H);13CNMR(100MHz,CDCl3)δ(ppm):53.65,53.86,69.97,71.66,86.33,127.60,128.00,128.06,128.23,128.67,128.73,129.80,130.37,130.94,131.97,136.05,138.42,164.09,168.86,170.58;31PNMR(160MHz,CDCl3):197.80;IR(KBr)ν(cm-1):3364,3082,2934,2856,1746(C=O),1712,1651,1584,1461,1376,1192(P=O),1165,1047(C-O-C),915,768(Ar);EI-MS(EI)m/z(%):283(32),282(16),281(100),170(1),143(6);ElementalAnal.CalcdforC22H22ClFN2O7PS(525):C,50.34;H,4.22;N,5.34.Found:C,50.78;H,4.15;N,5.67.
I-6
(4-bromophenyl)(dimethoxyphosphoryl)methyl2-chloro-6-((4,6-dimethoxypyrimidin-2-yl)thio)benzoate
Yellowsoild;Yield14%;m.p.42~44℃;1HNMR(400MHz,CDCl3,TMS)δ(ppm):3.64~3.74(m,12H,4×(OCH3)),5.72(s,1H,pyridineH),6.31(d,1H,J=13.6Hz,P-CH),7.28~7.62(m,7H,Ar-H);13CNMR(100MHz,CDCl3)δ(ppm):53.93,69.32,71.01,86.36,122.98,128.72,129.74,130.50,130.88,131.15,131.45,136.10,138.21,164.12,168.76,170.63;31PNMR(160MHz,CDCl3):17.17;IR(KBr)ν(cm-1):3325,2932,2854,1749(C=O),1653,1581,1461,1376,1192(P=O),1133,1047(C-O-C),915,756(Ar);ElementalAnal.CalcdforC22H21BrClN2O7PS(604):C,43.76;H,3.51;N,4.64.Found:C,43.88;H,3.95;N,5.00.
I-7
(dimethoxyphosphoryl)(p-tolyl)methyl2-chloro-6-((4,6-dimethoxypyrimidin-2-yl)thio)benzoate
Yellowoil;Yield22%;nD 201.5572;1HNMR(400MHz,CDCl3,TMS)δ(ppm):2.34(s,3H,-CH3),3.63~3.77(m,12H,4×(OCH3)),5.70(s,1H,pyridineH),6.35(d,1H,J=12.8Hz,P-CH),7.29~7.60(m,7H,Ar-H);13CNMR(100MHz,CDCl3)δ(ppm):21.10.53.63,53.83,86.31,126.82,128.01,128.69,128.88,128.96,129.35,129.66,130.34,130.94,135.46,136.04,138.52,170.56;31PNMR(160MHz,CDCl3):18.03;IR(KBr)ν(cm-1):3324,2931,1745(C=O),1581,1552,1460,1391,1376,1192(P=O),1166,1048(C-O-C),914,756(Ar);EI-MS(EI)m/z(%):309(4),283(40),282(22),281(100),171(2),170(2);ElementalAnal.CalcdforC23H24ClN2O7PS(539):C,51.26;H,4.49;N,5.20.Found:C,51.67;H,4.82;N,5.62.
I-8
(dimethoxyphosphoryl)(4-nitrophenyl)methyl2-chloro-6-((4,6-dimethoxypyrimidin-2-yl)thio)benzoate
Yellowsoild;Yield41%;m.p.108~109℃;1HNMR(400MHz,CDCl3,TMS)δ(ppm):3.64~3.78(m,12H,4×(OCH3)),5.73(s,1H,pyridineH),6.43(d,1H,J=14Hz,P-CH),7.44~8.17(m,7H,Ar-H);13CNMR(100MHz,CDCl3)δ(ppm):53.85,53.89,54.00,54.08,69.25,70.92,86.42,123.37,127.57,128.79,128.84,129.86,130.46,130.71,130.88,135.84,136.22,137.91,139.51,147.78;31PNMR(160MHz,CDCl3):16.26;IR(KBr)ν(cm-1):3333,2875,1760(C=O),1626,1587,1554,1520,1462,1376,1194(P=O),1167,1045(C-O-C),918,760(Ar);EI-MS(EI)m/z(%):569(M+),311(5),309(20),283(40),282(17),281(100),247(5),109(9);ElementalAnal.CalcdforC22H21ClN3O9PS(569):C,46.36;H,3.71;N,7.37.Found:C,46.87;H,4.41;N,7.59.
I-9
(4-chlorophenyl)(dimethoxyphosphoryl)methyl2-chloro-6-((4,6-dimethoxypyrimidin-2-yl)thio)benzoate
Yellowoil;Yield45%;nD 201.5667;1HNMR(400MHz,CDCl3,TMS)δ(ppm):3.66~3.74(m,12H,4×(OCH3)),5.72(s,1H,pyridineH),6.33(d,1H,J=13.2Hz,P-CH),7.35~7.61(m,7H,Ar-H);13CNMR(100MHz,CDCl3)δ(ppm):53.62,53.68,53.76,53.86,69.33,71.03,86.37,128.48,128.80,129.49,129.55,130.38,130.48,130.70,130.90,134.67,134.71,136.10,138.24,163.99,164.08,168.79,170.66;31PNMR(160MHz,CDCl3):17.31;IR(KBr)ν(cm-1):3481,2995,2955,2854,1748(C=O),1712,1582,1550,1491,1461,1392,1376,1192(P=O),1166,1047(C-O-C),915,758(Ar);EI-MS(EI)m/z(%):311(18),310(10),309(44),283(40),282(19),281(100),247(3),170(4),142(3),141(2),140(2),139(12),109(2);ElementalAnal.CalcdforC22H21Cl2N2O7PS(559):C,47.24;H,3.78;N,5.01.Found:C,47.82;H,3.58;N,4.98.
I-10
(3-chlorophenyl)(dimethoxyphosphoryl)methyl2-chloro-6-((4,6-dimethoxypyrimidin-2-yl)thio)benzoate
Yellowoil;Yield56%;nD 201.5661;1HNMR(400MHz,CDCl3,TMS)δ(ppm):3.67~3.74(m,12H,4×(OCH3)),5.70(s,1H,pyridineH),6.32(d,1H,J=13.6Hz,P-CH),7.29~7.62(m,7H,Ar-H);13CNMR(100MHz,CDCl3)δ(ppm):53.59,53.65,53.79,69.28,70.95,86.37,126.17,128.00,128.06,128.82,129.45,130.32,130.46,130.86,134.08,136.00,138.07,163.90,163.99,168.66,170.59;31PNMR(160MHz,CDCl3):17.14;IR(KBr)ν(cm-1):3481,3069,2995,2954,2854,1754(C=O),1712,1648,1592,1476,1376,1193(P=O),1133,1040(C-O-C),915,753(Ar);EI-MS(EI)m/z(%):560(M+),311(10),310(5),309(29),283(38),282(17),281(100),247(4),172(2),170(6),142(4),141(3),140(2),139(10),110(2),109(3);ElementalAnal.CalcdforC22H21Cl2N2O7PS(560):C,47.24;H,3.78;N,5.01.Found:C,47.71;H,3.68;N,5.05.
I-11
(dimethoxyphosphoryl)(furan-2-yl)methyl2-chloro-6-((4,6-dimethoxypyrimidin-2-yl)thio)benzoate
Yellowsoild;Yield26%;m.p.89~91℃;1HNMR(400MHz,CDCl3,TMS)δ(ppm):3.66~3.81(m,12H,4×(OCH3)),5.69(s,1H,pyridineH),6.52(d,1H,J=15.2Hz,P-CH),6.35~7.59(m,6H,Ar-H);13CNMR(100MHz,CDCl3)δ(ppm):53.48,53.54,53.70,53.76,62.50,64.25,86.22,110.60,112.56,112.62,128.75,130.32,130.40,130.94,135.88,138.23,143.70,145.44,163.88,163.97,168.82,170.55;31PNMR(160MHz,CDCl3):15.67;IR(KBr)ν(cm-1):3481,3120,2955,2855,1748(C=O),1712,1647,1584,1551,1462,1436,1192(P=O),1166,1047(C-O-C),915,758(Ar).
I-12
(diethoxyphosphoryl)(furan-2-yl)methyl2-chloro-6-((4,6-dimethoxypyrimi-din-2-yl)thio)benzoate
Yellowoil;Yield35%;nD 201.5506;1HNMR(400MHz,CDCl3,TMS)δ(ppm):1.31~1.33(t,6H,-CH2CH 3),3.67(s,6H,2×(OCH3)),4.08~4.13(m,4H,-CH2-),5.67(s,1H,pyridineH),6.47(d,1H,J=15.2Hz,P-CH),6.32~7.57(m,6H,Ar-H);13CNMR(100MHz,CDCl3)δ(ppm):16.09,16.18,16.24,53.79,53.91,63.37,63.43,63.51,64.98,86.30,110.57,112.40,112.46,128.85,130.28,130.32,130.97,135.88,138.25,143.50,145.82,164.08,168.84,170.56,170.61,170.71;31PNMR(160MHz,CDCl3):12.96;IR(KBr)ν(cm-1):3473,2986,2933,2857,1749(C=O),1712,1647,1582,1551,1461,1391,1376,1192(P=O),1165,1047(C-O-C),915,749(Ar).
I-13
1-(5,5-dimethyl-2-oxido-1,3,2-dioxaphosphinan-2-yl)ethyl2-chloro-6-((4,6-dimethoxypyrimidin-2-yl)thio)benzoate
Yellowoil;Yield17%;nD 201.5736;1HNMR(400MHz,CDCl3,TMS)δ(ppm):1.16(s,6H,C(CH2)(CH 3)),1.63(d,3H,-CH 3),3.72(s,6H,2×(OCH3)),3.91~4.07(m,4H,2×(CH2)),5.68(s,1H,pyridineH),6.43(d,1H,J=14Hz,P-CH),7.44~8.17(m,7H,Ar-H);13CNMR(100MHz,CDCl3)δ(ppm):14.55,24.78,32.35,33.04,33.12,50.37,53.94,54.04,86.05,86.57,126.95,127.34,128.88,129.50,129.77,130.39,135.54,136.25,144.39,170.07,170.71,170.87,171.95;31PNMR(160MHz,CDCl3):11.74;IR(KBr)ν(cm-1):3327,2931,2855,1744(C=O),1684,1627,1587,1460,1391,1375,1193(P=O),1163,1050(C-O-C),914,754(Ar).
I-14
(5,5-dimethyl-2-oxido-1,3,2-dioxaphosphinan-2-yl)(phenyl)methyl2-chloro-6-((4,6-dimethoxypyrimidin-2-yl)thio)benzoate
Yellowoil;Yield22%;nD 201.5566;1HNMR(400MHz,CDCl3,TMS)δ(ppm):1.16(s,6H,C(CH2)(CH 3)),3.69(s,6H,2×(OCH3)),3.94~4.14(m,4H,2×(CH2)),5.70(s,1H,pyridineH),6.46(d,1H,J=11.6Hz,P-CH),7.29~8.15(m,8H,Ar-H);13CNMR(100MHz,CDCl3)δ(ppm):21.64,30.81,53.92,70.45,72.09,86.47,127.75,128.26,128.51,128.60,128.84,129.82,130.37,130.43,130.96,131.84,133.62,136.11,138.10,164.20,168.68,170.69;31PNMR(160MHz,CDCl3):7.26;IR(KBr)ν(cm-1):3326,2934,1743(C=O),1711,1655,1579,1461,1376,1192(P=O),1165,1052(C-O-C),916,734(Ar).
I-15
1-(dimethoxyphosphoryl)ethyl-2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)benzoate
Whitesoild,yield52%,m.p.42~43℃.1HNMR(CDCl3,TMS,600MHz)δ(ppm):1.19(dd,3H,J=7.2Hz,J=16.8Hz,P-CH-CH 3),3.64~3.70(dd,6H,J=10.2Hz,J=27.6Hz,2×(OCH3)),3.80(s,12H,4×(OCH3)),5.24(t,J=14.4Hz,1H,CHCH3),5.77(s,2H,2×(pyrimidineH)),7.14~7.54(m,3H,Ar-H);IR(KBr)υ(cm-1):3441,1750(C=O),1604,1567,1348,952,816(Ar),1197(P=O),1166,1065(C-O-C);MS(ESI)m/z:567[M+1]+;ElementalAnal.CalcdforC23H27N4O11P(566.45):C,48.77;H,4.80;N,9.89.Found:C,48.91;H,4.67;N,9.27.
I-15
(dimethoxyphosphoryl)(furan-2-yl)methyl-2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)benzoate
Yellowsoild,yield46%,m.p.41~44℃.1HNMR(CDCl3,TMS,600MHz)δ(ppm):3.58~3.60(dd,6H,J=10.6Hz,J=34.6Hz,2×(OCH3)),3.67(s,12H,4×(OCH3)),5.64(s,2H,2×(pyrimidineH)),6.20(d,J=15.0Hz,1H,CH),6.34~7.46(m,6H,Ar-H);IR(KBr)υ(cm-1):3443,1759(C=O),1604,1567,1348,976,816(Ar),1197(P=O),1166,1063(C-O-C);MS(ESI)m/z:619[M+1]+;ElementalAnal.CalcdforC26H27N4O12P(618.49):C,50.49;H,4.40;N,9.06.Found:C,50.86;H,4.78;N,9.53.I-16
(2,4-dichlorophenyl)(dimethoxyphosphoryl)methyl-2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)benzoate
Whitesolid,yield38%,m.p.48~50℃.1HNMR(CDCl3,TMS,400MHz)δ(ppm):3.57~3.70(dd,6H,J=10.8Hz,J=44.4Hz,2×(OCH3)),3.76(s,12H,4×(OCH3)),5.72(s,2H,2×(pyrimidineH)),6.64(d,J=13.6Hz,1H,CH),7.13~7.52(m,6H,Ar-H);13CNMR(150MHz,DMSO-d6)δ(ppm):53.2,53.8,65.1,66.3,84.7,120.3,127.0,128.8,128.9,131.2,131.6,133.8,134.9,151.1,161.4,161.5,163.2,172.3;IR(KBr)υ(cm-1):3444,2958,1746(C=O),1602,1567,1473,954,815Ar),1195(P=O),1066(C-O-C);MS(EI)m/z(%):697(M+,1),385(100),386(22),413(41);ElementalAnal.CalcdforC28H27Cl2N4O11P(697.85):C,48.22;H,3.90;N,8.03.Found:C,48.98;H,3.61;N,8.29.
I-17
(dimethoxyphosphoryl)(4-nitrophenyl)methyl-2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)benzoate
Whitesolid,yield45%,m.p.61~63℃.1HNMR(CDCl3,TMS,400MHz)δ(ppm):3.64~3.76(dd,6H,J=11.2Hz,J=38.0Hz,2×(OCH3)),3.77(s,12H,4×(OCH3)),5.73(s,2H,2×(pyrimidineH)),6.22(d,J=14.8Hz,1H,CH),7.17~8.12(m,7H,Ar-H);13CNMR(150MHz,DMSO-d6)δ(ppm):53.9,54.4,84.6,119.8,120.3,120.4,123.1,128.5,128.6,131.7,139.5,147.4,151.1,161.6,163.4,172.4,172.5;IR(KBr)υ(cm-1):3443,2958,1748(C=O),1603,1567,1472,819,774(Ar),1195(P=O),1065(C-O-C);MS(EI)m/z(%):673(M+,2),385(100),386(41),413(11);ElementalAnal.CalcdforC28H25N5O13P(673.52):C,49.93;H,4.19;N,10.40.Found:C,49.52;H,3.99;N,10.56.
I-18
(dimethoxyphosphoryl)(p-tolyl)methyl-2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)benzoate
Whitesolid,yield40%,m.p.59~61℃.1HNMR(CDCl3,TMS,400MHz)δ(ppm):1.60(s,3H,CH3),3.68~3.78(dd,6H,J=11.6Hz,J=40.2Hz,2×(OCH3)),3.80(s,12H,4×(OCH3)),5.76(s,2H,2×(pyrimidineH)),6.66(d,J=10.2Hz,1H,CH),7.09~7.60(m,7H,Ar-H);13CNMR(150MHz,DMSO-d6)δ(ppm):53.8,84.5,119.4,119.9,120.2,120.5,120.6,131.2,131.7,132.5,148.8,151.5,161.0,163.3,163.7,172.4,172.5;IR(KBr)υ(cm-1):3443,2958,1760(C=O),1603,1567,1473,989,816(Ar),1194(P=O),1166,1065(C-O-C);MS(EI)m/z(%):642(M+,1),413(100),414(22),415(3);ElementalAnal.CalcdforC29H31N4O11P(642.55):C,54.21;H,4.86;N,8.72.Found:C,54.63;H,4.91;N,8.59.
I-19
(2-chlorophenyl)(dimethoxyphosphoryl)methyl-2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)benzoate
Whitesolid,yield50%,m.p.49~51℃.1HNMR(CDCl3,TMS,600MHz)δ(ppm):3.59~3.69(dd,6H,J=10.8Hz,J=48.6Hz,2×(OCH3)),3.77(s,12H,4×(OCH3)),5.72(s,2H,2×(pyrimidineH)),6.72(d,J=13.2Hz,1H,CH),7.10~7.56(m,7H,Ar-H);MS(ESI)m/z:663[M+1]+;ElementalAnal.CalcdforC28H28ClN4O11P(662.58):C,50.73;H,4.26;N,8.45.Found:C,50.41;H,4.19;N,8.58.
I-20
(dimethoxyphosphoryl)(4-methoxyphenyl)methyl-2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)benzoate
Whitesolid,yield48%,m.p.64~66℃.1HNMR(CDCl3,TMS,600MHz)δ(ppm):3.70~3.80(dd,J=11.2Hz,J=38.0Hz,6H,2×(OCH3)),3.82(s,12H,4×(OCH3)),3.85(s,3H,OCH3),5.75(s,2H,2×(pyrimidineH)),6.67(d,J=12.6Hz,1H,CH),7.13~7.84(m,7H,Ar-H);IR(KBr)υ(cm-1):3447,2956,1746(C=O),1602,1568,954,815(Ar),1196(P=O),1165,1069(C-O-C);MS(ESI)m/z:659[M+1]+;ElementalAnal.CalcdforC29H31N4O12P(658.35):C,52.89;H,4.74;N,8.51.Found:C,53.02;H,4.59;N,8.87.
I-21
(dimethoxyphosphoryl)(4-fluorophenyl)methyl-2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)benzoate
Whitesolid,yield43%,m.p.63~67℃.1HNMR(CDCl3,TMS,600MHz)δ(ppm):3.57~3.67(dd,J=10.8Hz,J=32.4Hz,6H,2×(OCH3)),3.76(s,12H,4×(OCH3)),5.70(s,2H,2×(pyrimidineH)),6.74(d,J=11.8Hz,1H,CH),7.19~8.05(m,7H,Ar-H);IR(KBr)υ(cm-1):3441,2957,1746(C=O),1602,1567,957,819(Ar),1196(P=O),1065(C-O-C);MS(ESI)m/z:647[M+1]+;ElementalAnal.CalcdforC28H28FN4O11P(646.51):C,52.02;H,4.37;N,8.67.Found:C,51.89;H,4.09;N,8.86.
I-22
(4-chlorophenyl)(dimethoxyphosphoryl)methyl-2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)benzoate
Whitesolid,yield56%,m.p.46~48℃.1HNMR(CDCl3,TMS,400MHz)δ(ppm):3.58~3.61(d,6H,J=10.8Hz,2×(OCH3)),3.77(s,12H,4×(OCH3)),5.72(s,2H,2×(pyrimidineH)),6.10(d,J=12.8Hz,1H,CH),7.13~7.53(m,7H,Ar-H);13CNMR(150MHz,DMSO-d6)δ(ppm):53.2,53.8,84.6,120.3,120.4,128.2,129.3,130.5,131.5,134.3,151.1,161.8,163.3,172.4;IR(KBr)υ(cm-1):3442,1747(C=O),1604,1569,1348,952,818(Ar),1165(P=O),1066(C-O-C);MS(ESI)m/z:663[M+1]+,685[M+Na]+;ElementalAnal.CalcdforC28H28ClN4O11P(662.58):C,50.73;H,4.26;N,8.45.Found:C,51.41;H,4.05;N,8.77.
I-23
(4-bromophenyl)(dimethoxyphosphoryl)methyl-2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)benzoate
Whitesolid,yield51%,m.p.48~51℃.1HNMR(CDCl3,TMS,600MHz)δ(ppm):3.59~3.67(dd,J=10.6Hz,J=32.6Hz,6H,2×(OCH3)),3.79(s,12H,4×(OCH3)),5.74(s,2H,2×(pyrimidineH)),6.59(d,J=11.6Hz,1H,CH),7.05~8.13(m,7H,Ar-H);13CNMR(150MHz,DMSO-d6)δ(ppm):53.2,53.8,84.6,120.0,120.3,122.6,129.5,129.6,131.0,131.2,131.6,151.0,151.1,161.7,163.3,172.4;IR(KBr)υ(cm-1):3441,2958,1745(C=O),1604,1568,952,817(Ar),1195(P=O),1165,1067(C-O-C);MS(EI)m/z(%):707(M+,2),385(100),386(28),413(74);ElementalAnal.CalcdforC28H28BrN4O11P(707.34):C,47.54;H,3.99;N,7.92.Found:C,47.07;H,4.08;N,7.73.
实施例2除草活性测试
(1)供试药剂及配制
测试化合物为II系列化合物,为95%原药。对照药剂为41%草甘膦异丙铵盐水剂和2,4-D。用分析天平(0.0001g)称取一定质量的原药,加溶剂DMF,配制成1.0%的制剂,然后用0.1%吐温-80乳化剂的蒸馏水稀释备用,对照药剂直接用水稀释后备用。
(2)试验靶标
稗草(Echinochloacrusgalli)、马唐(Digitariaadscendens)、狗尾草(Setariafaberii)、苘麻(Abutilontheophrasti)、反枝苋(Amaranthusretroflexus)和芥菜(Brassicajuncea),供试种子由浙江化工研究院种子库提供。
(3)试验方法
将供试植物种子分别均匀播入内径9cm盆钵中,于温室中培养。当供试杂草长至2.5~3叶期时,在自动喷雾装置上进行芽后茎叶处理。每处理2次重复,设空白对照,处理后静置4~5小时,待叶片上药液干后,移入温室内培养。每天观察植株生长情况,定期记录受害症状,于药后15天目测调查综合除草活性。
(4)评价标准
用目测法评价药剂对植株茎或根抑制、畸形、白化、烂等综合影响程度,0%为无除草活性,100%受害植株完全死亡,目测法评价标准见表1。
表1化合物的除草活性数据
注:(1)表中测试剂量为150gai/ha。
芽后茎叶处理结果表明:所测试化合物对六种杂草表现出一定的防效,除I-7外,化合物对稗草、狗尾草、反枝苋的防效为60~85%。I-1和I-13对禾本科植物狗尾草的防效75%,与商品化除草剂嘧草硫醚的防效相当。对双子叶植物的抑制率较高普遍高于对单子叶植物的抑制率,化合物I-16、I-20对双子叶植物苘麻的抑制率达100%,化合物I-15、I-17对单子叶植物的抑制率也达到90%以上。其中化合物I-16的除草活性最高,在150gai/ha时对六种植物的抑制率均达到100%。
在本说明书的描述中,参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不一定指的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
尽管已经示出和描述了本发明的实施例,本领域的普通技术人员可以理解:在不脱离本发明的原理和宗旨的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由权利要求及其等同物限定。
Claims (10)
1.一种含嘧啶环的膦酸酯类化合物,其特征在于,所述化合物为式I所示化合物或式I所示化合物的对映异构体、非对映异构体、外消旋体、药学上可接受的盐、结晶水合物或溶剂合物,
其中,
X为O或S;
R1为甲基、任选取代的苯基或呋喃基;
R2为
R3为氯或
2.根据权利要求1所述的含嘧啶环的膦酸酯类化合物,其特征在于,所述R1为甲基、苯基、至少一个卤素取代的苯基、至少一个甲基取代的苯基、至少一个甲氧基取代的苯基、至少一个硝基取代的苯基或呋喃基,任选地,所述卤素为氟、氯、溴。
3.根据权利要求1所述的含嘧啶环的膦酸酯类化合物,其特征在于,所述R1为甲基、苯基、4-甲氧基苯基、4-甲基苯基、4-硝基苯基、3-氯苯基、4-氯苯基、2,4-二氯苯基、2-溴苯基、4-溴苯基、4-氟苯基或2-呋喃基。
4.根据权利要求1所述的含嘧啶环的膦酸酯类化合物,其特征在于,所述化合物为下列化合物或者所述下列化合物的对映异构体、非对映异构体、外消旋体、药学上可接受的盐、结晶水合物或溶剂合物:
5.一种制备权利要求1~4任一项所述含嘧啶环的膦酸酯类化合物的方法,其特征在于,包括:
使式A所示化合物与式B所示化合物进行接触,以便获得式I所示化合物;
其中X、R1、R2、R3是如权利要求1~4任一项中所定义的。
6.根据权利要求5所述的方法,其特征在于,所述接触是使式A所示化合物、式B所示化合物以及DMAP溶解在二氯甲烷里,冷却至0摄氏度滴加DCC,在室温搅拌10个小时进行的。
7.根据权利要求5所述的方法,其特征在于,所述式A所示化合物与所述式B所示化合物、DCC、DMAP的摩尔比为1:1:1:0.01~0.02。
8.根据权利要求5所述的方法,其特征在于,进一步包括:
通过柱层析,分离所述式I所示化合物,其中,所述柱层析采用石油醚与乙酸乙酯的混合物作为分离相,并且石油醚与乙酸乙酯的体积比为1:2。
9.一种除草剂,其特征在于,包括权利要求1~4任一项中所定义的化合物。
10.一种除杂草的方法,其特征在于,为所述杂草施加权利要求1~4任一项所述的化合物,或者权利要求9所述的农药,
任选地,所述杂草为稗草(Echinochloacrusgalli)、马唐(Digitariaadscendens)、狗尾草(Setariafaberii)、苘麻(Abutilontheophrasti)、反枝苋(Amaranthusretroflexus)或者芥菜(Brassicajuncea)。
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